CN208352343U - A kind of perovskite solar cell module - Google Patents
A kind of perovskite solar cell module Download PDFInfo
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- CN208352343U CN208352343U CN201821027923.6U CN201821027923U CN208352343U CN 208352343 U CN208352343 U CN 208352343U CN 201821027923 U CN201821027923 U CN 201821027923U CN 208352343 U CN208352343 U CN 208352343U
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The utility model relates to a kind of perovskite solar cell module include: multiple single-unit perovskite solar battery cells and the connection unit for connecting adjacent single-unit perovskite solar battery cell, wherein, the single-unit perovskite solar battery cell includes the substrate for being sequentially overlapped setting, conductive layer, hole blocking layer, mesoporous shelf layer, patterned perovskite active layer and carbon electrode, the connection unit includes the insulating tape between the conductive layer of adjacent single-unit perovskite solar battery cell, connect the carbon electrode of adjacent single-unit perovskite solar battery cell；The perovskite active layer of the adjacent single-unit perovskite solar battery cell is discontinuous, and the connection unit does not include perovskite active layer.The utility model can effectively improve the performance of perovskite solar cell module.
Description
Technical field
The utility model belongs to technical field of solar batteries, in particular to a kind of perovskite solar cell module.
Background technique
With the gradually aggravation of energy crisis and environmental pollution, demand of the mankind to renewable energy is increasing.The sun
Can have it is safe and pollution-free, by geographical conditions the advantages such as do not limited, be to be most widely used in various renewable energy, most have
One kind of development prospect.And in the technology of various effective use solar energy, photovoltaic power generation is undoubtedly most promising direction
One of.In numerous novel solar batteries, perovskite solar battery (perovskite solar cells) has excellent
Photoelectric conversion performance, required raw material rich reserves, preparation process is simple, is most promising solar battery
One of.
Although the photoelectric conversion efficiency of perovskite solar battery has reached 20% or more, with silica-based solar cell phase
Closely, but its battery size all very littles, less than 1cm2, therefore, it is necessary to develop large-sized perovskite solar battery to promote
Industrialization.Battery size increase directly can be dramatically increased into Carrier recombination probability, so as to cause photoelectric current, photovoltage and conversion
Efficiency drastically reduces.By the way that multiple concatenated methods of single-unit perovskite solar battery are prepared perovskite solar battery mould
Block, can, energy loss can be effectively prevented from.But the preparation method of perovskite active layer often uses spin-coating method, in adjacent list
The remaining perovskite thin film in the junction of batteries will increase series resistance, also be unfavorable for the long-time stability of device, therefore right
The graphical preparation of perovskite is very crucial.
Patent document 1 discloses a kind of large area perovskite solar cell module, removes marker space by etching technics
The perovskite active layer in domain, but the technical solution increases the complexity of technique.Anish Priyadarshi et al.
(Energy Environ.Sci., 2016,9,3687--3692) and patent document 2 individually disclose a kind of based on calcining carbon electricity
The large area perovskite solar cell module of pole.Perovskite needs subsequent filling to infiltrate into battery structure in the technical solution
In, the homogeneity of perovskite is more difficult to control, it is also difficult to perovskite be avoided to infiltrate into the separated region of adjacent single battery.Cause
This still lacks simple and easy to do and lower-cost module design in perovskite area of solar cell.
Existing technical literature:
Patent document 1: Chinese patent discloses CN106910827A；
Patent document 2: Chinese patent discloses CN105576135A.
Utility model content
In view of the above-mentioned problems in the prior art, the technical problem to be solved by the utility model is to provide one kind
Perovskite solar cell module and preparation method thereof can effectively improve the performance of perovskite solar cell module.
On the one hand, the perovskite solar cell module of the utility model, comprising: multiple single-unit perovskite solar batteries
Unit and the connection unit for connecting adjacent single-unit perovskite solar battery cell, wherein the single-unit perovskite solar energy
Battery unit includes the substrate for being sequentially overlapped setting, conductive layer, hole blocking layer, mesoporous shelf layer, the work of patterned perovskite
Property layer and carbon electrode, the connection unit includes between the conductive layer of adjacent single-unit perovskite solar battery cell
The carbon electrode of the adjacent single-unit perovskite solar battery cell of insulating tape, connection；The adjacent single-unit perovskite solar energy
The perovskite active layer of battery unit is discontinuous, and the connection unit does not include perovskite active layer.
According to the utility model, which is based on patterned perovskite active layer.Perovskite
Graphically refer to and is directly realized by stripe-arrangement by coating processes, the perovskite thin film separated between each other.In the prior art
In, perovskite be graphically by preparing film after, then etch part perovskite thin film formation.It is straight in the utility model
Coating processes were connected to obtain patterned perovskite thin film, simplify technique, it is thin to perovskite also to can avoid subsequent etching
The destruction of film, and avoid the dust pollution of perovskite etched away.Pass through graphically avoiding adjacent for perovskite active layer
Perovskite is remained between single-unit perovskite solar battery, can effectively reduce loss of the electric current when passing through connection unit.
Also, further including the auxiliary electrode of the adjacent single-unit perovskite solar battery cell of connection, institute in the utility model
Stating auxiliary electrode is silver wire, width 0.01-2mm, with a thickness of 0.1-20 μm.
Silver wire auxiliary electrode can be improved electronics capacity gauge, reduces electric current and passes through each concatenated single-unit solar battery
When unit, caused energy loss.That is, will further improve electric current collection ability if introducing auxiliary electrode；It can
The series resistance between single battery is effectively reduced, to greatly improve charge-trapping ability.
Also, each single-unit perovskite solar battery cell is arranged on one piece of substrate, adjacent single-unit in the utility model
It is series connection between perovskite solar battery cell.The serial module structure of preparation strip cell can be avoided cell area increasing
Greatly, the increase of Carrier recombination rate caused by carrier transport path increases effectively prevents solar-electricity pool area amplification band
The problem of efficiency come drastically reduces.
Also, the width of the single-unit perovskite solar battery cell is 5-20mm, preferably 6- in the utility model
12mm.DSC is that there are two silver wires, practical electron-transport path 6mm wide in the unit two sides of 12mm wide, therefore preferably 6-12mm is that have
What data were supported.
When module substrate size constancy, if the width of single-unit perovskite solar battery cell is narrow, concatenated item
Number will increase, and the connection unit for being not involved in power generation is consequently increased, and will be greatly reduced the effective area and aperture opening ratio of battery.If single
The width for saving perovskite solar battery cell is wide, then the carrier transport path inside single battery unit increases, current-carrying
Sub- recombination rate improves, and can reduce the transfer efficiency of battery module.
Also, the width of the connection unit is 0.2-8mm, preferably 0.3-3.5mm in the utility model.Connection unit
Width it is wide, the invalid that does not generate electricity will be increased, reduce the aperture opening ratio of battery module, and the width of connection unit is narrow,
Etched line, which is likely difficult to carve completely, breaks off edge, cannot achieve effective cascaded structure.
Also, the substrate is glass in the utility model, the conductive layer includes indium tin oxide layer or the oxidation for adulterating fluorine
Tin layers；
The hole blocking layer includes TiO2, ZnO or SnO2One or more of combination；
The mesoporous shelf layer includes TiO2、ZrO2Or Al2O3One or more of combination；
It include one or more of perovskite material ABX in the perovskite active layer3, A be methylamine, carbonamidine group or caesium from
Son, B are Pb or Sn ion, and X is halogen I, Cl or Br；
The carbon electrode includes the combination of one or more of graphite flake, carbon black, carbon fiber or graphene.Carbon electrode comes
Source is abundant, and fermi level matches with perovskite material, and have can low temperature preparation advantage, compared to needing high temperature and pressure heat
The noble metal electrode of vapor deposition, preparation process is easy, low in cost, more friendly to environment.And carbon electrode has hydrophobicity, institute
The perovskite solar battery long-time stability of preparation are more preferable.
On the other hand, the utility model provides a kind of preparation method of above-mentioned perovskite solar cell module, feature
It is,
The following steps are included:
(1) conductive layer on substrate is performed etching, is formed exhausted between adjacent single-unit perovskite solar battery cell
Marginal zone；
(2) hole blocking layer is prepared on the conductive layer and insulating tape；
(3) mesoporous shelf layer is prepared on the hole blocking layer；
(4) patterned perovskite active layer is prepared in the mesoporous shelf layer, wherein the adjacent single-unit calcium titanium
The perovskite active layer of mine solar battery cell is discontinuous；
(5) carbon electrode is prepared on perovskite active layer, obtains the perovskite solar cell module.
Photoelectric conversion efficiency can be effectively improved according to perovskite solar cell module prepared by the utility model, together
When avoid contact of the perovskite with auxiliary electrode, facilitate the raising of device stability, and hole blocking layer can not have to etching,
Enormously simplify preparation process.
Preferably, also auxiliary electrode can be prepared between adjacent single-unit perovskite solar battery cell.
Also, in the utility model, the preparation method of the patterned perovskite active layer include scraper method, print process,
The combination of one or more of slot coated, spray coating method.
According to the utility model, graphical perovskite active layer can be effectively formed.
According to following specific embodiments and attached drawing is referred to, is better understood with the above-mentioned and other mesh of the utility model
, feature and advantage.
Detailed description of the invention
Fig. 1 is the schematic cross-section of perovskite solar cell module in embodiment 1；
Fig. 2 is the schematic cross-section of perovskite solar cell module in embodiment 2；
Fig. 3 is the schematic cross-section of perovskite solar cell module in comparative example 1；
Fig. 4 is the schematic cross-section of perovskite solar cell module in comparative example 2；
Fig. 5 is the schematic diagram of the graphical perovskite thin film of an implementation form；
Fig. 6 is embodiment 1 (rectangular dotted line), embodiment 2 (circular dotted lines), embodiment 3 (triangle dotted line), comparative example 1
The current density voltage curve figure of perovskite solar cell module in (diamond shape dotted line) and comparative example 2 (star dotted line)；
Appended drawing reference:
1, substrate,
2, conductive layer,
3, hole blocking layer,
4, mesoporous shelf layer,
5, perovskite active layer,
6, carbon electrode,
7, auxiliary electrode.
Specific embodiment
For the problems such as perovskite solar battery preparation process is complicated in the prior art, the utility model provides one kind
Perovskite solar cell module and preparation method thereof, simple process, and photoelectric conversion efficiency can be effectively improved.The perovskite
Solar cell module includes: multiple single-unit perovskite solar battery cells single-unit perovskite solar-electricity adjacent with connecting
The connection unit of pool unit, wherein the single-unit perovskite solar battery cell includes the substrate for being sequentially overlapped setting, conduction
Layer, hole blocking layer, mesoporous shelf layer, patterned perovskite active layer and carbon electrode, the connection unit include being set to phase
The adjacent single-unit perovskite solar-electricity of insulating tape, connection between the conductive layer of adjacent single-unit perovskite solar battery cell
The carbon electrode of pool unit；The perovskite active layer of the adjacent single-unit perovskite solar battery cell is discontinuous, such as into
Strip segmentation is gone, the connection unit does not include perovskite active layer.The utility model can reduce resistance at connection unit,
Current loss is avoided, auxiliary electrode is avoided to contact with perovskite, improves device stability.
The battery module is based on patterned perovskite active layer, can also be further introduced into auxiliary electrode, such as silver wire,
Improve the photoelectric conversion efficiency of device.
Furthermore, the perovskite solar cell module of the utility model, it may include more than two single-unit perovskites
Solar battery cell, each single-unit perovskite solar battery cell are arranged on one piece of substrate.
In above-mentioned perovskite solar cell module, it is preferable that between adjacent single-unit perovskite solar battery cell
Pass through series connection.Specifically, the carbon electrode of previous single-unit perovskite solar battery and the latter single-unit perovskite sun
The conductive layer of energy battery is connected.
In above-mentioned perovskite solar cell module, the width of the single-unit perovskite solar battery cell is 5-
20mm, preferably 6-12mm.The width of the connection unit is 0.2-8mm, preferably 0.3-3.5mm.The auxiliary electrode is
Silver wire, width 0.01-2mm, with a thickness of 0.1-20 μm.
In above-mentioned single-unit perovskite solar battery cell, the substrate can be glass, and the conductive layer may include oxidation
Indium tin layer or the stannic oxide layer for adulterating fluorine；The hole blocking layer may include TiO2, ZnO or SnO2One or more of group
It closes；The mesoporous shelf layer may include TiO2、ZrO2Or Al2O3One or more of combination；In the perovskite active layer
Including one or more of perovskite material ABX3, A is methylamine, carbonamidine group or cesium ion, and B is Pb or Sn ion, and X is halogen family member
Plain I, Cl or Br；The carbon electrode includes the combination of one or more of graphite flake, carbon black, carbon fiber or graphene.
The preparation method of above-mentioned perovskite solar cell module, comprising the following steps:
(1) conductive layer on substrate is performed etching, is formed exhausted between adjacent single-unit perovskite solar battery cell
Marginal zone；
(2) hole blocking layer is prepared on the conductive layer and insulating tape；
(3) mesoporous shelf layer is prepared on the hole blocking layer；It preferably, can also be in adjacent single-unit perovskite solar energy
Auxiliary electrode is prepared between battery；
(4) patterned perovskite active layer is prepared in the mesoporous shelf layer, wherein the adjacent single-unit calcium titanium
The perovskite active layer of mine solar battery cell is discontinuous；
(5) carbon electrode is prepared on perovskite active layer, obtains the perovskite solar cell module.
Realize that perovskite is graphical by coating processes in the utility model, on the other hand one side superior performance is stablized
Property is more preferable.In other words, in common large area perovskite solar battery manufacturing process, perovskite thin film is all pattern to be carried out
Change, that is, carry out strip segmentation, usually first apply a whole face perovskite thin film, the method for then using laser ablation will
Perovskite thin film carries out strip segmentation.And it is exactly strip point that the advantage of the utility model, which is the perovskite thin film for being directly coated with out,
It has been cut that, eliminate the process and technique that strip is cut, carried out strip segmentation according to laser ablation, not only more procedures,
And the perovskite etched away inevitably generates dust pollution.
Specifically, in above-mentioned steps (4) preparation method of titanium ore active layer may include scraper method, print process, slot coated,
The combination of one or more of spray coating method.
In addition, step (2) to (3), (5) described preparation method may include spin coating, spraying, silk-screen printing, scraper method, slit
One of rubbing method or a variety of combinations.
The utility model is described in further detail below by way of specific embodiment.
Embodiment 1
Fig. 1 is the schematic cross-section of perovskite solar cell module in embodiment 1.As shown in Figure 1, the perovskite sun
Energy battery module includes: multiple single-unit perovskite solar battery cells single-unit perovskite solar battery list adjacent with connecting
The connection unit of member, wherein the single-unit perovskite solar battery cell includes substrate 1, the conductive layer for being sequentially overlapped setting
2, hole blocking layer 3, mesoporous shelf layer 4, patterned perovskite active layer 5 and carbon electrode 6, the connection unit include being set to
The adjacent single-unit perovskite solar energy of insulating tape between the conductive layer of adjacent single-unit perovskite solar battery cell, connection
The auxiliary electrode 7 and carbon electrode of battery unit；The perovskite active layer of the adjacent single-unit perovskite solar battery cell
Discontinuously, the connection unit does not include perovskite active layer.In the present embodiment 1, hole blocking layer 3 is continuous.But this is practical new
Type is without being limited thereto, and the film of hole blocking layer 3 can be continuous between each single-unit perovskite solar battery cell, can also be with
Discontinuously.
As shown in figure 5, perovskite active layer 5 is mutually separated individual strip-type figure, and it is arranged on same substrate.Such as
Shown in Fig. 1, auxiliary electrode 7 connects the carbon electrode of the first sub- battery unit and the cathode of adjacent second sub- battery unit, improves
Electric current flows through the collection of adjacent cells, reduces the loss of electric current.
Perovskite solar cell module in the present embodiment 1 can be prepared by the following method:
(1) laser ablation is carried out to the conductive layer covered on substrate, to form adjacent single-unit perovskite solar battery list
Insulating tape between member, etching width are 1mm；
(2) the electro-conductive glass 10min after lye, deionized water, acetone, EtOH Sonicate etching is used respectively, with compression
Air blow drying；
(3) spin coating TiO on electro-conductive glass after etching2Compacted zone, precursor solution are tetraisopropyl titanate
(0.3mol/L), acetylacetone,2,4-pentanedione (0.45mol/L), hydrochloric acid (0.09mol/L), water (1.8mol/L) ethanol solution.Presoma
It is paved with electro-conductive glass, spin coating revolving speed 3000rpm, time 20s.Existed after 500 DEG C of calcining 1h with titanium tetrachloride aqueous solution (40mM)
70 DEG C carry out processing 40min, obtain hole blocking layer, thickness is about 10-60nm；
(4) TiO is printed on the hole blocking layer2Mesoporous shelf layer, in 500 DEG C of calcining 1h, with a thickness of 1 μm；
(5) silver wire auxiliary electrode is printed between adjacent single-unit perovskite solar battery cell, in 500 DEG C of calcining 1h,
With a thickness of 5 μm；
(6) the slot coated perovskite light absorbent CH in the mesoporous shelf layer3NH3PbI3, anneal at 100 DEG C
10min, obtains perovskite active layer, and perovskite active layer width is 10mm, spacing 3mm；
(7) carbon electrode is printed on the perovskite active layer, in 100 DEG C of drying 30min, carbon electrode is with a thickness of 50 μm.
Embodiment 2
The embodiment is that the hole blocking layer to illustrate in the utility model can also be discontinuous.
The preparation method of hole blocking layer in 1 step of embodiment (3) is changed to silk-screen printing, barrier slurry is metatitanic acid four
The mixed liquor of isopropyl ester (0.3mL), ethyl cellulose (0.7g) and terpinol (16mL), prepares discontinuous using silk-screen printing
Hole blocking layer.
Other preparation methods are same as Example 1.
By the comparison of the embodiment 1 and embodiment 2 of Fig. 6 it is found that perovskite battery module provided by the utility model, empty
Cave transport layer can be continuous, can also be discontinuous, can get high performance device.
Embodiment 3
The present embodiment is to illustrate not applying auxiliary electrode also to can get heavy-duty battery module in the utility model.
The preparation method of hole blocking layer in 1 step of embodiment (3) is changed to silk-screen printing, barrier slurry is metatitanic acid four
The mixed liquor of isopropyl ester (0.3mL), ethyl cellulose (0.7g) and terpinol (16mL), prepares discontinuous using silk-screen printing
Hole blocking layer.
Step (5) in embodiment 1 is not done.
Other preparation methods are same as Example 1.
By the comparison of the embodiment 1-3 in Fig. 6 it is found that battery module provided by the utility model, can introduce auxiliary electricity
Pole can not also introduce auxiliary electrode, can obtain high transformation efficiency.
Comparative example 1
The comparative example is the structure and preparation method thereof to illustrate perovskite solar cell module in the prior art.It is right
In ratio 1, perovskite is filled in entire 4 to 6 layers of structure.Preparation method is as follows:
(1) laser ablation is carried out to the conductive layer covered on substrate, to form adjacent single-unit perovskite solar battery list
Insulating tape between member, etching width are 1mm；
(2) spin coating TiO on electro-conductive glass after etching2Compacted zone, thickness are about 10-60nm.After 500 DEG C of calcining 1h
It is handled with titanium tetrachloride aqueous solution, obtains hole blocking layer；
(3) TiO is printed on the hole blocking layer2Mesoporous shelf layer, in 500 DEG C of calcining 1h, with a thickness of 1 μm；
(4) in the TiO2ZrO is printed in mesoporous shelf layer2Mesoporous shelf layer, in 500 DEG C of calcining 1h, with a thickness of 2 μm；
(5) carbon electrode is printed in the mesoporous shelf layer, in 400 DEG C of calcining 1h, with a thickness of 10 μm；
(6) perovskite solution is permeated into the mesoporous layer and carbon electrode, in 100 DEG C of annealing 30min, obtains perovskite too
Positive energy battery module.
By the comparison of embodiment 1-3 and comparative example 1 in Fig. 6 it is found that perovskite solar-electricity provided by the utility model
Pond module is higher than the photoelectric conversion efficiency of prior art.
Comparative example 2
The comparative example is to illustrate the patterned gain effect of perovskite active layer.
According to the method in embodiment 1, direct spin coating obtains an entire perovskite active layer in steps of 5, other steps
It is rapid identical.
By the comparison of embodiment 1-3 and comparative example 2 in Fig. 6 it is found that the graphical perovskite active layer of the utility model
Device performance can be substantially improved.
Table 1
Under the objective for the essential characteristic for not departing from the utility model, the utility model can be presented as diversified forms, therefore
Implementation form in the utility model is to be illustrative rather than definitive thereof, since the scope of the utility model is defined by the claims and
It is non-to be limited by specification, and fall in all changes in the full scope of equivalents of the range that claim defines or the range that it is defined
Change is understood to be included in the claims.
Claims (8)
1. a kind of perovskite solar cell module characterized by comprising
Multiple single-unit perovskite solar battery cells and the connection list for connecting adjacent single-unit perovskite solar battery cell
Member,
Wherein, the single-unit perovskite solar battery cell includes the substrate, conductive layer, hole barrier for being sequentially overlapped setting
Layer, mesoporous shelf layer, patterned perovskite active layer and carbon electrode,
The connection unit includes the insulating tape being set between the conductive layer of adjacent single-unit perovskite solar battery cell, connects
Connect the carbon electrode of adjacent single-unit perovskite solar battery cell；
The perovskite active layer of the adjacent single-unit perovskite solar battery cell is discontinuous, and the connection unit does not include
Perovskite active layer.
2. perovskite solar cell module according to claim 1, which is characterized in that further include the adjacent single-unit of connection
The auxiliary electrode of perovskite solar battery cell, the auxiliary electrode are silver wire, width 0.01-2mm, with a thickness of 0.1-20
μm。
3. perovskite solar cell module according to claim 1, which is characterized in that each single-unit perovskite solar-electricity
Battery cell arrangements are connected in series between adjacent single-unit perovskite solar battery cell on one piece of substrate.
4. perovskite solar cell module according to claim 1, which is characterized in that the single-unit perovskite solar energy
The width of battery unit is 5-20mm.
5. perovskite solar cell module according to claim 4, which is characterized in that the single-unit perovskite solar energy
The width of battery unit is 6-12mm.
6. perovskite solar cell module according to claim 1, which is characterized in that the width of the connection unit is
0.2-8mm。
7. perovskite solar cell module according to claim 6, which is characterized in that the width of the connection unit is
0.3-3.5mm。
8. perovskite solar cell module according to any one of claim 1 to 7, which is characterized in that the substrate
For glass, the conductive layer includes indium tin oxide layer or the stannic oxide layer for adulterating fluorine；
The hole blocking layer includes TiO2, ZnO or SnO2One or more of combination；
The mesoporous shelf layer includes TiO2、ZrO2Or Al2O3One or more of combination；
It include one or more of perovskite material ABX in the perovskite active layer3, A is methylamine, carbonamidine group or cesium ion, B
For Pb or Sn ion, X is halogen I, Cl or Br；
The carbon electrode includes the combination of one or more of graphite flake, carbon black, carbon fiber or graphene.
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