CN107565027B - Based on nano-onions carbon: PC61The perovskite solar battery of BM composite electron transport layer - Google Patents
Based on nano-onions carbon: PC61The perovskite solar battery of BM composite electron transport layer Download PDFInfo
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- CN107565027B CN107565027B CN201710762014.0A CN201710762014A CN107565027B CN 107565027 B CN107565027 B CN 107565027B CN 201710762014 A CN201710762014 A CN 201710762014A CN 107565027 B CN107565027 B CN 107565027B
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Abstract
The present invention relates to one kind to be based on nano-onions carbon: PC61The perovskite solar battery of BM composite electron transport layer, the solar battery uses eurymeric structure, including substrate layer, transparent conductive anode layer, hole transmission layer, perovskite photoactive layer, composite electron transport layer and the metal cathode layer set gradually from the bottom up；Composite electron transport layer is the solid union layer structure that PC61BM material and nano-onions carbon material mix composition in proportion；The mass percent of nano-onions carbon material and PC61BM material is respectively as follows: nano-onions carbon 1%~10% in lamination layer structure；PC61BM 99%~90%.The present invention significantly reduces the series resistance of device, reduces electronics in electron transfer layer/photoactive layer interface recombination probability, improves the fill factor of device；Electron-transport is improved to the quantity of cathode simultaneously, improves carrier transport rate.
Description
Technical field
The present invention relates to a kind of solar batteries, belong to new energy area of solar cell；It is based on receiving more particularly to one kind
Rice onion carbon: PC61The perovskite solar battery of BM composite electron transport layer.
Background technique
With the increase year by year of global energy requirements amount, urgently to be resolved is become to the effective use of renewable energy and is asked
Topic.At present most of energy for using in the world from fossil fuel exploitation, including petroleum, natural gas and coal etc..
However, these resources are limited.Account for 99% or more earth gross energy solar energy have it is inexhaustible, do not have
The characteristics of pollution, thus become one of the new energy that scientists from all over the world develop and utilize.Perovskite (perovskite) is Germany
Mineralogist's Gustaf Ross (Gustav Rose) was sent out in 1839 on Russia, the domestic Urals, middle part
Existing perovskite rock specimens determine that great geologist Lev Perovski names this ore in the heart with him.The ore
It is common metallo-organic compound crystal, main component is calcium titanate (CaTiO3).The perovskite battery of later people's meaning,
It is not but to have used compound similar with perovskite crystal structure made of this ore materials that are found with him.
At 2009, the palace slope power rate of Tong Yinheng creek university, which is first passed through, is applied to dyestuff as light-absorption layer for one layer of very thin perovskite
Sensitization solar battery is manufactured that perovskite solar battery.Photoelectric conversion rate at that time is 3.8%.Later researcher couple
Battery is improved, and transfer efficiency is once doubled.Although transfer efficiency improves, also fatal to be asked in face of one
Topic --- the metal halide in perovskite is easy to be destroyed by the liquid electrolyte of battery, causes stability test low, the service life is short.
In August, 2012, by the South Korea of Graz that (Gr tzel) leader at Jun Guan university and Lausanne Institute of Technology laboratory
A kind of solid hole mobile material (hole transport materials, HTM) is introduced into solar battery, imitates battery
Rate has once been increased to 10%, and solves the problems, such as that battery is unstable, and novel perovskite solar battery was than former
It is easier to encapsulate when with liquid electrolyte.After this, perovskite solar battery becomes new research hotspot.
In the perovskite solar battery correlative study to emerge one after another, scientist be also found, perovskite not only light absorptive
Good and good charge-transporting material.They constantly improve perovskite material and structure, to improve perovskite battery
Photoelectric conversion rate.Then just in the same year, the TiO2 in battery has been carried out generation with aluminium by Oxonian Henry Si Naisi
It replaces, such perovskite is just not only the absorbed layer of light in cell piece, similarly can be used as the semiconductor material of transmission charge.By
This, the transfer efficiency of perovskite battery once rises to 15%.In August, 2015, foreign citizen of Chinese origin's science of University of California in Los Angeles
The research team of family Yang Yang leader, delivers current research paper on " science " (Science) periodical and claims, they are by improving calcium
Perovskite like structure layer, selection are more suitable for transmitting the material of charge, allow the electrode at battery both ends that can collect more electricity.Current research
In, the transfer efficiency of perovskite solar battery has been up to 19.3%, become the field most.
Although its perovskite structure is extremely unstable however, its photoelectric conversion efficiency of perovskite solar battery is higher
It is fixed, it is easy to decompose under water oxygen environment, and it is slow to be easy to appear performance due to its special charge transporting mechanism for perovskite battery
It is stagnant, that is, plus forward voltage and when backward voltage, performance difference is larger.Disadvantages mentioned above results in perovskite battery distance in fact
With changing also, it will take time.Currently, calcium titanium improves by preparing suitable electronics and its hole transmission layer in countries in the world study group
The photoelectric conversion efficiency of mine solar cell increases its stability, and it is sluggish to reduce performance.Traditional planar structure perovskite solar energy
Battery device generally uses PC61BM is as its electron transfer layer, so that the efficiency acquisition of perovskite solar battery significantly mentions
It rises.But due to PC61BM conductivity is not high, and air stability is poor, so that the aerial stability of device is poor, device lifetime
It is shorter.Also, it is most of to use PC61The planar structure perovskite solar cell properties sluggishness of BM electron transfer layer is more bright
Aobvious and Scientific Research Problem urgently to be resolved.
Nano-onions carbon (Carbon Onions, CNOs) is the abbreviation of nano onion-like Fullerenes, it is same by several layers
The biggish Carbon Cluster of the graphite shell composition of bulbus cordis shape, the C that innermost layer is made of 60 carbon atoms60, each shell
Carbon atom number can be according to 60n2(n is the number of plies) calculates.Nano-onions carbon is the spherical full carbon molecules of set, is equivalent to major diameter
It is a kind of special shape of carbon nanotube than the carbon nanotube for being approximately equal to 1:1.Nano-onions carbon is as a kind of novel carbon materials
The features such as material, the electric conductivity with superelevation, transparent and stability is strong.Hereafter, special fowler this kind of for carbon nano-onions
The research of olefinic substance just starts quietly to rise, and has become a hot topic of research.
By way of combining a variety of organic-inorganic materials, it is to improve perovskite that how research, which optimizes electron transfer layer,
Solar cell photoelectric transfer efficiency reduces performance sluggishness, improves the key of stability, and the emphasis of this area research at present
And difficult point.
Summary of the invention
Based on the above technical problem, the present invention provides one kind to be based on nano-onions carbon: PC61BM composite electron transport layer
Perovskite solar battery, to solve, previous perovskite solar battery carrier transport speed is slow, performance is sluggish and steady
The technical problem of qualitative difference.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
One kind being based on nano-onions carbon: PC61The perovskite solar battery of BM composite electron transport layer, the solar battery
Using eurymeric structure, including substrate layer, transparent conductive anode layer, the hole transmission layer, perovskite set gradually from the bottom up
Photoactive layer, composite electron transport layer and metal cathode layer；
Wherein,
Composite electron transport layer is PC61BM material and nano-onions carbon material mix the solid union layer knot of composition in proportion
Structure；
Nano-onions carbon material and PC in lamination layer structure61The mass percent of BM material is respectively as follows:
Nano-onions carbon 1%~10%；
PC61BM 99%~90%.
Based on above technical scheme, the hole transmission layer is thin by the solid that the aqueous dispersions of PEDOT:PSS are prepared
Film, aqueous dispersions concentration are 0.5~2mg/ml.
Based on above technical scheme, the perovskite photoactive layer is CH3NH3PbI3Perovskite structure film, with a thickness of
240~300nm.
Based on above technical scheme, the composite electron transport layer is with a thickness of 5~20nm.
Based on above technical scheme, the nano-onions carbon material is that nano-onions carbon dispersion liquid is prepared, and partial size is
20~40nm, concentration are 1~5mg/ml.
Based on above technical scheme, the metal material of the metal cathode layer is one or more of Ag, Al, Cu
Mixture, metal cathode layer thickness range be 100~200nm.
Based on above technical scheme, the substrate layer material is glass or transparent polymer, the transparent polymer material
For polyethylene, polymethyl methacrylate, polycarbonate, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin, polyacrylic acid
One or more kinds of mixtures.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1, the present invention fills PC by mixing nano-onions carbon61Gap between BM and perovskite thin film optimizes interfacial contact,
Conducive to the transmission of carrier, and the charge hesitation of nano-onions carbon itself can offset the hesitation of perovskite battery,
To which the performance for reducing battery entirety is sluggish.
2, the present invention significantly reduces the series resistance of device by the nano-onions carbon of introducing high conductivity, reduces
Electronics improves the fill factor of device in electron transfer layer/photoactive layer interface recombination probability；Electronics is improved simultaneously
It is transferred to the quantity of cathode, improves carrier transport rate, to promote the short circuit current of device.
3, by the nano-onions carbon particle of mixed stability, by PC61Gap and its cavity in BM film are filled,
The ability of electron transfer layer isolation water oxygen is effectively improved, avoiding leads to calcium since water oxygen enters perovskite photoactive layer
Perovskite like structure decomposes, every the water oxygen stability for improving device.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention；
Marked in the figure: 1, substrate layer；2, transparent conductive anode layer；3, hole transmission layer；4, perovskite photoactive layer；
5, composite electron transport layer；6, metal cathode layer.
Specific embodiment
The present invention will be further described below with reference to the drawings.Embodiments of the present invention include but is not limited to following reality
Apply example.
Embodiment
As shown in Figure 1, a kind of be based on nano-onions carbon: PC61The perovskite solar battery of BM composite electron transport layer, should
Solar battery use eurymeric structure, including set gradually from the bottom up substrate layer 1, transparent conductive anode layer 2 (ITO,
English name Indium Tin Oxides, i.e. tin indium oxide), hole transmission layer 3, perovskite photoactive layer 4, composite electron transmission
Layer 5 and metal cathode layer 6；
Wherein,
Composite electron transport layer 5 is PC61BM material and nano-onions carbon material mix the solid union layer of composition in proportion
Structure；
Nano-onions carbon material and PC in lamination layer structure61The mass percent of BM material is respectively as follows:
Nano-onions carbon 1%~10%；
PC61BM 99%~90%.
In above embodiments, 2 thickness range of transparent conductive anode layer is 20~40nm.
Preferably, the solid film that the hole transmission layer 3 is prepared by the aqueous dispersions of PEDOT:PSS, water dispersion
Liquid concentration is 0.5~2mg/ml.
Preferably, the perovskite photoactive layer 4 is CH3NH3PbI3Perovskite structure film, with a thickness of 240~300nm.
Preferably, the composite electron transport layer 5 is with a thickness of 5~20nm.
Preferably, the nano-onions carbon material is that nano-onions carbon dispersion liquid is prepared, and partial size is 20~40nm, dense
Degree is 1~5mg/ml.
Preferably, the metal material of the metal cathode layer 6 is the mixture of one or more of Ag, Al, Cu,
Metal cathode layer thickness range is 100~200nm.
Preferably, 1 material of substrate layer be glass or transparent polymer, the transparent polymer material be polyethylene,
The one or two of polymethyl methacrylate, polycarbonate, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin, polyacrylic acid
Above mixture.
The present embodiment fills PC by mixing nano-onions carbon61Gap between BM and perovskite thin film optimizes interfacial contact,
Conducive to the transmission of carrier, and the charge hesitation of nano-onions carbon itself can offset the hesitation of perovskite battery,
To which the performance for reducing battery entirety is sluggish；By introducing the nano-onions carbon of high conductivity, the string of device is significantly reduced
Join resistance, reduces electronics in electron transfer layer/photoactive layer interface recombination probability, improve the fill factor of device；Together
When improve electron-transport to the quantity of cathode, carrier transport rate is improved, to promote the short circuit current of device；Pass through
The nano-onions carbon particle of mixed stability, by PC61Gap and its cavity in BM film are filled, and effectively improve electricity
The ability of sub- transport layer isolation water oxygen, avoid causes perovskite structure to decompose since water oxygen enters perovskite photoactive layer,
Every the water oxygen stability for improving device.
In the following, in conjunction with specific data list specific embodiment, the present invention will be further explained.
Specific embodiment
Control group 1
The substrate as composed by substrate layer 1 and transparent conductive anode layer 2 to surface roughness less than 1nm carries out clear
It washes, with being dried with nitrogen after cleaning；2 surface rotary coating PEDOT:PSS solution of transparent conductive anode layer (running parameter: turn
Fast 3000rpm, time 40s) prepare hole transmission layer 3；And film will be formed by and toasted (running parameter: temperature 135
DEG C, time 30min)；Spin coating prepares perovskite photoactive layer 4 (thickness 250nm) in transparent conductive anode layer 2；In calcium
The 4 surface spin coating of titanium ore photoactive layer prepares nano-onions carbon and prepares (the thickness 20nm of composite electron transport layer 5；In metal cathode layer
(thickness 100nm constitutes perovskite solar cell device to evaporation metal cathode Ag on 6.
Under standard test condition: air quality AM 1.5, luminous intensity 100mW/cm2, then the performance parameter number of the battery
According to as shown in Table 1:
The performance parameter for the battery that one control group 1 of table is constituted
By table one as can be seen that being mixed into nano-onions carbon and PC61The composite electron transport layer 4 of BM, can effectively be promoted
The fill factor of perovskite solar battery, short circuit current, to promote its photoelectric conversion efficiency.
Secondly, the positive and negative of the battery sweeps fill factor and its photoelectric conversion efficiency data are as shown in Table 2:
The positive and negative of battery that two control group 1 of table is constituted sweeps fill factor and its photoelectric conversion efficiency
It can be seen from Table 2 that being mixed into nano-onions carbon and PC61The composite electron transport layer 4 of BM, can be effectively reduced calcium
The performance of titanium ore solar battery is sluggish.
Finally, the performance degradation data when battery is stored in air are as shown in Table 3:
The performance degradation when battery that three control group 1 of table is constituted is stored in air
By table three as can be seen that being mixed into nano-onions carbon and PC61The composite electron transport layer 4 of BM, can effectively be promoted
The aerial stability of perovskite solar battery.
It is as described above the embodiment of the present invention.Described previously is each preferred embodiment of the invention, each preferred
Preferred embodiment in embodiment if not obvious contradictory or premised on a certain preferred embodiment, it is each preferably
Embodiment can arbitrarily stack combinations use, and the design parameter in the embodiment and embodiment is merely to understand table
State the invention verification process of inventor, the scope of patent protection being not intended to limit the invention, scope of patent protection of the invention
Still it is subject to the claims, it is all to change with equivalent structure made by specification and accompanying drawing content of the invention, together
Reason should be included within the scope of the present invention.
Claims (7)
1. one kind is based on nano-onions carbon: PC61The perovskite solar battery of BM composite electron transport layer, which is characterized in that should
Solar battery use eurymeric structure, including set gradually from the bottom up substrate layer, transparent conductive anode layer, hole pass
Defeated layer, perovskite photoactive layer, composite electron transport layer and metal cathode layer；
Wherein,
Composite electron transport layer is PC61BM material and nano-onions carbon material mix the solid union layer structure of composition in proportion；
Nano-onions carbon material and PC in lamination layer structure61The mass percent of BM material is respectively as follows:
Nano-onions carbon 1%~10%；
PC61BM 99%~90%.
2. perovskite solar battery according to claim 1, which is characterized in that the hole transmission layer is by PEDOT:
The solid film that the aqueous dispersions of PSS are prepared, aqueous dispersions concentration are 0.5~2mg/ml.
3. perovskite solar battery according to claim 1, which is characterized in that the perovskite photoactive layer is
CH3NH3PbI3Perovskite structure film, with a thickness of 240~300nm.
4. perovskite solar battery according to claim 1, which is characterized in that the composite electron transport layer with a thickness of
5~20nm.
5. perovskite solar battery according to claim 1, which is characterized in that the nano-onions carbon material is nanometer
Onion carbon dispersion liquid is prepared, and partial size is 20~40nm, and concentration is 1~5mg/ml.
6. perovskite solar battery according to claim 1, which is characterized in that the metal material of the metal cathode layer
For the mixture of one or more of Ag, Al, Cu, metal cathode layer thickness range is 100~200nm.
7. perovskite solar battery according to claim 1, which is characterized in that the substrate layer material is for glass or thoroughly
Bright polymer, the transparent polymer material are polyethylene, polymethyl methacrylate, polycarbonate, polyurethanes, gather
The mixtures of the one or more of acid imide, vinyl chloride-vinyl acetate resin, polyacrylic acid.
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| CN106098944A (en) * | 2016-07-13 | 2016-11-09 | 电子科技大学 | A kind of solaode based on nano-onions carbon composite anode cushion |
| CN106960908A (en) * | 2017-03-23 | 2017-07-18 | 华南师范大学 | A kind of cathodic modification type plane perovskite solar cell and preparation method thereof |
| CN107068865A (en) * | 2016-12-12 | 2017-08-18 | 苏州大学 | A kind of perovskite solar cell and preparation method thereof |
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| CN106098944A (en) * | 2016-07-13 | 2016-11-09 | 电子科技大学 | A kind of solaode based on nano-onions carbon composite anode cushion |
| CN107068865A (en) * | 2016-12-12 | 2017-08-18 | 苏州大学 | A kind of perovskite solar cell and preparation method thereof |
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