CN111106245A - Perovskite battery for inhibiting electrode corrosion and preparation method thereof - Google Patents
Perovskite battery for inhibiting electrode corrosion and preparation method thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 47
- 230000007797 corrosion Effects 0.000 title claims abstract description 46
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000012964 benzotriazole Substances 0.000 claims abstract description 31
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 229910052802 copper Inorganic materials 0.000 claims description 25
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- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 230000005764 inhibitory process Effects 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004332 silver Substances 0.000 claims description 4
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- OUVNAZAUHZDDSD-UHFFFAOYSA-N butanoic acid;methanamine Chemical compound [NH3+]C.CCCC([O-])=O OUVNAZAUHZDDSD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
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- -1 amine cation Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
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- 238000006056 electrooxidation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
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- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 4
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- UCFCTSYWEPBANH-UHFFFAOYSA-N copper benzotriazol-1-ide Chemical compound [Cu+2].C1=CC=C2[N-]N=NC2=C1.C1=CC=C2[N-]N=NC2=C1 UCFCTSYWEPBANH-UHFFFAOYSA-N 0.000 description 1
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- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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Abstract
The invention discloses a perovskite battery for inhibiting electrode corrosion and a preparation method thereof, which are characterized in that an electrode corrosion inhibiting layer containing N, S heteroatoms is arranged between an electron transmission layer and a metal electrode, wherein benzotriazole and derivatives thereof are used as inhibitors, and a compact and insoluble polymer film is formed on the surface of the electrode to effectively protect the metal electrode of the perovskite battery. Compared with the prior art, the invention has the advantages of inhibiting perovskite and metal electrode in halogen (Cl)‑、Br‑、I‑) Electrochemical corrosion in the environment, the chemical reaction between the metal electrode and the perovskite is blocked, and the effect of the perovskite battery caused by the electrode corrosion is effectively solvedRate attenuation, simple structure, convenient manufacture further has improved perovskite battery's stability and life.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite cell for inhibiting electrode corrosion and a preparation method thereof.
Background
The conversion efficiency of perovskite solar cells has reached 25%, and the stability of the devices, which is not only caused by the perovskite layer but also closely related to the metal electrodes in the cell, has become the biggest bottleneck problem limiting the commercialization thereof. In one aspect, decomposition products of perovskites, such as HI and I2Can react with common metal electrodes such as Al, Ag and Cu to further accelerate the decomposition of perovskite; on the other hand, ion migration of perovskites is another major cause of device degradation, but the ion migration process is reversible, and it can be fully recovered after a period of time in the dark state, and may not cause a permanent efficiency drop in the device. However, once the migrating ions (I-) react with the metal electrode, this reversible ion migration process is broken down, thereby causing a decay in the efficiency of the perovskite device. This is also the reason why for perovskite cells the lifetime of half-cells (without transport layer and metal electrodes) is generally longer than that of a complete cell.
The perovskite battery of the prior art has electrode corrosion, so that the efficiency of a perovskite device is attenuated, and the stability and the service life of the perovskite battery are influenced.
Disclosure of Invention
The invention aims to provide a perovskite battery for inhibiting electrode corrosion and a preparation method thereof aiming at the defects of the prior art, wherein benzotriazole and derivatives thereof are adopted as inhibitors, a compact and insoluble polymer film is formed on the surface of an electrode, the metal electrode of the perovskite battery is effectively protected, the chemical reaction between the metal electrode and perovskite is blocked, and the perovskite and the metal electrode are inhibited from reacting in halogen (Cl)-、Br-、I-) The electrochemical corrosion in the environment, the corrosion resistance of the metal electrode is good, the problem of efficiency attenuation of the perovskite battery caused by electrode corrosion is effectively solved, the structure is simple, the manufacture is convenient, the stability of the perovskite battery is further improved, and the service life of the perovskite battery is further prolonged.
The specific technical scheme for realizing the purpose of the invention is as follows: a perovskite solar thin film battery for inhibiting electrode corrosion comprises a hole transport layer, a perovskite thin film, an electron transport layer and a metal electrode which are arranged on a substrate in a laminated mode, and is characterized in that an electrode corrosion inhibiting layer containing N, S heteroatoms is arranged between the electron transport layer and the metal electrode, and the perovskite solar thin film battery for inhibiting chemical reactions between the metal electrode and perovskite is formed.
A preparation method of a perovskite battery for inhibiting electrode corrosion is characterized in that a cavity transmission layer, a perovskite thin film, an electron transmission layer and a metal electrode are sequentially deposited on a substrate by adopting a solution spin coating or evaporation process.
The electrode corrosion inhibition layer is a polymer film formed by spin coating or vapor deposition, the thickness of the electrode corrosion inhibition layer is 1-10 nm, and the thickness of the electrode corrosion inhibition layer is preferably 1-5 nm in consideration of the improvement effect on the conversion efficiency and stability of the battery; the polymer film is one or a mixture of more than two of benzotriazole and derivatives thereof and mercapto benzothiazole, and because two N heteroatoms in the benzotriazole can generate weak interaction with metal atoms, the polymer film is more beneficial to adsorption and coordination on the surface of a metal electrode, thereby being beneficial to corrosion prevention of the metal electrode and improving the stability of the perovskite battery. In addition, benzotriazole has good solubility in ethanol, isopropanol, chlorobenzene, toluene and other conventional solvents, can be more easily formed into a film by a solution spin coating method, and can also be adjusted in thickness in the perovskite battery within a larger range, so that the polymer film is preferably benzotriazole.
The perovskite film is ABX prepared by spin coating3The thickness of the organic-inorganic hybrid material film layer is 400 nm-500 nm; the ABX3In the organic-inorganic hybrid material, A is CH3NH3 +、HC(NH2)2 +Or CH3CH2NH3 +An organic amine cation; b is Pb2+、Sn2+Or Ge2+(ii) a X is Cl-、Br-、I-Or SCN-An anion. Due to (HC (NH)2)2PbI3)0.95(CH3NH3PbBr3)0.05The forbidden band width is 1.51eV, and the band width is good in the range of 400nm to 800nmGood absorption, therefore, the perovskite ABX3The organic-inorganic hybrid material is more preferably (HC (NH)2)2PbI3)0.95(CH3NH3PbBr3)0.05。
The hole transport layer is a poly [3- (methylamine butyrate) thiophene ] (P3CT-N) thin film layer prepared by spin coating, and the thickness of the hole transport layer is 5 nm-20 nm.
The electron transport layer consists of a PCBM layer, a C60 layer and a TPBi layer which are sequentially prepared in a laminated mode, the thickness of the electron transport layer is 50 nm-100 nm, the PCBM layer is a thin film layer prepared by spin coating through a solution method, and the thickness of the PCBM layer is 20 nm-50 nm; the C60 layer is a thin film layer prepared by vacuum evaporation, the thickness of the thin film layer is 20 nm-40 nm, and the TPBi layer is a thin film layer prepared by solution method spin coating, and the thickness of the TPBi layer is 8 nm-10 nm.
The metal electrode is a copper or silver layer prepared by vacuum evaporation, and the thickness of the metal electrode is 100 nm-300 nm.
The substrate is a silicon wafer, an ITO conductive glass sheet or a stainless steel sheet.
Compared with the prior art, the invention has good stability and service life of devices, the electrode corrosion inhibition layer contains heteroatoms such as N, S and the like, can be chemically adsorbed and coordinated on the metal electrode, a compact and insoluble polymer film is formed on the surface of the electrode, and can effectively protect the metal electrode of the perovskite battery, thereby blocking the chemical reaction between the metal electrode and the perovskite, and the compact polymer film can also inhibit the Cl content of the metal electrode in the perovskite-、Br-、I-And the electrochemical corrosion in a halogen environment further improves the corrosion resistance of the metal electrode, further inhibits the efficiency attenuation of the perovskite solar cell caused by the electrode corrosion, ensures that the perovskite solar cell has good stability, and prolongs the service life of the device.
Drawings
FIG. 1 is a schematic diagram of a perovskite cell structure for inhibiting electrode corrosion according to the present invention;
FIG. 2 is an X-ray photoelectron spectrum of Cu 2 p;
FIG. 3 is an X-ray photoelectron spectrum of N1 s;
FIG. 4 is a graph of the oxidation-reduction curve of copper;
FIG. 5 is a Tafel polarization curve for copper;
FIG. 6 shows a copper electrode in a halogen environment (I)-) X-ray diffraction patterns for the next different etch times;
FIG. 7 is an I-V curve of a perovskite cell of the present invention that inhibits electrode corrosion;
FIG. 8 is a graph of the stability of a perovskite cell of the present invention in air to inhibit electrode corrosion;
FIG. 9 is a graph of the thermal stability of a perovskite cell of the present invention inhibiting electrode corrosion;
fig. 10 is a graph of the maximum power output stability of a perovskite cell of the invention with suppressed electrode corrosion under continuous illumination.
Detailed Description
Referring to the attached drawing 1, the perovskite battery for inhibiting electrode corrosion of the invention is composed of a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4, an electrode corrosion inhibiting layer 5 and a metal electrode 6 which are sequentially stacked, wherein the substrate 1 is any one of a silicon wafer, a glass sheet and a stainless steel sheet, and because ITO is a metal compound with good transparent conductive performance and has the characteristics of wide forbidden bandwidth, high light transmittance in a visible light spectrum, low resistivity and the like, the substrate 1 is preferably ITO conductive glass.
The hole transport layer 2 is poly [3- (methylamine butyrate) thiophene]A layer of (P3CT-N) material having a thickness of 5nm to 20nm, an energy level of P3CT-N of 5.26eV relative to a conventional hole transport layer PEDOT: PSS (energy level 5.11eV), and selected perovskite (HC (NH)2)2PbI3)0.95(CH3NH3PbBr3)0.05The valence band (5.3eV) is closer, and the reduction of the cell efficiency caused by energy level mismatching can be effectively avoided; p3CT-N is preferably 10nm thick; the chemical structural formula of the P3CT-N is as follows:
the thickness of the perovskite thin film 3 is 400 nm-500 nm. In view of the balanced transport of carriers, a thickness of 450nm is preferable.
The electron transmission layer 4 is composed of a PCBM layer, a C60 layer and a TPBi layer which are sequentially stacked; the thickness of the PCBM layer is 20 nm-50 nm; the thickness of the C60 layer is 20 nm-40 nm; the thickness of the TPBi layer is 8 nm-10 nm; the thickness of the electron transmission layer 4 is 50 nm-100 nm; the PCBM is prepared by a solution method through spin coating, can effectively penetrate into and cover cavities possibly existing on the surface of the perovskite, and is preferably 20nm thick; the C60 is prepared by vacuum evaporation, so that the obtained C60 layer is more compact and uniform, and the thickness is preferably 40 nm; the TPBi is used as a hole blocking layer, can inhibit recombination at an electrode interface and improve the performance of a device, and the thickness is preferably 8 nm.
The electrode corrosion inhibition layer 5 is one or a mixture of more than two of benzotriazole and derivatives thereof, mercaptobenzothiazole and the like, and the benzotriazole is preferably selected in consideration of the characteristics of better anti-corrosion effect and easiness in preparation of the benzotriazole. The benzotriazole may be incorporated into the perovskite cell by solution spin coating or vacuum evaporation. Considering that the solution spin coating is easy to realize, a solution spin coating method is preferred, and considering the good solubility of isopropanol on benzotriazole and no damage to the perovskite at the lower layer, the preferred solvent is isopropanol; the benzotriazole is not favorable for collecting carriers when being too thick, and is poor in corrosion resistance efficiency when being too thin, so that the thickness is preferably 1-5 nm; the benzotriazole structure is as follows:
the electrode 5 is made of gold, silver or copper and has a thickness of 100nm to 300nm, but is preferably a copper electrode in view of the high cost of gold as an electrode and the short life of silver as an electrode.
The corrosion prevention mechanism of the copper benzotriazole to the copper electrode is as follows:
the perovskite solar cell can effectively avoid chemical reaction between a perovskite layer and a metal electrode, and can inhibit electrochemical corrosion of the metal electrode in a halogen environment, so that the perovskite solar cell not only has high conversion efficiency, but also has good stability.
Referring to the attached figure 2, after the benzotriazole is deposited on the copper electrode, the X-ray photoelectron spectrum of Cu 2p shifts, which shows that chemical coordination exists between the Benzotriazole (BTA) and copper.
Referring to FIG. 3, after benzotriazole is deposited on a copper electrode, the X-ray photoelectron spectrum of N1s is shifted, which shows that benzotriazole coordinates with copper through N atoms.
Referring to fig. 4, the oxidation-reduction curve of the copper electrode shows a distinct oxidation-reduction peak, indicating that the copper electrode is susceptible to oxidation-reduction corrosion; after deposition of benzotriazole (BTA/Cu), the oxidation reduction peak of copper almost disappears, which shows that benzotriazole can effectively inhibit electrochemical oxidation reduction corrosion of copper.
Referring to fig. 5, in the tafel polarization curve of the copper electrode, the corrosion current of copper is significantly higher than that of deposited benzotriazole (BTA/Cu), which indicates that the corrosion rate of copper is significantly reduced after deposition of benzotriazole, i.e., the benzotriazole inhibits corrosion of copper.
Referring to FIG. 6, the copper electrode is in a halogen environment (I)-) The corrosion under the condition is characterized by X-ray diffraction (XRD), and with the increase of time, the XRD peak belonging to Cu is gradually weakened and finally disappears, while the XRD peak belonging to CuI is gradually strengthened, which indicates that the halogen (I)-) Copper is easy to corrode under the environment and a product CuI is generated. After deposition of benzotriazole (Cu-BTA), XRD peaks belonging to Cu exist all the time and XRD peaks belonging to CuI do not appear, which shows that the benzotriazole can really inhibit corrosion of copper in a halogen environment.
The present invention will be described in further detail with reference to specific examples.
Example 1
Referring to the attached figure 1, the perovskite battery for inhibiting the electrode corrosion comprises a substrate 1, a hole transport layer 2, a perovskite thin film 3, an electron transport layer 4, an electrode corrosion inhibiting layer 5 and a metal electrode 6 which are sequentially laminated, and the perovskite battery is specifically prepared by the following steps:
a. selecting ITO conductive glass as a substrate 1, washing with an ITO cleaning agent and deionized water to remove grease and organic matters, then sequentially ultrasonically washing with deionized water, acetone and isopropanol, blow-drying with nitrogen, and further processing with ozone plasma cleaning.
b. Preparing a P3CT-N methanol solution with the concentration of 1mg/mL as a P3CT-N spin coating solution, and spin-coating a P3CT-N solution on an ITO conductive glass substrate 1 by using a spin coater, wherein the spin coating speed is 4000 revolutions per minute and the time is 45 seconds, and obtaining a film with the thickness of 10nm as a hole transport layer 2.
c. 721.6mg HC (NH)2)PbI3、28.8mg CH3NH3PbBr3And 15mg of CH3NH3Dissolving Cl in 1mL of mixed solution of N, N-dimethylformamide and dimethyl sulfoxide in a volume ratio of 4:1 to prepare perovskite precursor solution; and (3) spin-coating the perovskite precursor solution on the hole transport layer 2 by using a spin coater at the spin speed of 2000 rpm for 10 seconds, then spin-coating at the spin speed of 4000 rpm for 20 seconds, and annealing at 140 ℃ for 20 minutes after the spin coating is finished to obtain the perovskite thin film 3 with the thickness of 400 nm.
d. Preparing a chlorobenzene solution of PCBM with the concentration of 10mg/mL as PCBM spin-coating solution, and spin-coating the PCBM solution on the perovskite thin film 3 at the rotating speed of a spin coater of 2000 rpm for 60 seconds to form a thin film with the thickness of 20nm as a PCBM layer; then forming a C60 layer with the thickness of 40nm on the PCBM layer by adopting a vacuum thermal evaporation method; finally, a TPBi layer with the thickness of 8nm is formed on the C60 layer by adopting a vacuum thermal evaporation method.
e. Preparing 1mg/mL benzotriazole isopropanol solution as spin-coating solution, spin-coating the spin-coating solution on the electron transport layer 4 to form a polymer film with the thickness of 5nm as an electrode corrosion inhibition layer 5, wherein the rotation speed of a spin coater is 5000 rpm, and the spin-coating time is 45 seconds.
f. A layer of copper was deposited on the electrode corrosion-inhibiting layer 5 by vacuum thermal deposition to form a metal electrode 6 having a thickness of 100 nm.
Referring to fig. 7, I-V tests prove that the prepared perovskite solar thin film cell still has excellent cell efficiency after devices containing benzotriazole.
Referring to fig. 8, stability detection of the perovskite solar thin film cell prepared in the above manner in air shows that the cell containing benzotriazole has more excellent air stability.
Referring to fig. 9, the thermal stability of the perovskite solar thin film cell prepared above at a temperature of 85 ℃ is detected, which shows that the cell containing benzotriazole has more excellent thermal stability.
Referring to fig. 10, the Maximum Power Point (MPP) detection of the perovskite solar thin film cell prepared above under continuous illumination shows that the cell containing benzotriazole has more excellent operation stability.
The above embodiments are only for further illustration of the present invention and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included in the scope of the claims of the present invention.
Claims (4)
1. A perovskite cell for inhibiting electrode corrosion comprises a hole transport layer, a perovskite thin film, an electron transport layer and a metal electrode which are stacked on a substrate, and is characterized in that an electrode corrosion inhibiting layer containing N, S heteroatoms is arranged between the electron transport layer and the metal electrode to form a perovskite solar thin film cell of a protective electrode.
2. The preparation method of the perovskite battery for inhibiting the electrode corrosion according to claim 1, which is characterized in that a hole transport layer, a perovskite thin film, an electron transport layer and a metal electrode are sequentially deposited on a substrate by adopting a solution spin coating or evaporation coating process, wherein the electrode corrosion inhibiting layer is a polymer thin film deposited by spin coating or evaporation coating, and the thickness of the electrode corrosion inhibiting layer is 1-10 nm; the polymer film is one or a mixture of more than two of benzotriazole and derivatives thereof and mercapto benzothiazole; the perovskite film is ABX prepared by spin coating3Organic-inorganic hybridizationThe material film layer is 400 nm-500 nm thick; the substrate is a silicon wafer, an ITO conductive glass sheet or a stainless steel sheet; the hole transport layer is poly [3- (methylamine butyrate) thiophene prepared by spin coating]A thin film layer having a thickness of 5nm to 20 nm; the electron transmission layer consists of a PCBM layer, a C60 layer and a TPBi layer which are sequentially prepared in a laminated mode, and the thickness of the electron transmission layer is 50 nm-100 nm; the metal electrode is a copper or silver layer prepared by vacuum evaporation, and the thickness of the metal electrode is 100 nm-300 nm.
3. The method of making an electrode corrosion inhibiting perovskite battery as defined in claim 2, wherein said ABX is3In the organic-inorganic hybrid material, A is CH3NH3 +、HC（NH2）2 +Or CH3CH2NH3 +An organic amine cation; b is Pb2+、Sn2+Or Ge2+(ii) a X is Cl-、Br-、I-Or SCN-An anion.
4. The method for preparing the electrode corrosion inhibition perovskite battery according to claim 2, characterized in that the PCBM layer is a thin film layer prepared by solution spin coating, and the thickness of the PCBM layer is 20 nm-50 nm; the C60 layer is a thin film layer prepared by vacuum evaporation, the thickness of the thin film layer is 20 nm-40 nm, and the TPBi layer is a thin film layer prepared by spin coating through a solution method, and the thickness of the TPBi layer is 8 nm-10 nm.
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