WO2022037653A1 - 一种叠层电池 - Google Patents
一种叠层电池 Download PDFInfo
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- WO2022037653A1 WO2022037653A1 PCT/CN2021/113582 CN2021113582W WO2022037653A1 WO 2022037653 A1 WO2022037653 A1 WO 2022037653A1 CN 2021113582 W CN2021113582 W CN 2021113582W WO 2022037653 A1 WO2022037653 A1 WO 2022037653A1
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- hole transport
- perovskite
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- transport layer
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- QWANGZFTSGZRPZ-UHFFFAOYSA-N aminomethylideneazanium;bromide Chemical compound Br.NC=N QWANGZFTSGZRPZ-UHFFFAOYSA-N 0.000 claims description 23
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 23
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 22
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- 238000001771 vacuum deposition Methods 0.000 description 2
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Definitions
- the present disclosure relates to the field of photovoltaic technology, and in particular, to a stacked battery.
- the purpose of the present disclosure is to provide a stacked battery, so as to form a functional layer with a high degree of thin film order on the bottom battery, thereby improving the photoelectric conversion efficiency of the stacked battery.
- the present disclosure provides a stacked battery.
- the stacked battery includes: a bottom battery, the bottom battery has a textured surface; a hole transport layer formed on the textured surface of the bottom battery; a second order inducing layer and a perovskite absorption layer formed on the hole transport layer, The second order inducing layer is located between the hole transport layer and the perovskite absorber layer; and a transparent conductive layer formed on the perovskite absorber layer.
- the inducing material contained in the second order inducing layer is an organic ammonium salt or an inorganic lead compound.
- the perovskite absorbing layer is grown on the second order inducing layer, and under the buffering effect of the second order inducing layer, the perovskite absorbing layer can avoid the molecular disorder on the surface of the hole transport layer. Negative Effects.
- the perovskite absorber layer can grow in an orderly manner under the induction of the second order-inducing layer, and has higher crystallinity and larger grain size. At this time, the perovskite absorber layer has fewer defects and higher photoelectric conversion efficiency.
- the second order-inducing layer acts as an intermediate layer between the hole transport layer and the perovskite absorption layer, which can reduce the energy range between the films, form an energy level match that is conducive to hole transport, and improve the efficiency of the tandem battery. hole transport properties.
- the inducing material of the second order inducing layer is an organic ammonium salt or an inorganic lead compound
- the organic ammonium salt and inorganic lead compound and the perovskite material of the perovskite absorption layer have a high degree of crystal structure matching, similar properties, and are easy to use. Induced growth of highly ordered perovskite absorber layers.
- the above-mentioned inorganic lead compound is one or more of lead oxide, lead bromide, lead iodide, lead chloride, lead acetate, lead thiocyanate and lead sulfide.
- These inorganic lead compounds are metal oxides and have good compatibility with the metal oxide hole transport layer, so that a better interface contact can be formed between the second order inducing layer and the hole transport layer.
- both the inorganic lead compound and the perovskite material of the perovskite absorber layer are lead compounds, and the two have good compatibility, which makes it easier to induce the growth of the perovskite absorber layer for the second order inducing layer.
- the thickness of the second order inducing layer is 1 nm ⁇ 20 nm.
- the above-mentioned tandem battery further includes a first order inducing layer.
- the first order inducing layer is located between the bottom cell and the hole transport layer.
- the hole transport layer can grow in an orderly manner, with higher crystallinity and larger grain size, thereby The defects of the hole transport layer are reduced, and the hole transport performance of the hole transport layer is improved.
- the first order inducing layer acts as an intermediate layer between the hole transport layer and the bottom cell, which can reduce the energy level difference between the films and form an energy level between the hole transport layer and the bottom cell that is favorable for hole transport. matching, thereby improving the hole transport performance of the tandem battery.
- the inducing material of the first order inducing layer is a rod-shaped molecular material
- the rod-shaped molecular material is easy to stand upright on the underlying film through close packing to form a highly ordered geometric channel.
- the highly ordered geometric channel can induce the oriented growth of the upper organic film along the geometric channel through strong interaction.
- the first order inducing layer containing the rod-shaped molecular material has a better order growth inducing effect on the upper film.
- rod-like molecular materials have properties similar to liquid crystals in thin films, and their liquid crystal phase temperature is low, and it is easy to form a large-area highly ordered first order induction through the fluidity of liquid crystals at low temperatures.
- Floor is easy to form a large-area highly ordered first order induction through the fluidity of liquid crystals at low temperatures.
- the inducing material contained in the first order inducing layer is a metal oxide
- the material of the hole transport layer is an inorganic hole transport material
- the metal oxide is an inorganic material, and the material properties are similar to the inorganic hole transport layer made of the inorganic material, so that a better interface contact can be formed between the first order inducing layer and the hole transport layer.
- the compatibility is better, and it is easier to induce the orderly growth of the hole transport layer.
- the thickness of the above-mentioned first order inducing layer is 1 nm ⁇ 20 nm.
- the rod-like molecular materials and the like in the first order-inducing layer of this thickness are likely to have properties similar to liquid crystals, so that a large-area ordered thin film is easily formed.
- the above-mentioned rod-shaped molecular material is BPTT
- the metal oxide is zinc oxide
- the thickness of the above hole transport layer is 5 nm ⁇ 100 nm.
- the processes for forming the first order inducing layer, the second order inducing layer and the hole transport layer are magnetron sputtering process, laser pulse deposition process, thermal evaporation coating process, chemical vapor deposition process, solution coating process, gel-sol process, or hydrothermal synthesis of nanoparticles.
- the method for forming the above-mentioned perovskite absorber layer includes:
- Lead iodide and cesium bromide are formed on the second order-inducing layer by co-evaporation,
- the perovskite material film is annealed to form a perovskite absorber layer.
- FIG. 1 is a schematic structural diagram of a laminated battery according to an embodiment of the present disclosure
- FIG. 3 is a schematic structural diagram of a p-type crystalline silicon-perovskite tandem battery provided by an embodiment of the present disclosure.
- FIGS. 4-14 are schematic diagrams of states of various stages of a method for fabricating a p-type crystalline silicon-perovskite tandem battery provided by the implementation of the present disclosure.
- the perovskite absorber layer is often deposited directly on the hole transport layer described above.
- the hole transport layer is made of inorganic semiconductor materials
- the perovskite material of the perovskite absorption layer as an organic-inorganic hybrid material, has a compatibility problem with nickel oxide. If the perovskite material is deposited directly on the inorganic material, the disorder of the inorganic material will increase the crystallization nucleation sites of the perovskite material and lead to the growth of small-sized grains, and the controllability of the film growth is poor. It can be seen that both the hole transport layer and the perovskite absorption layer face the problems of poor interface compatibility, small grain size, and low film order. These defects often affect the performance of each functional layer and reduce the photoelectric conversion efficiency of tandem cells.
- the stacked battery can be a perovskite battery as a top battery, a crystalline silicon battery, a polycrystalline silicon battery, an ingot monocrystalline silicon battery, a copper indium gallium selenide battery, a perovskite battery, a gallium arsenide battery, or an organic photovoltaic battery. Any one of the tandem batteries is a bottom battery, and is not limited to this.
- the tandem cell may further include a tunneling recombination layer 20 on the bottom cell 10 , so as to realize the tunneling recombination collection of photogenerated carriers of the bottom cell 10 and the perovskite top cell.
- the tunneling composite layer 20 can be tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), titanium-doped indium oxide (ITIO), fluorine-doped tin oxide (FTO), aluminum-doped
- the tunneling composite layer 20 is made of transparent metal oxides such as zinc oxide (AZO).
- the first order inducing layer 31 in order to improve the order degree of the first order inducing layer 31 , parameters such as the thickness of the first order inducing layer 31 can be adjusted, so that the inducing material used for making the first order inducing layer 31 has a liquid crystal-like properties. Therefore, a large-area ordered thin film is formed, which is beneficial to improve the order degree of the first order inducing layer 31 .
- the first order inducing layer 31 has a high degree of order, it is favorable for the orderly growth of the hole transport layer 32 on the upper layer, thereby reducing the defects of the hole transport layer 32 and improving the hole transport performance.
- the above hole transport layer 32 is formed on the first order inducing layer 31 .
- the process of forming the hole transport layer 32 may be a magnetron sputtering process, a laser pulse deposition process, a thermal evaporation coating process, a chemical vapor deposition process, a solution coating process, a gel-sol process or a hydrothermal synthesis nanoparticle process.
- the thickness of the hole transport layer 32 may be 5 nm ⁇ 100 nm.
- the thickness of the hole transport layer 32 is 5 nm, 10 nm, 30 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or the like.
- the first order inducing layer 31 has weak epitaxial ability, and weak epitaxial interaction (van der Waals effect) can be used to form lattice matching between the first order inducing layer 31 and the hole transport layer 32 Therefore, the orderly growth of the hole transport layer 32 is induced, thereby realizing the regulation of the microstructure of the hole transport layer 32 .
- a rod-shaped molecular material can be selected as the first order inducing layer 31 .
- the inductive material of the order inducing layer 31 induces the hole transport layer 32 made of the organic hole transport material.
- Rod-like molecular materials easily stand upright on the underlying thin film (tunneling composite layer 20 ) by close packing, forming a highly ordered geometric channel.
- rod-like molecular materials have properties similar to liquid crystals in thin films, and their liquid crystal phase temperature is low, and it is easy to form large-area highly ordered films through the fluidity of liquid crystals at low temperatures.
- the rod-shaped molecular material is easy to form a highly ordered first order inducing layer 31 , and thus has a better ordered growth induction effect.
- the rod-shaped molecular material can be selected from dibenzothiophene (BPTT).
- BPTT can form structurally stable geometric channels, which can induce the growth of highly ordered and stable thin films.
- a metal oxide can also be selected as the inducing material of the first order inducing layer 31 to induce the hole transporting layer 32 made of inorganic hole transporting material.
- the metal oxide is an inorganic material, and the material properties are similar to the inorganic hole transport layer 32 made of the inorganic material, so that a better interface contact can be formed between the first order inducing layer 31 and the hole transport layer 32, The compatibility is better, and it is easier to induce the orderly growth of the hole transport layer 32 .
- the metal oxide can be zinc oxide.
- the material of the hole transport layer 32 may include one or more of PTAA, Cz2T, Spiro-OMeTAD, Spiro-TTB, copper phthalocyanine, and nickel oxide, and is not limited thereto.
- the van der Waals effect (weak interaction) of the geometric channel on the surface of the BPTT film can be used to induce the ordered growth of the copper phthalocyanine material.
- the weak interaction between the BPTT film and the copper phthalocyanine film there is only an orientation relationship between the two, and there is no strict lattice matching relationship. Copper phthalocyanine hole transport layer.
- the material properties of the hole transport layer 32 to be induced to grow can be further selected according to the material properties of the hole transport layer 32 and the material with strong compatibility and interaction with the hole transport layer 32 is further selected to manufacture the first order inducing layer. 31.
- the inducing material contained in the first order inducing layer 31 may be zinc oxide.
- the molecules of the inducing material contained in the first order inducing layer 31 may be BPTT.
- BPTT is a rigid rod-like molecule, which is easy to form a highly ordered film on the surface of the tunneling composite layer 20, and its terminal benzene rings form geometric channels with specific orientations on the surface of the crystal array.
- the van der Waals force between Cz2T molecules and BPTT molecules is a weak interaction, and there is an orientation relationship between the growth of Cz2T molecules and the first order inducing layer 31 of BPTT, so that The Cz2T molecules are neatly stacked along the geometric channels formed by the BPTT molecules to form the hole transport layer 32 with a high degree of order.
- there is no strict lattice matching relationship between the Cz2T molecules and the BPTT molecules so the thickness of the hole transport layer 32 can be prevented from being affected by the first order inducing layer 31 .
- the hole transport layer 32 can grow in an orderly manner, and has a higher crystallinity and a larger grain size. At this time, the hole transport layer 32 has fewer defects and has better hole transport performance.
- the first order inducing layer 31 acts as an intermediate layer between the hole transport layer 32 and the tunneling composite layer 20 , which can reduce the energy level difference between the films, between the hole transport layer 32 and the tunneling composite layer 20 The energy level matching that is favorable for hole transport is formed, thereby improving the hole transport performance of the tandem battery.
- the second order inducing layer 33 is formed on the hole transport layer 32 .
- the process for forming the second order inducing layer 33 can be a magnetron sputtering process, a laser pulse deposition process, a thermal evaporation coating process, a chemical vapor deposition process, a solution coating process, a gel-sol process or a hydrothermal method to synthesize nanoparticles craft.
- the thickness of the second order inducing layer 33 fabricated by the above method may be 1 nm ⁇ 20 nm.
- the thickness of the second order inducing layer 33 is 1 nm, 5 nm, 8 nm, 10 nm, 12 nm, 18 nm, 20 nm and so on.
- the above-mentioned perovskite absorber layer 34 is formed on the second order inducing layer 33 .
- the method of forming the perovskite absorber layer 34 may include forming lead iodide and cesium bromide on the hole transport layer 32 using a co-evaporation method. A mixed solution of formamidine hydroiodide and formamidine hydrobromide is coated on lead iodide and cesium bromide to form a perovskite material thin film. The perovskite material thin film is annealed to form the perovskite absorption layer 34 .
- an organic ammonium salt can be selected as the inducing material or one whose properties are similar to the perovskite material.
- Inorganic lead compounds are used as inducing materials.
- the inducing material of the second order inducing layer is an organic ammonium salt or an inorganic lead compound
- the organic ammonium salt and the inorganic lead compound and the perovskite material of the perovskite absorption layer 34 have a high degree of crystal structure matching and similar properties, The growth of a highly ordered perovskite absorber layer 34 is easily induced.
- the organic ammonium salt can be ammonium acetate or the like.
- the inorganic lead compound may be one or more of lead oxide, lead bromide, lead iodide, lead chloride, lead acetate, lead thiocyanate and lead sulfide. These inorganic lead compounds are metal oxides and have good compatibility with the metal oxide hole transport layer 32 , so that a better interface can be formed between the second order induction layer 33 and the hole transport layer 32 touch.
- the inorganic lead compound and the perovskite material of the perovskite absorption layer 34 are both lead compounds, and the two have good compatibility, so that the second order inducing layer 33 is easier to induce the growth of perovskite absorption Layer 34.
- an electron transport layer 35 may also be provided between the above-mentioned transparent conductive layer 36 and the perovskite absorption layer 34 to realize the transport of photogenerated carriers.
- the material of the electron transport layer 35 can be SnO 2 or the like.
- an n-type heavily doped layer 12 is formed on the surface of the p-type crystalline silicon wafer 11 having a textured surface by a diffusion process such as ion implantation.
- the p-type crystalline silicon wafer 11 has a pn junction, and the structure obtained in the above steps is defined as the bottom cell 10 .
- a first order inducing layer 31 with a thickness of 1 nm-20 nm is formed on the through composite layer 20 .
- a perovskite absorption layer 34 with a thickness of 250 nm to 1000 nm is formed on the second order inducing layer 33 .
- a perovskite absorption layer 34 with a thickness of 250 nm to 1000 nm is formed on the second order inducing layer 33 .
- a mixed solution of formamidine hydroiodide (FAI) and formamidine hydrobromide (FABr) is coated on lead iodide and cesium bromide, and the mixed solution of FAI and FABr reacts with lead iodide and cesium bromide.
- a thin film of perovskite material is formed.
- the solvent of the mixed solution of FAI and FABr may be ethanol or isopropanol.
- a magnetron sputtering process is used to form a second order inducing layer (thickness 1 nm) made of lead bromide on the hole transport layer.
- the tenth step is to use a magnetron sputtering process to form a transparent conductive layer (30 nm) of IWO material on the electron transport layer.
- the p-type crystalline silicon-perovskite tandem cell includes a p-type crystalline silicon bottom cell, a tunneling composite layer, a first order inducing layer made of zinc oxide, and a hole transport made of nickel oxide, which are stacked in sequence. layer, a second order inducing layer made of lead oxide, a perovskite absorption layer, an electron transport interface layer, a leakage repair layer, an electron transport layer and a transparent conductive layer.
- the first step is to provide a p-type crystalline silicon wafer.
- the p-type crystalline silicon wafer is sequentially polished, textured and cleaned to form a p-type crystalline silicon wafer with textured surfaces.
- an n-type heavily doped layer is formed on the surface of the p-type crystalline silicon wafer with textured surface by using an ion implantation process.
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Abstract
Description
Claims (10)
- 一种叠层电池,其特征在于,包括:底电池,所述底电池具有绒面;形成在所述底电池的绒面上的空穴传输层;形成在所述空穴传输层上的第二有序诱导层和钙钛矿吸收层,所述第二有序诱导层位于所述空穴传输层和所述钙钛矿吸收层之间;以及形成在所述钙钛矿吸收层上的透明导电层;其中,所述第二有序诱导层含有的诱导材料为有机铵盐或无机铅化合物。
- 根据权利要求1所述的叠层电池,其特征在于,所述无机铅化合物为氧化铅、溴化铅、碘化铅、氯化铅、醋酸铅、硫氰化铅和硫化铅中的一种或多种。
- 根据权利要求1所述的叠层电池,其特征在于,所述第二有序诱导层的厚度为1nm~20nm。
- 根据权利要求1所述的叠层电池,其特征在于,所述叠层电池还包括第一有序诱导层,所述第一有序诱导层位于所述底电池和所述空穴传输层之间;所述第一有序诱导层含有的诱导材料为棒状分子材料,所述空穴传输层的材料采用有机空穴传输材料,或,所述第一有序诱导层含有的诱导材料为金属氧化物,所述空穴传输层的材料采用无机空穴传输材料;所述第一有序诱导层的厚度为1nm~20nm。
- 根据权利要求4所述的叠层电池,其特征在于,所述棒状分子材料为BPTT,所述金属氧化物为氧化锌。
- 根据权利要求1~5任一项所述的叠层电池,其特征在于,所述空穴传输层的材料包括PTAA、Cz2T、Spiro-OMeTAD、Spiro-TTB、酞菁铜、氧化镍中的一种或多种。
- 根据权利要求1~5任一项所述的叠层电池,其特征在于,所述空穴传输层的厚度为5nm~100nm。
- 根据权利要求1~5任一项所述的叠层电池,其特征在于,形成所述第二有序诱导层以及空穴传输层的工艺为磁控溅射工艺、激光脉冲沉积工艺、 热蒸发镀膜工艺、化学气相沉积工艺、溶液涂布工艺、凝胶-溶胶工艺或水热法合成纳米粒子工艺。
- 根据权利要求1~5任一项所述的叠层电池,所述钙钛矿材料的化学通式为ABX3,其中,A为CH3NH3阳离子、C4H9NH3阳离子、NH2=CHNH2阳离子、Cs阳离子中的一种或多种;B为Pb2+、Sn2+中的一种或两种;X为Cl-、Br-、I-中的一种或多种。
- 根据权利要求1~5任一项所述的叠层电池,其特征在于,形成所述钙钛矿吸收层的方法包括:采用共蒸法在所述第二有序诱导层上形成碘化铅和溴化铯,在所述碘化铅和溴化铯上涂布甲脒氢碘酸盐及甲脒氢溴酸盐混合溶液,形成钙钛矿材料薄膜;对所述钙钛矿材料薄膜进行退火处理,形成钙钛矿吸收层。
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CN114937717A (zh) * | 2022-05-30 | 2022-08-23 | 江苏日托光伏科技股份有限公司 | 一种钙钛矿-hbc叠层双面电池制备方法 |
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CN112086535B (zh) * | 2020-08-20 | 2022-08-09 | 隆基绿能科技股份有限公司 | 一种叠层电池 |
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WO2024021939A1 (zh) * | 2022-07-29 | 2024-02-01 | 青海黄河上游水电开发有限责任公司 | 基于MXene材料互联的两端式叠层太阳能电池及其制备方法 |
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CN112086535A (zh) | 2020-12-15 |
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