钙钛矿基三结叠层太阳电池的研究进展

许畅; 郑德旭; 董心睿; 吴飒建; 武明星; 王开; 刘生忠

doi:10.7498/aps.73.20241187

摘要

单结太阳电池的能量转换效率受限于Shockley-Queisser理论极限, 而突破该极限的最有效策略是构建多结叠层太阳电池. 多结叠层太阳电池通过堆叠多个子电池, 可针对太阳光谱的特定部分进行优化. 钙钛矿材料具有连续可调的能带结构, 为多结叠层电池中的吸光材料组合提供了新的选项. 在钙钛矿基叠层太阳电池领域, 三结叠层太阳电池已经取得了一定进展, 在光伏产业中展现出巨大潜力. 本文首先重点介绍了三结叠层太阳能器件结构及面临的科学问题, 然后介绍了钙钛矿基三结叠层电池的研究进展, 包括钙钛矿/钙钛矿/硅叠层电池、钙钛矿/钙钛矿/有机叠层电池和全钙钛矿叠层电池. 最后, 本文分析了进一步提升三结叠层太阳电池性能的研究方向, 为制备高效三结电池提供了指导.

关键词:

Abstract

The energy conversion efficiency of single-junction solar cells is limited by the Shockley-Queisser theory and the most effective strategy to break through this limit is to fabricate multi-junction tandem solar cells. Perovskite materials provide a continuously tunable energy band structure, offering a new option for light-absorbing materials in multi-junction tandem cells. In the field of perovskite-based multi-junction tandem solar cells, triple-junction tandem solar cells have demonstrated great potential. The present paper introduces the configuration of triple-junction solar cells and its facing three scientific challenges. 1) Ensuring energy level alignment among sub-cells is a critical concern for three-junction batteries. Specifically, the top wide-band gap sub-cell must possess a band gap ranging from 1.8 to 2.2 eV; however, current perovskite material systems with wide-band gaps exhibit certain defects. 2) It is essential to achieve current matching in multi-junction tandem solar cells while optimizing the absorption layer and minimizing parasitic absorption in order to maximize the current output of solar cells. 3) The functional layers of multi-junction tandem solar cells are stacked sequentially using different deposition methods, which imposes higher compatibility requirements on the intermediate interconnect layers. Subsequently, the research progress of perovskite-based triple-junction tandem solar cells is introduced, including perovskite/perovskite/silicon tandem solar cells, perovskite/perovskite/organic tandem solar cells, and all-perovskite tandem solar cells. Their respective highest efficiencies are 19.4%, 23.87%, and 27.1%. Finally, this paper explores the research directions for further improving the performance of triple-junction solar cells. In addition to improving energy conversion efficiency, perovskite-based solar cells must also solve the stability problems in order to achieve future commercialization, and provide guidance for the development of efficient triple-junction cells.

Keywords:

作者及机构信息

1.
中国科学院大学, 中国科学院太阳能光电转换与利用重点实验室, 材料科学与光电子工程中心, 大连化学物理研究所, 大连　116023

2.
河北师范大学化学与材料科学学院, 河北省无机纳米材料重点实验室, 薄膜太阳电池材料与器件河北省工程研究中心, 石家庄　050024

3.
中国核能电力股份有限公司, 北京　100089

4.
中核光电科技(上海)有限公司, 上海　201306

通信作者: 王开, wangkai@dicp.ac.cn ; 刘生忠, szliu@dicp.ac.cn

基金项目: 国家重点研发计划(批准号: 2022YFE0138100)和国家自然科学基金(批准号: 22279140, U20A20252, 52350710208, U21A20102, 62174103)资助的课题.

Authors and contacts

1.
Key Laboratory of Photoelectric Conversion and Utilization of Solar Energy, Center of Materials Science and Optoelectronics Engineering, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, University of Chinese Academy of Sciences, Dalian 116023, China

2.
Thin-film Solar Cell Materials and Devices Engineering Research Center of Hebei Province, Hebei Province Key Laboratory of Inorganic Nanomaterials, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China

3.
China National Nuclear Power Co., Ltd., Beijing 100089, China

4.
China National Nuclear Power Optoelectronics Technology (Shanghai) Co., Ltd., Shanghai 201306, China

Corresponding author: Wang Kai, wangkai@dicp.ac.cn ; Liu Sheng-Zhong, szliu@dicp.ac.cn

Funds: Project supported by the National Key Research and Development Program of China (Grant No. 2022YFE0138100) and the National Natural Science Foundation of China (Grant Nos. 22279140, U20A20252, 52350710208, U21A20102, 62174103).

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施引文献

图 1 (a) 三结叠层太阳电池光响应原理; (b) 三结钙钛矿基叠层太阳电池效率演变; (c) 三结钙钛矿基叠层太阳电池结构示意图

Fig. 1. (a) Principle of light response of triple-junction tandem solar cells; (b) PCE evolution of triple-junction tandem solar cells; (c) schematic illustration of the triple-junction perovskite based tandem solar cells.

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图 2 (a) 全钙钛矿叠层太阳电池的最大实际PCE为36.6%时的EQE曲线^[6]; (b) 全钙钛矿叠层太阳电池的最大实际PCE为36.6%时的J-V曲线^[6]; (c) 钙钛矿/钙钛矿/硅叠层太阳电池的最大实际PCE为38.8%时的EQE曲线^[6]; (d) 钙钛矿/钙钛矿/硅叠层太阳电池的最大实际PCE为38.8%时的J-V曲线^[6]

Fig. 2. (a) EQE curves for an all-perovskite tandem solar cell with a maximum practical PCE of 36.6%^[6]; (b) J-V curves for an all-perovskite tandem solar cell with a maximum practical PCE of 36.6%^[6]; (c) EQE curves for a perovskite/perovskite/silicon solar cell with a maximum practical PCE of 38.8%^[6]; (d) J-V curves for a perovskite/perovskite/silicon solar cell with a maximum practical PCE of 38.8%^[6].

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图 3 (a) 叠层太阳电池结构及横截面SEM图像^[74]; (b) 子电池及叠层太阳电池J-V曲线^[75]; (c) 全钙钛矿叠层太阳电池结构^[77]; (d) 叠层太阳电池在暗态和光照下的J-V曲线^[76]; (e) 钙钛矿前驱体结晶过程示意图^[79]; (f) 钙钛矿的相偏析抑制机制示意图^[78]

Fig. 3. (a) Schematic structure of tandem solar cells and cross sectional SEM image^[74]; (b) J-V curves of sub-cells and three-junction tandem solar cell^[75]; (c) schematic structure of all perovskite triple-junction tandem solar cells^[77]; (d) J-V curves of tandem solar cells in dark state and light^[76]; (e) schematics of perovskite precursors during the crystallization process^[79]; (f) schematic illustration of the suppression mechanism of light-induced phase segregation^[78].

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图 4 (a) 叠层太阳电池结构及截面SEM图像^[67]; (b) 叠层太阳电池结构及截面SEM图像^[80]; (c) 性能最佳的叠层太阳电池J-V曲线, 插图为叠层太阳电池结构示意图^[69]; (d) 反溶剂沉积方法和气淬技术制备的钙钛矿电池横截面SEM图像^[81]

Fig. 4. (a) Schematic structure of tandem solar cells and cross sectional SEM images^[67]; (b) schematic structure of tandem solar cells and cross sectional SEM images^[80]; (c) J-V curve of the champion tandem solar cell, illustrated with schematic structure of the tandem solar cell^[69]; (d) cross sectional SEM image of perovskite cell prepared by anti-solvent dripping and gas quenching method^[81].

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图 5 (a) 添加剂工程工作机理示意图^[82]; (b) 宽带隙钙钛矿混合相和分离相示意图^[83]; (c) 薄膜的XRD图^[84]; (d) 经认证的叠层太阳电池J-V曲线^[85]

Fig. 5. (a) Schematic diagram of the working mechanism of additive engineering^[82]; (b) illustration of the mixed-phase and segregated-phase of wide-bandgap perovskites^[83]; (c) XRD pattern of film^[84]; (d) certified tandem solar cells J-V curves^[85].

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表 1 单节宽带隙钙钛矿太阳电池光伏性能汇总表

Table 1. Summary of photovoltaic performance of single wide-band gap perovskite solar cells.

组分	禁带宽度/eV	开路电压/V	短路电流密度 /(mA·cm^–2)	填充因子/%	能量转换效率/%	Ref.
Cs_0.15MA_0.15FA_0.70Pb(I_0.15Br_0.85)₃	2.05	1.27	9.4	70.4	8.4	[74]
FA_0.83Cs_0.17Pb(Br_0.7I_0.3)₃	1.94	1.28	11.9	76.0	11.6	[75]
Cs_0.2FA_0.8PbI_0.9Br_2.1	1.73	1.07	9.9	76.0	8.1	[76]
Cs_0.2FA_0.8PbI_0.9Br_2.1	1.99	1.262	11.2	73.5	10.4	[77]
Rb_0.15Cs_0.85PbI_1.75Br_1.25	2.0	1.30	12.4	84.7	13.6	[78]
Cs_0.15FA_0.85Pb(I_0.4Br_0.6)₃	1.97	1.44	12.8	83.0	15.3	[79]
CsFAPbIBr	1.8	\	\	\	\	[67]
Cs_0.2FA_0.8Pb(I_0.45Br_0.55)₃	1.90	1.09	11.7	71	9.1	[80]
MAPb(I_0.5Br_0.35Cl_0.15)₃	1.96	1.28	14.16	76.6	13.88	[69]
Cs_0.05(FA_0.55MA_0.45)_0.95Pb(I_0.55Br_0.45)₃	1.83	1.12	13.6	74.6	11.3	[81]
Cs_0.1FA_0.9PbBr_2.1I_0.9	1.98	1.38	14.0	76.6	15.0	[82]
Rb_0.05Cs_0.12FA_0.83PbI_0.95Cl_0.05Br₂	1.98	1.33	13.05	76.7	13.4	[83]
FA_0.8Cs_0.2Pb(I_0.5Br_0.5)₃	1.84	1.27	16.4	77.0	16.0	[84]
FA_0.60MA_0.15Cs_0.25Pb(I_0.45Br_0.5OCN_0.05)₃	1.93	1.422	14.18	83.79	16.9	[85]

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表 2 单片三结钙钛矿基叠层太阳电池光伏性能汇总表

Table 2. Summaries for PV performance of monolithic triple-junction perovskite-based tandem solar cells.

类型	宽带隙	中间带隙	窄带隙	开路电压/V	短路电流密度 /(mA·cm^–2)	填充因子/%	正扫/反扫效率/%	认证效率/%	面积 /cm²	Ref.
钙钛矿/ 钙钛矿/ 有机	Cs_0.15MA_0.15FA_0.70Pb (I_0.15Br_0.85)₃ (2.05 eV)	Cs_0.15MA_0.15FA_0.70Pb (I_0.85Br_0.15)₃ (1.62 eV)	PM6:BTP-eC9:PCBM (1.33 eV)	3.03	9.1	70.4	19.4	\	0.1	[74]
钙钛矿/ 钙钛矿/ 有机	Cs_0.15MA_0.15FA_0.70Pb (I_0.15Br_0.85)₃ (2.05 eV)	Cs_0.15MA_0.15FA_0.70Pb (I_0.85Br_0.15)₃ (1.62 eV)	PM6:BTP-eC9:PCBM (1.33 eV)	\	\	\	19.2	\	0.1	[74]
钙钛矿/ 钙钛矿/ 钙钛矿	FA_0.83Cs_0.17Pb(Br_0.7I_0.3)₃ (1.94 eV)	MAPbI₃ (1.57 eV)	MAPb_0.75Sn_0.25I₃ (1.34 eV)	2.7	8.3	0.43	6.7	\	0.092	[75]
	FA_0.83Cs_0.17Pb(Br_0.7I_0.3)₃ (1.94 eV)	MAPbI₃ (1.57 eV)	MAPb_0.75Sn_0.25I₃ (1.34 eV)	\	\	\	\	\	0.092	[75]
	Cs_0.1(FA_0.66MA_0.34)_0.9 PbI₂Br (1.73 eV)	FA_0.66MA_0.34 PbI_2.85Br_0.15 (1.57 eV)	FA_0.66MA_0.34 Pb_0.5Sn_0.5I₃ (1.23eV)	2.78	7.4	81	17.3	\	0.067	[76]
	Cs_0.1(FA_0.66MA_0.34)_0.9 PbI₂Br (1.73 eV)	FA_0.66MA_0.34 PbI_2.85Br_0.15 (1.57 eV)	FA_0.66MA_0.34 Pb_0.5Sn_0.5I₃ (1.23eV)	2.78	7.42	82	17.0	\	0.067	[76]
	Cs_0.2FA_0.8PbI_0.9Br_2.1 (1.99 eV)	Cs_0.05FA_0.95Pb I_2.55Br_0.45 (1.60 eV)	MA_0.3FA_0.7Pb_0.5 Sn_0.5I₃ (1.22 eV)	2.80	8.8	81	20.1	\	0.049	[77]
	Cs_0.2FA_0.8PbI_0.9Br_2.1 (1.99 eV)	Cs_0.05FA_0.95Pb I_2.55Br_0.45 (1.60 eV)	MA_0.3FA_0.7Pb_0.5 Sn_0.5I₃ (1.22 eV)	2.793	8.8	80.7	19.9	\	0.049	[77]
	Rb_0.15Cs_0.85PbI_1.75Br_1.25 (2.0 eV)	Cs_0.05FA_0.9MA_0.05Pb (I_0.9Br_0.1)₃ (1.60 eV)	Cs_0.05FA_0.7MA_0.25Pb_0.5 Sn_0.5I₃-0.05SnF₂ (1.22 eV)	3.215	9.71	77.93	24.33	23.29	0.049	[78]
	Rb_0.15Cs_0.85PbI_1.75Br_1.25 (2.0 eV)	Cs_0.05FA_0.9MA_0.05Pb (I_0.9Br_0.1)₃ (1.60 eV)	Cs_0.05FA_0.7MA_0.25Pb_0.5 Sn_0.5I₃-0.05SnF₂ (1.22 eV)	3.210	9.63	78.67	24.32	23.29	0.049	[78]
	Cs_0.15FA_0.85Pb(I_0.4Br_0.6)₃ (1.97 eV)	Cs_0.05FA_0.9MA_0.05Pb (I_0.85Br_0.15)₃ (1.77 eV)	Cs_0.05FA_0.7MA_0.25 Pb_0.5Sn_0.5I₃ (1.22 eV)	3.33	9.7	78	25.1	23.87	0.049	[79]
	Cs_0.15FA_0.85Pb(I_0.4Br_0.6)₃ (1.97 eV)	Cs_0.05FA_0.9MA_0.05Pb (I_0.85Br_0.15)₃ (1.77 eV)	Cs_0.05FA_0.7MA_0.25 Pb_0.5Sn_0.5I₃ (1.22 eV)	\	\	\	\	23.87	0.049	[79]
钙钛矿/ 钙钛矿/ 硅	CsFAPbIBr (1.8 eV)	CsFAPbIBr (1.53 eV)	Si (1.10 eV)	2.688	7.7	68.0	14.0	\	1.42	[67]
	CsFAPbIBr (1.8 eV)	CsFAPbIBr (1.53 eV)	Si (1.10 eV)	2.692	7.7	58.7	12.1	\	1.42	[67]
	Cs_0.2FA_0.8Pb(I_0.45Br_0.55)₃ (1.90 eV)	Cs_0.1FA_0.9PbI₃ (1.55 eV)	Si (1.10 eV)	2.74	8.54	86.0	20.1	\	1.03	[80]
	Cs_0.2FA_0.8Pb(I_0.45Br_0.55)₃ (1.90 eV)	Cs_0.1FA_0.9PbI₃ (1.55 eV)	Si (1.10 eV)	\	\	\	\	\	1.03	[80]
	MAPb(I_0.5Br_0.35Cl_0.15)₃ (1.96 eV)	Cs_0.2MA_0.05FA_0.75PbI₃ (1.56 eV)	Si (1.10 eV)	2.78	10.18	78.60	22.23	\	0.1875	[69]
	MAPb(I_0.5Br_0.35Cl_0.15)₃ (1.96 eV)	Cs_0.2MA_0.05FA_0.75PbI₃ (1.56 eV)	Si (1.10 eV)	2.78	10.19	76.90	21.79	\	0.1875	[69]
	Cs_0.05(FA_0.55MA_0.45)_0.95 Pb(I_0.55Br_0.45)₃ (1.83 eV)	Cs_0.05(FA_0.9MA_0.1)_0.95Pb (I_0.95Br_0.05)₃ (1.56 eV)	Si (1.10 eV)	2.87	8.9	78.1	20.1	\	1.0	[81]
	Cs_0.05(FA_0.55MA_0.45)_0.95 Pb(I_0.55Br_0.45)₃ (1.83 eV)	Cs_0.05(FA_0.9MA_0.1)_0.95Pb (I_0.95Br_0.05)₃ (1.56 eV)	Si (1.10 eV)	2.86	8.9	77.9	20.0	\	1.0	[81]
	Cs_0.1FA_0.9PbBr_2.1I_0.9 (1.98 eV)	Rb_0.05Cs_0.1FA_0.85PbI₃ (1.52 eV)	Si (1.10 eV)	3.04	11.9	72.9	26.4	\	1.0	[82]
	Cs_0.1FA_0.9PbBr_2.1I_0.9 (1.98 eV)	Rb_0.05Cs_0.1FA_0.85PbI₃ (1.52 eV)	Si (1.10 eV)	3.01	11.9	71.1	25.5	\	1.0	[82]
	Rb_0.05Cs_0.12FA_0.83PbI_0.95 Cl_0.05Br₂ (1.98 eV)	Cs_0.05(FA_0.98MA_0.02)_0.95Pb (I_0.98Br_0.02)₃ (1.55 eV)	Si (1.10 eV)	2.995	11.76	70.80	25.0	24.19	1.04	[83]
	Rb_0.05Cs_0.12FA_0.83PbI_0.95 Cl_0.05Br₂ (1.98 eV)	Cs_0.05(FA_0.98MA_0.02)_0.95Pb (I_0.98Br_0.02)₃ (1.55 eV)	Si (1.10 eV)	2.980	11.73	68.4	23.9	24.19	1.04	[83]
	FA_0.8Cs_0.2Pb(I_0.5Br_0.5)₃ (1.84 eV)	FAPbI₃ (1.52 eV)	Si (1.10 eV)	2.84	11.6	0.74	24.4	\	1.0	[84]
	FA_0.8Cs_0.2Pb(I_0.5Br_0.5)₃ (1.84 eV)	FAPbI₃ (1.52 eV)	Si (1.10 eV)	2.86	11.5	0.73	24.0	\	1.0	[84]
	FA_0.60MA_0.15Cs_0.25Pb (I_0.45Br_0.5OCN_0.05)₃ (1.93 eV)	FA_0.9Cs_0.1PbI₃ (1.55 eV)	Si (1.10 eV)	3.132	11.58	76.15	27.62	27.1	1.0	[85]
	FA_0.60MA_0.15Cs_0.25Pb (I_0.45Br_0.5OCN_0.05)₃ (1.93 eV)	FA_0.9Cs_0.1PbI₃ (1.55 eV)	Si (1.10 eV)	\	\	\	\	27.1	1.0	[85]

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