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钙钛矿太阳能电池稳定性研究进展

朱彧 杜晨 王硕 马瑞新 王成彦

朱彧, 杜晨, 王硕, 马瑞新, 王成彦. 钙钛矿太阳能电池稳定性研究进展[J]. 工程科学学报, 2020, 42(1): 16-25. doi: 10.13374/j.issn2095-9389.2019.06.24.006
引用本文: 朱彧, 杜晨, 王硕, 马瑞新, 王成彦. 钙钛矿太阳能电池稳定性研究进展[J]. 工程科学学报, 2020, 42(1): 16-25. doi: 10.13374/j.issn2095-9389.2019.06.24.006
ZHU Yu, DU Chen, WANG Shuo, MA Rui-xin, WANG Cheng-yan. Research progress on the stability of perovskite solar cells[J]. Chinese Journal of Engineering, 2020, 42(1): 16-25. doi: 10.13374/j.issn2095-9389.2019.06.24.006
Citation: ZHU Yu, DU Chen, WANG Shuo, MA Rui-xin, WANG Cheng-yan. Research progress on the stability of perovskite solar cells[J]. Chinese Journal of Engineering, 2020, 42(1): 16-25. doi: 10.13374/j.issn2095-9389.2019.06.24.006

钙钛矿太阳能电池稳定性研究进展

doi: 10.13374/j.issn2095-9389.2019.06.24.006
基金项目: 中央高校基础研究基金资助项目(230201606500078);国家自然科学基金资助项目(U1702252,U1302274,51674026)
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    E-mail:chywang@yeah.net

  • 中图分类号: O472

Research progress on the stability of perovskite solar cells

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  • 摘要: 从钙钛矿晶格结构和器件结构入手,介绍了钙钛矿电池的发展历程,总结了A位,B位及X位的组分调控方法、一步法、两步法及其他成膜方法,形貌控制方法,最后,详细讨论了钙钛矿太阳能电池稳定性的影响因素,光热湿等因素是引起钙钛矿晶体分解,导致电池性能下降的主要原因。最后,稳定性问题已经成为阻碍钙钛矿电池产业化的最大的障碍,介绍了钙钛矿太阳能电池当前稳定性问题的主要解决方案:开发更稳定的钙钛矿结构,开发用于控制晶粒生长的新添加剂,以及选择具有优异性能的空穴传输层和电子传输层。
  • 图  1  钙钛矿电池器件效率发展图

    Figure  1.  Perovskite battery device efficiency development chart

    图  2  钙钛矿材料结构

    Figure  2.  Perovskite material structure

    图  3  不同A位阳离子下(a)钙钛矿的容忍因子及(b)钙钛矿的3种晶体结构[1516]

    Figure  3.  (a) Tolerance factors for perovskites at different A sites and (b) three crystal structures of perovskites[1516]

    图  4  MA和FA结构模型

    Figure  4.  MA and FA structural models

    图  5  铷、铯掺杂部分取代甲脒阳离子制备的器件性能测试曲线. (a) Cs掺杂钙钛矿器件的性能;(b) Rb掺杂钙钛矿器件的性能;(c) Rb掺杂钙钛矿器件的稳定性测试[20]

    Figure  5.  Rubidium and cesium doped part substituted formamidine cationic preparation of the device performance test curves: (a) performance of Cs doped perovskite devices; (b) performance of Rb doped perovskite devices; (c) stability testing of Rb doped perovskite devices[20]

    图  6  (a) MAPb1‒abSnaCubI3‒2bBr2b钙钛矿结构示意图;(b) 铅‒锡‒铜三元体系钙钛矿器件结构图;(c) MAPb0.9Sn0.05Cu0.05I2.9Br0.1组分的器件效率[24]

    Figure  6.  (a) Schematic diagram of the MAPb1‒abSnaCubI3‒2bBr2b perovskite structure; (b) Pb‒Sn‒Cu ternary system perovskite device structure diagram; (c) MAPb0.9Sn0.05Cu0.05I2.9Br0.1 component device efficiency[24]

    图  7  控制I与Br含量得到一系列不同吸收带的钙钛矿材料[26]

    Figure  7.  Controlling the I and Br contents to obtain a series of perovskite materials with different absorption bands[26]

    图  8  通过Cl离子掺杂控制钙钛矿结晶形貌[27]. (a) 实验流程示意图(PbI2:碘化铅,MAI:甲基碘化铵,MACl:甲基氯化铵);(b) Cl离子掺杂器件的最佳性能图

    Figure  8.  Crystal morphology of perovskite controlled by Cl ion doping[27]: (a) schematic diagram of experimental process (PbI2: lead iodide, MAI: methyl ammonium iodide, MACl: methyl ammonium chloride); (b) optimal performance diagram of Cl ion doped devices

    图  9  MAPbI3薄膜在不同气氛下85 ℃保持24 h后的衰减情况[28]. (a) 无处理,(b) N2气氛,(c) O2气氛,(d) 空气

    Figure  9.  Attenuation of the MAPbI3 film after heating at 85 ℃ for 24 h in different atmospheres[28]: (a) without treatment; (b) N2 atmosphere; (c) O2 atmosphere; (d) air

    图  10  MAPbI3器件在N2气氛下连续光照老化后的器件性能(a)与离子的排布情况(b)[38]

    Figure  10.  Device performance (a) and ion arrangement (b) of MAPbI3 devices after continuous illumination aging under the N2 atmosphere[38]

    图  11  PEA阳离子含量对CH3NH3PbI3形成能及稳定性(a)和CH3NH3PbI3器件性能(b)的影响[46]

    Figure  11.  Effect of PEA cation content on the formation energy and stability of CH3NH3PbI3 (a) and the performance of CH3NH3PbI3 devices (b)[46]

    图  12  MAAc/TSC添加剂制备钙钛矿薄膜. (a) MAAc/TSC添加剂的结构示意图;(b) CH3NH3PbI3薄膜生长过程;(c) 器件的连续光照稳定性和热稳定性测试[55]

    Figure  12.  Preparation of perovskite thin films by MAAc/TSC additive: (a) schematic diagram of the MAAc/TSC additive; (b) CH3NH3PbI3 film growth process; (c) continuous illumination stability and thermal stability test[55]

    图  13  ADAHX对钙钛矿薄膜的界面修饰. (a) ADAHX结构式;(b) ADAHX分子模型;(c) 钙钛矿薄膜的接触角测试;(d) 界面修饰示意图[58]

    Figure  13.  Interface modification of perovskite thin films by ADAHX: (a) structural formula of ADAHX; (b) molecular model of ADAHX; (c) contact angle test of perovskite thin films; (d) schematic diagram of interface modification[58]

    图  14  CuCrO2作为空穴传输层所制备的器件表征图. (a) 钙钛矿表面形貌;(b) CuCrO2薄膜表面形貌;(c) Spiro-OMeTAD做空穴传输层的器件截面图;(d) CuCrO2做空穴传输层的器件截面图;(e) 器件湿度稳定性测试(CCO:CuCrO2,cl-TiO2:致密TiO2层,mp-TiO2:介孔TiO2层,HTM:空穴传输层)

    Figure  14.  Device characterization diagram prepared by CuCrO2 as a hole transport layer: (a) surface morphology of perovskite; (b) surface morphology of CuCrO2 film; (c) cross section of device for hole transport layer of Spiro-OMeTAD; (d) cross-sectional view of device for hole transport layer of CuCrO2; (e) device humidity stability test (CCO: CuCrO2, cl-TiO2: compact TiO2 layer, mp-tio2: mesoporous TiO2 layer, HTM: hole transport layer)

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