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Impact of lithium dopants in hole-transporting layers on perovskite solar cell stability under day–night cycling

Nature Energy volume 10, pages 1226–1236 (2025) Cite this article

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Abstract

Lithium cation dopants enhance hole-transport efficiency and optimize interfacial charge extraction in the hole-transporting layers of perovskite solar cells. Although the migration of lithium cations is known to induce phase transition from α-phase to δ-phase in perovskites, reports of long-term device stability present apparent contradictions. Here we show that, under dark/light alternating conditions, lithium migration induces a rapid degradation of the α-phase perovskite. This degradation is not observed under continuous light-only or dark-only conditions commonly used within the field to test the devices. To address the instability under dark/light cycling, we replace the lithium dopant with a methylammonium dopant. Importantly, we show no unreacted methylammonium dopant in the hole-transport layer film different to the lithium dopant, hinting at a better device stability. We achieve an efficiency of 26.1% (25.6% certified) and T95 lifetimes (that is, time for the device efficiency to decay to 95% of its initial value) of over 1,200 h of continuous light–dark cycling (ISOS-LC-1 certified) and 3,000 voltage-on/off cycles, conditions that are relevant to real-world operation.

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Fig. 1: Lithium distributions in dark and light conditions.
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Fig. 2: Lithium migration and phase instability in perovskites.
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Fig. 3: Phase instability mechanism in perovskites.
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Fig. 4: Doping ability and photovoltaic efficiency comparisons.
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Fig. 5: Solar cell stability comparisons under different conditions.
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Data availability

All data generated in this study are provided in the article and Supplementary Information, and the raw data supporting this study are available from the Source Data file. Source data are provided with this paper.

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Acknowledgements

We thank X. Wang at Carl Zeiss Co. for FIB-SEM and TOF-SIMS measurement. We thank Y. Yang at Shanghai Synchrotron Radiation Facility for GIWAXS measurement. Funding: this work is supported financially by the National Natural Science Foundation of China (62374085, 62288102, 62204114, 62205143, 62075094), the Fundamental Research Funds for the Central Universities, Sun Yat-sen University (number 24lgzy008) and the Natural Science Foundation of Jiangsu Province (BK20211537).

Author information

Author notes

  1. These authors contributed equally: Jinzheng Zhao, Jiupeng Cao, Jingjin Dong.

Authors and Affiliations

  1. State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM), School of Flexible Electronics (Future Technologies), Nanjing Tech University (NanjingTech), Nanjing, China

    Jinzheng Zhao, Jiupeng Cao, Jingjin Dong, Zihao Li, Ying Chu, Aifei Wang, Fangfang Wang, Jingyu Zhang, Bocong Zhang, Xiaopeng Hu, Wenjian Yan & Tianshi Qin

  2. School of Flexible Electronics (SoFE) and State Key Laboratory of Optoelectronic Materials and Technologies (OEMT), Sun Yat-sen University, Shenzhen, China

    Jinzheng Zhao, Bingxu Liu, Rui Xu, Chi Zhang, Shaohua Chen, Laiyuan Wang, Gaojie Chen, Wei Huang & Tianshi Qin

  3. Henan Institute of Flexible Electronics (HIFE), Zhengzhou, China

    Wei Huang

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Contributions

J. Zhao: writing—original draft, software, methodology, formal analysis, data curation. J.C.: writing—original draft, software, methodology, investigation. J.D.: validation, software, data curation, methodology. Z.L.: validation, software, data curation. Y.C.: software, data curation. A.W.: validation. F.W.: validation. B.L.: data curation. R.X.: data curation. J. Zhang: software. B.Z.: software. X.H.: data curation. W.Y.: data curation. C.Z.: methodology. S.C.: data curation. L.W.: software. G.C.: software. W.H.: resources, funding acquisition. T.Q.: writing—review and editing, supervision, resources, project administration, validation, methodology, investigation, funding acquisition.

Corresponding authors

Correspondence to Wei Huang or Tianshi Qin.

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Nature Energy thanks Seong Sik Shin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information (download PDF )

Supplementary methods, Figs. 1–47, Tables 1–18, Videos 1–3 and references.

Reporting Summary (download PDF )

Supplementary Video 1 (download MP4 )

Video of the reaction to the CV test above. Forty µl of LiTFSI acetonitrile solution (520 mg ml−1) and 20 ml of dichloromethane were added to the electrolytic cell. The working electrode clamp secured the FTO substrate, whereas the gold electrode was used as the reference electrode, all within a nitrogen atmosphere. The sealed cell was then connected to the electrochemical workstation to perform a CV cycle test at ±1.5 V.

Supplementary Video 2 (download MP4 )

Video of the reaction of lithium tablets with FAI. About 5 mg of lithium tablets was put into 2 ml of 1 mol l−1 FAI anhydrous DMSO solution and sealed. The above operation was done in an argon environment.

Supplementary Video 3 (download MP4 )

Video of the phase-transition experiment of perovskite films induced by LiMDA⁺. Solution 1, containing pure acetonitrile (ACN); solution 2, containing LiMDA⁺, was prepared through the following steps. First, 10 mg of FAI were dissolved in 20 ml of ACN. A polished lithium piece was then added, and the mixture was shaken for 10 minutes to ensure complete reaction. Afterward, the excess lithium piece was removed. All steps were carried out inside an argon glovebox. The sample is a perovskite film (perovskite/SnO2/FTO).

Supplementary Data 1 (download XLSX )

Statistical source data.

Supplementary Data 2 (download XLSX )

Statistical source data.

Supplementary Data 3 (download XLSX )

Statistical source data.

Supplementary Data 4 (download XLSX )

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Supplementary Data 5 (download XLSX )

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Zhao, J., Cao, J., Dong, J. et al. Impact of lithium dopants in hole-transporting layers on perovskite solar cell stability under day–night cycling. Nat Energy 10, 1226–1236 (2025). https://doi.org/10.1038/s41560-025-01856-z

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