Citation: Vanita Vanita, Roland Schoch, Pascal Puphal, Hasan Yilmaz, Matthias Bauer, Oliver Clemens. Structural and electrochemical behaviour of bilayer manganite LaSr₂Mn₂O_6.96 cathode for all-solid-state fluoride ion batteries[J]. Acta Physico-Chimica Sinica, ;2026, 42(3): 100181. doi: 10.1016/j.actphy.2025.100181 shu

Structural and electrochemical behaviour of bilayer manganite LaSr₂Mn₂O_6.96 cathode for all-solid-state fluoride ion batteries

1.
University of Stuttgart, Institute for Materials Science, Materials Synthesis Group, Heisenbergstraße 3, 70569 Germany
2.
Institute of Inorganic Chemistry and Center for Sustainable Systems Design (CSSD), Paderborn University, Warburger Straße 100, 33098 Paderborn, Germany
3.
Max-Planck-Institute, Heisenbergstr. 1, 70569 Stuttgart, Germany

Corresponding author: Oliver Clemens, oliver.clemens@imw.uni-stuttgart.de
Received Date: 30 June 2025
Revised Date: 27 August 2025
Accepted Date: 4 September 2025

In this study, we explore the potential of the Ruddlesden-Popper (RP)-type bilayer manganite LaSr₂Mn₂O_6.96 as an intercalation-based cathode material for all-solid-state fluoride ion batteries (FIBs). Structural changes of LaSr₂Mn₂O_6.96 during fluoride intercalation and de-intercalation were analyzed via ex situ X-ray diffraction, revealing that F⁻ insertion induces the formation of three distinct tetragonal phases. To understand the complex behavior of these phases, we examined the changes in the Mn oxidation state and coordination environment using X-ray absorption spectroscopy and magnetic measurements. Under stack pressure (20 kN), electrochemical cycling of LaSr₂Mn₂O_6.96 in the potential range of 1 V to −1 V exhibited a continuous increase in specific capacity from capacity of ~30 mAh g⁻¹ to ~68 mAh g⁻¹ over 200 cycles, with ~99% coulombic efficiency and no signs of capacity fading. This makes the bilayer manganite LaSr₂Mn₂O_6.96 a promising candidate for a cycling stable cathode for all-solid-state FIBs, especially under the application of stack pressure.
- Battery,
- All solid-state fluoride ion battery,
- Fluorination,
- Defluorination,
- Ruddlesden-Popper type structure,
- Bilayer manganite,
- Intercalation-type cathode,
- Electrochemical performance
1. [1]
  D. Ahmed, K. M. Maraz, Mater. Eng. Res. 5 (2023) 265, https://doi.org/10.25082/MER.2023.01.003 doi: 10.25082/MER.2023.01.003
2. [2]
  I. Hadjipaschalis, A. Poullikkas, V. Efthimiou, Renew. Sustain. Energy Rev. 13 (2009) 1513, https://doi.org/10.1016/j.rser.2008.09.028 doi: 10.1016/j.rser.2008.09.028
3. [3]
  M. Li, J. Lu, Z. Chen, K. Amine, Adv. Mater. 30 (2018) 1800561, https://doi.org/10.1002/adma.201800561 doi: 10.1002/adma.201800561
4. [4]
  M. J. Lain, E. Kendrick, J. Power Sources 493 (2021) 229690, https://doi.org/10.1016/j.jpowsour.2021.229690 doi: 10.1016/j.jpowsour.2021.229690
5. [5]
  C. Arbizzani, G. Gabrielli, M. Mastragostino, J. Power Sources 196 (2011) 4801, https://doi.org/10.1016/j.jpowsour.2011.01.068 doi: 10.1016/j.jpowsour.2011.01.068
6. [6]
  S. Hess, M. Wohlfahrt-Mehrens, M. Wachtler, J. Electrochem. Soc. 162 (2015) A3084, https://doi.org/10.1149/2.0121502jes doi: 10.1149/2.0121502jes
7. [7]
  H. Lee, N. Sitapure, S. Hwang, J. S.-I. Kwon, Comput. Chem. Eng. 153 (2021) 107415, https://doi.org/10.1016/j.compchemeng.2021.107415 doi: 10.1016/j.compchemeng.2021.107415
8. [8]
  X. Gao, Y.-N. Zhou, D. Han, J. Zhou, D. Zhou, W. Tang, J. B. Goodenough, Joule 4 (2020) 1864, https://doi.org/10.1016/j.joule.2020.06.016 doi: 10.1016/j.joule.2020.06.016
9. [9]
  H. Vikström, S. Davidsson, M. Höök, Appl. Energy 110 (2013) 252, https://doi.org/10.1016/j.apenergy.2013.04.005 doi: 10.1016/j.apenergy.2013.04.005
10. [10]
  S. E. Kesler, P. W. Gruber, P. A. Medina, G. A. Keoleian, M. P. Everson, T. J. Wallington, Ore Geol. Rev. 48 (2012) 55, https://doi.org/10.1016/j.oregeorev.2012.05.006 doi: 10.1016/j.oregeorev.2012.05.006
11. [11]
  G. M. Mudd, S. M. Jowitt, Econ. Geol. 109 (2014) 1813, https://doi.org/10.2113/econgeo.109.7.1813 doi: 10.2113/econgeo.109.7.1813
12. [12]
  X. Fu, D. N. Beatty, G. G. Gaustad, G. Ceder, R. Roth, R. E. Kirchain, M. Bustamante, C. Babbitt, E. A. Olivetti, Environ. Sci. Technol. 54 (2020) 2985, https://doi.org/10.1021/acs.est.9b04975 doi: 10.1021/acs.est.9b04975
13. [13]
  F. Gschwind, G. Rodriguez-Garcia, D. Sandbeck, A. Gross, M. Weil, M. Fichtner, N. Hörmann, J. Fluorine Chem. 182 (2016) 76, https://doi.org/10.1016/j.jfluchem.2015.12.002 doi: 10.1016/j.jfluchem.2015.12.002
14. [14]
  M. Zhang, X. Cao, Y. Hao, H. Wang, J. Pu, B. Chi, Z. Shen, Energy Rev. 3 (2024) 100083, https://doi.org/10.1016/j.enrev.2024.100083 doi: 10.1016/j.enrev.2024.100083
15. [15]
  M. A. Nowroozi, I. Mohammad, P. Molaiyan, K. Wissel, A. R. Munnangi, O. Clemens, J. Mater. Chem. A 9 (2021) 5980, https://doi.org/10.1039/d0ta11656d doi: 10.1039/d0ta11656d
16. [16]
  A. W. Xiao, G. Galatolo, M. Pasta, Joule 5 (2021) 2823, https://doi.org/10.1016/j.joule.2021.09.016 doi: 10.1016/j.joule.2021.09.016
17. [17]
  H. Nakano, T. Matsunaga, T. Mori, K. Nakanishi, Y. Morita, K. Ide, K.-i. Okazaki, Y. Orikasa, T. Minato, K. Yamamoto, Chem. Mater. 33 (2020) 459, https://doi.org/10.1021/acs.chemmater.0c04570 doi: 10.1021/acs.chemmater.0c04570
18. [18]
  I. Mohammad, R. Witter, M. Fichtner, M. Anji Reddy, ACS Appl. Energy Mater. 1 (2018) 4766, https://doi.org/10.1021/acsaem.8b00864 doi: 10.1021/acsaem.8b00864
19. [19]
  Y. Yu, M. Lei, D. Li, C. Li, Adv. Energy Mater. 13 (2023) 2203168, https://doi.org/10.1002/aenm.202203168 doi: 10.1002/aenm.202203168
20. [20]
  Y. Yu, G. Li, C. Li, Adv. Funct. Mater. 35 (2025) 2410891, https://doi.org/10.1002/adfm.202410891 doi: 10.1002/adfm.202410891
21. [21]
  G. Li, D. Li, M. Lei, C. Li, Adv. Energy Mater. 15 (2025) 2404282, https://doi.org/10.1002/aenm.202404282 doi: 10.1002/aenm.202404282
22. [22]
  G. Li, Y. Yu, D. Li, C. Li, Adv. Funct. Mater. 34 (2024) 2406421, https://doi.org/10.1002/adfm.202406421 doi: 10.1002/adfm.202406421
23. [23]
  D. T. Thieu, M. Hammad, H. Bhatia, T. Diemant, V. S. K. Chakravadhanula, R. J. Behm, C. Kubel, M. Fichtner, Adv. Funct. Mater. 27 (2017) 1701051, https://doi.org/10.1002/adfm.201701051 doi: 10.1002/adfm.201701051
24. [24]
  I. Mohammad, R. Witter, Mater. Lett. 244 (2019) 159, https://doi.org/10.1016/j.matlet.2019.02.052 doi: 10.1016/j.matlet.2019.02.052
25. [25]
  M. A. Nowroozi, I. Mohammad, P. Molaiyan, K. Wissel, A. R. Munnangi, O. Clemens, J. Mater. Chem. A 9 (2021) 5980, https://doi.org/10.1039/d0ta11656d doi: 10.1039/d0ta11656d
26. [26]
  M. A. Nowroozi, K. Wissel, M. Donzelli, N. Hosseinpourkahvaz, S. Plana-Ruiz, U. Kolb, R. Schoch, M. Bauer, A. M. Malik, J. Rohrer, S. Ivlev, F. Kraus, O. Clemens, Commun. Mater. 1 (2020) 27, https://doi.org/10.1038/s43246-020-0030-5 doi: 10.1038/s43246-020-0030-5
27. [27]
  K. Wissel, A. M. Malik, S. Vasala, S. Plana-Ruiz, U. Kolb, P. R. Slater, I. da Silva, L. Alff, J. Rohrer, O. Clemens, Chem. Mater. 32 (2020) 3160, https://doi.org/10.1021/acs.chemmater.0c00193 doi: 10.1021/acs.chemmater.0c00193
28. [28]
  K. Wissel, R. Schoch, T. Vogel, M. Donzelli, G. Matveeva, U. Kolb, M. Bauer, P. R. Slater, O. Clemens, Chem. Mater. 33 (2021) 499, https://doi.org/10.1021/acs.chemmater.0c01762 doi: 10.1021/acs.chemmater.0c01762
29. [29]
  M. A. Nowroozi, S. Ivlev, J. Rohrer, O. Clemens, J. Mater. Chem. A 6 (2018) 4658, https://doi.org/10.1039/c7ta09427b doi: 10.1039/c7ta09427b
30. [30]
  M. A. Nowroozi, K. Wissel, J. Rohrer, A. R. Munnangi, O. Clemens, Chem. Mater. 29 (2017) 3441, https://doi.org/10.1021/acs.chemmater.6b05075 doi: 10.1021/acs.chemmater.6b05075
31. [31]
  Y. Wang, K. Yamamoto, Y. Tsujimoto, T. Matsunaga, D. Zhang, Z. Cao, K. Nakanishi, T. Uchiyama, T. Watanabe, T. Takami, H. Miki, H. Iba, K. Maeda, H. Kageyama, Y. Uchimoto, Chem. Mater. 34 (2022) 609, https://doi.org/10.1021/acs.chemmater.1c03189 doi: 10.1021/acs.chemmater.1c03189
32. [32]
  V. Vanita, G. Mezzadra., C. Tealdi, O. Clemens, ACS Appl. Energy Mater. 8 (2025) 7562, https://doi.org/10.1021/acsaem.5c00875 doi: 10.1021/acsaem.5c00875
33. [33]
  S. Vasala, A. Jakob, K. Wissel, A. I. Waidha, L. Alff, O. Clemens, Adv. Electron Mater. 6 (2020) 1900974, https://doi.org/10.1002/aelm.201900974 doi: 10.1002/aelm.201900974
34. [34]
  H. Miki, K. Yamamoto, C. Shuo, T. Matsunaga, M. Kumar, N. Thakur, Y. Sakaguchi, T. Watanabe, H. Iba, H. Kageyama, Y. Uchimoto, Solid State Ionics 406 (2024) 116480, https://doi.org/10.1016/j.ssi.2024.116480 doi: 10.1016/j.ssi.2024.116480
35. [35]
  H. Miki, K. Yamamoto, H. Nakaki, T. Yoshinari, K. Nakanishi, S. Nakanishi, H. Iba, J. Miyawaki, Y. Harada, A. Kuwabara, Y. Wang, T. Watanabe, T. Matsunaga, K. Maeda, H. Kageyama, Y. Uchimoto, J. Am. Chem. Soc. 146 (2024) 3844, https://doi.org/10.1021/jacs.3c10871 doi: 10.1021/jacs.3c10871
36. [36]
  G. Galatolo, O. Alshangiti, C. Di Mino, G. Matthews, A. W. Xiao, G. J. Rees, M. Schart, Y. A. Chart, L. F. Olbrich, M. Pasta, ACS Energy Lett. 9 (2023) 85, https://doi.org/10.1021/acsenergylett.3c02228 doi: 10.1021/acsenergylett.3c02228
37. [37]
  H. Chen, T. Aalto, V. Vanita, O. Clemens, Small Struct. 5 (2024) 2300570, https://doi.org/10.1002/sstr.202300570 doi: 10.1002/sstr.202300570
38. [38]
  M. H. Ehsani, M. E. Ghazi, P. Kameli, F. S. Razavi, J. Alloy Compd. 586 (2014) 261, https://doi.org/10.1016/j.jallcom.2013.10.002 doi: 10.1016/j.jallcom.2013.10.002
39. [39]
  V. Vanita, A. I. Waidha, S. Vasala, P. Puphal, R. Schoch, P. Glatzel, M. Bauer, O. Clemens, J. Mater. Chem. A 12 (2024) 8769, https://doi.org/10.1039/d4ta00704b doi: 10.1039/d4ta00704b
40. [40]
  L. Aikens, L. Gillie, R. Li, C. Greaves, J. Mater. Chem. A 12 (2002) 264, https://doi.org/10.1039/B105550J doi: 10.1039/B105550J
41. [41]
  C. Greaves, J. L. Kissick, M. G. Francesconi, L. D. Aikens, L. J. Gillie, J. Mater. Chem. A 9 (1999) 111, https://doi.org/10.1039/A804447C doi: 10.1039/A804447C
42. [42]
  R. S. Liu, L. Y. Jang, J. M. Chen, J. B. Wu, R. G. Liu, J. G. Lin, C. Y. Huang, Solid State Commun. 105 (1998) 605, https://doi.org/10.1016/S0038-1098(98)80003-3 doi: 10.1016/S0038-1098(98)80003-3
43. [43]
  M. Abu-Samak, U. Kumar, A. M. Quraishi, R. Kumar, S. Kumar, S. Dalela, M. A. Ahmad, B. L. Choudhary, P. A. Alvi, Phys. B 628 (2022) 413562, https://doi.org/41356210.1016/j.physb.2021.413562 doi: 10.1016/j.physb.2021.413562
44. [44]
  T. Yamamoto, Int. Tables Crystallogr. 1 (2024) 80, https://doi.org/10.1107/S157487072000751X doi: 10.1107/S157487072000751X
45. [45]
  M. Kubota, H. Yoshizawa, H. Fujioka, K. Hirota, K. Ohoyama, Y. Endoh, Y. Moritomo, J. Phys. Soc. Jpn. 69 (2000) 1606, https://doi.org/10.1143/JPSJ.69.1606 doi: 10.1143/JPSJ.69.1606
46. [46]
  I. B. Sharma, D. Singh, Proc. Indian Acad. Sci. Chem. Sci. 107 (1995) 189, https://doi.org/10.1007/BF02884435 doi: 10.1007/BF02884435
47. [47]
  A. S. Erchidi Elyacoubi, R. Masrour, A. Jabar, E. K. Hlil, J. Low Temp. Phys. 203 (2021) 419, https://doi.org/10.1007/s10909-021-02592-w doi: 10.1007/s10909-021-02592-w
48. [48]
  Tommi Hendrik Aalto, T. Widder, Eberhard Goering, Peter Nagel, Kerstin Wissel, Oliver Clemens Preprint, https://doi.org/10.26434/chemrxiv-2025-qlbkp
49. [49]
  T. H. Aalto, R. Talei, K. Küster, G. Schmitz, O. Clemens, Batteries Supercaps (2025) 2500195, https://doi.org/10.1002/batt.202500195 doi: 10.1002/batt.202500195
50. [50]
  H. Chen, R. Schoch, J. N. Chotard, Y. M. Thiebes, K. Wissel, R. Niewa, M. Bauer, O. Clemens, Small Methods (2025) e2500374, https://doi.org/10.1002/smtd.202500374 doi: 10.1002/smtd.202500374
1. [1]
  Guangnan SHAN , Yuhui WANG , Yueru WU . Preparation and electrochemical performance of α-MnO₂ electrode material for aqueous zinc ion battery. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 479-487. doi: 10.11862/CJIC.20250292
2. [2]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-0. doi: 10.3866/PKU.WHXB202406014
3. [3]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
4. [4]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-0. doi: 10.3866/PKU.WHXB202311030
5. [5]
  Zhuo Wang , Xue Bai , Kexin Zhang , Hongzhi Wang , Jiabao Dong , Yuan Gao , Bin Zhao . MOF-Templated Synthesis of Nitrogen-Doped Carbon for Enhanced Electrochemical Sodium Ion Storage and Removal. Acta Physico-Chimica Sinica, 2025, 41(3): 100026-0. doi: 10.3866/PKU.WHXB202405002
6. [6]
  Zhaoxuan ZHU , Lixin WANG , Xiaoning TANG , Long LI , Yan SHI , Jiaojing SHAO . Application of poly(vinyl alcohol) conductive hydrogel electrolytes in zinc ion batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 893-902. doi: 10.11862/CJIC.20240368
7. [7]
  Kun Xu , Xinxin Song , Zhilei Yin , Jian Yang , Qisheng Song . Comprehensive Experimental Design of Preferential Orientation of Zinc Metal by Heat Treatment for Enhanced Electrochemical Performance. University Chemistry, 2024, 39(4): 192-197. doi: 10.3866/PKU.DXHX202309050
8. [8]
  Yuting ZHANG , Zunyi LIU , Ning LI , Dongqiang ZHANG , Shiling ZHAO , Yu ZHAO . Nickel vanadate anode material with high specific surface area through improved co-precipitation method: Preparation and electrochemical properties. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2163-2174. doi: 10.11862/CJIC.20240204
9. [9]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
10. [10]
  Xuechen Hu , Qiuying Xia , Fan Yue , Xinyi He , Zhenghao Mei , Jinshi Wang , Hui Xia , Xiaodong Huang . Electrochemical Characteristics of LiNbO₃ Anode Film and Its Applications in All-Solid-State Thin-Film Lithium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2309046-0. doi: 10.3866/PKU.WHXB202309046
11. [11]
  Keke Gao , Haozhe Xu , Xingkun Liu , Chunwen Sun . Cr-doped lithium-rich manganese-based materials as a cathode for high-performance all-solid-state lithium batteries. Acta Physico-Chimica Sinica, 2026, 42(3): 100200-0. doi: 10.1016/j.actphy.2025.100200
12. [12]
  Zhongyan Cao , Youzhi Xu , Menghua Li , Xiao Xiao , Xianqiang Kong , Deyun Qian . Electrochemically Driven Denitrative Borylation and Fluorosulfonylation of Nitroarenes. University Chemistry, 2025, 40(4): 277-281. doi: 10.12461/PKU.DXHX202407017
13. [13]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
14. [14]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-0. doi: 10.3866/PKU.WHXB202310034
15. [15]
  Yajuan Zhang , Jinliang Li , Xi Zhang , Yue Li , Peng Sun , Hao Xu , Likun Pan . Mitigate pressure dependence in sulfide-based all-solid-state batteries via structural and interfacial engineering of Ni-rich cathodes. Acta Physico-Chimica Sinica, 2026, 42(4): 100204-0. doi: 10.1016/j.actphy.2025.100204
16. [16]
  Da Wang , Xiaobin Yin , Jianfang Wu , Yaqiao Luo , Siqi Shi . All-Solid-State Lithium Cathode/Electrolyte Interfacial Resistance: From Space-Charge Layer Model to Characterization and Simulation. Acta Physico-Chimica Sinica, 2024, 40(7): 2307029-0. doi: 10.3866/PKU.WHXB202307029
17. [17]
  Peicai Li , Xubin Wang , Qinghua Zhang , Bowen Wang , Xiaohui Rong , Yong-Sheng Hu , Zhongtao Li . High-rate and long-cycling P2-type cathode material for sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(5): 100214-0. doi: 10.1016/j.actphy.2025.100214
18. [18]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5−xMn_0.5V_1.5−xZr_x (PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-0. doi: 10.3866/PKU.WHXB202407023
19. [19]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
20. [20]
  Xiangyu CAO , Jiaying ZHANG , Yun FENG , Linkun SHEN , Xiuling ZHANG , Juanzhi YAN . Synthesis and electrochemical properties of bimetallic-doped porous carbon cathode material. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 509-520. doi: 10.11862/CJIC.20240270

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(605)
HTML views(65)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Structural and electrochemical behaviour of bilayer manganite LaSr2Mn2O6.96 cathode for all-solid-state fluoride ion batteries

Metrics

通讯作者: 陈斌, bchen63@163.com

Structural and electrochemical behaviour of bilayer manganite LaSr₂Mn₂O_6.96 cathode for all-solid-state fluoride ion batteries