Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries

Yang Wang; Xiaoshuang Zhang; Tianqi Yang; Jiayuan Xiang; Haijun Yang; Long Wang; Tengfei Zhang; Shenghui Shen; Zhong Qiu; Guoxiang Pan; Yongqi Zhang; Fangfang Tu; Yuanyuan Jiang; Yuhong Zhang; Wei Gong; Yang Xia; Jun Zhang; Wenkui Zhang; Bingbao Mei; Qi Liu; Xinhui Xia

doi:10.1002/adma.73107

Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries

Yang Wang (Co-first Author)
, Xiaoshuang Zhang (Co-first Author)
, Tianqi Yang^*
, Jiayuan Xiang
, Haijun Yang
, Long Wang
, Tengfei Zhang
, Shenghui Shen
, Zhong Qiu
, Guoxiang Pan
, Yongqi Zhang^*
, Fangfang Tu
, Yuanyuan Jiang
, Yuhong Zhang
, Wei Gong
, Yang Xia
, Jun Zhang
, Wenkui Zhang
, Bingbao Mei
, Qi Liu

Xinhui Xia^*

^*Corresponding author for this work

Department of Physics

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

Abstract

Iron-based mixed phosphate Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) is one of the most promising cathodes for sodium-ion batteries due to its good rate capability and long lifespan, while its practical application is hindered by sluggish ionic/electronic kinetics and interfacial instability. Herein, we report a novel solid-source ammonium fluoride (NH₄F) plasma-driven synergistic “Trinity” engineering strategy to realize simultaneous reconstruction of NFPP cathodes in bulk, interface, and surface architectures. Mechanistic investigations reveal that the coupling reactions between the NH₄F plasma and NFPP lattice/surface trigger simultaneous bulk F-substitution and F/N interface doping as well as surface reconstruction. Specifically, the bulk F⁻ substitution strengthens Fe─O bonding and widens Na⁺ channels. Concurrently, plasma-generated radicals promote the formation of F/N co-doped carbon network and NaF at the interface, while also promoting the development of a NaF-rich cathode electrolyte interphase at the surface via modulating the NFPP/electrolyte status. This trinity engineering establishes fast transport pathways and a stable cathode electrolyte interface, effectively minimizing charge transfer impedance while suppressing deleterious side reactions. Consequently, the optimized cell exhibits high capacity and superior high-rate cycling life with 95.5% retention after 6000 cycles at 30 C. The developed plasma-driven approach offers mechanistic insights for the synergistic optimization of polyanionic cathodes for advanced sodium ion storage. © 2026 Wiley-VCH GmbH.

Original language	English
Article number	e73107
Number of pages	14
Journal	Advanced Materials
Volume	38
Issue number	28
Online published	19 Apr 2026
DOIs	https://doi.org/10.1002/adma.73107
Publication status	Published - 18 May 2026

Funding

This work was supported by Key Scientific Research Project of Hangzhou (Grant No. 2024SZD1B12), Natural Science Foundation of Zhejiang Province (Grant No. LD25E020003), National Natural Science Foundation of China (Grant Nos. 52372235, U20A20253, 22379020, 22279116), Science and Technology Department of Zhejiang Province (Grant No. 2023C01231), Science and Technology Project of Huzhou (Grant No. 2024GZ02), National Science Foundation of Sichuan Province (Grant No. 2024NSFSC0951), Zhejiang Provincial Postdoctoral Research Project (Grant No. ZJ2023080). The authors thank the Shanghai Synchrotron Radiation Facility of BL20U1(https://cstr.cn/31124.02.SSRF.BL20U1) for the assistance on XAFS measurements.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Research Keywords

ammonium fluoride
cathode
Na4Fe3(PO4)2P2O7
plasma
sodium ion batteries

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Wang, Y., Zhang, X., Yang, T., Xiang, J., Yang, H., Wang, L., Zhang, T., Shen, S., Qiu, Z., Pan, G., Zhang, Y., Tu, F., Jiang, Y., Zhang, Y., Gong, W., Xia, Y., Zhang, J., Zhang, W., Mei, B., ... Xia, X. (2026). Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries. Advanced Materials, 38(28), Article e73107. https://doi.org/10.1002/adma.73107

@article{e5af9f5389154e38b4a8f88b3c8aa01d,

title = "Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries",

abstract = "Iron-based mixed phosphate Na4Fe3(PO4)2P2O7 (NFPP) is one of the most promising cathodes for sodium-ion batteries due to its good rate capability and long lifespan, while its practical application is hindered by sluggish ionic/electronic kinetics and interfacial instability. Herein, we report a novel solid-source ammonium fluoride (NH4F) plasma-driven synergistic “Trinity” engineering strategy to realize simultaneous reconstruction of NFPP cathodes in bulk, interface, and surface architectures. Mechanistic investigations reveal that the coupling reactions between the NH4F plasma and NFPP lattice/surface trigger simultaneous bulk F-substitution and F/N interface doping as well as surface reconstruction. Specifically, the bulk F− substitution strengthens Fe─O bonding and widens Na+ channels. Concurrently, plasma-generated radicals promote the formation of F/N co-doped carbon network and NaF at the interface, while also promoting the development of a NaF-rich cathode electrolyte interphase at the surface via modulating the NFPP/electrolyte status. This trinity engineering establishes fast transport pathways and a stable cathode electrolyte interface, effectively minimizing charge transfer impedance while suppressing deleterious side reactions. Consequently, the optimized cell exhibits high capacity and superior high-rate cycling life with 95.5\% retention after 6000 cycles at 30 C. The developed plasma-driven approach offers mechanistic insights for the synergistic optimization of polyanionic cathodes for advanced sodium ion storage. {\textcopyright} 2026 Wiley-VCH GmbH.",

keywords = "ammonium fluoride, cathode, Na4Fe3(PO4)2P2O7, plasma, sodium ion batteries",

author = "Yang Wang and Xiaoshuang Zhang and Tianqi Yang and Jiayuan Xiang and Haijun Yang and Long Wang and Tengfei Zhang and Shenghui Shen and Zhong Qiu and Guoxiang Pan and Yongqi Zhang and Fangfang Tu and Yuanyuan Jiang and Yuhong Zhang and Wei Gong and Yang Xia and Jun Zhang and Wenkui Zhang and Bingbao Mei and Qi Liu and Xinhui Xia",

year = "2026",

month = may,

day = "18",

doi = "10.1002/adma.73107",

language = "English",

volume = "38",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "Wiley-Blackwell",

number = "28",

}

Wang, Y, Zhang, X, Yang, T, Xiang, J, Yang, H, Wang, L, Zhang, T, Shen, S, Qiu, Z, Pan, G, Zhang, Y, Tu, F, Jiang, Y, Zhang, Y, Gong, W, Xia, Y, Zhang, J, Zhang, W, Mei, B, Liu, Q & Xia, X 2026, 'Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries', Advanced Materials, vol. 38, no. 28, e73107. https://doi.org/10.1002/adma.73107

Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries. / Wang, Yang (Co-first Author); Zhang, Xiaoshuang (Co-first Author); Yang, Tianqi et al.
In: Advanced Materials, Vol. 38, No. 28, e73107, 18.05.2026.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries

AU - Wang, Yang

AU - Zhang, Xiaoshuang

AU - Yang, Tianqi

AU - Xiang, Jiayuan

AU - Yang, Haijun

AU - Wang, Long

AU - Zhang, Tengfei

AU - Shen, Shenghui

AU - Qiu, Zhong

AU - Pan, Guoxiang

AU - Zhang, Yongqi

AU - Tu, Fangfang

AU - Jiang, Yuanyuan

AU - Zhang, Yuhong

AU - Gong, Wei

AU - Xia, Yang

AU - Zhang, Jun

AU - Zhang, Wenkui

AU - Mei, Bingbao

AU - Liu, Qi

AU - Xia, Xinhui

PY - 2026/5/18

Y1 - 2026/5/18

N2 - Iron-based mixed phosphate Na4Fe3(PO4)2P2O7 (NFPP) is one of the most promising cathodes for sodium-ion batteries due to its good rate capability and long lifespan, while its practical application is hindered by sluggish ionic/electronic kinetics and interfacial instability. Herein, we report a novel solid-source ammonium fluoride (NH4F) plasma-driven synergistic “Trinity” engineering strategy to realize simultaneous reconstruction of NFPP cathodes in bulk, interface, and surface architectures. Mechanistic investigations reveal that the coupling reactions between the NH4F plasma and NFPP lattice/surface trigger simultaneous bulk F-substitution and F/N interface doping as well as surface reconstruction. Specifically, the bulk F− substitution strengthens Fe─O bonding and widens Na+ channels. Concurrently, plasma-generated radicals promote the formation of F/N co-doped carbon network and NaF at the interface, while also promoting the development of a NaF-rich cathode electrolyte interphase at the surface via modulating the NFPP/electrolyte status. This trinity engineering establishes fast transport pathways and a stable cathode electrolyte interface, effectively minimizing charge transfer impedance while suppressing deleterious side reactions. Consequently, the optimized cell exhibits high capacity and superior high-rate cycling life with 95.5% retention after 6000 cycles at 30 C. The developed plasma-driven approach offers mechanistic insights for the synergistic optimization of polyanionic cathodes for advanced sodium ion storage. © 2026 Wiley-VCH GmbH.

AB - Iron-based mixed phosphate Na4Fe3(PO4)2P2O7 (NFPP) is one of the most promising cathodes for sodium-ion batteries due to its good rate capability and long lifespan, while its practical application is hindered by sluggish ionic/electronic kinetics and interfacial instability. Herein, we report a novel solid-source ammonium fluoride (NH4F) plasma-driven synergistic “Trinity” engineering strategy to realize simultaneous reconstruction of NFPP cathodes in bulk, interface, and surface architectures. Mechanistic investigations reveal that the coupling reactions between the NH4F plasma and NFPP lattice/surface trigger simultaneous bulk F-substitution and F/N interface doping as well as surface reconstruction. Specifically, the bulk F− substitution strengthens Fe─O bonding and widens Na+ channels. Concurrently, plasma-generated radicals promote the formation of F/N co-doped carbon network and NaF at the interface, while also promoting the development of a NaF-rich cathode electrolyte interphase at the surface via modulating the NFPP/electrolyte status. This trinity engineering establishes fast transport pathways and a stable cathode electrolyte interface, effectively minimizing charge transfer impedance while suppressing deleterious side reactions. Consequently, the optimized cell exhibits high capacity and superior high-rate cycling life with 95.5% retention after 6000 cycles at 30 C. The developed plasma-driven approach offers mechanistic insights for the synergistic optimization of polyanionic cathodes for advanced sodium ion storage. © 2026 Wiley-VCH GmbH.

KW - ammonium fluoride

KW - cathode

KW - Na4Fe3(PO4)2P2O7

KW - plasma

KW - sodium ion batteries

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UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-105036038234&origin=recordpage

U2 - 10.1002/adma.73107

DO - 10.1002/adma.73107

M3 - RGC 21 - Publication in refereed journal

SN - 0935-9648

VL - 38

JO - Advanced Materials

JF - Advanced Materials

IS - 28

M1 - e73107

ER -

Plasma-Tailored Bulk-Interface-Surface Trinity Engineering of Iron-Based Mixed Phosphate Cathodes for Advanced Sodium Ion Batteries

Abstract

Funding

UN SDGs

Research Keywords

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