journal article·2026-02-27Open access

Improvement of Cycling Stability of Core–Shell Structured Ni-Rich NMC Cathodes by Using a Tungsten Oxide Stabilization Interlayer

Bilal Tasdemir, Svitlana Krüger, Pinank Sohagiya, Apurba Ray, Bilge Saruhan

Batteries· Volume 12· Issue 3

Abstract

The growing demand for higher-energy lithium-ion batteries, encompassing consumer electronics, stationary grid storage, and electric mobility to specialized sectors like aerospace, medical devices, and industrial robotics, requires cathode materials that offer higher capacity while remaining cost-effective. This trend has intensified the development of nickel-rich LiNi1−x−yMnxCoyO2 (NMC) systems. However, high-Ni NMCs such as LiNi0.9Mn0.05Co0.05O2 (NMC90) suffer from limited thermal and cycling stability. Core–shell architectures using LiNi0.6Mn0.2Co0.2O2 (NMC622) as a shell can partially alleviate these drawbacks, but structural degradation caused by interdiffusion between the core and shell persists as a major challenge. This study investigates whether a tungsten oxide interlayer can act as a protective barrier that suppresses interdiffusion, stabilizes the crystal structure, and improves long-term electrochemical performance. In this work, NMC cathode powders were synthesized via a one-pot oxalate co-precipitation route, followed by structural characterization using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and ion scattering spectroscopy (ISS). Electrochemical performance, including capacity retention, cycling stability, and internal resistance, was evaluated through galvanostatic charge–discharge (GCD) testing and electrochemical impedance spectroscopy (EIS). The core–shell configuration delivered higher specific discharge capacity compared to the individually synthesized core-only and shell-only reference materials, and the incorporation of a tungsten oxide interlayer resulted in a twofold increase in cycle life. These results demonstrate that tungsten oxide effectively enhances cycling stability by inhibiting core–shell interdiffusion, offering a promising pathway toward more durable high-Ni NMC cathodes.
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Research context

OpenAlex topics: Advancements in Battery Materials · Supercapacitor Materials and Fabrication · Transition Metal Oxide Nanomaterials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

German Aerospace Center (DLR e.V), Institute for Frontier Materials on Earth and in Space, Linder Hoehe, 51147 Cologne, Germany

Funding

European Union

References (64)

Show source-provided references
1. Lithium-ion cells for space applications: Aspects of durability10.1016/j.asr.2023.01.038 ↗
2. A review on battery technology for space application10.1016/j.est.2023.106792 ↗
3. Performance of commercial Li-ion cells for future NASA missions and aerospace applications10.1149/1945-7111/abf05f ↗
4. Energy-efficient battery management system for healthcare devices10.1016/j.est.2022.104358 ↗
5. A review of Li-ion batteries for autonomous mobile robots: Perspectives and outlook for the future10.1016/j.jpowsour.2022.231943 ↗
6. Warner, J. (2019). Lithium-Ion Battery Chemistries: A Primer, Elsevier.10.1016/B978-0-12-814778-8.00003-X ↗
7. Pan, L. (2025, December 03). The Evolution of Lithium-Ion Batteries Because of Electric Vehicles—Large Battery. Available online: https://www.large-battery.com/blog/electric-vehicles-lithium-battery-advancements-2025/.
8. Strategies toward the development of high-energy-density lithium batteries10.1016/j.est.2024.111666 ↗
9. Review—Surface coatings for cathodes in lithium ion batteries: From crystal structures to electrochemical performance10.1149/1945-7111/ac60f3 ↗
10. High-nickel cathodes for lithium-ion batteries: From synthesis to electricity10.1016/j.est.2024.110536 ↗
11. Optimizing high-energy lithium-ion batteries: A review of single crystalline and polycrystalline nickel-rich layered cathode materials: Performance, synthesis and modification10.1007/s00339-024-07897-7 ↗
12. Degradation mechanisms and mitigation strategies of nickel-rich NMC-based lithium-ion batteries10.1007/s41918-019-00053-3 ↗
13. Optimized Al doping improves both interphase stability and bulk structural integrity of Ni-rich NMC cathode materials10.1021/acsaem.9b02372 ↗
14. Impact of Microcrack Generation and Surface Degradation on a nickel-rich layered LiNi0.9Co0.05Mn0.05O2 cathode for lithium-ion batteries10.1021/acs.chemmater.7b03268 ↗
15. Advanced concentration gradient cathode material with two-slope for high-energy and safe lithium batteries10.1002/adfm.201501430 ↗
16. Teichert, P., Eshetu, G.G., Jahnke, H., and Figgemeier, E. (2020). Degradation and aging routes of Ni-rich cathode based Li-ion batteries. Batteries, 6.10.3390/batteries6010008 ↗
17. A single-pot co-precipitation synthesis route for Ni-rich layered oxide materials with high cycling stability10.1002/celc.202200859 ↗
18. Charge compensation mechanisms in Ni-rich nmc cathodes10.1002/batt.202500167 ↗
19. TEM and Raman spectroscopy evidence of layered to spinel phase transformation in layered LiNi1/3Mn1/3Co1/3O2 upon cycling to higher voltages10.1016/j.jelechem.2014.09.005 ↗
20. Relationship of chemical composition and moisture sensitivity in LiNixMnyCo1−x−yO2 for lithium-ion batteries10.1115/1.4051208 ↗
21. Improvement of structural and electrochemical properties of NMC layered cathode material by combined doping and coating10.1016/j.electacta.2021.139577 ↗
22. Impact of surface coating on electrochemical and thermal behaviors of a Li-rich Li1.2Ni0.16Mn0.56Co0.08O2 cathode10.1039/D0RA02060E ↗
23. Improving high-voltage cycling performance of nickel-rich NMC layered oxide cathodes for rechargeable lithium–ion batteries by Mg and Zr co-doping
24. Review of the scalable core-shell synthesis methods: The improvements of Li-Ion battery electrochemistry and cycling stability10.1002/smtd.202300345 ↗
25. Binary-compositional core-shell structure Ni-rich cathode material with radially oriented primary particles in shell for long cycling lifespan lithium-ion batteries10.1016/j.mtener.2023.101292 ↗
26. Synthesis and characterization of Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 with the microscale core−shell structure as the positive electrode material for lithium batteries10.1021/ja053675g ↗
27. Synthesis and characterization of core–shell NMC microparticles as cathode materials for Li-ion batteries: Insights from ex situ and in situ microscopy and spectroscopy techniques10.1039/D4MA00994K ↗
28. García-Alonso, J., Krüger, S., Saruhan, B., Maestre, D., and Méndez, B. (2024). Synthesis and characterisation of core–shell microparticles formed by Ni-Mn-Co xxides. Molecules, 29.10.3390/molecules29122927 ↗
29. Cobalt-free nickel-rich positive electrode materials with a core–shell structure10.1021/acs.chemmater.9b03515 ↗
30. An evaluation of a systematic series of cobalt-free Ni-rich core-shell materials as positive electrode materials for Li-ion batteries10.1149/1945-7111/ac285d ↗
31. Impact of shell composition, thickness and heating temperature on the performance of nickel-rich cobalt-free core-shell materials10.1149/1945-7111/abd571 ↗
32. Nanostructured high-energy cathode materials for advanced lithium batteries10.1038/nmat3435 ↗
33. Pushing the limit of layered transition metal oxide cathodes for high-energy density rechargeable Li ion batteries10.1039/C8EE00227D ↗
34. LiNi0.9Co0.09W0.01O2: A new type of layered oxide cathode with high cycling stability10.1002/aenm.201902698 ↗
35. Tungsten infused grain boundaries enabling universal performance enhancement of Co-free Ni-rich cathode materials10.1149/1945-7111/ac3c26 ↗
36. Preventing interdiffusion during synthesis of Ni-rich core–shell cathode materials10.1021/acsenergylett.2c01009 ↗
37. Surface modification of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode material by tungsten oxide coating for improved electrochemical performance in lithium-ion batteries10.1021/acsami.9b02889 ↗
38. Cai, W., Chen, R., Yang, Y., Yi, M., and Xiang, L. (2018). Removal of SO42− from Li2CO3 by recrystallization in Na2CO3 solution. Crystals, 8.10.3390/cryst8010019 ↗
39. Cation distribution and chemical deintercalation of Li1-xNi1+xO210.1016/0025-5408(90)90028-Z ↗
40. Combining in situ synchrotron X-ray diffraction and absorption techniques with transmission electron microscopy to study the origin of thermal instability in overcharged cathode materials for lithium-ion batteries10.1002/adfm.201200693 ↗
41. Tuning of thermal stability in layered Li(NixMnyCoz)O210.1021/jacs.6b07771 ↗
42. Optimization of the composition of the Li1−zNi1+zO2 electrode materials: Structural, magnetic, and electrochemical studies10.1149/1.1836614 ↗
43. Effects of lithium excess and Ni content on the electrochemical performance of Li1+x(Ni0.45−xMn0.4Co0.15)O2 lithium-ion cathode materials in stoichiometric state10.1088/2053-1591/ab2019 ↗
44. Synthesis of layered cathode material 0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 by an improved co-precipitation method for lithium-ion battery10.1016/j.jpowsour.2014.01.068 ↗
45. High-energy W-doped Li[Ni0.95Co0.04Al0.01]O2 cathodes for next-generation electric vehicles10.1016/j.ensm.2020.08.013 ↗
46. Synthesis and electrochemical behavior of Li[Li0.1Ni0.35−x/2CoxMn0.55−x/2]O2 cathode materials10.1016/j.ssi.2003.08.003 ↗
47. Enhancement of the high-voltage electrochemical performance of an LiNi0.5Co0.2Mn0.3O2 cathode via WO3 coating10.1016/j.apsusc.2020.145259 ↗
48. Ultrahigh Ni-rich (90%) layered oxide-based cathode active materials: The advantages of tungsten (W) incorporation in the precursor cathode active material
49. Xu, L., Bao, C., Zhou, H., and Li, J. (2023). The modification of WO3 for lithium batteries with nickel-rich ternary cathode materials. Processes, 11.10.3390/pr11061756 ↗
50. Oxalate co-precipitation synthesis of LiNi0.6Co0.2Mn0.2O2 for low-cost and high-energy lithium-ion batteries10.1016/j.mtcomm.2019.02.001 ↗
51. Improving the electrochemical performance of LiNi1/3Co1/3Mn1/3O2 cathode material via tungsten modification10.1016/j.electacta.2018.11.202 ↗
52. Unveiling the parasitic-reaction-driven surface reconstruction in Ni-rich cathode and the electrochemical role of Li2CO310.1016/j.jechem.2023.05.048 ↗
53. XPS investigation of surface reactivity of electrode materials: Effect of the transition metal10.1021/am5089764 ↗
54. Quantitative analysis of Ni2+/Ni3+ in Li[NixMnyCoz]O2 cathode materials: Non-linear least-squares fitting of XPS spectra10.1016/j.apsusc.2018.02.114 ↗
55. Designing surface coating strategies with tungsten on single crystal NMC materials by XPS10.1002/aenm.202503051 ↗
56. WO3 coating improves the cyclic stability of LiNi0.9Co0.05Mn0.05 as cathode materials for lithium-ion batteries10.1016/j.electacta.2024.144913 ↗
57. Review on the synthesis of LiNixMnyCo1-x-yO2 (NMC) cathodes for lithium-ion batteries10.1016/j.mtener.2022.101066 ↗
58. Valuation of surface coatings in high-energy density lithium-ion battery cathode materials10.1016/j.ensm.2021.03.015 ↗
59. Volmer-Weber growth of nano-island heterostructures on spinel cathodes: A route to stable high-voltage lithium-ion batteries10.1039/D5SC07152F ↗
60. Facile modification using organic acid molecules to neutralize residual alkaline compounds for stabilizing LiNi0.95Co0.04Mn0.01O2 cathode material10.26599/EMD.2025.9370056 ↗
61. High-nickel NMA: A cobalt-free alternative to NMC and NCA cathodes for lithium-ion batteries10.1002/adma.202002718 ↗
62. Characterisation of batteries by electrochemical impedance spectroscopy10.1016/j.egyr.2020.03.029 ↗
63. Application of electrochemical impedance spectroscopy to commercial Li-ion cells: A review10.1016/j.jpowsour.2020.228742 ↗
64. Investigations on novel electrolytes, solvents and SEI additives for use in lithium-ion batteries: Systematic electrochemical characterization and detailed analysis by spectroscopic methods10.1016/j.progsolidstchem.2014.04.003 ↗