Synergistic aluminum lattice doping and surface coating for high-performance Co-free Ni-rich cathodes

Lang Wen; Liang Shan; Yunhan Hu; Yiyong Zhang; Wen Lu; Wen-Hua Zhang; Junqiao Ding

doi:10.1088/1674-4926/25110009

J. Semicond. > Just Accepted

ARTICLES

Synergistic aluminum lattice doping and surface coating for high-performance Co-free Ni-rich cathodes

Lang Wen¹, Liang Shan², Yunhan Hu², Yiyong Zhang^4,, Wen Lu^5,, Wen-Hua Zhang^{1, 3} and Junqiao Ding^{2, 3, 6,}

+ Author Affiliations

1. Yunnan Key Laboratory of Carbon Neutrality and Green Low-carbon Technologies, School of Materials and Energy, Yunnan University, Kunming 650091, China
2. Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; School of Chemical Science and Technology, Yunnan University, Kunming 650091, China
3. Southwest United Graduate School, Kunming, 650092, China
4. National Local Joint Engineering Research Center for Lithium-ion Batteries and Materials Preparation Technology, Key Laboratory of Advanced Batteries Materials of Yunnan Province, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
5. Institute of Energy Storage Technologies, Yunnan University, Kunming 650091, China
6. National Center for International Joint Research of Photoelectronic Energy Materials and Application

Author Bio:

Lang Wen got his master’s degree in 2020 from Sichuan University of Science & Engineering, Zigong, China. Now he is a doctoral student at Yunnan University. His research focuses on cobalt-free and nickel-rich cathode materials.

Yiyong Zhang received his doctoral degree from Xiamen University, Xiamen, China, in 2018. He is currently an Associate Professor with the Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, China. His current research interests focused on the electrochemical energy storage and electrochemical in-situ characterization technology including lithium-sulfur batteries, metal sulfides, carbon-based, and silicon-based lithium/sodium negative electrodes.

Wen Lu is currently a professor and Director of the Institute of Energy Storage Technologies at Yunnan University. He obtained his PhD from the University of Wollongong in Australia and conducted his postdoctoral research at Carleton University in Canada. His research activities have been focused on the applications of electrochemistry and new materials to the development of a range of electrochemical devices including energy conversion and storage devices, electrochromic devices, electrochemical sensors and biosensors, electromechanical actuators, and environmental remediation devices.

Junqiao Ding received his doctoral degree from Changchun Insititute of Applied Chemistry Chinese Academy of Sciences, Changchun, China. He is currently a Researcher at the School of Chemical Science and Technology, Yunnan University, Kunming, China. He is an outstanding mentor of the Chinese Academy of Sciences, a Yunnan Province "Yunling Scholar", and a member of the editorial board of the Journal of Semiconductors. His research mainly focuses on organic polymer optoelectronic materials and devices. He has successfully developed low-cost, high-efficiency dendritic iridium phosphorescent complexes, thermally activated delayed fluorescence polymers, and pure organic room-temperature electrophosphorescent polymers.

Corresponding author: Yiyong Zhang, zhangyiyong2018@kust.edu.cn; Wen Lu, wenlu@ynu.edu.cn; Junqiao Ding, dingjunqiao@ynu.edu.cn

DOI: 10.1088/1674-4926/25110009CSTR: 32376.14.1674-4926.25110009

Abstract: LiNi_0.9Mn_0.1O₂ (LNM91) is a promising cobalt-free, high-energy cathode material for next-generation lithium-ion batteries, but its commercialization is challenged by rapid capacity fading resulting from bulk and interfacial structural degradation. Herein, an in-situ surface-to-bulk dual-modification strategy is developed to synthesize 6Al-LNM91 (6 mol% Al modified LNM91) via a one-step calcination process based on Al diffusion chemistry. This method concurrently constructs a protective LiAlO₂ coating and incorporates Al³⁺ into the bulk lattice, effectively enhancing the structural integrity of the cathode during cycling. The optimized 6Al-LNM91 cathode delivers a remarkable rate capability of 165 mA∙h∙g⁻¹ at 10 C and maintains 94.03% capacity retention after 120 cycles at 0.5 C (2.8 − 4.4 V), substantially outperforming the pristine material (76.82% of LNM91). This organic solvent-free, single-step modification approach offers a scalable and efficient route for improving high-nickel layered oxide cathodes.

Key words: in situ dual modification, Al doping, LiAlO₂ coating, cobalt-free nickel-rich cathode, LiNi_0.9Mn_0.1O₂

References

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Fig. 1. (Color online) Schematic diagram of the simultaneous Al doped and LiAlO₂ coated LNM91 cathode structures.

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Fig. 2. (Color online) XRD patterns of (a) Al modified NM91 precursors (NM91: black, 1Al-NM91: red, 2Al-NM91: blue, 4Al-NM91: cyan, 6Al-NM91: green, 8Al-NM91: magenta), (b) AlOOH and (c) LiAlO₂. (d) TEM images of 6Al-LNM91 and (e) corresponding EDS elemental mapping for Ni, Mn, O, and Al. XPS spectra and fitting results for LNM91 (black) and 6Al-LNM91(green): (f) Ni 2p, (g) Al 2p. (h) O 1s.

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Fig. 3. (Color online) Voltage profiles at 0.1 C with 2.8 − 4.4 V for the (a) first and (b) fifth cycle. (c) Rate performance. Cycling performances at 0.5 C both (d) 2.8 − 4.4V and (e) 2.8 − 4.7 V. (f) The cycling performance of pristine and 6Al-LNM91 cathode in full cells at 1 C between 2.8 − 4.3 V. (LNM91: black, 1Al-LNM91: red, 2Al-LNM91: blue, 4Al-LNM91: cyan, 6Al-LNM91: green, 8Al-LNM91: magenta)

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Fig. 4. (Color online) (a) dQ/dV curves of the first cycle at 0.5 C within 2.8 − 4.4 V, (b) magnified view of the the H2−H3 phase transition. The dQ/dV curves of (c) LNM91 and (d) 6Al-LNM91 during cycling at 0.5 C within 2.8 − 4.4 V. (LNM91: black, 1Al-LNM91: red, 2Al-LNM91: blue, 4Al-LNM91: cyan, 6Al-LNM91: green, 8Al-LNM91: magenta)

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Fig. 5. (Color online) Ex-situ XRD patterns of pristine (a) LNM91 and (b) 6Al-LNM91 electrodes during the first charge process from 3.5 V to 4.5 V at 0.1 C.

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Fig. 6. (Color online) (a) GITT results of LNM91 (black) and 6Al-LNM91 (green) after activation. EIS spectra (b) before and (c) after cycles. SEM images after 120th cycles for (d) LNM91 and (e) 6Al-LNM91. (f) Schematic illustration of the performance deterioration for LNM91 and the stabilizing effect of Al modification.

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Table 1. Rietveld refined results for XRD patterns of different cathode materials.

Materials	a/Å	c/Å	V/Å³	c/a	I(003)/I(104)	Li-O/Å	Li⁺/Ni²⁺	R_wp
LNM91	2.873	14.197	101.492	4.941	1.29	2.0943	10.11%	2.96%
1Al-LNM91	2.884	14.256	102.661	4.944	1.22	2.1043	8.13%	3.41%
2Al-LNM91	2.881	14.249	102.432	4.945	1.28	2.1079	4.37%	4.09%
4Al-LNM91	2.879	14.246	102.251	4.949	1.45	2.1069	5.13%	3.73%
6Al-LNM91	2.878	14.240	102.153	4.948	1.43	2.1081	5.44%	3.75%
8Al-LNM91	2.872	14.226	101.585	4.954	1.44	2.1010	7.62%	3.52%

DownLoad: CSV

Table 2. the rate and cycles performances of all cathodes

Materials	Rate at 10 C		0.5 C cycles at 4.4 V			0.5 C cycles at 4.7 V
Materials	Capacity mA∙h g⁻¹	Retention	1st Capacity mA∙h g⁻¹	120th Capacity mA∙h g⁻¹	Retention	1st Capacity mA∙h g⁻¹	100th Capacity mA∙h g⁻¹	Retention
LNM91	103.17	48.99%	199.22	153.04	76.82%	202.53	117.82	58.17%
1Al-LNM91	123.15	56.26%	206.66	162.97	78.86%	--	--	--
2Al-LNM91	133.96	61.49%	205.46	168.37	81.95%	--	--	--
4Al-LNM91	156.58	75.13%	198.06	171.70	86.69%	--	--	--
6Al-LNM91	165.47	78.79%	196.56	184.83	94.03%	206.12	172.20	83.54%
8Al-LNM91	143.50	72.54%	183.38	170.88	93.19%	--	--	--

DownLoad: CSV

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[4]	Park G T, Namkoong B, Kim S B, et al. Introducing high-valence elements into cobalt-free layered cathodes for practical lithium-ion batteries. Nat Energy, 2022, 7(10): 946 doi: 10.1038/s41560-022-01106-6
[5]	Aishova A, Park G T, Yoon C S, et al. Cobalt-free high-capacity Ni-rich layered Li [Ni_0.9Mn_{0. 1}] O₂ cathode. Adv Energy Mater, 2020, 10(4): 1903179
[6]	Wei S X, Cui C J, Jin Y, et al. Enhancement of Li intercalation kinetics of LiFePO₄ nanoparticles with mesoporous carbon. Energy Mater, 2024, 4(5): 400062 doi: 10.20517/energymater.2024.20
[7]	Huang M T, Wang M, Yang L M, et al. Direct regeneration of spent lithium-ion battery cathodes: From theoretical study to production practice. Nano Micro Lett, 2024, 16(1): 207 doi: 10.1007/s40820-024-01434-0
[8]	Liu Y, Dong J Y, Guan Y B, et al. In situ 3D conductive networks and interfacial bonding to stabilize oxygen vacancies for single-crystal Ni-rich cathodes. Adv Mater, 2026, 38(5): e15106 doi: 10.1002/adma.202515106
[9]	Wang H Y, Dong J Y, Zhang H Y, et al. Enhancing structural and thermal stability of ultrahigh-Ni cathodes via anion-cation codoping induced surface reconstruction strategy. J Energy Chem, 2025, 106: 9 doi: 10.1016/j.jechem.2025.01.077
[10]	Li C, Liu J Z, Su Y F, et al. Enhancing chemomechanical stability and high-rate performance of nickel-rich cathodes for lithium-ion batteries through three-in-one modification. Energy Storage Mater, 2025, 74: 103893 doi: 10.1016/j.ensm.2024.103893
[11]	Wang H Y, Shi Q, Dong J Y, et al. Consolidating surface lattice via facile self-anchored oxygen layer reconstruction toward superior performance and high safety nickel-rich oxide cathodes. Adv Funct Mater, 2025, 35(20): 2422806 doi: 10.1002/adfm.202422806
[12]	Zheng J X, Ye Y K, Liu T C, et al. Ni/Li disordering in layered transition metal oxide: Electrochemical impact, origin, and control. Acc Chem Res, 2019, 52(8): 2201 doi: 10.1021/acs.accounts.9b00033
[13]	Hu C Z, Ma J T, Li A F, et al. Structural reinforcement through high-valence Nb doping to boost the cycling stability of co-free and Ni-rich LiNi_0.9Mn_{0. 1}O₂ cathode materials. Energy Fuels, 2023, 37(11): 8005
[14]	Li L J, Chen Q H, Jiang M Z, et al. Uncovering mechanism behind tungsten bulk/grain-boundary modification of Ni-rich cathode. Energy Storage Mater, 2025, 75: 104016 doi: 10.1016/j.ensm.2025.104016
[15]	Shi Q, Wu F, Wang H Y, et al. Smart-responsive sustained-release capsule design enables superior air storage stability and reinforced electrochemical performance of cobalt-free nickel-rich layered cathodes for lithium-ion batteries. Energy Storage Mater, 2024, 67: 103264 doi: 10.1016/j.ensm.2024.103264
[16]	Wang L, Wang J Q, Lu Y F, et al. A review of Ni-based layered oxide cathode materials for alkali-ion batteries. Chem Soc Rev, 2025, 54(9): 4419 doi: 10.1039/D3CS00911D
[17]	Yoon C S, Jun D W, Myung S T, et al. Structural stability of LiNiO₂ cycled above 4. 2 V. ACS Energy Lett, 2017, 2(5): 1150
[18]	Li H Y, Cormier M, Zhang N, et al. Is cobalt needed in Ni-rich positive electrode materials for lithium ion batteries? J Electrochem Soc, 2019, 166(4): A429
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Received: 11 November 2025 Revised: 09 December 2026 Online: Accepted Manuscript: 03 February 2026

Article Navigation > Journal of Semiconductors > 2026 > Accepted Manuscript

Lang Wen, Liang Shan, Yunhan Hu, Yiyong Zhang, Wen Lu, Wen-Hua Zhang, Junqiao Ding. Synergistic aluminum lattice doping and surface coating for high-performance Co-free Ni-rich cathodes[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/25110009 ****L Wen, L Shan, Y H Hu, Y Y Zhang, W Lu, W - H Zhang, and J Q Ding, Synergistic aluminum lattice doping and surface coating for high-performance Co-free Ni-rich cathodes[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/25110009

Citation:

L Wen, L Shan, Y H Hu, Y Y Zhang, W Lu, W - H Zhang, and J Q Ding, Synergistic aluminum lattice doping and surface coating for high-performance Co-free Ni-rich cathodes[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/25110009

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Synergistic aluminum lattice doping and surface coating for high-performance Co-free Ni-rich cathodes

DOI: 10.1088/1674-4926/25110009

CSTR: 32376.14.1674-4926.25110009

Lang Wen¹,
Liang Shan²,
Yunhan Hu²,
Yiyong Zhang^4,,
Wen Lu^5,,
Wen-Hua Zhang^{1, 3},
Junqiao Ding^{2, 3, 6,}

1.
Yunnan Key Laboratory of Carbon Neutrality and Green Low-carbon Technologies, School of Materials and Energy, Yunnan University, Kunming 650091, China
2.
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education; School of Chemical Science and Technology, Yunnan University, Kunming 650091, China
3.
Southwest United Graduate School, Kunming, 650092, China
4.
National Local Joint Engineering Research Center for Lithium-ion Batteries and Materials Preparation Technology, Key Laboratory of Advanced Batteries Materials of Yunnan Province, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
5.
Institute of Energy Storage Technologies, Yunnan University, Kunming 650091, China
6.
National Center for International Joint Research of Photoelectronic Energy Materials and Application

More Information

Lang Wen got his master’s degree in 2020 from Sichuan University of Science & Engineering, Zigong, China. Now he is a doctoral student at Yunnan University. His research focuses on cobalt-free and nickel-rich cathode materials
Yiyong Zhang received his doctoral degree from Xiamen University, Xiamen, China, in 2018. He is currently an Associate Professor with the Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming, China. His current research interests focused on the electrochemical energy storage and electrochemical in-situ characterization technology including lithium-sulfur batteries, metal sulfides, carbon-based, and silicon-based lithium/sodium negative electrodes
Wen Lu is currently a professor and Director of the Institute of Energy Storage Technologies at Yunnan University. He obtained his PhD from the University of Wollongong in Australia and conducted his postdoctoral research at Carleton University in Canada. His research activities have been focused on the applications of electrochemistry and new materials to the development of a range of electrochemical devices including energy conversion and storage devices, electrochromic devices, electrochemical sensors and biosensors, electromechanical actuators, and environmental remediation devices
Junqiao Ding received his doctoral degree from Changchun Insititute of Applied Chemistry Chinese Academy of Sciences, Changchun, China. He is currently a Researcher at the School of Chemical Science and Technology, Yunnan University, Kunming, China. He is an outstanding mentor of the Chinese Academy of Sciences, a Yunnan Province "Yunling Scholar", and a member of the editorial board of the Journal of Semiconductors. His research mainly focuses on organic polymer optoelectronic materials and devices. He has successfully developed low-cost, high-efficiency dendritic iridium phosphorescent complexes, thermally activated delayed fluorescence polymers, and pure organic room-temperature electrophosphorescent polymers
Corresponding author: zhangyiyong2018@kust.edu.cn; wenlu@ynu.edu.cn; dingjunqiao@ynu.edu.cn
Received Date: 2025-11-11
Revised Date: 2026-12-09

Available Online: 2026-02-03

Abstract

Abstract

LiNi_0.9Mn_0.1O₂ (LNM91) is a promising cobalt-free, high-energy cathode material for next-generation lithium-ion batteries, but its commercialization is challenged by rapid capacity fading resulting from bulk and interfacial structural degradation. Herein, an in-situ surface-to-bulk dual-modification strategy is developed to synthesize 6Al-LNM91 (6 mol% Al modified LNM91) via a one-step calcination process based on Al diffusion chemistry. This method concurrently constructs a protective LiAlO₂ coating and incorporates Al³⁺ into the bulk lattice, effectively enhancing the structural integrity of the cathode during cycling. The optimized 6Al-LNM91 cathode delivers a remarkable rate capability of 165 mA∙h∙g⁻¹ at 10 C and maintains 94.03% capacity retention after 120 cycles at 0.5 C (2.8 − 4.4 V), substantially outperforming the pristine material (76.82% of LNM91). This organic solvent-free, single-step modification approach offers a scalable and efficient route for improving high-nickel layered oxide cathodes.
- in situ dual modification,
- Al doping,
- LiAlO₂ coating,
- cobalt-free nickel-rich cathode,
- LiNi_0.9Mn_0.1O₂

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