Synergistic effect of Mg-Ti co-doped LiNi0.5Mn1.5O4 on improving material structural stability and electrochemical performance

HUANG Zhende; PENG Di

doi:10.7513/j.issn.1004-7638.2025.06.012

Volume 46 Issue 6

Dec. 2025

Turn off MathJax

Article Contents

Article Navigation > IRON STEEL VANADIUM TITANIUM > 2025 > 46(6): 98-105

HUANG Zhende, PENG Di. Synergistic effect of Mg-Ti co-doped LiNi0.5Mn1.5O4 on improving material structural stability and electrochemical performance[J]. IRON STEEL VANADIUM TITANIUM, 2025, 46(6): 98-105. doi: 10.7513/j.issn.1004-7638.2025.06.012

Citation:

HUANG Zhende, PENG Di. Synergistic effect of Mg-Ti co-doped LiNi_0.5Mn_1.5O₄ on improving material structural stability and electrochemical performance[J]. IRON STEEL VANADIUM TITANIUM, 2025, 46(6): 98-105. doi: 10.7513/j.issn.1004-7638.2025.06.012

Citation:

PDF( 1408 KB)

Synergistic effect of Mg-Ti co-doped LiNi_0.5Mn_1.5O₄ on improving material structural stability and electrochemical performance

doi: 10.7513/j.issn.1004-7638.2025.06.012

HUANG Zhende,
PENG Di^,

Guangxi Vocational and Technical Institute of Industry, Nanning 530001, Guangxi, China

More Information

Received Date: 2025-04-15
Accepted Date: 2025-06-19
Rev Recd Date: 2025-06-14

Available Online: 2025-12-31

Publish Date: 2025-12-31

Abstract

Abstract

Mg-Ti co-doped LNMO samples LiNi_0.5-xMg_xTi_yMn_1.5-yO₄ (x= 0, 0.02; y= 0, 0.03) were synthesized using self-aggregation method, as spinel cathod materil. Through XRD, FTIR, SEM, and EDS material characterization, as well as electrochemical performance testing, the correlation between the crystal morphology, particle size, distribution uniformity, charge discharge rate performance, and cycling capacity stability of Mg-Ti co doped LiNi_0.5Mn_1.5O₄ samples were systematically analyzed and studied. The results show that Mg-Ti co-doping can appropriately increase the Mn³⁺content, enhance the disorder degree of Fd3m space group, reduce the crystal particle size and make the distribution more uniform, which help to improve the rate performance and cycling capacity stability. At 1C and 10C rates, the discharge capacities of LiNi_0.48Mg_0.02Ti_0.03Mn_1.47O₄ material were 133 mAh/g and 102 mAh/g, respectively. After 200 cycles of 1C at room temperature, the discharge capacity remained at 123 mAh/g, with a capacity retention rate of 92.5%. The results of the influence of crystal structure and morphology on the electrochemistry of materials indicate that Mg-Ti co-doped has a synergistic effect, which significantly affects the rate performance and cycling stability of LiNi_0.5Mn_1.5O₄.
- Mg-Ti co-doped,
- synergistic effect,
- LiNi_0.5Mn_1.5O₄,
- charge discharge rate performance

FullText(HTML)

References(34)

References

[1]	LEE S, JIN W, KIM S H, et al. Oxygen vacancy diffusion and condensation in lithium-ion battery cathode materials[J]. Angewandte Chemie International Edition, 2019, 58(31): 10478-10485. doi: 10.1002/anie.201904469
[2]	PARK S, JEONG S Y, LEE T K, et al. Replacing conventional battery electrolyte additives with dioxolone derivatives for high-energy-density lithium-ion batteries[J]. Nature Communications, 2021, 12: 838. doi: 10.1038/s41467-021-21106-6
[3]	LEE S M, KIM J, MOON J, et al. A cooperative biphasic MoOx-MoPx promoter enables a fast-charging lithium-ion battery[J]. Nature Communications, 2021, 12(1): 39. doi: 10.1038/s41467-020-20297-8
[4]	HOU J, LU L, WANG L, et al. Thermal runaway of lithium-ion batteries employing LiN(SO₂F)₂ based concentrated electrolytes[J]. Nature Communications, 2020, 11: 5100. doi: 10.1038/s41467-020-18868-w
[5]	LIU H, LIANG G, GAO C, et al. Insight into the improved cycling stability of sphere-nanorod-like micro-nanostructured high voltage spinel cathode for lithium-ion batteries[J]. Nano Energy, 2019, 66: 104100. doi: 10.1016/j.nanoen.2019.104100
[6]	SUN W, LI Y, XIE K, et al. Constructing hierarchical urchin-like LiNi_0.5Mn_1.5O₄ hollow spheres with exposed {111} facets as advanced cathode material for lithium-ion batteries[J]. Nano Energy, 2018, 54: 175-183. doi: 10.1016/j.nanoen.2018.10.006
[7]	YU X, YU W A, MANTHIRAM A, et al. Advances and prospects of high-voltage spinel cathodes for lithium-based batteries[J]. Small Methods, 2021, 5(5): 2001196. doi: 10.1002/smtd.202001196
[8]	LIANG G, PETERSON V K, SEE K W, et al. Developing high-voltage spinel LiNi_0.5Mn_1.5O₄ cathodes for high-energy-density lithium-ion batteries: current achievements and future prospects[J]. Journal of Materials Chemistry A, 2020, 8: 15373-15398. doi: 10.1039/D0TA02812F
[9]	LIANG W, WANG P, DING H, et al. Granularity control enables high stability and elevated temperature properties of micron-sized single-crystal LiNi_0.5Mn_1.5O₄ cathodes at high voltage[J]. Journal of Materiomics, 2021, 7(5): 1049-1060. doi: 10.1016/j.jmat.2021.02.003
[10]	GUO J, LI Y, CHEN Y, et al. Stable interface Co₃O₄ coated LiNi_0.5Mn_1.5O₄ for lithium-ion batteries[J]. Journal of Alloys and Compounds, 2019, 811: 152031. doi: 10.1016/j.jallcom.2019.152031
[11]	LIU D, FAN X, LI Z, et al. A cation/anion co-doped Li_1.12Na_0.08Ni_0.2Mn_0.6O_1.95F_0.05 cathode for lithium-ion batteries[J]. Nano Energy, 2019, 58: 786-796. doi: 10.1016/j.nanoen.2019.01.080
[12]	LIANG G, WU Z, DIDIER C, et al. A long cycle-life high-voltage spinel lithium-ion battery electrode achieved by site-selective doping[J]. Angewandte Chemie International Edition, 2020, 59(26): 10594-10602. doi: 10.1002/anie.202001454
[13]	GAO Y, YU H, SANDINENI P, et al. Fe doping in LiNi_0.5Mn_1.5O₄ by atomic layer deposition followed by annealing: depths and occupation sites[J]. The Journal of Physical Chemistry C, 2021, 125(14): 7560-7567. doi: 10.1021/acs.jpcc.1c00225
[14]	WEI A, MU J, HE R, et al. Enhancing electrochemical performance and structural stability of LiNi_0.5Mn_1.5O₄ cathode material for rechargeable lithium-ion batteries by boron doping[J]. Ceramics International, 2021, 47(1): 226-237. doi: 10.1016/j.ceramint.2020.08.125
[15]	LI X, ZHANG Y, LI W, et al. The synergetic effect of LiMg_0.5Mn_1.5O₄ coating and Mg²⁺ doping on improving electrochemical performances of high-voltage LiNi_0.5Mn_1.5O₄ by sol-gel selfcombustion method[J]. ChemistrySelect, 2020, 5(8): 2593-2601. doi: 10.1002/slct.201904719
[16]	GUAN P, ZHOU L, YU Z, et al. Recent progress of surface coating on cathode materials for high-performance lithium-ion batteries[J]. Journal of Energy Chemistry, 2020, 43: 220-235.
[17]	WEI L, TAO J, YANG Y, et al. Surface sulfidization of spinel LiNi_0.5Mn_1.5O₄ cathode material for enhanced electrochemical performance in lithium-ion batteries[J]. Chemical Engineering Journal, 2020, 380: 122268.
[18]	CHU C T, MONDAL A, KOSOVA N V, et al. Improved high-temperature cyclability of AlF₃ modified spinel LiNi_0.5Mn_1.5O₄ cathode for lithium-ion batteries[J]. Applied Surface Science, 2020, 530: 147169. doi: 10.1016/j.apsusc.2020.147169
[19]	MU J, ZHANG L, HE R, et al. Enhancing the electrochemical performance of LiNi_0.5Mn_1.5O₄ cathode material by a conductive LaCoO₃ coating[J]. Journal of Alloys and Compounds, 2021, 865: 158629. doi: 10.1016/j.jallcom.2021.158629
[20]	YOON T, SOON J, LEE T J, et al. Dissolution of cathode-electrolyte interphase deposited on LiNi_0.5Mn_1.5O₄ for lithium-ion batteries[J]. Journal of Power Sources, 2021, 503: 230051. doi: 10.1016/j.jpowsour.2021.230051
[21]	MA D H, WANG J W, WANG H F, et al. Mg²⁺ and Cr³⁺ Co-doped LiNi_0.5Mn_1.5O₄ derived from Ni/Mn bimetal oxide as high-performance cathode for lithium-ion batteries[J]. Nanomaterials, 2025, 15(6): 429.
[22]	ZHENG X Y, LIU W J, QU Q T, et al. Bi-functions of titanium and lanthanum co-doping to enhance the electrochemical performance of spinel LiNi_0.5Mn_1.5O₄ cathode[J]. Journal of Materiomics, 2019, 5(2): 156-163.
[23]	WEI A, LI W, CHANG Q, et al. Effect of Mg²⁺/F⁻co-doping on electrochemical performance of LiNi_0.5Mn_1.5O₄ for 5 V lithium-ion batteries[J]. Electrochimica Acta, 2019, 323: 134692. doi: 10.1016/j.electacta.2019.134692
[24]	CHEN G, AN J, MENG Y, et al. Cation and anion co-doping synergy to improve structural stability of Li- and Mn-rich layered cathode materials for lithium-ion batteries[J]. Nano Energy, 2019, 57: 157-165. doi: 10.1016/j.nanoen.2018.12.049
[25]	KIM J H, MYUANG S T, YOON C S, et al. Comparative study of LiNi_0.5Mn_1.5O_4-δ and LiNi_0.5Mn_1.5O₄ cathodes having two crystallographic structures: Fd3m and P4332[J]. Chemistry of Materials, 2004, 16(5): 906-914. doi: 10.1021/cm035050s
[26]	LIU R R, DENG X, LIU X R, et al. Facet dependent SEI formation on the LiNi_0.5Mn_1.5O₄ cathode identified by in situ single particle atomic force microscopy[J]. Chemical Communications, 2014, 50(99): 15756-15759. doi: 10.1039/C4CC07290A
[27]	HSU C S, HSIAO Y S, ZHANG C, et al. The effect of dual-doping on the electrochemical performance of LiNi_0.5Mn_1.5O₄ and its application in full-cell lithium-ion batteries[J]. Ceramics International, 2022, 48(10): 14778-14788. doi: 10.1016/j.ceramint.2022.02.015
[28]	TU J G, ZHANG B K, LI Y, et al. Comprehensive crystal structural insights into phase evolution of spinel Co-free lithium nickel manganese oxide[J]. ACS Energy Letters, 2025, 10(8): 1892-1910.
[29]	WU L B, WANG S, NIU Y, et al. High-rate LiNi_0.5Mn_1.5O₄ cathode materials for Li-ion batteries by the strategy of multi-ion co-doping[J]. Chemical Engineering Journal, 2025, 516: 163892.
[30]	MU J P, WEI A J, HE R, et al. Exploring the synergistic effect of Li⁺and Br⁻co-doping on improving the microstructural and electrochemical performances of LiNi_0.5Mn_1.5O₄ cathode materials[J]. Journal of the Taiwan Insititue of Chemical Engineers, 2022, 138: 104437. doi: 10.1016/j.jtice.2022.104437
[31]	KOCAK T, WU L Y, WANG J, et al. The effect of vanadium doping on the cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode for high voltage lithium-ion batteries[J]. Journal of Electroanalytical chemistry, 2021, 881: 114926. doi: 10.1016/j.jelechem.2020.114926
[32]	ZONG B, LANG Y Q, YAN S H, et al. Influence of Ti doping on microstructure and electrochemical performance of LiNi_0.5Mn_1.5O₄ cathode material for lithium-ion batteries[J]. Materials Today Communications, 2020, 24: 101003. doi: 10.1016/j.mtcomm.2020.101003
[33]	LIN F C, GUO J B, WANG L Y, et al. Synergistic effect of Mg and Y co-dopants on enhancement of electrochemical properties of LiNi_0.5Mn_1.5O₄ spinel[J]. Electrochimica Acta, 2021, 399: 139433.
[34]	WANG J, NIE Y, MIAO C, et al. Enhanced electrochemical properties of Ni-rich layered cathode materials via Mg²⁺and Ti⁴⁺ co-doping for lithium-ion batteries[J]. Journal of Colloid and Interface Science, 2021, 601: 853-862. doi: 10.1016/j.jcis.2021.05.167