CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Lingbing Wu,Shan Wang,Yao Niu,Zhengyao Sun,Xianghua Yao,Youlong Xu
LiNi 0.5 Mn 1.5 O 4 (LNMO) is a high-profile cathode material for lithium-ion batteries with high voltage and high specific energy. However, its practical application is severely hindered by the dissolution of Mn, primarily induced by the Jahn-Teller effect, which leads to significant capacity degradation, especially under high current densities. In this research, LiNi 0.5-7/3x Cu x Al x Mn 1.5-7/3x Ti x V x O 4 (x = 0, 0.5 %, 1 %, 3 %) was synthesized via a sol–gel method employing a multivalent ion co-doping strategy, denoted as CATV. X-ray diffraction analyses that the increase in the (311)/(400) peak ratio of CATV-1 % indicates a higher concentration of Mn 3+ , which enhances the structural disorder of the material, thereby improving its electronic conductivity. By improving the ratio of the (110) plane, which is perpendicular to the lithium-ion diffusion pathway, the lithium-ion diffusion coefficient was enhanced by three orders of magnitude. Furthermore, the Mn dissolution issue originating from the (111) plane was mitigated which shows in XRF that the Mn content deposited on the negative lithium sheet was reduced by 50 %. Specifically, it delivered specific capacity of 136.2 mAh·g −1 at 0.1C and maintained 81.74 % of its capacity after 300 cycles at 1C. Under 20C charge–discharge condition, it reached 108 mAh·g −1 , doubling that of the undoped sample. These findings provide new possibilities for the commercial application of CATV materials.
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高影响因子
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
·
2014
·Vol. 18
·期 7
·2027-2033
·
IF 2.234
Chen Dongrui,Li Benzhen,Liao Youhao,Lan Hongwei,Lin Haibin,Xing Lidan,Wang Yating,Li Weishan
Three samples, LiNi 0.5 Mn 1.5 O 4 , LiNi 0.4 Mn 1.4 Co 0.2 O 4 , and LiNi 0.4 Mn 1.4 Cr 0.15 Co 0.05 O 4 , were prepared by sol–gel method and characterized by powder X-ray diffraction, Fourier transformed infrared spectroscope, scanning electron microscopy, Brunauer–Emmett–Teller surface area, four-probe resistance, cyclic voltammetry, electrochemical impedance spectroscopy, and charge–discharge test. It is found that the co-doped sample LiNi 0.4 Mn 1.4 Cr 0.15 Co 0.05 O 4 exhibits an improved performance compared with the Co-doped sample LiNi 0.4 Mn 1.4 Co 0.2 O 4 and the undoped sample LiNi 0.5 Mn 1.5 O 4 , especially at elevated temperature. At 25 °C, the discharge capacity of LiNi 0.4 Mn 1.4 Cr 0.15 Co 0.05 O 4 is 130 mAh g −1 at 0.1 C and 103 mAh g −1 at 10 C. At an elevated temperature (55 °C), its 1 C discharge capacity is 136 mAh g −1 and maintains 95.6 % of its initial capacity after 100 cycles. Compared with the reported results of LiNi 0.4 Mn 1.4 Co 0.2 O 4 and LiNi 0.475 Mn 1.475 Co 0.05 O 4 , the co-doped sample LiNi 0.4 Mn 1.4 Cr 0.15 Co 0.05 O 4 , with least content of Co, 0.05, possesses not only the high C-rate capacity but also the structural stability. The mechanism on the electrochemical performance improvement of LiNi 0.5 Mn 1.5 O 4 by the co-doping was discussed.
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高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Zhengwu Wang,Yannan Zhang,Bao Zhang,Dong Yang,Kai Zhou,Yixue Huang,Fei Wang,Jianguo Duan,Xianshu Wang,Peng Dong,Yingjie Zhang
Spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) has gained significant attention as a promising cathode material for lithium-ion batteries due to its high working voltage (>4.7 V) and energy density . However, challenges such as electrolyte decomposition-induced material interface erosion and transition metal dissolution under high operating voltage hinder its commercial use. In this study, a thin and uniform Sm 2 O 3 layer has been successfully deposited on the surface of LNMO using a wet chemical method . A comprehensive investigation of surface morphology , crystal structure, and electrochemical performance of the modified LNMO is conducted. The results demonstrate that the Sm 2 O 3 surface modification acts as a robust multifunctional protective layer, effectively shielding against hydrofluoric acid-induced chemical attack and enhancing the migration efficiency of lithium ions . Notably, the capacity retention rate of LNMO@Sm 2 O 3 (3 wt%) remains up to 88 % after 280 cycles, significantly surpassing the uncoated counterpart. The coated material exhibits a capacity of 114 mAh g −1 even under 10 C rate conditions. Moreover, the AC impedance values and manganese dissolution of the modified material in the organic electrolyte are considerably lower than those of the uncoated counterpart. Theoretical calculations strongly support the experimental findings, revealing higher Mn vacancy formation energy and density of states at the Fermi energy level for the Sm 2 O 3 -modified electrodes. This research contributes to the field of surface modification and paves the way for further enhancements in the electrochemical performance of other high-voltage manganese-based lithium-ion batteries (LIBs).
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
纳米技术
·
表面工程
·
锂电池
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高影响因子
ACTA MATERIALIA
·
2024
·
IF 8.3
Jinping Mu,Xiaohui Li,Rui He,Lijing Sun,Xue Bai,Lihui Zhang,Xi Zhang,Zhenfa Liu,Jing Gao,Aijia Wei
High-voltage (5-V) lithium–ion batteries (LIBs) have garnered substantial interest due to their superior energy density. Nevertheless, the unstable interphase of high-voltage LIBs can cause electrolyte decomposition, electrode collapse, transition metal dissolution, and lithium dendrite growth during cycling, which impedes their widespread commercial use. To mitigate these challenges, various alkali-metal phosphates were incorporated into a carbonate-based electrolyte as film-forming additives, aiming to improve the electrochemical performance of LiNi 0.5 Mn 1.5 O 4 (LNMO)-based LIBs. Following a detailed comparison of the electrochemical performances of various alkali-metal phosphates, KH 2 PO 4 and NaH 2 PO 4 were selected for an in-depth investigation in this research. The highly protective passivation film generated by KH 2 PO 4 and NaH 2 PO 4 on the electrode surface provided significant protection by effectively inhibiting continuous electrolyte decomposition. This finding was supported by density functional theory calculations and a variety of electrochemical and characterization tests. The H 2 PO 4 − primarily contributed to the formation of the cathode electrolyte interphase film on the cathode surface. KH 2 PO 4 (via the electrostatic shielding effect of K + ions) and NaH 2 PO 4 (through the co-precipitation of Na + and Li + ions) both effectively inhibited the growth of lithium dendrites on the lithium metal anode. Additionally, the KH 2 PO 4 and NaH 2 PO 4 additives regulated the amount of HF in the electrolyte through acid–base equilibrium reactions. The electrolytes containing additives significantly enhanced the electrochemical performances of Li||Li, LNMO/Li, LNMO/graphite, and LNMO/Li 4 Ti 5 O 12 cells. LNMO/Li half-cells with standard electrolyte (STD) supplemented with KH 2 PO 4 and NaH 2 PO 4 additives demonstrated capacity retentions of 92.9 % and 90.0 % after 500 cycles at 5 C, respectively, in contrast to only 79.4 % for the STD electrolyte alone. Furthermore, the LNMO/graphite full cell exhibited an increased capacity retention, reaching 81.1 % (STD+KH 2 PO 4 ) and 78.29 % (STD+NaH 2 PO 4 ), up from 70.8 % with the STD, after 100 cycles at 0.5 C. Given their ease of use, affordability, and widespread availability, KH 2 PO 4 and NaH 2 PO 4 additives show significant potential to enhance the electrochemical properties of high-voltage LIBs.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yinyin Zhang,Fangzhong Liu,Ting Song,Yong Pei,Xianyou Wang,Xiongwei Wu,Manjun Xiao,Qi Deng,Bei Long
The electrochemical performances of LiNi 0.5 Mn 1.5 O 4 (LNMO) materials are strongly correlated with the ratio of disordered to ordered phases. Nevertheless, there are few reports on the adjustment of ordered and disordered phase ratio. In this paper, the ratio of ordered to disordered phases in LNMO is successfully adjusted by using a quaternary molten salt, which is proven by XRD refinement, FT-IR, and XPS. Reductive quaternary molten salt and Co doping are favorable for Ni/Mn cation disorder, leading to the increased disordered phase. LNMO with an appropriate ratio of ordered to disordered phases can exhibit enhanced electronic/ionic transfer rate and structural stability, revealed by electrochemical tests and ex situ characterizations. Therefore, the optimized material delivers a reversible capacity of 121 mA h g −1 at 20 mA g −1 and a long cyclic life with 61 mA h g −1 at 1000 mA g −1 over 1200 cycles. The present work offers a new idea for achieving a regulated ratio of ordered to disordered phases in LNMO.
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高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Shentuo Zheng,Yikun Yi,Feng Hai,Xin Gao,Xiaolu Tian,Zhendi Wu,Jingyu Guo,Wei Tang,Weibo Hua,Long Qu,Mingtao Li
The development of high-voltage cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) by conventional solid-state methods is hampered by its rapid capacity decay due to the impurity phases, inhomogeneous particle size, and dissolution of transition metals. To realize large-scale production and application of LNMO, a two-step modified solid-state method with Mn 2 O 3 nanosheets as a precursor is proposed here. The resulting material (P-LNMO) shows a reduced rock salt impurity phase and enhanced ionic transport through a more uniform control of particle size. As a result, the cycling stability of the disordered LNMO is remarkably improved, where LNMO half-cell capacity retention is 89.5 % at ambient temperature after 1000 cycles. What's more, the LNMO/Graphite full-cell is further assembled showing a discharge specific capacity of 110 mAh g −1 at 1C, and remains 97 % of its initial capacity after 100 cycles. The excellent electrochemical performance indicates that this modified solid-state approach brings a new avenue to the synthesis of LNMO for the upcoming generation of commercial lithium-ion batteries.
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高影响因子
Journal of Materials Chemistry A
·
2026
·
IF 9.2
Shengrui Cui,Chengliang Lin,Fangfang Dong,Mingxu Duan,Mengqiu Li,Abdul Majid,Ayaulym Belgibayeva,Yongcheng Jin
As a promising high-voltage cathode material candidate for next-generation high-energy-density lithium-ion batteries (LIBs), spinel-type LiNi0.5Mn1.5O4 (LNMO) has attracted significant attention due to its high operating voltage (~4.7 V). However, its intrinsic structural instability and severe surfacial side reactions lead to poor cycling stability and rate capability. This study presents an innovative low-temperature calcination strategy to synthesize Ti/F co-doped LNMO (LNMO-TiF3-x) cathode materials, utilizing TiF3 as a dual-functional dopant. Both experimental and theoretical investigations demonstrate that the introduced Ti3+/Ti4+ redox couple activates additional Mn-based capacity within the 4.2 V region, while contributing a minor yet measurable reversible capacity. Simultaneously, Ti/F co-doping strengthens the lattice through covalent bonding, effectively suppressing transition metal dissolution and synergistically enhancing cycling stability. Furthermore, Ti4+ doping expands the (111) lattice spacing, which facilitates Li+ diffusion kinetics and significantly enhances rate capabilities. The optimized LNMO-TiF3-4 exhibits outstanding performance, delivering 131.9 mAh g-1 at 10 C and maintaining 72.4% capacity retention after 1000 cycles at 5 C. This work not only demonstrates the high electrochemical performance of LNMO-TiF3-x but also offers new insights into bulk-interface synergistic engineering for advanced high-voltage cathode materials.
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高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Chengliang Lin,Jiaxuan Yin,Shengrui Cui,Xiang Huang,Wei Liu,Yongcheng Jin
High-voltage spinel LiNi0.5Mn1.5O4 (LNMO), which has the advantages of high energy density, low cost, environmental friendliness, and being cobalt-free, is considered one of the most promising cathode materials for the next generation of power lithium-ion batteries. However, the side reaction at the interface between the LNMO cathode material and electrolyte usually causes a low specific capacity, poor rate, and poor cycling performance. In this work, we propose a facilitated method to build a well-tuned dual structure of LiF coating and F– doping LNMO cathode material via simple calcination of LNMO with LiF at low temperatures. The experimental results and DFT analysis demonstrated that the powerful interface protection due to the LiF coating and the higher lithium diffusion coefficient caused by F– doping effectively improved the electrochemical performance of LNMO. The optimized LNMO-1.3LiF cathode material presents a high discharge capacity of 140.3 mA h g–1 at 1 C and 118.7 mA h g–1 at 10 C. Furthermore, the capacity is retained at 75.4% after the 1000th cycle at 1 C. Our research provides a concrete guidance on how to effectively boost the electrochemical performance of LNMO cathode materials.
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PubMed
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Dongsheng Lu,Jia He,Yijing Qiu,Jin Zhu,Mingyu Zhang,Yuepeng Cai
Using high voltage cathode materials is one of the main ways to improve energy density of Li ion batteries. However, the oxidation of commercial carbonate electrolyte on the cathode makes the batteries suffer serious capacity degradation. In this work triallyl phosphate (TAP) as an electrolyte additive is used to improve the cycle life of LiNi0.5Mn1.5O4 (LNMO)/graphite high voltage lithium ion cell. 1.0 wt % TAP has the best effect; it increases the retention rate of discharge capacity of the cell by about 20% compared with that without additive after 150 cycles at 0.2C. The results of electrochemical measurements, several spectral analyses, and theoretical calculation show that TAP can be electrochemically oxidized prior to the solvents EC and EMC and quickly forms a low molecular weight polymer deposit layer on the cathode, which can effectively prevent electrolyte oxidation and LNMO dissolution. In the absence of interference from electrolyte oxidation products, a dense SEI layer can be formed on the graphite anode whether TAP exists or not. Therefore, although TAP can also be electrochemically reduced to change the composition of the anode SEI layer, the improvement of the cycling performance of LNMO/graphite cell should be attributed to the oxidation reaction of TAP on the cathode.
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Advanced Materials Interfaces
·
2020
·Vol. 8
·期 3
·2001588
·
IF 4.948
Canhuang Li,Siyong Wu,Yijing Qiu,Dongsheng Lu
As the most promising cathode material in new energy resources, LiNi 0.5 Mn 1.5 O 4 (LNMO) are widely researched due to its high platform, low cost, and environment-friendliness, when they are assembled with graphite into battery which can lead to a faster capacity decay because of unstable solid–liquid interface. This work is devoted to stabilize electrolyte and protect interface of LNMO/graphite full battery by adding multifunctional additive, tributyl phosphate (TBP). Theory calculation which exhibits disconnection of TBP can participate in the reaction to form a uniform and dense cathode electrolyte interface film (8–10 nm) and solid electrolyte interface film around 15 nm on both electrodes, more importantly, the existence of phosphoric acid functional group can hinder the attack of hydrofluoric acid and protect electrode film. Besides, comparing with its homolog, the high-voltage LiNi 0.5 Mn 1.5 O 4 /graphite battery with 1% TBP shows a preponderant discharged capacity retention of 77.8% after 150 cycles, while the blank is only 66%, this work provides a direction for electrolyte additives’ selection at high voltage and has far-reaching significance for the application of phosphate ester materials.
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Fangfang Dong,Shengrui Cui,Chengliang Lin,Xin Wan,Ning Wang,Xiang Huang,Wei Liu,Yongcheng Jin
The insufficient structural stability of high-voltage spinel cobalt-free LiNi 0.5 Mn 1.5 O 4 (LNMO) throughout the cycling process hinders its widespread application. To address these issues, we incorporate elemental iodine into LNMO during the precursor preparation process using an ethanol-assisted hydrothermal method and successfully modify the bulk and interface coating structure of LNMO-3% I 2 . The incorporation of iodine not only induces the formation of a cavity and fast lithium-ion transfer pathway within the particles but also facilitates the development of a thin LiI coating layer on the surface of cathode materials. Compared with bared LNMO, LNMO-3% I 2 exhibits a capacity retention of 90.31% following 500 cycles at 1C and a capacity retention of 88.74% even following 450cycles at a high-rate of 50C. Furthermore, the cells with LNMO-3% I 2 demonstrate an excellent electrochemical performance under both high temperatures of 40 ℃ and low temperatures of −15 ℃. This study offers valuable insights into the simultaneous optimization of internal and external structures in cathode materials, thereby enhancing the long-term cycling performance of high-voltage lithium-ion batteries.
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PubMed
高影响因子
Journal of Energy Storage
·
2025
·
IF 9.8
Liqin Xiong,Zheng Cheng,Guorong Hu,Yanbing Cao,Zhongdong Peng,Bin Zhang,Ke Du
High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) emerges as an ideal cathode for high energy density lithium-ion batteries due to its 4.7 V operating voltage and low-cost manganese-rich composition. However, the severe interfacial degradation caused by transition metal dissolution and pervasive electrolyte decomposition compromises practical viability in commercial lithium-ion batteries, critically under elevated-temperature operation. To address this problem, we constructed a covalently anchored bis[3-(trimethoxysilyl)propyl]amine (BTPA) coating layer on the LNMO surface through atomic-scale grafting. The BTPA-coated LNMO confers exceptional cyclic stability and rate capability, representing a transformative advancement in cathode performance. At 50 °C, BTPA-coated LNMO cathode maintains 96.10 % capacity retention after 100 cycles at 1C, significantly outperforming pristine LNMO (58.92 % retention), while demonstrating exceptional rate capability with 109.42 mAh·g −1 delivered at 10C compared to 92.71 mAh·g −1 for the pristine LNMO. The synergistic suppression of Mn 3+ formation and parasitic reactions underpins unprecedented high-temperature cyclability, establishing a paradigm for extreme-condition energy storage.
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