JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2019
·Vol. 30
·期 5
·5098-5108
·
IF 2.195
Zhou Hongming,Liu Bin,Xiao Demin,Yin Chengjie,Li Jian
Spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode with high voltage plateau at around 4.7 V (vs. Li/Li + ) has attracted great attention. While the unsatisfactory electrochemical performance at high voltage hinders its practical application in next generation lithium ion batteries. Based on our previous research, FEC as electrolyte additive significantly improves the electrochemical performance of high voltage LNMO cell. The LNMO/Li cell with 4 wt% FEC shows the best rate capability, 76% capacity retention even at 5C. And the high temperature cycling performance of LNMO/G full cell with FEC is improved. The result from Raman indicates that FEC can transform the association structure of AGGs in the electrolytes to the salvation structure of SSIPs which increases the conductivity of electrolyte. EIS, SEM, TEM, XPS and FTIR analyses indicate that a more stable CEI film has been formed on the cathode surface with appropriate FEC as additive, which can promote the transport of lithium ions and inhibit the dissolution of transition metal elements.
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高影响因子
Journal of Materials Chemistry A
·
2024
·
IF 10.7
Jinping Mu,Xiaohui Li,Rui He,Lijing Sun,Xue Bai,Lihui Zhang,Xi Zhang,Zhenfa Liu,Jing Gao,Ai-Jia Wei
Spinel-type LiNi0.5Mn1.5O4 (LNMO) materials have attracted broad attention as components of rechargeable lithium-ion batteries (LIBs) due to their high energy density. However, continuous decomposition of electrolyte at high working voltage hinders its practical application in carbonate-solvent-based electrolytes. In this work, 4-methyl-1,3,2-dioxathiolane-2,2-dioxide (MDTD) was added as a functional electrolyte additive to the standard electrolyte (i.e., 1 M LiPF6–ethylene carbonate/ethyl methyl carbonate/dimethyl carbonate) to enhance the electrochemical performances of LNMO-based LIBs. Specifically, addition of a 0.5% additive in the standard electrolyte significantly improved the capacity retention of LNMO/Li half-cells from 78.5 to 95.8% after 500 cycles at 5 C, increased the capacity retention of LNMO/graphite full-cells from 70.8 to 80.9% after 100 cycles at 0.5 C, and enhanced the capacity retention of LNMO/LTO full cells from 37.2 to 81.8% after 200 cycles at 5 C. In addition, the standard electrolyte containing 0.5% MDTD also improved the cycling performance of LNMO/Li half-cells at 45°C, expanding the applicable temperature range. Comprehensive characterization combined with theoretical calculations allowed to reveal the action mechanism of the additive. In this mechanism, MDTD is decomposed subsequently involved in the decoration of the electrode–electrolyte interfacial films (for the LNMO, Li, and graphite electrodes), providing it with improved conductivity, protection, and resistance to electrolyte oxidation/reduction decomposition features. These findings suggest that use of the MDTD additive is a promising strategy to optimize high-voltage electrolytes for the industrialization of LNMO-based LIBs.
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高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2017
·
IF 3.012
Hongming Zhou,Demin Xiao,Chengjie Yin,Zhaohui Yang,Kaiwen Xiao,Jian Li
The electrolytes based on lithium difluoro(oxalate)borate (LiODFB) and sulfolane (SL) including LiODFB-ethylene carbonate (EC)/dimethyl carbonate (DMC) and LiPF 6 -EC/DMC as the references have been studied on electrochemical performance and interfacial stability in Li/LiNi 0.5 Mn 1.5 O 4 cells. LiODFB-containing electrolytes show outstanding electrochemical stability within 5.5 V due to the passivation phenomenon on the cathodes, while LiPF 6 -containing electrolytes undergo continuous decomposition beyond 4.5 V. The initial charge/discharge profiles and cyclic voltammetry (CV) curves prove that the cell with LiODFB-SL/DMC(2:1 by vol.) electrolyte has lower degree of polarization and better reversibility. The cathode with LiODFB-SL/DMC(2:1 by vol.) electrolyte displays the best cycling performance and the cathode with LiPF 6 -EC/DMC(1:1 by vol.) electrolyte displays the worst cycling performance. AC impedance shows that the cell cycling with LiODFB-SL/DMC(2:1 by vol.) electrolyte has much smaller resistance of charge transfer on cathode/electrolyte interface than the cell cycling with LiODFB-EC/DMC(1:1 by vol.) electrolyte. The characterization of the cathode surfaces indicates that a more homogeneous and compact passivation layer forms on the cathode cycling with LiODFB-SL/DMC(2:1 by vol.) electrolyte to greatly improve the interfacial stability for the reason that SL motivates the passivation reaction of LiODFB and itself participates the formation of the passivation layers. Therefore, LiODFB-SL/DMC(2:1 by vol.) is a promising electrolyte for LiNi 0.5 Mn 1.5 O 4 cathode.
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高影响因子
Advanced Energy Materials
·
2025
·Vol. 15
·期 34
·2502226
·
IF 26
Mengting Guo,Changping Wang,Yize Niu,Mingyue Ruan,Dong Yang,Fei Wang,Haonan Wang,Nankai Wang,Ying Jiang,Tianyi Li,Yan He,Qiang Li
The high-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is a promising cathode material for lithium-ion batteries due to its high energy and power densities, excellent thermal stability, low cost, and environmental benignity. However, the presence of Mn 3+ induces Jahn─Teller (J─T) distortion, leading to Mn─O bond elongation, lattice stress, and degradation of both structural and electrochemical stability during cycling. To address this,a bond-length engineering strategy is proposed by co-doping Fe at the Mn 16d sites and Sb at the vacant 16c positions to suppress the J─T effect and stabilize the crystal structure. Electron paramagnetic resonance (EPR), in situ X-ray diffraction (XRD), and density functional theory (DFT) calculations confirm that the Mn─O bond regulation strategy effectively mitigates MnO 6 octahedral distortion, reduces phase transitions, and enhances structural robustness. Moreover, Sb incorporation expands the lattice, facilitating Li + diffusion. As a result, the optimized FeSb-LNMO delivers remarkable electrochemical performance, retaining 98% of its initial capacity after 200 cycles at 1C, and achieving 85.6% capacity retention over 1000 cycles at 5C. This work introduces a novel bond-length engineering approach via multi-site doping to overcome degradation in high-voltage LNMO, enabling ultra-fast charging and long-term cycling stability.
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高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Ziming Wang,Rui Wang,Hanbo Wang,Sheng Wan,Yan Wang,Haiping Zhou,Binhui Liu,Yumei Tian,Kechang Li,Haiyan Lu
High-voltage spinel LiNi 0 . 5 Mn 1 . 5 O 4 (LNMO) has emerged as a promising cobalt-free cathode candidate for lithium-ion batteries, yet its practical implementation is hindered by structural instability stemming from the Jahn-Teller effect. Herein, we propose an effective germanium doping strategy to suppress this effect. The optimized Ge Mof -LNMO exhibits exceptional electrochemical performance, delivering an initial capacity of 153.7 mAh g −1 at 0.1 C with remarkable cycling stability (82.1 % retention after 1000 cycles) while maintaining elevated operating voltages (4.67–4.53 V). Mechanistic investigations through electrochemical impedance spectroscopy coupled with distribution of relaxation times analysis at various charge states reveal that Ge incorporation enhances interfacial stability and charge transfer kinetics. Density functional theory calculations demonstrate that the formation of Ge-O bonds not only stabilizes the lattice structure but also optimizes electron distribution, effectively suppressing Jahn-Teller distortion. Notably, when paired with biomass-derived carbon (synthesized from Hami melon peel) as the anode in full cells, Ge Mof -LNMO demonstrates superior compatibility and cycling stability, highlighting its potential for practical applications. This work provides valuable design strategies for developing stable high-voltage spinel cathodes in next-generation energy storage systems.
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高影响因子
CERAMICS INTERNATIONAL
·
2021
·
IF 4.527
Xiang Ji,Xinyi Dai,Fuzhong Wu,Yi Mai,Haijun Chen,Yijing Gu
LiNi 0.5 Mn 1.5 O 4 (LNMO) is a promising next-generation cathode material for high energy density lithium-ion batteries, but the application of LNMO is blocked because of its inherent side effects with electrolytes at high voltages, namely, serious Mn dissolution and capacity attenuation. A novel LiNi 0.5 Mn 1.5-x Sr x O 4 material (x = 0, 0.05, 0.1, 0.15, and 0.2) was successfully prepared using the sol-gel method, and the effect of varying in situ Sr 2+ -doping on the crystal structure, morphology, and electrochemical performance was researched. A series of characterizations showed that the Sr-doped LNMO structure contains less Mn 3+ , which enhances its cycling stability. In addition, Sr doping promotes morphological changes more remarkably. Accompanied by the appearance of (100) surfaces, the morphology of LNMO changes from an octahedron to a truncated octahedron. The (100) surface can effectively inhibit side reactions with the electrolyte and steady the structure at the working voltage, which also helps support Li + transport kinetics. The Sr-doped LiNi 0.5 Mn 1.4 Sr 0.1 O 4 (expressed as LNMO-Sr0.1) cathode exhibits preeminent cycling stability, after 500 cycles at 1C, the capacity retention is 86.63 %. CV and EIS results show that the right amount of Sr doping efficiently reduces electrode polarization and charge transfer resistance and increases the Li + diffusion coefficient .
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高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Jinping Mu,Xiaohui Li,Rui He,Lijing Sun,Xue Bai,Lihui Zhang,Peng Liu,Zhenfa Liu,Jing Gao,Aijia Wei
High-voltage lithium-ion batteries (LIBs) with LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode are considered promising energy sources due to their high energy density . However, enhancing the stability of the electrode/electrolyte interface remains critical for the practical application of LIBs. In this work, lithium-containing inorganic phosphates (LiPO 3 , Li 3 PO 4 , and LiH 2 PO 4 ) were used as multifunctional inorganic additives to improve the stability of the electrode/electrolyte interface in 5.0 V, LNMO-based LIBs with carbonate-based electrolytes. Based on theoretical calculations and experimental evaluations of the electrochemical performance , LiPO 3 was selected as the optimal additive for further study in LNMO/Li and LNMO/Li 4 Ti 5 O 12 cells. The LNMO/Li half-cells with LiPO 3 delivered an initial discharge capacity of 108.8 mAh∙g −1 and retained a capacity of 94.9 % after 500 cycles at 5C, compared to 75.1 mAh∙g −1 and 79.4 % for the standard electrolyte. The increased cycling stability was ascribed to the ability of the multifunctional, film-forming LiPO 3 additive to form stable interfacial films on both the cathode and anode , thus, inhibiting side reactions between the electrodes and electrolyte. Moreover, as an HF scavenger, LiPO 3 reduced the HF content in the electrolyte to ensure the structural integrity of LNMO and inhibit the dissolution of transition metal ions . In the LNMO/Li 4 Ti 5 O 12 full cells, the addition of LiPO 3 effectively enhanced the cycling performance, and the capacity retention after 400 cycles at 5C was 79.1 %, compared to only 12.3 % for the standard electrolyte. Considering its simplicity, low cost, and feasibility, the addition of LiPO 3 as a multifunctional electrolyte additive showed excellent prospects for commercial applications.
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高影响因子
ELECTROCHIMICA ACTA
·
2022
·
IF 7.336
Yang Xia,Xiaohang Ren,Zhen Xiao,Yongping Gan,Jun Zhang,Hui Huang,Xinping He,Qinzhong Mao,Guoguang Wang,Wenkui Zhang
Increasing the charging cut-off voltage is an effective strategy to achieve high energy density Ni-rich layered oxide cathode materials, however the dramatic deterioration of cycling lifespan and thermal stability still remain great challenges in large-scale practical applications. Herein, a rationally designed core-shell structure LiNi 0.9 Co 0.1 O 2 @LiNi 0.5 Mn 1.5 O 4 composite composed of spinel structure Mn-rich LiNi 0.5 Mn 1.5 O 4 shell and layered structure Ni-rich LiNi 0.9 Co 0.1 O 2 core is proposed to enhance the structure stability and thermal stability under high-voltage application scenario. Compared to the pristine LiNi 0.9 Co 0.1 O 2 cathode, the core-shell structure LiNi 0.9 Co 0.1 O 2 @LiNi 0.5 Mn 1.5 O 4 composite with optimized LiNi 0.5 Mn 1.5 O 4 shell exhibits high reversible specific capacity (195.5 mA h g − 1 at 0.5 C), remarkable cycling stability (86% capacity retention after 100 cycles) and superior rate capability (162.5 mA h g − 1 at 5.0 C) within 2.8 V-4.5 V. The comprehensively improved electrochemical performance is mainly attributed to the Mn-rich LiNi 0.5 Mn 1.5 O 4 shell, which not only effectively prevents the phase transition and microstructural collapse, but also ameliorates the Li + transport ability, high-voltage charging capability and thermal stability. Such novel core-shell structure LiNi 0.9 Co 0.1 O 2 @LiNi 0.5 Mn 1.5 O 4 composite as promising cathode is highly expected to greatly promote the practical application of high energy density lithium-ion batteries.
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高影响因子
Journal of Physical Chemistry C
·
2025
·
IF 3.2
Mingyu Zhang,Jin Zhu,Yunyan Gai,Mengshuang Li,Yuepeng Cai,Dongsheng Lu
Enhancing the operating voltage (>4.3 V vs Li/Li+) of cathodes is a critical strategy for increasing the energy density of lithium-ion batteries (LIBs). However, in high-voltage LIBs employing conventional carbonate-based electrolytes, solvent-dominated electrode–electrolyte interfacial reactions hinder the formation of a stable cathode–electrolyte interface, resulting in rapid capacity degradation. In this work, suberonitrile (SUN) is used as an additive to regulate the structure of a commercial carbonate electrolyte (1 M LiPF6+ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (3/7, v/v)), and the electrolyte containing SUN has a localized high-concentration electrolyte-like structure. Because the attraction of Li+-SUN is weaker than that of Li+-EC and Li+-EMC, while the attraction of PF6–-SUN is stronger than that of PF6–-EC and PF6–-EMC, SUN closely contacts PF6– by squeezing out the solvent molecules near PF6–, which pulls the PF6– into the Li+ solvation sheath. This unique electrolyte configuration shifts the interfacial chemistry from solvent-derived to SUN/anion-dominated, enhancing the stability of the electrode/electrolyte interface in high-voltage LiNi0.5Mn1.5O4/graphite cells. Consequently, the cell employing the 1.0 wt % SUN-containing electrolyte demonstrates a 14.3% improvement in capacity retention after 200 cycles at a 0.3C rate compared to that with the baseline electrolyte.
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高影响因子
JOURNAL OF POWER SOURCES
·
2023
·
IF 9.2
Jin Zhu,Mingyu Zhang,Yunyan Gai,Ronghua Zeng,Yuepeng Cai,Dongsheng Lu
Tosylmethyl isocyanide (TosMIC) is used as electrolyte additive to study the effect on the cycling performance of LiNi 0.5 Mn 1.5 O 4 (LNMO)/graphite 5V lithium-ion cell. The constant current charge and discharge measurement results shows that the capacity retention rate of the cell containing 0.3 wt% TosMIC increases by 18% after 200 cycles, while 1.0 wt% TosMIC worsens the cycling performance of the cell. The decomposition product PF 5 of electrolyte salt LiPF 6 may interact with TosMIC to form TosMIC-PF 5 complex. The results of surface and electrochemical analysis indicate that the complex can be oxidized at the cathode and reduced at the anode simultaneously prior to the solvent molecules of the electrolyte. Theoretical calculation further shows that TosMIC-PF 5 can be oxidized to form a dimer (TosMIC-PF 5 ) 2 at 4.46V ( vs . Li/Li + ), which may be deposited on the LNMO cathode to help form a coating layer . This coating layer can be rapidly formed in the first cycle and can significantly alleviate the oxidation of the electrolyte, but it cannot inhibit the decomposition of excessive additive. Two proposed reduction reactions of TosMIC-PF 5 occur at 1.66 V and 2.00 V ( vs . Li/Li + ). Unfortunately, the reduction of this additive has a negative impact on the cycling performance of the cell.
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高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2020
·Vol. 26
·期 53
·12233-12241
·
IF 4.857
Chunlei Tan,Na Wang,Qichang Pan,Yan Li,Yu Li,Qiannan Ji,Xiaoping Fan,Fenghua Zheng,Hongqiang Wang,Qingyu Li
Graphical Butyric anhydride was used as carbonate-based electrolyte additive to construct a thin, uniform cathode–electrolyte interphase (CEI) film that can alleviate the decomposition of the electrolyte and prevent the dissolution of metal ions to maintain the structural stability of LiNi 0.5 Mn 1.5 O 4 (LNMO) during the cycling process, and improve the electrochemical performance of LNMO cathodes in carbonate-based electrolytes. Butyric anhydride (BA) is used as an effective functional additive to improve the electrochemical performance of a high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode. In the presence of 0.5 wt % BA, the capacity retention of a LNMO/Li cell is significantly improved from 15.3 to 88.4 % after 200 cycles at 1 C. Furthermore, the rate performance of the LNMO/Li cell is also effectively enhanced, and the capacity goes up to 112 mAh g −1 even at 5 C, which is considerably higher than that of a LNMO/Li cell in electrolyte without BA additive (95.4 mAh g −1 at 5 C). Linear sweep voltammetry and cyclic voltammetry results reveal that the BA additive can be preferentially oxidized to construct a stable cathode electrolyte interphase (CEI) film on the LNMO cathode. Subsequently, the BA-derived CEI film can alleviate the decomposition of the electrolyte and the dissolution of Mn and Ni ions from the LNMO cathode as well as maintain the structural stability of LNMO during the cycling process; this leads to outstanding electrochemical performance. Thus, this work provides an effective and low-cost functional electrolyte for high-voltage LNMO-based LIBs.
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PubMed
高影响因子
Nanoscale
·
2019
·Vol. 11
·期 18
·8967-8977
·
IF 6.97
Li Li,Rui Zhao,Tinghua Xu,Dandan Wang,Du Pan,Kun Zhang,Caiyan Yu,Xia Lu,Guanjie He,Ying Bai
LiNi0.5Mn1.5O4 (LNMO) spinel has drawn increasing attention due to its high voltage, stabilized electrochemical performance and safety features as a cathode for lithium-ion batteries. However, the main challenge lies in its unstable surface structure, especially at elevated temperatures. In this paper, we decorate the LNMO precursor with a solid electrolyte of Li1.4Al0.4Ti1.6(PO4)3 (LATP) via a facile sol–gel method, followed by a co-crystallization process at 820 °C, to successfully generate a LATP modification shell at the surface of LNMO. The LATP modification shell could not only optimize the morphology of LNMO including the limitation of particle growth and control of crystalline orientation, but also realize ion doping during the co-crystallization process. By tuning the LATP contents, the 2 wt% LATP modification is found to be the most effective at balancing the interfacial stability and Li+ diffusion kinetics of LNMO, as well as enhancing its rate capability and capacity retention at high temperatures. As a result, the 2 wt% LATP-modified LNMO cathode exhibits a high reversible capacity of 84.8 mA h g−1 after 500 cycles with a capacity retention of 68.9%, and a superior rate capability (102.0 mA h g−1 at 20 C) at room temperature. Moreover, this electrode also delivers a good capacity retention of 85.7% after 100 cycles at 55 °C, which is ascribed to the stabilized interface with a LATP protective layer.
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PubMed
高影响因子
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