JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2019
·Vol. 166
·期 8
·A1456
·
IF 3.12
Hao Zheng,Xin Zhou,Sheng Cheng,Ru Xia,Shuping Nie,Xin Liang,Yi Sun,Hongfa Xiang
Influence of separator wettability toward nonaqueous electrolyte was investigated in lithium-ion batteries using high-voltage LiNi0.5Mn1.5O4 cathode. A fluorinated ether of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (HFE) was introduced as a co-solvent into the control electrolyte and polyolefin separator wettability toward nonaqueous electrolyte was effectively enhanced. Even though conductivity of the electrolyte bulk decreased after HFE was introduced, ionic conductivity of the electrolyte-soaking separator increased due to the enhanced separator wettability. From cycling stability of the half cells using high-voltage LiNi0.5Mn1.5O4 cathode, all electrolytes containing 10%, 20% and 30% HFE have superiority to the control electrolyte, and the 20% HFE containing electrolyte is the optimal. Microscopical analysis revealed that oxidative decomposition of HFE-containing electrolyte on the LiNi0.5Mn1.5O4 cathode was suppressed effectively with the thinner cathode electrolyte interface than that in the control electrolyte. In Li4Ti5O12|LiNi0.5Mn1.5O4 full cells, the 20% HFE containing electrolyte exhibited the enhanced cycling stability and rate capability compared to the control of 1 mol L−1 LiPF6/propylene carbonate. This work here reveals the effect of fluorinated ether co-solvent on separator wettability and further the superior separator wettability is critical to the oxidation stability of the electrolyte in lithium-ion batteries using high-voltage cathode.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
SURFACE & COATINGS TECHNOLOGY
·
2024
·
IF 5.3
Dongjia Li,Bo Xiao,Xinyi Dai,Chao Wang,Yawei Wei,Haijun Chen,Yi Mai,Fuzhong Wu,Jiexi Wang
Amid the fast growth of lithium-ion batteries, LiNi 0.5 Mn 1.5 O 4 (LNMO) with a 4.7 V working voltage and cost advantages has gained significant attention. The instability of LNMO structure during high-voltage cycling leads to significant side reactions with the electrolyte, hindering its commercial development. Our study introduces a co-crystallization calcination strategy to enhance the optimization of LNMO. This study utilized a straightforward wet chemistry approach to combine the precursor of NASICON-type solid electrolyte Mg 0.5 Ti 2 (PO 4 ) 3 (MTP) with the precursor of LNMO. Subsequently, a MTP coating was formed in-situ on the surface of LNMO through a single-step calcination process. Co-crystallization and calcination processes limit LNMO particle secondary growth, shorten Li + diffusion path , achieve Mg 2+ and Ti 4+ co-doping, enhance structural stability , and result in triple modification, leading to a significant improvement in electrochemical performance . Among them, LNMO with a 1 % molar ratio modified by MTP reaches 81.7 % of the initial capacity after 500 cycles at room temperature and 84.3 % after 180 cycles at 55 °C. Under identical conditions, unmodified samples have 39.3 % and 76.3 %, respectively. Our research explores a novel application of NASICON-type solid electrolytes in modifying LNMO cathode material .
研究领域:
材料科学
·
能源存储与转换
✓ 已验证
DOI
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.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2014
·Vol. 2
·期 32
·12835-12848
·
IF 0
Zhanjun Chen,Ruirui Zhao,Peng Du,Hang Hu,Tao Wang,Licai Zhu,Hongyu Chen
Alternative micro-sized LiNi0.5Mn1.5O4 spinels with octahedral structure (showing only one type of {111} crystal face) or chamfered polyhedral structure with extra other faces have been synthesized via a controllable method. A possible growth model, complexing–pyrolyzing-oriented, is also proposed for the formation of chamfered polyhedral LiNi0.5Mn1.5O4 spinel based on the experimental results in this paper. The chamfered polyhedral LiNi0.5Mn1.5O4 can provide a large capacity of 103 mA h g−1 even at a discharge rate as high as 50 C, which is far superior to that of the octahedral structure. Besides, the capacity retentions of the chamfered polyhedral composites are found to be 90.82% at 25 °C after 500 cycles and 90.00% at 55 °C after 200 cycles, which are also better than those of the octahedral composites. These results represent the first experimental evidence for lattice-plane anisotropy in LiNi0.5Mn1.5O4 crystals. Moreover, the pseudo-sphere structure is beneficial for obtaining high volumetric energy density and excellent processability in practical applications. In short, we have revealed for the first time that, through chamfering an octahedron to a pseudo-sphere-like polyhedron rather than doping or coating, a micro-sized LiNi0.5Mn1.5O4 spinel with good compatibility between energy/power density and cycle life can be synthesized successfully without sacrificing other properties.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机固体化学
·
纳米结构材料
✓ 已验证
DOI
Journal of Physical Chemistry C
·
2024
·
IF 3.3
Weikang Mei,Guobao Xu,Hongyu Wang
Li4Ti5O12 (LTO)/LiNi0.5Mn1.5O4 (LNMO) batteries have appealing features, such as suitable energy density and high safety. A proper binder of the LNMO cathode and electrolyte can improve the performance of batteries. Herein, we first combined the polyacrylic acid (PAA) binder with an ester-based electrolyte due to their homologous structure. This system has better performance than other binders of LNMO cathode, like poly(vinylidene fluoride) (PVDF), styrene–butadiene rubber (SBR), and polytetrafluoroethylene (PTFE). In the methyl acetate (MA) electrolyte, the LTO/LNMO battery with the PAA binder exhibited the highest discharge capacity (137 mAh g–1 at 0.5 C) and the best rate performance (112 mAh g–1 at 5 C). In addition, MA boosted the low-temperature performance of this battery, which can work at −40 °C with a remarkable reversible capacity of 90 mAh g–1 and a discharge capacity of 140 mAh g–1.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
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.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
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.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Small
·
2018
·Vol. 14
·期 37
·1802244
·
IF 9.598
Jingchao Chai,Bingbing Chen,Fang Xian,Peng Wang,Huiping Du,Jianjun Zhang,Zhihong Liu,Huanrui Zhang,Shanmu Dong,Xinhong Zhou,Guanglei Cui
Notorious lithium dendrite causes severe capacity fade and harsh safety issues of lithium metal batteries, which hinder the practical applications of lithium metal electrodes in higher energy rechargeable batteries. Here, a kind of 3D-cross-linked composite network is successfully employed as a flexible-rigid coupling protective layer on a lithium metal electrode. During the plating/stripping process, the composite protective layer would enable uniform distribution of lithium ions in the adjacent regions of the lithium electrode, resulting in a dendrite-free deposition at a current density of 2 mA cm −2 . The LiNi 0.5 Mn 1.5 O 4 -based lithium metal battery presents an excellent cycling stability at a voltage range of 3.5–5.0 V with the induction of 3D-cross-linked composite protective layer. From an industrial field application of view, thin lithium metal electrodes (40 µm, with 4 times excess lithium) can be used in LiNi 0.5 Mn 1.5 O 4 (with industrially significant loading of 18 mg cm −2 and 2.6 mAh cm −2 )-based lithium metal batteries, which reveals a promising opportunity for practical applicability in high energy lithium metal batteries.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
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.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）