LANGMUIR
·
2025
·
IF 3.9
Ling Lin,Shuang Yuan,Huahui Chen,Peng Xu,Tao Zhu,Long Li,Jiaojing Shao
The cobalt-free, high-voltage spinel-type cathode LiNi0.5Mn1.5O4 (LNMO) exhibits high energy and power densities, rendering it a promising candidate for incorporation into next-generation lithium-ion batteries (LIBs). However, its high operating voltage of 4.7 V can lead to electrolyte decomposition, causing structural damage. In addition, the irreversible loss of active lithium in the early cycles reduces capacity performance, hindering its commercial application. To take full advantage of the catalytic effect of LNMO and the prelithiation of sacrificial salt, this work involved blending sacrificial salts (Li2C2O4, Li2CO3, and CH3COOLi) with LNMO to form prelithiated electrodes (LNMO-Sac) and investigating the influence of different sacrificial salts on the performance of LIBs. The results demonstrate that LNMO could efficiently catalyze the decomposition of sacrificial salts and promote the formation of a more stable electrode–electrolyte interface after cycling to mitigate structure destruction of electrodes caused by electrolyte decomposition. Compared with other sacrificial salts, Li2C2O4 provided a highly efficient supplement of active lithium and improved the electrochemical performance of the battery. Thus, LNMO-Li2C2O4 achieved an excellent discharge capacity of 137.9 mAh g–1 at 1C, and capacity retention of 85.9% after 500 cycles, superior to that of LNMO without prelithiation. Moreover, the LNMO-LO/Gr full cell presented an initial capacity of 117.9 mAh g–1 and retained 79.4 mAh g–1 after 300 cycles. This work demonstrates the feasibility of a sacrificial salt as a lithium replenishment strategy for LNMO in practical applications.
研究领域:
材料科学
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能源存储技术
✓ 已验证
产品关联
DOI
PubMed
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.
研究领域:
材料科学
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电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Tingting Feng,Guozhu Yang,Shu Zhang,Ziqiang Xu,Haiping Zhou,Mengqiang Wu
Using localized high-concentration electrolytes (LHCEs), which have high oxidation resistance and low viscosity, in high-voltage lithium-ion batteries can facilitate the low-temperature operation of the batteries. In this study, a new short-chain fluorinated diluent 1,1,2,2-tetrafluoroethyl methyl ether is used to prepare a methyl acetate-based LHCE that shows good stability against a LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode. Furthermore, an LNMO||Li battery (3–4.9 V vs. Li/Li + ) with the LHCE shows good cycling stability at room temperature at 1C. Owing to the excellent low-temperature performance of the LHCE, the battery can discharge 80.85% of its room temperature capacity at 0.2C at the temperature of −50 °C and show reversible charge/discharge behavior at 0.1C at the temperature of −40 °C. In this study, LHCEs are successfully used to realize a high-voltage battery that could operate with a relatively high current density (≥0.1C) at a low temperature (-50 °C).
研究领域:
材料科学
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Chunlei Tan,Zhikang Huang,Yu Li,You Li,Yujie Zou,Xiaohui Zhang,Lisan Cui,Feiyan Lai,Guanhua Yang,Chenggui Jing,Hongqiang Wang,Qingyu Li
The poor cyclic stability is the key point to restricting the commercial application of LNi 0.5 Mn 1.5 O 4 -based lithium-ion batteries (LNMO-based LIBs) on high voltage (5 V-class). Once the working voltage is over 4.3 V, the parasitic reactions on the LNMO interphase will be the trigger for a series of problems such as the continuous decomposition of electrolytes and dissolution of transition metal ions. The glyceryl triacetate (GT) has been used as a functional additive to reconstruct a cathode electrolyte interphase (CEI) film to suppress the parasitic reactions and safeguard the LNMO structure. Compared to the influence of GT and propionic anhydride (PA) on the electrochemical performance of LNMO on high voltage, the LNMO/Li cell with GT exhibits exciting discharge capacity retention of 84.9 % compared with PA (17.6 %) and base electrolyte (BE, 8.6 %) after 500 cycles at 1C. The LNMO/Li cell with GT also has a remarkable rate performance in which capacity retention of 5C/2C is 85.7%, higher than 0.5 wt% PA (75.5%) and BE (62.1%). By characterizations, it is reasoningly demonstrated that the GT not only can be preferentially oxidized to form a robust CEI film on the LNMO surface to prevent the parasitic reaction but also rapidly capture the free transition metal ions and bind trace H 2 O in the electrolyte to improve the stability of LIBs. Simultaneously, the electrons from the carboxyl group of GT occupy the d-orbital of transition metal from LNMO, further effectively reducing the activity of LNMO. Particularly, the glycerol generated by the reaction of GT with H 2 O can effectively capture HF, H 2 O, and other small molecules under hydrogen-bond interaction, thereby improving the stability of LNMO LIBs.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Youguo Huang,Yan Li,Chunlei Tan,Zhikang Huang,Qichang Pan,Youqi Chu,Fenghua Zheng,Hongqiang Wang,Qingyu Li
LiNi0.5Mn1.5O4 (LNMO) is considered one of the most promising cathode materials for high-energy-density lithium-ion batteries (LIBs). However, the practical application of the LNMO cathode is seriously limited by the poor cycling performance. Hence, methyl phenyl sulfone (MPS) is investigated as an electrolyte additive to modify the cathode–electrolyte interphase and furthermore enhance the electrochemical performance of the LNMO cathode at a high voltage (5 V class). Results evidenced that the cycling performance of LNMO/Li cells was improved remarkably and with a high capacity retention of 89.8% after 400 cycles at 1 C in the 0.1 wt % MPS-containing electrolyte. Subsequently, the rate capability is also significantly improved with a high capacity of 110.2 mAh g–1 even at 5 C. Furthermore, the reason for the much-improved electrochemical performance of the LNMO/Li cell is further investigated in detail. Our investigation reveals that MPS additive can alleviate the decomposition of LiPF6 and is oxidized to form a protective layer, which inhibits the decomposition of electrolyte and dissolution of transition metals and then stabilizes the structure of the LNMO cathode during the cycling process. As a result, such a functional additive provides a cost-efficient choice to achieve the high performance of the LNMO cathode in high-voltage LIBs.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2021
·Vol. 45
·期 44
·20681-20689
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IF 3.591
Ping Zhang,Shi-You Li,Xiao-Hong Wei,Chun-Lei Li,Shu-Juan Meng,Xiao-Ling Cui,Qiong Su,Dong-Ni Zhao
Lithium-ion batteries with high-energy density are a hot spot in current research, and the 5 V class of high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode materials attracts widespread attention because of its high specific capacity. However, the traditional electrolyte causes unnecessary reactions with the LNMO interface at high voltage, so choosing a suitable electrolyte is key to the development of the above-mentioned battery system. Here, we introduce 1,3,6-hexanetrinitrile (HTN) as the high-voltage additive to improve the oxidation stability of LNMO/Li cells. Compared with the conventional nitrile-based additive adiponitrile (ADN), the HTN additive can provide more nitrile functional groups to reduce the problem of decreased electrolyte viscosity caused by adding too much ADN. Besides, in order to improve the suboptimal performance of HTN in the mesocarbon microbead (MCMB) anode, methyl benzenesulfonate (MBS) MBS with characteristics of a protecting lithium metal anode at low potential is compounded in the electrolyte to improve the performance of LNMO/MCMB batteries. The synergy and complementary advantages of HTN and MBS improve the overall performance of the LNMO/MCMB battery system. Modification of commercial electrolyte systems with compound additives as required becomes a major direction for the future design of electrolyte formulation.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ACTA PHYSICO-CHIMICA SINICA
·
2024
·
IF 10.8
Aoyu Huang,Jun Xu,Yu Huang,Gui Chu,Mao Wang,Lili Wang,Yongqi Sun,Zhen Jiang,Xiaobo Zhu
5 V-class LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode material is emerging as a promising cobalt-free alternative to meet the growing demand for affordable, high-performance lithium-ion batteries (LIBs). However, LNMO faces significant electrochemical challenges, particularly interfacial instability with commercial electrolytes due to its high operating potentials. This instability leads to the dissolution of transition metals and consequently electrode crosstalk, which severely deteriorates electrochemical performance. Surface coating is extensively investigated to reduce interfacial side reactions for enhanced cycling stability. Traditional methods typically require multiple steps, including dispersion, mixing, drying, and calcination, which can be time-consuming and complex. Additionally, the resulting ceramic coatings are often rigid and unevenly distributed due to lattice mismatches, potentially leading to poor interfacial contact and increased resistance. In this study, tetraethyl orthosilicate (TEOS) is proposed as a streamlined slurry additive to in situ form an ethoxy-functional polysiloxane (EPS) film on the surface of LNMO particles during electrode preparation. Post-mortem X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analyses reveal the crucial role of the EPS film in addressing interfacial instability issues. First, the EPS film serves as an artificial cathode-electrolyte interface (CEI) with a robust Si–O–Si bonding network, which is less vulnerable under high potentials. Second, the remaining ethoxy-functional groups in EPS scavenge HF by forming stable Si–F bonds, thereby suppressing the detrimental transition metal dissolution and crosstalk. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) further confirm the stability of the EPS film and the enhanced structural stability of the modified LNMO. Galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) results demonstrate that EPS reduces the overall impedance and improves ion diffusion kinetics by forming stable electrode-electrolyte interfaces. As a result, compared to the baseline, the optimized LNMO cathode exhibits significantly improved cycling stability in both half cells (84.6 % vs. 51.4 % capacity retention after 1000 cycles) and full cells when paired with commercial graphite anodes (83.3 % vs. 53.4 % retention after 500 cycles). This strategy, further validated under elevated temperatures of 50 °C and in pouch-type cells, is expected to pave the way for the development of next-generation high-performance LIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2019
·
IF 5.162
Xi Zheng,Ying Liao,Zhongru Zhang,Jianping Zhu,Fucheng Ren,Huajin He,Yuxuan Xiang,Yezhen Zheng,Y. Yang
Ethyl-(2,2,2-trifluoroethyl) carbonate (ETFEC) is investigated as a solvent component in high-voltage electrolytes for LiNi 0.5 Mn 1.5 O 4 (LNMO). Our results show that the self-discharge behavior and the high temperature cycle performance can be significantly improved by the addition of 10% ETFEC into the normal carbonate electrolytes, e.g., the capacity retention improved from 65.3% to 77.1% after 200 cycles at 60 °C. The main reason can be ascribed to the high stability of ETFEC which prevents large oxidation of the electrolyte on the cathode surface . In addition, we also explore the feasibility of electrolytes using single fluoriated-solvents with and without additives. Our results show that the cycle performance of LNMO material can be greatly improved in 1 M LiPF 6 + pure ETFEC-solvent system with 2 wt% ethylene carbonate (EC) or ethylene sulfate (DTD). The capacity retention of the LNMO materials is 93% after 300 cycles, even better than that of carbonate-based electrolytes. It is shown that the additives are oxidized on the surface of LNMO particles and contribute to the formation of cathode/electrolyte interphase (CEI) films. This composite CEI film plays a crucial role in suppressing the serious decomposition of the electrolyte at high voltage.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2024
·
IF 5.5
Zhengqing Pei,Jiawei Wang,Haifeng Wang,Kexin Zheng,Qian Wang,Jiexin Zhou,Dehua Ma,Ju Lu,Fanghai Lu
The study investigated the evolution of LNMO (LiNi0.5Mn1.5O4) morphology and surface orientation as a function of increasing temperature. The results show that at an initial calcination temperature of 750 °C, LNMO exhibits spherical polyhedral with (111), (110), and (100) facets and relatively small particle sizes. In response to increasing temperatures, the particle size increases, the number of crystal facets decreases, and the material ultimately transitions to a typical spinel structure. Notably, the LNMO material calcined at 750 °C demonstrates a high lithium-ion migration rate, retaining 81.24% of its capacity after 500 cycles at a 2 C rate. This exceptional performance is attributed to the exposure of multiple crystal facets, suitable particle size, and the presence of Mn³⁺, which collectively stabilize the crystal structure and provide suitable pathways for Li⁺ transport.
研究领域:
材料科学
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电化学
·
无机化学
·
能源材料
·
固态化学
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）