JOURNAL OF POWER SOURCES
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2014
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IF 5.211
Borong Wu,Yonghuan Ren,Daobin Mu,Xiaojiang Liu,Feng Wu
LiNi 0.5 Mn 1.5 O 4 electrode modification is achieved in this work through adding inorganic lithium carbonate (Li 2 CO 3 ) into carbonate electrolyte. Superior cyclic stability of the cathode in the range of 5–2 V is attained, a capacity of 0.3698 mAh g −1 is lost per cycle, which is half of the value in the Li 2 CO 3 -free condition. The capacity loss above and below 3.5 V are both alleviated in the presence of Li 2 CO 3 . Its effect on both the electrolyte bulk and the cathode surface is analyzed with SEM , TEM and XPS measurements. The density functional theory (DFT) calculation is carried out to discuss the modification mechanism. It is speculated that Ni 4+ ⋯CO 3 2− coordination may be formed through the interaction between Ni and O, weakening the oxidizability of Ni 4+ on the electrode surface . In addition, Li 2 CO 3 can consume PF 5 in the electrolyte. The interphase film can also maintain thin and steady during the cycling within 5–2 V.
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高影响因子
CHEMISTRY OF MATERIALS
·
2024
·
IF 7.2
Yingbo Deng,Zengzhu Li,Honghao Wang,Lunhua He,Bingkai Zhang,Mingjian Zhang
Extending the lower cutoff potential of spinel LiNi0.5Mn1.5O4 to 2 V holds the potential to significantly increase the energy density from approximately 600 to around 900 W h/kg by utilizing an extra ∼2.7 V plateau. However, precisely adjusting the length of the ∼2.7 V plateau has proven to be a challenging task, and the decisive structural factor has remained elusive. In this study, a thorough and comparative investigation employing time-of-flight neutron powder diffraction, aberration-corrected scanning transmission electron microscopy, combined with theoretical calculations, has unveiled, for the first time, the key structural feature influencing the length of the ∼2.7 V plateau, a specific point defect, that is, Ni occupation at the 16c octahedral site. It drives Li ions at the neighboring 8a tetrahedral site to move to the 16c site and accelerates the T1 → T2 phase transition, resulting in a shorter ∼2.7 V plateau. Ultimately, the cathode material with the vacant 16c site exhibits a prolonged ∼2.7 V plateau, achieving a higher energy density of approximately 900 W h/kg than that of the cathode material with ∼5.4% Ni at the 16c site (around 800 W h/kg). These findings offer valuable insights for achieving high-energy-density and cost-effective spinel cathodes through meticulous microstructure regulation.
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高影响因子
CERAMICS INTERNATIONAL
·
2018
·Vol. 45
·期 4
·5100-5110
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IF 3.057
Qian Chang,Aijia Wei,Wen Li,Xue Bai,Lihui Zhang,Rui He,Zhenfa Liu
The high-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is a potential cathode material for lithium-ion batteries with outstanding energy density and power density. Here, we document a facile approach to prepare Al 2 O 3 -modified LNMO cathode materials. The Al 2 O 3 -modified LNMO materials were synthesized via a one-step solid-state reaction and then modified with Al 2 O 3 via a wet chemical technique. The impacts of Al 2 O 3 modification on the structure and electrochemical properties of LNMO materials were examined by X-ray diffraction, Fourier-transform infrared spectroscopy, Raman spectroscopy , scanning electron microscopy, transmission electron microscopy , energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy , charge-discharge tests, cyclic voltammetry measurements, electrochemical impedance spectroscopy , and aging tests. Throughout the modification process, several Al 3+ were noted to substitute for Ni 2+ , resulting in a decrease of Mn 4+ to Mn 3+ ; this increased the electronic conductivity and lowered the electrochemical polarization of the LNMO material. An amorphous Al 2 O 3 coating layer developed on the surface of the LNMO particles in the modification, and this could alleviate the strike of HF caused by electrolyte decomposition as well as the development of a solid electrolyte interphase . Thus, the 0.5 wt% Al 2 O 3 -modified LNMO material had decreased R sf and R ct and greater D Li values with a rate capability and cycling stability better than LNMO. The rate capability was 105.6 and 83.3 mAh g –1 at high C rates of 5 C and 7 C, as opposed to 83.3 and 54.9 mAh g –1 , respectively; the room temperature (25 °C) capacity retention was 92.6% at 1 C after 200 cycles, as opposed to 87.0%. The high-temperature (55 °C) capacity retention was 90.9% at 1 C rate after 200 cycles as opposed to 86.5%. Thus, this is an easy and feasible method to improve the electrochemical performance of LNMO cathode materials for industrialization.
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高影响因子
COMPOSITES PART B-ENGINEERING
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2025
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IF 14.2
Shengrui Cui,Fangfang Dong,Chengliang Lin,Mingxu Duan,Mengqiu Li,Ayaulym Belgibayeva,Abdul Majid,Yongcheng Jin
High-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathodes offer high energy density and cost efficiency for next-generation lithium-ion batteries but suffer from structural degradation and interfacial side reactions. This study addresses these challenges through a cobalt phthalocyanine (CoPc) modification strategy that synergistically integrates bulk doping and surface coating. By neutralizing residual surface alkali and optimizing calcination processes, Co 3+ ions are selectively doped into Mn 4+ sites to expand lattice parameters, while an in-situ-formed Co 3 O 4 nanocoating chemically passivates the surface, suppressing Mn dissolution and promoting stable CEI formation. The optimized LNMO-5 wt% CoPc (using CoPc content is 5 wt%) cathode demonstrates outstanding electrochemical stability, retaining 81.4 % capacity after 700 cycles at 1C and delivering 95.2 mAh g −1 at 20C over 1000 cycles. It also exhibits superior temperature-adaptability with 68.1 mAh g −1 capacity at 5C/-15 °C and 68.3 % capacity retention at 40 °C after 300 cycles at 1C. This work establishes a “bulk-surface” co-optimized framework to resolve the inherent stability-rate trade-off in spinel cathodes, advancing the development of long-term high-power lithium-ion batteries.
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高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Huiling Chen,Pan He,Meng Li,Yuehua Wen,Gaoping Cao,Jingyi Qiu,Hai Ming,Pengcheng Zhao,Songtong Zhang
In this paper, sulfonated graphene (SA-GE) with the functions of both high electronic conductivity and fast Li+ transport is utilized to modify high-voltage LiNi0.5Mn1.5O4. We show that LiNi0.5Mn1.5O4 modified with 2 wt % SA-GE exhibits extremely long cycling life, achieving a great capacity retention of 98.0% after 1000 cycles at the loading of 2.6 mg cm–2 and 99.0% after 350 cycles at the loading of 6.0 mg cm–2 under 1C. Besides, the rate capability is also greatly improved (discharge capacity remains 78.5 mAh g–1 at 10C). It is revealed that the SA-GE-involved layer could significantly inhibit the rapid growth of the cathode electrolyte interphase (CEI) layer at 5.0 V, which mainly contributes to an enhanced Li+ diffusion kinetics without sacrificing the electronic conductivity of graphene coating. Thus, the polarization degree and charge transfer resistance are significantly mitigated. Furthermore, structure degradation of the cathode is avoided by reducing the side reactions and the dissolution of transition-metal ions. It is thus well demonstrated that chemical decorations of graphene modifiers with an optimized amount of functionized sulfonic acid groups can be a promising strategy to construct lithium-ion batteries with long life and high energy density.
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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.
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PubMed
高影响因子
MATERIALS RESEARCH BULLETIN
·
2017
·
IF 2.446
Haoxiang Zhong,Jiarong He,Lingzhi Zhang
5 V LiNi 0.5 Mn 1.5 O 4 (LNMO) cathodes are prepared using carboxymethyl chitosan (CCTS) as a water soluble binder and carbon coated aluminum foils (CAl) as current collector in Li-ion batteries (LIBs). CCTS exhibits an electrochemical oxidation potential as high as 5.0 V. The electrochemical performance of LNMO cathode with CCTS binder is investigated and compared with the commercial non-aqueous polyvinylidene difluoride (PVDF). CCTS-CAl-LNMO electrode shows higher capacity retention (95.8%) than that of PVDF-CAl-LNMO (92.9%) and PVDF-Al-LNMO (88.52%) after 100 cycles. And, CCTS-CAl-LNMO electrode exhibits better rate capability than PVDF-CAl-LNMO, and PVDF-Al-LNMO, retaining specific capacity of 95.8 mAhg −1 at 10C rate, only 87.6 mAhg −1 and 1 mAhg −1 for PVDF-CAl-LNMO, and PVDF-Al-LNMO, respectively. This approach can also be extended its use to other cathode materials such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM).
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高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2017
·
IF 2.764
Haoxiang Zhong,Jidian Lu,Aiqin He,Minghao Sun,Jiarong He,Lingzhi Zhang
Carboxymethyl chitosan/poly (ethylene oxide) (CCTS/PEO) composite is firstly reported as a water soluble binder for the application of 5 V LiNi 0.5 Mn 1.5 O 4 cathode in Li-ion batteries. Both CCTS and PEO show a high electrochemical oxidation potential of above 5.0 V (vs. Li/Li + ). The electrochemical performances of LiNi 0.5 Mn 1.5 O 4 (LNMO) cathodes with CCTS/PEO composite binders of different mass rates are investigated, it is found that LiNi 0.5 Mn 1.5 O 4 cathode with an optimized CCTS/PEO (85/15, w/w) composite exhibits a slightly better cycling performance than that of polyvinylidene fluoride (PVDF), retaining 81.4% capacity as compared with 79.8% for PVDF at 0.5C rate after 200 cycles. LNMO with PEO/CCTS (85/15, w/w) exhibited the better rate capability than that of PVDF. These results demonstrate that CCTS/PEO composite can be potentially used as a water-soluble binder for 5 V LNMO cathode.
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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 .
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Jianling Guo,Yuan Zhang,Shaoxiong Fu,Shuaipeng Yan,Yaqiang Lang,Li Wang,Guangchuan Liang
The practical application of high-voltage LiNi0.5Mn1.5O4 is heavily restricted by serious capacity degradation, especially at high temperatures. Commercial polyolefin separators have shortcomings of poor electrolyte wettability and severe thermal shrinkage. In addition, polyolefin separators cannot prevent the penetration of lithium dendrites for lithium anodes, resulting in electrochemical performance degradation and potential safety concern for lithium-ion batteries. Herein, a homogeneous suspension containing sepiolite is electrospun onto the surface of a poly(propylene) (PP) substrate to produce a composite separator for high-voltage LiNi0.5Mn1.5O4 batteries. Different from previous research, the PP substrate is modified on single and double sides, respectively. The influence of a single-side coating separator on the cathode and the anode is studied. It is found that the sepiolite electrospinning layer can uniformly distribute the current density and form uniform lithium-ion deposition, which can avoid the growth of lithium dendrites. The different assembly directions of the single-side coating separator show great differences in battery performance. The LiNi0.5Mn1.5O4/Li battery using the single-side coating separator with the sepiolite electrospinning layer facing the Li anode shows better cycling stability (74.4% after 200 cycles at 55 °C), greatly alleviating the capacity fading of LiNi0.5Mn1.5O4 batteries at high temperature. The stable solid electrolyte interphase (SEI) layer on the anode surface plays a predominant role in the cycle life of the battery. The single-side coating separator with the sepiolite electrospinning layer facing the anode is more suitable for high-voltage LiNi0.5Mn1.5O4 batteries.
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高影响因子
MATERIALS SCIENCE FORUM
·
2019
·
IF 0
Ai Jia Wei,Wen Li,Li Hui Zhang,Zhen Fa Liu
Spinel powders of Nd-doped LiNi0.5NdxMn1.5−xO4 with different Nd3+ contents (x = 0, 0.01, and 0.02) have been synthesized by a solid-state ball milling method. The samples was characterized by XRD, SEM and EDS. XRD shows the doping of Nd3+ did not destroy the formation of spinel LNMO.The results show that LiNi0.5Nd0.01Mn1.49O4 sample exhibits a higher rate performance with specific discharge capacities of 134.8, 137.2, 136.5, 130.4, 123.8, 106.4, and 83.1 mAh g−1 at 0.2, 0.5, 1, 2, 3, 5, and 7 C (1 C = 140 mAh g−1), respectively. The results indicate that the Nd3+ doping could reduce the electrode polarization and enhance the rate capacities.
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CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Chunlei Tan,Jing Yang,Qichang Pan,Yan Li,Yu Li,Lisan Cui,Xiaoping Fan,Fenghua Zheng,Hongqiang Wang,Qingyu Li
A series of anhydrides have been used as additives in carbonate-based electrolytes for optimizing the interphase of LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode material to enhance the electrochemical performance of high-voltage (5 V-class) lithium-ion batteries (LIBs). The cyclic stability and rate performance of high-voltage LNMO/Li cells were remarkably enhanced by introducing the anhydride additives into electrolyte. Specifically, the LNMO cathode in the electrolyte with butyric anhydride (BA) additives exhibits high capacity retention of 84.8% after 300 cycles at 1C, and outstanding rate capability of 112 mA h g −1 at 5C. By characterizations, it is rationally demonstrated that the cathode electrolyte interphase (CEI) can be optimized via using different anhydride additives which strongly depend on the molecular structure of anhydride, caused by the electronic and steric hindrance effects during the oxidation process. As a result, the butyric anhydride (BA) derived CEI film exhibits the most suitable microstructure on the LNMO surface, which not only can inhibit the continuous electrolyte decomposition but also facilitate the lithium-ion diffusion coefficient. Moreover, the anhydride can further consume the trace water of electrolyte to stabilize LiPF 6 salt and scavenge the erosive HF. Therefore, such an electrolyte additive presents a potential which practical application in high voltage lithium-ion batteries.
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