Scientific Reports
·
2019
·Vol. 9
·期 1
·1-16
·
IF 4.011
An Fuqiang,Zhao Hongliang,Zhou Weinan,Ma Yonghong,Li Ping
Recently, high-energy density cells containing nickel-rich cathodes and silicon-based anodes have become a practical solution for increasing the driving range of electric vehicles. However, their long-term durability and storage performance is comparatively poor because of the unstable cathode-electrolyte-interphase (CEI) of the high-reactivity cathode and the continuous solid-electrolyte-interphase (SEI) growth. In this work, we study several electrolyte systems consisting of various additives, such as S-containing (1,3,2-dioxathiolane 2,2-dioxide (DTD), DTD + prop-1-ene-1,3-sultone (PES), methylene methanedisulfonate (MMDS)) and Si-containing (tris(trimethylsilyl) phosphate (TTSP) and tris(trimethylsilyl) borate (TMSB)) compounds, in comparison to the baseline electrolyte (BL = 1.0 M LiPF 6 + 3:5:2 w-w:w EC: EMC: DEC + 0.5 wt% lithium difluoro(oxalato)borate (LiDFOB) + 2 wt% lithium bis(fluorosulfonyl)imide (LiFSI) + 2 wt% fluoroethylene carbonate (FEC) + 1 wt% 1,3-propane sultone (PS)). Generally, electrolytes with Si-containing additives, particularly BL + 0.5% TTSP, show a lower impedance increase in the full cell, better beginning-of-life (BOL) performance, less reversible capacity loss through long-term cycles and better storage at elevated temperatures than do electrolytes with S-containing additives. On the contrary, electrolytes with S-containing additives exhibit the advantage of low SEI impedance but yield a worse performance in the full cell than do those with Si-containing additives. The difference between two types of additives is attributed to the distinct function of the electrodes, which is characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS), which was performed on full cells and half cells with fresh and harvested electrodes.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xiaoyan Zhang,Yufei Ren,Juyan Zhang,Xiangkun Wu,Chunhai Yi,Lan Zhang,Suitao Qi
Nickel-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) with respect to Li metal can enhance the energy density of lithium batteries effectively. However, the unstable Li deposition, together with the dissolution and migration of transition metal (TM) ions toward the anode deteriorate the cycle performance of NCM811||Li battery, especially when commercial carbonate electrolyte is used. Herein, tris(trimethylsilyl)phosphite (TMSPi) and fluoroethylene carbonate (FEC) are used to construct a dual-additive electrolyte, by which both electrodes can be protected. It is found that TMSPi can be preferentially adsorbed on the cathode surface through its strong coordination with Ni4+, playing the role as a HF scavenger and suppressing TM ions dissolution, as well as mitigating the structural degradation of the cathode effectively. When it comes to the lithium anode, the presence of TMSPi may lead to side reactions with Li metal, accompanied by fast dendrite growth. The introduction of FEC could facilitate the formation of stable electrode/electrolyte interfaces on both sides. Particularly, reduce the direct contact between TMSPi and Li anode, thus ameliorate the incompatibility issue. Consequently, the NCM811||Li cell with dual-additive demonstrates excellent capacity retention of 81.2% after 500 cycles at 1 C rate. As a sharp contrast, it only retains 13.9% in the one with blank electrolyte. The findings of this work provide a new insight into enhancing the cycle performance of NCM811||Li system via the synergistic effect between additives.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2021
·Vol. 17
·期 52
·2104282
·
IF 13.281
Wei Huang,Wenjin Li,Lve Wang,He Zhu,Min Gao,Huan Zhao,Jinling Zhao,Xueling Shen,Xiaodan Wang,Ze Wang,Chuanlei Qi,Wei Xiao,Lei Yao,Jiantao Wang,Weidong Zhuang,Xueliang Sun
Ni-rich layered oxides are significantly promising cathode materials for commercial high-energy-density lithium-ion batteries. However, their major bottlenecks limiting their widespread applications are capacity fading and safety concerns caused by their inherently unstable crystal structure and highly reactive surface. Herein, surface structure and bulk charge regulation are concurrently achieved by introducing high-valence Ta 5+ ions in Ni-rich cathodes, which exhibit superior electrochemical properties and thermal stability, especially a remarkable cyclic stability with a capacity retention of 80% for up to 768 cycles at a 1C rate versus Li/Li + . Due to the partial Ta enrichment on surface, the regulated surface enables high reversibility of Li + insertion/extraction by preventing surface Ni reduction in deep charging. Moreover, bulk charge regulation that boosts charge density and its localization on oxygen remarkably suppresses microcracks and oxygen loss, which in turn prevents the fragmentation of the regulated surface and structural degradation associated with oxygen skeleton. This study highlights the significance of an integrated optimization strategy for Ni-rich cathodes and, as a case study, provides a novel and deep insights into the underlying mechanisms of high-valence ions substitution of Ni-rich layered cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING
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2018
·Vol. 124
·期 10
·1-7
·
IF 1.604
Xie Tian,Sun Fugen,Zhou Xiaoqing,Liu Li,Liu Zhenyuan,Liu Liekai,Wu Zilong,Yue Zhihao,Zhou Lang,Tang Hao
Material synthesis plays an important role in determining the performance and cost of final devices. In this paper, rheological phase method has been applied to conveniently synthesize carbon-coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 (LNCM622/C) as the cathode material of high-performance lithium-ion batteries (LIBs), avoiding the use of co-precipitation route with complicated procedures and environmental issues. Importantly, the addition of citric acid enabled a relative low temperature of crystallization initiation of the reaction of forming LNCM622/C, which is crucial for the material synthesis. As a result, highly ordered LNCM622/C materials have been obtained with a final calcinating temperature of 900 °C, which is comparable to that being used in co-precipitation route. It is worth mentioning that the synthesis reaction was processed in air without the extra-oxygen gas supply. By varying lithium contents (Li/TM = 0.95, 1.00, 1.05, 1.10, 1.15, and 1.20 by molar, TM = Ni, Co, and Mn), the structure and morphology of resulted LNCM622/C materials were changed, leading to different electrochemical performances of corresponded LIBs. It was found that the Li/TM = 1.15 sample had the best initial discharged capacity at 0.1 °C rate (177.1 mAh g − 1 ), whereas the Li/TM = 1.05 sample showed the best cycling and rate performance (100.6 mAh g − 1 at 1 °C) among synthesized samples. Overall, these results suggest that rheological phase method can be considered as an effective route for synthesizing carbon-coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode materials for 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 Materials Chemistry A
·
2021
·Vol. 9
·期 14
·9354-9363
·
IF 12.732
Zheng Si,Baozhao Shi,Jin Huang,Ye Yu,You Han,Jinli Zhang,Wei Li
Nickel-rich layered oxides (LiNixCoyMn1−x−yO2) (x ≥ 0.8, NCM) are intensively developed cathode materials for lithium-ion batteries owing to their high energy and low price, however, their application is impeded by poor cycle stability. Herein we explored a Ti and F co-doped Li(Ni0.8Co0.1Mn0.1)O2 cathode through a solid phase reaction using the precursors of TiO2 and NH4F. Combining the characterization results of XRD, Ar sputtering assisted XPS, HRTEM, in situ XRD, etc, it is illustrated that Ti4+ and F− co-modification can synergistically modulate the lattice parameter and the Ni2+/Li+ mixing degree for the Li(Ni0.8Co0.1Mn0.1)O2 cathode material. Particularly, density functional theory (DFT) calculations demonstrate that Ti and F co-doping is beneficial to form stable crystal structures with a layered phase and rock-salt phase. Ti4+ and F− co-dopants induce the formation of an ultra-thin rock-salt phase on the cathode surface, which provides a protective layer on the nickel-rich cathode surface, so as to enhance the electrochemical performance. The optimal Ti4+ and F− co-doped sample 0.5Ti@0.5F-NCM shows a superior discharge capacity of 202.2 mA h g−1 at 1C and 45 °C, and a capacity retention of 88.1% after 200 cycles, much higher than the retention of 45.2% for NCM. For 0.5Ti@0.5F-NCM, the lithium-ion diffusion coefficients after the 1st and 100th cycles are 2.67 × 10−11 cm2 s−1 and 7.14 × 10−12 cm2 s−1 respectively, larger than those of the pristine NCM (1.37 × 10−11 cm2 s−1 and 4.52 × 10−12 cm2 s−1). The Ti4+ and F− co-doping can suppress the H2–H3 phase change of the cathode during the charge and discharge process and reduce the charge transfer resistance. The results provide a simple and feasible design strategy via cation@anion dopants to boost the electrochemical performance of nickel-rich cathodes for lithium-ion batteries.
研究领域:
材料科学
·
能源科学
✓ 已验证
DOI
高影响因子
NANO
·
2021
·
IF 1.556
Tianqi Zhou,Canxing Yang,Han Wu,Guodong Jiang,Jian Xiong,Qing Ai,Renzhong Huang,Songdong Yuan
Al 2 O 3 –ZrO 2 was coated on the surface of nickel-rich cathode materials by the sol–gel method to improve its electrochemical performance. The nanometer-thick Al 2 O 3 –ZrO 2 coating layer refrains the side reaction between the electrolyte and the electrode, thus preventing the collapse of LiNi 0 . 8 Co 0 . 1 Mn 0 . 1 O 2 layered structure and protecting the stability of the material. The electrochemical test shows that LiNi 0 . 8 Co 0 . 1 Mn 0 . 1 O 2 coated with Al 2 O 3 –ZrO 2 has good cycle and rate performance. Under the cut-off voltage of 2.8–4.5 V, LiNi 0 . 8 Co 0 . 1 Mn 0 . 1 O 2 coated with Al 2 O 3 –ZrO 2 delivered an initial capacity which was 166.7 mAh g − 1 at 1C (200 mAh g − 1 ) rate, and the capacity retention rate was 77.7% after 200 cycles. The pristine LiNi 0 . 8 Co 0 . 1 Mn 0 . 1 O 2 delivered an initial capacity which was 166.4 mAh g − 1 at 1C rate, and the capacity retention rate was 51.7% after 200 cycles. The EIS and CV provided the enhanced electrochemical performance of LiNi 0 . 8 Co 0 . 1 Mn 0 . 1 O 2 coated with Al 2 O 3 –ZrO 2 which was due to accelerating Li + diffusion of nickel-rich materials and electrolytes.
研究领域:
材料科学
·
电化学
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能源存储
✓ 已验证
DOI
高影响因子
Journal of Cleaner Production
·
2024
·
IF 9.7
Jiaming Li,Youjian Yang,Jiaxin Yang,Shuwei Lan,Zhaowen Wang
Around the world the number of scrapped lithium-ion batteries (LIBs), which are rich in valuable elements worthy of recycling, is increasing. In this study, a method using cryolite-based electrolyte to recycle cathode materials from spent lithium nickel-cobalt-manganese oxide (LNCM) batteries is proposed. Firstly, a molten cryolite-based electrolyte is used to decompose the microstructure of spent LIB cathode material, releasing valuable lithium element into the electrolyte, which can be used in aluminum electrolysis industry. As nickel-cobalt-manganese oxides have low solubilities in the cryolite-based electrolyte, they sink to the bottom of the molten electrolyte, which is then cooled down, forming an upper and lower layer. Lithium element can be quickly and conveniently separated from nickel-cobalt-manganese oxides, which are enriched in the lower layer of the electrolyte. Then, a hydrochloric acid solution is used to leach nickel-cobalt-manganese components from the lower layer of the cryolite-based electrolyte. The effects of acid concentration, liquid-solid ratio, and temperature on the leaching process are investigated through single factor experiments. The highest leaching rates of nickel, cobalt, and manganese elements reach 99.47%, 98.94%, and 98.27%, respectively. By using NaOH + NH 3 ·H 2 O to adjust the pH of the leaching solution, coprecipitation of nickel, cobalt, and manganese elements occur, producing a hydroxide precursor and resulting in recovery rates of over 99%. The recycled hydroxide precursor and new lithium source are then roasted to regenerate an LNCM811 cathode material, which has a layered microstructure and is assembled into a battery. Test results show that the battery has a discharge capacity of 200.8 mAh·g −1 initially and 170.4 mAh·g −1 after 100 cycles.
研究领域:
材料科学
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环境工程
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2020
·
IF 7.098
Xiaoyu Zhao,Minghui Feng,Yaoxin Jiao,Yingbing Zhang,Yanfei Wang,Zuoliang Sha
With the increasing global demand for lithium, lithium extraction from seawater/brine attracted extensive attentions. Selective lithiation desalination battery is a novel and promising model for this process since its good performances on selectivity , extraction capacity and energy consumption. However, multi-metal composition and possible corrosiveness of seawater/brine requires high capacity electrode with high selectivity and cycle stability. To address this issue, this work proposed a less layer graphene gauze modified Ni-rich cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 core-shell structure microsphere (rGO/NCM) with shell thickness of 3 nm. The graphene gauze offers high electron transfer pathways instead of ion transfer between lattices, which reduced the NCM lattice collapse probability effectively. This was verified by ex-situ XRD and electrochemical results of high capacity, good cycle stability and rate performance in both organic and aqueous systems. In the desalination battery composed of rGO/NCM as positive and activated carbon (AC) as negative, rGO/NCM//AC delivered high Li + extraction efficiencies reaching 13.84 mg/g per 1 cycle in simulated brine by consuming only 1.4 Wh/mol Li + . The overall process produced 93% Li + in simulated brine at optimized operating conditions. The results indicated that rGO/NCM//AC desalination battery is a promising electrochemical lithium extraction approach.
研究领域:
材料科学
·
电化学工程
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF ENERGY RESEARCH
·
2020
·Vol. 45
·期 4
·6041-6053
·
IF 3.741
Yanfang Xie,Fuzhong Wu,Xinyi Dai,Yi Mai,Yijing Gu,Huixin Jin,Junqi Li
Summary Nickel-cobalt-manganese ternary cathode materials are known as one of the most promising future cathode materials for Li-ion batteries (LIBs) due to their high discharge capacity, environmental friendliness, and low cost. In this paper, submicron LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) primary particles with good crystallinity and dispersibility have been synthesized combine a coprecipitation method used ethanol as solvent with solid-phase sintering technology. A feeding strategy through separate dropping of sodium carbonate and ammonia is adopted; the structure and properties of NCM523 under different pH conditions are investigated. It is found that the NCM523 synthesized at pH = 8 (NCM523-8) exhibits a uniform particle size of about 300 nm, with good crystallinity. The NCM523-8 exhibits an excellent high-potential cycling performance, with an initial discharge capacity of 193.6 mAh g −1 at 0.2 C in the voltage of 3.0 to 4.5 V, and the capacity retention is 91% after 100 cycles. It also shows excellent rate performance with a reversible capacity of 130 mAh g −1 at 5 C. The superior high-potential electrochemical performance is attributed to the improved lithium-ion diffusion coefficient and stabilized structure by the special structural characteristics as evidenced by cyclic voltammetry, electrochemical impedance spectroscopy, and X-ray diffraction.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Lifan Wang,Danya Gong,Siheng Niu,Leiying Wang,Qinling Shi,Xindong Wang,Jinli Qiao,Guicheng Liu,Chun Zhan
Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP)-based all-solid-state lithium battery (ASSLB) assembled with Ni-rich layered cathode (NCM), of much interest because of its high energy–density and safety, presents many challenges, one of which is poor interfacial instability resulting in large interfacial resistance. Nevertheless, the mechanism of electrochemical side reactions on the interfacial deterioration hasn’t been much investigated specifically, despite their close relationships in electrochemical performance. Herein, we report that the fundamental origin of interfacial chemical reactions is the migration of Ni 2+ from the nickel-rich cathodes to the NCM/LATP interface, for the first time, and the simultaneous chemical reaction with Ti 4+ in LATP, followed by the decomposition of LATP. In view of this, an elaborately designed regulation strategy, in-situ construction of the layered perovskite La 4 NiLiO 8 buffer layer , is proposed to effectively reduce the content of Ni 2+ on the surface of the nickel-rich cathodes and alleviate the chemical reaction between Ni 2+ and Ti 4+ , thereby improving the interfacial stability between NCM and LATP. As a result, the assembled ASSLBs with the La 4 NiLiO 8 buffer layer exhibit high initial discharge capacity (171.49 mAh/g) and excellent cycling performance with 89.47 % capacity retention after 100 cycles at 0.1C.
研究领域:
材料科学
·
电化学
·
能源存储技术
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
·
IF 5.8
Wei Wang,Wenhua Cheng,Zhenjie Liu,Murong Xi,Zhouliang Tan,Yadong Wang,Weilu Zhang,Pingping Chang,Zihan Qi,Huan Zhou,Han Zhang,Juan Ding,Yudai Huang
The commercialization of Ni-rich layered oxide cathode materials has been severely hampered by rapid capacity degradation and safety issues. Here, we demonstrate a lattice reconstruction strategy to improve the structural and thermal stability of LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) via calcium. The enhanced stability of NCM83 is ascribed to the formation of Ca-O bond, which is stronger than TM-O (TM=Ni, Mn, Co) bond. The lattice reconstruction enables metal-O (M-O) bond more stable which mitigates the loss of lattice oxygen, thus improving the reversibility of the H2-H3 phase transition in NCM83. Moreover, Ca 2+ acts as a pillar, facilitating the transport of Li + . The lattice-reconstructed Ni-rich cathode material with 0.5 % Ca can maintain a capacity retention ratio of 97.3 % at 1 C after 150 cycles. As compared with the pristine NCM83 cathode, the high-voltage cycling stability at 4.5 V and high-temperature performance at 55 °C are increased by 17.9 % and 12.2 %, respectively. This work actually proposes a new approach to design and construct high-performance Ni-rich cathode materials for practical lithium-ion batteries.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
Advanced Science
·
2025
·
IF 14.1
Kang Liu,Yuying Zhang,Mengmeng Wang,Xiaohong Zhu,Roya Maboudian,Daniel C.W. Tsang
Impurities are pivotal in determining the quality of the critical metal products derived from spent lithium-ion batteries (LIBs), but there is a lack of understanding of their potential impacts. The mechanisms by which Aluminium (Al) impurities permeate the active crystals of spent ternary nickel─cobalt─manganese oxide (NCM) cathode materials and interact with critical metal sites are elucidated. During frictional contact, the substitution of transition metals by Al impurities disrupts the bonding between critical metals and oxygen, leading to the formation of more stable Al─O covalent bonds. Al can preferentially substitute for Co, altering the local coordination and electronic structure of transition metals. Owing to the strong interaction of Al─O, the Fermi level shifts downward, thus increasing the stabilization of lattice oxygen in the NCM cathode materials and consequently delaying the dissolution of NCM cathode materials. In different extraction environments, the invasion of Al retards the release of lattice oxygen and inhibits the dissolution of NCM in formic acid but enhances those in ammonia solution and shows mixed results in deep eutectic solvents. These crucial findings will help to elucidate the mechanisms of Al impurities in the recycling industry chain of retired LIBs, thereby enhancing the recovery of high-quality critical metal products.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）