CHEMISTRY-A EUROPEAN JOURNAL
·
2024
·Vol. 30
·期 25
·e202400088
·
IF 3.9
Xin Li,Xin Lai,Qingquan Kong,Xuguang An,Jing Zhan,Xiaolei Li,Xiaonan Liu,Weitang Yao
P2-type layered manganese-based oxides have attracted considerable interest as economical, cathode materials with high energy density for sodium-ion batteries (SIBs). Despite their potential, these materials still face challenges related to sluggish kinetics and structural instability. In this study, a composite cathode material, Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @Na 3 V 2 O 2 (PO 4 ) 2 F was developed by surface-coating P2-type Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 with a thin layer of Na 3 V 2 O 2 (PO 4 ) 2 F to enhance both the electrochemical sodium storage and material air stability. The optimized Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @5wt %Na 3 V 2 O 2 (PO 4 ) 2 F exhibited a high discharge capacity of 176 mA h g −1 within the 1.5-4.1 V range at a low current density of 17 mA g −1 . At an increased current density of 850 mA g −1 within the same voltage window, it still delivered a substantial initial discharge capacity of 112 mAh g −1 . These findings validate the significant enhancement of ion diffusion capabilities and rate performance in the P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 material conferred by the composite cathode. Graphical We propose a composite cathode material, Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @Na 3 V 2 O 2 (PO 4 ) 2 F, featuring synergistic modification through doping and coating. The optimized Na 0.67 Ni 0.23 Mn 0.67 V 0.1 O 2 @5wt %Na 3 V 2 O 2 (PO 4 ) 2 F exhibited a high discharge capacity of 176 mAh g −1 within the 1.5–4.1 V range at a low current density of 17 mA g −1 . At an increased current density of 850 mA g −1 within the same voltage window, it still delivered a substantial initial discharge capacity of 112 mAh g −1 .
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
固体化学
✓ 已验证
DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2023
·
IF 6.1
Danlei Qiao,Yixuan Zhang,Chang Su,Guoqiang Liu,Qingxiang Wang,Lei Wen
Al-doped Fe-Mn and Ni-Mn based materials with P2-type layered structure has been synthesized and tested as a positive electrode material for rechargeable sodium batteries. The modification mechanisms of Al doping in Fe-Mn and Ni-Mn based materials have been discussed. The synthesized Al-doped Ni-Mn based material Na 0.67 Mn 0.8 Ni 0.16 Al 0.04 O 2 delivers a reversible capacity of 135.1 mAh g −1 , which corresponds to 92.1% of the initial capacity with excellent cyclability for 200 cycles. What’s more, it can still remain a capacity of 96.2 mAh g −1 at a current density of 2000 mA g −1 . When the voltage range increase to 1.5 – 4.3 V, its initial discharge capacity can reach 190.3 mAh g −1 .
研究领域:
材料科学
·
电化学
·
能量存储
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2023
·
IF 13.1
Yiran Sun,Pengfei Zhou,Siyu Liu,Zhongjun Zhao,Yihao Pan,Xiangyan Shen,Xiaozhong Wu,Jinping Zhao,Junying Weng,Jin Zhou
P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) is promising cathode material for sodium-ion batteries (SIBs) due to its high specific capacity and fast Na + diffusion rate. Nonetheless, the irreversible P2-O2 phase transformation, Na + /vacancy ordering, and transition metal (TM) dissolution seriously damage its cycling stability and restrict its commercialization process. Herein, Na occupation manipulation and interface stabilization are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and introducing lithium difluorophosp (LiPO 2 F 2 ) film-forming electrolyte additive . The Zn/Ti co-doping regulates the occupancy ratio of Na e /Na f at Na sites and disorganizes the Na + /vacancy ordering, resulting in a faster Na + diffusion kinetics and reversible P2-Z phase transition for P2-Na 0.67 Ni 0.28 Zn 0.05 Mn 0.62 Ti 0.05 O 2 (NNZMTO). Meanwhile, the LiPO 2 F 2 additive can form homogeneous and ultrathin cathode-electrolyte interphase (CEI) on NNZMTO surface, which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution, surface structure transformation, and micro-crack generation. Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mechanism of NNZMTO with LiPO 2 F 2 additive. As a result, the NNZMTO displays outstanding capacity retention of 94.44% after 500 cycles at 1C with 0.3 wt% LiPO 2 F 2 , excellent rate performance of 92.5 mA h g −1 at 8C with 0.1 wt% LiPO 2 F 2 , and remarkable full cell capability. This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials, which provides a promising direction for developing high-performance cathodes for SIBs.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
固态化学
·
电池技术
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Yu Duan,Zihan Ma,Jiaxuan He,Yingying Huang,Shuo Bao,Jinlin Lu
P2-type layered cathode materials have low energy density due to low initial Na content. In this research, high sodium content P2-type cathode material Na0.8Li0.08Ni0.23Mn0.67Cu0.1O1.92F0.08 (NMC-LF), was synthesized by a simple high-temperature solid-phase method. The strong electronegativity of F allows the local TM-O bond to be transformed into a TM-F bond, and the TMO6 octahedron becomes more stable. The doping of Li+ not only maintains structural stability but also transforms the two-phase reaction in the high-voltage range into a solid-solution reaction. This leads to an effective suppression of the irreversible P2–O2 phase transition in the high-voltage region. At 20 mA·g–1, the initial discharge capacity of NMC-LF reaches 131.05 mAh·g–1. At a high current density of 200 mA·g–1, the discharge capacity reaches 101.9 mAh·g–1 and remains at 99.31% after 150 cycles. The diffusion coefficient of NMC-LF is as high as 8.67 × 10–13 cm2·s–1. Furthermore, the structural evolution during material formation is elaborated by high-temperature XRD, and it is determined that there are no impurities at 900 °C. Under the joint synergy of Li/F/Cu and the design of high sodium content, the long-cyclic and high-rate performance has been significantly improved. In-situ XRD tests show that Li/F/Cu codoping inhibits the P2–O2 phase transition and enhances structural reversibility. This provides a new idea for the research of layered cathode materials.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2017
·
IF 6.395
Wei-Lin Pang,Xiao-Hua Zhang,Jin-Zhi Guo,Jin-Yue Li,Xin Yan,Bao-Hua Hou,Hong-Yu Guan,Xing-Long Wu
Recently, sodium-ion batteries (SIBs) have been considered as the promising alternative for lithium-ion batteries. Although layered P2-type transition metal oxides are an important class of cathode materials for SIBs, there are still some hurdles for the practical applications, including low specific capacity as well as poor cycling and rate properties. In this study, the electrochemical properties of layered Mn-based oxides have been effectively improved via Al doping, which cannot only promote the formation of layered P2-type structure in the preparation processes but also stabilize the lattice during the successive Na-intercalation/deintercalation due to suppression of the Jahn-Teller distortion of Mn 3+ . Among the as-prepared series of Na 2/3 Mn 1- x Al x O 2 ( x = 0, 1/18, 1/9, and 2/9), Na 2/3 Mn 8/9 Al 1/9 O 2 with x = 1/9 exhibits the optimal doping effect with the best electrochemical properties, in terms of the highest specific capacity of 162.3 mA h g −1 at 0.1 C, the highest rate capability, and the best cycling stability in comparison to the undoped Na 2/3 MnO 2 and the other two materials with different Al-doped contents. Both cyclic voltammetry at varied scan rates and galvanostatic intermittent titration technique disclose the optimal electrode kinetics (the highest Na-diffusion coefficient) of the best Na 2/3 Mn 8/9 Al 1/9 O 2 .
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
Journal of Energy Chemistry
·
2021
·
IF 9.676
Pengfei Zhou,Jing Zhang,Zhennan Che,Zuhao Quan,Ju Duan,Xiaozhong Wu,Junying Weng,Jinping Zhao,Jin Zhou
P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 is considered as a promising cathode material for sodium-ion battery (SIBs) because of its high capacity and discharge potential. However, its practical use is limited by Na + /vacancy ordering and P2-O2 phase transition. Herein, a Ti 4+ /F − co-doping strategy is developed to address these issues. The optimal P2-Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 1.9 F 0.1 exhibits much enhanced sodium storage performance in the high voltage range of 2.0–4.4 V, including a cycling stability of 77.2% over 300 cycles at a rate of 2 C and a high-rate capability of 87.7 mAh g −1 at 6 C. Moreover, the P2-Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 1.9 F 0.1 delivers reversible capacities of 82.7 and 128.1 mAh g −1 at −10 and 50 °C at a rate of 2 C, respectively. The capacity retentions over 200 cycles at −10 °C is 94.2%, implying more opportunity for practical application. In-situ X-ray diffraction analysis reveals that both P2-O2 phase transitions and Na + /vacancy ordering is suppressed by Ti 4+ /F − co-doping, which resulting in fast Na + diffusion and stable phase structure. The hard carbon//P2-Na 0.67 Ni 0.33 Mn 0.37 Ti 0.3 O 1.9 F 0.1 full cell exhibits a high energy density of 310.2 Wh kg −1 and remarkable cyclability with 82.1% retention after 300 cycles at 1 C in the voltage range of 1.5–4.2 V. These results demonstrate that the co-doping Ti 4+ /F − is a promising strategy to improve the electrochemical properties of P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 , providing a facile tactic to develop high performance cathode materials for SIBs.
研究领域:
材料科学
·
电化学
·
能源存储
·
无机化学
·
固态化学
·
电池技术
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Cao Jiang,Biao Chen,Maowen Xu,Jian Jiang
The single ionic doping helps suppress the detrimental phase transition when P2-type layered cathodes are charged to a high voltage above 4.0 V ( vs. Na + /Na). However, this is realized at the sacrifice of their electrochemical redox centers and output capacities. To achieve both high voltage tolerance and capacity, we herein propose a cooperative Al cation and F anion co-doping strategy. The XANES detections affirm that substituting Ni/O with Al/F intends to augment the amount of highly active Mn 3+ cations in cathodes, making more contributions on specific capacities for sodium-ion batteries (SIBs). Besides, this co-doping treatment would disorder the transition metal ionic arrangements of cathodes, disrupting long-range Jahn-Teller effects and impeding other undesired phases generation. As a proof-of-concept demonstration, our designed Na 2/3 Ni 0.23 Al 0.1 Mn 2/3 O 1.95 F 0.05 (NAF) cathodes show a delivered capacity as high as 142.0 mAh g −1 (0.2C), and an impressive capacity retention of 86.7 % after all cycling. The in-situ XRD detections reveal no apparent O2 phase peaks emerge until 4.23 V upon deep Na + extraction from NAF. This work provides a key understanding toward cation/anion co-doping effects, opening up a useful avenue for rational design of practical P2-type cathodes for SIBs.
研究领域:
电化学储能
·
材料科学
·
固态化学
·
能源材料
·
电池技术
✓ 已验证
DOI
高影响因子
TRANSACTIONS OF TIANJIN UNIVERSITY
·
2025
·Vol. 31
·期 3
·278-291
·
IF 8.5
Chi Shuxiu,Wang Chenhui,Liao Jie,Sun Peng,Fei Yaohan,Han You,Zhang Jinli,Wu Jiangjiexing,Li Wei
Aiming at inhibiting the irreversible P2–O2 phase transition of conventional P2-type cathode materials at high voltage and enhancing the cycling stability of sodium-ion batteries, in this article, based on a strategy of adjusting the Na + ion occupancy within the crystal structure, Na 0.67 Ni 0.33 Mn 0.67– x Fe x O 2 (NM– x Fe, x = 0.10, 0.15, 0.20) cathode materials were synthesized by high shear mixer (HSM)-assisted co-precipitation method and evaluated the electrochemical performance at high voltage (4.35 V). The optimal sample NM–0.15Fe exhibits an initial discharge capacity of 130.8 mAh/g (0.1 C), with exceptional retention of 95.9% after 100 cycles (1 C). XRD analysis reveals that Fe intercalation promotes the more amount of Nae-similar occupation; the Nae/Naf ratio equals 1.93 for NM–0.15Fe versus 1.62 for NM, which enhances Na + diffusion kinetics, as confirmed by GITT tests. Through characterizations of in situ XRD, XPS, HRTEM, CV, etc., it is illustrated that the Fe 3+ intercalation can effectively disrupt the Na + /vacancy ordering and inhibit the harmful P2–O2 phase transition, and then improve the cycling stability of the cathode. DFT calculations disclose that intercalated Fe can reduce the electron densities of adjacent transition metallic elements, generating more repulsive forces impacted on sodium and consequently appearance of more Nae sites, leading to a lower Na + diffusion energy barrier. Such strategy of modulating Na occupation sites in crystal structure is conducive to the development of low-cost and high-performance layered cathode materials for sodium-ion batteries.
研究领域:
电化学储能
·
材料科学
·
固态化学
·
能源材料
·
电池技术
·
过渡金属氧化物
✓ 已验证
产品关联
DOI
高影响因子
Energy Storage Materials
·
2021
·
IF 17.789
Dongxiao Wang,Shuyin Xu,Jianlin Wang,Xiaohui Rong,Feiyu Zhou,Lifen Wang,Xuedong Bai,Bingan Lu,Chengjun Zhu,Yuesheng Wang,Yong-sheng Hu
Room-temperature Na-ion batteries have attracted great interest for over a decade owing to their natural abundance and similar intercalation chemistry with Li-ion. However, due to the uncontrolled decomposition of electrolyte and formation of solid electrolyte interphase, the large majority of sodium anode materials exhibit extremely low initial Coulombic efficiency and unsatisfactory cycling stability. Here we introduce a novel layered material, P2-Na 0.547 [M g 0.25 M n 0.75 ]O 2 , as an SEI-free negative electrode. This material, delivers a reversible capacity of 126 mAh g −1 with a high initial Coulombic efficiency of 108%, and capacity retention of ∼80% after 1000 cycles at 4C rate. Pairing with Na 3 V 2 (PO 4 ) 3 cathode, excellent rate performance of ∼60% capability at 15C, and extra-high initial Coulombic efficiency of 97% are achieved, all attributed to the SEI-free feature of Na 0.547 [M g 0.25 M n 0.75 ]O 2 . These results demonstrate the practical potential of our SEI-free anode material for high-power and long-life Na-ion batteries.
研究领域:
储能
·
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2019
·
IF 4.175
Wei-Lin Pang,Jin-Zhi Guo,Xiao-Hua Zhang,Chao-Ying Fan,Xue-Jiao Nie,Hai-Yue Yu,Wen-Hao Li,Qiong Yang,Xing-Long Wu
Sodium-ion batteries (SIBs) have been considered as one of foremost promising alternatives for the widely used lithium-ion batteries. In order to assemble high-performance SIBs, cathode materials with stable structure and superior electrochemical properties are needed emphatically. In this work, we prepare a new layered oxide material, P2-type Na 2/3 Mn 1/2 Co 1/3 Cu 1/6 O 2 (P2-MCC) with the morphology of hexagonal micro-prisms, by a sol-gel method. When used as cathode material for SIBs, the P2-MCC exhibits good cycling stability ( e.g. , >83.5% capacity retention after 100 cycles at 100 mA g −1 ) and superior high-rate performance. Moreover, it also owns an attractive ability of fast-charging, e.g. , a high capacity retention of ∼66% after 100 cycles as charging at a high current density of 200 mA g −1 and discharging at a low current density of 10 mA g −1 . Such good electrochemical properties can be originated from the synergetic improvement of selected multi-metallic ions and enhanced electrode kinetics (high apparent Na-diffusion kinetics) which is demonstrated by the galvanostatic intermittent titration technique, electrochemical impedance spectroscopy and cyclic voltammetry at various scan rates.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2019
·Vol. 54
·期 7
·5584-5594
·
IF 3.442
Lv Tingjian,Guan Li,Xiao Peng,Zhang Dongyun,Chang Chengkang
In this work, we report the preparation and the enhanced electrochemical performance of P2-type Na 0.67 Li x (Mn 0.5 Fe 0.25 Co 0.25 ) 1− x O 2 layered cathode materials with different Li substitutions via a nanomilling-assisted solid-state method. The experimental results show that the introduced lithium ions can greatly improve the performance of the material after entering the transition metal layer. Among these synthesized samples, the Na 0.67 Li 0.03 (Mn 0.5 Fe 0.25 Co 0.25 ) 0.97 O 2 electrode exhibits an exceptionally high specific capacity of 190.6 mAh g −1 at 0.1 C rate and a capacity retention of 89.5% after 30 cycles. Obviously, the specific capacity retention is improved by 15.3% compared with the pristine Na 0.67 (Mn 0.5 Fe 0.25 Co 0.25 )O 2 without Li incorporation (the specific capacity retention is only 74.2% after 30 cycles). Simultaneously, the sample also shows a large increase in rate performance compared to the pristine material. All of the enhancement can be explained by the fact that the introduced Li ions suppress the phase transition during the charge–discharge process and avoid the volume expansion of the electrode, which significantly reduce the occurrence of micro-cracks within the electrode. The reduced polarization, the decreased internal resistance of the prepared electrodes and the increased sodium ion diffusion coefficient, as confirmed from the CV and EIS measurements, can be regarded as the three major reasons for the enhanced electrochemical performance of the Li ion-substituted materials.
研究领域:
材料科学
·
电化学
·
储能技术
·
固态化学
·
纳米技术
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Pengju Zhang,Jinglin Mu,Mingyu Xie,Tianyu Xue,Minghui Ding,Zhen Zhou,Junying Weng,Pengfei Zhou
Activating anionic redox reactions (ARR) in P2-type layered oxide cathodes has drawn great attention as a promising strategy to break through the bottleneck of their energy density limit. However, irreversible lattice oxygen loss and detrimental structure distortion associated with ARR are still challenges, resulting in severe capacity fading and sluggish reaction kinetics. Herein, we designed a novel P2-Na 0.67 Li 0.15 Mg 0.1 Mn 0.75 O 2 (NLMOMg0.1) sphere as a cathode for sodium-ion batteries (SIBs), leveraging the synergistic effect of Li/Mg co-doping and a LiPO 2 F 2 film-forming additive to enhance the reversibility and reaction kinetics of ARR. The Li/Mg co-doping effectively activates ARR and reduces the Mn 3+ ratio, weakening the Jahn-Teller effect and and minimizing structure distortion. The LiPO 2 F 2 film-forming additive in the electrolyte can form a stable cathode-electrolyte interphase film on the surface of NLMOMg0.1, significantly suppressing side reactions between the electrode and electrolyte and thereby preventing irreversible lattice oxygen loss. Impressively, NLMOMg0.1 with 0.2 wt% LiPO 2 F 2 additive attains a high capacity of 159.1mAh g −1 and an outstanding retention rate of 97.1 % at 0.5C after 300 cycles. In-situ X-ray diffraction (XRD) experiments confirm the excellent structural stability, and in-situ differential electrochemical mass spectrometry (DEMS) and in-situ optical microscope tests demonstrate the inhibition of lattice oxygen loss during the cycling process. This study provides practical guidelines for designing layered oxide cathode materials for SIBs with high stability and dynamics.
研究领域:
材料科学
·
电化学
·
储能技术
·
纳米技术
✓ 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）