ELECTROCHIMICA ACTA
·
2019
·
IF 5.383
Ranran Li,Yanying Liu,Zhen Wang,Jianling Li
Sodium-ion batteries (SIBs) have been considered to be an appealing alternative as alternatives for Lithium-ion batteries (LIBs) on account of abundant resources and low prices. Different cathode materials have been extensively studied, especially layered oxides (P2 or O3). However, it is crucial to design an appropriate cathode material for SIBs with excellent comprehensive performance. Herein, a biphasic cathode material with P2 and O3 structures is successfully synthesized by Sn substitution in Na 0.67 Ni 0.33 Mn 0.67 O 2 , which is clearly proved by the XRD and HRTEM results. And Fullprof program refinement is used to determine the optimal phase ratio of P2 and O3. Besides, the XRD tests at different voltages illustrate that the cathode material has good reversibility and structural stability during charge and discharge. Due to the synergistic effect of P2 and O3 phase, when the phase ratio is about 1:1, the biphasic material P2/O3–Na 0.67 Ni 0.33 Mn 0.57 Sn 0.1 O 2 exhibits the most outstanding electrochemical performance. The P2/O3–Na 0.67 Ni 0.33 Mn 0.57 Sn 0.1 O 2 cathode delivers a high reversible initial capacity of 155.2 mA h g −1 during the voltage range from 2.0V up to 4.3V with an excellent initial Coulombic efficiency of 98.95%, as well as the satisfactory rate performances and cycling performance. GITT testing also demonstrates the D Na+ of biphasic material is more stable and conducive to the diffusion of sodium ions . These results will pave a significant way for designing cathode material for SIBs with different structure by the substitution of transition metal elements.
研究领域:
材料科学
·
能源存储
✓ 已验证
DOI
高影响因子
Materials Today Energy
·
2022
·
IF 9.257
Jingjun Zhai,Haocheng Ji,Wenhai Ji,Rui Wang,Zhongyuan Huang,Tingting Yang,Chaoqi Wang,Taolve Zhang,Ziwei Chen,Wenguang Zhao,Akhil Tayal,Lei Jin,Jun Wang,Yinguo Xiao
Layered transition metal oxides have been broadly studied due to their great potential in application as cathodes for sodium-ion batteries. However, many single-phase layered transition metal oxides, especially those crystallized in P2- or O3-type structure, possess their individual characteristics incurring unsatisfactory overall performances with respect to the reversible capacity, rate capability, and cycling stability. Here, an effective strategy of constructing the P2/O3 biphasic structure is realized in layered cathode Na 0.7 Ni 0.4 Mn 0.4 Ti 0.2 O 2 through Ti substitution. Through high-resolution scanning transmission electron microscopy and X-ray diffraction, the formation of P2/O3 intergrowth structure was clarified and the proportion of the two phases was determined. Benefitting from the presence of intergrowth structure, the layered cathode provides a competitive rate capability of 100 mAh/g at a high rate of 5 C as well as a prominent cycling stability of 80.04% capacity retention after 300 cycles at 5 C. The improved performance is closely related to the highly reversible phase transition process from P2/O3 to OP4/P3 with less strain and enhanced Na + kinetics. These findings evidence that exploring novel multiphase cathodes is an effective approach to improve the electrochemical performances of cathode for sodium-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Physical Chemistry C
·
2016
·
IF 4.509
Zheng-Yao Li,Jicheng Zhang,Rui Gao,Heng Zhang,Lirong Zheng,Zhongbo Hu,Xiangfeng Liu
The effects of Li substitution for Ti on the structure and electrochemical performances of Co-free Na0.67Mn0.55Ni0.25Ti0.2–xLixO2 (x = 0, 0.1, 0.2) layered cathode materials for sodium ion batteries have been comprehensively investigated. X-ray diffraction and Rietveld refinement results demonstrate that Li mainly occupies TM (TM = transition metal) sites in the crystal structure to maintain the P2 structure majority and a small amount of Li atoms enter Na sites to generate some O3 phase. The discharge voltage, reversible capacity, rate capability, cycling performance, and Coulombic efficiency all have been improved by Li substitution, which can be largely attributed to the integration of P2 and O3. Li substitution also raises the average discharge voltage from 2.6 to 3.1 V. Na0.67Mn0.55Ni0.25Li0.2O2 (L02) can deliver an initial capacity of about 158 mA h g–1 at 0.05C (12 mA g–1) in comparison with the Li-free sample (147 mA h g–1). Even at the high rates of 480 (2C), 1200 (5C), and 1920 (8C) mA g–1, L02 can also display ca. 93, 65, and 38 mA h g–1 discharge capacities, respectively. The rate capability is higher than what is reported in the previous Li-substituted cathode materials. In addition, Li substitution in transition-metal sites generates more defects to maintain the charge neutrality, which enhances the electronic conductivity and also has a positive effect on the Na ion diffusion coefficient. The electronic conductivity and Na ion diffusion coefficient have been enhanced by 122% and 29%, respectively, with the substitution of Li for Ti. Our results also show that the oxidation peaks become sharper with increasing Li content, which indicates the feasibility of Na ion intercalation/deintercalation in the integrated P2/O3 phase. This study also offers some new insights into designing high-performance cathode materials for sodium ion batteries.
研究领域:
材料科学
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Ping Zhang,Guohua Zhang,Yukun Liu,Yuxin Fan,Xinyue Shi,Yiming Dai,Shiwen Gong,Jingrong Hou,Jiwei Ma,Yunhui Huang,Renyuan Zhang
Fe/Mn-based layered oxide cathode is regarded as a competitive candidate for sodium-ion batteries (SIBs) because of its high theoretical capacity, earth abundance and low cost. However, its poor cycling stability still remains a major bottleneck. Herein, P 2/O3 biphasic Na 0.67 Fe 0.425 Mn 0.425 Cu 0.15 O 2 layered oxide is successfully synthesized via a sol–gel method. It is observed that Cu substitution can facilitate the conversion of P 2 to O3 phase, and the P 2/O3 composite structure can be obtained with an appropriate amount of Cu. Meanwhile, in-situ XRD reveals that constructing P 2/O3 composite structure can realize the highly reversible phase transition process of P 2/O3– P 2/ P 3–OP4/OP2 and decrease the lattice mismatch during Na + insertion/extraction. Consequently, the biphasic P 2/O3-Na 0.67 Fe 0.425 Mn 0.425 Cu 0.15 O 2 electrode exhibits 87.1 % capacity retention after 100 cycles at 1C, while the single phase P 2-Na 0.67 Fe 0.5 Mn 0.5 O 2 electrode has only 36.4 %. Therefore, the constructing biphasic structure is proved to be an effective strategy for designing high-performance Fe/Mn-based layered oxide cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Bei Hu,Fushan Geng,Chong Zhao,Bertrand Doumert,Julien Trébosc,Olivier Lafon,Chao Li,Ming Shen,Bingwen Hu
The layered Mn-based oxides (NaxMnO2), which is one of the most promising cathode families for rechargeable sodium-ion batteries, have received considerable attention because of their tunable electrochemical performances and low costs. Herein, a novel P2/O3 intergrown Li-containing Na0.8Li0.27Mn0.68Ti0.05O2 cathode material prepared by Ti-substitution into Mn-site is reported. Benefiting from the synergistic effects of the biphasic composite structure and inactive d0 element substitution, this P2/O3 electrode exhibits high initial charge/discharge capacity and excellent cycling performance. The combination of different characterization techniques including solid-state NMR, electron paramagnetic resonance, X-ray adsorption spectroscopy, and high-resolution transmission electron microscopy gives insights into the local electronic environment, the redox chemistry, and also the microstructure rigidity of these cathode materials upon cycling. On the basis of comprehensive comparison with the Ti-free P2/O3-Na0.8Li0.27Mn0.73O2, the observed improvement on the electrochemical performance is primarily attributed to the mitigation of notorious Mn3+/Mn4+ redox and the enhanced stability of the oxygen charge compensation behavior. From the viewpoint of structure evolution, Ti-substitution restrains the Li+ loss and irreversible structural degradation during cycling. This study provides an in-depth understanding of the electronic and crystal structure evolutions after inactive d0 element substitution and may shed light on the rational design of high-performance P2/O3 biphasic Mn-based layered cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Jiatai Wang,Yan Tan,Xi Wen,Hongyun Liu,Chao Fan,Yibo Zhang,Yuan Xu,Xingyu Zhao,Mengting Li,Jian Li,Jingfu Hu
Sodium-ion batteries (SIBs) have emerge as promising alternatives to lithium-ion batteries (LIBs), attributed to their abundant sodium resources and economical pricing. Among various cathode materials , P2 and O3-type layered oxides have garnered significant attention for their superior electrochemical properties . In this study, NaNi 0.5 Mn 0.45 Mg 0.05 O 2 (P2/O3-NMM) cathode material was effectively synthesized using a homogeneous coprecipitation technique with di-n-butylamine as the precipitating agent. The findings indicate that the P2/O3-NMM cathode material synthesized at 850 ℃ for 16 h exhibits a capacity retention of 62.33 % after 200 cycles at a current density of 1 C. The results indicate the biphasic synergy of P2/O3 integrates the rapid Na + migration of the P2 phase with the high capacity of the O3 phase, substantially improving cathode electrochemical performance . This work provides an effective strategy for developing biphase cathodes in SIBs.
✓ 已验证
产品关联
DOI
高影响因子
SOLID STATE IONICS
·
2025
·
IF 3.3
Xuelei Li,Wei Da,Zhihui Xu,Qingwen Li,Huirong Liu,Kai Lv,Aruuhan Bayaguud
Sodium ion batteries (SIBs) have shown broad application prospects in the field of energy storage due to their low cost, high safety, wide operating temperature range, fast charging, and environmental friendliness. As one of the key components of SIBs, layered oxide cathodes have significant advantages such as high specific capacity, feasible energy density, and high operating voltage, but they also face challenges of poor interface stability and insufficient air stability. In this work, a P2/O3 biphasic system Na 0.67 Ni 0.33 Fe 0.33 Mn 0.33 O 2 (Na0.67NFM) is synthesized by a sol-gel and subsequent solid phase calcination method. Furthermore, the structural characteristics of Na0.67NFM calcined at 900 °C (Na0.67NFM-900) are investigated, revealing that it maintains a high stability even after exposure in humid ambient air for 5 days. Although a small amount of Na 2 CO 3 and NaHCO 3 is produced on the surface of Na0.67NFM-900, the main P2/O3 structure still maintains overall integrity into the internal bulk phase. Therefore, the electrochemical performance of Na0.67NFM cathode is not significantly affected after short-term air exposure. After 200 cycles at 1C, the capacity retention of Na0.67NFM-900 cathode still remains 72.3 %, which is almost comparable to that of the unexposed one (75.7 %). This work indicates that Na0.67NFM is a promising candidate cathode material with exceptional air stability for SIBs.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Xu Zhu,Haojie Dong,Yifeng Liu,Yi-Hu Feng,Yongwei Tang,Lianzheng Yu,Shao-Wen Xu,Guang-Xu Wei,Shuai Sun,Mengting Liu,Bing Xiao,Rong Xu,Yao Xiao,Shulei Chou,Peng-Fei Wang
Sodium-ion batteries (SIBs) have captured widespread attention for grid-scale energy storage owing to the wide distribution and low cost of sodium resources. Delivery of high energy density with stable retention remains a challenge in developing cathode candidates for rechargeable SIBs. Inspired by the concept of “cationic potential”, here, we present a hierarchical crystalline domain in hexagonal particles with target chemical composition (Na0.8Li0.03Mg0.05Ni0.28Fe0.05Mn0.54Ti0.05O2) from the inner bulk O3 phase (71.1 wt %) to the outer P2-type shell (28.9 wt %) of the structure. Benefiting from the mitigated mechanical stress of the predominant bulk O3 phase under the protection of the surficial P2 crystalline domain at the microscale during Na+ (de)intercalation, the brittle fracture, plastic yielding, and structural damage of the bulk O3 phase are effectively prohibited during battery cycling, thereby achieving good structural integrity. As a consequence, the biphasic P2/O3–Na0.8Li0.03Mg0.05Ni0.28Fe0.05Mn0.54Ti0.05O2 material exhibits satisfactory electrochemical properties, with a high energy density of 506 Wh kg–1 and good capacity retention of 85.5% over 200 cycles. This work highlights the importance of tailoring the crystalline domain to mitigate the reaction-induced stress and particle fracture of layered biphasic cathode materials for high-energy SIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2024
·
IF 5.9
Yixuan Zhang,Guo-Qiang Liu,Chang Su,Danlei Qiao,Xiaojing Xu,Jiaguan Chen,Guang-Yin Liu,Qiang Sun,Lei Wen
Layered oxides are the widely investigated cathodes for sodium-ion batteries (SIBs), especially their pure phases (e.g., P2, O3). In this work, we report a series of Mn-Ni-Fe based cathode materials with P2/O3 bi-phase, which possesses advantages of both P2 and O3 structures. At first, the manuscript shows a synthesis phase diagram of Na 0.83 Mn x Ni y Fe 1-x-y O 2 to pre-screen and select the P2/O3 bi-phase material Na 0.83 Mn 1/2 Ni 1/3 Fe 1/6 O 2 . Then, it is found that the cationic ratio has a significant impact on the phase formation. The structure of the materials gradually changes with the various of the Mn/Ni ratio. When the Mn/Ni ratio reaches 3/2, P2/O3 bi-phase is formed. Moreover, Fe content will influence the P2/O3 ratio in the bi-phase material. In particular, the synthesized bi-phase Na 0.83 Mn 3/6 Ni 2/6 Fe 1/6 O 2 has a P2/O3 ratio of 71/29 wt%. It delivers a high specific capacity of 136.6 mA h g −1 (at current density 20 mA g −1 ) between 2.0 and 4.0 V and 94.8% retention (at current density 100 mA g −1 ) after 100 cycles. In addition, an 85.6 mA h g −1 discharge capacity can be maintained at a superior high current density of 2000 mA g −1 . The work offers critical guidance to the rational design of the bi-phase layered cathode materials.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2023
·
IF 20.4
Pengfei Zhou,Zhennan Che,Jing Liu,Jingkai Zhou,Xiaozhong Wu,Junying Weng,Jinping Zhao,Heng Cao,Jin Zhou,Fangyi Cheng
Layered sodium manganese-based oxides are highly attractive cathode materials for sodium-ion batteries but suffer from limited initial coulombic efficiency (ICE) and poor structural stability. Herein, a high-entropy biphasic Na 0.7 Mn 0.4 Ni 0.3 Cu 0.1 Fe 0.1 Ti 0.1 O 1.95 F 0.1 cathode material is reported to exhibit remarkable ICE, rate capability and cyclability. In-situ structural analysis during the preparation of cathode reveals tunable P2/O3 ratios by changing the sintering temperature. The synthesized high-entropy oxide with a P2/O3 ratio of 23:77 (wt%) delivers a high ICE of 97.6%, a considerable discharge capacity of 86.7 mAh g −1 at current density of 800 mA g −1 , and respectable capacity retention in a wide temperature range from -40 to 50 °C. Additionally, full cell coupling Na 0.7 Mn 0.4 Ni 0.3 Cu 0.1 Fe 0.1 Ti 0.1 O 1.95 F 0.1 and hard carbon exhibits an energy density of 268.3 Wh kg −1 at power density of 1172 W Kg −1 based on the mass of cathode. Combined experimental and computational investigations suggest that the as-prepared Na 0.7 Mn 0.4 Ni 0.3 Cu 0.1 Fe 0.1 Ti 0.1 O 1.95 F 0.1 cathode favors reversible structural evolution, fast Na + diffusion kinetics, and low energy barriers due to the unique P2/O3 biphasic structure and high-entropy effect. This study brings an in-depth insight into the design and preparation of high-entropy P2/O3 biphasic cathode to build advanced sodium-ion batteries.
研究领域:
材料科学
·
储能技术
·
电化学
·
无机化学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·Vol. 35
·期 46
·2509099
·
IF 19
Yichen He,Yonglin Huo,Maowen Xu,Yuruo Qi
Layered cathode materials for sodium ion batteries (SIBs) have garnered significant attention due to their high theoretical capacity and tunable crystal structure. However, they still confront severe structural attenuation at high voltages, especially those undergoing anionic redox reactions. To mitigate these limitations and elucidate the underlying mechanism, herein, a biphasic cathode material, Na 0.67 Fe 0.3 Mn 0.5 Li 0.1 Mg 0.1 O 2 , comprising 76.6% P2 and 23.4% O3 phases is proposed. The “Na─O─Mg” structure with robust Mg─O bonds enhances oxygen redox activity but also suppresses lattice oxygen evolution at elevated voltages, enabling a high initial discharge capacity of 187.8 mA h g⁻¹ at 0.1C. Moreover, the biphasic structure suppresses O/P structural rearrangement and mitigates harmful phase changes via forming OP2 phase at high-voltage, resulting in excellent cycling stability with a capacity retention of 96.6% after 100 cycles at 1C within an extended voltage window of 1.8–4.3 V. These findings deepen the understanding in the interlocking effect of biphasic materials and offer valuable insights for designing high-performance cathode materials.
研究领域:
材料科学
·
电化学
·
能量存储
·
电池技术
✓ 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）