IONICS
·
2020
·Vol. 27
·期 2
·657-666
·
IF 2.394
Hu Guorong,Liu Yanhua,Li Wei,Peng Zhongdong,Wu Jiahui,Xue Zhichen,Shi You,Fan Ju,Sun Qian,Cao Yanbing,Du Ke
P2-type Na 0.67 Ni 0.25 Mn 0.75 O 2 is considered as one of the most promising cathode materials for sodium-ion batteries due to its high initial capacity and operating voltage based on the Ni 2+ /Ni 4+ redox reaction. However, it suffers from rapid capacity decay caused by P2–O2 phase transition when the cutoff voltage is above 4.2 V (vs. Na + /Na). Herein, a high-voltage phase transition from P2 to an amorphous phase with poor crystallinity has been proved to be the main cause of material deterioration and Mn redox process is another cause. Cu-substituted Na 0.67 (Ni 0.25 Mn 0.75 ) 1−x Cu x O 2 ( x = 0, 0.05, 0.1, 0.2) with active redox couples of Ni 2+ /Ni 4+ and Cu 2+ /Cu 3+ has been fabricated for solving these issues. It is proved that Cu substitution can reduce the Mn 3+ /Mn 4+ reaction below 3 V (vs. Na + /Na) and suppress the high-voltage phase transition effectively at deep de-sodiated state, resulting in the significantly enhanced cycle life and rate capability of Na 0.67 Ni 0.25 Mn 0.75 O 2 .
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Rui Huang,Shaohua Luo,Pengyu Li,Qi Sun,Guodong Hao,Jie Feng,Lixiong Qian,Shengxue Yan,Jing Guo
Mn-rich ternary cathodes are highly regarded as a potential option for sodium-ion batteries (SIBs) due to their low cost and high theoretical capacity. Nonetheless, cycling stability was hindered by the occurrence of high-voltage phase transitions. In this work, Na0.67(Ni0.1Mn0.8Fe0.1)1–xMgxO2 (NaNMF-Mgx) cathode materials with high-voltage zero-phase transitions property were successfully synthesized. Amazingly, it was found that there was a valuable strengthening in the occupancy of stabler Nae sites by employing the Mg-doping strategy; and the calculation highlighted excellent structural stability and conductivity of NaNMF-Mg0.04, which has the lowest thermodynamic formation energy and a narrow band gap. The combination of theory and experiment demonstrated the underlying mechanisms of Mg substitution. Especially, Mg doping had the potential to regulate Nae/Naf ratio, and the ratio of NaNMF-Mg0.04 reached the maximum, indicating its most remarkable “rich-Nae” effect. Moreover, ex-situ XRD and ADF-STEM certified that NaNMF-Mg0.04 cathode maintained an intact P2 phase structure during high-voltage charging process. The “rich-Nae” and “zero-phase transitions” effects enabled NaNMF-Mg0.04 cathode to express remarkable initial capacitance (119.5 mAh g–1, 0.1 C), stability (80.0% over 200 cycles), and energy density (356.5 Wh kg–1). This unique mechanism provided fresh insights into revisiting the relationship between structure and performance and might open up a new idea for designing novel Mn-rich ternary cathodes with zero-phase transitions property in the future.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
·
2015
·Vol. 19
·期 6
·1827-1831
·
IF 2.446
Hou Junke,Song Jie,Niu Yubin,Cheng Chuanjun,He Hong,Li Yutao,Xu Maowen
P2-type Na 0.67 Ni 0.33 Ti 0.67 O 2 is explored as a titanium-based anode material for sodium ion batteries. The as-prepared Na 0.67 Ni 0.33 Ti 0.67 O 2 delivers a reversible capacity of 129.2 mAh g −1 at 0.05 C with smooth charge–discharge curves. A simple carbon-coating technique was used to improve the electronic conductivity of Na 0.67 Ni 0.33 Ti 0.67 O 2 particles. The carbon-coated Na 0.67 Ni 0.33 Ti 0.67 O 2 delivers a higher reversible capacity of 163.7 mAh g −1 and exhibits better rate capability than the as-prepared Na 0.67 Ni 0.33 Ti 0.67 O 2 .
研究领域:
电化学储能
·
无机非金属材料
·
能源材料
·
功能陶瓷
·
二次电池技术
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Lin Zhang,Chenchen Wang,Yanchen Liu,Meng Ren,Juan Du,Aibing Chen,Fujun Li
Manganese-based layered oxides are one of the most promising cathode materials for sodium-ion batteries (SIBs) due to their high specific capacity and low cost of manganese and sodium. However, they are limited by the poor cycling stability caused by irreversible phase transitions and Jahn-Teller effect of Mn 3+ . Herein, Mo-doped P2-Na 0.67 Mn 1-x Mo x O 2 suppress the irreversible phase transition of P2-OP4 resulted from gliding of MnO 2 -slabs. It reveals that no phase transition occurs under high voltage via Mo elements doping into MnO 6 -layers. P2-Na 0.67 Mn 1-x Mo x O 2 displays high cyclic stability with a high capacity retention of 86.4% after 100 cycles and improved rate performance with an average working voltage of 2.61 V. The research provides a new perspective for designing novel layered oxide cathodes design toward high-performance SIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Feng Li,Yuhang Tian,Yanyun Sun,Peiyu Hou,Xianqi Wei,Xijin Xu
High-voltage and low-cost manganese-based P 2-type oxides show real promise as promising cathode for sodium-ion batteries (SIBs). But the P 2 − O2 phase transformation and Na + /vacancy ordering results in the inferior structural stability and Na + diffusion coefficient , which further leads to rapid decay of capacity and poor rate capability. Herein, in consideration of the synergetic effects of dual cationic doping, electrochemically inactive Li + and active Co 3+ codoping are proposed to solve the above issues. The novel two-step doping strategy, Co doping during synthesis of precursors via coprecipitation reaction followed by Li doping during solid-state reaction, are rationally developed. As anticipated, the Li/Co codoped P 2-type oxide exhibits the absence of P 2 − O2 phase transformation and Na + /vacancy disordering, which gives rise to an outstanding cycling stability (86.7% capacity retention within 100 cycles at 0.1C) and high-rate capability (reversible capacity of 109 mAh g −1 even at 10C). In addition, the full-cells composed of the codoped P 2-type positive and hard carbon negative show high energy-density, good lifespan and high-rate property. This proposed cationic codoping provides an effective and scalable tactics for modulating the structural properties of high-voltage P 2-type cathodes for advanced SIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-12
·
IF 17.694
Fu Fang,Liu Xiang,Fu Xiaoguang,Chen Hongwei,Huang Ling,Fan Jingjing,Le Jiabo,Wang Qiuxiang,Yang Weihua,Ren Yang,Amine Khalil,Sun Shi-Gang,Xu Gui-Liang
P2-type sodium manganese-rich layered oxides are promising cathode candidates for sodium-based batteries because of their appealing cost-effective and capacity features. However, the structural distortion and cationic rearrangement induced by irreversible phase transition and anionic redox reaction at high cell voltage (i.e., >4.0 V) cause sluggish Na-ion kinetics and severe capacity decay. To circumvent these issues, here, we report a strategy to develop P2-type layered cathodes via configurational entropy and ion-diffusion structural tuning. In situ synchrotron X-ray diffraction combined with electrochemical kinetic tests and microstructural characterizations reveal that the entropy-tuned Na 0.62 Mn 0.67 Ni 0.23 Cu 0.05 Mg 0.07 Ti 0.01 O 2 (CuMgTi-571) cathode possesses more {010} active facet, improved structural and thermal stability and faster anionic redox kinetics compared to Na 0.62 Mn 0.67 Ni 0.37 O 2 . When tested in combination with a Na metal anode and a non-aqueous NaClO 4 -based electrolyte solution in coin cell configuration, the CuMgTi-571-based positive electrode enables an 87% capacity retention after 500 cycles at 120 mA g −1 and about 75% capacity retention after 2000 cycles at 1.2 A g −1 .
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
Nanomaterials
·
2024
·Vol. 14
·期 24
·1989
·
IF 4.4
Kexin Zheng,Jiawei Wang,Haifeng Wang,Zhengqing Pei,Qian Wang,Xinjie Zhou,Dehua Ma,Ju Lu
The P2-Na0.7MnO2.05cathode material has long been constrained by phase transitions induced by the Jahn–Teller (J–T) effect during charge–discharge cycles, leading to suboptimal electrochemical performance. In this study, we employed a liquid phase co-precipitation method to incorporate Ti during the precursor Mn3O4synthesis, followed by calcination to obtain Na0.7TixMn(1−x)O2.05materials. We investigated the effects of Ti doping on the structure, morphology, Mn3+concentration, and Na+diffusion coefficients of Na0.7TixMn(1−x)O2.05. Our findings revealed that the 7% Ti-doped NTMO-007 sample exhibited reduced grain agglomeration and smaller particle sizes compared to the undoped sample, thereby enhancing the electrode–electrolyte contact area and electrochemical activity. Additionally, Ti doping increased the crystal cell volume of Na0.7MnO2.05and broadened the Na+transport channels, significantly enhancing the Na+diffusion coefficient. At a 0.5 C rate, the NTMO-007 sample demonstrated a specific capacity of 143.3 mAh g−1with an 81.8% capacity retention after 100 cycles, markedly outperforming the undoped NMO sample, which had a capacity retention of only 61.5%.
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
Inorganic Chemistry Frontiers
·
2025
·
IF 6.4
Yurong Wu,Ziyun Zhang,Jiangshan Huo,Runguo Zheng,Zhishuang Song,Zhiyuan Wang,Yanguo Liu,Dan Wang
P2-type layered oxides have emerged as promising cathode candidate materials for potassium-ion batteries. Nevertheless, unsatisfactory cycling stability hinders their practical application, chiefly arising from deleterious phase transitions and the Jahn–Teller distortion of Mn3+. Herein, an anion-doping strategy where F− is incorporated into P2-K0.6Zn0.1Ti0.05Al0.05Mn0.8O2 (KTMO) cathode materials is proposed. Raman spectroscopy was employed to investigate the local chemical environment of these materials. The results revealed a slight shift to higher wavenumbers in the Eg and A1g peaks, which was ascribed to the shortening of the average TM–O bond length triggered by the addition of F. Ex situ XRD analysis revealed that the material K0.6Zn0.1Ti0.05Al0.05Mn0.8O1.93F0.07 effectively suppresses undesirable phase transitions. Moreover, the maximum variation in the lattice parameter c is only 2.2% during potassium insertion/extraction, which fully demonstrates the outstanding performance of this material in terms of structural stability. This strategy brings about excellent cycling stability with a reversible capacity of 131.8 mA h g−1 and capacity retention of 76.8% after 100 cycles, within a voltage range of 2.0–4.0 V. These findings offer novel insights into the design of cathode materials possessing optimized structures and enhanced performance for potassium-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
VACUUM
·
2025
·
IF 3.9
Shaojun Shi,Panye Jin,Zhixiong Huang,Jialei Kou,Hongmei Ji,Wenyu Yin,Xiaoyan Tang,Han Mao
With the development of sodium ion battery which is considered as the alternative of lithium ion battery, better performance is required. However, its poor structure stability and rate capability due to the Jahn–Teller distortion of Mn 3+ and poor charge transfer between transition metal and oxygen-ion limit its application. Here, Sm-doped P2-type layered oxide Na 0.67 Li 0.1 Mn 0.62 Fe 0.18 Cu 0.09 Sm 0.01 O 2 with spherical secondary hierarchy was obtained through microwave-assisted method. Pure P2-shaped layered oxide is obtained. And the tiny shift of the diffraction spectrum indicates the effect of doping. The electrochemical performance of the doped oxide improves obviously. Even at a high current density of 1.0A g −1 , the capacity is still as high as 60.3 mAh g −1 , much higher than that of undoped one. The cycle stability is also improved. Electrochemical impedance spectroscopy (EIS) and Distribution of relaxation times (DRT) are taken to further study the mechanism. It reveals that the doped samarium not only serves as the pillar to stable the structure of the layered oxide, but also makes faster charge transfer between transition metal ions and oxide ions due to the Multielectron structure of samarium. Thus, such Sm-doping strategy may offer a solution toward the application bottleneck of layered oxides for sodium-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Rui Huang,Shaohua Luo,Qi Sun,Xin Yan,Haoran Zhang,Lixiong Qian,Xin Liu,Xingzhong Cao,Peng Zhang,Shengxue Yan
Fe/Mn-based cathode is considered a viable choice for sodium-ion batteries (SIBs) because of its affordability and high theoretical capacity. Nonetheless, bad actually comprehensive performance still impede its commercial application. In this work, based on the systematic study of P2-Na 2/3 Fe 1/2 Mn 1/2 O 2 cathode materials with fewer Mn vacancies (NFM-Q), we realized a superior rate, cycling performance, air stability and more importantly unraveled the operation mechanism. Specifically, dual function of fewer Mn vacancies were explicitly clarified, which included the effect of shrinking sodium layers and the sodium-ion diffusion promoting effect, as confirmed by combining XRD, XANES, XAFS, EIS and GITT. So Mn vacancy engineering had the potential to break the contradiction between “sodium limiting” based on air-stabilization mechanism and “sodium promoting” based on kinetics. This has rarely been found before. And a series of characterizations strongly declared rapidly cooling rate could effectively regulated the creation of Mn vacancies. As a result, NFM-Q cathode not only delivered outstanding discharge capacity (192.7 mAh/g), cycling stability (123.8 mAh/g, 65 %, after 50 cycles) and energy density (574.0 Wh Kg −1 ), but also possessed splendid air stability (185.8 mA h/g, 61.8 % after 50 cycles and immersion). Moreover, ex-situ XRD and XAS further expounded structural evolution and charge compensation mechanism of NFM-Q cathode, confirming its superior performance. This work might offer fresh understanding about the roles of Mn vacancy engineering, which could open up new possibilities on the material design and the property improvement of Fe/Mn-based cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
·
2021
·Vol. 26
·期 1
·269-280
·
IF 2.647
Li Xueying,Wang Jiangang,Duan Fenyan,Tao Luwen,Xu Teng,Chen Lizhuang,Yuan Aihua,Wang Xiaolong
The electrode materials with long cycle life are important for the large-scale application of sodium ion batteries. In this work, P2-type Na 0.71 Co 0.96- x Ti x O 2 ( x = 0, 0.057, 0.073, 0.09) were synthesized by molten-salt method. The Ti doping content could influence the crystallographic unit cell volume, particle size, oxygen vacancies, and surface charge density of those samples. When x = 0.073, the P2-type Na 0.71 Co 0.96- x Ti x O 2 ( x = 0.073) exhibits superior reversible capacity and rate performance due to the appropriate synergistic effect. In particular, the initial discharge capacity of NCTO-0.073 is about 118.5 mAh g −1 at 100 mA g −1 . Even the current density gets to 1000 mA g −1 , the initial discharge capacity remains 71.7 mAh g −1 after 1000 cycling with the capacity retention of 67.90%. The electrochemical kinetics analysis further prove that the P2-type Na 0.71 Co 0.96- x Ti x O 2 ( x = 0.073) owns outstanding electrical conductivity and fast sodium ion diffusion behavior to promote the electrochemical reaction during the charging/discharging. These results will contribute to the industrialized application of stable high-performance cathodes for sodium ion batteries.
研究领域:
材料科学
·
电化学
·
能量存储
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2025
·
IF 5.5
Guofeng Jia,Hongrun Qiu,Jiaqi Meng,Long Li,Shiyu Yang,Lijuan Zhang,Jianwei Li,Fayan Zhu,Min Wang
The conventional P2-type cathode material suffers from irreversible structural degradation, lattice-oxygen release, and severe capacity fading at the high-charge state during cycling. This study systematically investigates the failure mechanisms associated with the structural evolution and oxygen loss of LiNi0.5Mn0.5O2 in the high-charge state while also revealing the positive impact of Cr doping. Cr substitution in the lithium layer increases the proportion of lattice-oxygen content, lowers the oxygen activation plateau during the first cycle, and restrains structural degradation during cycling. These improvements are attributed to the high degree of delocalized Mn–O bonds caused by robust Cr–O covalency. As a result, an extraordinarily stable voltage (decay rate <0.76 mV per cycle) and a high capacity-retention rate are achieved. Insights into the structural stability of LiNi0.5Mn0.5O2 in a high-charge state provide valuable guidance for designing and optimizing Co-free layered cathode materials with enhanced performance.
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
危险品化学品经营许可证（带存储）