JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Min Xu,Junjie Lu,Zhefei Sun,Ming Yang,Bifu Sheng,Minfeng Chen,Jizhang Chen,Qiaobao Zhang,Xiang Han
Single crystalline Ni-rich layered oxide cathodes show high energy density and low cost, have been regarded as one of the most promising candidates for next generation lithium-ion batteries (LIBs). Extending the cycling voltage window will significantly improve the energy density, however, suffers from bulk structural and interfacial chemistry degradation, leading to rapidly cycle performance deterioration. Here, we propose a dual-modification strategy to synthesize La doping and Li 3 BO 3 (LBO) coating layers modified LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) by a facile one-step heating treatment processing. In-situ EIS and XRD, ex-situ XPS techniques are applied to demonstrate that the La diffused amorphous domains and Li 3 BO 3 passivating layers dampen the lattice distortion, enhance the interfacial chemistry behavior as well as lithium ion transportation kinetics. Specifically, surface La doping amorphous domains successfully suppress the intense lattice stress and volume changes induced by the phase transitions during lithiation/delithiation, thus avoiding the intergranular crack and enhancing the mechanical stability of the material. Moreover, the LBO layer formed by the consumption of residual lithium prevents successive parasitic reactions at the interface as well as provides rapid Li-ion diffusion channels. Furthermore, the coating layer also diminishes the residual lithium compounds, increasing the atmosphere stability and safety of LIBs. Consequently, the La doping and LBO coating NCM811 exhibits an exceptional initial specific capacity (230.6 mAh/g) at 0.5C under a high cutoff voltage of 4.8 V, and a 73.8 % capacity retention following 100 cycles. In addition, a superior specific capacity of 133.8 mAh/g is provided even at a high current density (4C). Our work paves a promising road to tackle the integral structure deterioration and interfacial instability of Ni-rich cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Guohua Zhu,Xiaoyan Zhang,Yongguang Liu,Fangbo Ma,Jing Suo,Ling Wang,Shan Liu
Layered oxide cathodes have attracted widespread attention due to their high-voltage and high discharge capacity. Nevertheless, the irreversible redox reactions of layered oxide cathode and decomposition of electrolyte at high-voltage greatly reduce the reversibility of the batteries. Herein, we employ a double-doping (Li&B) strategy to enhance the electrochemistry performance of the layered NaNi 0.3 Fe 0.3 Mn 0.4 O 2 (NNFM) cathode at high voltage. It proved that the dissolution of the transition metal can be restricted by double doping, and the irreversible phase transition is mitigated even at high voltage. As a result, battery with the double-doping cathode exhibits excellent electrochemistry performance, which achieves a capacity of 175 mAh g −1 at 0.2C, maintaining a capacity retention of approximately 87.3% over 100 cycles at 1C, and demonstrates exceptional rate performance. This work presents a novel insight into the doping technique for the high-performance cathode materials and offers a general method for the high energy Na-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Zhijie Zhang,Yilin Zhou,Xiaodong Zhang,Jixian Ma,Miaoning Yao,Jie Sun,Tong He,Xuexia He,Zhibin Lei,Ruibin Jiang,Zong-huai Liu,Qi Li
Na-rich manganese-based layered oxide cathodes have presented potential applications in high energy–density sodium-ion batteries due to their cost-effectiveness and large theoretical specific capacity. However, the low kinetics of anionic redox reaction and lattice distortion caused by the Mn 3+ Jahn-teller effect greatly hindered the actual capacity, rate, and cycling performances of these cathodes. Herein, a Li + substitution induced O3/O′3 biphasic tailoring strategy has been proposed for constructing the Na-rich NaLi 0.2 Mn 0.8 O 2 (NLMO) cathode. Compared with conventional O′3-Na 1.2 Mn 0.8 O 2 (NMO) cathode, the O3/O′3-NLMO cathode enabled to provide an ultrahigh capacity of 233 mAh g −1 , superior capacity retention of 86 % after 50 cycles, and outstanding rate performance with the recorded-up capacity of 165 mAh g −1 at a high current density of 200 mA g −1 . In addition, NLMO also displayed rapid Na + -diffusion and more structural reversibility of O3/O′3-P3-O1-P3-O3/O′3 during the entire charging and discharging processes. The above excellent performances of NLMO cathode could be attributed to the well-designed O3/O′3 biphasic structure that provides the synergistic function of drastically enhancing reaction kinetics of anionic (O − /O 2– ) couple and efficiently alleviating multiphase transitions caused by Mn 4+ /Mn 3+ cationic couple. This unique finding of Li + substitution induced biphasic structure provides an insight for developing economical and high-performance Na-rich oxide 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
ACS Nano
·
2024
·
IF 15.8
Qi Wang,Guihui Yu,Bi Luo,Weijie Ji,Zihang Liu,Minghuang Li,Yutong Nong,Yi Tian,Xiaowei Wang,Jiafeng Zhang,Chi-Liang Chen,Chung-Kai Chang,Zhiyuan Sang,Zaowen Zhao,Ruirui Zhao,Ji Liang
Advancing the high-voltage stability of the O3-type layered cathodes for sodium-ion batteries is critical to boost their progress in energy storage applications. However, this type of cathode often suffers from intricate phase transition and structural degradation at high voltages (i.e., >4.0 V vs Na+/Na), resulting in rapid capacity decay. Here, we present a Li/Ti cosubstitution strategy to modify the electronic configuration of oxygen elements in the O3-type layered oxide cathode. This deliberate modulation simultaneously mitigates the phase transitions and counteracts the weakening of the shielding effect resulting from the extraction of sodium ions, thus enhancing the electrostatic bonding within the TM layer and inducing and optimizing the O3–OP2 phase transition occurring in the voltage range of 2.0–4.3 V. Consequently, the cosubstituted NaLi1/9Ni1/3Mn4/9Ti1/9O2 exhibits an astounding capacity of 161.2 mAh g–1 in the voltage range of 2.0–4.3 V at 1C, and stable cycling up to 100 cycles has been achieved. This work shows the impact mechanism of element substitution on interlayer forces and phase transitions, providing a crucial reference for the optimization of O3-type materials.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Yu-Xin Chang,Yu-Jie Guo,Ya-Xia Yin,Wei-Huan He,Mengmeng Yan,Li-Rong Zheng,Jing Zhang,Qinghua Zhang,Dong Su,Xing Zhang,Jianfeng Mao,Guanjie Li,Shilin Zhang,Sailong Xu
O3-type layered oxide cathodes (NaxTMO2) for sodium-ion batteries (SIBs) have attracted significant attention as one of the most promising potential candidates for practical energy storage applications. The poor Na+ diffusion kinetics is, however, one of the major obstacles to advancing large-scale practical application. Herein, we report bismuth-doped O3-NaNi0.5Mn0.5O2 (NMB) microspheres consisting of unique primary nanoplatelets with the radially oriented {010} active lattice facets. The NMB combines the advantages of the oriented and exposed electrochemical active planes for direct paths of Na+ diffusion, and the thick primary nanoplatelets for less surface parasitic reactions with the electrolyte. Consequently, the NMB cathode exhibits a long-term stability with an excellent capacity retention of 72.5% at 1C after 300 cycles and an enhanced rate capability at a 0.1C to 10C rate (1C = 240 mA g–1). Furthermore, the enhancement is elucidated by the small volume change, thin cathode-electrolyte-interphase (CEI) layer, and rapid Na+ diffusion kinetics. In particular, the radial orientation-based Bi-doping strategy is demonstrated to be effective at boosting electrochemical performance in other layered oxides (such as Bi-doped NaNi0.45Mn0.45Ti0.1O2 and NaNi1/3Fe1/3Mn1/3O2). The results provide a promising strategy of utilizing the advantages of the oriented active facets of primary platelets and secondary particles to develop high-rate layered oxide cathodes for SIBs.
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
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2023
·
IF 10.9
Zhi-Xiong Huang,Xue-Li Zhang,Xin-Xin Zhao,Hong-Yan Lü,Xin-Yi Zhang,Yong-Li Heng,Hongbo Geng,Xing-Long Wu
Sodium-ion batteries (SIBs) are proved as one of the most acceptable candidates for replacing lithium-ion batteries in some fields by virtue of a similar “rocking chair” mechanism and the abundance of sodium. The voltage, rate performance, and energy density of these batteries are mainly determined by the cathodes. Hence, a Li-Ni-Co co-substituted P2-Na 0.67 [Li 0.1 (Mn 0.7 Ni 0.2 Co 0.1 ) 0.9 ]O 2 (NLMNC) with ribbon superstructure is prepared with the aim of multi-ion synergistic modification. Owing to the addition of Ni and Co, the Jahn–Teller distortion of Mn can be suppressed corresponding with the improved structural stability, and a little bit of oxygen redox activities is triggered. When with the substitution of 10% Li, the X-ray diffraction (XRD) peaks of NLMNC show the ribbon superstructure at about 21° and 22°. The smooth charge/discharge profiles of the NLMNC cathode exhibit the solid-solution reaction. In addition, the platform at high voltage disappears corresponding with the existing oxygen redox activities being suppressed which may be related to the ribbon superstructure and the promotion of the Ni redox. Such NLMNC cathode can deliver a reversible discharge capacity of 123.5 mA h g –1 at 10 mA g –1 . Even if the current density increases to 500 mA g –1 , a reversible discharge capacity of 112.8 mA h g –1 still can be obtained. The distinguished cycling stability is related to the reversible migration of Li + between the metal oxide layer and the interlayer and low volume change during cycling. It is also needing to be mentioned that the capacity retention of NLMNC cathode is about 94.4% (based on the highest discharge capacity) after 100 cycles. This work presents an effective route to develop high-performance cathodes for 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
·
2023
·
IF 9.9
Yu Zhou,Molin Sun,Meilan Cao,Yijin Zeng,Mingru Su,Aichun Dou,Xiaochuan Hou,Yunjian Liu
Layered sodium iron manganese oxide cathodes have attracted great interest owing to their high specific capacity and cost-effective metal resources, while the detrimental phase transitions and surface structural degradation severely limit their commercial applications. In this work, the bulk and surface structure stability of a P 2-Na 0.67 Fe 0.5 Mn 0.5 O 2 cathode can be synergically enhanced by a one-step Li/Nb co-doping strategy. Structural characterizations reveal that Li doping promotes the formation of P 2/O3 biphasic structure and makes the unfavorable P 2-OP4 phase transition convert into a smooth solid-solution reaction. Nb doping enhances the mobility of sodium ions and forms strong Nb-O bonds, thereby enhancing the stability of the TMO 2 layer structure. In particular, the Nb element induces the surface reorganization of an atomic-scale NaNbO 3 coating layer, which could effectively prevent the dissolution of metals and surface side reactions. The synergistic mechanism of enhanced electrochemical performance is proved by multiple characterizations during cycling. As a result, the as-prepared Na 0.67 Li 0.1 Fe 0.5 Mn 0.38 Nb 0.02 O 2 exhibits improved capacity retention of 85.4 % than raw material (45.7 %) after 100 cycles at 0.5C (1C = 174 mA g −1 ) within 2.0–4.0 V. This co-regulating strategy provides a promising approach to designing highly stable sodium-ion battery cathodes. Furthermore, a full cell of Na 0.67 Li 0.1 Fe 0.5 Mn 0.38 Nb 0.02 O 2 with hard carbon displays excellent cycling stability (85.1 % capacity retention after 100 cycles), making its commercial operation possible. This synergistic strategy of biphasic structure and surface reorganization is a critical route to accelerate the application of layer oxide cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Chemical Science
·
2025
·
IF 7.4
Yifan Wu,Xincan Cai,Weiyi Lin,Yingdong Deng,Qing Zhang,Haoyuan Li,Pu Yan,Guohui Zhong,Jin Xie
Solid-state calcination profoundly influences the structural integrity and electrochemical performance of polycrystalline layered oxide cathode materials in lithium-ion batteries. As temperatures increase, heterogeneous phase transitions driven by solid-state diffusion can result in structural non-uniformity. In this study, we employ operando characterization techniques and high-resolution electron microscopy to scrutinize the inherent heterogeneity observed in the early-stage of the solid-state lithiation process and its subsequent influence on the formation and merging of resultant LiNi0.9Co0.05Mn0.05 (NCM90) grains on the surface of the secondary particle. We found that a conformal atomic layer deposited WO3 layer on the hydroxide precursor could be in situ lithiated to form LixWOy compounds, which are stable and non-dissolvable at the grain boundaries, further acting as a segregation layer to prevent the merging of grains during the formation of a layered phase on the surface of secondary particles, which preserves the route for the uniform lithiation of the inner part of the secondary particles. These investigations shed light on the effect of solid-state reaction heterogeneity and present a novel methodology for mitigating the persistent challenge by grain boundary engineering.
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
Nano Energy
·
2025
·
IF 17.1
Yuxi Zou,Xiaoguang Fu,Zhibo Zhao,Bingqi Chen,Zibo Zhu,Wanying Zuo,Lu Zhang,Wenxi Guo,Qingchi Xu,Meidan Ye
Ion doping is an effective strategy to alleviate the phase transition and irreversible lattice oxygen reactions of layered oxide cathodes for sodium ion batteries, but it still lacks sufficient understanding on the mechanism of elemental action and the interactions between transition metal atoms. In this work, Zn/Fe co-doped P2-Na 0.67 Mn 0.6 Ni 0.3 Zn 0.05 Fe 0.05 O 2 (NMNO-ZF) materials are facile synthesized and indicated that the doped Zn enables to sustain the structural stability of NMNO-ZF to inhibit the phase transition and also cooperates with Fe to trigger the reversible lattice oxygen reaction at high voltages. Density functional theory (DFT) calculations reveal that Zn plays the role of inducing enhanced d-p coupling of Mn/Fe-O in NMNO-ZF. Namely, the Zn-reinforced Mn-O bonds give favorable structural stability to NMNO-ZF, while the Zn-modulated Fe-O bonds greatly improves the reversibility of lattice oxygen redox. Consequently, NMNO-ZF can achieve a reversible capacity of 139.17 mAh g −1 , with almost no capacity degradation after 100 cycles at 120 mAh g −1 , and a capacity retention rate of 89 % even after 2000 cycles at 1.2 A g −1 . Moreover, NNMO-ZF also shows stable cycling capability in the full cell with a capacity retention of 81 % after 400 cycles at 600 mAh g −1 . This study unveils the charge compensation mechanism of Zn/Fe co-doping in layered oxide materials, providing more experimental and theoretical supports for designing highly stable cathodes for SIBs.
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
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Zhe Xu,Haidi Yang,Xuesen Zhao,Runguo Zheng,Zhishuang Song,Zhiyuan Wang,Hongyu Sun,Yanguo Liu,Dan Wang
O3-NaNi1/3Fe1/3Mn1/3O2 has attracted much attention as a cathode for sodium-ion batteries, because of its low cost and high sodium-ion storage capacity. However, its slow Na+ diffusion kinetics and harmful P3–O3′ phase transition with severe bulk strain at high voltage leads to poor rate capability and fast capacity fading. Herein, we propose a multivariate doping strategy with Cu, Mg, and Ti ions to solve the above problems of the O3-NaNi1/3Fe1/3Mn1/3O2 cathode. The O3–Na(Ni1/3Fe1/3Mn1/3)0.9Cu0.03Mg0.02Ti0.05O2 (NFMCMT) cathode exhibits enlarged Na+ diffusion channels and a strengthened layered structure, which improves the Na+ diffusion kinetics, suppresses the harmful P3–O3′ phase transition at high voltages, and inhibits the intragranular fatigue cracks, leading to enhanced rate capability and cycling performance. As a result, the NFMCMT exhibits outstanding performance in the 2–4.1 V voltage window, delivers a discharge capacity of 151.2 mAh g–1 with the 81.5% capacity retention for 100 cycles at 0.1 C, and 83.1% capacity retention for 300 cycles at 5 C. Especially in the rate performance, the NFMCMT delivers a 115.6 mAh g–1 and 100.1 mAh g–1 discharge capacity even at 5 and 10 C. This work provides an effective multivariate doping strategy for development of high-performance layered oxide cathodes for sodium-ion batteries.
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
ACS Nano
·
2025
·
IF 16
Junyi Dai,Jiahao Li,Yu Yao,Yan-Ru Wang,Mingze Ma,Ruilin Bai,Yinbo Zhu,Xianhong Rui,Hengan Wu,Yan Yu
P2-type layered oxides, such as Na0.67Ni0.33Mn0.67O2, represent a promising class of cathode materials for Sodium-ion batteries (SIBs) due to their high theoretical energy density. However, their cycling stability is often compromised by severe phase transitions and irreversible lattice oxygen redox reactions at high voltages. In this work, we develop a Zn and Al codoping approach to design a Na0.71Ni0.28Zn0.05Mn0.62Al0.05O2 (ZA-NNMO) cathode for stable SIBs. Geometric phase analysis reveals that the introduction of inert Zn significantly mitigates the lattice distortion and transition-metal-ion migration, thereby inhibiting detrimental phase transition and structural collapse. The doped Al element in the Mn site strengthens the Al–O interaction, facilitating reversible O2––O2n– (0 < n < 4) reactions at high voltages and effectively curtailing irreversible lattice oxygen oxidation, as confirmed by in situ differential electrochemical mass spectrometry. As a result, the ZA-NNMO cathode delivers superior electrochemical performance in terms of high output voltage of 3.6 V, highly competitive energy density of 470 W h kg–1 and good cyclability (80.2% of capacity retention after 1400 cycles at 1.0 A g–1). This work presents a robust methodology for improving the reversibility and stability of layered oxide cathodes in SIBs.
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
Journal of Energy Chemistry
·
2023
·
IF 13.1
Guoliang Liu,Weile Xu,Jianghua Wu,Yong Li,Liping Chen,Shuyue Li,Qinghui Ren,Juan Wang
O3-NaNi 1/3 Fe 1/3 Mn 1/3 O 2 is a promising layered cathode material with high specific capacity, low cost, and simple synthesis. However, sluggish kinetic hindrance is attributed to the size discrepancy between the large Na-ion and narrow tetrahedral interstitial positions, leading to inferior rate capacity and low reversible capacity. Herein, F − with light‐weight and strong electronegativity is introduced to substitute O atoms in the bulk structure, which intensifies the bond strength of transition metal and oxygen and enlarges the Na + diffusion channel. In addition, density-functional theory (DFT) calculations demonstrate that the electrostatic interaction is weakened between Na + in the tetrahedral site and the transition-metal cation directly below it, dramatically reducing the migration barriers of Na + diffusion. Consequently, the as-obtained NaNi 1/3 Fe 1/3 Mn 1/3 O 1.95 F 0.05 sample displays outstanding rate performance of 86.7 mA h g −1 at 10 C and excellent capacity retention of 84.1% after 100 cycles at 2 C. Moreover, a full cell configuration using a hard carbon anode reaches the energy density of 307.7 Wh kg −1 . This strategy paves the way for novel means of modulating the Na-ion migration path for high-rate O3-type layered cathode materials.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）