CERAMICS INTERNATIONAL
·
2023
·
IF 5.2
Zhangyi Huang,Wanying Guo,Yang Shi,Ruichong Chen,Zhijun Wang,Yutong Zhang,Junjing Duan,Jianqi Qi,Haomin Wang
The Gd 2 Zr 2 O 7 (GZO)-based ceramic waste form exhibits promising potential for radioactive waste immobilization. However, the isomorphic immobilization capacity and irradiation effects of GZO-based ceramic waste forms with varying waste loads remain inadequately understood. This study employed a facile combustion method to synthesize ceramic powders and utilized conventional sintering with a relatively short dwelling time to fabricate GZO-based ceramic waste forms. We investigated the isomorphic immobilization behavior and He ion irradiation effects of the synthesized waste forms. The outcomes demonstrate that GZO effectively immobilizes simulated waste composed of 11 types of oxides, achieving a waste load as high as 50 wt% with a single pyrochlore phase and homogeneous element distribution. Under He + irradiation, aggravated structural degradations, including exacerbated lattice swelling, increased amorphization degree, and premature He bubble chain/microcrack formation, were observed in GZO-based waste forms with an increasing waste load.
研究领域:
材料科学
·
核能工程
·
放射化学
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产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-14
·
IF 15.7
Zhang Hang,Li Jiayang,Liu Jinhang,Gao Yun,Fan Yameng,Liu Xiaohao,Guo Chaofei,Liu Haoxuan,Chen Xiudong,Wu Xingqiao,Liu Yang,Gu Qinfen,Li Li,Wang Jiazhao,Chou Shu-Lei
Low-cost Fe-based Prussian blue analogues often suffer from capacity degradation, resulting in continuous energy loss, impeding commercialization for practical sodium-ion batteries. The underlying cause of capacity decrease remains mysterious. Herein, we show that irreversible phase transitions, structural degradation, deactivation of surface redox centres, and dissolution of transition metal ions in Prussian blue analogues accumulate continuously during cycling. These undesirable changes are responsible for massive destruction of their morphology, leading to the capacity decay. A dual regulation strategy is applied to alleviate the above-mentioned problems of Prussian blue analogues. The designed 18650/33140 cylindrical cells using modified Prussian blue analogues and hard carbon display improved cycling stability and wide-temperature working performance (−40 o C–100 o C). The findings resolve the controversy over the origins of Prussian blue analogues cathode degradation, emphasize the necessity of eliminating irreversible crystal/structural changes to guarantee enhanced cycling stability, and demonstrate the potential of Prussian blue analogues cathode for commercial 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
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Honglin Yan,Xiaoya Gao,Xiangting Yue,Yuan Ha,Zhimin Li
Ni-rich LiNi 0.80 Co 0.15 Al 0.05 (NCA) cathode material with high energy density always suffers from structural degradation during cycles, resulting in rapid capacity fading and severe voltage decay. In this study, a solid-state electrolyte film of Li 1.8 Sc 0.8 Ti 1.2 (PO 4 ) 3 (LSTP) is constructed on the surface of NCA cathode via a chemical route to enhance the cycling stability of NCA cathode. The Ex-situ XRD, EIS, dQ/dV, and SEM analyses show that the structural degradation of NCA derives mainly from the corrosion of electrolyte rather than H2-H3 phase transition, which gives rise to the extremely weak phase transitions of H1-M−H2−H3 after cycles. Besides the isolation role of LSTP film, it is found that Ti 4+ ions in LSTP incorporate into the subsurface structure of NCA, which can accelerate the Li + diffusion, reduce the Li + /Ni 2+ disorder, reinforce the crystal structure, and enlarge the inter-slab spacing of NCA. Consequently, the coated NCA-2 %LSTP cathode reveals well structural integrity and evident phase transition behavior, delivering stable cycling performance with a superior capacity retention of 96.8 % at 1.0C after 100 cycles. This study not only deeply analyzes the mechanism of the structural degradation of NCA, but also demonstrates an efficient improving approach through LSTP modification.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Energies
·
2024
·Vol. 17
·期 12
·2954
·
IF 3
Xuqiu Xie,Wenjing Jia,Changyuan Liu,Yongzhe Li,Anhou Xu,Xundao Liu
Perfluorosulfonated anionic ionomers are known for their robust ion conductivity and chemical and mechanical stability. However, the structure and transport property degradation of perfluorinated cationic polymers (PfCPs) are not well understood. Herein, we propose an ion-exchange strategy to identify the structural degradation, ion transport mechanisms, and architectural reformation of PfCPs. Particularly, we demonstrate that the utility of a –SO2–N+strategy employing the Menshutkin reaction cannot yield reliable PfCPs and anion-exchange membranes, but can yield an unreliable zwitterionic intermediate (cations–anions molar ratio is approximately 7.6%). Moreover, the degradation products were efficiently reformed as proton exchange membranes (PEMs), and the as-reformed PEMs achieved an ion-exchange capacity (IEC) value (0.89 mmol g−1), meanwhile retaining more than 94.7% of their initial capacity. Furthermore, the fuel cell assembled with reformed PEMs displayed a power density of 0.91 Wcm−2at 2.32 A cm−2, which was 90.1% of that of the robust perfluorosulfonic acid PEMs. Our combined findings shed some fresh light on the state of understanding of the structure–property relationship in PfCPs.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
Nature Communications
·
2020
·Vol. 11
·期 1
·1-12
·
IF 12.121
Zuo Wenhua,Qiu Jimin,Liu Xiangsi,Ren Fucheng,Liu Haodong,He Huajin,Luo Chong,Li Jialin,Ortiz Gregorio F.,Duan Huanan,Liu Jinping,Wang Ming-Sheng,Li Yangxing,Fu Riqiang,Yang Yong
Air-stability is one of the most important considerations for the practical application of electrode materials in energy-harvesting/storage devices, ranging from solar cells to rechargeable batteries. The promising P2-layered sodium transition metal oxides (P2-Na x TmO 2 ) often suffer from structural/chemical transformations when contacted with moist air. However, these elaborate transitions and the evaluation rules towards air-stable P2-Na x TmO 2 have not yet been clearly elucidated. Herein, taking P2-Na 0.67 MnO 2 and P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 as key examples, we unveil the comprehensive structural/chemical degradation mechanisms of P2-Na x TmO 2 in different ambient atmospheres by using various microscopic/spectroscopic characterizations and first-principle calculations. The extent of bulk structural/chemical transformation of P2-Na x TmO 2 is determined by the amount of extracted Na + , which is mainly compensated by Na + /H + exchange. By expanding our study to a series of Mn-based oxides, we reveal that the air-stability of P2-Na x TmO 2 is highly related to their oxidation features in the first charge process and further propose a practical evaluating rule associated with redox couples for air-stable Na x TmO 2 cathodes.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
PubMed
高影响因子
TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA
·
2024
·
IF 4.7
Chen LIANG,Bang TONG,Shi LI,Ze-sen WEI,Jin-hua SUN,Qing-song WANG
To reveal how the performance of LiNi x Co y Mn z O 2 (NCM) changes as a function of transition metal (TM) composition, the effect of TM ratio on the structure, morphology, electrochemical performance and thermal behavior of different NCMs was systematically investigated. Increasing Ni content leads to higher reversible capacity but worse rate capability and cycling stability. Inhibited kinetics of Li + and poor electronic conductivity cause major capacity loss in Ni-rich NCMs. Comparison of thermal behaviors was carried out via in-situ and ex-situ micro-calorimetry. With the decrease of Ni content, the thermal stability is significantly improved. The oxygen release related to phase transitions was evaluated based on Li residuals in delithiated NCMs, which verifies that Ni-rich materials exhibit severer structural deterioration, lower onset temperature and more heat release. Comprehensive characterization identifies that LiNi 0.5 Co 0.3 Mn 0.2 O 2 strikes a well-balanced combination of electrochemical performance and safety features.
研究领域:
材料科学
·
电化学
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能源存储
·
无机化学
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热分析
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DOI
高影响因子
ADVANCED MATERIALS
·
2022
·Vol. 34
·期 13
·2108541
·
IF 32.086
Liang Xue,Qinghua Zhang,Yalan Huang,He Zhu,Lili Xu,Shiying Guo,Xiaohui Zhu,Hanghui Liu,Yin Huang,Jiangfeng Huang,Lude Lu,Shengli Zhang,Lin Gu,Qi Liu,Junwu Zhu,Hui Xia
Aqueous lithium-ion batteries (ALIBs) with nonflammable feature attract great attention for large-scale energy storage. However, the layered cathode materials (such as LiCoO 2 ) present serious capacity decay in ALIBs. The degradation mechanism of layered cathode materials in ALIBs is still not clear and an effective strategy to improve cycling stability remains a great challenge. In this work, the authors use LiCoO 2 as a typical example to investigate its structural degradation in aqueous electrolytes. It is found that H + insertion accelerated irreversible layered-to-spinel phase transition is the main reason causing structural degradation and fast capacity fading in LiCoO 2 . Subsequently, Li-excess Li 1+ t Co 1− t O 2− t with intermediate spin Co 3+ is developed to mitigate H + influence and the adverse phase transition in aqueous electrolyte. It is interesting to discover that reversible water intercalation/deintercalation occurs in the layered structure during charge/discharge, which effectively suppresses the layered-to-spinel phase transition with cycling. Benefiting from the stabilized layered structure, the Li-excess Li 1.08 Co 0.92 O 1.92 shows a significantly improved cycling performance in the neutral aqueous electrolyte with a large specific capacity and excellent rate capability. This work provides a promising structural regulation strategy for the layered cathode materials, enabling their potential application in ALIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Xiangdong Zhu,Caiyan Shen,Tian Qiu,Yu Zhang,Wei Xu,Guorong Hu,Yanbing Cao,Zhongdong Peng,Ke Du
Driven by the growing demand for energy density of lithium-ion batteries, ultra-nickel- rich layered oxides LiNi x Co y Mn z O 2 (x > 0.9) (ultra-Ni-rich NCM) cathodes attract considerable attention. However, these cathode materials suffer from severe structural degradation during cycling, primarily due to phase transitions, which significantly hinders their long-term application. In this work, ultra-Ni-rich NCM cathode materials with Co- and Mn-rich surface architectures are synthesized using Co/Mn-rich shell precursors and are systematically investigated to evaluate the suitability of different surface chemistries under various electrochemical conditions. The results reveal that the Co-rich surface significantly enhances the electrochemical kinetics by mitigating the Li + concentration gradient between the surface and bulk, thereby effectively suppressing structural degradation. In contrast, the Mn-rich surface, due to the presence of electrochemically inert Mn 4+ , leads to sluggish kinetics and incomplete phase transitions within the voltage window of 2.8–4.3 V. This results in a lower capacity but notably improved structural integrity. Upon increasing the upper cutoff voltage to 4.4V, the Mn-rich shell cathode undergoes more complete phase transitions, leading to a substantial improvement in capacity while maintaining superior structural stability.
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产品关联
DOI
高影响因子
Energy Storage Materials
·
2022
·
IF 20.831
Tong Zhou,Xinrun Yu,Fan Li,Jianwei Zhang,Bowen Liu,Longlong Wang,Yuan Yang,Zhiwei Hu,Jun Ma,Chao Li,Guanglei Cui
Nickel-rich layered transition metal oxide is limited by the poor structural stability during cycling as cathode materials for next-generation lithium-based automotive batteries . In the past, the poor electrochemical performance was mainly attributed to cracks and formation of rock-salt phase on the particle surface at high potentials. Rarely is the effect of bulk phase structure evolution on properties discussed. Here, we report a bulk oxygen release induced dynamic accumulative electrochemical–mechanical coupling failure mechanism. Domain-like rock salt phases are generated due to the oxygen release and transition metals migration in the bulk region of LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) particles at the first cycle high cutoff voltage. Then, reversible compressive/tensile lattice strain alternately dominate around the domain boundary and accumulate with cycling, leading to capacity fading and becoming the origin of intracrystalline cracks. The results suggest that, in addition to the side effects from the surface, the structural transformation of the bulk plays an important role in the capacity fading. The stabilization of lattice oxygen in bulk region is a feasible solution to suppress the structural transition and the inhomogeneous stress distribution.
研究领域:
材料科学
·
电化学
·
储能技术
·
锂离子电池
·
固态物理
✓ 已验证
DOI
高影响因子
Carbon Energy
·
2024
·
IF 19.5
Qihang Ding,Zewen Jiang,Kean Chen,Hui Li,Jingzhe Shi,Xinping Ai,Dingguo Xia
High-voltage LiCoO 2 (LCO) can deliver a high capacity and therefore significantly boost the energy density of Li-ion batteries (LIBs). However, its cyclability is still a major problem in terms of commercial applications. Herein, we propose a simple but effective method to greatly improve the high-voltage cyclability of an LCO cathode by constructing a surface LiF modification layer via pyrolysis of the lithiated polyvinylidene fluoride (Li-PVDF) coating under air atmosphere. Benefitting from the good film-forming and strong adhesion ability of Li-PVDF, the thus-obtained LiF layer is uniform, dense, and conformal; therefore, it is capable of acting as a barrier layer to effectively protect the LCO surface from direct exposure to the electrolyte, thus suppressing the interfacial side reactions and surface structure deterioration. Consequently, the high-voltage stability of the LCO electrode is significantly enhanced. Under a high charge cutoff voltage of 4.6 V, the LiF-modified LCO (LiF@LCO) cathode demonstrates a high capacity of 201 mA h g −1 at 0.1 C and a stable cycling performance at 0.5 C with 80.5% capacity retention after 700 cycles, outperforming the vast majority of high-voltage LCO cathodes reported so far.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2020
·Vol. 27
·期 8
·2717-2723
·
IF 4.857
Zhuoran Lv,Wujie Dong,Bingquan Jia,Shaoning Zhang,Miao Xie,Wei Zhao,Fuqiang Huang
Graphical Linked by MOFs : Sn 2 O(CN 2 ) with loosely packed crystal structure possesses a metal–organic framework-like porous framework, which mitigates volume expansion and Sn atom aggregation. Sn 2 O(CN 2 ) shows a significantly enhanced lithium storage performance compared to traditional tin oxide. Metal-organic frameworks (MOFs) can become promising electrode materials for advanced lithium-ion batteries (LIBs), because their loosely packed porous structures may mitigate volume expansion and metal atom aggregation, which occur at the respective metal oxides. However, they suffer from poor electrical conductivity and irreversible structural degradation upon charge/discharge processes, which impede their practical utilization. Herein, we investigate MOF-like Sn 2 O(CN 2 ) as a new electrode material. The conductive yet flexible [N=C=N] linkers are tilted between [Sn 4 O] nodes and cross-linked into a porous quasi-layered structure. Such structure offers abundant channels for fast Li-ion transport and tolerance of enormous volume expansion. Notably, anisotropic [N=C=N] 2− arrays hardly migrate so that Sn 0 nanodots are physically separated via robust [N=C=N] 2− framework during discharge, thereby effectively preventing the formation of large Sn islands. Owing to the structural advantage, the Sn 2 O(CN 2 ) electrode exhibits an initial Coulombic efficiency as high as ∼80 %. With the addition of graphite as conductive supporter, the electrode provides 978 mAh g −1 at 1.0 A g −1 even after 300 cycles. Such MOF-like carbodiimides hold potential for the advanced electrodes in LIBs and other battery systems.
研究领域:
材料科学
·
能量存储
·
电池技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Nano
·
2023
·
IF 17.1
Lianshan Ni,Hongyi Chen,Jinqiang Gao,Yu Mei,Haoji Wang,Wentao Deng,Guoqiang Zou,Hongshuai Hou,Xiaobo Ji
Further popularization of ultrahigh-Ni layered cathodes for high-energy lithium-ion batteries (LIBs) is hampered by their grievous structural and interfacial degeneration upon cycling. Herein, by leveraging the strong electronegativity and low solubility properties of Sb element, a multifunctional modification that couples atomic/microstructural reconstruction with interfacial shielding is well designed to improve the LiNi0.94Co0.04Al0.02O2 (NCA) cathode by combining Sb5+ doping and Li7SbO6 coating. Notably, a robust O framework is established by regulating local O coordination owing to the incorporation of a strong Sb–O covalence bond, leading to the inhibited lattice O evolution at high voltage, as revealed by synchrotron X-ray absorption spectroscopy. Moreover, the radially aligned primary particles with (003) crystallographic texture and refined/elongated sizes are achieved by the pinning of Sb on grain boundaries and are confirmed by scanning transmission electron microscopy, resulting in the fast Li+ diffusion and mitigated particle cracking. Additionally, in situ construction of the Li7SbO6 ionic conductive layer on grain boundaries can effectively boost interfacial stability and Li+ kinetics. As a result, the optimal Sb-modified NCA delivers a high capacity retention of 94.6% after 200 cycles at 1 C and a good rate capacity of 183.9 mAh g–1 at 10 C, which is expected to be applied to next-generation advanced LIBs.
研究领域:
材料科学
·
电化学
·
储能
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）