Energy Storage Materials最新文献_第7页

Weak solvation effects and molecular-rich layers induced water-poor Helmholtz layers boost highly stable Zn anode 弱溶解效应和分子富集层诱导的贫水亥姆霍兹层促进高度稳定的锌阳极

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-22 DOI: 10.1016/j.ensm.2024.103856

Xin Wang , Hui Peng , Huan Zheng , Zhiyuan Liu , Kanjun Sun , Guofu Ma , Ziqiang Lei

The advancement of aqueous Zn-based energy storage systems encounters major challenges due to the occurrence of side reactions and the growth of dendrites caused by the highly active nature of water in the aqueous electrolyte. Herein, a zwitterion additive named sulfonated amphoteric betaine (referred to as DMAPS) regulates the Zn²⁺ electrolyte environment through a weak solvation effect to promote highly stable Zn anodes. The inherently occurring anionic (-SO₃^-) and cationic (-NR₄⁺) counterions in the DMAPS chain can be effectively separated under an external electric field to enable the creation of distinct ion migration pathways, thereby significantly enhancing the transportation of electrolyte ions. Moreover, DMAPS can be adsorbed onto the surface of Zn anode to form a H₂O-poor Helmholtz layer, which can serve as a protective barrier to suppress corrosion of the Zn anode by free H₂O and inhibits the formation of differential electric field to facilitate the directional deposition of Zn²⁺. In addition, density functional theory (DFT) and molecular dynamics (MD) further assisted in demonstrating the intrinsic mechanism of the reconstruction of the solvated sheath structure of Zn²⁺ by DMAPS. As a result, the Zn//Zn symmetric cell in ZnSO₄+DMAPS solution can be cycled steadily for 2100 h at a current density of 1 mA cm^-2 and 1 mAh cm^-2. The assembled Zn ion hybrid capacitor with ZnSO₄+DMAPS electrolyte was stably cycled for 20,000 cycles with 90% capacity retention at 5 A g^-1.

由于水基电解质中水的高活性会导致副反应的发生和枝晶的生长，因此水基锌储能系统的发展遇到了重大挑战。在此，一种名为磺化两性甜菜碱（简称 DMAPS）的齐聚剂添加剂通过弱溶解效应调节 Zn2+ 电解质环境，从而促进高度稳定的 Zn 阳极。DMAPS 链中固有的阴离子（-SO3-）和阳离子（-NR4+）在外加电场的作用下可以有效分离，从而形成不同的离子迁移路径，显著提高电解质离子的迁移能力。此外，DMAPS 还能吸附在 Zn 阳极表面，形成贫 H2O 的赫尔姆霍兹层，作为保护屏障抑制游离 H2O 对 Zn 阳极的腐蚀，并抑制差分电场的形成，促进 Zn2+ 的定向沉积。此外，密度泛函理论（DFT）和分子动力学（MD）进一步证明了 DMAPS 重构 Zn2+ 溶剂鞘结构的内在机制。因此，ZnSO4+DMAPS 溶液中的 Zn//Zn 对称电池可在 1 mA cm-2 和 1 mAh cm-2 的电流密度下稳定循环 2100 小时。使用 ZnSO4+DMAPS 电解质组装的锌离子混合电容器在 5 A g-1 的条件下可稳定循环 20,000 次，容量保持率达 90%。

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引用次数: 0

Dielectric additive induced weak Li solvation towards stabilized solid electrolyte interface for 4.6V lithium metal batteries 电介质添加剂诱导弱锂离子溶入稳定的固体电解质界面，用于 4.6 V 锂金属电池

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-22 DOI: 10.1016/j.ensm.2024.103854

Farwa Mushtaq , Haifeng Tu , Liming Zhao , Lu Wang , Bingbing Tang , Zhigang He , Yufang Cao , Zhenghui Hou , Jiajia Ran , Jian Wang , Muhammad Zahid , Yongyi Zhang , Meinan Liu

Developing stable electrode-electrolyte interphases on Li metal anode (LMA) and high voltage cathode is crucial for producing durable Li metal batteries. Electrolyte engineering has been regarded as an efficient way to in-situ construct stable and robust interphase. Herein, a dielectric electrolyte system is proposed by introducing LiNbO₃ nanoparticles to liquid carbonate-based electrolyte for regulating Li⁺ solvation structure, and thus inducing stable inorganic-rich solid electrolyte interphase. Moreover, these dielectric nano LiNbO₃ additives can regulate the Li⁺ flux through their build-in electric field to guide dendrite free Li deposition. These multi-functional features of LiNbO₃ allow for exceptional cyclic performance in both symmetric cell configuration (3300 h at 0.5 mA cm⁻² and 1 mA h cm⁻²) and Li||LiNi_0.8Co_0.1Mn_0.1O₂ half-cell charged at 4.6 V with capacity retention of 80% over 200 cycles. These results demonstrate great potential of dielectric electrolyte on improving the performance of lithium metal batteries.

在锂金属阳极（LMA）和高压阴极上开发稳定的电解质间相对于生产耐用的锂金属电池至关重要。电解质工程被认为是在原位构建稳定而坚固的电解质相的有效方法。本文提出了一种介电电解质系统，通过在液态碳酸盐电解质中引入 LiNbO3 纳米粒子来调节 Li+ 溶解结构，从而诱导稳定的富无机 SEI。此外，这些介电纳米 LiNbO3 添加剂还能通过其内置电场调节 Li+ 通量，从而引导无枝晶锂沉积。铌酸锂（LNO）的这些多功能特性使其在对称电池配置（在 0.5 mA cm-2 和 1 mA h cm-2 条件下分别充电 3300 小时）和在 4.6 V 电压下充电的 Li||LiNi0.8Co0.1Mn0.1O2 半电池中都具有优异的循环性能，在 200 次循环中容量保持率达到 80%。这些结果表明电介质电解液在提高锂金属电池性能方面具有巨大潜力。

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引用次数: 0

Interfacial space confinement engineering toward ultrastable all-climate aqueous zinc ion batteries 面向超稳定全气候锌离子水电池的界面空间约束工程

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-21 DOI: 10.1016/j.ensm.2024.103853

Wenli Li , Jie Zhang , Yang Wang , Xiangyi Gu , Guosheng Duan , Qinghua Zhang , Yang Hou , Zhongjian Li , Bin Yang , Zhizhen Ye , Jianguo Lu

The interfacial instability, particularly uncontrollable Zn nucleation and deposition, significantly impeding the commercialization of aqueous zinc ion batteries (ZIBs). Herein, we propose an interfacial space confinement strategy to enable the dendrite-free anode, specifically through constructing a zincophilic buffer layer based on hollow Sn@C. The porous Sn@C contributes to modify the electrical double layer structure, which greatly alleviates the concentration polarization during high-rate plating. In-situ experimental results demonstrate the inhibited H₂O-mediated parasitic side reactions and the absence of dendrite deposition morphology. Based on the improved thermodynamics and kinetics, zincophilic buffer layers can deliver low nucleation overpotential (20 mV), ultrastable cycle life (> 5000 h), and excellent zinc utilization rate (62.4%). Importantly, the full batteries with zincophilic buffer layer exhibit excellent electrochemical stability over -40 to 70 °C, pushing forward the construction of advanced all-climate ZIBs.

界面的不稳定性，尤其是无法控制的锌成核和沉积，严重阻碍了水性锌离子电池（ZIB）的商业化。在此，我们提出了一种界面空间限制策略，特别是通过构建基于中空Sn@C的亲锌缓冲层来实现无枝晶阳极。多孔的 Sn@C 有助于改变电双层结构，从而大大缓解了高速率电镀过程中的浓度极化问题。原位实验结果表明，由 H2O 介导的寄生副反应受到抑制，且无树枝状沉积形态。基于改进的热力学和动力学，亲锌缓冲层可以提供低成核过电位（20 mV）、超稳定循环寿命（5000 小时）和出色的锌利用率（62.4%）。重要的是，带有亲锌缓冲层的全电池在 -40 至 70°C 温度范围内表现出卓越的电化学稳定性，推动了先进的全气候 ZIB 的构建。

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引用次数: 0

Unlocking the potential: Innovations and strategies for electrolyte optimization in Zn-ion batteries 释放潜能：锌离子电池电解质优化的创新与战略

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-20 DOI: 10.1016/j.ensm.2024.103851

Muhammad Kashif Aslam , Iftikhar Hussain , Abdul Jabbar Khan , Shahid Hussain , Syed Shoaib Ahmad Shah , Ali H. Al-Marzouqi , Maowen Xu

Zn-ion batteries have emerged as promising energy storage devices due to their high energy density, low cost, and environmental friendliness. To fully exploit their potential, it is essential to enhance their performance through innovative strategies for electrolyte optimization. This article presents a comprehensive review of recent advancements and approaches aimed at improving the performance of Zn-ion batteries by optimizing the electrolyte. The review discusses the importance of electrolyte composition and its impact on ionic conductivity, stability, and safety. It explores various electrolyte components, such as solvents, salts, and additives, and highlights their influence on ion transport and the prevention of side reactions. Additionally, the challenges posed by the aqueous electrolyte system are addressed, with corresponding countermeasures suggested. Strategies for achieving high ionic conductivity and stability are discussed, including the use of novel solvents, salt combinations, and additives with improved properties. Furthermore, this article underscores the significance of advanced characterization and modeling in understanding electrolyte-electrode interactions and guiding electrolyte optimization efforts. In conclusion, emerging trends and future directions in electrolyte optimization for Zn-ion batteries are outlined, providing a roadmap for future research and development in this field.

由于能量密度高、成本低、环境友好，锰离子电池已成为一种前景广阔的储能设备。为了充分挖掘其潜力，必须通过创新的电解质优化策略来提高其性能。本文全面综述了旨在通过优化电解质提高锌离子电池性能的最新进展和方法。综述讨论了电解质成分的重要性及其对离子导电性、稳定性和安全性的影响。它探讨了各种电解质成分，如溶剂、盐和添加剂，并强调了它们对离子传输和防止副反应的影响。此外，还探讨了水性电解质系统带来的挑战，并提出了相应的对策。文章还讨论了实现高离子传导性和稳定性的策略，包括使用新型溶剂、盐组合和性能更好的添加剂。此外，本文还强调了先进的表征和建模在理解电解质-电极相互作用和指导电解质优化工作方面的重要意义。最后，文章概述了 Zn 离子电池电解质优化的新趋势和未来方向，为该领域的未来研究和开发提供了路线图。

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引用次数: 0

Earth-abundant, low-cost raw micro-silicon enabled by mechanically strengthened binder for high-capacity and long-life battery electrode 通过机械强化粘合剂实现地球资源丰富、成本低廉的微硅原料用于高容量和长寿命电池电极

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-20 DOI: 10.1016/j.ensm.2024.103852

Wengang Yan , Siyuan Ma , Yu Dong , Minghui Cao , Sheng Chen , Yongjian Li , Yun Lu , Lai Chen , Qing Huang , Yuefeng Su , Feng Wu , Ning Li

Nano-structured silicon materials with high capacity, are currently being gradually commercialized and composited with graphite in high-energy batteries, although their fabrication cost is rather high. However, the low-cost micro-silicon materials are always criticized and discarded in batteries due to the severe particle-to-electrode crack and huge volume change. Herein, inspired by the human ligament, a cross-linked binder with greatly enhanced mechanical properties is designed and fabricated to stabilize micro-silicon anodes. This biomimetic polymer can not only act as flexible “fibrils” in ligament, to adapt the high-volume change of silicon anode; but also act as “proteoglycan” in ligament to firmly hold these flexible fibrils and proactively constrain stress concentration of silicon anode. The combination of “soft to hard” hierarchical structure would endow binders with excellent elasticity and toughness. The pure micro-Si (5∼10 μm) electrodes with PSB binder exhibit high initial coulombic efficiency (ICE) of 93.3 % and favorable reversible capacity of ∼1500 mAh g⁻¹ at 4000 mA g⁻¹ after 600 cycles. Furthermore, the PSB binder also enables the μSi/GR//NCM811 full cell with 91.4 % capacity retention over 200 cycles. This functional PSB binders provide inspiration for constructing μSi anodes with high-ICE, high reversible capacity, and long-cycling life.

目前，具有高容量的纳米结构硅材料正逐步商业化，并与石墨复合用于高能电池，尽管其制造成本相当高。然而，低成本的微硅材料由于颗粒与电极之间存在严重裂纹和巨大的体积变化，在电池中一直被诟病和抛弃。本文受人体韧带的启发，设计并制造了一种机械性能大大增强的交联粘合剂，用于稳定微硅阳极。这种仿生物聚合物不仅可以作为韧带中的柔性 "纤维"，适应硅阳极的高体积变化；还可以作为韧带中的 "蛋白聚糖"，牢牢固定这些柔性纤维，主动约束硅阳极的应力集中。这种 "软硬结合 "的分层结构使粘结剂具有优异的弹性和韧性。使用 PSB 粘合剂的纯微硅（5∼10 μm）电极显示出 93.3% 的高初始库仑效率（ICE），在 4000 mA g-1 条件下循环 600 次后，可逆容量达到 1500 mAh g-1。此外，PSB 粘合剂还使μSi/GR//NCM811 全电池在 200 次循环后的容量保持率达到 91.4%。这种功能性 PSB 粘合剂为构建具有高ICE、高可逆容量和长循环寿命的 μSi 阳极提供了灵感。

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引用次数: 0

Integration of deformable matrix and lithiophilic sites for stable and stretchable lithium metal batteries 整合可变形基质和亲锂位点，打造稳定且可拉伸的金属锂电池

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-18 DOI: 10.1016/j.ensm.2024.103850

Sangyeop Lee , Yubin Lee , Woo-Jin Song , Dong-Yeob Han , Jieun Kang , Sungho Kim , Chanhyun Park , Hyeong-Jong Kim , Minsik Kong , Sung-Kyun Jung , Unyong Jeong , Gyujin Song , Soojin Park

In response to the growing interest in wearable devices, the demand for next-generation wearable devices that can endure various mechanical deformations such as folding and stretching is also increasing. As a result, the development of stretchable batteries, capable of operating under diverse conditions, is regarded as crucial for the advancement of these future wearable technologies. Many current studies on stretchable batteries suffer from limited energy density and complicated fabrication procedures. Thus, the development of batteries that meet both high stretchability and energy density remains challenging due to these factors. Herein, we propose a stretchable and lithiophilic matrix as a host for lithium (Li) metal anodes to realize stretchable Li metal batteries (LMBs), which consists of a polymer matrix embedded with silver nanoparticles (AgNPs). The lithiophilic AgNPs are incorporated both on the surface and within the elastic fiber matrix, providing facile Li nucleation kinetics and an electron-conductive network. Surface AgNPs serve as a primary electron pathway and offer numerous nucleation seeds to facilitate uniform Li electrodeposition. Meanwhile, AgNPs embedded in the matrix provide a sturdy conductive network even under mechanical deformation. Consequently, the structure-forming factors of stretchable lithiophilic Ag-incorporated matrix (SLiM) electrode contribute to enhanced electrochemical properties as a versatile Li metal host. As a proof of concept, the designed all-stretchable LMB with the SLiM electrode demonstrates minimal degradation of electrochemical performance in deformable conditions and confirms the feasibility of an LMB in stretchable application. This work provides insight into stretchable LMBs aimed at both highly deformable and high-energy-density wearable devices.

随着人们对可穿戴设备的兴趣与日俱增，对能够承受各种机械变形（如折叠和拉伸）的下一代可穿戴设备的需求也在不断增加。因此，开发能够在各种条件下工作的可拉伸电池被认为是推动这些未来可穿戴技术发展的关键。目前许多关于可拉伸电池的研究都存在能量密度有限和制造程序复杂的问题。因此，由于这些因素，开发同时满足高拉伸性和能量密度的电池仍然具有挑战性。在此，我们提出了一种可拉伸的亲锂基质作为锂（Li）金属阳极的宿主，以实现可拉伸的锂金属电池（LMBs），该基质由嵌入银纳米粒子（AgNPs）的聚合物基质组成。亲锂的 AgNPs 同时嵌入弹性纤维基体的表面和内部，提供了便捷的锂成核动力学和电子导电网络。表面的 AgNPs 可作为主要的电子通路，并提供大量成核种子，促进锂的均匀电沉积。同时，嵌入基质中的 AgNPs 即使在机械变形的情况下也能提供坚固的导电网络。因此，可拉伸亲锂掺杂银基质（SLiM）电极的结构形成因素有助于增强其作为多功能锂金属宿主的电化学特性。作为概念验证，采用 SLiM 电极设计的全拉伸 LMB 在可变形条件下的电化学性能退化极小，证实了 LMB 在拉伸应用中的可行性。这项工作为针对高变形和高能量密度可穿戴设备的可拉伸 LMB 提供了深入的见解。

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引用次数: 0

An oxygen-defective framework with intensified Lewis acidity reinforcing composite electrolyte for all-solid-state lithium metal batteries 用于全固态锂金属电池的具有强化路易斯酸性的缺氧框架强化复合电解质

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-18 DOI: 10.1016/j.ensm.2024.103847

Tong Duan, Jiamin Li, Lanlin Li, Qiangchao Sun, Xionggang Lu, Hongwei Cheng

Composite solid electrolytes (CSEs) are considered a key component of all-solid-state lithium metal batteries, regarded as the next generation of energy storage devices with high energy density and long operating life. Numerous studies have shown that the performance of CSEs is closely related to the structure of the fillers and the interactions between fillers and other components, including polymer matrices and lithium salts. To create more abundant interaction sites in CSEs, we designed a nanostructured framework with intensified Lewis acidity (PVDF-HFP/Ov-CeO₂) for poly(ethylene) oxide (PEO) electrolyte (denoted as Ov-CeO₂-CSE). The mystery concerning the nanostructured framework adsorbs with PEO polymer and dissociates TFSI⁻ and its influence on the electrochemical lithium ions storage performance is meticulously revealed by coupling experimental with theoretical results. Impressively, the prepared Ov-CeO₂-CSE shows improved ionic conductivity (1.76 × 10⁻⁴ S cm⁻¹ at 30 °C) and a good lithium-ion transference number (0.49). The Li||Ov-CeO₂-CSE||Li cell exhibits great cyclability over 3500 h at a current density of 0.1 mA cm⁻² (areal capacity: 0.1 mAh cm⁻², 60 °C). Furthermore, the Li||Ov-CeO₂-CSE||LFP cell delivers a high specific capacity of 154.6 mAh g⁻¹ at a current density of 0.5 C, stably maintained over 500 cycles. This work provides a potential strategy for designing multifunctional frameworks by efficient interfaces to build advanced all-solid-state lithium metal batteries.

复合固体电解质（CSE）被认为是全固态锂金属电池的关键成分，而全固态锂金属电池则被视为具有高能量密度和长工作寿命的下一代储能设备。大量研究表明，复合电解质的性能与填料的结构以及填料与聚合物基质和锂盐等其他成分之间的相互作用密切相关。为了在 CSE 中创造更多的相互作用位点，我们为聚环氧乙烷（PEO）电解质设计了一种具有更强路易斯酸度的纳米结构框架（PVDF-HFP/Ov-CeO2）（称为 Ov-CeO2-CSE）。通过将实验结果与理论结果相结合，细致地揭示了纳米结构框架吸附 PEO 聚合物并解离 TFSI- 及其对电化学锂离子存储性能影响的奥秘。令人印象深刻的是，制备的 Ov-CeO2-CSE 显示出更高的离子电导率（30 °C时为 1.76 × 10-4 S cm-1）和良好的锂离子传输数（0.49）。在 0.1 mA cm-2 的电流密度下，锂离子电池可循环使用 3500 小时（等容量：0.1 mAh cm-2，60 °C）。此外，在 0.5 C 的电流密度下，锂|Ov-CeO2-CSE||LFP 电池可提供 154.6 mAh g-1 的高比容量，并可在 500 次循环中稳定保持。这项工作为通过高效界面设计多功能框架以构建先进的全固态锂金属电池提供了一种潜在的策略。

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引用次数: 0

Grain-boundary engineering of Na3Bi/NaF dual-functional heterogeneous protective layer for highly stable sodium metal anodes 用于高稳定性钠金属阳极的 Na3Bi/NaF 双功能异质保护层的晶界工程技术

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-18 DOI: 10.1016/j.ensm.2024.103846

Yue Li , Huilong Dong , Kang Xu , Mingjing Chu , Xin Xu , Wenqing Zhao , Yiwei Xue , Qing Li , Yajun Tan , Chencheng Sun , Liang Cao , Huaixin Wei , Hongbo Geng

Sodium-metal batteries have been extensively recognized as a potential alternative to lithium-metal batteries. However, the huge volume expansion, inhomogeneous distribution of the electrical field, and sluggish Na⁺ diffusion at the electrolyte/electrode interface are insurmountable challenges to achieving high cycling performance and a long lifespan. In this work, a dual-functional heterogeneous protective layer consisting of Na₃Bi/NaF was constructed on the surface of metallic sodium (abbr. BiF₃/Na) by the spontaneous reduction reactions between metallic sodium and BiF₃ powder at room temperature. Attributing to the in-situ formation of rich grain boundaries and the built-in electric field between the components, the charge transfer, Na⁺ diffusion rate as well as mechanical strength of the BiF₃/Na anode were extensively improved. Consequently, the sodium metal anode with the Na₃Bi/NaF dual-functional heterogeneous layer achieves an excellent cycling capability and long cycling lifespan of more than 2000 h at a large current density of 2 mA cm^-2 and an area capacity of 1 mAh cm^-2. In addition, by further matching with the commercialized NaNi_1/3Fe_1/3Mn_1/3O₂ (NFM) cathode, the prepared BiF₃/Na||NFM full cell exhibits high durability (68.8 mAh g^-1 after 2000 cycles at 2 C). This work utilizing grain boundary engineering has provided a promising strategy for achieving dendrite-free sodium metal anodes and high-energy density sodium metal batteries.

钠金属电池已被广泛认为是锂金属电池的潜在替代品。然而，巨大的体积膨胀、不均匀的电场分布以及电解质/电极界面上缓慢的 Na+ 扩散都是实现高循环性能和长寿命不可逾越的挑战。在这项工作中，通过金属钠和 BiF3 粉末在室温下的自发还原反应，在金属钠（BiF3/Na）表面构建了由 Na3Bi/NaF 组成的双功能异质保护层。由于在原位形成了丰富的晶界以及各组分之间的内置电场，BiF3/Na 阳极的电荷转移、Na+ 扩散速率和机械强度都得到了极大的改善。因此，具有 Na3Bi/NaF 双功能异质层的金属钠阳极在 2 mA cm-2 的大电流密度和 1 mAh cm-2 的面积容量条件下实现了卓越的循环能力和超过 2000 小时的长循环寿命。此外，通过与已商业化的 NaNi1/3Fe1/3Mn1/3O2（NFM）阴极进一步匹配，制备的 BiF3/Na||NFM 全电池表现出很高的耐用性（在 2 C 下循环 2000 次后，电池容量为 68.8 mAh g-1）。这项利用晶界工程的研究为实现无树枝状突起的钠金属阳极和高能量密度钠金属电池提供了一种前景广阔的策略。

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引用次数: 0

Dual-site defects engineering to eliminate impurities and optimize reversible reaction kinetics of Na4Fe3(PO4)2P2O7 cathode for superior performance sodium ion batteries 消除杂质并优化 Na4Fe3(PO4)2P2O7 阴极可逆反应动力学的双位点缺陷工程，实现高性能钠离子电池

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-18 DOI: 10.1016/j.ensm.2024.103848

Wenbin Fei, Xiaoping Zhang, Keyi Sun, Yian Wang, Kexin Rao, Mengting Deng, Chengdong Tao, Ling Wu, Yulei Sui

Na₄Fe₃(PO₄)₂P₂O₇ is a prominent polyanionic material widely studied as a cathode for sodium-ion batteries, valued for its stable cycling performance and cost-effectiveness. However, the sluggish diffusion kinetics of Na⁺ associated with electrochemically inert NaFePO₄ impurities during synthesis strictly limit the rate performance and energy density of Na₄Fe₃(PO₄)₂P₂O₇. In this study, dual-site defects engineered Na_4–2_xFe_3–1.5_yLa_y(PO_4-_xBr_x)₂P₂O₇ cathode materials were synthesized using a facile mechanical activation method, by introducing trace amounts of LaBr₃ as additive. Fe defects originating from La doping eliminate the maricite-NaFePO₄ inert impurities and Na defects stemming from Br doping optimize the microchemical valence states and ion transport kinetics. The density functional theory demonstrates that Fe/Na dual-site defects in the lattice of Na₄Fe₃(PO₄)₂P₂O₇ reduce band gap and facilitate Na⁺ migration passageway, thereby leading to a superior rate capability and stable sodium storage performance. Moreover, the sodium storage mechanism of the dual-site defects engineered Na₄Fe₃(PO₄)₂P₂O₇ cathode material is revealed. The optimal dual-site defects engineered cathode sample delivers excellent rate performance (55.2 mAh g^-1 at 50 C) and long cycling stability (capacity retention of 93 % after 2000 cycles at 10 C). This study provides a promising strategy for engineering dual-site defects to synthesize impurities-free Na₄Fe₃(PO₄)₂P₂O₇ cathode material with superior electrochemical performance.

Na4Fe3(PO4)2P2O7是一种重要的多阴离子材料，被广泛研究用作钠离子电池的阴极，因其稳定的循环性能和成本效益而备受推崇。然而，合成过程中与电化学惰性 NaFePO4 杂质相关的 Na+ 缓慢扩散动力学严格限制了 Na4Fe3(PO4)2P2O7 的速率性能和能量密度。本研究通过引入微量的 LaBr3 作为添加剂，采用简便的机械活化法合成了双位缺陷工程 Na4-2xFe3-1.5yLay(PO4-xBrx)2P2O7 阴极材料。La 掺杂产生的 Fe 缺陷消除了云母-NaFePO4 惰性杂质，Br 掺杂产生的 Na 缺陷优化了微化学价态和离子传输动力学。密度泛函理论证明，Na4Fe3(PO4)2P2O7 晶格中的Fe/Na双位点缺陷降低了带隙，促进了Na+迁移通道的形成，从而使其具有优异的速率能力和稳定的储钠性能。此外，还揭示了双位点缺陷工程化 Na4Fe3(PO4)2P2O7 阴极材料的储钠机理。最佳双位点缺陷工程阴极样品具有优异的速率性能（50 C 时为 55.2 mAh g-1）和长期循环稳定性（10 C 时循环 2000 次后容量保持率为 93%）。这项研究为双位点缺陷工程提供了一种前景广阔的策略，可用于合成具有优异电化学性能的无杂质 Na4Fe3(PO4)2P2O7 阴极材料。

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引用次数: 0

Outside-in directional sodium deposition through self-supporting gradient fluorinated magnesium alloy framework toward high-rate anode-free Na batteries 通过自支撑梯度氟化镁合金框架实现由外而内的定向钠沉积，从而实现高倍率无阳极钠电池

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-18 DOI: 10.1016/j.ensm.2024.103840

Wei Guo , Xiaofei Liu , Yue Mu , Guichu Yue , Jingchong Liu , Keping Zhu , Zhimin Cui , Nü Wang , Zhonghui Chen , Yong Zhao

Constructing high-rate sodium anodes promotes the progress of high energy/power density Na metal batteries. However, it lacks effective strategies to regulate Na deposition behaviors under high current density and high capacity, greatly compromising their energy density, cycling life, and safety. Herein, we construct a self-supporting framework host consisting of nitrogen-doped carbon hollow nanofibers with uniformly embedded MgF₂ (MgF₂@NCHNFs), facilitating outside-in directional Na deposition. During the first Na plating, the MgF₂ in the tube wall of NCHNFs is in-situ converted to gradient fluorinated alloy architecture, where the outmost NaF homogenizes Na⁺ flux, the subsurface sodiophilic N sites and gradient distribution Mg sites facilitate Na deposition into the internal space of hollow nanofibers. Thus, the MgF₂@NCHNFs exhibit dendrite-free and directional Na deposition behaviors even at high rate (10 mA cm^-2) and high capacity (10 mAh cm^-2). The superiorities of the Na-MgF₂@NCHNFs are demonstrated in high-rate anode-less/anode-free sodium metal batteries using sodium vanadium phosphate and sulfur as cathodes. Furthermore, the pouch cells deliver a superhigh capacity retention of 96.0 % over 400 cycles at 2 C. This work provides a new strategy for practical applications of multifunctional Na hosts in sodium metal batteries, and can extend to other metal batteries.

构建高倍率钠阳极促进了高能量/功率密度钠金属电池的发展。然而，在高电流密度和高容量条件下，缺乏有效的钠沉积行为调控策略，从而大大影响了电池的能量密度、循环寿命和安全性。在此，我们构建了一种自支撑框架宿主，该宿主由均匀嵌入 MgF2 的掺氮碳中空纳米纤维（MgF2@NCHNFs）组成，可促进 Na 从外向内定向沉积。在第一次Na电镀过程中，NCHNFs管壁中的MgF2被原位转化为梯度氟化合金结构，其中最外层的NaF使Na+通量均匀化，亚表层亲氮位点和梯度分布的Mg位点促进Na沉积到中空纳米纤维的内部空间。因此，即使在高速率（10 mA cm-2）和高容量（10 mAh cm-2）条件下，MgF2@NCHNFs 也能表现出无树枝状和定向的 Na 沉积行为。在使用磷酸钒钠和硫作为阴极的高倍率无阳极/无阳极钠金属电池中，Na-MgF2@NCHNFs 的优越性得到了证实。此外，这种袋式电池在 2 C 温度下循环 400 次后可保持 96.0% 的超高容量。这项工作为多功能 Na 主材料在钠金属电池中的实际应用提供了一种新策略，并可扩展到其他金属电池。

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