Energy Storage Materials最新文献_第9页

Hyperstable low-tortuosity fast ion nanochannels for MXene electrodes 用于 MXene 电极的超稳定低迂回度快速离子纳米通道

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-17 DOI: 10.1016/j.ensm.2024.103829

Yuhang Zhang , Yongfa Cheng , Qixiang Zhang , Wenbin He , Yongxin Wang , Yanan Ma , Gengchen Yu , Mengjie Wang , Bowen Gao , Tao Huang , Binghui Ge , Yihua Gao , Li Wen , Siliang Wang , Yang Yue

The development of flexible MXene-based electrodes with hyperstable ion nanochannels and low tortuosity, remains daunting challenging for long-term wearable electronic devices. This paper presents a hydrogen-bonding enhanced holey MXene (HC-HMXene) electrode with maximum ion accessibility, optimized ion transport pathways, and hyperstable ion nanochannels. Specifically, three roles of introducing in-plane mesopores, reducing the lateral dimensions, and increasing the interlayer spacing in HMXene film notably enhance the electrolyte permeation efficiency and shorten the ion transport paths of the electrode (resulting in a 78.7-fold decrease in tortuosity). Thus, the constructed HC-HMXene electrode exhibits 41.1 times higher diffusion coefficient and 2.3 times higher specific capacitance than those of closely restacked film electrode with the same mass loading of MXene. Furthermore, the aramid nanofibers introduced among the MXene layers as interlocking agents bond the nanosheets via hydrogen interaction and significantly enhance the stability of the ion channel. Consequently, the HC-HMXene film effectively resists swelling behavior and maintains good structural stability in aqueous media. Moreover, the flexible sensing integrated system, powered by a HC-HMXene-based zinc ion microcapacitor, exhibits promising application prospects in real-time monitoring human physiological characteristics.

开发具有超稳定离子纳米通道和低迂回度的柔性 MXene 基电极，对于长期可穿戴电子设备来说仍然是一项艰巨的挑战。本文介绍了一种氢键增强型孔状 MXene（HC-HMXene）电极，它具有最大的离子可及性、优化的离子传输路径和超稳定的离子纳米通道。具体来说，在 HMXene 薄膜中引入面内介孔、减小横向尺寸和增大层间间距的三种作用显著提高了电解质渗透效率，缩短了电极的离子传输路径（使迂回度降低了 78.7 倍）。因此，所构建的 HC-HMXene 电极的扩散系数和比电容分别是相同质量 MXene 装载量的紧密堆叠薄膜电极的 41.1 倍和 2.3 倍。此外，在 MXene 层之间引入的芳纶纳米纤维作为互锁剂，通过氢相互作用将纳米片粘合在一起，显著提高了离子通道的稳定性。因此，HC-HMXene 薄膜能有效防止膨胀行为，并在水介质中保持良好的结构稳定性。此外，由基于 HC-HMXene 的锌离子微电容器驱动的柔性传感集成系统在实时监测人体生理特征方面具有广阔的应用前景。

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引用次数: 0

Li2CO3/LiF-Rich solid electrolyte interface stabilized lithium metal anodes for durable Li-CO2 batteries 用于耐用锂-CO2 电池的 Li2CO3/LiF 富固体电解质界面稳定锂金属阳极

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-16 DOI: 10.1016/j.ensm.2024.103843

Mengmeng Yang , Junxiang Zhang , Zhihong Ren , Bin Wang , Hao Li , Jianli Cheng

Lithium carbon dioxide (Li-CO₂) batteries are considered a promising next-generation energy storage device due to their high theoretical energy density and potential carbon neutralization. Despite numerous iterative advancements in cathode catalysts for Li-CO₂ batteries, the cycling stability still to be hindered by the growth of lithium dendrites during cycling, primarily due to uneven deposition and the side reaction of sufficient CO₂ with the Li metal anode. In this work, bisalt electrolyte (BE) consisting of LiPF₆ and LiTFSI is used as a localized anode surface stabilizer to achieve durable Li-CO₂ batteries. The introduction of PF₆^- promotes the decomposition and reduction of TFSI⁻, leading to the formation of LiF-rich inorganic SEI (Li₂CO₃/LiF-rich) with enhanced Li⁺ affinity and good electronic insulating properties. This effectively inhibits lithium dendrite formation while also insulating CO₂ and electrolytes from contacting the lithium anode. Consequently, the Li symmetric battery incorporating the novel BE exhibits a long cycling life of 912 h (∼3.8 times of the cell with a single-salt electrolyte (SE)). The BE based Li-CO₂ battery achieves an ultra-long cyclelife of 2720 h (∼2.6 times of SE battery) and outstanding rate capability. In addition, the assembled belt-shaped Li-CO₂ batteries could stably power a digital watch for 1267 h.

二氧化碳锂电池（Li-CO2）因其理论能量密度高、碳中和潜力大而被认为是一种前景广阔的下一代储能设备。尽管锂-CO2 电池的正极催化剂迭有进步，但其循环稳定性仍然受到循环过程中锂枝晶生长的阻碍，这主要是由于沉积不均匀以及充足的二氧化碳与锂金属阳极发生副反应造成的。在这项研究中，由 LiPF6 和 LiTFSI 组成的双盐电解质（BE）被用作局部阳极表面稳定剂，以实现耐用的锂-CO2 电池。PF6- 的引入促进了 TFSI- 的分解和还原，从而形成了富含 LiF 的无机 SEI（Li2CO3/LiF-rich），具有更强的 Li+ 亲和力和良好的电子绝缘性能。这不仅能有效抑制锂枝晶的形成，还能隔绝二氧化碳和电解质与锂阳极的接触。因此，采用新型 BE 的锂对称电池的循环寿命长达 912 小时（是采用单盐电解质（SE）电池的 3.8 倍）。基于 BE 的二氧化碳锂电池实现了 2720 小时的超长循环寿命（是 SE 电池的 2.6 倍）和出色的速率能力。此外，组装后的腰带型锂-CO2 电池可为数字手表稳定供电 1267 小时。

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引用次数: 0

Probing degradation at solid-state battery interfaces using machine-learning interatomic potential 利用机器学习原子间势探测固态电池界面的降解情况

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-16 DOI: 10.1016/j.ensm.2024.103842

Kwangnam Kim , Nicole Adelstein , Aniruddha Dive , Andrew Grieder , ShinYoung Kang , Brandon C. Wood , Liwen F. Wan

Solid-state batteries featuring fast ion-conducting solid electrolytes are promising next-generation energy storage technologies, yet challenges remain for practical deployment due to electro-chemo-mechanical instabilities at solid-solid interfaces. These interfaces, which include homogeneous/internal interfaces such as grain boundaries (GBs) and heterogeneous/external interfaces between solid-electrolyte and electrode materials, can impede Li-ion transport, deteriorate performance, and eventually lead to cell failure. Here we leverage large-scale molecular simulations, enabled by validated machine-learning interatomic potentials, to directly probe the onset of interfacial degradation at the garnet Li₇La₃Zr₂O₁₂ (LLZO) solid-electrolyte/LiCoO₂ (LCO) cathode interface. By surveying different interfacial geometries and compositions, it is found that Li-deficient interfaces can lead to severe interfacial disordering with cation mixing and Co interdiffusion from LCO into LLZO. By contrast, Li-sufficient interfaces are less disordered, although elemental segregation with local ordering is observed. As a consequence of Co interdiffusion, Co-rich regions are formed at the GBs of LLZO due to cation segregation and trapping effects. This behavior is independent of the GB tilting axis, degree of disorder at the GBs, and Co concentration, which implies Co clustering at GBs is a general phenomenon in polycrystalline LLZO and can dictate its overall transport and mechanical properties. Our findings elucidate the underlying fundamental mechanisms that give rise to experimentally observed physicochemical properties and provide guidelines for interface design that can mitigate interfacial degradation and improve cycling performance.

采用快速离子传导固体电解质的固态电池是前景广阔的下一代储能技术，但由于固固界面的电化学机械不稳定性，实际应用仍面临挑战。这些界面包括同质/内部界面，如晶界（GB），以及固态电解质和电极材料之间的异质/外部界面，会阻碍锂离子的传输，降低性能，最终导致电池失效。在这里，我们利用经过验证的机器学习原子间势能进行大规模分子模拟，直接探究石榴石锂7La3Zr2O12（LLZO）固体电解质/钴酸锂（LCO）阴极界面降解的起始点。通过研究不同的界面几何形状和成分，发现缺锂界面会导致严重的界面紊乱，阳离子混合和钴从 LCO 向 LLZO 的相互扩散。相比之下，锂元素充足的界面则不太无序，但也能观察到局部有序的元素偏析。由于钴的相互扩散，阳离子偏析和捕获效应在 LLZO 的 GB 处形成了富钴区。这种行为与 GB 倾斜轴、GB 处的无序程度和钴浓度无关，这意味着 GB 处的钴聚集是多晶 LLZO 中的一种普遍现象，可以决定其整体传输和机械性能。我们的研究结果阐明了导致实验观察到的物理化学特性的基本机制，并为减轻界面降解和改善循环性能的界面设计提供了指导。

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引用次数: 0

Nanofluid channels mitigated Zn2+ concentration polarization prolonged over 30 times lifespan for reversible zinc anodes 纳米流体通道减轻了 Zn2+ 浓度极化，使可逆锌阳极的寿命延长了 30 多倍

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-16 DOI: 10.1016/j.ensm.2024.103844

Jingying Li , Kui Xu , Jia Yao , Yiyuan Yang , Ziang Wu , Jieqiong Zhang , Xu Chen , Junjie Zheng , Yin Yang , Xingtai Liu , Xiaofang Wang , Yi Gan , Wei Hu , Lin Lv , Guokun Ma , Li Tao , Hanbin Wang , Jun Zhang , Hao Wang , Houzhao Wan

Despite interfacial engineering protects zinc anode from electrolyte corrosion, the suppressed kinetics process on the anode surface/interface circumscribes their cyclic stability, especially dendritic growth induced by ion concentration gradients. Here, the zinophilic nanofluid channels (ZNC) protective layer on zinc surface are designed for the rapid Zn²⁺ transport kinetic in the reversible cycling process. The ZNC demonstrates high separation pressure between ions and the channel surface due to the capillary effect, allowing Zn²⁺ to quickly migrate along the channel wall (Zn²⁺ transference numbers up to 0.72). Therefore, the unique channel modules alleviate concentration polarization from rapid Zn²⁺ consumption and maintain uniform deposition of Zn ions. Consequently, The ZNC protective layer anode exhibits significantly improved cycle life by >30 times (over 4000 h at 1 mA cm⁻²) that of bare Zn. The full battery exhibits stable cycling performance with excellent capacity retention (∼100 %) after 5000 cycles. Our work provides innovative insights into the role of nanofluids in improving the stability of zinc anodes, offering enlightening perspectives for long-cycle life zinc-based batteries.

尽管界面工程可保护锌阳极免受电解液腐蚀，但阳极表面/界面上的抑制动力学过程限制了其循环稳定性，特别是离子浓度梯度引起的树枝状生长。在此，我们在锌表面设计了亲锌纳米流体通道（ZNC）保护层，以便在可逆循环过程中实现快速的 Zn2+ 传输动力学。由于毛细管效应，ZNC 在离子和通道表面之间显示出很高的分离压力，使 Zn2+ 沿着通道壁快速迁移（Zn2+ 迁移数高达 0.72）。因此，独特的通道模块缓解了 Zn2+ 快速消耗造成的浓度极化，并保持了 Zn 离子的均匀沉积。因此，ZNC 保护层阳极的循环寿命显著提高，是裸锌的 30 多倍（1 mA cm-2 时超过 4000 小时）。完整的电池在循环 5000 次后显示出稳定的循环性能和出色的容量保持率（∼100%）。我们的工作为纳米流体在提高锌阳极稳定性方面的作用提供了创新性见解，为锌基电池的长循环寿命提供了富有启发性的前景。

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引用次数: 0

Elimination of hydrogen bonds in cellulose enables high-performance disordered carbon anode in sodium-ion batteries 消除纤维素中的氢键可实现钠离子电池中的高性能无序碳阳极

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-16 DOI: 10.1016/j.ensm.2024.103845

Yixuan Mao , Zonglin Yi , Lijing Xie , Liqin Dai , Fangyuan Su , Yilin Wang , Wenjun Ji , Xianxian Wei , Gongling Hui , Yonggang Chang , Wei Xie , Guohua Sun , Dong Jiang , Cheng-Meng Chen

Pre-oxidation remains an advantageous method to regulate the cross-linking structure of cellulose to prepare an increasingly disordered hard carbon applied in sodium-ion batteries. However, it is ambiguous how the introduction of oxygen affects the changes in the molecular structure of cellulose as well as the micro-structure of hard carbon. We herein systematically investigate the effect of air pre-oxidation on the crystallinity and cross-linking structure of cellulose macro-molecules by controlling the degree of oxidation. The findings indicate that the introduction of air can break the hydrogen bonding network of cellulose in advance and release a large number of reactive hydroxyl groups on the surface to be oxidized to form ether and ester cross-linking bonds. Ether bonds can transversely cross-link and extend the carbon layer and the bent carbon layers enclose a well-developed connective pore structure. Additionally, the breakage of oxygen-containing functional groups leads to the escape of large amounts of oxygen-containing gases to etch out more open pore structures with large pore sizes. Benefiting from these advantages, the prepared hard carbon possesses a specific capacity of 335 mAh g⁻¹ and 89 % of initial coulombic efficiency at 30 mA g⁻¹ by pre-oxidating at 300 °C for 12 h.

预氧化仍是调节纤维素交联结构的一种有利方法，可制备出应用于钠离子电池的越来越无序的硬质碳。然而，氧气的引入如何影响纤维素分子结构的变化以及硬碳的微观结构尚不明确。在此，我们通过控制氧化程度，系统地研究了空气预氧化对纤维素大分子结晶度和交联结构的影响。研究结果表明，空气的引入可以提前破坏纤维素的氢键网络，并在其表面释放出大量活性羟基，这些羟基被氧化后形成醚键和酯键交联。醚键可横向交联并延伸碳层，弯曲的碳层围成发达的连通孔隙结构。此外，含氧官能团的断裂会导致大量含氧气体逸出，从而蚀刻出孔径更大的开放式孔隙结构。得益于这些优势，制备的硬质碳在 300°C 预氧化 12 小时后，比容量达到 335 mAh-g-1，在 30 mA-g-1 的条件下，库仑效率达到 89%。

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引用次数: 0

Understanding ultrafast rechargeable Al/graphite battery by visualizing phase separation 通过可视化相分离了解超快可充电铝/石墨电池

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-15 DOI: 10.1016/j.ensm.2024.103838

Wen Luo , Naiying Hao , Shuai Gu , Hongzhi Wang , Fangchang Zhang , Chun Zeng , Huimin Yuan , Quanbing Liu , Jianqiu Deng , Yingzhi Li , Zhouguang Lu

Al/graphite batteries (ABs) using ionic liquid electrolytes exhibit exceptionally fast charging and cycling stability. However, the mechanisms underlying their high rate capabilities remains elusive. In this study, in situ optical microscopy is employed to investigate the intercalation dynamics of single-flake graphite in ABs. Observations reveal that surface reaction limitations, rather than AlCl₄⁻ mass transfer, primarily govern performance in the graphite cathode. During charging under varying current densities, the ABs display distinct phase separation behaviour with an intercalation wave morphology, indicating that surface reactions restrict the intercalation process. This finding explains the ultrafast recharge capability of ABs, where active sites in graphite become nearly fully intercalated with AlCl₄⁻ at high current densities. Additionally, slight rate performance loss occurs due to increasing ohmic and charge transfer polarisation (η_ohm and η_ct) at higher current densities. To address this limitation, we propose increasing the cut-off voltage as a straightforward and effective method to mitigate these polarization effects. This study offers valuable insights into the electrochemical behaviour of rechargeable secondary ion batteries by visualising their phase separation.

使用离子液体电解质的铝/石墨电池（ABs）具有极快的充电速度和循环稳定性。然而，其高倍率能力的内在机理仍然难以捉摸。本研究采用原位光学显微镜研究 AB 电池中单片石墨的插层动力学。观察结果表明，石墨阴极的性能主要受表面反应限制，而非 AlCl4- 的质量转移。在不同电流密度下充电期间，ABs 显示出明显的相分离行为和插层波形态，表明表面反应限制了插层过程。这一发现解释了 ABs 的超快充电能力，在高电流密度下，石墨中的活性位点几乎完全与 AlCl4- 插层。此外，在电流密度较高时，由于欧姆极化和电荷转移极化（ηohm 和 ηct）的增加，速率性能会略有下降。为了解决这一局限性，我们提出了提高截止电压这一直接有效的方法来缓解这些极化效应。这项研究通过对二次离子电池相分离的可视化，对二次离子电池的电化学行为提供了宝贵的见解。

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引用次数: 0

Microstructure reconstruction via confined carbonization achieves highly available sodium ion diffusion channels in hard carbon 通过密闭碳化重构微观结构，在硬碳中实现高可用钠离子扩散通道

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-15 DOI: 10.1016/j.ensm.2024.103839

Kai-Yang Zhang , Han-Hao Liu , Jun-Ming Cao , Jia-Lin Yang , Meng-Yuan Su , Xin-Yu Wang , Zhen-Yi Gu , Jiawei Wang , Bao Li , Yinglin Wang , Xing-Long Wu

Hard carbon is considered as the main candidate negative electrode material for sodium-ion batteries (SIBs) due to its high stability and electrochemical performance. However, the complex carbon structure and composition of hard carbon are difficult to achieve precise control during the preparation process, which leads to difficulties in accurately determining the attribution of electrochemical behavior. Here, we propose a confined carbonization strategy to achieve microstructure reconstruction of hard carbon, characterized by the anchoring of polymers in the mesopores of porous carbon to generate ordered carbon structures at high temperatures. The stacking of ordered carbon on micropores in porous carbon achieves the transition from exposed pores to closed pores (nano cleithral pores). Through mechanism detection, it is found that the ordered carbon structure provides sub nanochannels for sodium ion migration, which contributes to high slope capacity. In addition, the nano cleithral pores are sites filled with sodium ions and provide high plateau capacity. Benefiting from theses available sodium ion transport channels, carbon materials have achieved a transition from surface-controlled process to diffusion-controlled process in the sodium storage process via confined carbonization. The as-prepared carbon delivers a superior capacity of 356.2 mAh g^–1 (215.6 mAh g^–1 for plateau capacity) at 20 mA g^–1 with excellent rate and cycling performance. This work reveals the correlation between structure and electrochemical performance for carbon electrode, providing profound guidance for the precise preparation of high-performance carbon materials.

硬碳因其高稳定性和电化学性能被认为是钠离子电池（SIB）的主要候选负极材料。然而，硬碳的碳结构和成分复杂，在制备过程中难以实现精确控制，导致难以准确确定电化学行为的归因。在此，我们提出了一种密闭碳化策略来实现硬碳的微结构重构，其特点是将聚合物锚定在多孔碳的介孔中，从而在高温下生成有序的碳结构。有序碳在多孔碳微孔上的堆叠实现了从暴露孔到封闭孔（纳米裂隙孔）的转变。通过机理检测发现，有序碳结构为钠离子迁移提供了次纳米通道，从而提高了斜率容量。此外，纳米裂隙孔是充满钠离子的位点，可提供较高的高原容量。得益于这些可用的钠离子传输通道，碳材料通过密闭碳化实现了钠储存过程中从表面控制过程到扩散控制过程的转变。制备的碳材料在 20 mA g-1 的条件下可提供 356.2 mAh g-1 的超大容量（高原容量为 215.6 mAh g-1），并具有出色的速率和循环性能。这项工作揭示了碳电极结构与电化学性能之间的相关性，为精确制备高性能碳材料提供了深刻的指导。

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引用次数: 0

Partially sacrificial hybrid diluent regulated electrolytes boosting wide-temperature Li metal batteries 部分牺牲型混合稀释剂调节电解质促进宽温锂金属电池的发展

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-15 DOI: 10.1016/j.ensm.2024.103836

Ran He , Qinghui Zhang , Yuanyuan Hu , Haijiao Xie , ChaoYang Li , Zhenhua Yan , Kai Yang , Kuirong Deng

Designing electrolytes with superior interface compatibility for high-voltage and wide-temperature Li metal batteries (LMBs) is still challenging. Herein, a partially sacrificial hybrid diluent consisting of minor active diluent 1,3,5-trifluorobenzene (TFB) and main inert diluent fluorobenzene (FB) is proposed to regulate tetramethylene sulfone (TMS)-based localized high-concentration electrolyte (LHCE-FB-TFB) to tune the chemical activity at the electrolyte/electrode interfaces. The prior sacrificial decomposition of TFB with high LiF yielding activity cooperates with bis(fluorosulfonyl)imide (FSI⁻) anions to construct thin and durable LiF-rich solid-electrolyte interphases (SEIs) and cathode electrolyte interphases (CEIs), dramatically enhancing interface stability of Li metal anodes and LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathodes in a wide temperature range. Relatively inert low-viscosity FB exhibits powerful dilution effect, and endows the electrolyte with low viscosity and high ionic kinetics at low temperature, wide liquid range (−75∼60 °C), and favorable wettability. Li metal anodes with LHCE-FB-TFB achieve extremely stable and high-efficiency (99.3 %) cycles. LHCE-FB-TFB enables NCM811||Li cells with superior cycle performance under harsh conditions, including high voltage (4.5 V), wide temperature range from −20 °C to 60 °C, high areal capacity (3.6 mAh cm⁻²) and thin Li metal anode (50 μm). This work provides a promising strategy for the design of high-efficiency electrolytes for wide-temperature batteries.

为高电压、宽温度锂金属电池（LMB）设计具有优异界面兼容性的电解质仍然是一项挑战。本文提出了一种由次要活性稀释剂 1,3,5-三氟苯（TFB）和主要惰性稀释剂氟苯（FB）组成的部分牺牲型混合稀释剂，用于调节基于四亚甲基砜（TMS）的局部高浓度电解质（LHCE-FB-TFB），以调整电解质/电极界面的化学活性。具有高锂辉石产率活性的 TFB 经过事先牺牲分解，与双（氟磺酰）亚胺（FSI-）阴离子合作，构建了薄而耐用的富锂辉石固体电解质相间层（SEIs）和阴极电解质相间层（CEIs），从而在宽温度范围内显著提高了锂金属阳极和镍钴锰酸锂（NCM811）阴极的界面稳定性。相对惰性的低粘度 FB 具有强大的稀释作用，使电解液在低温、宽液体范围（-75∼60°C）和良好的润湿性条件下具有低粘度和高离子动力学特性。使用 LHCE-FB-TFB 的锂金属阳极可实现极其稳定和高效（99.3%）的循环。LHCE-FB-TFB 使 NCM811|| 锂电池在苛刻条件下具有卓越的循环性能，包括高电压（4.5 V）、-20°C 至 60°C 的宽温度范围、高电容（3.6 mAh cm-2）和薄锂金属阳极（50 μm）。这项工作为宽温电池高效电解质的设计提供了一种前景广阔的策略。

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引用次数: 0

A three-in-one strategy of high-entropy, single-crystal, and biphasic approaches to design O3-type layered cathodes for sodium-ion batteries 设计钠离子电池 O3 型层状阴极的高熵法、单晶法和双相法三合一策略

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-15 DOI: 10.1016/j.ensm.2024.103841

Kanghui Tian , Yuzhen Dang , Zhe Xu , Runguo Zheng , Zhiyuan Wang , Dan Wang , Yanguo Liu , Qinchao Wang

O3-type layered oxides are promising cathodes for sodium-ion batteries (SIBs). However, severe volume changes, irreversible phase transitions, and sluggish Na⁺ ion transport kinetics lead to structural collapse and severe capacity loss. Herein, a three-in-one strategy “high entropy, single crystal, and biphase” is proposed to design O3-type layered cathodes for SIBs, which achieves enhanced structural stability and Na⁺ transport kinetics by the combination effect of multimetal high-entropy, the single crystal, and Li substitution. The as-prepared high-entropy oxide (HEO) cathode, Na(Fe_1/6Co_1/6Ni_1/6Mn_1/6Ti_1/6)Li_1/6O₂, exhibits a high reversible capacity of 140.3 mAh g⁻¹, robust cycling stability, exceptional rate capability (86 mAh g⁻¹ at rates of 15C), excellent air-stability, and water-resistance ability. In situ X-ray diffraction reveals that the HEO cathode has highly reversible phase transitions and small volume change (ΔV=3.28 %). Ex situ X-ray absorption spectroscopy reveals that reversible Ni²⁺/Ni⁴⁺, Fe³⁺/Fe^3.6+, and Co³⁺/Co^3.6+ redox couples provide charge compensation for the high-entropy cathode at 2.0∼4.2 V. Notably, the full-cell battery based on the high-entropy cathode and hard carbon anode delivers a specific capacity of 134.3 mAh g⁻¹ and an energy density of 390.8 Wh kg⁻¹. This work provides valuable insights into the design of novel high-performance high-entropy cathodes for SIBs, highlighting a promising avenue for advancing rechargeable battery technology.

O3 型层状氧化物是钠离子电池（SIB）的理想阴极。然而，严重的体积变化、不可逆相变和缓慢的 Na+ 离子传输动力学会导致结构坍塌和严重的容量损失。本文提出了 "高熵、单晶、双相 "三位一体的钠离子电池 O3 型层状阴极设计策略，通过多金属高熵、单晶和锂置换的组合效应，实现结构稳定性和 Na+ 传输动力学的增强。制备的高熵氧化物（HEO）阴极--Na(Fe1/6Co1/6Ni1/6Mn1/6Ti1/6)Li1/6O2--显示出 140.3 mAh g-1 的高可逆容量、强大的循环稳定性、卓越的速率能力（在速率为 15C 时为 86 mAh g-1）、优异的空气稳定性和耐水性。原位 X 射线衍射显示，HEO 阴极具有高度可逆的相变和较小的体积变化（ΔV=3.28%）。原位 X 射线吸收光谱显示，可逆的 Ni2+/Ni4+、Fe3+/Fe3.6+ 和 Co3+/Co3.6+ 氧化还原偶在 2.0∼4.2 V 的电压下为高熵阴极提供电荷补偿。这项研究为设计用于 SIB 的新型高性能高熵阴极提供了有价值的见解，为推进可充电电池技术的发展提供了一条大有可为的途径。

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引用次数: 0

Tuning solvation behavior within electric double layer via halogenated MXene for reliable lithium metal batteries 通过卤代 MXene 调节电双层内的溶解行为，打造可靠的锂金属电池

IF 18.9 1区材料科学 Q1 CHEMISTRY, PHYSICAL

Energy Storage Materials

Pub Date : 2024-10-15 DOI: 10.1016/j.ensm.2024.103837

Qi Jin , TianZe Zhang , Zheng Dai , MingLi Zhao , LiLi Wu , Lu Li , XueQiang Zhang , XiTian Zhang

Solid electrolyte interphase (SEI)/electrolyte interface is critical in determining the lithium (Li) plating/stripping behavior. The solvation structure of Li-ion is well understood in the bulk electrolyte. Still, the mechanism of how SEI components affect the Li-ion solvation structure and desolvation energy barrier at the SEI/electrolyte interface is still unclear. Herein, Ti₃C₂ Maxine with single halogenated terminations (−Cl, −Br, −I) are synthesized and used as a model system, because their surface terminations induce a double halide-rich SEI formation (LiF and LiCl/LiBr/LiI). We examine the influence of the interaction strength between different Li halides and Li-ion on coordination number of Li ions and distribution of Li ions within the inner Helmholtz plane (IHP). A solvation sheath with a low solvent coordination number forms near the IHP of the LiBr interphase, improving the kinetics of Li deposition. Accordingly, half-cells utilising Li-carbon fiber/Ti₃C₂Br₂ electrodes exhibit a long lifespan of 12,000 h (1 mA cm⁻², 1 mAh cm⁻²). A pouch cell comprising Li-carbon fiber/Ti₃C₂Br₂ anode and LiFePO₄ cathode displays a capacity retention rate of 97 % after 300 cycles even at a low negative to positive electrode capacity ratio of 2.26. Our research provides crucial principles for the design of SEI components in Li metal batteries.

固体电解质间相（SEI）/电解质界面是决定锂（Li）电镀/剥离行为的关键。锂离子在块状电解质中的溶解结构已被充分了解。但 SEI 成分如何影响 SEI/电解质界面上的锂离子溶解结构和解溶解能垒的机制仍不清楚。在此，我们合成了具有单一卤化端点（-Cl、-Br、-I）的 Ti3C2 MXene 并将其用作模型体系，因为它们的表面端点会诱导形成富含双卤化物的 SEI（LiF 和 LiCl/LiBr/LiI）。我们研究了不同卤化锂和锂离子之间的相互作用强度对锂离子配位数和锂离子在内亥姆霍兹平面（IHP）内分布的影响。在锂硼相间的内赫尔姆霍兹面附近形成了溶剂配位数较低的溶解鞘，从而改善了锂沉积的动力学特性。因此，使用锂碳纤维/Ti3C2Br2 电极的半电池寿命长达 12000 小时（1 mA cm-2，1 mAh cm-2）。由锂碳纤维/Ti3C2Br2 阳极和磷酸铁锂阴极组成的袋式电池即使在正负极容量比为 2.26 的低水平条件下，经过 300 次循环后仍能保持 97% 的容量。我们的研究为锂金属电池中 SEI 组件的设计提供了重要原则。

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引用次数: 0