Journal of Energy Chemistry最新文献_第2页

Vanadium-site multivalent cation doping strategy of fluorophosphate cathode for low self-discharge sodium-ion batteries 低自放电钠离子电池氟磷酸盐正极钒位多价阳离子掺杂策略

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.003

Xinyuan Wang, Qian Wang, Jiakai Zhang, Yuanzhen Ma, Miao Huang, Xiaojie Liu

Na₃V₂O₂_x(PO₄)₂F₃₋₂_x (NVPOF) is considered one of the most promising cathode materials for sodium-ion batteries due to its favorable working potential and optimal theoretical specific capacity. However, its long-cycle and rate performance are significantly constrained by the low Na⁺ electronic conductivity of NVPOF. Furthermore, the prevalent self-discharge phenomenon restricts its applicability in practical applications. In this paper, the cathode material Na₃V_1.84Fe_0.16(PO₄)₂F₃ (x = 0.16) was synthesized by quantitatively introducing Fe³⁺ into the V-site of NVPOF. The introduction of Fe³⁺ significantly reduced the original bandgap and the energy barrier of NVPOF, as demonstrated through density functional theory calculations (DFT). When material x = 0.16 is employed as the cathode material for the sodium-ion battery, the Na⁺ diffusion coefficient is significantly enhanced, exhibiting a lower activation energy of 42.93 kJ mol⁻¹. Consequently, material x = 0.16 exhibits excellent electrochemical performance (rate capacity: 57.32 mA h g⁻¹ @10 C, cycling capacity: the specific capacity of 101.3 mA h g⁻¹ can be stably maintained after 1000 cycles at 1 C current density). It can also achieve a full charge state in only 2.39 min at a current density of 10 C while maintaining low energy loss across various stringent self-discharge tests. In addition, the sodium storage mechanism associated with the three-phase transition of Na_XV_1.84Fe_0.16(PO₄)₂F₃ (X = 1, 2, 3) was elucidated by a series of experiments. In conclusion, this study presents a novel approach to multifunctional advanced sodium-ion battery cathode materials.

Na3V2O2x(PO4)2F3−2x （NVPOF）由于具有良好的工作潜力和最佳的理论比容量，被认为是最有前途的钠离子电池正极材料之一。然而，NVPOF的低Na+电子导电性明显限制了其长周期和速率性能。此外，普遍存在的自放电现象限制了其在实际应用中的适用性。本文通过在NVPOF的v位上定量引入Fe3+，合成了正极材料Na3V1.84Fe0.16(PO4)2F3 （x = 0.16）。通过密度泛函理论计算（DFT）表明，Fe3+的引入显著降低了NVPOF的原始带隙和能垒。当材料x = 0.16作为钠离子电池正极材料时，Na+扩散系数显著提高，活化能较低，为42.93 kJ mol−1。因此，材料x = 0.16表现出优异的电化学性能（倍率容量：57.32 mA h g−1 @10 C，循环容量：在1 C电流密度下，循环1000次后可稳定保持101.3 mA h g−1的比容量）。在10℃的电流密度下，它也可以在2.39分钟内达到完全充电状态，同时在各种严格的自放电测试中保持低能量损失。此外，通过一系列实验阐明了NaXV1.84Fe0.16(PO4)2F3 （X = 1,2,3）三相转变相关的钠储存机制。总之，本研究为多功能高级钠离子电池正极材料提供了一条新途径。

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引用次数: 0

High-yield pentanes-plus production via hydrogenation of carbon dioxide: Revealing new roles of zirconia as promoter of iron catalyst with long-term stability 二氧化碳加氢高产正戊烷：揭示氧化锆促进铁催化剂长期稳定的新作用

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.010

Sheraz Ahmed , Junjung Rohmat Sugiarto , Wonjoong Yoon , Muhammad Irshad , Heuntae Jo , Syeda Sidra Bibi , Soek Ki Kim , Muhammad Kashif Khan , Jaehoon Kim

The metal oxide promoter decisively influences the overall performance of Fe catalysts in the direct hydrogenation of CO₂ to C₅₊ hydrocarbons. However, the roles of metal oxide promoter for Fe catalysts, particularly ZrO₂, have rarely been investigated. To plug this knowledge gap, a new Fe catalyst promoted with Na and partially reduced ZrO_x (Na-FeZrO_x-9) was developed in this study; the catalyst helped produce C₅₊ hydrocarbons in remarkably high yield (26.3% at 360 °C). In contrast to ZrO_x-free Fe-oxide, Na-FeZrO_x-9 exhibited long-term stability for CO₂ hydrogenation (750 h on-stream). The findings revealed multiple roles of ZrO_x. Notably, ZrO_x decorated the Fe-oxide particles after calcination, thereby suppressing excess particle aggregation during the reaction, and acted as a “coke remover” to eliminate the carbon deposited on the catalyst surface. Additionally, oxygen vacancy (O_v) sites in ZrO_x and electron transfer from ZrO_x to Fe sites facilitated the adsorption of CO₂ at the Zr-Fe interface.

在CO2直接加氢制C5+烃过程中，金属氧化物助剂对Fe催化剂的整体性能有决定性影响。然而，金属氧化物促进剂的作用，特别是ZrO2，很少被研究。为了填补这一空白，本研究开发了一种新的以Na和部分还原的ZrOx促进的Fe催化剂（Na- fezrox -9）；在360°C时，C5+碳氢化合物的产率高达26.3%。与不含zrox的Fe-oxide相比，Na-FeZrOx-9在CO2加氢过程中表现出长期稳定性（750 h）。研究结果揭示了ZrOx的多重作用。值得注意的是，ZrOx在煅烧后修饰了氧化铁颗粒，从而抑制了反应过程中过量的颗粒聚集，并起到了“除焦剂”的作用，消除了沉积在催化剂表面的碳。此外，ZrOx中的氧空位（Ov）位点和ZrOx向Fe位点的电子转移促进了CO2在Zr-Fe界面的吸附。

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引用次数: 0

Precursor-chemistry engineering toward ultrapermeable carbon molecular sieve membrane for CO2 capture 二氧化碳捕集用超渗透碳分子筛膜的前体化学工程

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.006

Mengjie Hou , Lin Li , Ruisong Xu , Yunhua Lu , Jing Song , Zhongyi Jiang , Tonghua Wang , Xigao Jian

Carbon capture is an important strategy and is implemented to achieve the goals of CO₂ reduction and carbon neutrality. As a high energy-efficient technology, membrane-based separation plays a crucial role in CO₂ capture. It is urgently needed for membrane-based CO₂ capture to develop the high-performance membrane materials with high permeability, selectivity, and stability. Herein, ultrapermeable carbon molecular sieve (CMS) membranes are fabricated by pyrolyzing a finely-engineered benzoxazole-containing copolyimide precursor for efficient CO₂ capture. The microstructure of CMS membrane has been optimized by initially engineering the precursor-chemistry and subsequently tuning the pyrolysis process. Deep insights into the structure-property relationship of CMSs are provided in detail by a combination of experimental characterization and molecular simulations. We demonstrate that the intrinsically high free volume environment of the precursor, coupled with the steric hindrance of thermostable contorted fragments, promotes the formation of loosely packed and ultramicroporous carbon structures within the resultant CMS membrane, thereby enabling efficient CO₂ discrimination via size sieving and affinity. The membrane achieves an ultrahigh CO₂ permeability, good selectivity, and excellent stability. After one month of long-term operation, the CO₂ permeability in the mixed gas is maintained at 11,800 Barrer, with a CO₂/N₂ selectivity exceeding 60. This study provides insights into the relationship between precursor-chemistry and CMS performance, and our ultrapermeable CMS membrane, which is scalable using thin film manufacturing, holds great potential for industrial CO₂ capture.

碳捕获是实现二氧化碳减排和碳中和目标的一项重要战略。膜分离技术作为一种高能效技术，在CO2捕集中起着至关重要的作用。开发具有高通透性、选择性和稳定性的高性能膜材料是膜基CO2捕集技术的迫切需要。本文通过热解一种精心设计的含苯并恶唑的共聚亚胺前驱体制备了超渗透性碳分子筛（CMS）膜，用于高效捕获二氧化碳。通过对前驱体化学的初步设计和对热解过程的调整，对CMS膜的微观结构进行了优化。通过实验表征和分子模拟的结合，深入了解了cms的结构-性质关系。我们证明了前驱体固有的高自由体积环境，加上热稳定性扭曲碎片的空间位阻，促进了CMS膜内松散堆积和超微孔碳结构的形成，从而通过粒度筛选和亲和力实现了有效的CO2识别。该膜具有超高的CO2渗透性、良好的选择性和优异的稳定性。经过一个月的长期运行，混合气中CO2渗透率保持在11800 Barrer， CO2/N2选择性超过60。这项研究提供了前驱体化学与CMS性能之间关系的见解，我们的超渗透CMS膜，可通过薄膜制造进行扩展，具有巨大的工业二氧化碳捕集潜力。

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引用次数: 0

Synergistic strain engineering of the perovskite films for improving flexible inverted perovskite solar cells under convex bending 改进凸面弯曲条件下柔性倒置包晶体太阳能电池的包晶体薄膜协同应变工程

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-17 DOI: 10.1016/j.jechem.2024.11.008

Yong Gang , Lu Xu , Silong Tu , Shusen Jiang , Yan Zhang , Hao Wang , Cheng Li , Xin Li

Flexible perovskite solar cells (fPSCs) have demonstrated commercial viability because of their promising lightness, flexibility, and low-cost advantages. However, in most applications, the fPSCs suffer from constant external stress, such as being kept at a convex bending state, imposing external stress on the brittle perovskite films and causing the fPSCs long-term stability problems. Overcoming these issues is vital. Herein, we propose an effective way to enhance the stability of the fPSCs under convex bending by modulating the residual stress of perovskite film for the first time. Specifically, we have carefully designed a synergistic strain engineering to toughen the perovskite films by introducing 1-butyl-3-methylimidazolium tetrafluoroborate, citric acid, and a novel cross-linker, 5-(1,2-dithiolan-3-yl) pentanoate into perovskite films simultaneously. Besides passivating the perovskite films, the multiple additives effectively convert the residual stress within the perovskite films from tensile to compressive type to alleviate the detrimental impact of bending on the flexible perovskite films. As a result, the optimal efficiencies of triple-additive modified fPSCs have achieved 22.19% (0.06 cm²) and 19.44% (1.02 cm²). More importantly, the strategy could significantly improve the stability of the perovskite films and fPSCs at a convex bending state. Our approach is inductive for the future practical field applications of high-performance fPSCs.

柔性过氧化物太阳能电池（fPSCs）因其轻巧、灵活和低成本等优势，已显示出商业可行性。然而，在大多数应用中，柔性透辉石太阳能电池都会受到持续的外部应力影响，如保持凸面弯曲状态，给脆性透辉石薄膜带来外部应力，从而导致柔性透辉石太阳能电池的长期稳定性问题。克服这些问题至关重要。在此，我们首次提出了一种通过调节包光体薄膜的残余应力来增强 fPSCs 在凸弯曲状态下稳定性的有效方法。具体来说，我们精心设计了一种协同应变工程，通过同时向包晶薄膜中引入 1-丁基-3-甲基咪唑四氟硼酸盐、柠檬酸和新型交联剂 5-（1,2-二硫环戊-3-基）戊酸酯来增韧包晶薄膜。除了使包晶石薄膜钝化，多种添加剂还能有效地将包晶石薄膜内的残余应力从拉伸型转化为压缩型，从而减轻弯曲对柔性包晶石薄膜的不利影响。因此，三重添加剂修饰的 fPSC 的最佳效率分别达到了 22.19%（0.06 平方厘米）和 19.44%（1.02 平方厘米）。更重要的是，该策略能显著提高包晶薄膜和 fPSC 在凸弯曲状态下的稳定性。我们的方法对未来高性能 fPSC 的实际现场应用具有指导意义。

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引用次数: 0

High-entropy sulfides enhancing adsorption and catalytic conversion of lithium polysulfides for lithium-sulfur batteries 高熵硫化物可增强用于锂硫电池的多硫化锂的吸附和催化转化能力

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-14 DOI: 10.1016/j.jechem.2024.11.002

Yating Huang , Jiajun Wang , Wei Zhao , Lujun Huang , Jinpeng Song , Yajie Song , Shaoshuai Liu , Bo Lu

Lithium-sulfur (Li-S) batteries with high energy density suffer from the soluble lithium polysulfide species. Traditional metal sulfides containing a single metal element used as electrocatalysts for Li-S batteries commonly have limited catalytic abilities to improve battery performance. Herein, based on the Hume-Rothery rule and solvothermal method, the high-entropy sulfide NiCoCuTiVS_x derived from Co₉S₈ was designed and synthesized, to realize the combination of small local strain and excellent catalytic performance. With all five metal elements (Ni, Co, Cu, Ti, and V) capable of chemical interactions with soluble polysulfides, NiCoCuTiVS_x exhibited strong chemical confinement of polysulfides and promoted fast kinetics for polysulfides conversion. Consequently, the S/NiCoCuTiVS_x cathode can maintain a high discharge capacity of 968.9 mA h g⁻¹ after 200 cycles at 0.5 C and its capacity retention is 1.3 times higher than that of S/Co₉S₈. The improved cycle stability can be attributed to the synergistic effect originating from the multiple metal elements, coupled with the reduced nucleation and activation barriers of Li₂S. The present work opens a path to explore novel electrocatalyst materials based on high entropy materials for the achievement of advanced Li-S batteries.

高能量密度的锂硫（Li-S）电池受到可溶性多硫化锂物种的影响。传统的含单一金属元素的金属硫化物作为锂-硫电池的电催化剂，通常在提高电池性能方面的催化能力有限。本文基于 Hume-Rothery 规则和溶热法，设计并合成了源自 Co9S8 的高熵硫化物 NiCoCuTiVSx，实现了局部应变小和催化性能优异的结合。由于五种金属元素（Ni、Co、Cu、Ti 和 V）都能与可溶性多硫化物发生化学作用，NiCoCuTiVSx 对多硫化物具有很强的化学约束作用，并能促进多硫化物的快速转化。因此，S/NiCoCuTiVSx 阴极在 0.5 C 下循环 200 次后，仍能保持 968.9 mA h g-1 的高放电容量，其容量保持率是 S/Co9S8 的 1.3 倍。循环稳定性的提高可归因于多种金属元素的协同效应，以及 Li2S 成核和活化障碍的降低。本研究为探索基于高熵材料的新型电催化剂材料以实现先进的锂-S 电池开辟了一条道路。

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引用次数: 0

Suppressing high voltage chemo-mechanical degradation in single crystal nickel-rich cathodes for high-performance all-solid-state lithium batteries 抑制高性能全固态锂电池用富镍单晶阴极的高压化学机械降解

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-13 DOI: 10.1016/j.jechem.2024.10.051

Yirong Xiao , Le Yang , Chaoyuan Zeng , Ze Hua , Shuangquan Qu , Niaz Ahmad , Ruiwen Shao , Wen Yang

Sulfide-based all-solid-state lithium batteries suffer from electrochemo-mechanical damage to Ni-rich oxide-based cathode active materials (CAMs), primarily caused by severe volume changes, results in significant stress and strain, causes micro-cracks and interfacial contact loss at potentials > 4.3 V(vs. Li/Li⁺). Quantifying micro-cracks and voids in CAMs can reveal the degradation mechanisms of Ni-rich oxide-based cathodes during electrochemical cycling. Nonetheless, the origin of electrochemical-mechanical damage remains unclear. Herein, We have developed a multifunctional PEG-based soft buffer layer (SBL) on the surface of carbon black (CB). This layer functions as a percolation network in the single crystal LiNi_0.83Co_0.07Mn_0.1O₂ and Li₆PS₅Cl composite cathode layer, ensuring superior ionic conductivity, reducing void formation and particle cracking, and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries (ASSLBs). High-angle annular dark-field STEM combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode. This strain produces lattice stretches, distortions, and curved transition metal oxide layers near the surface, contributing to structural degradation at elevated voltages. Consequently, ASSLBs with a LiNi_0.83Co_0.07Mn_0.1O₂ cathode containing LCCB-10 (CB/PEG mass ratio: 100/10) demonstrate a high areal capacity (2.53 mAh g⁻¹/0.32 mA g⁻¹) and remarkable rate capability (0.58 mAh g⁻¹ at 1.4 mA g⁻¹), with 88% capacity retention over 1000 cycles.

硫化物基全固态锂电池对富镍氧化物基正极活性材料（CAMs）的电化学-机械损伤主要是由剧烈的体积变化引起的，导致显著的应力和应变，导致微裂纹和界面接触损失。4.3 V (vs。李/李+)。定量分析cam中的微裂纹和空隙可以揭示富镍氧化物基阴极在电化学循环过程中的降解机理。尽管如此，电化学-机械损伤的起源仍不清楚。在此，我们在炭黑（CB）表面开发了一种基于聚乙二醇的多功能软缓冲层（SBL）。该层在单晶LiNi0.83Co0.07Mn0.1O2和Li6PS5Cl复合阴极层中起到渗透网络的作用，保证了优异的离子电导率，减少了空洞的形成和颗粒的开裂，促进了阴极活性材料在全固态锂电池（ASSLBs）中的均匀利用。高角度环形暗场STEM结合纳米x射线全息成像和等离子体聚焦离子束扫描电镜证实，peg基SBL减轻了阴极中反应非均质性引起的应变。这种应变在表面附近产生晶格拉伸、扭曲和弯曲的过渡金属氧化物层，导致在高电压下结构退化。因此，含有LCCB-10 （CB/PEG质量比：100/10）的LiNi0.83Co0.07Mn0.1O2阴极的asslb具有高的面容量（2.53 mAh g−1/0.32 mA g−1）和显着的倍率容量（0.58 mAh g−1,1.4 mA g−1），在1000次循环中容量保持率为88%。

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引用次数: 0

Very low Ru loadings boosting performance of Ni-based dual-function materials during the integrated CO2 capture and methanation process 在二氧化碳捕获和甲烷化一体化过程中，极低的 Ru 负荷可提高镍基双功能材料的性能

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-13 DOI: 10.1016/j.jechem.2024.11.001

Anastasios I. Tsiotsias , Eleana Harkou , Nikolaos D. Charisiou , Victor Sebastian , Dhanaji R. Naikwadi , Bart van der Linden , Atul Bansode , Dragos Stoian , George Manos , Achilleas Constantinou , Maria A. Goula

Herein, the effect of the Ru:Ni bimetallic composition in dual-function materials (DFMs) for the integrated CO₂ capture and methanation process (ICCU-Methanation) is systematically evaluated and combined with a thorough material characterization, as well as a mechanistic (in-situ diffuse reflectance infrared fourier-transform spectroscopy (in-situ DRIFTS)) and computational (computational fluid dynamics (CFD) modelling) investigation, in order to improve the performance of Ni-based DFMs. The bimetallic DFMs are comprised of a main Ni active metallic phase (20 wt%) and are modified with low Ru loadings in the 0.1–1 wt% range (to keep the material cost low), supported on Na₂O/Al₂O₃. It is shown that the addition of even a very low Ru loading (0.1–0.2 wt%) can drastically improve the material reducibility, exposing a significantly higher amount of surface-active metallic sites, with Ru being highly dispersed over the support and the Ni phase, while also forming some small Ru particles. This manifests in a significant enhancement in the CH₄ yield and the CH₄ production kinetics during ICCU-Methanation (which mainly proceeds via formate intermediates), with 0.2 wt% Ru addition leading to the best results. This bimetallic DFM also shows high stability and a relatively good performance under an oxidizing CO₂ capture atmosphere. The formation rate of CH₄ during hydrogenation is then further validated via CFD modelling and the developed model is subsequently applied in the prediction of the effect of other parameters, including the inlet H₂ concentration, inlet flow rate, dual-function material weight, and reactor internal diameter.

本文系统地评估了用于集成二氧化碳捕集与甲烷化工艺（ICCU-Methanation）的双功能材料（DFMs）中 Ru:Ni 双金属成分的影响，并结合全面的材料表征、机理（原位漫反射红外傅立叶变换光谱法（in-situ DRIFTS））和计算（计算流体动力学（CFD）建模）研究，以提高镍基 DFMs 的性能。双金属 DFM 由主要的镍活性金属相（20 wt%）和 0.1-1 wt% 的低 Ru 负载（以保持较低的材料成本）组成，支撑在 Na2O/Al2O3 上。研究表明，即使添加极低的 Ru 负荷（0.1-0.2 wt%），也能显著提高材料的还原性，暴露出更多的表面活性金属位点，Ru 高度分散在支撑物和镍相中，同时还形成一些小的 Ru 颗粒。这表现在 ICCU-甲烷化（主要通过甲酸中间体进行）过程中，CH4 产率和 CH4 生成动力学显著提高，其中 0.2 wt% 的 Ru 添加量效果最佳。这种双金属 DFM 在氧化性二氧化碳捕集气氛下也表现出很高的稳定性和相对较好的性能。随后，通过 CFD 建模进一步验证了氢化过程中 CH4 的形成率，并将所开发的模型用于预测其他参数的影响，包括入口 H2 浓度、入口流速、双功能材料重量和反应器内径。

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引用次数: 0

Construction of W1-Zn dinuclear sites to boost nitrite electroreduction to ammonia 构建 W1-Zn 双核位点，促进亚硝酸盐电还原成氨

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-13 DOI: 10.1016/j.jechem.2024.10.054

Zhuohang Li , Ying Zhang , Xiang Li , Ruizhi Liang , Ye Tian , Ke Chu

Electroreduction of nitrite to ammonia (NO₂RR) is recognized as an appealing method for achieving renewable NH₃ production and waste NO₂⁻ removal. Herein, monodispersed W-doped ZnO (W₁-ZnO) is developed as an efficient NO₂RR catalyst. Theoretical simulations and in situ spectroscopic measurements unravel that the enhanced NO₂RR property of W₁-ZnO originates from the creation of active W₁-Zn dinuclear sites to selectively activate NO₂⁻ and enhance the protonation energetics of NO₂⁻-to-NH₃ pathway, whilst repelling the competing H₂ evolution. Strikingly, W₁-ZnO equipped in flow cell shows an impressive NO₂RR performance with NH₃ yield rate of 970 μmol h⁻¹ cm⁻² and NH₃-Faradaic efficiency of 94.5%.

亚硝酸盐电还原为氨（NO2RR）被认为是实现可再生 NH3 生产和清除废弃 NO2- 的一种有吸引力的方法。本文开发了单分散掺杂 W 的氧化锌（W1-ZnO），作为一种高效的 NO2RR 催化剂。理论模拟和原位光谱测量揭示了 W1-ZnO 的 NO2RR 增强特性源于活性 W1-Zn 二核位点的产生，它能选择性地激活 NO2-，增强 NO2-到 NH3 途径的质子化能量，同时排斥竞争性的 H2 演化。引人注目的是，在流动池中装备的 W1-ZnO 显示出令人印象深刻的 NO2RR 性能，NH3 产率达到 970 μmol h-1 cm-2，NH3-Faradaic 效率达到 94.5%。

引用次数: 0

Improving Na3V2(PO4)2F3 half-cell performance with NaBF4-enhanced sodium difluoro(oxalato)borate electrolyte 用nabf4增强的二氟硼酸钠电解质改善Na3V2(PO4)2F3半电池性能

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-13 DOI: 10.1016/j.jechem.2024.10.053

Jia Zhang , Jianwei Li , Guofeng Jia , Huaiyou Wang , Min Wang

The global shift towards low-carbon energy storage has increased interest in sodium-ion batteries (SIBs) as a safer, cost-effective alternative to lithium-ion batteries. However, the commercial viability has been limited by compatibility issues between high-energy-density cathode materials, such as Na₃V₂(PO₄)₂F₃ (NVPF), and high-voltage electrolytes. Addressing the challenges, H-NaODFB (comprising 93.91% NaODFB and 5.85% NaBF₄) electrolyte significantly improves the electrochemical performance and stability of NVPF cathodes. Na/NVPF half-cells using H-NaODFB electrolyte retained 92.4% capacity after 900 cycles, while Na/Na symmetric cells demonstrated a cycle life exceeding 600 h at 0.5 mA cm⁻². The superior performance is attributed to improved Na⁺ (de)intercalation reversibility, lower interfacial impedance (619.8 vs. 10,650.0 Ω), and faster reaction kinetics compared to NaODFB alone. Advanced time of flight-secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS) and aberration corrected transmission electron microscope (AC-TEM), combined with first-principles calculations, revealed that NaBF₄ in the H-NaODFB electrolyte plays a critical role in forming a stable cathode electrolyte interphase (CEI). The CEI consists of an initial inorganic and organic layer, followed by a fluoroborate layer, and finally a stable organic–inorganic polymeric layer, enhancing electrode stability and preventing over-oxidation. These findings provide valuable insights for designing high-performance electrolytes for SIBs.

全球向低碳能源存储的转变增加了人们对钠离子电池（sib）的兴趣，钠离子电池是锂离子电池的一种更安全、更经济的替代品。然而，商业可行性受到高能量密度阴极材料(如Na3V2（PO4)2F3 (NVPF)）与高压电解质之间兼容性问题的限制。针对这一挑战，H-NaODFB（由93.91% NaODFB和5.85% NaBF4组成）电解质显著提高了NVPF阴极的电化学性能和稳定性。使用h - naodfb电解质的Na/NVPF半电池在900次循环后仍保持92.4%的容量，而Na/Na对称电池在0.5 mA cm−2下的循环寿命超过600小时。与NaODFB相比，其优越的性能归功于Na+ (de)嵌入可逆性的改善，更低的界面阻抗（619.8 vs. 10,650.0 Ω）和更快的反应动力学。先进的飞行时间离子质谱（TOF-SIMS）、x射线光电子能谱（XPS）和像差校正透射电镜（AC-TEM）结合第一线原理计算，揭示了H-NaODFB电解质中的NaBF4在形成稳定的阴极电解质间相（CEI）中起着关键作用。CEI由初始的无机和有机层组成，其次是氟硼酸盐层，最后是稳定的有机-无机聚合物层，增强了电极的稳定性并防止过氧化。这些发现为设计高性能sib电解质提供了有价值的见解。

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引用次数: 0

Breath inspired multifunctional low-cost inorganic colloidal electrolyte for stable zinc metal anode 用于稳定锌金属阳极的呼吸启发式多功能低成本无机胶体电解质

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry

Pub Date : 2024-11-08 DOI: 10.1016/j.jechem.2024.10.049

Mengyu Rong , Yifu Zhang , Xianfang Tan , Yang Wang , Na Gao , Chi Huang , Changgong Meng

The practical application of aqueous zinc-ion batteries (AZIBs) is primarily constrained by issues such as corrosion, zinc dendrite formation, and the hydrogen evolution reaction occurring at the zinc metal anode. To overcome these challenges, strategies for optimizing the electrolyte are crucial for enhancing the stability of the zinc anode. Inspired by the role of hemoglobin in blood cells, which facilitates oxygen transport during human respiration, an innovative inorganic colloidal electrolyte has been developed: calcium silicate-ZnSO₄ (denoted as CS-ZSO). This electrolyte operates in weak acidic environment and releases calcium ions, which participate in homotopic substitution with zinc ions, while the solvation environment of hydrated zinc ions in the electrolyte is regulated. The reduced energy barrier for the transfer of zinc ions and the energy barrier for the desolvation of hydrated ions imply faster ion transfer kinetics and accelerated desolvation processes, thus favoring the mass transfer process. Furthermore, the silicate colloidal particles act as lubricants, improving the transfer of zinc ions. Together, these factors contribute to the more uniform concentration of zinc ions at the electrode/electrolyte interface, effectively inhibiting zinc dendrite formation and reducing by-product accumulation. The Zn//CS-ZSO//Zn symmetric cell demonstrates stable operation for over 5000 h at 1 mA cm⁻², representing 29-fold improvement compared to the Zn//ZSO//Zn symmetric cell, which lasts only 170 h. Additionally, the Zn//CS-ZSO//Cu asymmetric cell shows stable average Coulombic efficiency (CE) exceeding 99.6% over 2400 cycles, significantly surpassing the performance of the ZSO electrolyte. This modification strategy for electrolytes not only addresses key limitations associated with zinc anodes but also provides valuable insights into stabilizing anodes for the advancement of high-performance aqueous zinc-ion energy storage systems.

锌离子水电池（AZIBs）的实际应用主要受到腐蚀、锌枝晶形成和锌金属阳极发生氢进化反应等问题的制约。为了克服这些挑战，优化电解质的策略对于提高锌阳极的稳定性至关重要。血红蛋白在血细胞中起着促进人类呼吸过程中氧气运输的作用，受此启发，一种创新的无机胶体电解质应运而生：硅酸钙-ZnSO4（简称 CS-ZSO）。这种电解质可在弱酸性环境中工作，并释放出钙离子，钙离子参与锌离子的同位取代，同时调节电解质中水合锌离子的溶解环境。锌离子转移的能量障碍和水合离子脱溶的能量障碍降低，意味着离子转移动力学加快，脱溶过程加速，从而有利于传质过程。此外，硅酸盐胶体颗粒还能起到润滑剂的作用，改善锌离子的转移。这些因素共同作用，使电极/电解质界面上的锌离子浓度更加均匀，有效抑制了锌枝晶的形成，减少了副产物的积累。Zn//CS-ZSO//Zn 对称电池在 1 mA cm-2 电流条件下可稳定工作 5000 小时以上，与仅能工作 170 小时的 Zn//ZSO//Zn 对称电池相比，性能提高了 29 倍。这种电解质改性策略不仅解决了锌阳极的主要局限性，还为稳定阳极以促进高性能水性锌离子储能系统的发展提供了宝贵的见解。

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