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The role of dopants in mitigating the chemo-mechanical degradation of Ni-rich cathode: A critical review 掺杂剂在减轻富镍阴极化学-机械降解中的作用:综述
Pub Date : 2025-01-20 DOI: 10.1002/ece2.92
Imesha Rambukwella, Hanisha Ponnuru, Cheng Yan

Ni-rich cathodes are more promising candidates to the increasing demand for high capacity and the ability to operate at high voltages. However, the high Ni content creates a trade-off between energy density and cycling stability, mainly caused by the chemo-mechanical degradation. Oxygen evolution, cation mixing, rock salt formation, phase transition, and crack formation contribute to the degradation process. To overcome this problem, strategies such as doping, surface coating, and core-shell structures have been employed. The advantage of doping is to engineer the cathode surface, structure, and particle morphology simultaneously. This review aims to summarize recent advances in understanding chemo-mechanical degradation mechanism and the role of different dopants in enhancing the thermal stability and overall electrochemical performance. The pinning and pillaring effects of dopants on suppressing oxygen evolution, cation mixing, and phase transition are introduced. It is found that the higher ionic radii enable dopants to reside on cathode particles, preserving the particle surface and refining particle morphology to suppress crack formation. Finally, the effect of doping on Li ion diffusion, rate capability, and long-term stability are discussed.

随着对高容量和高电压工作能力的需求不断增加,富镍阴极是更有希望的候选材料。然而,高镍含量造成了能量密度和循环稳定性之间的权衡,主要是由化学-机械降解引起的。析氧、阳离子混合、岩盐形成、相变和裂缝形成都有助于降解过程。为了克服这一问题,采用了掺杂、表面涂层和核壳结构等策略。掺杂的优点是可以同时设计阴极的表面、结构和颗粒形态。本文综述了近年来在化学-机械降解机制以及不同掺杂剂在提高热稳定性和整体电化学性能方面的作用方面的研究进展。介绍了掺杂剂在抑制析氧、阳离子混合和相变方面的钉钉和柱撑效应。发现较高的离子半径使掺杂剂能够驻留在阴极颗粒上,保持颗粒表面,细化颗粒形态,从而抑制裂纹的形成。最后讨论了掺杂对锂离子扩散、速率能力和长期稳定性的影响。
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引用次数: 0
1 min synthesis of phase pure nanocrystalline high-entropy sulfides for efficient water electrolysis 1分钟合成相纯纳米高熵硫化物用于高效水电解
Pub Date : 2025-01-17 DOI: 10.1002/ece2.91
Judith Zander, Roland Marschall

The development of noble-metal free electrocatalysts with low production cost is of utmost importance for sustainable water electrolysis. Herein, we present a fast flexible synthesis pathway for the preparation of a variety of different medium- and high-entropy spinel sulfides of various compositions, using a non-aqueous microwave-assisted synthesis without any H2S. Nanoparticulate high-entropy sulfides containing up to 8 different metal cations can be obtained after an extremely short synthesis time of only 1 min and comparatively low temperatures of 200–230°C. We further demonstrate the high activity of the obtained sulfides for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER).

开发低成本的无贵金属电催化剂是实现可持续水电解的重要手段。在此,我们提出了一种快速灵活的合成途径,用于制备各种不同组成的中高熵尖晶石硫化物,使用非水微波辅助合成,不含任何H2S。在极短的合成时间(仅为1分钟)和相对较低的200-230°C后,可以获得含有多达8种不同金属阳离子的纳米高熵硫化物。我们进一步证明了获得的硫化物在析氢反应(HER)和析氧反应(OER)中都具有高活性。
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引用次数: 0
Nanoflower MnxNi2−xP as efficient bifunctional catalyst for hydrogen production with urea-assisted energy-saving in alkaline freshwater and seawater 纳米花MnxNi2−xP作为高效双功能催化剂在碱性淡水和海水中尿素辅助节能制氢
Pub Date : 2025-01-05 DOI: 10.1002/ece2.90
Min Song, Xue Yang, Chenyang Guo, Shuo Zhang, Junwei Ma, Hongtao Gao

To achieve efficient and stable hydrogen production while addressing the corrosive effects of seawater on electrodes, integrating the energy-saving urea oxidation reaction (UOR) with the hydrogen evolution reaction (HER) presents a promising low-energy solution. However, developing low-cost, high-performance bifunctional electrocatalysts for both HER and UOR remains a significant challenge. In this work, we prepared bifunctional electrocatalysts featuring MnxNi2−xP nanoflower structures grown on nickel foam using a simple hydrothermal phosphatization method. These catalysts demonstrated excellent performance in alkaline freshwater and seawater, with notably low overpotentials of 251 and 257 mV for HER, and 1.33 and 1.37 V for UOR. Combining its bifunctional activity in UOR and HER in a two-electrode system, an energy saving of 0.19 V potential compared to water electrolysis through water oxidation can be acquired to reach 100 mA cm−2 current density. Moreover, the catalyst also maintains fairly stable after long-term testing, indicating its potential for efficient and energy-saving hydrogen production. Our study reveals that the synergistic interaction between Ni and Mn metals enhances the electronic structure of the electrocatalysts, significantly boosting both UOR and HER activities. Additionally, Mn doping alters the morphological structure, creating nanoflowers with abundant active sites, while nickel-iron phosphides improve the catalyst's corrosion resistance in seawater. This work provides valuable insights into the design of low-cost, stable non-precious metal electrocatalysts for seawater and freshwater splitting, combining hydrogen evolution with urea-assisted energy-saving.

为了实现高效稳定的制氢,同时解决海水对电极的腐蚀问题,将节能尿素氧化反应(UOR)与析氢反应(HER)相结合是一种很有前途的低能耗解决方案。然而,为HER和UOR开发低成本、高性能的双功能电催化剂仍然是一个重大挑战。在这项工作中,我们采用简单的水热磷化方法,在泡沫镍上制备了具有MnxNi2−xP纳米花结构的双功能电催化剂。这些催化剂在碱性淡水和海水中表现出优异的性能,HER的过电位分别为251和257 mV, UOR的过电位分别为1.33和1.37 V。结合其在UOR和HER双电极系统中的双功能活性,与通过水氧化进行电解相比,可获得0.19 V电位的节能,电流密度可达到100 mA cm−2。此外,该催化剂经过长期测试也保持了相当的稳定性,表明其具有高效节能制氢的潜力。我们的研究表明,Ni和Mn金属之间的协同作用增强了电催化剂的电子结构,显著提高了UOR和HER活性。此外,Mn的掺杂改变了催化剂的形态结构,形成了具有丰富活性位点的纳米花,而镍铁磷化物提高了催化剂在海水中的耐腐蚀性。这项工作为设计低成本,稳定的非贵金属电催化剂提供了有价值的见解,用于海水和淡水的分裂,将析氢与尿素辅助节能相结合。
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引用次数: 0
Thermoelectric performance enhancement of environmentally-friendly SrTiO3 epitaxial films by hydrogen substitution 氢取代法提高环保SrTiO3外延薄膜热电性能
Pub Date : 2024-12-25 DOI: 10.1002/ece2.89
Masatoshi Kimura, Masahiro Ochiai, Xinyi He, Takayoshi Katase, Hidenori Hiramatsu, Hideo Hosono, Toshio Kamiya

Developing high-efficiency and environmentally-friendly thermoelectric materials has been a significant challenge. Conventional thermometric materials consist of heavy (toxic) elements to reduce thermal conductivity (κ), while we demonstrated light-element hydride anion (H) substitution in SrTiO3 can largely reduce κ and enhance thermometric efficiency (ZT) without heavy elements. In this paper, we succeeded in maximizing the ZT of SrTiO3−xHx by applying topochemical reaction directly to SrTiO3 epitaxial films with CaH2, which realized wide-range control of carrier concentration (ne) from 1.5 × 1020 cm−3 to 4.1 × 1021 cm−3. The power factor (PF) showed a dome-shaped behavior with respect to ne, and the maximum PF = 22.5 μW/(cmK2) was obtained at the optimal ne = 3.4 × 1020 cm−3. Carrier transport analyses clarified that the carrier mobility was limited by impurity scattering of H-related impurities in the SrTiO3−xHx films, while the hydrogen substitution induced a much lower κ of 4.6 W/(mK) than other heavy-element substituted Sr1−xLaxTiO3 and SrTi1−xNbxO3 films in the wide ne range, resulting in the higher ZT value of 0.14 in maximum at room temperature. In addition, the ZT increased to 0.17 at 373 K due to the large decrease in κ for a SrTiO3−xHx film with the hydrogen concentration of 1.2 × 1021 cm−3. Further study on H substitution approach and modulation of the H state in transition metal oxides would lead to development of high ZT environmentally-friendly thermoelectric materials.

开发高效环保的热电材料一直是一项重大挑战。传统的测温材料由重(有毒)元素组成,以降低热导率(κ),而我们证明了在SrTiO3中取代轻元素氢化物阴离子(H−)可以在没有重元素的情况下大大降低κ并提高测温效率(ZT)。在本文中,我们通过与CaH2直接在SrTiO3外延膜上进行拓扑化学反应,成功地最大化了SrTiO3 - xHx的ZT,实现了载流子浓度(ne)从1.5 × 1020 cm−3到4.1 × 1021 cm−3的大范围控制。功率因数(PF)随ne的变化呈圆形,在最优ne = 3.4 × 1020 cm−3时,最大PF = 22.5 μW/(cmK2)。载流子输运分析表明,SrTiO3−xHx薄膜中h相关杂质的散射限制了载流子的迁移率,而氢取代在较宽的ne范围内诱导的κ值为4.6 W/(mK),远低于其他重元素取代的Sr1−xLaxTiO3和SrTi1−xNbxO3薄膜,导致室温下ZT值最高为0.14。此外,当氢浓度为1.2 × 1021 cm−3时,SrTiO3−xHx薄膜的κ值大幅降低,ZT在373 K时增加到0.17。进一步研究H -取代方法和过渡金属氧化物中H态的调制将有助于开发高ZT环保型热电材料。
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引用次数: 0
Modulation of Ti3C2Tx interlayer spacing and functional groups by Lewis-basic halides and their effects on Li+ storage properties 路易斯碱卤化物对Ti3C2Tx层间距和官能团的调制及其对Li+存储性能的影响
Pub Date : 2024-12-15 DOI: 10.1002/ece2.88
Xuke Li, Keke Guan, Lixiang Ding, Xinyue Wang, Haijun Zhang, Yaping Deng, Wen Lei

Surface and interfacial chemistry play a vital role in shaping the properties of two-dimensional transition metal carbides and nitrides (MXenes). This study focuses on utilizing Lewis-basic halides (LiCl/KCl) for thermal treatment of multilayered Ti3C2Tx, leading to the simultaneous modulation of interlayer spacing and surface functional groups. Compared to the pristine Ti3C2Tx, the LiCl/KCl treated sample (heating temperature: 450°C, denoted as LK-Ti3C2Tx-450) showcases a remarkable increase in the interlayer spacing and synergistic optimization of the functional groups. These modifications endow LK-Ti3C2Tx-450 with enhanced electrochemical properties, rendering it as a promising anode candidate for lithium-ion batteries. The increased interlayer spacing is particularly advantageous, as it facilitates efficient and rapid Li+ diffusion, a vital factor in enhancing the performance of energy storage devices.

表面和界面化学在形成二维过渡金属碳化物和氮化物(MXenes)的性质中起着至关重要的作用。本研究的重点是利用刘易斯碱卤化物(LiCl/KCl)对多层Ti3C2Tx进行热处理,导致层间距和表面官能团的同步调制。与原始Ti3C2Tx相比,LiCl/KCl处理后的样品(加热温度为450℃,标记为LK-Ti3C2Tx-450)层间距显著增加,官能团协同优化。这些修饰使LK-Ti3C2Tx-450具有增强的电化学性能,使其成为锂离子电池极具前景的阳极候选材料。层间距的增加是特别有利的,因为它促进了Li+的高效和快速扩散,这是提高储能设备性能的重要因素。
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引用次数: 0
Fundamental understanding of texturing electrodeposition metal zinc anodes for practical aqueous Zn-ion batteries 对实际含水锌离子电池中变形电沉积金属锌阳极的基本认识
Pub Date : 2024-12-15 DOI: 10.1002/ece2.86
Qiangchao Sun, Xijun Liu, Linhui Chang, Min Lin, Xionggang Lu, Hongwei Cheng

One of the most promising electrochemical energy storage technologies, aqueous zinc ion batteries (AZIBs), is garnering increasing attention due to their inherent safety, high sustainability, and low cost. However, the challenges posed by dendrite formation and side reactions resulting from uneven deposition of zinc metal anodes significantly impede the reversibility and cycling stability of AZIBs. Given the influence of crystallographic anisotropy on the diversity of deposited metal morphology and crystal orientation, a thorough understanding of the intrinsic texture of zinc is crucial in achieving a dendrite-free zinc anode. This review highlights groundbreaking efforts and significant advancements in promoting the orientational electrodeposition of zinc, encompassing fundamental crystallographic and electrocrystallization theories as well as approaches for achieving textured zinc electrodeposition. The goal is to provide a comprehensive understanding of the crystallography, electrochemistry, and induction mechanisms involved in controlling sustainable zinc orientational electrodeposition for AZIBs. Lastly, four critical research aspects are proposed to facilitate the commercialization of reliable AZIBs.

水溶液锌离子电池(azib)作为一种极具发展前景的电化学储能技术,因其固有的安全性、高可持续性和低成本而受到越来越多的关注。然而,由于锌金属阳极不均匀沉积导致的枝晶形成和副反应所带来的挑战,严重阻碍了azib的可逆性和循环稳定性。鉴于晶体各向异性对沉积金属形态和晶体取向多样性的影响,深入了解锌的内在织构对于实现无枝晶锌阳极至关重要。本文综述了在促进锌取向电沉积方面的突破性努力和重大进展,包括基本的晶体学和电结晶理论以及实现织构锌电沉积的方法。目的是全面了解azib的晶体学、电化学和诱导机制,这些机制与控制可持续的锌取向电沉积有关。最后,提出了四个关键的研究方面,以促进可靠的azib商业化。
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引用次数: 0
Band edge engineering of lead halide perovskites using carboxylic-based self-assembled monolayer for efficient photovoltaics 基于羧基自组装单层的卤化铅钙钛矿带边工程用于高效光伏
Pub Date : 2024-12-07 DOI: 10.1002/ece2.87
Yiheng Shi, Xinyuan Sui, Jingjing He, Zhanpeng Wei, Hua Gui Yang, Qiang Niu, Yu Hou, Shuang Yang

Perovskite solar cells are promising candidates for low-cost and efficient photovoltaic markets, but their efficiency is usually limited by the non-radiative recombination losses at the mismatched interface of perovskite and transport layers. Herein, we show that the band edges of perovskite thin films can be on-demand engineered by a series of carboxylic-based self-assembled monolayers. Experimental and theoretical studies indicate that the functionalized perovskite inherits the polarity of the monolayer with linear dependence of work function on the molecular dipole moments, which enables the management of interfacial charge transport process. Solar cells with 4-bromophenylacetic acid SAMs achieve about 6.48% enhancement in power conversion efficiency with the champion values over 23%.

钙钛矿太阳能电池是低成本和高效光伏市场的有希望的候选者,但其效率通常受到钙钛矿和输运层不匹配界面的非辐射复合损失的限制。在此,我们证明了钙钛矿薄膜的带边缘可以通过一系列羧基自组装单层按需设计。实验和理论研究表明,功能化的钙钛矿继承了单层的极性,并且功函数与分子偶极矩呈线性关系,从而能够管理界面电荷输运过程。采用4-溴苯乙酸SAMs的太阳能电池的功率转换效率提高约6.48%,冠军值超过23%。
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引用次数: 0
Advancing aqueous zinc-ion batteries with carbon dots: A comprehensive review 碳点锌离子电池的研究进展
Pub Date : 2024-12-03 DOI: 10.1002/ece2.83
Mingying Chen, Junjie Ma, Yanhong Feng, Quanping Yuan, Yinghong Wu, Yifan Liu, Guangzhi Hu, Xijun Liu

Recent years have witnessed a surge in research on aqueous zinc-ion batteries (AZIBs) due to their low cost, stability, and exceptional electrochemical performance, among other advantages. However, practical manufacturing and deployment of AZIBs have been hindered by challenges such as low energy density, significant precipitation-related side reactions, slow ion migration, and dendritic growth. Addressing these issues and enhancing the practical application of AZIBs necessitates the development of novel materials. Carbon dots (CDs), with their distinctive structure and superior electrochemical properties, represent an innovative class of carbon-based materials with broad potential applications for optimizing AZIBs' performance. This study offers a comprehensive review of how CDs can address the aforementioned challenges of AZIBs. It begins with an overview of AZIBs composition and mechanism before delving into the classification, preparation techniques, and functionalization strategies of CDs. The review also thoroughly summarizes the sophisticated roles of CDs as modifiers in electrolytes and electrodes, both positive and negative, and briefly discusses their potential application in membranes. Additionally, it provides a summary of current issues and difficulties encountered in utilizing CDs in AZIBs. This review aims to provide insights and guidance for designing and manufacturing the next generation of high-performance AZIBs.

近年来,水基锌离子电池(azib)因其成本低、稳定性好、电化学性能优异等优点而得到了广泛的研究。然而,azib的实际制造和部署一直受到诸如低能量密度、显著的沉淀相关副反应、缓慢的离子迁移和枝晶生长等挑战的阻碍。解决这些问题并加强azib的实际应用需要开发新型材料。碳点(cd)以其独特的结构和优异的电化学性能,代表了一类创新的碳基材料,在优化azib性能方面具有广阔的应用前景。本研究提供了cd如何解决上述azib挑战的全面回顾。在深入研究cd的分类、制备技术和功能化策略之前,首先概述azib的组成和机制。综述了CDs在电解质和电极中作为正极和负极改性剂的复杂作用,并简要讨论了其在膜中的潜在应用。此外,它还提供了在azib中使用cd时遇到的当前问题和困难的摘要。本文旨在为下一代高性能azib的设计和制造提供参考和指导。
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引用次数: 0
Thermal management matters in photovoltaic–electrocatalysis for solar hydrogen production 太阳能制氢光伏电催化中的热管理问题
Pub Date : 2024-12-01 DOI: 10.1002/ece2.84
Jie Chen, Xin Chen, Jie Sun, Jingkuo Qu, Xiangjiu Guan, Shaohua Shen

Photovoltaic–electrolysis (PV-EC) system currently exhibits the highest solar to hydrogen conversion efficiency (STH) among various technical routes. This perspective shifts the focus from the materials exploration in photovoltaics and electrolysis to the critical aspect of thermal management in a PV-EC system. Initially, the theoretical basis that elucidates the relationships between temperature and the performance of both photovoltaics and electrolyzers are presented. Following that, the impact of thermal management on the performance of PV-EC for solar hydrogen production is experimentally demonstrated by designing variables-controlling experiments. It is observed that while utilizing identical PV and EC cells under varying thermal conditions, the highest STH can reach 22.20%, whilst the lowest is only 15.61%. This variation underscores the significance of thermal management in optimizing PV-EC systems. Finally, increased efforts to enhancing heat transfer and optimizing heat distribution are proposed, thus facilitating the design of more efficient PV-EC systems with minimized thermal energy losses.

光伏-电解(PV-EC)系统是目前各种技术路线中太阳能到氢转换效率最高的。这一观点将焦点从光伏和电解中的材料探索转移到光伏- ec系统中热管理的关键方面。首先,给出了温度与光伏电池和电解槽性能之间关系的理论基础。随后,通过设计变量控制实验,实验证明了热管理对太阳能制氢PV-EC性能的影响。在不同热条件下使用相同的光伏电池和EC电池时,STH最高可达22.20%,最低仅为15.61%。这种变化强调了热管理在优化PV-EC系统中的重要性。最后,提出了加强传热和优化热分布的努力,从而促进设计更高效的光伏- ec系统,最大限度地减少热能损失。
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引用次数: 0
Tri(trimethylsilyl) phosphate as a multifunctional additive for moisture-resistant and long-cycling sodium-ion batteries 三(三甲基硅基)磷酸作为耐湿长循环钠离子电池的多功能添加剂
Pub Date : 2024-11-27 DOI: 10.1002/ece2.85
Qian Qiu, Longqing Huang, Shuai Wang, Shen Qiu, Wentao Hou, Jialing Zhu, Haoxiang Li, Xianyong Wu, Lan Xia

The sodium hexafluorophosphate (NaPF6)/carbonate solution is considered as the benchmark electrolyte for sodium-ion batteries (SIBs). However, this NaPF6 electrolyte undergoes hydrolysis and produces acidic compounds, which deteriorate the electrolyte quality, corrode electrodes, jeopardize electrode interphases, and eventually degrade battery performance. Herein, we introduce tris(trimethylsilyl) phosphate (TMSP) as a multifunctional additive to the carbonate electrolyte. We found that 10% TMSP could effectively remove H2O molecules and inhibit NaPF6 hydrolysis, thus improving the electrolyte stability against moisture during the long-term storage. Furthermore, the unique structure of TMSP promotes the formation of thinner, more uniform, and inorganic-rich interphases on the Na3V2(PO4)3 (NVP) cathode and hard carbon (HC) anode. Consequently, the NVP cathode, HC anode, and full cells demonstrate excellent cycling performance. This work suggests that tailoring the electrolyte formulation can provide multiple benefits for boosting SIB performances, such as stabilizing the electrolyte and regulating the electrolyte/electrode interphase, thereby promoting long-term cycling in sodium-ion batteries.

六氟磷酸钠(NaPF6)/碳酸盐岩溶液被认为是钠离子电池(sib)的基准电解质。然而,这种NaPF6电解质会发生水解并产生酸性化合物,从而使电解质质量恶化,腐蚀电极,破坏电极界面,最终降低电池性能。本文介绍了三甲基硅基磷酸三酯(TMSP)作为碳酸盐电解质的多功能添加剂。我们发现10%的TMSP可以有效去除H2O分子,抑制NaPF6水解,从而提高电解质在长期储存过程中的抗湿稳定性。此外,TMSP的独特结构促进了Na3V2(PO4)3 (NVP)阴极和硬碳(HC)阳极上形成更薄、更均匀、富无机的界面相。因此,NVP阴极、HC阳极和全电池表现出优异的循环性能。这项工作表明,定制电解质配方可以为提高SIB性能提供多种好处,例如稳定电解质和调节电解质/电极界面,从而促进钠离子电池的长期循环。
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引用次数: 0
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