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Editorial: Aqueous rechargeable batteries: Current status and what’s next 社论:水性可充电电池:现状与未来
Pub Date : 2024-05-07 DOI: 10.1016/j.nxener.2024.100129
Hong Jin Fan , Chunyi Zhi , Jiang Zhou , Dongliang Chao
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引用次数: 0
Synergistic coupling of optical field and built-in electric field for lithium-sulfur batteries with high cyclabilities and energy densities 高循环能力和高能量密度锂硫电池的光场和内置电场协同耦合效应
Pub Date : 2024-05-06 DOI: 10.1016/j.nxener.2024.100134
Yu-Hao Liu , Cheng-Ye Yang , Chun-Yu Yu , Jia-Cheng Yu , Mei-Chen Han , Jia-Hao Zhang , Yu Yu , Zhong-Zhen Yu , Jin Qu

Photo-assisted lithium sulfur batteries (PA-LSBs) provide vital and sustainable protocols for promoting sulfur redox reactions via powerful photoinduced effects. However, precise control of the stepwise adsorption, diffusion and photocatalytic conversion of polysulfides at the surface of photocatalysts is required to accelerate the photo-assisted process. Herein, optical field and built-in electric field synergistically-assisted LSBs are developed with a p-n junction of Co3O4-TiO2 on the carbon cloth, possessing a spontaneously generated built-in electric field and a well-matched energy band structure with sulfur redox reactions. Under light irradiation, the directional migration of soluble polysulfides and the space separation of photogenerated carriers are achieved with the synergistical coupling of the optical field and built-in electric field to precisely regulate the selective deposition of Li2S and inhibit the shuttle effect via an effective photocatalytic-promoted process, leading to a maximum capacity of 1087 mAh g−1 at 2 C and a low capacity attenuation of 0.068% per cycle at 5 C. A high areal capacity of 9.6 mAh cm−2 and a great potential photo-charge process can be realized with light irradiation. Furthermore, the stability of lithium metal anodes is improved accordingly. This work demonstrates a new insight to develop high-performance LSBs with a multifield synergistical coupling protocol.

光辅助锂硫电池(PA-LSBs)通过强大的光诱导效应,为促进硫氧化还原反应提供了重要的可持续方案。然而,要加速光助过程,就必须精确控制光催化剂表面多硫化物的逐步吸附、扩散和光催化转化。本文利用碳布上的 Co3O4-TiO2 p-n 结开发了光场和内置电场协同辅助的 LSB,它具有自发产生的内置电场和与硫氧化还原反应相匹配的能带结构。在光照射下,通过光场和内置电场的协同耦合,实现了可溶性多硫化物的定向迁移和光生载流子的空间分离,从而精确地调节了 Li2S 的选择性沉积,并通过有效的光催化促进过程抑制了穿梭效应,在 2 C 时实现了 1087 mAh g-1 的最大容量,在 5 C 时实现了每周期 0.068% 的低容量衰减。在光照射下,可实现 9.6 mAh cm-2 的高单位容量和潜力巨大的光充电过程。此外,锂金属阳极的稳定性也得到了相应提高。这项研究为利用多场协同耦合协议开发高性能 LSB 提供了新的思路。
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引用次数: 0
Scalable Slurry-Casting Fabrication of Ultrathin, Flexible, and High-Voltage Halide-based Composite Solid-State Electrolytes for Lithium Metal Batteries 为金属锂电池制造超薄、柔性和高电压卤化物基复合固态电解质的可扩展浆状铸造技术
Pub Date : 2024-05-02 DOI: 10.1016/j.nxener.2024.100120
Junjie Chen , Yu Wang , Yanke Lin , Jianbo Xu , Yiju Li , Tianshou Zhao

Flexible composite polymer electrolytes with high ionic conductivity, high voltage, and small thickness are critical for achieving scalable fabrication of high-energy-density solid-state lithium metal batteries (SSLMBs). Owing to the intrinsically lower density (2.5–3.0 g cm−3) than that of oxides (>4.0 g cm−3), high ionic conductivity (∼10−3 S cm−1), high modulus, and high voltage, halides can be used as effective functional Li-ion-conductive fillers to construct thin, lightweight, and high-performance composite polymer electrolytes while achieving high-energy-density of SSLMBs. Nevertheless, the chemical vulnerability of halide solid electrolyte materials to common polar solvents restricts the scalable slurry-casting fabrication of halide-based composite polymer electrolytes for practical SSLMBs. To this end, a bi-functional low-polarity solvent, dimethyl carbonate, is screened to render halides, which are usually slurry-incompatible, amenable to scalable slurry fabrication. As a result, an ultrathin (10 µm) and flexible halide-incorporated composite electrolyte with a high electrochemical window up to 4.8 V vs. Li+/Li, high thermal stability, and desirable self-extinguishing ability is developed. Benefiting from the multiple Li-ion transport mechanisms enabled by the interaction between fillers, salts, and polymers, the obtained composite polymer electrolyte can achieve a high ionic conductivity of 0.325 mS cm–1 at 25 °C. The assembled solid-state Li|LiFePO4 cell based on the halide-based composite electrolyte achieves a high capacity of 153 mAh g−1 at 0.2 C with a capacity retention of 98% after 175 cycles, and the Li|LiNi0.6Co0.2Mn0.2O2 cell can stably cycle at a cut-off voltage of 4.3 V and achieve a high capacity of 160 mAh g−1 at 0.2 C with a capacity retention of 89% after 170 cycles. This work provides an effective strategy for large-scale manufacturing of ultrathin and flexible halide-based composite electrolytes for high-performance SSLMBs.

具有高离子电导率、高电压和小厚度的柔性复合聚合物电解质对于实现高能量密度固态锂金属电池(SSLMB)的规模化制造至关重要。由于卤化物的密度(2.5-3.0 g cm-3)比氧化物的密度(4.0 g cm-3)低、离子电导率高(10-3 S cm-1)、模量高、电压高,因此卤化物可作为有效的功能性锂离子导电填料,用于构建薄型、轻质、高性能的复合聚合物电解质,同时实现 SSLMB 的高能量密度。然而,由于卤化物固体电解质材料易受普通极性溶剂的化学影响,因此限制了用于实用 SSLMB 的卤化物基复合聚合物电解质的规模化浆料浇铸制造。为此,我们筛选出一种双功能低极性溶剂--碳酸二甲酯,使通常与浆料不相容的卤化物也能用于可扩展的浆料制造。结果,一种超薄(10 微米)、柔韧的卤化物掺杂复合电解质被开发出来,这种电解质具有高达 4.8 V 的电化学窗口(相对于 Li+/Li)、高热稳定性和理想的自熄灭能力。得益于填料、盐和聚合物之间相互作用所产生的多种锂离子传输机制,所获得的复合聚合物电解质在 25 °C 时的离子电导率高达 0.325 mS cm-1。基于卤化物基复合电解质组装的固态锂|锂铁PO4电池在0.2 C条件下实现了153 mAh g-1的高容量,循环175次后容量保持率达98%;锂|镍0.6钴0.2锰0.2O2电池可在4.3 V截止电压下稳定循环,在0.2 C条件下实现了160 mAh g-1的高容量,循环170次后容量保持率达89%。这项工作为大规模制造用于高性能 SSLMB 的超薄、柔性卤化物基复合电解质提供了有效策略。
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引用次数: 0
A lithiated zeolite-based protective layer to boost the cycle performance of lithium−oxygen batteries via redox mediator sieving 基于锂化沸石的保护层可通过氧化还原介质筛分提高锂氧电池的循环性能
Pub Date : 2024-04-30 DOI: 10.1016/j.nxener.2024.100135
Huiping Wu , Zhaohan Shen , Wei Yu , Xinbin Wu , Shundong Guan , Yu-Hsien Wu , Kaihua Wen , Haocheng Yuan , Ying Liang , Hirotomo Nishihara , Ce-Wen Nan , Liangliang Li

Lithium–oxygen (Li–O2) batteries with ultra-high theoretical specific energy (3500 Wh kg−1) have attracted significant attention, but the sluggish electrochemical processes of discharge product Li2O2 lead to poor cycling stability. Redox mediators (RMs) as soluble catalysts are widely used to assist with the electrochemical formation/decomposition of Li2O2. However, the shuttle effect of RMs causes severe deterioration of both RMs and Li metal anodes. Herein, for the first time we synthesize a lithiated zeolite-based protective layer on Li anodes to mitigate the shuttle effect of 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) in Li–O2 batteries. The protective layer successfully blocks the migration of TEMPO toward the Li anode owing to the angstrom-level aperture size of lithiated zeolite. Due to the excellent redox-mediator-sieving capability of the protective layer, the cycle life of the Li−O2 batteries is significantly prolonged more than ten times at a current density of 250 mA g−1 and a limited capacity of 500 mA h g−1. This work demonstrates that the lithiated zeolite-based protective layer capable of molecular sieving is a facile and scalable way to mitigate the shuttle effect of RMs in Li–O2 batteries.

具有超高理论比能量(3500 Wh kg-1)的锂-氧(Li-O2)电池备受关注,但放电产物 Li2O2 的电化学过程缓慢,导致循环稳定性差。氧化还原介质(RMs)作为可溶性催化剂被广泛用于辅助 Li2O2 的电化学形成/分解。然而,RMs 的穿梭效应会导致 RMs 和锂金属阳极的严重退化。在此,我们首次在锂阳极上合成了一种基于石英化沸石的保护层,以减轻 2,2,6,6-四甲基哌啶氧基(TEMPO)在二氧化锰锂电池中的穿梭效应。由于石化沸石具有埃级孔径,保护层成功阻止了 TEMPO 向锂阳极的迁移。由于保护层具有出色的氧化还原介质吸收能力,在电流密度为 250 mA g-1 和有限容量为 500 mA h g-1 的条件下,锂离子电池的循环寿命显著延长了十倍以上。这项研究表明,具有分子筛分能力的石英化沸石基保护层是减轻二氧化铀锂电池中清除剂穿梭效应的一种简便且可扩展的方法。
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引用次数: 0
The evaluation and improvement for the energy performance of buildings: A case study 评估和改进建筑物的能效:案例研究
Pub Date : 2024-04-26 DOI: 10.1016/j.nxener.2024.100126
Atilla G. Devecioğlu, Burhan Bilici, Vedat Oruç

The aim of this study is to perform the thermal analysis of an existing building by a software, hence determine the possible improvements and energy savings. In this context, the existing model and two different improved models of a building are compared. The 1st case covers the existing situation of the building while the 2nd and 3rd cases are related to two improved cases for the building. The improvements are focused on heat insulation, infiltration and lighting system of the building. The results point out that 2nd and 3rd cases provide a reduction in electricity consumption by 15% compared to the 1st case. Similarly, annual natural gas consumption is decreased about by 76% and 90% in 2nd and 3rd cases, respectively in comparison with the 1st case. The total energy consumption by electricity and natural gas per unit area for 1st, 2nd and 3rd cases is also determined as 55.7, 35.7 and 33.1 kWh/m2, respectively. Moreover, annual CO2 emission is ensured to reduce nearly by 23% in both 2nd and 3rd cases compared to 1st situation.

本研究的目的是通过软件对现有建筑进行热分析,从而确定可能的改进措施和节能效果。在此背景下,我们对建筑物的现有模型和两种不同的改进模型进行了比较。第 1 个案例涉及建筑物的现有情况,而第 2 和第 3 个案例则涉及建筑物的两个改进案例。改进的重点是建筑物的隔热、渗透和照明系统。结果表明,与第一种情况相比,第二和第三种情况的耗电量减少了 15%。同样,与第一种情况相比,第二种和第三种情况的天然气年消耗量分别减少了 76% 和 90%。第 1、第 2 和第 3 个案例单位面积的电力和天然气总能耗分别为 55.7、35.7 和 33.1 千瓦时/平方米。此外,与第一种情况相比,第二种和第三种情况的二氧化碳年排放量确保减少近 23%。
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引用次数: 0
Electrochemical nitrate reduction to ammonia using copper-based electrocatalysts 使用铜基电催化剂电化学还原硝酸盐至氨
Pub Date : 2024-04-25 DOI: 10.1016/j.nxener.2024.100125
Rong Zhang , Shaoce Zhang , Huilin Cui , Ying Guo , Nan Li , Chunyi Zhi

Ammonia (NH3) is an ideal green fuel with high energy density and plays an indispensable role in fertilizer production. Electrochemical reduction of nitrate (NO3), a toxic pollutant in groundwater, has shown promising as a viable approach to converting waste into valuable NH3 under ambient conditions, offering an alternative to the energy-intensive Haber-Bosch process. Due to their high efficiency, copper (Cu)-based materials have shown great potential as electrocatalysts for the NO3 reduction reaction (NO3RR) to NH3. In this review, we provide a comprehensive summary of the fundamental principles underlying nitrate reduction over Cu-based electrocatalysts and discuss various strategies to enhance the performance of NO3 reduction, including facets, morphologies, size, surface functionalization, compositional engineering, and defect engineering. We also delve into the relationship between the electrocatalytic performance and structure characteristics of electrocatalysts and thoroughly examine the reaction mechanism involved in NO3RR. Furthermore, we highlight the existing challenges and prospective paths forward in this area of study. This review offers valuable insights and guidance for the strategic design and optimization of Cu-based electrocatalysts for NO3RR applications.

氨(NH3)是一种理想的绿色燃料,具有高能量密度,在化肥生产中发挥着不可或缺的作用。硝酸盐(NO3-)是地下水中的一种有毒污染物,电化学还原硝酸盐(NO3-)已被证明是在环境条件下将废物转化为有价值的 NH3 的一种可行方法,为高能耗的哈伯-博施工艺提供了一种替代方案。由于铜(Cu)基材料的高效性,它们作为将 NO3 还原成 NH3 反应(NO3-RR)的电催化剂已显示出巨大的潜力。在这篇综述中,我们全面总结了铜基电催化剂还原硝酸盐的基本原理,并讨论了提高 NO3 还原性能的各种策略,包括刻面、形态、尺寸、表面功能化、成分工程和缺陷工程。我们还深入探讨了电催化性能与电催化剂结构特征之间的关系,并深入研究了 NO3-RR 所涉及的反应机理。此外,我们还强调了这一研究领域的现有挑战和未来发展方向。本综述为用于 NO3-RR 应用的铜基电催化剂的战略设计和优化提供了宝贵的见解和指导。
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引用次数: 0
The exploration of the internal homogeneities for a LiFePO4 pouch lithium-ion battery with a 3D electrochemical-thermal coupled model 利用三维电化学-热耦合模型探索磷酸铁锂袋式锂离子电池的内部均匀性
Pub Date : 2024-04-24 DOI: 10.1016/j.nxener.2024.100127
Jianpeng Mi , Xiaolong Liu , Daiman Zhu , Longfei Chen , Yongli Li

Along with the battery charge/discharge processes, the migration of the Li ions inevitably leads to an inhomogeneous distribution of the battery internal electrochemical and thermal characteristics, deteriorating the battery capacity and safety. In this work, the internal characteristics of a 20 Ah pouch LiFePO4 lithium-ion battery have been investigated based on a 3D electrochemical-thermal coupled model. It is found that the reduction of the particle size for either the cathode or anode would increase the battery capacity. Moreover, with the modulation of the thickness of cathode (Lpos) and convective heat transfer coefficient (h), the homogeneity of solid lithium concentration and temperature has been optimized. A relatively smaller Lpos and an h higher than the critical value should be adopted. From the aspect of thermal distribution, as the discharge rate increases, the irreversible reaction heat always dominates, while the proportion of ohmic heat among the total heat increases, and the high temperature region always locates on the inner sides of the tabs. The methodology proposed in this work could be applied to pouch batteries with more repeated cell units and larger sizes.

随着电池充放电过程的进行,锂离子的迁移不可避免地会导致电池内部电化学和热特性的不均匀分布,从而降低电池容量和安全性。在这项工作中,基于三维电化学-热耦合模型研究了 20 Ah 袋装磷酸铁锂离子电池的内部特性。研究发现,无论是减小正极还是负极的颗粒尺寸,都会提高电池容量。此外,通过调节正极厚度(Lpos)和对流传热系数(h),固体锂浓度和温度的均匀性也得到了优化。应采用相对较小的 Lpos 和高于临界值的 h。从热分布来看,随着放电速率的增加,不可逆反应热始终占主导地位,而总热量中欧姆热的比例增加,高温区始终位于片的内侧。本研究提出的方法可用于重复电池单元更多和尺寸更大的袋式电池。
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引用次数: 0
Unlocking dendrite-free zinc metal anodes through anti-corrosive and Zn-ion-regulating interlayer 通过抗腐蚀和锌离子调节夹层实现无树枝状突起的锌金属阳极
Pub Date : 2024-04-17 DOI: 10.1016/j.nxener.2024.100124
Xuzi Zhang , Jialiang Wang , Hanlin Wang , Han Huang , Hao Zhang , Ge Li

Aqueous zinc-ion batteries (AZIBs) are a promising solution for large-scale energy storage due to their safety and cost-effectiveness. However, challenges like zinc dendrite growth and electrolyte corrosion hinder their practical use. Surface engineering methods have shown potential in stabilizing the zinc metal anode interface. In this study, we propose a successful approach by combining 2D g-C3N4 nanosheets with 3D ZIF8 nanoparticles to form a g-C3N4@ZIF8 artificial interface. The 3D ZIF8 support on the 2D g-C3N4 enables precise regulation of Zn2+ flux and efficient charge transfer, leading to improved electrochemical performance. Density functional theory confirms ZIF8's superior adsorption energy compared to g-C3N4. Strategically anchoring 3D ZIF8 nanoparticles within 2D g-C3N4 allows robust 3D diffusion of Zn2+, preventing dendrite formation and enabling dendrite-free Zn deposition. This structural design can enhance the performance of symmetric cells with an ultralong cycling lifespan of up to 6200 h at 0.25 mA cm−2/0.25 mA h cm−2 and superior rate capability, even at 40 mA cm−2. When combined with a V2O5 nanopaper cathode, our assembled AZIBs exhibit stable long-term performance. This research paves the way for more efficient and reliable AZIBs for large-scale energy storage.

锌离子水电池(AZIBs)因其安全性和成本效益而成为大规模储能的理想解决方案。然而,锌枝晶生长和电解质腐蚀等挑战阻碍了它们的实际应用。表面工程方法已显示出稳定锌金属阳极界面的潜力。在本研究中,我们提出了一种成功的方法,将二维 g-C3N4 纳米片与三维 ZIF8 纳米颗粒相结合,形成 g-C3N4@ZIF8 人工界面。二维 g-C3N4 上的三维 ZIF8 支持实现了对 Zn2+ 通量的精确调节和高效电荷转移,从而提高了电化学性能。密度泛函理论证实,与 g-C3N4 相比,ZIF8 具有更高的吸附能。将三维 ZIF8 纳米粒子策略性地锚定在二维 g-C3N4 中,可实现 Zn2+ 的稳健三维扩散,防止枝晶形成,实现无枝晶 Zn 沉积。这种结构设计可提高对称电池的性能,在 0.25 mA cm-2/0.25 mA h cm-2 的条件下,其循环寿命可长达 6200 小时,即使在 40 mA cm-2 的条件下,其速率能力也非常出色。当与 V2O5 纳米纸阴极结合使用时,我们组装的 AZIB 显示出稳定的长期性能。这项研究为实现更高效、更可靠的 AZIBs 大规模储能铺平了道路。
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引用次数: 0
Improved electro-kinetics of new electrolyte composition for realizing high-performance zinc-bromine redox flow battery 改进新型电解质成分的电动力学,实现高性能锌溴氧化还原液流电池
Pub Date : 2024-04-13 DOI: 10.1016/j.nxener.2024.100123
Yogapriya Vetriselvam , Gnana Sangeetha Ramachandran , Raghupandiyan Naresh , Karuppusamy Mariyappan , Ragupathy Pitchai , Mani Ulaganathan

Aqueous Redox Flow Batteries (ARFB) are the most prominent technology for large-scale energy storage applications. The energy density of the ARFBs is mainly determined by the electrolyte components, which highly influence the flow battery performance. In the present work, we acutely investigated the various electrolyte compositions and optimized the best electrolyte for realizing the high performance of Zn-Br2 ARFBs. The electrode kinetics, such as rate constant, exchange current density, conductivity, and diffusion coefficient, were analyzed using electrochemical techniques, cyclic voltammetry, and electrochemical impedance analysis. It was observed that zinc bromide (ZnBr2) + perchloric acid (HClO4) + 1-Ethyl-1-methylmorpholinium bromide (MEM) + N-ethyl-N-methylpyrrolidinium bromide (MEP) and ZnBr2 + zinc chloride (ZnCl2) + MEM + MEP electrolytes showed improved performance, where the redox kinetics of 2Br-/Br2 redox couple is greatly enhanced. The presence of perchloric acid unlocks the capacity of full electro-oxidation of bromide (Br-) to bromine (Br2) as it involves 1e- per Br-, which would be highly beneficial to attain high energy density. Further, Zn-Br2 RFB adopted with optimized electrolyte formulation ZnBr2 + HClO4 + MEM+ MEP shows a better round-trip efficiency and displays a stable long cycling performance over 200 cycles with an energy (EE) and coulombic efficiency (CE) of > 68% and > 92%, respectively.

水氧化还原液流电池(ARFB)是大规模储能应用中最突出的技术。ARFB 的能量密度主要由电解质成分决定,而电解质成分对液流电池的性能有很大影响。在本研究中,我们对各种电解质成分进行了深入研究,并优化了最佳电解质,以实现 Zn-Br2 ARFB 的高性能。我们使用电化学技术、循环伏安法和电化学阻抗分析法分析了电极动力学,如速率常数、交换电流密度、电导率和扩散系数。结果表明,溴化锌 (ZnBr2) + 高氯酸 (HClO4) + 1-乙基-1-甲基溴化吗啉 (MEM) + N-乙基-N-甲基溴化吡咯烷 (MEP) 和 ZnBr2 + 氯化锌 (ZnCl2) + MEM + MEP 电解质的性能有所改善,其中 2Br-/Br2 氧化还原对的氧化还原动力学大大增强。高氯酸的存在释放了将溴化物(Br-)完全电氧化成溴化物(Br2)的能力,因为每一个 Br- 都涉及 1e-,这对获得高能量密度非常有利。此外,采用优化电解质配方 ZnBr2 + HClO4 + MEM+ MEP 的 Zn-Br2 RFB 显示出更高的往返效率,并在 200 次循环中表现出稳定的长循环性能,能量(EE)和库仑效率(CE)分别为 68% 和 92%。
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引用次数: 0
Effective upcycling of NMC 111 to NMC 622 cathodes by hydrothermal relithiation and Ni-enriching annealing 通过水热再铁素体化和富镍退火,将 NMC 111 有效升级为 NMC 622 正极
Pub Date : 2024-04-10 DOI: 10.1016/j.nxener.2024.100122
Krystal Davis , George P. Demopoulos

It is imperative that a sustainable approach to the recycling of lithium-ion batteries (LIBs)—in particular the spent NMC cathodes—which reach their end-of-life (EOL) is realized as 11 million metric tonnes are expected to reach EOL by 2030. The current recycling processes based on pyrometallurgy and hydrometallurgy are not fully sustainable options as they recover only the value metals. By contrast direct recycling that aims in regenerating EOL LIB cathodes without breaking down the active compound’s crystal structure offers the most sustainable option. In this paper the direct recycling of NMC cathodes is investigated in combination with their upcycling. Upcycling is going to be in growing demand since the first generation NMC 111 cathode chemistries evolve to higher energy/nickel-rich formulations. In this work, the baseline is established for direct recycling of low and high nickel NMC cathodes by analyzing the three key steps of chemical delithiation of pristine NMC cathode material, hydrothermal relithiation (4M LiOH for 4 h at 220 °C), and annealing (4 h at 850 °C) in order to set the ground for investigating the upcycling of NMC 111 to NMC 622. Upcycling is affected via the co-addition of pre-calculated excess NiSO4 and Li2CO3 salts during annealing, following the hydrothermal relithiation step. Use of NiSO4 that is commonly used as p-CAM provides a lower cost alternative to Ni(OH)2 as Ni source. Characterization revealed the upcycled material to have been endowed with the typical α-NaFeO2 layered structure and have surface morphology and composition similar to pristine NMC material. The upcycled NMC 622 cathode yielded good cycling stability (91.5% retention after 100 cycles) and >99% Coulombic efficiency albeit with certain polarization loss justifying further optimization studies.

预计到 2030 年,将有 1100 万公吨的锂离子电池(LIBs)(尤其是废旧 NMC 正极)达到报废年限(EOL),因此必须采用可持续的方法对其进行回收利用。目前以火法冶金和湿法冶金为基础的回收工艺并不是完全可持续的选择,因为它们只能回收有价值的金属。相比之下,旨在不破坏活性化合物晶体结构的情况下再生 EOL LIB 阴极的直接回收工艺则是最具可持续性的选择。本文研究了 NMC 阴极的直接回收和升级再循环。随着第一代 NMC 111 阴极化学成分向高能量/富镍配方发展,升级再循环的需求将越来越大。在这项工作中,通过分析原始 NMC 阴极材料的化学脱硅、水热再脱硅(4M LiOH,4 小时,220 °C)和退火(4 小时,850 °C)这三个关键步骤,建立了直接循环利用低镍和高镍 NMC 阴极的基准,从而为研究将 NMC 111 向上循环利用为 NMC 622 奠定了基础。在水热再铁化步骤之后的退火过程中,通过共同添加预先计算过量的 NiSO4 和 Li2CO3 盐,影响了上循环。使用通常用作 p-CAM 的 NiSO4 作为镍源比使用 Ni(OH)2 成本更低。表征结果表明,上循环材料具有典型的 α-NaFeO2 层状结构,其表面形态和成分与原始 NMC 材料相似。上循环的 NMC 622 阴极具有良好的循环稳定性(100 次循环后保持率为 91.5%)和 99% 的库仑效率,尽管存在一定的极化损失,但仍值得进一步优化研究。
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