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Tailoring the Use of 8-Hydroxyquinolines for the Facile Separation of Iron, Dysprosium and Neodymium. 利用 8-羟基喹啉实现铁、镝和钕的便捷分离。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-11 Epub Date: 2024-07-08 DOI: 10.1002/cssc.202400286
Matteo Melegari, Martina Neri, Alex Falco, Matteo Tegoni, Monica Maffini, Fabio Fornari, Claudio Mucchino, Flavia Artizzu, Angela Serpe, Luciano Marchiò

Permanent magnets (PMs) containing rare earth elements (REEs) can generate energy in a sustainable manner. With an anticipated tenfold increase in REEs demand by 2050, one of the crucial strategies to meet the demand is developing of efficient recycling methods. NdFeB PMs are the most widely employed, however, the similar chemical properties of Nd (20-30 % wt.) and Dy (0-10 % wt.) make their recycling challenging, but possible using appropriate ligands. In this work, we investigated commercially available 8-hydroxyquinolines (HQs) as potential Fe/Nd/Dy complexing agents enabling metal separation by selective precipitation playing on specific structure/property (solubility) relationship. Specifically, test ethanolic solutions of nitrate salts, prepared to mimic the main components of a PM leachate, were treated with functionalized HQs. We demonstrated that Fe3+ can be separated as insoluble [Fe(QCl,I)3] from soluble [REE(QCl,I)4]- complexes (QCl,I -: 5-Cl-7-I-8-hydoxyquinolinate). Following that, QCl - (5-Cl-8-hydroxyquinolinate) formed insoluble [Nd3(QCl)9] and soluble (Bu4N)[Dy(QCl)4]. The process ultimately gave a solution phase containing Dy with only traces of Nd. In a preliminary attempt to assess the potentiality of a low environmental impact process, REEs were recovered as oxalates, while the ligands as well as Bu4N+ ions, were regenerated and internally reused, thus contributing to the sustainability of a possible metal recovery process.

含有稀土元素(REE)的永磁体(PM)可以以可持续的方式产生能量。预计到 2050 年,稀土元素的需求量将增加十倍,因此满足需求的重要战略之一就是开发高效的回收方法。钕铁硼永磁材料的应用最为广泛,然而,钕(20-30% 重量比)和镝(0-10% 重量比)的化学性质相似,这使得它们的回收具有挑战性,但使用适当的配体是可行的。在这项工作中,我们研究了市售的 8-羟基喹啉(HQs)作为潜在的铁/钕/镝络合剂,利用特定的结构/性能(溶解度)关系,通过选择性沉淀实现金属分离。具体来说,用官能化 HQs 处理硝酸盐的乙醇溶液(模拟 PM 浸出液的主要成分)。我们证明,Fe3+ 可作为不溶性[Fe(QCl,I)3]从可溶性[REE(QCl,I)4]-复合物(QCl,I-:5-Cl-7-I-8-hydoxyquinolinate)中分离出来。随后,QCl-(5-Cl-8-羟基喹啉酸酯)形成了不溶的[Nd3(QCl)9]和可溶的 (Bu4N)[Dy(QCl)4]。这一过程最终产生了含有镝而只有微量钕的溶液相。在评估低环境影响工艺潜力的初步尝试中,REEs 作为草酸盐被回收,而配体以及 Bu4N+ 离子则被再生并在内部重复使用,从而促进了可能的金属回收工艺的可持续性。
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引用次数: 0
Non-Fused π-Extension of Endcaps of Small Molecular Acceptors Enabling High-Performance Organic Solar Cells. 实现高性能有机太阳能电池的小分子受体端盖的非熔合π扩展。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-11 Epub Date: 2024-07-09 DOI: 10.1002/cssc.202400601
Fan Feng, Zunyuan Hu, Jianxiao Wang, Pengchao Wang, Cheng Sun, Xiaoning Wang, Fuzhen Bi, Yonghai Li, Xichang Bao

The modular structure of small molecular acceptors (SMAs) allows for versatile modifications of the materials and boosts the photovoltaic efficiencies of organic solar cells (OSCs) in recent years. As a critical component, the endcaps of SMAs have been intensively investigated and modified to control the molecular aggregation and photo-electronic conversion. However, most of the studies focus on halogenation or π-fusion extension of the endcap moieties, but overlook the non-fused π-extension approach, which could be a promising strategy to balance the self-aggregation and compatibility behaviors. Herein, we reported two new acceptors namely BTP-Th and BTP-FTh based on non-fused π-extension of the endcap by chlorinated-thiophene, of which the latter molecule has better co-planarity and crystallinity because of the intramolecular noncovalent interactions. Paired with donor PBDB-T, the optimal device of BTP-FTh reveals a greater efficiency of 14.81 % that that of BTP-Th (13.91 %). Nevertheless, the BTP-Th based device realizes a lower energy loss, enabling BTP-Th as a good candidate to serve as guest acceptor. As a result, the ternary solar cells of PM6 : BTP-eC9 : BTP-Th output a champion efficiency up to 18.71 % with enhanced open-circuit voltage. This study highlights the significance of rational decoration of endcaps for the design of high-performance SMAs and photovoltaic cells.

近年来,小分子受体(SMA)的模块化结构允许对材料进行多功能改性,并提高了有机太阳能电池(OSC)的光电效率。作为一个关键部件,SMA 的端盖受到了深入研究和改造,以控制分子聚集和光电转换。然而,大多数研究都集中于内盖分子的卤化或π-融合扩展,却忽视了非融合π-扩展方法,而这可能是平衡自聚集和相容性行为的一种有前途的策略。在此,我们报告了两种新的受体,即 BTP-Th 和 BTP-FTh,它们基于氯化噻吩对端帽的非融合π-延伸,其中后一种分子由于分子内的非共价相互作用而具有更好的共平面性和结晶性。与供体 PBDB-T 配对后,BTP-FTh 的最佳器件效率为 14.81%,高于 BTP-Th 的 13.91%。尽管如此,基于 BTP-Th 的器件实现了更低的能量损失,使 BTP-Th 成为客体受体的理想候选者。因此,PM6:BTP-eC9:BTP-Th 的三元太阳能电池输出了高达 18.71% 的冠军效率,并提高了开路电压。这项研究强调了合理装饰端盖对于设计高性能 SMA 和光伏电池的重要意义。
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引用次数: 0
Enhanced Fill Factor and Efficiency of Ternary Organic Solar Cells by a New Asymmetric Non-Fullerene Small Molecule Acceptor. 利用新型不对称非富勒烯小分子受体提高三元有机太阳能电池的填充因子和效率。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-11 Epub Date: 2024-07-09 DOI: 10.1002/cssc.202400691
Kun Wang, Jingshun Gao, Huiyan Wang, Qing Guo, Jianqi Zhang, Xia Guo, Maojie Zhang

Asymmetric non-fullerene small molecules acceptor (as-NF-SMAs) exhibit greater vitality in photovoltaic materials compared to their symmetric counterparts due to their larger dipole moments and stronger intermolecular interactions, which facilitate exciton dissociation and charge transmission in organic solar cells (OSCs). Here, we introduced a new as-NF-SMAs, named IDT-TNIC, as the third component in ternary organic solar cells (TOSCs). The asymmetric IDT-TNIC used indacenodithiophene (IDT) as the central core, alkylthio-thiophene as a unilateral π-bridge and extended end groups as electron-withdrawing. Due to the non-covalent conformational lock (NCL) established between O⋅⋅⋅S and S⋅⋅⋅S, the IDT-TNIC molecule preserves its coplanar structure effectively. Furthermore, IDT-TNIC exhibits complementary absorption and excellent compatibility with donor and acceptor materials, as well as optimized ladder energy level arrangement, resulting in a higher and more balanced μhe value, more homogeneous and suitable phase separation morphology in TOSCs. Thus, the PCE of the TOSCs reached 17 % when the weight ratio of PM6 : Y6 : IDT-TNIC was 1 : 1.1 : 0.1, and it is noteworthy that when the device area was increased to 1 cm2, the PCE could still be maintained at over 14 %. Detailed studies and analysis indicate that IDT-TNIC has great potential as a third component in OSCs and for large-scale printing in the future.

非对称非富勒烯小分子受体(as-NF-SMAs)与对称小分子受体相比,具有更大的偶极矩和更强的分子间相互作用,有利于有机太阳能电池(OSCs)中的激子解离和电荷传输,因而在光伏材料中具有更强的生命力。在这里,我们引入了一种名为 IDT-TNIC 的新型 AS-NF-SMAs 作为三元有机太阳能电池(TOSC)中的第三种成分。不对称 IDT-TNIC 以茚并二噻吩(IDT)为中心核,以烷基硫代噻吩为单侧 π 桥,以扩展端基团为电子吸收基团。由于在 O-S 和 S-S 之间建立了非共价构象锁(NCL),IDT-TNIC 分子有效地保持了共面结构。此外,IDT-TNIC 与供体和受体材料具有互补吸收性和良好的相容性,并优化了梯能级排列,从而使 TOSC 具有更高和更均衡的 μh/μe 值、更均匀和更合适的相分离形态。因此,当 PM6:Y6:IDT-TNIC 的重量比为 1:1.1:0.1 时,TOSC 的 PCE 达到 17%,值得注意的是,当器件面积增加到 1 cm2 时,PCE 仍能保持在 14% 以上。详细的研究和分析表明,IDT-TNIC 作为 OSC 中的第三种成分,在未来的大规模印刷中具有巨大的潜力。
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引用次数: 0
Chemical and Electrochemical Characterization of Hot-Pressed Li6PS5Cl Solid State Electrolyte: Operating Pressure-Invariant High Ionic Conductivity. 热压 Li6PS5Cl 固态电解质的化学和电化学特性:工作压力不变的高离子电导率。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-11 Epub Date: 2024-06-06 DOI: 10.1002/cssc.202400718
Yang Wang, Ryan Lim, Karl Larson, Aidan Knab, Daniela Fontecha, Spencer Caverly, Juhye Song, Chanhwi Park, Paul Albertus, Gary W Rubloff, Sang Bok Lee, Alexander C Kozen

Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li6PS5X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10-2 S cm-1) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250 °C. Moreover, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa.

硫化物固态电解质(SSE)是最有希望取代液体电解质的材料之一,这主要是因为它们具有可比的离子电导率。在硫化物固态电解质中,Argyrodites(Li6PS5X,X=Cl、Br、I)因其较高的理论离子电导率(~1×10-2 S cm-1)和对锂等活性金属阳极的界面稳定性而进一步脱颖而出。一般来说,固态电解质颗粒是在室温下从粉末原料中压制而成的,然而,通过冷压制成的颗粒始终具有体积密度低、孔隙率高的特点,这有利于界面降解反应,并允许树枝状突起通过孔隙和晶界传播。在这里,我们展示了热压独立 LPSCl SSE 粒子的机械和电化学影响,这种粒子具有接近理论的离子电导率、优异的循环性能和更强的机械稳定性。X 射线光电子能谱 (XPS)、扫描电子显微镜 (SEM) 和 X 射线衍射光谱 (XRD) 分析表明,在高达 250 °C 的热压后,阿基洛德石表面没有发生任何化学变化。此外,我们还利用电化学阻抗光谱(EIS)来了解阿基洛德SSE颗粒的机械稳定性与外部施加压力的函数关系,首次证明了压制的独立阿基洛德颗粒在外部压力低于14兆帕时具有接近理论的电导率。
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引用次数: 0
Upcycling Humins via Esterification Reactions of Hydroxyl Groups: From Functional Powders to PLA Foams and Compatibilized Blends. 通过羟基的酯化反应实现胡敏素的升级再循环:从功能性粉末到聚乳酸泡沫和复合混合物。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-11 Epub Date: 2024-07-12 DOI: 10.1002/cssc.202400403
Dilhan Kandemir, Peter Van Puyvelde, Anton Ginzburg

The valorization of humins side streams from bio-refineries holds significant economic and sustainability potential. One plausible strategy involves using them as building blocks to create new materials. However, humins pose conceptual challenges in their natural state due to their high viscosity, processing difficulties, and temperature sensitivity. This article presents a synthetic strategy for modifying humins properties to make them thermally stable and processable. Employing a sequence of esterification reactions and varying the reagent steric length, we showcase the selective transformation of humins into thermally-stable fine powders and low-viscosity liquids. We extend this approach by reacting humins with polyesters such as polylactic acids and polycaprolactone. In particular, we detail a one-pot single-step synthesis of micro-phase separated compatibilized blends of polylactic acid and humins capped with the polylactic acid arms. Processed via solution-casting, the obtained materials behave as high-strength thermoplastic elastomers having uniform foam morphologies and material characteristics superior to the pure polylactic acid. By varying the content of D-enantiomers, we demonstrate an additional possibility of manipulating the cellular structures of the foams. Finally, we provide a solution to product circularity by reporting a dissolution recycling method.

生物精炼厂产生的腐殖质副流的价值提升具有巨大的经济和可持续发展潜力。一种可行的策略是将腐殖质用作制造新材料的构件。然而,在自然状态下,腐殖质因其高粘度、加工困难和对温度敏感而带来了概念上的挑战。本文介绍了一种改变腐植酸特性的合成策略,使其具有热稳定性和可加工性。通过一系列酯化反应和改变试剂的立体长度,我们展示了如何将腐植酸选择性地转化为热稳定性的细粉末和低粘度液体。我们通过将腐植酸与聚乳酸和聚己内酯等聚酯进行反应,进一步扩展了这种方法。特别是,我们详细介绍了聚乳酸和腐植酸的微相分离相容混合物的一步法合成方法。通过溶液浇铸加工,获得的材料表现为高强度热塑性弹性体,具有均匀的泡沫形态和优于纯聚乳酸的材料特性。通过改变 D-对映体的含量,我们展示了操纵泡沫细胞结构的另一种可能性。最后,我们报告了一种溶解回收方法,为产品的循环利用提供了解决方案。
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引用次数: 0
A Binary Ionogel Electrolyte for the Realization of an All Solid-State Electrical Double-Layer Capacitor Performing at Low Temperature. 用于实现低温下全固态双层电容器的二元离子凝胶电解质。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-11 Epub Date: 2024-06-28 DOI: 10.1002/cssc.202400596
Emmanuel Pameté, Zhuanpei Wang, François Béguin

Over the last years, solid-state electrolytes made of an ionic liquid (IL) confined in a solid (inorganic or polymer) matrix, also known as ionogels, have been proposed to solve the leakage problems occurring at high temperatures in classical electrical double-layer capacitors (EDLCs) with an organic electrolyte, and thereof improve the safety. However, making ionogel-based EDLCs perform with reasonable power at low temperature is still a major challenge due to the high melting point of the confined IL. To overcome these limitations, the present contribution discloses ionogel films prepared in a totally oxygen/moisture-free atmosphere by encapsulating 70 wt % of an equimolar mixture of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide and 1-ethyl-3-methylimidazolium tetrafluoroborate - [EMIm][BF4]0.5[FSI]0.5 - into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) network. The further called "binary ionogel" films demonstrated a high flexibility and a good ionic conductivity of 5.8 mS cm-1 at 20 °C. Contrary to the ionogels prepared from either [EMIm][FSI] or [EMIm][BF4], displaying melting at Tm=-16 °C and -7 °C, respectively, the crystallization of confined [EMIm][BF4]0.5[FSI]0.5 is quenched in the binary ionogel, which shows only a glass transition at -101 °C. This quenching enables an increased ionicity and ionic diffusion at the interface with the PVdF host network, leading the binary ionogel membrane to display higher ionic conductivity below -20 °C than the parent binary [EMIm][BF4]0.5[FSI]0.5 liquid. Laminate EDLCs were built with a 100 μm thick binary ionogel separator and electrodes made from a hierarchical micro-/mesoporous MgO-templated carbon containing a reasonable proportion of mesopores to enhance the mass transport of ions, especially at low temperature where the ionic diffusion noticeably decreases. The EDLCs operated up to 3.0 V with ideal EDL characteristics from -40 °C to room temperature. Their output specific energy under a discharge power of 1 kW kg-1 is ca. 4 times larger than with a cell implementing the same carbon electrodes together with the binary [EMIm][BF4]0.5[FSI]0.5 liquid. Hence, this binary ionogel electrolyte concept paves the road for developing safe and flexible solid-state energy storage devices operating at subambient temperatures in extreme environments.

由离子液体(IL)封闭在固体基质中制成的固态电解质(也称为离子凝胶)已被提出用于防止双电层电容器(EDLC)的电解质泄漏,从而提高其安全性。然而,由于受限电解质的熔点较高,要使基于离子凝胶的双电层电容器在低温条件下以合理功率运行仍是一项重大挑战。为了克服这些限制,本论文披露了将 1-乙基-3-甲基咪唑鎓双(氟磺酰)亚胺和 1-乙基-3-甲基咪唑鎓四氟硼酸盐的二元混合物--[EMIm][BF4]0.5[FSI]0.5--封装到 PVdF-HFP 网络中制备的离子凝胶薄膜。由[EMIm][FSI]或[EMIm][BF4]制备的离子凝胶会出现冻结/熔化现象,与此相反,在二元离子凝胶中,封闭的[EMIm][BF4]0.5[FSI]0.5的结晶被淬灭,仅在-101 °C时出现玻璃化转变。这种淬火使得与 PVdF 主网络接口处的离子性和离子扩散增加,导致二元离子凝胶膜在 -20 °C 以下显示出比母体二元 [EMIm][BF4]0.5[FSI]0.5 液体更高的离子电导率。使用二元离子凝胶分离器和分层碳电极构建的层压式 EDLC 在-40 °C至室温范围内都能理想地运行,其输出能量是使用相同碳电极和二元[EMIm][BF4]0.5[FSI]0.5 离子液体的电池的约 4 倍。
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引用次数: 0
Circular Economy and Chemical Conversion for Polyester Wastes. 聚酯废料的循环经济和化学转化。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-07 DOI: 10.1002/cssc.202402100
Jingjing Cao, Xin Qiu, Fan Zhang, Shaohai Fu

Polyester waste in the environment threatens public health and environmental ecosystems. Chemical recycling of polyester waste offers a dual solution to ensure resource sustainability and ecological restoration. This minireview highlights the traditional recycling methods and novel recycling strategies of polyester plastics. The conventional strategy includes pyrolysis, carbonation, and solvolysis of polyesters for degradation and recycling. Furthermore, the review delves into exploring emerging technologies including hydrogenolysis, electrocatalysis, photothermal, photoreforming, and enzymatic for upcycling polyesters. It emphasizes the selectivity of products during the polyester conversion process and elucidates conversion pathways. More importantly, the separation and purification of the products, the life cycle assessment, and the economic analysis of the overall recycling process are essential for evaluating the environmental and economic viability of chemical recycling of waste polyester plastics. Finally, the review offers perspective into the future challenges and developments of chemical recycling in the polyester economy.

环境中的聚酯废料威胁着公众健康和环境生态系统。聚酯废料的化学回收为确保资源可持续性和生态恢复提供了双重解决方案。本小节重点介绍聚酯塑料的传统回收方法和新型回收策略。传统策略包括热解、碳化和溶解聚酯以实现降解和回收。此外,该综述还深入探讨了用于聚酯升级再循环的新兴技术,包括氢解、电催化、光热、光成形和酶解技术。报告强调了聚酯转化过程中产品的选择性,并阐明了转化途径。更重要的是,产品的分离和提纯、生命周期评估以及整个回收过程的经济分析对于评估废旧聚酯塑料化学回收的环境和经济可行性至关重要。最后,本综述对聚酯经济中化学回收的未来挑战和发展提出了展望。
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引用次数: 0
Lewis acid sites in hollow cobalt phytate micropolyhedra promote the electrocatalytic water oxidation. 中空植酸钴微多面体中的路易斯酸位点促进了电催化水氧化。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-07 DOI: 10.1002/cssc.202401932
Mingxing Chen, Jing Qi, Qizhen Chen, Ying Gao, Yajing Zhao, Shengbo Gao, Enbo Shangguan

The acid-base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt-based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M-CoPA, M = Cu, Sr) were synthesized by a cation-exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long-term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high-efficiency electrocatalysts for energy conversion systems.

金属中心的酸碱微环境对于构建先进的氧进化反应(OER)电催化剂至关重要。然而,对于钴基催化剂来说,酸性位点与 OER 性能之间的相关性仍不清楚。本文采用阳离子交换策略合成了空心植酸钴微多面体(M-CoPA,M = Cu、Sr)中的路易斯酸位点,并对其 OER 性能进行了系统研究。实验结果表明,路易斯酸性较强的 Cu2+ 位点在碱性电解质中表现出优异的内在活性和长期稳定性。光谱和电化学研究表明,中空植酸钴微多面体中的路易斯酸位点可以调节相邻钴中心的电子分布,进一步优化含氧物种的吸附强度。这项研究阐明了路易斯酸位点对 OER 动力学的影响,为开发能量转换系统的高效电催化剂提供了有效途径。
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引用次数: 0
Enhanced Performance of Lithium-Sulfur Batteries Using Construction Wastes: A Sustainable Approach to High-Loading Sulfur Cathodes. 利用建筑垃圾提高锂硫电池性能:高负载硫阴极的可持续方法。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-07 DOI: 10.1002/cssc.202402206
Yi-Chen Huang, Cheng-Che Wu, Sheng-Heng Chung

Advancing lithium-sulfur battery technology requires addressing both extrinsic cell-fabrication and intrinsic material challenges to improve efficiency, cyclability, and environmental sustainability. A key challenge is the low conductivity of sulfur cathodes, which is typically managed by incorporating conductive carbon materials. These materials enhance the performance of sulfur cathodes by facilitating high sulfur loading and improving polysulfide retention. In line with green chemistry principles and circular economy concepts, this study explores the use of recycled materials-specifically recycled quartz and board-as substrates for graphene coatings in lithium-sulfur cells. Recycled quartz bricks and blocks, predominantly SiO2, and recycled shelf boards, rich in Al2O3, are successfully coated with graphene, which significantly improves polysulfide adsorption and overall battery performance. The graphene-coated quartz exhibits high sulfur loading (8 mg cm-2), exceptional charge-storage capacity (1,114 mA·h g-1), and long cycle stability (200 cycles) with an energy density of 19 mW·h cm-2. This approach enhances the electrochemical performance of the lithium-sulfur cells and also aligns with sustainability goals by repurposing waste materials and minimizing environmental impact. This novel methodology demonstrates that integrating recycled materials can effectively address key challenges in lithium-sulfur battery technology, advancing both performance and environmental sustainability.

要推动锂硫电池技术的发展,就必须解决电池制造和材料内在两方面的挑战,以提高效率、循环性和环境可持续性。一个关键挑战是硫阴极的低导电性,这通常通过加入导电碳材料来解决。这些材料通过促进高硫含量和改善多硫化物保留来提高硫阴极的性能。根据绿色化学原则和循环经济理念,本研究探讨了在锂硫电池中使用回收材料(特别是回收石英和石英板)作为石墨烯涂层的基底。主要成分为二氧化硅的回收石英砖和石英块以及富含 Al2O3 的回收货架板成功地涂上了石墨烯,从而显著提高了多硫化物的吸附性和电池的整体性能。涂有石墨烯的石英具有高硫含量(8 mg cm-2)、优异的充电存储容量(1,114 mA-h g-1)和长循环稳定性(200 次循环),能量密度为 19 mW-h cm-2。这种方法不仅提高了锂硫电池的电化学性能,还通过废物再利用和最大限度地减少对环境的影响,实现了可持续发展的目标。这种新颖的方法表明,整合回收材料可以有效解决锂硫电池技术中的关键难题,同时提高性能和环境可持续性。
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引用次数: 0
Poly(ionic) Liquid-Enhanced Ion Dynamics in Cellulose-Derived Gel Polymer Electrolytes. 纤维素衍生凝胶聚合物电解质中的聚离子液体增强离子动力学。
IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-11-06 DOI: 10.1002/cssc.202401710
Tiago G Paiva, Maykel Klem, Sara L Silvestre, João Coelho, Neri Alves, Elvira Fortunato, Eurico Cabrita, Marta C Corvo

Gel polymer electrolytes (GPEs) are regarded as a promising alternative to conventional electrolytes, combining the advantages of solid and liquid electrolytes. Leveraging the abundance and eco-friendliness of cellulose-based materials,  GPEs were produced using methyl cellulose and incorporating various doping agents, either an ionic liquid (1-Butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr14][TFSI]), its polymeric ionic liquid analogue (Poly(diallyldimethylammonium bis(trifluoromethylsulfonyl)imide) [PDADMA][TFSI]), or an anionically charged backbone polymeric ionic liquid (lithium poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino) sulfonyl) imide] LiP[STFSI]). The ion dynamics and molecular interactions within the GPEs were thoroughly analyzed using Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy (ATR-FTIR), Heteronuclear Overhauser Enhancement Spectroscopy (HOESY), and Pulsed-Field Gradient Nuclear Magnetic Resonance Diffusion (PFG-NMR). Li+ transference numbers (tLi+) were successfully calculated. Our study found that by combining slow-diffusing polymeric ionic liquids (PILs) with fast-diffusing lithium salt, we were able to achieve transference numbers comparable to those of liquid electrolytes, especially with the anionic PIL, LiP[STFSI]. This research highlights the influence of the polymer's nature on lithium-ion transport within GPEs. Additionally, micro supercapacitor (MSC) devices assembled with these GPEs exhibited capacitive behavior. These findings suggest that further optimization of GPE composition could significantly improve their performance, thereby positioning them for application in sustainable and efficient energy storage systems.

凝胶聚合物电解质(GPEs)结合了固态和液态电解质的优点,被视为传统电解质的一种有前途的替代品。利用纤维素基材料的丰富性和生态友好性,我们使用甲基纤维素并加入各种掺杂剂(离子液体(1-丁基-1-甲基吡咯烷鎓双三氟甲基磺酰亚胺[Pyr14][TFSI]))生产出了 GPE、其聚合物离子液体类似物(聚(二烯丙基二甲基铵双(三氟甲基磺酰基)亚胺) [PDADMA][TFSI]),或带阴离子的骨架聚合物离子液体(聚[(4-苯乙烯磺酰基)(三氟甲基(S-三氟甲基磺酰亚胺)磺酰基)亚胺]锂STFSI])。利用衰减全反射傅立叶变换红外光谱法(ATR-FTIR)、异核过豪瑟增强光谱法(HOESY)和脉冲场梯度核磁共振扩散法(PFG-NMR)对 GPE 内部的离子动力学和分子相互作用进行了深入分析。研究成功地计算出了 Li+ 转移数(tLi+)。我们的研究发现,通过将慢速扩散聚合物离子液体(PIL)与快速扩散锂盐相结合,我们能够获得与液态电解质相当的转移数,尤其是阴离子 PIL LiP[STFSI]。这项研究强调了聚合物性质对 GPE 内锂离子传输的影响。此外,用这些 GPE 组装的微型超级电容器 (MSC) 器件表现出了电容行为。这些研究结果表明,进一步优化 GPE 的组成可显著提高其性能,从而将其应用于可持续的高效储能系统。
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