Pub Date : 2024-11-11Epub Date: 2024-07-08DOI: 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.
{"title":"Tailoring the Use of 8-Hydroxyquinolines for the Facile Separation of Iron, Dysprosium and Neodymium.","authors":"Matteo Melegari, Martina Neri, Alex Falco, Matteo Tegoni, Monica Maffini, Fabio Fornari, Claudio Mucchino, Flavia Artizzu, Angela Serpe, Luciano Marchiò","doi":"10.1002/cssc.202400286","DOIUrl":"10.1002/cssc.202400286","url":null,"abstract":"<p><p>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 Fe<sup>3+</sup> can be separated as insoluble [Fe(Q<sub>Cl,I</sub>)<sub>3</sub>] from soluble [REE(Q<sub>Cl,I</sub>)<sub>4</sub>]<sup>-</sup> complexes (Q<sub>Cl,I</sub> <sup>-</sup>: 5-Cl-7-I-8-hydoxyquinolinate). Following that, Q<sub>Cl</sub> <sup>-</sup> (5-Cl-8-hydroxyquinolinate) formed insoluble [Nd<sub>3</sub>(Q<sub>Cl</sub>)<sub>9</sub>] and soluble (Bu<sub>4</sub>N)[Dy(Q<sub>Cl</sub>)<sub>4</sub>]. 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 Bu<sub>4</sub>N<sup>+</sup> ions, were regenerated and internally reused, thus contributing to the sustainability of a possible metal recovery process.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141086246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-11Epub Date: 2024-07-09DOI: 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.
{"title":"Non-Fused π-Extension of Endcaps of Small Molecular Acceptors Enabling High-Performance Organic Solar Cells.","authors":"Fan Feng, Zunyuan Hu, Jianxiao Wang, Pengchao Wang, Cheng Sun, Xiaoning Wang, Fuzhen Bi, Yonghai Li, Xichang Bao","doi":"10.1002/cssc.202400601","DOIUrl":"10.1002/cssc.202400601","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141086243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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 μh/μe 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.
{"title":"Enhanced Fill Factor and Efficiency of Ternary Organic Solar Cells by a New Asymmetric Non-Fullerene Small Molecule Acceptor.","authors":"Kun Wang, Jingshun Gao, Huiyan Wang, Qing Guo, Jianqi Zhang, Xia Guo, Maojie Zhang","doi":"10.1002/cssc.202400691","DOIUrl":"10.1002/cssc.202400691","url":null,"abstract":"<p><p>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 μ<sub>h</sub>/μ<sub>e</sub> 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 cm<sup>2</sup>, 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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141160623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-11Epub Date: 2024-06-06DOI: 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。
{"title":"Chemical and Electrochemical Characterization of Hot-Pressed Li<sub>6</sub>PS<sub>5</sub>Cl Solid State Electrolyte: Operating Pressure-Invariant High Ionic Conductivity.","authors":"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","doi":"10.1002/cssc.202400718","DOIUrl":"10.1002/cssc.202400718","url":null,"abstract":"<p><p>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 (Li<sub>6</sub>PS<sub>5</sub>X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10<sup>-2</sup> S cm<sup>-1</sup>) 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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141260414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-11Epub Date: 2024-07-12DOI: 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.
{"title":"Upcycling Humins via Esterification Reactions of Hydroxyl Groups: From Functional Powders to PLA Foams and Compatibilized Blends.","authors":"Dilhan Kandemir, Peter Van Puyvelde, Anton Ginzburg","doi":"10.1002/cssc.202400403","DOIUrl":"10.1002/cssc.202400403","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141154405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-11Epub Date: 2024-06-28DOI: 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.
{"title":"A Binary Ionogel Electrolyte for the Realization of an All Solid-State Electrical Double-Layer Capacitor Performing at Low Temperature.","authors":"Emmanuel Pameté, Zhuanpei Wang, François Béguin","doi":"10.1002/cssc.202400596","DOIUrl":"10.1002/cssc.202400596","url":null,"abstract":"<p><p>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][BF<sub>4</sub>]<sub>0.5</sub>[FSI]<sub>0.5</sub> - 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<sup>-1</sup> at 20 °C. Contrary to the ionogels prepared from either [EMIm][FSI] or [EMIm][BF<sub>4</sub>], displaying melting at T<sub>m</sub>=-16 °C and -7 °C, respectively, the crystallization of confined [EMIm][BF<sub>4</sub>]<sub>0.5</sub>[FSI]<sub>0.5</sub> 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][BF<sub>4</sub>]<sub>0.5</sub>[FSI]<sub>0.5</sub> 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<sup>-1</sup> is ca. 4 times larger than with a cell implementing the same carbon electrodes together with the binary [EMIm][BF<sub>4</sub>]<sub>0.5</sub>[FSI]<sub>0.5</sub> 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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141154380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Circular Economy and Chemical Conversion for Polyester Wastes.","authors":"Jingjing Cao, Xin Qiu, Fan Zhang, Shaohai Fu","doi":"10.1002/cssc.202402100","DOIUrl":"https://doi.org/10.1002/cssc.202402100","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589642","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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。
{"title":"Lewis acid sites in hollow cobalt phytate micropolyhedra promote the electrocatalytic water oxidation.","authors":"Mingxing Chen, Jing Qi, Qizhen Chen, Ying Gao, Yajing Zhao, Shengbo Gao, Enbo Shangguan","doi":"10.1002/cssc.202401932","DOIUrl":"https://doi.org/10.1002/cssc.202401932","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Enhanced Performance of Lithium-Sulfur Batteries Using Construction Wastes: A Sustainable Approach to High-Loading Sulfur Cathodes.","authors":"Yi-Chen Huang, Cheng-Che Wu, Sheng-Heng Chung","doi":"10.1002/cssc.202402206","DOIUrl":"10.1002/cssc.202402206","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Poly(ionic) Liquid-Enhanced Ion Dynamics in Cellulose-Derived Gel Polymer Electrolytes.","authors":"Tiago G Paiva, Maykel Klem, Sara L Silvestre, João Coelho, Neri Alves, Elvira Fortunato, Eurico Cabrita, Marta C Corvo","doi":"10.1002/cssc.202401710","DOIUrl":"https://doi.org/10.1002/cssc.202401710","url":null,"abstract":"<p><p>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.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":null,"pages":null},"PeriodicalIF":7.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589661","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}