Understanding the Effect of UV-Induced Cross-Linking on the Physicochemical Properties of Highly Performing PEO/LiTFSI-Based Polymer Electrolytes

Falco, Marisa; Simari, Cataldo; Ferrara, Chiara; Nair, Jijeesh Ravi; Meligrana, Giuseppina; Bella, Federico; Nicotera, Isabella; Mustarelli, Piercarlo; Winter, Martin; Gerbaldi, Claudio

doi:10.1021/acs.langmuir.9b00041

Cited by 59 publications

(62 citation statements)

References 46 publications

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“…The achievement of stable, cheap and reproducible PSCs will be fundamental in view of their worldwide diffusion in the energy scenario, as well as integration with energy storage technologies. [38][39][40][41][42][43][44][45][46][47]…”

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confidence: 99%

Carbon-based materials for stable, cheaper and large-scale processable perovskite solar cells

Fagiolari

Bella

2019

Energy Environ. Sci.

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Almost ten years after their first use in the photovoltaic (PV) field, perovskite solar cells (PSCs) are now hybrid devices that, in addition to having reached silicon performance, can accelerate the energy transition and boost the use of abundant elements for their manufacturing process. However, noble metals (in particular gold) represent the most typically used sources for back electrode fabrication, and this issue has been intensively considered by the research community in the last five years. This review shows how the most promising solution, considering also the need to develop a large-scale production process, is based on the use of carbon-based materials for the preparation of back electrodes. Graphite, carbon black, graphene and carbon nanotubes (CNTs) have been proposed, functionalized and characterized, leading to laboratory-scale solar cells and modules capable of providing excellent efficiencies and ensuring stability greater than those of gold-based devices. Strengthened by these results and its hydrophobizing properties, carbon has also started to be used as an electron transporting material (ETM), with excellent results on both rigid and flexible substrates. This review discusses the major advances and the updated state-of-the-art in the carbon-based PSC scenario, keeping a solid trajectory where the accessibility, low cost, high electrical conductivity, chemical stability and controllable porosity of carbon are highlighted and exploited in the design of upscalable hybrid solar cells. Broader contextToday, more than 75% of the world energy demand is met by traditional, non-sustainable energy resources, mainly based on coal, natural gas and oil. Photovoltaics represents a concrete action to mitigate fossil fuel consumption, and among all the developed solar cells, perovskite-based ones have shown the highest increase in terms of efficiency (currently above 25%). Halide perovskites, as a family of new-generation semiconductor materials, are also exploitable for light-emitting devices, photodetectors and memristors, but their use in photovoltaics gives rise to outstanding performances. Here, photogenerated charges pass through electron/hole transporting materials and are transferred to the external circuit by front and back electrodes. While the front electrode is a common conductive glass, many issues are now under study concerning the back electrode, traditionally made of gold. Indeed, replacing this expensive metal with a much cheaper alternative is vital for realizing affordable solar technologies. Carbon, in its multiple forms, represents the winning solution and the scientific community has recently shown its large scale processability, its power as a stability booster and some interesting effects at the perovskite/electrode interface. This review shows how carbon is becoming the winning ingredient for the scaling up and worldwide diffusion of perovskite solar cells.

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confidence: 99%

Carbon-based materials for stable, cheaper and large-scale processable perovskite solar cells

Fagiolari

Bella

2019

Energy Environ. Sci.

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234

188

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“…Few authors report cycling data of cross‐linked SPE systems where both high cycling rate and high temperature is utilized during cycling, making comparison with other systems difficult. While the cross‐linked poly(CL‐ co‐ TMC) system has too low ionic conductivity to cycle at high rates at room temperature, unlike some cross‐linked PEO/glyme systems, it has a lower overpotential compared to PEO systems at a similar cycling temperature and higher cycling rate . After 150 cycles the SPE starts showing some instability which is most likely due to side‐reactions occurring as the battery is charging, see Figure c.…”

Section: Resultsmentioning

confidence: 99%

“…There are many methods available to improve the mechanical properties of a polymer electrolyte without seriously compromising their conductive properties, such as increasing the molecular weight of the polymer, copolymerization with a mechanically robust block, addition of nanoparticles, and cross‐linking . By improving the mechanical stability, long‐term cycling will be possible.…”

Section: Introductionmentioning

confidence: 99%

Mechanically Stable UV‐Crosslinked Polyester‐Polycarbonate Solid Polymer Electrolyte for High‐Temperature Batteries

Johansson

Brandell

Mindemark

2020

Batteries & Supercaps

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Due to the mechanism with which solid polymer electrolytes use to conduct ions, these materials are generally more suitable for high‐temperature applications where the ionic conductivity is sufficient and where liquid electrolytes show insufficient stability. To enable high‐temperature cycling of polymer electrolytes, the mechanical stability has to be improved. Herein, we report successful long‐term cycling of a solid polyester‐polycarbonate – poly(ϵ‐caprolactone‐co‐trimethylene carbonate) (poly(CL‐co‐TMC)) – electrolyte cross‐linked through the addition of multifunctional acrylates and the use of UV‐irradiation, allowing stable cycling of cells for more than 100 cycles at 80 °C, with good rate capabilities (0.2 mA cm−2) and Coulombic efficiencies exceeding 99 %. Both the mechanical properties and the ionic conductivity of the mechanically stabilized poly(CL‐co‐TMC) were investigated and optimized to reduce the frequency dependence of the moduli while still achieving an acceptable ionic conductivity at elevated temperature. These results indicate that the poly(CL‐co‐TMC) system can straight‐forwardly be modified to allow for higher‐temperature applications.

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“…Die Einbindung von Lithiumsalz in eine UV‐quervernetzte Polyethylenoxid (PEO)‐Matrix ist ein wichtiges Beispiel für einen elastischen SPE bei dem die Kristallisation des PEOs bei Raumtemperatur verhindert werden kann . Weiterhin wurde berichtet, dass PEs nach UV‐induzierter Quervernetzung auch bei geringen Filmdicken eine hohe Formbeständigkeit aufweisen und als freistehende Membranen erhalten werden können, was solche Systeme zu vielversprechenden Kandidaten für die Kompensation morphologischer Änderungen macht . Basierend auf diesem Ansatz, zeigen quervernetzte ternäre Feststoff‐Polymer‐Elektrolyte (TSPEs), die den Plastifizierungseffekt einer ionischen Flüssigkeit (IL) ausnutzen, den nächsten Entwicklungsschritt zu hoch amorphen PEs mit verbesserter ionischer Leitfähigkeit auf …”

Section: Introductionunclassified

Benetzungsvorgänge und ihr Einfluss auf die elektrochemischen Eigenschaften von oberflächenangepassten Lithium‐Metall‐Elektroden in Kontakt mit quervernetzten Polymer‐Elektrolyten

et al. 2020

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Lithium‐Metall‐Batterien (LMBs) auf Basis von vernetzten Polymer‐Elektrolyten (PEs) sind vielversprechende Kandidaten für Batterien der nächsten Generation. Das Benetzungsverhalten von PEs auf unebenen Lithium‐Metall‐Oberflächen wurde jedoch in den meisten Studien bisher vernachlässigt. Hier wird gezeigt, dass mikroskalige Defektstellen mit gekrümmten Kanten eine entscheidende Rolle bei der benetzungsabhängigen, elektrochemischen Abscheidung von Lithium (Li) spielen. Die Benetzbarkeit und die viskoelastischen Eigenschaften von PEs werden in Zusammenhang gebracht und es wird der Einfluss der Benetzbarkeit auf die Keimbildung und Diffusion in der Nähe der Li|PE‐Grenzfläche untersucht. Es wird festgestellt, dass die Krümmung der Kanten an Li‐Defektstellen ein entscheidender Einflussfaktor für die Untersuchung von Benetzungsphänomenen ist. Das Auftreten von mikroskaligen Defekten und partieller Phasenseparation werden als Kernpunkte für unregelmäßige Nukleation identifiziert. Es wird betont, dass für eine stabile und beständige Langzeit‐Zyklenstabilität von PE‐basierten LMBs ein tieferes Verständnis des “weichen Festkörper”‐Festkörper‐Kontakts zwischen PEs und intrinsisch rauen Li‐Metall‐Oberflächen erforderlich ist.

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Understanding the Effect of UV-Induced Cross-Linking on the Physicochemical Properties of Highly Performing PEO/LiTFSI-Based Polymer Electrolytes

Cited by 59 publications

References 46 publications

Carbon-based materials for stable, cheaper and large-scale processable perovskite solar cells

Carbon-based materials for stable, cheaper and large-scale processable perovskite solar cells

Mechanically Stable UV‐Crosslinked Polyester‐Polycarbonate Solid Polymer Electrolyte for High‐Temperature Batteries

Benetzungsvorgänge und ihr Einfluss auf die elektrochemischen Eigenschaften von oberflächenangepassten Lithium‐Metall‐Elektroden in Kontakt mit quervernetzten Polymer‐Elektrolyten

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