The role of water on dehydrofluorination in PVDF/K2CO3 percolative composites

Zhu, Wenliang; Hoshida, Naoki; Jati, Galih Nurcahyo Pangeran; Yoshida, Yumi; Adachi, Kaoru; Zhu, Jiliang; Ihara, Manamu; Marin, Elia; Pezzotti, Giuseppe

doi:10.1016/j.mtcomm.2022.103884

Cited by 2 publications

(6 citation statements)

References 26 publications

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“…Accordingly, upon thermal treatments, more water will be involved to increase the efficiency of dehydrofluorination reactions. Indeed, we have newly confirmed that water plays a critical role on PVDF dehydrofluorination during thermal treatment . Because of this higher efficiency of the dehydrofluorination process, PKC showed a marked increase in I D / I G with the content of K 2 CO 3 up to 30 wt %.…”

Section: Discussionmentioning

confidence: 57%

“…Indeed, we have newly confirmed that water plays a critical role on PVDF dehydrofluorination during thermal treatment. 7 Because of this higher efficiency of the dehydrofluorination process, PKC showed a marked increase in I D / I G with the content of K 2 CO 3 up to 30 wt %. However, further increasing the carbonate content above the percolation threshold may produce filler agglomerates, thus increasing the filler/filler interface population to the detriment of the matrix/filler interface fraction, 4 and result in an insufficient amount of HF, as well as a preferential reaction to form KF again.…”

Section: Discussionmentioning

confidence: 97%

“…In a recent paper, we have reported the presence of a complex reaction loop in percolative composites PVDF/K 2 CO 3 to gradually consume the raw materials . After mixing the constituent phases, i.e., alkali metal carbonate (M 2 CO 3 , M = Li, Na, and K) and PVDF, in the presence of moisture, the composite samples before thermal treatment consisted of physically mixed PVDF and a certain amount of MHCO 3 as well as hydrated water in sesquihydrate or sesquicarbonate double salt systems because of moisture absorption. ,,, Upon thermal treatment, decompositions of MHCO 3 and hydrated compound release water, and the generated water further reacts with M 2 CO 3 to yield hydroxide due to the basic nature of M 2 CO 3 (pH > 7): 2 MH CO 3 → normalM 2 CO 3 + normalH 2 normalO + CO 2 normalM 2 CO 3 · italicn normalH 2 normalO → normalM 2 CO 3 + italicn normalH 2 normalO → MOH + MH CO 3 → ... …”

Section: Discussionmentioning

confidence: 99%

“…In a previous paper, we have reported that percolative composites consisting of potassium carbonate dispersed in polyvinylidene fluoride (PVDF) polymeric matrix showed a rather high dielectric constant and electrical conductivity at the percolation threshold (30 wt % K 2 CO 3 ) due to the formation of chemically activated interfaces in the composite, as interfacial polarization resulted in high values of dielectric permittivity . Further studies revealed the presence of a complex reaction loop for the formation of activated carbon (AC) from PVDF dehydrofluorination during thermal treatment, as the net effect of these reactions is to generate a carbon-based nanocomposite in the polymer matrix. , The system has many marked merits: e.g., low-cost raw materials, extremely simple fabrication procedure, mesoporous surface structure, high flexibility, and light weight, which makes it promising for portable, flexible, and wearable energy storage applications.…”

Section: Introductionmentioning

confidence: 99%

“… 5 Further studies revealed the presence of a complex reaction loop for the formation of activated carbon (AC) from PVDF dehydrofluorination during thermal treatment, as the net effect of these reactions is to generate a carbon-based nanocomposite in the polymer matrix. 6 , 7 The system has many marked merits: e.g., low-cost raw materials, extremely simple fabrication procedure, mesoporous surface structure, high flexibility, and light weight, which makes it promising for portable, flexible, and wearable energy storage applications.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Carbonate Source on the Dehydrofluorination Process in Polyvinylidene Fluoride/Alkali Metal Carbonate Composites

et al. 2023

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In this paper, Raman and X-ray photoelectron spectroscopies were applied to analyze compositional and structural variations of the generated activated carbon (AC), as induced by changing carbonate source in three different types of systems, PVDF/M2CO3 (M = Li, Na, and K). According to the variations of I D/I G and sp2/sp3 ratios, a strong dependence of the AC structure on the type and content of the initial carbonate was found, determined by practical dehydrofluorination reactions associated with oxygen incorporation in AC and side reactions, because of the property variation induced by the difference in the cation of the carbonate sources. This procedure clarified the process of PVDF dehydrofluorination and the formation of activated carbon, which helps to optimize the material performance of the percolative composite for flexible energy storage applications.

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Section: Discussionmentioning

confidence: 57%

Section: Discussionmentioning

confidence: 97%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Effect of Carbonate Source on the Dehydrofluorination Process in Polyvinylidene Fluoride/Alkali Metal Carbonate Composites

et al. 2023

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Side-Reactions of Polyvinylidene Fluoride and Polyvinylidene Chloride Binders with Aluminum Chloride-Based Ionic Liquid Electrolyte in Rechargeable Aluminum-Batteries

Zemlyanushin,

Müller,

Tsuda

et al. 2024

J. Electrochem. Soc.

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Rechargeable aluminum batteries (RABs) use a Lewis acidic aluminum chloride (AlCl3) and 1-Ethyl-3-methylimidazolium chloride (EMImCl) ionic liquid electrolyte. Electrode fabrication often relies on procedures from lithium-ion batteries (LIBs), including the use of Polyvinylidene fluoride (PVdF) as a binder. However, PVdF reacts with Al2Cl7- in the RAB electrolyte, making it unsuitable for new battery types. The literature lacks details on the products formed, changes in the ionic liquid electrolyte, and the implications for electrochemical performance. With potential European Chemical Agency restrictions on per- and polyfluoroalkyl substances (PFAS) by 2025, Polyvinylidene chloride (PVdC) is being explored as an alternative binder. In contact with AlCl3:EMImCl (1.50:1.00) electrolyte, both, PVdF and PVdC transform into amorphous carbon during dehydrofluorination and dehydrochlorination, respectively, as confirmed by Raman spectroscopy. Furthermore, via 19F-NMR, it is shown that the reaction time between the soaked polymers and the ionic liquid has a significant influence on the newly formed aluminum chlorofluoride complexes. Electrochemical tests of graphite-based electrodes indicate increasing specific capacity of PVdF compared to PVdC with a continuous number of cycles. Amorphous carbon can prevent the disintegration of graphite and enhance conductivity. Furthermore, newly formed AlF4- can run a co-intercalation and lead to increasing specific capacity.

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The role of water on dehydrofluorination in PVDF/K2CO3 percolative composites

Cited by 2 publications

References 26 publications

Effect of Carbonate Source on the Dehydrofluorination Process in Polyvinylidene Fluoride/Alkali Metal Carbonate Composites

Effect of Carbonate Source on the Dehydrofluorination Process in Polyvinylidene Fluoride/Alkali Metal Carbonate Composites

Side-Reactions of Polyvinylidene Fluoride and Polyvinylidene Chloride Binders with Aluminum Chloride-Based Ionic Liquid Electrolyte in Rechargeable Aluminum-Batteries

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