Pub Date : 2025-02-26DOI: 10.1016/j.polymer.2025.128195
Tingting Yang, Shengmei Huang, Jun Wang, Hongtao He, Jie Xu, Guofeng Hu, Jianping Zhou, Hongbo Liang, Chunhui Zhao
Anion exchange membranes (AEMs) are crucial materials in hydrogen production techniques via water electrolysis. Whereas, the “trade-off” between the conductivity and dimensional stability of AEMs, as well as poor alkaline stability, hinders the advancement of AEMs and water electrolysis technologies. Cross-linking serves as a pivotal strategy for addressing the 'trade-off' effect, thereby facilitating the fabrication of highly conductive and durable AEMs. In this study, a series of poly(carbazole)-based AEMs, designated as QPBHC-x, were synthesized utilizing the flexible cross-linker N,N,N',N'-tetramethyl-1,6-hexanediamine (TMHDA). The synthesized AEMs demonstrated reduced water uptake and enhanced alkaline stability in comparison to uncross-linked AEMs, while maintaining a conductivity retention exceeding 92% after immersion in 1 M NaOH solution at 80°C for 720 hours. AFM and SAXS analyses revealed the microphase separation structure in the prepared AEMs, which construct continuous ion channels and promote ion conduction. Specifically, the QPBHC-0.5 demonstrated a conductivity of 102.3 mS·cm-1 at 80 °C and exhibited a tensile strength of 46.6 MPa. Furthermore, anion exchange membrane water electrolysis (AEMWE) single cell (cathode: Pt/C and anode: NiFe2O4) based on QPBHC-0.75 achieved a current density of 1.40 A·cm-1 at 2 V in 1 M KOH (80 °C). Meanwhile, QPBHC-0.5 maintained stable operation for over 470 hours at 1.0 A·cm-1 in 1 M KOH (80 °C) with a voltage decay rate of 352 μV·h-1. These results indicate promising applications of cross-linked poly(carbazole)-based AEMs in water electrolysis.
{"title":"Durable cross-linked poly(carbazole)-based anion exchange membranes for alkaline water electrolysis","authors":"Tingting Yang, Shengmei Huang, Jun Wang, Hongtao He, Jie Xu, Guofeng Hu, Jianping Zhou, Hongbo Liang, Chunhui Zhao","doi":"10.1016/j.polymer.2025.128195","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128195","url":null,"abstract":"Anion exchange membranes (AEMs) are crucial materials in hydrogen production techniques via water electrolysis. Whereas, the “trade-off” between the conductivity and dimensional stability of AEMs, as well as poor alkaline stability, hinders the advancement of AEMs and water electrolysis technologies. Cross-linking serves as a pivotal strategy for addressing the 'trade-off' effect, thereby facilitating the fabrication of highly conductive and durable AEMs. In this study, a series of poly(carbazole)-based AEMs, designated as QPBHC-x, were synthesized utilizing the flexible cross-linker N,N,N',N'-tetramethyl-1,6-hexanediamine (TMHDA). The synthesized AEMs demonstrated reduced water uptake and enhanced alkaline stability in comparison to uncross-linked AEMs, while maintaining a conductivity retention exceeding 92% after immersion in 1 M NaOH solution at 80°C for 720 hours. AFM and SAXS analyses revealed the microphase separation structure in the prepared AEMs, which construct continuous ion channels and promote ion conduction. Specifically, the QPBHC-0.5 demonstrated a conductivity of 102.3 mS·cm<sup>-1</sup> at 80 °C and exhibited a tensile strength of 46.6 MPa. Furthermore, anion exchange membrane water electrolysis (AEMWE) single cell (cathode: Pt/C and anode: NiFe<sub>2</sub>O<sub>4</sub>) based on QPBHC-0.75 achieved a current density of 1.40 A·cm<sup>-1</sup> at 2 V in 1 M KOH (80 °C). Meanwhile, QPBHC-0.5 maintained stable operation for over 470 hours at 1.0 A·cm<sup>-1</sup> in 1 M KOH (80 °C) with a voltage decay rate of 352 μV·h<sup>-1</sup>. These results indicate promising applications of cross-linked poly(carbazole)-based AEMs in water electrolysis.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495764","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 poor interfacial adhesion between energetic crystals and polymer matrices results in undesirably low mechanical properties, limiting the application of energetic composites. Surface engineering has been widely implemented in materials science to regulate the mechanical properties. However, to achieve strong interfacial adhesion with precise control of interfacial structure is attractive and highly challenging for polymer bonded explosives. To address this issue, a covalent functionalization strategy were developed via the self-polymerization of dopamine on the surface of the energetic crystals, followed by the covalent grafting of fluoro-polymers using toluene-2,4-diisocyanate (TDI) as a bridging molecule. In-depth characterizations, combined with molecular dynamics simulation, have been systematically adopted to investigate the interfacial interaction and mechanical performance after covalent grafting of fluoro-polymers. Remarkably, both experimental results and numerical simulations revealed that the covalent functionalization and fluorine-containing binder system significantly increased the number of hydrogen bonds and interfacial interactions, thereby enhancing the interfacial adhesion between energetic crystals and the polymer matrix. Energetic composites with fluoro-polymer functionalization exhibited substantial interfacial enhancement effects. The mechanical properties of the composites improved with increasing grafted fluoro-polymer content. The composites based on energetic crystals with 2 wt% grafted fluoro-polymer exhibited optimal performance, with compressive and tensile fracture energies increased by 97.7% and 182.0%, respectively, compared to the unmodified composites. Additionally, computational simulations provided fundamental insights into how the interfacial structure affects the mechanical properties of energetic composites, confirming that the covalent functionalization and fluorine-containing binder system enhance interfacial adhesion by increasing hydrogen bond numbers and interfacial interactions.
{"title":"Fluoro-polymer Functionalization for Enhanced Interfacial Adhesion and Mechanical Properties in Polymer Bonded Explosives","authors":"Congmei Lin, Chengcheng Zeng, Shijun Liu, Bo Jin, Zhijian Yang, Jiahui Liu, Liping Pan, Chunliang Ji, Lixiao Hao, Yushi Wen, Feiyan Gong, Jiang Li, Shaoyun Guo","doi":"10.1016/j.polymer.2025.128178","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128178","url":null,"abstract":"The poor interfacial adhesion between energetic crystals and polymer matrices results in undesirably low mechanical properties, limiting the application of energetic composites. Surface engineering has been widely implemented in materials science to regulate the mechanical properties. However, to achieve strong interfacial adhesion with precise control of interfacial structure is attractive and highly challenging for polymer bonded explosives. To address this issue, a covalent functionalization strategy were developed via the self-polymerization of dopamine on the surface of the energetic crystals, followed by the covalent grafting of fluoro-polymers using toluene-2,4-diisocyanate (TDI) as a bridging molecule. In-depth characterizations, combined with molecular dynamics simulation, have been systematically adopted to investigate the interfacial interaction and mechanical performance after covalent grafting of fluoro-polymers. Remarkably, both experimental results and numerical simulations revealed that the covalent functionalization and fluorine-containing binder system significantly increased the number of hydrogen bonds and interfacial interactions, thereby enhancing the interfacial adhesion between energetic crystals and the polymer matrix. Energetic composites with fluoro-polymer functionalization exhibited substantial interfacial enhancement effects. The mechanical properties of the composites improved with increasing grafted fluoro-polymer content. The composites based on energetic crystals with 2 wt% grafted fluoro-polymer exhibited optimal performance, with compressive and tensile fracture energies increased by 97.7% and 182.0%, respectively, compared to the unmodified composites. Additionally, computational simulations provided fundamental insights into how the interfacial structure affects the mechanical properties of energetic composites, confirming that the covalent functionalization and fluorine-containing binder system enhance interfacial adhesion by increasing hydrogen bond numbers and interfacial interactions.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495690","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}
Aiming at developing new polymer absorbents for the physical CO2 capture, this work reports the synthesis and multi-scale characterization of two new families of poly(ionic liquid)s (PILs) obtained from polyepichlorohydrin (polyECH). PolyECH was quaternized with 1-methylimidazole quasi-quantitatively and the Cl anions were then exchanged by different salts to introduce BF4, AcO and TFSI anions for the first series of PILs. The second series was then obtained by varying the amount of 1-methylimidazole, leading to new PILs with TFSI anions and ionization ratios increasing from 0 to 94.6%. The chemical structure of the different PILs was characterized by different NMR techniques (1H, 13C, 2D 1H/13C HSQC, APT 13C). Their physical properties and morphology were investigated by DSC, rheology and SAXS/WAXS. The CO2 sorption properties were then assessed with a magnetic suspension balance (MSB) and discussed based on structure-morphology-properties relationships. The best CO2 sorption properties (159.3 mg CO2/g PIL at 10 bar and 35°C) were obtained with the PIL having TFSI anions and the highest ionization ratio (IR = 94.6%). The particularly high CO2 sorption of this PIL was related to its highest interchain d-spacing, inducing better accessibility to the CO2-philic ionic sites.
{"title":"Influence of anion and ionization ratio on CO2 sorption of poly(ionic liquid)s with imidazolium cations derived from polyepichlorohydrin: a multi-scale analysis","authors":"Anamaria Barrera Bogoya, Carole Arnal-Herault, Danielle Barth, Fabrice Mutelet, Bouchra Belaissaoui, Philippe Marchal, Yuki Tamura, Yuki Nakama, Shigetaka Hayano, Anne Jonquieres","doi":"10.1016/j.polymer.2025.128186","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128186","url":null,"abstract":"Aiming at developing new polymer absorbents for the physical CO<sub>2</sub> capture, this work reports the synthesis and multi-scale characterization of two new families of poly(ionic liquid)s (PILs) obtained from polyepichlorohydrin (polyECH). PolyECH was quaternized with 1-methylimidazole quasi-quantitatively and the Cl anions were then exchanged by different salts to introduce BF<sub>4</sub>, AcO and TFSI anions for the first series of PILs. The second series was then obtained by varying the amount of 1-methylimidazole, leading to new PILs with TFSI anions and ionization ratios increasing from 0 to 94.6%. The chemical structure of the different PILs was characterized by different NMR techniques (<sup>1</sup>H, <sup>13</sup>C, 2D <sup>1</sup>H/<sup>13</sup>C HSQC, APT <sup>13</sup>C). Their physical properties and morphology were investigated by DSC, rheology and SAXS/WAXS. The CO<sub>2</sub> sorption properties were then assessed with a magnetic suspension balance (MSB) and discussed based on structure-morphology-properties relationships. The best CO<sub>2</sub> sorption properties (159.3 mg CO<sub>2</sub>/g PIL at 10 bar and 35°C) were obtained with the PIL having TFSI anions and the highest ionization ratio (IR = 94.6%). The particularly high CO<sub>2</sub> sorption of this PIL was related to its highest interchain d-spacing, inducing better accessibility to the CO<sub>2</sub>-philic ionic sites.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495691","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 : 2025-02-25DOI: 10.1016/j.polymer.2025.128194
Hongli Cheng, Liangchun Zhou, Gaojie Han, Ming Huang, Fengmei Su, Liwei Mi, Yuezhan Feng, Chuntai Liu
Polyethylene fibers (PEFs) with high inherent thermal conductivity have been proved to be able to prepare fully organic thermally conductive composites. Herein, the effect of macroscopic fiber orientation and microscopic molecular chain orientation on the thermal conductivity of PEF composites was investigated. Specifically, four kinds of PEFs (PENT, PESF, U1PEF, U2PEF), were selected to prepare fully organic thermally conductive composites. The morphology results show that PENT distributed randomly and loosely in the composite, while the other three PEFs showed high orientation stacking arrangement. As a result, PENT composite shows a low thermal conductivity of 0.132 W/mK due to the absence of effective heat transfer channels and the serious phonon scattering at matrix-to-fiber interfaces. By comparison, the parallel arrangement of continuous fiber provides an ideal channel for phonon transport, so that PESF composite has substantial increase in thermal conductivity (6.543 W/mK). Furthermore, U1PEF and U2PEF composites with higher chain orientation and crystallinity in the inner of fibers, thus reveal the higher thermal conductivities of 11.07 and 15.48 W/mK. Therefore, it can be concluded that not only the fiber orientation distribution, but also the chain orientation structure of fibers both have an important influence on the thermal conductivity of PEF composites.
{"title":"Effect of Morphology and Structure of Polyethylene Fibers on Thermal Conductivity of PDMS Composites","authors":"Hongli Cheng, Liangchun Zhou, Gaojie Han, Ming Huang, Fengmei Su, Liwei Mi, Yuezhan Feng, Chuntai Liu","doi":"10.1016/j.polymer.2025.128194","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128194","url":null,"abstract":"Polyethylene fibers (PEFs) with high inherent thermal conductivity have been proved to be able to prepare fully organic thermally conductive composites. Herein, the effect of macroscopic fiber orientation and microscopic molecular chain orientation on the thermal conductivity of PEF composites was investigated. Specifically, four kinds of PEFs (PENT, PESF, U1PEF, U2PEF), were selected to prepare fully organic thermally conductive composites. The morphology results show that PENT distributed randomly and loosely in the composite, while the other three PEFs showed high orientation stacking arrangement. As a result, PENT composite shows a low thermal conductivity of 0.132 W/mK due to the absence of effective heat transfer channels and the serious phonon scattering at matrix-to-fiber interfaces. By comparison, the parallel arrangement of continuous fiber provides an ideal channel for phonon transport, so that PESF composite has substantial increase in thermal conductivity (6.543 W/mK). Furthermore, U1PEF and U2PEF composites with higher chain orientation and crystallinity in the inner of fibers, thus reveal the higher thermal conductivities of 11.07 and 15.48 W/mK. Therefore, it can be concluded that not only the fiber orientation distribution, but also the chain orientation structure of fibers both have an important influence on the thermal conductivity of PEF composites.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495698","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 : 2025-02-24DOI: 10.1016/j.polymer.2025.128191
Xiongbo Yang, Wendi Fan, Ruizhen Xu, Junmei Zhang, Qihao Dai, Long Wang, Xinyu Tan, Guiguang Qi, Yulong Qiao, Paul K. Chu
Passive daytime radiative cooling is a green, sustainable technology, however there are challenges in incorporating multifunctional radiative cooling technologies. In this paper, a biomimetic structure (PTP, porous tetra-needle zinc oxide whisker polydimethylsiloxane) with a needle-like structure on the surface and a porous structure in the interior is prepared by a simple process using inexpensive tetra-needle zinc oxide whiskers (T-ZnOw) as the filler particles and polydimethylsiloxane (PDMS) as the binder, which possesses the desired radiative cooling properties, and at the same time, it combines the anti-aging, thermal control flame retarding, and superhydrophobic properties. PTP film exhibits ideal reflectance (0.91) and emissivity (0.99), with an average temperature difference of 15.5 °C compared to Al, and maintains good radiative cooling performance under UV irradiation for 1000 h. The thermal conductivity of the PTP film is 0.931 W m-1 k-1. In the outdoor cooling test with a heat source, the average temperature difference is 13.3 °C compared to Al. The surface water contact angle (WCA) is 153.25° and the superhydrophobicity is maintained after more than 1400 h of aging. As a result, the PTP film has large potential in multi-temperature applications, such as buildings, factory sheds, and electrical appliances.
{"title":"Highly practical multifunctional radiative cooling films for multi-temperature applications","authors":"Xiongbo Yang, Wendi Fan, Ruizhen Xu, Junmei Zhang, Qihao Dai, Long Wang, Xinyu Tan, Guiguang Qi, Yulong Qiao, Paul K. Chu","doi":"10.1016/j.polymer.2025.128191","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128191","url":null,"abstract":"Passive daytime radiative cooling is a green, sustainable technology, however there are challenges in incorporating multifunctional radiative cooling technologies. In this paper, a biomimetic structure (PTP, porous tetra-needle zinc oxide whisker polydimethylsiloxane) with a needle-like structure on the surface and a porous structure in the interior is prepared by a simple process using inexpensive tetra-needle zinc oxide whiskers (T-ZnOw) as the filler particles and polydimethylsiloxane (PDMS) as the binder, which possesses the desired radiative cooling properties, and at the same time, it combines the anti-aging, thermal control flame retarding, and superhydrophobic properties. PTP film exhibits ideal reflectance (0.91) and emissivity (0.99), with an average temperature difference of 15.5 °C compared to Al, and maintains good radiative cooling performance under UV irradiation for 1000 h. The thermal conductivity of the PTP film is 0.931 W m<sup>-1</sup> k<sup>-1</sup>. In the outdoor cooling test with a heat source, the average temperature difference is 13.3 °C compared to Al. The surface water contact angle (WCA) is 153.25° and the superhydrophobicity is maintained after more than 1400 h of aging. As a result, the PTP film has large potential in multi-temperature applications, such as buildings, factory sheds, and electrical appliances.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477437","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 : 2025-02-22DOI: 10.1016/j.polymer.2025.128187
Boyuan An, Zhimin Xie, Bin’an Jiang, Dongjie Zhang, Yuyan Liu, Hanyu Ma
Free volume is a crucial concept for discussing the mobility of chain segments and the glass transition temperature (Tg) of polymers. Despite the necessity for a convenient approach to determine the free volume of thermosetting polymers, particularly epoxy resins, a suitable method is currently absent. The classical locally correlated lattice (LCL) theory is a significant method for calculating the hardcore volume and free volume of polymers. Based on this theory, the LCL equation of state (EOS) has been employed to calculate the free volume of several thermoplastic polymers via pressure-volume-temperature (PVT) data. For thermosetting polymers, such confined sites as cross-linked points constrain the mobility of the segment, the nonbonding interactions parameter q in the EOS will influence the hardcore volume Vhc(EOS). However, the EOS rarely involves such a constraint effect, resulting in an excessive Vhc(EOS) compared with the hardcore volume Vhc(PVT) obtained via the PVT. In view of the impact of confined sites on the nonbonding interactions, herein we propose a modified EOS (M-EOS) within the framework of LCL theory and determine the molecular parameters and hardcore volume Vhc(M-EOS) of thermosetting polymers. Vhc(M-EOS) is calculated closer to Vhc(PVT) than Vhc(EOS). Since the linear polymers have no cross-linked points, Vhc(M-EOS) is underestimated by the M-EOS in comparison with Vhc(PVT) of linear polymers. Consequently, the M-EOS and EOS are suitable for calculating the hardcore volume and free volume of thermosetting polymers and linear polymers, respectively. In this sense, the present work extends the scope of the application of the LCL theory to thermosetting polymers.
{"title":"Determination of the free volume of thermosetting polymers","authors":"Boyuan An, Zhimin Xie, Bin’an Jiang, Dongjie Zhang, Yuyan Liu, Hanyu Ma","doi":"10.1016/j.polymer.2025.128187","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128187","url":null,"abstract":"Free volume is a crucial concept for discussing the mobility of chain segments and the glass transition temperature (<em>T</em><sub><em>g</em></sub>) of polymers. Despite the necessity for a convenient approach to determine the free volume of thermosetting polymers, particularly epoxy resins, a suitable method is currently absent. The classical locally correlated lattice (LCL) theory is a significant method for calculating the hardcore volume and free volume of polymers. Based on this theory, the LCL equation of state (EOS) has been employed to calculate the free volume of several thermoplastic polymers via pressure-volume-temperature (PVT) data. For thermosetting polymers, such confined sites as cross-linked points constrain the mobility of the segment, the nonbonding interactions parameter <em>q</em> in the EOS will influence the hardcore volume V<sub>hc</sub>(EOS). However, the EOS rarely involves such a constraint effect, resulting in an excessive V<sub>hc</sub>(EOS) compared with the hardcore volume V<sub>hc</sub>(PVT) obtained via the PVT. In view of the impact of confined sites on the nonbonding interactions, herein we propose a modified EOS (M-EOS) within the framework of LCL theory and determine the molecular parameters and hardcore volume V<sub>hc</sub>(M-EOS) of thermosetting polymers. V<sub>hc</sub>(M-EOS) is calculated closer to V<sub>hc</sub>(PVT) than V<sub>hc</sub>(EOS). Since the linear polymers have no cross-linked points, V<sub>hc</sub>(M-EOS) is underestimated by the M-EOS in comparison with V<sub>hc</sub>(PVT) of linear polymers. Consequently, the M-EOS and EOS are suitable for calculating the hardcore volume and free volume of thermosetting polymers and linear polymers, respectively. In this sense, the present work extends the scope of the application of the LCL theory to thermosetting polymers.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"50 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143471094","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}
Exploring new electrode materials with cyclic stability and energy storage capacity is crucial for high-performance energy storage in portable electronics. Herein, we present PEDOT:PSS (PP)/delaminated MXene (d-Ti3C2Tx) binary nanocomposites for electrode material for flexible supercapacitor (FSC). PP/d-Ti3C2Tx (1:2 weight ratio, P1M2) on activated carbon cloth results in an excellent specific capacitance of 718.67 F g-1 at a current density of 3.5 A g-1 in 1 M H2SO4. PEDOT chains wrap the d-Ti3C2Tx nanosheets by an opposite electrostatic interaction, while PSS chains act as web-like carrier pathways between two adjacent nanosheets. First principle DFT simulations demonstrate that charge storage in PEDOT:PSS@Ti3C2Tx is enhanced compared to PEDOT@Ti3C2Tx, which describes the effect of PSS chains in the composite. Computationally obtained absorption spectra align well with experimental results, validating the proposed morphology. To employ the P1M2 electrode for FSC, P1M2-P1M2 symmetric solid-state supercapacitor (SSC) and P1M2-rGO asymmetric solid-state supercapacitor (ASC) have been fabricated using 1 M PVA-H2SO4 gel electrolyte. P1M2-P1M2 SSC and P1M2-rGO ASC exhibit a high specific capacitance of 260.23 F g-1 (0.5 A g-1) and 176.46 F g-1 (0.1 A g-1) receptively. Larger potential window, excellent specific capacitance retention of ∼89% for 5000 GCD cycles, and great performance retention over the bending and twisting conditions make the ASC device a marvelous candidate for the portable energy storage device. The ASC device shows change in specific energy (specific power) from 35.29 W h kg-1 (240 W kg-1) to 26.22 W h kg-1 (1200 W kg-1). An assembly of three such ASC devices glows a red LED for ∼2 min.
{"title":"High-performance flexible supercapacitor based on PEDOT:PSS wrapped delaminated Ti3C2Tx composite: experimental and DFT validation","authors":"Gourab Nandy, Swati Shaw, Subhradip Ghosh, Ashok Kumar Dasmahapatra","doi":"10.1016/j.polymer.2025.128185","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128185","url":null,"abstract":"Exploring new electrode materials with cyclic stability and energy storage capacity is crucial for high-performance energy storage in portable electronics. Herein, we present PEDOT:PSS (PP)/delaminated MXene (d-Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>) binary nanocomposites for electrode material for flexible supercapacitor (FSC). PP/d-Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> (<em>1:2</em> weight ratio, P1M2) on activated carbon cloth results in an excellent specific capacitance of <em>718.67</em> F g<sup>-1</sup> at a current density of <em>3.5</em> A g<sup>-1</sup> in <em>1</em> M H<sub>2</sub>SO<sub>4</sub>. PEDOT chains wrap the d-Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> nanosheets by an opposite electrostatic interaction, while PSS chains act as web-like carrier pathways between two adjacent nanosheets. First principle DFT simulations demonstrate that charge storage in PEDOT:PSS@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> is enhanced compared to PEDOT@Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub>, which describes the effect of PSS chains in the composite. Computationally obtained absorption spectra align well with experimental results, validating the proposed morphology. To employ the P1M2 electrode for FSC, P1M2-P1M2 symmetric solid-state supercapacitor (SSC) and P1M2-rGO asymmetric solid-state supercapacitor (ASC) have been fabricated using <em>1</em> M PVA-H<sub>2</sub>SO<sub>4</sub> gel electrolyte. P1M2-P1M2 SSC and P1M2-rGO ASC exhibit a high specific capacitance of <em>260.23</em> F g<sup>-1</sup> (<em>0.5</em> A g<sup>-1</sup>) and <em>176.46</em> F g<sup>-1</sup> (<em>0.1</em> A g<sup>-1</sup>) receptively. Larger potential window, excellent specific capacitance retention of <em>∼89%</em> for <em>5000</em> GCD cycles, and great performance retention over the bending and twisting conditions make the ASC device a marvelous candidate for the portable energy storage device. The ASC device shows change in specific energy (specific power) from <em>35.29</em> W h kg<sup>-1</sup> (<em>240</em> W kg<sup>-1</sup>) to <em>26.22</em> W h kg<sup>-1</sup> (<em>1200</em> W kg<sup>-1</sup>). An assembly of three such ASC devices glows a red LED for <em>∼2</em> min.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143470984","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 : 2025-02-22DOI: 10.1016/j.polymer.2025.128189
Yongqiang Guo , Lei Zhang , Kunpeng Ruan , Yi Mu , Mukun He , Junwei Gu
The preparation of thermally conductive silicone rubber composites incorporating aluminum nitride (AlN) as fillers has attracted considerable attention. However, the high susceptibility of AlN to hydrolysis and its limited compatibility with the silicone rubber matrix present significant challenges that hinder the enhancement of the composite's thermal conductivity. In this work, AlN was modified through surface functionalization via grafting with divinylbenzene-acryloyl chloride block copolymer (PDVB-b-PACl), followed by compounding with poly(methylhydrosiloxane) (PMHS) to fabricate thermally conductive AlN@PDVB-b-PACl/PMHS composites. The modification significantly improved the hydrophobicity of AlN@PDVB-b-PACl, as demonstrated by a contact angle of 134.1°compared to 26.4° for unmodified AlN. When the molecular weight of PDVB-b-PACl is 5000 g/mol, the grafting amount is 0.8 wt%, and the loading of AlN@PDVB-b-PACl is 85 wt%, the AlN@PDVB-b-PACl/PMHS composite exhibited an optimal thermal conductivity of 1.82 W/(m·K), an 810 % improvement over that of PMHS (0.20 W/(m·K)), and outperformed AlN/PMHS composites (1.58 W/(m·K)) with the same AlN loading. Additionally, the tensile strength of the composite was 0.58 MPa, approximately 2.4 times greater than that of PMHS (0.24 MPa).
{"title":"Enhancing hydrolysis resistance and thermal conductivity of aluminum nitride/polysiloxane composites via block copolymer-modification","authors":"Yongqiang Guo , Lei Zhang , Kunpeng Ruan , Yi Mu , Mukun He , Junwei Gu","doi":"10.1016/j.polymer.2025.128189","DOIUrl":"10.1016/j.polymer.2025.128189","url":null,"abstract":"<div><div>The preparation of thermally conductive silicone rubber composites incorporating aluminum nitride (AlN) as fillers has attracted considerable attention. However, the high susceptibility of AlN to hydrolysis and its limited compatibility with the silicone rubber matrix present significant challenges that hinder the enhancement of the composite's thermal conductivity. In this work, AlN was modified through surface functionalization <em>via</em> grafting with divinylbenzene-acryloyl chloride block copolymer (PDVB-<em>b</em>-PACl), followed by compounding with poly(methylhydrosiloxane) (PMHS) to fabricate thermally conductive AlN@PDVB-<em>b</em>-PACl/PMHS composites. The modification significantly improved the hydrophobicity of AlN@PDVB-<em>b</em>-PACl, as demonstrated by a contact angle of 134.1°compared to 26.4° for unmodified AlN. When the molecular weight of PDVB-<em>b</em>-PACl is 5000 g/mol, the grafting amount is 0.8 wt%, and the loading of AlN@PDVB-<em>b</em>-PACl is 85 wt%, the AlN@PDVB-<em>b</em>-PACl/PMHS composite exhibited an optimal thermal conductivity of 1.82 W/(m·K), an 810 % improvement over that of PMHS (0.20 W/(m·K)), and outperformed AlN/PMHS composites (1.58 W/(m·K)) with the same AlN loading. Additionally, the tensile strength of the composite was 0.58 MPa, approximately 2.4 times greater than that of PMHS (0.24 MPa).</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"323 ","pages":"Article 128189"},"PeriodicalIF":4.1,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143470985","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 : 2025-02-22DOI: 10.1016/j.polymer.2025.128162
J.J. Relinque, Enrique Martínez Campos, Marina León-Calero, Lucía Rodríguez-Rodríguez, Manuel Nieto-Diaz, Irene Novillo-Algaba, Koldo Artola, Rubén García Fernández, Jesús Mingorance, Iñaki García, Juan Rodríguez-Hernández
Herein, we describe the fabrication of 3D printed swabs by using stereolithography (SLA and DLP) 3D printing involving three university hospitals. SLA/DLP allows for the fabrication of complex structures with micrometer scale resolution. The fabricated models including specimens for mechanical testing were selected and fabricated using three different 3D printers and two different biocompatible materials. The discrepancies between the fabrication in different places as well as the factors involved in the fabrication (printing parameters, post-curing, and sterilization) have been thoroughly analyzed. Mechanical testing of normalized specimens confirmed the success in the delocalized fabrication following identical protocols with only slight variations, most probably due to the different equipment employed for the sterilization step. However significant variations were observed between the resulting printed parts depending on the material/technology employed. More precisely, those materials fabricated by DLP resulted in parts with lower elastic modulus while having similar elongation at break in comparison to those fabricated by SLA. Interestingly, both fabrication approaches enabled the production of materials that retain their properties after 14 days stored at different temperatures ranging from room temperature to -18ºC. Finally, cytotoxicity of swabs extracts has been evaluated using an endothelial cell line (C166-GFP) as an in vitro model using cell viability and metabolic activity as health indicators. According to our findings, the fabrication proposed produces cytocompatible swabs with high model fidelity that can be stored at least during 14 days without any loss of the mechanical properties.
{"title":"Fabrication of 3D printed swabs in University Hospital´s: point of care manufacturing, study of mechanical properties and biological compatibility","authors":"J.J. Relinque, Enrique Martínez Campos, Marina León-Calero, Lucía Rodríguez-Rodríguez, Manuel Nieto-Diaz, Irene Novillo-Algaba, Koldo Artola, Rubén García Fernández, Jesús Mingorance, Iñaki García, Juan Rodríguez-Hernández","doi":"10.1016/j.polymer.2025.128162","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128162","url":null,"abstract":"Herein, we describe the fabrication of 3D printed swabs by using stereolithography (SLA and DLP) 3D printing involving three university hospitals. SLA/DLP allows for the fabrication of complex structures with micrometer scale resolution. The fabricated models including specimens for mechanical testing were selected and fabricated using three different 3D printers and two different biocompatible materials. The discrepancies between the fabrication in different places as well as the factors involved in the fabrication (printing parameters, post-curing, and sterilization) have been thoroughly analyzed. Mechanical testing of normalized specimens confirmed the success in the delocalized fabrication following identical protocols with only slight variations, most probably due to the different equipment employed for the sterilization step. However significant variations were observed between the resulting printed parts depending on the material/technology employed. More precisely, those materials fabricated by DLP resulted in parts with lower elastic modulus while having similar elongation at break in comparison to those fabricated by SLA. Interestingly, both fabrication approaches enabled the production of materials that retain their properties after 14 days stored at different temperatures ranging from room temperature to -18ºC. Finally, cytotoxicity of swabs extracts has been evaluated using an endothelial cell line (C166-GFP) as an in vitro model using cell viability and metabolic activity as health indicators. According to our findings, the fabrication proposed produces cytocompatible swabs with high model fidelity that can be stored at least during 14 days without any loss of the mechanical properties.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143470983","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 : 2025-02-21DOI: 10.1016/j.polymer.2025.128184
Yu Zheng, Guo Lin, Liang He, Lifen Tong, Xiaobo Liu
Lithium-ion batteries (LiBs) are becoming more widely utilized for storing clean energy, but the safety and cycle life remain major concerns. This study focuses on developing porous composite films made from poly(ether ketone nitrile) (PENK) and poly(vinylidene fluoride) (PVDF), enhanced with Li6.5La3Zr1.5Ta0.5O12(LLZTO) filler. These films were fabricated using the non-solvent-induced phase separation (NIPS) method to address the insufficient thermal resilience and the inadequate electrolyte wettability of conventional polyolefin separators. The impact of LLZTO content levels on the film’s composition, heat resistance, mechanical characteristics, and electrochemical behavior were systematically assessed. The findings show that incorporating LLZTO significantly improves electrolyte wettability, thermal stability, and cycling performance. Additionally, LLZTO efficiently suppresses lithium dendrite formation, thereby improving battery safety and overall performance. The optimized PENK/PVDF composite films demonstrated superior thermal stability and maintained a high capacity over extended cycles, this makes it a highly promising option for the development of high-performance lithium-ion batteries.
{"title":"Poly(ether ketone nitrile)/Poly(vinylidene fluoride) Separators Reinforced by Li6.5La3Zr1.5Ta0.5O12 for Enhanced Thermal Stability and Safety in Lithium-Ion Batteries","authors":"Yu Zheng, Guo Lin, Liang He, Lifen Tong, Xiaobo Liu","doi":"10.1016/j.polymer.2025.128184","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128184","url":null,"abstract":"Lithium-ion batteries (LiBs) are becoming more widely utilized for storing clean energy, but the safety and cycle life remain major concerns. This study focuses on developing porous composite films made from poly(ether ketone nitrile) (PENK) and poly(vinylidene fluoride) (PVDF), enhanced with Li<sub>6.5</sub>La<sub>3</sub>Zr<sub>1.5</sub>Ta<sub>0.5</sub>O<sub>12</sub>(LLZTO) filler. These films were fabricated using the non-solvent-induced phase separation (NIPS) method to address the insufficient thermal resilience and the inadequate electrolyte wettability of conventional polyolefin separators. The impact of LLZTO content levels on the film’s composition, heat resistance, mechanical characteristics, and electrochemical behavior were systematically assessed. The findings show that incorporating LLZTO significantly improves electrolyte wettability, thermal stability, and cycling performance. Additionally, LLZTO efficiently suppresses lithium dendrite formation, thereby improving battery safety and overall performance. The optimized PENK/PVDF composite films demonstrated superior thermal stability and maintained a high capacity over extended cycles, this makes it a highly promising option for the development of high-performance lithium-ion batteries.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462443","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}
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