Pub Date : 2025-12-16DOI: 10.1016/j.jpcs.2025.113472
Nguyen Van Hoa , Le Hong Quan , Tran Ngoc Le
The binder-free electrode of Ni–Mo–S/N-doped carbon/nickel foam (NF/CNMS) was synthesized via a sustainable two-step hydrothermal–carbonization route using chitosan derived from shrimp shells as the nitrogen-rich carbon precursor. The integration of ultrathin Ni–Mo–S nanorods with conductive N-doped carbon on the 3D nickel foam produced a porous, flower-like architecture with abundant redox-active sites, fast ion transport, and excellent electrical conductivity. The optimized CNMS-3 electrode delivered a high specific capacitance of 1038 F g−1 at 1.0 A g−1, and approximately 69 % rate retention from 1 to 7 A g−1. In a symmetric device configuration (CNMS-3//CNMS-3), the electrode achieved an energy density of about 35 Wh kg−1 at approximately 500 W kg−1. Additionally, an asymmetric supercapacitor setup (with CNMS-3 as the cathode and CNC as the anode) yielded a specific capacitance of 194 F g−1, an energy density of roughly 45 Wh kg−1 at 1001 W kg−1, and retained over 80 % of its performance after 5000 cycles. This work highlights the novelty of combining a biomass-derived carbon precursor with bimetallic sulfides in a binder-free configuration, offering a cost-effective and scalable strategy for high-performance supercapacitors, thereby enhancing its practicality and applicability.
以虾壳壳聚糖为富氮碳前驱体，采用两步水热法制备了Ni-Mo-S /n掺杂碳/镍泡沫（NF/CNMS）无粘结剂电极。超薄Ni-Mo-S纳米棒与导电n掺杂碳在3D泡沫镍上的集成产生了多孔的花状结构，具有丰富的氧化还原活性位点，快速离子传输和优异的导电性。优化后的CNMS-3电极在1.0 a g−1时具有1038 F g−1的高比电容，在1至7 a g−1时保持率约为69%。在对称器件配置（CNMS-3//CNMS-3）中，电极在约500 W kg - 1时实现了约35 Wh kg - 1的能量密度。此外，非对称超级电容器设置（CNMS-3作为阴极，CNC作为阳极）产生了194 F g−1的比电容，在1001 W kg−1时能量密度约为45 Wh kg−1，并且在5000次循环后保持了80%以上的性能。这项工作强调了将生物质衍生的碳前驱体与双金属硫化物结合在无粘结剂配置中的新颖性，为高性能超级电容器提供了一种具有成本效益和可扩展的策略，从而提高了其实用性和适用性。
{"title":"A high-performance binder-free electrode composed of Ni–Mo–S/N-doped carbon/nickel foam for quasi-solid-state supercapacitors","authors":"Nguyen Van Hoa , Le Hong Quan , Tran Ngoc Le","doi":"10.1016/j.jpcs.2025.113472","DOIUrl":"10.1016/j.jpcs.2025.113472","url":null,"abstract":"<div><div>The binder-free electrode of Ni–Mo–S/N-doped carbon/nickel foam (NF/CNMS) was synthesized via a sustainable two-step hydrothermal–carbonization route using chitosan derived from shrimp shells as the nitrogen-rich carbon precursor. The integration of ultrathin Ni–Mo–S nanorods with conductive <em>N</em>-doped carbon on the 3D nickel foam produced a porous, flower-like architecture with abundant redox-active sites, fast ion transport, and excellent electrical conductivity. The optimized CNMS-3 electrode delivered a high specific capacitance of 1038 F g<sup>−1</sup> at 1.0 A g<sup>−1</sup>, and approximately 69 % rate retention from 1 to 7 A g<sup>−1</sup>. In a symmetric device configuration (CNMS-3//CNMS-3), the electrode achieved an energy density of about 35 Wh kg<sup>−1</sup> at approximately 500 W kg<sup>−1</sup>. Additionally, an asymmetric supercapacitor setup (with CNMS-3 as the cathode and CNC as the anode) yielded a specific capacitance of 194 F g<sup>−1</sup>, an energy density of roughly 45 Wh kg<sup>−1</sup> at 1001 W kg<sup>−1</sup>, and retained over 80 % of its performance after 5000 cycles. This work highlights the novelty of combining a biomass-derived carbon precursor with bimetallic sulfides in a binder-free configuration, offering a cost-effective and scalable strategy for high-performance supercapacitors, thereby enhancing its practicality and applicability.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113472"},"PeriodicalIF":4.9,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-16DOI: 10.1016/j.jpcs.2025.113467
S. Chibani , H. Ben Abdallah , W. Ouerghui , M. Batouche , T. Seddik
While the end members of the Ca1-xLaxMnO3 series are well studied, the evolution of Jahn–Teller distortions across the entire phase diagram remains unclear. One would naturally expect the strongest Jahn–Teller effects at x = 1, where the concentration of Mn3+ ions is highest. Using DFT + U calculations, we uncover a counterintuitive, non-monotonic evolution of the Jahn–Teller distortions, peaking at an intermediate doping of x = 0.25. This behavior is consistent with the competition between local electron–lattice coupling and enhanced electron itinerancy, leading to a suppression of the Jahn–Teller distortions at higher La content and a slight revival at x = 1. The resulting structural changes affect the electronic states and, in turn, drive pronounced anisotropies in the optical and magneto-optical Kerr responses. Our findings explain the non-monotonic Jahn–Teller strength in this series and provide specific spectroscopic fingerprints—such as Kerr rotation angles up to ∼2°—that can be directly tested experimentally, offering guidance for tuning the multifunctional properties of manganites.
{"title":"Non-monotonic Jahn–Teller distortions and their impact on the electronic and magneto-optical properties of La-doped CaMnO3: Insights from DFT","authors":"S. Chibani , H. Ben Abdallah , W. Ouerghui , M. Batouche , T. Seddik","doi":"10.1016/j.jpcs.2025.113467","DOIUrl":"10.1016/j.jpcs.2025.113467","url":null,"abstract":"<div><div>While the end members of the Ca<sub>1-x</sub>La<sub>x</sub>MnO<sub>3</sub> series are well studied, the evolution of Jahn–Teller distortions across the entire phase diagram remains unclear. One would naturally expect the strongest Jahn–Teller effects at x = 1, where the concentration of Mn<sup>3+</sup> ions is highest. Using DFT + U calculations, we uncover a counterintuitive, non-monotonic evolution of the Jahn–Teller distortions, peaking at an intermediate doping of x = 0.25. This behavior is consistent with the competition between local electron–lattice coupling and enhanced electron itinerancy, leading to a suppression of the Jahn–Teller distortions at higher La content and a slight revival at x = 1. The resulting structural changes affect the electronic states and, in turn, drive pronounced anisotropies in the optical and magneto-optical Kerr responses. Our findings explain the non-monotonic Jahn–Teller strength in this series and provide specific spectroscopic fingerprints—such as Kerr rotation angles up to ∼2°—that can be directly tested experimentally, offering guidance for tuning the multifunctional properties of manganites.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113467"},"PeriodicalIF":4.9,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hyperdoping of silicon beyond its equilibrium solubility limit by functional impurities offers a promising route to enhance near- and mid-infrared photovoltaic response by engineering optoelectronic properties within its nanoscale surface layers. In this study, we present the first contactless, time-resolved quantification of key conduction-band transport parameters—carrier scattering time (τc) and lifetime (τL)—in sulfur-hyperdoped (concentration CS ∼ 1018-1021 cm−3) nanocrystalline layers of crystalline Si(100) wafers, using femtosecond optical pump/terahertz probe spectroscopy. Carriers were photoinjected into the conduction band by 400-nm, 60-fs pulses and probed via THz-driven 2-ps transient currents, circumventing the need for electrical contacts. Laser-annealed samples exhibit a constant, ultrashort scattering time τc ≈ 75 fs, related to their high drift mobility μd ≈ 7 × 102 cm2/Vs up to the break concentration CB ≈ (2–4) × 1019 cm−3. Beyond this threshold, both τc and μd follow a power-law decay τc,μd ∼ (CS − CB)ν with the power exponent ν ≈ −0.64, indicative of photoexcited carrier transport governed in the network of impurity sulfur atoms by scattering cross-section rS2 ∝ CS−2/3. Strikingly, carrier lifetime τL mirrors this dependence (ν ≈ −0.70), revealing that each elementary scattering event underpins a multi-step (∼250 steps) relaxation pathway, involving TA-phonon emission and trap-assisted Shockley-Read-Hall recombination. Against the previous common expectations, when combined with the sublinear increase of IR (1–20 μm) absorption coefficient versus sulfur concentration, these findings justify—for the first time—a concentration-dependent figure-of-merit that peaks near the unexpectedly low CS ≈ CB ∼ 1019 cm−3, as the optimal regime for maximizing photovoltaic efficiency in sulfur-hyperdoped silicon. This work bridges ultrafast carrier dynamics with macroscopic optoelectronic performance, providing a quantitative design principle for next-generation hyperdoped photovoltaic materials.
{"title":"Ultrafast terahertz insight into photovoltaic performance of nanocrystalline hyperdoped silicon","authors":"S.I. Kudryashov , I.M. Podlesnykh , P.A. Chizhov , V.V. Bulgakova , A.A. Ushakov , S.G. Buga , V.A. Dravin , Yu.G. Goncharov , G.K. Krasin , E.V. Kuzmin , A.I. Vlasov , M.S. Kovalev","doi":"10.1016/j.jpcs.2025.113473","DOIUrl":"10.1016/j.jpcs.2025.113473","url":null,"abstract":"<div><div>Hyperdoping of silicon beyond its equilibrium solubility limit by functional impurities offers a promising route to enhance near- and mid-infrared photovoltaic response by engineering optoelectronic properties within its nanoscale surface layers. In this study, we present the first contactless, time-resolved quantification of key conduction-band transport parameters—carrier scattering time (τ<sub>c</sub>) and lifetime (τ<sub>L</sub>)—in sulfur-hyperdoped (concentration C<sub>S</sub> ∼ 10<sup>18</sup>-10<sup>21</sup> cm<sup>−3</sup>) nanocrystalline layers of crystalline Si(100) wafers, using femtosecond optical pump/terahertz probe spectroscopy. Carriers were photoinjected into the conduction band by 400-nm, 60-fs pulses and probed via THz-driven 2-ps transient currents, circumventing the need for electrical contacts. Laser-annealed samples exhibit a constant, ultrashort scattering time τ<sub>c</sub> ≈ 75 fs, related to their high drift mobility μ<sub>d</sub> ≈ 7 × 10<sup>2</sup> cm<sup>2</sup>/Vs up to the break concentration C<sub>B</sub> ≈ (2–4) × 10<sup>19</sup> cm<sup>−3</sup>. Beyond this threshold, both τ<sub>c</sub> and μ<sub>d</sub> follow a power-law decay τ<sub>c</sub>,μ<sub>d</sub> ∼ (C<sub>S</sub> − C<sub>B</sub>)<sup>ν</sup> with the power exponent <em>ν</em> ≈ −0.64, indicative of photoexcited carrier transport governed in the network of impurity sulfur atoms by scattering cross-section <em>r</em><sub>S</sub><sup>2</sup> ∝ C<sub>S</sub><sup>−2/3</sup>. Strikingly, carrier lifetime τ<sub>L</sub> mirrors this dependence (<em>ν</em> ≈ −0.70), revealing that each elementary scattering event underpins a multi-step (∼250 steps) relaxation pathway, involving TA-phonon emission and trap-assisted Shockley-Read-Hall recombination. Against the previous common expectations, when combined with the sublinear increase of IR (1–20 μm) absorption coefficient versus sulfur concentration, these findings justify—for the first time—a concentration-dependent figure-of-merit that peaks near the unexpectedly low C<sub>S</sub> ≈ C<sub>B</sub> ∼ 10<sup>19</sup> cm<sup>−3</sup>, as the optimal regime for maximizing photovoltaic efficiency in sulfur-hyperdoped silicon. This work bridges ultrafast carrier dynamics with macroscopic optoelectronic performance, providing a quantitative design principle for next-generation hyperdoped photovoltaic materials.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113473"},"PeriodicalIF":4.9,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As the demand for sustainable energy solutions grows, the development of eco-friendly, high-performance electrode materials is crucial for advancing supercapacitor technologies. Bio-waste derived carbon-based materials have gained significant interest due to their abundance, low cost, and environmental benefits. In this study, nitrogen and oxygen self-doped activated carbon, obtained from wood apple shells, was synthesized and systematically prepared for supercapacitor applications. The carbonization and activation processes are carried out using potassium hydroxide in a nitrogen atmosphere at 800 °C, resulting in activated carbon with an exceptionally high specific surface area of 1351.93m2g-1. The structural analysis conducted through Raman spectroscopy identified structural defects that enhance electrical conductivity, whereas Fourier-transform infrared spectroscopy (FTIR) validated the presence of hydroxyl, carboxyl, and ketonic groups that facilitate faradaic reactions. X-ray photoelectron spectroscopy (XPS) further elucidated the effective self-doping with nitrogen and oxygen, which produced a synergistic effect, significantly enhancing the charge storage capabilities. Scanning electron microscopy (SEM) highlighted a highly porous structure, favorable for efficient ion exchange and rapid electrochemical kinetics. Electrochemical evaluations in a three-electrode system demonstrated specific capacitances of 483.1 F g−1 in 6 M KOH and 218.1 F g−1 in 1 M Na2SO4 at 3 A g−1, underscoring the material's robust performance in both electrolytes. Moreover, a symmetric supercapacitor employing this material retains 83 % of capacitance retention following 5000 cycles, showcasing remarkable practical relevance. These findings highlight the potential of wood apple shell-derived activated carbon as a sustainable, high-performance material for next-generation energy storage systems.
随着对可持续能源解决方案需求的增长，开发环保、高性能的电极材料对于推进超级电容器技术至关重要。生物废物衍生的碳基材料因其丰富、低成本和环境效益而获得了极大的兴趣。本研究以木苹果壳为原料，合成并系统制备了用于超级电容器的氮氧自掺杂活性炭。在800℃的氮气气氛中使用氢氧化钾进行炭化和活化过程，得到的活性炭具有1351.93m2g-1的超高比表面积。通过拉曼光谱进行的结构分析确定了增强电导率的结构缺陷，而傅里叶变换红外光谱（FTIR）证实了促进法拉第反应的羟基、羧基和酮基的存在。x射线光电子能谱（XPS）进一步阐明了氮和氧的有效自掺杂，产生了协同效应，显著增强了电荷存储能力。扫描电子显微镜（SEM）显示高多孔结构，有利于有效的离子交换和快速的电化学动力学。在三电极系统中的电化学评价表明，在6 M KOH中比电容为483.1 F g−1，在3 a g−1下在1 M Na2SO4中比电容为218.1 F g−1，强调了该材料在两种电解质中的稳健性能。此外，采用这种材料的对称超级电容器在5000次循环后保持83%的电容保留，显示出显着的实际意义。这些发现突出了木苹果壳衍生活性炭作为下一代储能系统的可持续高性能材料的潜力。
{"title":"Synergistic effect of nitrogen and oxygen self-doping in bio-waste derived activated carbon for supercapacitor applications","authors":"Kirti Sharma , Sonia Grover , Pooja Kadyan , Sakshi Sharma , Naveen Kumar , Raj Kishore Sharma","doi":"10.1016/j.jpcs.2025.113471","DOIUrl":"10.1016/j.jpcs.2025.113471","url":null,"abstract":"<div><div>As the demand for sustainable energy solutions grows, the development of eco-friendly, high-performance electrode materials is crucial for advancing supercapacitor technologies. Bio-waste derived carbon-based materials have gained significant interest due to their abundance, low cost, and environmental benefits. In this study, nitrogen and oxygen self-doped activated carbon, obtained from wood apple shells, was synthesized and systematically prepared for supercapacitor applications. The carbonization and activation processes are carried out using potassium hydroxide in a nitrogen atmosphere at 800 °C, resulting in activated carbon with an exceptionally high specific surface area of 1351.93m<sup>2</sup>g<sup>-1</sup>. The structural analysis conducted through Raman spectroscopy identified structural defects that enhance electrical conductivity, whereas Fourier-transform infrared spectroscopy (FTIR) validated the presence of hydroxyl, carboxyl, and ketonic groups that facilitate faradaic reactions. X-ray photoelectron spectroscopy (XPS) further elucidated the effective self-doping with nitrogen and oxygen, which produced a synergistic effect, significantly enhancing the charge storage capabilities. Scanning electron microscopy (SEM) highlighted a highly porous structure, favorable for efficient ion exchange and rapid electrochemical kinetics. Electrochemical evaluations in a three-electrode system demonstrated specific capacitances of 483.1 F g<sup>−1</sup> in 6 M KOH and 218.1 F g<sup>−1</sup> in 1 M Na<sub>2</sub>SO<sub>4</sub> at 3 A g<sup>−1</sup>, underscoring the material's robust performance in both electrolytes. Moreover, a symmetric supercapacitor employing this material retains 83 % of capacitance retention following 5000 cycles, showcasing remarkable practical relevance. These findings highlight the potential of wood apple shell-derived activated carbon as a sustainable, high-performance material for next-generation energy storage systems.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113471"},"PeriodicalIF":4.9,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-13DOI: 10.1016/j.jpcs.2025.113466
Santunu Purohit , Hua Long , Zhidi Li , Zhongao Huang , Zijian He , Liyu Zhang , Shuzheng Chen , Kai Wang , Peixiang Lu
Interfacial excitons (IXs) in CuPc/CdSe nanowire (NW) heterostructures (HS) show enhanced nonlinear optoelectronic properties through hybridization, but their resonant dynamic behavior is still not well understood. Our combined experimental and theoretical study shows the resonant excitonic nature of these hybrid states: enhancement of second-harmonic generation (SHG) around 725 nm (B-exciton) and 835 nm (A-exciton) demonstrates the coexistence of IXs (760 nm) with efficient charge transfer, increasing the SHG intensity by about more than 14 times in CuPc/CdSe NW interface. First-principles DFT calculations confirm the type-II band alignment and hybridized interfacial states (1.62 eV) resulting from orbital interactions between the 2D-organic (CuPc) and 1D-inorganic (CdSe) components. However, transient reflection (TR) spectroscopy confirms the modified ultrafast charge transfer at the CuPc/CdSe NW interface, driven by type-II band alignment. TR spectroscopy supports intralayer A- and B- excitons resonance, attributed to Förster resonance energy transfer. On the other hand, the IXs peak shows a faster decay than bare CdSe NW, enhancing excitonic resonance signatures due to strong interlayer coupling. These findings advance our understanding of many-body exciton physics in 2D-organic/1D-inorganic hybrid systems, underscoring how nonlinear optics can probe charge-transfer-mediated SHG enhancements-a finding supported by traditional TR spectroscopy that offers valuable insights for designing optoelectronic devices.
{"title":"Unravelling the SHG enhancement in a CuPc/CdSe nanowire interface mediated by excitonic charge transfer","authors":"Santunu Purohit , Hua Long , Zhidi Li , Zhongao Huang , Zijian He , Liyu Zhang , Shuzheng Chen , Kai Wang , Peixiang Lu","doi":"10.1016/j.jpcs.2025.113466","DOIUrl":"10.1016/j.jpcs.2025.113466","url":null,"abstract":"<div><div>Interfacial excitons (IXs) in CuPc/CdSe nanowire (NW) heterostructures (HS) show enhanced nonlinear optoelectronic properties through hybridization, but their resonant dynamic behavior is still not well understood. Our combined experimental and theoretical study shows the resonant excitonic nature of these hybrid states: enhancement of second-harmonic generation (SHG) around 725 nm (B-exciton) and 835 nm (A-exciton) demonstrates the coexistence of IXs (760 nm) with efficient charge transfer, increasing the SHG intensity by about more than 14 times in CuPc/CdSe NW interface. First-principles DFT calculations confirm the type-II band alignment and hybridized interfacial states (1.62 eV) resulting from orbital interactions between the 2D-organic (CuPc) and 1D-inorganic (CdSe) components. However, transient reflection (TR) spectroscopy confirms the modified ultrafast charge transfer at the CuPc/CdSe NW interface, driven by type-II band alignment. TR spectroscopy supports intralayer A- and B- excitons resonance, attributed to Förster resonance energy transfer. On the other hand, the IXs peak shows a faster decay than bare CdSe NW, enhancing excitonic resonance signatures due to strong interlayer coupling. These findings advance our understanding of many-body exciton physics in 2D-organic/1D-inorganic hybrid systems, underscoring how nonlinear optics can probe charge-transfer-mediated SHG enhancements-a finding supported by traditional TR spectroscopy that offers valuable insights for designing optoelectronic devices.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113466"},"PeriodicalIF":4.9,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-12DOI: 10.1016/j.jpcs.2025.113458
Giulia Infurna , Corrado Albeggiani , Giuseppe Battaglia , Diego Tirelli , Lucia Campanelli , Giorgio Micale , Nadka Tz Dintcheva
This study investigates sustainable strategies for large-scale industrial production in the cable industry (e.g. sheathing applications), focusing on halogen-free flame-retardant (HFFR) additives in polyolefin composites. Three metal hydroxides are evaluated: precipitated aluminium hydroxide (p-ATH), precipitated magnesium hydroxide (p-MDH), and naturally milled magnesium hydroxide (nm-MDH). While p-ATH and p-MDH are chemically processed and carbon-intensive, nm-MDH is derived from untreated minerals, offering a lower environmental impact.
All hydroxides were characterised using XRD, TGA, morphological, and spectroscopic analyses. p-ATH and p-MDH show gibbsite and brucite structures, respectively, while nm-MDH features a brucite structure with minor dolomite content, enhancing flame resistance due to higher decomposition temperatures and inert gas release.
Flame-retardant polymer composites (FRPCs) were produced by melt-mixing 60 %wt. metal hydroxides into a polyolefin-based (i.e. EVA/LLDPE/MA-g-LLDPE) matrix. Rheological tests show that p-ATH-based FRPCs maintain liquid-like behaviour, while p-MDH and nm-MDH composites exhibit solid-like properties. Morphological analysis reveals better polymer-filler interaction in p-MDH and nm-MDH composites, supported by reactions with MA-g-LLDPE.
All FRPCs demonstrated excellent flame and thermal resistance. Additionally, metal hydroxides reduced oxidative degradation under UV-B exposure, suggesting improved weatherability.
{"title":"Sustainable and efficient metal hydroxides as halogen-free flame-retardant additives in polyolefin-based composites for cable sheathing applications","authors":"Giulia Infurna , Corrado Albeggiani , Giuseppe Battaglia , Diego Tirelli , Lucia Campanelli , Giorgio Micale , Nadka Tz Dintcheva","doi":"10.1016/j.jpcs.2025.113458","DOIUrl":"10.1016/j.jpcs.2025.113458","url":null,"abstract":"<div><div>This study investigates sustainable strategies for large-scale industrial production in the cable industry (<em>e.g.</em> sheathing applications), focusing on halogen-free flame-retardant (HFFR) additives in polyolefin composites. Three metal hydroxides are evaluated: precipitated aluminium hydroxide (p-ATH), precipitated magnesium hydroxide (p-MDH), and naturally milled magnesium hydroxide (nm-MDH). While p-ATH and p-MDH are chemically processed and carbon-intensive, nm-MDH is derived from untreated minerals, offering a lower environmental impact.</div><div>All hydroxides were characterised using XRD, TGA, morphological, and spectroscopic analyses. p-ATH and p-MDH show gibbsite and brucite structures, respectively, while nm-MDH features a brucite structure with minor dolomite content, enhancing flame resistance due to higher decomposition temperatures and inert gas release.</div><div>Flame-retardant polymer composites (FRPCs) were produced by melt-mixing 60 %wt. metal hydroxides into a polyolefin-based (<em>i.e.</em> EVA/LLDPE/MA-g-LLDPE) matrix. Rheological tests show that p-ATH-based FRPCs maintain liquid-like behaviour, while p-MDH and nm-MDH composites exhibit solid-like properties. Morphological analysis reveals better polymer-filler interaction in p-MDH and nm-MDH composites, supported by reactions with MA-g-LLDPE.</div><div>All FRPCs demonstrated excellent flame and thermal resistance. Additionally, metal hydroxides reduced oxidative degradation under UV-B exposure, suggesting improved weatherability.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113458"},"PeriodicalIF":4.9,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-12DOI: 10.1016/j.jpcs.2025.113465
M.J. Ferreira, J.F. Schneider
Planetary ball milling (PBM) is a common method used to produce electrode materials for solid-state Li-ion batteries. The transformations of Li-phosphate precursors induced by mechanical energy delivered during PBM were analyzed in the model compound LiCa(PO3)3. Starting from a crystalline phase, PBM produced a new glass state through a solid-state process at room temperature. The material was analyzed as a function of milling time using XRD, 31P and 7Li-NMR, and DSC. This glass is produced in an excited structural state, releasing an excess of enthalpy below Tg, akin to hyperquenched glasses. However, 31P NMR reveals that the crystal-to-amorphous transition does not occur by discontinuous melt-quench events, but progresses continuously through defect accumulation and bond distortions during the early stages of milling (<5 h), when the amorphized material exhibits a progressive increase in the degree of local disorder around Q2 groups. DSC shows a correlated rise in without a well-defined glass transition, even though 80 % of phosphates transitioned to distorted states. After 5 h of milling, structural and thermal parameters reach a stable regime and a glass transition is observed, indicating the amorphous structure has achieved its final configuration. The PBM-produced glass is less stable against devitrification than the melt-quenched counterpart, showing lower Tg, Tc, Tc -Tg, and crystallization enthalpy, and a higher Qn-disproportionation, indicating differences in middle-range order. 7Li-NMR demonstrates that Li+ mobility is similar in the crystal and in both melt-quenched and PBM-produced glasses.
{"title":"Crystal-to-glass transition during mechanical milling of Li phosphates: structural, thermal and Li-ion mobility behaviors in LiCa(PO3)3","authors":"M.J. Ferreira, J.F. Schneider","doi":"10.1016/j.jpcs.2025.113465","DOIUrl":"10.1016/j.jpcs.2025.113465","url":null,"abstract":"<div><div>Planetary ball milling (PBM) is a common method used to produce electrode materials for solid-state Li-ion batteries. The transformations of Li-phosphate precursors induced by mechanical energy delivered during PBM were analyzed in the model compound LiCa(PO<sub>3</sub>)<sub>3</sub>. Starting from a crystalline phase, PBM produced a new glass state through a solid-state process at room temperature. The material was analyzed as a function of milling time using XRD, <sup>31</sup>P and <sup>7</sup>Li-NMR, and DSC. This glass is produced in an excited structural state, releasing an excess of enthalpy <span><math><mrow><msub><mrow><mo>Δ</mo><mi>H</mi></mrow><mrow><mi>r</mi><mi>e</mi><mi>l</mi></mrow></msub></mrow></math></span> below T<sub>g</sub>, akin to hyperquenched glasses. However, <sup>31</sup>P NMR reveals that the crystal-to-amorphous transition does not occur by discontinuous melt-quench events, but progresses continuously through defect accumulation and bond distortions during the early stages of milling (<5 h), when the amorphized material exhibits a progressive increase in the degree of local disorder around Q<sup>2</sup> groups. DSC shows a correlated rise in <span><math><mrow><msub><mrow><mo>Δ</mo><mi>H</mi></mrow><mrow><mi>r</mi><mi>e</mi><mi>l</mi></mrow></msub></mrow></math></span> without a well-defined glass transition, even though 80 % of phosphates transitioned to distorted states. After 5 h of milling, structural and thermal parameters reach a stable regime and a glass transition is observed, indicating the amorphous structure has achieved its final configuration. The PBM-produced glass is less stable against devitrification than the melt-quenched counterpart, showing lower T<sub>g</sub>, T<sub>c</sub>, T<sub>c</sub> -T<sub>g</sub>, and crystallization enthalpy, and a higher Q<sup>n</sup>-disproportionation, indicating differences in middle-range order. <sup>7</sup>Li-NMR demonstrates that Li<sup>+</sup> mobility is similar in the crystal and in both melt-quenched and PBM-produced glasses.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113465"},"PeriodicalIF":4.9,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787107","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jpcs.2025.113459
Jianxun Zhao , Wenhao Fan , Wanqiang Liu , Qingcheng Liang , Peng Chen , Yong Cheng
Co0.9Cu0.1Si alloy was synthesized by mechanical alloying. Nitrogen-doped reduced graphene oxide (N-rGO), cobalt-doped reduced graphene oxide (Co-rGO), and cobalt-nitrogen co-doped reduced graphene oxide (Co–N-rGO) were successfully synthesized via a hydrothermal method and subsequently coated with alloy nanoparticles, to enhance the electrochemical hydrogen storage capabilities of composite materials. In comparison to the pristine alloy, the composite material exhibits superior discharge specific capacity, cycling stability, and kinetic performance. The Co–N@rGO coated sample demonstrates superior electrochemical performance compared to all other coated rGO composites. The results indicate that the optimal addition ratio of Co–N@rGO is 5 wt%. At this ratio, the battery achieves a maximum discharge capacity of 603.3 mAh/g. After 50 cycles, the capacity retention rate is 64.6 % of the initial maximum discharge capacity. The significant enhancement in the electrochemical energy storage performance of the composite materials can be primarily attributed to the synergistic effects of nitrogen doping, cobalt doping, and the intrinsic properties of reduced graphene oxide (rGO). rGO enhanced the electrical conductivity of the composite material, thereby improving the efficiency of charge transfer during electrochemical reactions. Nitrogen doping improved the wettability of the rGO surface with the electrolyte and generated numerous active sites for hydrogen adsorption, significantly enhancing the electrocatalytic performance of rGO. Cobalt deposition on rGO further increased the electrical conductivity of the composite, promoted hydrogen atom adsorption, and accelerated hydrogen diffusion. The integration of rGO with nitrogen doping and cobalt incorporation demonstrated a strong synergistic effect, significantly further enhancing the kinetic characteristics of the electrochemical reactions.
{"title":"Investigation into enhanced electrochemical hydrogen storage performance of Co0.9Cu0.1Si alloy via cobalt–nitrogen co-doped reduced graphene oxide coating","authors":"Jianxun Zhao , Wenhao Fan , Wanqiang Liu , Qingcheng Liang , Peng Chen , Yong Cheng","doi":"10.1016/j.jpcs.2025.113459","DOIUrl":"10.1016/j.jpcs.2025.113459","url":null,"abstract":"<div><div>Co<sub>0.9</sub>Cu<sub>0.1</sub>Si alloy was synthesized by mechanical alloying. Nitrogen-doped reduced graphene oxide (N-rGO), cobalt-doped reduced graphene oxide (Co-rGO), and cobalt-nitrogen co-doped reduced graphene oxide (Co–N-rGO) were successfully synthesized via a hydrothermal method and subsequently coated with alloy nanoparticles, to enhance the electrochemical hydrogen storage capabilities of composite materials. In comparison to the pristine alloy, the composite material exhibits superior discharge specific capacity, cycling stability, and kinetic performance. The Co–N@rGO coated sample demonstrates superior electrochemical performance compared to all other coated rGO composites. The results indicate that the optimal addition ratio of Co–N@rGO is 5 wt%. At this ratio, the battery achieves a maximum discharge capacity of 603.3 mAh/g. After 50 cycles, the capacity retention rate is 64.6 % of the initial maximum discharge capacity. The significant enhancement in the electrochemical energy storage performance of the composite materials can be primarily attributed to the synergistic effects of nitrogen doping, cobalt doping, and the intrinsic properties of reduced graphene oxide (rGO). rGO enhanced the electrical conductivity of the composite material, thereby improving the efficiency of charge transfer during electrochemical reactions. Nitrogen doping improved the wettability of the rGO surface with the electrolyte and generated numerous active sites for hydrogen adsorption, significantly enhancing the electrocatalytic performance of rGO. Cobalt deposition on rGO further increased the electrical conductivity of the composite, promoted hydrogen atom adsorption, and accelerated hydrogen diffusion. The integration of rGO with nitrogen doping and cobalt incorporation demonstrated a strong synergistic effect, significantly further enhancing the kinetic characteristics of the electrochemical reactions.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113459"},"PeriodicalIF":4.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jpcs.2025.113455
Huiqing Hu, Jun Tai, Liangcai Wang
This paper proposes a novel vacuum thermionic device with dual-graphene -electrode structure. By integrating the latest graphene thermionic emission theory, Langmuir space charge effect theory and near-field thermal radiation principles, we constructed a theoretical calculation model of thermoelectric performance of this device. Leveraging this model, we conduct a systematic optimization analysis of the device's thermoelectric performance, exploring the effects of key parameters such as electrode temperature, work function and electrode spacing. Our findings provide valuable insights for the design and optimization of high-efficiency vacuum thermionic devices with dual-graphene-electrode.
{"title":"Thermoelectric performance optimization of vacuum thermionic devices with dual-graphene-electrode","authors":"Huiqing Hu, Jun Tai, Liangcai Wang","doi":"10.1016/j.jpcs.2025.113455","DOIUrl":"10.1016/j.jpcs.2025.113455","url":null,"abstract":"<div><div>This paper proposes a novel vacuum thermionic device with dual-graphene -electrode structure. By integrating the latest graphene thermionic emission theory, Langmuir space charge effect theory and near-field thermal radiation principles, we constructed a theoretical calculation model of thermoelectric performance of this device. Leveraging this model, we conduct a systematic optimization analysis of the device's thermoelectric performance, exploring the effects of key parameters such as electrode temperature, work function and electrode spacing. Our findings provide valuable insights for the design and optimization of high-efficiency vacuum thermionic devices with dual-graphene-electrode.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113455"},"PeriodicalIF":4.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jpcs.2025.113447
Laila Almanqur
Progress in developing high-performance sustainable electrode materials is inevitable for advancing next-generation electrochemical energy storage systems. This study reports the synthesis, characterization and application of a novel barium-manganese-tin chalcogenide (BaMnSnS4) obtained by synthesizing chelation-assisted diethyldithiocarbamate ligand. The resulting chalcogenide material exhibited a mixed crystalline phase with an average crystallite size of 20.35 nm, as confirmed by X-ray diffraction and strong metal-sulfur bonding as evident by FTIR. The morphological analysis revealed fused rod-like particles, providing abundant active sites for ion transport. Optical measurements demonstrate semiconducting behavior with a direct band gap of 3.8 eV, suggesting potential photoactivity. Electrochemical testing in 1 M KOH using a three-electrode configuration shows exceptional capacitive performance, achieving a specific capacitance of 575.2 F g−1 and a power density of 4496 W kg−1. The low equivalent series resistance (Rs = 0.99 Ω) confirms excellent charge-transfer efficiency and interface stability. These results highlight BaMnSnS4 as a potential multifunctional electrode material, combining efficient redox activity, structural robustness and favorable electronic properties. This study proposes a sustainable synthesis approach and establishes a new chalcogenide-based platform for high-rate, high-power energy storage applications.
开发高性能可持续电极材料是推进下一代电化学储能系统的必然要求。本文报道了一种新型螯合辅助二乙基二硫代氨基甲酸酯配体的合成、表征和应用。通过x射线衍射和红外光谱（FTIR）分析，得到的硫族化合物为混合晶相，平均晶粒尺寸为20.35 nm。形态分析显示熔融棒状颗粒，为离子运输提供了丰富的活性位点。光学测量显示半导体行为，直接带隙为3.8 eV，表明潜在的光活性。在1 M KOH条件下，采用三电极结构进行电化学测试，显示出优异的电容性能，比电容达到575.2 F g−1，功率密度达到4496 W kg−1。低等效串联电阻（Rs = 0.99 Ω）证实了优异的电荷转移效率和界面稳定性。这些结果突出了BaMnSnS4作为一种潜在的多功能电极材料，具有高效的氧化还原活性，结构坚固性和良好的电子性能。本研究提出了一种可持续的合成方法，并建立了一个新的基于硫族化合物的高速率、高功率储能应用平台。
{"title":"Quaternary alkaline-transition metal sulfide (Ba–Mn–Sn) for advanced energy storage capacitive applications","authors":"Laila Almanqur","doi":"10.1016/j.jpcs.2025.113447","DOIUrl":"10.1016/j.jpcs.2025.113447","url":null,"abstract":"<div><div>Progress in developing high-performance sustainable electrode materials is inevitable for advancing next-generation electrochemical energy storage systems. This study reports the synthesis, characterization and application of a novel barium-manganese-tin chalcogenide (BaMnSnS<sub>4</sub>) obtained by synthesizing chelation-assisted diethyldithiocarbamate ligand. The resulting chalcogenide material exhibited a mixed crystalline phase with an average crystallite size of 20.35 nm, as confirmed by X-ray diffraction and strong metal-sulfur bonding as evident by FTIR. The morphological analysis revealed fused rod-like particles, providing abundant active sites for ion transport. Optical measurements demonstrate semiconducting behavior with a direct band gap of 3.8 eV, suggesting potential photoactivity. Electrochemical testing in 1 M KOH using a three-electrode configuration shows exceptional capacitive performance, achieving a specific capacitance of 575.2 F g<sup>−1</sup> and a power density of 4496 W kg<sup>−1</sup>. The low equivalent series resistance (R<sub>s</sub> = 0.99 Ω) confirms excellent charge-transfer efficiency and interface stability. These results highlight BaMnSnS<sub>4</sub> as a potential multifunctional electrode material, combining efficient redox activity, structural robustness and favorable electronic properties. This study proposes a sustainable synthesis approach and establishes a new chalcogenide-based platform for high-rate, high-power energy storage applications.</div></div>","PeriodicalId":16811,"journal":{"name":"Journal of Physics and Chemistry of Solids","volume":"211 ","pages":"Article 113447"},"PeriodicalIF":4.9,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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