Pub Date : 2025-01-17DOI: 10.1021/acs.chemmater.4c03098
Mads B. Amdisen, Torben R. Jensen
Solid-state calcium batteries can potentially contribute to future renewable energy storage systems, however the discovery of electrolytes with sufficiently high Ca2+ conductivity at ambient conditions is a challenge. Here we present mechanochemical synthesis and properties of five different urea calcium tetrahydridoborate compositions as well as three crystal structures, Ca(BH4)2·xCO(NH2)2, x = 2, 4, and 6. The orthorhombic structure of Ca(BH4)2·2CO(NH2)2 consists of dinuclear molecular units, [Ca2(BH4)4(OC(NH2)2)4], with the two Ca2+ ions bridged by three urea molecules. The low symmetry monoclinic structures of Ca(BH4)2·4CO(NH2)2 and Ca(BH4)2·6CO(NH2)2 consist of [Ca(BH4)2(OC(NH2)2)4] and [Ca(OC(NH2)2)6]2+ octahedra with BH4– counterions in the later, and all three structures are held together by dihydrogen bonds. The calcium ionic conductivity reaches a maximum of σ(Ca2+) = 2.46 × 10–7 S cm–1 for the composition Ca(BH4)2–3.30CO(NH2)2 at RT, and of σ(Ca2+) = 1.23 × 10–4 S cm–1 for Ca(BH4)2–6.52CO(NH2)2 at 70 °C. Activation energies in the range 0.5 < Ea < 2.4 eV depending on the urea content and heating or cooling during measurement of ionic conductivity and an ionic transport number of Tion = 0.997 are also reported. The investigation of this series of compounds and their composites provides approaches for optimizing multiple physical phenomena that facilitate increased cationic conductivity.
{"title":"Urea Calcium Borohydrides as Ca2+ Solid-State Electrolytes","authors":"Mads B. Amdisen, Torben R. Jensen","doi":"10.1021/acs.chemmater.4c03098","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03098","url":null,"abstract":"Solid-state calcium batteries can potentially contribute to future renewable energy storage systems, however the discovery of electrolytes with sufficiently high Ca<sup>2+</sup> conductivity at ambient conditions is a challenge. Here we present mechanochemical synthesis and properties of five different urea calcium tetrahydridoborate compositions as well as three crystal structures, Ca(BH<sub>4</sub>)<sub>2</sub>·<i>x</i>CO(NH<sub>2</sub>)<sub>2</sub>, <i>x</i> = 2, 4, and 6. The orthorhombic structure of Ca(BH<sub>4</sub>)<sub>2</sub>·2CO(NH<sub>2</sub>)<sub>2</sub> consists of dinuclear molecular units, [Ca<sub>2</sub>(BH<sub>4</sub>)<sub>4</sub>(OC(NH<sub>2</sub>)<sub>2</sub>)<sub>4</sub>], with the two Ca<sup>2+</sup> ions bridged by three urea molecules. The low symmetry monoclinic structures of Ca(BH<sub>4</sub>)<sub>2</sub>·4CO(NH<sub>2</sub>)<sub>2</sub> and Ca(BH<sub>4</sub>)<sub>2</sub>·6CO(NH<sub>2</sub>)<sub>2</sub> consist of [Ca(BH<sub>4</sub>)<sub>2</sub>(OC(NH<sub>2</sub>)<sub>2</sub>)<sub>4</sub>] and [Ca(OC(NH<sub>2</sub>)<sub>2</sub>)<sub>6</sub>]<sup>2+</sup> octahedra with BH<sub>4</sub><sup>–</sup> counterions in the later, and all three structures are held together by dihydrogen bonds. The calcium ionic conductivity reaches a maximum of σ(Ca<sup>2+</sup>) = 2.46 × 10<sup>–7</sup> S cm<sup>–1</sup> for the composition Ca(BH<sub>4</sub>)<sub>2</sub>–3.30CO(NH<sub>2</sub>)<sub>2</sub> at RT, and of σ(Ca<sup>2+</sup>) = 1.23 × 10<sup>–4</sup> S cm<sup>–1</sup> for Ca(BH<sub>4</sub>)<sub>2</sub>–6.52CO(NH<sub>2</sub>)<sub>2</sub> at 70 °C. Activation energies in the range 0.5 < <i>E</i><sub>a</sub> < 2.4 eV depending on the urea content and heating or cooling during measurement of ionic conductivity and an ionic transport number of <i>T</i><sub>ion</sub> = 0.997 are also reported. The investigation of this series of compounds and their composites provides approaches for optimizing multiple physical phenomena that facilitate increased cationic conductivity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"44 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987857","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-16DOI: 10.1021/acs.chemmater.4c03298
Taeseok Kim, Han Kim, Seung Ho Ryu, Gwang Min Park, Sung-Chul Kim, Sung Kwang Lee, Taek-Mo Chung, Sung Ok Won, Jeong Hwan Han, Sangtae Kim, Seong Keun Kim
Achieving uniform dopant distribution and fine compositional tuning in atomic layer deposition (ALD) processes remains a significant challenge, particularly for ultrathin films, due to their cyclic nature. This study systematically investigates the inherent limitations of compositional uniformity and the minimum thickness achievable in depositing doped films using ALD. Furthermore, a strategy is implemented to resolve the compositional nonuniformity in the ALD-grown doped films by employing inhibitors. Utilizing Sn-doped In2O3 films as the model system, this approach examines the influences of carboxylic acids, including acetic acid, isobutyric acid, and 2-ethylbutyric acid, as inhibitors, resulting in a significant reduction of the growth per cycle of a SnOx doping layer to 1/10 to 1/20 of the levels observed without inhibitors. The degree of inhibition correlates with the size of the carboxylic acid, allowing precise control over dopant composition and enabling uniform doping in films as thin as 2 nm. Also, atomistic simulations reveal that steric hindrance plays as the major inhibition mechanism among the carboxylic acids, providing mechanistic insights into the design criteria for optimal inhibitors. The results suggest that inhibitor-assisted ALD processes offer a viable pathway to improve dopant control and alleviate thickness limitations, enhancing the performance of advanced materials.
{"title":"Inhibitor-Assisted Atomic Layer Deposition for Uniformly Doped Ultrathin Films: Overcoming Compositional and Thickness Limitations","authors":"Taeseok Kim, Han Kim, Seung Ho Ryu, Gwang Min Park, Sung-Chul Kim, Sung Kwang Lee, Taek-Mo Chung, Sung Ok Won, Jeong Hwan Han, Sangtae Kim, Seong Keun Kim","doi":"10.1021/acs.chemmater.4c03298","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03298","url":null,"abstract":"Achieving uniform dopant distribution and fine compositional tuning in atomic layer deposition (ALD) processes remains a significant challenge, particularly for ultrathin films, due to their cyclic nature. This study systematically investigates the inherent limitations of compositional uniformity and the minimum thickness achievable in depositing doped films using ALD. Furthermore, a strategy is implemented to resolve the compositional nonuniformity in the ALD-grown doped films by employing inhibitors. Utilizing Sn-doped In<sub>2</sub>O<sub>3</sub> films as the model system, this approach examines the influences of carboxylic acids, including acetic acid, isobutyric acid, and 2-ethylbutyric acid, as inhibitors, resulting in a significant reduction of the growth per cycle of a SnO<sub><i>x</i></sub> doping layer to 1/10 to 1/20 of the levels observed without inhibitors. The degree of inhibition correlates with the size of the carboxylic acid, allowing precise control over dopant composition and enabling uniform doping in films as thin as 2 nm. Also, atomistic simulations reveal that steric hindrance plays as the major inhibition mechanism among the carboxylic acids, providing mechanistic insights into the design criteria for optimal inhibitors. The results suggest that inhibitor-assisted ALD processes offer a viable pathway to improve dopant control and alleviate thickness limitations, enhancing the performance of advanced materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"45 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-15DOI: 10.1021/acs.chemmater.4c02996
Banik Rai, Sandip Kumar Kuila, Rana Saha, Sankalpa Hazra, Chandan De, Jyotirmoy Sau, Venkatraman Gopalan, Partha Pratim Jana, Stuart S. P. Parkin, Nitesh Kumar
Trigonal Cr5Te8, a self-intercalated van der Waals ferromagnet with an out-of-plane magnetic anisotropy, has long been known to crystallize in a centrosymmetric structure. However, optical second harmonic generation experiments, together with comprehensive structural analysis, indicate that this compound rather adopts a noncentrosymmetric structure. Lorentz transmission electron microscopy reveals the presence of Néel-type skyrmions, consistent with its noncentrosymmetric structure. A large anomalous Hall conductivity of 102 Ω–1cm–1 at low temperature stems from intrinsic origin, which is larger than any previously reported values in the bulk Cr–Te system. Notably, spontaneous topological Hall resistivity arising from the skyrmionic phase has been observed. Our findings not only elucidate the unique magnetic and magneto-transport properties of noncentrosymmetric trigonal Cr5Te8, but also open new avenues for investigating the effects of broken inversion symmetry on material properties and their potential applications.
{"title":"Peculiar Magnetic and Magneto-Transport Properties in a Noncentrosymmetric Self-Intercalated van der Waals Ferromagnet Cr5Te8","authors":"Banik Rai, Sandip Kumar Kuila, Rana Saha, Sankalpa Hazra, Chandan De, Jyotirmoy Sau, Venkatraman Gopalan, Partha Pratim Jana, Stuart S. P. Parkin, Nitesh Kumar","doi":"10.1021/acs.chemmater.4c02996","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02996","url":null,"abstract":"Trigonal Cr<sub>5</sub>Te<sub>8</sub>, a self-intercalated van der Waals ferromagnet with an out-of-plane magnetic anisotropy, has long been known to crystallize in a centrosymmetric structure. However, optical second harmonic generation experiments, together with comprehensive structural analysis, indicate that this compound rather adopts a noncentrosymmetric structure. Lorentz transmission electron microscopy reveals the presence of Néel-type skyrmions, consistent with its noncentrosymmetric structure. A large anomalous Hall conductivity of 102 Ω<sup>–1</sup>cm<sup>–1</sup> at low temperature stems from intrinsic origin, which is larger than any previously reported values in the bulk Cr–Te system. Notably, spontaneous topological Hall resistivity arising from the skyrmionic phase has been observed. Our findings not only elucidate the unique magnetic and magneto-transport properties of noncentrosymmetric trigonal Cr<sub>5</sub>Te<sub>8</sub>, but also open new avenues for investigating the effects of broken inversion symmetry on material properties and their potential applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"1 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-15DOI: 10.1021/acs.chemmater.4c03295
Norihiro Mizoshita
The phase structures of hydrogen-bonded benzene-1,3,5-tricarboxamide (BTA) derivatives in divinylbenzene (DVB) solutions were examined together with the template effects of these derivatives during photopolymerization to make nanoporous polymers. BTA derivatives with linear or branched alkyl chains were found to form hydrogen-bonded supramolecular chains, solid crystalline nanofibers, or mesophase aggregates in DVB. These self-assembled structures caused the DVB/BTA molecular composites to adopt viscous liquid, nematic columnar liquid crystal, or physical gel states. The photopolymerization of DVB in homogeneous mixtures containing hydrogen-bonded supramolecular BTA chains resulted in macro-phase separation of the photo-cross-linked DVB and the BTA derivatives. In contrast, hydrogen-bonded crystalline BTA derivatives or mesophase nanofiber aggregates of these derivatives dispersed in DVB functioned as templates to produce nanoporous polymers after removal of the derivatives. A mesomorphic mixture exhibiting a structural transition from a homogeneous nematic columnar liquid crystal to a heterogeneous gel state enabled the preparation of uniaxially aligned nanoporous polymers. Horizontally- and vertically aligned nanoporous films were synthesized through shear-induced and electric-field-induced alignment of a nematic columnar phase. The use of self-assembled molecular additives provides a potential approach to controlling the nanostructures and improving the optical and electrical properties and functionalities of conventional polymeric materials and composites.
{"title":"Preparation of Uniaxially Aligned Nanoporous Polymer Films via Photopolymerization Using Self-Assembling Molecular Templates","authors":"Norihiro Mizoshita","doi":"10.1021/acs.chemmater.4c03295","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03295","url":null,"abstract":"The phase structures of hydrogen-bonded benzene-1,3,5-tricarboxamide (BTA) derivatives in divinylbenzene (DVB) solutions were examined together with the template effects of these derivatives during photopolymerization to make nanoporous polymers. BTA derivatives with linear or branched alkyl chains were found to form hydrogen-bonded supramolecular chains, solid crystalline nanofibers, or mesophase aggregates in DVB. These self-assembled structures caused the DVB/BTA molecular composites to adopt viscous liquid, nematic columnar liquid crystal, or physical gel states. The photopolymerization of DVB in homogeneous mixtures containing hydrogen-bonded supramolecular BTA chains resulted in macro-phase separation of the photo-cross-linked DVB and the BTA derivatives. In contrast, hydrogen-bonded crystalline BTA derivatives or mesophase nanofiber aggregates of these derivatives dispersed in DVB functioned as templates to produce nanoporous polymers after removal of the derivatives. A mesomorphic mixture exhibiting a structural transition from a homogeneous nematic columnar liquid crystal to a heterogeneous gel state enabled the preparation of uniaxially aligned nanoporous polymers. Horizontally- and vertically aligned nanoporous films were synthesized through shear-induced and electric-field-induced alignment of a nematic columnar phase. The use of self-assembled molecular additives provides a potential approach to controlling the nanostructures and improving the optical and electrical properties and functionalities of conventional polymeric materials and composites.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-15DOI: 10.1021/acs.chemmater.4c02513
Marita Wagner, Ada Herrero-Ruiz, Ester Verde-Sesto, Isabel Asenjo-Sanz, Luis M. Liz-Marzán
The chemical synthesis of nanomaterials has been a driving force in the advancement of nanoscience and nanotechnology. However, minor changes in the composition of the reactants and the presence of impurities can significantly alter the outcome of synthetic procedures that have been developed for a wide range of nanomaterials. The synthesis of gold nanostars (AuNSt) using poly(vinylpyrrolidone) (PVP) in N,N-dimethylformamide (DMF) is no exception to this issue, as several studies have reported PVP batch dependency of the synthesis. In this context, we set to analyze commercial PVP using 1H NMR and show that only those containing certain impurities are suitable for the synthesis of AuNSt. Following this finding, we synthesized our own PVP with the aim of replicating the synthesis conditions of commercial PVP, including its impurities. The results confirm that PVP synthesized using hydrogen peroxide as a radical initiator and ammonium hydroxide or calcium carbonate as the base, are suitable for the formation of AuNSt. Additionally, the base used in PVP synthesis was found to influence the reaction kinetics and, in turn, the shape of the resulting AuNSt. Control reactions with purified PVP show drastically decreased nanoparticle anisotropy, suggesting that the star shape is strongly dependent on the impurity profile, resulting from the selected PVP synthetic pathway. We present a solution toward customizing AuNSt shape via PVP synthesis and avoiding dependence on commercial PVP.
{"title":"Influence of Poly(vinylpyrrolidone) Synthesis Conditions on the Formation of Gold Nanostars","authors":"Marita Wagner, Ada Herrero-Ruiz, Ester Verde-Sesto, Isabel Asenjo-Sanz, Luis M. Liz-Marzán","doi":"10.1021/acs.chemmater.4c02513","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02513","url":null,"abstract":"The chemical synthesis of nanomaterials has been a driving force in the advancement of nanoscience and nanotechnology. However, minor changes in the composition of the reactants and the presence of impurities can significantly alter the outcome of synthetic procedures that have been developed for a wide range of nanomaterials. The synthesis of gold nanostars (AuNSt) using poly(vinylpyrrolidone) (PVP) in <i>N</i>,<i>N</i>-dimethylformamide (DMF) is no exception to this issue, as several studies have reported PVP batch dependency of the synthesis. In this context, we set to analyze commercial PVP using <sup>1</sup>H NMR and show that only those containing certain impurities are suitable for the synthesis of AuNSt. Following this finding, we synthesized our own PVP with the aim of replicating the synthesis conditions of commercial PVP, including its impurities. The results confirm that PVP synthesized using hydrogen peroxide as a radical initiator and ammonium hydroxide or calcium carbonate as the base, are suitable for the formation of AuNSt. Additionally, the base used in PVP synthesis was found to influence the reaction kinetics and, in turn, the shape of the resulting AuNSt. Control reactions with purified PVP show drastically decreased nanoparticle anisotropy, suggesting that the star shape is strongly dependent on the impurity profile, resulting from the selected PVP synthetic pathway. We present a solution toward customizing AuNSt shape via PVP synthesis and avoiding dependence on commercial PVP.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"31 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-13DOI: 10.1021/acs.chemmater.4c02998
Reinout F. Ubbink, Yan B. Vogel, Maarten Stam, Hua Chen, Arjan J. Houtepen
Electrochemical charging of films of semiconductor nanocrystals (NCs) allows precise control over their Fermi level and opens up new possibilities for use of semiconductor NCs in optoelectronic devices. Unfortunately, charges added to the semiconductor NCs are often lost due to electrochemical side reactions. In this work, we examine which loss processes can occur in electrochemically charged semiconductor NC films by comparing numerical drift-diffusion simulations with experimental data. Both reactions with impurities in the electrolyte solution, as well as reactions occurring on the surface of the nanomaterials themselves, are considered. We show that the Gerischer kinetic model can be used to accurately model the one-electron transfer between charges in the semiconductor NC and oxidant or reductant species in solution. Simulations employing the Gerischer model are in agreement with experimental results of charging of semiconductor NC films with ideal one-electron acceptors ferrocene and cobaltocene. We show that reactions of charges in the semiconductor NC film with redox species in solution are reversible when the reduction potential is in the conduction band of the semiconductor NC material but are irreversible when the reduction potential is in the band gap. Experimental charging of semiconductor NC films in the presence of oxygen is always irreversible in our system, even when the reduction potential of oxygen is in the conduction band of the semiconductor NC material. We show that the Gerischer model in combination with a coupled reversible-irreversible reaction mechanism can be used to model oxygen reduction. Finally, we model irreversible reduction reactions with the semiconductor NC material itself, such as reduction of ligands or surface ions. Simulations of semiconductor NC cyclic voltammograms in the presence of material reduction reactions strongly resemble experimental cyclic voltammograms of InP and CdSe NC films. This marks material reduction reactions at the semiconductor NC surface as a likely candidate for the irreversible behavior of these materials in electrochemical experiments. These results show that all reduction reactions with redox potentials in the band gap of semiconductor NCs must be suppressed in order to achieve stable charging of these materials.
{"title":"Where Do the Electrons Go? Studying Loss Processes in the Electrochemical Charging of Semiconductor Nanomaterials","authors":"Reinout F. Ubbink, Yan B. Vogel, Maarten Stam, Hua Chen, Arjan J. Houtepen","doi":"10.1021/acs.chemmater.4c02998","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02998","url":null,"abstract":"Electrochemical charging of films of semiconductor nanocrystals (NCs) allows precise control over their Fermi level and opens up new possibilities for use of semiconductor NCs in optoelectronic devices. Unfortunately, charges added to the semiconductor NCs are often lost due to electrochemical side reactions. In this work, we examine which loss processes can occur in electrochemically charged semiconductor NC films by comparing numerical drift-diffusion simulations with experimental data. Both reactions with impurities in the electrolyte solution, as well as reactions occurring on the surface of the nanomaterials themselves, are considered. We show that the Gerischer kinetic model can be used to accurately model the one-electron transfer between charges in the semiconductor NC and oxidant or reductant species in solution. Simulations employing the Gerischer model are in agreement with experimental results of charging of semiconductor NC films with ideal one-electron acceptors ferrocene and cobaltocene. We show that reactions of charges in the semiconductor NC film with redox species in solution are reversible when the reduction potential is in the conduction band of the semiconductor NC material but are irreversible when the reduction potential is in the band gap. Experimental charging of semiconductor NC films in the presence of oxygen is always irreversible in our system, even when the reduction potential of oxygen is in the conduction band of the semiconductor NC material. We show that the Gerischer model in combination with a coupled reversible-irreversible reaction mechanism can be used to model oxygen reduction. Finally, we model irreversible reduction reactions with the semiconductor NC material itself, such as reduction of ligands or surface ions. Simulations of semiconductor NC cyclic voltammograms in the presence of material reduction reactions strongly resemble experimental cyclic voltammograms of InP and CdSe NC films. This marks material reduction reactions at the semiconductor NC surface as a likely candidate for the irreversible behavior of these materials in electrochemical experiments. These results show that all reduction reactions with redox potentials in the band gap of semiconductor NCs must be suppressed in order to achieve stable charging of these materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"2 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-13DOI: 10.1021/acs.chemmater.4c02747
Tippi Verhelle, Arpan Dhara, Lowie Henderick, Matthias Minjauw, Louis De Taeye, Johan Meersschaut, Jolien Dendooven, Christophe Detavernier
Protective coatings on lithium-ion battery electrodes have proven to be an effective way to suppress detrimental side reactions, thereby improving the performance of lithium-ion batteries. Atomic layer deposition (ALD) provides conformal deposition of these layers with precise thickness control, ensuring optimized cathode protection. In this work, an ALD process is developed for the deposition of lithium borate coatings using lithiumbis(trimethylsilyl)amide (LiHMDS), H2O and trimethylborate (TMB). The ionic conductivity varies with deposition temperature: a value of 1.17 × 10–7 S cm–1 at 25 °C is obtained, with an activation energy of 0.58 eV. Using a supercycle approach to combine lithium borate with the known Li3PO4 process, and varying the cycle ratio, allows for the deposition of borophosphate coatings with tunable B/P ratios. As-deposited Li3PO4 films are crystalline, whereas lithium borate films are amorphous. Interestingly, a small amount of B incorporation (<1 at. %) enhances the crystallinity of the Li3PO4 films, which was attributed to a lower amount of C contamination (from 9.3 to 4.4 at. %). To explore the electrochemical properties of these layers, 10 nm coatings were deposited on a LiMn2O4 electrode as a model 2D system, where good Li-kinetics were proven. Next to this, they have shown to provide protection at elevated potentials. This work demonstrates that lithium borate and lithium borophosphate coatings are promising materials for interfacial layers and solid-state electrolytes to be used in next-generation lithium battery technologies.
{"title":"Atomic Layer Deposition of Lithium Borate and Lithium Borophosphate for Lithium-Ion Batteries","authors":"Tippi Verhelle, Arpan Dhara, Lowie Henderick, Matthias Minjauw, Louis De Taeye, Johan Meersschaut, Jolien Dendooven, Christophe Detavernier","doi":"10.1021/acs.chemmater.4c02747","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02747","url":null,"abstract":"Protective coatings on lithium-ion battery electrodes have proven to be an effective way to suppress detrimental side reactions, thereby improving the performance of lithium-ion batteries. Atomic layer deposition (ALD) provides conformal deposition of these layers with precise thickness control, ensuring optimized cathode protection. In this work, an ALD process is developed for the deposition of lithium borate coatings using lithiumbis(trimethylsilyl)amide (LiHMDS), H<sub>2</sub>O and trimethylborate (TMB). The ionic conductivity varies with deposition temperature: a value of 1.17 × 10<sup>–7</sup> S cm<sup>–1</sup> at 25 °C is obtained, with an activation energy of 0.58 eV. Using a supercycle approach to combine lithium borate with the known Li<sub>3</sub>PO<sub>4</sub> process, and varying the cycle ratio, allows for the deposition of borophosphate coatings with tunable B/P ratios. As-deposited Li<sub>3</sub>PO<sub>4</sub> films are crystalline, whereas lithium borate films are amorphous. Interestingly, a small amount of B incorporation (<1 at. %) enhances the crystallinity of the Li<sub>3</sub>PO<sub>4</sub> films, which was attributed to a lower amount of C contamination (from 9.3 to 4.4 at. %). To explore the electrochemical properties of these layers, 10 nm coatings were deposited on a LiMn<sub>2</sub>O<sub>4</sub> electrode as a model 2D system, where good Li-kinetics were proven. Next to this, they have shown to provide protection at elevated potentials. This work demonstrates that lithium borate and lithium borophosphate coatings are promising materials for interfacial layers and solid-state electrolytes to be used in next-generation lithium battery technologies.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"14 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-13DOI: 10.1021/acs.chemmater.4c02852
Tingru Chen, Eugenio H. Otal, Tien Quang Nguyen, Shunsuke Narumi, Michihisa Koyama, Nobuyuki Zettsu
This is the first demonstration of successful Y3+ doping, and Y3+-doped O3-NaFe0.4Ni0.3Mn0.3O2 (NaFNM) cathodes exhibit superior cyclability and C-rate capabilities. Y3+ doping enabled cells with 91% capacity retention at 1 C after 100 cycles and a high specific capacity of 102 mA h g–1 at a 7 C rate. Furthermore, the full cell delivered outstanding cycling stability, with a capacity retention of 80% after 500 cycles at 1 C and 71.3% after 1000 cycles. Operando X-ray diffraction spectroscopy (XRD) and X-ray absorption spectroscopy, along with simulations using density functional theory and neural network potential methods, provided comprehensive insights on the effects of Y3+ doping on the cycling characteristics. Our results confirm that Y3+ doping effectively stabilizes the O3 structure, enhances the electrochemical performance, and addresses the challenge of irreversible O3 to P3 phase transitions.
{"title":"Structural Stabilization and Superior Electrochemical Performance of Yttrium-Doped O3-NaFe0.4Ni0.3Mn0.3O2 Cathodes for Sodium-Ion Batteries","authors":"Tingru Chen, Eugenio H. Otal, Tien Quang Nguyen, Shunsuke Narumi, Michihisa Koyama, Nobuyuki Zettsu","doi":"10.1021/acs.chemmater.4c02852","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02852","url":null,"abstract":"This is the first demonstration of successful Y<sup>3+</sup> doping, and Y<sup>3+</sup>-doped O3-NaFe<sub>0.4</sub>Ni<sub>0.3</sub>Mn<sub>0.3</sub>O<sub>2</sub> (NaFNM) cathodes exhibit superior cyclability and C-rate capabilities. Y<sup>3+</sup> doping enabled cells with 91% capacity retention at 1 C after 100 cycles and a high specific capacity of 102 mA h g<sup>–1</sup> at a 7 C rate. Furthermore, the full cell delivered outstanding cycling stability, with a capacity retention of 80% after 500 cycles at 1 C and 71.3% after 1000 cycles. Operando X-ray diffraction spectroscopy (XRD) and X-ray absorption spectroscopy, along with simulations using density functional theory and neural network potential methods, provided comprehensive insights on the effects of Y<sup>3+</sup> doping on the cycling characteristics. Our results confirm that Y<sup>3+</sup> doping effectively stabilizes the O3 structure, enhances the electrochemical performance, and addresses the challenge of irreversible O3 to P3 phase transitions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"91 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-13DOI: 10.1021/acs.chemmater.4c02987
Zenglong Guo, Kangdi Niu, Gang Wang, Fuchen Hou, Junhao Lin
In two-dimensional (2D) materials, grain boundaries (GBs) often exhibit atomic structures and physical properties distinct from the basal plane, significantly impacting the overall properties of 2D films. Transition metal tellurides (TMTs), a subclass of transition metal dichalcogenides (TMDCs), display unique crystal structures and novel states, making them ideal for studying various physical phenomena. Despite the successful growth of centimeter-scale TMT films, limited research on GBs persists due to their high chemical reactivity and air sensitivity, which complicates atomic-scale investigations. In this review, we first introduce the fundamental crystal structure and physical properties of TMTs. We then summarize the growth methods for large-area TMT films and review the latest advances in understanding the atomic and electronic structures of GBs in TMT films grown by molecular beam epitaxy (MBE) and chemical vapor deposition (CVD), as revealed by scanning transmission electron microscopy (STEM) and scanning tunneling microscopy (STM). Finally, we discuss the challenges encountered in studying the atomic structures and properties of GBs in TMT films, and explore the potential applications of this research in the growth of single-crystal TMT films and future topological electronic devices. This review aims to draw attention to the challenges in researching GB structures and properties in TMTs, present the latest findings in the field, and foster further development in this area.
{"title":"Progress on the Intrinsic Grain Boundary Structures in Air-Sensitive Transition Metal Tellurides","authors":"Zenglong Guo, Kangdi Niu, Gang Wang, Fuchen Hou, Junhao Lin","doi":"10.1021/acs.chemmater.4c02987","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02987","url":null,"abstract":"In two-dimensional (2D) materials, grain boundaries (GBs) often exhibit atomic structures and physical properties distinct from the basal plane, significantly impacting the overall properties of 2D films. Transition metal tellurides (TMTs), a subclass of transition metal dichalcogenides (TMDCs), display unique crystal structures and novel states, making them ideal for studying various physical phenomena. Despite the successful growth of centimeter-scale TMT films, limited research on GBs persists due to their high chemical reactivity and air sensitivity, which complicates atomic-scale investigations. In this review, we first introduce the fundamental crystal structure and physical properties of TMTs. We then summarize the growth methods for large-area TMT films and review the latest advances in understanding the atomic and electronic structures of GBs in TMT films grown by molecular beam epitaxy (MBE) and chemical vapor deposition (CVD), as revealed by scanning transmission electron microscopy (STEM) and scanning tunneling microscopy (STM). Finally, we discuss the challenges encountered in studying the atomic structures and properties of GBs in TMT films, and explore the potential applications of this research in the growth of single-crystal TMT films and future topological electronic devices. This review aims to draw attention to the challenges in researching GB structures and properties in TMTs, present the latest findings in the field, and foster further development in this area.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"36 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 : 2025-01-12DOI: 10.1021/acs.chemmater.4c02765
Gabriele Lingua, Antonela Gallastegui, Yuliana Pairetti, Alejandro Herranz Berzosa, Kewei Cai, Fangfang Chen, David Mecerreyes, Maria Forsyth
Despite the advantages over traditional liquid electrolytes, solid-state polymer electrolytes present several challenges to be addressed for their widespread application in solid-state lithium metal batteries. In this work, we report a novel class of solid polymer electrolytes based on protic poly(diallylmethylammonium) bis(fluorosulfonyl)imide (poly(DAMAH)FSI) with high lithium bis(fluorosulfonyl)imide (LiFSI) salt content. Protic polymer electrolytes with different compositions show improved properties over their aprotic counterpart. We postulate that the protic nature of the polymer backbone positively affects the coordination of the FSI anions leading to a Li-FSI-polycation cocoordination environment with resultant high Li diffusivity of 4.1 × 10–11 m2 s–1 and ionic conductivity of 6.4 × 10–4 S cm–1 at 80 °C which is a factor almost 10 times higher than the equivalent aprotic systems (0.7 × 10–4 S cm–1 at 80 °C). The apparent superior salt dissociation ability leads to homogeneous mixtures with a 1:2 mol ratio of Poly(DAMAH)FSI:LiFSI characterized by a Li+ ion transport number of 0.67. The cyclic voltammetry of the polymer materials on a Cu working electrode indicates the stability of the N–H proton in these high LiFSI-containing electrolytes, allowing successful plating/stripping analysis using a protic polymer-based electrolyte in a Li/Li cell. We thus demonstrate for the first time, the potential of these solvent-free protic poly(ionic liquid)-based solid polymer electrolytes in Li/Li metal cells at a moderate temperature of 50 °C, paving the way for future investigation and implementation in Li metal and Li-ion cells.
尽管固态聚合物电解质比传统液态电解质更具优势，但要在固态锂金属电池中得到广泛应用，还需应对一些挑战。在这项研究中，我们报告了一类新型固态聚合物电解质，它基于原生聚（二烯丙基甲基铵）双（氟磺酰）亚胺（poly(DAMAH)FSI）和高含量双（氟磺酰）亚胺锂盐（LiFSI）。与无色聚合物相比，不同成分的原态聚合物电解质具有更好的性能。我们推测，聚合物骨架的质子性对 FSI 阴离子的配位产生了积极影响，从而形成了锂-FSI-多阳离子共配位环境，使锂离子在 80 °C 时的扩散率高达 4.1 × 10-11 m2 s-1，离子电导率高达 6.4 × 10-4 S cm-1，比等效的非沸腾体系（80 °C 时为 0.7 × 10-4 S cm-1）高出近 10 倍。由于盐解离能力明显较强，因此聚(DAMAH)FSI:LiFSI 的摩尔比为 1:2，形成了均匀的混合物，Li+ 离子迁移数为 0.67。聚合物材料在铜工作电极上的循环伏安法表明，N-H 质子在这些高含 LiFSI 的电解质中非常稳定，因此可以在锂/锂电池中使用基于原生聚合物的电解质成功进行电镀/剥离分析。因此，我们首次证明了这些无溶剂原生聚（离子液体）基固体聚合物电解质在 50 °C 的适中温度下在锂/锂金属电池中的应用潜力，为今后在锂金属和锂离子电池中的研究和应用铺平了道路。
{"title":"Protic Poly(ionic liquid)s with High Ionic Conductivity and Li+ Transport Number as Moderate Temperature Solid Electrolytes","authors":"Gabriele Lingua, Antonela Gallastegui, Yuliana Pairetti, Alejandro Herranz Berzosa, Kewei Cai, Fangfang Chen, David Mecerreyes, Maria Forsyth","doi":"10.1021/acs.chemmater.4c02765","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02765","url":null,"abstract":"Despite the advantages over traditional liquid electrolytes, solid-state polymer electrolytes present several challenges to be addressed for their widespread application in solid-state lithium metal batteries. In this work, we report a novel class of solid polymer electrolytes based on protic poly(diallylmethylammonium) bis(fluorosulfonyl)imide (poly(DAMAH)FSI) with high lithium bis(fluorosulfonyl)imide (LiFSI) salt content. Protic polymer electrolytes with different compositions show improved properties over their aprotic counterpart. We postulate that the protic nature of the polymer backbone positively affects the coordination of the FSI anions leading to a Li-FSI-polycation cocoordination environment with resultant high Li diffusivity of 4.1 × 10<sup>–11</sup> m<sup>2</sup> s<sup>–1</sup> and ionic conductivity of 6.4 × 10<sup>–4</sup> S cm<sup>–1</sup> at 80 °C which is a factor almost 10 times higher than the equivalent aprotic systems (0.7 × 10<sup>–4</sup> S cm<sup>–1</sup> at 80 °C). The apparent superior salt dissociation ability leads to homogeneous mixtures with a 1:2 mol ratio of Poly(DAMAH)FSI:LiFSI characterized by a Li<sup>+</sup> ion transport number of 0.67. The cyclic voltammetry of the polymer materials on a Cu working electrode indicates the stability of the N–H proton in these high LiFSI-containing electrolytes, allowing successful plating/stripping analysis using a protic polymer-based electrolyte in a Li/Li cell. We thus demonstrate for the first time, the potential of these solvent-free protic poly(ionic liquid)-based solid polymer electrolytes in Li/Li metal cells at a moderate temperature of 50 °C, paving the way for future investigation and implementation in Li metal and Li-ion cells.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"88 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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