ACS Applied Energy Materials最新文献

{"title":"S-Scheme Heterojunction Efficient Extraction of Hot Carriers in CsPbBr3/Bi4O5I2 for Enhanced Photocatalytic H2 Evolution and CO2 Reduction","authors":"Ye Zhang,&nbsp;Mai Zhang,&nbsp;Cong Luo,&nbsp;Yakun Li,&nbsp;Xue Zhang and Linlin Zhang*,&nbsp;","doi":"10.1021/acsaem.4c0241910.1021/acsaem.4c02419","DOIUrl":"https://doi.org/10.1021/acsaem.4c02419https://doi.org/10.1021/acsaem.4c02419","url":null,"abstract":"<p >This study investigates the photocatalytic capabilities of an S-scheme heterojunction formed by CsPbBr₃ and Bi₄O₅I₂ for H₂ evolution and CO₂ reduction. The heterojunction is designed to enhance the extraction of hot carriers and charge separation through interface engineering and an internal electric field. The initial <i>T</i>_c at higher pumping intensities indicates that CsPbBr₃ carriers injected into Bi₄O₅I₂ at higher energies and temperatures cooled from 1800 to 800 K within 200 fs after photoexcitation. Compared with CsPbBr₃, CsPbBr₃/Bi₄O₅I₂ showed substantial improvement in photocatalytic H₂ production from 59.08 to 1050.93 μmol h^–1 g^–1. Furthermore, the S-scheme CsPbBr₃/Bi₄O₅I₂ heterojunction displays outstanding photocatalytic CO₂ to CO performance, compared to pure CsPbBr₃, from 2.84 to 83.6 μmol h^–1 g^–1. These findings contribute to the understanding and development of S-scheme heterojunction extraction of hot carriers in perovskite materials for photocatalytic applications.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11988–11995 11988–11995"},"PeriodicalIF":5.4,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870183","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}

{"title":"4,4′,4″-Nitrilotribenzoic Acid/Graphitic Carbon Nitride Type II Heterostructures for Highly Efficient Photocatalytic Hydrogen Evolution from Water Splitting","authors":"Tania Tofaz,&nbsp;Xiao-Jie Lu,&nbsp;Shuai Chen,&nbsp;Jing-Han Li,&nbsp;Hao-Yang Ding,&nbsp;Ikram Ullah,&nbsp;Sadia Habib,&nbsp;Ghulam Murtaza and An-Wu Xu*,&nbsp;","doi":"10.1021/acsaem.4c0250910.1021/acsaem.4c02509","DOIUrl":"https://doi.org/10.1021/acsaem.4c02509https://doi.org/10.1021/acsaem.4c02509","url":null,"abstract":"<p >The metal-free polymer semiconductor pristine carbon nitride (CN) has garnered notable interest; however, its poor photocatalytic activity constrains its practical uses. Herein, we synthesize cost-effective, nonhazardous, boron (B)-doped graphitic carbon nitride (BCN) through thermal polymerization. The successful grafting of BCN with 4,4′,4″-nitrilotribenzoic acid (NBA) donor molecules via an amide covalent bond presents the construction of BCN-NBA type II heterostructures. This extended π-conjugated NBA electron donor loaded on BCN exhibits band gap enhancement with wideband optical absorbance in the visible range and augmented efficiency for the spatial charge separation and transport of photogenerated charges owing to the formation of type II heterojunction. The optimal BCN-NBA-3 photocatalyst shows enhanced H₂ production mobility with a rate of 208.67 μmol h^–1 at visible light illumination (λ ≥ 420 nm) with 1% Pt as cocatalyst and a high apparent quantum efficiency (AQE) of 8.16% at 450 nm monochromatic light. Compared with pure CN (10.67 μmol h^–1), about 19.56 folds higher H₂ evolution rate is observed for BCN-NBA-3 at visible light irradiation. Furthermore, the as-prepared photocatalyst displayed robust photocatalytic hydrogen generation for 16 h. This work emphasizes the possibility of using organic covalently functionalized CN to construct highly efficient heterostructured photocatalysts and opens up an avenue for practical applications in hydrogen production.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"12016–12026 12016–12026"},"PeriodicalIF":5.4,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870098","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}

{"title":"Influence of the Densification Process on the Thermoelectric Properties of p-Type SnSe Co-doped with Na and Cu as well as Na and Ag","authors":"Andrew Golabek,&nbsp;Nikhil Kumar Barua,&nbsp;Luke T. Menezes,&nbsp;Ehsan Niknam,&nbsp;Zan Yang and Holger Kleinke*,&nbsp;","doi":"10.1021/acsaem.4c0216910.1021/acsaem.4c02169","DOIUrl":"https://doi.org/10.1021/acsaem.4c02169https://doi.org/10.1021/acsaem.4c02169","url":null,"abstract":"<p >SnSe has been at the forefront of thermoelectric material research ever since its single crystal was reported to exhibit record-breaking peak <i>zT</i> values in excess of 2 along two directions some 10 years ago. Recent reports indicated the importance of the processing parameters for its transport properties, notably including the purification methods to remove oxide impurities. Here, we investigated the different influences of different consolidation methods on the properties including the stability of SnSe using different <i>p</i>-type dopants, comparing hot pressing with spark plasma sintering. Ultimately, we were able to achieve very comparable results with hot pressing as with spark plasma sintering, which bodes well for the upscaling of the process in industrial settings. In fact, the highest <i>zT</i> value of 0.96 at 673 K was obtained for a hot-pressed sample codoped with Na and Ag. Notably, the Ag-containing samples exhibited higher <i>zT</i> values than those with Cu. However, since all samples began to exhibit cracks after the measurements and inconsistently changing thermoelectric properties, the stability of these materials needs to be improved before any potential usage in a thermoelectric device.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11852–11858 11852–11858"},"PeriodicalIF":5.4,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875047","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}

{"title":"Enhancing Electrocatalysis: Engineering the Fe–Nx–C Electrocatalyst for Oxygen Reduction Reaction Using Fe-Functionalized Silica Hard Templates","authors":"Mohsin Muhyuddin,&nbsp;Silvia Mostoni,&nbsp;Hilah Clara Honig,&nbsp;Lorenzo Mirizzi,&nbsp;Lior Elbaz,&nbsp;Roberto Scotti,&nbsp;Massimiliano D’Arienzo* and Carlo Santoro*,&nbsp;","doi":"10.1021/acsaem.4c0121510.1021/acsaem.4c01215","DOIUrl":"https://doi.org/10.1021/acsaem.4c01215https://doi.org/10.1021/acsaem.4c01215","url":null,"abstract":"<p >The availability of robust and accessible active sites in iron–nitrogen-carbon (Fe–N_<i>x</i>-C) electrocatalysts is essential to optimize the oxygen reduction reaction (ORR), which is the main obstacle in the commercial realization of fuel cells. Herein, a modified hard templating method to develop efficient Fe–N_<i>x</i>-C has been presented that not only ensured the generation of a porous architecture but also helped in the homogeneous distribution of Fe throughout the structure. First, silica nanoparticles (NPs) were grown via the Stöber process and then functionalized atomically with iron through two different types of silane chains, i.e., (3-aminopropyl)triethoxysilane (APTES) and N-(2-Aminoethyl)-3-aminopropyltriethoxysilane (EDTMS). The Fe-functionalized silica simultaneously acting as a sacrificial template as well as an iron source was then impregnated with nicarbazin, which was a carbon and nitrogen precursor. The dried mix was subject to pyrolysis (H1) followed by acid washing to dissolve silica templates, and then, again, it was subjected to another pyrolysis treatment (H2). At each proceeding step, ORR activity in both acidic and alkaline media was improved and the samples obtained at the last stage (i.e., H2) outperformed the other counterparts collected at the initial stages of the fabrication pathway. Eventually, the electrocatalyst developed using EDTMS-type silane attached to silica NPs (E_FeNC_H2) demonstrated the highest onset potentials of 990 mV vs RHE in alkaline media and 862 mV vs RHE in acidic media. Moreover, the lower peroxide yield of E_FeNC_H2 signifying nearly direct 4e^– ORR was attributed to the highest specific surface area (627 m² g^–1) and the optimum combination of active moieties dispersed in the porous carbonaceous framework.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11691–11702 11691–11702"},"PeriodicalIF":5.4,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsaem.4c01215","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Flexible Substituted Benzo[1,2-B:4,5-B’]dithiophene-Cored D-π-D Hole-Transporting Materials for Perovskite Solar Cells","authors":"An Zhang,&nbsp;Yu Chen*,&nbsp;Yuanyuan Xu,&nbsp;Hongyan Wang,&nbsp;Xueping Zong,&nbsp;Zhe Sun,&nbsp;Mao Liang and Song Xue,&nbsp;","doi":"10.1021/acsaem.4c0183410.1021/acsaem.4c01834","DOIUrl":"https://doi.org/10.1021/acsaem.4c01834https://doi.org/10.1021/acsaem.4c01834","url":null,"abstract":"<p >Here, four star-shaped D-π-D-π-D molecules S01–S04 were designed and synthesized, with thiophene (S01), bithiophene (S02), 3,4-ethylenedioxothiophene (S03), and hexyloxy-substituted benzo[1,2-b:4,5-b’]dithiophene (S04) as the central core, alkenyl as the π-brigde, and methoxytriphenylamine as the end groups, respectively. S04 with alkenyl bridges endowed hole transport materials (HTMs) with a long conjugation length and a deep highest occupied molecular orbital (HOMO) level. The π-bridge of the double bond can regulate the dihedral angles of the conjugate plane in the HTM molecules. Theoretical calculations show that a twisted dihedral angle between the central core and the carbon–carbon double bond is as low as 12.7° for S01, 9.4° for S02, 11.4° for S03, and 10.9° for S04, respectively. S04 has a negative charge on two O atoms instead of the S atom for S01–S03. The long alkoxy side chains may more effectively reduce molecular aggregations in the spin-coating process. A S04 film has a smoother surface with a lower root-mean-square (RMS) value (4.16 nm). As a result, S01, S02, S03 and S04 devices show photoelectric conversion efficiencies (PCEs) of 18.78%, 16.67%, 15.70%, and 21.07%, under simulated AM 1.5 G irradiation (100 mW cm^–2). The device performance of S04 is higher than that of Spiro-OMeTAD (19.65%). S01–S04 devices maintained more than 80% of the initial efficiency after 500 h under a relative humidity (RH) of 30%.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11741–11753 11741–11753"},"PeriodicalIF":5.4,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870097","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}

{"title":"Enhanced Photothermal Catalytic CO2 Reduction to High Selective C2H4 by Cooperative Interaction of Oxygen Vacancy and WTe2 Semimetal Cocatalyst In Situ Grown on WO3 Hollow Spheres","authors":"Xiaoyue Zhang,&nbsp;Yong Yang*,&nbsp;Yingjie Hu,&nbsp;Yong Chen*,&nbsp;Jinyou Shen and Yong Tu,&nbsp;","doi":"10.1021/acsaem.4c0221210.1021/acsaem.4c02212","DOIUrl":"https://doi.org/10.1021/acsaem.4c02212https://doi.org/10.1021/acsaem.4c02212","url":null,"abstract":"<p >Photothermal catalytic CO₂ reduction offers a dual solution to the greenhouse effect and energy crisis. Enhancing this process through the development of effective cocatalysts has proven to be a practical approach. In this study, the WO_2.9/WTe₂ photothermal catalyst was synthesized via an in situ growth method. The catalyst achieved an ethylene production rate of 122.9 μmol·g^–1, with a selectivity of 78%. Even at a reactor temperature of 240 °C, the ethylene yield reached 475.3 μmol·g^–1. This improvement in yield can be attributed to the synergistic effects of the semimetal cocatalyst WTe₂ and oxygen vacancies, which exhibit superior catalytic activity. In situ DRIFTS and DFT analyses highlighted the critical role of intermediary aldehyde groups in facilitating C–C coupling. WO_2.9 contributes by modulating the band gap and enhancing CO₂ adsorption via oxygen vacancies, while WTe₂ effectively captures intermediate aldehyde groups, fostering a surface rich in intermediates and promoting C–C bond formation. Additionally, thermal energy accelerates CO₂ activation and the C–C coupling process, creating optimal conditions for generating C₂₊ products. This research provides innovative strategies for designing photothermal catalysts and new insights into producing multicarbon fuels through a synergistic photothermal catalytic approach.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11859–11872 11859–11872"},"PeriodicalIF":5.4,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875051","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}

{"title":"Controlling Oxygen Vacancies in Sr0.875La0.1TiO3 with the Nano Titanium for Optimizing Thermoelectric Performance","authors":"Zhihao Lou,&nbsp;Ziyao Wei,&nbsp;Jianjun Gou,&nbsp;Jie Xu,&nbsp;Chunlin Gong and Feng Gao*,&nbsp;","doi":"10.1021/acsaem.4c0280710.1021/acsaem.4c02807","DOIUrl":"https://doi.org/10.1021/acsaem.4c02807https://doi.org/10.1021/acsaem.4c02807","url":null,"abstract":"<p >The nanosized titanium powder exhibits a strong oxygen capture ability, which can effectively increase the carrier concentration of SrTiO₃. However, it is essential to prevent oxidation before sintering. In this study, the impact of cold isostatic pressing (CIP) and calcination in an argon atmosphere on the microstructure and thermoelectric properties of Sr_0.875La_0.1TiO₃/nano Ti ceramics was explored. The results indicate that the carrier concentration of samples prepared by CIP can be significantly enhanced while simultaneously reducing the thermal conductivity through a notable grain size reduction of titanium oxide and augmentation of oxygen vacancy concentration. At 1073 K, the <i>ZT</i> value of the sample calcined in air and prepared by CIP was 0.22, exhibiting a 27% enhancement compared to that of the sample formed by dry press. Therefore, the combination of CIP and nanoscale Ti provides an efficient approach to manipulate the electrical and thermal transport properties of SrTiO₃ thermoelectric ceramics.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"12119–12130 12119–12130"},"PeriodicalIF":5.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875042","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}

{"title":"Conductive Metal–Organic Frameworks for Rechargeable LiOH-Based Li–O2 Batteries","authors":"Yehui Wu,&nbsp;Kun Zhang,&nbsp;Hankun Wang,&nbsp;Xihao Wang,&nbsp;Xingyu Ma,&nbsp;Shengchuang Du,&nbsp;Tiansheng Bai,&nbsp;Yuanfu Deng,&nbsp;Deping Li*,&nbsp;Lijie Ci* and Jingyu Lu*,&nbsp;","doi":"10.1021/acsaem.4c0251310.1021/acsaem.4c02513","DOIUrl":"https://doi.org/10.1021/acsaem.4c02513https://doi.org/10.1021/acsaem.4c02513","url":null,"abstract":"<p >The discharge product Li₂O₂ in conventional Li–O₂ batteries (LOBs) is highly reactive to trigger side reactions and deteriorate the battery performance; these can be circumvented to a great extent in a LiOH-based lithium–oxygen battery, which, however, suffers from efficient catalysis of LiOH formation and decomposition. Herein, we report the first introduction of conductive metal–organic frameworks [conductive MOFs (cMOFs)] to catalyze the LiOH chemistry in LOBs. Specifically, we synthesized three cMOF materials based on M–HHTP (monometallic Ni–HHTP, Co–HHTP, and bimetallic NiCo–HHTP, with HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene). Among them, the bimetallic NiCo–HHTP, benefiting from the synergistic effect of two metal elements, exhibits the best performance in catalyzing the LiOH chemistry of LOBs. It delivers a high discharge capacity (17,845.9 mA h g^–1 at a current density of 100 mA g^–1), excellent rate capability (6445.9 mA h g^–1 at 500 mA g^–1), reduced overpotential and side reactions, as well as high cycle stability, demonstrating great potential to promote the development of high-performance LiOH-based LOBs.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"12027–12035 12027–12035"},"PeriodicalIF":5.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875043","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}

{"title":"Construction of Cationic Vacancy-Rich Mulberry-Like MnCo2O4.5 Nanostructures with High Surface Area for High-Performance Hybrid Supercapacitors","authors":"Prasad Kumcham,&nbsp;Thupakula Venkata Madhukar Sreekanth*,&nbsp;Kisoo Yoo* and Jonghoon Kim*,&nbsp;","doi":"10.1021/acsaem.4c0189710.1021/acsaem.4c01897","DOIUrl":"https://doi.org/10.1021/acsaem.4c01897https://doi.org/10.1021/acsaem.4c01897","url":null,"abstract":"<p >Incorporating cationic vacancies into high surface area mesoporous structured materials is a viable strategy for improving the electrochemical performance of electrochemical energy storage/conversion devices. We successfully developed a mesoporous mulberry-like MnCo₂O_4.5 (MCO–DMF) with cation metal vacancies via a solvothermal route using dimethylformamide (DMF) as the solvent. The large surface area of the mulberry-like morphology offers numerous electroactive sites and a high permeation of electrolyte ions, giving rise to an excellent electrochemical performance. For comparison, spheres like MnCo₂O_4.5 (MCO-IPA) were prepared without cationic vacancies using isopropyl alcohol (IPA) as a solvent. The cationic vacancies (Mn) in MCO–DMF were identified by employing various analytical techniques such as energy-dispersive X-ray spectroscopy, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. The cation vacancies accelerated the charge transfer kinetics over the electrode–electrolyte interface in MCO–DMF with abundant electroactive sites. In the backdrop of supercapacitor application, the MCO–DMF electrode established a high specific capacity of 628.2 C g^–1 at 0.75 A g^–1 than the MCO-IPA electrode (380.6 C g^–1) with a greater cycling performance of 95.1% retention at 5 A g^–1 after 10,000 cycles. The MCO–DMF||AC hybrid supercapacitor (HSC) device exhibited a specific capacity of 165.5 C g^–1 at 0.75 A g^–1 within a potential window of 0.0–1.5 V. The HSC device also has a noteworthy energy and power densities of 58.5 Wh kg^–1 and 1026.7 W kg^–1, respectively, with a remarkable cycle stability of 91.4% capacity retention after 10,000 cycles.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11754–11765 11754–11765"},"PeriodicalIF":5.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870180","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}

{"title":"NaSICON Prepared by a Solution-Assisted Reaction Shows Enhanced Stability for High-Voltage Aqueous Redox-Flow Batteries","authors":"Ibrahim Munkaila Abdullahi,&nbsp;Kang-Ting Tseng,&nbsp;Sanat Vibhas Modak,&nbsp;Zeinab Ismail,&nbsp;Jeff Sakamoto and David G. Kwabi*,&nbsp;","doi":"10.1021/acsaem.4c0173910.1021/acsaem.4c01739","DOIUrl":"https://doi.org/10.1021/acsaem.4c01739https://doi.org/10.1021/acsaem.4c01739","url":null,"abstract":"<p >Sodium superionic conductors (NaSICONs) have garnered considerable attention as ion-exchange membranes in aqueous redox-flow batteries because they can eliminate crossover-induced capacity fade. Two challenges to their practical use are microstructural instability in aqueous solutions and low total conductivity (typically ≤1 mS/cm at room temperature), which causes high cell resistance. In this study, we evaluate the potential for NaSICON synthesized via a solution-assisted solid-state reaction (NZSP_SA-SSR) to address these challenges. Upon immersion in a series of neutral pH to strongly alkaline electrolytes, NZSP_SA-SSR pellets show a more stable impedance and microstructure over time than conventional NaSICON pellets synthesized from commercially available powder (NZSP_COMM). We observe prominent etching of the glassy phase in NZSP_COMM, whereas the amount of glassy phase in NZSP_SA-SSR is negligible. NZSP_SA-SSR pellets show no significant change in the microstructure even when exposed to solutions with high (∼1 M) concentrations of K⁺ ions and strongly oxidizing NaMnO₄. We assemble a 1.9 V Zn-MnO₄ flow cell containing a NZSP_SA-SSR membrane, and it demonstrates good cycling stability for close to 100 h. NZSP_SA-SSR also shows promise for accommodating other high-voltage cell chemistries, such as a pH-decoupled NaCrPDTA-NaMnO₄ system with an open-circuit potential of ∼1.7 V.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11724–11732 11724–11732"},"PeriodicalIF":5.4,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870171","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}