Chemistry of Materials最新文献

{"title":"Photovoltaic Efficiency Optimization of Electrodeposited MAPbI3 Perovskite: Impact of Ammonium Valeric Acid Iodide Additive","authors":"Romain Lavoipierre,&nbsp;Emilie Planes,&nbsp;Lionel Flandin and Lara Perrin*,&nbsp;","doi":"10.1021/acs.chemmater.4c0221710.1021/acs.chemmater.4c02217","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02217https://doi.org/10.1021/acs.chemmater.4c02217","url":null,"abstract":"<p >Electrodeposition is being investigated as an alternative method for developing large-area perovskite active layers for carbon-based solar cells. This study focuses on incorporating the 5-ammonium valeric acid iodide (5-AVAI) additive into the established MAPbI₃ perovskite. Previous research has shown that 5-AVAI can enhance the performance and stability of similar solar cells produced via spin-coating, drop-casting, or inkjet printing. However, its impact on solar cells with electrodeposited active layers remains unexplored. This research investigated the synthesis and characterization of mixed 3D–2D perovskites in the (MAPbI₃)_1–<i>x</i>((AVA)₂PbI₄)_<i>x</i> family processed by electrodeposition. By varying both the conversion times and 5-AVAI concentrations, we analyzed the structural, optical, and photovoltaic properties of these novel perovskites. An intricate interplay between the conversion parameters and the perovskite properties is evident. Notably, photovoltaic devices with a specific quantity of 5-AVAI showed a 65% enhancement in the power conversion efficiency after 150 h of post-treatment at 40 °C under vacuum. These findings open the way to the improved performance of electrodeposited MAPbI₃ perovskites.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609384","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}

{"title":"Photovoltaic Efficiency Optimization of Electrodeposited MAPbI3 Perovskite: Impact of Ammonium Valeric Acid Iodide Additive","authors":"Romain Lavoipierre, Emilie Planes, Lionel Flandin, Lara Perrin","doi":"10.1021/acs.chemmater.4c02217","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02217","url":null,"abstract":"Electrodeposition is being investigated as an alternative method for developing large-area perovskite active layers for carbon-based solar cells. This study focuses on incorporating the 5-ammonium valeric acid iodide (5-AVAI) additive into the established MAPbI₃ perovskite. Previous research has shown that 5-AVAI can enhance the performance and stability of similar solar cells produced via spin-coating, drop-casting, or inkjet printing. However, its impact on solar cells with electrodeposited active layers remains unexplored. This research investigated the synthesis and characterization of mixed 3D–2D perovskites in the (MAPbI₃)_1–<i>x</i>((AVA)₂PbI₄)_<i>x</i> family processed by electrodeposition. By varying both the conversion times and 5-AVAI concentrations, we analyzed the structural, optical, and photovoltaic properties of these novel perovskites. An intricate interplay between the conversion parameters and the perovskite properties is evident. Notably, photovoltaic devices with a specific quantity of 5-AVAI showed a 65% enhancement in the power conversion efficiency after 150 h of post-treatment at 40 °C under vacuum. These findings open the way to the improved performance of electrodeposited MAPbI₃ perovskites.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541657","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}

{"title":"Optimal Ti-Substitution in Layered Oxide Cathodes for Na-Ion Batteries","authors":"Elisa Grépin, Yue Zhou, Biao Li, Gwenaëlle Rousse, Jean-Marie Tarascon, Sathiya Mariyappan","doi":"10.1021/acs.chemmater.4c02501","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02501","url":null,"abstract":"Sodium layered oxides Na_<i>x</i>MO₂ (<i>x</i> ≤ 1 and M = transition metal ions) gain interest as sodium-ion battery (NIB) cathodes due to their high energy density and cost-effectiveness. The nature of transition metal ions (M) defines the material properties, and the substitution of M with redox inactive Ti⁴⁺ is often seen as beneficial in reducing phase transitions during cycling and thus improving the cycle life. In this respect, our present study focuses on understanding the origin of this improvement by studying the highly substituted P2 Na_0.67Ni_0.30Zn_0.03Mn_{0.67–<i>y</i>}Ti_<i>y</i>O₂ (0 ≤ <i>y</i> ≤ 0.67) phases based on their electrochemical performance combined with structural analyses and DFT calculations. The results indicate that Ti⁴⁺, by increasing the M–O bond ionicity, disrupts the Na⁺-vacancy ordering at lower voltages (&lt;4 V, until ∼60% SOC) and reduces the participation of O 2<i>p</i> in the redox process, thereby suppressing Na-removal and the extent of P2–O2 phase transition at high voltages. We show that this effect becomes maximum for <i>y</i> = 0.52 (P2 Na_0.67Ni_0.30Zn_0.03Mn_0.15Ti_0.52O₂) and beyond, for which we observe a nearly solid-solution-like behavior of the P2-type structure. However, the d⁰ Ti⁴⁺ is prone to cation migration leading to poor structural reversibility as observed from operando XRD analyses, making the highly Ti⁴⁺-substituted material less suitable for practical applications. An optimum ratio of <i>y</i> = 0.3 (Na_0.67Ni_0.3Zn_0.03Mn_0.37Ti_0.3O₂) is beneficial for the cycle life as well as rate capability, and the study points to the importance of carefully selecting transition metal combinations in the finest ratio to achieve the best performing sodium layered oxide electrode materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541602","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}

{"title":"Guinier–Preston Zones Featuring PtCu Nanocrystals: Coherency Strain Fields Reshaping the Band Structure for Oxygen Reduction Electrocatalysis","authors":"Zhiguo Chen,&nbsp;Jingkun Chen,&nbsp;Jingbo Fu,&nbsp;Qiheng Wang,&nbsp;Yonghong Chen* and Jingjun Liu*,&nbsp;","doi":"10.1021/acs.chemmater.4c0148510.1021/acs.chemmater.4c01485","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01485https://doi.org/10.1021/acs.chemmater.4c01485","url":null,"abstract":"<p >Microstructurally distorted Pt-based nanoalloys with unusual structural defects like Guinier–Preston (GP) zones with in situ coherency strain fields may be suitable for substantially improving their electrocatalytic performance for the oxygen reduction reaction (ORR) in acidic conditions. Herein, GP zones contributing PtCu nanoalloys were first fabricated by additive manufacturing, starting with the formation of metallic Cu clusters as orderly crystal nuclei on ZIF-8-derived carbon, followed by the additive manufacturing of chemically reduced Pt and Cu on the formed clusters in ethylene glycol at 190 °C. The atomic-scale GP zones give rise to high-level coherent strain fields across the nanocrystals, boosting the ORR kinetics. This catalyst exhibits an ultrahigh oxygen reduction half-wave potential of 0.934 V (vs RHE) and a mass activity (MA) of 0.68 A mg_Pt^–1. After the accelerated degradation test of 50,000 cycles, the achieved MA improved instead of decreasing, rising from 0.68 to 0.89 A mg_Pt^–1, surpassing that of commercial Pt/C significantly. The significantly improved activity is attributed to the coherency strain fields reshaping the band structure and reconstructing a favorable charge density for active Pt sites. Importantly, the interface-anchored GP zones, maintaining a completely coherent relationship with the matrix, can effectively impede metal atom migration, segregation, or leaching, thus enhancing long-term stability. Therefore, the novel GP-type alloys may pave another way for designing advanced catalysts in the realm of current energy storage and conversion fields like fuel cells.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609390","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}

{"title":"Relating Local Structure to Thermoelectric Properties in Pb1–xGexBi2Te4","authors":"Jinfeng Dong, Yukun Liu, Jue Liu, Lei Hu, Yilin Jiang, Xian Yi Tan, Yuansheng Shi, Dongwang Yang, Kivanc Saglik, Ady Suwardi, Qian Li, Jing-Feng Li, Vinayak P. Dravid, Qingyu Yan, Mercouri G. Kanatzidis","doi":"10.1021/acs.chemmater.4c02649","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02649","url":null,"abstract":"Layered compounds have garnered widespread interest owing to their nontrivial physical properties, particularly their potential as thermoelectric materials. We systematically investigated PbBi₂Te₄, a compound derived from Bi₂Te₃ and PbTe. Synchrotron X-ray diffraction and transmission electron microscopy revealed that PbBi₂Te₄ adopts and maintains the <i>R</i>3̅<i>m</i> phase from 300 to 723 K, without any phase transition. Moreover, neutron pair distribution function analysis confirmed that the short-range local structure was consistent with the high-symmetry <i>R</i>3̅<i>m</i> structure. PbBi₂Te₄ exhibits a negative Seebeck coefficient, indicating electron-dominated transport. It has a low lattice thermal conductivity (ca. 0.6 Wm^–1K^–1) and a ZT value of 0.4 at 573 K. The effects of GeBi₂Te₄ alloying in PbBi₂Te₄ (Pb_1–<i>x</i>Ge_<i>x</i>Bi₂Te₄, where <i>x</i> ranges from 0.0 to 0.6) were also investigated. Due to alloying-induced point defect scattering and the off-centering effects of Ge²⁺, the room-temperature lattice thermal conductivity decreased to 0.55 Wm^–1K^–1 when <i>x</i> = 0.5. Combined with a maintained weighted mobility (ca. 60 cm²V^–1s^–2), the room-temperature ZT increased to 0.28. This value could further increase to 0.65 with a reduction in lattice thermal conductivity to its lower-limit value. A high ZT of 1.0 is also predicted for pristine PbBi₂Te₄ at 473 K, demonstrating its potential as a near-room-temperature thermoelectric system.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536542","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}

{"title":"Onset Reaction Mechanism of Cr and S Poisoning on Perovskite Oxide Surfaces","authors":"Mengren Bill Liu, Bilge Yildiz","doi":"10.1021/acs.chemmater.4c01936","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01936","url":null,"abstract":"Perovskite oxides serve as oxygen electrode materials in solid oxide fuel and electrolysis cells. These compounds are susceptible to poisoning by volatile chromium and sulfur species in the gas environment. The reaction mechanism of chromium and sulfur poisoning on perovskite oxide surfaces as a function of surface chemistry has not been resolved to date. Understanding the role of different surface chemistries in this degradation mechanism can help to guide the engineering of more stable surfaces. In this study, we take a state-of-the-art perovskite oxide (ABO₃), La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF), as a model oxygen electrode material. We investigate the onset of poisoning reactions by CrO₃ and SO₂, and their activity on different surface terminations of LSCF by density functional theory (DFT) calculations and <i>ab initio</i> molecular dynamics (AIMD) simulations. We find that both CrO₃ and SO₂ molecules bind more strongly onto the AO-terminated surfaces than do the BO₂ surfaces. AO-terminated LSCF surfaces, especially the Sr sites, result in more strongly adsorbed species with reduced mobility at the surface. The adsorption of CrO₃ and SO₂ on Sr sites of an AO-terminated LSCF surface forms atomic coordinations similar to SrCrO₄ and SrSO₄, thereby serving as nucleation sites for the formation of these secondary phases. We find two physical traits, surface oxygen Bader charge and subsurface oxygen 2p-band center, that correlate with the distinctly different adsorption energies of these species on the AO- and BO₂-terminated surfaces. This indicates that the electrostatic interaction and charge transfer between the adsorbate and the surface play a major role in the onset of these poisoning reactions on perovskite oxides. The results reveal the role of surface chemistry in affecting the thermodynamics and the kinetics of CrO₃ and SO₂ reactions at perovskite oxide surfaces and inform effective strategies for mitigation.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536627","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}

{"title":"Designing Particle Morphologies for Materials with Solid Transport Limitations: A Case Study of Lithium and Manganese Rich Cathode Oxides","authors":"Deepti Tewari,&nbsp;Arturo Gutierrez,&nbsp;Jason Croy and Venkat Srinivasan*,&nbsp;","doi":"10.1021/acs.chemmater.3c0241110.1021/acs.chemmater.3c02411","DOIUrl":"https://doi.org/10.1021/acs.chemmater.3c02411https://doi.org/10.1021/acs.chemmater.3c02411","url":null,"abstract":"<p >A lithium and manganese rich nickel–manganese–cobalt oxide (LMR-NMC) cathode is a promising candidate for next-generation batteries due to its high specific capacity, low cost, and low cobalt content. However, the material suffers from poor rate capability due to the diffusion limitations of lithium in the cathode particles. Understanding the material performance requires careful control of the morphology of the cathode particles, taking into account the primary and agglomerated diffusion pathways and the presence of pores, some of which could be closed from electrolyte infiltration. In this study, we use a microstructure-based mathematical model combined with experimental data to understand the role of the complex cathode particle morphology in the rate performance of the material. Scanning electron microscopy images of cathodes made under different synthesis conditions, which results in different agglomerate morphologies, serve as the input into the mathematical model. The model is then compared to rate data to understand the controlling parameters. The presence of intra-agglomerate closed pores results in a large agglomerate diffusion length in comparison to the ideal condition, where the primary particles are agglomerated in an open and dispersed manner such that the entire interfacial area is available for electrochemical reaction. Smaller primary and agglomerate diffusion lengths result in better electrochemical performance. This points us toward designing the morphology of the cathode particles to compensate for the diffusion limitation of LMR-NMC while maximizing the density.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609130","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}

{"title":"Mitigating Calendar Aging in Si-NMC Batteries with Advanced Dual-Salt Glyme Electrolytes","authors":"Guang Yang*,&nbsp;Katie Browning,&nbsp;Harry M Meyer III,&nbsp;Yuanshun Li,&nbsp;Nathan R. Neale,&nbsp;Gabriel M. Veith and Jagjit Nanda*,&nbsp;","doi":"10.1021/acs.chemmater.4c0097110.1021/acs.chemmater.4c00971","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00971https://doi.org/10.1021/acs.chemmater.4c00971","url":null,"abstract":"<p >In addressing the critical challenge of calendar aging in silicon (Si)-based lithium-ion batteries, this study introduces a groundbreaking strategy utilizing glyme-type dual-salt electrolytes (lithium bis(trifluoromethanesulfonyl)imide [LiTFSI] and lithium difluoro(oxalato)borate [LiDFOB]). These electrolytes are demonstrated to significantly mitigate parasitic reactions and capacity loss in Si-NMC (lithium nickel manganese cobalt oxide) full cells, especially when compared with traditional carbonate-based electrolytes. Our exhaustive mechanistic analysis reveals that such electrolytes not only preserve the integrity of the Si anode but also improve the cathode/electrolyte interphases (CEI) through the formation of a conformal coating on the high-voltage cathode surface. This dual-salt approach, enhanced by the addition of a phosphate additive, effectively decelerates calendar aging, marking a substantial advance in the quest for durable and reliable Si-based energy storage technologies. The findings underscore the vital role of electrolyte composition in extending the calendar life of Si batteries, offering an alternative avenue toward maximizing the performance and longevity of next-generation Li–Si batteries.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609129","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}

{"title":"Relating Local Structure to Thermoelectric Properties in Pb1–xGexBi2Te4","authors":"Jinfeng Dong,&nbsp;Yukun Liu,&nbsp;Jue Liu,&nbsp;Lei Hu,&nbsp;Yilin Jiang,&nbsp;Xian Yi Tan,&nbsp;Yuansheng Shi,&nbsp;Dongwang Yang,&nbsp;Kivanc Saglik,&nbsp;Ady Suwardi,&nbsp;Qian Li,&nbsp;Jing-Feng Li,&nbsp;Vinayak P. Dravid,&nbsp;Qingyu Yan* and Mercouri G. Kanatzidis*,&nbsp;","doi":"10.1021/acs.chemmater.4c0264910.1021/acs.chemmater.4c02649","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02649https://doi.org/10.1021/acs.chemmater.4c02649","url":null,"abstract":"<p >Layered compounds have garnered widespread interest owing to their nontrivial physical properties, particularly their potential as thermoelectric materials. We systematically investigated PbBi₂Te₄, a compound derived from Bi₂Te₃ and PbTe. Synchrotron X-ray diffraction and transmission electron microscopy revealed that PbBi₂Te₄ adopts and maintains the <i>R</i>3̅<i>m</i> phase from 300 to 723 K, without any phase transition. Moreover, neutron pair distribution function analysis confirmed that the short-range local structure was consistent with the high-symmetry <i>R</i>3̅<i>m</i> structure. PbBi₂Te₄ exhibits a negative Seebeck coefficient, indicating electron-dominated transport. It has a low lattice thermal conductivity (ca. 0.6 Wm^–1K^–1) and a ZT value of 0.4 at 573 K. The effects of GeBi₂Te₄ alloying in PbBi₂Te₄ (Pb_1–<i>x</i>Ge_<i>x</i>Bi₂Te₄, where <i>x</i> ranges from 0.0 to 0.6) were also investigated. Due to alloying-induced point defect scattering and the off-centering effects of Ge²⁺, the room-temperature lattice thermal conductivity decreased to 0.55 Wm^–1K^–1 when <i>x</i> = 0.5. Combined with a maintained weighted mobility (ca. 60 cm²V^–1s^–2), the room-temperature ZT increased to 0.28. This value could further increase to 0.65 with a reduction in lattice thermal conductivity to its lower-limit value. A high ZT of 1.0 is also predicted for pristine PbBi₂Te₄ at 473 K, demonstrating its potential as a near-room-temperature thermoelectric system.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609171","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}

{"title":"Designing Particle Morphologies for Materials with Solid Transport Limitations: A Case Study of Lithium and Manganese Rich Cathode Oxides","authors":"Deepti Tewari, Arturo Gutierrez, Jason Croy, Venkat Srinivasan","doi":"10.1021/acs.chemmater.3c02411","DOIUrl":"https://doi.org/10.1021/acs.chemmater.3c02411","url":null,"abstract":"A lithium and manganese rich nickel–manganese–cobalt oxide (LMR-NMC) cathode is a promising candidate for next-generation batteries due to its high specific capacity, low cost, and low cobalt content. However, the material suffers from poor rate capability due to the diffusion limitations of lithium in the cathode particles. Understanding the material performance requires careful control of the morphology of the cathode particles, taking into account the primary and agglomerated diffusion pathways and the presence of pores, some of which could be closed from electrolyte infiltration. In this study, we use a microstructure-based mathematical model combined with experimental data to understand the role of the complex cathode particle morphology in the rate performance of the material. Scanning electron microscopy images of cathodes made under different synthesis conditions, which results in different agglomerate morphologies, serve as the input into the mathematical model. The model is then compared to rate data to understand the controlling parameters. The presence of intra-agglomerate closed pores results in a large agglomerate diffusion length in comparison to the ideal condition, where the primary particles are agglomerated in an open and dispersed manner such that the entire interfacial area is available for electrochemical reaction. Smaller primary and agglomerate diffusion lengths result in better electrochemical performance. This points us toward designing the morphology of the cathode particles to compensate for the diffusion limitation of LMR-NMC while maximizing the density.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536671","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}