Rare Metals最新文献_第2页

Recent fluorination strategies in solid electrolytes for high-voltage solid-state lithium-ion batteries 高压固态锂离子电池固体电解质氟化策略研究进展

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-07 DOI: 10.1007/s12598-025-03244-8

An-Chun Tang, Er-Hai Hu, Bei-Er Jia, Chu-Bin Wan, Zi-Yue Wen, Shuen Tso, Xin Ju, Qing-Yu Yan

{"title":"Recent fluorination strategies in solid electrolytes for high-voltage solid-state lithium-ion batteries","authors":"An-Chun Tang, Er-Hai Hu, Bei-Er Jia, Chu-Bin Wan, Zi-Yue Wen, Shuen Tso, Xin Ju, Qing-Yu Yan","doi":"10.1007/s12598-025-03244-8","DOIUrl":"10.1007/s12598-025-03244-8","url":null,"abstract":"<div><p>High-voltage solid-state lithium-ion batteries (SSLIBs) have attracted considerable research attention in recent years due to their high-energy-density and superior safety characteristics. However, the integration of high-voltage cathodes with solid electrolytes (SEs) presents multiple challenges, including the formation of high-impedance layers from spontaneous chemical reactions, electrochemical instability, insufficient interfacial contact, and lattice expansion. These issues significantly impair battery performance and potentially lead to battery failure, thus impeding the commercialization of high-voltage SSLIBs. The incorporation of fluorides, known for their robust bond strength and high free energy of formation, has emerged as an effective strategy to address these challenges. Fluorinated electrolytes and electrode/electrolyte interfaces have been demonstrated to significantly influence the reaction reversibility/kinetics, safety, and stability of rechargeable batteries, particularly under high voltage. This review summarizes recent advancements in fluorination treatment for high-voltage SEs, focusing on solid polymer electrolytes (SPEs), inorganic solid electrolytes (ISEs), and composite solid electrolytes (CSEs), along with the performance enhancements these strategies afford. This review aims to provide a comprehensive understanding of the structure–property relationships, the characteristics of fluorinated interfaces, and the application of fluorinated SEs in high-voltage SSLIBs. Further, the impacts of residual moisture and the challenges of fluorinated SEs are discussed. Finally, the review explores potential future directions for the development of fluorinated SSLIBs.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 4","pages":"2268 - 2293"},"PeriodicalIF":9.6,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786435","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A crystalline Sm(III)-containing antimonotungstate with efficient catalytic activity in three-component reaction for isoindolinones synthesis 含Sm（III）的反单钨酸盐晶体在三组分反应合成异吲哚酮中具有高效的催化活性

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-07 DOI: 10.1007/s12598-024-03179-6

Hao-Qi Liu, Jia-Wei Cao, Wei Tang, Zhou-Fu Lin, Ke Li, Wei-Jian Xu, Zhi-Bin Zhang, Yu-Feng Liu, Guo-Ping Yang

{"title":"A crystalline Sm(III)-containing antimonotungstate with efficient catalytic activity in three-component reaction for isoindolinones synthesis","authors":"Hao-Qi Liu, Jia-Wei Cao, Wei Tang, Zhou-Fu Lin, Ke Li, Wei-Jian Xu, Zhi-Bin Zhang, Yu-Feng Liu, Guo-Ping Yang","doi":"10.1007/s12598-024-03179-6","DOIUrl":"10.1007/s12598-024-03179-6","url":null,"abstract":"<div><p>The development of the three-component catalytic system for constructing isoindolinones from simple feedstocks is both significant and challenging. In this study, a unique tartrate-linked dimeric samarium-antimonotungstate [Sm<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>(tar)(Sb<sub>2</sub>W<sub>21</sub>O<sub>72</sub>)]<sub>2</sub><sup>20−</sup> (<b>Sm</b><sub><b>4</b></sub><b>tar</b><sub><b>2</b></sub>, H<sub>4</sub>tar = tartaric acid) was synthesized via a one-step method at room temperature using an acetate buffer solution. The dimeric polyanion of <b>Sm</b><sub><b>4</b></sub><b>tar</b><sub><b>2</b></sub> shows a centrosymmetric structure with a parallelogram-like arrangement and comprises two enantiomeric {Sm<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>(Sb<sub>2</sub>W<sub>21</sub>O<sub>72</sub>)} moieties connected by two enantiomeric tar ligands. <b>Sm</b><sub><b>4</b></sub><b>tar</b><sub><b>2</b></sub> demonstrates efficient catalytic activity in the three-component reaction involving 2-acylbenzoic acids, primary amines, and phosphine oxides to form 3,3-disubstituted isoindolinones. The advantages of this catalytic system include simple feedstocks, green and reusable catalyst, and operational simplicity with water as the sole by-product. This finding enables an effective molecular fragment assembly strategy for synthesizing isoindolinone drug precursor skeletons.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3995 - 4002"},"PeriodicalIF":9.6,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Monoatomic metalloporphyrinoid catalysts for efficient oxygen reduction 高效氧还原的单原子金属卟啉类催化剂

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-07 DOI: 10.1007/s12598-024-03151-4

Ying Yao, Xiao-Ting Chen, Xinyuan Zhang, Shangbin Jin, Zhihong Tian, Guoliang Li, Li-Ming Yang

{"title":"Monoatomic metalloporphyrinoid catalysts for efficient oxygen reduction","authors":"Ying Yao, Xiao-Ting Chen, Xinyuan Zhang, Shangbin Jin, Zhihong Tian, Guoliang Li, Li-Ming Yang","doi":"10.1007/s12598-024-03151-4","DOIUrl":"10.1007/s12598-024-03151-4","url":null,"abstract":"<div><p>In this research, we present a comprehensive investigation on the catalyst screening, reaction mechanism, and electrocatalytic properties of two-dimensional monoatomic metalloporphyrinoid (MPor) materials for the oxygen reduction reaction (ORR). Through a combination of high-throughput screening, first-principles DFT calculations, and molecular dynamics simulations, we uncovered some promising oxygen reduction catalysts with limiting potentials of 0.60, 0.57, 0.56 V under acidic medium, and −0.17, −0.20, −0.21 V under basic medium for M = Co, Fe, Mn, respectively. Full reaction pathway search demonstrates that CoPor is a special case with 2e<sup>–</sup> and 4e<sup>–</sup> paths under both acidic and basic media, and for FePor and MnPor, only 4e<sup>–</sup> path is viable. In-depth analyses indicate that the adsorption free energy of OH and limiting potential shows the volcano curve relationship, which can guide the design and optimization of the ORR catalysts. The crystal orbital Hamiltonian population (COHP) between M and O in O<sub>2</sub>-MPor can well explain why only CoPor has a 2e<sup>–</sup> path, while other metals do not, because the Co–O bond is much weaker compared to other M–O bonds. Our research will shed some insights on designing efficient ORR catalysts, and stimulate the experimental efforts in this direction.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3920 - 3933"},"PeriodicalIF":9.6,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tailoring L21 strengthening in lightweight AlFeNiTiV complex concentrated alloys for elevated-temperature applications 定制用于高温应用的轻质AlFeNiTiV复杂浓缩合金的L21强化

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-07 DOI: 10.1007/s12598-025-03241-x

Hong-Mei Chen, Ze-Yun Cai, Jie Chen, Jun-Zhi Li, Tao Hong, Wei-Zong Bao, Guo-Qiang Xie

{"title":"Tailoring L21 strengthening in lightweight AlFeNiTiV complex concentrated alloys for elevated-temperature applications","authors":"Hong-Mei Chen, Ze-Yun Cai, Jie Chen, Jun-Zhi Li, Tao Hong, Wei-Zong Bao, Guo-Qiang Xie","doi":"10.1007/s12598-025-03241-x","DOIUrl":"10.1007/s12598-025-03241-x","url":null,"abstract":"<div><p>Complex concentrated alloys (CCAs) containing the L2<sub>1</sub> phase are recognized for their exceptional strength and thermal stability, positioning them as strong candidates for transformative applications in aerospace, energy, and structural sectors. This investigation delves into the AlFe<sub><i>x</i></sub>NiTiV<sub>40−<i>x</i></sub> (<i>x</i> = 0, 10, 20, 30, 35, 40; at%) CCAs, aiming to unlock the synergistic potential of BCC and L2<sub>1</sub> phases. By conducting an in-depth analysis of microstructure, phase behavior, and mechanical properties, the intricate relationships between chemistry, structure, and properties are illuminated within this alloy system. The Al<sub>15</sub>Fe<sub>35</sub>Ni<sub>30</sub>Ti<sub>15</sub>V<sub>5</sub> alloy demonstrates remarkable mechanical properties, achieving a yield strength of 2140.9 MPa and ultimate compressive strength of 2699.7 MPa, primarily through solid solution strengthening and precipitation hardening. Notably, its low lattice mismatches and nanoprecipitate strengthening yield an impressive specific yield strength at 600 °C (245.2 MPa(g·cm<sup>−3</sup>)<sup>−1</sup>). Phase modulation achieves the synergistic optimization of specific strengths at both room and high temperatures in CCAs containing the L2<sub>1</sub> phase, opening new avenues for designing advanced lightweight and high strength alloys for elevated-temperature applications.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 5","pages":"3479 - 3495"},"PeriodicalIF":9.6,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861135","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

One-pot synthesis of MIL-68(In)-derived CdIn2S4/In2S3 tubular heterojunction for highly selective CO2 photoreduction 高选择性CO2光还原MIL-68（In）衍生CdIn2S4/In2S3管状异质结的一锅合成

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-06 DOI: 10.1007/s12598-024-03193-8

Dan-Dan Wang, Meng-Yang Xu, Zhao-Xin Lin, Jia-Hui Wu, Wei-Ting Yang, Hong-Ji Li, Zhong-Min Su

{"title":"One-pot synthesis of MIL-68(In)-derived CdIn2S4/In2S3 tubular heterojunction for highly selective CO2 photoreduction","authors":"Dan-Dan Wang, Meng-Yang Xu, Zhao-Xin Lin, Jia-Hui Wu, Wei-Ting Yang, Hong-Ji Li, Zhong-Min Su","doi":"10.1007/s12598-024-03193-8","DOIUrl":"10.1007/s12598-024-03193-8","url":null,"abstract":"<div><p>The goal of photocatalytic CO<sub>2</sub> reduction is to obtain a single energy-bearing product with high efficiency and stability. Consequently, constructing highly selective photocatalysts with enhanced surface and optoelectronic properties is crucial for achieving this objective. Here, we have developed a simple one-pot vulcanization method to synthesize a MIL-68(In)-derived CdIn<sub>2</sub>S<sub>4</sub>/In<sub>2</sub>S<sub>3</sub> heterojunction that exhibited stable and high selectivity. Multiple characterizations of the CdIn<sub>2</sub>S<sub>4</sub>/In<sub>2</sub>S<sub>3</sub> heterojunction revealed a hierarchical tubular structure with numerous surface reactive sites, a high visible-light utilization rate (<i>λ</i> < 600 nm), efficient charge separation, and a prolonged charge-carrier lifetime. Moreover, an S-scheme charge transfer mechanism, based on the interleaved band between the two components, improved the reduction capability of the electrons. Benefiting from the compositional and structural synergy, the yield CO by CdIn<sub>2</sub>S<sub>4</sub>/In<sub>2</sub>S<sub>3</sub>-250 (CI-250) reached 135.62 μmol·g<sup>−1</sup>·h<sup>−1</sup>, which was 49.32 times and 32.88 times higher than that of In<sub>2</sub>S<sub>3</sub> and CdIn<sub>2</sub>S<sub>4</sub>, respectively. The CdIn<sub>2</sub>S<sub>4</sub>/In<sub>2</sub>S<sub>3</sub> heterojunction exhibited a quantum efficiency of 4.23% with a CO selectivity of 71%. Four cycle tests confirmed the good stability and recyclability of the CI-250. This work provides a new approach for designing and preparing high-performance hollow MOFs-based photocatalysts for scalable and sustainable CO<sub>2</sub> reduction.</p></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3956 - 3969"},"PeriodicalIF":9.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The synergistic inhibition of the growth of intermetallic compounds at Sn-0.7Cu/Cu interface by Al and Pt Al和Pt对Sn-0.7Cu/Cu界面金属间化合物生长的协同抑制作用

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-06 DOI: 10.1007/s12598-024-03200-y

An-Cang Yang, Yao-Ping Lu, Bin Zhang, Yong-Hua Duan, Li-Shi Ma, Shan-Ju Zheng, Ming-Jun Peng, Meng-Nie Li, Zhi-Hang Xu

{"title":"The synergistic inhibition of the growth of intermetallic compounds at Sn-0.7Cu/Cu interface by Al and Pt","authors":"An-Cang Yang, Yao-Ping Lu, Bin Zhang, Yong-Hua Duan, Li-Shi Ma, Shan-Ju Zheng, Ming-Jun Peng, Meng-Nie Li, Zhi-Hang Xu","doi":"10.1007/s12598-024-03200-y","DOIUrl":"10.1007/s12598-024-03200-y","url":null,"abstract":"<div><p>The construction of intermetallic compounds (IMCs) connection layers with special compositions by adding small amounts of alloying elements has been proven to be an effective strategy for improving the reliability of electronic component interconnect. However, the synergistic effect mechanism of multi-component alloy compositions on the growth behavior of IMCs is not clear. Herein, we successfully prepared a new quaternary alloy solder with a composition of Sn-0.7Cu-0.175Pt-0.025Al (wt%) using the high-throughput screening (HTS) method. The results showed that it possesses excellent welding performance with an inhibition rate over 40% on the growth of IMCs layers. For Cu<sub>6</sub>Sn<sub>5</sub>, the co-doping of Al and Pt not only greatly improves its thermodynamic stability, but also effectively suppresses the phase transition. Meanwhile, the co-doping of Al and Pt also significantly delays the generation time of Kirkendall defects. The substitution sites of Al and Pt in Cu<sub>6</sub>Sn<sub>5</sub> have been explored using atomic resolution imaging and advanced data informatics, indicating that Al and Pt preferentially substitute Sn and Cu atoms, respectively, to generate (Cu, Pt)<sub>6</sub>(Sn, Al)<sub>5</sub>. A one-dimensional (1D) kinetic model of the IMCs layer growth at the Sn solder/Cu substrate interface was derived and validated, and the results showed that the error of the derived mathematical model is less than 5%. Finally, the synergistic mechanism of Al and Pt co-doping on the growth rate of Cu<sub>6</sub>Sn<sub>5</sub> was further elucidated. This work provides a feasible route for the design and development of multi-component alloy solders.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"4208 - 4225"},"PeriodicalIF":9.6,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938464","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multifunctional sulfonate additive induced CEI layer enables ultra-stable PEO based solid-state sodium batteries 多功能磺酸盐添加剂诱导的CEI层实现了超稳定的PEO基固态钠电池

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-05 DOI: 10.1007/s12598-024-03188-5

Jing-Chao Liu, Tao You, Yi-Fan Zhao, Feng-Quan Liu, Jie-Dong Li, Long-Long Wang, Chen Wang, Lin Li

{"title":"Multifunctional sulfonate additive induced CEI layer enables ultra-stable PEO based solid-state sodium batteries","authors":"Jing-Chao Liu, Tao You, Yi-Fan Zhao, Feng-Quan Liu, Jie-Dong Li, Long-Long Wang, Chen Wang, Lin Li","doi":"10.1007/s12598-024-03188-5","DOIUrl":"10.1007/s12598-024-03188-5","url":null,"abstract":"<div><p>Polyethylene oxide (PEO)-based solid polymer electrolytes are considered as promising material for solid-state sodium metallic batteries (SSMBs). However, their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries. Herein, a uniform, sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate (NaPVS). The 5 wt% NaPVS-Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP)|PEO-sodium hexauorophosphate (NaPF<sub>6</sub>)|Na battery shows a higher initial capacity of 111.2 mAh·g<sup>−1</sup> and an ultra-high capacity retention of 90.5% after 300 cycles. The 5 wt% NaPVS-Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>2</sub>F<sub>3</sub> (NVPF) |PEO-NaPF<sub>6</sub>|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh·g<sup>−1</sup> at 0.5C for 100 cycles with a capacity retention of 79%, which is much better than that of the pristine-NVPF (PR-NVPF)|PEO-NaPF<sub>6</sub>|Na battery (33.2%). The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery, thus bolstering its viability for high-energy applications. In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature. This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3817 - 3826"},"PeriodicalIF":9.6,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Molten salts assisted synthesis of single crystalline NCM811 with surface modification for high energy density lithium-ion batteries 熔盐辅助合成高能量密度锂离子电池用表面改性单晶NCM811

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-04 DOI: 10.1007/s12598-024-03199-2

Bi-Fu Sheng, Jun-Jie Lu, Zhe-Fei Sun, Min-Feng Chen, Min Xu, Han-Rui Zhao, Qing-Qing Zhou, Chu-Yang Li, Bin Wang, Qiao-Bao Zhang, Ji-Zhang Chen, Xiang Han

{"title":"Molten salts assisted synthesis of single crystalline NCM811 with surface modification for high energy density lithium-ion batteries","authors":"Bi-Fu Sheng, Jun-Jie Lu, Zhe-Fei Sun, Min-Feng Chen, Min Xu, Han-Rui Zhao, Qing-Qing Zhou, Chu-Yang Li, Bin Wang, Qiao-Bao Zhang, Ji-Zhang Chen, Xiang Han","doi":"10.1007/s12598-024-03199-2","DOIUrl":"10.1007/s12598-024-03199-2","url":null,"abstract":"<div><p>Single crystalline nickel rich Li [Ni<sub><i>x</i></sub>Co<sub><i>y</i></sub>Mn<sub>1-x–y</sub>]O<sub>2</sub> (SCNCM) layered oxide cathodes show higher ionic conductivity and better structure integrity than polycrystalline NCM (PCNCM) cathodes by eliminating grain boundaries. However, it remains challenges in the controlled synthesis process and restricted cycling stability of SCNCM. Herein, take single crystalline nickel rich Li [Ni<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>]O<sub>2</sub> (SC811) as an example, a dual molten salts (LiOH and Li<sub>2</sub>SO<sub>4</sub>) assisted secondary calcination method is proposed, for which LiOH salt improves primary crystal size and Li<sub>2</sub>SO<sub>4</sub> prevents the aggravation of NCM nanocrystals. To further reduce the interfacial side reactions, Mg-doping and B-coating surface modification was carried out, which effectively suppress anisotropic lattice changes and Li/Ni disorder. In addition, a thin and uniform H<sub>3</sub>BO<sub>3</sub> coating effectively prevents direct contact between the electrode and electrolyte, thus reducing harmful parasitic reactions. The single crystal structure engineering and surface modification strategy of oxide layered cathodes significantly improve the cycling stability of the modified SC811 cathode. For example, during a long-term cycling of 470 cycles, a high-capacity retention of 74.2% obtained at 1C rate. Our work provides a new strategy for engineering high energy nickel rich layered oxide NCM cathodes.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3749 - 3760"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Capacitance decay mechanism of vanadium nitride supercapacitor electrodes in KOH electrolytes 氢氧化钾电解液中氮化钒超级电容器电极的电容衰减机理

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-04 DOI: 10.1007/s12598-025-03245-7

Xiu-Li Li, Hao Song, Yong-Hui Zhang, Yu-Lei Ren, Qi-Fei Guo, Zi-Huan Tang, Zhuo Li, Biao Gao, Paul K. Chu, Kai-Fu Huo

{"title":"Capacitance decay mechanism of vanadium nitride supercapacitor electrodes in KOH electrolytes","authors":"Xiu-Li Li, Hao Song, Yong-Hui Zhang, Yu-Lei Ren, Qi-Fei Guo, Zi-Huan Tang, Zhuo Li, Biao Gao, Paul K. Chu, Kai-Fu Huo","doi":"10.1007/s12598-025-03245-7","DOIUrl":"10.1007/s12598-025-03245-7","url":null,"abstract":"<div><p>Vanadium nitride (VN) is a promising pseudocapacitive material due to the high theoretical capacity, rapid redox Faradaic kinetics, and appropriate potential window. Although VN shows large pseudocapacitance in alkaline electrolytes, the electrochemical instability and capacity degradation of VN electrode materials present significant challenges for practical applications. Herein, the capacitance decay mechanism of VN is investigated and a simple strategy to improve cycling stability of VN supercapacitor electrodes is proposed by introducing VO<sub>4</sub><sup>3−</sup> anion in KOH electrolytes. Our results show that the VN electrode is electrochemical stabilization between −1.0 and −0.4 V (vs. Hg/HgO reference electrode) in 1.0 M KOH electrolyte, but demonstrates irreversible oxidation and fast capacitance decay in the potential range of −0.4 to 0 V. In situ electrochemical measurements reveal that the capacitance decay of VN from −0.4 to 0 V is ascribed to the irreversible oxidation of vanadium (V) of N–V–O species by oxygen (O) of OH<sup>−</sup>. The as-generated oxidization species are subsequently dissolved into KOH electrolytes, thereby undermining the electrochemical stability of VN. However, this irreversible oxidation process could be hindered by introducing VO<sub>4</sub><sup>3−</sup> in KOH electrolytes. A high volumetric specific capacitance of 671.9 F·cm<sup>−3</sup> (1 A·cm<sup>−3</sup>) and excellent cycling stability (120.3% over 1000 cycles) are achieved for VN nanorod electrode in KOH electrolytes containing VO<sub>4</sub><sup>3−</sup>. This study not only elucidates the failure mechanism of VN supercapacitor electrodes in alkaline electrolytes, but also provides new insights into enhancing pseudocapacitive energy storage of VN-based electrode materials.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3909 - 3919"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Lithophilic alloy and 3D grid structure synergistically reinforce dendrite-free Li–Sn/Cu anode for ultra-long cycle life lithium metal battery 亲锂合金和三维网格结构协同增强了超长循环寿命锂金属电池无枝晶锂锡铜阳极

IF 9.6 1区材料科学

Rare Metals Pub Date : 2025-03-04 DOI: 10.1007/s12598-024-03102-z

Jie Liu, Hao Xu, Xin-Bin Li, He-Na Ming, Sheng-Long Shang, Shuai Liu

{"title":"Lithophilic alloy and 3D grid structure synergistically reinforce dendrite-free Li–Sn/Cu anode for ultra-long cycle life lithium metal battery","authors":"Jie Liu, Hao Xu, Xin-Bin Li, He-Na Ming, Sheng-Long Shang, Shuai Liu","doi":"10.1007/s12598-024-03102-z","DOIUrl":"10.1007/s12598-024-03102-z","url":null,"abstract":"<div><p>Lithium (Li) metal is considered the most promising anode material for the next generation of secondary batteries due to its high theoretical specific capacity and low potential. However, the application of Li anode in rechargeable Li metal batteries (LMBs) is hindered due to the short cycle life caused by uncontrolled dendrite growth. In this work, a dendrite-free anode (Li–Sn/Cu) is reinforced synergistically by lithophilic alloy, and a 3D grid structure is designed. Li<sup>+</sup> diffusion and uniform nucleation are effectively induced by the lithophilic alloy Li<sub>22</sub>Sn<sub>5</sub>. Moreover, homogeneous deposition of Li<sup>+</sup> is caused by the reversible gridded Li plating/stripping effect of Cu mesh. Furthermore, the local space electric field is redistributed throughout the 3D conductive network, whereby the tip effect is suppressed, thus inhibiting the growth of Li dendrites. Also, the volume expansion of the anode during cycling is eased by the 3D grid structure. The results show that the Li–Sn/Cu symmetric battery can stably cycle for more than 10,000 h at 2 mA·cm<sup>−2</sup> and 1 mAh·cm<sup>−2</sup> with a low overpotential. The capacity retention of the LiFePO<sub>4</sub> full battery remains above 90.7% after 1,000 cycles at 1C. This work provides a facile, low-cost, and effective strategy for obtaining Li metal batteries with ultra-long cycle life.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3735 - 3748"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0