Alloying Motif Confined in Intercalative Frameworks toward Rapid Li‐Ion Storage

Abstract

High‐capacity alloying‐type anodes suffer poor rate capability due to their great volume expansion, while high‐rate intercalation‐type anodes are troubled with low theoretical capacity. Herein, a novel mechanism of alloying in the intercalative frameworks is proposed to confer both high‐capacity and high‐rate performances on anodes. Taking the indium‐vanadium oxide (IVO) as a typical system, alloying‐typed In is dispersed in the stable intercalative V 2 O 3 to form a solid solution. The alloying‐typed In element provides high lithium storage capacity, while the robust, Li‐conductive V−O frameworks effectively alleviate the volume expansion and aggregation of In. Benefiting from the above merits, the anode exhibits a high specific capacity of 1364 mA h g −1 at 1 A g −1 and an extraordinary cyclic performance of 814 mA h g −1 at 10 A g −1 after 600 cycles (124.9 mA h g −1 after 10 000 cycles at 50 A g −1 ). The superior electrochemical rate capability of (In,V) 2 O 3 solid solution anode rivals that of the reported alloying anode materials. This strategy can be extended for fabricating other alloying/intercalation hybrid anodes, such as (Sn,V)O 2 and (Sn,Ti)O 2 , which demonstrates the universality of confining alloying motifs in intercalative frameworks for rapid and high‐capacity lithium storage.

Anionic Activity in Fast-Charging Batteries: Recent Advances, Prospects, and Challenges

“…To enhance the reversibility of alloying-type anodes, a bimetal-oxide model that restricts alloying motifs in intercalative frameworks was devised to regulate the M−O band covalency for high-rate energy storage. 26 Recently, the indium−vanadium oxide, (In,V) 2 O 3 , was developed for highrate Li storage by dispersing alloying M2-type indium in the intercalative rigid M1−X, V 2 O 3 framework to produce a solidsolution oxide. 26 Such new anode structures can maintain high capacity derived from alloying indium species and high structural stability by using an intercalative V−O matrix, exhibiting an exceptional cyclic performance (125 mAh g −1 at 50 A g −1 over 10,000 cycles).…”

“…26 Recently, the indium−vanadium oxide, (In,V) 2 O 3 , was developed for highrate Li storage by dispersing alloying M2-type indium in the intercalative rigid M1−X, V 2 O 3 framework to produce a solidsolution oxide. 26 Such new anode structures can maintain high capacity derived from alloying indium species and high structural stability by using an intercalative V−O matrix, exhibiting an exceptional cyclic performance (125 mAh g −1 at 50 A g −1 over 10,000 cycles). The density of states calculation revealed that (In,V) 2 O 3 is metallic in contrast to the semiconducting In 2 O 3 (Figure 4e).…”

“…As fast-charging and large-capacity rechargeable batteries have become increasingly significant components of electric vehicles, tremendous efforts have been devoted to synergistically coupling alloying-type materials with enhanced pseudocapacitive behavior and high reaction reversibility. ,− …”

“…To enhance the reversibility of alloying-type anodes, a bimetal-oxide model that restricts alloying motifs in intercalative frameworks was devised to regulate the M–O band covalency for high-rate energy storage . Recently, the indium–vanadium oxide, (In,V) 2 O 3 , was developed for high-rate Li storage by dispersing alloying M2-type indium in the intercalative rigid M1–X, V 2 O 3 framework to produce a solid-solution oxide .…”

“…19,23,24 Theoretically, the storage properties of conversion, alloying, and intercalation-type electrode materials are inextricably linked to the variation of metal−anion bonding strengths. 25,26 Upon discharge in LIBs, the intercalative electrodes with the rigid framework are accompanied by curtailed metal−anion bonding strengths as Li + is inserted into the interstitial sites. However, the conversion/alloying-type electrodes often undergo breakage of metal−anion bonds (Figure 1).…”