Molecular Engineered Safer Organic Battery through the Incorporation of Flame Retarding Organophosphonate Moiety

Lee, Hyun Ho; Nam, Dongsik; Kim, Choon-Ki; Kim, Koeun; Lee, Yong-Won; Ahn, Young Jun; Lee, Jae Bin; Kwak, Ja Hun; Choe, Wonyoung; Choi, Nam‐Soon; Hong, Sung You

doi:10.1021/acsami.7b19349

Cited by 5 publications

(2 citation statements)

References 47 publications

(77 reference statements)

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“…Complex versions of these compounds worthy of further discussion are metal–organic frameworks (MOFs). Very recently, MOFs have been the focus of extensive investigation as anode materials due to unique properties such as controlled pore size, redox activity, structural diversity, and well-established postprocess method. − In analogy to transition metal oxides, the conversion reaction occurs in MOFs by inducing the reduction of transition metal and the formation of Li-containing organic species as final products. ,, In 2015, however, Lee et al discovered that further charge was passed after completion of the conversion reaction at nickel(II) terephthalate (NiTP), delivering a high capacity of ∼1100 mAh g –1 . This value is remarkably higher than the theoretical capacity of ∼240 mAh g –1 based on an expected two-electron conversion reaction.…”

Section: Phenomena Proposed To Give Rise To Abnormal Reversible Capacitymentioning

confidence: 99%

Exploring Anomalous Charge Storage in Anode Materials for Next-Generation Li Rechargeable Batteries

et al. 2020

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To advance current Li rechargeable batteries further, tremendous emphasis has been made on the development of anode materials with higher capacities than the widely commercialized graphite. Some of these anode materials exhibit capacities above the theoretical value predicted based on conventional mechanisms of Li storage, namely insertion, alloying, and conversion. In addition, in contrast to conventional observations of loss upon cycling, the capacity has been found to increase during repeated cycling in a significant number of cases. As the internal environment in the battery is very complicated and continuously changing, these abnormal charge storage behaviors are caused by diverse reactions. In this review, we will introduce our current understanding of reported reactions accounting for the extra capacity. It includes formation/decomposition of electrolyte-derived surface layer, the possibility of additional charge storage at sharp interfaces between electronic and ionic sinks, redox reactions of Li-containing species, unconventional activity of structural defects, and metallic-cluster like Li storage. We will also discuss how the changes in the anode can induce capacity increase upon cycling. With this knowledge, new insights into possible strategies to effectively and sustainably utilize these abnormal charge storage mechanisms to produce vertical leaps in performance of anode materials will be laid out.

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Section: Phenomena Proposed To Give Rise To Abnormal Reversible Capacitymentioning

confidence: 99%

Exploring Anomalous Charge Storage in Anode Materials for Next-Generation Li Rechargeable Batteries

et al. 2020

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“…This approach intrinsically circumvents the dissolution penalty by adopting salt structures . In addition, several research groups have reported that binary metal–organic complexes can be applied as high-capacity electrode materials for lithium-ion or sodium-ion batteries, by co-utilizing transition-metal redox couples and redox-active organic ligands. ,− However, the role of nanosized metallic clusters embedded in an organic ligand matrix toward reversible electrochemical (de)lithiation has remained unclear to date. Herein, we unravel the metal-dependent solid-state redox reversibility of coordination polymer frameworks through the comprehensive screening of the first-row transition-metal (3d-metal) cations and inverse-Würster-type molecules.…”

Section: Introductionmentioning

confidence: 99%

Coordination Polymers for High-Capacity Li-Ion Batteries: Metal-Dependent Solid-State Reversibility

Lee

Park

et al. 2018

ACS Appl. Mater. Interfaces

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Electrode materials exploiting multielectron-transfer processes are essential components for large-scale energy storage systems. Organic-based electrode materials undergoing distinct molecular redox transformations can intrinsically circumvent the structural instability issue of conventional inorganic-based host materials associated with lattice volume expansion and pulverization. Yet, the fundamental mechanistic understanding of metal-organic coordination polymers toward the reversible electrochemical processes is still lacking. Herein, we demonstrate that metal-dependent spatial proximity and binding affinity play a critical role in the reversible redox processes, as verified by combined C solid-state NMR, X-ray absorption spectroscopy, and transmission electron microscopy. During the electrochemical lithiation, in situ generated metallic nanoparticles dispersed in the organic matrix generate electrically conductive paths, synergistically aiding subsequent multielectron transfer to π-conjugated ligands. Comprehensive screening on 3d-metal-organic coordination polymers leads to a high-capacity electrode material, cobalt-2,5-thiophenedicarboxylate, which delivers a stable specific capacity of ∼1100 mA h g after 100 cycles.

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Thermal‐Responsive and Fire‐Resistant Materials for High‐Safety Lithium‐Ion Batteries

Li¹,

Wang²,

Zhu³

et al. 2021

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is due to their high specific energy density, long cycling lifespan, and portability. [7][8][9][10] Currently, state-of-the-art LIBs (without packaging materials) can achieve a high specific energy density of ≈250 Wh kg −1 . Next-generation LiS and Li-air systems can further increase the battery energy densities beyond 600 and 900 Wh kg −1 , respectively. [11,12] With the energy density increasing, more attention should be paid to the safety of LIBs, as the chemical energy can be abruptly released in the forms of fires and explosions once the battery is not properly handled. [13][14][15][16][17][18] Currently, the safety issues are also regarded as one of the significant challenging barriers that limit the widespread adoption of LIBs for modern electrical vehicles. [19,20] A typical lithium-ion cell is composed of an anode, a cathode, liquid electrolytes, and a separator, [1] as illustrated in Figure 1A. The active materials are mixed with polymer binders and conductive carbon additives and then coated onto aluminum and copper foil current collectors to make the cathode and anode, respectively. Layered, spinel, and polyanion-type lithium-transitional metal oxides and phosphates including LiCoO 2 , LiMn 2 O 4 , LiFePO 4 , and their derivatives (LiMn x Ni y O 4 , LiNi 1−y−z Mn y Co z O 2 , etc.) have been used as cathode materials for LIBs due to their high lithium intercalation capacity and potential. [5] Graphite is the most frequently used anode material for LIBs because of its high abundance, low cost, and good reversibility. [21,22] Other materials such as carbon, [23] silicon, [24][25][26] and transition metal oxides-based materials with various structures and compositions have been studied as anodes for LIBs. [27][28][29] Some of them show promising capacity but there are still many challenges in scaled-up productions and practical applications. [30,31] For details of studies on structural design and performance optimization of the LIB anode materials, readers may refer to a comprehensive review published recently. [32] The liquid electrolyte provides a medium for fast Li + ions transport. [33,34] The separator is applied to prevent direct contact between the cathode and anode while permitting the ion transfer. [35][36][37][38] During the charging process, Li + ions are deintercalated from the cathode host and insert into the anode. On discharge, Li + ions migrate reversely from the above process, and electrons pass through the external circuit, supplying electricity [1] (Figure 1A). A passivation layer of solid-electrolyte-interphase (SEI) is generated on the anode surface during the initial few charging cycles, As one of the most efficient electrochemical energy storage devices, the energy density of lithium-ion batteries (LIBs) has been extensively improved in the past several decades. However, with increased energy density, the safety risk of LIBs becomes higher too. The frequently occurred battery accidents worldwide remind us that safeness is a crucial requirement for LIBs, especially in environments ...

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Molecular Engineered Safer Organic Battery through the Incorporation of Flame Retarding Organophosphonate Moiety

Cited by 5 publications

References 47 publications

Exploring Anomalous Charge Storage in Anode Materials for Next-Generation Li Rechargeable Batteries

Exploring Anomalous Charge Storage in Anode Materials for Next-Generation Li Rechargeable Batteries

Coordination Polymers for High-Capacity Li-Ion Batteries: Metal-Dependent Solid-State Reversibility

Thermal‐Responsive and Fire‐Resistant Materials for High‐Safety Lithium‐Ion Batteries

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