Effect of alkali and alkali earth metals on reactions of stable free radicals during biomass pyrolysis: An in-situ EPR study

Ma, Liqun; Syed‐Hassan, Syed Shatir A.; Zhou, Jian; Deng, Wei; Xiong, Yimin; Wang, Xuepeng; Hu, Xun; Xu, Jun; Jiang, Long; Su, Sheng; Hu, Song; Wang, Yi; Xiang, Jun

doi:10.1016/j.fuproc.2023.107916

Cited by 17 publications

(1 citation statement)

References 52 publications

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“…The volatile content of biomass is generally higher than that of coal/petroleum coke. Biomass contains a significant amount of hydroxyl and carboxyl groups in cellulose and hemicellulose, which release OH and H radicals during pyrolysis/combustion (as shown in Figure 12) [67,68]. These radicals migrate to the surface of coal coke/petroleum coke, reducing the carbon structure density of coal coke/petroleum coke and thereby enhancing their subsequent reactivity [69,70].…”

Section: Non-catalytic Synergistic Mechanismmentioning

confidence: 99%

AAEM Species Migration/Transformation during Co-Combustion of Carbonaceous Feedstocks and Synergy Behavior on Co-Combustion Reactivity: A Critical Review

Jiao,

Tian,

et al. 2023

Energies

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Co-combustion is a crucial route for the high-efficiency utilization and clean conversion of different carbonaceous feedstocks (biomass, coal, petroleum coke, etc.). The migration and transformation of alkali and alkaline earth metals (AAEMs) are not only related to ash-related issues in actual application, but also directly affect the reaction behavior of binary particles during co-conversion. This review paper summarizes research progress in the detection methods (online and offline) and influencing factors (feedstock type, feedstock blending ratio, reaction temperature, reaction time) of AAEMs migration and transformation during the co-combustion of carbonaceous feedstocks. Furthermore, it provides a detailed summary of research progress on factors (feedstock blending ratio, heating rate, etc.) influencing the co-combustion reactivity of carbonaceous feedstocks, synergy behavior, and its mechanisms. The influence of feedstock type on AAEMs migration and transformation during co-combustion is mainly related to the composition categories, chemical forms and contents of intrinsic mineral in binary feedstocks. The increase in the combustion temperature will intensify the release of inherent AAEMs in carbonaceous feedstocks, and promote AAEM deactivation. For high K and Cl-containing biomass, a higher biomass proportion in blends would result in more AAEMs release during the co-combustion process. Conversely, an increase in coal proportion in blends will directly favor the reduction or inhibition of AAEMs release. Synergy behavior during co-pyrolysis and subsequent char co-combustion is usually presented as an inhibition effect and an synergistic effect, respectively. The synergistic mechanisms of carbonaceous feedstock co-combustion reactions can be divided into two categories: non-catalytic synergistic mechanisms related to the excitation and migration of biomass-based free radicals and catalytic synergistic mechanisms related to biomass-based AAEMs catalysis. Additionally, future research prospects are also proposed based on the systematic review.

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Section: Non-catalytic Synergistic Mechanismmentioning

confidence: 99%

AAEM Species Migration/Transformation during Co-Combustion of Carbonaceous Feedstocks and Synergy Behavior on Co-Combustion Reactivity: A Critical Review

Jiao,

Tian,

et al. 2023

Energies

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Tailored Regulation of Graphite Microcrystals via Tandem Catalytic Carbonization for Enhanced Electrochemical Performance of Hard Carbon in the Low‐Voltage Plateau

Zhou,

Zhang,

et al. 2024

Adv Funct Materials

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The sodium storage behavior in the plateau region is crucial for determining the capacity and rate capability of hard carbon (HC) anodes in sodium‐ion batteries (SIBs). Key structural features for achieving excellent plateau performance include extended graphite domains and increased interlayer spacing. However, synchronously optimizing these two structures is challenging due to their inherent trade‐off. Herein, a tandem catalytic carbonization strategy is developed to construct HC with long graphite domains (La = 5.31 nm) and large interlayer spacing (d002 = 0.389 nm) simultaneously. Comprehensive in situ and ex situ tests unravel the catalytic selective bond breaking and aromatization effects of ZnCl2, the catalytic graphitic layers enlargement and occupied effects of formed ZnO and Zn in different temperature stages, leading to the formation of the unique structure. The optimal HCZ‐0.1 exhibits a high reversible capacity of 346.9 mAh g−1 with a plateau capacity of 249.4 mAh g−1, and high‐rate performance (114.0 mAh g−1 at 5 A g−1). In addition, the sodium storage mechanism and origin of enhanced Na+ kinetics of HCZ‐0.1 are also revealed. This work offers a precise method to engineer the graphite microcrystal structure in HC for superior sodium storage in the plateau region.

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Releasing Free Radicals in Precursor Triggers the Formation of Closed Pores in Hard Carbon for Sodium‐Ion Batteries

Wang,

Yi,

Xie

et al. 2024

Advanced Materials

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Increasing closed pore volume in hard carbon is considered to be the most effective way to enhance the electrochemical performance in sodium‐ion batteries. However, there lack of systematic insights into the formation mechanisms of closed pores at molecular level. In this study, a regulation strategy of closed pores via adjustment of the content of free radicals is reported. Sufficient free radicals are exposed by part delignification of bamboo, which is related to the formation of well‐developed carbon layers and rich closed pores. In addition, excessive free radicals from nearly total delignification lead to more reactive sites during pyrolysis, which competes for limited precursor debris to form smaller microcrystals and therefore compact the material. The optimal sample delivers large closed pore volume of 0.203 cm3 g−1, which leads to high reversible capacity of 350 mAh g−1 at 20 mA g−1 and enhanced Na+ transfer kinetics. This work provides insights into the formation mechanisms of closed pores at molecular level, enabling rational design of hard carbon pore structures.This article is protected by copyright. All rights reserved

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Effect of alkali and alkali earth metals on reactions of stable free radicals during biomass pyrolysis: An in-situ EPR study

Cited by 17 publications

References 52 publications

AAEM Species Migration/Transformation during Co-Combustion of Carbonaceous Feedstocks and Synergy Behavior on Co-Combustion Reactivity: A Critical Review

AAEM Species Migration/Transformation during Co-Combustion of Carbonaceous Feedstocks and Synergy Behavior on Co-Combustion Reactivity: A Critical Review

Tailored Regulation of Graphite Microcrystals via Tandem Catalytic Carbonization for Enhanced Electrochemical Performance of Hard Carbon in the Low‐Voltage Plateau

Releasing Free Radicals in Precursor Triggers the Formation of Closed Pores in Hard Carbon for Sodium‐Ion Batteries

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