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石墨炔在水系离子电池中的研究进展

徐显敏 封文聪 任静柯 罗雯

徐显敏, 封文聪, 任静柯, 罗雯. 石墨炔在水系离子电池中的研究进展. 新型炭材料(中英文). doi: 10.1016/S1872-5805(24)60852-8
引用本文: 徐显敏, 封文聪, 任静柯, 罗雯. 石墨炔在水系离子电池中的研究进展. 新型炭材料(中英文). doi: 10.1016/S1872-5805(24)60852-8
XU Xian-min, FENG Wen-cong, REN Jing-ke, LUO Wen. A review of graphdiyne in aqueous ion batteries. New Carbon Mater.. doi: 10.1016/S1872-5805(24)60852-8
Citation: XU Xian-min, FENG Wen-cong, REN Jing-ke, LUO Wen. A review of graphdiyne in aqueous ion batteries. New Carbon Mater.. doi: 10.1016/S1872-5805(24)60852-8

石墨炔在水系离子电池中的研究进展

doi: 10.1016/S1872-5805(24)60852-8
基金项目: 国家重点研发计划项目(2022YFB2404300)和国家大学生创新创业训练计划项目(202310497015)。
详细信息
    作者简介:

    徐显敏. E-mail:322294@whut.edu.cn

    通讯作者:

    罗 雯,博士,副教授. E-mail:luowen_1991@whut.edu.cn

  • 中图分类号: TQ127.1+1

A review of graphdiyne in aqueous ion batteries

Funds: National Key Research and Development Program of China(2022YFB2404300) and National Innovation and Entrepreneurship Training Program for College Students(202310497015).
More Information
  • 摘要: 石墨炔(Graphdiyen,GDY)是一种全新的炭材料,具有特殊的炭杂化排列方式、独特的化学性质和电子结构以及独特的孔隙结构等优点,在电化学储能领域具有良好的应用前景。新兴的水系离子电池具有低成本和高安全性等优点,然而,高性能电极材料的开发、新型隔膜体系的设计以及稳定界面的策略等仍是水系离子电池面临的主要挑战。石墨炔在负极保护、正极包覆、隔膜设计以及稳定界面pH值等方面,可以改善离子传输与界面沉积行为、电解液不稳定等问题。特别是石墨炔自下而上的分子结构设计策略使其具有易修饰、掺杂的特点,改性的石墨炔类似物具有更加优异的性能,拓宽了其在水系离子电池中的应用。本文系统综述了石墨炔的结构与性质以及合成方法,特别对石墨炔在水系离子电池中的研究进行了总结。此外,对石墨炔在水系离子电池中应用时仍存在的问题与挑战进行了探讨,对石墨炔在水系离子电池中的发展进行了展望。
  • 图  1  石墨炔家族结构的多样性:(a) 六种石墨炔异构体(GDY,α-GY,β-GY,γ-GY,δ-GY以及6,6,12-GY)的化学结构; (b) 炔烃换位反应合成γ-Graphyne[36]

    Figure  1.  Various structures of graphyne: (a) The chemical structures of six kinds of graphyne: GDY, α-GY, β-GY, γ-GY, δ-GY, and 6,6,12-GY. (b) The synthesis of γ-Graphyne by Alkyne metathesis[36]. Reprinted with permission

    图  2  石墨炔的表征分析. (a-f)模拟的石墨炔堆叠模型以及对应的TEM/SAED照片:(a, d)对应AA堆叠模型,(b, e)对应AB堆叠模型,(c, f)对应ABC堆叠模型[37]; (g)石墨炔的拉曼光谱图[38]; (h)石墨炔的C元素窄区XPS谱图[1]; (i)石墨炔的孔径分布图[38]

    Figure  2.  Characterization analysis of GDY. (a-f) Considered stacking structures and corresponding TEM/SAED simulation patterns of GDY from the top view: AA stacking (a, d), AB stacking (b, e), and ABC stacking (c, f)[37]. (g) Raman spectrum of GDY[38]. (h) XPS spectrum of GDY with narrow scan for element C[1]. (i) Pore size distribution of GDY[38]. Reprinted with permission

    图  3  石墨炔的性质. (a)石墨炔结构中储存和传输离子的示意图[42]; (b)入射光与石墨炔的相互作用示意图[49]; (c)硫掺杂石墨炔的室温铁磁性示意图[54]; (d)石墨炔和其他类似物的应力-应变曲线[56]

    Figure  3.  Properties of GDY. (a) Illustration for the structural features of GDY on ions transport and storages[42]. (b) Schematic diagram of the interaction of the incident light with GDY[49]. (c) Schematic illustration of room-temperature ferromagnetism in sulfur-doped GDY[54]. (d) Stress-strain results of GDY and other extended graphynes[56]. Reprinted with permission

    图  4  石墨炔的合成方法. (a)通过化学反应合成石墨炔薄膜的反应流程图[1]; (b)石墨炔纳米墙的合成示意图[58]; (c)单晶石墨炔纳米片的气/液界面合成和结构示意图[59]; (d)水/界面机械搅拌法制备石墨炔薄膜[60]; (e)爆炸法合成石墨炔[61]; (f)在石墨烯上生长单晶石墨炔薄膜的合成工艺及其OM、SEM和AFM图像[62]

    Figure  4.  Synthetic methods of GDY. (a) The synthetic route of GDY films by chemical reactions[1]. (b) Schematic illustration of the experimental setup for the synthetic of GDY nanowall[58]. (c) Schematic illustration of the gas/liquid interfacial synthesis and the structure of crystalline GDY nanosheet[59]. (d) The preparation of GDY thin film through mechanical stirring strategy at the water/oil interface[60]. (e) The preparation process of GDY by an explosion method[61]. (f) Synthetic process of single-crystalline GDY film on graphene and the OM, SEM and AFM images of the GDY film on graphene[62]. Reprinted with permission

    图  5  石墨炔的结构调控与改性策略. (a) Cl-GDY的合成流程图[64]; (b) GDY单元分子结构的氮掺杂示意图[63]; (c) 剪切GDY连接键制备HSGY示意图[67]; (d)HSGY的结构和孔径[68]; (e) BGDY的能带结构计算[66]; (f) γ-GY上过渡金属原子的相关氧化态(Q),局部磁矩(m)和原子磁矩(Dm)的变化[71]

    Figure  5.  Structural regulations and modification strategies of GDY. (a) The synthetic route to Cl-GDY[64]. (b) Schematic representation N-doping process of GDY, the unit structure of GDY molecule is shown as the inset[63]. (c) Schematic diagram of tailoring acetylenic bonds of GDY to prepare HsGY[67]. (d) The structure and pore size of HsGY[68]. (e) Calculated electronic band structure of BGDY[66]. (f) The related oxidation state (Q), local magnetic moment (m), and variation of the atomic magnetic moment (Dm) of TM adatoms on γ-GY[71]. Reprinted with permission

    图  6  石墨炔在水系锌离子电池负极保护中的应用. (a) Zn/GDY的可逆电镀/剥离过程示意图[98]; (b) Zn负极和Zn-GDYO负极的镀锌行为示意图[99]; (c) 双场模拟由离子隧道型人工界面层实现的Zn2+浓度场的再分布[100]

    Figure  6.  Applications of GDY in anode protection of aqueous zinc-ion batteries. (a) Schematic illustration of the reversible plating/stripping process of the Zn/GDY [98]. (b) Schematic illustration of the Zn plating behavior of free Zn anode and Zn-GDYO anode [99]. (c) Dual-field simulations uncover the redistribution of Zn2+ concentration field achieved by ion-tunnel-type artificial interface layer[100]. Reprinted with permission

    图  7  石墨炔在水系锌离子电池正极包覆中的应用. (a) GDY在Mn3O4的电化学反应过程中的作用[101]; (b) 以K0.25·MnO2@GDY作为正极的锌离子电池的优异性能示意图[102]; (c) MnO2@GDYO杂化3D纳米花结构的形成过程示意图[103]

    Figure  7.  Applications of GDY in cathode cladding of aqueous zinc-ion batteries. (a) The role of GDY in the electrochemical evolution of Mn3O4[101]; (b) Schematic representation of a high performance zinc ion battery incorporating the K0.25·MnO2@GDY cathode[102]; (c) Schematic illustration of the formation of the MnO2@GDYO hybrid 3D nanoflowers[103]. Reprinted with permission

    图  8  石墨炔在水系锌离子电池隔膜设计中的应用. (a) 具有GDYO隔膜的水系锌离子电池结构示意图[104]; (b) 无GDYO隔膜的水系锌离子电池结构示意图[104]; (c) GDYO隔膜的SEM照片[104]; (d) 分别在有GDYO隔膜和无GDYO隔膜情况下的锌对称电池曲线[104];(e) 10 C电流密度下具有GDYO隔膜的Zn–MnO2电池的循环性能曲线[104]

    Figure  8.  Applications of GDY in membrane design of aqueous zinc-ion batteries. (a) Schematic representation of aqueous Zn-ion batteries with GDYO membrane[104]. (b) Schematic representation of aqueous Zn-ion batteries without GDYO membrane[104]. (c) SEM images of GDYO membrane[104]. (d) Zn stripping/plating from Zn/Zn symmetrical cells with or without GDYO membrane respectively[104]. (e) Long-term cycle performance of a Zn–MnO2 battery featuring a GDYO membrane measured at a rate of 10 C[104]. Reprinted with permission

    图  9  石墨炔在水系锌离子电池稳定界面pH值中的应用. (a) 自制的原位pH表征平台模型[105]; (b) 锌负极区域的实时pH变化[105]; (c) 理论计算显示的水合锌离子中配位水分子与NGDY和纤维素的相互作用[105]; (d) NGDY稳定界面pH值和抑制锌枝晶的机理示意图[105]

    Figure  9.  Applications of GDY in stabilizing interface pH of aqueous zinc-ion batteries. (a) The home-made operando pH detection configuration[105]. (b) Real-time interface pH change at the Zn anode region[105]. (c) Theoretical computation showing the interaction of the coordinated water in hydrated zin ions with NGDY and cellulose[105]. (d) Schematic diagram demonstrating the NGDY-assisted stabilization of interface pH and suppressions of Zn dendrites[105]. Reprinted with permission

    图  10  石墨炔在水系镁离子电池中的应用. (a) Cu-MoS2@HsGDY纳米胶囊的制备过程示意图[109]; (b) 不同反应阶段中Cu-MoS2@HsGDY结构的(a-c)STEM和(d-f)TEM照片[109]; (c) GSMB的工作原理和界面过程示意图[110]

    Figure  10.  Applications of GDY in aqueous magnesium-ion batteries. (a) Schematic illustration of the fabrication of hierarchical porous Cu-MoS2@HsGDY nanocapsule formed in one continuous process[109]. (b) (a−c) STEM images and (d−f) TEM images of the intermediates of Cu-MoS2@HsGDYcollected at different reaction stages in the continuous process[109]. (c) Schematic illustration of the working mechanism and interfacial process of the GSMB[110]. Reprinted with permission

    图  11  石墨炔在水系铝离子电池中的应用. (a) ${\rm{AlCl}}_4^{-} $以最大程度嵌入GDY结构示意图[114]; (b) ${\rm{AlCl}}_4^{-} $以最大程度嵌入HsGY结构示意图[114]; (c) ${\rm{AlCl}}_4^{-} $通过GDY三角孔扩散的活化屏障计算[115]; (d) ${\rm{AlCl}}_4^{-} $通过GDY炔键基团扩散的活化屏障计算[115]

    Figure  11.  Applications of GDY in aqueous aluminum-ion batteries. The intercalation of ${\rm{AlCl}}_4^{-} $ in the fully loaded bilayer of (a) GDY and (b) HsGY[114]. Carbon, aluminum, and chlorine atoms are represented by brown, gray and green balls, respectively. Energy barrier for diffusion of ${\rm{AlCl}}_4^{-} $ between the two layers of GDY (c) from the cavity site and (d) from sp site[115]. Reprinted with permission

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  • 收稿日期:  2024-01-22
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