Rational Design of Bimetallic Zeolitic Imidazolate Framework‐Derived C, N Dual‐Doped ZnO/Co for Boosting Lithium Storage

Hollow Porous N and Co Dual-Doped Silicon@Carbon Nanocube Derived by ZnCo-Bimetallic Metal–Organic Framework toward Advanced Lithium-Ion Battery Anodes

“…34−36 Among the various MOFs, bimetallic zeolitic imidazolate frameworks (ZnCo-ZIFs; ZIF-8 and ZIF-67) have emerged as excellent self-sacrificial templates for synthesizing various nitrogen-doped Co-based carbon nanocomposite anode materials for realizing exceptional energy storage in LIBs, owing to their high surface area, adjustable pore size by imidazole linker modification, and exceptional chemical and thermal stability. 37 Moreover, ZIF-derived nanocomposites consist of N-doped mesoporous to porous carbon skeletons with high graphitization, which can efficiently buffer against the large volume expansion of Si NPs, improve the electronic conductivity, and shorten the diffusion length for Li + . 38,39 Recently, ZIFs-derived materials, including porous cage-like carbon/nano-Si nanocomposites prepared by nano-Si@zeolitic imidazolate frameworks (ZIF-8)-templated method (cage-like nano-Si/C; ∼1168 mA h g −1 at 100 mA g −1 ), 40 mesoporous silicon hollow nanocubes through magnesiothermic reduction reaction (MRR) of silica-coated ZIF-8 (m-Si HCs; ∼1050 mAh g −1 at 15 C), 8 hollow cube-like Si/SiO 2 @C nanocomposite by carbonization of ZIF-8 coated with SiO 2 (hollow cube-like Si/SiO 2 @C; ∼1280 mA h g −1 at 500 mA g −1 ), 41 cage-like mesoporous Si@ZIF-67 core−shells obtained by carbonization of ZIF-67 coated with a 20 nm Si NPs (cage-like Si@ZIF-67-600; ∼1230 mA h g −1 at 0.5 A g −1 , and ∼1180 mA h g −1 at 1 A g −1 ), 42 Si-nanoparticle core and N-doped/Coincorporated carbon shell prepared by carbonization of ZIF-67 wrapped with Si NPs (Si@Co−NC; ∼191.4 mA h g −1 at 1000 mA g −1 ), 43 micron bread-like N-doped Si/C core−shell by carbonization of ZIF-8 incorporated with Si NPs (micron bread-like Si/C composite with a high Si content of 71 wt %; Figure 1.…”

“…Among the various MOFs, bimetallic zeolitic imidazolate frameworks (ZnCo-ZIFs; ZIF-8 and ZIF-67) have emerged as excellent self-sacrificial templates for synthesizing various nitrogen-doped Co-based carbon nanocomposite anode materials for realizing exceptional energy storage in LIBs, owing to their high surface area, adjustable pore size by imidazole linker modification, and exceptional chemical and thermal stability . Moreover, ZIF-derived nanocomposites consist of N-doped mesoporous to porous carbon skeletons with high graphitization, which can efficiently buffer against the large volume expansion of Si NPs, improve the electronic conductivity, and shorten the diffusion length for Li + . , Recently, ZIFs-derived materials, including porous cage-like carbon/nano-Si nanocomposites prepared by nano-Si@zeolitic imidazolate frameworks (ZIF-8)-templated method (cage-like nano-Si/C; ∼1168 mA h g –1 at 100 mA g –1 ), mesoporous silicon hollow nanocubes through magnesiothermic reduction reaction (MRR) of silica-coated ZIF-8 (m-Si HCs; ∼1050 mAh g –1 at 15 C), hollow cube-like Si/SiO 2 @C nanocomposite by carbonization of ZIF-8 coated with SiO 2 (hollow cube-like Si/SiO 2 @C; ∼1280 mA h g –1 at 500 mA g –1 ), cage-like mesoporous Si@ZIF-67 core–shells obtained by carbonization of ZIF-67 coated with a 20 nm Si NPs (cage-like Si@ZIF-67-600; ∼1230 mA h g –1 at 0.5 A g –1 , and ∼1180 mA h g –1 at 1 A g –1 ), Si-nanoparticle core and N-doped/Co-incorporated carbon shell prepared by carbonization of ZIF-67 wrapped with Si NPs (Si@Co–NC; ∼191.4 mA h g –1 at 1000 mA g –1 ), micron bread-like N-doped Si/C core–shell by carbonization of ZIF-8 incorporated with Si NPs (micron bread-like Si/C composite with a high Si content of 71 wt %; ∼1155 mA h g –1 at 2 A g –1 , and long-life cyclic stability of 1109 mAh g –1 at 3 A g –1 and 804 mAh g –1 at 5 A g –1 ), saclike-silicon nanoparticles anchored spongy matrix through ZIF-8 to anchor saclike silicon via molten salt magnesiothermic reduction method (Si@N-C with a content 77.58% Si NPs; ∼1448 mAh g –1 at 2 A g –1 and 848 mAh g –1 at 4 A g –1 ), silicon-wrapped N-doped carbon nanotubes prepared by controllable thermal pyrolysis with ZIF-67 (Si@N-doped CNTs; ∼1144 mAh g –1 at 1 A g –1 and 1264 mAh g –1 at 1/4 C), ZIF-67 encapsulated Si@CNTs by chemical vapor deposition and MOF self-template methods (Si@CNTs@ZIF; ∼568.8 mAh g –1 at 1 A g –1 ), and mesoporous cobalt (Co), N co-doped double carbon-coated silicon/carbon/MOF multicore yolk-shell obtained by Sol-gel and MOF self-template methods (Si@C@ZIF-67–800N; ∼1107 mAh g –1 at 0.5 A g –1 and 852 mAh g –1 at 1 A g –1 ), have been scrutinized as high-capacity anode materials with tiny volume changes for long-life-span LIBs.…”