Advances in the use of carbonaceous scaffolds for constructing stable composite Li metal anodes
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摘要: 因为锂金属电池(LMBs)具有高能量密度、高理论比容量和低氧化电位等优点,被认为是后锂离子电池(LIBs)中理想的能量存储装置之一。然而,锂金属阳极(LMA)面临着多种障碍,包括低库仑效率(CE)、大体积膨胀、锂枝晶的形成、低安全和低稳定性及短寿命,这些问题阻碍了LMBs的实际应用。由于低密度、高机械强度、稳定的化学性质和大比表面积等优势,碳基材料受到了广泛关注。建立复合碳基LMA是各种策略中的一种有效选择,因为其具有缓解体积膨胀、降低局部电流密度以及提供均匀Li+沉积的活性成核位点的能力。本文综述了复合碳基LMA的最新研究进展,包括碳基复合材料、元素金属及其化合物与碳基材料的复合物,以及它们与阳极界面稳定性和结构的关系。最后,本文总结并提出了关于将碳基材料作为LMA支架的观点和见解。Abstract: Compositing lithium metal anodes (LMAs) with carbon-based materials has been given much attention because of the latter’s low density, high mechanical strength, stable electrochemical properties, and large specific surface area. Such a composite LMA stands out because of its ability to reduce the volume expansion, lower the local current density, and provide active nucleation sites for uniform Li+ plating. Recent research advances in carbon-based materials as scaffolds to make composite anodes are reviewed, including composites with pure metals and their alloys, and compositing strategies to improve anode stability.
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Figure 2. (a) Schematic diagram of the production steps of S-3DG/S and the transmission path and framework of Li and electrons[66]. (b) Schematic of LMA: nanoporous N-doped graphene synthesis[71]. (c) Li foil, graphene-Li, and N-doped graphene-Li symmetrical cells with 1 mAh cm−2 stripping/plating capacity and 1 mA cm−2 current density and voltage characteristics[71]. (d) Schematic diagram of 3DCu@NG manufacturing[72]. (e) The production steps of the NCNT-CC film[73]. (f) Schematic diagram of the deposition behavior of lithium deposition on CF and NOCA@CF[75]. (g) Schematic diagram of the NPCQP-900 synthesis process[76]. (h) Adsorption energy doped with carbon and lithium atoms[76]. ( Reprinted with permission )
Figure 3. (a) Graphical depiction of the NSC@Ni synthesis method[81]. (b) Optimal configuration of lithium atoms adsorbed at PlN, PdN, PlN-S and PdN-S sites[81]. (c) The fabrication process of PGCF-Li[82]. (d)The SEM image of PGCF-Li is 10 mAh cm−2[82]. (e) Dual-function schematic diagram of a carbon surface with an electron-deficient structure[83]. (f) Physical characterization of the CNT sponge in HRTEM images[84]. (g) Morphology of carbon nanotube sponge during lithium plating/stripping: schematic representation of lithium discharged to carbon nanotube sponge’s electrochemical plating/stripping process[84]. ( Reprinted with permission )
Figure 4. (a) A diagrammatic representation of the nanoseeding approach for the homogeneous deposition of lithium metal on a 3D host material Joule heat anchors AgNPs evenly to the CNF substrate, which is responsible for Li deposition and growth. Thus, lithium metal is guided into the 3D substrate to generate a homogeneous lithium anode[91]. (b) Schematic diagram of the 3D-AGBN host preparation process with the layered characteristics of the solution[94]. (c) The Li plating/stripping process within the Au@aCNT is shown in the TEM snapshot and the corresponding schematic[96]. (d) Schematic of embedded AuNP entering the interior of the tube by breaking through the separation layer upon lithiation[96]. (e) Li is directed deposition to the bottom of the Li/AuCF anode[97]. (f) Formation of multi-dimensional structures through deposition of single Zn atoms[98]. (g) A Schematic representation of the difference in electron density and surface binding energy between graphene, ZnSAs, and N-graphene[98]. ( Reprinted with permission )
Figure 5. (a) A diagrammatic representation of the peeling and electroplating behavior lithium foil in a planar form and Li@NRA-CC electrode, mechanisms of breakdown by pitting corrosion, SEI fracture, and dendritic growth, and it describes the synergistic influence of interconnected 3D CC and Co-N-C NRAs on lithium stripping/plating behavior[108]. (b) Process flow diagram for the production of OCCu-Li electrode[109]. (c) Schematic of synthetic procedures of VO2-CNT/CNF@Li electrode[111]. (d) Schematic diagram of the NiS@C-HS manufacturing process[112]. (e) Schematic of the sulfur hosts NiS@C-HS and typical C-HS@NiS[112]. (f) Voltage profiles during initial Li plating on different substrates at 1 mA cm−2[113]. ( Reprinted with permission )
Figure 6. (a) Describe the first-principles calculation of CP binding energy[114]. (b) CP electrodes CE at 1 mA cm−2 and 1 mAh cm−2 at different current densities and different capacities[114] . (c) SEM image of surface topography after Li@NF 100 cycles at 1 mA cm−2[115]. (d) High-resolution XPS spectra of N 1s for CNT-CoP@NC[116]. (e) Lithium nucleation and electroplating process diagram on the Cu foil and CNT-CoP@NC electrode[116]. (f) Process diagram of the preparation process of the CC/Li/Li3N composite electrode[117]. (g) NZP/NF synthesis process diagram[119]. (h) A diagrammatic representation of the preparation process of LiCu3P/CoP@C/CNT[120]. ( Reprinted with permission )
Figure 7. (a) A diagrammatic representation of the reaction mechanism of Li-Ti3C2Tx-CC with a bare lithium electrode[126]. (b) Diagram of lithium plating on MXene@CNF film[127]. (c) Schematic diagram of the lithium stripping/plating process of AlF3@CNF interlayer. A potential gradient (∆E) is formed as the resistance between layers increases[128]. (d) Schematic diagram of lithium metal deposition on BGCF[129]. ( Reprinted with permission )
Figure 8. (a) schematic process of the Li plating on bare CuNW and GDY@CuNW current collectors[135]. (b) impedance variations at different cycles (1.0 mA cm−2 , 1.0 mAh cm−2 )[135]. (c) Raman spectra of GDY and Ni/GDY[136]. (d) Under the conditions of 1 mAh cm−2/1 mA cm−2, the Li plating and stripping efffciency of Ni/GDY electrodes[136]. (e) Schematic lithium plating on bare Cu foil and Cu-GDY NWs[137]. (f) Cycling performance of full cells with LFP at 0.5 C[137]. ( Reprinted with permission )
Table 1. Performance of LMBs using carbonaceous scaffolds as 3D current collectors
Current collector Half cell performance
(Cycle Number/h, CE)Operating conditions (Current censity/(mA cm−2),
Areal capacity/(mAh cm−2))Refs 3D-printed GO frameworks 300, 95.5% 1, 1 [65] Sulfur doped 3D graphene/sulfur particles 100, 93.9% 0.5, 1 [66] N-doped graphene modified 3D porous Cu 50, 97.0% 1, 2 [72] N-doped carbon nanotube modified carbon cloth 400, 99.7% 1, 1 [73] N/O dual-doped 3D porous carbon 350, 95.7% 1, 1 [75] N, P dual-doped carbon 200, 97.5% 1, 1 [76] 3D N, O co-doped carbon nanosphere 600, 98.2% 0.5, 0.5 [80] CNT sponge as a 3D porous 90, 98.5% 1, 2 [84] Table 2. Performance of LMBs using elemental metal composite as 3D current collectors
Table 3. Performance of LMBs using composite with metallic oxygen/sulphur/selenium compounds as 3D current collectors
Current collector Half cell performance
(Cycle number/h,CE)Operating conditions (Current density/(mA cm−2),
Areal capacity/(mAh cm−2))Refs Nanorod arrays modified carbon cloth 100, 97.5% 2, 4 [108] Vanadium oxide modified carbon nanotube films 500, 99% 1, 1 [111] 3D carbon aerogel decorated with cobalt selenide nanoparticles 100, 99.3% 6, 6 [113] Table 4. Performance of LMBs using composite with metal nitrides/phosphides as 3D current collectors
Current collector Half cell performance
(Cycle number/h, CE)Operating conditions (Current density/(mA cm−2),
Areal capacity/(mAh cm−2))Refs Aluminum nitride nanosheets as an additive and carbon
paper as 3D current collector350, 95.8% 1, 1 [114] Nitride decorated nickel foams 300, 97.0% 1, 3 [115] Construction of nickel phosphide nanosheets modified with nickel foam 280, 98.5% 1, 1 [119] Nitrogen-doped hollow porous polyhedron carbon 400, 96.9% 1, 1 [116] Table 5. Performance of LMBs using composite with metal-carbide composites and fluoride/bromide/iodide as 3D current collectors
Current collector Half cell performance
(Cycle number/h, CE)Operating conditions (Current density/(mA cm−2),
Areal capacity/(mAh cm−2))Reference Ti3C2Tx MXene films mixed with trace cellulose nanofibers 200, 98.9% 0.5, 2 [127] AlF3 particles embedded within carbon nanofibers 450, 97.2% 1, 1 [128] CuBr- and Br-doped graphene-like film modified
Cu foam300, 98.8% 2, 2 [129] Table 6. Performance of LMBs using composite with other carbon-based forms as 3D current collectors
Current collector Half cell performance
(Cycle number/h, CE)Operating conditions (Current density/(mA cm−2),
Areal capacity/(mAh cm−2))Reference The CuNW electrode modified by GDY nanofilms 200, 96.5% 0.5, 0.5 [135] Ni-anchored graphdiyne modified copper foam substrate 200, 98.5% 1, 1 [136] grew GDY nanofilms on a Cu nanowire network 500, 99.2% 1, 2 [137] -
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