The role of carbon materials in suppressing dendrite formation in lithium metal batteries
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摘要: 锂金属有低还原电位和高比容量,是高能量密度电池负极材料的最终选择。然而,不可控的锂枝晶导致差的循环寿命和安全问题,对锂金属电池的实际应用构成了重大挑战。对锂枝晶形成机制的理解对于指导抑制枝晶生长的有效策略的发展至关重要。本文首先整理了近年来为理解锂枝晶形成过程而提出的几个具有代表性和影响力的模型。炭材料凭借其优异的导电性、电化学稳定性、机械性能和可塑性,已被广泛开发用于防止锂枝晶的形成。基于对上述主流锂枝晶形成模型的全面理解和认识,进一步全面汇总了近年来石墨烯、碳纳米管、炭纤维和空心炭等先进炭材料在应对锂枝晶形成方面的优势和策略。最后,对炭材料抑制锂枝晶的局限性和未来研究方向进行了总结和展望,为进一步开发高性能金属锂电极用先进炭材料提供了参考。Abstract: This review highlights several recent models of Li dendrite formation that have been proposed. Based on the comprehensive understanding and insight gained from these models, carbon materials have been developed to prevent the formation of Li dendrites by virtue of their exceptional electrical conductivity, electrochemical stability, mechanical properties and mouldability. A comprehensive review of the advantages of using carbon materials, such as graphene, carbon nanotubes, carbon fibers and hollow carbons, to deal with the formation of Li dendrites in recent years is provided. Finally, the limitations of carbon materials and future research directions for inhibiting Li dendrite formation are summarized as a reference for the development of new carbon materials for high-performance Li metal anodes.
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Key words:
- Lithium metal batteries /
- Lithium dendrite /
- Carbon materials /
- SEI /
- Substrates
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Figure 2. (a) Schematic illustration of electrodeposition[47]. (b) Schematic illustration of a nucleus with a spherical cap shape. Behavioral patterns during the early stages of nucleation and growth, and the growth electrodeposit size varies with time[50]. (c) Scheme of the cell. The relationship between ion concentration Cc, and Ca, and the electrostatic potential[51]. (d) A nonuniform SEI renders irregular Li deposition[56]. (Reprinted with permission)
Figure 3. (a) Schematic diagram of the spray process and optical image of the reduction process for the preparation of SR-G-Li. The cycling stability of the bare Li and SR-G-Li electrodes at 5 mA cm−2[72]. (b) Schematic illustration of Li deposition on Cu and GBL||Cu. The cycling performance at 3.0 mA cm−2 with 3 mAh cm−2[74]. (c) Schematic illustration of Li depositing and stripping on graphene substrate[75]. (d) Comparative diagram of Li nucleation and plating on N-doped graphene and copper foil[77]. (e) Schematic diagram of Li nucleation and deposition on the Cu foil and rGO−Cu2O/Cu[80]. (Reprinted with permission)
Figure 4. (a) Schematic diagram of preparation of the sparked rGO films and layered Li–rGO composite film, and the corresponding SEM images[81]. (b) Schematic diagram of the 0 V overpotential Li nucleation on ERG and uniform Li plating on the ERG-hybridized 3D CNF substrate. Deposition curves of Li at 0.2 mA cm−2 on SiO2@ERG-CNF and SiO2@ERGPyC-CNF[86]. (c) Schematic illustration of Li plating and stripping on bare Zn and the Zn with tent-like nanocavities interface anchored by Zn-O-C bond. The cycling stability of Li||LFP cells with different Li anodes at 5 C[7]. (Reprinted with permission)
Figure 5. (a) Schematic diagram of preparation of the LiCSMF electrode. Cycling performance at 40 mA cm−2 with 2 mAh cm−2[88]. (b) Schematic illustration of Li deposition on Li foils with GZCNT interface, and the cycling stability of the pouch cells of Li foils with/without GZCNT at 1 mA cm–2 with 1 mAh cm–2[91]. (c) Schematic of preparation of the Li-CNT-AB[93]. (d) Schematic diagram of the preparation of OPA−Li−CNT sphere by molecular self-assembly [94]. (Reprinted with permission)
Figure 6. (a) SEM image and the multifunctionality of GCF electrode[96]. (b) Schematic illustration of Li deposition and stripping on the CNF and CNF-TiN, and the corresponding CE profiles at 1 mA cm−2 with 6 mAh cm−2[98]. (c) Schematic diagram of Li plating/stripping behavior on Li/CF composite anode, and the performance of pouch cells with S cathodes[99]. (d) Schematic representation of the self-smoothness of the Li-C electrode in cycling. SEM images of the pristine and cycled Li–C electrode[100]. (e) Schematic of the Li composite film prepared with hydrophilic or hydrophobic carbon scaffolds[101]. (f) Schematic diagram of the preparation of CC-Zn-CMFs[102]. (g) Schematic and SEM image of the cycled electrode with/without upper SAFeNi@LNCP modulation layer[103]. (Reprinted with permission)
Figure 7. (a) Schematic illustration of the Li plating/stripping behavior on different structures[104]. (b) Schematic illustration of Li metal nanocapsules design and preparation of hollow carbon with Au NPs[105]. (c) Schematic diagrams of the Li plating and stripping on Cu foil and N-HPCSs[107]. (d) Schematic illustration and SEM images of Li plating on the CB[108]. (e) Schematic illustration of the Li nucleation and plating/stripping on the Co@N-G substrate. Coulombic efficiencies of different electrodes at 1, 3, 10, 15 mA cm−2 with 1 mAh cm−2[109]. (f) Schematic diagrams of the Li deposition on c-Au@ZIF-8 and TA-ZIF-67 host based electrodes. Coulombic efficiencies of different electrodes at 10 mA cm−2 with 1 mAh cm−2[111]. (Reprinted with permission)
Figure 8. (a) Schematic diagram of typical Li+ intercalation in graphite layers and superdense Li diffusion in atomic channels[112]. (b) Schematic diagram of the preparation and protective mechanism of GF–LiF–Li[113]. (c) Comparative schematic illustration of the Li deposition on Cu foil and MCMB-F electrode[114]. (d) Comparative schematic diagrams of the Li plating on Li with or without graphite–SiO2 bilayer-modified [115]. (e) Schematic diagram of the preparation of RC[116]. (f) Schematic diagram of the preparation of MgO@WC/Li composite electrode[117]. (g) Comparative schematic diagrams of the Li+ in bare Li anode and LAL/Li anode upon Li deposition. And the preparation of the LAL[118]. (h) Schematic of the bifunctional effects of nitro-C60 additive[119]. (Reprinted with permission)
Table 1. Summary of the electrochemical performance of electrodes based on different advanced carbon materials
Electrode Symmetric cell Full cell Reference SR-G-Li 1000 cycles at 5 mA cm−2, 1 mAh cm−2 LiFePO4||SR-G-Li, 1 C, 128.8 mAh g−1 after 300 cycles [72] GBL 600 h at 3 mA cm−2, 3 mAh cm−2 LiFePO4||GBL||Li, 1C, 100 mAh g−1 after 1600 cycles [74] NG basedLi metal anodes 150 cycles at 1 mA cm−2, 0.042 mAh cm−2 - [77] rGO−Cu2O/Cu@Li 300 h at 0.5 mA cm−2 LiFePO4||rGO−Cu2O/Cu@Li, 2 C, 94.3 mA h g−1 [80] Layered Li–rGO electrodes Beyond 100 cycles at 3 mA cm−2, mAh cm−2 LiCoO2||Li–rGO, 10 C, ~70 mAh g–1 [81] Li-SiO2@ERG-CNF 1000 h at 0.5 mA cm−2, 1 mAh cm−2 LiFePO4||Li-SiO2@ERG-CNF, 1 C,
106.9 mAh g−1 after 1000 cycles[86] Li@TLI-GO/Zn/CC >1600 h at 1 mA cm−2, 1 mAh cm-2 LiFePO4|| Li@TLI-GO/Zn/CC, 5 C, capacity
retention of 94.6% after 3000 cycles[7] LiCSMF 2000 cycles at 40 mA cm−2, 2 mAh cm−2 S-CSMF||LiCSMF, 1 C, 200 cycles [88] GZCNT-coated Li 100 h at 10 mA cm−2 S||GZCNT-coated Li, 0.2 C, 1.73 mAh cm–2 after 200 cycles [91] Li-CNT-AB 100 cycles at 3 mA cm−2, 1 mAh cm−2 LiFePO4||Li-CNT-AB, CE of ~ 98.7% after 700 cycles. [93] OPA−Li−CNT 200 cycles at 3 mA cm−2, 0.5 mAh cm−2 LiFePO4||OPA−Li−CNT, 1 C, 250 cycles [94] GCF@Li over 300 h at 2 mA cm−2 LiFePO4||GCF@Li, 300 cycles with a capacity retention of 80% [96] CNF-TiN 200 cycles at 3 mA cm−2 LiFePO4||CNF-TiN, 122.4 mAh g−1 after 250 cycles [98] Li/CF 90 h with a small polarizationvoltage of 120 mV S||Li/CF, 3.25 mAh cm−2, 0.1 C, a capacity
retention rate of 98% after 100 cycles[99] Li-C anode 500 h at 1 mA cm−2, 1 mAh cm−2 NMC||Li-C, 350–380 Wh kg−1 for 200 cycles [100] Li@CF 270 cycles at 3 mA cm−2, 1 mAh cm−2 Mg/Ti-LiNiO2||Li@CF, 0.5 C, 127 mAh g−1 after 140 cycles [101] CC-Zn-CMFs 2000 h at 1 mA cm−2, 1 mAh cm−2 Mg/Ti-LiNiO2||CC-Zn-CMFs-Li, 200 cycles
without obvious capacity decay[102] SAFeNi@LNCP-Li 650 h at 5 mA cm−2, 20 mAh cm−2 SAFeNi@LNCP||SAFeNi@LNCP-Li, 5 C, 856 mA h g−1 [103] N-HPCSs - N-HPCSs/S||Li/Cu@N-HPCSs, 1 C, 907 mAh g−1,
a capacity retention rate of 80.1% after 400 cycles[107] Li-Co@N-G 1000 h at 1 mA cm−2, 1 mAh cm−2 NCM||Li-Co@N-G, 1 C, a capacity retention of 92% after 100 cycles [109] BDLC 2000 h at 1 mA cm−2, 1 mAh cm−2 100% capacity retention is achieved over 370 cycles [112] Li@MCMB-F - LiFePO4||Li@MCMB-F, 2.4 mAh cm−2 for 110 times
at a capacity decay of 0.01% per cycle[114] MgO@WC - LiCoO2||MgO@WC/Li, 1 C, 300 cycles [117] LAL/Li >1000 h at 60 mA cm−2, 60 mAh cm−2 LAL/Li-air, stably cycled for over 450 cycles [118] Nitro-C60 >400 h at 1 mA cm−2, 1 mAh cm−2 S||Li, retention of 63.2% over 100 cycles [119] -
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