Research Progress on Hard Carbon Anode for Li/Na-ion Batteries

doi:10.15541/jim20230365

Abstract

Abstract:

With rapid development of lithium ion batteries (LIB) and sodium ion batteries (SIB), hard carbon (HC) as new anode material has earned much attention. Besides its rich precursor sources and low cost, HC has higher Li⁺ storage capacity and better rate performance than graphite for LIB. Furthermore, it is also recognized as the most commercially potential anode material for SIB. However, low initial Coulombic efficiency is a common issue for HC. In addition, it is believed that the specific capacity can be further improved with the clarification of the Li/Na ion storage mechanism. In recent years, many researches on electrochemical mechanism have been conducted with some model assumptions proposed for better understanding the mechanism. This review introduced the structures and preparation approaches of HC as well as its application in LIB and SIB. The advantages, especially in fast charging, coating and other subdivision were discussed, and the different modification strategies such as pore structure design, doping, optimizing interface between electrode and electrolyte were summarized, aiming at the increase of capacity and the improvement of Coulombic efficiency of batteries.

Key words: anode material, lithium ion battery, sodium ion battery, hard carbon, review

CLC Number:

TQ152

HU Mengfei, HUANG Liping, LI He, ZHANG Guojun, WU Houzheng. Research Progress on Hard Carbon Anode for Li/Na-ion Batteries[J]. Journal of Inorganic Materials, 2024, 39(1): 32-44.

Figures/Tables 9

Fig. 1 Over-view on the application and modification strategies of hard carbon in Li/Na ion batteries

Fig. 2 Formation scheme of hard carbon, soft carbon and graphite[3]

Fig. 3 Biomass carbon precursors and their properties (a) General biomass carbon precursors; (b) Rate performance and Coulombic efficiency of carbon from coffee waste in LIB[16]; (c) Schematic of synthesis and proposed mechanism of pitch/lignin-derived carbon[22]

Fig. 4 (a) Three different mechanisms of lithium/sodium ion storage in hard carbon[28], and (b) four different models of sodium storage in hard carbon[39]

Fig. 5 Hard carbon in fast-charging application (a) Schematic of ion diffusion pathways in carbon fiber (CF); (b) Lithium-ion diffusion coefficient of CF and carbon sphere (CS) measured by potentiostatic intermittent titration technique (PITT); (c) Cycling performance of Li||CF and Li||graphite cells[45]; (d) Z'-ω0.5 plots in low-frequency region calculated from electrochemical impedance spectroscopy (EIS) measurement; (e) DLi and electrical conductivity plots of CNFs[47] in which the mass ratio of polyacrylonitrile to pitch can be tuned as 10/0, 9/1, 7/3, and 5/5 for PAN-800, PCTP9-1, PCTP7-3, PCTP5-5, respectively; (f) Rate performance of N-GCNs in LIBs from 0.1 to 20 A·g-1 (CE: Coulombic efficiency)[49]

Fig. 6 Hard carbon as coating layer for anode (a) Multistep heating in different carbonization procedures; (b) Charge-discharge profiles of the sample with carbonization 2# in (a)[50]; (c) Illustration of resorcinol-formaldehyde resin (RF) coated nano Si[53]; (d) TEM image of Si-C-G-15 composite; (e) PITT results of Si-C-G-15 and capacity contributions of each component (AC: amorphous carbon; NG: natural graphite; SiNPs: silicon nano-particles)[54]

Fig. 7 Doping and pre-oxidation strategies (a) Schematic illustration of fabrication process of S-NCNFs; (b) TEM image of S-NCNFs and corresponding S, N, and C elemental mappings[62]: (c) Capacity of hard carbon derived from pitch (HCP) with and without pre-oxidization[64]; (d) Specfic capacity and initial Coulombic efficiency of lignin spheres hard carbon (LSHC) with pre-oxidation at different temperatures[65]

Fig. 8 (a) Schematic showing the control of the nanopores in a typical porous carbon (left) to produce molecular sieve carbon (right), and comparison between their different IEDLs, charge/discharge curves for first two cycles of (b) porous carbon and (c) molecular seive carbon anodes[66]

Fig. 9 Strategies for improving initial Coulombic efficiency (a) Schematic of the influence of ALD-Al2O3 coating on hard carbon[67]; (b) Charge/discharge curves of P-doped C (PO/C) and C prepared at 800 ℃ without doping (C-800) at 0.1 A·g-1; (c) Illustration of different compositions of the SEI on the surface of PO/C electrode[68]; (d) Illustration of closed pore in hard carbon; (e) Galvanostatic initial discharge-charge profiles of HC-21-x (x: pyrolysis temperature)[70]; (f) Schematic illustration of Na storage mechanism in HC-GLC electrode[73]

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