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摘要: 钠离子电池在未来大规模固定式电网储能中的潜在应用引起了人们的广泛关注。随着钠离子电池的商业化发展，利用可持续生物质资源开发高性能炭负极材料已成为制造低成本钠离子电池的一项重要策略。本文综述了以生物质废弃物为原料制备先进炭负极材料用于钠离子电池的最新进展。首先，系统地讨论了炭负极储钠机制的历史观点，以明确其构效关系。其次，介绍了炭材料孔结构设计、杂原子掺杂、晶体结构控制和形貌调控等策略有效地提高生物质基炭负极的储钠性能。最后，从合成方法、微观结构和生产成本的角度，展望了生物质基炭负极材料用于商业化钠离子电池的可能以及未来的研究方向和挑战。Abstract: Sodium-ion batteries (SIBs) have attracted tremendous attention for large-scale stationary grid energy storage. With the upcoming commercialization of SIBs in the foreseeable future, developing high-performance carbon anodes from sustainable biomass is becoming increasingly important in the preparation of cost-effective SIBs. This review summarizes advanced carbon anodes for SIBs derived from various lignocellulose biomass waste. The history of our understanding of sodium storage mechanisms in carbon anodes is first discussed to clarify their structure-performance relationships. Conventional preparation strategies including pore structure design, heteroatom doping, control of the graphitic structure, and morphology control and their effects on the sodium storage capability of biomass-derived carbon anodes are then discussed. Finally, the practical applications, future research directions and challenges for the use of biomass-derived carbon anodes for SIBs are discussed from the aspects of synthesis methods, microstructure control and production costs.
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Key words:
- Biomass /
- Carbon /
- Anode /
- Mechanism /
- Microstructure /
- Sodium-ion batteries
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Figure 1. (a) Ragone plot of electrochemical energy storage devices, the relationship between power density versus energy density[69]. (b) Elemental abundance in the earth’s crust[70]. (c) Cost comparison of model SIBs and LIBs[71]. (d) Schematic illustration of the architecture of SIBs. Reprinted with permission
Figure 2. Proposed sodiation mechanisms for carbon anodes. (a) “Insertion-filling” model[83]. (b) “Adsorption-insertion” model[83]. (c) “Adsorption-insertion” model[76]. (d) “Adsorption-filling” mechanism[78]. (e) “Adsorption-insertion-filling” mechanism[79]. (f) “Adsorption-insertion-filling” mechanism[82]. (g) “Adsorption/insertion-filling” mechanism[84]. Reprinted with permission
Figure 3. The microstructure-dependent sodium storage mechanism of HCs[88]. Reprinted with permission
Figure 4. (a) Schematic illustration of the natural structure of wood, and the composition of the cell wall[96]. (b) Schematic representation for the typical microstructures of the carbons obtained at 1000 and 3000 °C[99]. Scanning electron microscopy images of (c) cucumber stem-derived carbon[101], (d) poplar wood-derived carbon[102], (e) lotus stem-derived carbon[103], (f) cherry petals derived carbon[104], (g) apricot shells derived carbon[105], (h) beechwood derived carbon[106], (i) pine pollen derived carbon[107], and (j) bamboo-like derived carbon[108]. Reprinted with permission
Figure 5. Preparation of porous carbons by chemical activation strategy. (a) Peanut shell-derived porous carbon prepared by KOH activation[117]. (b) Cotton seed hull-derived porous carbon prepared by fungi-enabled degradation and KOH activation[119]. (c) Samara-derived porous carbon prepared by KHCO3 activation[120]. (d) Peanut shell-derived porous carbon prepared by H3PO4 activation[124]. (e) Magnolia petals derived porous carbon prepared by ZnCl2 activation[128]. (f) Platanus bark-derived porous carbon prepared by H2SO4 washing[129]. Reprinted with permission
Figure 7. Preparation of hard carbons by direct carbonization. (a) A freestanding and thick hard carbon with well-defined channels in original wood[157]. (b) Walnut shell derived hard carbon[158]. (c) Argan shells derived hard carbon[159]. (d) Cork-derived hard carbon[160]. (e) Date palm derived hard carbon[161]. Reprinted with permission
Figure 9. Preparation of the nanostructured carbons. (a) Zero-dimensional carbon spherules[165]. (b) One-dimensional hollow carbon microtubes[168]. (c) One-dimensional hard carbon microtubes[85]. (d) Two-dimensional sulfur-doped carbon sheets[172]. (e) Two-dimensional carbon nanosheets[173]. (f) Three-dimensional honeycomb-like carbon[131]. Reprinted with permission
Figure 11. Sodium storage performance of hard carbons derived from various biomass. (a) Hard carbon derived from cork at 1200-1600 °C[160]. (b) Hard carbon derived from corn cob at 1000-1600 °C[184]. (c) Hard carbon derived from pinecone at 500-1600 °C[189]. (d) Hard carbon from starch at 900-1700 °C[183]. (e) Hard carbon from waste tea at 1000-1600 °C[185]. Reprinted with permission
Figure 12. Summary of future directions and challenging perspectives of biomass-derived carbon anodes for practical SIBs applications
Table 1. Electrochemical performances of biomass-derived carbon materials with different sources and structures
Biomass precursor Temperature (°C) Structures Electrochemical performance Ref. BET
(m2 g−1)Interlayer spacing
(nm)ID/IG ICE
(%)Reversible capacity
(mAh g−1)Cycling
stabilityaRate
performancebCotton 1000 538 4.14 - 26 88 - - [85] 1300 38 4.1 83 315 97/0.1C 180/1C 1600 14 4.02 85 294 - - Wheat starch 900 6.33 3.75 1.36 80 256 92.5/0.4C 51/4C [183] 1100 5.44 3.74 1.28 85.2 320 93.2/0.4C 83/4C 1300 3.67 3.73 1.24 86.5 336 93.8/0.4C 122/4C 1500 1.6 3.68 1.23 90.5 305 94.5/0.4C 156/4C 1700 1.5 3.51 1.04 93.9 235 94.7/0.4C 82/4C Argan shell 800 99 4 - 66.2 232 91.3/25 mA g−1 - [159] 1000 7.7 4 77.9 286 93.1/25 mA g−1 1200 3.9 3.93 81.2 296 96.6/25 mA g−1 1300 2.6 3.88 83.9 300 98.3/25 mA g−1 Acid-treated argan shell 800 380 3.91 - 76.9 286 94.5/25 mA g−1 - [159] 1000 270 3.9 83.9 299 95.9/25 mA g−1 1200 23 3.93 79 333 96.9/25 mA g−1 1300 24 3.85 86.8 312 98.4/25 mA g−1 Wine cork 800 11.67 4.03 2.87 61 256 80.8/0.1C 170/2C [160] 1200 9.23 3.97 2.47 71 311 84.8/0.1C 140/2C 1400 8.57 3.92 2.22 76 326 88/0.1C 116/2C 1600 5.54 3.76 1.89 81 358 87/0.1C 108/2C Corn cob 1000 5.49 4.08 - 81 267 93.9/0.2C 120/2C [184] 1300 3.73 3.98 86 298 97/0.2C 95/2C 1600 1.43 3.89 87 286 93.1/0.2C 80/2C Waste tea 1000 56 3.79 - 67 218 81/0.2C 47/2C [185] 1200 38 3.75 68 230.5 82/0.2C 58.1/2C 1400 14 3.73 69 282.4 83/0.2C 67.3/2C 1600 4 3.66 73 226.3 85/0.2C 35/2C Rice husk 1100 2.68 4.03 1.16 64 323 - 150/1000 mA g−1 [186] 1300 0.27 3.95 1.23 66 372 183/1000 mA g−1 1500 0.23 3.84 1.31 68 327 166/1000 mA g−1 Cellulose 800 425 4.09 - 55.2 197 - - [159] Acid-treated cellulose 800 352 4.05 - 78.9 285 - - [159] Lignin 800 4.4 3.91 - 64 158 - - [159] Acid treated Lignin 800 287 4.04 - 75.4 285 - - [159] Note: a Capacity retention (%)/current density. b Rate capacity (mAh g−1)/current density. 
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