Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries

doi:10.1007/s40820-024-01351-2

Abstract

Abstract:

Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries; however, its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries. The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials, explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials, and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials. This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials, with particular focuses on their molecular, crystalline, and aggregation structures. Furthermore, the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses. Finally, future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.

Key words: Cellulose, Hard carbon, Anode materials, Rate performance, Sodium-ion batteries

Fujuan Wang, Tianyun Zhang, Tian Zhang, Tianqi He, Fen Ran. Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries[J]. Nano-Micro Letters, 2024, 16(1): 148-.

Fujuan Wang, Tianyun Zhang, Tian Zhang, Tianqi He, Fen Ran. [J]. Nano-Micro Letters, 2024, 16(1): 148-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01351-2

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/148

Figures/Tables 18

Table 1 The proportion of cellulose in different raw materials

Raw materials	Cellulose	Hemi-cellulose	Lignin	References
Wood	40-50%	13-32%	27-32%	[24]
Bamboo	40-55%	14-25%	16-34%	[14]
Flax	62.1%	16.7%	1.8%	[25]
Hemp	67%	16.1%	0.8%	[25]
Jute	70-75%	12.0%	0.2%	[23]
Ramie	68.8%	13.1%	1.9%
Kapok	64.4%	22-45%	19%
Cotton	92.7%	5.7%	-	[24]
Bacterial cellulose	100%	0	0	[20]

Fig. 1 a The supra-molecular structure and aggregation structure of cellulose (the primary three conformations of hydroxyl group in the insert Fig.); b conversion between homogeneous polycrystalline of cellulose (the abbreviation of EDA, GLY and AML refer to ethanediamine, glycerinum and liquid ammonia; and c the reaction active groups of cellulose molecular chains

Table 2 Lattice parameters of the most common cellulose allomorphs

Allomorph	Crystal system	Chain arrangement	a (nm)	b (nm)	c (nm)	α (°)	β (°)	γ (°)	References
Cellulose I_α	One chain triclinic	Parallel	0.674	0.593	1.036	117	113	81	[36]
Cellulose I_β	Two chain monoclinic	Parallel	0.801	0.817	1.036	90	90	97.3
Cellulose II	Two chain monoclinic	Antiparallel	0.81	0.903	1.031	90	90	117.1	[37]
Cellulose III_I	One chain monoclinic	Parallel	0.448	0.785	1.031	90	90	106.96	[38]
Cellulose III_II	Two chain monoclinic	Antiparallel	1.025	0.778	1.034	90	90	122.4	[39]
Cellulose IV_I	Two chains
Orthorhombic	Parallel	0.803	0.813	1.034	90	90	90	[40]
Cellulose IV_II	Two chains
Orthorhombic	Antiparallel	0.799	0.810	1.034	90	90	90

Fig. 3 Evolution of cellulose-based carbon as pyrolysis temperature changing: a TGA, DTG, and DSC curves of cellulose pyrolysis[13]; b the containing different carbon groups [50]; c ternary phase diagram of C, H, O during cellulose pyrolysis evolution [14]; d SSA and d₀₀₂ values [51]; a adapted with permission [13], Copyright 2022, Elsevier Limited. b adapted with permission [50], Copyright 2015, WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim; c adapted with permission [14], Copyright 2016, American Chemical Society; d adapted with permission [51], Copyright 2016, Elsevier B.V. and Science Press

Fig. 4 Various structures of cellulose-based carbon materials, including microspheres derived from wood-based cellulose carbon [66], nanosheets derived from cellulose acetate and kraft lignin [67], microfibers derived from bacterial cellulose [63], nanosponge derived from stem pith of helianthus annuus [68], microarray derived from filter paper [69], and nanoshell derived from cellulose [64]. Microspheres: adapted with permission [66], Copyright 2016, WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. Nanosheets: adapted with permission [67], Copyright 2018, American Chemical Society. Microfibers: adapted with permission [63], Copyright 2019, the Royal Society of Chemistry. Nanosponge: adapted with permission [68], Copyright 2021, Elsevier Limited on behalf of Chinese Society for Metals. Microarray: adapted with permission [69], Copyright 2022 Elsevier B.V. Nanoshell: adapted with permission [64,70], Copyright 2018, Elsevier B.V

Fig. 5 The cellulose-based carbon materials’ structure: a microcrystalline morphology [82]; b the structure parameters of a carbon microcrystalline cell; c-e the values of L_a, d₀₀₂, and L_c calculated by characterization methods in our previous work [82]; f the sodium storage mechanism for complete crystalline carbon [83]. a and c-e, adapted with permission [82], Copyright 2022, Elsevier Limited. f adapted with permission [83]. Copyright 2022, Elsevier Limited

Fig. 6 The relationship of sodium storage and rate performance for cellulose-based carbon in our previous work: a GCD curves; b rate capacity at different current densities [82]; c the fitted curves of capacity versus rate data with semi-empirical equation for batteries electrodes; d CV curves at different sweeps; e capacity ratios at sweep speed 0.1 mV s⁻¹; f the b value & peak current under different sweep rates [76]; g capacity ratios at different sweep rates; and h the comparing rate capacity in the different cellulose-derived hard carbon materials. a, b Adapted with permission[82], Copyright 2022, Elsevier Limited. d-f Adapted with permission [76], Copyright 2022, the Royal Society of Chemistry

Table 3 Comparison of diffusion coefficients, capacity, and ion diffusion lengths of different cellulose-derived carbon materials

Precursors	T (℃)	Charge transfer impedance (Ω)	Ion diffusion coefficient (cm² s⁻¹)	Ion diffusion length (mm)	Rate performance		References
Precursors	T (℃)	Charge transfer impedance (Ω)	Ion diffusion coefficient (cm² s⁻¹)	Ion diffusion length (mm)	Current density (A g⁻¹)	Capacity (mAh g⁻¹)	References
Bacterial cellulose	1050	-	3.5 × 10^-12	5.25 × 10^-8	0.03	222.9	[76]
Bacterial cellulose	1050	-	3.5 × 10^-12	5.25 × 10^-8	1	68.9	[76]
Cotton	1300	-	1.35 × 10^-9	2.43 × 10^-5	0.015	275	[81]
Cotton	1300	-	1.35 × 10^-9	2.43 × 10^-5	0.3	180	[81]
Bacterial cellulose	800	325.7	-	-	0.05	355	[63]
Bacterial cellulose	800	325.7	-	-	10	255	[63]
Fire wood	1300	26.6	4.2 × 10^-8	2.52 × 10^-4	0.05	276	[98]
Fire wood	1300	26.6	4.2 × 10^-8	2.52 × 10^-4	1	108	[98]
Bacterial cellulose	1300	270*	-	-	0.2	271	[89]
Bacterial cellulose	1300	270*	-	-	20	128	[89]
Cellulose	800	454.6	4.77 × 10^-10	2.86 × 10^-6	0.02	308	[131]
Cellulose	800	454.6	4.77 × 10^-10	2.86 × 10^-6	1	120	[131]
Cellulose nanocrystals/polyethylene oxide	1300	80	3.0 × 10^-10	5.4 × 10^-6	0.03	290	[132]
Cellulose nanocrystals/polyethylene oxide	1300	80	3.0 × 10^-10	5.4 × 10^-6	0.6	105	[132]
Oxide bacterial cellulose	1000	250*	-	-	0.05	276	[133]
Oxide bacterial cellulose	1000	250*	-	-	5	81	[133]
Microcrystalline cellulose	1000	107.2	-	-	0.05	293.5	[70]
Microcrystalline cellulose	1000	107.2	-	-	2	86.1	[70]
Kraft Lignin/Cellulose Acetate	1000	180	-	-	0.05	326	[67]
Kraft Lignin/Cellulose Acetate	1000	180	-	-	0.5	143	[67]
Cellulose nanocrystals	1000	-	-	-	0.02	375	[72]
Cellulose nanocrystals	1000	-	-	-	0.2	220	[72]
Filter/pitch	1000	-	2.2 × 10^-10	3.96 × 10^-5	0.03	282	[134]
Filter/pitch	1000	-	2.2 × 10^-10	3.96 × 10^-5	1.2	92*	[134]
rGO/CNF	300	48	-	-	0.02	320	[135]
rGO/CNF	300	48	-	-	3.2	100	[135]
Lotus leaves	800	10.2	1.2 × 10^-9*	2.16 × 10^-5	0.04	250	[136]
Lotus leaves	800	10.2	1.2 × 10^-9*	2.16 × 10^-5	2.0	78	[136]
Cellulose	1300	-	-	-	0.025	353	[16]
Cellulose	1300	-	-	-	2.0	240*	[16]
Microcrystalline cellulose	1200	200	-	-	0.02	302	[137]
Microcrystalline cellulose	1200	200	-	-	0.5	261	[137]
Bass-wood	500	35.78	2 × 10^-12	2.4 × 10^-8	0.1	371.4
Bass-wood	500	35.78	2 × 10^-12	2.4 × 10^-8	2.0	187.4	[138]

Fig. 7 a The solvation structure; b requirement of high ionic conductivity and fast ion transportation between the electrode and electrolytes; c requirements for the electrode surface [160]; d different SEI components in different electrolytes [164]; e inferior electrolyte-philic electrode materials; f superior electrolyte-philic electrode materials [165]; g Na⁺ ions number density inside nanopores [166]; h alkali-metal storage states on the carbon layer due to the M-M (mental-mental) and M-C (mental-carbon) interactions [167]. a-c Adapted with permissioned [160], Copyright 2022, the Royal Society of Chemistry. d Adapted with permissioned [164], Copyright 2022, the Royal Society of Chemistry. e-f Adapted with permissioned [165], Copyright 2023, the Royal Society of Chemistry. g Adapted with permissioned [166], The Royal Society of Chemistry. h Adapted with permissioned [167], Copyright 2020, Elsevier B.V

Fig. 8 The strategies of improving rate capacity of cellulose-derived carbon materials at cellulose materials level. Optimizing valid ion transport paths strategies on the above line are doping in cellulose precursors [178,179], combining in cellulose precursors [180], and polymerizing in cellulose precursors [76]; building robust charge transport network strategies on the below line are introducing defects and groups [181], improving the crystalline structure [73,89], and regulating porous structure [182]. Doping: Adapted with permission [178,179], Copyright 2020, Elsevier B.V. and Copyright 2021, Royal Society of Chemistry. Combing: Adapted with permission [180]. Copyright 2012, American Chemical Society. Polymering: Adapted with permission [76], Copyright 2022, the Royal Society of Chemistry. Defects/groups: Adapted with permission [181], Copyright 2020, WILEY‐VCH Verlag GmbH & Co. KGaA. Porous structure: Adapted with permission [182], Copyright 2022, Elsevier Limited. Crystalline structure: Adapted with permissioned [73,89], Copyright 2022, Wiley‐VCH GmbH and Copyright 2019, Elsevier B.V

Fig. 9 N-doping [185]: a fabrication of N-doping composite electrode; b EIS spectra of N-doping electrodes at charging state after cycles and the inset images of equivalent circuits; and c illustration of N-doping carbon with different doping sites. N/S co-doping [66]: d the sodium storage behavior occurring in the N/S-doped carbon; and e graphical illustration of the carbon structures in common graphite, undoped hard carbon, and N/S co-doped hard carbon with different interlayer distances and their influences on the Na-storage capabilities. N-doping: a-c Adapted with permission [185], Copyright 2018, Elsevier B.V. N/S co-doping: d, e adapted with permission [66],Copyright 2016, WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

Fig. 10 a Types of sulfur groups in carbon matrix [178]. S-doping [63]: b preparation of S-doped carbon nanofibers; c the diffusion path of Na⁺; and d the undoped and S-doped carbon density of states. e Types of phosphonic groups in the carbon matrix [178]. Double atoms doping [186]: f rate performance of huCP/g-C₃N₄ as anode for SIBs; and g electron transfer and Na⁺ diffusion of huCP/g-C₃N₄ electrode. a Adapted with permission [178], Copyright 2020, Elsevier B.V. b-e Adapted with permission [63] Copyright 2018, The Royal Society of Chemistry. f, g Adapted with permission [186] Copyright 2017, Elsevier Limited

Fig. 11 a Schematic reduction and microwaving of GO-CNF; b rate performance of MrGO-CNF at various current density [135]; c schematic illustration of the prepared porous Co₃O₄@N-CNFs composite; d SEM image of the Co₃O₄@N-CNFs [184]; e rate performance and capacity retention rates of various carbons; f the contribution ratios of slope capacity and plateau capacity; and g FTIR spectra of commercial paper towels and coal pitch [195]. a, b Adapted with permission [135], Copyright 2019, WILEY‐VCH Verlag GmbH & Co. KGaA. c-d Adapted with permission [184], Copyright 2020, Elsevier B.V. e-g Adapted with permission [195], Copyright 2021, American Chemical Society

Fig. 12 a Preparation of activated carbon monolith with microscale layer shape and nanoscale 3D-3D cross-linked structure, BC-PAN-AC [203]; b schematic illustration of fabrication route of PMMA/BC composite monolith and its conversion to functional activated carbon [204]; c schematic of the synthesis process of CNC/PEO-derived VCAs anodes; and d typical SEM images of a cross-sectional and top-view (inset) of the CNC/PEO aerogels. e EIS analysis of various cool rate [132]; and f rate performance of BC/PMMA derived carbon anode for SIBs [76]. a Adapted with permission [203] Copyright 2018, Elsevier Limited. b Adapted with permission [204] Copyright 2018, Elsevier Limited. c-e Adapted with permission [132] Copyright 2022 Advanced Functional Materials published by Wiley‐VCH GmbH. f Adapted with permission [76] Copyright 2022, the Royal Society of Chemistry

Fig. 13 a Transportation process of Na⁺ and electron in the carbon network [210]; b the innovative in-situ engineering process for residual group control; and c atomic structure of Na⁺ absorbed on pure graphene, and different defect graphene [211]. d Fabrication process from HC to BHC-CO₂ and BHC-CO₂-H₂; e distributions in C1s pattern of O-containing groups for HC, BHC-CO₂, and BHC-CO₂-H₂; f rate performances of HC, BHC-CO₂, and BHC-CO₂-H₂ anodes at various current densities; and g adsorption energy of adsorption energy of Na on the pristine carbon surface and near ether, ketone, hydroxyl, as well as carboxyl [70]. a adapted with permission [210], Copyright 2016, WILEY‐VCH Verlag GmbH & Co. KGaA; b, c adapted with permission [211], Copyright 2019, Published by Elsevier Limited. d-g Adapted with permission [70], Copyright 2019 American Chemical Society

Fig. 14 a Strategy of preparing high-dense conductive ramie carbon (hd-CRC by pyrolysis after chemical stripping and capillary evaporation on dense cellulose molecules, b TEM image of hd-CRC revealing the highly graphitized microcrystals (hGMCs) [217]; c The rate performance for four carbon samples with different shell number [218]; d Comparison of d₀₀₂, I_D/I_G, and e L_a and L_c of different samples; f Model of short graphitic layer and nanopore about DFT calculation [84]; the correction of g the specific surface area and slope capacity, h the values of d₀₀₂ and plateau capacity [82]. a, b Adapted with permission [217]. Copyright 2023, Wiley‐VCH GmbH. c Adapted with permission [218]. Copyright 2018, WILEY‐VCH Verlag GmbH & Co. KGaA, d-f Adapted with permission [84], Copyright 2022, Wiley‐VCH GmbH. g, h Adapted with permission [82] Copyright 2022, Elsevier Limited

Fig. 15 Pore structure: a pore size distribution and b N₂ adsorption/desorption isotherms of different hard carbon samples, and c schematic diagram of Na⁺ diffusion path in NHC-7 during operation [225]; d the relationship of pore structure and ICE, slope capacity, and plateau capacity; e schematic illustration of the pore structure evolution during various thermal treatment processes; and f sodium-ion battery based on CAC-1300 anode and NVP cathode [226]. g The relationship between the plateau capacity and the mass ratio of the filler/host, ACGC, LCGC, and HCGC are corresponding active carbon, lower surface area, and higher surface area after carbonization obtained carbon, and h the capacity-potential curve [227]; and i comparison of the A parameters from SAXS in the Porod equation with BET surface area against the amount of MP [134]. a-c Adapted with permission[225] Copyright 2020, The Nonferrous Metals Society of China and Springer-Verlag GmbH Germany. d-f Adapted with permission [226] Copyright 2022 Wiley‐VCH GmbH. g, h Adapted with permission [227] Copyright 2022, Springer Nature. i Adapted with permission [134] Copyright 2019, WILEY‐VCH Verlag GmbH & Co. KGaA

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