Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion BatteriesClick to copy article linkArticle link copied!
- Daniel AntoránDaniel AntoránAragón Institute of Engineering Research (I3A), Thermochemical Processes Group, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, SpainDepartment of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, SpainMore by Daniel Antorán
- Darío AlviraDarío AlviraAragón Institute of Engineering Research (I3A), Thermochemical Processes Group, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, SpainDepartment of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, SpainMore by Darío Alvira
- M. Eser PekerM. Eser PekerFaculty of Science, Department of Chemistry, Ege University, 35100 Izmir, TurkeyMore by M. Eser Peker
- Hugo MalónHugo MalónDepartment of Mechanical Engineering, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, SpainMore by Hugo Malón
- Silvia IrustaSilvia IrustaDepartment of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, SpainAragón Institute of Nanoscience and Materials (INMA), CSIC─University of Zaragoza, Campus Río Ebro, Edificio I+D, C/ Mariano Esquillor s/n, 50018 Zaragoza, SpainNetworking Research Center on Bioengineering, Biomaterials and Nanomedicine, CIBER-BBN, 28029 Madrid, SpainMore by Silvia Irusta
- Víctor SebastiánVíctor SebastiánDepartment of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, SpainAragón Institute of Nanoscience and Materials (INMA), CSIC─University of Zaragoza, Campus Río Ebro, Edificio I+D, C/ Mariano Esquillor s/n, 50018 Zaragoza, SpainNetworking Research Center on Bioengineering, Biomaterials and Nanomedicine, CIBER-BBN, 28029 Madrid, SpainMore by Víctor Sebastián
- Joan J. Manyà*Joan J. Manyà*Email: [email protected]Aragón Institute of Engineering Research (I3A), Thermochemical Processes Group, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, SpainDepartment of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, SpainMore by Joan J. Manyà
Abstract
The present study reports the promising potential of waste hemp-hurd-derived carbons as anodes in sodium-ion batteries (SIBs). Carbons were produced through an easily scalable process consisting of pyrolysis of raw biomass at 500 °C followed by mild chemical activation of the resulting char through wet impregnation with K2CO3 and subsequent heating of the solid phase (after filtration and drying) up to 700 or 800 °C under nitrogen. The best electrochemical performance was observed for the hard carbon activated at a char-K2CO3 mass ratio of 1:4 and heated up to 800 °C, which exhibited an excellent initial coulombic efficiency (73%) and achieved reversible charge capacities of 267 and 79 mAh g–1 at 0.03 and 1 A g–1, respectively. This material also exhibited an impressive cyclic stability and rate capability, with a capacity retention of 96% after 300 cycles at a current density of 2 A g–1. This more than satisfactory performance could be related to the textural and structural features of the hard carbon, which include moderate interconnected microporosity (with pore sizes below 1 nm), an appropriate concentration of defects in the carbon structure, relatively large interplanar distances, and a certain number of closed pores.
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You are free to share(copy and redistribute) this article in any medium or format and to adapt(remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:
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Introduction
Experimental Section
Synthesis of WHH-Derived Hard Carbons
Figure 1
Figure 1. Schematic representation of the procedure adopted to synthesize HC-based electrode materials.
Physicochemical Characterization
Electrochemical Measurements
Results and Discussion
Properties of Raw WHH
proximate analysis (wt %) | lignocellulosic constituents and extractives (wt % in dry basis) | ||
---|---|---|---|
moisture | 9.24 ± 0.56 | hemicellulose | 38.1 ± 1.84 |
volatile matter (dry basis) | 81.3 ± 1.96 | cellulose | 32.0 ± 3.36 |
fixed carbon (dry basis) | 15.7 ± 0.88 | lignin | 23.8 ± 1.66 |
ash (dry basis) | 3.00 ± 0.33 | extractives | 3.10 ± 0.23 |
ultimate analysis (wt % in dry ash-free basis) | main inorganic species detected by ICP-MS (g kg–1 dry WHH) | ||
---|---|---|---|
C | 46.3 ± 0.21 | K | 14.0 |
H | 5.70 ± 0.13 | Ca | 10.8 |
N | 0.50 ± 0.04 | Al | 10.4 |
O (by difference) | 44.5 | Mg | 1.70 |
P | 1.40 | ||
Si | 1.02 | ||
Na | 0.40 |
Properties of WHH-Derived Hard Carbons
Figure 2
Figure 2. HRTEM micrographs of HC-700-4 (a, b), HHC-800-1 (c), and HHC-800-4 (d, e). Insets (squares) show enlarged views of micrographs to enhance visualization of the lattice fringes.
Figure 3
Figure 3. XRD patterns of WHH-derived carbons (a) and Raman spectra of HC-700-4 (b) and HC-800-4 (c).
material | d002 (nm) | La (nm) | Lc (nm) | AD1/AG | AD3/AG |
---|---|---|---|---|---|
HC-700-1 | 0.396 | 1.544 | 0.962 | 2.77 ± 0.128 | 0.829 ± 0.061 |
HC-700-2 | 0.402 | 1.889 | 0.894 | 4.01 ± 0.342 | 0.986 ± 0.087 |
HC-700-4 | 0.397 | 2.347 | 0.806 | 4.09 ± 0.547 | 1.08 ± 0.14 |
HC-800-1 | 0.395 | 2.497 | 0.969 | 3.85 ± 1.01 | 1.11 ± 0.16 |
HC-800-2 | 0.389 | 2.319 | 0.948 | 3.91 ± 1.18 | 0.767 ± 0.064 |
HC-800-4 | 0.397 | 1.598 | 0.883 | 6.17 ± 0.432 | 1.28 ± 0.087 |
C 1s | N 1s | |||||
---|---|---|---|---|---|---|
material | peak 1 (285.0 eV), C–C, C═C, Csp2–N | peak 2 (285.8–286.7 eV), C–O, C═O, Csp3–N | peak 3 (288.4–289.1 eV), O–C═O, C bonded to heteroatoms | peak 1 (398.8–399.1 eV), pyridinic N | peak 2 (400.0–401.0 eV), pyrrolic + pyridine N | peak 3 (401.1–401.3 eV), graphitic N |
WHH char | 82 | 10 | 8 | 18 | 82 | |
HC-700-1 | 71 | 22 | 7 | 40 | 60 | |
HC-700-2 | 58 | 26 | 16 | 17 | 83 | |
HC-700-4 | 61 | 31 | 8 | 10 | 90 | |
HC-800-1 | 66 | 24 | 10 | 26 | 74 | |
HC-800-2 | 72 | 15 | 13 | 23 | 77 | |
HC-800-4 | 59 | 29 | 12 | 33 | 67 |
material | SBETa (m2 g–1) | SBETb (m2 g–1) | micropore volumec (cm3 g–1) | mesopore volumec (cm3 g–1) | ultramicropore volumed (cm3 g–1) |
---|---|---|---|---|---|
WHH char | 159.8 | 107.5 | 0.0668 | 0.0205 | 0.0323 |
HC-700-1 | 205.2 | 151.2 | 0.0679 | 0.0366 | 0.0281 |
HC-700-2 | 207.8 | 176.1 | 0.0947 | 0.0015 | 0.0308 |
HC-700-4 | 266.0 | 179.8 | 0.1156 | 0.0067 | 0.0298 |
HC-800-1 | 26.23 | 157.6 | 0.0213 | 0.0003 | 0.0273 |
HC-800-2 | 65.80 | 151.2 | 0.0331 | 0.0094 | 0.0246 |
HC-800-4 | 333.5 | 192.3 | 0.1408 | 0.0095 | 0.0372 |
From N2 adsorption isotherm.
From CO2 adsorption isotherm.
From N2 adsorption data using a NLDFT model.
From CO2 adsorption data using a NLDFT model.
Electrochemical Performance
Figure 4
Figure 4. CV curves obtained using two-electrode setups for the first three cycles of HC-700-1 (a), HC-700-4 (b), HC-800-1 (c), and HC-800-4 (d).
Figure 5
Figure 5. GCD curves obtained using two-electrode half-cells for the first five cycles (0.03 A g–1) of HC-700-1 (a), HC-700-4 (b), HC-800-1 (c), and HC-800-4 (d).
Figure 6
Figure 6. Charge specific capacities at various current densities ranging from 0.03 to 1 A g–1 (two-electrode setup).
precursor | HC synthesis | reversible capacity (mAh g–1) at current density (A g–1) | ICE (%) | capacity retention (%) | ref |
---|---|---|---|---|---|
corn stalk | carbonization at 1200 °C followed by dual N–P doping | 143 at 1; 122 at 2 | 53 | 91 (after 2000 cycles at 1 A g–1) | (49) |
apple waste | activation with H3PO4 and subsequent carbonization at 1100 °C | 112 at 1; 86 at 2 | 61 | 100 (after 1000 cycles at 1 A g–1) | (50) |
pistachio shells | hydrothermal pretreatment with NaOH at 165 °C for 6 h and subsequent carbonization at 1000 °C | 95 at 1.2; 56 at 3 | 62 | 100 (after 500 cycles at 0.4 A g–1) | (51) |
pomelo peels | chemical activation via H3PO4 impregnation and further heating at 700 °C | 118 at 1; 94.5 at 2 | 27 | 85 (after 230 cycles at 0.05 A g–1) | (11) |
coffee grounds | chemical activation via KOH impregnation and further heating at 900 °C | 141 at 1 | 52 | 92 (after 200 cycles at 1 A g–1) | (52) |
orange peels | chemical activation via KOH impregnation and further heating at 800 °C | 125 at 1 | 42 | 94 (after 100 cycles at 1 A g–1) | (53) |
peanut shells | chemical activation via H3PO4 impregnation and further heating at 800 °C | 140 at 1; 110 at 2 | 56 | 81 (after 120 at 0.02 A g–1) | (54) |
peanut shells | hydrothermal pretreatment with NaOH at 165 °C for 4 h and subsequent carbonization at 800 °C | 100 at 1.5 | 58 | 97 (after 100 cycles at 0.02 A g–1) | (55) |
peanut shells | chemical activation via KOH impregnation and further heating at 600 °C | 150 at 1 | 33 | 86 (after 3000 cycles at 1 A g–1) | (56) |
peanut skin | hydrothermal pretreatment with H2SO4 at 180 °C for 24 h and subsequent activation with KOH impregnation and further heating at 800 °C | 154 at 1; 47 at 10 | 33 | 43 (after 200 cycles at 0.5 A g–1) | (57) |
Figure 7
Figure 7. Cycling performance of HC-800-4 over 300 cycles at 2 A g–1 (a), DNa+ values estimated from GITT measurements (for selected HCs) during sodiation (b) and desodiation (c).
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.energyfuels.3c01040.
Schematic of the electrochemical cells used; additional data from characterization of materials (SEM and HRTEM images, Raman and XPS spectra, elemental composition, adsorption isotherms, and pore sizes distributions); additional GCD curves; specific charge capacities (using two- and three-electrode setup); and values of the apparent diffusion coefficients (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
This work is part of the research project PID2019-107737RB-I00, funded by MCIN/AEI/10.13039/501100011033. The authors acknowledge the funding from the Aragon Government (ref T22_20R). D. Alvira also acknowledges the funding from the Aragon Government with a grant for postgraduate research contracts (2019–2023). LMA-ELECMI and NANBIOSIS ICTs are gratefully acknowledged.
NLDFT | non-local density functional theory |
SEM-EDX | scanning electron microscopy coupled with energy dispersive X-ray spectroscopy |
HRTEM | high-resolution transmission electron microscopy |
XRD | X-ray diffraction |
XPS | X-ray photoelectron spectroscopy |
References
This article references 58 other publications.
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- 7Huang, J.; Zhang, W.; Yu, P.; Dong, H.; Zheng, M.; Xiao, Y.; Hu, H.; Liu, Y.; Liang, Y. Direct carbonization of black liquor powders into 3D honeycomb-like porous carbons with a tunable disordered degree for sodium-ion batteries. New J. Chem. 2020, 44, 10697– 10702, DOI: 10.1039/D0NJ01228AGoogle Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtFKgt7nE&md5=6391eee07f44dadf50894cd6226d3275Direct carbonization of black liquor powders into 3D honeycomb-like porous carbons with a tunable disordered degree for sodium-ion batteriesHuang, Jianyu; Zhang, Weicai; Yu, Peifeng; Dong, Hanwu; Zheng, Mingtao; Xiao, Yong; Hu, Hang; Liu, Yingliang; Liang, YeruNew Journal of Chemistry (2020), 44 (25), 10697-10702CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)As an environmentally unfriendly and low-cost byproduct produced during the manufg. of pulp and paper, ca.170 million tons of black liquor is generated per yr in the world. Efforts to effectively convert black liquor into high-value products are very crit. but remain challenging. Herein, we successfully prep. porous carbons using black liquor powders as precursors through a simple carbonization technique without any extra activators or templates. The black liquor-derived porous carbons (BL-PCs) exhibit a remarkable three-dimensional (3D) honeycomb-like morphol. and a hierarchical porous structure. Addnl., the disordered degree of BL-PCs can be controlled by simply regulating carbonization temp. A combination of 3D honeycomb-like morphol., hierarchical porous structure and decreased disordered degree not only contributes to the fast electrolyte ion transport, but also improves the rate performance and cycling stability when BL-PCs are used as anode materials for sodium-ion batteries. A typical BL-PC anode exhibits attractive electrochem. performances, including high rate capability and long-term cycling stability.
- 8Xu, T.; Qiu, X.; Zhang, X.; Xia, Y. Regulation of surface oxygen functional groups and pore structure of bamboo-derived hard carbon for enhanced sodium storage performance. Chem. Eng. J. 2023, 452, 139514 DOI: 10.1016/j.cej.2022.139514Google Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisF2ht73M&md5=88b2eea7f21ee4847a7d9249043abecaRegulation of surface oxygen functional group and pore structure of bamboo-derived hard carbon for enhanced sodium storage performanceXu, Tianyue; Qiu, Xuan; Zhang, Xiang; Xia, YongyaoChemical Engineering Journal (Amsterdam, Netherlands) (2023), 452 (Part_4), 139514CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)Hard carbon materials with long low-voltage plateau have been used as the anode materials for sodium ion batteries which are considered to be one of the most potential large-scale energy storage systems. Herein, carbonyl groups and closed micropores are introduced into bamboo-derived hard carbon materials simultaneously to enhance the sodium ion storage performance. The carbonyl groups are demonstrated to enhance the reversible sodium adsorption in the sloping region and closed micropores are beneficial to sodium ion storage in the low-voltage plateau region. Moreover, the introducing carbonyl groups improve the reversible sloping capacity not at the expense of increasing sp. surface area and deteriorating the initial Coulombic efficiency. The hard carbon carbonized at 1300°C delivers a high reversible specific capacity of 348.5 mAh g-1 at c.d. of 30 mA g-1 with a charge/discharge Coulombic efficiency of 84.1%, and keeps a specific capacity of 295.9 mAh g-1 with a capacity retention of 91.6% at a c.d. of 300 mA g-1 after 500 cycles. This work provides a novel strategy to precisely regulate the microstructure for biomass-derived hard carbon for superior sodium ion storage performance.
- 9Karatrantos, A.; Cai, Q. Effects of pore size and surface charge on Na ion storage in carbon nanopores. Phys. Chem. Chem. Phys. 2016, 18, 30761– 30769, DOI: 10.1039/C6CP04611HGoogle Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsF2mtbnL&md5=65929d768752f13c151b00d06defed59Effects of pore size and surface charge on Na ion storage in carbon nanoporesKaratrantos, Argyrios; Cai, QiongPhysical Chemistry Chemical Physics (2016), 18 (44), 30761-30769CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Na ion batteries (NIBs) are considered as a promising low cost and sustainable energy storage technol. To better design nanoporous carbons as anode materials for NIBs, mol. dynamics simulations have been employed to study the behavior of Na+ ions (as well as PF6- ions) confined within carbon nanopores, in the presence of non-aq. (org.) solvent. The effects of pore size and surface charge d. were quantified by calcg. ionic d. profiles and concn. within the pores. Carbon slit pores of widths 0.72-10 nm were considered. The carbon surfaces were charged with densities of 0 (neutral pores), -0.8e nm-2, -1.2e nm-2, and -2e nm-2. Org. solns. of Na+ and PF6- at 1 M concns. were considered under operating conditions of sodium ion batteries. As the surface charge d. increases, more Na+ ions enter the pores. In all pores, when the surface is highly charged the Na+ ions move toward the neg. charged graphene surfaces because of counterion condensation effects. In some instances, our results reveal the formation of multiple layers of adsorbed Na+ inside the pores. Both the nanopore width and surface charge alter the d. profiles of ions and solvent inside the pores.
- 10Li, W.; Huang, J.; Feng, L.; Cao, L.; Ren, Y.; Li, R.; Xu, Z.; Li, J.; Yao, C. Controlled synthesis of macroscopic three-dimensional hollow reticulate hard carbon as long-life anode materials for Na-ion batteries. J. Alloys Compd. 2017, 716, 210– 219, DOI: 10.1016/j.jallcom.2017.05.062Google Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXns1Orurs%253D&md5=8aab8b62ac8a2416526c294a61f74b44Controlled synthesis of macroscopic three-dimensional hollow reticulate hard carbon as long-life anode materials for Na-ion batteriesLi, Wenbin; Huang, Jianfeng; Feng, Liangliang; Cao, Liyun; Ren, Yijie; Li, Ruizi; Xu, Zhanwei; Li, Jiayin; Yao, ChunyanJournal of Alloys and Compounds (2017), 716 (), 210-219CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)The controlled conversion of biomass is necessary for their efficient utilization. We report the controlled synthesis of a novel macroscopic 3-dimensional hollow reticulate hard C by hydrothermal pretreatment and further low temp. (600°) pyrolysis method. The carbonization mechanism is presented based on DTA, which shows that the hydrothermal pretreatment gets through the reticulate structure by removing flavonoids and the pyrolysis temp. is a key factor for inheriting the unique architecture. Tested against Na, the hard C exhibits good cycling stability, showing capacity retention of 90% after 1000 cycles. The excellent Na-ion storage property is attributed to the interconnected 3-dimensional architecture, the abundant O-contg. functional groups and the large interlayer spacing.
- 11Hong, K.-l.; Qie, L.; Zeng, R.; Yi, Z.; Zhang, W.; Wang, D.; Yin, W.; Wu, C.; Fan, Q.; Zhang, W.; Huang, Y. h. Biomass derived hard carbon used as a high performance anode material for sodium ion batteries. J. Mater. Chem. A 2014, 2, 12733, DOI: 10.1039/C4TA02068EGoogle Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVKmtbrO&md5=9b28ca12b1ea3a55e7e2ada7ae1e05f9Biomass derived hard carbon used as a high performance anode material for sodium ion batteriesHong, Kun-lei; Long, Qie; Zeng, Rui; Yi, Zi-qi; Zhang, Wei; Wang, Duo; Yin, Wei; Wu, Chao; Fan, Qing-jie; Zhang, Wu-xing; Huang, Yun-huiJournal of Materials Chemistry A: Materials for Energy and Sustainability (2014), 2 (32), 12733-12738CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A porous hard carbon material was synthesized by the simple pyrolysis of H3PO4-treated biomass, i.e., pomelo peels, at 700 °C in N2. The as-obtained hard carbon had a 3D connected porous structure and a large sp. surface area of 1272 m2 g-1. XPS anal. showed that the carbon material was functionalized by O-contg. and P-contg. groups. The porous hard carbon was used as an anode for sodium ion batteries and exhibited good cycling stability and rate capability, delivering a capacity of 181 mA h g-1 at 200 mA g-1 after 220 cycles and retaining a capacity of 71 mA h g-1 at 5 A g-1. The sodium storage mechanisms of the porous hard carbon can be explained by Na+ intercalation into the disordered graphene layers, redox reaction of the surface O-contg. functional groups and Na+ storage in the nanoscale pores. However, the porous hard carbon demonstrated a low coulombic efficiency of 27%, resulting from the formation of a solid electrolyte interphase film and the side reactions of surface phosphorus groups.
- 12Di Stasi, C.; Greco, G.; Canevesi, R. L. S.; Izquierdo, M. T.; Fierro, V.; Celzard, A.; González, B.; Manyà, J. J. Influence of activation conditions on textural properties and performance of activated biochars for pyrolysis vapors upgrading. Fuel 2020, 289, 119759 DOI: 10.1016/j.fuel.2020.119759Google ScholarThere is no corresponding record for this reference.
- 13Hayashi, J.; Horikawa, T.; Takeda, I.; Muroyama, K.; Nasir Ani, F. Preparing activated carbon from various nutshells by chemical activation with K2CO3. Carbon 2002, 40, 2381– 2386, DOI: 10.1016/S0008-6223(02)00118-5Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XmvVWgt7o%253D&md5=0d54763caa9603447385f223bd3a073fPreparing activated carbon from various nutshells by chemical activation with K2CO3Hayashi, Jun'ichi; Horikawa, Toshihide; Takeda, Isao; Muroyama, Katsuhiko; Nasir Ani, FaridCarbon (2002), 40 (13), 2381-2386CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Science Ltd.)We have prepd. activated carbons by chem. activation with K2CO3 from five kinds of nutshells: almond shell, coconut shell, oil palm shell, pistachio shell, and walnut shell. When prepd. at 1073 K, the activated carbons from all the nutshells had the max. sp. surface areas. Based on the max. values of sp. surface area, the activated carbons prepd. were classified into two groups: Group-L and Group-S. The former group included activated carbons with high sp. surface area and the latter included those with lower sp. surface area, resp. It was found that K2CO3 effectively worked as an activation reagent, but differently in the temp. ranges below 800 and above 900 K. Due to impregnation, cellulose and hemi-cellulose were modified by K2CO3 and accordingly the wt. loss behaviors of the nutshells were changed in the temp. range below 800 K. In the temp. range above 900 K, carbon in the chars was removed as CO by the redn. of K2CO3 to increase the sp. surface area and the pore vol. It was deduced that the difference between the sp. surface areas of Group-L and those of Group-S correspond to the difference between wt. loss behaviors in the temp. range above 900 K.
- 14Wei, H.; Chen, J.; Fu, N.; Chen, H.; Lin, H.; Han, S. Biomass-derived nitrogen-doped porous carbon with superior capacitive performance and high CO2 capture capacity. Electrochim. Acta 2018, 266, 161– 169, DOI: 10.1016/j.electacta.2017.12.192Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFCksrY%253D&md5=cd5e1c2abf5e8bfb8755ca3ccda859deBiomass-derived nitrogen-doped porous carbon with superior capacitive performance and high CO2 capture capacityWei, Huanming; Chen, Jing; Fu, Ning; Chen, Haijun; Lin, Hualin; Han, ShengElectrochimica Acta (2018), 266 (), 161-169CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)N-doped porous C was synthesized through a low-cost approach that use H2O chestnut as a C source and melamine as a N source through KOH activation for 2 h at 600-900°C. The obtained samples exhibit predominant characteristics with highly developed micropores, an ultralarge sp. surface area (3401 m2g-1) and a high N content (4.89 at.%). These characteristics endow N-doped porous C with a high specific capacity of 346 Fg-1 and a high energy d. of 22.4 Whkg-1 at 0.5 Ag-1 in 6 moldm-3 KOH. It also exhibits an excellent cycling stability with a retention of nearly 97.6% capacity after 5000 cycles at 1 Ag-1. The unique pore structure and high N content of porous C provide an important contribution to CO2 adsorption capacity, which can reach up to 6.0 mmolg-1 (at 0° and 1 bar) and 4.7 mmolg-1 (at 25 °C and 1 bar), and to high CO2/N2 selectivity. The synthesized porous C exhibit considerable potential in electrochem. energy storage and solid adsorption.
- 15Li, S.; Han, K.; Li, J.; Li, M.; Lu, C. Preparation and characterization of super activated carbon produced from gulfweed by KOH activation. Microporous Mesoporous Mater. 2017, 243, 291– 300, DOI: 10.1016/j.micromeso.2017.02.052Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXjtlyitL0%253D&md5=8892f1aff83b57ac8e521bfa5491c594Preparation and characterization of super activated carbon produced from gulfweed by KOH activationLi, Shijie; Han, Kuihua; Li, Jinxiao; Li, Ming; Lu, ChunmeiMicroporous and Mesoporous Materials (2017), 243 (), 291-300CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)In this study, gulfweed was used as precursor material for the prepn. of super activated carbon (SAC) by chem. activation method with KOH. An L16 (43) (four three-level factors) orthogonal design table was established, and the influences of the activation temp., the activation time and the impregnation ratio on the pore structure were explored. The prepd. SACs had been characterized by N2 adsorption-desorption anal., x-ray diffraction, SEM and FT-IR. When using the impregnation ratio of 4:1 at 850° for 120 min, the sp. surface area of the prepd. SACs reached the max. value, which is 3362 m2/g. All the sp. surface areas of the SACs obtained under various exptl. conditions are higher than 2200 m2/g. From the anal. of the orthogonal expt., the optimum technol. conditions are as follows: the activation temp. is 800°, the activation time is 120 min, and the impregnation ratio is 4:1. The sp. surface area of SAC was strongly influenced by the activation temp., activation time and impregnation ratio.
- 16Sevilla, M.; Ferrero, G. A.; Fuertes, A. B. Beyond KOH activation for the synthesis of superactivated carbons from hydrochar. Carbon 2017, 114, 50– 58, DOI: 10.1016/j.carbon.2016.12.010Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitVGmtL3O&md5=7781e8d2021ae1f275de2afc25e46f45Beyond KOH activation for the synthesis of superactivated carbons from hydrocharSevilla, Marta; Ferrero, Guillermo A.; Fuertes, Antonio B.Carbon (2017), 114 (), 50-58CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)A novel activating agent for the prodn. of highly microporous carbons with textural properties that match those of superactivated carbons prepd. by KOH activation, i.e. BET surface areas of 2600-3000 m2 g-1, pore vols. of ∼1.3-1.6 cm3 g-1 and pore size distributions in the supermicropore-small mesopore (<3 nm) region, is studied. It consists of a mixt. of melamine and potassium oxalate, a substance which is less corrosive than KOH, imposing less tech. restrictions. Addnl. advantages of this activating agent are that the morphol. of the particles is not altered and, importantly, the product yield is almost double that of KOH activation. The advantageous textural characteristics of the produced materials are combined with a relatively good electronic cond. of ∼2-3 S cm-1. When tested as supercapacitor electrodes using conventional electrolytes such as H2SO4 and TEABF4/AN, and less conventional ones such as EMImTFSI/AN, these carbons match the performance of benchmark KOH activated carbons and surpass that of com. activated carbons specifically designed for supercapacitor applications.
- 17Fechler, N.; Fellinger, T. P.; Antonietti, M. “salt templating”: A simple and sustainable pathway toward highly porous functional carbons from ionic liquids. Adv. Mater. 2013, 25, 75– 79, DOI: 10.1002/adma.201203422Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhsVehur%252FP&md5=dad47476daa9f4231a67c890d3ed5df5"Salt Templating": A Simple and Sustainable Pathway toward Highly Porous Functional Carbons from Ionic LiquidsFechler, Nina; Fellinger, Tim-Patrick; Antonietti, MarkusAdvanced Materials (Weinheim, Germany) (2013), 25 (1), 75-79CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Salt templating was presented as a new technique for the prepn. of functional carbons with very high apparent surface areas, higher than for any zeolite or activated carbons and approaching the value of single-layer graphene. This technique was illustrated with the prepn. of highly porous nitrogen- or nitrogen/B-doped carbons derived from 3 eutectic mixts. and different ionic liq. (ILs). The pore morphol. solely depends on the nature of the templating salt and not on the IL; thus, the main porosity is due to a templating effect by the porogen. The main advantages of the described synthesis are the formation of a homogeneous starting soln., which can be easily shaped and processed, a simple aq. removal of the porogen after carbonization and the single step approach. This offers the opportunity of tuning the morphologies of the materials from micro-to mesoporous with apparent sp. surface areas up to 2000 m2g-1. Also, the porogen can be recovered for further use which eventually results in a closed-loop process including salt recycling. Since there exist misc. combinations of ILs, porogen salts, and even metals, a variety of new and highly porous materials with tailor-made morphologies including heteroatom-doped carbons as well as metal-contg. composites can be envisioned. Thus, salt templating approach offers a step toward sustainable future chem. and materials design which enables custom-made synthesis of materials optimizing their performance, e.g., in the field of catalysis, gas or energy storage systems.
- 18Wang, L.; Rao, L.; Xia, B.; Wang, L.; Yue, L.; Liang, Y.; DaCosta, H.; Hu, X. Highly efficient CO2 adsorption by nitrogen-doped porous carbons synthesized with low-temperature sodium amide activation. Carbon 2018, 130, 31– 40, DOI: 10.1016/j.carbon.2018.01.003Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXltlWqsQ%253D%253D&md5=09b377a048a93bcc02ffc5088c90aa5fHighly efficient CO2 adsorption by nitrogen-doped porous carbons synthesized with low-temperature sodium amide activationWang, Liwei; Rao, Linli; Xia, Binbin; Wang, Linlin; Yue, Limin; Liang, Yuqing; Da Costa, Herbert; Hu, XinCarbon (2018), 130 (), 31-40CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)This work provides a simple and cost-effective way to synthesize carbonaceous sorbents with superior CO2 capture performance under ambient conditions. Using a carbonized com. phenolic resin as carbon precursor and NaNH2 as both activation agent and nitridation reagent, nitrogen-doped porous carbons were synthesized by a single-step reaction at 400-500°. The resulting carbons were highly microporous with large amts. of nitrogen content and CO2 uptake capacities up to 4.64 and 7.13 mmol/g, at atm. pressure and, resp., 25° and 0°. A systematic study showed that the synergetic effect of narrow microporosity and nitrogen content dets. the sorbents' CO2 capture capability. In addn., these phenolic-resin-derived porous carbons demonstrate excellent recyclability, stability, and dynamic CO2 capture capacity, as well as reasonable heat of adsorption and CO2/N2 selectivity. The multiple merits of these cost-effective phenolic-resin-based carbons combined with a single-step and low-temp. prepn. procedure reveal that they are excellent candidates for CO2 capture.
- 19Hayashi, J.; Horikawa, T.; Muroyama, K.; Gomes, V. G. Activated carbon from chickpea husk by chemical activation with K2CO3: Preparation and characterization. Microporous Mesoporous Mater. 2002, 55, 63– 68, DOI: 10.1016/S1387-1811(02)00406-7Google Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XmtVGqu74%253D&md5=a277002d8795e4fbdd91b1a7ab710adbActivated carbon from chickpea husk by chemical activation with K2CO3: preparation and characterizationHayashi, Jun'ichi; Horikawa, Toshihide; Muroyama, Katsuhiko; Gomes, Vincent G.Microporous and Mesoporous Materials (2002), 55 (1), 63-68CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Science B.V.)Activated carbon was prepd. from chickpea husk by chem. activation with K2CO3. At 1073 K, the sp. surface area of activated carbon prepd. with an impregnation ratio of 1.0 yielded the max. value of 1778 m2/g. From the results of the yield of the activated carbon and the reagent recovery ratio, it was concluded that the carbon involved in the husk char was removed as CO by redn. of K2CO3 above 1000 K. The fractal dimension changed slightly between 773 and 973 K, and it decreased rapidly between 973 and 1173 K. It was deduced that this decrease of the fractal dimension was due to the decompn. of the cross-linked structure and the small crystallite structure. The micropore vol. and the sp. surface area increased by the release of plugged pore due to the decompn. of the cross-linked structure. It was further deduced that the mesopore vol. increased and the micropore vol. decreased by combination of micropores due to the decompn. of small crystallites.
- 20Adinata, D.; Wan Daud, W. M. A.; Aroua, M. K. Preparation and characterization of activated carbon from palm shell by chemical activation with K2CO3. Bioresour. Technol. 2007, 98, 145– 149, DOI: 10.1016/j.biortech.2005.11.006Google Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD28risVCgtQ%253D%253D&md5=2301cd4770c3bff98be23c078e0d9471Preparation and characterization of activated carbon from palm shell by chemical activation with K2CO3Adinata Donni; Wan Daud Wan Mohd Ashri; Aroua Mohd KheireddineBioresource technology (2007), 98 (1), 145-9 ISSN:0960-8524.Palm shell was used to prepare activated carbon using potassium carbonate (K2CO3) as activating agent. The influence of carbonization temperatures (600-1000 degrees C) and impregnation ratios (0.5-2.0) of the prepared activated carbon on the pore development and yield were investigated. Results showed that in all cases, increasing the carbonization temperature and impregnation ratio, the yield decreased, while the adsorption of CO2 increased, progressively. Specific surface area of activated carbon was maximum about 1170 m2/g at 800 degrees C with activation duration of 2 h and at an impregnation ratio of 1.0.
- 21Carvalho, A.; Gomes, M.; Mestre, A.; Pires, J.; Brotas de Carvalho, M. Activated carbons from cork waste by chemical activation with K2CO3. Carbon 2004, 42, 672– 674, DOI: 10.1016/j.carbon.2003.12.075Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtVKit74%253D&md5=4fcb870651b90129eec58b2f3df56d0fActivated carbons from cork waste by chemical activation with K2CO3. Application to adsorption of natural gas componentsCarvalho, A. P.; Gomes, M.; Mestre, A. S.; Pires, J.; Brotas de Carvalho, M.Carbon (2004), 42 (3), 672-674CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Science Ltd.)Cork waste was used to produce activated carbons by chem. activation with K2CO3. The adsorption isotherms of methane, carbon dioxide, ethane and nitrogen, e.g., in natural or landfill gas, were detd. at ambient temp on a granular sample using a clay binder.
- 22Carrott, P. J. M.; Ribeiro Carrott, M. M. L.; Mourão, P. A. M. Pore size control in activated carbons obtained by pyrolysis under different conditions of chemically impregnated cork. J. Anal. Appl. Pyrolysis 2006, 75, 120– 127, DOI: 10.1016/j.jaap.2005.04.013Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFyisr4%253D&md5=80e94b55d89c54a056b0729db1e1169bPore size control in activated carbons obtained by pyrolysis under different conditions of chemically impregnated corkCarrott, P. J. M.; Ribeiro Carrott, M. M. L.; Mourao, P. A. M.Journal of Analytical and Applied Pyrolysis (2006), 75 (2), 120-127CODEN: JAAPDD; ISSN:0165-2370. (Elsevier B.V.)Activated carbons were prepd. by the pyrolysis of cork impregnated with potassium and sodium hydroxides and carbonates as well as phosphoric acid and the effect of five exptl. parameters, namely method of impregnation, impregnant concn., mass ratio, precursor particle size, and pyrolysis temp., were studied. It is shown that cork is a versatile precursor and allows us to prep. a wide variety of materials with quite different pore structural characteristics by precise control of the impregnation and pyrolysis conditions. Even under relatively mild conditions, it was possible to produce cork based carbons with high pore vols., in the range 0.5-0.7 cm3 g-1, and to simultaneously control the mean pore width over a three-fold range from a value as low as 0.7 nm up to a value as high as 2.2 nm. The best materials produced present pore structural characteristics which are significantly different to the vast majority of com. activated carbons. In particular, the possibility of obtaining such high pore vols. in essentially microporous materials, contg. virtually no mesoporosity in most cases, is noteworthy. Furthermore, the fact that it was possible with some samples to combine high pore vol. and very narrow micropore size is a particularly notable achievement.
- 23European Commission. Hemp Production on the EU. https://agriculture.ec.europa.eu/farming/crop-productions-and-plant-based-products/hemp_en (accessed January 27, 2023).Google ScholarThere is no corresponding record for this reference.
- 24Um, J. H.; Ahn, C. Y.; Kim, J.; Jeong, M.; Sung, Y. E.; Cho, Y. H.; Kim, S. S.; Yoon, W. S. From grass to battery anode: Agricultural biomass hemp-derived carbon for lithium storage. RSC Adv. 2018, 8, 32231– 32240, DOI: 10.1039/C8RA06958AGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhslCntLrP&md5=c97a3973d651a49cbf44bf4ad9b29ba2From grass to battery anode: agricultural biomass hemp-derived carbon for lithium storageUm, Ji Hyun; Ahn, Chi-Yeong; Kim, Jinsoo; Jeong, Mihee; Sung, Yung-Eun; Cho, Yong-Hun; Kim, Seung-Soo; Yoon, Won-SubRSC Advances (2018), 8 (56), 32231-32240CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Biomass-derived carbon, as a low-cost material source, is an attractive choice to prep. carbon materials, thus providing an alternative to byproduct and waste management. Herein, we report the prepn. of carbon from hemp stem as a biomass precursor through a simple, low-cost, and environment-friendly method with using steam as the activating agent. The hemp-derived carbon with a hierarchically porous structure and a partial graphitization in amorphous domains was developed, and for the first time, it was applied as an anode material for lithium-ion battery. Natural hemp itself delivers a reversible capacity of 190 mA h g-1 at a rate of 300 mA g-1 after 100 cycles. Ball-milling of hemp-derived carbon is further designed to control the phys. properties, and consequently, the capacity of milled hemp increases to 300 mA h g-1 along with excellent rate capability of 210 mA h g-1 even at 1.5 A g-1. The milled hemp with increased graphitization and well-developed meso-porosity is advantageous for lithium diffusion, thus enhancing electrochem. performance via both diffusion-controlled intercalation/deintercalation and surface-limited adsorption/desorption. This study not only demonstrates the application of hemp-derived carbon in energy storage devices, but also guides a desirable structural design for lithium storage and transport.
- 25Wang, H.; Xu, Z.; Kohandehghan, A.; Li, Z.; Cui, K.; Tan, X.; Stephenson, T. J.; King’ondu, C. K.; Holt, C. M. B.; Olsen, B. C. Interconnected Carbon Nanosheets Derived from Hemp for Ultrafast Supercapacitors with High Energy. ACS Nano 2013, 7, 5131– 5141, DOI: 10.1021/nn400731gGoogle Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXntFWgu7Y%253D&md5=82fd8d2653f9b71c168c5d670f5791c4Interconnected Carbon Nanosheets Derived from Hemp for Ultrafast Supercapacitors with High EnergyWang, Huanlei; Xu, Zhanwei; Kohandehghan, Alireza; Li, Zhi; Cui, Kai; Tan, Xuehai; Stephenson, Tyler James; King'ondu, Cecil K.; Holt, Chris M. B.; Olsen, Brian C.; Tak, Jin Kwon; Harfield, Don; Anyia, Anthony O.; Mitlin, DavidACS Nano (2013), 7 (6), 5131-5141CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)The authors created unique interconnected partially graphitic C nanosheets (10-30 nm in thickness) with high sp. surface area (up to 2287 m2 g-1), significant vol. fraction of mesoporosity (up to 58%), and good elec. cond. (211-226 S m-1) from hemp bast fiber. The nanosheets are ideally suited for low (down to 0°) through high (100°) temp. ionic-liq.-based supercapacitor applications: At 0° and a c.d. of 10 A g-1, the electrode maintains a capacitance of 106 F g-1. At 20, 60, and 100° and an extreme c.d. of 100 A g-1, there is excellent capacitance retention (72-92%) with the specific capacitances being 113, 144, and 142 F g-1, resp. These characteristics favorably place the materials on a Ragone chart providing among the best power-energy characteristics (on an active mass normalized basis) ever reported for an electrochem. capacitor: At a very high power d. of 20 kW kg-1 and 20, 60, and 100°, the energy densities are 19, 34, and 40 W-h kg-1, resp. Also the assembled supercapacitor device yields a max. energy d. of 12 W-h kg-1, which is higher than that of com. available supercapacitors. By taking advantage of the complex multilayered structure of a hemp bast fiber precursor, such exquisite carbons were able to be achieved by simple hydrothermal carbonization combined with activation. This novel precursor-synthesis route presents a potential for facile large-scale prodn. of high-performance carbons for a variety of diverse applications including energy storage.
- 26Wang, P.; Zhu, K.; Ye, K.; Gong, Z.; Liu, R.; Cheng, K.; Wang, G.; Yan, J.; Cao, D. Three-dimensional biomass derived hard carbon with reconstructed surface as a free-standing anode for sodium-ion batteries. J. Colloid Interface Sci. 2020, 561, 203– 210, DOI: 10.1016/j.jcis.2019.11.091Google Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitleis7zL&md5=e28727acf3dce19245480a288f0c4cfcThree-dimensional biomass derived hard carbon with reconstructed surface as a free-standing anode for sodium-ion batteriesWang, Pengfei; Zhu, Kai; Ye, Ke; Gong, Zhe; Liu, Ran; Cheng, Kui; Wang, Guiling; Yan, Jun; Cao, DianxueJournal of Colloid and Interface Science (2020), 561 (), 203-210CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)A 3-dimensional free-standing hard C (FHC) electrode is synthesized by carbonizing the hemp haulm and employed as anode for Na-ion batteries directly. A high current charging-discharging process is carried out to reconstruct surface structure of the FHC. Surface reconstructed FHC display a high capacity of 256 mAh/g and enhanced rate ability. With the formation of order surface structure, the plateau capacity increase and more Na ions can insert into the FHC. This work demonstrates the importance of surface structure for Na ion diffusion and storage and provide a new strategy to design high-performance anode materials.
- 27Rodríguez-Correa, C.; Hehr, T.; Voglhuber-Slavinsky, A.; Rauscher, Y.; Kruse, A. Pyrolysis vs. hydrothermal carbonization: Understanding the effect of biomass structural components and inorganic compounds on the char properties. J. Anal. Appl. Pyrolysis 2019, 140, 137– 147, DOI: 10.1016/j.jaap.2019.03.007Google Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtlOrs7Y%253D&md5=4284f25d625eb2686990c4b9e7c56b52Pyrolysis vs. hydrothermal carbonization: Understanding the effect of biomass structural components and inorganic compounds on the char propertiesRodriguez Correa, Catalina; Hehr, Tobias; Voglhuber-Slavinsky, Ariane; Rauscher, Yannik; Kruse, AndreaJournal of Analytical and Applied Pyrolysis (2019), 140 (), 137-147CODEN: JAAPDD; ISSN:0165-2370. (Elsevier B.V.)The influence and role of the different biomass components during HTC and pyrolysis as well as its effects on the char properties were studied. For this, three agricultural residues (wheat straw, pine bark and macauba nut shell) in three different forms (original, leached with acetic acid and synthetic mixts.) were chosen as precursors. Synergies between the biomass components were evidenced: the biomass samples with the higher lignin content lead to higher biochar yields and the biomass samples in general lead to higher yields than the synthetic mixts. Furthermore, the viscoelastic nature of lignin was overshadowed by the rigidity of cellulose in the real biomass samples leading to thermally more stable biochars with larger surface areas. Leaching the inorgs. from the biomass lead to biochars with the largest surface areas and it had a pos. impact on the carbon contents and calorific values.
- 28Greco, G.; Videgain, M.; Di Stasi, C.; González, B.; Manyà, J. J. Evolution of the mass-loss rate during atmospheric and pressurized slow pyrolysis of wheat straw in a bench-scale reactor. J. Anal. Appl. Pyrolysis 2018, 136, 18– 26, DOI: 10.1016/j.jaap.2018.11.007Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1Chs7zJ&md5=1aa10f6ef04508095e170c4ef78f75dfEvolution of the mass-loss rate during atmospheric and pressurized slow pyrolysis of wheat straw in a bench-scale reactorGreco, Gianluca; Videgain, Maria; Di Stasi, Christian; Gonzalez, Belen; Manya, Joan J.Journal of Analytical and Applied Pyrolysis (2018), 136 (), 18-26CODEN: JAAPDD; ISSN:0165-2370. (Elsevier B.V.)In the present study, the effects of the abs. pressure (0.1 or 0.5 MPa) and the reactor atm. (pure N2 or a mixt. of CO2/N2) on the pyrolysis behavior of wheat straw pellets (at 500 °C) were investigated. The most interesting aspect of this work was the use of a weighing platform (with a max. capacity of 100 kg and a resoln. of 0.5 g) to monitor the real-time mass-loss data for the biomass sample (with an initial mass of 400 g). It was obsd. that an increased pressure considerably affects the mass-loss profiles during the pyrolysis process, leading to higher devolatilization rates in a shorter period of time. Regardless of the pyrolysis atm., an increase in the abs. pressure led to higher yields of gas at the expense of produced water and condensable org. compds. This finding could be due to the fact that an increased pressure favors the exothermic secondary reactions of the intermediate volatile org. compds. in both liq. and vapor phases. The switch from pure N2 to a mixt. of CO2 and N2 at 0.1 MPa also led to a remarkable increase in the yield of produced gas at the expense of the total liq. This could be mainly due to the promotion of the thermal cracking of the volatile org. compds. at a high partial pressure of CO2, which is also consistent with the measured higher yields of CH4 and CO. The increased yield of CO can also be seen as a direct result of the enhanced reverse Boudouard reaction, which can also explain the much higher sp. surface area (and ultra-micropore vol.) measured for the biochar produced under the same operating conditions (0.1 MPa and a mixt. CO2/N2 as pyrolysis medium).
- 29Greco, G.; Di Stasi, C.; Rego, F.; González, B.; Manyà, J. J. Effects of slow-pyrolysis conditions on the products yields and properties and on exergy efficiency: A comprehensive assessment for wheat straw. Appl. Energy 2020, 279, 115842 DOI: 10.1016/j.apenergy.2020.115842Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVynur%252FP&md5=e8c9d6044c5bd3012561f1878e537b76Effects of slow-pyrolysis conditions on the products yields and properties and on exergy efficiency: A comprehensive assessment for wheat strawGreco, Gianluca; Di Stasi, Christian; Rego, Filipe; Gonzalez, Belen; Manya, Joan J.Applied Energy (2020), 279 (), 115842CODEN: APENDX; ISSN:0306-2619. (Elsevier Ltd.)In the present work, the effects of the peak temp. (400-550°C), abs. pressure (0.2-0.9 MPa), gas residence time (100-200 s) and reactor atm. (pure N2 or a mixt. of CO2/N2) on the pyrolysis behavior of wheat straw pellets were investigated. A factorial design of expts. was adopted to assess the effects of the above-mentioned factors on the pyrolysis products, the exergy efficiencies related to them and to the overall process, and the heat required. The pyrolysis energy/exergy assessment is nowadays of great interest, for the scaling of the installations from lab-scale to com.-scale. Results showed that, as expected, the peak temp. was the most influential factor on the yields and distributions of all the pyrolysis products as well as the char properties related to its potential stability and pore size distribution. However, an increased pressure enhanced the release of the gas species at the expense of the liq. products, without altering the final char yield. The char exergy efficiency was neg. affected by an increase in peak temp., whereas its effect on the exergy efficiency of the produced gas resulted to be pos. It was also found that pressurized pyrolysis favored the exergy efficiency of the process, even at relatively high pyrolysis peak temp. For the biomass feedstock and the range of operating conditions studied here, thermodn. irreversibilities of the pyrolysis system were considerably lowered when the process was conducted at 550°C, 0.9 MPa and using a mixt. of CO2 and N2 as carrier gas at relatively short residence times.
- 30Zhang, T.; Mao, J.; Liu, X.; Xuan, M.; Bi, K.; Zhang, X. L.; Hu, J.; Fan, J.; Chen, S.; Shao, G. Pinecone biomass-derived hard carbon anodes for high-performance sodium-ion batteries. RSC Adv. 2017, 7, 41504– 41511, DOI: 10.1039/C7RA07231GGoogle Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsVersbnK&md5=d3a51c0bcf458d1c87b2a815595752e2Pinecone biomass-derived hard carbon anodes for high-performance sodium-ion batteriesZhang, Tao; Mao, Jing; Liu, Xiaolin; Xuan, Minjie; Bi, Kai; Zhang, Xiao Li; Hu, Junhua; Fan, Jiajie; Chen, Shimou; Shao, GuoshengRSC Advances (2017), 7 (66), 41504-41511CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Hard-carbon is considered as one of the most promising anode materials for sodium-ion batteries (SIBs). Now it is imperative to develop a proper prepn. method to obtain hard carbon anode particles with high initial coulombic efficiency and good cycling performance. In this paper, we have successfully prepd. high performance hard carbon anodes, by selecting abundant and low-cost pinecones as biomass precursor and optimizing the prepn. parameters of pinecone-derived hard carbon (PHC). The microstructure of PHC is studied by X-ray diffraction (XRD), Raman spectroscopy, high-resoln. transmission electron microscopy (HRTEM) as well as nitrogen adsorption-desorption isotherm methods. The performance of PHC is highly dependent on the carbonization temp. Increasing carbonization temp. of pinecone precursor can reduce surface area and thus improve the initial coulombic efficiency. Varying carbonization temp. can also adjust the slope and plateau capacity of PHC, and then regulate the energy d. and power characteristics of PHC in battery operation. PHC1400 still delivers a capacity of 334 mA h g-1 after 120 cycles, with a high initial coulombic efficiency of 85.4%. Our results suggest that PHC is a promising anode material for practical large-scale SIB application.
- 31Manyà, J. J.; Alvira, D.; Azuara, M.; Bernin, D.; Hedin, N. Effects of Pressure and the Addition of a Rejected Material from Municipal Waste Composting on the Pyrolysis of Two-Phase Olive Mill Waste. Energy Fuels 2016, 30, 8055– 8064, DOI: 10.1021/acs.energyfuels.6b01579Google Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVOitrzL&md5=b90f191fdc305a7181bb04489b1051cbEffects of Pressure and the Addition of a Rejected Material from Municipal Waste Composting on the Pyrolysis of Two-Phase Olive Mill WasteManya, Joan J.; Alvira, Dario; Azuara, Manuel; Bernin, Diana; Hedin, NiklasEnergy & Fuels (2016), 30 (10), 8055-8064CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)This work examines the effect of the abs. pressure (0.1 or 1.0 MPa) and the addn. of a high-ash rejected material from municipal solid waste (MSW) composting (RC) on the slow pyrolysis of two-phase olive mill waste (OW). The expts. were conducted in a batch pyrolysis system using an initial mass of 750 g of feedstock. Three types of initial materials were tested: the OW alone, a mixt. of OW and pure additives (5 wt % K2CO3 and 5 wt % CaO), and a mixt. of OW and RC (10 wt %). For the OW without any additive, an increased pressure led to a market increase in the carbonization efficiency (i.e., fixed carbon yield). At atm. pressure, the addn. of either additives (CaO + K2CO3) or RC led to important changes in the pyrolysis behavior as a result of the catalytic role of the alkali and alk. earth metals (AAEMs). However, this catalytic effect, which is translated into an enhancement of the decompn. of both the hemicellulose and cellulose fractions, was not obsd. at 1.0 MPa. The potential stability of all of the produced biochars appeared to be very high, given the results obtained from both proximate and ultimate analyses. This high stability was confirmed by 13C and 1H solid-state NMR, which showed that the carbon contained in the biochars was composed mainly or entirely of highly condensed arom. structures. However, the highest values of stable C (Edinburgh stability tool) and R50,x (recalcitrance index) were obtained for biochars produced from the OW + RC mixts. at any pressure. In summary, the addn. of the rejected material from MSW composting appears to be a very cost-effective measure to obtain a potentially high-stable biochar, even at atm. pressure.
- 32Xi, Y.; Wang, Y.; Yang, D.; zhang, Z.; Liu, W.; Li, Q.; Qiu, X. K2CO3 activation enhancing the graphitization of porous lignin carbon derived from enzymatic hydrolysis lignin for high performance lithium-ion storage. J. Alloys Compd. 2019, 785, 706– 714, DOI: 10.1016/j.jallcom.2019.01.039Google Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvF2ns74%253D&md5=54bdc884128fc166c3ef281cdceefa5bK2CO3 activation enhancing the graphitization of porous lignin carbon derived from enzymatic hydrolysis lignin for high performance lithium-ion storageXi, Yuebin; Wang, Yuanyuan; Yang, Dongjie; Zhang, Zhekun; Liu, Weifeng; Li, Qiong; Qiu, XueqingJournal of Alloys and Compounds (2019), 785 (), 706-714CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)As an abundant natural arom. polymer with high carbon content, lignin can be regarded as an abundant carbon matrix precursor to develop cost-effective and environmental friendly porous carbon for energy storage materials. However, the porous lignin-derived carbon remains a great challenge as an anode for Li-ion batteries due to its low degree of graphitization. In this paper, a low-cost, productive and scalable industrial method has been adopted to fabricate highly graphitized lignin-based porous carbon (PLC-EHL-K2CO3) with K2CO3 activation using enzymic hydrolysis lignin (EHL) as a raw material. PLC-EHL-K2CO3 was composed of multilevel lamellar structure possessing high sp. surface area and macro- and mesoporous. Notably, the graphitization of PLC-EHL-K2CO3 was significantly improved compared with the common KOH activation. Meanwhile, the structure of lignin is an important factor affecting the structure of PLC, such as the mol. wt. and oxygen functional groups. The high sp. surface area, large pore vol. and unique multilevel lamellar morphol. bestow PLC an excellent lithium storage performance, and PLC-EHL-K2CO3 electrode displays a desirable reversible capacity of 520 mAh·g-1 at a c.d. of 200 mA g-1 over 200 cycles and increases 47.3% than PLC-EHL-KOH, and even at 1 A g-1 a specific capacity of 260 mAh·g-1 can be retained after 1000 cycles. This higher graphitization porous carbon material from low-cost renewable lignin is a good candidate for lithium storage equipment.
- 33Govind Raj, K.; Joy, P. A. Role of localized graphitization on the electrical and magnetic properties of activated carbon. J. Am. Ceram. Soc. 2017, 100, 5151– 5161, DOI: 10.1111/jace.15035Google Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVyrtr%252FK&md5=85124e236b4b30d01b99d765b39661a3Role of localized graphitization on the electrical and magnetic properties of activated carbonGovind Raj, Kovummal; Joy, Pattayil AliasJournal of the American Ceramic Society (2017), 100 (11), 5151-5161CODEN: JACTAW; ISSN:0002-7820. (Wiley-Blackwell)The correlation between the magnetic and elec. properties of activated carbon with its microstructure is studied. The changes in the microstructure of activated carbon, after activation at 3 different temps. (800°, 900°, and 1000°) using different amts. of the activating agent, KOH (KOH/C ratio of 1:1, 2:1, 3:1, and 4:1), are studied using X-ray diffraction and Raman spectroscopy. The results showed the formation of localized nanographitic domains, along with the changes in the surface area and porosity of the activated carbon. The changes in the microstructure are found to be directly correlated with the magnetic properties and elec. cond. The interplay between ordering and disordering parameters in the activated carbon is found to det. the elec. cond. and magnetic properties.
- 34Au, H.; Alptekin, H.; Jensen, A. C. S.; Olsson, E.; O’Keefe, C. A.; Smith, T.; Crespo-Ribadeneyra, M.; Headen, T. F.; Grey, C. P.; Cai, Q. A revised mechanistic model for sodium insertion in hard carbons. Energy Environ. Sci. 2020, 13, 3469– 3479, DOI: 10.1039/D0EE01363CGoogle Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFyktLjJ&md5=a7181f3c171e70a094942fc79cb26548A revised mechanistic model for sodium insertion in hard carbonsAu, Heather; Alptekin, Hande; Jensen, Anders C. S.; Olsson, Emilia; O'Keefe, Christopher A.; Smith, Thomas; Crespo-Ribadeneyra, Maria; Headen, Thomas F.; Grey, Clare P.; Cai, Qiong; Drew, Alan J.; Titirici, Maria-MagdalenaEnergy & Environmental Science (2020), 13 (10), 3469-3479CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Hard carbons have shown considerable promise as anodes for emerging sodium-ion battery technologies. Current understanding of sodium-storage behavior in hard carbons attributes capacity to filling of graphitic interlayers and pores, and adsorption at defects, although there is still considerable debate regarding the voltages at which these mechanisms occur. Here, ex situ23Na solid-state NMR and total scattering studies on a systematically tuned series of hard carbons revealed the formation of increasingly metallic sodium clusters in direct correlation to the growing pore size, occurring only in samples which exhibited a low voltage plateau. Combining exptl. results with DFT calcns., we propose a revised mechanistic model in which sodium ions store first simultaneously and continuously at defects, within interlayers and on pore surfaces. Once these higher energy binding sites are filled, pore filling occurs during the plateau region, where the densely confined sodium takes on a greater degree of metallicity.
- 35Ramirez, N.; Sardella, F.; Deiana, C.; Schlosser, A.; Müller, D.; Kißling, P. A.; Klepzig, L. F.; Bigall, N. C. Capacitive behavior of activated carbons obtained from coffee husk. RSC Adv. 2020, 10, 38097– 38106, DOI: 10.1039/D0RA06206EGoogle Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVyiu73N&md5=ef8c407d0a77303a459a75294bd7c11eCapacitive behavior of activated carbons obtained from coffee huskRamirez, Nathalia; Sardella, Fabiana; Deiana, Cristina; Schlosser, Anja; Mueller, Dennis; Kissling, Patrick A.; Klepzig, Lars F.; Bigall, Nadja C.RSC Advances (2020), 10 (62), 38097-38106CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Sustainable agroindustry has presented many challenges related to waste management. Most of its residues are lignocellulosic biomass materials with great application potential due to their chem. compn., hence the use of biomass-derived carbon materials in energy storage has received growing interest in recent years. In this work, highly micro-porous carbonaceous materials using the endocarp of the coffee fruit or coffee husk (CH) as precursor are obtained. Specifically, three different activating agents (KOH, K2CO3, and steam) to derive activated carbons (ACs) with good capacitive properties are tested. The properties of ACs such as surface chem., texture, crystal graphite size, and order in the carbonaceous structure are assessed and compared. The capacitive behavior inherent to the activation routes is also characterized by means of Cyclic Voltammetry (CV), Galvanostatic Charge/Discharge (GCD) and Electrochem. Impedance Spectroscopy (EIS). The obtained specific capacitance values range from 106 to 138 F g-1 for a discharge current of 0.5 A g-1. These results nominate coffee husk as a good precursor of carbonaceous materials suitable for energy storage.
- 36Alvira, D.; Antorán, D.; Manyà, J. J. Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guide. J. Energy Chem. 2022, 75, 457– 477, DOI: 10.1016/j.jechem.2022.09.002Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisFOhsLvJ&md5=7106065e03537d80b8349eeac4395df5Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guideAlvira, Dario; Antoran, Daniel; Manya, Joan J.Journal of Energy Chemistry (2022), 75 (), 457-477CODEN: JECOFG; ISSN:2095-4956. (Science Press)Sodium-ion batteries (SIBs) are considered as a promising candidate to replace lithium-ion batteries (LIBs) in large-scale energy storage applications. Abundant sodium resources and similar working principles make this technol. attractive to be implemented in the near future. However, the development of high-performance carbon anodes is a focal point to the upcoming success of SIBs in terms of power d., cycling stability, and lifespan. Fundamental knowledge in electrochem. and physicochem. techniques is required to properly evaluate the anode performance and move it in the right direction. This review aims at providing a comprehensive guideline to help researchers from different backgrounds (e.g., nanomaterials and thermochem.) to delve into this topic. The main components, lab configurations, procedures, and working principles of SIBs are summarized. Moreover, a detailed description of the most used electrochem. and physicochem. techniques to characterize electrochem. active materials is provided.
- 37Väli, R.; Jänes, A.; Thomberg, T.; Lust, E. Synthesis and characterization of D-glucose derived nanospheric hard carbon negative electrodes for lithium- and sodium-ion batteries. Electrochim. Acta 2017, 253, 536– 544, DOI: 10.1016/j.electacta.2017.09.094Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFGjsrrJ&md5=cf95b5026bf8c439be3272311abd2b40Synthesis and characterization of D-glucose derived nanospherical hard carbon negative electrodes for lithium- and sodium-ion batteriesVali, R.; Janes, A.; Thomberg, T.; Lust, E.Electrochimica Acta (2017), 253 (), 536-544CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)The electrochem. performance of glucose-derived hard C (GDHC) anode was evaluated using Li- and Na-salts in ethylene carbonate and propylene carbonate electrolyte mixts. The LiPF6/EC:PC (1:1) system exhibits high capacity at low current densities (400 mAh g-1 at 25 mA g-1) and also good power characteristics retaining 150 mAh g-1 capacity at 2 A g-1 c.d. The best overall performance was achieved with 1 M NaPF6/EC:PC (1:1) electrolyte based system with capacities of 175 mAh g-1 at 0.1 V vs. Na/Na+ and 330 mAh g-1 at 1.5 V vs. Na/Na+. The electrode was phys. characterized ex-situ using SEM, Raman and TOF-SIMS methods TOF-SIMS anal. revealed that the solid electrolyte interphase is more inorg. on the neg. electrode in the Na-cell than on the neg. electrode the Li-cell. The pos. ion-specific images established by TOF-SIMS anal. show the nonhomogeneous distribution of various fragments from the pristine GDHC, which is caused by slightly inhomogeneous mixt. of GDHC and conducting C black (Super P) particles.
- 38Cao, L.; Hui, W.; Xu, Z.; Huang, J.; Zheng, P.; Li, J.; Sun, Q. Rape seed shuck derived-lamellar hard carbon as anodes for sodium-ion batteries. J. Alloys Compd. 2017, 695, 632– 637, DOI: 10.1016/j.jallcom.2016.11.135Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvVKqu7jL&md5=76d015686bfe7f97a1cdadadb60db97cRape seed shuck derived-lamellar hard carbon as anodes for sodium-ion batteriesCao, Liyun; Hui, Wenle; Xu, Zhanwei; Huang, Jianfeng; Zheng, Peng; Li, Jiayin; Sun, QianqianJournal of Alloys and Compounds (2017), 695 (), 632-637CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)Hard carbon with large interlayer spacing is suitable as the anode material for sodium-ion batteries. Rape seed shuck derived lamellar hard carbon is synthesized through hydrothermal and pyrolysis processes. As the anode, it exhibited good cycling stability, delivering a capacity of 143 mAh g-1 after 200 cycles at 100 mA g-1. The promising performances are attributed to the sheet structure with expanded interlayer distance (0.39 nm) and much void which can lower the sodium-ion insertion-extn. barrier and promote Na-ion diffusion and storage. The effect of pyrolysis temp. on the performance is also investigated.
- 39Sadezky, A.; Muckenhuber, H.; Grothe, H.; Niessner, R.; Pöschl, U. Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information. Carbon 2005, 43, 1731– 1742, DOI: 10.1016/j.carbon.2005.02.018Google Scholar39https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXltFGrtLc%253D&md5=045e6d9ee2eb3d84bd001fca25bc7f62Raman microspectroscopy of soot and related carbonaceous materials. Spectral analysis and structural informationSadezky, A.; Muckenhuber, H.; Grothe, H.; Niessner, R.; Poeschl, U.Carbon (2005), 43 (8), 1731-1742CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Exptl. conditions and math. fitting procedures for the collection and anal. of Raman spectra of soot and related carbonaceous materials were investigated and optimized with a Raman microscope system operated at 3 different laser excitation wavelengths (514, 633, and 780 nm). Several band combinations for spectral anal. were tested, and a combination of 4 Lorentzian-shaped bands (G, D1, D2, D4) at about 1580, 1350, 1620, and 1200 cm-1, resp., with a Gaussian-shaped band (D3) at ∼1500 cm-1 was best suited for the 1st-order spectra. The 2nd-order spectra were best fitted with Lorentzian-shaped bands at about 2450, 2700, 2900, and 3100 cm-1. Spectral parameters (band positions, full widths at half max., and intensity ratios) are reported for several types of industrial C black (Degussa Printex, Cabot Monarch), diesel soot (particulate matter from modern heavy duty vehicle and passenger car engine exhaust, NIST SRM1650), spark-discharge soot (Palas GfG100), and graphite. Several parameters, in particular the width of the D1 band at ∼1350 cm-1, provide structural information and allow to discriminate the sample materials, but the characterization and distinction of different types of soot is limited by the exptl. reproducibility of the spectra and the statistical uncertainties of curve fitting. The results are discussed and compared with x-ray diffraction measurements and earlier Raman spectroscopic studies of comparable materials, where different measurement and fitting procedures was applied.
- 40Wang, X.; Chen, Q.; Zhu, H.; Chen, X.; Yu, G. In-situ study on structure evolution and gasification reactivity of biomass char with K and Ca catalysts at carbon dioxide atmosphere. Carbon Resour. Convers. 2023, 6, 27– 33, DOI: 10.1016/j.crcon.2022.10.002Google Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XivVGlsrnI&md5=bc9d458c3b72c1bf398fe82f435d56c4In-situ study on structure evolution and gasification reactivity of biomass char with K and Ca catalysts at carbon dioxide atmosphereWang, Xingjun; Chen, Qian; Zhu, Huaili; Chen, Xueli; Yu, GuangsuoCarbon Resources Conversion (2023), 6 (1), 27-33CODEN: CRCACJ; ISSN:2588-9133. (KeAi Communications Co., Ltd.)The structural evolution and gasification reactivity of biochar prepd. from the pyrolysis of wheat straw were investigated by in-situ Raman spectroscopy and thermogravimetric anal. The Raman spectra consisted of a combination of four Lorentzian bands (D1, D2, D4, G) and one Gaussian band (D3) in the first-order region. The exptl. results showed that the addn. of catalysts or the presence of ash could improve the CO2 gasification reactivity of biochar and result in a larger ID1/IG ratio and a lower IG/IALL ratio, meaning that the carbon structure was less ordered, and there were also more active sites such as amorphous carbon and cross-linked structures; Ca-based catalysts and K-based catalysts changed the evolution of biochar structure in a different way in CO2 atmosphere, the ID3/ID1 of Ca-based biochar was close to the value of non-catalyst biochar and decreased slowly, indicating that the Ca-based catalysts can stabilize the arom. rings, while the IG/IALL of K-based biochar decreases significantly and the ID3/ID1 increased significantly, indicating the increase of carbon structure defects and the cracking of large arom. rings in bio-char into small ones; a scheme of K and Ca reaction with biochar in CO2 gasification process was proposed.
- 41Yu, J.; Guo, Q.; Ding, L.; Gong, Y.; Yu, G. Studying effects of solid structure evolution on gasification reactivity of coal chars by in-situ Raman spectroscopy. Fuel 2020, 270, 117603 DOI: 10.1016/j.fuel.2020.117603Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXkvFCltL0%253D&md5=ddbeb0b34780c3004ae45ffeca06ee02Studying effects of solid structure evolution on gasification reactivity of coal chars by in-situ Raman spectroscopyYu, Junqin; Guo, Qinghua; Ding, Lu; Gong, Yan; Yu, GuangsuoFuel (2020), 270 (), 117603CODEN: FUELAC; ISSN:0016-2361. (Elsevier Ltd.)This study focuses on characteristics of structure evolution during pyrolysis and subsequent char gasification of lignite and bituminous coal. Coal pyrolysis was conducted on induction-heating reactor. As pyrolysis temp. increased, the graphitization degree of char increased, and the amt. of C-O and -CH in char decreased, resulting in poorer gasification reactivity of char. Char gasification was conducted by thermogravimetric analyzer (TGA), high-temp. stage microscope (HTSM) and in-situ Raman system to study gasification reactivity, in-situ evolution of morphol. structure and in-situ evolution of C structure, resp. As gasification proceeded, the projected area of char particle decreased rapidly 1st and then kept consistent, and degree of graphitization of char gradually increased. In-situ Raman parameters indicated difference in increasing rate of graphitization between lignite char and bituminous char decreased with increasing temp. Higher temp. deactivated the alkali metals, leading to attenuation of their inhibitory effect on graphitization. Gasification reactivity index R0.9 was in pos. correlated with in-situ ID1/IG value, and corresponding correlation coeff. (R2) for TGA and HTSM were 0.8108 and 0.9829, resp. The higher R2 for HTSM was due to the weaker diffusion effect. In-situ Raman parameter was more suitable for predicting gasification reactivity of single particle char.
- 42Mubari, P. K.; Beguerie, T.; Monthioux, M.; Weiss-Hortala, E.; Nzihou, A.; Puech, P. The X-ray, Raman and TEM Signatures of Cellulose-Derived Carbons Explained. C 2022, 8, 4 DOI: 10.3390/c8010004Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xos1emsL0%253D&md5=b99853a7708bc2893ccaa226c6311435The X-ray, Raman and TEM Signatures of Cellulose-Derived Carbons ExplainedMubari, Petros Kasaira; Beguerie, Theotime; Monthioux, Marc; Weiss-Hortala, Elsa; Nzihou, Ange; Puech, PascalC (2022), 8 (1), 4CODEN: CABCC3; ISSN:2311-5629. (MDPI AG)Structural properties of carbonized cellulose were explored to conjugate the outcomes from various characterization techniques, namely X-ray diffraction (XRD), Raman spectroscopy, and high-resoln. transmission electron microscopy. All these techniques have evidenced the formation of graphene stacks with a size distribution. Cellulose carbonized at 1000 and 1800°C at a heating rate of 2°C/min showed meaningful differences in Raman spectroscopy, whereas in XRD, the differences were not well pronounced, which implies that the crystallite sizes calcd. by each technique have different significations. In the XRD patterns, the origin of a specific feature at a low scattering angle commonly reported in the literature but poorly explained so far, was identified. The different approaches used in this study were congruous in explaining the observations that were made on the cellulose-derived carbon samples. The remnants of the basic structural unit (BSU) are developed during primary carbonization. Small graphene-based crystallites inherited from the BSUs, which formerly developed during primary carbonization, were found to coexist with larger ones. Even if the three techniques give information on the av. size of graphenic domains, they do not see the same characteristics of the domains; hence, they are not identical, nor contradictory but complementary. The arguments developed in the work to explain which characteristics are deduced from the signal obtained by each of the three characterization techniques relate to physics phenomena; hence, they are quite general and, therefore, are valid for all kind of graphenic materials.
- 43Singh, B.; Fang, Y.; Cowie, B. C. C.; Thomsen, L. NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars. Org. Geochem. 2014, 77, 1– 10, DOI: 10.1016/j.orggeochem.2014.09.006Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhs1ehsLfK&md5=0dfdb8376f347e434f38d3cf6e5b0f98NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biocharsSingh, Balwant; Fang, Yunying; Cowie, Bruce C. C.; Thomsen, LarsOrganic Geochemistry (2014), 77 (), 1-10CODEN: ORGEDE; ISSN:0146-6380. (Elsevier Ltd.)The oxidn. of surface functional groups on biochar increases its reactivity and may contribute to the cation exchange capacity of soil. In this study, two Eucalyptus wood biochars, produced at 450 °C (B450) and 550 °C (B550), were incubated sep. in each of the four contrasting soils for up to 2 years at 20 °C, 40 °C and 60 °C. Carbon functional groups of the light fraction (< 1.8 g/cm3) of the control and biochar amended soils (fresh and aged for 1 and 2 years at 20 °C, 40 °C and 60 °C) were investigated using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and XPS. The spectra of biochar and light fractions of the control and biochar amended soils showed two distinct peaks at ∼285.1 eV and 288.5 eV, which were attributed to the C1s-π*C=C transitions of arom. C and C1s-π*C=O transitions of carboxylic C, carboxyamide C and carbonyl C. The proportion of arom. C was substantially greater in the light fraction of the biochar amended soils than the corresponding light fraction of the control soils. Also, the proportion of arom. C was much higher in the light fraction of the B550 amended soils than in the corresponding B450 amended soils. Neither NEXAFS nor XPS results show any consistent change in the proportion of arom. C of biochar amended soils after 1 yr ageing. However, XPS anal. of hand-picked biochar samples showed an increase in the proportion of carboxyl groups after ageing for 2 years, with an av. value of 8.9% in the 2 yr aged samples compared with 3.0% in the original biochar and 6.4% in the control soil. Our data suggest that much longer ageing time will be needed for the development of a significant amt. of carboxyl groups on biochar surfaces.
- 44Ayiania, M.; Smith, M.; Hensley, A. J. R.; Scudiero, L.; McEwen, J. S.; Garcia-Perez, M. Deconvoluting the XPS spectra for nitrogen-doped chars: An analysis from first principles. Carbon 2020, 162, 528– 544, DOI: 10.1016/j.carbon.2020.02.065Google Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksFKiu7s%253D&md5=23cdd53d95f688f22f340bd2b36ba407Deconvoluting the XPS spectra for nitrogen-doped chars: An analysis from first principlesAyiania, Michael; Smith, Matthew; Hensley, Alyssa J. R.; Scudiero, Louis; McEwen, Jean-Sabin; Garcia-Perez, ManuelCarbon (2020), 162 (), 528-544CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Quantifying the content of surface nitrogen and oxygen contg. functional groups in amorphous nitrogen doped carbons via deconvolution of C 1s x-ray photoelectron (XPS) spectra remains difficult due to limited information in the literature. To improve the interpretation of XPS spectra of nitrogen-doped carbons, the C 1s, N 1s and O 1s core level energy shifts have been calcd. for various nitrogenated carbon structures via DFT. Furthermore, we propose an expanded method to improve the self-consistency of the XPS interpretation based on a seven-peak C 1s deconvolution (3 C-C peaks, 3 C-N/-O peaks, and π-π* transition peaks). With the DFT calcns., spectral components arising from surface-defect carbons could be distinguished from arom. sp2 carbon. The deconvolution method proposed provides C/(N + O) ratios in very good agreement (error less than 5%) with those obtained from total C 1s, N 1s and O 1s peaks. Our deconvolution strategy provides a simple guideline for obtaining high-quality fits to exptl. data on the basis of a careful evaluation of exptl. conditions and results.
- 45Deng, X.; Li, J.; Shan, Z.; Sha, J.; Ma, L.; Zhao, N. A N, O co-doped hierarchical carbon cathode for high-performance Zn-ion hybrid supercapacitors with enhanced pseudocapacitance. J. Mater. Chem. A 2020, 8, 11617– 11625, DOI: 10.1039/D0TA02770GGoogle Scholar45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXptFGrtLg%253D&md5=a155900c76daf11ecd350728162aa7b4A N, O co-doped hierarchical carbon cathode for high-performance Zn-ion hybrid supercapacitors with enhanced pseudocapacitanceDeng, Xiaoyang; Li, Jiajun; Shan, Zhu; Sha, Junwei; Ma, Liying; Zhao, NaiqinJournal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (23), 11617-11625CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Zn-ion hybrid supercapacitors (ZHSs) are an advanced energy storage system with high energy/power d. However, the development of cathodes with high-performance is still a challenge. Herein, N, O co-doped hierarchical porous carbon (HPC) integrated with carbon cloth (CC) was fabricated as a promising cathode for aq. ZHSs, which delivered a high specific capacity of 138.5 mA h g-1 with excellent rate performance ( 75 mA h g-1 at 20 A g-1) and superb cycling stability without decay after 10 000 cycles. As a result, an exceptionally high energy d. of 110 W h kg-1 and attractive power d. of 20 kW kg-1 can be obtained. More importantly, the dual cation (H+ and Zn2+) chem. absorption process for addnl. capacity is firstly proposed and verified by ex situ expts., while the pptn./dissoln. process of zinc hydroxide sulfate hydrate is explained. Furthermore, a quasi-solid-state HPC/CC-based ZHS device based on gel electrolyte also showed promising potential for practical applications. This work provides a new pathway to develop carbon-based cathode materials for sustainable ZHSs.
- 46Alvin, S.; Yoon, D.; Chandra, C.; Cahyadi, H. S.; Park, J. H.; Chang, W.; Chung, K. Y.; Kim, J. Revealing sodium ion storage mechanism in hard carbon. Carbon 2019, 145, 67– 81, DOI: 10.1016/j.carbon.2018.12.112Google Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVarsLs%253D&md5=38b3afcef22cf445274c04bcd7f2c3feRevealing sodium ion storage mechanism in hard carbonAlvin, Stevanus; Yoon, Dohyeon; Chandra, Christian; Cahyadi, Handi Setiadi; Park, Jae-Ho; Chang, Wonyoung; Chung, Kyung Yoon; Kim, JaehoonCarbon (2019), 145 (), 67-81CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Although many studies have demonstrated the excellent potential of hard carbon as an anode in sodium ion batteries, the contribution of its active sites to the capacities of the sloping and plateau voltage regions is not yet clear. Herein, systematical investigation of the relationship between the active sites and sodium ion (Na+) storage in the sloping and plateau voltage regions was presented. In light of the physicochem. properties of the lignin-derived hard carbon (graphitization degree, interlayer spacing, micropore size distribution, and sp. surface area), the results of Na+ ion diffusivity, and the change in these properties during Na+ ion insertion/extn. (as characterized by ex situ techniques), new mechanistic insights into Na+ ion storage were proposed. At the beginning of the sodiation process, Na+ ions were adsorbed on defect/edge sites; then partial micropore filling occurred in the sloping region above 0.1 V. In the plateau region below 0.1 V, Na+ ions were intercalated in the graphitic layers, and further adsorption in the micropores occurred near the cutoff potential. Furthermore, sodium clustering occurred below 0.1 V owing to the high concn. of Na+ ions in the micropores.
- 47Wahid, M.; Gawli, Y.; Puthusseri, D.; Kumar, A.; Shelke, M. V.; Ogale, S. Nutty Carbon: Morphology Replicating Hard Carbon from Walnut Shell for Na Ion Battery Anode. ACS Omega 2017, 2, 3601– 3609, DOI: 10.1021/acsomega.7b00633Google Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtFGltrbP&md5=b061c3620084f254b5b69bafc6e4c910Nutty Carbon: Morphology Replicating Hard Carbon from Walnut Shell for Na Ion Battery AnodeWahid, Malik; Gawli, Yogesh; Puthusseri, Dhanya; Kumar, Ajay; Shelke, Manjusha V.; Ogale, SatishchandraACS Omega (2017), 2 (7), 3601-3609CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)Efficient Na ion intercalation/deintercalation in the semigraphitic lattice of a hard carbon derived from the walnut shell is demonstrated. High-temp. (1000 °C) pyrolysis of walnut shells under an inert atm. yields a hard carbon with a low surface area (59 m2 g-1) and a large interplanar c axis sepn. of 0.39-0.36 nm as compared to 0.32 nm for graphite, suitable for Na ion intercalation/deintercalation. A stable reversible capacity of 257 mAh g-1 is obsd. at a c.d. of 50 mA g-1 for such nutshell-derived carbon (NDC) with an impressive rate performance. No loss of electrochem. performance is obsd. for high current cycling (100 mA g-1 → 2 A g-1 → 100 mA g-1). Addnl., the NDC shows remarkably stable electrochem. performance up to 300 charge-discharge cycles at 100 mA g-1 with a minimal drop in capacity.
- 48Alvira, D.; Antorán, D.; Manyà, J. J. Plant-derived hard carbon as anode for sodium-ion batteries: A comprehensive review to guide interdisciplinary research. Chem. Eng. J. 2022, 447, 137468 DOI: 10.1016/j.cej.2022.137468Google Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhsFyhurzO&md5=65675a22026100a37f8eb86859b3939dPlant-derived hard carbon as anode for sodium-ion batteries: A comprehensive review to guide interdisciplinary researchAlvira, Dario; Antoran, Daniel; Manya, Joan J.Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 447 (), 137468CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)A review. Sodium-ion batteries (SIBs) are one of the most promising candidates to replace lithium-ion batteries (LIBs) in grid-scale energy storage applications. SIBs technol. is still in an early development stage and new feasible and low-cost active materials are required. The design of high-performance anodes and the fully understanding of the sodium storage mechanisms are the main bottleneck to overcome. Hard carbons (HCs) are extensively studied as anode material since sodium ions can be intercalated in pseudographitic domains and reversibly adsorbed in surface edges, defects and nanopores. This review aims at providing a comprehensive overview of the current state of knowledge of plant-derived HC anodes in SIBs, which can be helpful for researchers from different backgrounds working in the field. Working principles of SIBs are summarized, together with a detailed description of the Na-ion storage mechanisms in hard carbon anodes proposed to date. Finally, an exhaustive literature review on the performance of plant-derived HCs in SIBs is presented, with special focus on the synthesis pathways (including activation and/or doping treatments).
- 49Qin, D.; Liu, Z.; Zhao, Y.; Xu, G.; Zhang, F.; Zhang, X. A sustainable route from corn stalks to N, P-dual doping carbon sheets toward high performance sodium-ion batteries anode. Carbon 2018, 130, 664– 671, DOI: 10.1016/j.carbon.2018.01.007Google Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVyhsL8%253D&md5=cc1f1061ec260c1b71d933943c4cb41cA sustainable route from corn stalks to N, P-dual doping carbon sheets toward high performance sodium-ion batteries anodeQin, Decai; Liu, Zhanying; Zhao, Yanzhang; Xu, Guiyin; Zhang, Fang; Zhang, XiaogangCarbon (2018), 130 (), 664-671CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)High performance is indispensable for amorphous carbon materials toward sodium-ion batteries anode. Heteroatom doping has proved to be an effective strategy to improve the electrochem. performance of carbon-based materials. In this paper, N, P dual-doped carbon sheets (N, P-CS) from the rinds of corn stalks have been successfully synthesized via a hydrothermal reaction using the cheap (NH4)2HPO4 as nitrogen and phosphorus source. SEM and TEM images showed that the N, P-CS was composed of loose and stacked graphitic carbon sheets, which facilitated the penetration of electrolyte and ion diffusion. Higher ID/IG value (1.692) implied more defective sites on the surface of graphitic sheet to be generated after N and P co-doping, which combined with larger graphene layer distance (0.391 nm) contributed to the high performance of the N, P-CS. When used as anode for sodium ion batteries, it presents a specific capacity of 277mAh g-1 after 100 cycles at 0.25C, and a specific capacity of 202 mAh g-1 after 200 cycles at 1C. Even at a high rate of 5C, a stable specific capacity of 105 mAh g-1 still could be delivered after 2000 cycles, suggesting an excellent cycle stability and superior rate capability.
- 50Wu, L.; Buchholz, D.; Vaalma, C.; Giffin, G. A.; Passerini, S. Apple-Biowaste-Derived Hard Carbon as a Powerful Anode Material for Na-Ion Batteries. ChemElectroChem 2016, 3, 292– 298, DOI: 10.1002/celc.201500437Google Scholar50https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVWqsLnK&md5=8b2b97813e80c52a3cb30c1719a266f7Apple-Biowaste-Derived Hard Carbon as a Powerful Anode Material for Na-Ion BatteriesWu, Liming; Buchholz, Daniel; Vaalma, Christoph; Giffin, Guinevere A.; Passerini, StefanoChemElectroChem (2016), 3 (2), 292-298CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)Modern industrial agriculture is strongly influenced by product norms and stds., resulting in massive amts. of fresh fruit that is left in the field or wasted in spite of their good nutritional value. Herein, we present the synthesis of hard carbon from natural apple biowaste, and its use of biomass is a suitable strategy for the development of cheap and powerful carbon-based active materials for Na-ion batteries. The hard carbon exhibits a good rate capability [112 mAh g-1 at 5 C (1 A g-1)], excellent long-term cycling stability (1000 cycles at 5 C), and high specific capacity (245 mAh g-1 at 0.1 C) with full retention after 80 cycles. The full capacity (250 mAh g-1) of the hard carbon is also obtained in Na-ion cells by using the layered P2-type NaxNi0.22Co0.11Mn0.66O2 cathode. The good electrochem. performance as well as the low cost and environmental friendliness of the apple-biowaste-derived hard carbon proves its suitability for future Na-ion batteries.
- 51Xu, S.-D.; Zhao, Y.; Liu, S.; Ren, X.; Chen, L.; Shi, W.; Wang, X.; Zhang, D. Curly hard carbon derived from pistachio shells as high-performance anode materials for sodium-ion batteries. J. Mater. Sci. 2018, 53, 12334– 12351, DOI: 10.1007/s10853-018-2472-4Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpvVKktb8%253D&md5=c1c9efbd0adc40ec46ed3e494194d030Curly hard carbon derived from pistachio shells as high-performance anode materials for sodium-ion batteriesXu, Shou-Dong; Zhao, Yang; Liu, Shibin; Ren, Xiaoxia; Chen, Liang; Shi, Wenjing; Wang, Xiaomin; Zhang, DingJournal of Materials Science (2018), 53 (17), 12334-12351CODEN: JMTSAS; ISSN:0022-2461. (Springer)Sodium-ion batteries (SIBs) have drawn more attention to serve as one of the promising energy storage devices owing to the abundance of sodium resources and similar characters with lithium element. Hard carbon materials derived from biomass or biomass waste have been considered to act as candidate anode materials for SIBs. In this paper, we have successfully prepd. curly hard carbon materials using pistachio shells as biomass template via a two-step approach including hydrothermal treatment and following a pyrolysis process at various temps. Phys. properties of pistachio shell-derived hard carbons (PSHCs) including microstructure, morphol. and pore size distribution are evaluated by X-ray diffraction, Raman spectrum and N2 sorption anal. The PSHCs carbonized at 1000 °C (PSHC-1000) with av. micropores of 0.7398 nm and larger interlayer space of the (002) crystal plane deliver the highest reversible capacity of 317 mAh g-1 at 0.1C, also show the excellent long-term cycling and rate performances. Electrochem. impedance spectroscopy technol. is introduced to study the kinetics parameters during the first sodiation process of PSHC-1000 electrode, and also to compare the resistance of the charge transfer process for all the PSHCs. Results exhibit PSHC-1000 electrode with the symmetry factor of 0.1352 has the smallest charge transfer resistance, leading to more easily transportation of electrons and ions. This work can provide a simple and green route for prepn. of hard carbon materials derived from biomass waste with unique morphol. and microstructure which can exhibit an excellent electrochem. performance.
- 52Chiang, P. H.; Liu, S. F.; Hung, Y. H.; Tseng, H.; Guo, C. H.; Chen, H. Y. Coffee-Ground-Derived Nanoporous Carbon Anodes for Sodium-Ion Batteries with High Rate Performance and Cyclic Stability. Energy Fuels 2020, 34, 7666– 7675, DOI: 10.1021/acs.energyfuels.0c01105Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtFSrt7bO&md5=f7cd310030d9d477a587a0e550be56dfCoffee-Ground-Derived Nanoporous Carbon Anodes for Sodium-Ion Batteries with High Rate Performance and Cyclic StabilityChiang, Peng-Hsuan; Liu, Shih-Fu; Hung, Yu-Hsuan; Tseng, Hsin; Guo, Chun-Han; Chen, Han-YiEnergy & Fuels (2020), 34 (6), 7666-7675CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)Here, we evaluate the suitability of natural biowaste-derived carbon anodes for sodium-ion batteries (NIBs). Specifically, we utilize eco-friendly, renewable, low-cost coffee grounds (CGs) as precursors and KOH as an activating agent in the prepn. of nanoporous carbon (NPC) anodes for NIBs. The relationship between pore size/surface area and the battery performance is discussed carefully. When tested, the sample CGNPC1-5 exhibits a high reversible capacity of about 223 mA h g-1 (50 mA g-1) with a capacity retention up to 92% at the 250th cycle and a high capacity of 141 mA h g-1 at 1 A g-1. Importantly, the rate test over a range of 0.05-2.5 A g-1 demonstrates the excellent reversibility of CGNPCs. The higher percentage of mesopores and macropores in samples CGNPC1-5 and CGNPC1-10 than those of CGNPC1-0 and CGNPC1-1 facilitates Na-ion transportation, thus exhibiting higher capacities even at high rates. In summary, CGNPCs are promising as sustainable carbonic anodes for NIBs not only owing to their low price and eco-friendly properties but also because of their good cycling stability and ideal rate performance.
- 53Xiang, J.; Lv, W.; Mu, C.; Zhao, J.; Wang, B. Activated hard carbon from orange peel for lithium/sodium ion battery anode with long cycle life. J. Alloys Compd. 2017, 701, 870– 874, DOI: 10.1016/j.jallcom.2017.01.206Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhslemsr8%253D&md5=ac5e489885bb727ac7c8579ddebb7aa2Activated hard carbon from orange peel for lithium/sodium ion battery anode with long cycle lifeXiang, Jianyong; Lv, Weiming; Mu, Congpu; Zhao, Jing; Wang, BochongJournal of Alloys and Compounds (2017), 701 (), 870-874CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)Activated non-graphitizable orange peel derived hard C (OPDHC-A) with micropores structure was prepd. by pyrolysis at 800° and KOH activation. The detd. BET surface areas are 638 m2/g. At 0.05 A g-1, an initial capacity 878 mA h g-1 at 1 A g-1 for Li ion battery (LIB) and 497 mA h g-1 at 0.5 Ag-1 for Na ion battery (NIB) were achieved. Importantly, 3000 cycling stability at 2 A g-1 for LIB and 1000 cycling stability at 1 A g-1 for NIB can been obtained. The excellent performance may be attributed to the disorder activated hard C structure with micropores structure which facilitate electrolyte penetration and provide sites for Li+ and Na+ ion storage.
- 54Dou, X.; Hasa, I.; Saurel, D.; Jauregui, M.; Buchholz, D.; Rojo, T.; Passerini, S. Impact of the Acid Treatment on Lignocellulosic Biomass Hard Carbon for Sodium-Ion Battery Anodes. ChemSusChem 2018, 11, 3276– 3285, DOI: 10.1002/cssc.201801148Google Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVWhsr7O&md5=22cb0aa0140994249ff89f76a81967f1Impact of the acid treatment on lignocellulosic biomass hard carbon for sodium-ion battery anodesDou, Xinwei; Hasa, Ivana; Saurel, Damien; Jauregui, Maria; Buchholz, Daniel; Rojo, Teofilo; Passerini, StefanoChemSusChem (2018), 11 (18), 3276-3285CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)The investigation of phosphoric acid treatment on the performance of hard carbon from a typical lignocellulosic biomass waste (peanut shell) is herein reported. A strong correlation is discovered between the treatment time and the structural properties and electrochem. performance in sodium-ion batteries. Indeed, a prolonged acid treatment enables the use of lower temps., i.e., lower energy consumption, for the carbonization step as well as improved high-rate performance (122 mAh g-1 at 10 C).
- 55Ren, X.; Xu, S. D.; Liu, S.; Chen, L.; Zhang, D.; Qiu, L. Lath-shaped biomass derived hard carbon as anode materials with super rate capability for sodium-ion batteries. J. Electroanal. Chem. 2019, 841, 63– 72, DOI: 10.1016/j.jelechem.2019.04.033Google Scholar55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXns1Grtbg%253D&md5=e9c6b47b304d10985f608a398a9893d3Lath-shaped biomass derived hard carbon as anode materials with super rate capability for sodium-ion batteriesRen, Xiaoxia; Xu, Shou-Dong; Liu, Shibin; Chen, Liang; Zhang, Ding; Qiu, LiJournal of Electroanalytical Chemistry (2019), 841 (), 63-72CODEN: JECHES; ISSN:1873-2569. (Elsevier B.V.)Biomass wastes or biomass derived hard C materials with the advantages of green, as well as economic and high reversible capacity have became the promising anode materials for Na ion batteries (SIBs). Despite this, the poor rate capability hinders their further development. Here, the authors synthesized lath-shaped hard C materials derived from peanut shells by a two-step approach, a hydrothermal pretreatment for different treatment time 1st, and then a carbonized process at 800°. Morphol. and structural characterizations (SEM, XRD and Raman) prove the hydrothermal pretreatment has a great influence on morphol. transformation, the layer spacing, as well as the defect concn. which can enhance the adsorption sites of Na+ and shorten the transport route of Na ions. The PSDHCs-4 (hydrothermal treatment for 4 h) electrode can deliver the highest reversible capacity of 256 ± 5 mAh g-1, and show the best capacity retention of 97 ± 2% at the current rate of 0.1 C after 100 cycles. More importantly, PSDHCs-4 electrode shows the excellent rate performances with a reversible capacity of 261, 244, 206, 163, 125, and 100 mAh g-1 at the current rates of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0 C, resp. These remarkable electrochem. properties indicate that PSDHCs-4 material should be a promising anode material for SIBs.
- 56Lv, W.; Wen, F.; Xiang, J.; Zhao, J.; Li, L.; Wang, L.; Liu, Z.; Tian, Y. Peanut shell derived hard carbon as ultralong cycling anodes for lithium and sodium batteries. Electrochim. Acta 2015, 176, 533– 541, DOI: 10.1016/j.electacta.2015.07.059Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVajtb%252FE&md5=993a4e527716104639b302c67047599cPeanut shell derived hard carbon as ultralong cycling anodes for lithium and sodium batteriesLv, Weiming; Wen, Fusheng; Xiang, Jianyong; Zhao, Jing; Li, Lei; Wang, Limin; Liu, Zhongyuan; Tian, YongjunElectrochimica Acta (2015), 176 (), 533-541CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)The peanut shells derived porous hard carbons (PSDHCs) by pyrolysis have been studied as anodes of Li/Na batteries (LIBs/NIBs). Directly from the starting peanut shells, 600° is the favorable pyrolysis temp. for prepn. of the PSDHC sample (PSDHC-600) with the best electrochem. performances for LIB applications. Also, from the activated peanut shells in KOH soln., the produced PSDHC-600A by pyrolysis at 600° is obsd. to offer greatly enhanced Li+/Na+ ion storage. For LIB applications, PSDHC-600A delivers a retained capacity of 474 mA h g-1 after 400 cycles at 1 A g-1, larger than 314 mA h g-1 of PSDHC-600. At a high current rate of 5 A g-1, PSDHC-600A sustains over 10000 cycles with no obvious sign of fade in capacity, and a capacity of 310 mA h g-1 is still retained. For NIB applications, a capacity of 193 mA h g-1 is retained after 400 cycles at 0.25 A g-1, >130 mA h g-1 of PSDHC-600. Even at 1 A g-1, PSDHC-600A can be stably cycled over 3000 cycles, and a capacity of 129 mA h g-1 is still retained. In comparison to PSDHC-600, the enhanced electrochem. properties of PSDHC-600A can be attributed to the finer porous structure with the increased percentage of nanoscale pores of diam. <2 nm and the larger sp. surface area.
- 57Wang, H.; Yu, W.; Shi, J.; Mao, N.; Chen, S.; Liu, W. Biomass derived hierarchical porous carbons as high-performance anodes for sodium-ion batteries. Electrochim. Acta 2016, 188, 103– 110, DOI: 10.1016/j.electacta.2015.12.002Google Scholar57https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvF2ku7jN&md5=5e7dfa182e86d78e0aa123b82e736c4aBiomass derived hierarchical porous carbons as high-performance anodes for sodium-ion batteriesWang, Huanlei; Yu, Wenhua; Shi, Jing; Mao, Nan; Chen, Shougang; Liu, WeiElectrochimica Acta (2016), 188 (), 103-110CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)The electrochem. performance of Na ion battery was improved by using peanut skin derived hierarchical porous C as an anode. Using the structure/compn. of the peanut skin, hierarchical porous carbons with high surface area and sheet-like structure are successfully achieved through combined carbonization and activation with or without hydrothermal pretreatment. Tested against Na, peanut skin derived C exhibits good rate capability and cycling stability, delivering a high initial charge capacity of 431 mAh g-1 at 0.1 A g-1, retaining a reversible capacity of 47 mAh g-1 at 10 A g-1, and showing a capacity retention of 83-86% after 200 cycles. The reason that peanut skin derived C works so well is that it uniquely combines highly accessible surface area and nanopores, dilated intergraphene spacing, and intrinsically open sheet-like structure, which are capable of reversibly accumulating Na ions through surface adsorption and Na intercalation.
- 58Darjazi, H.; Bottoni, L.; Moazami, H. R.; Rezvani, S. J.; Balducci, L.; Sbrascini, L.; Staffolani, A.; Tombesi, A.; Nobili, F. From waste to resources: transforming olive leaves to hard carbon as sustainable and versatile electrode material for Li/Na-ion batteries and supercapacitors. Mater. Today Sustainability 2023, 21, 100313 DOI: 10.1016/j.mtsust.2022.100313Google ScholarThere is no corresponding record for this reference.
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Abstract
Figure 1
Figure 1. Schematic representation of the procedure adopted to synthesize HC-based electrode materials.
Figure 2
Figure 2. HRTEM micrographs of HC-700-4 (a, b), HHC-800-1 (c), and HHC-800-4 (d, e). Insets (squares) show enlarged views of micrographs to enhance visualization of the lattice fringes.
Figure 3
Figure 3. XRD patterns of WHH-derived carbons (a) and Raman spectra of HC-700-4 (b) and HC-800-4 (c).
Figure 4
Figure 4. CV curves obtained using two-electrode setups for the first three cycles of HC-700-1 (a), HC-700-4 (b), HC-800-1 (c), and HC-800-4 (d).
Figure 5
Figure 5. GCD curves obtained using two-electrode half-cells for the first five cycles (0.03 A g–1) of HC-700-1 (a), HC-700-4 (b), HC-800-1 (c), and HC-800-4 (d).
Figure 6
Figure 6. Charge specific capacities at various current densities ranging from 0.03 to 1 A g–1 (two-electrode setup).
Figure 7
Figure 7. Cycling performance of HC-800-4 over 300 cycles at 2 A g–1 (a), DNa+ values estimated from GITT measurements (for selected HCs) during sodiation (b) and desodiation (c).
References
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- 3Zhou, X.; Wan, L.-J.; Guo, Y.-G. Binding SnO2 Nanocrystals in Nitrogen-Doped Graphene Sheets as Anode Materials for Lithium-Ion Batteries. Adv. Mater. 2013, 25, 2152– 2157, DOI: 10.1002/adma.2013000713https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXislymu70%253D&md5=d2f4520b8658394a82ead01af7868873Binding SnO2 Nanocrystals in Nitrogen-Doped Graphene Sheets as Anode Materials for Lithium-Ion BatteriesZhou, Xiaosi; Wan, Li-Jun; Guo, Yu-GuoAdvanced Materials (Weinheim, Germany) (2013), 25 (15), 2152-2157CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)By using in situ hydrazine monohydrate vapor redn. to form SnO2 nanocrystal/nitrogen-doped reduced graphene oxide (SnO2NC@N-RGO) hybrid material, we have enabled SnO2 nanocrystals to approach the theor. capacity of SnO2 as an anode material for lithium-ion batteries. The as-obtained hybrid SnO2NC@N-RGO also exhibits excellent properties in terms of cycling performance and rate capability as well as cycle life for lithium-ion batteries, benefiting from the nanosized SnO2 particles, the highly conductive graphene, and the Sn-N bond formed between graphene and SnO2 nanocrystals. Moreover, this approach, i.e., the desirable confinement of SnO2 nanocrystals in graphene sheets, would be very helpful in boosting the electrochem. performance of other nanomaterials.
- 4Dunn, B.; Kamath, H.; Tarascon, J. M. Electrical energy storage for the grid: A battery of choices. Science 2011, 334, 928– 935, DOI: 10.1126/science.12127414https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhsVGktL%252FJ&md5=5035bfda7631ad9d075e8836e61146efElectrical Energy Storage for the Grid: A Battery of ChoicesDunn, Bruce; Kamath, Haresh; Tarascon, Jean-MarieScience (Washington, DC, United States) (2011), 334 (6058), 928-935CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)A review. The increasing interest in energy storage for the grid can be attributed to multiple factors, including the capital costs of managing peak demands, the investments needed for grid reliability, and the integration of renewable energy sources. Although existing energy storage is dominated by pumped hydroelec., there is the recognition that battery systems can offer a no. of high-value opportunities, provided that lower costs can be obtained. The battery systems reviewed here include sodium-sulfur batteries that are com. available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for com. electronics and elec. vehicles is being applied to grid storage.
- 5Sun, J.; Xu, Y.; Lv, Y.; Zhang, Q.; Zhou, X. Recent Advances in Covalent Organic Framework Electrode Materials for Alkali Metal-Ion Batteries. CCS Chem. 2023, 5, 1259– 1276, DOI: 10.31635/ccschem.023.202302808There is no corresponding record for this reference.https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=&md5=9874b665cc7a056b8e2f928dd3112440
- 6Kim, H.; Hong, J.; Yoon, G.; Kim, H.; Park, K. Y.; Park, M. S.; Yoon, W. S.; Kang, K. Sodium intercalation chemistry in graphite. Energy Environ. Sci. 2015, 8, 2963– 2969, DOI: 10.1039/C5EE02051D6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtlaqurzN&md5=250c7333d104659b257c418527d2f55eSodium intercalation chemistry in graphiteKim, Haegyeom; Hong, Jihyun; Yoon, Gabin; Kim, Hyunchul; Park, Kyu-Young; Park, Min-Sik; Yoon, Won-Sub; Kang, KisukEnergy & Environmental Science (2015), 8 (10), 2963-2969CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)The insertion of guest species in graphite is the key feature utilized in applications ranging from energy storage and liq. purifn. to the synthesis of graphene. Recently, it was discovered that solvated-Na-ion intercalation can occur in graphite even though the insertion of Na ions alone is thermodynamically impossible; this phenomenon enables graphite to function as a promising anode for Na-ion batteries. In an effort to understand this unusual behavior, we investigate the solvated-Na-ion intercalation mechanism using in operando X-ray diffraction anal., electrochem. titrn., real-time optical observation, and d. functional theory (DFT) calcns. The ultrafast intercalation is demonstrated in real time using millimeter-sized highly ordered pyrolytic graphite, in which instantaneous insertion of solvated-Na-ions occurs (in less than 2 s). The formation of various stagings with solvated-Na-ions in graphite is obsd. and precisely quantified for the first time. The atomistic configuration of the solvated-Na-ions in graphite is proposed based on the exptl. results and DFT calcns. The correlation between the properties of various solvents and the Na ion co-intercalation further suggests a strategy to tune the electrochem. performance of graphite electrodes in Na rechargeable batteries.
- 7Huang, J.; Zhang, W.; Yu, P.; Dong, H.; Zheng, M.; Xiao, Y.; Hu, H.; Liu, Y.; Liang, Y. Direct carbonization of black liquor powders into 3D honeycomb-like porous carbons with a tunable disordered degree for sodium-ion batteries. New J. Chem. 2020, 44, 10697– 10702, DOI: 10.1039/D0NJ01228A7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtFKgt7nE&md5=6391eee07f44dadf50894cd6226d3275Direct carbonization of black liquor powders into 3D honeycomb-like porous carbons with a tunable disordered degree for sodium-ion batteriesHuang, Jianyu; Zhang, Weicai; Yu, Peifeng; Dong, Hanwu; Zheng, Mingtao; Xiao, Yong; Hu, Hang; Liu, Yingliang; Liang, YeruNew Journal of Chemistry (2020), 44 (25), 10697-10702CODEN: NJCHE5; ISSN:1144-0546. (Royal Society of Chemistry)As an environmentally unfriendly and low-cost byproduct produced during the manufg. of pulp and paper, ca.170 million tons of black liquor is generated per yr in the world. Efforts to effectively convert black liquor into high-value products are very crit. but remain challenging. Herein, we successfully prep. porous carbons using black liquor powders as precursors through a simple carbonization technique without any extra activators or templates. The black liquor-derived porous carbons (BL-PCs) exhibit a remarkable three-dimensional (3D) honeycomb-like morphol. and a hierarchical porous structure. Addnl., the disordered degree of BL-PCs can be controlled by simply regulating carbonization temp. A combination of 3D honeycomb-like morphol., hierarchical porous structure and decreased disordered degree not only contributes to the fast electrolyte ion transport, but also improves the rate performance and cycling stability when BL-PCs are used as anode materials for sodium-ion batteries. A typical BL-PC anode exhibits attractive electrochem. performances, including high rate capability and long-term cycling stability.
- 8Xu, T.; Qiu, X.; Zhang, X.; Xia, Y. Regulation of surface oxygen functional groups and pore structure of bamboo-derived hard carbon for enhanced sodium storage performance. Chem. Eng. J. 2023, 452, 139514 DOI: 10.1016/j.cej.2022.1395148https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisF2ht73M&md5=88b2eea7f21ee4847a7d9249043abecaRegulation of surface oxygen functional group and pore structure of bamboo-derived hard carbon for enhanced sodium storage performanceXu, Tianyue; Qiu, Xuan; Zhang, Xiang; Xia, YongyaoChemical Engineering Journal (Amsterdam, Netherlands) (2023), 452 (Part_4), 139514CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)Hard carbon materials with long low-voltage plateau have been used as the anode materials for sodium ion batteries which are considered to be one of the most potential large-scale energy storage systems. Herein, carbonyl groups and closed micropores are introduced into bamboo-derived hard carbon materials simultaneously to enhance the sodium ion storage performance. The carbonyl groups are demonstrated to enhance the reversible sodium adsorption in the sloping region and closed micropores are beneficial to sodium ion storage in the low-voltage plateau region. Moreover, the introducing carbonyl groups improve the reversible sloping capacity not at the expense of increasing sp. surface area and deteriorating the initial Coulombic efficiency. The hard carbon carbonized at 1300°C delivers a high reversible specific capacity of 348.5 mAh g-1 at c.d. of 30 mA g-1 with a charge/discharge Coulombic efficiency of 84.1%, and keeps a specific capacity of 295.9 mAh g-1 with a capacity retention of 91.6% at a c.d. of 300 mA g-1 after 500 cycles. This work provides a novel strategy to precisely regulate the microstructure for biomass-derived hard carbon for superior sodium ion storage performance.
- 9Karatrantos, A.; Cai, Q. Effects of pore size and surface charge on Na ion storage in carbon nanopores. Phys. Chem. Chem. Phys. 2016, 18, 30761– 30769, DOI: 10.1039/C6CP04611H9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsF2mtbnL&md5=65929d768752f13c151b00d06defed59Effects of pore size and surface charge on Na ion storage in carbon nanoporesKaratrantos, Argyrios; Cai, QiongPhysical Chemistry Chemical Physics (2016), 18 (44), 30761-30769CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Na ion batteries (NIBs) are considered as a promising low cost and sustainable energy storage technol. To better design nanoporous carbons as anode materials for NIBs, mol. dynamics simulations have been employed to study the behavior of Na+ ions (as well as PF6- ions) confined within carbon nanopores, in the presence of non-aq. (org.) solvent. The effects of pore size and surface charge d. were quantified by calcg. ionic d. profiles and concn. within the pores. Carbon slit pores of widths 0.72-10 nm were considered. The carbon surfaces were charged with densities of 0 (neutral pores), -0.8e nm-2, -1.2e nm-2, and -2e nm-2. Org. solns. of Na+ and PF6- at 1 M concns. were considered under operating conditions of sodium ion batteries. As the surface charge d. increases, more Na+ ions enter the pores. In all pores, when the surface is highly charged the Na+ ions move toward the neg. charged graphene surfaces because of counterion condensation effects. In some instances, our results reveal the formation of multiple layers of adsorbed Na+ inside the pores. Both the nanopore width and surface charge alter the d. profiles of ions and solvent inside the pores.
- 10Li, W.; Huang, J.; Feng, L.; Cao, L.; Ren, Y.; Li, R.; Xu, Z.; Li, J.; Yao, C. Controlled synthesis of macroscopic three-dimensional hollow reticulate hard carbon as long-life anode materials for Na-ion batteries. J. Alloys Compd. 2017, 716, 210– 219, DOI: 10.1016/j.jallcom.2017.05.06210https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXns1Orurs%253D&md5=8aab8b62ac8a2416526c294a61f74b44Controlled synthesis of macroscopic three-dimensional hollow reticulate hard carbon as long-life anode materials for Na-ion batteriesLi, Wenbin; Huang, Jianfeng; Feng, Liangliang; Cao, Liyun; Ren, Yijie; Li, Ruizi; Xu, Zhanwei; Li, Jiayin; Yao, ChunyanJournal of Alloys and Compounds (2017), 716 (), 210-219CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)The controlled conversion of biomass is necessary for their efficient utilization. We report the controlled synthesis of a novel macroscopic 3-dimensional hollow reticulate hard C by hydrothermal pretreatment and further low temp. (600°) pyrolysis method. The carbonization mechanism is presented based on DTA, which shows that the hydrothermal pretreatment gets through the reticulate structure by removing flavonoids and the pyrolysis temp. is a key factor for inheriting the unique architecture. Tested against Na, the hard C exhibits good cycling stability, showing capacity retention of 90% after 1000 cycles. The excellent Na-ion storage property is attributed to the interconnected 3-dimensional architecture, the abundant O-contg. functional groups and the large interlayer spacing.
- 11Hong, K.-l.; Qie, L.; Zeng, R.; Yi, Z.; Zhang, W.; Wang, D.; Yin, W.; Wu, C.; Fan, Q.; Zhang, W.; Huang, Y. h. Biomass derived hard carbon used as a high performance anode material for sodium ion batteries. J. Mater. Chem. A 2014, 2, 12733, DOI: 10.1039/C4TA02068E11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVKmtbrO&md5=9b28ca12b1ea3a55e7e2ada7ae1e05f9Biomass derived hard carbon used as a high performance anode material for sodium ion batteriesHong, Kun-lei; Long, Qie; Zeng, Rui; Yi, Zi-qi; Zhang, Wei; Wang, Duo; Yin, Wei; Wu, Chao; Fan, Qing-jie; Zhang, Wu-xing; Huang, Yun-huiJournal of Materials Chemistry A: Materials for Energy and Sustainability (2014), 2 (32), 12733-12738CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A porous hard carbon material was synthesized by the simple pyrolysis of H3PO4-treated biomass, i.e., pomelo peels, at 700 °C in N2. The as-obtained hard carbon had a 3D connected porous structure and a large sp. surface area of 1272 m2 g-1. XPS anal. showed that the carbon material was functionalized by O-contg. and P-contg. groups. The porous hard carbon was used as an anode for sodium ion batteries and exhibited good cycling stability and rate capability, delivering a capacity of 181 mA h g-1 at 200 mA g-1 after 220 cycles and retaining a capacity of 71 mA h g-1 at 5 A g-1. The sodium storage mechanisms of the porous hard carbon can be explained by Na+ intercalation into the disordered graphene layers, redox reaction of the surface O-contg. functional groups and Na+ storage in the nanoscale pores. However, the porous hard carbon demonstrated a low coulombic efficiency of 27%, resulting from the formation of a solid electrolyte interphase film and the side reactions of surface phosphorus groups.
- 12Di Stasi, C.; Greco, G.; Canevesi, R. L. S.; Izquierdo, M. T.; Fierro, V.; Celzard, A.; González, B.; Manyà, J. J. Influence of activation conditions on textural properties and performance of activated biochars for pyrolysis vapors upgrading. Fuel 2020, 289, 119759 DOI: 10.1016/j.fuel.2020.119759There is no corresponding record for this reference.
- 13Hayashi, J.; Horikawa, T.; Takeda, I.; Muroyama, K.; Nasir Ani, F. Preparing activated carbon from various nutshells by chemical activation with K2CO3. Carbon 2002, 40, 2381– 2386, DOI: 10.1016/S0008-6223(02)00118-513https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XmvVWgt7o%253D&md5=0d54763caa9603447385f223bd3a073fPreparing activated carbon from various nutshells by chemical activation with K2CO3Hayashi, Jun'ichi; Horikawa, Toshihide; Takeda, Isao; Muroyama, Katsuhiko; Nasir Ani, FaridCarbon (2002), 40 (13), 2381-2386CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Science Ltd.)We have prepd. activated carbons by chem. activation with K2CO3 from five kinds of nutshells: almond shell, coconut shell, oil palm shell, pistachio shell, and walnut shell. When prepd. at 1073 K, the activated carbons from all the nutshells had the max. sp. surface areas. Based on the max. values of sp. surface area, the activated carbons prepd. were classified into two groups: Group-L and Group-S. The former group included activated carbons with high sp. surface area and the latter included those with lower sp. surface area, resp. It was found that K2CO3 effectively worked as an activation reagent, but differently in the temp. ranges below 800 and above 900 K. Due to impregnation, cellulose and hemi-cellulose were modified by K2CO3 and accordingly the wt. loss behaviors of the nutshells were changed in the temp. range below 800 K. In the temp. range above 900 K, carbon in the chars was removed as CO by the redn. of K2CO3 to increase the sp. surface area and the pore vol. It was deduced that the difference between the sp. surface areas of Group-L and those of Group-S correspond to the difference between wt. loss behaviors in the temp. range above 900 K.
- 14Wei, H.; Chen, J.; Fu, N.; Chen, H.; Lin, H.; Han, S. Biomass-derived nitrogen-doped porous carbon with superior capacitive performance and high CO2 capture capacity. Electrochim. Acta 2018, 266, 161– 169, DOI: 10.1016/j.electacta.2017.12.19214https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFCksrY%253D&md5=cd5e1c2abf5e8bfb8755ca3ccda859deBiomass-derived nitrogen-doped porous carbon with superior capacitive performance and high CO2 capture capacityWei, Huanming; Chen, Jing; Fu, Ning; Chen, Haijun; Lin, Hualin; Han, ShengElectrochimica Acta (2018), 266 (), 161-169CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)N-doped porous C was synthesized through a low-cost approach that use H2O chestnut as a C source and melamine as a N source through KOH activation for 2 h at 600-900°C. The obtained samples exhibit predominant characteristics with highly developed micropores, an ultralarge sp. surface area (3401 m2g-1) and a high N content (4.89 at.%). These characteristics endow N-doped porous C with a high specific capacity of 346 Fg-1 and a high energy d. of 22.4 Whkg-1 at 0.5 Ag-1 in 6 moldm-3 KOH. It also exhibits an excellent cycling stability with a retention of nearly 97.6% capacity after 5000 cycles at 1 Ag-1. The unique pore structure and high N content of porous C provide an important contribution to CO2 adsorption capacity, which can reach up to 6.0 mmolg-1 (at 0° and 1 bar) and 4.7 mmolg-1 (at 25 °C and 1 bar), and to high CO2/N2 selectivity. The synthesized porous C exhibit considerable potential in electrochem. energy storage and solid adsorption.
- 15Li, S.; Han, K.; Li, J.; Li, M.; Lu, C. Preparation and characterization of super activated carbon produced from gulfweed by KOH activation. Microporous Mesoporous Mater. 2017, 243, 291– 300, DOI: 10.1016/j.micromeso.2017.02.05215https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXjtlyitL0%253D&md5=8892f1aff83b57ac8e521bfa5491c594Preparation and characterization of super activated carbon produced from gulfweed by KOH activationLi, Shijie; Han, Kuihua; Li, Jinxiao; Li, Ming; Lu, ChunmeiMicroporous and Mesoporous Materials (2017), 243 (), 291-300CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier B.V.)In this study, gulfweed was used as precursor material for the prepn. of super activated carbon (SAC) by chem. activation method with KOH. An L16 (43) (four three-level factors) orthogonal design table was established, and the influences of the activation temp., the activation time and the impregnation ratio on the pore structure were explored. The prepd. SACs had been characterized by N2 adsorption-desorption anal., x-ray diffraction, SEM and FT-IR. When using the impregnation ratio of 4:1 at 850° for 120 min, the sp. surface area of the prepd. SACs reached the max. value, which is 3362 m2/g. All the sp. surface areas of the SACs obtained under various exptl. conditions are higher than 2200 m2/g. From the anal. of the orthogonal expt., the optimum technol. conditions are as follows: the activation temp. is 800°, the activation time is 120 min, and the impregnation ratio is 4:1. The sp. surface area of SAC was strongly influenced by the activation temp., activation time and impregnation ratio.
- 16Sevilla, M.; Ferrero, G. A.; Fuertes, A. B. Beyond KOH activation for the synthesis of superactivated carbons from hydrochar. Carbon 2017, 114, 50– 58, DOI: 10.1016/j.carbon.2016.12.01016https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XitVGmtL3O&md5=7781e8d2021ae1f275de2afc25e46f45Beyond KOH activation for the synthesis of superactivated carbons from hydrocharSevilla, Marta; Ferrero, Guillermo A.; Fuertes, Antonio B.Carbon (2017), 114 (), 50-58CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)A novel activating agent for the prodn. of highly microporous carbons with textural properties that match those of superactivated carbons prepd. by KOH activation, i.e. BET surface areas of 2600-3000 m2 g-1, pore vols. of ∼1.3-1.6 cm3 g-1 and pore size distributions in the supermicropore-small mesopore (<3 nm) region, is studied. It consists of a mixt. of melamine and potassium oxalate, a substance which is less corrosive than KOH, imposing less tech. restrictions. Addnl. advantages of this activating agent are that the morphol. of the particles is not altered and, importantly, the product yield is almost double that of KOH activation. The advantageous textural characteristics of the produced materials are combined with a relatively good electronic cond. of ∼2-3 S cm-1. When tested as supercapacitor electrodes using conventional electrolytes such as H2SO4 and TEABF4/AN, and less conventional ones such as EMImTFSI/AN, these carbons match the performance of benchmark KOH activated carbons and surpass that of com. activated carbons specifically designed for supercapacitor applications.
- 17Fechler, N.; Fellinger, T. P.; Antonietti, M. “salt templating”: A simple and sustainable pathway toward highly porous functional carbons from ionic liquids. Adv. Mater. 2013, 25, 75– 79, DOI: 10.1002/adma.20120342217https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhsVehur%252FP&md5=dad47476daa9f4231a67c890d3ed5df5"Salt Templating": A Simple and Sustainable Pathway toward Highly Porous Functional Carbons from Ionic LiquidsFechler, Nina; Fellinger, Tim-Patrick; Antonietti, MarkusAdvanced Materials (Weinheim, Germany) (2013), 25 (1), 75-79CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Salt templating was presented as a new technique for the prepn. of functional carbons with very high apparent surface areas, higher than for any zeolite or activated carbons and approaching the value of single-layer graphene. This technique was illustrated with the prepn. of highly porous nitrogen- or nitrogen/B-doped carbons derived from 3 eutectic mixts. and different ionic liq. (ILs). The pore morphol. solely depends on the nature of the templating salt and not on the IL; thus, the main porosity is due to a templating effect by the porogen. The main advantages of the described synthesis are the formation of a homogeneous starting soln., which can be easily shaped and processed, a simple aq. removal of the porogen after carbonization and the single step approach. This offers the opportunity of tuning the morphologies of the materials from micro-to mesoporous with apparent sp. surface areas up to 2000 m2g-1. Also, the porogen can be recovered for further use which eventually results in a closed-loop process including salt recycling. Since there exist misc. combinations of ILs, porogen salts, and even metals, a variety of new and highly porous materials with tailor-made morphologies including heteroatom-doped carbons as well as metal-contg. composites can be envisioned. Thus, salt templating approach offers a step toward sustainable future chem. and materials design which enables custom-made synthesis of materials optimizing their performance, e.g., in the field of catalysis, gas or energy storage systems.
- 18Wang, L.; Rao, L.; Xia, B.; Wang, L.; Yue, L.; Liang, Y.; DaCosta, H.; Hu, X. Highly efficient CO2 adsorption by nitrogen-doped porous carbons synthesized with low-temperature sodium amide activation. Carbon 2018, 130, 31– 40, DOI: 10.1016/j.carbon.2018.01.00318https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXltlWqsQ%253D%253D&md5=09b377a048a93bcc02ffc5088c90aa5fHighly efficient CO2 adsorption by nitrogen-doped porous carbons synthesized with low-temperature sodium amide activationWang, Liwei; Rao, Linli; Xia, Binbin; Wang, Linlin; Yue, Limin; Liang, Yuqing; Da Costa, Herbert; Hu, XinCarbon (2018), 130 (), 31-40CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)This work provides a simple and cost-effective way to synthesize carbonaceous sorbents with superior CO2 capture performance under ambient conditions. Using a carbonized com. phenolic resin as carbon precursor and NaNH2 as both activation agent and nitridation reagent, nitrogen-doped porous carbons were synthesized by a single-step reaction at 400-500°. The resulting carbons were highly microporous with large amts. of nitrogen content and CO2 uptake capacities up to 4.64 and 7.13 mmol/g, at atm. pressure and, resp., 25° and 0°. A systematic study showed that the synergetic effect of narrow microporosity and nitrogen content dets. the sorbents' CO2 capture capability. In addn., these phenolic-resin-derived porous carbons demonstrate excellent recyclability, stability, and dynamic CO2 capture capacity, as well as reasonable heat of adsorption and CO2/N2 selectivity. The multiple merits of these cost-effective phenolic-resin-based carbons combined with a single-step and low-temp. prepn. procedure reveal that they are excellent candidates for CO2 capture.
- 19Hayashi, J.; Horikawa, T.; Muroyama, K.; Gomes, V. G. Activated carbon from chickpea husk by chemical activation with K2CO3: Preparation and characterization. Microporous Mesoporous Mater. 2002, 55, 63– 68, DOI: 10.1016/S1387-1811(02)00406-719https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD38XmtVGqu74%253D&md5=a277002d8795e4fbdd91b1a7ab710adbActivated carbon from chickpea husk by chemical activation with K2CO3: preparation and characterizationHayashi, Jun'ichi; Horikawa, Toshihide; Muroyama, Katsuhiko; Gomes, Vincent G.Microporous and Mesoporous Materials (2002), 55 (1), 63-68CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Science B.V.)Activated carbon was prepd. from chickpea husk by chem. activation with K2CO3. At 1073 K, the sp. surface area of activated carbon prepd. with an impregnation ratio of 1.0 yielded the max. value of 1778 m2/g. From the results of the yield of the activated carbon and the reagent recovery ratio, it was concluded that the carbon involved in the husk char was removed as CO by redn. of K2CO3 above 1000 K. The fractal dimension changed slightly between 773 and 973 K, and it decreased rapidly between 973 and 1173 K. It was deduced that this decrease of the fractal dimension was due to the decompn. of the cross-linked structure and the small crystallite structure. The micropore vol. and the sp. surface area increased by the release of plugged pore due to the decompn. of the cross-linked structure. It was further deduced that the mesopore vol. increased and the micropore vol. decreased by combination of micropores due to the decompn. of small crystallites.
- 20Adinata, D.; Wan Daud, W. M. A.; Aroua, M. K. Preparation and characterization of activated carbon from palm shell by chemical activation with K2CO3. Bioresour. Technol. 2007, 98, 145– 149, DOI: 10.1016/j.biortech.2005.11.00620https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BD28risVCgtQ%253D%253D&md5=2301cd4770c3bff98be23c078e0d9471Preparation and characterization of activated carbon from palm shell by chemical activation with K2CO3Adinata Donni; Wan Daud Wan Mohd Ashri; Aroua Mohd KheireddineBioresource technology (2007), 98 (1), 145-9 ISSN:0960-8524.Palm shell was used to prepare activated carbon using potassium carbonate (K2CO3) as activating agent. The influence of carbonization temperatures (600-1000 degrees C) and impregnation ratios (0.5-2.0) of the prepared activated carbon on the pore development and yield were investigated. Results showed that in all cases, increasing the carbonization temperature and impregnation ratio, the yield decreased, while the adsorption of CO2 increased, progressively. Specific surface area of activated carbon was maximum about 1170 m2/g at 800 degrees C with activation duration of 2 h and at an impregnation ratio of 1.0.
- 21Carvalho, A.; Gomes, M.; Mestre, A.; Pires, J.; Brotas de Carvalho, M. Activated carbons from cork waste by chemical activation with K2CO3. Carbon 2004, 42, 672– 674, DOI: 10.1016/j.carbon.2003.12.07521https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtVKit74%253D&md5=4fcb870651b90129eec58b2f3df56d0fActivated carbons from cork waste by chemical activation with K2CO3. Application to adsorption of natural gas componentsCarvalho, A. P.; Gomes, M.; Mestre, A. S.; Pires, J.; Brotas de Carvalho, M.Carbon (2004), 42 (3), 672-674CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Science Ltd.)Cork waste was used to produce activated carbons by chem. activation with K2CO3. The adsorption isotherms of methane, carbon dioxide, ethane and nitrogen, e.g., in natural or landfill gas, were detd. at ambient temp on a granular sample using a clay binder.
- 22Carrott, P. J. M.; Ribeiro Carrott, M. M. L.; Mourão, P. A. M. Pore size control in activated carbons obtained by pyrolysis under different conditions of chemically impregnated cork. J. Anal. Appl. Pyrolysis 2006, 75, 120– 127, DOI: 10.1016/j.jaap.2005.04.01322https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhtFyisr4%253D&md5=80e94b55d89c54a056b0729db1e1169bPore size control in activated carbons obtained by pyrolysis under different conditions of chemically impregnated corkCarrott, P. J. M.; Ribeiro Carrott, M. M. L.; Mourao, P. A. M.Journal of Analytical and Applied Pyrolysis (2006), 75 (2), 120-127CODEN: JAAPDD; ISSN:0165-2370. (Elsevier B.V.)Activated carbons were prepd. by the pyrolysis of cork impregnated with potassium and sodium hydroxides and carbonates as well as phosphoric acid and the effect of five exptl. parameters, namely method of impregnation, impregnant concn., mass ratio, precursor particle size, and pyrolysis temp., were studied. It is shown that cork is a versatile precursor and allows us to prep. a wide variety of materials with quite different pore structural characteristics by precise control of the impregnation and pyrolysis conditions. Even under relatively mild conditions, it was possible to produce cork based carbons with high pore vols., in the range 0.5-0.7 cm3 g-1, and to simultaneously control the mean pore width over a three-fold range from a value as low as 0.7 nm up to a value as high as 2.2 nm. The best materials produced present pore structural characteristics which are significantly different to the vast majority of com. activated carbons. In particular, the possibility of obtaining such high pore vols. in essentially microporous materials, contg. virtually no mesoporosity in most cases, is noteworthy. Furthermore, the fact that it was possible with some samples to combine high pore vol. and very narrow micropore size is a particularly notable achievement.
- 23European Commission. Hemp Production on the EU. https://agriculture.ec.europa.eu/farming/crop-productions-and-plant-based-products/hemp_en (accessed January 27, 2023).There is no corresponding record for this reference.
- 24Um, J. H.; Ahn, C. Y.; Kim, J.; Jeong, M.; Sung, Y. E.; Cho, Y. H.; Kim, S. S.; Yoon, W. S. From grass to battery anode: Agricultural biomass hemp-derived carbon for lithium storage. RSC Adv. 2018, 8, 32231– 32240, DOI: 10.1039/C8RA06958A24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhslCntLrP&md5=c97a3973d651a49cbf44bf4ad9b29ba2From grass to battery anode: agricultural biomass hemp-derived carbon for lithium storageUm, Ji Hyun; Ahn, Chi-Yeong; Kim, Jinsoo; Jeong, Mihee; Sung, Yung-Eun; Cho, Yong-Hun; Kim, Seung-Soo; Yoon, Won-SubRSC Advances (2018), 8 (56), 32231-32240CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Biomass-derived carbon, as a low-cost material source, is an attractive choice to prep. carbon materials, thus providing an alternative to byproduct and waste management. Herein, we report the prepn. of carbon from hemp stem as a biomass precursor through a simple, low-cost, and environment-friendly method with using steam as the activating agent. The hemp-derived carbon with a hierarchically porous structure and a partial graphitization in amorphous domains was developed, and for the first time, it was applied as an anode material for lithium-ion battery. Natural hemp itself delivers a reversible capacity of 190 mA h g-1 at a rate of 300 mA g-1 after 100 cycles. Ball-milling of hemp-derived carbon is further designed to control the phys. properties, and consequently, the capacity of milled hemp increases to 300 mA h g-1 along with excellent rate capability of 210 mA h g-1 even at 1.5 A g-1. The milled hemp with increased graphitization and well-developed meso-porosity is advantageous for lithium diffusion, thus enhancing electrochem. performance via both diffusion-controlled intercalation/deintercalation and surface-limited adsorption/desorption. This study not only demonstrates the application of hemp-derived carbon in energy storage devices, but also guides a desirable structural design for lithium storage and transport.
- 25Wang, H.; Xu, Z.; Kohandehghan, A.; Li, Z.; Cui, K.; Tan, X.; Stephenson, T. J.; King’ondu, C. K.; Holt, C. M. B.; Olsen, B. C. Interconnected Carbon Nanosheets Derived from Hemp for Ultrafast Supercapacitors with High Energy. ACS Nano 2013, 7, 5131– 5141, DOI: 10.1021/nn400731g25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXntFWgu7Y%253D&md5=82fd8d2653f9b71c168c5d670f5791c4Interconnected Carbon Nanosheets Derived from Hemp for Ultrafast Supercapacitors with High EnergyWang, Huanlei; Xu, Zhanwei; Kohandehghan, Alireza; Li, Zhi; Cui, Kai; Tan, Xuehai; Stephenson, Tyler James; King'ondu, Cecil K.; Holt, Chris M. B.; Olsen, Brian C.; Tak, Jin Kwon; Harfield, Don; Anyia, Anthony O.; Mitlin, DavidACS Nano (2013), 7 (6), 5131-5141CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)The authors created unique interconnected partially graphitic C nanosheets (10-30 nm in thickness) with high sp. surface area (up to 2287 m2 g-1), significant vol. fraction of mesoporosity (up to 58%), and good elec. cond. (211-226 S m-1) from hemp bast fiber. The nanosheets are ideally suited for low (down to 0°) through high (100°) temp. ionic-liq.-based supercapacitor applications: At 0° and a c.d. of 10 A g-1, the electrode maintains a capacitance of 106 F g-1. At 20, 60, and 100° and an extreme c.d. of 100 A g-1, there is excellent capacitance retention (72-92%) with the specific capacitances being 113, 144, and 142 F g-1, resp. These characteristics favorably place the materials on a Ragone chart providing among the best power-energy characteristics (on an active mass normalized basis) ever reported for an electrochem. capacitor: At a very high power d. of 20 kW kg-1 and 20, 60, and 100°, the energy densities are 19, 34, and 40 W-h kg-1, resp. Also the assembled supercapacitor device yields a max. energy d. of 12 W-h kg-1, which is higher than that of com. available supercapacitors. By taking advantage of the complex multilayered structure of a hemp bast fiber precursor, such exquisite carbons were able to be achieved by simple hydrothermal carbonization combined with activation. This novel precursor-synthesis route presents a potential for facile large-scale prodn. of high-performance carbons for a variety of diverse applications including energy storage.
- 26Wang, P.; Zhu, K.; Ye, K.; Gong, Z.; Liu, R.; Cheng, K.; Wang, G.; Yan, J.; Cao, D. Three-dimensional biomass derived hard carbon with reconstructed surface as a free-standing anode for sodium-ion batteries. J. Colloid Interface Sci. 2020, 561, 203– 210, DOI: 10.1016/j.jcis.2019.11.09126https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitleis7zL&md5=e28727acf3dce19245480a288f0c4cfcThree-dimensional biomass derived hard carbon with reconstructed surface as a free-standing anode for sodium-ion batteriesWang, Pengfei; Zhu, Kai; Ye, Ke; Gong, Zhe; Liu, Ran; Cheng, Kui; Wang, Guiling; Yan, Jun; Cao, DianxueJournal of Colloid and Interface Science (2020), 561 (), 203-210CODEN: JCISA5; ISSN:0021-9797. (Elsevier B.V.)A 3-dimensional free-standing hard C (FHC) electrode is synthesized by carbonizing the hemp haulm and employed as anode for Na-ion batteries directly. A high current charging-discharging process is carried out to reconstruct surface structure of the FHC. Surface reconstructed FHC display a high capacity of 256 mAh/g and enhanced rate ability. With the formation of order surface structure, the plateau capacity increase and more Na ions can insert into the FHC. This work demonstrates the importance of surface structure for Na ion diffusion and storage and provide a new strategy to design high-performance anode materials.
- 27Rodríguez-Correa, C.; Hehr, T.; Voglhuber-Slavinsky, A.; Rauscher, Y.; Kruse, A. Pyrolysis vs. hydrothermal carbonization: Understanding the effect of biomass structural components and inorganic compounds on the char properties. J. Anal. Appl. Pyrolysis 2019, 140, 137– 147, DOI: 10.1016/j.jaap.2019.03.00727https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmtlOrs7Y%253D&md5=4284f25d625eb2686990c4b9e7c56b52Pyrolysis vs. hydrothermal carbonization: Understanding the effect of biomass structural components and inorganic compounds on the char propertiesRodriguez Correa, Catalina; Hehr, Tobias; Voglhuber-Slavinsky, Ariane; Rauscher, Yannik; Kruse, AndreaJournal of Analytical and Applied Pyrolysis (2019), 140 (), 137-147CODEN: JAAPDD; ISSN:0165-2370. (Elsevier B.V.)The influence and role of the different biomass components during HTC and pyrolysis as well as its effects on the char properties were studied. For this, three agricultural residues (wheat straw, pine bark and macauba nut shell) in three different forms (original, leached with acetic acid and synthetic mixts.) were chosen as precursors. Synergies between the biomass components were evidenced: the biomass samples with the higher lignin content lead to higher biochar yields and the biomass samples in general lead to higher yields than the synthetic mixts. Furthermore, the viscoelastic nature of lignin was overshadowed by the rigidity of cellulose in the real biomass samples leading to thermally more stable biochars with larger surface areas. Leaching the inorgs. from the biomass lead to biochars with the largest surface areas and it had a pos. impact on the carbon contents and calorific values.
- 28Greco, G.; Videgain, M.; Di Stasi, C.; González, B.; Manyà, J. J. Evolution of the mass-loss rate during atmospheric and pressurized slow pyrolysis of wheat straw in a bench-scale reactor. J. Anal. Appl. Pyrolysis 2018, 136, 18– 26, DOI: 10.1016/j.jaap.2018.11.00728https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1Chs7zJ&md5=1aa10f6ef04508095e170c4ef78f75dfEvolution of the mass-loss rate during atmospheric and pressurized slow pyrolysis of wheat straw in a bench-scale reactorGreco, Gianluca; Videgain, Maria; Di Stasi, Christian; Gonzalez, Belen; Manya, Joan J.Journal of Analytical and Applied Pyrolysis (2018), 136 (), 18-26CODEN: JAAPDD; ISSN:0165-2370. (Elsevier B.V.)In the present study, the effects of the abs. pressure (0.1 or 0.5 MPa) and the reactor atm. (pure N2 or a mixt. of CO2/N2) on the pyrolysis behavior of wheat straw pellets (at 500 °C) were investigated. The most interesting aspect of this work was the use of a weighing platform (with a max. capacity of 100 kg and a resoln. of 0.5 g) to monitor the real-time mass-loss data for the biomass sample (with an initial mass of 400 g). It was obsd. that an increased pressure considerably affects the mass-loss profiles during the pyrolysis process, leading to higher devolatilization rates in a shorter period of time. Regardless of the pyrolysis atm., an increase in the abs. pressure led to higher yields of gas at the expense of produced water and condensable org. compds. This finding could be due to the fact that an increased pressure favors the exothermic secondary reactions of the intermediate volatile org. compds. in both liq. and vapor phases. The switch from pure N2 to a mixt. of CO2 and N2 at 0.1 MPa also led to a remarkable increase in the yield of produced gas at the expense of the total liq. This could be mainly due to the promotion of the thermal cracking of the volatile org. compds. at a high partial pressure of CO2, which is also consistent with the measured higher yields of CH4 and CO. The increased yield of CO can also be seen as a direct result of the enhanced reverse Boudouard reaction, which can also explain the much higher sp. surface area (and ultra-micropore vol.) measured for the biochar produced under the same operating conditions (0.1 MPa and a mixt. CO2/N2 as pyrolysis medium).
- 29Greco, G.; Di Stasi, C.; Rego, F.; González, B.; Manyà, J. J. Effects of slow-pyrolysis conditions on the products yields and properties and on exergy efficiency: A comprehensive assessment for wheat straw. Appl. Energy 2020, 279, 115842 DOI: 10.1016/j.apenergy.2020.11584229https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVynur%252FP&md5=e8c9d6044c5bd3012561f1878e537b76Effects of slow-pyrolysis conditions on the products yields and properties and on exergy efficiency: A comprehensive assessment for wheat strawGreco, Gianluca; Di Stasi, Christian; Rego, Filipe; Gonzalez, Belen; Manya, Joan J.Applied Energy (2020), 279 (), 115842CODEN: APENDX; ISSN:0306-2619. (Elsevier Ltd.)In the present work, the effects of the peak temp. (400-550°C), abs. pressure (0.2-0.9 MPa), gas residence time (100-200 s) and reactor atm. (pure N2 or a mixt. of CO2/N2) on the pyrolysis behavior of wheat straw pellets were investigated. A factorial design of expts. was adopted to assess the effects of the above-mentioned factors on the pyrolysis products, the exergy efficiencies related to them and to the overall process, and the heat required. The pyrolysis energy/exergy assessment is nowadays of great interest, for the scaling of the installations from lab-scale to com.-scale. Results showed that, as expected, the peak temp. was the most influential factor on the yields and distributions of all the pyrolysis products as well as the char properties related to its potential stability and pore size distribution. However, an increased pressure enhanced the release of the gas species at the expense of the liq. products, without altering the final char yield. The char exergy efficiency was neg. affected by an increase in peak temp., whereas its effect on the exergy efficiency of the produced gas resulted to be pos. It was also found that pressurized pyrolysis favored the exergy efficiency of the process, even at relatively high pyrolysis peak temp. For the biomass feedstock and the range of operating conditions studied here, thermodn. irreversibilities of the pyrolysis system were considerably lowered when the process was conducted at 550°C, 0.9 MPa and using a mixt. of CO2 and N2 as carrier gas at relatively short residence times.
- 30Zhang, T.; Mao, J.; Liu, X.; Xuan, M.; Bi, K.; Zhang, X. L.; Hu, J.; Fan, J.; Chen, S.; Shao, G. Pinecone biomass-derived hard carbon anodes for high-performance sodium-ion batteries. RSC Adv. 2017, 7, 41504– 41511, DOI: 10.1039/C7RA07231G30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsVersbnK&md5=d3a51c0bcf458d1c87b2a815595752e2Pinecone biomass-derived hard carbon anodes for high-performance sodium-ion batteriesZhang, Tao; Mao, Jing; Liu, Xiaolin; Xuan, Minjie; Bi, Kai; Zhang, Xiao Li; Hu, Junhua; Fan, Jiajie; Chen, Shimou; Shao, GuoshengRSC Advances (2017), 7 (66), 41504-41511CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Hard-carbon is considered as one of the most promising anode materials for sodium-ion batteries (SIBs). Now it is imperative to develop a proper prepn. method to obtain hard carbon anode particles with high initial coulombic efficiency and good cycling performance. In this paper, we have successfully prepd. high performance hard carbon anodes, by selecting abundant and low-cost pinecones as biomass precursor and optimizing the prepn. parameters of pinecone-derived hard carbon (PHC). The microstructure of PHC is studied by X-ray diffraction (XRD), Raman spectroscopy, high-resoln. transmission electron microscopy (HRTEM) as well as nitrogen adsorption-desorption isotherm methods. The performance of PHC is highly dependent on the carbonization temp. Increasing carbonization temp. of pinecone precursor can reduce surface area and thus improve the initial coulombic efficiency. Varying carbonization temp. can also adjust the slope and plateau capacity of PHC, and then regulate the energy d. and power characteristics of PHC in battery operation. PHC1400 still delivers a capacity of 334 mA h g-1 after 120 cycles, with a high initial coulombic efficiency of 85.4%. Our results suggest that PHC is a promising anode material for practical large-scale SIB application.
- 31Manyà, J. J.; Alvira, D.; Azuara, M.; Bernin, D.; Hedin, N. Effects of Pressure and the Addition of a Rejected Material from Municipal Waste Composting on the Pyrolysis of Two-Phase Olive Mill Waste. Energy Fuels 2016, 30, 8055– 8064, DOI: 10.1021/acs.energyfuels.6b0157931https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhsVOitrzL&md5=b90f191fdc305a7181bb04489b1051cbEffects of Pressure and the Addition of a Rejected Material from Municipal Waste Composting on the Pyrolysis of Two-Phase Olive Mill WasteManya, Joan J.; Alvira, Dario; Azuara, Manuel; Bernin, Diana; Hedin, NiklasEnergy & Fuels (2016), 30 (10), 8055-8064CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)This work examines the effect of the abs. pressure (0.1 or 1.0 MPa) and the addn. of a high-ash rejected material from municipal solid waste (MSW) composting (RC) on the slow pyrolysis of two-phase olive mill waste (OW). The expts. were conducted in a batch pyrolysis system using an initial mass of 750 g of feedstock. Three types of initial materials were tested: the OW alone, a mixt. of OW and pure additives (5 wt % K2CO3 and 5 wt % CaO), and a mixt. of OW and RC (10 wt %). For the OW without any additive, an increased pressure led to a market increase in the carbonization efficiency (i.e., fixed carbon yield). At atm. pressure, the addn. of either additives (CaO + K2CO3) or RC led to important changes in the pyrolysis behavior as a result of the catalytic role of the alkali and alk. earth metals (AAEMs). However, this catalytic effect, which is translated into an enhancement of the decompn. of both the hemicellulose and cellulose fractions, was not obsd. at 1.0 MPa. The potential stability of all of the produced biochars appeared to be very high, given the results obtained from both proximate and ultimate analyses. This high stability was confirmed by 13C and 1H solid-state NMR, which showed that the carbon contained in the biochars was composed mainly or entirely of highly condensed arom. structures. However, the highest values of stable C (Edinburgh stability tool) and R50,x (recalcitrance index) were obtained for biochars produced from the OW + RC mixts. at any pressure. In summary, the addn. of the rejected material from MSW composting appears to be a very cost-effective measure to obtain a potentially high-stable biochar, even at atm. pressure.
- 32Xi, Y.; Wang, Y.; Yang, D.; zhang, Z.; Liu, W.; Li, Q.; Qiu, X. K2CO3 activation enhancing the graphitization of porous lignin carbon derived from enzymatic hydrolysis lignin for high performance lithium-ion storage. J. Alloys Compd. 2019, 785, 706– 714, DOI: 10.1016/j.jallcom.2019.01.03932https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvF2ns74%253D&md5=54bdc884128fc166c3ef281cdceefa5bK2CO3 activation enhancing the graphitization of porous lignin carbon derived from enzymatic hydrolysis lignin for high performance lithium-ion storageXi, Yuebin; Wang, Yuanyuan; Yang, Dongjie; Zhang, Zhekun; Liu, Weifeng; Li, Qiong; Qiu, XueqingJournal of Alloys and Compounds (2019), 785 (), 706-714CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)As an abundant natural arom. polymer with high carbon content, lignin can be regarded as an abundant carbon matrix precursor to develop cost-effective and environmental friendly porous carbon for energy storage materials. However, the porous lignin-derived carbon remains a great challenge as an anode for Li-ion batteries due to its low degree of graphitization. In this paper, a low-cost, productive and scalable industrial method has been adopted to fabricate highly graphitized lignin-based porous carbon (PLC-EHL-K2CO3) with K2CO3 activation using enzymic hydrolysis lignin (EHL) as a raw material. PLC-EHL-K2CO3 was composed of multilevel lamellar structure possessing high sp. surface area and macro- and mesoporous. Notably, the graphitization of PLC-EHL-K2CO3 was significantly improved compared with the common KOH activation. Meanwhile, the structure of lignin is an important factor affecting the structure of PLC, such as the mol. wt. and oxygen functional groups. The high sp. surface area, large pore vol. and unique multilevel lamellar morphol. bestow PLC an excellent lithium storage performance, and PLC-EHL-K2CO3 electrode displays a desirable reversible capacity of 520 mAh·g-1 at a c.d. of 200 mA g-1 over 200 cycles and increases 47.3% than PLC-EHL-KOH, and even at 1 A g-1 a specific capacity of 260 mAh·g-1 can be retained after 1000 cycles. This higher graphitization porous carbon material from low-cost renewable lignin is a good candidate for lithium storage equipment.
- 33Govind Raj, K.; Joy, P. A. Role of localized graphitization on the electrical and magnetic properties of activated carbon. J. Am. Ceram. Soc. 2017, 100, 5151– 5161, DOI: 10.1111/jace.1503533https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtVyrtr%252FK&md5=85124e236b4b30d01b99d765b39661a3Role of localized graphitization on the electrical and magnetic properties of activated carbonGovind Raj, Kovummal; Joy, Pattayil AliasJournal of the American Ceramic Society (2017), 100 (11), 5151-5161CODEN: JACTAW; ISSN:0002-7820. (Wiley-Blackwell)The correlation between the magnetic and elec. properties of activated carbon with its microstructure is studied. The changes in the microstructure of activated carbon, after activation at 3 different temps. (800°, 900°, and 1000°) using different amts. of the activating agent, KOH (KOH/C ratio of 1:1, 2:1, 3:1, and 4:1), are studied using X-ray diffraction and Raman spectroscopy. The results showed the formation of localized nanographitic domains, along with the changes in the surface area and porosity of the activated carbon. The changes in the microstructure are found to be directly correlated with the magnetic properties and elec. cond. The interplay between ordering and disordering parameters in the activated carbon is found to det. the elec. cond. and magnetic properties.
- 34Au, H.; Alptekin, H.; Jensen, A. C. S.; Olsson, E.; O’Keefe, C. A.; Smith, T.; Crespo-Ribadeneyra, M.; Headen, T. F.; Grey, C. P.; Cai, Q. A revised mechanistic model for sodium insertion in hard carbons. Energy Environ. Sci. 2020, 13, 3469– 3479, DOI: 10.1039/D0EE01363C34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFyktLjJ&md5=a7181f3c171e70a094942fc79cb26548A revised mechanistic model for sodium insertion in hard carbonsAu, Heather; Alptekin, Hande; Jensen, Anders C. S.; Olsson, Emilia; O'Keefe, Christopher A.; Smith, Thomas; Crespo-Ribadeneyra, Maria; Headen, Thomas F.; Grey, Clare P.; Cai, Qiong; Drew, Alan J.; Titirici, Maria-MagdalenaEnergy & Environmental Science (2020), 13 (10), 3469-3479CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Hard carbons have shown considerable promise as anodes for emerging sodium-ion battery technologies. Current understanding of sodium-storage behavior in hard carbons attributes capacity to filling of graphitic interlayers and pores, and adsorption at defects, although there is still considerable debate regarding the voltages at which these mechanisms occur. Here, ex situ23Na solid-state NMR and total scattering studies on a systematically tuned series of hard carbons revealed the formation of increasingly metallic sodium clusters in direct correlation to the growing pore size, occurring only in samples which exhibited a low voltage plateau. Combining exptl. results with DFT calcns., we propose a revised mechanistic model in which sodium ions store first simultaneously and continuously at defects, within interlayers and on pore surfaces. Once these higher energy binding sites are filled, pore filling occurs during the plateau region, where the densely confined sodium takes on a greater degree of metallicity.
- 35Ramirez, N.; Sardella, F.; Deiana, C.; Schlosser, A.; Müller, D.; Kißling, P. A.; Klepzig, L. F.; Bigall, N. C. Capacitive behavior of activated carbons obtained from coffee husk. RSC Adv. 2020, 10, 38097– 38106, DOI: 10.1039/D0RA06206E35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVyiu73N&md5=ef8c407d0a77303a459a75294bd7c11eCapacitive behavior of activated carbons obtained from coffee huskRamirez, Nathalia; Sardella, Fabiana; Deiana, Cristina; Schlosser, Anja; Mueller, Dennis; Kissling, Patrick A.; Klepzig, Lars F.; Bigall, Nadja C.RSC Advances (2020), 10 (62), 38097-38106CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Sustainable agroindustry has presented many challenges related to waste management. Most of its residues are lignocellulosic biomass materials with great application potential due to their chem. compn., hence the use of biomass-derived carbon materials in energy storage has received growing interest in recent years. In this work, highly micro-porous carbonaceous materials using the endocarp of the coffee fruit or coffee husk (CH) as precursor are obtained. Specifically, three different activating agents (KOH, K2CO3, and steam) to derive activated carbons (ACs) with good capacitive properties are tested. The properties of ACs such as surface chem., texture, crystal graphite size, and order in the carbonaceous structure are assessed and compared. The capacitive behavior inherent to the activation routes is also characterized by means of Cyclic Voltammetry (CV), Galvanostatic Charge/Discharge (GCD) and Electrochem. Impedance Spectroscopy (EIS). The obtained specific capacitance values range from 106 to 138 F g-1 for a discharge current of 0.5 A g-1. These results nominate coffee husk as a good precursor of carbonaceous materials suitable for energy storage.
- 36Alvira, D.; Antorán, D.; Manyà, J. J. Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guide. J. Energy Chem. 2022, 75, 457– 477, DOI: 10.1016/j.jechem.2022.09.00236https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XisFOhsLvJ&md5=7106065e03537d80b8349eeac4395df5Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guideAlvira, Dario; Antoran, Daniel; Manya, Joan J.Journal of Energy Chemistry (2022), 75 (), 457-477CODEN: JECOFG; ISSN:2095-4956. (Science Press)Sodium-ion batteries (SIBs) are considered as a promising candidate to replace lithium-ion batteries (LIBs) in large-scale energy storage applications. Abundant sodium resources and similar working principles make this technol. attractive to be implemented in the near future. However, the development of high-performance carbon anodes is a focal point to the upcoming success of SIBs in terms of power d., cycling stability, and lifespan. Fundamental knowledge in electrochem. and physicochem. techniques is required to properly evaluate the anode performance and move it in the right direction. This review aims at providing a comprehensive guideline to help researchers from different backgrounds (e.g., nanomaterials and thermochem.) to delve into this topic. The main components, lab configurations, procedures, and working principles of SIBs are summarized. Moreover, a detailed description of the most used electrochem. and physicochem. techniques to characterize electrochem. active materials is provided.
- 37Väli, R.; Jänes, A.; Thomberg, T.; Lust, E. Synthesis and characterization of D-glucose derived nanospheric hard carbon negative electrodes for lithium- and sodium-ion batteries. Electrochim. Acta 2017, 253, 536– 544, DOI: 10.1016/j.electacta.2017.09.09437https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhsFGjsrrJ&md5=cf95b5026bf8c439be3272311abd2b40Synthesis and characterization of D-glucose derived nanospherical hard carbon negative electrodes for lithium- and sodium-ion batteriesVali, R.; Janes, A.; Thomberg, T.; Lust, E.Electrochimica Acta (2017), 253 (), 536-544CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)The electrochem. performance of glucose-derived hard C (GDHC) anode was evaluated using Li- and Na-salts in ethylene carbonate and propylene carbonate electrolyte mixts. The LiPF6/EC:PC (1:1) system exhibits high capacity at low current densities (400 mAh g-1 at 25 mA g-1) and also good power characteristics retaining 150 mAh g-1 capacity at 2 A g-1 c.d. The best overall performance was achieved with 1 M NaPF6/EC:PC (1:1) electrolyte based system with capacities of 175 mAh g-1 at 0.1 V vs. Na/Na+ and 330 mAh g-1 at 1.5 V vs. Na/Na+. The electrode was phys. characterized ex-situ using SEM, Raman and TOF-SIMS methods TOF-SIMS anal. revealed that the solid electrolyte interphase is more inorg. on the neg. electrode in the Na-cell than on the neg. electrode the Li-cell. The pos. ion-specific images established by TOF-SIMS anal. show the nonhomogeneous distribution of various fragments from the pristine GDHC, which is caused by slightly inhomogeneous mixt. of GDHC and conducting C black (Super P) particles.
- 38Cao, L.; Hui, W.; Xu, Z.; Huang, J.; Zheng, P.; Li, J.; Sun, Q. Rape seed shuck derived-lamellar hard carbon as anodes for sodium-ion batteries. J. Alloys Compd. 2017, 695, 632– 637, DOI: 10.1016/j.jallcom.2016.11.13538https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhvVKqu7jL&md5=76d015686bfe7f97a1cdadadb60db97cRape seed shuck derived-lamellar hard carbon as anodes for sodium-ion batteriesCao, Liyun; Hui, Wenle; Xu, Zhanwei; Huang, Jianfeng; Zheng, Peng; Li, Jiayin; Sun, QianqianJournal of Alloys and Compounds (2017), 695 (), 632-637CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)Hard carbon with large interlayer spacing is suitable as the anode material for sodium-ion batteries. Rape seed shuck derived lamellar hard carbon is synthesized through hydrothermal and pyrolysis processes. As the anode, it exhibited good cycling stability, delivering a capacity of 143 mAh g-1 after 200 cycles at 100 mA g-1. The promising performances are attributed to the sheet structure with expanded interlayer distance (0.39 nm) and much void which can lower the sodium-ion insertion-extn. barrier and promote Na-ion diffusion and storage. The effect of pyrolysis temp. on the performance is also investigated.
- 39Sadezky, A.; Muckenhuber, H.; Grothe, H.; Niessner, R.; Pöschl, U. Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information. Carbon 2005, 43, 1731– 1742, DOI: 10.1016/j.carbon.2005.02.01839https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2MXltFGrtLc%253D&md5=045e6d9ee2eb3d84bd001fca25bc7f62Raman microspectroscopy of soot and related carbonaceous materials. Spectral analysis and structural informationSadezky, A.; Muckenhuber, H.; Grothe, H.; Niessner, R.; Poeschl, U.Carbon (2005), 43 (8), 1731-1742CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Exptl. conditions and math. fitting procedures for the collection and anal. of Raman spectra of soot and related carbonaceous materials were investigated and optimized with a Raman microscope system operated at 3 different laser excitation wavelengths (514, 633, and 780 nm). Several band combinations for spectral anal. were tested, and a combination of 4 Lorentzian-shaped bands (G, D1, D2, D4) at about 1580, 1350, 1620, and 1200 cm-1, resp., with a Gaussian-shaped band (D3) at ∼1500 cm-1 was best suited for the 1st-order spectra. The 2nd-order spectra were best fitted with Lorentzian-shaped bands at about 2450, 2700, 2900, and 3100 cm-1. Spectral parameters (band positions, full widths at half max., and intensity ratios) are reported for several types of industrial C black (Degussa Printex, Cabot Monarch), diesel soot (particulate matter from modern heavy duty vehicle and passenger car engine exhaust, NIST SRM1650), spark-discharge soot (Palas GfG100), and graphite. Several parameters, in particular the width of the D1 band at ∼1350 cm-1, provide structural information and allow to discriminate the sample materials, but the characterization and distinction of different types of soot is limited by the exptl. reproducibility of the spectra and the statistical uncertainties of curve fitting. The results are discussed and compared with x-ray diffraction measurements and earlier Raman spectroscopic studies of comparable materials, where different measurement and fitting procedures was applied.
- 40Wang, X.; Chen, Q.; Zhu, H.; Chen, X.; Yu, G. In-situ study on structure evolution and gasification reactivity of biomass char with K and Ca catalysts at carbon dioxide atmosphere. Carbon Resour. Convers. 2023, 6, 27– 33, DOI: 10.1016/j.crcon.2022.10.00240https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XivVGlsrnI&md5=bc9d458c3b72c1bf398fe82f435d56c4In-situ study on structure evolution and gasification reactivity of biomass char with K and Ca catalysts at carbon dioxide atmosphereWang, Xingjun; Chen, Qian; Zhu, Huaili; Chen, Xueli; Yu, GuangsuoCarbon Resources Conversion (2023), 6 (1), 27-33CODEN: CRCACJ; ISSN:2588-9133. (KeAi Communications Co., Ltd.)The structural evolution and gasification reactivity of biochar prepd. from the pyrolysis of wheat straw were investigated by in-situ Raman spectroscopy and thermogravimetric anal. The Raman spectra consisted of a combination of four Lorentzian bands (D1, D2, D4, G) and one Gaussian band (D3) in the first-order region. The exptl. results showed that the addn. of catalysts or the presence of ash could improve the CO2 gasification reactivity of biochar and result in a larger ID1/IG ratio and a lower IG/IALL ratio, meaning that the carbon structure was less ordered, and there were also more active sites such as amorphous carbon and cross-linked structures; Ca-based catalysts and K-based catalysts changed the evolution of biochar structure in a different way in CO2 atmosphere, the ID3/ID1 of Ca-based biochar was close to the value of non-catalyst biochar and decreased slowly, indicating that the Ca-based catalysts can stabilize the arom. rings, while the IG/IALL of K-based biochar decreases significantly and the ID3/ID1 increased significantly, indicating the increase of carbon structure defects and the cracking of large arom. rings in bio-char into small ones; a scheme of K and Ca reaction with biochar in CO2 gasification process was proposed.
- 41Yu, J.; Guo, Q.; Ding, L.; Gong, Y.; Yu, G. Studying effects of solid structure evolution on gasification reactivity of coal chars by in-situ Raman spectroscopy. Fuel 2020, 270, 117603 DOI: 10.1016/j.fuel.2020.11760341https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXkvFCltL0%253D&md5=ddbeb0b34780c3004ae45ffeca06ee02Studying effects of solid structure evolution on gasification reactivity of coal chars by in-situ Raman spectroscopyYu, Junqin; Guo, Qinghua; Ding, Lu; Gong, Yan; Yu, GuangsuoFuel (2020), 270 (), 117603CODEN: FUELAC; ISSN:0016-2361. (Elsevier Ltd.)This study focuses on characteristics of structure evolution during pyrolysis and subsequent char gasification of lignite and bituminous coal. Coal pyrolysis was conducted on induction-heating reactor. As pyrolysis temp. increased, the graphitization degree of char increased, and the amt. of C-O and -CH in char decreased, resulting in poorer gasification reactivity of char. Char gasification was conducted by thermogravimetric analyzer (TGA), high-temp. stage microscope (HTSM) and in-situ Raman system to study gasification reactivity, in-situ evolution of morphol. structure and in-situ evolution of C structure, resp. As gasification proceeded, the projected area of char particle decreased rapidly 1st and then kept consistent, and degree of graphitization of char gradually increased. In-situ Raman parameters indicated difference in increasing rate of graphitization between lignite char and bituminous char decreased with increasing temp. Higher temp. deactivated the alkali metals, leading to attenuation of their inhibitory effect on graphitization. Gasification reactivity index R0.9 was in pos. correlated with in-situ ID1/IG value, and corresponding correlation coeff. (R2) for TGA and HTSM were 0.8108 and 0.9829, resp. The higher R2 for HTSM was due to the weaker diffusion effect. In-situ Raman parameter was more suitable for predicting gasification reactivity of single particle char.
- 42Mubari, P. K.; Beguerie, T.; Monthioux, M.; Weiss-Hortala, E.; Nzihou, A.; Puech, P. The X-ray, Raman and TEM Signatures of Cellulose-Derived Carbons Explained. C 2022, 8, 4 DOI: 10.3390/c801000442https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xos1emsL0%253D&md5=b99853a7708bc2893ccaa226c6311435The X-ray, Raman and TEM Signatures of Cellulose-Derived Carbons ExplainedMubari, Petros Kasaira; Beguerie, Theotime; Monthioux, Marc; Weiss-Hortala, Elsa; Nzihou, Ange; Puech, PascalC (2022), 8 (1), 4CODEN: CABCC3; ISSN:2311-5629. (MDPI AG)Structural properties of carbonized cellulose were explored to conjugate the outcomes from various characterization techniques, namely X-ray diffraction (XRD), Raman spectroscopy, and high-resoln. transmission electron microscopy. All these techniques have evidenced the formation of graphene stacks with a size distribution. Cellulose carbonized at 1000 and 1800°C at a heating rate of 2°C/min showed meaningful differences in Raman spectroscopy, whereas in XRD, the differences were not well pronounced, which implies that the crystallite sizes calcd. by each technique have different significations. In the XRD patterns, the origin of a specific feature at a low scattering angle commonly reported in the literature but poorly explained so far, was identified. The different approaches used in this study were congruous in explaining the observations that were made on the cellulose-derived carbon samples. The remnants of the basic structural unit (BSU) are developed during primary carbonization. Small graphene-based crystallites inherited from the BSUs, which formerly developed during primary carbonization, were found to coexist with larger ones. Even if the three techniques give information on the av. size of graphenic domains, they do not see the same characteristics of the domains; hence, they are not identical, nor contradictory but complementary. The arguments developed in the work to explain which characteristics are deduced from the signal obtained by each of the three characterization techniques relate to physics phenomena; hence, they are quite general and, therefore, are valid for all kind of graphenic materials.
- 43Singh, B.; Fang, Y.; Cowie, B. C. C.; Thomsen, L. NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biochars. Org. Geochem. 2014, 77, 1– 10, DOI: 10.1016/j.orggeochem.2014.09.00643https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhs1ehsLfK&md5=0dfdb8376f347e434f38d3cf6e5b0f98NEXAFS and XPS characterisation of carbon functional groups of fresh and aged biocharsSingh, Balwant; Fang, Yunying; Cowie, Bruce C. C.; Thomsen, LarsOrganic Geochemistry (2014), 77 (), 1-10CODEN: ORGEDE; ISSN:0146-6380. (Elsevier Ltd.)The oxidn. of surface functional groups on biochar increases its reactivity and may contribute to the cation exchange capacity of soil. In this study, two Eucalyptus wood biochars, produced at 450 °C (B450) and 550 °C (B550), were incubated sep. in each of the four contrasting soils for up to 2 years at 20 °C, 40 °C and 60 °C. Carbon functional groups of the light fraction (< 1.8 g/cm3) of the control and biochar amended soils (fresh and aged for 1 and 2 years at 20 °C, 40 °C and 60 °C) were investigated using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and XPS. The spectra of biochar and light fractions of the control and biochar amended soils showed two distinct peaks at ∼285.1 eV and 288.5 eV, which were attributed to the C1s-π*C=C transitions of arom. C and C1s-π*C=O transitions of carboxylic C, carboxyamide C and carbonyl C. The proportion of arom. C was substantially greater in the light fraction of the biochar amended soils than the corresponding light fraction of the control soils. Also, the proportion of arom. C was much higher in the light fraction of the B550 amended soils than in the corresponding B450 amended soils. Neither NEXAFS nor XPS results show any consistent change in the proportion of arom. C of biochar amended soils after 1 yr ageing. However, XPS anal. of hand-picked biochar samples showed an increase in the proportion of carboxyl groups after ageing for 2 years, with an av. value of 8.9% in the 2 yr aged samples compared with 3.0% in the original biochar and 6.4% in the control soil. Our data suggest that much longer ageing time will be needed for the development of a significant amt. of carboxyl groups on biochar surfaces.
- 44Ayiania, M.; Smith, M.; Hensley, A. J. R.; Scudiero, L.; McEwen, J. S.; Garcia-Perez, M. Deconvoluting the XPS spectra for nitrogen-doped chars: An analysis from first principles. Carbon 2020, 162, 528– 544, DOI: 10.1016/j.carbon.2020.02.06544https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksFKiu7s%253D&md5=23cdd53d95f688f22f340bd2b36ba407Deconvoluting the XPS spectra for nitrogen-doped chars: An analysis from first principlesAyiania, Michael; Smith, Matthew; Hensley, Alyssa J. R.; Scudiero, Louis; McEwen, Jean-Sabin; Garcia-Perez, ManuelCarbon (2020), 162 (), 528-544CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Quantifying the content of surface nitrogen and oxygen contg. functional groups in amorphous nitrogen doped carbons via deconvolution of C 1s x-ray photoelectron (XPS) spectra remains difficult due to limited information in the literature. To improve the interpretation of XPS spectra of nitrogen-doped carbons, the C 1s, N 1s and O 1s core level energy shifts have been calcd. for various nitrogenated carbon structures via DFT. Furthermore, we propose an expanded method to improve the self-consistency of the XPS interpretation based on a seven-peak C 1s deconvolution (3 C-C peaks, 3 C-N/-O peaks, and π-π* transition peaks). With the DFT calcns., spectral components arising from surface-defect carbons could be distinguished from arom. sp2 carbon. The deconvolution method proposed provides C/(N + O) ratios in very good agreement (error less than 5%) with those obtained from total C 1s, N 1s and O 1s peaks. Our deconvolution strategy provides a simple guideline for obtaining high-quality fits to exptl. data on the basis of a careful evaluation of exptl. conditions and results.
- 45Deng, X.; Li, J.; Shan, Z.; Sha, J.; Ma, L.; Zhao, N. A N, O co-doped hierarchical carbon cathode for high-performance Zn-ion hybrid supercapacitors with enhanced pseudocapacitance. J. Mater. Chem. A 2020, 8, 11617– 11625, DOI: 10.1039/D0TA02770G45https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXptFGrtLg%253D&md5=a155900c76daf11ecd350728162aa7b4A N, O co-doped hierarchical carbon cathode for high-performance Zn-ion hybrid supercapacitors with enhanced pseudocapacitanceDeng, Xiaoyang; Li, Jiajun; Shan, Zhu; Sha, Junwei; Ma, Liying; Zhao, NaiqinJournal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (23), 11617-11625CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)Zn-ion hybrid supercapacitors (ZHSs) are an advanced energy storage system with high energy/power d. However, the development of cathodes with high-performance is still a challenge. Herein, N, O co-doped hierarchical porous carbon (HPC) integrated with carbon cloth (CC) was fabricated as a promising cathode for aq. ZHSs, which delivered a high specific capacity of 138.5 mA h g-1 with excellent rate performance ( 75 mA h g-1 at 20 A g-1) and superb cycling stability without decay after 10 000 cycles. As a result, an exceptionally high energy d. of 110 W h kg-1 and attractive power d. of 20 kW kg-1 can be obtained. More importantly, the dual cation (H+ and Zn2+) chem. absorption process for addnl. capacity is firstly proposed and verified by ex situ expts., while the pptn./dissoln. process of zinc hydroxide sulfate hydrate is explained. Furthermore, a quasi-solid-state HPC/CC-based ZHS device based on gel electrolyte also showed promising potential for practical applications. This work provides a new pathway to develop carbon-based cathode materials for sustainable ZHSs.
- 46Alvin, S.; Yoon, D.; Chandra, C.; Cahyadi, H. S.; Park, J. H.; Chang, W.; Chung, K. Y.; Kim, J. Revealing sodium ion storage mechanism in hard carbon. Carbon 2019, 145, 67– 81, DOI: 10.1016/j.carbon.2018.12.11246https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtVarsLs%253D&md5=38b3afcef22cf445274c04bcd7f2c3feRevealing sodium ion storage mechanism in hard carbonAlvin, Stevanus; Yoon, Dohyeon; Chandra, Christian; Cahyadi, Handi Setiadi; Park, Jae-Ho; Chang, Wonyoung; Chung, Kyung Yoon; Kim, JaehoonCarbon (2019), 145 (), 67-81CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)Although many studies have demonstrated the excellent potential of hard carbon as an anode in sodium ion batteries, the contribution of its active sites to the capacities of the sloping and plateau voltage regions is not yet clear. Herein, systematical investigation of the relationship between the active sites and sodium ion (Na+) storage in the sloping and plateau voltage regions was presented. In light of the physicochem. properties of the lignin-derived hard carbon (graphitization degree, interlayer spacing, micropore size distribution, and sp. surface area), the results of Na+ ion diffusivity, and the change in these properties during Na+ ion insertion/extn. (as characterized by ex situ techniques), new mechanistic insights into Na+ ion storage were proposed. At the beginning of the sodiation process, Na+ ions were adsorbed on defect/edge sites; then partial micropore filling occurred in the sloping region above 0.1 V. In the plateau region below 0.1 V, Na+ ions were intercalated in the graphitic layers, and further adsorption in the micropores occurred near the cutoff potential. Furthermore, sodium clustering occurred below 0.1 V owing to the high concn. of Na+ ions in the micropores.
- 47Wahid, M.; Gawli, Y.; Puthusseri, D.; Kumar, A.; Shelke, M. V.; Ogale, S. Nutty Carbon: Morphology Replicating Hard Carbon from Walnut Shell for Na Ion Battery Anode. ACS Omega 2017, 2, 3601– 3609, DOI: 10.1021/acsomega.7b0063347https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtFGltrbP&md5=b061c3620084f254b5b69bafc6e4c910Nutty Carbon: Morphology Replicating Hard Carbon from Walnut Shell for Na Ion Battery AnodeWahid, Malik; Gawli, Yogesh; Puthusseri, Dhanya; Kumar, Ajay; Shelke, Manjusha V.; Ogale, SatishchandraACS Omega (2017), 2 (7), 3601-3609CODEN: ACSODF; ISSN:2470-1343. (American Chemical Society)Efficient Na ion intercalation/deintercalation in the semigraphitic lattice of a hard carbon derived from the walnut shell is demonstrated. High-temp. (1000 °C) pyrolysis of walnut shells under an inert atm. yields a hard carbon with a low surface area (59 m2 g-1) and a large interplanar c axis sepn. of 0.39-0.36 nm as compared to 0.32 nm for graphite, suitable for Na ion intercalation/deintercalation. A stable reversible capacity of 257 mAh g-1 is obsd. at a c.d. of 50 mA g-1 for such nutshell-derived carbon (NDC) with an impressive rate performance. No loss of electrochem. performance is obsd. for high current cycling (100 mA g-1 → 2 A g-1 → 100 mA g-1). Addnl., the NDC shows remarkably stable electrochem. performance up to 300 charge-discharge cycles at 100 mA g-1 with a minimal drop in capacity.
- 48Alvira, D.; Antorán, D.; Manyà, J. J. Plant-derived hard carbon as anode for sodium-ion batteries: A comprehensive review to guide interdisciplinary research. Chem. Eng. J. 2022, 447, 137468 DOI: 10.1016/j.cej.2022.13746848https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhsFyhurzO&md5=65675a22026100a37f8eb86859b3939dPlant-derived hard carbon as anode for sodium-ion batteries: A comprehensive review to guide interdisciplinary researchAlvira, Dario; Antoran, Daniel; Manya, Joan J.Chemical Engineering Journal (Amsterdam, Netherlands) (2022), 447 (), 137468CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)A review. Sodium-ion batteries (SIBs) are one of the most promising candidates to replace lithium-ion batteries (LIBs) in grid-scale energy storage applications. SIBs technol. is still in an early development stage and new feasible and low-cost active materials are required. The design of high-performance anodes and the fully understanding of the sodium storage mechanisms are the main bottleneck to overcome. Hard carbons (HCs) are extensively studied as anode material since sodium ions can be intercalated in pseudographitic domains and reversibly adsorbed in surface edges, defects and nanopores. This review aims at providing a comprehensive overview of the current state of knowledge of plant-derived HC anodes in SIBs, which can be helpful for researchers from different backgrounds working in the field. Working principles of SIBs are summarized, together with a detailed description of the Na-ion storage mechanisms in hard carbon anodes proposed to date. Finally, an exhaustive literature review on the performance of plant-derived HCs in SIBs is presented, with special focus on the synthesis pathways (including activation and/or doping treatments).
- 49Qin, D.; Liu, Z.; Zhao, Y.; Xu, G.; Zhang, F.; Zhang, X. A sustainable route from corn stalks to N, P-dual doping carbon sheets toward high performance sodium-ion batteries anode. Carbon 2018, 130, 664– 671, DOI: 10.1016/j.carbon.2018.01.00749https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVyhsL8%253D&md5=cc1f1061ec260c1b71d933943c4cb41cA sustainable route from corn stalks to N, P-dual doping carbon sheets toward high performance sodium-ion batteries anodeQin, Decai; Liu, Zhanying; Zhao, Yanzhang; Xu, Guiyin; Zhang, Fang; Zhang, XiaogangCarbon (2018), 130 (), 664-671CODEN: CRBNAH; ISSN:0008-6223. (Elsevier Ltd.)High performance is indispensable for amorphous carbon materials toward sodium-ion batteries anode. Heteroatom doping has proved to be an effective strategy to improve the electrochem. performance of carbon-based materials. In this paper, N, P dual-doped carbon sheets (N, P-CS) from the rinds of corn stalks have been successfully synthesized via a hydrothermal reaction using the cheap (NH4)2HPO4 as nitrogen and phosphorus source. SEM and TEM images showed that the N, P-CS was composed of loose and stacked graphitic carbon sheets, which facilitated the penetration of electrolyte and ion diffusion. Higher ID/IG value (1.692) implied more defective sites on the surface of graphitic sheet to be generated after N and P co-doping, which combined with larger graphene layer distance (0.391 nm) contributed to the high performance of the N, P-CS. When used as anode for sodium ion batteries, it presents a specific capacity of 277mAh g-1 after 100 cycles at 0.25C, and a specific capacity of 202 mAh g-1 after 200 cycles at 1C. Even at a high rate of 5C, a stable specific capacity of 105 mAh g-1 still could be delivered after 2000 cycles, suggesting an excellent cycle stability and superior rate capability.
- 50Wu, L.; Buchholz, D.; Vaalma, C.; Giffin, G. A.; Passerini, S. Apple-Biowaste-Derived Hard Carbon as a Powerful Anode Material for Na-Ion Batteries. ChemElectroChem 2016, 3, 292– 298, DOI: 10.1002/celc.20150043750https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXitVWqsLnK&md5=8b2b97813e80c52a3cb30c1719a266f7Apple-Biowaste-Derived Hard Carbon as a Powerful Anode Material for Na-Ion BatteriesWu, Liming; Buchholz, Daniel; Vaalma, Christoph; Giffin, Guinevere A.; Passerini, StefanoChemElectroChem (2016), 3 (2), 292-298CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)Modern industrial agriculture is strongly influenced by product norms and stds., resulting in massive amts. of fresh fruit that is left in the field or wasted in spite of their good nutritional value. Herein, we present the synthesis of hard carbon from natural apple biowaste, and its use of biomass is a suitable strategy for the development of cheap and powerful carbon-based active materials for Na-ion batteries. The hard carbon exhibits a good rate capability [112 mAh g-1 at 5 C (1 A g-1)], excellent long-term cycling stability (1000 cycles at 5 C), and high specific capacity (245 mAh g-1 at 0.1 C) with full retention after 80 cycles. The full capacity (250 mAh g-1) of the hard carbon is also obtained in Na-ion cells by using the layered P2-type NaxNi0.22Co0.11Mn0.66O2 cathode. The good electrochem. performance as well as the low cost and environmental friendliness of the apple-biowaste-derived hard carbon proves its suitability for future Na-ion batteries.
- 51Xu, S.-D.; Zhao, Y.; Liu, S.; Ren, X.; Chen, L.; Shi, W.; Wang, X.; Zhang, D. Curly hard carbon derived from pistachio shells as high-performance anode materials for sodium-ion batteries. J. Mater. Sci. 2018, 53, 12334– 12351, DOI: 10.1007/s10853-018-2472-451https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpvVKktb8%253D&md5=c1c9efbd0adc40ec46ed3e494194d030Curly hard carbon derived from pistachio shells as high-performance anode materials for sodium-ion batteriesXu, Shou-Dong; Zhao, Yang; Liu, Shibin; Ren, Xiaoxia; Chen, Liang; Shi, Wenjing; Wang, Xiaomin; Zhang, DingJournal of Materials Science (2018), 53 (17), 12334-12351CODEN: JMTSAS; ISSN:0022-2461. (Springer)Sodium-ion batteries (SIBs) have drawn more attention to serve as one of the promising energy storage devices owing to the abundance of sodium resources and similar characters with lithium element. Hard carbon materials derived from biomass or biomass waste have been considered to act as candidate anode materials for SIBs. In this paper, we have successfully prepd. curly hard carbon materials using pistachio shells as biomass template via a two-step approach including hydrothermal treatment and following a pyrolysis process at various temps. Phys. properties of pistachio shell-derived hard carbons (PSHCs) including microstructure, morphol. and pore size distribution are evaluated by X-ray diffraction, Raman spectrum and N2 sorption anal. The PSHCs carbonized at 1000 °C (PSHC-1000) with av. micropores of 0.7398 nm and larger interlayer space of the (002) crystal plane deliver the highest reversible capacity of 317 mAh g-1 at 0.1C, also show the excellent long-term cycling and rate performances. Electrochem. impedance spectroscopy technol. is introduced to study the kinetics parameters during the first sodiation process of PSHC-1000 electrode, and also to compare the resistance of the charge transfer process for all the PSHCs. Results exhibit PSHC-1000 electrode with the symmetry factor of 0.1352 has the smallest charge transfer resistance, leading to more easily transportation of electrons and ions. This work can provide a simple and green route for prepn. of hard carbon materials derived from biomass waste with unique morphol. and microstructure which can exhibit an excellent electrochem. performance.
- 52Chiang, P. H.; Liu, S. F.; Hung, Y. H.; Tseng, H.; Guo, C. H.; Chen, H. Y. Coffee-Ground-Derived Nanoporous Carbon Anodes for Sodium-Ion Batteries with High Rate Performance and Cyclic Stability. Energy Fuels 2020, 34, 7666– 7675, DOI: 10.1021/acs.energyfuels.0c0110552https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtFSrt7bO&md5=f7cd310030d9d477a587a0e550be56dfCoffee-Ground-Derived Nanoporous Carbon Anodes for Sodium-Ion Batteries with High Rate Performance and Cyclic StabilityChiang, Peng-Hsuan; Liu, Shih-Fu; Hung, Yu-Hsuan; Tseng, Hsin; Guo, Chun-Han; Chen, Han-YiEnergy & Fuels (2020), 34 (6), 7666-7675CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)Here, we evaluate the suitability of natural biowaste-derived carbon anodes for sodium-ion batteries (NIBs). Specifically, we utilize eco-friendly, renewable, low-cost coffee grounds (CGs) as precursors and KOH as an activating agent in the prepn. of nanoporous carbon (NPC) anodes for NIBs. The relationship between pore size/surface area and the battery performance is discussed carefully. When tested, the sample CGNPC1-5 exhibits a high reversible capacity of about 223 mA h g-1 (50 mA g-1) with a capacity retention up to 92% at the 250th cycle and a high capacity of 141 mA h g-1 at 1 A g-1. Importantly, the rate test over a range of 0.05-2.5 A g-1 demonstrates the excellent reversibility of CGNPCs. The higher percentage of mesopores and macropores in samples CGNPC1-5 and CGNPC1-10 than those of CGNPC1-0 and CGNPC1-1 facilitates Na-ion transportation, thus exhibiting higher capacities even at high rates. In summary, CGNPCs are promising as sustainable carbonic anodes for NIBs not only owing to their low price and eco-friendly properties but also because of their good cycling stability and ideal rate performance.
- 53Xiang, J.; Lv, W.; Mu, C.; Zhao, J.; Wang, B. Activated hard carbon from orange peel for lithium/sodium ion battery anode with long cycle life. J. Alloys Compd. 2017, 701, 870– 874, DOI: 10.1016/j.jallcom.2017.01.20653https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhslemsr8%253D&md5=ac5e489885bb727ac7c8579ddebb7aa2Activated hard carbon from orange peel for lithium/sodium ion battery anode with long cycle lifeXiang, Jianyong; Lv, Weiming; Mu, Congpu; Zhao, Jing; Wang, BochongJournal of Alloys and Compounds (2017), 701 (), 870-874CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)Activated non-graphitizable orange peel derived hard C (OPDHC-A) with micropores structure was prepd. by pyrolysis at 800° and KOH activation. The detd. BET surface areas are 638 m2/g. At 0.05 A g-1, an initial capacity 878 mA h g-1 at 1 A g-1 for Li ion battery (LIB) and 497 mA h g-1 at 0.5 Ag-1 for Na ion battery (NIB) were achieved. Importantly, 3000 cycling stability at 2 A g-1 for LIB and 1000 cycling stability at 1 A g-1 for NIB can been obtained. The excellent performance may be attributed to the disorder activated hard C structure with micropores structure which facilitate electrolyte penetration and provide sites for Li+ and Na+ ion storage.
- 54Dou, X.; Hasa, I.; Saurel, D.; Jauregui, M.; Buchholz, D.; Rojo, T.; Passerini, S. Impact of the Acid Treatment on Lignocellulosic Biomass Hard Carbon for Sodium-Ion Battery Anodes. ChemSusChem 2018, 11, 3276– 3285, DOI: 10.1002/cssc.20180114854https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhsVWhsr7O&md5=22cb0aa0140994249ff89f76a81967f1Impact of the acid treatment on lignocellulosic biomass hard carbon for sodium-ion battery anodesDou, Xinwei; Hasa, Ivana; Saurel, Damien; Jauregui, Maria; Buchholz, Daniel; Rojo, Teofilo; Passerini, StefanoChemSusChem (2018), 11 (18), 3276-3285CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)The investigation of phosphoric acid treatment on the performance of hard carbon from a typical lignocellulosic biomass waste (peanut shell) is herein reported. A strong correlation is discovered between the treatment time and the structural properties and electrochem. performance in sodium-ion batteries. Indeed, a prolonged acid treatment enables the use of lower temps., i.e., lower energy consumption, for the carbonization step as well as improved high-rate performance (122 mAh g-1 at 10 C).
- 55Ren, X.; Xu, S. D.; Liu, S.; Chen, L.; Zhang, D.; Qiu, L. Lath-shaped biomass derived hard carbon as anode materials with super rate capability for sodium-ion batteries. J. Electroanal. Chem. 2019, 841, 63– 72, DOI: 10.1016/j.jelechem.2019.04.03355https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXns1Grtbg%253D&md5=e9c6b47b304d10985f608a398a9893d3Lath-shaped biomass derived hard carbon as anode materials with super rate capability for sodium-ion batteriesRen, Xiaoxia; Xu, Shou-Dong; Liu, Shibin; Chen, Liang; Zhang, Ding; Qiu, LiJournal of Electroanalytical Chemistry (2019), 841 (), 63-72CODEN: JECHES; ISSN:1873-2569. (Elsevier B.V.)Biomass wastes or biomass derived hard C materials with the advantages of green, as well as economic and high reversible capacity have became the promising anode materials for Na ion batteries (SIBs). Despite this, the poor rate capability hinders their further development. Here, the authors synthesized lath-shaped hard C materials derived from peanut shells by a two-step approach, a hydrothermal pretreatment for different treatment time 1st, and then a carbonized process at 800°. Morphol. and structural characterizations (SEM, XRD and Raman) prove the hydrothermal pretreatment has a great influence on morphol. transformation, the layer spacing, as well as the defect concn. which can enhance the adsorption sites of Na+ and shorten the transport route of Na ions. The PSDHCs-4 (hydrothermal treatment for 4 h) electrode can deliver the highest reversible capacity of 256 ± 5 mAh g-1, and show the best capacity retention of 97 ± 2% at the current rate of 0.1 C after 100 cycles. More importantly, PSDHCs-4 electrode shows the excellent rate performances with a reversible capacity of 261, 244, 206, 163, 125, and 100 mAh g-1 at the current rates of 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0 C, resp. These remarkable electrochem. properties indicate that PSDHCs-4 material should be a promising anode material for SIBs.
- 56Lv, W.; Wen, F.; Xiang, J.; Zhao, J.; Li, L.; Wang, L.; Liu, Z.; Tian, Y. Peanut shell derived hard carbon as ultralong cycling anodes for lithium and sodium batteries. Electrochim. Acta 2015, 176, 533– 541, DOI: 10.1016/j.electacta.2015.07.05956https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVajtb%252FE&md5=993a4e527716104639b302c67047599cPeanut shell derived hard carbon as ultralong cycling anodes for lithium and sodium batteriesLv, Weiming; Wen, Fusheng; Xiang, Jianyong; Zhao, Jing; Li, Lei; Wang, Limin; Liu, Zhongyuan; Tian, YongjunElectrochimica Acta (2015), 176 (), 533-541CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)The peanut shells derived porous hard carbons (PSDHCs) by pyrolysis have been studied as anodes of Li/Na batteries (LIBs/NIBs). Directly from the starting peanut shells, 600° is the favorable pyrolysis temp. for prepn. of the PSDHC sample (PSDHC-600) with the best electrochem. performances for LIB applications. Also, from the activated peanut shells in KOH soln., the produced PSDHC-600A by pyrolysis at 600° is obsd. to offer greatly enhanced Li+/Na+ ion storage. For LIB applications, PSDHC-600A delivers a retained capacity of 474 mA h g-1 after 400 cycles at 1 A g-1, larger than 314 mA h g-1 of PSDHC-600. At a high current rate of 5 A g-1, PSDHC-600A sustains over 10000 cycles with no obvious sign of fade in capacity, and a capacity of 310 mA h g-1 is still retained. For NIB applications, a capacity of 193 mA h g-1 is retained after 400 cycles at 0.25 A g-1, >130 mA h g-1 of PSDHC-600. Even at 1 A g-1, PSDHC-600A can be stably cycled over 3000 cycles, and a capacity of 129 mA h g-1 is still retained. In comparison to PSDHC-600, the enhanced electrochem. properties of PSDHC-600A can be attributed to the finer porous structure with the increased percentage of nanoscale pores of diam. <2 nm and the larger sp. surface area.
- 57Wang, H.; Yu, W.; Shi, J.; Mao, N.; Chen, S.; Liu, W. Biomass derived hierarchical porous carbons as high-performance anodes for sodium-ion batteries. Electrochim. Acta 2016, 188, 103– 110, DOI: 10.1016/j.electacta.2015.12.00257https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhvF2ku7jN&md5=5e7dfa182e86d78e0aa123b82e736c4aBiomass derived hierarchical porous carbons as high-performance anodes for sodium-ion batteriesWang, Huanlei; Yu, Wenhua; Shi, Jing; Mao, Nan; Chen, Shougang; Liu, WeiElectrochimica Acta (2016), 188 (), 103-110CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)The electrochem. performance of Na ion battery was improved by using peanut skin derived hierarchical porous C as an anode. Using the structure/compn. of the peanut skin, hierarchical porous carbons with high surface area and sheet-like structure are successfully achieved through combined carbonization and activation with or without hydrothermal pretreatment. Tested against Na, peanut skin derived C exhibits good rate capability and cycling stability, delivering a high initial charge capacity of 431 mAh g-1 at 0.1 A g-1, retaining a reversible capacity of 47 mAh g-1 at 10 A g-1, and showing a capacity retention of 83-86% after 200 cycles. The reason that peanut skin derived C works so well is that it uniquely combines highly accessible surface area and nanopores, dilated intergraphene spacing, and intrinsically open sheet-like structure, which are capable of reversibly accumulating Na ions through surface adsorption and Na intercalation.
- 58Darjazi, H.; Bottoni, L.; Moazami, H. R.; Rezvani, S. J.; Balducci, L.; Sbrascini, L.; Staffolani, A.; Tombesi, A.; Nobili, F. From waste to resources: transforming olive leaves to hard carbon as sustainable and versatile electrode material for Li/Na-ion batteries and supercapacitors. Mater. Today Sustainability 2023, 21, 100313 DOI: 10.1016/j.mtsust.2022.100313There is no corresponding record for this reference.
Supporting Information
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Schematic of the electrochemical cells used; additional data from characterization of materials (SEM and HRTEM images, Raman and XPS spectra, elemental composition, adsorption isotherms, and pore sizes distributions); additional GCD curves; specific charge capacities (using two- and three-electrode setup); and values of the apparent diffusion coefficients (PDF)
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