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Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion Batteries
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Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion Batteries
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  • Daniel Antorán
    Daniel Antorán
    Aragón Institute of Engineering Research (I3A), Thermochemical Processes Group, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, Spain
    Department of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, Spain
  • Darío Alvira
    Darío Alvira
    Aragón Institute of Engineering Research (I3A), Thermochemical Processes Group, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, Spain
    Department of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, Spain
  • M. Eser Peker
    M. Eser Peker
    Faculty of Science, Department of Chemistry, Ege University, 35100 Izmir, Turkey
  • Hugo Malón
    Hugo Malón
    Department of Mechanical Engineering, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, Spain
    More by Hugo Malón
  • Silvia Irusta
    Silvia Irusta
    Department of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, Spain
    Aragón Institute of Nanoscience and Materials (INMA), CSIC─University of Zaragoza, Campus Río Ebro, Edificio I+D, C/ Mariano Esquillor s/n, 50018 Zaragoza, Spain
    Networking Research Center on Bioengineering, Biomaterials and Nanomedicine, CIBER-BBN, 28029 Madrid, Spain
  • Víctor Sebastián
    Víctor Sebastián
    Department of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, Spain
    Aragón Institute of Nanoscience and Materials (INMA), CSIC─University of Zaragoza, Campus Río Ebro, Edificio I+D, C/ Mariano Esquillor s/n, 50018 Zaragoza, Spain
    Networking Research Center on Bioengineering, Biomaterials and Nanomedicine, CIBER-BBN, 28029 Madrid, Spain
  • Joan J. Manyà*
    Joan J. Manyà
    Aragón Institute of Engineering Research (I3A), Thermochemical Processes Group, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, Spain
    Department of Chemical Engineering and Environmental Technologies, University of Zaragoza, Campus Río Ebro, C/ María de Luna 3, 50018 Zaragoza, Spain
    *Email: [email protected]
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Energy & Fuels

Cite this: Energy Fuels 2023, 37, 13, 9650–9661
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https://doi.org/10.1021/acs.energyfuels.3c01040
Published June 8, 2023

Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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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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Copyright © 2023 The Authors. Published by American Chemical Society

Introduction

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Batteries are a growing source of interest as the world moves toward a more sustainable energy scenario. In the last 30 years, considerable progress was made in the research of new electrochemical energy storage (EES) systems, lithium-ion batteries (LIBs) being the most implemented technology since its commercialization by Sony in 1990s, owing to their high energy density and long cycle-life. (1) However, the supply of raw materials for LIBs (e.g., lithium, cobalt, and natural graphite) may become strained in the future, due to the limited availability of such materials as well as geopolitical factors. (2,3) In addition, the need for stabilizing the electricity system from intermittent renewable sources in the carbon-neutral future requires a massive expansion of energy storage capacity, (4) which has to be materialized using alternative post-lithium EES technologies based on more abundant and sustainable raw materials.
Among the different alternatives to LIBs, sodium-ion batteries (SIBs) have received growing attention by the research community, since sodium is more abundant, widely distributed, and cheaper than lithium. Both elements have similar standard reduction potentials (−3.04 V vs SHE for Li+/Li and −2.71 V vs SHE for Na+/Na) and tend to lose an electron from the outer energy level. In spite of these shared features, developing SIBs still requires intensive research efforts aimed at, among other things, finding high-performance electrode materials. (5) For the anode (or negative electrode), where graphite (which is extensively used in commercial LIBs) is not suitable due to thermodynamic issues, (6) hard carbons (HCs) have been widely considered as promising candidates since they can provide a number of active sites to reversibly store sodium ions. This is because HCs keep highly disordered structures with randomly oriented pseudographitic domains, some residual heteroatoms, and larger interlayer spacing (in comparison with graphitic carbons). Furthermore, lignocellulosic biomass can be used as a precursor of HCs, resulting in attractive valorization routes for biomass waste streams, on the one side, and low-cost and abundant raw materials for post-lithium EES systems, on the other. The resulting biomass-derived HCs can inherit or develop further appropriate porous nanostructures, such as 3D honeycomb-like networks, that can shorten the diffusion paths of Na ions and provide a number of ion buffering reservoirs. (7) Nevertheless, fine tuning the textural and structural features of biomass-derived carbons toward active anode materials with superior performance is still a big challenge. (8)
Activation processes could be useful to regulate the pore size distribution of the resulting HCs. In this sense, a hierarchical porous structure (containing mainly narrow micropores and certain large micropore and mesopore volumes) could significantly enhance charge transfer kinetics. (9,10) However, excessively large surface areas usually lead to the formation of thick solid electrolyte interphases (SEIs), resulting in low initial coulombic efficiency (ICE) values. As an interesting example in this regard, Hong et al. reported an impressive rate capability (95 and 71 mAh g–1 at 2 and 5 A g–1, respectively) for pomelo peel-derived carbons produced through chemical activation with H3PO4; (11) however, the authors reported an ICE of only 27%, disabling this electrode material for real applications.
Activated carbons are commonly synthesized via physical (using an oxidative gas under controlled degrees of burnout) or chemical processes. (12) In the latter case, the raw material is impregnated with a chemical agent and subsequently heated under an inert atmosphere. (13) KOH is the most frequently used chemical since large specific surface areas and total pore volumes can be obtained. (14,15) However, using KOH at an industrially relevant scale is challenging due to corrosion issues. Alternatively, K2CO3 can be used as a chemical agent toward a mild activation approach, (16−18) which may result in moderate porosity developments. (19−22)
Waste hemp hurd (WHH), which is the lignocellulosic residue from industrial hemp stalks used for the production of fibers, was selected as biomass feedstock in the preset study. It accounts for ∼50 wt % of the whole plant biomass. Since there is a growing interest for hemp cultivation, due to the related environmental benefits, one can expect a growing production of WHH worldwide. Only in the EU, hemp production grew by 64% from 2015 to 2019. (23) Although the use of WHH as a precursor of electrode materials for LIBs and supercapacitors has already been investigated (see, for instance, the studies by Um et al. (24) and Wang et al. (25)), its suitability as a raw material for anodes in SIBs has been scarcely assessed. However, the study by Wang et al., (26) who reported a promising reversible specific capacity of 256 mAh g–1 (at 0.374 A g–1) for a surface-reconstructed (via high current charging and discharging pretreatment) WHH-derived hard carbon, should be highlighted.
With all of the above in mind, the specific aim of the present study is to produce HCs from WHH via mild chemical activation with K2CO3 and subsequent annealing at moderate temperature (i.e., 700 and 800 °C) as a fully scalable, environmentally benign, and economically sound production process. As outlined in the following sections, the best HC tested exhibited an electrochemical performance─in terms of specific capacity, cycling stability, and rate capability─that was comparable to that reported for other biomass-derived HCs, which were synthesized at higher carbonization temperatures and/or using more expensive and/or corrosive chemical agents. More insistingly, the best-performing material reported here exhibited an ICE of 73%, which was certainly high for biomass-derived carbon.

Experimental Section

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Synthesis of WHH-Derived Hard Carbons

Waste hemp (Cannabis sativa L.) hurd from Narlisaray (Black Sea region of Turkey) was used as biomass feedstock. The as-received WHH was characterized in terms of proximate and elemental analyses, contents of inorganic species in ash by ICP-MS, and determination of the contents of main biomass constituents (i.e., hemicelluloses, cellulose, and lignin) using a method reported by Rodríguez-Correa et al. (27) Biomass (previously sieved to 5 mm in length) was first pyrolyzed at atmospheric pressure, an average heating rate of 5 °C min–1, and a highest temperature of 500 °C. For this purpose, a bench-scale fixed-bed reactor, working under a steady pure nitrogen flow (leading to a gas residence time of 100 s at 500 °C), was used (see more details on the pyrolysis device in previous works (28,29)). The resulting WHH-based char was then chemically activated with K2CO3 through wet impregnation at char-activating agent mass ratios of 1:1, 1:2, and 1:4. The resulting mixtures were stirred for 2 h at 50 °C, filtered, and dried overnight at 120 °C and finally heated under nitrogen at a heating rate of 10 °C min–1 until 1 h after the target highest carbonization temperature (700 or 800 °C) was reached. A tubular reactor (made of EN 2.4816 alloy, 600 mm long and 28 mm ID), placed inside a vertical tubular furnace (model EVA 12/300 from Carbolite Gero), was employed. The gas hourly space velocity (GHSV) was fixed at 7000 h–1, considering a void factor of 0.5. The resulting material was cooled to room temperature and then washed with HCl aqueous solution (2 mol dm–3) to remove the excess of inorganic impurities and unreacted K2CO3. Finally, activated carbons were rinsed with distilled water until neutral pH, dried at 110 °C overnight, and ground and sieved to particle sizes below 90 μm. The produced hard carbons were named as HC–TR, where T is the activation temperature and R refers to the impregnation mass ratio. Figure 1 graphically summarizes the procedure adopted for the synthesis of WHH-derived HCs.

Figure 1

Figure 1. Schematic representation of the procedure adopted to synthesize HC-based electrode materials.

Physicochemical Characterization

The microporosity of the produced HCs was assessed from both N2 and CO2 adsorption isotherms at −196 and 0 °C, respectively, which were acquired using an Autosorb-iQ-XR2 analyzer from Quantachrome Instruments. Specific surface areas (SBET) were calculated by the Brunauer–Emmett–Teller equation. Micropore and mesopore volumes were estimated from N2 adsorption data, whereas the ultramicropore volume (for pore sizes below 0.7 nm) was calculated from CO2 adsorption data. NLDFT models (for slit pore geometry) in QuadraWin 6.0 software were adopted.
The morphology and elemental composition on the surface of the synthesized HCs were analyzed using SEM-EDX (Inspect F50A microscope from FEI). HRTEM (Titan microscope from FEI, with a SuperTwin objective lens and a CETCOR Cs-objective, allowing a point-to-point resolution of 0.08 nm) images were also obtained to investigate the structural features of HCs. Digitalmicrograph software was used to measure interlayer distances from HRTEM images. Structural characterization was further assessed by X-ray diffraction (Empyrean instrument from Malvern Panalytical at a wavelength of 0.154 nm) and Raman spectroscopy (alpha 300 microscope from Witec with samples excited at 532 nm). For the latter technique, each HC was analyzed on at least three different surface locations for a depth of 3 μm. XPS (Axis Supra spectrometer from Katros, using monochromatic Al Kα radiation source running at 1486 eV) was also applied to identify the oxygen- and nitrogen-containing functional groups on the surface from deconvolution of C 1s and N 1s regions. Peaks were fitted using Gaussian–Lorentzian sum functions after Shirley-type background subtraction in CasaXPS software.

Electrochemical Measurements

Working electrodes were prepared by mixing the WHH-derived HC with acetylene black (as conductive agent) and styrene–butadiene rubber (SBR) and carboxymethyl cellulose (CMC) (as binder compounds) at a mass ratio of 80:10:5:5. A homogeneous slurry was obtained by adding DI water with vortex agitation and magnetic stirring. The resulting mixture was uniformly coated on a high-purity aluminum sheet (current collector) using a baker applicator to obtain a 100-μm-thickness film. The resulting composite electrode was then punched (12 mm diameter) and dried under vacuum at 120 °C overnight. The final mass loading of the electrodes was 1.97 ± 0.37 mg cm–2. Tailored t-type Swagelok half-cells were used to measure the electrochemical performance of WHH-based HCs (working electrode, WE) under a constant pressure of 0.2 N mm–2 (see Figure S1). The plugs were made of EN 1.4044 stainless steel, and a high-density polyethylene tube was used to host the electrodes. The cells were assembled in an argon-filled glovebox, with O2 and H2O contents less than 0.5 ppm. A sodium metal disc (12 mm diameter) was used as the counter electrode (CE) and reference electrode (RE) in two-electrode setups, while an additional disc of metal sodium (5 mm diameter) was used as the RE in the three-electrode cell (see Figure S1). To separate the electrode compartments, a glass fiber filter was used. The electrolyte (60 μL) was composed of a solution of NaTFSI (1 mol dm–3) in a mixture (1:1 vol) of dimethyl carbonate and ethylene carbonate as the solvent.
Electrochemical measurements were performed using a potentiostat-galvanostat (model SP-200 from Bio-Logic) at room temperature. Galvanostatic discharge/charge (GCD) measurements were conducted within a potential window of 0.01–2.5 V (vs Na/Na+), whereas cyclic voltammetry (CV) curves were obtained at a scan rate of 0.1 mV s–1 within the same voltage window. Galvanostatic intermittent titration technique (GITT) measurements were also conducted at a constant current density of 0.03 A g–1, a pulse time of 20 min, and relaxation periods of 1 h at an open circuit.

Results and Discussion

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Properties of Raw WHH

Table 1 reports the results from proximate, elemental, inorganic species, and biomass constituent analyses for the biomass feedstock. The observed relatively high mass ratio of volatile matter to fixed carbon (5.18), coupled with the high content of holocellulose, could favor the porosity development of intermediate pyrolytic char and derived carbons. On the other hand, the reasonably low ash content (i.e., below 5%) is crucial to minimize the negative effect of inorganic species, which might occupy some sodium storage active sites and trigger side reactions during sodiation. (30) However, the presence of both K and Ca (the most abundant species in WHH ash) can be interesting, since it is widely accepted that they play a key role in promoting devolatilization as well as secondary charring reactions, (31) leading to morphological and structural changes in the resulting HCs. In conclusion, the properties of WHH seem to be appropriate for the purpose of this study.
Table 1. Summarized Properties of Raw WHH Samples Used in the Present Study
proximate analysis (wt %)lignocellulosic constituents and extractives (wt % in dry basis)
moisture9.24 ± 0.56hemicellulose38.1 ± 1.84
volatile matter (dry basis)81.3 ± 1.96cellulose32.0 ± 3.36
fixed carbon (dry basis)15.7 ± 0.88lignin23.8 ± 1.66
ash (dry basis)3.00 ± 0.33extractives3.10 ± 0.23
ultimate analysis (wt % in dry ash-free basis)main inorganic species detected by ICP-MS (g kg–1 dry WHH)
C46.3 ± 0.21K14.0
H5.70 ± 0.13Ca10.8
N0.50 ± 0.04Al10.4
O (by difference)44.5Mg1.70
 P1.40
Si1.02
Na0.40

Properties of WHH-Derived Hard Carbons

Mass yields of the produced HCs (in dry basis, with respect to raw WHH) ranged from 8.8 to 15%, depending on the severity of the activation process. From Figures S2b and S3─which show SEM images of the raw WHH, WHH-derived char, and two chemically activated carbons (HP-700-1 and HP-800-1)─it can be seen that the resulting char after the pyrolysis step at 500 °C retained the fiber-shaped morphology of the raw WHH (with fibers of ∼10 μm diameter). This morphology was still maintained after chemical activation. However, HC-800-1 exhibited more distinguishable macropores as a consequence of the higher extent of K2CO3 decomposition and subsequent release of gas species at 800 °C.
For their part, the HRTEM images and the corresponding fast Fourier transform (FTT) patterns shown in Figures 2 and S4 provided valuable insights into the nanostructural features of HCs. A highly amorphous structure can be observed for both WHH-derived char and HC-700-1, with highly disordered and curled carbon layers (see Figure S4a,b). Nevertheless, considerable thinner carbon sheets with large randomly oriented ordered domains (and relatively short interlayer distances) were observed for HC-700-4 (see Figure 2a,b). For HCs carbonized at 800 °C, however, a mostly disordered structure with locally ordered domains having relatively large interplanar distances (up to 0.445 nm) was observed (see Figure 2c,d). This tendency is consistent with the FFT patterns shown in Figure S4, where the sharpest diffraction rings were visible for HCs annealed at 700 °C. Furthermore, Figure 2d clearly shows that highly ordered microdomains were located around pores for HC-800-4; this could be explained by deposition of recondensed/repolymerized volatiles and/or a higher extent of catalytic graphitization by locally available metallic potassium. (32,33) HC-800-4 also exhibited a certain number of small closed pores, as shown in Figure 2e. This finding was a bit unexpected since much higher annealing temperatures (typically above 1000 °C) are required for developing closed porosity. (34)

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 3a displays the XRD spectra obtained for the WHH-derived HCs. As expected, two wide peaks centered at ca. 23 and 44° were observed, corresponding to (002) and (100 and 101) planes for graphitic crystallites within turbostratic structures. (35) From the interplanar spacing between graphene layers (d002), apparent crystallite thickness along the c-axis (Lc), and apparent crystallite width along the a-axis (La) values reported in Table 2 and calculated using the Bragg’s and Scherrer’s equations, (36) some considerations can be made. First, the interplanar spacing was considerably greater than that of graphite (0.335 nm) for all of the carbons synthesized in the present study, indicating an a priori favorable scenario for Na-ion storage. (37,38) Second, the trend observed for La values seems to be consistent with the aforementioned HRTEM results, since smaller values were estimated for HC-800-4 (more disordered) in comparison with the HCs prepared at lower impregnation ratios and/or lower annealing temperatures.

Figure 3

Figure 3. XRD patterns of WHH-derived carbons (a) and Raman spectra of HC-700-4 (b) and HC-800-4 (c).

Table 2. Structural Features of WHH-Derived HCs from XRD and Raman Analyses
materiald002 (nm)La (nm)Lc (nm)AD1/AGAD3/AG
HC-700-10.3961.5440.9622.77 ± 0.1280.829 ± 0.061
HC-700-20.4021.8890.8944.01 ± 0.3420.986 ± 0.087
HC-700-40.3972.3470.8064.09 ± 0.5471.08 ± 0.14
HC-800-10.3952.4970.9693.85 ± 1.011.11 ± 0.16
HC-800-20.3892.3190.9483.91 ± 1.180.767 ± 0.064
HC-800-40.3971.5980.8836.17 ± 0.4321.28 ± 0.087
With regard to Raman spectroscopy results, Figure 3b,c shows the decomposed spectra for HC-700-4 and HC-800-4 (see also Figure S5 for the rest of the HCs), assuming one Gaussian-shaped band (D3) and four Lorentzian-shaped bands (G, D1, D2, and D4). (39) These bands are consensually attributed to disordered graphitic lattices (D1, D2, and D4), amorphous carbon (D3), and graphitic sp2 bonding (G). Curve fitting was performed using the Pick Analyzer tool in OriginPro software. The resulting AD1/AG and AD3/AG area ratios, which are commonly used to characterize the degree of disorder of biomass chars, (40−42) are also listed in Table 2. From the values of both area ratios, it can be deduced that the higher the impregnation ratio at a given temperature, the higher the degree of disorder. At 800 °C, a marked increase in both AD1/AG and AD3/AG area ratios was observed when the highest impregnation ratio was used. Hence, the information extracted from Raman spectra was qualitatively consistent with the findings deduced from HRTEM and XRD data.
From Table 3, which summarizes the data obtained from XPS measurements and deconvolutions of C 1s and N 1s regions (see Figures S6 and S7, respectively), it can be seen that K2CO3 activation led to a marked increase in the availability of oxygen-containing surface groups, even when HCs were produced at 800 °C. This is consistent with the trend observed for the oxygen content measured by EDX (see Table S1). Regarding the N-containing groups, pyrrolic N (N-5) was converted into more stable quaternary (graphitic) N when the highest carbonization temperature increased up to 800 °C. In the case of HC-800-4, the observed slightly lower proportion of quaternary N (compared to that of HC-800-1 and HC-800-2) could be ascribed to its higher degree of structural disorder. It could be hypothesized that K-catalyzed etching reaction between CO2 and the carbon matrix leads to a slight increase in the amount of edge N.
Table 3. XPS Peak Assignments and Area Percentages for C 1s and N 1s regions (43−45) (Deconvoluted C 1s and N 1s Spectra for Selected Carbons are Given in Figures S6 and S7)
 C 1sN 1s
materialpeak 1 (285.0 eV), C–C, C═C, Csp2–Npeak 2 (285.8–286.7 eV), C–O, C═O, Csp3–Npeak 3 (288.4–289.1 eV), O–C═O, C bonded to heteroatomspeak 1 (398.8–399.1 eV), pyridinic Npeak 2 (400.0–401.0 eV), pyrrolic + pyridine Npeak 3 (401.1–401.3 eV), graphitic N
WHH char821081882 
HC-700-1712274060 
HC-700-25826161783 
HC-700-4613181090 
HC-800-166241026 74
HC-800-272151323 77
HC-800-459291233 67
Concerning the textural properties, Table 4 reports the results obtained from the N2 and CO2 adsorption isotherms shown in Figure S8. As can be seen, K2CO3 activation did not result in a marked increase in porosity. The largest BET specific surface areas (335.5 and 192.3 m2 g–1 from N2 and CO2 adsorption, respectively), which were obtained for the carbon produced under the more severe activation conditions (HC-800-4), were considerably lower than those reported in the literature; for instance, Xi et al. reported a surface area of 2300 m2 g–1 for K2CO3-activated waste lignin-derived carbons. (32) The mild activation that has been achieved in the present study can be explained by the fact that the slurry obtained after wet impregnation was filtered, leading to chars with far lower contents of activating agent than expected. With regard to the pore size distributions (obtained from both adsorbates assuming a NLDFT-based model) shown in Figures S9 and S10, the following considerations can be made: (1) activation did not result in any increase in the volume of mesopores, quite the contrary, with the exception of HC-700-1; (2) the volume of ultramicropores hardly changed with respect to that of the WHH-derived char; and (3) most of the new porosity observed for HC-700-4 and HC-800-4 was in the form of micropores with widths comprised between 0.7 and 1.0 nm.
Table 4. Textural Features Deduced from N2 and CO2 Adsorption Isotherms Given in Figure S8
materialSBETa (m2 g–1)SBETb (m2 g–1)micropore volumec (cm3 g–1)mesopore volumec (cm3 g–1)ultramicropore volumed (cm3 g–1)
WHH char159.8107.50.06680.02050.0323
HC-700-1205.2151.20.06790.03660.0281
HC-700-2207.8176.10.09470.00150.0308
HC-700-4266.0179.80.11560.00670.0298
HC-800-126.23157.60.02130.00030.0273
HC-800-265.80151.20.03310.00940.0246
HC-800-4333.5192.30.14080.00950.0372
a

From N2 adsorption isotherm.

b

From CO2 adsorption isotherm.

c

From N2 adsorption data using a NLDFT model.

d

From CO2 adsorption data using a NLDFT model.

Electrochemical Performance

The acquired CV curves (for the first three discharge–charge cycles) are shown in Figure 4. The two characteristic peaks appearing at ca. 0.01 V (cathodic) and 0.15–0.25 V (anodic) can be mainly ascribed to the reversible insertion/extraction of Na ions, respectively. (46) On the other hand, the broad cathodic peak observed at 0.25–1.25 V for all of the carbons during the first discharge can be attributed to SEI formation as well as to irreversible adsorption of Na ions on high binding energy sites (e.g., structural defects and surface functional groups). (47) Interestingly, the area of this irreversible peak was considerably lower for HC-800-4, despite its higher surface area. This finding is in agreement with the previous study by Zheng et al., (1) who stated that porous carbons having a developed narrow microporosity─as is the case of HC-800-4─did not result in a thicker SEI, since the electrolyte solvent and the anion will probably be unable to diffuse into and wet the narrow micropores (i.e., below 1 nm). Furthermore, the almost overlapped CV profiles obtained for the second and third cycles confirmed the stability of the formed SEI layer.

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).

The first five galvanostatic discharge–charge cycles at a current density of 0.03 A g–1 for the selected carbons using two-electrode half-cells are shown in Figure 5 (see also Figure S11 for the rest of the HCs). As expected, all of the profiles showed a slope region (from 2.5 to ca. 0.15 V) and a plateau region (from ca. 0.15 to 0.01 V). According to the current state of knowledge, the slope region could mainly be ascribed to adsorption of Na ions on the surface and at defects, whereas the second one is commonly associated to slower filling processes (of graphitic interlayers and closed pores). (48) In the case of the WHH-derived char, the plateau region was negligible (see Figure S11a), largely due to its poor conductivity caused by an excessively low degree of graphitization. Among all of the tested HCs, HC-800-4 exhibited the best sodium storage performance at 0.03 A g–1, with first discharge and charge capacities of 359.5 and 261.7 mAh g–1, respectively. In consonance with the CV results, this material exhibited the highest ICE (73%). The better performance of HC-800-4 in terms of reversible capacity is due to the large plateau contribution, suggesting that this carbon possesses more Na-ion storage sites with low binding energies. In this sense, the closed pores observed for HC-800-4 (see Figure 2e) can be accessible to Na ions, which can then fill them at very low voltages. (34) The developed narrow microporosity observed for this HC, coupled with large enough interplanar distances between graphene layers, can provide effective diffusion pathways, allowing Na ions to reach these closed pores.

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).

To assess the rate capability of HC-based working electrodes, five discharge–charge cycles at different current densities were performed using two-electrode half-cells. As clearly shown in Figure 6, HC-800-4 was always the best-performing material regardless of the current density applied, exhibiting reversible charging capacities of 267, 240, 204, 102, and 79 mAh g–1 when cycled at 0.03, 0.06, 0.1, 0.5 and 1 A g–1; respectively (see all measured charge capacities per unit mass and per unit area in Tables S2 and S3, respectively). Although better rate capabilities have already been reported in the literature for biomass-derived HCs, (11,49−57) it should be noted that more severe operating conditions (i.e., higher carbonization temperatures and/or more corrosive chemical agents) were adopted for producing the active materials. In addition, and as highlighted in Table 5, all of these previous studies reported ICE values considerably lower than that of the best-performing HC reported here (73%).

Figure 6

Figure 6. Charge specific capacities at various current densities ranging from 0.03 to 1 A g–1 (two-electrode setup).

Table 5. Electrochemical Performance of Several Biomass-Derived HCs─as Anodes in SIBs─Reported in the Literature
precursorHC synthesisreversible capacity (mAh g–1) at current density (A g–1)ICE (%)capacity retention (%)ref
corn stalkcarbonization at 1200 °C followed by dual N–P doping143 at 1; 122 at 25391 (after 2000 cycles at 1 A g–1) (49)
apple wasteactivation with H3PO4 and subsequent carbonization at 1100 °C112 at 1; 86 at 261100 (after 1000 cycles at 1 A g–1) (50)
pistachio shellshydrothermal pretreatment with NaOH at 165 °C for 6 h and subsequent carbonization at 1000 °C95 at 1.2; 56 at 362100 (after 500 cycles at 0.4 A g–1) (51)
pomelo peelschemical activation via H3PO4 impregnation and further heating at 700 °C118 at 1; 94.5 at 22785 (after 230 cycles at 0.05 A g–1) (11)
coffee groundschemical activation via KOH impregnation and further heating at 900 °C141 at 15292 (after 200 cycles at 1 A g–1) (52)
orange peelschemical activation via KOH impregnation and further heating at 800 °C125 at 14294 (after 100 cycles at 1 A g–1) (53)
peanut shellschemical activation via H3PO4 impregnation and further heating at 800 °C140 at 1; 110 at 25681 (after 120 at 0.02 A g–1) (54)
peanut shellshydrothermal pretreatment with NaOH at 165 °C for 4 h and subsequent carbonization at 800 °C100 at 1.55897 (after 100 cycles at 0.02 A g–1) (55)
peanut shellschemical activation via KOH impregnation and further heating at 600 °C150 at 13386 (after 3000 cycles at 1 A g–1) (56)
peanut skinhydrothermal pretreatment with H2SO4 at 180 °C for 24 h and subsequent activation with KOH impregnation and further heating at 800 °C154 at 1; 47 at 103343 (after 200 cycles at 0.5 A g–1) (57)
From Figure 6, it can also be seen that as the current density returned to 0.03 A g–1, the charge specific capacities were very similar to those measured during the first five cycles. In particular, HC-800-4 recovered 95% of its initial capacity (253 mAh g–1 vs 267 mAh g–1), indicating a good stability of the electrode when relatively high current rates were applied.
Since it is well known that using two-electrode half-cell setups can lead to discharge capacity underestimation, due to additional overpotentials introduced by the metallic sodium CE, (36) the rate capability test was repeated for HC-800-4 using a three-electrode half-cell (see Figure S1a). As shown in Figure S12, the use of a two-electrode cell resulted in a considerable underestimation of capacity, especially at relatively low current rates. However, at 0.5 and 1 A g–1, the measured discharge capacities only differed by 3–4%. The three-electrode setup was used for measuring the cycling stability of HC-800-4 over 300 cycles at a high current density of 2 A g–1. Figure 7a displays the resulting charge capacities, which were of ca. 50 mAh g–1 at this high current rate. After 300 cycles at 2 A g–1, when the current rate was set to its initial value (0.03 A g–1), 96% of the initial reversible capacity was retained, confirming the excellent cycling stability of the electrode.

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).

Figure 7b,c and Tables S4–S7 show the apparent diffusion coefficients (DNa+) deduced from GITT measurements (at 0.03 A g–1) for sodiation and desodiation processes, respectively (see the Supporting Information for more details). The WE was previously subjected to three CV scans at 0.1 mV s–1 to allow the formation and stabilization of the SEI. From Figure 7b, different sodiation mechanisms can be identified along the voltage profile. The relatively fast first stage taking place above 0.1 V could mainly be ascribed to adsorption of Na ions on the surface and at structural defects. For its part, the decrease in DNa+ values at voltages below 0.1 V could probably be linked to slower intercalation (into graphene interlayers) and pore filling processes. Moreover, the overcoming of the repulsive forces arising from the interactions between Na ions and the surface of the electrode to diffuse into the microcrystalline phase can also explain the observe decrease in the apparent diffusion coefficients. (58) In the case of HC-800-4, the sudden increase in DNa+ at ca. 0.02 V could be attributed to the fact that certain Na ions reached the closed micropores available in this material, as revealed by the HRTEM image given in Figure 2e. With regard to the desodiation process (see Figure 7c), the marked negative peak observed for HC-800-4 at ca. 0.1 V is consistent with the considerations made for the opposite process and could indicate that the Na ions trapped into the closed pores did not reach sufficient diffusion paths for their fast desorption. In addition, the positive peak observed for HC-700-1, HC-700-4, and HC-800-1 at 0.9–1.1 V─probably related to desorption of Na ions from surface functional groups─was not observed for HC-800-4. This could suggest that the slope region for this more disordered carbon material could be more attributed to adsorption of Na ions at structural defects rather than on surface functional groups.

Conclusions

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To sum up, the findings of the preset study indicate that hard carbons produced from waste hump hurd via mild chemical activation with K2CO3 at 800 °C exhibit remarkable electrochemical performance as anodes in SIBs. The balance attained for HC-800-4 in terms of material features, which is translated into a moderate interconnected microporosity (with pore sizes below 1 nm), an appropriate concentration of defects in the carbon structure─coupled with the presence of pseudographitic domains having large interplanar distances─and a certain number of closed pores, can explain the observed relatively high capacity at high current rates. In comparison with other hard carbon-based anodes synthesized via more energy-intense, expensive, and/or difficult to scale-up processes, the best-performing WHH-derived carbon reported herein represents a very interesting starting-point candidate for two main reasons: (1) the possibility to easily scale up the production process to industrially relevant capacities, and (2) its relatively high ICE. Further research on improving its specific capacity at industrially relevant current densities─through, for instance, heteroatom doping and encapsulation of redox-active nanoparticles─without compromising, or ever increasing, the ICE will be crucial to definitely establish the potential of waste hemp-hurd-derived hard carbons.

Supporting Information

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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)

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Author Information

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  • Corresponding Author
    • Joan J. Manyà - 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, SpainOrcidhttps://orcid.org/0000-0002-0118-3254 Email: [email protected]
  • Authors
    • Daniel Antorán - 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, Spain
    • Darío Alvira - 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, SpainOrcidhttps://orcid.org/0000-0002-5526-3962
    • M. Eser Peker - Faculty of Science, Department of Chemistry, Ege University, 35100 Izmir, Turkey
    • Hugo Malón - Department of Mechanical Engineering, University of Zaragoza, Escuela Politécnica Superior, Crta. de Cuarte s/n, 22071 Huesca, Spain
    • Silvia Irusta - Department 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, SpainOrcidhttps://orcid.org/0000-0002-2966-9088
    • Víctor Sebastián - Department 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, SpainOrcidhttps://orcid.org/0000-0002-6873-5244
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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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.

Abbreviations

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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

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Energy & Fuels

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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).

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  • Supporting Information

    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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