Waste Management 120 (2021) 280–289

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Coffee-derived activated carbon from second biowaste for

supercapacitor applications
Alberto Adan-Mas a,⇑, Lorena Alcaraz b, Pablo Arévalo-Cid a, Félix. A. López-Gómez b, Fátima Montemor a
a
Centro de Química Estrutural-CQE, Departamento Egenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal
b
National Center for Metallurgical Research (CENIM), Spanish National Research Council (CSIC), Avda. Gregorio del Amo, 8, 28040 Madrid, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The electrochemical energy storage performance of activated carbons (ACs) obtained from coffee-derived
Received 5 August 2020 biowastes was assessed. ACs were obtained from spent coffee ground second waste, after polyphenol
Revised 25 October 2020 extraction, by means of a hydrothermal process followed by physical or chemical activation. The resulting
Accepted 22 November 2020
materials exhibited microporous structures with a total specific area between 585 and 2330 m2
g1.
Scanning electron microscopy (SEM) revealed a highly porous microstructure in the case of the chemi-
cally activated carbons, while physical activation led to a cracked micro-sized morphology. The electro-
Keywords:
chemical properties of the materials for supercapacitor applications were investigated in 1 M Na2SO4.
Activated carbon
Biowaste
After chemical activation, the coffee-derived material displayed a capacitance of 84 F
g1 at 1 A
g1 in
Supercapacitors a 1.9 V voltage window, with 70% capacitance retention at 10 A
g1 and 85% retention after 5000 cycles
Electrochemical energy storage of continuous charge-discharge. This work demonstrates how coffee secondary biowaste can be conve-
niently activated to perform as electrochemical energy storage material, contributing to its revalorization
and reinsertion in a circular economy.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction beverage consumed worldwide (Yun et al., 2020), being the second
most ingested agrofood after tea (Ahsan et al., 2018). According to
Circular economy has gained growing attention in the quest for the International Coffee Organization (Organization, 2019), coffee
a sustainable economic and environmental development production reached 9.5 ktons in 2018 and is continually increasing.
(Korhonen et al., 2018). As Gallopolous and Frosch (Frosch and Thus, the amount of coffee wastes (i.e., the residues left after
Gallopoulos, 1989) pointed out, the ‘‘extract-produce-use-dump” extracting the coffee solution from the coffee beans such as the
approach is extremely inefficient from the materials perspective. pulp, husk, coffee beans and spent coffee grounds (Atabani et al.,
Waste from one industrial process can serve as precursor material 2019)) increases alongside coffee consumption. For this reason, dif-
for another (Ardolino and Arena, 2019). Therefore, circular econ- ferent solutions to re-use these wastes must be researched and
omy is being investigated in industries as diverse as automotive developed (Campos-Vega et al., 2015; Thiagamani et al., 2017;
(Buruzs and Torma, 2017), construction (Smol et al., 2015) and tex- Atabani et al., 2019). Coffee wastes have been used as biomass
tile (Koszewska, 2018), just to cite a few. The food industry is no (Limousy et al., 2013), to increase soil fertility and plant growth
exception (Jurgilevich et al., 2016), with approximately 30–50% (Ribeiro et al., 2017), to extract added-value organic compounds
of food intended for human consumption being wasted and a (Low et al., 2015) and as filling for building materials with
trillion-dollar cost per year dedicated to atone for inefficiencies improved properties (Arulrajah et al., 2014; Yun et al., 2020).
in the food economy. Thus, great economic and environmental Spent coffee grounds contain considerable amounts of high
benefits could be attained with an adequate integration of circular value-added compounds (carbohydrates, proteins, and pectins,
economy in this sector and a better understanding of the food- among others) (Moreira et al., 2018). So, this waste can be a source
energy nexus (Slorach et al., 2020). of several products, including polyphenols, which have interesting
Amongst waste produced by the food industry, coffee residues antioxidants properties. Different methods for the extraction of
are worth considering for reuse. Nowadays, coffee is an important polyphenols have previously been reported, such as microwave
extraction, ultrasonic extraction, Soxhlet extraction, heat reflux
extraction and ultrahigh pressure extraction (Rajbhar et al.,
⇑ Corresponding author. 2015). Recently, a hydro-alcoholic process has been developed to
E-mail address: [email protected] (A. Adan-Mas). successfully extract polyphenols (Ramón-Gonçalves et al., 2019).

https://doi.org/10.1016/j.wasman.2020.11.043
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
A. Adan-Mas, L. Alcaraz, P. Arévalo-Cid et al. Waste Management 120 (2021) 280–289

This process generates a carbonaceous subproduct that can be fur- (Ramón-Gonçalves et al., 2019). Subsequently, the obtained pre-
ther treated to obtain activated carbons, concluding the whole pro- cursor was turned into activated carbon (AC) by both physical
cess with almost zero residue. This process is an interesting and chemical processes.
alternative for waste management: it reduces the cost of raw
materials and produces a carbon residue that can be used in other 2.1.1. Physical activation process
potential applications. Thus, the obtention of an initial precursor Physical activation was carried out in a quartz reactor at differ-
by a hydro-alcoholic extraction, followed by a subsequent activa- ent temperatures. In this process, 20 g of precursor were added
tion step markedly improves the microstructural features of the into the reactor with a N2 flow at a rate of 0.5 mL∙min1 to act as
final activated carbons (Jain et al., 2016). Considering the carbona- gas carrier during the heating ramp (10 °C/min). When the tar-
ceous nature of coffee residues, the recovery of active carbon mate- geted temperature was achieved, deionized water was introduced
rials can be done through two main strategies: physical and in the reactor by means of a peristaltic pump, with an analogous
chemical activation (Yahya et al., 2015). flow rate, during 60 min. After cooling down to room temperature,
Obtaining ACs from natural biowaste has been widely proposed physically ACs were obtained, thereafter designated as PA-1, PA-2
in the bibliography. Different sources of biomass-derived activated and PA-3 after treatment at 700 °C, 750 °C and 800 °C, respectively,
carbons (ACs) have been used for different applications. For exam- according to conditions previously described by Zhou et al (Zhou
ple, polystyrene waste (Min et al., 2019), bamboo cane et al., 2018).
(Pradhananga et al., 2017), agricultural waste (Chen et al., 2020),
cashew nut shell (Spagnoli et al., 2017) or olive stone (González 2.1.2. Chemical activation process
et al., 2009) have been explored as precursor materials for water Chemical activation of 1 g of SCG-P was performed by mixing it
treatment, separation and purification, catalysis and pharmaceuti- with KOH (potassium hydroxide, 85% pellet for analysis, PanReac)
cal applications (Yahya et al., 2015; Wong et al., 2018). Amid their in a 1:1.5 ratio (Ramón-Gonçalves et al., 2019). The homogenized
different potential applications, carbonaceous materials have been mixtures were placed in alumina crucibles and treated in a Carbo-
also used in electrochemical energy storage. In particular, coffee lite STF 15 tubular oven under a nitrogen carrier (150 mL∙min1).
wastes have been investigated as precursor material for superca- Different analyses were carried out by varying time and/or temper-
pacitive devices. ature of the treatment. The heating rate for all cases was 7 °C/min.
However, most of the work addressing the use of coffee After cooling down to room temperature, the resulting solid was
biowastes focuses on the development of devices, investigating washed several times with Milli-Q water until neutral pH was
2-electrode systems instead of providing a comprehensive achieved, to obtain the corresponding chemically ACs, hencefor-
physico-chemical analysis of the material and its correlation with ward labelled as CA-1, for chemical activation at 775 °C during
the electrochemical response. Alternatively, this work focuses on 30 min; CA-2 for a 30-min chemical activation at 850 °C and CA-
the electrochemical investigation of the material and the effect of 3 for a 60-min chemical activation at 850 °C.
synthesis conditions thereof. The in-depth investigation of the It is worth noting that the temperature range and treatment
electrode material in a 3-electrode system enables its use in asym- time were selected by means of a factorial process based on 11
metric systems, of great interest in the recent years. In addition, experiments that considered the trade-off between material
the cycling stability of these materials is reported here, which, to burn-off and morphological features. More information can be
the best of our knowledge, has not been explored in current liter- found in (Ramón-Gonçalves et al., 2019).
ature. Furthermore, it is worth noting that studying these materials
in organic or highly alkaline/acidic aqueous electrolytes may result 2.2. Physico-chemical characterization
in a high environmental or economic impact for a potential appli-
cation, thus, alternative inexpensive electrolytes are used. The porous structure of the different ACs obtained was charac-
The quest for sustainable electrode materials and electrolytes terized by N2 adsorption. Experiments were performed at 77 K
with low environmental impact shall be considered as part of the using a Micromeritics ASAP 2010 Accelerated Surface Area and
recovery, reuse and recycle perspective integrated in the circular Porosimetry System. The specific surface was determined by ana-
economy context. The present work reports the recovery and acti- lysing the adsorption isotherm via the BET equation and DFT mod-
vation of coffee ground second waste after beverage preparation els, employing Micromeritics and Quantachrome software. The BET
and polyphenol extraction by two routes: physical and chemical and DFT results were compared using Kaneko and Dubinin equa-
activation. The resulting material was evaluated as electrode mate- tions (Lobato et al., 2017). The activation degree (also known as
rial for supercapacitive electrochemical energy storage applica- burn-off, defined as the percentage of the carbonaceous material
tions in a non-toxic and inexpensive neutral aqueous electrolyte burnt mass after the thermal treatment) could be calculated from
1 M Na2SO4. equation (1):
x1  x2
burn  off ð%Þ ¼
100 ð1Þ
x1
2. Materials and methods
where x1 and x2 are the carbonaceous material mass (dry ash-free
2.1. Synthesis of activated carbons [daf] basis) before and after activation. It is worth noting that the
selection of temperatures has been done according to the burn-off
Spent coffee grounds (SCG) from commercial coffee were pro- rate and, in general, higher temperatures have not been used due
vided by a commercial canteen of the National Center for Metallur- to excessive burn-off. X’Pert Philips PMD diffractometer using
gical Research (Superior Council of Scientific Investigations) in graphite-monochromized Cu Ka radiation (k = 1.54056 Å) with a
Madrid, 2019, after beverage preparation. First, to obtain the corre- Panalytical X’celerator detector was used to obtain X-ray diffraction
sponding solid spent coffee ground precursor (SCG-P), SCGs were patterns. An i-RamanÒ spectrometer from B&W Tek with an excita-
subjected to extraction in a hydro-alcoholic medium by means of tion laser beam of 532 nm was used to collect Raman spectra. The
a Berghof BR3000 reactor. To that end, 45 g of SCG were added spectra were obtained with an acquisition time of 6 s, 2 s accumu-
to 600 mL of a hydro-alcoholic solution (mixture 50:50 EtOH: lations and a 6-time multiplier. The powder samples were directly
H2O, v/v) (ethanol, Merck, 99.8% (v/v)) at 393 K for 30 min with placed on the sample holder, without any additional treatment. In
a constant pressure of 50 bars, as indicated by Ramón-Gonçalves addition, ACs surfaces were examined by scanning electron
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A. Adan-Mas, L. Alcaraz, P. Arévalo-Cid et al. Waste Management 120 (2021) 280–289

microscopy (SEM) using a JEOL-6400 and an electron bean acceler- low pressures, a great increase in the amount of gas was found,
ated at 15 keV. For SEM observations, the activated carbons samples indicating the development of microporosity in the carbon struc-
were placed on an adhesive conductive carbon disk and measured ture (Zhou et al., 2014). The lower and the upper parts of the hys-
directly, with no additional coating. teresis loops represent the filling and the emptying of the
mesopores, respectively (Gregg et al., 1967). In all cases, the
2.3. Electrochemical characterization obtained shapes of the isotherms, according to the IUPAC
(Alothman, 2012), are of type I for low (p/p0) (usually from micro-
To investigate the electrochemical properties of ACs, available porous materials), and of type IV for high (p/p0) (typical from
in powder form after activation, an electrode slurry containing mesoporous materials). Type I isotherms shape is concave to the
the active carbon must be prepared. To that end, the ink was pre- relative pressure axis, and sharply increase at low p/p0 reaching
pared using standard conditions reported elsewhere (Gören et al., a plateau. The Type IV isotherm exhibits a hysteresis loop, and
2015), this is, by mixing 80% of active material, 15% conductive car- tends to level off at high relative pressure (Ben Yahia et al.,
bon and 5% polyvinylidene difluoride (PVDF) dispersed in N- 2013). These results reveal the presence of both micropores and
Methyl-2-Pyrrolidone (NMP). The resulting slurry was coated on mesopores (Alcaraz et al., 2018). As previously reported (Zhou
Toray Carbon PaperÒ, used as conductive substrate and dried at et al., 2014), the coexistence of mesopores and micropores in car-
40 °C for 12 h. The mass of active material in the resulting elec- bonaceous materials is appropriate for supercapacitor applications
trode is in the range from 1.5 to 4 mg. Electrochemical tests were since charge storage occurs primarily at the micropores, while the
performed in 1 M Na2SO4 electrolyte using a three-electrode cell mesopores provide fast mass-transport of electrolyte, enhancing
configuration. The coated carbon paper served as working elec- the electrode-electrolyte interactions.
trode, a 2.5  2.5 cm2 platinum foil was used as counter electrode Table 1 summarizes the results obtained from BET and DFT
and a saturated calomel electrode (SCE) served as reference. A analyses. The results reveal that a microporous structure seems
potentiostat Gamry Instruments IFC1000-07087 was used for the present in all cases, since the total pore volume is very similar to
electrochemical tests. Cyclic voltammetry was performed at scan the volume of the micropores (W0). The real specific surface areas,
rates ranging from 25 mV
s1 to 250 mV
s1. Galvanostatic named as Stotal, were calculated using the Dubinin-Radushkevich
charge-discharge curves were obtained at different specific cur- equation (Nguyen and Do, 2001). Results evidence that the specific
rents (1–10 A
g1). Electrochemical impedance spectroscopy (EIS) surface areas for chemically activated ACs were higher than the
was used to further elucidate the electrochemical properties of ones obtained for the physically activated ACs, independently of
the best-performing ACs for energy storage applications. EIS was the activation time and temperature conditions. It is worth men-
performed, after a 2000 s open circuit potential to ensure signal tioning that the surface areas determined from BET were, in all
stabilization, by applying a sinusoidal perturbation with 10 mV cases, higher than the total surface areas calculated from the Dubi-
amplitude in the frequency range from 0.01 to 104 Hz. Cycling sta- nin equation. It has been reported that when the pore size is higher
bility tests were performed by means of continuous galvanostatic than 1 nm, the BET equation usually tends to overestimate the
charge-discharge at 10 A
g1 for 5000 cycles. results. Some methods, like the BJH-method, are based on the pore
condensation phenomena and are applicable to analyze the size of
the mesopore. However, by means of BJH, micropores and narrow
3. Results and discussion mesopores are not correctly evaluated. Other methods, like the
Dubinin-Radushkevich theory, only describe the micropore filling.
3.1. Textural properties For this reason, a more realistic description for a material contain-
ing micro- and mesopores is obtained using theories based on sta-
The specific surface area for all ACs was evaluated by N2 tistical analysis, such as DFT, that provide a comprehensive pore
adsorption-desorption isotherms. The shapes of N2 isotherms size analysis and relate molecular and macroscopic phenomena
obtained were analogous for the samples undergoing the same (Landers et al., 2013).
activation process. For example, Fig. 1 shows the N2 isotherms at The activation degrees (burn-off) for all ACs are displayed in
77 K obtained for the chemically (CA) and physically (PA) ACs. At Table 1. It is observed that when the temperature of the activation
process increases, the burn-off also does. The burn-off values
obtained vary between 88% and 96%.

3.2. X-ray diffraction (XRD)

XRD patterns of the different ACs are shown in Fig. 2a. In all
cases, two broad diffraction peaks around 2h values of 25° and
42° are well demarcated, corresponding, respectively, to the
(0 0 2) and (1 0 0) planes of graphitic carbon (Yun et al., 2015).
The peak at 42° indicates the formation of a higher degree of intra-
layer condensation of graphite (Zequine et al., 2017). This effect is
more noticeable in the XRD patterns of the samples corresponding
to physically activated carbons (i.e. PA-1, PA-2 and PA-3), where
the activation may have led to a higher graphitization degree.

3.3. Raman spectroscopy

Comparative Raman spectra of all the ACs are shown in Fig. 2b.
It has been widely reported in literature that polycrystalline gra-
phites show two broad bands. One of them, the G band, appears
Fig. 1. N2 adsorption-desorption isotherms of a physically activated carbon (PA) at around 1580 cm1; while the other one, known as the D band,
and a chemically activated carbon (CA). is located at 1355 cm1. These are attributed to E2g and A1g modes,
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Table 1
Textural properties of all the synthesized ACs based on BET, DFT and burn-off analysis. Vp: Total pore volume, Wo: Micropore volume, Lo: Average micropore size, Smi:
Microporous surface, Se: Non-microporous surface, SBET: BET surface area; SDFT: DFT surface area.

Samples Vp (cm3/g) Wo (cm3/g) Lo (nm) Smi (m2/g) Se (m2/g) SBET (m2/g) SDFT (m2/g) Burn-off (wt, % daf)
PA-1 0.21 0.19 1.69 14.05 470.73 484.79 656.44 86
PA-2 0.27 0.24 1.83 26.32 568.59 595.03 784.10 95
PA-3 1.03 0.30 4.19 244.83 736.83 981.12 943.86 96
CA-1 0.67 0.63 1.69 1575.30 26.76 1602.23 1311.10 88
CA-2 1.17 1.07 2.00 2265.10 65.59 2330.17 2088.45 95
CA-3 1.16 1.03 2.21 2014.80 94.78 2109.08 1927.45 96

agreement with those of XRD measurements, where a higher

graphitization degree was found for these samples. These results
suggest a higher disorder degree in the CA samples, while better
structural alignment is obtained for the physically activated ACs.

3.4. Scanning electron microscopy (SEM)

Fig. 3 shows SEM micrographs of the different ACs. As observed,

the different processes carried out to obtain the ACs, either by
chemical or physical treatment, yielded different surface mor-
phologies. Considering the results obtained by N2 adsorption/des-
orption, the resulting images illustrate empty cavities in the
material surface, indicating that both the micropores and meso-
pores calculated by means of the isotherms are located within
the carbon particle walls. Physically activated ACs (Fig. 3a-c) exhi-
bit a surface morphology with fewer number of pores. In these
cases, the carbonaceous materials show a pitted and cracked sur-
face, typically found in physically ACs (Williams and Reed, 2006).
Different conditions for the same process yield similar surface
morphologies. On the other hand, chemically activated ACs (Fig. 3-
d-f) exhibit homogeneous surface morphology in all cases, with a
larger number of pores. This porous morphology is typically
observed in carbons activated with KOH treatments and are caused
by the chemical interaction between the chemical reagent and the
precursor surface (Pagketanang et al., 2015; Le Van et al., 2019).

3.5. Electrochemical characterization

3.5.1. Effect of the activation process parameters for supercapacitive

applications
The electrochemical properties of coffee-derived ACs have been
investigated in 1 M Na2SO4 aqueous electrolyte. Fig. 4a,b displays
cyclic voltammetry and galvanostatic charge-discharge results for
the physically ACs after 1 h thermal treatment at temperatures
ranging from 700 °C to 800 °C. As observed, the temperature has
a critical effect on the electrochemical response of these materials.
Cyclic voltammetry results, from 0.45 V to 0.9 V vs. SCE, evidence
Fig. 2. (a) XRD patterns of all obtained ACs by both physical and chemical
an increase in the total capacitance per unit of mass with increas-
activations. (b) Raman spectra of the ACs. ing temperature. Discharge curves, presented in Fig. 4b, evidence
lower ohmic drop for the ACs treated at higher temperatures.
These ACs present specific capacitance values of 31 F
g1, 67 F
g1
respectively (Sfyris et al., 2017). The former is related to the degree and 72 F
g1 at 1 A
g1 for PA-1, PA-2 and PA-3 respectively. When
of disorder of the sample originating from sp3 carbons, while the capacitance retention is considered, all carbon-based materials sig-
latter, associated with a hexagonal carbon structure, is related to nificantly lose charge storage capability when doubling the applied
the number of defects, this is, sp3 and sp2 hybridized carbons specific current. Then, capacitance retention linearly decreases at
accordingly. The ratio of the D band intensity (ID) to the G band higher currents to values below 60% at 10 A
g1.
intensity (IG) (i.e. ID/IG) also provides information about the disor- Considering the cycling stabilities of these materials, the phys-
der of the carbon. In addition, in the case of the amorphous carbon, ically activated ACs treated at lower temperatures undergo an acti-
overlapped bands at around 1400 cm1 and 1550 cm1 can be vation process that increases their initial capacitance up to 12%.
observed (Shimodaira et al., 2000). In the present case, all Raman This may be associated to increased wettability and therefore, bet-
spectra show two major peaks at 1308 cm1 and 1585 cm1, asso- ter electrode-electrolyte interaction with time. In the case of the
ciated to the D and G bands, respectively. Regarding the intensity sample treated at 800 °C, its capacitance retention was kept above
ratio in the case of the physically ACs, the G band intensity is 99% after continuous charge-discharge at 10 A
g1 for 4000 cycles.
higher than the intensity of the D band. These results are in good Then, it slowly decreased to approximately 92% after the last 1000
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Fig. 3. SEM micrographs of (a) PA-1, (b) PA-2, (c) PA-3, (d) CA-1, (e) CA-2 and (f) CA-3 activated materials.

cycles. As expected for supercapacitive carbonaceous materials, all by the galvanostatic discharge curves of the three materials
presented excellent cyclability performance in neutral media with obtained at 1 A
g1 (Fig. 5b).
negligible degradation during continuous charge-discharge In a similar manner, capacitance retention at higher applied
cycling. currents also improved with increasing exposure time at higher
Results regarding the electrochemical response of the chemi- temperatures. In this case, while the two samples treated for
cally activated ACs are displayed in Fig. 5 while comparative 0.5 h showed a capacitance retention at 10 A
g1 around 50%, the
results with the precursor material (SCG-P) are displayed in sample treated during 1 h retains 70% of the initial capacitance
Fig. S1. The sample treated at 850 °C for 0.5 h was compared to when the applied current is ten-folded. Finally, when the cycling
the one treated at 775 °C for the same time, and the results stability of these samples is considered, capacitance retention of
revealed that the active potential window is slightly increased, the best performing material, CA-3, is 85% after 5000 cycles at 10
indicating that an increase in temperature improves the superca- A
g1, slightly lower than the 93% of CA-1 and identical to CA-2.
pacitive response. Moreover, when the exposure time at 850 °C is In this case, values of capacitance retention are lower than for
increased to 1 h, the active potential is window greatly improved the physically activated ACs.
to nearly 1.9 V, from 1.1 V to 0.8 V vs. SCE. This phenomenon
results in an overall increase in the charge storage capabilities of 3.5.2. Comparison of activation method
the materials, whose capacitance increases from 55 F
g1 for Considering the results presented in section 3.5.1, CA-3 and PA-
CA1 to 62 F
g1 for CA-2 and then to 84 F
g1 for CA-3, as observed 3 exhibit the best electrochemical performance after chemical and
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Fig. 4. Electrochemical results in 1 M Na2SO4 for physically activated ACs treated at different temperatures. (a) Cyclic voltammetry comparison at 50 mV
s1 (b) Galvanostatic
charge-discharge comparison at 1A
g1 (c) Capacitance retention results at different applied specific currents and (d) Capacitance retention after continuous charge discharge
at 10 A
g1 during 5000 cycles.

physical activation, respectively. When performance at different A detailed comparison of other coffee-derived materials is reported
scan rates is considered, Fig. 6a and c, both materials maintained in literature - see Table S1.
a quasi-squared shape at lower and higher scan rates. However, Fig. 7 depicts the electrochemical impedance spectroscopy results
due to the higher resistance that the physically activated sample for both materials. In general, electrochemical double layer capaci-
displayed, an obvious tilt of the voltammogram was observed tors changes from a pure resistor at high frequencies to a capacitive
above 100 mV
s1. On the other hand, the chemically activated behaviour at low frequencies. At high frequencies, the ACs show a
sample relatively maintained the quasi-squared shape for scan resistive behaviour and when the imaginary part tends to zero in
rates as high as 250 mV
s1. the Nyquist plot (Fig. 7c), the bulk resistance, also known as equiva-
The effect of resistance is also observed by galvanostatic charge- lent series resistance, can be determined. This resistance arises from
discharge and electrochemical impedance spectroscopy. When the the contact and ionic resistances associated with the migration of
discharge curves are considered, Fig. 6b and d, there is an obvious ions, although it also accounts for the ohmic resistance introduced
increase in the ohmic drop at higher applied currents for the phys- by the wiring and the current collector, as well as the electrolyte (Li
ically activated sample, whereas the chemically activated sample et al., 2015). This behaviour is also characterized by a low impedance
displays lower resistance. Both samples, nonetheless, exhibit modulus value (Fig. 7a) and a phase angle close to 0° (Fig. 7b). At high
quasi-linear discharge curves, as expected for a purely carbon- to mid frequencies, a depressed semicircle appears in the Nyquist
based material. It is worth mentioning that the coulombic effi- plot, as a result of the internal resistance of the electrode. The larger
ciency for both samples is always maintained above 92%, showing this value, the more resistant the electrode material is, since this
the excellent energy efficiency associated to electrochemical dou- semicircle mainly arises from the ionic resistance of the electrolyte
ble layer capacitance. The results are comparable to literature. inside the porous structure and the electronic resistance of the ACs
For example, Ruoff et al. prepared activated coffee grounds with (Yang et al., 2013). Considering that both materials were prepared
ZnCl2 (Rufford et al., 2008), while Chiu et al. (Chiu and Lin, 2019) under identical conditions to avoid non-homogeneity among the
compared different activating agents such as KOH, that displayed samples, the chemically activated sample presents a smaller
capacitance values of 368 F
g1 at 0.05 A
g1 in 1 M H2SO4 for depressed semicircle, indicating better electrode-electrolyte interac-
the former and 105 F
g1 at 0.5 A
g1 in 2 M KOH for the latter. tion and better overall conductivity (Li et al., 2015).

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Fig. 5. Electrochemical results in 1 M Na2SO4 for samples CA-1, CA-2 and CA-3 (a) Cyclic voltammetry at 50 mV
s1 (b) Galvanostatic charge-discharge at 1A
g1 (c)
Capacitance retention results at different applied specific currents and (d) Capacitance retention after continuous charge discharge at 10 A
g1 during 5000 cycles.

00 00
In the mid-frequency, the material changes from resistive to 0 Z ðxÞ Z ðxÞ
C ðxÞ ¼ ¼ ð3Þ
capacitive. At this point, ions accumulate contributing to the xjZ ðxÞj 2
2pf jZ ðxÞj2
capacitive behaviour and the phase angle changes, from 0° to
almost 90° alongside a change of slope in the modulus of impe- 0 0
00 Z ðxÞ Z ðxÞ
dance. This is caused by the effect of the electrode’s thickness C ðxÞ ¼ ¼ ð4Þ
and porosity in the interaction of the active material with the elec- xjZ ðxÞj2 2pf jZ ðxÞj2
trolyte. Nonetheless, certain diffusion-controlled phenomena can
0 00
be observed in the inset of the Nyquist plot, with a slope close to where x is the angular frequency, C ðxÞ and C ðxÞ are the real and
45° in a short interval of frequencies, caused by ion diffusion and the imaginary part of the complex capacitance respectively, where
0
pore penetration of the electrolyte inside the ACs. C ðxÞ is the complex capacitance, Z ðxÞ is the real part of the impe-
At low frequencies, the phase angle approaches approximately 00
dance, Z ðxÞ is its imaginary part and jZ ðxÞj is the modulus of
85°, evidencing the capacitive response of the system. This is impedance. As observed, the factor of merit for the chemically acti-
observed in the Nyquist plot as a quasi-vertical line parallel to vated AC is only 6 s, while for the physically activated AC it is 12 s.
the imaginary axis. The capacitive behaviour displayed by these The real capacitance also displayed a much higher value for CA-3, as
ACs is almost ideal at low frequencies. Again, the chemically acti- expected. This factor of merit, or relaxation time, can be directly
vated material presents a performance closer to the ideal capaci- correlated to ionic transport in the porous electrode, which is
tive behaviour, with a phase angle closer to 90° than the clearly enhanced for the chemically activated material. Impedance
physically activated AC. results presented after different numbers of charge-discharge are
A complex capacitance analysis for the real and imaginary com- also displayed, showing the invariant chemical nature of the ACs,
ponents of the capacitance is calculated (Fig. 7d). This is repre- with negligible increase in resistance with continuous cycling, in
sented by the following equations (Taberna et al., 2003): accordance with the results observed by cycling stability tests.
0 00 Considering the results altogether, scanning electron micro-
C ðxÞ ¼ C ðxÞ  jC ðxÞ ð2Þ scopy evidenced a more open structure for the chemically acti-

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Fig. 6. Cyclic voltammetry at different scan rates and galvanostatic charge-discharge at different applied specific currents for (a, b) CA-3 and (c,d) PA-3.

vated material, while bigger agglomerates were obtained for PA-3. 4. Conclusions
Raman results also evidenced a more disordered structure, while
XRD correlated to lower graphitization degrees. These properties Activated carbons (ACs) were obtained from spent coffee
are directly associated with the bigger surface areas calculated ground recovered after use in beverage preparation and polyphe-
by BET, and ultimately allows the better electrochemical response. nol extraction by means of a hydrothermal step followed by phys-
While both activation methods suggest that higher temperatures ical or chemical activation. The specific surface areas of the
are linked to enhanced electrochemical performance, results evi- physically activated ACs were in the 585–981 m2
g1 range, while
dence that chemical activation leads to a more open microstruc- it was between 1602 and 2330 m2
g1 for the chemically activated
ture. This facilitates electrolyte penetration, thus diffusion paths ACs. X-ray diffraction patterns exhibit two broad peaks at around
are shortened, improving the electrode-electrolyte interaction, 25° and 42°, characteristic of carbonaceous materials with certain
reducing system resistance, and leading to higher capacitance graphitization degree, which is more intense in the case of physi-
and better performance at high applied currents. cally activated ACs. Scanning electron microscopy images reveal
For that reason, chemical activation seems to be the most suit- different morphologies with a greater number of micropores for
able alternative to recover coffee second biowaste and to transform ACs chemically activated. In contrast, fewer pores and a pitted
it into AC for supercapacitive electrochemical energy storage appli- and cracked surface was obtained for the physically activated ACs.
cations. Finally, this approach also promotes posterior recovery The physically activated material exhibits a capacitance of 72
and recyclability by using a sustainable low-impact neutral aque- F
g1 at 1 A
g1 in a 1.1 V voltage range, with 60% capacitance
ous electrolyte and reintroduces a functional material with good retention when the applied specific current is ten-folded and a
material lifetime and cycling stability, fitting within the scope of 100% capacitance retention after 5000 continuous charge-
circular economy. discharge cycles. On the other hand, the chemically activated car-

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A. Adan-Mas, L. Alcaraz, P. Arévalo-Cid et al. Waste Management 120 (2021) 280–289

Fig. 7. Electrochemical impedance spectroscopy results for the chemically activated (CA-3) and physically activated (PA-3) carbons. (a) Frequency vs. impedance modulus, (b)
Frequency vs. phase angle and (c) Nyquist plot (d) Complex capacitance analysis.

bon shows a capacitance of 84 F
g1 at 1 A
g1 in a larger voltage (FCT) under the project numbers numbers PTDC/QUI-
range from 1.1 V to 0.8 V vs. SCE. Moreover, it exhibits 70% capac- ELT/28299/2017, UID/QUI/00100/2019 and UIDB/00100/2020.
itance retention at 10 A
g1 and 85% retention after 5000 cycles of
continuous charge-discharge. The better performance of the chem-
ically activated materials results from the combination of high Appendix A. Supplementary material
thermal treatment temperature with the microporous morphology
granted by KOH treatment. This morphology and thermal activa- Supplementary data to this article can be found online at
tion lead to better electrode-electrolyte interactions, with reduced https://doi.org/10.1016/j.wasman.2020.11.043.
resistance and increased active voltage range. In conclusion, this
route is a promising strategy to reduce coffee waste by recovering References
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