Journal Pre-proofs

Preparation and Electrochemical Properties of Graphene Quantum Dots/

Biomass Activated Carbon Electrodes

Ying Li, Feifei Wu, Xuan Jin, Humin Xu, Xuefeng Liu, Gang Shi

PII: S1387-7003(19)30935-9
DOI: https://doi.org/10.1016/j.inoche.2019.107718
Reference: INOCHE 107718

To appear in: Inorganic Chemistry Communications

Received Date: 3 October 2019

Revised Date: 3 December 2019
Accepted Date: 4 December 2019

Please cite this article as: Y. Li, F. Wu, X. Jin, H. Xu, X. Liu, G. Shi, Preparation and Electrochemical Properties
of Graphene Quantum Dots/Biomass Activated Carbon Electrodes, Inorganic Chemistry Communications (2019),
doi: https://doi.org/10.1016/j.inoche.2019.107718

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© 2019 Published by Elsevier B.V.

 Preparation and Electrochemical Properties of Graphene Quantum
Dots/Biomass Activated Carbon Electrodes

Ying Li§1*, Feifei Wu§2, Xuan Jin1, Humin Xu1, Xuefeng Liu1, Gang Shi1*

1Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School

of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
2Suzhou Institute of Nanotech and Nanobionics, Chinese Academy of Science,
Suzhou 215123, China

∗Corresponding author. E-mail address: liying@jiangnan.edu.cn (Y. Li);

shigang0720@126.com (G. Shi)
§ Author Contributions: Y. Li and F. Wu contributed equally

Abstract
Graphene quantum dots and biomass activated carbon have enormous potential for
electrochemical application, which composites as anode materials for lithium ion
battery are rarely reported. Here, the rice husk based activated carbon was modified
by graphene quantum dots, exhibiting excellent electrochemical performance as an
electrode for lithium ion battery. The results show that, with the introduction of
graphene quantum dots, the charge transfer resistance of the electrode was reduced
from 577.7 Ω to 123.9 Ω, and the lithium ion diffusion coefficient was increased by
175 times. Meanwhile, the introduction of graphene quantum dots plays an important
role in improving the cycle stability of the battery.

Keywords: biomass activated carbon; graphene quantum dots; lithium ion battery;
electrochemical properties

1
1. Introduction
With the rapid development of science and technology, the photoelectric
materials have attracted much attention due to their unique properties[1,2]. Especially,
the lithium ion battery is one of the most popular photoelectric materials, such as the
mobile phones, hybrid vehicles, aeronautical facility and so on[3,4]. With the extensive
application, the lithium ion battery with better performance is expected, which will be
realized by improving the electrochemical properties of anode materials.
In recent years, the biomass waste has become to be a kind of functional material
and attracted extensive attention from researchers at home and abroad due to its low
cost, environmental protection and recyclability. Furthermore, the activated carbon, as
the high value-added products of biomass waste, exhibits good electrochemical
property for their high specific surface area and plentiful cavity[5-8]. So far, the
research on the electrochemical properties of activated carbon has mainly focused on
the applications of double-layer capacitance [9-11] and super capacitor [12,13]. In contrast,
there are rare reports on the biomass carbon as an electrode of lithium ion battery. Fey
et al. [14] obtained activated carbon via high temperature pyrolysis of rice husk and
they have demonstrated that the introduction of rice husk based activated carbon as
electrode material can improve the electrochemical property of lithium ion battery.
Although this kind of lithium ion battery owns high specific capacity, the efficiency is
still lower, which is necessary to do further regulation and improvement. Similarly, Li
et al.[15] extracted activated carbon from grapefruit skin. Then, the activated carbon
doped with Fe3O4 was used for anode material of lithium ion battery. This study has
proved that the discharge specific capacity of lithium ion battery is still high under
high current density.
As a member of the graphene family, graphene quantum dots (GQDs) have
nanoscale dimension with a few nanometers. Due to their unique quantum
confinement effect and boundary effect[16-19], GQDs are usually used as a modified
material to improve the property of raw materials. This composite modified by GQDs
has broad application in the field of super capacitor[20], optoelectronic device[21] and
lithium ion battery[22-24]. Although both of the biomass carbon and GQDs have great
potential in the electrochemical application, there are few reports on the
electrochemical performance of their composite material.
Here, we propose an innovative anode material to explore the electrochemical
property of lithium ion battery. This innovative material composes of rice husk-based

2
activated carbon (RHAC) and GQDs modified with phenylalanine. The study results
show that with the introduction of GQDs, the charge transfer resistance of the
electrode is reduced from 577.7 Ω to 123.9 Ω, and the lithium ion diffusion
coefficient is increased by 175 times. Meanwhile, the introduction of GQDs plays an
important role in improving the cycle stability of the battery.
2. Results and discussions
2. 1 Analysis of specific surface area and pore structure for RHAC
The specific surface area and pore volume of the RHAC are 1722 m2/g and 1.86
mL/g, respectively. As shown in Fig. 1(a), the adsorption capacity of RHAC increases
sharply at lower P/P0 value, which indicates that the micropore accounts for a large
proportion. Furthermore, a hysteresis loop appearing in the curve indicates that there
exists mesoporous structure. Fig. 1(b) shows the pore size distribution of RHAC.
Clearly, the pore structure of RHAC mainly consists of micropores structure with the
pore diameter of about 0.8 nm and mesopores structure with the pore diameter of 2-6
nm. That is to say, the pore structure of RHAC belongs to micro-mesopore coexisting
structure.

Fig. 1 (a) Adsorption/desorption curve and (b) pore size distribution of RHAC.

2.2 Analysis of Raman and fluorescence spectroscopy for GQDs

As illustrated from the Raman spectrum of GQDs in Fig. 2(a), there are two
characteristic peaks at 1335 cm-1 and 1586 cm-1, corresponding to the typical D band
and G bond, respectively. Fig. 2(b) is the fluorescence excitation and emission spectra
of GQDs. The energy level transition of the molecule can be reflected from the
fluorescence spectrogram. It can be seen from Fig. 2(b) that the emission wavelength
is comparatively long, due to the high conjugation degree in the molecules at the edge
of GQDs, making the wavelength red shift.

3
Fig. 2 (a) Raman spectrum of GQDs; (b) fluorescence excitation and emission spectra of GQDs.

2.3 Infrared spectroscopy analysis

The FT-IR spectrum of RHAC-GQDs is shown in Fig. 3. It’s well known that
the broad peak around 3400 cm-1 is related to the stretching vibration of O-H and N-H.
And the vibrational peaks at 1040 cm-1 and 675 cm-1 are attributed to the stretching
vibration of C-N and C-O, respectively[25]. According to the above analysis, there
exist hydroxyl, carbonyl, carboxyl and amino groups on the surface of the composite
material, which indicates that RHAC was successfully modified by GQDs.

Fig. 3 FT-IR spectrum of RHAC-GQD composite.

2.4 XRD analysis

The X-ray diffraction (XRD) patterns of RHAC and RHAC-GQDs are illustrated
in Fig. 4(a) and 4(b). It can be seen from the following figure that there is no
significant difference between RHAC and RHAC-GQDs, which means that the
introduction of GQDs does not affect the structure of the original RHAC. In addition,
due to the low crystallinity of GQDs, the diffraction peak of the RHAC-GQDs is
wider than that of RHAC, especially the peak of 41o.

4
Fig. 4 XRD patterns of (a) RHAC and (b) RHAC-GQD composite.

2.5 SEM analysis

Fig. 5(a) and 5(b) shows the SEM images of RHAC and RHAC-GQDs.
Compared with RHAC, RHAC-GQDs have a tighter structure and a smoother surface,
which could prevent the electrode material falling off and increase the battery life.
Moreover, GQDs attached to the surface of RHAC could prevent the dissolution of
the active material.

Fig. 5 SEM images of (a) RHAC and (b) RHAC-GQD composite.

2.6 Cyclic voltammetry test analysis

To study the behavior of lithium ions in the discharge/charge process, the cyclic
voltammetry curves of RHAC and RHAC-GQDs are shown in Fig. 6. Compared with
the first cycle, the cathodic peak appears between 0.5 and 1 V in the second cycle, due
to the formation of SEI (solid electrolyte interface) film by the reaction of lithium ions
and electrolyte. When the potential is scanned from negative potential to positive
potential, an oxidation peak appears between 0.1 and 0.5 V for both electrodes, which
belongs to the desorption peak of lithium ions extraction. Comparing Fig. 6(a) with
Fig. 6(b), the cyclic voltammetry of the RHAC-GQDs shows better coincidence,

5
indicating that the introduction of GQDs can provide much better cycle stability of the
electrode material.

Fig. 6 Cyclic voltammetry curves of (a) RHAC and (b) RHAC-GQD composite.

2.7 Constant current charge and discharge test analysis

The charge/discharge curves of RHAC and RHAC-GQDs are measured at the
current density of 100 mA/g, as shown in Fig. 7. In the first cycle, the discharge
capacity and charge capacity of RHAC are 350.0 and 289.5 mAh/g, respectively (Fig.
7(a)). And RHAC-GQDs show 431.1 and 315.7 mAh/g of discharge capacity and
charge capacity, respectively (Fig. 7(b)). RHAC-GQDs shows apparently higher
discharge capacity than RHAC without GQDs. Note that, as compared with the first
discharge capacity, the second discharge capacity of electrode material slightly
decreases, since lithium ions were intercalated with the electrode material to react and
form a layer of SEI film during the first discharge, resulting in the loss of electrode
material. In addition, the coulombic efficiency of RHAC-GQDs (88.9%) is higher
than that of RHAC (82.8%) in first cycle, revealing that introducing GQDs could
release more reversible Li ions. Clearly, the modification of GQDs can apparently
increase the coulombic efficiency of RHAC. Furthermore, the capacity of
RHAC-GQDs (381.1 mAh/g) is higher than that of RHAC (283.6 mAh/g) in second
cycle, suggesting that RHAC-GQDs owns superior cycling performance as compared
to RHAC.

6
Fig. 7 The first (solid line) and second (dash line) charge/discharge profiles at 100 mA/g: (a) RHAC
and (b) RHAC-GQD composite.

Fig. 8(a) shows the discharge capacity of RHAC and RHAC-GQDs at different
current density of 100 mA/g, 200 mA/g, 400 mA/g, 800 mA/g, 1600 mA/g and 100
mA/g, respectively. At current density of 100 mA/g, 200 mA/g, 400 mA/g, 800 mA/g
and 1600 mA/g, the discharge capacity of RHAC-GQDs is ~80 mAh/g, ~76 mAh/g,
~54 mAh/g, ~102 mAh/g and ~82 mAh/g higher than that of RHAC, respectively.
Furthermore, when the current density returns to 100 mA/g, the capacity of RHAC
decreases quickly from 350.0 mAh/g to 124.9 mAh/g, and the capacity of
RHAC-GQDs decreases slowly from 431.1 mAh/g to 267.5 mAh/g. GQDs can
enhance the discharge capacity of RHAC, and improve the rate performance.
Besides, it can also be seen that the discharge capacity of both electrode materials in
the second cycle is much lower than that in the first cycle, proving that the SEI film
was formed during the first discharge process described above. Fig. 8(b) is a
discharge cycle performance of RHAC and RHAC-GQDs at a current density of 100
mA/g. Here, the discharge capacity of RHAC-GQDs, with excellent cycle stability, is
concentrated between 350 and 380 mAh/g. However, the discharge capacity of RHAC
decreases apparently as the increase of cycle times. After 100 cycles, the discharge
capacity of RHAC decreases from 280.1 mAh/g to 157.4 mAh/g. To clarify, the
discharge capacity of the first cycle is not taken into account in contrast to the course
of the study. The above results indicate that the introduction of GQDs can apparently
improve the cycle performance of RHAC electrode material.

7
Fig. 8 (a) The discharge capacity curves at various electric current density of RHAC (black curve) and
RHAC-GQDs (blue curve); (b) The discharge capacity profiles of RHAC (black curve) and
RHAC-GQDs (red curve) at 100 mA/g.
2.8 Electrochemical impedance analysis
Fig. 9 shows the electrochemical impedance spectroscopy (EIS) after 50 cycles
of RHAC and RHAC-GQDs with different GQDs content. In EIS, the Nyquist plot
contains a semi-circular arc and a diagonal line. The semi-circular arc belongs to the
high frequency region and the diameter of the semicircle represents the
charge-transfer impedance (Rct) of the electrode material, which is closely related to
the formation of the SEI film. The oblique line belongs to the low frequency region,
indicating that the diffusion in the low frequency region is hindered, which is closely
related to the diffusion of lithium ions into the electrode material, namely solution
impedance (Rs)[26]. The effect of different GQDs content on the charge transfer
resistance change of RHAC-GQDs is shown in Fig. 9. It is found that Rct is first
increased and then decreased along with the increase of GQDs content. Due to that
the activated carbon possesses mesopores, GQDs can be absorbed in the activated
carbon and lower Rct of activated carbon. However, too much GQDs result in the
blocked pores of activated carbon, and increase Rct. When the GQDs content is 0.5 g,
Rct of activated carbon with GQDs is lowest. Meanwhile, Rct of optimal activated
carbon with GQDs is also lower than that of activated carbon without GQDs. From
Table 1, we can know that the Rct values of RHAC and RHAC-GQDs composite are
calculated to be 577.7 and 123.9 Ω, respectively. The lower Rct of RHAC-GQDs
composite is attributed to the additional carbon from GQDs, which provides superior
electroconductivity of RHAC-GQDs composite as compared to RHAC.

8
Fig. 9 The 50th Nyquist plots of (a) RHAC and (b) RHAC-GQD composite.

Table 1 The data of equivalent circuit for RHAC and RHAC-GQDs.

Rs (Ω) Rct (Ω) D (cm2 s-1)

RHAC 228.3 577.7 1.521E-14

RHAC-GQDs 32.4 123.9 2.662E-12
Note: Rs is the impedance of the solution, Rct is the charge transfer impedance and D is the lithium
ion diffusion coefficient.

Here, the lithium ion diffusion coefficient D is calculated from the low frequency
region data according to formula (1)[27,28].
𝑅2𝑇2
𝐷 = 2𝐴2𝑛4𝐹4𝐶2𝜎2 (1)
Where, R is the gas volume constant; T is the absolute temperature; A is the surface
area of the cathode material; n is the number of electron transfer in the redox process;
F is the Faraday constant; C is the concentration of lithium ions in the electrolyte; σ is
the Warburg coefficient. According to the EIS analysis, the impedance of the
RHAC-GQDs electrode is smaller than that of the original RHAC electrode. Besides,
RHAC-GQDs owns a larger lithium ion diffusion coefficient, which is beneficial to
increase the conductivity of electrode materials. Both of these indicate that the
introduction of GQDs is beneficial to improve not only the diffusion of lithium ions
between SEI film and electrode materials but also the conductivity of RHAC
electrode materials.
3. Conclusions
Briefly, RHAC modified with GQDs has higher discharge capacity, higher
coulombic efficiency value, better rate performance and electrical conductivity, which
indicate that GQDs can efficiently improve the electrochemical performance of

9
RHAC. Moreover, the RHAC-GQDs composite exhibits good cycle stability,
indicating that RHAC-GQDs has a promising application t in the research field of
lithium ion battery.
4. Experimental Section
4.1 Reagents and instruments
Phosphoric acid of analytical grade (AR) is purchased from Aladdin Reagent Co.
Ltd. Acetylene black (AR), citric acid and phenylalanine are purchased from
Sinopharm Chemical Reagent Co., Ltd, Shanghai. All of the reagents are directly used
without any further purification. Sodium alginate (AR) is purchased from
Sigma-Aldrich Inc.. LiPF6 electrolyte (1 mol·L-1, EC+EDC) is purchased from
Taiyuan Liyuan Lithium Battery Technology Co. Ltd..
A muffle furnace (SX2-8-10, Shanghai ZheTai Machinery Manufacturing Co.
Ltd.) is used to obtain the composite material. Automatic surface area and pore size
analyzer (ASAP2020, Micromeritics Instrument Corporation), total reflection fourier
infrared spectrometer (Nicolet 6700, American Thermo Fisher Scientific Co. Ltd.),
Scanning electron microscope (SEM, S-4800，Japan Hitachi Co., Ltd.), Fluorescence
spectrophotometer (FS5 and Lifespec II，Edinburgh instruments Co., Ltd.) and Raman
spectormeter (inVia，Renishaw trading Co., Ltd.) are used to analyze the structure and
morphology characterization. Electrochemical workstation (CHI660D, Shanghai
Chenhua Instrument Co. Ltd.) is used to characterize the electrochemical property of
composite material.
4.2 Preparation of RHAC and GQDs
In order to obtain RHAC, 10 g rice husk was immersed into 50 g phosphoric acid
(60 wt%) and then calcined at 500 °C under the protection of argon.
GQDs were obtained by high-temperature heating and drying method[29]. Here,
citric acid and phenylalanine were used as precursor and functional reagent,
respectively. First, 3 g citric acid and 2.5 g phenylalanine were dissolved into 2 mL
sodium hydroxide solution. After drying at 100 ℃, the ropy substance can be obtained.
Second, the ropy substance was dried in an oven at 80 ℃ for 3 days. Then, the dried
solid was crushed into powder and heated in a muffle furnace at 200 ℃ for 2 h. After
cooling to room temperature, the as-prepared brownish black product was dissolved
into 25 mL deionized water. Then, the solution was treated by centrifuging at 10000
rpm for 30 min. After separating insoluble particles, the obtained supernatant was

10
placed into dialysis bag to do further purification by ultrapure water. Finally, GQSDs
modified with phenylalanine were obtained by freeze-drying the dialyzed solution.
4.3 Preparation of RHAC-GQDs
0.5 g (or 0.2 g, or 1.0 g) GQDs were completely dissolved into the deionized
water by ultrasonic processing for 2 h to form a dispersed solution. Then, 0.5 g RHAC
was dissolved uniformly into the above dispersed solution by stirring and oscillating.
In order to ensure sufficient reaction, the mixed solution was heated in a water bath at
90 °C for 3.5 h. At last, the composite product (RHAC-GQDs) can be obtained by
calcining the dried sample at 450 ° C for 6 h under the protection of Ar/H2.
4.4 Electrode preparation and battery assembly
Preparation of the electrode: The electrode material and the conductive agent
acetylene black were mixed with a mass ratio of 8:1 and ground in an agate mortar for
1 h. The ground mixture was added into 2% sodium alginate with a mass ratio of 9:1.
After stirring for 24 h, they were mixed uniformly. Then, the mixed electrode slurry
was uniformly coated on a copper foil wiped with absolute ethanol by an automatic
coater. Finally, it was placed in a 110 ℃ vacuum oven to be dried overnight.
Assembling battery: RHAC and RHAC-GQDs were emerged as anode materials
in the button cells (CR2025), respectively. 1 moL/L LiPF6 was used as electrolyte,
and the microporous polypropylene was used as lithium ion battery membranes. This
assembly process was finished in a glove box filled with argon.
Acknowledgements
This work was supported by the Natural Science Foundation of China (21671081),
Fundamental Research Funds for the Central Universities (JUSRP51626B) and MOE
& SAFEA for the 111 Project (B13025).
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14
Graphical abstract

The rice husk based activated carbon modified by graphene quantum dots
exhibits excellent electrochemical performance as an electrode for lithium ion battery,
which reduces the charge transfer resistance, increases the lithium ion diffusion
coefficient and improves the cycle stability of the battery.

TOC figure：

15
Highlights:

► RHAC were successfully modified by GQDs.

► RHAC-GQDs exhibits perfect electrochemical performance for lithium ion battery.

► This method extends the application field of RHAC.

16
Declaration of interests

☒ The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this
paper.

☐The authors declare the following financial interests/personal relationships which

may be considered as potential competing interests:

17
 Author Statement

Ying Li: Conceptualization, Methodology, Investigation, Resources, Writing -

Original Draft

Feifei Wu: Methodology, Investigation, Resources, Writing - Original Draft

Xuan Jin: Writing - Review & Editing, Data Curation

Humin Xu: Data Curation

Xuefeng Liu: Investigation

Gang Shi: Conceptualization, Validation, Supervision, Project administration,

Funding acquisition

18