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DOI: 10.1039/C9TA02244A.

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Room Temperature Production of Graphene Oxide with Thermally-
labile Oxygen Functional Groups for Improved Lithium Ion
Batteries Fabrication and Performance
Published on 23 March 2019. Downloaded by Tulane University on 3/23/2019 1:23:46 PM.

Received 00th January 20xx,

Accepted 00th January 20xx
Jiadong Qin†, Yubai Zhang†, Sean E. Lowe, Lixue Jiang, Han Yeu Ling, Ge Shi, Porun Liu, Shanqing
DOI: 10.1039/x0xx00000x Zhang, Yu Lin Zhong*, Huijun Zhao*
Graphene oxide (GO) has drawn intense research interest over the past decade, contributing to remarkable progress in its
relevant applications. The chemical production of GO, however, is challenged by destructive and slowly-propagating
oxidation, especially for large flake graphite. Herein, we reported a simple but effective method to produce well-oxidized
and less defective GO by chemically oxidizing commercially-available expandable graphite at room temperature (25 °C).
Compared to natural graphite with similar flake sizes, expandable graphite afforded faster complete oxidation under the
same oxidizing conditions. In addition, chemical oxidation at room temperature, relative to higher temperatures (35 and 45
°C), resulted in reduced defect concentration in GO. Furthermore, the GO derived from the oxidation of expandable graphite
at room temperature exhibited superior electrical conductivity after mild thermal treatment at 150 °C. Considering the
energy-saving in both the GO synthesis and reduction, the low temperature GO conversion process can be easily integrated
into many other electroconductive applications. As a proof of concept, we achieved a good LiFePO 4 (without carbon-coating)
cathode formulation with our GO, contributing as a 2D binder (before annealing), and obtained a conductive cathode with
improved capacity and high rate performance after mild thermal annealing at 150 °C.

To facilitate oxidation and exfoliation, one strategy is to pre-

intercalate the graphite to form graphite intercalation
Introduction compound (GIC) with increased interlayer spacing and
Graphene and graphene-based materials are appealing to a weakened Van der Vaal interaction between graphite layers.21
myriad of applications, such as energy storage devices,1 In 1999, Kovtyukhova et al. demonstrated a two-step oxidation
electrocatalysis,2 and sensors.3 As one of the most important method in which natural graphite was pre-intercalated in
precursor to graphene materials, graphene oxide (GO) has been concentrated H2SO4, K2S2O8 and P2O5, followed by the Hummers
widely adopted in both lab-scale research and industrial method.22 It was later found that the pre-treated graphite was
production due to its excellent chemical processability and more susceptible to oxidation and exfoliation into monolayer
production scalability.4-6 Currently, the exfoliation of chemically GO sheets and hence the protocol has been adopted in many
oxidized graphite, produced via the modified Hummers more recent works.9, 23 This two-step oxidation route, however,
method, to GO is the most popular GO synthesis method owing presents challenges for the mass production of GO due to the
to its rich oxygen functional groups and quantitative yield of time-consuming pre-treatment, which involves the wetting and
single-layer GO.7-15 However, the harsh conditions in the strong drying of graphite. Another strategy is to employ expanded
chemical oxidation will incur permanent defects, uncontrollable graphite, which features a worm-like structure, as the starting
functionality and even fragmentation in the resultant GO.16-19 In material to produce GO. The expanded graphite is typically
addition, it is limited by the slow diffusion of oxidizing agents.20 achieved by the thermal expansion of graphite bisulfate, a type
Particularly for large flake graphite, oxidants will have difficulty of graphite intercalation compounds (GIC), also known as
reaching the core region of the graphite, resulting in non- expandable graphite. In 2009, Luo et al. synthesized high-
uniform oxidation and cracking in the GO sheets.18 Therefore, quality GO sheets using microwave-expanded graphite, where
much effort has been put into optimizing the chemical oxidation the interlayer galleries were dramatically expanded, as the
method, mainly focusing on the starting materials and oxidation starting material.24 Since then, several research groups have
conditions. shown that expanded graphite is a more suitable graphite
source for preparing large-area GO sheets than natural
graphite.25-27 Recently, Lu et al. proposed a new type of
Centre for Clean Environment and Energy, School of Environment and Science, chemically expandable graphite in which the expansion was
Griffith University Gold Coast Campus, Queensland 4222, Australia. *Email: initiated by the oxygen evolution from the chemical reaction of
[email protected], [email protected]
† These authors contribute equally to this work.
CrO3 graphite intercalant with H2O2.28 Though the expanded
† Electronic Supplementary Information (ESI) available: Table S1-S4 and Figure S1- graphite was very readily oxidized even under mild agitation-
S6. See DOI: 10.1039/x0xx00000x

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free condition, this novel method is challenged by the Materials

complicated procedures and the introduction of toxic Cr6+ The expandable graphite used in the experiments was received
ions.28 from Asbury Graphite Mills (Grade 1721). The natural flake
With regards to oxidation conditions, Eigler et al. kept the graphite was from Sigma-Aldrich (Product No. 332461). Both
oxidation at temperature below 10 °C to yield highly intact GO graphite sources were carefully sieved to control the flake sizes

Journal of Materials Chemistry A Accepted Manuscript

with preserved the structural integrity.29, 30 However, this low- between 200 and 300 µm for the GO synthesis reactions.
temperature method has its limitations, namely the time- KMnO4 (99.0%), concentrated H2SO4 (98%), H2O2 aqueous
consuming procedures and low GO yield. Apart from lowering solution (30% w/w) and hydrochloric acid (32 wt.%) were
the reaction temperature, it has been reported that the purchased from Chem-supply. Deionized water was used in all
addition of a small amount of water to the chemical oxidation experimental procedures, including synthesis reaction and
system not only promoted oxidation but also reduced the purification.
Published on 23 March 2019. Downloaded by Tulane University on 3/23/2019 1:23:46 PM.

defects in GO.31, 32
Typically, the reduction of GO, by which its electrical Synthesis of graphene oxide from expandable graphite (GIC)
conductivity can be restored, is required for the majority of and natural graphite (NG) under different conditions.
applications such as lithium ion batteries (LIBs) and The GO synthesis procedures were based on a modified
supercapacitors.9, 33 The common reduction methods involve Hummers method as illustrated in Figure 1.14, 40 The flake
chemical reduction (such as hydrazine and hydroiodic acid)34, 35 graphite (1 g) was mixed with concentrated H2SO4 (50 mL) in a
and thermal treatment at high temperature19, 36. Zhu and co- 500 mL three-neck flask which was placed in the ice bath with
workers reduced GO dispersion in an anhydrous organic mechanical stirring at 120 rpm. After cooling to below 10 °C,
solvent, propylene carbonate, by heating at only 150 °C, but for KMnO4 (3 g) was slowly added to the mixture and the mixture
12 hours.37 The mild thermal reduction, without the need for kept in the ice bath for 1 h. Then, removing the ice bath, the
reducing agent or high temperature treatment, will be very temperature was elevated to the designated temperature (25,
useful for the incorporation of reduced GO (rGO) into a wide 35 and 45 °C) at which point the mixture was stirred for a
range of electroconductive applications. For example, it has specified period (4, 6 and 8 h.). After this stage, the water bath
been shown that rGO worked well as the conductive additive in was replaced by an ice bath to minimize the temperature rise in
lithium ion batteries (LIBs) electrodes, effectively improving the following steps. 150 mL of chilled water was slowly dropped
charge transport due to its good conductivity, high surface area into the mixture via a peristaltic pump over a period of 90 min
and flexible two dimensional structure.6, 36, 38 The low and then the reaction system was kept in the ice bath for
temperature thermal treatment could help to simplify the another 30 min. At the end of reaction, H2O2 was added to the
fabrication of LIBs by allowing GO to be blended with electrode mixture dropwise to react away the residual KMnO4 until the
materials and then reduced in situ. Due to its good dispersibility color of the resulting product no longer changed. To remove
in multiple solvents, unreduced GO can be homogeneously metal ions, 300 mL diluted aqueous HCl solution (1:9) was
mixed with LiFePO4 particles. This can enable the uniform added to the product. The product was allowed to settle
coating/wrapping of GO around the particles, minimizing the overnight. The resulting sediment was washed with water and
unwanted polarization in LIBs.39 centrifuged at 13000 rpm for 15 min repeatedly until the pH of
In this work, we report a mild GO production approach from supernatant stabilized at ~4. Finally, the resultant sediment was
large-sized expandable graphite (graphite bisulfate, a type of resuspended in deionized water to a total volume of 200 mL.
GIC) flakes via the modified Hummers method, resulting in The GO products made from expandable graphite and natural
more thorough oxidation than natural graphite under the same graphite are denoted as GOGIC and GONG, respectively, and the
conditions. We optimized the oxidation temperature and time oxidation temperatures and reaction time are abbreviated as,
for this GIC-based GO synthesis and found that well-oxidized GO for example, GOGIC-25-4h (the product derived from the GIC,
was obtained at an oxidation temperature of 25 °C for 8 h with a 25 °C, 4 h reaction time).
(denoted as GOGIC-25-8h). This GO, synthesized at room
temperature, was found to be less defective and more prone to Yield Calculation
deoxygenation during low temperature annealing (150 °C). 5 mL of the purified GO aqueous dispersion was cast into a
After 150 °C thermal reduction in air, GOGIC-25-8h restored dense film on a nylon membrane via vacuum filtration and then
more sp2 carbon atoms and was also more conductive than dried in a 60 °C oven overnight. The polymer membrane was
other GO oxidized at higher temperature, which indicates the then gently peeled off and the weight of the freestanding GO
facile removal of oxygenated functional groups. Our work also film which was used to calculate the concentration of GO (CGO,
demonstrates that the GOGIC-25-8h was able to blend well in mg/mL). The yield of GO was calculated by the equation
typical LiFePO4 (without carbon-coating) cathode formulation YGO=CGO×VGO/mGr where VGO is the total volume of GO solution
and helped to deliver pronounced improvement in the capacity after purification (200 mL) and mGr is the mass of starting
and high rate performance of LIBs after mild thermal annealing graphite. Specially, in the case of GOGIC, mGr only refers to the
process. graphite component, excluding the intercalating compounds.

Characterizations
Experimental

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Figure 1. Schematic overview of the experimental design, including GO synthesis routes with different conditions, characterizations and
application tests.

X-ray diffraction (XRD) patterns were measured on a Bruker D8 test was performed on natural graphite. The electrical
advance diffractometer with Cu Kα radiation (λ = 1.5418 Å). The conductivity measurements for the rGO films of similar weight
chemical compositions of GO samples were analyzed by X-ray (~100 µg) were conducted on a Jandel RM3000 four-point probe
photoelectron spectroscopy (XPS, Kratos Axis ULTRA system with a linear arrayed head (probe spacing of 1 mm).
incorporating a 165 mm hemispherical electron energy
analyzer). Scanning electron microscopy (SEM) was conducted LIB testing.
on a Joel JSM-7500FA microscopy with accelerating voltage of To prepare the control LIB cathodes, 10 wt.% polyvinylidene
15.0 kV. Atomic force microscopy (AFM) images were collected difluoride (PVDF), 10 wt.% carbon black, and 80 wt.% LiFePO4
from a Bruker Dimension Icon AFM using peak force tapping (LFP) were mixed with N-methyl-2-pyrrolidone (NMP) by
mode. The statistical analysis of flake thickness was based on magnetic stirring for 24 h. The homogeneous slurry was cast
the line profiles of ~80 pieces of GO sheets from AFM images. onto the aluminium foil which was then dried in an 80 °C
Raman spectroscopy was carried out on individual GO sheets vacuum oven for 12 h. The assembly of coin cells (2032) was
using a Reinshaw inVia Raman microscope with a 532 nm laser. conducted in an argon-filled glove box. Lithium foil was used as
The samples were prepared by spin-coating diluted GO an anode, and 1 M LiPF6 dissolved in ethylene carbonate (EC)
dispersion (~0.1 mg/mL) onto a conductive silicon wafer (for and diethyl carbonate (DEC) with a volume ratio of 1:1 served
SEM and AFM) or thermal oxide silicon wafer (for Raman as the electrolyte. The testing voltage in constant current mode
analysis). Attenuated-total-reflectance Fourier transform ranged from 2.5 to 3.8 V, and the cells were charged under the
infrared (ATR-FTIR) spectra were acquired from a Bruker Alpha constant voltage mode at 3.8 V until the current reached 10%
spectrometer coupled with a platinum ATR single-reflection of the current rate. To show the effects of different reduced
diamond module. TGA of GO film samples was performed on a GOGIC in LIBs, half of the carbon black was replaced with GOGIC-
Netzsch STA 449F3 analyzer under 100% argon or 20% 25-8h and GOGIC-45-4h, respectively, in the cathode
oxygen/80% argon. For the argon atmosphere experiment, GO compounds. The GO samples in the aqueous dispersions were
samples were heated from 50 to 700 °C at the rate of 5 K/min. freeze-dried for the preparation of electrodes. The freeze-dried
For the oxygen atmosphere experiment, the GO samples were GOGIC was dispersed into NMP, forming an 8 mg/mL dispersion
rapidly heated from 50 °C to 150, 175 or 200 °C (heating rate: and then LFP, carbon black and PVDF were added. Prior to
30 K/min), and the samples were kept at the high temperature battery assembly, GOGIC/LFP cathodes were annealed in a 150
for 6 h. To measure the graphite content in the expandable °C oven for 5 h in air. The charge and discharge performance
graphite (GIC), it was heated from 50 to 1000 °C at the rate of 5 tests were carried out using a Neware battery tester (Shenzhen,
K/min under argon atmosphere. As a contrast, the same TGA China) with potential range between 2.5 and 3.8 V. The cyclic

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voltammetry (CV) measurement was performed on a CHI 660D to the left (from 10.6° to 10.1°) when the oxidation time is doubled
electrochemical workstation with a scan rate of 0.1 mV s-1. at 45 °C, which is associated with the interlayer expansion and the

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Figure 2. XRD patterns for (a) GONG from different oxidation conditions, (b) GOGIC oxidized at 25 °C for different times. (c) GOGIC oxidized at
different temperature for 4 h, and (d) Yield comparison between GONG and GOGIC.

oxidation degree of GO.15

As evident in Figure 2b, it was easier to oxidize GIC at 25 °C. The
Results and discussions graphitic peak was much weaker in GOGIC-25-4h (relative to the
The effects of graphite sources. product derived from NG using the same oxidation conditions), and
GO samples were prepared by oxidizing expandable graphite (GIC) the graphitic peak disappeared after prolonging the oxidation time
and natural graphite (NG), respectively, at different temperatures to 8 h. Meanwhile, the left shift in the GO peak (from 11.1° to 10.5°)
(25, 35 and 45 °C) for varying time (4, 6 and 8 h) with the modified reflected the expansion in interlayer spacing (from 8.0 Å to 8.4 Å) and
Hummers method and the products were examined via X-ray hence the slight increase in the degree of oxidation with reaction
diffraction (XRD). The XRD patterns of the two starting materials time at 25 °C. The GIC can also be completely transformed into GO
(Figure S1) showed GIC had greater interlayer spacing between after 4 h of oxidation at higher temperatures of 35 °C and 45 °C,
graphene layers (3.41 Å vs 3.36 Å) and lower crystallinity (broader evidenced by the absence of the graphitic peaks in Figure 2c.
graphitic peak) than NG. This suggests that GIC, with less compact Therefore, using GIC as the starting material allows for milder
structure, can provide more accessible paths for the diffusion of reaction condition and more effective oxidation. Note that the small
oxidizing agents than NG. Experimentally, this advantage of GIC can and broad peaks at around 21° in the XRD patterns can be attributed
be demonstrated by the XRD results of GONG and GOGIC (Figure 2a-c). to the randomly packed single graphene layers.43
Examining Figure 2a, despite subjecting to prolonged oxidation time To measure the graphite content in GIC, the material was heated to
(8 h) and sufficiently high temperature (45 °C), GONG still showed a 1000 °C under the argon atmosphere in order to gasify the
pronounced broad graphitic peaks at about 26° (corresponding to intercalants, water and remove any oxygen functionalities.24, 44 The
the interlayer spacing d ≈ 3.4 Å), which is related to unoxidized TGA curves (Figure S2) showed 76 wt. % of material remained in GIC,
graphite.41, 42 In addition, for GONG-25-4h and GONG-25-8h, the attributed to the graphite component of GIC,45 while NG did not lose
position of the sharp low-angle peak, also known as GO peak, did not any mass after heated to 1000 °C. Therefore, the yield of GOGIC can
change and was about 10.9° (d = 8.1 Å). This suggests that the be calculated with respect to the starting graphitic material and
interlayer distance between GO sheets did not change with the compared with that of GONG, as illustrated in Figure 2d. In general,
oxidation time at 25 °C.41 In contrast, there was a shift in the GO peak the GOGIC had higher yield than GONG under the same reaction

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Figure 3. Morphological characterizations of fully oxidized GOGIC samples. (a), (c) and (e): SEM images of GOGIC sheets coated onto the Si
wafers and the corresponding flake size distributions. (b), (d) and (f): Frequency distributions of the number of layers in the GO samples
(statistics were based on more than 80 GO flakes). The insets are the AFM images of the individual GO sheets and their corresponding height
profiles.

conditions and the gap became even wider at higher temperatures 27.3 ± 18.6 and 24.5 ± 22.0 (mean ± standard deviation) µm,
due to the greater extend of oxidation in GIC. In comparison to other respectively. It is noteworthy that GOGIC-25-8h had the smallest
reported room or low temperature synthesis, our yield of 190 % for average lateral size as well as the highest content of < 20 µm flakes.
GOGIC-25-8h is one of the highest so far.29, 32, 46 Although the oxidation proceeded at lower temperature, GOGIC-25-
8h was also subjected to 8h of mechanical stirring which likely led to
Morphological characterizations of fully oxidized GO GIC. the mechanical cleavage of the GO sheets.18, 47 Examining the
In the subsequent work, only the fully oxidized samples (GO GIC-25- thickness distributions of GOGIC sheets from AFM images (Figure 3b,
8h, GOGIC-35-4h and GOGIC-45-4h) were further characterized and d and f), the majority of GOGIC sheets were successfully exfoliated
compared. The lateral size distributions of GO sheets were obtained down to single layer. The single-layer sheets were between 1.0 and
statistically from SEM images (Figure 3a, c and e). For GOGIC-25-8h, 1.5 nm thick, consistent with previous literature reports.15, 48
GOGIC-35-4h and GOGIC-45-4h, the average sizes were 20.1 ± 17.9,

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Figure 4. Chemical properties of different GOGIC samples. (a) Raman spectra of GOGIC flakes. (b) TGA curves for heating GO in argon at a 5
K/min heating rate. (c) The corresponding first derivative of the TGA curves in the temperature range 50 ~ 300 °C. (d-f) TGA curves for thermal
annealing of GOGIC at 150, 175 and 200 °C under 20 % oxygen/80 % argon atmosphere.

Chemical characterizations of fully oxidized GOGIC before and after 35-4h (175 °C). In fact, the removal of oxygenated function groups
thermal reduction. from GO basal planes always accompanies the formation of various
To further investigate the effects of different oxidation conditions, gases, including CO2, CO and H2O.51 Because the gasification process
Raman spectroscopy (Figure S3) was used to discriminate different must overcome the interlayer interactions, it can be inferred that
carbon atoms, typically featuring D (~1350 cm -1), G (~1585 cm -1) and GOGIC-45-4h with the highest Td had the greatest amount of carboxyl
2D (~2700 cm-1) peaks. The D peak is attributed to the breathing group with strong hydrogen bonding ability.31
modes of six-atom carbon rings in proximity to defect areas. The 2D Mild thermal annealing in ambient air is a simple and effective route
peak is the overtone of the D peak, while the G peak is related to the to deoxygenate GO.52 By comparing the weight changes for GOGIC
motion of sp2 carbon atoms.49 The ratio of the defect-activated D annealed at different constant temperatures (Figure 4d-f), GOGIC-25-
peak to G peak is an important parameter to reveal the defect 8h saw the most weight loss at 150 °C, relative to other conditions,
density in GO. According to Ferrari and Robertson,50 for graphene while GOGIC-45-4h lost more weight at 175 and 200 °C, implying
materials, ID/IG initially increases with defect density at low defect deoxygenation of GOGIC-25-8h occurred more readily at lower
concentration (stage 1) and subsequently declines after reaching a temperature than GOGIC-45-4h. As shown in Table S1, the percentage
certain defect concentration (stage 2). From the Raman spectra of of residual mass changed from 69% to 65% in GOGIC-25-8h as raising
various GOGIC in Figure S3, the value of ID/IG tended to decrease with the annealing temperature from 150 to 200 °C. This change was
longer oxidation time or higher temperature. Therefore, all GOGIC much smaller than that in GOGIC-35-4h or GOGIC-45-4h, also indicative
samples were likely to be in the stage 2 state because more defects of the easier deoxygenation of GOGIC-25-8h at 150 °C. In addition,
will be introduced to the honeycomb lattice in graphene layers as the GOGIC-35-4h always experienced the lowest mass reduction,
proceeding chemical oxidation or the elevating temperature. 18, 29 regardless of the annealing temperature, suggesting that GOGIC-35-
Comparing the fully oxidized GOGIC samples (Figure 4a), the defect 4h was less oxidized than GOGIC-25-8h and GOGIC-45-4h. This was
density increased in the following sequence: GO GIC-25 -8h < GOGIC-35 consistent with the XPS scan which showed GOGIC-35-4h had the
-4h < GOGIC-45-4h. highest C/O ratio from XPS survey scan (Figure S4). In addition,
The weight change in GOGIC with increasing temperature was during the 150 °C thermal treatment, the residual weights of GOGIC-
tracked using thermogravimetric analysis (TGA, Figure 4b), and it was 25-8h and GOGIC-45-4h became stable after 5 h (d), corresponding to
found that the greatest weight loss was observed for GOGIC-45-4h. the completion of thermal reduction.
Only 53.6% of the material remained after heating to 700 °C, which The XPS C 1s peak (Figure 5) can be deconvoluted into five
suggested it had the highest content of thermally labile oxygenated components, including the C=C/C-C in aromatic rings (284.6 eV), C-O
function groups. Moreover, the corresponding first derivative TGA (286.1 eV), C=O (287.5 eV), COOH (289.0 eV) and π-π* satellite (290.6
curves (Figure 4c) were plotted to give insight into the peak eV),53 and the fractions of these components in each sample are
decomposition temperature (Td) where GO samples underwent the summarized in Table S2 and Table S3. Among the GOGIC samples
greatest rate of change in the weight.31, 32 It was obvious that GOGIC- (Figure 5a, c, e and Table S2), the highest fraction of C=C/C-C was
45-4h had a higher Td (198 °C) than GOGIC-25-8h (181 °C) and GOGIC- found in GOGIC-35-4h (56.6%) and the lowest was in GOGIC-45-4h

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Figure 5. XPS C 1s spectra for the fully oxidized GOGIC samples, and the thermally reduced GOGIC samples which were annealed at 150 °C for
5 h.

(45.1%), which indicated GOGIC-35-4h retained the most intact sp2 To investigate the changes in the functionalities after thermal
graphitic carbon while GOGIC-45-4h was the most oxygen- reduction, the three reduced GOGIC samples, annealed at 150 °C for
functionalized. GOGIC-25-8h had the least amounts of C=O and COOH 5 h, were examined by XPS (Figure 5b, d and f). As shown in Table
(7.33%) compared to GOGIC-35-4h (7.62%) and GOGIC-45-4h (9.53%). S3, rGOGIC-25-8h had the largest increase in the content of sp2 carbon
Due to the fact that carbonyl and carboxyl groups preferentially form with thermal treatment (from 48.18% to 72.56%). This is indicative
at the edge of GO flakes or vacancy defects,31, 53, 54 GOGIC-25-8h was of its considerably easier deoxygenation and restoration of sp2
the least defective among all fully oxidized GOGIC samples, consistent domains at 150 °C thermal treatment, consistent with the isothermal
with results from the Raman spectra (Figure 4a) and the previous TGA result (Figure 4d). Comparing the sheet resistances of the
reports for GO produced at room temperature.32 Hence, room- ultrathin rGOGIC films (all annealed at 150 °C for 5 h) measured using
temperature oxidation can more effectively maintain the structural the four-point probe, rGOGIC-25-8h (0.81 ± 0.34 MΩ/□, mean ±
integrity of GO. Comparing the ATR-FTIR spectra for GOGIC (Figure standard deviation) was more conductive than rGOGIC-35-4h (1.13 ±
S5), GOGIC-35-4h had a weaker peak at ~1722 cm-1 which suggested 0.14 MΩ/□) and rGOGIC-45-4h (8.48 ± 0.73 MΩ/□), which is related to
a lower concentration of carbonyl group, and this is also in the higher fraction of graphitic carbon in rGOGIC-25-8h. The π-π*
agreement with the XPS results. satellite peak became more pronounced after thermal reduction of

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Figure 6. Electrochemical performances for rGOGIC-25-8h and rGOGIC-45-4h modified LFP cathodes in LIBs. The LIB’s cathode with only carbon
black as conductive additive served as a control. (a) Cyclic voltammetry for GO modified LIBs and the control at a scan rate of 0.1 mV s-1. (b)
The voltage profiles for the second charge/discharge cycle at 0.1 C. Inset is a magnification of the 9-23 mAh g-1 region. (c) Performance test
for LIBs showing the discharge rate capacity at different rates and the cycling stability at 2 C (1 C = 170 mA g-1).

all GOGIC samples, due to the formation of π conjugation in redox reaction in LFP cathodes. LFP-carbon black had greater
graphene.55 separation between the two redox peaks than rGO modified LFP,
indicating rGO assisted in reducing polarization and improving the
Application of GOGIC and mild annealing condition for LIBs reversibility of LFP cathodes. The charge/discharge profiles in Figure
Because of its facile thermal recovery of conductivity, we employed 6b exhibited a voltage plateau at ~ 3.42 V vs. Li+/Li for all LIBs
the GOGIC as a 2D binder and conductive (after thermal annealing) samples, also correlated with the redox reaction in LFP. Apparently,
additive in LiFePO4 (LFP) cathodes for LIBs. Carbon black was used as LFP-rGOGIC-25-8h can reach the highest discharge capacity up to
a control conductive additive. In the experimental condition, 50% of 170.8 mAh g-1 at 0.1 C rate. This value is similar to the theoretical
the carbon black was replaced with either GOGIC-25-8h or GOGIC-45- specific capacity of LFP (170 mAh g-1) which is likely contributed by
4h. As aforementioned, the residual weights of GOGIC-25-8h and the reversible redox reaction between Li+ of the electrolyte and
GOGIC-45-4h stabilized after 5 h of thermal treatment at 150 °C, as rGO.39 Besides, the wider gap between discharge and charge
shown in Figure 4d. As such, the blended cathode materials were plateaus in LFP-carbon black (inset in Figure 6b) indicated its higher
annealed at 150 °C in air for 5 h prior to the assembly of LIB coin- polarization than LFP-rGOGIC-25-8h or LFP-rGOGIC-45-4h, which was in
cells. SEM images (Figure S6) showed the LFP particles were good agreement with the CV result. According to Figure 6c, all LIBs
homogeneously wrapped by GO sheets, which facilitated the showed good reversibility in discharge capacity as the current rate
formation of a conducting network after mild thermal annealing. As returned to 5 C and 10 C. It also clearly showed the addition of GO
shown in Figure 6a, cyclic voltammetry (CV) for the control and the can enhance the specific capacity at different discharge rate (except
two experimental cathodes displayed a pair of redox peaks during the highest rate 20 C for LIB with rGOGIC-45-4h) relative to LIB without
the anodic/cathodic scan, associated with the reversible Fe2+/Fe3+ GO additives (carbon black only), and improve the cycle life due to

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TOC

Journal of Materials Chemistry A Accepted Manuscript

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We reported a room-temperature synthesis method to produce

graphene oxide with thermally-labile oxygen functional groups.

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