Supporting information for

Interface Chemistry Engineering for Stable Cycling of Reduced GO/SnO2

Nanocomposites for Lithium Ion Battery

Lei Wang†,‡, Dong Wang†, Zhihui Dong†, Fengxing Zhang‡, and Jian Jin†*

†
i-LAB and Nano-Bionics Division, Suzhou Institute of Nano-Tech & Nano-Bionics, Chinese
Academy of Sciences, Suzhou, Jiangsu, 215123, China.

‡
Key Laboratory of Synthesis and Natural Functional Molecular Chemistry (Ministry of
Education), College of Chemistry & Materials Science, Northwest University, Xi’an, Shaanxi,
710069, China.

Details for Experiment:

Materials: Cu foil, electrolyte, 2032 coin cell cases were purchased from Land Electronic., Ltd,

China. The other reagents used in this work were purchased from Aldrich Sigma or Alfa Aesar.

Millipure water (18.2 MΩ) was used in all of experiments.

Instruments and Characterization: SEM was measured on a Quanta 400 FEG field-emission

scanning electron microscope. TEM was measured on a Tecnai G2 F20 S-Twin field-emission

transmission electron microscope. XRD was collected on a Bruke D8. FTIR spectroscopy

measurement was performed using a Thermo FTIR spectrometer. XPS was measured on an

ESCALAB 205 (Thermofisher scientific, Inc). TG measurement was performed using a

TG/DTA 6200. Electrochemical measurements were carried out using Land battery analyzers.

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Preparation of GO: GO was prepared by Hummers’ method1 with little modification. Native

graphite flake (2 g) was mixed with concentrated H2SO4 (3 mL), K2S2O8 (1 g), and P2O5 (1 g),

and then incubated at 80 °C for 6 h to preoxidize the graphite. The product was then dried in air

at ambient temperature overnight, after washing with distilled water until neutral and filtering.

This preoxidized graphite was then subjected to oxidation by Hammer's method. The preoxidized

graphite powder (2 g) was placed in concentrated H2SO4 (46 mL) at 0 °C. KMnO4 (3 g) was

added gradually with stirring while keeping the temperature of the mixture below 20 °C. The

mixture was then stirred at 35 °C for 2 h, followed by the addition of distilled water (92 mL), and

stirring was continued for 15 min. Distilled water (280 mL) was then added to terminate the

reaction. Subsequently, 30% H2O2 (4 mL) was added and the color of the mixture changed to

bright yellow. The mixture was centrifuged and washed with 10% HCl solution (500 mL) to

remove residual metal ions. The precipitate was then washed with distilled water and centrifuged

repeatedly until the solution became neutral. To exfoliate the oxidized graphite, the product was

treated with an ultrasonic probe at 300 W for 30 min, followed by centrifuging at 13,000 rpm for

30 min. The exfoliated GO was obtained in the supernatant.

Preparation of RGO/SnO2 aerogels: GO was prepared by a modified Hummers’ method

(Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80, 1339.). RGO/SnO2 aerogel was

prepared by in-situ hydrolysis of SnCl4 on GO. In detail, 60 ml of GO (~4 mg/ml) and 0.3 g of

SnCl4·5H2O were mixed, followed by ultrasonication for 1 hour to form a homogeneous

suspension. The reaction mixture was then transferred to a Teflon beaker (100 ml) and heated to

160 °C and hold for 15 hours to produce RGO/SnO2 aerogels. The as-prepared RGO/SnO2

aerogel was finally cooled down to room temperature and frozen dried under vacuum.

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Preparation of PD-coated RGO/SnO2 composite: 1 g RGO/SnO2 aerogel was dispersed in a tris-

HCl (pH=8.5) dopamine (1 g/L, 1L) solution through ultrasonication and then, polymerized for 2

hours to form a PD-coated RGO/SnO2 composite. PD-coated RGO/SnO2 composite was

collected by centrifugation at 5000 rpm and washed by water 3 times for further use.

Preparation of working electrodes and crosslink reaction: Working electrodes were prepared by

casting slurry containing PD-coated RGO/SnO2, carbon black and polyacrylic acid in a weight

ratio of 80:10:10 in water, and then coating it onto a Cu foil current collector using doctor-blade

method. The electrode was air-dried at 60 °C for at least 12 hours to eliminate water. For

crosslink reaction, the dried electrode was heated to 150 °C for 2 hours under vacuum condition

(< 100 Pa). The mass of electrode was accurately weighted using a microbalance (Sartarious,

0.001mg resolution). The final slurry mass loading is 2 mg in each working electrode.

Electrochemical Measurement: To test battery performance, 2032 type coin cells were made of

working electrode, Celgard 2250 separator, and Li metal foil as a counter electrode. The

electrolyte consisted of 1 M LiPF6 in a 1:1 (volume) mixture of ethylene carbonate (EC), and

diethyl carbonate (DEC). The coin cells were assembled inside an Ar2 filled glove box. The

working electrodes were cycled between 2 V and 0.01 V vs Li+/Li. EIS measurements were

performed on a CHI 660D electrochemical work station over the frequency range from 100 kHz

to 10 mHz.

Preparation of samples for FTIR measurement: For FTIR measurement of the electrode material

before cycling, the electrode materials were shaved carefully by a doctor blade and mixed with

3
KBr for FTIR measurement. For FTIR measurement of the electrode material after cycled, the

cell was disassembled by a cell-disassembly instrument (MIT Company) firstly. And the

electrode was washed by ethanol several times to wash away the electrolyte. After air dried, the

electrode materials were shaved out from current collector carefully by a doctor-blade for FTIR

measurement.

Preparation of samples for strain-stress measurement: PD-coated RGO/SnO2 composite was

mixed with PAA solution and stirred for 1 day at room temperature to form a homogeneous

slurry. The mass ratio of PD-coated RGO/SnO2 composite and PAA is 1:1. The slurry was then

coated on a cellulose film using doctor blade method and dried at 60 °C. After that, the cellulose

was dissolved in acetone and residual PD-coated RGO/SnO2 composite/PAA films were

collected and dried for strain-stress measurement. For measurement of the sample with crosslink,

the collected PD-coated RGO/SnO2 composite/PAA films from cellulose was heated to 150 °C

for 2 hours under vacuum condition (< 100 Pa) and cool down to room temperature for strain-

stress measurement.

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Supplemental Figures:

Figure S1. AFM image and height profile of as-prepared GO. The thickness is about 1 nm.

Figure S2. XRD spectrum of RGO/SnO2 aerogel. It matches well with standard SnO2 crystal
(JCPDS no. 41-1445).

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Figure S3. N2 adsorption and desorption curves and pore size distribution of RGO/SnO2 aerogel
after freeze-dring treatment.

Figure S4. N2 adsorption and desorption curves and pore size distribution of PD-coated
RGO/SnO2 nanosheets.

Figure S5. TG and DTG curve of RGO/SnO2 aerogel (a). Weight loss at 250-600 C is oxidation
of RGO. It is calculated that the weight percent of SnO2 is 75 wt% and RGO is 25 wt%. TG and
DTG curve of PD (b). All tests were carried out in air.

6
Figure S6. Charge/discharge profiles of bare RGO/SnO2 composite based anode at a current
density of 100 mA/g.

Figure S7. Cyclic performance of bare RGO/SnO2 composite based anode at a current density of
100 mA/g.

7
Figure S8. Cyclic performance of PD-coated RGO/SnO2 composite based anode with crosslink
at a current density of 100 mA/g.

Figure S9. Cyclic performance of PD-coated RGO/SnO2 composite based anode with crosslink
at a current density of 500 mA/g. (Current density of the first cycle is 100 mA/g)

8
Figure S10 Nyquist plots of three types of electrodes: (a) bare RGO/SnO2 composite, (b) PD-
coated RGO/SnO2 composite without crosslink, and (c) PD-coated RGO/SnO2 composite with
crosslink after 5 cycles and 50 cycles.

9
Figure S11. FTIR spectra of the anode materials after 200 cycles test. The C=O bond of amide
group at 1631 cm-1 is still maintained.

Figure S12 DF-STEM image and corresponding element mapping images of C, N, O, and Sn of
PD-coated RGO/SnO2 composite with crosslink after 200 cycles.

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Table S1. Discharge/charge capacity at different cycle times of the three electrodes (current
density is 100 mA/g).

Table S2. Discharge capacity of two electrodes (with crosslink or without crosslink) at different
current density.

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