Supporting Information

Construction of MnCo-BTC@C Microspheres by

Annealing Bimetal-organic Framework with
Enhanced Lithium Storage

Wen Zhenga,b, Yaobing Fanga,b, Li Lib,c and Wenhui Yuana,b,*

a School of Chemistry and Chemical Engineering, South China University of

Technology, Guangzhou, 510640, China.

b Guangdong Engineering Technology Research Center of Advanced Insulating

Coating, South China University of Technology−Zhuhai Institute of Modern

Industrial Innovation, Zhuhai 519175, China.

c School of Environment and Energy, South China University of Technology,

Guangzhou 510006, China.

*Corresponding author.

Email address: cewhyuan@scut.edu.cn (Wenhui Yuan)

Synthesis of the MC-BTC MOF

All the reagents and solvents were purchased from commercial suppliers and used

without further purification. Firstly, 4 mmol manganese nitrate solution (50 wt % in

H2O, Aladdin Chemistry Co. Ltd), 2 mmol cobalt nitrate hexahydrate (≥99% purity,

Aladdin Chemistry Co. Ltd), and 3 mmol 1,3,5-benzenetricarboxylic acid (≥98% purity,

Macklin, Shanghai) successively dissolved in 60 mL absolute ethanol (≥99.7% purity,

Guanghua, Guangdong) and then stirred in a magnetic stirrer for 30 minutes.

Afterwards, the resulting solution was placed in a polytetrafluoroethylene (PE) high-

pressure autoclave. The autoclave was completely covered and heated at 150°C for 24

h. After cooling to room temperature, the resulting precipitate was collected by

centrifugation and washing completely with absolute ethanol 3 times. Finally, MC-BTC

MOF product was harvested by vacuum desiccation at 110°C for 12h.

Synthesis of the MC-BTC@C microspheres

The as-prepared MC-BTC MOFs were annealed at 400 oC at a heating rate of 5

oC/ min for 4 h in Ar (99.9999%).

Material Characterization

The morphology and microstructure of the MC-BTC MOFs and the MC-BTC@C

microspheres were analyzed by a scanning electron microscopy (SEM, HITACHI,

SU8220), a transmission electron microscopy (TEM, JEM-2100F). The structure of the

MC-BTC MOFs and the MC-BTC@C microspheres was characterized by a Bruker D8

Advance diffractometer X-ray diffractometer (XRD, Cu-Kα radiation source, λ=1.5418

Å) and Fourier transform infrared spectrometer (FTIR, Bruker VERTEX 70). The
Raman spectrum of MC-BTC@C was recorded using a HJY LabRAM Aramis with an

excitation wavelength of 532 nm. The thermal behavior was examined by a

simultaneous thermal analyzer (TGA, NETZSCH 209F1) at a heating rate 10 °C/min

under a N2 atmosphere. A Micromeritics ASAP2460 analyzer was used to testing

specific surface area and pore size distribution. The chemical states of elements were

evaluated by a Kratos Axis Ulra DLD X-ray photoelectron spectrometer (XPS, Al-Kα

radiation, hν=1486.6 eV).

Electrochemical Measurements

The working electrodes were prepared by mixing 70 wt% as-prepared MC-BTC

(or MC-BTC@C) materials, 20 wt% acetylene black, and 10 wt% polyvinylidene

fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP). The formed slurries were pasted

onto a copper foil and dried at 80°C in a vacuum oven for 12h. Then, the loaded Cu foil

was cut into disk electrodes (with a diameter of 14 mm). The mass loading of the active

material on each of the disk electrodes was 1.2–1.4 mg/cm2. The CR2016 coin-type

cells were carried out in an Ar-filled glovebox, using a Celgard 2500 as the separator,

and a solution of 1.0 M LiPF6 dissolved in 1:1 (v/v) mixture of ethylene carbonate (EC)

and diethyl carbonate (DEC) as the electrolyte. Galvanostatic charging/discharging

(GCD) measurements were conducted over a potential range of 0.01-3.0 V on a Neware

CT-4008 battery testing system. Cyclic Voltammetry (CV) was conducted using a

Gamry electrochemical workstation in the potential window of 0.01-3.00 V.

Electrochemical Impedance Spectroscopy (EIS) was also performed on a Gamry

electrochemical workstation with a frequency range of 0.1 Hz to 100 kHz.

Figure S1. TG curve of MC-BTC under a N2 atmosphere at a heating rate of 10 °C min-1

Figure S2. the optical photographs of (a) MC-BTC and (b) MC-BTC@C.
Figure S3. High-resolution TEM images of MC-BTC@C.

Figure S4. (a) CV curves for the MC-BTC@C microspheres at different scan rates; (b) the
corresponding plots log (i) vs log (v)

Figure S5. The SEM image of the MC-BTC@C electrode after 150 cycles at 1000 mA g-1.
Table S1. Comparison between the reported MOFs as anode materials for LIBs.

First Discharge
Specific Capacity
Current Density /After Cycles
Materials Cycle Number Ref.
(mA g-1) Discharge
Specific Capacity
(mA h g-1)

Co2(OH)2BDC 50 100 1385/650 [1]

CoBTC-EtOH 100 100 1790/856 [2]

CoBTC-DMF 100 100 1774/830 [2]

CoBTC-DMF/EtOH 100 100 1767/820 [2]

Ni-BTC 200 100 1913/1085 [3]

Mn-BTC 103 100 1717/694 [4]

Cu3(BTC)2 96 50 740/500 [5]

Mn-1,4-BDC 100 100 1548/715 [6]

Fe-MIL-88B 60 100 1507/745 [7]

Mn-LCP 50 50 1870/390 [8]

Fe-BTC 100 100 1765/1021 [9]

Fe(Zn)-BDC 100 120 1685/863 [10]

Ni–Me4bpz 50 100 320/120 [11]

Ni-NTC 100 80 1823/248 [12]

LiNi-NTC 100 80 1084/482 [12]

CoZn-ZIF 100 100 1336/606 [13]

Ni-CAT 200 200 1440/626 [14]

MC-BTC@C 200 100 2318/1176 This work

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