Supplementary Information

Mass production of large-pore phosphorus-doped mesoporous carbon for fast-rechargeable lithium-ion batteries

Jinxiu Wang, Yuan Xia, Yao Liu, Wei Li* and Dongyuan Zhao*

Department of Chemistry and Shanghai Key Lab of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Fudan University, Shanghai 200433, P. R. China.

*Corresponding Authors

E-mail: welichem@fudan.edu.cn, dyzhao@fudan.edu.cn

Table S1. Textural properties and chemical compositions of the pristine ordered mesoporous carbon (OMC) and the P-doped mesoporous carbon of PMC-0.4, PMC-0.8 and PMC-1.2.

Sample

Textual properties

Chemical composition (at %)

SBET

(m2g-1)

Smicro

(m2g-1)

Vp

(cm3g-1)

Dp

(nm)

d002

(Å)

P

O

MC

678

409

0.38

3.6

3.69

0

10.01

PMC-0.4

630

339

0.51

6.6

3.75

1.04

11.48

PMC-0.8

504

282

0.49

10.5

3.74

1.33

11.76

PMC-1.2

338

157

0.51

14.2

3.79

1.90

13.37

Table S2. Electrochemical performances of the pristine ordered mesoporous carbon (OMC) and the P-doped mesoporous carbon of PMC-0.4, PMC-0.8 and PMC-1.2

sample

initial capacity

(mAh g−1)

cyclability at 200th cycle (mAh g−1)

charge-transfer resistances (Ω)

discharge

charge

OMC

643

281

242

99.4

PMC-0.4

1053

385

330

78.7

PMC-0.8

1220

525

420

34.4

PMC-1.2

1265

622

500

6.9

Figure S1. Photograph of PU foam (a) and the P-doped mesoporous carbon of PMC-1.2 (b), SEM image of PU foam (c).

Figure S2. FESEM (a, c) and TEM (b, d) of the P-doped mesoporous carbon of PMC-0.4 (a, b) and PMC-0.8 (c, d).

Figure S3. HRTEM images of the pristine ordered mesoporous carbon (a) and the P-doped mesoporous carbon of PMC-0.4 (b) and PMC-0.8 (c).

Figure S4. XPS spectra of the pristine ordered mesoporous carbon (OMC) and the P-doped mesoporous carbon of PMC-0.4, PMC-0.8 and PMC-1.2.

Figure S5. TG curves of the triblock copolymer F127, tricresyl phosphate and PU foam from 25 to 900 °C with a heating rate of 5 °C min-1, recorded in N2.

Figure S6. SAXS patterns of the as-made samples of the pristine ordered mesoporous carbon (a) and the P-doped mesoporous carbon of PMC-0.4 (b), PMC-0.8 (c) and PMC-1.2 (d) before the carbonization.

Figure S7. Cyclic voltammograms (a, c, e) and galvanostatic charge–discharge curves (b, d, f) of the pristine ordered mesoporous carbon (a, b) and the P-doped mesoporous carbon of PMC-0.4 (c, d) and PMC-0.8 (e, f).

Figure S8. The first 10 cycling performance and couloumbic efficiency of the P-doped mesoporous carbon samples of PMC-0.4 (a), PMC-0.8 (b), PMC-1.2 (c) and the pristine ordered mesoporous carbon (d) at a current of 50 mA g−1 before (A) and after (B) the electrode material was prelithiated.

Figure S9. Galvanostatic intermittent titration technique (GITT) profile as a function of time during the 10th cycle in the voltage range of 0.01-2.0 V (vs. Li+/Li) of the pristine ordered mesoporous carbon (a) and P-doped mesoporous carbons of PMC-0.4 (b), PMC-0.8 (c) and PMC-1.2 (d).

In the GITT tests, the cell was first discharged at a constant current flux (I0 = 0.1 mA) for an interval of 10 min followed by an open-circuit stand for 30 min (Δtp) to allow the cell voltage to relax to its steady-state value (Es). During Ip sequences Li-ions insert into the electrode grains, while starting from the surface and building up a concentration gradient. During open-circuit periods, equilibration occurs by Li-ion diffusion, causing a change in voltage over time. The change in voltage directly correlates with the change in Li-ion concentration and enables the calculation of DLi+ within the active materials. The calculation of DLi+ by GITT was accomplished by using equation as follow:

where l is the thickness of the electrode (~30 μm). ΔEs and ΔEt can be measured with the Potential-Time curve (Figure S9).