Copyright WILEY‐VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2015.

 

Supporting Information 
 

for Adv. Energy Mater., DOI: 10.1002/aenm.201501870 
 

Effect of Chemical Doping on Cathodic Performance of
Bicontinuous Nanoporous Graphene for Li-O2 Batteries
Jiuhui Han, Xianwei Guo, Yoshikazu Ito, Pan Liu, Daisuke
Hojo, Tsutomu Aida, Akihiko Hirata, Takeshi Fujita, Tadafumi
Adschiri, Haoshen Zhou, and Mingwei Chen*

A. Chen CREST. Sendai 980-8577. Dr. School of Materials Science and Engineering. Dr. Japan Prof. Japan Prof. Tsukuba. W. Prof. Dr. Dr. W. 1 . Tohoku University. Daisuke Hojo. H. P. Umezono 1-1-1. Akihiko Hirata. JST. Adschiri. Haoshen Zhou. Tohoku University. Japan. Guo. Sendai 980-8577. and Mingwei Chen* J. Yoshikazu Ito. Dr. Chen State Key Laboratory of Metal Matrix Composites. Dr. E-mail: mwchen@wpi-aimr. M. T.jp Dr. Ito. PR China. H. Takeshi Fujita. Aida New Industry Creation Hatchery Center.tohoku. Shanghai Jiao Tong University. W. Japan § These authors contributed equally to this work.Supporting Information Effect of chemical doping on cathodic performance of bicontinuous nanoporous graphene for Li-O2 batteries Jiuhui Han§. 4-1-8 Honcho Kawaguchi. Xianwei Guo§. 305-8568. Liu. Tsutomu Aida. T. Saitama 332-0012. Hojo. X. S. Y. Zhou Energy Technology Research Institute. Fujita. Tadafumi Adschiri. M. T. Hirata. Prof. Han. National Institute of Advanced Industrial Science and Technology (AIST). Shanghai 200030. D. Prof.ac. Chen WPI Advanced Institute for Materials Research. M. Pan Liu. W.

N-doped and S-doped graphene. respectively. The molecular structures at the upper left corner show the precursors used for the CVD growth of the different nanoporous graphene samples. (a) Schematic illustration of the preparation process of the nanoporous graphene samples.a Inner channel CVD at 800 C Ar + H2 + precursor np-Ni pores ligaments Ni etching with HCl Outer channel Ni coarsening Graphene growth Inner channel b Nanoporous Ni Graphene on nanoporous Ni Nanoporous graphene (Pore size: 10-20 nm) (Pore size: 200-400 nm) (Pore size: 200-400 nm) Benzene Nanoporous non-doped graphene c d Pyridine Nanoporous N-doped graphene Thiophene Nanoporous S-doped graphene Figure S1. 2 . (b-d) Schematic of the structure of nanoporous non-doped.

f) SEM images of the surface of nanoporous graphene sheets. (e.d) Cross-sectional SEM images of nanoporous graphene after removal of Ni. (a.a b c d e f Figure S2.b) Cross-sectional SEM images of nanoporous graphene on nanoporous Ni. (c. 3 .

101 MPa).2 0.175 2.0 0. Raman band measurements of the nanoporous graphene samples for Figure 2d in the main text. (a) Nitrogen absorption and desorption isotherm of nanoporous non-doped.595 Nanoporous S-doped graphene 1357 25 1583 15 1615 14 2702 43 0. N-doped and S-doped graphene. Unit of the spectra and line width is cm-1.813 0.a b 3500 Non-doped graphene N-doped graphene S-doped graphene 2500 25 Non-doped graphene N-doped graphene S-doped graphene 20 dVp / dlog(dp) 3 Volume/g (cm /g) 3000 2000 1500 1000 500 15 260 nm 230 nm 10 260 nm 5 0 0 0. Ndoped and S-doped graphene.6 0.0 1 P/P0 10 100 1000 dp/nm Figure S3.4 0.0 K (0.894 Nanoporous N-doped graphene 1361 39 1588 28 1622 18 2705 55 0. (b) The pore size distribution of the nanoporous non-doped. X-axis was normalized with the vapor pressure of nitrogen (P0) at 77. Table S1.653 1.537 4 . D band Line width G band Line width D' band Line width 2D band Line width ID/IG I2D/IG Nanoporous non-doped graphene 1358 22 1588 13 -- 2706 30 0.8 1.

The potential was scanned from the open-circuit voltage to 5.6 0.u.2 0.4 3. XPS analysis of the chemical composition of nanoporous N-doped and S-doped graphene.1 Voltage (V) a 5.0 4. The test was conducted in 1. b 1.) Intensity (a.) Intensity (a.8 4.4 4.5 4.8 5.2 3.3 V at the rate of 1. (b) Galvanostatic charge tests of nanoporous N-doped graphene based Li-O2 cells 5 .01 4.0 3. It shows that serious electrolyte decomposition is stimulated at potentials above 5.4 Potential (V) 0.u.2 5.0 0.06 V.0 4.2 4.4 1.0 5.2 4.79 V 200 mA/g 300 mA/g 500 mA/g 0 1 2 3 4 5 6 Time (h) Figure S5.06 V 0.0 4.u.82 V 4.0 M LiTFSI/TEGDME electrolyte.5 Potential (V) 5.2 5.8 0.) N-doped graphene O1s Ni2p S 2p 1200 1000 800 600 400 200 280 0 282 Binding energy / eV 284 286 288 290 292 Binding energy (eV) Figure S4.) C 1s C-C C 1s C-H C 1s C-O C 1s C=O C 1s -COO Background Envelope Intensity (a.6 4.2 0.5 5.0 atm O2 atmosphere.0 3. (a) Current-voltage response of a plain Li-O2 cell using a nanoporous N-doped graphene cathode and a 1.75 V 4.6 3.0 mV/s.u. (b.0 3.d) C 1s spectra.8 3.4 4.c) XPS survey spectra. (a.4 1 Current (mA) Current (mA) 1.a b O1s N1s Ni 2p 1200 1000 800 N-doped graphene C1s 600 400 200 0 280 282 Binding energy / eV c 284 286 288 290 292 Binding energy (eV) d S-doped graphene S-doped graphene C1s C 1s C-C C 1s C-H C 1s C-O C 1s C=O C 1s -COO Background Envelope Intensity (a.0 5.6 4.

respectively. SEM images of the broken tubular ligaments showing that Li2O2 is not only formed at outer channels. The electrolyte reaction should be insignificant in the Li-O2 battery operation potential window of 2. Figure S6. The electrolyte decomposition takes places at stable voltages of 4. 6 .82 V at the current densities of 200. 4.6 V. Nanoporous N-doped graphene electrodes discharged to ~7000 mAh/g at 300 mA/g.79 and 4.75.3-4.without prior discharge (in 1. 300 and 500 mA/g. but also at the inner graphene channels.0 atm O2).

(b) Electron diffraction patterns of pristine N-doped graphene (left) and the discharged N-doped graphene (right). a b Figure S8.a b Pristine Discharged c 100 101 Prisitne Discharged  112 110 Intensity (counts)   0 15 30 45 60 75 Q (1/nm) Figure S7. (a) TEM image of a nanoporous N-doped graphene electrode discharged to ~7000 mAh/g at 300 mA/g. 7 . (a) Cross-sectional SEM images of a fully discharged S-doped graphene electrode. (c) Intensity profile along the orange lines in (b). (b) Cross-sectional SEM image of a fully recharged S-doped graphene electrode. showing the formation of toroidal Li2O2 particles.

showing the uniform distribution of the discharge products along the thickness from the electrolyte side to the O2 side.30 V). 8 . Cross-sectional SEM micrographs of the fully discharged nanoporous N-doped graphene electrode (discharged to 2.1 2 3 4 1 2 3 4 Figure S9.

a b 5. No residual Li2O2 can be found in the recharged electrode. (a) Cross-sectional SEM image of the thick nanoporous N-doped graphene (~70 μm in thickness). In spite of different thicknesses.d) SEM images of pristine (c) and fully recharged (d) ~70 μm N-doped graphene electrodes.0 M LiTFSI/TEGDME at the current density of 200 mA/g.0 0 2000 4000 6000 8000 10000 Capacity (mAh/g) c Pristine d Recharged Figure S10. The cells were tested in 1. (c.5 3.0 Voltage (V) 4.5 2. 9 . the two kinds of electrodes show similar reversible capacities. (b) Galvanostatic discharge-charge profiles of Li-O2 batteries using ~35 μm and ~70 μm nanoporous N-doped graphene as the air electrodes.0 35 um N-doped graphene 70 um N-doped graphene 3.0 2.5 70 μm 4. The samples were prepared from 100 μm NiMn alloy sheets.

The electrolyte used is 1. Galvanostatic discharge-charge cycles of nanoporous N-doped graphene based Li-O2 battery tested at the capacity limit of 500 mAh/g and the current density of 300 mA/g.5 5.0 2.5 4.30 V for discharging recorded at the current density of 200 mA g-1.5 3.5.0 0 2000 4000 6000 8000 10000 -1 Capacity (mAh g ) Figure S12.0 M LiTFSI/TEGDME. The battery is stabilized after the first 10 cycles.0 1.5 2.5 2. with a stable reversible capacity of ~3000 mAh g-1 up to 50 cycles.0 Voltage (V) 4.5 0 100 200 300 400 500 Capacity (mAh/g) Figure S11. 5. 10 . Galvanostatic discharge-charge cycles with a threshold potential of 2.0 15 20 30 40 50 1 2 5 10 3.5 4.0 Voltage (V) 4.0 2.5 3.0 80 100 120 140 1 20 40 60 3.

0 1 5 10 3.5 0 500 1000 1500 2000 Capacity (mAh/g) Figure S13. Galvanostatic discharge-charge cycles of nanoporous non-doped graphene based Li-O2 battery tested at the cut-off capacity of 2000 mAh/g and the current density of 300 mA/g.5 2.5 4.5.5 3.0 M LiTFSI/TEGDME.0 Voltage (V) 4.0 15 20 21 2. 11 .0 1.5 5. The electrolyte used is 1.

75-2. This work This work Not fully recoverable 100 cycles (at 1000 mAh/g) 300 cycles (at 1000 mAh/g) 20 cycles (at 500 mAh/g) Not recoverable -- 2 Not recoverable -- 3 Fully recoverable Fully recoverable 20 cycles (at 1000 mAh/g) 5 cycles (at 2.Table S2.and S-doped graphene based Li-O2 battery with the state-of-the-art graphene-based and other best LiO2 batteries.30 Hierarchically porous graphene 186 LiTFSI/TEGDME 2.8 ~3.4 V.55 775 LiTFSI/TEGDME 2.59 4.1 V.78 4.65 4.1 V.52 Porous graphene 242-358 LiClO4/DMSO 2.75 3.8 -- -- Graphene nanosheets 309 LiClO4/PC* 2.70 -- N-doped graphene nanosheets -- LiPF6/TEGDME ~2.97 2332 (at 50 mA/g) Recoverable Graphene flakes 455 LiTFSI/DME 2.5-4.80 ∼5300 (at 50 mA/g) Not fully recoverable Nanoporous N-doped graphene Nanoporous S-doped graphene N-doped graphene/carbon nanotube (with Co9S8) N-doped graphene/graphene-tube nanocomposites (with Fe 12 10400 (at 200 mA/g) 4920 (at 200 mA/g) 29375 (at 200 mA/g) 15000 (at 0.80 3. 11001600 mAh/g) 1 4 5 6 1 7 8 . Cathode materials Operating voltage (V) BET surface area (m2/g) Electrolyte 772 Maximum discharge capacity (Cmax) (mAh/g) Reversibility of Cmax Discharge Charge LiTFSI/TEGDME 2.85 3.1 ∼3700 (at 50 mA/g) Not fully recoverable 449 LiPF6/TEGDME 2.79 ~3. 15002400 mAh/g) 10 cycles (at 1280 mAh/g) 100 cycles (at 1000 mAh/g) 50 cycles (at 2.60 17710 mAh/gC# (at 200 mA/gC) Fully recoverable 278 LiPF6/TEGDME ∼2. Comparison of the nanoporous N.5-4.80 -- -- -- Porous graphene/Ru 254 LiClO4/DMSO 2. 10001500 mAh/g) 50 cycles (at 2.0-4.1 mA/cm2 & 2 atm) 11660 (at 75 mA/g) Cycling life and cycling capacity Ref.8-4.5 -- Graphene foams 110 LiCF3SO3/ TEGDME ~2.

86 3.8-5.6 Co3O4 nanofibers/ graphene nanoflakes -- LiTFSI/TEGDME 2.6 ~3.75 3.6 4.65 3. Capacity values followed by the unit “mAh/gC” refer to values normalized by mass of the graphene component of the cathodes.1 Nanoporous gold 50 LiClO4/DMSO ~2.7 ~3.8 4.3 Graphene/MnO2 -- LiPF6/ EC-DMC* 2.64 -- -- Not fully recoverable Recoverable Recoverable Not fully recoverable *As these electrolytes are not stable[21]. ~320 mAh/g) 100 cycles (at 300 mAh/g) 100 cycles (at ~350 mAh/g) 100 cycles (at 1000 mAh/g) 205 cycles (at 1000 mAh/g) 10 cycles (at 500 mAh/g) 100 cycles (at 300 mAh/gRu) 9 10 11 12 13 14 15 16 17 18 19 20 .6 ~3.2 -- -- Ru/TiSi2 100 LiClO4/DME 2.2 Fully recoverable Graphene/ MnCo2O4 -- LiClO4/PC* 2.3-4.85 Graphene/Co3O4 -- LiPF6/TEGDME ~2.5 -- -- Honeycomb-like palladium-modified hollow spherical carbon 127 LiCF3SO3/ TEGDME 2.0 V.0 12254 (at 500 mA/g) Not fully recoverable C/Al2O3/Pd -- LiCF3SO3/ TEGDME ~2.2-4.083 mA/cm2) 3784 mAh/gC (at 100 mA/gC) 2304 (at 200 mA/gC) ~ 14000 mAh/gC (at 140 mA/gC) 10500 mAh/gC (at 200 mA/gC) Graphene/MnO2 108 LiClO4/DME 2.65 4.3 ~320 (at 500 mA/g) Fully recoverable Nanoporous gold 50 LiClO4/DMSO with TTF ~2.4 -- -- TiC 15 LiClO4/DMSO 2.7 4.7 ~3.55 ~3.species) 3660 (at 0.0-4. # 13 132 cycles (at 492 mAh/g) 40 cycles (at 1000 mAh/gC) 25 cycles (at 2900 mAh/gC) <18 cycles (at 2000 mAh/gC) 80 cycles (at 1000 mAh/gC) 100 cycles (at 2.7 ~350 (at 1mA/cm2) Fully recoverable Super P carbon -- LiCF3SO3/ TEGDME ~2. the results may not be very reliable.0-2.5-2.

8 1.96 V 3.0 2.0 4.0 Discharge Charge 3.0 0 1000 2000 3000 4000 5000 Discharge/charge potential (V) a 5.0 A/g Voltage (V) 4.0 0.0 A g-1 at the controlled capacity of 500 mAh g-1.0 3.5 2.6 0. 1.b 5.5 4.0 0.5 4.5 1.0 2.5 2.5 2.0 Current demsity (A/g) Figure S14.4 0.0 M LiTFSI/TEGDME electrolyte was used for all the tests.2 0.2 0.5 0. 14 .0 Capacity (mAh/g) 0.3 0. (a) Discharge-charge profiles of a nanoporous S-doped graphene based Li-O2 battery tested at various current densities ranging from 0.1 to 1.5 3.1 5. (b) Discharge/charge potential versus the current dnesity.

4 V 2.0 2. Li /Li) geo Current (mA/cm 2 ) b 1.4 V 2.0 -1.4 V 2.2-4.2-4. CVs for N-doped graphene (a).4 V 2.0-4.3-4.2-4.3-4.4 V 2.40 V) in O2saturated 1.0 4.0 -0.0 -2.4 V 2.5 N-doped graphene 2.5-4.5 3.0 4. S-doped graphene (b) and non-doped graphene (c) collected in different potential windows (using a constant upper potential of 4.4 V -1.0 3.5 -2. Li /Li) Figure S15.5 + Potential (V vs.5 4.4-4. Li /Li) geo Current (mA/cm 2 ) c 1.geo Current (mA/cm 2 ) a 1.5 4.5 Non-doped graphene 0.0-4.0 0.4 V 2.4 V 2.5 2.0 M LiTFSI/TEGDME at 50 mV/s.5 + Potential (V vs.1-4.6-4.4 V 2.0 -0.4 V 2.1-4.5 S-doped graphene 2.1-4.4 V 2.5 0.4-4.0 0.0 -1.5-4.5 1.5 1.4 V 2.0 3.4 V 2.5 -1.4 V 2.4 V 2.5 3.4 V 2.5 2.4 V 2.5-4.4 V 2.5 0.0 2.0 0.5 3.0 4. 15 .0-4.0 3.5 -2.6-4.0 2.4-4.0 -2.4 V 2.6-4.5 -1.0 -1.5 + Potential (V vs.5 4.4 V 2.0 -0.3-4.

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