Supporting Information

 Wiley-VCH 2014
69451 Weinheim, Germany

Synthesis of Two-Dimensional Transition-Metal Phosphates with

Highly Ordered Mesoporous Structures for Lithium-Ion Battery
Applications**
Dan Yang, Ziyang Lu, Xianhong Rui, Xiao Huang, Hai Li, Jixin Zhu, Wenyu Zhang,
Yeng Ming Lam, Huey Hoon Hng, Hua Zhang,* and Qingyu Yan*
anie_201404615_sm_miscellaneous_information.pdf

Supporting Information
Experimental
Chemicals: Iron (III) chloride (FeCl3, anhydrous, 99 %), manganese (II) chloride
(MnCl2, anhydrous), cobalt (II) chloride (CoCl2), 1-Octadecene (ODE, technical
grade, 90 %), Tetradecylphosphonic acid (TDPA, 97 %) and sodium oleate (NaOA,
82 % fatty acids (as oleic acid) basis, powder) were purchased from Sigma-Aldrich
and used as received.
Synthesis of amorphous MPO4 (M= Fe, Co, Mn) with ordered mesoporous structure.
To start, iron oleate (Fe(OA)3) was synthesized as precursor. The detailed procedure
is as follows: FeCl3 and NaOA were dissolved in 10 mL methanol separately and then
the FeCl3/methanol solution was slowly added into the NaOA/methanol solution and
sonicated for about 2 hours. The as-obtained precipitate was collected and dried in
vacuum oven overnight, and then re-dispersed in ODE (1 mM). Similarly, Mn(OA)2
and Co(OA)2 were synthesized by replacing FeCl3 with MnCl2 and CoCl2,
respectively. In a typical synthesis of FePO4, 0.5 mmol Fe(OA)3, and 139 mg TDPA
were added into 10 mL ODE solution in a flask. Then the mixed solution was heated
to 320 oC under Ar protection. During the heating process, the colour of the solution
changed from light brown to white and then to light brown again. After reaction, the
product was washed by hexane for 3-4 times and collected by centrifuging. The dried
product was then annealed under H2 atmosphere at 400 oC for 5 h. The synthesis of
Mn3(PO4)2 or Co3(PO4)2 was conducted in a similar procedure by using Co(OA)2 or
Mn(OA)2 as precursor instead of Fe(OA)3.
Note that the low annealing temperature is critical to maintain the ordered porous
structure. TEM image for FePO4 annealed at 450 oC under H2 atmosphere for 1 h
shows that the ordered porous structure was partly ruined (Figure S19). For the
sample annealed at 500 oC under H2 atmosphere for 3 h, small-angle XRD result
shown in Figure S20a indicates that the ordered porous structure was vanished.
Wide-angle XRD shown in Figure S20b indicates that the amorphous FePO4 sample
was converted to crystallized Fe4(P2O7)3 during the annealing process.
Characterization: The morphology of the samples was characterized with a
transmission electron microscope (TEM) system (JEOL, Model JEM-2010F)
operating at 200 kV. Crystal phase of samples were investigated using a Bruker D8
Advance diffractometer X-ray diffraction (XRD) at the 2 range of 2o to 80o with Cu
K radiation. Small angle X-ray scattering was tested by FACTs, School of Materials
Science and Engineering, NTU. X-ray photoelectron spectroscopy (XPS) of the
resulting composites was performed with an X-ray photoelectron spectrometer
(Kratos AXIS Ultra) using monochromatic Al K (1486.71 eV) X-ray radiation (15
kV and 10 mA); 160 eV pass energy was used for the survey scan, whereas 40 eV was
used for the high-resolution scan. The specific surface area was calculated by
Brunauer Emmett Teller (BET) method using a nitrogen adsorption/desorption
(Quantachhrome Instruments, Autosorb AS-6B), and Differential scanning
S1

calorimetry (DSC, Q10) was carried out from room temperature to 320 oC at a heating
rate of 10 K min-1. Thermogravimetric analysis (TGA, Q500) was carried out from
room temperature to 700 oC at a heating rate of 10 K min-1 in air.
Electrochemical measurements: Electrochemical measurements were conducted at
room temperature, using two-electrode Swagelok cells with pure lithium metal as both
the counter electrode and the reference electrode. The working electrode consisted of
the active material (FePO4), a conductive agent (carbon black, Super P-Li) and a
polymer binder [poly(vinylidene difluoride), PVDF, Aldrich] in a 70:20:10 ratio (by
weight). The electrolyte consisted of 1.0 M LiPF6 in a 50:50 wt:wt solution of
ethylene carbonate and diethyl carbonate. The cell was assembled in an Ar-filled
glovebox with moisture and oxygen concentrations of <1.0 ppm. The cycling tests
were performed with a NEWARE battery tester at different C-rate with a voltage
window of 2-4 V.

Supplementary Figures

Scheme S1. The solvothermal reaction for synthesis of FePO4.

Figure S1. XPS spectra of the FePO4: (a) Fe 2p and (b) P 2p.

S2

Figure S2. XPS spectra of the FePO4: (a) O 1s and (b) C 1s.

Intensity (a.u.)

800

1000

1200

1400

1600

Raman Shift (cm-1)

1800

Figure S3. Raman spectrum of the FePO4.

S3

Intensity (a.u.)
20

30

40

50

2(degree)

60

70

Figure S4. Wide-angle XRD pattern of as-prepared FePO4 sample.

Figure S5. Nitrogen adsorption-desorption curves for the FePO4 flakes with ordered
mesoporous structure. Inset: Pore size distribution analyzed by the BJH model.

S4

Figure S6. XPS spectra of (a) Mn2p, (b) P2p and (c) O1s for mesoporous Mn3(PO4)2.

Figure S7. XPS spectra of (a) Co2p, (b) P2p and (c) O1s for mesoporous Co3(PO4)2.

S5

Figure S8. Low-magnification TEM image of as-prepared mesoporous Mn3(PO4)2.

S6

Figure S9. Low-magnification TEM image of as-prepared mesoporous Co3(PO4)2.

S7

Figure S10. AFM and height profile for a typical Mn3(PO4)2 nanoflake.

Figure S11. AFM and height profile for a typical Co3(PO4)2 nanoflake.

S8

Intensity (a.u.)
30

40

50

2(degree)

60

70

Intensity (a.u.)

Figure S12. Wide-angle XRD pattern of as-prepared Mn3(PO4)2 sample.

20

30

40

50

2(degree)

60

70

Figure S13. Wide-angle XRD pattern of as-prepared Co3(PO4)2 sample.

S9

Figure S14. Nitrogen adsorption-desorption curves for the Mn3(PO4)2 with ordered
mesoporous structure. Inset: pore size distribution analyzed by the BJH model.

Figure S15. Nitrogen adsorption-desorption curves for the Co3(PO4)2 with ordered
mesoporous structure. Inset: pore size distribution analyzed by the BJH model.
S10

4.0
st

1 charge

Voltage (V)

3.5

3.0
st

1 Discharge

2.5

2.0

0.1C
0.5C 0.2C

20

40

60

80

100

120

140

160

Capacity (mAh/g)
Figure S16. The initial galvanostatic charge-discharge voltage profiles for
mesoporous FePO4 nanoflakes at different c rates.

Figure S17. TEM image of FePO4 flakes after the cycling test at 0.1 C for 100 cycles,
showing the ordered mesoporous structures were preserved.

S11

Heat flow (W/g)

Iron oleat + TDPA

Iron oleate
TDPA

50

100

150

200

250

300

350

Temperature ( C)
Figure S18. DSC results showing the transition of precursors during the heating
process.

Figure S19. TEM image of FePO4 annealed at 450 oC under H2 for 1 h.

S12

Figure S20. (a) Small-angle and (b) wide-angle XRD patterns of Fe4(P2O7)3 annealed
under H2 at 500 oC for 3 h.

S13