Vanadium diphosphide as a negative electrode material for sodium secondary batteries

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Tables and Figures

Table 1 Summary of ball-milling conditions and electrochemical performance of VxPy compounds

for NIBs and LIBs

VxPy/Li or Na

Electrochemical performancea

Ball-milling conditions

Speed

(rpm)

Time

(h)

Crystal system

(space group)

Ball:

powder

ratio (w/w)

20:1

1st cycle discharge

capacity (mAh g−1)

/ rate (mA g−1)

291/100

Electrolyte

VP/Li [42]

unknown

VP1.75@C/Li

[46]

300

60

20:1

tetragonal

(P−4m2)

882/100

LiPF6 in EC/DMC

VP1.75/Na [45]

300

60

20:1

tetragonal

(P−4m2)

240/50

NaClO4 in EC/DMC

with 5 vol% FEC

VP1.75-1.25P/Na

[73]

400

20

50:1

tetragonal

(P−4m2)

560/100

740/100*

600

50

10:1

monoclinic

(C2/m)

890/100

Na[FSA][C3C1pyrr][FSA] (2:8

mol ratio)

LiPF6 in EC/DMC

VP2/Li [44]

VP2/Na

(this work)

850

20

50:1

monoclinic

(C2/m)

49/100

243/100*

VP4/Li [43]

48

20:1

monoclinic

(C2/c)

1290/-

hexagonal

(P63/mnc)

aTemperature

bMolar

is 25°C unless specified with asterisk (90 °C for the one with asterisk)

concentration of electrolyte = 1 M unless specified; ratio of solvents = 1:1 v/v unless specified

26

LiPF6 in EC/DEC

Na[FSA][C3C1pyrr][FSA] (2:8

mol ratio)

LiPF6 in EC/DEC

023

−205

−504

020

400

−313

−203

−201

200

−202

110

001

Intensity

003

111

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VP2

10

20

30 40 50 60

2 q / deg. (Cu-Ka)

70

80

Fig. 1 The XRD pattern of the pristine VP2 powder prepared by HEBM. The reference pattern of

VP2 is also shown for comparison [75].

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(a)

(c)

200 nm

(b)

(d)

(e)

0.25 nm

0.19 nm

10 nm

5 nm

Fig. 2 (a) SAED pattern, (b) HRTEM image, (c) STEM-EDX mapping, (d) magnified HRTEM

image, and (e) FFT power spectrum of the pristine VP2 powder.

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Voltage / V

2.0

1.5

1.0

2.5

Voltage / V

1st

2nd

3rd

(a)

0.5

1st

2nd

3rd

2.0

1.5

1.0

0.5

0.0

(c)

Charge

Discharge

400

300

200

100 mA g-1

100 200

500

1000

2000

4000

100

8000

0.0

8000

2.0

100

(d)

1.5

1.0

0.5

0.0

50 100 150 200 250

Capacity / mAh g

−1

100 200 300 400 500

Capacity / mAh g−1

300

10

20

30

100

250 (e)

90

200

Discharge capacity at 25 °C

Discharge capacity at 90 °C

Coulombic efficiency at 25 °C

Coulombic efficiency at 90 °C

150

100

80

70

60

50

100

200

300

Cycle number

40

Cycle number

400

Coulombic efficiency / %

100 200 300 400 500

Capacity / mAh g−1

Discharge capacity / mAh g−1

Voltage / V

500

(b)

Capacity / mAh g−1

2.5

50

500

Fig. 3 Electrochemical behavior of VP2 in a Na/VP2 coin-type cell with the IL electrolyte (cut-off

voltage: 0.005–2.0 V and counter electrode: Na metal disc). Galvanostatic charge-discharge curves

for the first three cycles at (a) 25 and (b) 90 °C (current density: 100 mAg−1). (c) Rate capability

at 90 °C (current density: 100–8000 mAg−1) and (d) galvanostatic charge-discharge curves of the

last cycle for each rate. (e) Cycleability for 500 cycles at 25 and 90 °C (rate: 100 mAg−1 for the

first three cycles to activate the electrode and 500 mA g−1 for the rest of cycles).

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(a)

2500

40

-Im (Z) / ohm

30

2000

20

13896 Hz

20615 Hz

10

1500

60

25 °C

60 °C

90 °C

50

10

20

30

40

(b)

50

1000

1st

3rd

10th

50th

100th

500th

50

-Im (Z) / ohm

3000

500

40

30

6396 Hz

20

10

38 Hz

20615 Hz

125 Hz

500 1000 1500 2000 2500 3000

Re (Z) / ohm

(c)

10

20 30 40

Re (Z) / ohm

50

60

CPE

CPE

R1

R2

R3

Fig. 4 (a) Nyquist plots of the VP2/VP2 symmetric cell using the IL electrolyte at 25, 60, and 90 °C.

The electrodes were charged in the Na/IL/VP2 half-cell configuration to the cell voltage of 0.5 V

and retrieved to prepare the symmetric cells. Inset shows the magnified view of the plots. (b)

Nyquist plot of the Na/VP2 half-cell using the IL electrolyte during 500 cycles at 90 °C. (c)

Equivalent circuit for fitting Nyquist plots in both symmetric cell and half-cell cases. All the EIS

tests were performed with an amplitude of 20 mV and frequency range of 100 kHz−10mHz.

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(b)

(a)

25 µm

25 µm

Fig. 5 SEM images of the VP2 electrode before and after cycling. (a) pristine electrode and (b)

after 500 cycles at 90 °C using the IL electrolyte.

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(a)

Al

(b)

Na3P

Current density

= 10 mA g−1

Pristine

Charged

Discharged

Current density

= 100 mA g−1

Intensity

Intensity

Al

VP2

Na3P

VP2

25 30 35 40 45 50 55 60 30 35 40 45 50 55 60

2 q / ° (Cu-Ka)

2 q / ° (Cu-Ka)

Fig. 6 Ex situ XRD patterns of the VP2 electrode before and after charge-discharge (pristine,

charged to 0.005 V, and discharged to 2.0 V). Current density: (a) 10 mA g−1 and (b) 100 mA g−1.

The reference patterns of VP2 and Na3P are shown for comparison [75, 91].

32

1.4

Fourier transformation magnitude

Normalized absorbance/ a.u.

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(a)

1.2

1.0

Pristine

Charged 0.005 V

Discharged 2 V

0.8

0.6

0.4

0.2

0.0

5460

5480

5500

Energy / eV

5520

(b)

10

Pristine

Charged 0.005 V

Discharged 2 V

Interatomic distance (R) / Å

Fig. 7 XAFS analysis data of the VP2 electrode before and after charge-discharge (pristine, charged

to 0.005 V, and discharged to 2.0 V). (a) V K-edge XANES spectra, (b) Fourier transforms of the

V K-edge EXAFS oscillations. Charging-discharging current density = 100 mA g−1.

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(a)

VP2 (300–900 ppm)

POx

Discharged

Na3P (−208.7 ppm)

Charged

Pristine

1200

800

400

-400

P Chemical shift / ppm

-800

31

80% site occupancy P

Na

(b)

Na+

e−

VP2

VP2-x (x ~ 0.37)

xNa3P

Fig. 8 (a) 31P MAS NMR spectra of VP2 in pristine powder, charged (0.005 V) and discharged state

(2.0 V). The charging and discharging rates were 100 mA g−1. (b) Schematic representation of the

conversion reaction mechanism of VP2.

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