Supporting Information

for Adv. Funct. Mater., DOI: 10.1002/adfm.202204364

Efficient Sodium Storage in Selenium Electrodes

Achieved by Selenium Doping and Copper Current
Collector Induced Displacement Redox Mechanisms
Weijia Meng, Zhenzhen Dang, Diansen Li,* Lei Jiang,
and Daining Fang
Supplementary Information for
Efficient sodium storage in selenium electrodes achieved by selenium doping and copper
current collector induced displacement redox mechanisms

Weijia Meng†, Zhenzhen Dang†, Diansen Li*, Lei Jiang, Daining Fang

Weijia Meng, Zhenzhen Dang, Prof. Diansen Li, Prof. Lei Jiang
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology, Ministry of
Education, School of Chemistry, Beihang University, Beijing 100191, China
Corresponding author. E-mail addresses: lidiansen@buaa.edu.cn

Prof. Diansen Li
Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University,
Beijing 100191, China

Prof. Daining Fang

State Key Laboratory for Turbulence & Complex Systems, College of Engineering, Peking
University, Beijing, 100871, China

† These authors contributed equally to this work.

S1
Experimental Section
Synthesis of SiO2: SiO2 nanospheres with a mean diameter of ~300 nm was synthesized through
a typical Stöber method. 3.15 ml of NH3-H2O was mixed with 75 ml of ethanol and 10 ml of
deionized water. After stirring for 30 min, 6 mL of tetrabutyl orthosilicate (TEOS) was added
dropwise to the above mixed solution under stirring. The reaction temperature was kept at 25 °C
for 1 h under stirring. The final product obtained by centrifugation, which were washed three
times with deionized (DI) water and ethanol.
Synthesis SiO2@SiO2/RF: SiO2 (1 g), resorcinol (0.64 g), formaldehyde (0.96 ml), ethidene
diamine (0.64 ml), and TEOS (0.3 ml) were added sequentially to a mixture of 60 mL of ethanol
and 140 ml of DI water and stirred continuously at 30 °C for 24 h. The solution was then
centrifuged and washed 3-5 times with deionized water and ethanol, respectively, and the
powder obtained was dried at 60 °C overnight.
Synthesis SiO2@SiO2/C: The as-prepared samples were annealed at 800 °C (5 °C min-1) for 4
h in N2 gas to carbonize the polymer into carbon.
Synthesis of nitrogen-doped hollow porous carbon spheres (NHPCs): The black product after
annealing was dispersed into 2 M NaOH to remove the silica template, forming nitrogen-doped
hollow porous carbon spheres (NHPCs). HPCs were synthesized using the same method, except
that EDA was not added.
Synthesis of Se/NHPCs: Se powder (99.99%) and NHPCs with a weight ratio of 2:1 (1:1) were
mixed and heated at 160 °C for 12 h followed by 350 °C for 3 h in N2 atmosphere to obtain the
2-Se/NHPCs (1-Se/NHPCs).
Synthesis of Se/Carbon ECP (Se/KP): Se powder (99.99%) and ECP with a weight ratio of 2:1
was mixed and heated at 160 °C for 12 h followed by 350 °C for 3 h in N2 atmosphere to obtain
the Se/KP.
Na3V2(PO4)3@C-BN (NVP@C-BN): NVP@C-BN was prepared according to previous
literature reports.[1]
Material Characterizations: The morphologies and structures of the as-synthesized samples
were characterized by a field-emission gun scanning electron microscope (SEM, Hitachi 7500)
and a transmission electron microscopy (TEM, JEOL JEM-2200F). The X-ray diffraction
patterns of the products were recorded by a Rigaku Dmax 2200 X-ray diffractometer with Cu-

S2
Kα radiation (λ = 1.5416 Å). X-ray photoelectron spectroscopy measurements were performed
on an ESCALAB 250 photoelectron spectrometer. The Brunauer-Emmett-Teller (BET) surface
area of samples was recorded using a surface area and pore distribution analyzer instrument (V-
Sorb 2800P, Gold APP Instruments Corporation, China). Raman spectroscopy (LabRam
HR800) and Fourier transforms infrared spectroscopy (FTIR, INX10) were performed at room
temperature to analyze the structures of carbon or selenium in the samples. Thermogravimetric
analyses of the Se content was conducted on a STA 449 F5 Jupiter from room temperature to
750 °C.
Electrochemical tests: The electrode film of Se/NHPCs was prepared by mixing Se/NHPCs,
Super-P, and CMC with a mass ratio of 8:1:1 in deionized water. The slurry was then casted on
the Cu foil and dried at 60°C overnight. The electrode film of NVP@C-BN was prepared by
mixing NVP@C-BN, Super-P, and PVDF with a mass ratio of 7:2:1 in NMP. The slurry was
then casted on the Al foil and dried at 60 °C overnight. The effective mass loading of Se/NHPCs
and NVP@C-BN is about 1.2-1.5 mg cm-2. CR2032 coin cells were assembled by coupling the
electrode film with sodium metal foil and glass fiber separator in an Ar-filled glovebox. The
electrolyte was 1 M NaClO4 in diethylene glycol dimethyl ether (EC/DEC). Galvanostatic
charge/discharge tests were performed using a LAND battery system at a voltage window of
0.01~3 V (vs Na+/Na). For the GITT tests, the cell was discharged/charged at 0.05 A g-1 with
current pulse duration of 10 min and interval time of 2 h. Cyclic voltammetry (CV) at 0.01~3
V (vs Na+/Na) and electrochemical impedance spectroscopy (EIS) at an open circuit voltage in
the frequency range of 0.01-100 KHz were carried out using a CHI660e electrochemical
workstation (CHENHUA, Shanghai, China). Since we mainly test the performance of the anode
material in the full cell, an excessive amount of cathode material was used. In assembling the
full cell, we prepared the 2-Se/NHPCs electrode with an active material loading of ~0.8 mg cm-
2
and the cathode electrode with an active material loading of ~5 mg cm-2. The active material
loading can be controlled by controlling the thickness of the electrode using a four-sided
preparator (VS 1803/60/2). The capactiy ratio of the active material of the cathode and anode
is 1.2-1.5:1. The potential range was selected at 0.5-4.2 V. The calculation of energy density
and power density is based on the mass of the active anode material. The energy (E, Wh Kg-1)

S3
and power (P, W Kg-1) density were calculated from the galvanostatic discharge curves by using
the following equations:
𝐼 𝐼
C= 𝑑𝐸 =∆𝐸 (F g-1) (S1)
( )×𝑚 ×𝑚
𝑑𝑡 ∆𝑡

𝐶𝑉 2
E=2×3.6 (Wh kg-1) (S2)
3600𝐸
P= (S3)
∆𝑡

In the formulas, I represent the constant discharge current, ΔE and Δt are the discharge
voltage and corresponding discharge time, respectively, and m indicates the mass of the
corresponding active electrode material.
Theoretical Simulation: The density functional theory (DFT) computations were carried out
using the Vienna ab initio simulation package (VASP).[2] During all calculations, the
generalized gradient approximation (GGA) and the projector augments wave (PAW)
pseudopotentials with the exchange and correlation in the Perdew-Burke-Ernzerhof (PBE) were
employed.[3] A cut-off energy of 400 eV was used for the plane wave basis set to ensure
convergence. The convergence threshold is set as 10-5 eV in energy and 0.01 eV/Å in force,
respectively. A one-layer 5 × 5 slab model was constructed to model the graphene structure.
For all slab models, a 15 Å thick vacuum layer is added along the z direction. The Van der
Walls interaction is included by the DFT-D3 method. A one-layer 2 × 3 × 3 slab model was
constructed to model the Cu2Se structure, and the 1 × 3 × 3 Monkhorst-Pack k-points mesh was
adopted for all slab calculations. The binding energy (Eb) of Na2Se on the substrates is defined
as Eb = Esub+Na2Se-Esub-ENa2Se, where Esub, ENa2Sen, and Esub+Na2Sen represent the total energies of
substrate (graphene, N-doped graphene and Cu2Se), Na2Se, and composite system of Na2Se
binding with the substrate. Differential charge density is calculated by vesta code.

S4
Figure S1. Adsorption configurations of Na2Se on the surface of (a) pristine carbon, (b) N-5,
(c) N-6, (d) N-Q doped carbon.

Figure S2. The DCD distributions between (a) Na2Se and pristine carbon, (b) N-5 doped carbon,
(c) N-6 doped carbon, and (d) N-Q doped carbon, respectively (the electron accumulation and
depletion are colored yellow and cyan, respectively).

S5
Figure S3. (a) The SEM images, and (b) XRD pattern of SiO2.

Figure S4. (a-b) The SEM images, and (c-d) TEM images of NHPCs.

S6
Figure S5. The XRD pattern of (a) pure Se and (b) HPCs and NHPCs.

Figure S6. The Raman spectrae of pure Se.

S7
Figure S7. The thermogravimetric curves of 1-Se/NHPCs and 2-Se/NHPCs samples.

Figure S8. (a) the XPS survey spectra of 2-Se/NHPCs samples, (b) high-resolution XPS spectra
of C 1s.

S8
Figure S9. High-resolution XPS spectra of N 1s for 2-Se/NHPCs sample after substrate
deduction

Figure S10. (a) XPS, (b) C 1s, (c) Se 3d, (d) N 1s XPS spectrums of the 1-Se/NHPCs composite,
respectively.

S9
Figure S11. Geometrically optimized model and corresponding Eb between (a) Na2Se and
carbon, (b) 3 at% N doped carbon, (c) 3 at% Se doped carbon, (d) 3 at% N and 3 at% Se doped
carbon, (e) 3 at% N and 9 at% Se doped carbon, respectively.

Figure S12. The DCD distribution between (a) Na2Se and carbon, (b) 3 at% N doped carbon,
(c) 3 at% Se doped carbon, (d) 3 at% N and 3 at% Se doped carbon, (e) 3 at% N and 9 at% Se
doped carbon, respectively.

S10
Figure S13. The charge/discharge curves at various current densities.

Figure S14. The SEM images of 2-Se/HPCs.

Figure S15. The charge/discharge curves at 0.1 A g-1 of (a) 2-Se/NHPCs and (b) 2-Se/HPCs,

S11
(c) the charge/discharge curves at 1 A g-1 of 2-Se/NHPCs, (d-e) cycle performance at 0.1 A g-
1
, (f) cycle performance at 1 A g-1.
The 2-Se/NHPCs electrode delivers a specific capacity of 564.7/1007.5 mAh g-1,
corresponding the initial coulomb efficiency (ICE) of 56.05%, and the 1-Se/NHPCs electrode
delivers a specific capacity of 348.4/584.5 mAh g-1, corresponding the ICE of 59.61%.

Figure S16. The rate performance for bulk Se particle.

Figure S17. (a-b) The SEM images and (c-d) TEM images of cycled electrode.

S12
Figure S18. Digital photo of the separator after cycled (left: 2-Se/NHPCs electrode, right: bulk
Se electrode).

Figure S19. The electrochemical performance for NVP cathode: (a) XRD pattern, (b-c) SEM
images, (d) cycle performance at 1 A g-1, (e) rate performance.

S13
Figure S20. The electrochemical performance of the full battery: (a) The charge/discharge
curves at 0.1 A g-1, and (b) corresponding cycle performance. (c) The charge/discharge curves
at various current densities, and (d) corresponding rate performance. (e) Average discharge
voltage, and (f) corresponding energy density-power density curve.

Figure S21. (a) Plots of peak current versus the corresponding sweep rate and (b) Plot of
normalized capacity versus corresponding sweep rate-1/2, inset CV curve showing the capacitive
contribution at 1 mV s-1 (shaded area).

S14
Figure S22. (a) CV curves at various current densities, (b) plots of peak current versus the
corresponding sweep rate, (c) CV curve showing the capacitive contribution at 1 mV s-1 (shaded
area), (d) contribution ratio of capacitive controlled at different scan rates of 1-Se/NHPCs
electrodes.

Figure S23. (a) GITT curves during discharge-charge process, (b) diffusion coefficient of 1-
Se/NHPCs and 2-Se/NHPCs electrodes during discharge and charge processes.

S15
Figure S24. (a) EIS test at 0.05 A g-1 for the tenth cycle, and (b) plots of -1/2 versus the Z’.
The electrochemical impedance spectroscopy (EIS) also is used to characterize the DNa+ and it
could be decided by using the following eqs:
ω = 2πf (S4)
Zre = R + σω− 1/2 (S5)
DNa+ = 0.5R2T2/A2n4F4C2σ2 (S6)
R, T, A, n, F, and C are constants, σ is the Warburg coefficient, determined by the slope of the
fitting linear of Z′-ω-1/2. It can be seen that the larger σ, the smaller the diffusion coefficient
(DNa+).

Figure S25. (a) The XRD pattern during the third cycle for 2-Se/NHPCs sample, and (b)
corresponding partial enlarged view

S16
Figure S26. The dQ/dV curves of 2-Se/NHPCs for (a) the first, and (b) the third cycles.
During the initial stage of discharge, the Se species reacted with the Cu current collector
to first generate the CuSe component.[4] By comparing the CV curves of CuSe and Cu2Se
reported in the literature, it can be concluded that the R1 reduction peak at 2.03 V can be
attributed to the conversion of Cu2+ to Cu+, and the O1 oxidation peak corresponds to the
conversion of Cu+ to Cu2+.[5] In the subsequent cycles, the gradual disappearance of R1
indicating that the process is irreversible, and the transformations of Cu+ and Cu dominate
(corresponding to the R2 reduction peak and the O2 oxidation peak).[6] The reduction peaks at
1.25 V and 0.68 V correspond to the transitions of Se to Se- and Se- to Se2-, respectively, and
the corresponding oxidation peaks are O4 and O3 at the first cycle, respectively.[7] It is clear that
the above single-electron transfer process is highly reversible, implying the excellent cycling
stability of the electrode.

Figure S27. Ex situ XPS analysis results of 2-Se/NHPCs carried out at various charge–
discharge states.
S17
Figure S28. The HRTEM images of cycled electrode for 2-Se/NHPCs, and the FFT patterns of
the corresponding region at (a) D 1.14 V, (b-c) D 0.01 V, and (d-e) C 3 V.

Figure S29. The SEM images of Se/KB composite.

S18
Figure S30. The electrochemical performance for Se/KB composite. (a) The charge/discharge
curves at 0.1 A g-1, (b) the cycle performance at 0.1 A g-1 and (c) 1 A g-1, (d) the rate
performance.

Figure S31. The XRD pattern of Se/KB electrode discharged to 0.01 V at the third cycle.

S19
Figure S32. Electrochemical performance tested by coating 2-Se/NHPCs on aluminum current
collectors: (a) the charge/discharge curves at 0.01 A g-1, (b) rate performance, and (c) the cycle
performance at 0.1 A g-1.

Figure S33. SEM images of the Cu collector at 0.5 A g-1 for Se and 2-Se/NHPCs electrodes
after (a), (d) 1 cycle, (b), (e) 100 cycles, and (c), (f) 200 cycles, respectively.

S20
Figure S34. Electrochemical performance of Se electrodes in different electrolytes. (a) and (b)
1M NaClO4 in DME 3% FEC, (c) and (d) 1M NaClO4 EC/PC 3%FEC, (e) and (f) 1M NaClO4
EC/DEC 5%FEC.

Cu2Se CuO Cu2Se

Intensity (a.u.)

EC/DEC

DME

EC/PC

27 30 33 36 39 42 45

2q (degree)

Figure S35. The XRD pattern of cycled electrodes at different electrolyte.

S21
 Table S1. The XPS result of elemental contents in the two samples.
Sample C 1s N 1s Se 3d
1-Se/NHPCs
89.51 5.3 5.2
(Atomic%)
2-Se/NHPCs
86.93 4.85 8.23
(Atomic%)

Table S2. The XPS result of elemental contents in the 2-Se/NHPCs after the third cycle.
Sample C 1s N 1s Se 3d Cu 2p Cu LM2
2-Se/NHPCs
69.71 4.62 6.71 10.87 7.98
(Atomic%)

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