Journal of Alloys and Compounds 932 (2023) 167647

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Research Article

Sodium decavanadate encapsulated Mn-BTC POM@MOF as high-capacity

cathode material for aqueous sodium-ion batteries ]]
]]]]]]
]]

⁎
Irfan Ullah a, Tanveer ul Haq b,c, Aqeel Aslam Khan a, Abid Inayat d, Muhammad Shoaib a,e, ,
⁎⁎
Ali Haider d, Murtaza Saleem a, Syed Mustansar Abbas f, Michael A. Pope g, Irshad Hussain a,
a
Department of Chemistry & Chemical Engineering, SBA School of Science and Engineering Lahore University of Management Sciences, Lahore 54792, Pakistan
b
Sustainable Energy Engineering, Frank H. Dotterweich College of Engineering, Texas A & M University, Kingsville, TX 78363-8202, USA
c
Department of Chemistry, College of Sciences, University of Sharjah, P.O. Box, 27272 Sharjah, UAE
d
Department of Chemistry, Quaid-i-Azam University, 45320 Islamabad, Pakistan
e
Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada
f
Nanoscience and Technology Department, National Centre for Physics, QAU Campus Islamabad, Pakistan
g
Department of Chemical Engineering, Quantum Nano Centre, University of Waterloo, Ontario, N2L 3G1 Canada

a r t i cl e i nfo a bstr ac t

Article history: Aqueous sodium-ion batteries are the promising candidates for large scale energy storage applications
Received 16 March 2022 owing to their cost effectiveness and environmental safety. However, the development of a stable cathode
Received in revised form 26 August 2022 material with high capacity is still a challenging task for the commercial viability of aqueous electrolyte-
Accepted 16 October 2022
based sodium-ion batteries. This work demonstrates the development of a hierarchically nanostructured
Available online 18 October 2022
high-capacity cathode material by encapsulating sodium decavanadate Na6V10O28 (NaDV) in the scaffold of
manganese-based metal-organic framework Mn-BTC (where BTC is 1,3,5-benzenetricarboxylic acid) by an
Keywords:
Polyoxometallates (POMs) in situ synthesis. The uniform distribution of NaDV in the pores of Mn-BTC enables the multielectron redox
Metal organic frameworks (MOFs) properties of NaDV whereas the diverse 3D diffusion channels, high surface area, and flexible architecture of
High capacity cathode materials Mn-BTC ensure high intercalation capacity by suppressing the agglomeration and providing faster ionic
Aqueous sodium ion batteries diffusion kinetics in the NaDV@Mn-BTC nano-hybrid cathode material. The Mn-BTC framework not only
ensures the stabilization of NaDV but also enhances sodium storage capacity by the involvement of Mn in
the redox process. The NaDV@Mn-BTC cathode material exhibits high reversible capacity of 137 mAh/g at
1 C rate. High capacity of this cathode material suggests that the development of these nano-hybrid ma­
terials is a feasible approach to design high energy cathode materials for aqueous batteries.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction expansion and lattice change of the host material occurs due to re­
peated intercalation/deintercalation of Na+, causing structural de­
The growing demand for large scale energy storage systems terioration, and thus limiting the choice of appropriate electrode
mainly for stationary applications has made aqueous sodium-ion materials for the advancement of aqueous sodium-ion batteries. [2]
batteries attractive in recent years due to the abundance of sodium The development of a stable and high-energy cathode material is
and safety of aqueous electrolytes. Various types of cathode mate­ still a primary challenge for the commercialization of aqueous so­
rials have been explored for sodium-ion batteries such as layered dium-ion batteries. [3] Polyoxometalates (POMs) are recently ex­
transition metal oxides, phosphates, sulfates, pyrophosphates, plored materials for battery applications [4], which are nanosized
fluorophosphates, and Prussian blue analogues. [1] Most of the discrete metal-oxide-cluster anions exhibiting unique compositional
aforementioned materials have layered structures, where volume and structural properties. [5] POMs are known as “electron sponges”,
owing to their multielectron redox potential and fast reversible
charge transfer properties. [6] However, their low surface area [7],
⁎
Corresponding author at: Department of Chemistry & Chemical Engineering, SBA high solubility [8], and aggregation in electrolyte solution reduce
School of Science and Engineering Lahore University of Management Sciences, Lahore their potential to be used as electrode material in batteries. [9] To
54792, Pakistan. address these issues, various types of support materials (SiO2, C3N4,
⁎⁎
Corresponding author.
E-mail addresses: [email protected] (M. Shoaib),
MOF etc.) have been investigated to stabilize POMs. [10] Among the
[email protected] (I. Hussain). potential support materials, metal-organic frameworks (MOFs) can

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I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

offer hierarchically porous architecture with the intriguing attri­ 2.2. Synthesis of NaDV, Mn-BTC and NaDV@Mn-BTC
butes of high surface area, distinct interior voids, low density, robust
stability, and short mass and charge transport pathways. [11] Na6[V10O28].16 H2O (NaDV) was synthesized by a previously re­
Therefore, encapsulation of POM moieties into MOF architecture to ported method [28], and its detail is given in the supporting in­
form POM@MOF hybrid materials via facile solvothermal synthesis formation. Whereas NaDV@Mn-BTC was synthesized by an in situ
method is a promising strategy to regulate the surface area and synthesis by dissolving Mn(OOCCH3)20.4 H2O (0.05 g) and PVP
solution stability of POMs. [12] The assembling of MOF cations (0.3 g) in 10 mL H2O, followed by the addition of 0.02 g NaDV. Then,
around POM anions [13] offers good dispersal of POM in MOF fra­ benzene tricarboxylic acid (0.09 g) solution in 10 mL ethanol water
mework at molecular level. [14] The judicious development of mixture (1:1) was added dropwise. The resulting solution was
POM@MOF selectively combines the outstanding redox capability of stirred for 1 h at room temperature, the obtained precipitate was
POMs with the short multi-channeled charge transfer diffusion filtered and washed with ethanol and then dried at 80 °C for 2 h.
pathways and additional metal active centers of MOFs [15] that Pristine Mn-BTC was also synthesized by the same method as de­
enables improved sodium storage capabilities along with high cy­ scribed above in the absence of NaDV.
cling stability by minimizing the volume changes during the redox
process. [16] The research in the field of POMOF materials is yet at its 2.3. Materials characterizations
early stages and the development of such nano-hybrid materials has
great potential for energy storage applications. [17] Among the The phase structures of the synthesized materials were obtained
POMs, polyoxovanadates are the most promising electrode materials by powder X-ray diffraction analysis using (PXRD D2 phaser, Bruker)
having high specific capacity owing to the stable multielectron redox equipped with CuKα radiation source (λ = 1.5418 Å) within the 2θ
reaction during insertion/extraction processes. [18] The “electron/ diffraction angle range of 5–80º. The morphological information was
ion sponge” feature of vanadates associated with multi Na+ accom­ acquired by scanning electron microscopy (SEM) using FEI NOVA
modation capability ensures their high capacity when employed as SEM-450, while elemental analysis was conducted using energy
cathode materials for Na-ion batteries. [19] The improvement of dispersive X-ray spectroscopy (EDX) (INCAX-Act). High-angle an­
specific capacity and stability by intercalating active metals [20], nular dark-field scanning transmission electron microscopy (HAADF-
protective coating [21], and electrolyte modification [22] are the STEM), and TEM (JEM2100F, JEOL with 200 KV) was performed to
currently employed promising strategies for the advancement of determine the surface structure. Chemical states and surface com­
aqueous batteries performance. position were examined by X-ray photoelectron spectroscopy (XPS)
Recent reports illustrate pronounced advancement in various using PHI 500 Versa Probe II spectrometer UIVAC-PHI. Functional
types of cathode materials for SIBs application. [23] For example, group analysis was performed using Fourier transform infrared
Young et al. developed graphene supported Na3V2(PO4)3 as an effi­ spectroscopy (FTIR, Bruker Alpha II). Brunauer-Emmett-Teller (BET)
cient cathode material with a specific capacity of 90 mAh/g for SIBs. surface area and corresponding pore size distribution measurements
[24]. Later on Tirado et al. reported an enhancement in the capacity were carried out by Quantachrome NOVA 2200e sorption analyzer
of Na3V2(PO4)3 by chromium substitution up to 107 mAh/g that is while degassing the samples at 120 °C overnight followed by N2
ascribed to the decrease in polarization curve between charge and physisorption under liquid nitrogen temperature (−196 K). Thermal
discharge. [25] Recently, Lin et al. reported MoO4−2-doped stability of all the samples was determined by thermogravimetric
Na3V2(PO4)3 with further improved capacity of 108 mAh/g due to the analysis using Perkin Elmer TGA instrument within the temperature
accelerating counter ion diffusion by MoO4−2 in the architecture of range of 25–800 °C in air with a heating rate of 5 °C/min.
Na3V2(PO4)3. Similarly, various efforts have been devoted to the Mn
based materials. For example, Simatovic et al. have recently reported 2.4. Electrochemical measurements
NaxMnO2 nanorods as cathode material with high specific capacity
i.e.,123 mAh/g in SIBs. [26] Despite of significant advancement, there All the electrochemical measurements were performed in
is still a dire need of developing practically viable cathode materials Na2SO4 aqueous electrolyte (3 M, 99.95 % (Alfa Aesar) using CHI660
that can work within the narrow potential window in order to avoid potentiostat in an acid-cleaned standard three-electrode setup. The
electrolysis of aqueous medium to ensure large scale application of cathode material was prepared by making a uniform slurry of
SIBs in energy storage system. NaDV@Mn-BTC with conducting carbon, and polyvinyl difluoride
Considering the stable and reversible redox attributes of sodium (PVDF) in a weight ratio of 85:10:5 using N-methyl-pyrrolidone
decavanadate (Na6V10O28, NaDV) and controlled porous architecture (NMP) as a solvent. The slurry's thin film was drop casted on fluorine
of Mn-BTC with Mn2+ redox active metal center, herein we report the doped tin oxide (FTO) by spin coating followed by drying at 120 °C
development of a promising cathode material by encapsulating for 8 h in vacuum oven. The Pt wire and Ag/AgCl were used as
NaDV in the scaffold of Mn-BTC based MOF. The Mn-BTC having high counter and reference electrodes respectively.
surface area with a pore size distribution of 0.92 nm can effectively
host NaDV having the dimensions of 0.83 nm in its framework. [27] 3. Results and discussion
The systematic electrochemical investigation of the NaDV@Mn-BTC
cathode material was performed in this study that showed its su­ The NaDV@Mn-BTC nano-hybrid material was synthesized by an
perior sodium storage capabilities demonstrating its potential for in situ encapsulation method, also known as “bottle around ship”
next-generation aqueous sodium-ion batteries. method, which is currently the most viable strategy to enclose POMs
in cages of MOFs. [29] The precursors of Mn-BTC and pre-synthe­
2. Experimental section sized NaDV were reacted in a reaction vessel under solvothermal
conditions. The synthesis route of NaDV@Mn-BTC is summarized in
2.1. Chemicals & materials Fig. 1, while those of pristine NaDV and Mn-BTC are described in the
supporting information. The color change of materials in the optical
Sodium metavanadate (NaVO3), manganese acetate tetrahydrate images of NaDV, Mn-BTC and NaDV@Mn-BTC in Fig. S1 indicates the
(Mn(OOCCH3)2·4 H2O), benzene tricarboxylic acid (C9H6O6), hydro­ successful encapsulation of NaDV in the pores of Mn-BTC.
chloric acid (HCl), sodium sulfate (Na2SO4) and polyvinyl pyrroli­ The phase purity and crystal structure of NaDV, Mn-BTC and
done (PVP, K-30) were purchased from Alfa Aesar and used without NaDV@Mn-BTC were studied by powder X-ray diffraction technique
any further purification. (PXRD), and the measured patterns are shown in Fig. 2(a). The PXRD

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I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

towards higher wavenumber indicating the oxidation of manganese

and increased force of attraction with the carboxylate ligand. While,
the corresponding stretching vibration of V]O and V-O-V are
shifted to lower wavenumber in NaDV@Mn-BTC indicating the re­
duction of vanadium, resulting in the development of electrostatic
interaction between NaDV and Mn-BTC. The IR spectrum of Mn-BTC
compared to that of pristine BTC (Fig. S1d) shows the disappearance
of broad ν-OH of the carboxyl group at 2400–3400 cm−1 and C]O at
1720 cm−1 indicating the removal of hydrogen and attachment of
carboxylate to manganese. Furthermore, the appearance of bands
displayed at 1627, 1581, 1443, and 1370 cm−1 are attributed to the
asymmetric and corresponding symmetric stretching vibrations of
metal chelated carboxylate (-COOM) group. [33].
The surface morphology of NaDV in Mn-BTC structure was stu­
died by scanning electron microscopy (SEM). The SEM images of Mn-
Fig. 1. Schematic illustration of synthesis of NaDV@Mn-BTC nano-hybrid material. BTC show the formation of highly branched flowers, where each
flower is further composed of nanorods extended in a 3D manner
pattern of Mn-BTC shows characteristic reflections, i.e., (010), (200), and their diameter gradually decreases from their base towards the
(121), (030) and (331) at the 2θ values of 11.2°, 19.9°, 28.4°, 32.7°, tips, as shown in Fig. 3(a) and 3(b). NaDV forms polyhedral crystals
39.3° and 41.7°, respectively which are in agreement with the lit­ of variable size and geometry, stacked on top of each other as shown
erature. [30] All these diffraction planes are indexed to the Mn-BTC in Fig. 3(c, d). After encapsulation of NaDV in Mn-BTC framework,
structure and no additional peak for any impurity phase was found. SEM images in Fig. 3(e-f) reveal the assembling and entangling of
The peak sharpness reveals the high crystallinity of Mn-BTC fra­ Mn-BTC nanorods with each other and interconnection with NaDV
mework. The PXRD measurement of NaDV was performed and nanocrystals, forming a 3D network architecture. The development
compared with that of the simulated pattern from single crystal XRD of this interconnected network facilitates the electronic conduction
data, as PXRD pattern of NaDV is not well reported in literature. The at nanorods and nanocrystals interfaces. The EDX spectra and ele­
diffraction peaks from synthesized NaDV are in agreement with the mental maps were acquired to further understand the elemental
main phases of the simulated pattern shown in Fig. S2. The slight composition and purity of the synthesized materials, the EDX
difference may be due to the varying amount of water of crystal­ spectra are shown in Fig. S3. The EDX spectrum of Mn-BTC shows the
lization in precipitated powder that is a well-known phenomenon presence of Mn, C, and O only, whereas, EDX spectra of NaDV show
for POM systems. [31] The appearance of all the characteristic re­ Na, V and O only and that of NaDV@Mn-BTC reveals the homo­
flections of Mn-BTC and NaDV in the PXRD pattern of NaDV@Mn- geneous distribution of Mn, V, C, O and Na. The EDX spectra of all
BTC at their respective positions demonstrates that expected nano- these materials indicate high purity and expected percentage com­
hybrid material was successfully synthesized. The slight shift of position of respective elements.
diffraction peaks of Mn-BTC towards lower 2θ in the XRD spectrum The elemental mapping shown in Fig. 3(g-p) further validates
of NaDV@Mn-BTC and the corresponding shift of the peaks of NaDV that the composition of each respective nanostructure is in close
to higher 2θ demonstrate interaction and encapsulation of NaDV in agreement with the EDX results. To further understand the complex
Mn-BTC architecture. surface structure and integration at molecular level in NaDV@Mn-
The IR measurements shown in Fig. 2(b) provide further evidence BTC nano-hybrid, transmission electron microscopic (TEM) and
of the encapsulation of NaDV in the scaffold of Mn-BTC. The IR high-angle annular dark-field, scanning transmission electron mi­
spectrum of NaDV shows a characteristic peak at 953 cm−1 that is croscopy measurements were performed. The TEM images of Mn-
attributed to ν V]O terminal. The peaks at 813 and 749 cm−1 are BTC, NaDV and NaDV@Mn-BTC in Fig. 4(a, f and k) clearly show in­
ascribed to asymmetric ν O-V-O while the peak at 566 cm−1 is due to dividual nanorods, nanocrystals and crystals encapsulated nanorods,
symmetric stretching vibration of ν V-O-V. [32] The IR spectrum of respectively. The high-angle annular dark-field scanning transmis­
NaDV@Mn-BTC shows all the Mn-BTC peaks with a slight shift sion electron microscopy (HAADF-STEM) and elemental mapping

Fig. 2. PXRD patterns (a) and IR spectra (b) of Mn-BTC, NaDV and NaDV@Mn-BTC.

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I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

Fig. 3. SEM images of Mn-BTC (a, b) NaDV (c, d) and NaDV@Mn-BTC (e, f), elemental mapping of Mn-BTC (g-i), NaDV (j-l) and NaDV@Mn-BTC (m-p).

were performed to further confirm the encapsulation and integra­ encapsulated at two different levels as revealed by SEM and TEM
tion of NaDV in the Mn-BTC nanorods. images. NaDV hexagonal crystals are interconnected with Mn-BTC
Elemental mapping for Mn-BTC is shown in Fig. 4(c-e), and that flowers as shown by SEM images and at the molecular level NaDV is
of NaDV and NaDV@Mn-BTC are shown in Fig. 4(h-j) and 4(l-o) re­ encapsulated by Mn-BTC framework as confirmed by TEM, HAADF-
spectively. The HAADF-STEM and corresponding elemental mapping STEM and their relevant elemental maps. Furthermore, the selected
contrast show the equal distribution of Mn, C, and O in Mn-BTC area electron diffraction (SAED) analysis shown in (Fig. S4) illustrates
nanorods, and that of V, O and Na in NaDV crystals. Interestingly, the well defined single crystalline diffraction pattern for Mn-BTC and
elemental mapping of Mn-BTC nanorods present in NaDV@Mn-BTC NaDV. The diffraction pattern of NaDV@Mn-BTC demonstrates two
shows uniform distribution of V in the nanorod as shown in Fig. 4(n), sets of diffraction spots corresponding to NaDV and Mn-BTC.
even though these rods are consisted of Mn-BTC (Mn, C and O). Surface area plays an important role in understanding the
Uniform distribution of V in the Mn-BTC nanorods confirms the structural and electrochemical properties. The adsorption-deso­
encapsulation of NaDV in Mn-BTC nanorods at the molecular level. rption isotherm for Mn-BTC and NaDV@Mn-BTC were measured and
So, this NaDV@Mn-BTC nano-hybrid material is integrated and are displayed in Fig. S5(a) and S5(c), indicating the high surface area

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I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

Fig. 4. TEM images of (a) Mn-BTC, (f) NaDV and (k) NaDV@Mn-BTC, HAADF-STEM images of (b) Mn-BTC, and (g) NaDV. Elemental mapping of (c-e) Mn-BTC, (h-j) NaDV and (l-o)
NaDV@Mn-BTC.

of pristine Mn-BTC i.e., 321 m2g−1, while that of NaDV@Mn-BTC peak at − 0.14 V can be attributed to the V4+/V5+ redox pair, in con­
material is reduced to 78 m2g−1 along with the change of isotherm sistent with the cathodic and andic peaks in pure NaDV (Fig. S8a),
from type I to type III. This pronounced decrease in the surface area with a weak additional redox couple at 0.072 and 0.053 V attributed
demonstrates the encapsulation of NaDV in the pores of Mn-BTC. to Mn3+/Mn4+ redox process. NaDV@Mn-BTC nano-hybrid material
Furthermore, the pore size distribution analysis of the pristine Mn- delivered charge/discharge capacity of 137 mAh/g as shown in
BTC in Fig. S5 (b) shows the narrow size distribution of 0.92 nm Fig. 5(b), that is significantly higher than 28 mAh/g from Mn-BTC
indicating micropores and a small peak centered at 3.98 nm shows (Fig. S7b) and 71 mAh/g from NaDV (Fig. S8b) individually, in addi­
mesopores while that of NaDV@Mn-BTC in Fig. S5(d) shows peaks at tion to high-rate capability and stability compared to NaDV (Fig. S8
1.74 and 7.6 nm, corresponding to micropores and mesopores, re­ c-d). The high stability and rate capability of Mn-BTC as shown in
spectively. The shifting and broadening of the pore size distribution (Fig. S7c-d) demonstrate that Mn-BTC offers stability to NaDV and
of NaDV@Mn-BTC illustrate the random orientation of NaDV in the the formation of NaDV@Mn-BTC nano-hybrid synergistically en­
pores of the Mn-BTC host. The presence of volatile components and hance the electrochemical performance compared to individual Mn-
thermal stability of these materials was studied by thermogravi­ BTC and NaDV. As mentioned earlier, polyoxometalates despite their
metric analysis (TGA). The thermal decomposition of Mn-BTC de­ multi electron transfer capability, suffer from low surface area, high
monstrates two successive weight losses of 17 % and 41 % at about solubility and aggregation in electrolytes.
150 and 545 °C, which are attributed to the removal of water content These limitations can be overcome by encapsulating these ma­
and pyrolysis of BTC linker, respectively (Fig. S6). The thermogravi­ terials in MOFs architecture. This strategy significantly enhanced the
metric pattern of NaDV reveals one weight loss of 23 % at about electrochemical cycling as well as the rate capability of NaDV@Mn-
190 °C, which is ascribed to the elimination of water of crystal­ BTC nano-hybrid material as it exhibited high-rate performance with
lization, the remaining vanadium oxide cluster shows high stability charging capacities of 137, 95, 63 and 30 mAh/g at 1 C, 2 C, 5 C and
up to 800 °C. While the TGA pattern of the NaDV@Mn-BTC shows 03 10 C respectively (where 1 C = 146 mA/g) as shown in Fig. 5(c). It can
sequential weight losses. The 1st loss of 6 % at 65 °C can be attributed be observed that when the current rate is switched back to the lower
to the elimination of water from Mn-BTC, whereas the 2nd loss of 11 value of 1 C, the cell capacity is recovered to 115 mAh/g, showing
% at about 146 °C can be ascribed to the removal of water of crys­ high-capacity retention after high-rate cycling. The coulombic effi­
tallization of NaDV, and the 3rd loss of 32 % at 538 °C can be at­ ciency and cycling stability measurements performed at 1 C show
tributed to the decomposition of BTC linker. Most importantly, the Coulombic efficiency of 97.1 % and capacity retention of 81 % after
NaDV@Mn-BTC shows high thermal stability compared to that of 100 cycles as shown in Fig. 5(d). Moreover, long cycling at high rate
Mn-BTC. was performed to demonstrate the structural stability. The long
The electrochemical performance of NaDV, Mn-BTC and NaDV@ cycling results reveal 62 % capacity retention after 1000 cycles at the
Mn-BTC materials was evaluated as a cathode material for sodium- high rate of 5 C (Fig. S9). The overall high stability reveals that the
ion battery in aqueous electrolyte. The cyclic voltammogram of the Mn-BTC nano-flowers network can act as protecting web, averting
NaDV@Mn-BTC material demonstrates stable and reversible cycleing NaDV structure from being damaged and maintaining the structural
in aqueous electrolyte as shown in Fig. 5(a), indicating enhanced integrity of NaDV during electrochemical cycling. The mixture of
structural and hydrolytic stability compared to that of pristine Mn- NaDV/Mn-BTC was also made by mixing the pre-synthesized NaDV
BTC (Fig. S7a) and NaDV (Fig. S8a). The strong anodic peak in the CV and Mn-BTC and its performance was compared to that of the in situ
profile of NaDV@Mn-BTC at 0.29 V and the corresponding cathodic synthesized NaDV@Mn-BTC. The capacity of the composite is lower

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I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

Fig. 5. (a) Cyclic voltammogram (CV) at the scan rate of 50 mV/s, (b) charge discharge capacity, (c) rate capability and (d) cycling stability along with Coulombic efficiency of
NaDV@Mn-BTC.

(119 mAh/g) as shown in (Fig. S10) compared to that of the in situ promising compared to other recently reported NaDV and other
synthesized material i.e., 137 mAh/g. The lower capacity of NaDV/ vanadium-based cathode materials as shown in comparative ana­
Mn-BTC mixture may be due to the lack of synergistic effect of in­ lysis of table S1.
terconnected network formation. As illustrated by the SEM analysis To gain a deeper insight of the charge/discharge mechanism of
(Fig S11), the NaDV crystals in the mixture are separated at the NaDV@Mn-BTC cathode material, we studied its valance state
bottom due to its high density compared to that of Mn-BTC nanorods changes before and after the electrochemical charge process by
in contrast to that of in situ synthesized composite where NaDV using X-ray photoelectron spectroscopy (XPS). The survey scan (Fig.
crystals are trapped in the nanorods resulting in the formation of 3D S15a) indicates that NaDV@Mn-BTC is composed of Na, Mn, V, O, and
interconnected network (Fig. 3e,f). C. The Mn 2p spectrum for pristine Mn-BTC was best fitted with a
Electrochemical impedance spectroscopy (EIS) measurements pair of spin-orbit doublet of Mn2+ 2p3/2 and Mn2+ 2p1/2 respectively
were performed to understand the origin of high stability and rate [34] (Fig. S15b). The high-resolution V2p spectrum of pristine NaDV
performance of NaDV@Mn-BTC compared to that of NaDV and Mn- (Fig. S15c) shows two characteristic peaks at binding energy of 517.1
BTC. As illustrated in Fig. S12, EIS measurements show that elec­ and 524.4 eV corresponding to V2p3/2 and V2p1/2 illustrating that
trolyte resistance (Re) is 4.2 Ω, while the charge transfer resistance ∼80 % of vanadium is in V5+ state and the peaks at 516 and 522.7 eV
(Rct) for NaDV, Mn-BTC and NaDV@Mn-BTC are 35.4, 57.8 and 20.8 Ω show that ∼20 % of vanadium is in V4+ state, which is in accordance
respectively. The EIS result demonstrates that the encapsulation of with literature. [35] The XPS spectra of NaDV@Mn-BTC in Fig. 6(a)
NaDV in the scaffold of Mn-BTC improves the charge transfer ki­ show that ∼70 % of vanadium is in V4+ state while ∼30 % is in V5+
netics and thus decreases the ohmic resistance of electrode material state. Similarly, the Mn2p3/2 and Mn2p1/2 representative peaks in
in the solution resulting in improved electrochemical and rate per­ Fig. 6(b) located at 642 and 653.8 eV show the presence of Mn3+
formance. The structural integrity of NaDV@Mn-BTC material after while those at 543.4 and 655 eV illustrate Mn4+ state in NaDV@Mn-
100 cycles was also studied by using SEM, TEM and elemental ana­ BTC nano-hybrid. These results show that the valence states of V and
lysis. The SEM, TEM and corresponding elemental composition Mn are different in pristine NaDV and Mn-BTC compared to that of
images (Fig. S13) revealed that NaDV@Mn-BTC preserved its struc­ NaDV@Mn-BTC nano-hybrid that indicates reduction of V and cor­
tural features after long term charge/discharge cycles, demon­ responding oxidation of Mn during in situ synthesis that further
strating excellent stability of NaDV@Mn-BTC after intercalation/ confirms the integration of NaDV and Mn-BTC in our nano-hybrid
deintercalation of Na+. The SEM image of pristine NaDV after 100 material at molecular level. The XPS spectra of fully charged NaDV@
cycles (Fig. S14) shows the breakdown of NaDV crystals demon­ Mn-BTC material up to 1 V in Fig. 6(c) shows the V2p3/2 and V2p1/2
strating that the pristine NaDV crystals are susceptible to electrolyte peaks located at 517.4 and 524.7 eV, indicating the complete oxida­
and side reactions occurring on the surface compared to that of Mn- tion of vanadium to V5+ state at the end of charge process. While the
BTC protected NaDV, which act as protecting web in maintaining the XPS spectra of Mn at fully charged state in Fig. 6(d) indicates oxi­
structural integrity of NaDV. The performance of NaDV@Mn-BTC is dation of Mn3+ to Mn4+ during charging. The XPS spectra of

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I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

Fig. 6. XPS spectra for (a) V2p (b) Mn2p in pristine NaDV@Mn-BTC, (c) V2p (d) Mn2p in charged NaDV@Mn-BTC, and (e) V2p (f) Mn2p in discharged NaDV@Mn-BTC.

discharged NaDV@Mn-BTC up to − 1 V were also measured and enhanced the electrochemical storage performance by synergisti­
shown in Fig. 6(e) and 6(f) that show the decreased intensity of cally consolidating the reversible redox features of NaDV and open
peaks at 516 and 523.5 eV corresponding to the complete reduction framework with additional metal active sites of Mn-BTC MOF. The
of V5+ to V4+ state. [19] The spectra of Mn at fully discharge state high porosity and structural flexibility of Mn-BTC MOF integrated
demonstrate the presence of Mn3+ and Mn2+, indicating the reduc­ with electron/ion sponge feature of NADV perfectly combined the
tion of Mn. These changes in the binding energies illustrates that requirements of a promising cathode material resulting in the en­
V4+/V5+ is an active redox couple and at the same time, Mn is also hancement of sodium ion intercalation, charge transfer kinetics, and
contributing directly in the redox process and may also indirectly structural stability. The NaDV@Mn-BTC material delivered high ca­
contribute by the transfer of electrons to and from vanadium. The pacity of 137 mAh/g with remarkable rate performance and dur­
reduction of V justifies the high capacity of NaDV@Mn-BTC com­ ability. The assimilation of various structural features and electronic
pared to that of pristine NaDV, owing to the high aptitude of reduced attributes in a single material signifies a viable strategy for the ra­
V for providing electrons during the charging process. The NaDV@ tional design of efficient and robust material for high energy storage
Mn-BTC nano-hybrid material with two redox-active centers (Mn, V) performance.
is capable of delivering a multi-electron redox. The synergy achieved
between NaDV guest and Mn-BTC host in this design is a way for­
ward to design high energy and stable electrode materials. CRediT authorship contribution statement

Irfan Ullah: Conceptualization, Methodology, Investigation, Data

4. Conclusions curation, Validation, Formal analysis, Writing – original draft.
Tanveer ul Haq: Investigation, Data curation, Validation and help in
In summary, NaDV@Mn-BTC nano-hybrid material was success­ Writing – original draft. Aqeel Aslam Khan: Investigation, Data
fully synthesized and utilized as a high-capacity cathode material for curation, Validation and help in Writing – original draft. Abid Inayat:
aqueous sodium-ion battery. The experimental results demonstrated Data curation, Validation, and support in electrochemical char­
that the encapsulation of NaDV in the scaffold of Mn-BTC effectively acterization of materials. Muhammad Shoaib: Investigation,

7
I. Ullah, T. ul Haq, A.A. Khan et al. Journal of Alloys and Compounds 932 (2023) 167647

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