Received: 12.02.2019. Accepted: 19.03.2019. Published: 29.03.2019.Na-ion battery is one of the best alternatives to Li-ion battery. Abundance of sodium on earth is three orders of magnitude higher than lithium, which should make Na-ion battery technology cheaper. But alkaline-ion battery prices, which tend to increase because of the massive world demand, also depend on the choice of electrode materials. Therefore, cost-effective electrode development remains an important subject of research because this will allow Na-ion battery to be even more competitive. Electrochemical performances of anhydrous VOSO4 as electrode for Na-ion battery are reported in this letter. Two anhydrous phases of vanadyl sulfate have been studied. The first one, α-VOSO4, shows that up to 0.8 sodium per formula unit (Na/f.u.) can be intercalated in this phase, and a reversible intercalation of 0.4 Na/f.u. has been observed with a strong polarization. The second one, β-VOSO4, can intercalate up to 0.9 Na/f.u. with a reversible inter- calation of 0.4 Na/f.u. leading to a reversible capacity of 64 mAh/g

Deriouche, W.

Anger, E.

Amdouni, N.

Pralong, V.

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Sodium intercalation into α- and β-VOSO4

Eastern Kentucky University

English

Eastern Progress, 18 Mar 2010

Archive Ouverte en Sciences de l'Information et de la Communication

Eastern Progress, 22 Apr 2010

Na-ion battery is one of the best alternatives to Li-ion battery. Abundance of sodium on earth is three orders of magnitude higher than lithium, which should make Na-ion battery technology cheaper. But alkaline-ion battery prices, which tend to increase because of the massive world demand, also depend on the choice of electrode materials. Therefore, cost-effective electrode development remains an important subject of research because this will allow Na-ion battery to be even more competitive. Electrochemical performances of anhydrous VOSO4 as electrode for Na-ion battery are reported in this letter. Two anhydrous phases of vanadyl sulfate have been studied. The first one, α-VOSO4, shows that up to 0.8 sodium per formula unit (Na/f.u.) can be intercalated in this phase, and a reversible intercalation of 0.4 Na/f.u. has been observed with a strong polarization. The second one, β-VOSO4, can intercalate up to 0.9 Na/f.u. with a reversible intercalation of 0.4 Na/f.u. leading to a reversible capacity of 64 mAh/g

Ural Federal University: URFU Journal Systems / Журнальный портал УРФУ

31DOI: 10.15826/chimtech.2019.6.1.04Deriouche W., Anger E., Amdouni N., Pralong V.Chimica Techno Acta. 2019. Vol. 6, No. 1. P. 31–36.ISSN 2409–5613W. Deriouchea,b, E. Angera, N. Amdounib, V. Pralonga,*a Normandie Univ, ENSICAEN, UNICAEN, CNRS, CRISMAT, 14000 Caen, Franceb Unite de Recherche Physico-chimique des Materiaux Condenses, Universite Tunis El Manar, Faculte des Sciences de Tunis, Campus Universitaire, 2092 El Manar Tunis, Tunisiae-mail: valerie.pralong@ensicaen.frSodium intercalation into α- and β-VOSO4Na-ion battery is one of the best alternatives to Li-ion battery. Abundance of sodium on earth is three orders of magnitude higher than lithium, which should make Na-ion battery technology cheaper. But alkaline-ion battery prices, which tend to increase because of the massive world demand, also depend on the choice of electrode materials. Therefore, cost-effective electrode development remains an important subject of research because this will allow Na-ion battery to be even more competitive. Electrochemical performances of anhydrous VOSO4 as electrode for Na-ion battery are reported in this letter. Two anhydrous phases of vanadyl sulfate have been studied. The first one, α-VOSO4, shows that up to 0.8 sodium per formula unit (Na / f.u.) can be intercalated in this phase, and a reversible intercalation of 0.4 Na / f.u. has been observed with a strong polarization. The second one, β-VOSO4, can intercalate up to 0.9 Na / f.u. with a reversible inter-calation of 0.4 Na / f.u. leading to a reversible capacity of 64 mAh / g.Keywords: VOSO4; Na-ion Batteries; cathode; vanadium sulfate.Received: 12.02.2019. Accepted: 19.03.2019. Published: 29.03.2019.© Deriouche W., Anger E., Amdouni N., Pralong V., 2019IntroductionThe search for new materials that could be used as electrode material for the Na-ion batteries is one of today’s most chal-lenging issues. Many families of transition metal oxides as well as transition metal poly-anionic frameworks have been proposed these last five years. Among them, Na-Super-Ionic-Conductors (NaSICON) are one the most popular materials due to their good cycling ability and Na+ mobility. How-ever, sulfates represent an interesting and low-cost class with only few reported mem-bers. Therefore, few sodiated iron sulfates [1–4] can be found in the literature and only one example of sodiated vanadate sulfate has been reported up to date (Na2VO(SO4)2) as an electrode material for Na-ion battery [5]. This material delivers a reversible capac-ity of 60 mAh / g at 4.5 V vs Na+ / Na. In this work, we report the use of an-hydrous vanadyl sulfate as an electrode material for Na-ion battery. Anhydrous VOSO4 exists in two forms at room tem-perature: α-VOSO4 is tetragonal and is formed by dehydration of its hydrate below 280 °C [6], β-VOSO4 is orthorhombic and may be prepared either from the reaction of H2SO4 and V2O5 [7] or by dehydration 32above 280 °C, although decomposition oc-curs when using this last method [8]. The charge-discharge profile of both known phases, α- and β-VOSO4, will be discussed.Experimental The alpha form, α-VOSO4, was prepared by a simple dehydration of VOSO4·xH2O (5 g, Sigma Aldrich) at 260 °C for 2 days, then stored in a glove-box to prevent re-hydration from air moisture. On the other hand, β-VOSO4 was prepared by a pre-cipitation reaction starting from stoichi-ometric amounts of hydrated vanadium oxysulfide VOSO4·xH2O (1.8 g) heated at  140  °C in  100 mL of  sulphuric acid solution (0.1M H2SO4) for 2 hours. The resulted green mixture was then filtered and washed with water. The obtained pow-der is then left overnight at 160 °C in an oven before being stored in argon-filled glove-box. The compounds were characte-rized by X-ray powder diffraction (XRD) using a  Philips X’Pert 2 diffractometer with Bragg-Brentano geometry (Cu Kα radiation). Note that due to their instabil-ity in air, the reduced phases’ XRD pat-terns were registered under vacuum using a chamber attached to the XRD instru-ment. The electrochemical characterization was performed in cells build in Swagelok compression tube fitting with a solution 1M NaClO4 in propylene carbonate (PC) as electrolyte and metallic sodium as coun-ter electrode. The working electrode was prepared from a mixture of active mate-rial with acetylene black in a weight ratio of 50:50. The electrochemical cells were cy-cled at constant current between 1.0–3.0 V at different galvanostatic rates on a VMP III potentiostat / galvanostat (Biologic SA, Claix, France) at room temperature. Results and discussionFirst report on preparation of the phase alpha of anhydrous vanadyl sulfate was published in 1965 by J. Tudo [6]. Its crys-tal structure was optimized and its mag-netic properties studied by R. J. Arnott and J. M. Longo in 1970 [9]. They suggest that trace of water was present in Tudo’s sample. This phase crystallizes within a tetragonal structure (space group: P4 / n) with a  = 6.258 Å, c = 4.122 Å and a volume of V = 161.42(3) Å3. Along the c-axis, we can ob-serve continuous chains of corner-shared VO6 octahedra, as shown in Fig. 1. All these chains are corner-shared with SO4 tetrahe-dra forming a three-dimensional network.First report on the phase beta of anhy-drous vanadyl sulfate was published in 1927 by A. Sieverts and E. L. Müller [7]. In 1970, its crystal structure and its magnetic pro-perties have been studied in the same paper than α-VOSO4 [9]. This phase crystallizes within an orthorhombic structure (space group: Pnma) with a = 7.384 Å, b = 6.275 Å, c = 7.078 Å and a volume of V = 327.92(3) Å3. β-VOSO4 is described by Gaubicher et al. as chains of corner-sharing distorded vanadium oxygen octahedra along the a-axis. Those chains are linked to sulphate groups which alternately point in opposite directions along the c-axis [10]. Interestingly, Gaubicher et al. published the reversible intercalation of 0.6 lithium ions into β-VOSO4 at 2.84 V vs Li+ / Li. After a first intercalation of 0.9 lithium through a biphasic process at 1.75 V, a solid solution reaction takes place. The structure of the reduced phase Li0.9VOSO4 has not been solved [10]. We investigated the charge-discharge profile of α-VOSO4 carried out at C / 20 33between 1.0 and 3.0 V (Fig. 2a). Th e slope of the curve suggests that a solid solution process occurs during both charge and discharge. Th e theoretical capacity for the intercalation of 1 sodium per VOSO4 is 160 mAh / g. Th e fi rst discharge allows the intercalation of 0.8 Na / f.u. at an average voltage of 1.58 V with an average of 0.6 Na / f.u. reversibly deintercalated aft er 4 cycles. Th is corresponds to a reversible capacity of 96 mAh / g. Th e intercalation and deintercalation of sodium occur in two distinct processes centered respectively at 1.45 then 1.15 V for the intercalation and 2.42 then 2.68 V for the deintercala-tion, as observed on Fig. 2b. The charge-discharge profi le of β-VOSO4 carried out at C / 20 between 1.0 and 3.0 V is depicted in Fig. 2c. Th e slope of the curve suggests also that a solid solution process occurs during both charge and discharge. Th e fi rst discharge allows the intercalation of 0.9 Na / f.u. at an aver-age voltage of 1.58 V, but only 0.4 Na / f.u. were reversibly deintercalated, correspond-ing to a reversible capacity of 64 mAh / g. Th is potential characterizes the V4+ / V3+ re-dox potential. Th e capacity remains almost unchanged aft er 4 cycles. Th e intercalation 0 20 40 60 80-800-600-400-2000200400600800100012001400Counts2θ2θP4/na = 6.2673(2)c = 4.1068(2)V = 161.313(9)χ2 = 2.36α-VOSO4β-VOSO4a0 50 100-4000-20000200040006000800010000CountsPnmaa = 7.3837(2)b = 6.2750(2)c = 7.0776(2)V = 327.925(9)χ2 = 4.81bFig. 1. (a) Rietveld refi nement of the XRD pattern for α-VOSO4 and its structure along the c-axis; (b) Rietveld refi nement of the XRD pattern for β-VOSO4 and its structure along the a-axis34and deintercalation of sodium occur in two distinct processes centered respectively at 1.90 and 2.40 V for the intercalation and 2.30 and 2.85 V for the deintercalation pro-cess, as observed in Fig. 2d. According to the electrochemical study (lower polarization and almost no shift on capacity after few cycles), β-VOSO4 seems more suitable for the intercalation of Na and therefore should be more deeply investigated. Best performance of β-VOSO4 can be explained by the channels observed in α-VOSO4 structure (1.5 Å) being smal-ler than in b-VOSO4 structure (2 Å) (see Fig.  1). The difference in  channel sizes comes from a difference of configuration of SO4 tetrahedra in these structures. In the α-VOSO4 structure, SO4 tetrahedra are linked to four channels of VO6 octahedra. In contrast, only three channels of VO6 oc-tahedra are connected to the SO4 channels in the β-VOSO4 structure. Consequently, the structure is more constrained with less space between VO6 octahedra chains in a-VOSO4 than in β-VOSO4. To complete our study, we decreased the size of  the particles of  α-VOSO4 by  using a  mechanochemical process (250 rpm / 1.5 hrs). Although this ball mill-ing process effectively nanostructured our 0.0 0.2 0.4 0.6 0.8 1.00.51.01.52.02.53.0x in NaxVOSO4Volts vs Na+/Naa0 50 100 150Capacity (mAh/g)1.0 1.5 2.0 2.5 3.0-2-1012Derivative curve1.451.152.682.42d(Q–Q0)/dE (mAh/V)E (V vs Na+/Na)b0.0 0.2 0.4 0.6 0.8 1.01.01.52.02.53.0Volts vs Na+/Na0 50 100 150x in NaxVOSO4Capacity (mAh/g)c1.0 1.5 2.0 2.5 3.0-5-4-3-2-1012Derivative curve1.90 2.401.582.852.30d(Q–Q0)/dE (mAh/V)E (V vs Na+/Na)dFig. 2. (a) Potential-capacity curves of α-VOSO4 at the galvanostatic rate of C / 20 between 3.0 and 1.0 V; (b) corresponding derivative curves; (c) potential-capacity curves of β-VOSO4 at the galvanostatic rate of C / 20 between 3.0 and 1.0 V; (d) corresponding derivative curves 35material, as shown on the following X-ray pattern (Fig. 3, middle line), this did not improve the electrochemical properties of our material. Attempts to chemically reduce either α- or β-VOSO4 using sodium naphthalenide in THF have been unsuccessful due to the dissolution of the material in THF.Finally, ex situ XRD pattern has been obtained after the first reduction of α-VOSO4. This shows that an amorphi-zation process occurred during the inter-calation of sodium into α-VOSO4 phase (Fig. 3, upper line).ConclusionsIn this work, we demonstrated that α- and β-VOSO4 can be used as an electrode material in Na-ion battery. To the best of our knowledge, this is only the second vanadyl sulfate based material used in Na-ion battery. The β phase exhibits smaller polarization than the α phase. Intercala-tion and deintercalation of 0.4 Na / f.u. have been observed, which correspond to a ca-pacity of 65 mAh / g. This reversible ca-pacity is quite low, but could be improved by playing with the particle size as well as carbon coating, even though nanosiz-ing has been unsuccessful on the α phase. Then, due to  its attractive price and its cycling capability, further investigations on the intercalation of sodium in β-VOSO4 are in progress.Acknowledgements The authors gratefully acknowledge the CNRS, the Minister of Education and Research, the Region of Normandy and Labex “Energy Materials & Clean Combustion Center” for funding this work. We also thank J. Thuillier, S. Duffour and S. Gascoin for technical help.References1. Singh P, Shiva K, Celio H, Goodenough JB. Eldfellite, NaFe(SO4)2: an intercalationcathode host for low-cost Na-ion batteries. Energy Environ Sci. 2015;8:3000–5.DOI:10.1039 / C5EE02274F.2. Mason CW, Gocheva I, Hoster HE, Yu DYW. Iron(III) sulfate: a stable, cost effec-tive electrode material for sodium ion batteries. Chem Commun. 2014;50:2249–51.DOI:10.1039 / C3CC47557C.3. Meng Y, Zhang S, Deng C. Superior sodium — lithium intercalation and depressedmoisture sensitivity of a hierarchical sandwich-type nanostructure for a graphene —sulfate composite: a case study on Na2Fe(SO4)2·2H2O. J Mater Chem A. 2015;3:4484–92.DOI:10.1039 / C4TA06711H.20 40 60 80 Na intercalation Ball milling Starting material2θFig. 3. Powder X-ray diffraction pattern of as prepared a-VOSO4 phase (lower curve); powder X-ray diffraction pattern of a-VOSO4 phase after ball milling (middle curve); powder X-ray diffraction pattern of a-VOSO4 phase after Na intercalation (upper curve)364. Barpanda P, Oyama G, Nishimura S, Chung SC, Yamada A. A 3.8-V earth-abundant sodium battery electrode. Nat Commun. 2014;5:4358. DOI:10.1038 / ncomms5358.5. Sun M, Rousse G, Saubanère M, Doublet ML, Dalla Corte D, Tarascon JM. A2VO(SO4)2 (A = Li, Na) as Electrodes for Li-Ion and Na-Ion Batteries. Chem Ma-ter. 2016;28:6637–43. DOI:10.1021 / acs.chemmater.6b02759.6. Tudo J. Vanadyl sulfate and its reduction by hydrogen sulfide: vanadium sulfides. Rev Chim Miner. 1965;2(1):58–177.7. Sieverts A, Müller EL. Vanadinverbindungen und siedende Schwefelsäure. Z Für Anorg Allg Chem. 1928;173(1):313–23. German. DOI:10.1002 / zaac.19281730128.8. Paufler P, Filatov SK, Bubnova RS, Krzhizhanovskaya MG. Synthesis and thermal behaviour of pauflerite, β-VOSO4, and its α-modification. Z Kristallogr — Cryst Mater. 2014;229:725–9. DOI:10.1515 / zkri-2014–1752.9. Longo JM, Arnott RJ. Structure and magnetic properties of VOSO4. J Solid State Chem. 1970;1(3-4):394–8. DOI:10.1016 / 0022–4596(70)90121–0.10. Gaubicher J, Chabre Y, Angenault J, Lautié A, Quarton M. Lithium electrochemical intercalation in β-VOSO4. J Alloys Compd. 1997;262–3:34–8.  DOI:10.1016 / S0925-8388(97)00325–3.

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Sodium intercalation into α- and β-VOSO4

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Eastern Kentucky University

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Ural Federal University: URFU Journal Systems / Журнальный портал УРФУ