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Selective Sodium Intercalation into Sodium Nickel-Manganese Sulfate for Dual Na-Li-Ion Batteries


Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions – a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex-situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2.4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC:DMC) and sodium electrolytes (NaPF6 dissolved in EC/DEC). Based on ex-situ XRD and TEM analysis, it is found out that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex-situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mAh/g is reached. The selective intercalation properties determine the sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries, that is thought to combine the advantages of individual lithium and sodium batteries.

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Publication details

The article was received on 14 Mar 2018, accepted on 09 Apr 2018 and first published on 09 Apr 2018

Article type: Paper
DOI: 10.1039/C8CP01667D
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Selective Sodium Intercalation into Sodium Nickel-Manganese Sulfate for Dual Na-Li-Ion Batteries

    D. Manasieva, R. Kukeva, E. Zhecheva and R. Stoyanova, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP01667D

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