Electrode Materials with the Na<sub>0.44</sub>MnO<sub>2</sub> Structure: Effect of Titanium Substitution on Physical and Electrochemical Properties

Doeff, Marca M.; Saint, Juliette; Wilcox, James D.

doi:10.1021/cm800247u

Cited by 44 publications

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“…11,12 A series of titanium-substituted Na 0.44 MnO 2 and Li 0.44 MnO 2 materials, in which Ti 4+ partially occupies MO 6 polyhedra, have also been reported as positive electrodes for sodium and lithium-ion batteries. 10 Doping with titanium increases the unit cell size and in the case of lithiated materials, raises the potential of lithium intercalation/deintercalation 13 and leads to higher capacities. For instance, Li x Ti 0.22 Mn 0.78 O 2 is reported to deliver about 10-20% more capacity than Li x MnO 2 .…”

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confidence: 99%

LiMnTiO₄with the Na_0.44MnO₂Structure as a Positive Electrode for Lithium-Ion Batteries

Amigues¹,

Glass²

2015

J. Electrochem. Soc.

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A metastable polymorph of LiMnTiO 4 with the Na 0.44 MnO 2 structure has been synthesized via ion-exchange from its sodium analogue, NaMnTiO 4 . The structure was determined from a combination of X-ray and Neutron Powder Diffraction data. LiMnTiO 4 has the Pbam space group, with a = 9.074(5), b = 24.97(1) and c = 2.899(2) Å. The shapes and dimensions of the channels are slightly modified as compared to NaMnTiO 4 with displaced alkali metal positions and occupancies. LiMnTiO 4 was cycled vs Li at room temperature and up to 0.89 lithium ions can be reversibly inserted into the structure, with a discharge capacity of 137 mAh/g after 20 cycles at C/20. At 60 • C all the lithium is removed at the end of the first charge at C/20, with subsequent cycles showing reversible insertion of 1.06 Li-ions. © The Author Lithium-ion batteries are widely used in consumer electronics. However, efficiency, rate capability, cost and safety are all still issues which limit the current use of Li-ion batteries. The limiting component in Li-ion batteries is the positive electrode and as such this has been the focus of much research. One of the most promising positive electrodes is LiFePO 4 which crystallizes in the olivine structure with Li ions in one dimensional channels. LiFePO 4 exhibits high thermal stability, is environmentally benign and has good electrochemical properties, reaching 90% of its theoretical capacity when coated with carbon.1,2 However, its relatively low operating voltage of 3.3 V, and its poor electronic conductivity leads to limitations when cycled at high rates and makes it suitable for low power applications only. Despite these factors, there has been an increased interest in cathode materials possessing one-dimensional channels due to the high stability upon lithiation and delithiation demonstrated by LiFePO 4 .One such material with one-dimensional channels is Na 0.44 MnO 2 . Na 0.44 MnO 2 is particularly interesting because of its large tunnels for sodium intercalation/deintercalation 4-10 which results in high capacities and rate performance. The structure of Na 0.44 MnO 2 is comprised of two and three leg chains of edge-sharing polyhedra which share corners to form a three-dimensional network with two crystallographically distinct tunnels along the z axis, as shown in Figure 1. The transitional metal oxide framework is complex having MO 6 /MO 5 polyhedra occupied by either Mn 3+ or Mn 4+ ions. This ordering is driven by the Jahn-Teller distortions from the d 4 Mn 3+ cations present in the structure. The Na-ions occupy sites in both the smaller, one dimensional (1D) and larger S-shaped channels with co-ordination to oxygen of 7 in the 1D channels and 6 and 7 in the S-shaped channels. The partial occupancy of Na + is reported to allow for the observed high capacities, enhanced ionic conductivity and rate performance. The lithiated analogue of Na 0.44 MnO 2 has been reported to have outstanding cycling at room temperature and 85• C, delivering 80 to 95% of the theoretical capacity, 131 mAh/g, with high rate d...

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confidence: 99%

LiMnTiO₄with the Na_0.44MnO₂Structure as a Positive Electrode for Lithium-Ion Batteries

Amigues¹,

Glass²

2015

J. Electrochem. Soc.

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“…Various Na-Mn oxides such as NaMn 1/3 Ni 1/3 Co 1/3 PO 4 [6], Na x Mn 5 O 10 [7], Na 2 Mn 5 O 10 [8], and Na 4 Mn 9 O 18 have been extensively researched as active materials in SIB systems due to the presence of the extensive channels for Na ion intercalation and deintercalation [9]. Among them, Na 4 Mn 9 O 18 exhibits the MnO 6 octahedra and MnO 5 square cone, which are able to constitute the wide S-type double tunnels for Na ion diffusion [10]. Whitacre et al reported the Na 4 Mn 9 O 18 as a positive electrode material for an aqueous sodium ion battery (ASIB), and this material cathode displayed a capacity of 45 mAh·g −1 at a current density of C/8 rate [11].…”

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Electrochemical Properties of an Na4Mn9O18-Reduced Graphene Oxide Composite Synthesized via Spray Drying for an Aqueous Sodium-Ion Battery

et al. 2017

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An aqueous sodium ion battery (ASIB) with metal Zn as anode and Na4Mn9O18-reduced graphene oxide (Na4Mn9O18-RGO) as cathode has been developed. In this work, spherical Na4Mn9O18-RGO composite particles were prepared via spray drying. The aqueous battery exhibits stable cyclability and high specific capacities. Typically, a high initial discharge capacity of 61.7 mAh·g−1 is attained at a high current rate of 4 C, and a stabilizing reversible capacity of 58.9 mAh·g−1 was obtained after 150 cycles. The network interlaced by RGO sheets provided fast electron conduction paths and structural stability to accommodate the mechanical stresses induced by sodium insertion and extraction, so the Na4Mn9O18-RGO electrode displayed superior electrochemical performance in the ASIB.

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“…1,2,3,4,5 However, a significant portion of the capacity lies above 4.4 V vs. Li/Li + , limiting the energy density attainable with conventional electrolytes. 6 Above 4.2 V a substantial increase of interfacial impedance has been reported that results in considerable power loss and arises from the formation of surface films due to electrolyte oxidation and LiPF 6 decomposition.…”

Section: Introductionmentioning

confidence: 99%

FTIR and Raman Study of the Li[sub x]Ti[sub y]Mn[sub 1−y]O[sub 2] (y=0, 0.11) Cathodes in Methylpropyl Pyrrolidinium Bis(fluoro-sulfonyl)imide, LiTFSI Electrolyte

Hardwick

Saint

Lucas

et al. 2009

J. Electrochem. Soc.

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Electrode Materials with the Na_0.44MnO₂ Structure: Effect of Titanium Substitution on Physical and Electrochemical Properties

Abstract: Partial titanium substitution of electrodes with the Na 0. 44

Cited by 44 publications

References 21 publications

LiMnTiO₄with the Na_0.44MnO₂Structure as a Positive Electrode for Lithium-Ion Batteries

LiMnTiO₄with the Na_0.44MnO₂Structure as a Positive Electrode for Lithium-Ion Batteries

Electrochemical Properties of an Na4Mn9O18-Reduced Graphene Oxide Composite Synthesized via Spray Drying for an Aqueous Sodium-Ion Battery

FTIR and Raman Study of the Li[sub x]Ti[sub y]Mn[sub 1−y]O[sub 2] (y=0, 0.11) Cathodes in Methylpropyl Pyrrolidinium Bis(fluoro-sulfonyl)imide, LiTFSI Electrolyte

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Electrode Materials with the Na0.44MnO2 Structure: Effect of Titanium Substitution on Physical and Electrochemical Properties

Abstract: Partial titanium substitution of electrodes with the Na 0. 44

Cited by 44 publications

References 21 publications

LiMnTiO4with the Na0.44MnO2Structure as a Positive Electrode for Lithium-Ion Batteries

LiMnTiO4with the Na0.44MnO2Structure as a Positive Electrode for Lithium-Ion Batteries

Electrochemical Properties of an Na4Mn9O18-Reduced Graphene Oxide Composite Synthesized via Spray Drying for an Aqueous Sodium-Ion Battery

FTIR and Raman Study of the Li[sub x]Ti[sub y]Mn[sub 1−y]O[sub 2] (y=0, 0.11) Cathodes in Methylpropyl Pyrrolidinium Bis(fluoro-sulfonyl)imide, LiTFSI Electrolyte

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Electrode Materials with the Na_0.44MnO₂ Structure: Effect of Titanium Substitution on Physical and Electrochemical Properties

LiMnTiO₄with the Na_0.44MnO₂Structure as a Positive Electrode for Lithium-Ion Batteries

LiMnTiO₄with the Na_0.44MnO₂Structure as a Positive Electrode for Lithium-Ion Batteries