A nasicon-type phase as intercalation electrode: NaTi2(PO4)3

Delmas, Claude; Cherkaoui, F.; Nadiri, A.; Hagenmuller, Paul

doi:10.1016/0025-5408(87)90112-7

Cited by 229 publications

(168 citation statements)

References 8 publications

Supporting

Mentioning

156

Contrasting

Unclassified

Order By: Relevance

“…34 In 1987 and 1988, Delmas et al demonstrated that NASICON-type compounds, NaTi 2 (PO 4 ) 3 , can be electrochemically active with Na in a reversible manner. 26,27 Later NaNbFe(PO 4 ) 3 , Na 2 TiFe(PO 4 ) 3 and Na 2 TiCr(PO 4 ) 3 were explored. 29À31 Since then, most studies of this family of compounds were focused on Li-ion batteries, because the cell performance was generally poor in Na-ion batteries.…”

Section: Polyanion Compoundsmentioning

confidence: 99%

Recent Advances in Sodium Intercalation Positive Electrode Materials for Sodium Ion Batteries

Lee

Meng

2013

Funct. Mater. Lett.

View full text Add to dashboard Cite

Significant progress has been achieved in the research on sodium intercalation compounds as positive electrode materials for Na-ion batteries. This paper presents an overview of the breakthroughs in the past decade for developing high energy and high power cathode materials. Two major classes, layered oxides and polyanion compounds, are covered. Their electrochemical performance and the related crystal structure, solid state physics and chemistry are summarized and compared.

show abstract

Section: Polyanion Compoundsmentioning

confidence: 99%

Recent Advances in Sodium Intercalation Positive Electrode Materials for Sodium Ion Batteries

Lee

Meng

2013

Funct. Mater. Lett.

View full text Add to dashboard Cite

show abstract

“…offer a wide compositional variety exhibiting a NASICON-type structure. [16][17][18] Among them, Na 3 V 2 (PO 4 ) 3 has demonstrated interesting properties as a cathode material because of the high operating voltage and good cyclability. [19][20][21][22] Multivalent vanadium atom lends a significant electronic conductivity which promotes the chemical diffusion of sodium ions to this compound.…”

mentioning

confidence: 99%

Effect of Iron Substitution in the Electrochemical Performance of Na₃V₂(PO₄)₃as Cathode for Na-Ion Batteries

Aragón

Lavela

Ortiz

2015

J. Electrochem. Soc.

145

View full text Add to dashboard Cite

Na 3 V 2-x Fe x (PO 4 ) 3 /C (0 ≤ x ≤ 0.5) samples were prepared by a simple sol-gel method. X-ray diffraction patterns revealed high purity and crystalline phosphate indexed in the R-3c space group. On increasing the iron content, the cell volume increases due to the slightly higher radius of Fe 3+ . Cyclic voltammetry showed two signals at ca. 3.5 and 4.0 V, which evidence a linear dependence of potential on the level of substitution. The appearance of the short plateau at ca. 4.0 V is closely related to the higher iron substitution levels. The evaluation of XPS and 57 Fe Mössbauer spectra of charged and discharged electrodes allow ascribing the 4.0 V plateau to V 4+ /V 5+ redox reaction and the extraction/insertion of extra sodium ions from octahedral M1 sites. Galvanostatic cycling showed capacity values as high as 115 mA h g −1 for samples with x = 0.1, 0. Now that lithium-ion battery (LIB) technology is reaching maturity, a number of reports are advising for the future scarcity of the lithium resources. A full implementation of LIB in the electric vehicle market would involve important constraints on Li production and an undesirable increase of the cost of Li is expected at the long term.1-4 For these reasons, market is alternatively looking forward beyond LIB and new chemistries are being explored. [5][6][7][8] Sodium is an abundant and non-toxic alkali element which can be implemented in insertion based batteries. The electrochemical principles are identical to those of lithium batteries. In fact, a number of recent reports have demonstrated the reliability of sodium batteries to provide reversible energy storage devices. [9][10][11][12] Nevertheless, the larger ionic radius and atomic weight leads to a less performing behavior. Thus, low theoretical capacity and cell voltage, slow diffusion, high unit cell volume change and hence structural impact are detected in electrodes subjected to sodium insertion. Recently, Ceder et al. have reported that the lower voltage for sodium insertion is predominantly a cathodic effect because of the diminished energy gain when inserting this alkaline ion into the host structure. Also, they pointed out to open structures, as layered and NASICON ones, as the most favored frameworks to provide phase stability on cycling. 13 The optimistic arguments promoting these cathode materials are mainly based on an easy transfer reaction of less solvated large ions and high sodium conductivity. 14,15 In this regard, transition metal phosphates with general stoichiometry A x B 2 (PO 4 ) 3 (A: Li + , Na + , etc; B: Fe 3+ , V 3+ , Ti 4+ .) offer a wide compositional variety exhibiting a NASICON-type structure. [16][17][18] Among them, Na 3 V 2 (PO 4 ) 3 has demonstrated interesting properties as a cathode material because of the high operating voltage and good cyclability. [19][20][21][22] Multivalent vanadium atom lends a significant electronic conductivity which promotes the chemical diffusion of sodium ions to this compound. Nevertheless, the electronic conductivity is not high enoug...

show abstract

“…With each electrolyte the cell could deliver discharge capacity of around 110-115 mAh/g, quite close to the 120 mAh/g storage capacity of NaTi 2 (PO 4 ) 3 /C in sodium cells reported previously. [10][11][12][13] However, polarization was found to be least with the 0305 electrolyte (≈0.343 V): attractively flat chargedischarge plateaus were obtained with this electrolyte. From cycling stability viewpoint, the 0305 electrolyte outperformed the other two with no capacity fade over 40 cycles; the cells using 0105 and 0505 electrolytes displayed rapid capacity fade within 15 cycles (see Figure 1b).…”

Section: Resultsmentioning

confidence: 99%

“…The latter point is pertinent as the NaTi 2 (PO 4 ) 3 /C//Mg cell operated at higher overpotential than would be expected strictly from thermodynamic considerations: a NaTi 2 (PO 4 ) 3 /C//Mg cell using dual-salt electrolyte should show its charge-discharge curves at 0.34 V lower than that seen for NaTi 2 (PO 4 ) 3 //Na cells (2.1 V vs Na/Na + ). [10][11][12][13] Hence the expected operating potential should be 1.76 V, however the observed average potential was 1.42 V (vs Mg/Mg 2+ ). Firstly, Figure 2a confirmed that scratching the Mg foil with sandpaper was effective in removing the oxide passivation layer found in pristine Mg foils:…”

Section: Resultsmentioning

confidence: 99%

Communication—Mg(TFSI)₂-Based Hybrid Magnesium-Sodium Electrolyte: Case Study with NaTi₂(PO₄)₃//Mg Cell

Rudola¹,

Azmansah²,

Balaya³

2018

J. Electrochem. Soc.

View full text Add to dashboard Cite

Currently, only two types of hybrid Mg-Na electrolytes are known. Herein, we report a new hybrid Mg-Na electrolyte, based on Mg(TFSI) 2 and NaBF 4 salts in diglyme solvent, which engenders non-dendritic cycling of Mg metal when used in hybrid Mg-Na cells. Using NaTi 2 (PO 4 ) 3 as sodium intercalation-type cathode, NaTi 2 (PO 4 ) 3 /C vs Mg cell delivered discharge capacity approaching 120 mAh/g with flat plateau at 1.25 V vs Mg/Mg 2+ , along with relatively good rate performance and cycling stability. © 2018 The Electrochemical Society. [DOI: 10.1149/2.1091805jes] Manuscript submitted December 18, 2017; revised manuscript received March 30, 2018. Published April 7, 2018 Recently, different 'hybrid batteries' have gained attention as they combine benefits of different battery chemistries such as Mg//LiFePO 4 , Zn//LiMn 2 O 4 etc.1,2 Hybrid batteries based on Mg and Na chemistries may be particularly attractive from cost perspective as both Mg and Na resources are earth-abundant while Li resources are scarcer and current Li-ion cathodes production expensive. Such hybrid magnesium-sodium batteries (HMNBs) offer the benefits of high volumetric/gravimetric specific capacity associated with Mg metal as anode (3833 mAh/cm 3 /2234 mAh/g), while also enjoying the kinetically facile Na-ion cathodes.1 This is because such HMNBs operate by reversible Mg plating/stripping at Mg anode and Na + extraction/insertion at the cathode during each charge/discharge cycle.1 Due to higher reduction potential of Mg/Mg 2+ vs Na/Na + redox couple (−2.37 V for Mg/Mg 2+ and −2.71 V for Na/Na + vs S.H.E), Mg 2+ (and not Na + ) will reduce first at the anode thus getting plated during charging and correspondingly getting stripped during discharging upon oxidation. HMNBs also ensures much higher specific energy density vs that of Na metal batteries (for same cathode) on account of the higher volumetric/gravimetric specific capacity of Mg metal as anode vs that of Na metal as anode (1128 mAh/cm 3 /1166 mAh/g). The lynchpin for the HMNB concept is the dual-salt electrolyte which enables simultaneous transport of Na + and Mg 2+ ions. HMNBs were first reported by Walter et al. using FeS 2 as Na-ion cathode, Mg metal as anode and borohydride salts (Mg(BH 4 ) 2 and NaBH 4 ) in diethylene glycol dimethyl ether (diglyme) as dual-salt electrolyte.3 Afterwards, there have been three other reports of HMNBs using either borohydrides-based electrolyte and TiS 2 cathode, 4 or [Mg 2 Cl 2 ][AlCl 4 ] 2 and NaAlCl 4 in dimethoxyethane (monoglyme) electrolyte and either Na 3 V 2 (PO 4 ) 3 or FeFe(CN) 6 cathode. 5,6 These reports demonstrated good cycling performance of HMNBs.In this contribution, we investigated dual-salt HMNB electrolytes based on magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2 ) as Mg(TFSI) 2 -based electrolytes have been reported to be good candidates for rechargeable Mg batteries with good cycle life till 100 cycles. 7,8 The observed cycling performance of a novel HMNB configuration, NaTi 2 (PO 4 ) 3 /C vs Mg (NaTi 2 (PO 4 ) 3 /C//...

show abstract

A nasicon-type phase as intercalation electrode: NaTi2(PO4)3

Cited by 229 publications

References 8 publications

Recent Advances in Sodium Intercalation Positive Electrode Materials for Sodium Ion Batteries

Recent Advances in Sodium Intercalation Positive Electrode Materials for Sodium Ion Batteries

Effect of Iron Substitution in the Electrochemical Performance of Na₃V₂(PO₄)₃as Cathode for Na-Ion Batteries

Communication—Mg(TFSI)₂-Based Hybrid Magnesium-Sodium Electrolyte: Case Study with NaTi₂(PO₄)₃//Mg Cell

Contact Info

Product

Resources

About

A nasicon-type phase as intercalation electrode: NaTi2(PO4)3

Cited by 229 publications

References 8 publications

Recent Advances in Sodium Intercalation Positive Electrode Materials for Sodium Ion Batteries

Recent Advances in Sodium Intercalation Positive Electrode Materials for Sodium Ion Batteries

Effect of Iron Substitution in the Electrochemical Performance of Na3V2(PO4)3as Cathode for Na-Ion Batteries

Communication—Mg(TFSI)2-Based Hybrid Magnesium-Sodium Electrolyte: Case Study with NaTi2(PO4)3//Mg Cell

Contact Info

Product

Resources

About

Effect of Iron Substitution in the Electrochemical Performance of Na₃V₂(PO₄)₃as Cathode for Na-Ion Batteries

Communication—Mg(TFSI)₂-Based Hybrid Magnesium-Sodium Electrolyte: Case Study with NaTi₂(PO₄)₃//Mg Cell