New Cathode Materials for Rechargeable Lithium Batteries: The 3-D Framework Structures Li3Fe2(XO4)3(X=P, As)

Masquelier, Christian; Padhi, A. K.; Nanjundaswamy, K. S.; Goodenough, John B

doi:10.1006/jssc.1997.7629

Cited by 302 publications

(262 citation statements)

References 17 publications

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“…Hence, on the basis of the higher valence redox couple, one would expect the potentials in the silicates to be higher than those in the phosphates. In addition, the anion group can also affect the potential through its hybridization with the transition metal [1,29,30]. Our results confirm that the potential of the silicate olivines (Fig.…”

Section: Resultssupporting

confidence: 84%

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

Zhou

Cococcioni

Kang

et al. 2004

Electrochemistry Communications

417

315

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The Li intercalation potential of LiMPO 4 and LiMSiO 4 compounds with M = Fe, Mn, Co, and Ni is computed with the GGA+U method. It is found that this approach is considerably more accurate than standard LDA or GGA methods. The calculated potentials for LiFePO 4 , LiMnPO 4 and LiCoOPO 4 agree to within 0.1 V with experimental results. The LiNiPO 4 potential is predicted to be above 5 V. The potentials of the silicate materials are all found to be rather high, but LiFeSiO 4 and LiCoSiO 4 have negligible volume change upon Li extraction.Keywords: Battery cathode; Density functional theory; LDA+U; Olivine; Redox potential Introduction First principles computations have shown to be relevant for predicting many of the properties of Li-insertion materials used as electrodes in rechargeable Li batteries [1][2][3][4][5][6][7][8][9]. One of the critical properties for a Li intercalation material is the potential at which Li can be removed and inserted. While a high potential increases the energy density of the material, if this potential is too high, Li can not be practically removed, and side reactions such as electrolyte breakdown, can occur in the cell. A low potential can also lead to moisture sensitivity of the electrode material. Hence, knowledge of the thermodynamic potential is one crucial aspect when determining whether new materials can be used as cathode materials in rechargeable lithium batteries. In this communication, we predict the potential of LiNiPO 4 , LiMnSiO 4 , LiFeSiO 4 , LiCoSiO 4 and LiNiSiO 4 using the highly accurate GGA+U method.The electrochemical activity of LiFePO 4 [10] and Li 3 V 2 (PO 4 ) 3 [11][12][13][14] has spawned considerable interest in materials with poly-anion groups, as they may be considerably more stable than close-packed oxides at the end of charging. Currently, LiFePO 4 and Li 3 V 2 (PO 4 ) 3 are of commercial interest, though the rather low potential of LiFePO 4 gives it too low an energy density to compete with layered oxides in applications where volumetric or gravimetric energy density is most important. In this communication we use ab-initio computations to predict the potential of other phosphates and silicates in the olivine structure. While ab-initio methods have previously been used to predict the potential of insertion electrodes, we use a more accurate quantum mechanical approach in this work, allowing us to predict the insertion potentials within 0.1-0.2V. We find that of the compounds investigated, LiFePO 4 actually has the lowest potential. Among the phosphate compounds, the potential of LiNiPO 4 is found to be too high to be of practical interest. LiMnSiO 4 , LiFeSiO 4 , LiCoSiO 4 and LiNiSiO 4 also have high potentials, with only the Mn and Fe material just below 5V.

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Section: Resultssupporting

confidence: 84%

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

Zhou

Cococcioni

Kang

et al. 2004

Electrochemistry Communications

417

315

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“…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.

151

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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...

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“…[1] For example, Li3V2(PO4)3 has been proposed as a benchmark providing promising results. [2] Li3Fe2(PO4)3 as an iron-based alternative is another interesting candidate with NASICON structure, which can host up to 1.8 additional Li + ions (redox couple of Fe 3+ /Fe 2+ ) with great reversibility and a lithiation plateau at 2.8 V. [3][4][5][6][7] However, reversible delithiation of Li3Fe2(PO4)3 at high potentials has not yet been successfully achieved. In this work, we will exploit the possible lithium extraction from Li3Fe2(PO4)3 using a combined computational and spectroscopy analysis.…”

mentioning

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Charge Localization in the Lithium Iron Phosphate Li₃Fe₂(PO₄)₃ at High Voltages in Lithium‐Ion Batteries

et al. 2015

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Possible changes in the oxidation state of the oxygen ion in the lithium iron phosphate Li3Fe2(PO4)3 at high voltages in lithium‐ion (Li‐ion) batteries are studied using experimental and computational analysis. Results obtained from synchrotron‐based hard X‐ray photoelectron spectroscopy and density functional theory (DFT) show that the oxidation state of O2− ions is altered to higher oxidation states (Oδ−, δ<2) upon charging Li3Fe2(PO4)3 to 4.7 V.

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New Cathode Materials for Rechargeable Lithium Batteries: The 3-D Framework Structures Li3Fe2(XO4)3(X=P, As)

Cited by 302 publications

References 17 publications

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

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

Charge Localization in the Lithium Iron Phosphate Li₃Fe₂(PO₄)₃ at High Voltages in Lithium‐Ion Batteries

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New Cathode Materials for Rechargeable Lithium Batteries: The 3-D Framework Structures Li3Fe2(XO4)3(X=P, As)

Cited by 302 publications

References 17 publications

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M=Fe, Mn, Co, Ni

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

Charge Localization in the Lithium Iron Phosphate Li3Fe2(PO4)3 at High Voltages in Lithium‐Ion Batteries

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Product

Resources

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

Charge Localization in the Lithium Iron Phosphate Li₃Fe₂(PO₄)₃ at High Voltages in Lithium‐Ion Batteries