Raman spectroscopic study of phase transitions in Li<sub>3</sub>PO<sub>4</sub>

Popović, L.; Manoun, Bouchaib; Waal, D. de; Nieuwoudt, Michél K.; Comins, J. D.

doi:10.1002/jrs.954

Cited by 71 publications

(41 citation statements)

References 14 publications

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“…A model structure obtained by tripling one of the parameters in the unit cell of the lowtemperature form (ˇ) 85 gives P-O bond lengths far outside the normal expected range for orthophosphates. Valence bond calculation showed that the structure was not reliable; 10 bond valence sums at the P atoms were in good agreement with expected formal oxidation state of P 5C for the first two forms (ˇand ), but not for the third form (˛). In order to gain an insight into its structure, phase transitions of Li 3 PO 4 were monitored by Raman spectroscopy.…”

Section: Applicationmentioning

confidence: 87%

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Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates

Popović

Waal

Boeyens

2005

J. Raman Spectrosc.

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142

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A linear empirical correlation was established between Raman stretching wavenumbers of phosphorus-oxygen bonds and their bond lengths in inorganic crystalline phosphates. Although established on samples of inorganic crystalline phosphates, the correlation can be applied to glassy and amorphous phosphate materials (GAMs). Their unpolarized vibrational spectra are often similar because they are determined largely by short-range order. The correlation was used to predict P -O bond length in the a-form of Li 3 PO 4 , which is stable over only a small range of temperatures below the melting-point. It can also be used to estimate the length of P -O single bonds, terminal P -O and O -P -O chain bonds and terminal double bonds in many technologically important amorphous materials containing phosphate groups. This correlation is expected to offer invaluable insight into the structures of phosphate species for which diffraction or other spectroscopic techniques provide incomplete structural information. That would enhance the value of Raman spectroscopy as a complementary technique in structural studies of phosphates.

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Section: Applicationmentioning

confidence: 87%

“…In order to gain an insight into its structure, phase transitions of Li 3 PO 4 were monitored by Raman spectroscopy. 10 The previously established correlation [Eqn (11), Fig. 1 Table 5).…”

Section: Applicationmentioning

confidence: 99%

Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates

Popović

Waal

Boeyens

2005

J. Raman Spectrosc.

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142

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“…Fortunately, there have been several reports of experimental measurements of Raman and infrared absorption spectra of crystalline Li 3 PO 4 (Tarte (1967); Harbach and Fischer (1974); Riedener et al (2000); Smith et al (2002); Mavrin et al (2003); Popović et al (2003)); therefore our simulations of the zone center phonon modes serve as a validity check the calculations. Figure 1 shows two similar but distinct crystal structures of Li 3 PO 4 for which the normal modes have been studied.…”

Section: Calculational Methodsmentioning

confidence: 96%

“…IV was taken from Ref. [Popović et al (2003)]. These are compared with calculated results using PAW and USPP formalisms and LDA and GGA exchange-correlation functionals.…”

Section: Calculational Methodsmentioning

confidence: 99%

First Principles Modeling of Electrolyte Materials in All-Solid-State Batteries

Holzwarth

2014

Physics Procedia

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“…15,16 The β form is also stable but it irreversibly transforms to the γ phase at high temperatures (400-600 • C). [17][18][19] The γ-Li 3 PO 4 has an orthorhombic Pnma structure (#62), which is similar to the well-studied olivine cathode materials: LiFePO 4 , FePO 4 , etc. 20 There has been some theoretical research on β and γ-Li 3 PO 4 solid electrolytes.…”

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confidence: 95%

Electrode-Electrolyte Interface for Solid State Li-Ion Batteries: Point Defects and Mechanical Strain

Longo

Xiong

et al. 2014

J. Electrochem. Soc.

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In this work, we present an ab-initio investigation of point defects in solid electrolyte γ-Li 3 PO 4 and in negative electrode-electrolyte interface (Li/γ-Li 3 PO 4 ). Our results on Li defects on γ-Li 3 PO 4 exhibit that Li interstitial defects dominate over vacancy defects, and that Li vacancy-interstitial pair defect formation energy in the interface is comparable to the sum of Li vacancy defect in the electrode and Li ion interstitial defects in the electrolyte region. Our study reveals that the high Li ion defect formation energy is the determining factor for the low ionic conductivity across Li metal/electrolyte interface. Moreover, in a realistic interface, the mechanical strain at the interface increases with the concentration of the impurities produced as a result of the cycling of the battery or due to surface impurities, also affecting the electrostatic potential and charge distribution. Thus, the study of the Li metal/electrolyte interface provides information on the defect formation and mechanical stability and, hence, it helps to understand the realistic modeling of the interface as a way to improve the ionic conductivity and stability of future solid state Li-ion batteries.There have been intense research activities focused on improving energy and power densities of Li-ion batteries for future applications in various micro devices. 1 A lot of research has been dedicated to understand the conduction phenomenon in all components of the Li-ion cell; cathode, electrolyte and anode. Among various electrolytes, solid electrolytes have several advantages over the currently used liquid and polymer electrolytes for microelectronics applications. 2-6 Recently, lithium phosphorous oxynitride (LiPON), which was developed and studied by Oak Ridge National Laboratory, has been adopted as an electrolyte in thin-film batteries 7-10 The Li 3 PO 4 is one of the natural and synthetic crystalline materials of the LiPON family. We know that, to be an ideal solid electrolyte, it must have high ionic and low electronic conductivities; it should be permeable to Li ions (Li + ) and impermeable to electrons from/to the electrodes. These electrolytes are important due to their stability in general and with the interfaces formed with cathode and anode materials in particular. LiPON are found to be suitable to use in thin films because of their chemical and physical stability. However, the main hindrance of solid electrolytes for the commercial use in new applications is their low ionic conductivity, which results in relatively low energy output of the Li-ion battery. [11][12][13][14] As previously mentioned in the literature, Li 3 PO 4 has three crystalline forms, labeled as α, β, and γ. 15,16 The crystal structure of α-Li 3 PO 4 has not been fully determined yet, while the crystal structures of β-and γ-Li 3 PO 4 are already well known. Both β-and γ-Li 3 PO 4 have been observed by several experimental groups, but the activated transport measurements have been limited to the γ-Li 3 PO 4 phase. 15,16 The β form is also stable ...

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Raman spectroscopic study of phase transitions in Li₃PO₄

Cited by 71 publications

References 14 publications

Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates

Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates

First Principles Modeling of Electrolyte Materials in All-Solid-State Batteries

Electrode-Electrolyte Interface for Solid State Li-Ion Batteries: Point Defects and Mechanical Strain

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Raman spectroscopic study of phase transitions in Li3PO4

Cited by 71 publications

References 14 publications

Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates

Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates

First Principles Modeling of Electrolyte Materials in All-Solid-State Batteries

Electrode-Electrolyte Interface for Solid State Li-Ion Batteries: Point Defects and Mechanical Strain

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Raman spectroscopic study of phase transitions in Li₃PO₄