Structure and ionic conduction study on Li3PO4 and LiPON (Lithium phosphorous oxynitride) with the Density-Functional Tight-Binding (DFTB) method

Li, Junchao; Wei, Lai

doi:10.1016/j.ssi.2020.115329

Cited by 9 publications

(13 citation statements)

References 38 publications

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“…This is due to the overall reduced anion charge of [P 2 O 6 N] 5− in comparison to two [PO 4 ] 3− that exerts smaller coulombic attraction on Li + and thereby enables higher Li + mobility. Instead of these beneficial double tetrahedra, the structure contains even more highly charged [PO 3 N] 4− and [PO 2 N 2 ] 5− , as well as isolated O 2− that was also shown to decrease Li + ion mobility due to larger electrostatic interaction [18,45] …”

Section: Resultsmentioning

confidence: 99%

Comprehensive Investigation of Anion Species in Crystalline Li⁺ ion Conductor Li_27−x[P₄O_7+xN_9−x]O₃ (x≈1.9(3))

Schneider

Wendinger

Baran

et al. 2023

Chemistry A European J

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The Li + ion conductor Li 27 À x [P 4 O 7 + x N 9 À x ]O 3 (x � 1.9) has been synthesized from P 3 N 5 , Li 3 N and Li 2 O in a Ta ampoule at 800 °C under Ar atmosphere. The cubic compound crystallizes in space group I43d with a = 12.0106(14) Å and Z = 4. It contains both non-condensed [PO 2 N 2 ] 5À and [PO 3 N] 4À tetrahedra as well as O 2À ions, surrounded by Li + ions. Charge neutrality is achieved by partial occupancy of Li positions, which was refined with neutron powder diffraction data. Measurements of the partial ionic and electronic conductivity show a total ionic conductivity of 6.6 × 10 À 8 S cm À 1 with an activation energy of 0.46 � 0.02 eV and a bulk ionic conductivity of 4 × 10 À 6 S cm À 1 at 25 °C, which is close to the ionic conductivity of amorphous lithium nitridophosphate. This makes Li 27 À x [P 4 O 7 + x N 9 À x ]O 3 an interesting candidate for investigation of structural factors affecting ionic conductivity in lithium oxonitridophosphates.x N 1 + x with pairs of corner-sharing tetrahedra [P 2 O 6 N] 5À with a bridging N atom has been reported. [21] Crystalline lithium [a] S.

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Section: Resultsmentioning

confidence: 99%

Comprehensive Investigation of Anion Species in Crystalline Li⁺ ion Conductor Li_27−x[P₄O_7+xN_9−x]O₃ (x≈1.9(3))

Schneider

Wendinger

Baran

et al. 2023

Chemistry A European J

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“…Hotcent and TANGO codes provide default values for any other parameter not explicitly described here. This methodology has also been used by other authors to parametrize the Al–O interaction in ultrathin films; , applied to Li–P, Li–O, and Li–N to study the structural and dynamical properties of crystalline and amorphous lithium phosphorus oxynitride; and used to study diffusion and conduction in lithium garnet oxides . It has also been used to perform nonadiabatic molecular dynamics of PAH-related complexes …”

Section: Methodsmentioning

confidence: 99%

Density Functional Tight-Binding Model for Lithium–Silicon Alloys

et al. 2023

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The predictive power of molecular dynamic simulations is mainly restricted by the time scale and model accuracy. Many systems of current relevance are of such complexity that they require addressing both issues simultaneously. This is the case of silicon electrodes in Li-ion batteries, where different Li x Si alloys are formed during charge/discharge cycles. While first-principles treatments for this system are seriously limited by the computational cost of exploring its large conformational space, classical force fields are not transferable enough to represent it accurately. Density Functional Tight Binding (DFTB) is an intermediate complexity approach capable of capturing the electronic nature of different environments with a relatively low computational cost. In this work, we present a new set of DFTB parameters suited to model amorphous Li x Si alloys. Li x Si is the usual finding upon cycling the Si electrodes in the presence of Li ions. The model parameters are constructed with a particular emphasis on their transferability for the entire Li x Si composition range. This is achieved by introducing a new optimization procedure that weights stoichiometries differently to improve the prediction of their formation energies. The resulting model is shown to be robust for predicting crystal and amorphous structures for the different compositions, giving excellent agreement with DFT calculations and outperforming state-of-the-art ReaxFF potentials.

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“…18,19 This enhancement is ascribed to the presence of N bridges at high Li + contents, which favors the mobility of Li and effectively renders P/O/N immobility. 17,20 Thus, controlling the nitrogen content is key to achieving a higher ionic conductivity. 21,22 Both computational and experimental studies have demonstrated that amorphous rather than crystalline LiPON is a better Li conductor attributed to increases in diffusion/conduction due to reduction of overall electrostatic interactions and higher disorder within the material.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, studies show that N doping of the O site in Li 3 PO 4 promotes faster Li diffusion and improves electrochemical stability attributed to introduction of disorder and decreases in electrostatic energy. , The room temperature ionic conductivity of amorphous LiPON (∼3 × 10 –6 ) is 2 orders of magnitude greater than Li 3 PO 4 . , This enhancement is ascribed to the presence of N bridges at high Li + contents, which favors the mobility of Li and effectively renders P/O/N immobility. , …”

Section: Introductionmentioning

confidence: 99%

“…Thus, controlling the nitrogen content is key to achieving a higher ionic conductivity. , Both computational and experimental studies have demonstrated that amorphous rather than crystalline LiPON is a better Li conductor attributed to increases in diffusion/conduction due to reduction of overall electrostatic interactions and higher disorder within the material. ,,, Recently, we demonstrated that the introduction of Si into Li x PON polymer electrolytes enhances ionic conductivity and lowers the activation energy of the polymer electrolyte (Li x SiPON) by shortening the distance between Li + binding sites. , With this background, here we investigate the effect of N introduction into amorphous Li 4 SiO 4 -like polymer analogs.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical Performance of Li_xSiON Polymer Electrolytes Derived from an Agriculture Waste Product, Rice Hull Ash

Temeche

Zhang

Laine

2021

ACS Appl. Polym. Mater.

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The electrochemical performance of Li x SiON (x = 2, 4, and 6) polymer electrolytes derived from the agricultural waste, rice hull ash (RHA, 80−90 wt % SiO 2 ), is reported. Silica can be extracted from RHA by base-catalyzed reaction with hexylene glycol forming the spirosiloxane [(C 6 H 12 O 2 ) 2 Si, SP] that distills from the reaction solution. Li x SiON polymer electrolytes form on reacting SP with xLiNH 2 , offering a low-cost, lowtemperature, and green synthesis route. The effect of N and Li + concentrations in the polymer electrolytes are correlated with ionic and electrical conductivity. X-ray photoelectron spectroscopy studies confirm that N and Li contents increase with increasing LiNH 2 content. The amorphous nature and high Li + contents of the Li 6 SiON electrolyte provide an optimal ionic conductivity (6.5 × 10 −6 ) at ambient temperature when coated on Celgard. Furthermore, the Li x SiON polymer electrolytes offer high Li + transference numbers (∼0.75−1), enabling assembly of Li symmetric cells with high critical current densities (3.75 mA cm −2 ). Finally, Li-SPAN (sulfurized, carbonized polyacrylonitrile) half-cells with Li 6 SiON polymer electrolytes deliver discharge capacities of ∼765 and 725 mAh/g at 0.25 and 0.5 C rates over 50 cycles.

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Structure and ionic conduction study on Li3PO4 and LiPON (Lithium phosphorous oxynitride) with the Density-Functional Tight-Binding (DFTB) method

Cited by 9 publications

References 38 publications

Comprehensive Investigation of Anion Species in Crystalline Li⁺ ion Conductor Li_27−x[P₄O_7+xN_9−x]O₃ (x≈1.9(3))

Comprehensive Investigation of Anion Species in Crystalline Li⁺ ion Conductor Li_27−x[P₄O_7+xN_9−x]O₃ (x≈1.9(3))

Density Functional Tight-Binding Model for Lithium–Silicon Alloys

Electrochemical Performance of Li_xSiON Polymer Electrolytes Derived from an Agriculture Waste Product, Rice Hull Ash

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Structure and ionic conduction study on Li3PO4 and LiPON (Lithium phosphorous oxynitride) with the Density-Functional Tight-Binding (DFTB) method

Cited by 9 publications

References 38 publications

Comprehensive Investigation of Anion Species in Crystalline Li+ ion Conductor Li27−x[P4O7+xN9−x]O3 (x≈1.9(3))

Comprehensive Investigation of Anion Species in Crystalline Li+ ion Conductor Li27−x[P4O7+xN9−x]O3 (x≈1.9(3))

Density Functional Tight-Binding Model for Lithium–Silicon Alloys

Electrochemical Performance of LixSiON Polymer Electrolytes Derived from an Agriculture Waste Product, Rice Hull Ash

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Comprehensive Investigation of Anion Species in Crystalline Li⁺ ion Conductor Li_27−x[P₄O_7+xN_9−x]O₃ (x≈1.9(3))

Comprehensive Investigation of Anion Species in Crystalline Li⁺ ion Conductor Li_27−x[P₄O_7+xN_9−x]O₃ (x≈1.9(3))

Electrochemical Performance of Li_xSiON Polymer Electrolytes Derived from an Agriculture Waste Product, Rice Hull Ash