Tin Phosphate Electrode Materials Prepared by the Hydrolysis of Tin Halides for Application in Lithium Ion Battery

Edfouf, Zineb; Aragón, M.J.; León, Bernardo; Vicente, C.; Tirado, J.L.

doi:10.1021/jp809932k

Cited by 11 publications

(6 citation statements)

References 25 publications

(55 reference statements)

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“…49 Similar EIS graphs are found in Sn, Si-containing compounds. [49][50][51][52][53] The EIS data after 25th cycles show almost the same tendency as the first cycle with only little changes in both the SEI film resistance and charge transfer resistance value. These results further improved the theory that the germanium incorporated in the Li 3 PO 4 matrix is electrochemically stable and reversible during the Li-Ge alloying and dealloying.…”

Section: Resultsmentioning

confidence: 98%

NASICON-Structured LiGe₂(PO₄)₃ with Improved Cyclability for High-Performance Lithium Batteries

et al. 2009

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LiGe 2 (PO 4 ) 3 (LGP) with a NASICON structure is synthesized through the solid state method. Well-crystallized LGP obtained at 900°C shows a total lithium (Li) ion conductivity of 7.2 × 10 -7 S/cm. For the first time, the Li reversible capability of bulk LGP is measured to be 460 mAh/g at a charge rate of 150 mA/g in the voltage range from 0.001 to 1.5 V. Very good capacity retention of 92% after 25 cycles is achieved in comparison to 28% of GeO 2 . At a very high charge rate of 1500 mA/g the LGP reveals excellent capacity retention of 77% after 1000 cycles. The average discharge and charge plateau is in the range from 0 to 0.4 V vs. Li. Mechanisms for the improved cycling performance of the LGP in comparison with GeO 2 are discussed, suggesting that Li 3 PO 3 acts as a more stable and conductive inactive matrix to buffer volume expansion during Li alloying. Our results may suggest a direction to design better material systems with a combination of active and inactive materials.

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Section: Resultsmentioning

confidence: 98%

NASICON-Structured LiGe₂(PO₄)₃ with Improved Cyclability for High-Performance Lithium Batteries

et al. 2009

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“…Seeking novel materials in Li-ion battery applications attracts the most interest in recent experimental [25][26][27][28] and theoretical work. [29][30][31] In this contribution, our calculations suggest an overall strategy to design the Li-ion battery materials by systematically investigating the Li-intercalated structure evolution, Li diffusion barrier, and Li-host physics.…”

Section: Discussionmentioning

confidence: 99%

Mo−S−I Nanowires: A Promising Anode Material for Lithium-Ion Batteries. A First-Principles Study

2009

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One of the important issues in the development of new Li-ion battery technologies is to seek novel electrode materials with higher energy densities and a faster charge-discharge process. Using the first-principles calculations based on density functional theory, we systematically study the lithium interaction with the recently reported inorganic Mo 12 S 9 I 9 nanowires. Eleven initial Li positions are optimized to identify the rich energetically preferable sites for Li adsorption in the nanowire at the sulfur bridge planes and on the nanowire between dressing S and I atoms. The charge density and the electronic band structure are calculated to investigate the Li-host physics. Using the climbing image nudged elastic band method, we obtain that the diffusion barrier for Li migration into the Mo 12 S 9 I 9 nanowire is 0.86 eV, which is far lower than that of Li diffusion into the carbon nanotube through the sidewall (about 10 eV [Meunier et al. Phys. ReV. Lett. 2002, 88, 075506.]). These results indicate that the Mo 12 S 9 I 9 nanowire will be a promising candidate material for anodes in Li-ion battery application.

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“…In that case, it was proposed that the matrix is formed by alkali phosphates 9,12 as observed for other tin phosphates such as Sn 2 ClPO 4 , 19 SnHPO 4 , 19−21 or Sn 2 P 2 O 7 . 22 However, no operando techniques were used to follow the reaction mechanisms and the effect of the phosphate-based matrix to maintain the dispersion.…”

Section: Introductionmentioning

confidence: 99%

“…For both LiSn 2 (PO 4 ) 3 and NaSn 2 (PO 4 ) 3 , the observed two-step voltage profiles of the first discharge suggest similar transformations of the pristine material followed by Li–Sn alloying reactions, providing high capacity. In that case, it was proposed that the matrix is formed by alkali phosphates , as observed for other tin phosphates such as Sn 2 ClPO 4 , SnHPO 4 , − or Sn 2 P 2 O 7 . However, no operando techniques were used to follow the reaction mechanisms and the effect of the phosphate-based matrix to maintain the dispersion.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Performance and Mechanisms of NaSn₂(PO₄)₃/C Composites as Anode Materials for Li-Ion Batteries

et al. 2018

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NaSn2(PO4)3/C composites obtained by solid-state and pyrolysis reactions present high capacity retention and high-rate capability as anode materials for Li-ion batteries. The structure of NaSn2(PO4)3 was analyzed by combining X-ray diffraction and density functional theory to confirm the R3̅ space group. The composite is formed by submicrometer particles with a cube-like shape coated by pyrolytic carbon that improves the electronic percolation. The 119Sn Mössbauer spectroscopy shows the existence of Sn4+ with a more ionic character than SnO2, which can be related to the inductive effect of the phosphate groups. This technique was used in the operando mode to follow the reaction with lithium during the first discharge that is a crucial step for improving the performance. A two-step mechanism has been identified that consists of the irreversible transformation of the pristine material into Sn0 species for the first half of the discharge followed by reversible Li–Sn alloying reactions. The Mössbauer spectra of the Sn0 species differ from the spectrum of βSn because of their nanosize and the existence of chemical bonds with the sodium phosphate matrix formed during the conversion reaction. The first part of the discharge should be considered as a restructuration of the pristine material leading to the dispersion of Sn0 small particles in strong interaction with the phosphate matrix and providing good cyclability. Such a mechanism strongly differs from the insertion mechanism of NaTi2(PO4)3/C that contains a transition metal with the same oxidation state as Sn4+.

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Tin Phosphate Electrode Materials Prepared by the Hydrolysis of Tin Halides for Application in Lithium Ion Battery

Cited by 11 publications

References 25 publications

NASICON-Structured LiGe₂(PO₄)₃ with Improved Cyclability for High-Performance Lithium Batteries

NASICON-Structured LiGe₂(PO₄)₃ with Improved Cyclability for High-Performance Lithium Batteries

Mo−S−I Nanowires: A Promising Anode Material for Lithium-Ion Batteries. A First-Principles Study

Electrochemical Performance and Mechanisms of NaSn₂(PO₄)₃/C Composites as Anode Materials for Li-Ion Batteries

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Tin Phosphate Electrode Materials Prepared by the Hydrolysis of Tin Halides for Application in Lithium Ion Battery

Cited by 11 publications

References 25 publications

NASICON-Structured LiGe2(PO4)3 with Improved Cyclability for High-Performance Lithium Batteries

NASICON-Structured LiGe2(PO4)3 with Improved Cyclability for High-Performance Lithium Batteries

Mo−S−I Nanowires: A Promising Anode Material for Lithium-Ion Batteries. A First-Principles Study

Electrochemical Performance and Mechanisms of NaSn2(PO4)3/C Composites as Anode Materials for Li-Ion Batteries

Contact Info

Product

Resources

About

NASICON-Structured LiGe₂(PO₄)₃ with Improved Cyclability for High-Performance Lithium Batteries

NASICON-Structured LiGe₂(PO₄)₃ with Improved Cyclability for High-Performance Lithium Batteries

Electrochemical Performance and Mechanisms of NaSn₂(PO₄)₃/C Composites as Anode Materials for Li-Ion Batteries