Enhancing lithium-ion conductivity in NASICON glass-ceramics by adding yttria

Визгалов, В.А.; Nestler, Tina; Trusov, Lev A.; Бобриков, И.А.; Ivankov, Oleksandr I.; Авдеев, М. В.; Motylenko, Mykhaylo; Brendler, Erica; Vyalikh, Anastasia; Meyer, Dirk C.; Itkis, Daniil M.

doi:10.1039/c7ce01910f

Cited by 34 publications

(33 citation statements)

References 38 publications

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“…In contrast, for sample LYGP‐C‐728, the overall room temperature conductivity is found to be two orders of magnitude higher than the reported one for the unsubstituted NASICON (LiGe 2 (PO 4 ) 3 ). A similarly surprising result was reported by Vizgalov et al who showed that the addition of Y 2 O 3 in the glass batch of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 , resulted in the crystallization of YPO 4 upon thermal treatment. They also evidenced an increase in the ionic conductivity compared to the unsubstituted LGP NASICON phase and they attributed this enhancement to the presence of YPO 4 microcrystals, which promote better contact between the NASICON grains.…”

Section: Discussionsupporting

confidence: 68%

Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics

Silva¹,

Nieto‐Muñoz

Rodrigues

et al. 2020

J Am Ceram Soc

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This work reports structural and lithium-ion mobility studies in NASICON singleor multiple phase Li 1+x M x Ge 2−x (PO 4 ) 3 (M = Ga 3+ , Sc 3+ , Y 3+ ) glass-ceramics using solid-state NMR techniques, X-ray powder diffraction, and impedance spectroscopy. X-ray powder diffraction data show the successful incorporation of Ga 3+ and Sc 3+into the Ge 4+ octahedral sites of the NASICON structure at the levels of x = 0.5 and 0.4, respectively. The glass-to-crystal transition was further characterized by multinuclear NMR and electrical conductivity measurements. Among the studied samples, the gallium-containing glass-ceramic presented the highest DC conductivity, 1.1 × 10 −4 S/cm at room temperature, whereas for the Sc-containing samples, the maximum room temperature conductivity that could be reached was 4.8 × 10 −6 S/ cm. No indications of any substitution of Ge 4+ by Y 3+ could be found. K E Y W O R D S ionic conductivity, nuclear magnetic resonance, phosphates, structure How to cite this article: d'Anciães Almeida Silva I, Nieto-Muñoz AM, Rodrigues ACM, Eckert H. Structure and lithium-ion mobility in Li 1.5 M 0.5 Ge 1.5 (PO 4 ) 3 (M = Ga, Sc, Y) NASICON glass-ceramics. J Am Ceram Soc. 2020;103:4002-4012. https ://doi.

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Section: Discussionsupporting

confidence: 68%

Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics

Silva¹,

Nieto‐Muñoz

Rodrigues

et al. 2020

J Am Ceram Soc

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“…When substituting Na + with Li + , a NASICON-type lithium ion conductor can be acquired with a general formula of LiM 2 (PO 4 ) 3 (M = Ti, Ge, Hf, Zr, Sn). Like the LZP, the conductivity of the LTP and LGP is also on the order of 10 −5 -10 −6 S cm −1 , [76,77] far lower than the conductivity of liquid electrolytes (≈10 −2 S cm −1 ). [73] Similar to the Na 1+x Zr 2 Si x P 3−x O 12 , the ideal LZP has a rhombohedral structure, while Li atoms occupy Wyckoff positions of splitting 36f sites around 6b sites.…”

Section: Nasicon-type Ssesmentioning

confidence: 96%

“…The total ionic conductivity of polycrystalline NASICON-type lithium ion conductors is usually on the order of 10 −4 S cm −1 , while their bulk conductivity is considerably higher than 10 −4 S cm −1 . Compared with pristine conductors, notable enhancements have been described for Li-doped LAGP (1.9 × 10 −4 S cm −1 ), [85] B 2 O 3 -doped LAGP (6.9 × 10 −4 S cm −1 ), [86] Li 2 O-doped LAGP (7.25 × 10 −4 S cm −1 ), [87] SiO 2 -doped LATP (over 10 −3 S cm −1 ), [88] Y 2 O 3 -doped LAGP (5 × 10 −4 S cm −1 ), [77] and Bi 2 O 3 -doped LATP (9.4 × 10 −4 S cm −1 ). [83] M. Gellert et al [84] reported that the GB resistance was caused by a number of barriers.…”

Section: Garnet-type Ssesmentioning

confidence: 99%

“…However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted before the commercialization of all-solid-state Li-ion batteries (ASSLIBs). Like the LZP, the conductivity of the LTP and LGP is also on the order of 10 −5 -10 −6 S cm −1 , [76,77] far lower than the conductivity of liquid electrolytes (≈10 −2 S cm −1 ). Then, two critical issues in the ASSLIBs are highlighted: interfacial incompatibility of the electrodes and SSEs and internal stresses.…”

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confidence: 96%

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Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Liu

et al. 2019

Advanced Energy Materials

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The continuous depletion of fossil fuels, the increase of oil prices, and the need to decrease CO 2 emissions have stimulated intensive research on developing alternative renewable and clean energy sources. [1] Among these alternative energy sources, rechargeable Li-ion batteries (LIBs) are one of the promising candidates. To date, the LIBs basically consisting of a positive electrode (cathode), an electrolyte, and a negative electrode (anode) have widespread applications, such as portable electronic devices, pure electric vehicles (PEVs), and hybrid electric vehicles (HEVs). [2] The state-of-the-art electrolytes are usually the lithium salts (LiPF 6 , LiBF 4 , and LiCF 3 SO 3 ) dissolved in organic solvents, i.e., ethylene carbonate, propylene carbonate, polyethylene oxide, and dimethyl carbonate, [3] which exhibit excellent wetting of the electrodes and produce a fast transfer of Li + ions upon charging and discharging. However, they suffer from flammability, poor electrochemical stability, limited temperature range of operation, and low power density. [4] There is an ever-increasing demand for batteries with a higher energy and power density, although current LIBs offer volumetric and gravimetric energy densities up to 770 Wh L −1 and 260 Wh kg −1 , respectively. [5] To improve the energy/power density of LIBs, one way is to adopt high-potential cathode materials such as LiNi 0.5 Mn 1.5 O 4 (LNMO). The high-voltage plateau of LNMO (≈4.7 V vs Li/Li + ) makes its energy density 20-30% higher than the energy density of commercial LiCoO 2 and LiFePO 4 . [6] However, successful commercialization of the LNMO is restricted in high-energy LIBs due to electrolyte decomposition and side reaction of the cathodes and liquid electrolytes when operating at high voltages. [7,8] The other way to improve the energy/power density is to replace the conventional graphite anode with Li metal. The Li metal, with a low anode potential (−3.04 V vs standard hydrogen electrode) and high specific capacity (3862 mAh g −1 for the Li anode versus 372 mAh g −1 for the graphite anode), [9][10][11] has been considered as the "Holy Grail" of battery technologies. When paired with sulfur and oxygen, the theoretical energy density of Li-S (≈2567 Wh kg −1 ) and Li-O 2 (≈3505 Wh kg −1 ) batteries is far higher than the theoretical energy density of conventional LIBs (≈387 Wh kg −1 ). [12][13][14][15] When Li metal approaches the liquid electrolytes, however, unstable Li/electrolyte interface Rechargeable Li-ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid-state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted befor...

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“…It had a sandwiched structure with graphene working electrode, Li-conductive solid electrolyte and metallic Li counter electrode. Graphene was transferred from Cu foil onto a solid glass-ceramic NASICON-type electrolyte (Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ) plate prepared in-house [36]. PMMAbased graphene transfer technique described elsewhere [37] was used.…”

Section: Photoemission Study Of the All-solid-state Li-o 2 Cellsmentioning

confidence: 99%

Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge

et al. 2018

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One of the key factors responsible for the poor cycleability of Li-O 2 batteries is a formation of byproducts from irreversible reactions between electrolyte and discharge product Li 2 O 2 and/or intermediate LiO 2 . Among many solvents that are used as electrolyte component for Li-O 2 batteries, acetonitrile (MeCN) is believed to be relatively stable towards oxidation. Using near ambient pressure X-ray photoemission spectroscopy (NAP XPS), we characterized the reactivity of MeCN in the Li-O 2 battery. For this purpose, we designed the model electrochemical cell assembled with solid electrolyte. We discharged it first in O 2 and then exposed to MeCN vapor. Further, the discharge was carried out in O 2 + MeCN mixture. We have demonstrated that being in contact with Li-O 2 discharge products, MeCN oxidizes. This yields species that are weakly bonded to the surface and can be easily desorbed. That's why they cannot be detected by the conventional XPS. Our results suggest that the respective chemical process most probably does not give rise to electrode passivation but can decrease considerably the Coulombic efficiency of the battery.

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Enhancing lithium-ion conductivity in NASICON glass-ceramics by adding yttria

Abstract: The lithium conductivity of NASICON glass-ceramic electrolytes can be increased 5 times just by using additives, which change the glass crystallization patterns.

Cited by 34 publications

References 38 publications

Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics

Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge

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Enhancing lithium-ion conductivity in NASICON glass-ceramics by adding yttria

Abstract: The lithium conductivity of NASICON glass-ceramic electrolytes can be increased 5 times just by using additives, which change the glass crystallization patterns.

Cited by 34 publications

References 38 publications

Structure and lithium‐ion mobility in Li1.5M0.5Ge1.5(PO4)3 (M = Ga, Sc, Y) NASICON glass‐ceramics

Structure and lithium‐ion mobility in Li1.5M0.5Ge1.5(PO4)3 (M = Ga, Sc, Y) NASICON glass‐ceramics

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Notable Reactivity of Acetonitrile Towards Li2O2/LiO2 Probed by NAP XPS During Li–O2 Battery Discharge

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Product

Resources

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Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics

Structure and lithium‐ion mobility in Li_1.5M_0.5Ge_1.5(PO₄)₃ (M = Ga, Sc, Y) NASICON glass‐ceramics