Sol-gel synthesis and electrochemical properties extracted by phase inflection detection method of NASICON-type solid electrolytes LiZr 2 (PO 4 ) 3 and Li 1.2 Zr 1.9 Ca 0.1 (PO 4 ) 3

Cassel, Alice; Fleutot, Benoît; Courty, Matthieu; Viallet, V.; Morcrette, Mathieu

doi:10.1016/j.ssi.2017.07.009

Cited by 30 publications

(20 citation statements)

References 22 publications

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“…Pareek et al [440] conducted a recent study on the conductivity of NASICON-type lithium tin zirconium phosphate (LiSnZr(PO 4 ) 3 ) with PVDF and LiTFSI polymer-salt matrix. Xie et al [441,442], Prabhu et al [443], and Cassel et al [444] studied bare and Ca-doped LiZr 2 P 3 O 12 and reported room-temperature conductivities in the range of 10 −4 -10 −6 S cm −1 . In addition, Abdel-Hameed et al [445] investigated the effect of F − and B 3+ ions and heat treatment on the enhancement of electrochemical and electrical properties of nanosized LiTi 2 (PO 4 ) 3 glass-ceramic for ASSB and Kahlaoui et al [446] examined the influence of preparation temperature on ionic conductivity of titanium-defective Li 1+4x Ti 2−x (PO 4 ) 3 NASICON-type oxide solid electrolytes.…”

Section: Li-analogues Of Nasiconmentioning

confidence: 99%

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

et al. 2020

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Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and β-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

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Section: Li-analogues Of Nasiconmentioning

confidence: 99%

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

et al. 2020

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“…The bulk and grain boundary resistance of each cubic grain (R b ; R gb ) can be written in Equations (6) and 7, whereas the total bulk and grain boundary resistance (R tot b ; R tot gb ) can be calculated from σ tot b and σ tot gb as shown in Equations (8) and (9), respectively.…”

Section: Bulk Conductivities (σX B ) and Grain Boundary Conductance (mentioning

confidence: 99%

“…Lilley et al and Breuer et al reported that at temperatures well below room temperature (~173 K) the bulk conductivity contributions are easily separated from the grain boundary response [2,4]. As the bulk conductivities are usually more than one order of magnitude higher than the grain boundary conductivities [5][6][7][8][9][10][11][12], the grain boundary conductivities are the limiting factor of ionic transport. However, the dominant factors of the individual bulk and grain boundary conductivities have not been comprehensively elucidated.…”

Section: Introductionmentioning

confidence: 99%

Essential structural and experimental descriptors for bulk and grain boundary conductivities of Li solid electrolytes

Tanaka

Komori

et al. 2020

Science and Technology of Advanced Materials

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We present a computational approach for identifying the important descriptors of the ionic conductivities of lithium solid electrolytes. Our approach discriminates the factors of both bulk and grain boundary conductivities, which have been rarely reported. The effects of the interrelated structural (e.g. grain size, phase), material (e.g. Li ratio), chemical (e.g. electronegativity, polarizability) and experimental (e.g. sintering temperature, synthesis method) properties on the bulk and grain boundary conductivities are investigated via machine learning. The data are trained using the bulk and grain boundary conductivities of Li solid conductors at room temperature. The important descriptors are elucidated by their feature importance and predictive performances, as determined by a nonlinear XGBoost algorithm: (i) the experimental descriptors of sintering conditions are significant for both bulk and grain boundary, (ii) the material descriptors of Li site occupancy and Li ratio are the prior descriptors for bulk, (iii) the density and unit cell volume are the prior structural descriptors while the polarizability and electronegativity are the prior chemical descriptors for grain boundary, (iv) the grain size provides physical insights such as the thermodynamic condition and should be considered for determining grain boundary conductance in solid polycrystalline ionic conductors.

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“…16 When LZP is placed in contact with Li metal, a passivating interphase consisting of Li 3 P and Li 8 ZrO 6 forms and the stable oxidation state of the Zr 4+ cation against this layer provides chemical stability. 5,15,30 LiTi 2 (PO 4 ) 3 (LTP) offers an improved Li + ion conductivity over LZP as a consequence of the suitability of the diffusion channels provided by Ti's apt ionic radius (the ionic radii of Ti 4+ and Zr 4+ are 60.5 and 72.0 pm, respectively), which permits facile Li + movement along the M1-M2-M1 channel. 22,25,31,32 However, the reactivity of LTP against Li metal combined with the variable Ti 3+ /Ti 4+ redox couple suggests suitability as an electrode material.…”

Section: ■ Introductionmentioning

confidence: 99%

In Situ Diffusion Measurements of a NASICON-Structured All-Solid-State Battery Using Muon Spin Relaxation

McClelland

Booth

El‐Shinawi

et al. 2021

ACS Appl. Energy Mater.

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In situ muon spin relaxation is demonstrated as an emerging technique that can provide a volume-averaged local probe of the ionic diffusion processes occurring within electrochemical energy storage devices as a function of state of charge. Herein, we present work on the conceptually interesting NASICON-type all-solid-state battery LiM 2 (PO 4 ) 3 , using M = Ti in the cathode, M = Zr in the electrolyte, and a Li metal anode. The pristine materials are studied individually and found to possess low ionic hopping activation energies of ∼50−60 meV and competitive Li + self-diffusion coefficients of ∼10 –10 –10 –9 cm 2 s –1 at 336 K. Lattice matching of the cathode and electrolyte crystal structures is employed for the all-solid-state battery to enhance Li + diffusion between the components in an attempt to minimize interfacial resistance. The cell is examined by in situ muon spin relaxation, providing the first example of such ionic diffusion measurements. This technique presents an opportunity to the materials community to observe intrinsic ionic dynamics and electrochemical behavior simultaneously in a nondestructive manner.

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Sol-gel synthesis and electrochemical properties extracted by phase inflection detection method of NASICON-type solid electrolytes LiZr 2 (PO 4 ) 3 and Li 1.2 Zr 1.9 Ca 0.1 (PO 4 ) 3

Cited by 30 publications

References 22 publications

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

Essential structural and experimental descriptors for bulk and grain boundary conductivities of Li solid electrolytes

In Situ Diffusion Measurements of a NASICON-Structured All-Solid-State Battery Using Muon Spin Relaxation

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