Complex formation and ionic conductivity of polyphosphazene solid electrolytes

Blonsky, Peter M.; Shriver, Duward F.; Austin, Paul E.; Allcock, Harry R.

doi:10.1016/0167-2738(86)90123-2

Cited by 190 publications

(110 citation statements)

References 7 publications

Supporting

Mentioning

107

Contrasting

Order By: Relevance

“…[54][55][56] The solid electrolyte is sandwiched between two cation reversible electrodes (in this case Li metal) and is polarized by the application of a small constant potential difference between the electrodes ( V = 10 mV). Under the electric field, positive and negative ions can migrate to the oppositely polarized electrode.…”

Section: Resultsmentioning

confidence: 99%

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH₄Electrolyte

Das

Ngene

Norby

et al. 2016

J. Electrochem. Soc.

106

View full text Add to dashboard Cite

In this work we characterize all-solid-state lithium-sulfur batteries based on nano-confined LiBH 4 in mesoporous silica as solid electrolytes. The nano-confined LiBH 4 has fast ionic lithium conductivity at room temperature, 0.1 mScm −1 , negligible electronic conductivity and its cationic transport number (t + = 0.96), close to unity, demonstrates a purely cationic conductor. The electrolyte has an excellent stability against lithium metal. The behavior of the batteries is studied by cyclic voltammetry and repeated charge/discharge cycles in galvanostatic conditions. The batteries show very good performance, delivering high capacities versus sulfur mass, typically 1220 mAhg −1 after 40 cycles at moderate temperature (55 • During the past decade, the quest for promising next generation energy storage systems has led significant attention to secondary batteries with high specific energy such as lithium/sulfur (Li/S) batteries (1675 mAhg −1 sulfur at 2.15 V), 1-6 which have 3 to 5 times higher energy densities than commercial state-of-art Li-ion batteries, e.g. 7 The inexpensive, abundant and environmentally benign nature of sulfur makes this battery more appealing for large scale application purposes (e.g. transportation, portable and residential applications) than other metal-ion battery systems. However, there are still numerous scientific and technical challenges for practical application. During discharge in Li/S batteries, lithium ions move spontaneously through the electrolyte from the negative electrode, typically lithium metal, silicon or tin-based compounds, to the positive sulfur electrode and S is ultimately reduced to form Li 2 S, while electrons flow through the external circuit. During charge, Li 2 S is oxidized back to S and Li + by applying an external voltage. The overall electrochemical reaction is:However, the electrochemical reduction of sulfur in Li/S battery occurs through the formation of a series of intermediate lithium polysulfides, Li 2 S x (2 ≤ x ≤ 8). 8,9 These intermediates are soluble in most liquid organic solvents/electrolytes and shuttling between the sulfur cathode and Li anode results in fast self-discharge during storage and low coulombic efficiencies during charging. Therefore, a grand challenge for Li/S batteries is to suppress this mechanism, for example by encapsulation or coating of the sulfur electrode, 10-14 use of impermeable membranes, 15 and/or the use of suitable electrolytes that minimize the solubility and diffusivity of the polysulfides. [16][17][18] Another possibility is to use fast ion-conducting solids, i.e. solid electrolytes with an ionic conductivity (σ ∼ 10 −4 to 10 −1 Scm −1 ) comparable to that of standard liquid electrolytes (e.g. σ ∼10−2 Scm −1 for 1.0 M LiFP 6 in organic solvent). Nanoconfinement of LiBH 4 in nanoporous carbon scaffolds has been reported by various groups to improve the BH 4 − rotational diffusivity and lithium mobility at room temperature.46-49 However, due to their high electronic conductivity, nano-scaffolds of carbon are not ver...

show abstract

Section: Resultsmentioning

confidence: 99%

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH₄Electrolyte

Das

Ngene

Norby

et al. 2016

J. Electrochem. Soc.

106

View full text Add to dashboard Cite

show abstract

“…In the original form introduced by Blonsky et al, the method was restricted to dilute electrolyte solutions with a constant diffusion coefficient. 21 Bruce and Vincent 6 extended it to electrolyte solutions with a variable ionic diffusion coefficient. In this extension, it is argued that the thermodynamic factor has to be close to unity in order to apply the dilute solution theory.…”

Section: Theorymentioning

confidence: 99%

Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number

Ehrl

Landesfeind

Wall

et al. 2017

J. Electrochem. Soc.

View full text Add to dashboard Cite

In the literature, various numerical methods for the simulation of ion-transport in concentrated binary electrolytes for lithium ion batteries can be found, whereas the corresponding transport parameters are rarely discussed. In this contribution, a novel method for the determination of the transference number in non-aqueous electrolytes is proposed. The method is based on data from a concentration cell and on the value of the thermodynamic factor obtained from independent measurements based on quantifying the redox potential of ferrocene. The concentration dependent transference numbers obtained by this new method are compared to values obtained by the classical approach, which is based on experiments in a polarization cell and a concentration cell. For the latter, a set of commonly used and some newly proposed analysis methods as well as their theoretical justification are discussed. Using an exemplary electrolyte (lithium perchlorate in a mixture of ethylene carbonate and diethyl carbonate), we will demonstrate that our newly proposed method based on concentration cell experiments and a thermodynamic factor derived from independent measurements is a more accurate approach for obtaining concentration dependent transference numbers. At the end, the experimentally determined concentration dependent transference numbers are compared to data available in the literature.

show abstract

“…The amorphous X-ray appearance of both phases is due to the high TiCI 4 proportion leading to abundant HCI formation during hydrolysis. Crystalline PEO polymer is known to have a comb structure [6], where the comb-like teeth consist of short-chain oligoethers that contain the Lewis-base [7]. If the teeth are too long, the materials looks like crystalline PEO, which occured in our case for n > 8.…”

Section: Discussionmentioning

confidence: 92%

TiO₂–Polymer Nano–Composites bySol–Gel

Pierre

Campet

Han

et al. 1994

Active and Passive Electronic Components

View full text Add to dashboard Cite

Sol-gel processes make it possible to develop new hybrid electrolyte materials of the type ceramic-polymer, known as Nano-Crystallite-Insertion-Material (NCIM). They can be used in reversible alkali electrochemical cells after insertion with cations such as Li +. In the present study, TiOe-polyethylene oxide hybrid materials were synthesized from TiCI 4 and from Ti ethoxide. Their structure is analyzed in relation with the processing parameters. A primary evaluation of the nanoscale composite materials for reversible Li insertion was performed.

show abstract

Complex formation and ionic conductivity of polyphosphazene solid electrolytes

Cited by 190 publications

References 7 publications

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH₄Electrolyte

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH₄Electrolyte

Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number

TiO₂–Polymer Nano–Composites bySol–Gel

Contact Info

Product

Resources

About

Complex formation and ionic conductivity of polyphosphazene solid electrolytes

Cited by 190 publications

References 7 publications

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH4Electrolyte

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH4Electrolyte

Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number

TiO2–Polymer Nano–Composites bySol–Gel

Contact Info

Product

Resources

About

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH₄Electrolyte

All-Solid-State Lithium-Sulfur Battery Based on a Nanoconfined LiBH₄Electrolyte

TiO₂–Polymer Nano–Composites bySol–Gel