Nonaqueous Electrolytes: Advances in Lithium Salts

Henderson, Wesley A.

doi:10.1007/978-1-4939-0302-3_1

Cited by 12 publications

(6 citation statements)

References 623 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The relatively low cathode operating potential also makes it unlikely to cause electrode passivation by the oxidative decomposition of electrolyte . There is also no known detrimental side reaction of NVP or vanadium dissolution from it (the use of ClO 4 – salts also alleviates cathode instability due to the release of chemically active species such as HF from PF 6 – salts). After ruling out these possibilities, we hypothesize that the origin of capacity fading is mainly caused by the cycling-induced volume change in NVP.…”

Section: Resultsmentioning

confidence: 99%

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na₃V₂(PO₄)₃/C Composite

Jiang

Zhang

Lee

2017

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

The cost of large-scale battery-based energy storage systems can be substantially reduced by using long cycle-life active battery materials which can be easily synthesized. This paper describes the synthesis of a sodium vanadium phosphate (Na 3 V 2 (PO 4 ) 3, NVP)/carbon composite as the sodium ion battery (NIB) cathode material by a facile solid-state method which can increase the cost competitiveness of NIBs relative to the lithium ion batteries (LIBs). The NVP synthesized as such features NVP particles tethering to a cellular carbon network formed in situ by the carbonization of a low melting polymer percolating the NVP particles. The immobilization of the NVP particles can better preserve their electrical integration within the electrode, the loss of which is conjectured to be the major cause of capacity loss. The hypothesis was validated by performance comparison with a conventional carbon-coated NVP/C composite with the same initial discharge capacity but which showed a more severe capacity fading in extended cycling. This study presents not only a new strategy to extend the cycle life of cathode materials but also a cost-effective way to produce them.

show abstract

Section: Resultsmentioning

confidence: 99%

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na₃V₂(PO₄)₃/C Composite

Jiang

Zhang

Lee

2017

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…In addition to the size and shape of the anion, the anion’s charge delocalization is a key determinant of both the solvate solution interactions and which thermally stable solvate crystalline phases form in solvent–lithium salt electrolytes. ,− For the salts studied, in dilute liquid electrolytes, the solvation (solvent···Li + cation) interactions increase in the following order ,− LiCF 3 SO 3 < LiBF 4 < LiClO 4 < LiPF 6 with a corresponding decrease in the ionic association (anion···Li + cation) interactions. Crystalline solvate phases with a greater extent of solvation are stabilized for more weakly coordinating anions.…”

Section: Resultsmentioning

confidence: 99%

Structural Interactions within Lithium Salt Solvates: Cyclic Carbonates and Esters

et al. 2014

Self Cite

View full text Add to dashboard Cite

Only limited information is available regarding the manner in which cyclic carbonate and ester solvents coordinate Li + cations in electrolyte solutions for lithium batteries. One approach to gleaning significant insight into these interactions is to examine crystalline solvate structures. To this end, eight new solvate structures are reported with ethylene carbonate, γ-butyrolactone, and γ-valerolactone: (EC) 3 :LiClO 4 , (EC) 2 :LiClO 4 , (EC) 2 :LiBF 4 , (GBL) 4 :LiPF 6 , (GBL) 1 :LiClO 4 , (GVL) 1 :LiClO 4 , (GBL) 1 :LiBF 4 , and (GBL) 1 :LiCF 3 SO 3 . The crystal structure of (EC) 1 :LiCF 3 SO 3 is also re-reported for comparison. These structures enable the factors that govern the manner in which the ions are coordinated and the ion/solvent packingin the solid-stateto be scrutinized in detail.

show abstract

“…A detailed understanding of such interactions will greatly aid in the development and utilization of diverse lithium salts for electrolyte formulations. 7 …”

mentioning

confidence: 99%

Electrolyte Solvation and Ionic Association

Borodin

Han

Daubert

et al. 2015

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

Molecular dynamics (MD) simulations of acetonitrile (AN) mixtures with LiBF 4 , LiCF 3 SO 3 and LiCF 3 CO 2 provide extensive details about the molecular-and mesoscale-level solution interactions and thus explanations as to why these electrolytes have very different thermal phase behavior and electrochemical/physicochemical properties. The simulation results are in full accord with a previous experimental study of these (AN) n -LiX electrolytes. This computational study reveals how the structure of the anions strongly influences the ionic association tendency of the ions, the manner in which the aggregate solvates assemble in solution and the length of time in which the anions remain coordinated to the Li + cations in the solvates which result in dramatic variations in the transport properties of the electrolytes. Understanding the origin of the widely varying transport properties (e.g., viscosity, ionic conductivity and diffusion coefficients) of battery electrolytes remains a key challenge. The present work continues a detailed study into the solution structure of electrolytes-ion solvation and ionic association interactions-to provide mechanistic explanations for electrolyte properties. Previous manuscripts have examined in detail acetonitrile electrolytes with numerous lithium salts: (AN) n -LiX. [1][2][3][4][5][6] Electrolytes with the most strongly associated anions studied (i.e., CF 3 SO 3 − and CF 3 CO 2 − ), in which anion. . . Li + cation coordination (i.e., ionic association interactions) is a prominent feature of solvate formation, were found to have a much lower ionic conductivity than electrolytes with more weakly coordinating anions (e.g., PF 6 − and ClO 4 − ). 3 This is as one might expect once the ionic association tendency of the salts is well understood, but the details of why the conductivity values are low are missing.Two particularly notable points from the previous studies are that:(1) The average solvation numbers, obtained from a Raman spectroscopic analysis, for the (AN) n -LiCF 3 CO 2 solutions were found to be almost constant near a value of 1 (i.e., one AN molecule per Li + cation) over a wide concentration range, even for very dilute solutions. It remains unclear, however, as to why such electrolytes have such a low degree of solvation and why highly concentrated (>5 M) liquid electrolytes-perhaps contrary to expectations-can be prepared with LiCF 3 CO 2 with this being the case.(2) Experimental measurements of the solution structure and transport properties of (AN) n -LiCF 3 SO 3 mixtures were unobtainable due to the rapid crystallization of a solid solvate phase (i.e., (AN) 1 :LiCF 3 SO 3 ) from the electrolytes. 1 Liquid electrolytes with this salt can, however, be readily studied using molecular dynamics (MD) simulations to better understand how and why solution interactions differ for differing anions.The present work therefore delves deeper into the molecular-and mesoscale-level interactions using MD simulations applied to the characterization of (AN) n -LiCF 3 SO 3 and -LiCF ...

show abstract

Nonaqueous Electrolytes: Advances in Lithium Salts

Cited by 12 publications

References 623 publications

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na₃V₂(PO₄)₃/C Composite

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na₃V₂(PO₄)₃/C Composite

Structural Interactions within Lithium Salt Solvates: Cyclic Carbonates and Esters

Electrolyte Solvation and Ionic Association

Contact Info

Product

Resources

About

Nonaqueous Electrolytes: Advances in Lithium Salts

Cited by 12 publications

References 623 publications

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na3V2(PO4)3/C Composite

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na3V2(PO4)3/C Composite

Structural Interactions within Lithium Salt Solvates: Cyclic Carbonates and Esters

Electrolyte Solvation and Ionic Association

Contact Info

Product

Resources

About

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na₃V₂(PO₄)₃/C Composite

A Polymer-Infused Solid-State Synthesis of a Long Cycle-Life Na₃V₂(PO₄)₃/C Composite