Synthesis, Characterization, and Properties of Weakly Coordinating Anions Based on<i>tris</i>-Perfluoro-<i>tert</i>-Butoxyborane

LeBlanc, Francis A.; Decken, Andreas; Cameron, T. Stanley; Passmore, Jack; Rautiainen, J. Mikko; Whidden, Thomas K.

doi:10.1021/acs.inorgchem.6b02670

Cited by 13 publications

(9 citation statements)

References 71 publications

(118 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Many other applications possess novel features 4,23,45 and have shown themselves capable of unravelling quite complex thermochemistry. 21,23,[43][44][45] Further applications continue to emerge, 42 and a recent review of the main features of VBT has appeared. 7 More recently, ionic strength, I and formula unit volume, V m essential components of VBThave found application as measures of the enhanced stability brought about to Zintl structures as part of a recently emerging interpretation and new realm of crystallography in which the Zintl-Klemm [46][47][48][49] concept has been revived and extended and which now, once correctly applied, enables the prediction and rationalisation of crystal structures.…”

Section: +mentioning

confidence: 99%

Absolute ion hydration enthalpies and the role of volume within hydration thermodynamics

Housecroft

Jenkins

2017

RSC Adv.

View full text Add to dashboard Cite

show abstract

Section: +mentioning

confidence: 99%

Absolute ion hydration enthalpies and the role of volume within hydration thermodynamics

Housecroft

Jenkins

2017

RSC Adv.

View full text Add to dashboard Cite

show abstract

“…For bulkier ligands such as PFTB, the steric effect is stronger in the borate than in the aluminate anions; for example, the optimized bond length of Al–O is 1.7–1.9 Å in Ca[Al(PFTB) 4 ] 2 , and the length of B–O is 1.3–1.5 Å in Ca[B(PFTB) 4 ] 2 . This partially contributes to the instability of Ca[B(PFTB) 4 ] 2 while the aluminate counterpart is stable …”

Section: Resultsmentioning

confidence: 99%

Computational Predictions of the Stability of Fluorinated Calcium Aluminate and Borate Salts

Jeong

Kamphaus

Redfern

et al. 2023

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

Energy storage concepts based on multivalent ions, such as calcium, have great potential to become next-generation batteries due to their low cost and comparable cell voltage and energy density to Li-ion batteries. However, the development of Ca batteries is still hindered by the lack of suitable materials that grant a long cycle life. Specific to electrolyte materials, developing a calcium salt that is chemically stable under ambient conditions and enables reversible electrodeposition of Ca is critical. In this work, we use first-principles calculations to study the intrinsic and reductive stability of twelve Ca salts with fluorinated aluminate and borate anions and analyze the decomposition products formed on the metal anode surface that are critical to early-stage solid electrolyte interphase formation. We found anions with significant steric hindrance and a high degree of fluorination are intrinsically less stable and deemed unviable designs for Ca salt. Aluminate salts are generally less reactive with the Ca anode than their borate counterparts, and a high degree of fluorination leads to weaker reductive stability. Calcium fluoride is the most prominent decomposition product on the anode surface, and carbide-like motifs were also found from the decomposition of the designed salts.

show abstract

“…All reactions were performed at approximately 0.1 M salt concentration in DME, a concentration chosen to provide the best solubility for Mg-anion products and to ensure a weak coordination environment for anions. For some cases (where ROH = tftb, hftb, and pftb), two unique peaks were observed, with characteristic signals corresponding to the anionic four-coordinate B (0–10 ppm) and the neutral three-coordinate B (15–25 ppm), − respectively. We note that it is difficult to monitor these reactions over time because the NMR samples cannot be sealed if they evolve gaseous byproducts (H 2 ).…”

Section: Resultsmentioning

confidence: 99%

Reductive Decomposition Kinetics and Thermodynamics That Govern the Design of Fluorinated Alkoxyaluminate/Borate Salts for Mg-Ion and Ca-Ion Batteries

et al. 2022

View full text Add to dashboard Cite

The rational design of electrolytes has been a longstanding challenge in chemistry and materials science. In this work, we demonstrate a computational rationale for improving the performance of weakly coordinating electrolytes in currently challenging multivalent-ion battery applications, based on enhanced thermodynamic and kinetic stability against reductive decomposition. A series of fluorinated alkoxyborate and alkoxyaluminate salts are systematically examined based on their reduction and oxidation potentials and, motivated by NMR spectroscopy, detailed reductive decomposition pathways involving the breaking of Al/B−O, C−O, or C−F bonds are obtained. Based on the decomposition kinetics, the hexafluoro-tert-isopropoxy (hfip) ligand for borates and the trifluoro-tert-butoxy (tftb) ligand for aluminates are identified as promising ligands for constructing the salt anions. This borate prediction corroborates previous experimental work on Mg[B(hfip) 4 ] 2 and Ca[B(hfip) 4 ] 2 , in which excellent electrochemical properties were reported. We find that steric factors govern the B−O bond-breaking decomposition kinetics while electronic factors are more important for aluminate salts. There is more charge transfer character in the aluminate transition states compared with borates for Al/B−O bond-breaking decomposition and thus electron-withdrawing ligands tend to stabilize the aluminate transition states. Such molecular-level understandings allow for better design principles for developing new electrolytes with improved stability and performance.

show abstract

Synthesis, Characterization, and Properties of Weakly Coordinating Anions Based ontris-Perfluoro-tert-Butoxyborane

Cited by 13 publications

References 71 publications

Absolute ion hydration enthalpies and the role of volume within hydration thermodynamics

Absolute ion hydration enthalpies and the role of volume within hydration thermodynamics

Computational Predictions of the Stability of Fluorinated Calcium Aluminate and Borate Salts

Reductive Decomposition Kinetics and Thermodynamics That Govern the Design of Fluorinated Alkoxyaluminate/Borate Salts for Mg-Ion and Ca-Ion Batteries

Contact Info

Product

Resources

About