Crystal structure and ionic conductivity of the soft solid crystal: isoquinoline3•(LiCl)2

Fall, Birane; Jalil, AbdelAziz; Gau, Michael R.; Chereddy, Sumanth; Zdilla, Michael J.; Wunder, Stephanie L.; Chinnam, Parameswara Rao

doi:10.1007/s11581-017-2206-7

Cited by 7 publications

(3 citation statements)

References 41 publications

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“…Previous work in our group has focused on co-crystals of lithium (or sodium) salts with a coordinating ligand that has "soft" (polarizable), weakly electron-donating atoms, e.g. dimethyl formamide (DMF) with LiCl 11 or NaClO4 12 , isoquinoline with LiCl 13 , or adiponitrile (ADN) with NaClO4 14 , where the weaker binding promotes higher conductivity. Some of these cocrystals melt at moderate temperatures, 12,14 and can therefore be melt-cast, in contrast with inorganic electrolytes, where the grains need to be sintered at high pressures and temperatures.…”

Section: Introductionmentioning

confidence: 99%

A Soft-Solid Co-Crystalline Electrolyte Combining Advantages of Organics and Ceramics: Thermally, Electrochemically Stable, Highly Conductive (Adiponitrile)2LiPF6

Fall

Prakash

Aguirre

et al. 2021

Preprint

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The solid electrolyte (ADN)2LiPF6 is described. The structure exhibits adiponitrile (ADN)-based channels based on XRD analysis, through which the -C≡N-solvated Li + ions migrate. High conductivity (σ ~ 10 -4 S/cm) and high lithium ion transference number (tLi + = 0.54) results from weak interactions between "hard" (charge-dense) Li + ions and "soft" (electronically polarizable) -C≡N, compared with the stronger interactions of previously reported "hard" ether oxygen contacts of polyethylene oxide (PEO) or glymes. The surface of the crystal is a liquid nanolayer that binds the grains so that ionically conductive pellets are easily formed without high pressure/temperature treatments. (ADN)2LiPF6(s) has a wide electrochemical stability window of 0 to 5 V.Li 0 /(ADN)2LiPF6/LiFePO4 half cells exhibit cycling for > 50 cycles at C/20, C/10, C/5 rates with capacities of 140 mAh-g -1 to 100 mAh-g -1 and efficiencies > 95%. MD simulations and PWDFT calculations offer insights into the molecular basis of the physical and conductivity properties.

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Section: Introductionmentioning

confidence: 99%

A Soft-Solid Co-Crystalline Electrolyte Combining Advantages of Organics and Ceramics: Thermally, Electrochemically Stable, Highly Conductive (Adiponitrile)2LiPF6

Fall

Prakash

Aguirre

et al. 2021

Preprint

Self Cite

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show abstract

“…Previous work in other groups 12 and in our group has focused on co-crystals of lithium (or sodium) salts with a coordinating ligand that has "soft" (polarizable), weakly electron-donating atoms, e.g. dimethyl formamide (DMF) with LiCl 13 or NaClO4 14 , isoquinoline with LiCl 15 , or adiponitrile (Adpn) with NaClO4 16 , where the weaker binding promotes higher conductivity. Unlike inorganic ceramics where grain boundaries can be resistive, in the case of the soft-solid cocrystals, the grain boundaries are fluid, permitting easy reformation upon cracking.…”

Section: Introductionmentioning

confidence: 99%

A soft co-crystalline solid electrolyte for lithium-ion batteries

et al. 2023

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Soft solid electrolyte materials are promising alternative choices for conventional battery electrolytes. Here, we have synthesized, characterized and calculated structural, thermal and electrochemical properties of an adiponitrile-based lithium-ion electrolyte which combines the advantages of organic and ceramic materials. This solid material is (Adpn)2LiPF6, (Adpn = adiponitrile) wherein (Adpn)-based channels solvate Li + ions through weak C≡N---Li + contacts.The surface of the crystal is a liquid nanolayer that binds the grains so that ionically conductive pellets are easily formed without high pressure/temperature treatments, which self-heals if fractured and which provide liquid-like conduction paths through the grain boundaries. High conductivity (σ ~ 10 -4 S/cm) and high lithium-ion transference number (tLi + = 0.54) result from weak interactions between "hard" (charge-dense) Li + ions and "soft" (electronically polarizable) -C≡N, compared with the stronger interactions of previously reported "hard" ether oxygen contacts of polyethylene oxide (PEO) or glymes. The proposed mechanism of conduction is one in which Li + ion migration occurs preferentially along the low activation energy path at the co-crystal grain boundaries and within the interstitial regions between the co-crystals, with bulk conductivity comprising a smaller but extant contribution to the observed conductivity. (Adpn)2LiPF6(s) has a wide electrochemical stability window of 0 to 5 V. Li 0 /(Adpn)2LiPF6/LiFePO4 cells exhibit cycling for > 50 cycles at C/20, C/10, C/5 rates with capacities of 140 mAh-g -1 to 100 mAh-g -1 and Coulombic efficiencies ~ 99%, and mitigation of the deleterious reactions with Li metal due to the high ionic strength. LTO/(Adpn)2LiPF6/NMC622 full cells were cycled at C-rates of C/20 to 1C with Coulombic efficiencies > 96%, with no dendritic failure after 100 cycles. Novel MD approaches addressing multiple conduction pathways and PWDFT calculations offer insights into the molecular basis of the physical and conductivity properties.

show abstract

Section: Introductionmentioning

confidence: 99%

A Soft-Solid Co-Crystalline Electrolyte Combining Advantages of Organics and Ceramics: Thermally, Electrochemically Stable, Highly Conductive (Adiponitrile)2LiPF6

Fall

Prakash

Aguirre

et al. 2021

Preprint

Self Cite

View full text Add to dashboard Cite

The solid electrolyte (ADN)2LiPF6 is described. The structure exhibits adiponitrile (ADN)-based channels based on XRD analysis, through which the -C≡N-solvated Li+ ions migrate. High conductivity (σ ~ 10-4 S/cm) and high lithium ion transference number (tLi+ = 0.54) results from weak interactions between “hard” (charge-dense) Li+ ions and “soft” (electronically polarizable) -C≡N, compared with the stronger interactions of previously reported “hard” ether oxygen contacts of polyethylene oxide (PEO) or glymes. The surface of the crystal is a liquid nanolayer that binds the grains so that ionically conductive pellets are easily formed without high pressure/temperature treatments. (ADN)2LiPF6(s) has a wide electrochemical stability window of 0 to 5 V. Li0/(ADN)2LiPF6/LiFePO4 half cells exhibit cycling for > 50 cycles at C/20, C/10, C/5 rates with capacities of 140 mAh-g-1 to 100 mAh-g-1 and efficiencies > 95%. MD simulations and PWDFT calculations offer insights into the molecular basis of the physical and conductivity properties.

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Crystal structure and ionic conductivity of the soft solid crystal: isoquinoline3•(LiCl)2

Cited by 7 publications

References 41 publications

A Soft-Solid Co-Crystalline Electrolyte Combining Advantages of Organics and Ceramics: Thermally, Electrochemically Stable, Highly Conductive (Adiponitrile)2LiPF6

A Soft-Solid Co-Crystalline Electrolyte Combining Advantages of Organics and Ceramics: Thermally, Electrochemically Stable, Highly Conductive (Adiponitrile)2LiPF6

A soft co-crystalline solid electrolyte for lithium-ion batteries

A Soft-Solid Co-Crystalline Electrolyte Combining Advantages of Organics and Ceramics: Thermally, Electrochemically Stable, Highly Conductive (Adiponitrile)2LiPF6

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