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To guide the selection of a suitable fluorinated ether (FE) co-solvent for lithium metal batteries, it is crucial to understand the relationship between the organic structures of the FEs and the electrochemical performance of an FE-containing electrolyte. In this work, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (FEE), 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (TTE), and 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (OFDEE) were chosen as representative FE co-solvents because of their distinct structural properties. The structure-activity relationship between the FEs and the electrochemical performance of Li||LiNi

A complementary electrolyte system with 0.8 M lithium bis(fluorosulfonylimide) (LiFSI) salt and 2 wt % lithium perchlorate (LiClO4) additive in fluoroethylene carbonate (FEC)/ethyl methyl carbonate (EMC) solution enables not only stable cycling of lithium metal batteries (LMBs) with practical loading ( 4 mAh/cm2) but also outstanding degradation stability toward the end of cycle life when compared to the conventional electrolyte. Although the use of LiFSI salt can increase the electrolyte conductivity and lengthen the cycle life of LMBs, the aged lithium anode morphology formed by the sacrificial decomposition of LiFSI is highly porous, leading to an abrupt cell capacity drop toward the end of cycling. Moreover, the inability to stop aluminum corrosion by the LiFSI-based electrolyte also causes cracking of the cathode tab during prolonged cycling. It is observed that a highly porous aged lithium consumed electrolyte at a higher rate, leading to the dry-out of electrolyte solvents. On the contrary, dense aged lithium anode morphology increased the localized current applied on the lithium, causing the formation of lithium dendrite. Thus, porosity control is the key to enhance battery performance. In this complementary system, LiClO4 was introduced as an advanced additive to not only improve the capacity retention rate but also mitigate the abrupt capacity drop toward the end of cycle life because LiClO4 acted as a pore astringent reducing the porosity of the aged lithium metal anode to the desired level. Moreover, the addition of LiClO4 can also suppress the Al corrosion, allowing stable high-voltage cycling of LMBs. The synergistic effect of combining LiFSI salt and a LiClO4 additive leads to an electrolyte system that can facilitate the application of high-energy LMBs with practical electrode loading.

A new class of fluorinated sulfones, β-fluorinated sulfones, were designed and synthesized as electrolyte solvents for high voltage lithium-ion batteries. While the oxidation potential of β-fluorinated sulfones is slightly lower than that of α-fluorinated sulfones, it is still significantly higher than the oxidation potential of regular sulfones, which already possess fairly high anodic stability. However, β-fluorinated sulfones exhibit a significant decrease in reduction potential compared to α-fluorinated sulfones, rendering them more stable towards graphite anodes. Moreover, the reduced lithium solvating power of β-fluorinated sulfones compared to regular sulfones mitigates the transition metal dissolution of cathodes. Taken together, these middle ground properties of β-fluorinated sulfone-based electrolytes enable the very stable long-term cycling of graphite‖LiNi0.6Co0.2Mn0.2O2 full cells. The outstanding performance of β-fluorinated sulfones designed by applying the “golden middle way” paves a new path for the development of an effective electrolyte system.

Purpose: This study was designed to identify the underlying molecular genetic cause of idiopathic hypogonadotropic hypogonadism (IHH) in a nonconsanguineous Chinese family. Methods: All the family members underwent medical history evaluation, physical examination, and laboratory studies. Whole-exome sequencing and RNA sequencing was performed on 2 affected siblings and unaffected parents. All candidate variants were confirmed in all family members by Sanger sequencing and silico function prediction. Results: The proband and his twin brother were diagnosed with IHH, and an autosomal recessive mode of inheritance was identified. Whole-exome sequencing identified the compound heterozygous variants c.9230G>A (p.Arg3077Gln) and c.12883G>A (p.Val4295Met) in DNAH5 in both affected siblings. Sanger sequencing verified that c.9230G>A in DNAH5 was from the unaffected mother and c.12883G>A was from the unaffected father. In addition, we found heterozygous mutations in BBS2 (c.1705delC, p.Gln569fs) and NR5A1 (c.460G>A, p.Ala154Thr) in the siblings, which were from their father.Conclusion: Compound heterozygous variants in DNAH5 were identified in the affected siblings, and were predicted to be pathogenic by silico analysis. This is the first report that suggests variants in DNAH5 are relevant to the pathogenesis of IHH. This study expands the variant spectrum of genes associated with IHH.

This study aimed to compare the vision-related quality of life (VRQoL) between Defocus Incorporated Soft Contact (DISC) lenses and single-vision spectacles in Chinese children, in order to evaluate their visual performance and subjective acceptance of this bifocal designed contact lenses treatment.Chinese participants aged 7 to 12 years, with myopia of -4.00 to -0.75 D, astigmatism 1.50 D, and monocular best-corrected visual acuity 0.0 or better, were recruited in the study. All participants had been wearing DISC lenses, or single-vision spectacles, for the last 6 to 18 months and were requested to complete the routine ocular examination and Chinese version of the Pediatric Refractive Error Profile (PREP 2) questionnaire. The questionnaire consisted of 7 scales: vision, symptoms, appearance, activities, handling, peer perception, and overall score. According to their habitual correction modalities, fifty-four children were allocated to the DISC group and 56 to the single-vision spectacles group. A generalized linear model was fitted to assess variables associated with the PREP 2 score.Participants wearing DISC lenses scored significantly higher than those wearing single-vision spectacles for vision, appearance, activities, peer perception, and overall (all P 0.05). The improvement of VRQoL in the DISC group was mainly represented in appearance, peer perception, and activities. The quality of life improved more for older participants on scales of vision, symptoms, handling, appearance, and overall score (all P 0.05). The interaction between treatment and age was statistically significant for the activities scale (P 0.05).DISC lens wear significantly improves VRQoL in Chinese children compared with single-vision spectacles for most of the survey scales, especially in the areas of appearance, peer perception, and activities. The benefits provided by DISC lenses contribute to greater satisfaction than single-vision spectacles for myopic children.

Despite the exceptionally high energy density of lithium metal anodes, the practical application of lithium-metal batteries (LMBs) is still impeded by the instability of the interphase between the lithium metal and the electrolyte. To formulate a functional electrolyte system that can stabilize the lithium-metal anode, the solvation behavior of the solvent molecules must be understood because the electrochemical properties of a solvent can be heavily influenced by its solvation status. We unambiguously demonstrated the solvation rule for the solid-electrolyte interphase (SEI) enabler in an electrolyte system. In this study, fluoroethylene carbonate was used as the SEI enabler due to its ability to form a robust SEI on the lithium metal surface, allowing relatively stable LMB cycling. The results revealed that the solvation number of fluoroethylene carbonate must be ≥1 to ensure the formation of a stable SEI in which the sacrificial reduction of the SEI enabler subsequently leads to the stable cycling of LMBs.

High energy density Li-ion battery with ultra-stable electrolyte is essential to facilitate the massive application of electric vehicles. Despite being used ubiquitously in Li-ion batteries, lithium hexafluorophosphate (LiPF6) is not stable both chemical and electrochemically, rendering the battery using LiPF6 based electrolyte. While lithium bis(fluorosulfonyl)imide (LiFSI) based electrolyte possesses both higher conductivity and better compatibility with the electrode materials compared to the traditional LiPF6 electrolyte, the high cost and the inability to suppress aluminum corrosion hinder its application in Li-ion batteries. In this work, we developed a bi-salt electrolyte by blending LiPF6 and LiFSI, as well as introducing Lithium difluoroborate (LiDFOB) as the anti-corrosion additive to mitigate the Al corrosion. Although the newly formulated electrolyte shows promising result at coin cell level, the big format pouch cell using the new electrolyte failed after prolonged cycling due to the detachment of the Cu tab. Based on the NMR results, we revealed that Al corrosion was accelerated by the change in the electrolyte formulation during cycling, and the situation was further escalated by the high state of charge (SOC). Most importantly, the Al3+ ions dissolved from the cathode side migrated to the anode side and formed alloy with Li and Cu, triggering the detachment of Cu tab, which was confirmed by SEM, ICP-MS and HRXRD. Owing to the higher current density and temperature on the tab region, it has significantly higher chance to be torn apart. In sum, it is imperative to precisely control both the SOC and the amount of LiFSI added to minimize the corrosion problem.

This study aimed to develop and evaluate an adapted Chinese version of the Pediatric Refractive Error Profile2 (PREP2) and to evaluate its acceptability, reliability, and validity in a population of Chinese children with refractive error.The Chinese version of the PREP2 was translated using a standardized procedure and then administered to consecutive outpatients with refractive error. Reliability was assessed by the Cronbach's alpha coefficient for internal consistency and test-retest reliability. Validity of the questionnaire was assessed by item discriminant validity, construct validity, known-groups validity, and concurrent validity.A total of 104 subjects were recruited for the study and all completed the Chinese version of the PREP2 questionnaire with no problems. A random sample of 50 patients completed the questionnaire twice within one week. The Cronbach's alpha coefficients ranged from 0.71 to 0.89 across scales, and the intraclass correlation coefficient ranged from 0.86 to 0.92, indicating excellent internal consistency and test-retest reliability. The item-scale correlation coefficients between the items and the corresponding scales ranged from 0.39 to 0.88. The translated questionnaire had good discriminatory power between contact lens wearers and spectacle wearers. Significant correlations were found between the scales and traditional clinical parameters, such as spherical equivalent and uncorrected visual acuity, showing good construct and concurrent validity.The Chinese version of the PREP2 exhibited good internal consistency, test-retest reliability, item-scale correlation, discriminatory power, construct validity, and concurrent validity. Therefore, it may be adopted as an acceptable, reliable, and valid instrument for the measurement of vision-related quality of life in Chinese children with refractive error.

Hydrofluoroethers (HFEs) have been adopted widely as electrolyte cosolvents for battery systems because of their unique low solvating behavior. The electrolyte is currently utilized in lithium-ion, lithium-sulfur, lithium-air, and sodium-ion batteries. By evaluating the relative solvating power of different HFEs with distinct structural features, and considering the shuttle factor displayed by electrolytes that employ HFE cosolvents, we have established the quantitative structure-activity relationship between the organic structure and the electrochemical performance of the HFEs. Moreover, we have established the linear free-energy relationship between the structural properties of the electrolyte cosolvents and the polysulfide shuttle effect in lithium-sulfur batteries. These findings provide valuable mechanistic insight into the polysulfide shuttle effect in lithium-sulfur batteries, and are instructive when it comes to selecting the most suitable HFE electrolyte cosolvent for different battery systems.

The lithium metal battery (LMB) is one of the most promising next-generation battery systems due to its ultrahigh energy density. However, problematic dendrite formation and low Coulombic efficiency (CE) greatly limit its practical application. Carbonate electrolyte solvents are still indispensable for the operation of LMBs using a transition metal oxide cathode. We determined the impact of different cyclic carbonates, which actively participate in the formation of the solid-electrolyte interface (SEI), on the stable cycling of LMBs using a nickel-rich layered cathode LiNi0.6Mn0.2Co0.2O2 (NMC622). The substitution of fluorine atoms in the cyclic carbonate profoundly enhances the stability of the lithium metal anode while fluoroalkyl and alkoxy substituents are detrimental. Cyclic carbonate trans-difluoroethylene carbonate (DFEC) was identified as a novel SEI enabler on the lithium metal anode, facilitating the formation of a protective SEI with relatively high lithium fluoride content. A Li/NMC622 cell utilizing DFEC electrolyte solvent as SEI enabler displayed a capacity retention larger than 82% after 400 cycles and an average CE of 99.95%. In contrast, the cycling retention after 400 cycles for a Li/NMC622 cell using monofluoroethylene carbonate was only 31% with an average CE of 99.73%. Other fluoroalkyl or alkoxy cyclic carbonates do not provide improved stabilization of the lithium metal anode over ethylene carbonate. The fundamental studies in this work provide critical insight for the further development of advanced electrolytes in LMBs.

From dictating the redox potential of electrolyte solvents to shaping the stability of solid-electrolyte interfaces, solvation plays a critical role in the electrochemistry of electrolytes. To efficiently design functional electrolytes for lithium batteries, it is particularly important to understand the relative solvating ability of each individual organic solvent, because most of the electrolyte systems are comprised of two or more electrolyte solvents. Using a newly developed internally referenced diffusion-ordered spectroscopy technique and diffusion coefficient–coordination ratio (D–α) analysis, we successfully constructed a solvating power series for common electrolyte solvents. We demonstrated the usefulness of this solvating power series in designing more reliable electrolyte system by selecting an appropriate fluorinated electrolyte solvent for a high-voltage lithium metal battery (LMB) as an example. For a methyl(2,2,2-trifluoroethyl)carbonate-based electrolyte, we identified fluoroethylene carbonate as a more desirable cyclic carbonate co-solvent than difluoroethylene carbonate for LMB due to its significantly higher ability to solvate lithium ions.

Relative solvating power, that is, the ratio of the coordination ratios between a solvent and the reference solvent, was used to probe the quantitative structure-activity relationship of electrolyte solvents and the lithium polysulfide (LiPS) dissolution in lithium-sulfur batteries. Internally referenced diffusion-ordered nuclear magnetic resonance spectroscopy (IR-DOSY) was used to determine the diffusion coefficient and coordination ratio, from which the relative solvating power can be easily measured. The higher the relative solvating power of an ethereal solvent, the more severe will be the LiPS dissolution and the lower the coulombic efficiency of the lithium-sulfur battery. A linear relationship was established between the logarithm of relative solvating power of a solvent and the degree of LiPS dissolution, rendering relative solvating power an important parameter in choosing the electrolyte solvent for lithium-sulfur batteries.

A novel methodology is reported on the use of internally referenced diffusion-ordered spectroscopy (IR-DOSY) in divulging the solution structure of lithium-ion battery electrolytes. Toluene was utilized as the internal reference for 1H-DOSY analysis due to its exceptionally low donor number and reasonable solubility in various electrolytes. With the introduction of the internal reference, the solvent coordination ratio of different species in the electrolytes can be easily determined by 1H-DOSY or 7Li-DOSY. This new technique was applied to different carbonate electrolytes, and the results were consistent with a Fourier transform infrared (FTIR) analysis. Compared to conventional vibrational spectroscopy, this IR-DOSY technique avoids the complicated deconvolution of the spectrum and allows determination of the solvent coordination ratio of different species in electrolyte systems with two or more organic solvents.

Manganese oxides, notably γ-MnO2 and modified derivatives, have played a major role in electrochemical energy storage for well over a century. They have been used as the positive electrode in primary (single discharge) Leclanche dry cells and alkaline cells, as well as in primary and secondary (rechargeable) lithium cells with non-aqueous electrolytes. Lithiated manganese oxides, such as LiMn2O4 (spinel) and layered lithium–nickel–manganese–cobalt (NMC) oxide systems, are playing an increasing role in the development of advanced rechargeable lithium-ion batteries. These manganese-rich electrodes have both cost and environmental advantages over their nickel counterpart, NiOOH, the dominant cathode material for rechargeable nickel–cadmium and nickel–metal hydride batteries, and their cobalt counterpart, LiCoO2, the dominant cathode material in lithium-ion batteries that power cell phones. An additional benefit is that tetravalent manganese can be used as a redox-active and/or stabilizing ‘spectator’ ion in lithiated mixed-metal oxide electrodes. This paper provides an overview of the historical development of manganese-based oxide electrode materials and structures, leading to advanced systems for lithium-ion battery technology; it updates a twenty-year old review of manganese oxides for lithium batteries. The narrative emanates largely from strategies used to design manganese oxide electrode structures at the Council for Scientific and Industrial Research, South Africa (1980–1994), Oxford University, UK (1981–1982), and Argonne National Laboratory, USA (1994–2017); it highlights the worldwide evolution of ideas and recent trends to improve the design, stability, and electrochemical capacity of structurally integrated, manganese-rich electrode materials.

A new single-solvent electrolyte system comprising lithium bis(fluorosuflonyl) imide (LiFSI) and β-fluorinated sulfone (TFPMS) was designed to enable very stable long-term cycling of high-voltage lithium-ion batteries. Compared to other fluorinated solvents such as α-fluorinated sulfone (FMES) and fluorinated carbonate (FEMC), which are prone to reduction on the graphite anode, the LiFSI-TFPMS system displayed outstanding compatibility with graphite. While regular carbonate and sulfone from the LiFSI electrolyte system are compatible with the graphite anode, their high solvating power not only induces severe corrosion on the aluminum cathode current collector at high voltage, but also renders a low aggregation level at a normal salt concentration (about 1.0 M), resulting in the formation of an unstable solid-electrolyte interphase (SEI) on the graphite anode. Owing to the low solvating power of TFPMS, the aggregation level of the LiFSI-TFPMS system is relatively high even at normal salt concentration, which not only facilitates the formation of a robust SEI by the sacrificial decomposition of LiFSI, but also suppresses the aluminum corrosion of the LiFSI electrolyte system at high voltage. Together with the high intrinsic anodic stability of TFPMS, the superior cycling performance of graphite||LiNi0.6Co0.2Mn0.2O2 cells was achieved by employing the non-flammable LiFSI-TFPMS single-solvent electrolyte system.

The understanding of the reaction mechanism and temporal speciation of the lithium–sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ 7Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversible accumulation of Li2S is observed on the Li metal anode after four cycles because of sulfur shuttling. The application of the method presented here to study electrolyte/additive development and lithium protection research can be readily env...

A high performance lithium–sulfur (Li–S) battery comprising a symmetric fluorinated diethoxyethane electrolyte coupled with a fish-scale porous carbon/S composite electrode was demonstrated. 1,2-Bis(1,1,2,2-tetrafluoroethoxy)ethane (TFEE) was first studied as a new electrolyte solvent for Li–S chemistry. When co-mixed with 1,3-dioxolane (DOL), the DOL/TFEE electrolyte suppressed the polysulfide dissolution and shuttling reaction. When coupled with a fish-scale porous carbon/S composite electrode, the Li–S cell exhibited a significantly high capacity retention of 99.5% per cycle for 100 cycles, which is far superior to the reported numerous systems.

New fluorinated sulfones were synthesized and evaluated in high voltage lithium-ion batteries using a LiNi0.5Mn0.3Co0.2O2 (NMC532) cathode. Fluorinated sulfones with an α-trifluoromethyl group exhibit enhanced oxidation stability, reduced viscosity and superior separator wettability as compared to their non-fluorinated counterparts. Their improved performance in high voltage NMC532/graphite cells makes them promising high voltage electrolytes for next generation high voltage high energy lithium-ion batteries.

To facilitate the massive commercialization of electric vehicles, it is imperative to enhance the energy density of the state-of-the-art lithium battery technology. [1] Lithium metal battery (LMB) is considered as a promising energy storage system because of the exceptionally low electrochemical potential and ultrahigh specific capacity of the lithium metal anode. [2-4] Yet, the extensive application of LMBs is still obstructed by the extreme reactivity of lithium metal, which leads to severe safety problems. [5-6] To tackle this issue, the re-design of the electrolyte is viewed as the most practical approach due to its cost effectiveness. [7-8] In this presentation, we successfully establish a solvation rule for the SEI enabler to achieve stable cycling of the lithium metal anode through a variety of electrochemical and solvation studies such as a Li/Cu cell test and IR-DOSY analysis. Fluoroethylene carbonate (FEC) was used as the exemplary solid-electrolyte interphase (SEI) enabler because it is the most common SEI enabler in the LMB electrolyte, and it is able to form a desirable SEI on the lithium metal surface. The results of all electrochemical studies point to the existence of a critical ratio between FEC and a co-solvent (e.g., DMC, EMC, and EA) for the stable cycling of LMBs. If the FEC/co-solvent ratio is lower than the critical ratio, not only will an unstable SEI be formed, but the SEI will also be gradually deteriorated by the significant decomposition of lithium complexes, with Li+ solvated solely by the co-solvent/non-SEI enabler. We discovered that the solvation number of FEC must be ≥ 1 to ensure the formation of a stable SEI, which mainly resulted from the sacrificial reduction of the SEI enabler and subsequent repair of the SEI to facilitate stable cycling of LMBs. This finding is crucial for the future development of functional electrolytes in that the ratio of FEC to co-solvent must exceed the critical volume/molar ratio for the solvation number of FEC to be ≥ 1. Reference: Schmuch, R.; Wagner, R.; Hörpel, G.; Placke, T.; Winter, M., Nature Energy 2018, 3, 267–278. Li, X.; Zheng, J.; Engelhard, M. H.; Mei, D.; Li, Q.; Jiao, S.; Liu, N.; Zhao, W.; Zhang, J. G.; Xu, W., ACS Applied Materials & Interfaces 2018, 10 (3), 2469-2479. Xu, W.; Wang, J.; Ding, F.; Chen, X.; Nasybulin, E.; Zhang, Y.; Zhang, J.-G., Energy Environ. Sci. 2014, 7 (2), 513– Fang, C.; Li, J.; Zhang, M.; Zhang, Y.; Yang, F.; Lee, J. Z.; Lee, M. H.; Alvarado, J.; Schroeder, M. A.; Yang, Y.; Lu, B.; Williams, N.; Ceja, M.; Yang, L.; Cai, M.; Gu, J.; Xu, K.; Wang, X.; Meng, Y. S., Nature 2019, 572, 511. Alvarado, J.; Schroeder, M. A.; Pollard, T. P.; Wang, X.; Lee, J. Z.; Zhang, M.; Wynn, T.; Ding, M.; Borodin, O.; Meng, Y. S.; Xu, K., Environ. Sci. 2019, 12, 780. Liang, X.; Pang, Q.; Kochetkov, I. R.; Sempere, M. S.; Huang, H.; Sun, X.; Nazar, L. F. Nature Energy 2017, 2 (9), 17119. Zheng, J.; Engelhard, M. H.; Mei, D.; Jiao, S.; Polzin, B. J.; Zhang, J.-G.; Xu, W. Nature Energy 2017, 2, 17012. Cao, X.; Ren, X.; Zou, L.; Engelhard, M. H.; Huang, W.; Wang, H.; Matthews, B. E.; Lee, H.; Niu, C.; Arey, B. W.; Cui, Y.; Wang, C.; Xiao, J.; Liu, J.; Xu, W.; Zhang, J.-G., Nature Energy 2019, 4, 796.

Understanding the decaying mechanism in lithium-ion batteries (LIBs) is critical to establishing a stable electrolyte system. Despite the advent of various novel electrolyte solvents designated for high-voltage LIBs, their working principles are not fully understood. Currently, oxidative decomposition of electrolytes is believed to be the major cause of capacity fade, and tremendous effort has been devoted to discovering a new electrolyte with enhanced anodic stability. However, the oxidative decomposition process cannot solely explain the rapid decay of some electrolyte systems with intrinsic high anodic stability when used with a high-nickel layered oxide cathode such as LiNi0.6Mn0.2Co0.2O2 (NMC622). In this report, a study of the quantitative structure-activity relationship was conducted to deepen the mechanistic understanding of the decay in high-voltage LIBs. The results obtained from the newly introduced molecular pair analysis and linear free-energy relationship (LFER) studies were highly consistent with the solvation-involved decaying mechanism in a high-nickel layered oxide cathode cycling at high voltage (> 4.5 V vs. Li/Li+). There was no evidence correlating the solvation ability of electrolyte solvents with the decay of a high-nickel layered oxide cathode cycling at a relatively low voltage (

State-of-the-art lithium-ion batteries (LIBs) are based on a lithium transition metal oxide cathode, a graphite anode and a nonaqueous carbonate electrolyte. To further increase the energy and power density of LIBs, silicon anodes have been intensively explored due to their high theoretical capacity, low operation potential, and low cost. However, the main challenges for Si anode are the large volume change during lithiation/delithiation process and the instability of the solid-electrolyte-interphase associated with this process. Recently, significant progress has been achieved via advanced material fabrication technologies and rational electrolyte design in terms of improving the Coulombic efficiency and capacity retention. In this paper, new developments in advanced electrolyte and additive for LIBs with Si anode were systematically reviewed, and perspectives over future research were suggested.

Triethlylphosphite (TEP) and tris(2,2,2-trifluoroethyl) phosphite (TTFP) have been evaluated as electrolyte additives for high-voltage Li-ion battery cells using a Ni-rich layered cathode material LiNi0.5Co0.2Mn0.3O2 (NCM523) and the conventional carbonate electrolyte. The repeated charge/discharge cycling for cells containing 1 wt % of these additives was performed using an NCM523/graphite full cell operated at the voltage window from 3.0-4.6 V. During the initial charge process, these additives decompose on the cathode surface at a lower oxidation potential than the baseline electrolyte. Impedance spectroscopy and post-test analyses indicate the formation of protective coatings by both additives on the cathode surface that prevent oxidative breakdown of the electrolyte. However, only TTFP containing cells demonstrate the improved capacity retention and Coulombic efficiency. For TEP, the protective coating is also formed, but low Li(+) ion mobility through the interphase layer results in inferior performance. These observations are rationalized through the inhibition of electrocatalytic centers present on the cathode surface and the formation of organophosphate deposits isolating the cathode surface from the electrolyte. The difference between the two phosphites clearly originates in the different properties of the resulting phosphate coatings, which may be in Li(+) ion conductivity through such materials.

Organic sulfone compounds have been widely used as high-voltage electrolytes for lithium-ion batteries for decades. However, owing to the complexity of the synthesis of new sulfones, only a few commercially available sulfones have been studied. In this paper, we report the synthesis of new sulfone compounds with various substituent groups and the impact of the substituent group on the oxidation stability of sulfones. Electrochemical floating tests using a 5 V LiNi0.5Mn1.5O4 spinel cathode and density functional theory calculations showed that the cyclopentyl-substituted sulfone McPS suffered from oxidation instability, starting from 4.9 V versus Li+/Li, as observed by the large leakage currents. On the other hand, the isopropyl-substituted sulfone MiPS and tetramethylene substituted sulfone TMS showed much improved oxidation stability under identical testing conditions. The substitution structure of the sulfone plays a significant role in the determination of its oxidative stability and should first be considered for the development of new sulfone-based electrolytes for high-voltage, high-energy lithium-ion batteries.

Spent lithium ion batteries that contain valuable metal elements such as Co, Ni, Mn, Cu are being landfilled in many countries and raising resources depletion and human toxicity potentials. Low cost and high efficiency recovery process is highly desired. In this work we confirmed that high performance Ni1/3Mn1/3Co1/3(OH)2 precursor and LiNi1/3Mn1/3Co1/3O2 cathode material can be synthesized from leaching solution of a lithium ion battery recovery stream. The precursor was synthesized from a typical co-precipitation process with carefully controlling the reaction parameters. Electrochemical properties including rate capacity and cycle life were tested to evaluate the final product. The results show that the cathode material synthesized from spent lithium ion battery recovery stream is performing a discharge capacity of 158 mAh/g at first cycle of 0.1C and 139 mAh/g at first cycle of 0.5C cycle life test. After 100 and 200 cycles, still over 80% and 65% of capacity is remained, respectively. The materials are also evaluated independently at Argonne National Laboratory.

A novel redox shuttle additive, 1,4-bis(trimethylsilyl)-2,5-dimethoxybenzene (BTMSDB), is shown to deliver superb overcharge protection of LiFePO4 electrode in Li-ion batteries. Using this molecule as a chemical probe, we trace the cause of the eventual failure of this additive to the gradual loss of steric protection in the corresponding radical cation, providing the much needed mechanistic insight in the factors controlling the long-term efficiency of overcharge protection.

A new class of electrolyte additives based on cyclic fluorinated phosphate esters was rationally designed and identified as being able to stabilize the surface of a LiNi0.5Mn0.3Co0.2O2 (NMC532) cathode when cycled at potentials higher than 4.6 V vs Li+/Li. Cyclic fluorinated phosphates were designed to incorporate functionalities of various existing additives to maximize their utilization. The synthesis and characterization of these new additives are described and their electrochemical performance in a NMC532/graphite cell cycled between 4.6 and 3.0 V are investigated. With 1.0 wt % 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (TFEOP) in the conventional electrolyte the NMC532/graphite cell exhibited much improved capacity retention compared to that without any additive. The additive is believed to form a passivation layer on the surface of the cathode via a sacrificial polymerization reaction as evidenced by X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonsance (NMR) analysis...

High-energy, inexpensive and safe electrochemistries have been the main goals of lithium-ion battery research for many years. Historically, manganese-based cathodes have long been studied for their attractive cost and safety characteristics [1]. However, due to issues related to both surface and bulk instabilities, manganese-rich electrodes have yet to find substantial success in the high-energy lithium-ion battery market. With current trends in cathode chemistries leaning heavily toward Ni-rich compositions, the factors of cost and safety are again at the forefront of research and development efforts. This paper reports the recent progress made at Argonne National Laboratory (USA) to stabilize manganese-rich cathode structures and surfaces with a specific focus on composite materials with intergrown layered and spinel components; it presents an overview of their electrochemical properties in terms of capacity, energy, and cycle-life in cells with metallic lithium, graphite, and Li4Ti5O12 anodes. These layered-spinel cathodes show promise as alternatives to highly nickel-rich electrode compositions, which bodes well for continued advances.

Silicon is a very promising anode material for lithium ion batteries. It has a 4200 mAh/g theoretical capacity, which is ten times higher than that of commercial graphite anodes. However, when lithium ions diffuse to Si anodes, the volume of Si will expand to almost 400% of its initial size and lead to the crack of Si. Such a huge volume change and crack cause significant capacity loss. Meanwhile, with the crack of Si particles, the conductivity between the electrode and the current collector drops. Moreover, the solid electrolyte interphase (SEI), which is generated during the cycling, reduces the discharge capacity. These issues must be addressed for widespread application of this material. In this work, caramel popcorn shaped porous silicon particles with carbon coating are fabricated by a set of simple chemical methods as active anode material. Si particles are etched to form a porous structure. The pores in Si provide space for the volume expansion and liquid electrolyte diffusion. A layer of amorphous carbon is formed inside the pores, which gives an excellent isolation between the Si particle and electrolyte, so that the formation of the SEI layer is stabilized. Meanwhile, this novel structure enhances the mechanical properties of the Si particles, and the crack phenomenon caused by the volume change is significantly restrained. Therefore, an excellent cycle life under a high rate for the novel Si electrode is achieved.

Developing a high-voltage enabling electrolyte is extremely critical for the success of the next generation high-energy density lithium-ion battery especially for electric vehicles. Material scientists have developed new cathode materials with improved specific capacity[1,2] and operating voltage (5 V vs. Li+/Li).[3,4] However, designed for a 4V-class lithium-ion chemistry, the conventional electrolyte suffers from oxidation instability on the charge cathode/electrolyte interface at high charging voltages which leads to severe transition metal (TM) dissolution and rapid capacity fading. The voltage instability of electrolyte becomes the bottleneck for the extensive application of the high voltage cathode materials. Thus, new electrolytes with elevated voltage stability has been widely explored.[5-8] Here we report a new class of fluorinated electrolytes comprising novel fluorinated sulfones including ((trifluoromethyl)sulfonyl)ethane (FMES), 1-((trifluoromethyl)sulfonyl)propane (FMPS) and 2-((trifluoromethyl)sulfonyl)propane (FMIS).[9] These compounds have been synthesized via new synthetic routes and evaluated as electrolyte materials under high voltage operation. The results indicate that sulfones with an α-trifluoromethyl group possess enhanced oxidative potential and reduced viscosity as compared to their non-fluorinated counterparts. The α-fluorinated sulfones also show enhanced wetting ability with polyolefin separator. A facile synthesis method for a reported sulfone 1,1,1-trifluoro-3-(methylsulfonyl)propane (FPMS) was also developed. With the new reaction method, large quantity of material was obtained and comprehensive electrochemical properties of FPMS as high voltage electrolyte was evaluated. Unlike the α-fluorinated sulfones, the γ-fluorinated sulfones resemble the property of the non-fluorinated ones. References: [1] Nyten, A.; Abouimrance, A.; Armand, M.; Gustafsson, T.; Thomas, J. O. Electrochem. Commun., 2005, 7, 156-160. [2] Ellis, B. L.; Makahnoul, R. M.; Makimura, Y.; Toghill, K.; Nazar, L. F., Nat. Mater., 2007, 6, 749-753. [3] Hu, M.; Pang, X.; Zhou, Z. J., Power Sources, 2013, 237, 229-242. [4] Santhanam, R.; Rambabu, B. J., Power Sources, 2010, 195, 5442-5451. [5] He, M.; Su, C. C.; Feng, Z.; Zeng, L.; Wu, T.; Bedzyk, M. J.; Fenter, P.; Wang, Y.; Zhang, Z., Adv. Energy Mater., 2017, 7, 1700109. [6] He, M.; Su, C. C.; Peebles, C.; Feng, F.; Connell, J. G.; Liao, C.; Wang, Y.; Shkrob, I. A.; Zhang, Z., ACS Appl. Mater. Interface, 2016, 8(18), 11450-11458. [7] Kunduraciz, M.; Amatucci, G.G., J. Electrochem. Soc., 2006, 153, A1345-A1352. [8] Wolfenstine, J.; Aleen, J., J. Power Sources, 2005, 142, 389-390. [9] Su, C. C.; He, M.; Redfern, P. C.; Curtiss, L. A.; Shkrob, I. A.; Zhang, Z., Energy Environ. Sci., 2017, 10, 900-904. Figure 1

Direct evidence of Mg2+ intercalation into a spinel-type Mn2O4 is provided. By com­bining tools with different sensitivities, from atomic-resolution X-ray spectro­scopy to bulk X-ray diffraction, it is demonstrated that Mg2+ reversibly occupies the tetrahedral sites of the spinel structure through the reduction of Mn when the electrochemical reaction is performed.

Lithium-ion batteries have been widely applied in portable electronics due to its high energy density. [1] It is essential to improve the state-of-the-art LIBs, which are far from their maximum theoretical energy density, in order to power up electric vehicles. [2] Researchers have shown that the physiochemical properties, such as conductivity, electrochemical window and ability to form solid electrolyte interphase (SEI), depend on the solution structures of the electrolyte. [3] Thus, it is crucial to determine the solution structures of the electrolyte and the relative solvating ability of various solvents for designing advanced electrolyte systems. Novel method utilizing specific 2D-NMR technique was successfully developed to probe the solvation state of different electrolyte solvents. The result obtained by this technique agreed with the measurement by vibrational spectroscopy. Most importantly, unlike the vibrational spectroscopy measurement, this method can be easily applied to electrolyte system with two or more electrolyte solvents. For example, it is not impossible to determine the solvation state of a ternary-solvent electrolyte comprising EC, EMC and DMC by vibrational spectroscopy due to the severe overlapping of peaks. However, the solvation state can be easily determined with the new method developed. Therefore, this new technique provides an important experimental tool in examining the solvation state of different electrolyte solvents. Application of this newly developed technique in revealing the electrochemical performance of various electrolytes on Li-ion batteries will also be discussed. References: [1] (a) Tarascon, J.-M.; Armand, M., Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 414, 359-367. (b) Armand, M.; Tarascon, J.-M., Building Better Batteries. Nature 2008, 451, 652-657. [2] Goodenough, J. B.; Park, K.-S., The Li-Ion Rechargeable Battery: A Perspective. Journal of the American Chemical Society 2013, 135, 1167-1176. [3] (a) Seo, D. M.; Reininger, S.; Kutcher, M.; Redmond, K.; Euler, W. B.; Lucht, B. L., Role of Mixed Solvation and Ion Pairing in the Solution Structure of Lithium Ion Battery Electrolytes. The Journal of Physical Chemistry C 2015, 119 (25), 14038-14046. (b) Xu, K., Electrolytes and interphases in Li-ion batteries and beyond. Chemical reviews 2014, 114 (23), 11503-618.

A high voltage LiNi0.5Mn0.3Co0.2O2/graphite cell with a fluorinated electrolyte formulation 1.0 m LiPF6 fluoroethylene carbonate/bis(2,2,2-trifluoroethyl) carbonate is reported and its electrochemical performance is evaluated at cell voltage of 4.6 V. Comparing with its nonfluorinated electrolyte counterpart, the reported fluorinated one shows much improved Coulombic efficiency and capacity retention when a higher cut-off voltage (4.6 V) is applied. Scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy data clearly demonstrate the superior oxidative stability of the new electrolyte. The structural stability of the bulk cathode materials cycled with different electrolytes is extensively studied by X-ray absorption near edge structure and X-ray diffraction.

Lithium sulfur (Li-S) battery is a promising alternative technology of lithium ion batteries. However, due to the complicity of the chemistry in Li-S batteries, the mechanism is not well understood. In addition, the co-existence of soluble species and insoluble species limits the application of other characterization techniques. The sensitivity and element selectivity make NMR spectroscopy a powerful tool to study the changes in local chemical environment and speciation process in Li-S batteries. In this study, in situ 7Li NMR spectroscopy was employed where plastic pouch cells were assembled and cycled in the magnet while NMR spectra were acquired simultaneously. Method to quantitatively study entire lithium inventory in a Li-S battery is developed and implemented, and the cell design is optimized for electrochemical performance and spectroscopic resolution. This methodology can be readily extended to Li-S batteries with other electrolytes where the speciation process can be tracked and analyzed. The development of electrolyte will also benefit greatly from the detailed understanding of the Li-S battery speciation process as well as the additive development. [1] See, et. al., J. Am. Chem. Soc., 2014, 136 (46), pp 16368–16377 [2] Xiao, et. al., Nano Lett., 2015, 15, 3309-3316

Organic carbonate electrolytes are commonly used in lithium ion batteries due to their wide electrochemical stability window and high lithium salt solubility. However, the high voltage of some cathode materials is above the stability of these conventional carbonate electrolytes (>4.5V vs. Li+/Li). One method of increasing the anodic stability of the organic carbonates is through substitution of the solvents with a fluorinated carbonates. In this work, we evaluate the stability of electrolyte formulations comprising combinations of either ethylene carbonate, fluoroethylene carbonate, or difluoroethylene carbonate as cyclic carbonates, and ethyl methyl carbonate or hexafluorodiethyl carbonate as linear carbonates. Stability of these electrolytes at both positive and negative electrodes was determined by lithium/graphite half cell tests, as well as 60 hour potentiostatic hold tests at 4.6 V vs. Li+/Li with NMC (LiNi0.5Mn0.3 Co0.2O2) cathodes and either graphite or LTO (Li4Ti5O12) anodes. In potentiostatic holds with NMC cathodes, the fluorinated electrolytes show enhanced stability (lower oxidation current) with the graphite anodes, while fluorethylene carbonate containing formulations show higher oxidation currents with the LTO anodes. These results indicate the feasibility of fluorinated electrolytes in enabling high voltage cathodes through stability of the cathode/electrolyte interface. Acknowledgements The work at Argonne National Laboratory was performed under the auspices of the U.S. Department of Energy (DOE), Office of Vehicle Technologies, under Contract No. DE-AC02-06CH11357. The submitted issue has been created by the University of Chicago as Operator of Argonne National Laboratory (“Argonne”) under Contract No. W-31-109-Eng-38 with the U.S. Department of Energy. The U.S. Government retains for itself, and others acting on its behalf, a paid-up, non-exclusive, irrevocable, worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.