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Lithium metal has been considered the "holy grail" anode material for rechargeable batteries despite the fact that its dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanying solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and mesostructures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)-electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nanoscale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation-dominated EDLi (5 min at 0.5 mA cm-2) is amorphous, while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials but also yield crucial structural information on the EDLi evolution with and without electrolyte additives.

Abstract: The effects of six types of aprotic organic solvents on the discharge performance and discharge products in Li-O2 batteries are systematically investigated. A large amount of Li2O2 is identified in the air electrodes discharged in glyme-based electrolytes, while only a small amount of Li2O2 is detected in the air electrodes discharged in the electrolytes of nitrile, ionic liquid, phosphate, and sulfoxide. Li2CO3 and LiF are also found as byproducts whose compositions are related to the solvents. Li2CO3 is produced from oxidation and decomposition of the solvent, not from the oxidation of the carbon-based air electrode, as revealed by using a 13C-labeled carbon electrode and the solid-state 13C-magic angle spinning nuclear magnetic resonance technique. LiF in the discharge products can be attributed to the attack of superoxide radical anions to the Teflon binder and/or the F-containing imide salt. The formation of these byproducts will significantly reduce the Coulombic efficiency and cycle life of the Li-air batteries. Among the studied solvents, dibutyl diglyme is the suitable solvent for Li-O2 batteries based on its overall properties. However, better electrolytes that can ensure the formation of Li2O2 but minimize other reaction products need to be further investigated for long cycling rechargeable Li-air batteries. [Copyright &y& Elsevier]

Abstract: It is well known that LATP (Li1+x+y Al x Ti2−x Si y P3−y O12) glass is a good lithium (Li)-ion conductor. However, the interaction between LATP glass and H+ ions in aqueous electrolytes (including the diffusion and surface adsorption of H+ ions) needs to be well understood before the long-term application of LATP glass in an aqueous electrolyte can be realized. In this work, we investigate H+-ion diffusion in LATP glass and their interactions with the glass surface using both experimental and modeling approaches. Our results indicate that the apparent H+-related current observed in the initial cyclic voltammetry scan should be attributed to the adsorption of H+ ions on the LATP glass rather than the bulk diffusion of H+ ions. Furthermore, density functional theory calculations indicate that the H+-ion diffusion energy barrier (3.21 eV) is much higher than that for Li+ ions (0.79 eV) and Na+ ions (0.79 eV) in a NASICON-type LiTi2(PO4)3 material. As a result, H+-ion conductivity in LATP glass is negligible at room temperature. However, significant surface corrosion was found after the LATP glass in a strong alkaline electrolyte. Therefore, to prevent LATP glass from corrosion, appropriate electrolytes must be developed for long-term operation of LATP in aqueous Li–air batteries. [Copyright &y& Elsevier]

Abstract: The Li–O2 chemistry in nonaqueous liquid carbonate electrolytes and the underlying reason for its limited reversibility was systematically investigated. X-ray diffraction data showed that regardless of discharge depth lithium alkylcarbonates (lithium propylenedicarbonate (LPDC), or lithium ethylenedicarbonate (LEDC), with other related derivatives) and lithium carbonate (Li2CO3) are constantly the main discharge products, while lithium peroxide (Li2O2) or lithium oxide (Li2O) is hardly detected. These lithium alkylcarbonates are generated from the reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. More significantly, in situ gas chromatography/mass spectroscopy analysis revealed that Li2CO3 and Li2O cannot be oxidized even when charged to 4.6V vs. Li/Li+, while LPDC, LEDC and Li2O2 are readily oxidized, with CO2 and CO released from LPDC and LEDC and O2 evolved from Li2O2. Therefore, the apparent reversibility of Li–O2 chemistry in an organic carbonate-based electrolyte is actually an unsustainable process that consists of (1) the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharging and (2) the subsequent oxidation of these same alkylcarbonates during charging. Therefore, a stable electrolyte that does not lead to an irreversible by-product formation during discharging and charging is necessary for truly rechargeable Li–O2 batteries. [Copyright &y& Elsevier]

Abstract: The charging process of Li2O2-based air electrodes in Li–O2 batteries with organic carbonate electrolytes was investigated using in situ gas chromatography/mass spectroscopy (GC/MS) to analyze gas evolution. A mixture of Li2O2/Fe3O4/Super P carbon/polyvinylidene fluoride (PVDF) was used as the starting air electrode material, and 1-M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in carbonate-based solvents was used as the electrolyte. We found that Li2O2 was actively reactive to 1-methyl-2-pyrrolidinone and PVDF that were used to prepare the electrode. During the first charging (up to 4.6V), O2 was the main component in the gases released. The amount of O2 measured by GC/MS was consistent with the amount of Li2O2 that decomposed during the electrochemical process as measured by the charge capacity, which is indicative of the good chargeability of Li2O2. However, after the cell was discharged to 2.0V in an O2 atmosphere and then recharged to ∼4.6V, CO2 was dominant in the released gases. Further analysis of the discharged air electrodes by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy indicated that lithium-containing carbonate species (lithium alkyl carbonates and/or Li2CO3) were the main discharge products. Therefore, compatible electrolytes and electrodes, as well as the electrode-preparation procedures, need to be developed for rechargeable Li-air batteries for long term operation. [Copyright &y& Elsevier]

Abstract: In this paper, we report the electrochemical characteristics of a novel cathode material, Li2CoPO4F, prepared by solid-state reactions. The solid-state reaction mechanism involved in synthesizing the Li2CoPO4F also is analyzed in this paper. When cycled between 2.0V and 5.0V during cyclic voltammetry measurements, the Li2CoPO4F samples present one, fully reversible anodic reaction at 4.81V. When cycled between 2.0V and 5.5V, peaks occurring at 4.81V and 5.12V in the first anodic scan evolved to one broad oxidative, mound-like pattern in subsequent cycles. Correspondingly, the X-ray diffraction (XRD) pattern of the Li2CoPO4F electrode discharged from 5.5V to 2.0V is slightly different from the patterns exhibited by a fresh sample and the sample discharged from 5.0V to 2.0V. This difference may correspond to a structural relaxation that appears above 5V. In the constant current cycling measurements, the Li2CoPO4F samples exhibited a capacity as high as 109mAhg−1 and maintained a good cyclability between 2.0V and 5.5V vs. Li/Li+. XRD measurements confirmed that the discharged state is Li2CoPO4F. Combining these XRD results and electrochemical data proved that up to 1mol Li+ is extractable when charged to 5.5V. [ABSTRACT FROM AUTHOR]

Abstract: In this work, Li/air batteries based on nonaqueous electrolytes were investigated in ambient conditions (with an oxygen partial pressure of 0.21atm and relative humidity of ∼20%). A heat-sealable polymer membrane was used as both an oxygen-diffusion membrane and as a moisture barrier for Li/air batteries. The membrane also can minimize the evaporation of the electrolyte from the batteries. Li/air batteries with this membrane can operate in ambient conditions for more than one month with a specific energy of 362Whkg−1, based on the total weight of the battery including its packaging. Among various carbon sources used in this work, Li/air batteries using Ketjenblack (KB) carbon-based air electrodes exhibited the highest specific energy. However, KB-based air electrodes expanded significantly and absorbed much more electrolyte than electrodes made from other carbon sources. The weight distribution of a typical Li/air battery using the KB-based air electrode was dominated by the electrolyte (∼70%). Lithium metal anodes and KB-carbon account for only 5.12% and 5.78% of the battery weight, respectively. We also found that only ∼20% of the mesopore volume of the air electrode was occupied by reaction products after discharge. To further improve the specific energy of the Li/air batteries, the microstructure of the carbon electrode needs to be further improved to absorb much less electrolyte while still holding significant amounts of reaction products. [Copyright &y& Elsevier]

[Display omitted] Rechargeable lithium (Li) metal batteries (LMBs) with ultrahigh-nickel (Ni) layered oxide cathodes offer a great opportunity for applications in electrical vehicles. However, increasing Ni content inherently arouses a tradeoff between specific capacity and electrochemical cyclability due to the aggressive side reactions with electrolyte contributed by the highly reactive Ni species. Here, a protective and stable cathode/electrolyte interphase featuring enriched and evenly-distributed LiF is in situ formed on ultrahigh-Ni cathode LiNi 0.94 Co 0.06 O 2 (NC) with an advanced ether-based localized high-concentration electrolyte (LHCE), which concurrently shows good compatibility with Li metal anode. Subsequently, the NC cathode can deliver high capacity retentions of 81.4% after 500 cycles at 25 °C and 91.6% after 100 cycles at 60 °C in the voltage range of 2.8–4.4 V in Li||NC cells at 1C cycling rate (1.5 mA cm−2). Meanwhile, the conductive electrode/electrolyte interphases formed in LHCE enable a high reversible capacity of about 209 mAh g−1 at 3C charging rate. This work provides an effective approach and important insight from the perspective of in situ ultrahigh-Ni cathode/electrolyte interphase protection for high energy–density, long-lasting LMBs. [ABSTRACT FROM AUTHOR]

Rechargeable lithium (Li) metal batteries with conventional LiPF 6 -carbonate electrolytes have been reported to fail quickly at charging current densities of about 1.0 mA cm −2 and above. In this work, we demonstrate the rapid charging capability of Li||LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) cells can be enabled by a dual-salt electrolyte of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(oxalato)borate (LiBOB) in a carbonate solvent mixture. The cells using the LiTFSI-LiBOB dual-salt electrolyte significantly outperform those using the LiPF 6 electrolyte at high charging current densities. At the charging current density of 1.50 mA cm −2 , the Li||NCA cells with the dual-salt electrolyte can still deliver a discharge capacity of 131 mAh g −1 and a capacity retention of 80% after 100 cycles. The Li||NCA cells with the LiPF 6 electrolyte start to show fast capacity fading after the 30th cycle and only exhibit a low capacity of 25 mAh g −1 and a low retention of 15% after 100 cycles. The reasons for the good chargeability and cycling stability of the cells using the LiTFSI-LiBOB dual-salt electrolyte can be attributed to the good film-formation ability of the electrolyte on the Li metal anode and the highly conductive nature of the sulfur-rich interphase layer. [ABSTRACT FROM AUTHOR]

The practical application of lithium (Li) metal anode in rechargeable Li batteries is hindered by both the growth of Li dendrites and the low Coulombic efficiency (CE) during repeated charge/discharge cycles. Recently, we have discovered that CsPF 6 as an electrolyte additive can significantly suppress Li dendrite growth and lead to highly compacted and well aligned Li nanorod structures during Li deposition on copper substrates. In this paper, the effect of CsPF 6 additive on the performance of rechargeable Li metal batteries with lithium iron phosphate (LFP) cathode is further studied. Li|LFP coin cells with CsPF 6 additive in electrolytes show well protected Li anode surface, decreased resistance, enhanced rate capability and extended cycling stability. In Li|LFP cells, the electrolyte with CsPF 6 additive shows excellent long-term cycling stability (at least 500 cycles) at a charge current density of 0.5 mA cm −2 without internal short circuit. At high charge current densities, the effect of CsPF 6 additive becomes less significant. Future work needs to be done to protect Li metal anode, especially at high charge current densities and for long cycle life. [ABSTRACT FROM AUTHOR]

In this work, localized high concentration electrolytes (LHCEs) based on tetramethylene sulfone (TMS) were designed. Similar to LHCEs based on other solvents, TMS-based LHCEs can achieve excellent compatibility with high energy density lithium-ion batteries (LIBs) when combined with a proper additive. The unique solvation structure of LHCEs facilitates the synergetic decomposition of anion, solvent and additive in the solid electrolyte interphase (SEI) formation. Proper combinations of the three constituents of the solvation sheaths in LHCEs can promote the formation of highly effective SEI on graphite negative electrode. The absence of LiPF 6 in LHCEs also suppresses the degradation of positive electrode materials in LIBs. The superior interphasial properties of LHCEs are the key to realizing the long lifespan of high energy density LIBs. • Tetramethylene sulfone (TMS) based LHCEs with different additives were studied. • Additive-free TMS-LHCE outperforms conventional electrolyte in Gr.||Ni-rich LIBs. • Proper additives in TMS-LHCE can further boost performance of Gr.||Ni-rich LIBs. • Electrolyte solvation structure/content govern interphase and battery performance. [ABSTRACT FROM AUTHOR]

Abstract: To understand the limited cycle life performance and poor energy efficiency associated with rechargeable lithium–oxygen (Li–O2) batteries, the discharge products of primary Li–O2 cells at different depths of discharge (DOD) were systematically analyzed using XRD, FTIR and Ultra-high field MAS NMR. When discharged to 2.0V, the reaction products of Li–O2 cells include a small amount of Li2O2 along with Li2CO3 and RO–(C;OLi in the alkyl carbonate-based electrolyte. However, regardless of the DOD, there is no Li2O detected in the discharge products in the alkyl-carbonate electrolyte. For the first time it was revealed that in an oxygen atmosphere the high surface area carbon significantly reduces the electrochemical operation window of the electrolyte, and leads to plating of insoluble Li salts on the electrode at the end of the charging process. Therefore, the impedance of the Li–O2 cell continues to increase after each discharge and recharge process. After only a few cycles, the carbon air electrode is completely insulated by the accumulated Li salt terminating the cycling. [Copyright &y& Elsevier]