Tailoring Solvation Solvent in Localized High-Concentration Electrolytes for Lithium||Sulfurized Polyacrylonitrile.

Sulfurized polyacrylonitrile (SPAN) is a promising cathode material for lithium-sulfur (Li-S) batteries due to its significantly reduced polysulfide (PS) dissolution compared to that of elemental S cathodes. Although conventional carbonate-based electrolytes are stable with SPAN electrodes, they are unstable with Li metal anodes. Recently, localized high-concentration electrolytes (LHCEs) have been developed to improve the stability of Li anodes. Here, we report a new strategy to further improve the performance of Li||SPAN batteries by replacing the conventional solvating solvent 1,2-dimethoxyethane (DME) in LHCEs with a new solvating solvent, 1,2-diethoxyethane (DEE). The new optimal DEE-LHCE exhibits less reactivity against Li2S2, alleviates PS dissolution, forms a better cathode-electrolyte interphase layer on the SPAN cathode, and enhances SPAN structural reversibility even at elevated temperatures (45 °C). Compared to DME-LHCE, DEE-LHCE with the same salt and diluent leads to better performance in Li||SPAN batteries (with 82.9% capacity retention after 300 cycles at 45 °C), preservation of the SPAN cathode structure, and suppression of volume change of the Li metal anode. A similar strategy on tailoring the solvating solvents in LHCEs can also be used in other rechargeable batteries to improve their electrochemical performances.

Important Role of Ion Flux Regulated by Separators in Lithium Metal Batteries.

Polyolefin separators are the most common separators used in rechargeable lithium (Li)-ion batteries. However, the influence of different polyolefin separators on the performance of Li metal batteries (LMBs) has not been well studied. By performing particle injection simulations on the reconstructed three-dimensional pores of different polyethylene separators, it is revealed that the pore structure of the separator has a significant impact on the ion flux distribution, the Li deposition behavior, and consequently, the cycle life of LMBs. It is also discovered that the homogeneity factor of Li-ion toward Li metal electrode is positively correlated to the longevity and reproducibility of LMBs. This work not only emphasizes the importance of the pore structure of polyolefin separators but also provides an economic and effective method to screen favorable separators for LMBs.

Seroprevalence of five diarrhea-related pathogens in bovine herds of scattered households in Inner Mongolia, China between 2019 and 2022.

Bovine diarrhea is a multi-factorial disease and remains one of the biggest health problems in animal husbandry. The endemic trends of the main pathogens responsible for bovine diarrhea in Inner Mongolia have not been analyzed systematically before. Therefore, the purpose of this study was to estimate the prevalence of bovine diarrhea pathogens found in the scattered households of Inner Mongolia in China. Additionally, we assessed for differences in the prevalence of infection based on age and region, as well as determined local prevalence rates and the rates of mixed infections. Using a two-stage random sampling strategy, 3,050 serum samples were collected from 72 bovine herds in 11 leagues and cities in Inner Mongolia, and the positive rates of BVDV, BRV, BCoV, K99, and Mycobacterium paratuberculosis (M. paratuberculosis) antibodies in the samples were detected by ELISA to determine the epidemic trends and epidemic differences of the five pathogens in Inner Mongolia. The positive rates of antibodies based on serum samples were: BVDV, 18.79% (95% CI [17.44-20.22]); BRV, 12.39% (95% CI [11.27-13.61]); BCoV, 12.82% (95% CI [11.68-14.05]); K99, 13.80% (95% CI [12.62-15.07]); and M. paratuberculosis, 10.79% (95% CI [9.74-11.94]). The prevalence rates of BRV, BCoV and K99 at 0-2 months were significantly different from that at 2-6 months, 6-18 months and adult cattle (P < 0.05). The prevalence of BVDV and M. paratuberculosis was the highest in adult cattle, which was significantly different from that in other age groups (P < 0.05). Furthermore, obvious regional epidemiological differences among the five diseases were observed. There was a mixed infection of BRV+BCoV in each age stage, the highest mixed infection being BVDV+BRV+K99 at 0-2 months of age. Our results showed that the cattle of scattered households in the Inner Mongolia of China were endemicly infected with several important cattle pathogens. Most of the pathogens studied occurred between 0-2 months of age and were mixed infections, which greatly influences the health of the cattle and leads to economic loss. These findings are of practical significance for the future prevention and control of bovine diarrhea in the Inner Mongolia or other regions of China.

Dynamic Molecular Investigation of the Solid-Electrolyte Interphase of an Anode-Free Lithium Metal Battery Using In Situ Liquid SIMS and Cryo-TEM.

We use in situ liquid secondary ion mass spectroscopy, cryogenic transmission electron microscopy, and density functional theory calculation to delineate the molecular process in the formation of the solid-electrolyte interphase (SEI) layer under the dynamic operating conditions. We discover that the onset potential for SEI layer formation and the thickness of the SEI show dependence on the solvation shell structure. On a Cu film anode, the SEI is noticed to start to form at around 2.0 V (nominal cell voltage) with a final thickness of about 40-50 nm in the 1.0 M LiPF6/EC-DMC electrolyte, while for the case of 1.0 M LiFSI/DME, the SEI starts to form at around 1.5 V with a final thickness of about 20 nm. Our observations clearly indicate the inner and outer SEI layer formation and dissipation upon charging and discharging, implying a continued evolution of electrolyte structure with extended cycling.

A Systematic Study on the Effects of Solvating Solvents and Additives in Localized High-Concentration Electrolytes over Electrochemical Performance of Lithium-Ion Batteries.

Localized high-concentration electrolytes (LHCEs) based on five different types of solvents were systematically studied and compared in lithium (Li)-ion batteries (LIBs). The unique solvation structure of LHCEs promotes the participation of Li salt in forming solid electrolyte interphase (SEI) on graphite (Gr) anode, which enables solvents previously considered incompatible with Gr to achieve reversible lithiation/delithiation. However, the long cyclability of LIBs is still subject to the intrinsic properties of the solvent species in LHCEs. Such issue can be readily resolved by introducing a small amount of additive into LHCEs. The synergetic decompositions of Li salt, solvating solvent and additive yield effective SEIs and cathode electrolyte interphases (CEIs) in most of the studied LHCEs. This study reveals that both the structure and the composition of solvation sheaths in LHCEs have significant effect on SEI and CEI, and consequently, the cycle life of energetically dense LIBs.

Direct in situ measurements of electrical properties of solid-electrolyte interphase on lithium metal anodes.

The solid-electrolyte interphase (SEI) critically governs the performance of rechargeable batteries. An ideal SEI is expected to be electrically insulative to prevent persistently parasitic reactions between the electrode and the electrolyte and ionically conductive to facilitate Faradaic reactions of the electrode. However, the true nature of the electrical properties of the SEI remains hitherto unclear due to the lack of a direct characterization method. Here we use in situ bias transmission electron microscopy to directly measure the electrical properties of SEIs formed on copper and lithium substrates. We reveal that SEIs show a voltage-dependent differential conductance. A higher rate of differential conductance induces a thicker SEI with an intricate topographic feature, leading to an inferior Coulombic efficiency and cycling stability in Li∣∣Cu and Li∣∣LiNi0.8Mn0.1Co0.1O2 cells. Our work provides insight into the targeted design of the SEI with desired characteristics towards better battery performance.

SOMAS: a platform for data-driven material discovery in redox flow battery development.

Aqueous organic redox flow batteries offer an environmentally benign, tunable, and safe route to large-scale energy storage. The energy density is one of the key performance parameters of organic redox flow batteries, which critically depends on the solubility of the redox-active molecule in water. Prediction of aqueous solubility remains a challenge in chemistry. Recently, machine learning models have been developed for molecular properties prediction in chemistry and material science. The fidelity of a machine learning model critically depends on the diversity, accuracy, and abundancy of the training datasets. We build a comprehensive open access organic molecular database "Solubility of Organic Molecules in Aqueous Solution" (SOMAS) containing about 12,000 molecules that covers wider chemical and solubility regimes suitable for aqueous organic redox flow battery development efforts. In addition to experimental solubility, we also provide eight distinctive quantum descriptors including optimized geometry derived from high-throughput density functional theory calculations along with six molecular descriptors for each molecule. SOMAS builds a critical foundation for future efforts in artificial intelligence-based solubility prediction models.

Pinned Electrode/Electrolyte Interphase and Its Formation Origin for Sulfurized Polyacrylonitrile Cathode in Stable Lithium Batteries.

Sulfurized polyacrylonitrile (SPAN) represents one of the most promising directions for high-energy-density lithium (Li)-sulfur batteries. However, the practical application of Li||SPAN is currently limited by the insufficient chemical/electrochemical stability of electrode/electrolyte interphase (EEI). Here, a pinned EEI layer is designed for stabilizing a SPAN cathode by regulating the EEI formation mechanism in an advanced LiFSI/ether/fluorinated-ether electrolyte. Computational simulations and experimental investigations reveal that, benefiting from the nonsolvating nature, the fluorinated-ether can not only act as a protective shield to prevent the Li polysulfides dissolution but also, more importantly, endow a diffusion-controlled EEI formation process. It promotes the formation of a uniform, protective, and conductive EEI layer pinning into SPAN surface region, enabling the high loading Li||SPAN batteries with superior cycling stability, wide temperature performance, and high-rate capability. This design strategy opens an avenue for exploring advanced electrolytes for Li||SPAN batteries and guides the interface design for broad types of battery systems.

Nonsacrificial Additive for Tuning the Cathode-Electrolyte Interphase of Lithium-Ion Batteries.

Solid-electrolyte interphases is essential for stable cycling of rechargeable batteries. The traditional approach for interphase design follows the decomposition of additives prior to the host electrolyte, which, as governed by the thermodynamic rule, however, inherently limits the viable additives. Here we report an alternative approach of using a nonsacrificial additive. This is exemplified by the localized high-concentration electrolytes, where the fluoroethylene carbonate (FEC) plays a nonsacrificial role for modifying the chemistry, structure, and formation mechanism of the cathode-electrolyte interphase (CEI) layers toward enhanced cycling stability. On the basis of ab initio molecular dynamics simulations, we further reveal that the unexpected activation of the otherwise inert species in the interphase formation is due to the FEC-Li+ coordinated environment that altered the electronic states of reactants. The nonsacrificial additive on CEI formation opens up alternative avenues for the interphase design through the use of the commonly overlooked, anodically stable compounds.

Graphical Gaussian process regression model for aqueous solvation free energy prediction of organic molecules in redox flow batteries.

The solvation free energy of organic molecules is a critical parameter in determining emergent properties such as solubility, liquid-phase equilibrium constants, pKa and redox potentials in an organic redox flow battery. In this work, we present a machine learning (ML) model that can learn and predict the aqueous solvation free energy of an organic molecule using the Gaussian process regression method based on a new molecular graph kernel. To investigate the performance of the ML model for electrostatic interaction, the nonpolar interaction contribution of the solvent and the conformational entropy of the solute in the solvation free energy, three data sets with implicit or explicit water solvent models, and contribution of the conformational entropy of the solute are tested. We demonstrate that our ML model can predict the solvation free energy of molecules at chemical accuracy with a mean absolute error of less than 1 kcal mol-1 for subsets of the QM9 dataset and the Freesolv database. To solve the general data scarcity problem for a graph-based ML model, we propose a dimension reduction algorithm based on the distance between molecular graphs, which can be used to examine the diversity of the molecular data set. It provides a promising way to build a minimum training set to improve prediction for certain test sets where the space of molecular structures is predetermined.

High-sensitivity determination of available cobalt in soil using laser-induced breakdown spectroscopy assisted with laser-induced fluorescence.

Conventional laser-induced breakdown spectroscopy could not conduct high-sensitivity determination of available cobalt due to spectral interference and weak spectral intensity. To improve the poor detection sensitivity of available cobalt in soil, available cobalt was extracted from soil and prepared. Laser-induced breakdown spectroscopy assisted with laser-induced fluorescence was introduced to excite and detect the cobalt element. The results showed that coefficients of the calibration curve for the available cobalt element could reach 0.9991, and the limits of detection could reach 0.005 mg/kg in soil under optimized conditions, which were all much better than conventional LIBS and reach the international minimum detection standards. This work provides a possible approach for detecting available trace elements in soil.

Toward the Practical Use of Cobalt-Free Lithium-Ion Batteries by an Advanced Ether-Based Electrolyte.

The criticality of cobalt (Co) has been motivating the quest for Co-free positive electrode materials for building lithium (Li)-ion batteries (LIBs). However, the LIBs based on Co-free positive electrode materials usually suffer from relatively fast capacity decay when coupled with conventional LiPF6-organocarbonate electrolytes. To address this issue, a 1,2-dimethoxyethane-based localized high-concentration electrolyte (LHCE) was developed and evaluated in a Co-free Li-ion cell chemistry (graphite||LiNi0.96Mg0.02Ti0.02O2). Extraordinary capacity retentions were achieved with the LHCE in coin cells (95.3%), single-layer pouch cells (79.4%), and high-capacity loading double-layer pouch cells (70.9%) after being operated within the voltage range of 2.5-4.4 V for 500 charge/discharge cycles. The capacity retentions of counterpart cells using the LiPF6-based conventional electrolyte only reached 61.1, 57.2, and 59.8%, respectively. Mechanistic studies reveal that the superior electrode/electrolyte interphases formed by the LHCE and the intrinsic chemical stability of the LHCE account for the excellent electrochemical performance in the Co-free Li-ion cells.

A Polymer-in-Salt Electrolyte with Enhanced Oxidative Stability for Lithium Metal Polymer Batteries.

The lithium (Li) metal polymer battery (LMPB) is a promising candidate for solid-state batteries with high safety. However, high voltage stability of such a battery has been hindered by the use of polyethylene oxide (PEO), which oxidizes at a potential lower than 4 V versus Li. Herein, we adopt the polymer-in-salt electrolyte (PISE) strategy to circumvent the disadvantage of the PEO-lithium bis(fluorosulfonyl)imide (LiFSI) system with EO/Li ≤ 8 through a dry ball-milling process to avoid the contamination of the residual solvent. The obtained solid-state PISEs exhibit distinctly different morphologies and coordination structures which lead to significant improvement in oxidative stability. P(EO)1LiFSI has a low melting temperature, a high ionic conductivity at 60 °C, and an oxidative stability of ∼4.5 V versus Li/Li+. With an effective interphase rich in inorganic species and a good stability of the hybrid polymer electrolyte toward Li metal, the LMPB constructed with Li||LiNi1/3Co1/3Mn1/3O2 can retain 74.4% of capacity after 186 cycles at 60 °C under the cutoff charge voltage of 4.3 V. The findings offer a promising pathway toward high-voltage stable polymer electrolytes for high-energy-density and safe LMPBs.

Optimization of Magnesium-Doped Lithium Metal Anode for High Performance Lithium Metal Batteries through Modeling and Experiment.

Lithium (Li)-magnesium (Mg) alloy with limited Mg amount, which can also be called Mg-doped Li (Li-Mg), has been considered as a potential alternative anode for high energy density rechargeable Li metal batteries. However, the optimum doping-content of Mg in Li-Mg anode and the mechanism of the improved performance are not well understood. Herein, density functional theory (DFT) calculations are used to investigate the effect of Mg amount in Li-Mg anode. The Li-Mg with about 5 wt. % Mg (abbreviated as Li-Mg5) has the lowest absorption energy of Li, thus all the surface area can be "controlled" by Mg atoms, leading to the smooth and continuous deposition of Li on the surface around the Mg center. A localized high concentration electrolyte enables Li-Mg5 to exhibit the best cycling stability in Li metal batteries with high-loading cathode and lean electrolyte under 4.4 V high-voltage, which is approaching the demand of practical application. This electrolyte also helps generate an inorganic-rich solid electrolyte interphase, which leads to smooth, compact and less corrosion layer on the Li-Mg5 surface. Both theoretical simulations and experimental results prove that Li-Mg5 has optimum Mg content and gives best battery cycling performance.

Advanced Low-Flammable Electrolytes for Stable Operation of High-Voltage Lithium-Ion Batteries.

Despite being an effective flame retardant, trimethyl phosphate (TMPa ) is generally considered as an unqualified solvent for fabricating electrolytes used in graphite (Gr)-based lithium-ion batteries as it readily leads to Gr exfoliation and cell failure. In this work, by adopting the unique solvation structure of localized high-concentration electrolyte (LHCE) to TMPa and tuning the composition of the solvation sheaths via electrolyte additives, excellent electrochemical performance can be achieved with TMPa -based electrolytes in Gr∥LiNi0.8 Mn0.1 Co0.1 O2 cells. After 500 charge/discharge cycles within the voltage range of 2.5-4.4 V, the batteries containing the TMPa -based LHCE with a proper additive can achieve a capacity retention of 85.4 %, being significantly higher than cells using a LiPF6 -organocarbonates baseline electrolyte (75.2 %). Meanwhile, due to the flame retarding effect of TMPa , TMPa -based LHCEs exhibit significantly reduced flammability compared with the conventional LiPF6 -organocarbonates electrolyte.

Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries.

Electrolyte is very critical to the performance of the high-voltage lithium (Li) metal battery (LMB), which is one of the most attractive candidates for the next-generation high-density energy-storage systems. Electrolyte formulation and structure determine the physical properties of the electrolytes and their interfacial chemistries on the electrode surfaces. Localized high-concentration electrolytes (LHCEs) outperform state-of-the-art carbonate electrolytes in many aspects in LMBs due to their unique solvation structures. Types of fluorinated cosolvents used in LHCEs are investigated here in searching for the most suitable diluent for high-concentration electrolytes (HCEs). Nonsolvating solvents (including fluorinated ethers, fluorinated borate, and fluorinated orthoformate) added in HCEs enable the formation of LHCEs with high-concentration solvation structures. However, low-solvating fluorinated carbonate will coordinate with Li+ ions and form a second solvation shell or a pseudo-LHCE which diminishes the benefits of LHCE. In addition, it is evident that the diluent has significant influence on the electrode/electrolyte interphases (EEIs) beyond retaining the high-concentration solvation structures. Diluent molecules surrounding the high-concentration clusters could accelerate or decelerate the anion decomposition through coparticipation of diluent decomposition in the EEI formation. The varied interphase features lead to significantly different battery performance. This study points out the importance of diluents and their synergetic effects with the conductive salt and the solvating solvent in designing LHCEs. These systematic comparisons and fundamental insights into LHCEs using different types of fluorinated solvents can guide further development of advanced electrolytes for high-voltage LMBs.

Double Feature Extraction Method of Ship-Radiated Noise Signal Based on Slope Entropy and Permutation Entropy.

In order to accurately identify various types of ships and develop coastal defenses, a single feature extraction method based on slope entropy (SlEn) and a double feature extraction method based on SlEn combined with permutation entropy (SlEn&PE) are proposed. Firstly, SlEn is used for the feature extraction of ship-radiated noise signal (SNS) compared with permutation entropy (PE), dispersion entropy (DE), fluctuation dispersion entropy (FDE), and reverse dispersion entropy (RDE), so that the effectiveness of SlEn is verified, and SlEn has the highest recognition rate calculated by the k-Nearest Neighbor (KNN) algorithm. Secondly, SlEn is combined with PE, DE, FDE, and RDE, respectively, to extract the feature of SNS for a higher recognition rate, and SlEn&PE has the highest recognition rate after the calculation of the KNN algorithm. Lastly, the recognition rates of SlEn and SlEn&PE are compared, and the recognition rates of SlEn&PE are higher than SlEn by 4.22%. Therefore, the double feature extraction method proposed in this paper is more effective in the application of ship type recognition.

Role of inner solvation sheath within salt-solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries.

Functional electrolyte is the key to stabilize the highly reductive lithium (Li) metal anode and the high-voltage cathode for long-life, high-energy-density rechargeable Li metal batteries (LMBs). However, fundamental mechanisms on the interactions between reactive electrodes and electrolytes are still not well understood. Recently localized high-concentration electrolytes (LHCEs) are emerging as a promising electrolyte design strategy for LMBs. Here, we use LHCEs as an ideal platform to investigate the fundamental correlation between the reactive characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. The effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate, and ether) on the stability of high-voltage LMBs are systematically studied. The stabilities of electrodes in different LHCEs indicate the intrinsic synergistic effects between the salt and the solvent when they coexist on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte interphases and thus the battery performances.

Enabling Ether-Based Electrolytes for Long Cycle Life of Lithium-Ion Batteries at High Charge Voltage.

Lithium-ion batteries (LIBs) with high-nickel (Ni) content LiNixMnyCozO2 (x + y + z = 1) (NMC with Ni ≥ 0.6) cathodes operated at high charge voltages have been considered as one of the most promising candidates for addressing the challenge of increasing energy density demand. Conventional LiPF6-organocarbonate electrolytes exhibit incompatibility with such cell chemistries under certain testing conditions because of the instability of electrode/electrolyte interphases. In response to this challenge, ether-based electrolytes with finely tuned structure and composition of solvation sheaths were developed and evaluated in graphite (Gr)∥NMC811 cell chemistry in 2.5-4.4 V, despite ethers being conventionally considered to be unfavorable electrolyte solvents for LIBs because of their anodic instability above 4.0 V and cointercalation into Gr electrodes. The functional ether-based electrolytes in this work enable both excellent cycle life and high rate capability of Gr∥NMC811 cells. Mechanistic studies reveal that the unique structure and composition of the solvation sheath of the functional ether electrolytes are the main reasons behind their excellent anodic stability and effective protection of the Gr electrode and, consequently, the extraordinary cell performances when operated at high charge cutoff voltages. This work also provides a feasible approach in developing highly stable functional electrolytes for high-energy density LIBs.