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Although solid-state lithium (Li)-metal batteries promise both high energy density and safety, existing solid ion conductors fail to satisfy the rigorous requirements of battery operations. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact with electrodes. Conversely, polymer ion conductors that are Li-metal-stable usually provide better interfacial compatibility and mechanical tolerance, but typically suffer from inferior ionic conductivity owing to the coupling of the ion transport with the motion of the polymer chains1-3. Here we report a general strategy for achieving high-performance solid polymer ion conductors by engineering of molecular channels. Through the coordination of copper ions (Cu2+) with one-dimensional cellulose nanofibrils, we show that the opening of molecular channels within the normally ion-insulating cellulose enables rapid transport of Li+ ions along the polymer chains. In addition to high Li+ conductivity (1.5 × 10-3 siemens per centimetre at room temperature along the molecular chain direction), the Cu2+-coordinated cellulose ion conductor also exhibits a high transference number (0.78, compared with 0.2-0.5 in other polymers2) and a wide window of electrochemical stability (0-4.5 volts) that can accommodate both the Li-metal anode and high-voltage cathodes. This one-dimensional ion conductor also allows ion percolation in thick LiFePO4 solid-state cathodes for application in batteries with a high energy density. Furthermore, we have verified the universality of this molecular-channel engineering approach with other polymers and cations, achieving similarly high conductivities, with implications that could go beyond safe, high-performance solid-state batteries.
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Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI)2], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI)2], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.
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Continuous lithium (Li) depletion shadows the increase in energy density and safety properties promised by zero-excess lithium metal batteries (ZELMBs). Guiding the Li deposits toward more homogeneous and denser lithium morphology results in improved electrochemical performance. Herein, a lithium nitrate (LiNO3 ) enriched separator that improves the morphology of the Li deposits and facilitates the formation of an inorganic-rich solid-electrolyte interphase (SEI) resulting in an extended cycle life in Li||Li-cells as well as an increase of the Coulombic efficiency in Cu||Li-cells is reported. Using a LiNi0.6 Co0.2 Mn0.2 O2 positive electrode in NCM622||Cu-cells, a carbonate-based electrolyte, and a LiNO3 enriched separator, an extension of the cycle life by more than 50 cycles with a moderate capacity fading compared to the unmodified separator is obtained. The relative constant level of LiNO3 in the electrolyte, maintained by the LiNO3 enriched separator throughout the cycling process stems at the origin of the improved performance. Ion chromatography measurements carried out at different cycles support the proposed mechanism of a slow and constant release of LiNO3 from the separator. The results indicate that the strategy of using a LiNO3 enriched separator instead of LiNO3 as a sacrificial electrolyte additive can improve the performance of ZELMBs further by maintaining a compact and thus stable SEI layer on Li deposits.
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Lithium metal batteries operated with high voltage cathodes are predestined for the realization of high energy storage systems, where solid polymer electrolytes offer a possibility to improve battery safety. Al2O3_PCL is introduced as promising hybrid electrolyte made from polycaprolactone (PCL) and Al2O3 nanoparticles that can be prepared in a one-pot synthesis as a random mixture of linear PCL and PCL-grafted Al2O3. Upon grafting, synergistic effects of mechanical stability and ionic conductivity are achieved. Due to the mechanical stability, manufacture of PCL-based membranes with a thickness of 50 µm is feasible, yielding an ionic conductivity of 5·10-5 S cm-1 at 60 °C. The membrane exhibits an impressive performance of Li deposition in symmetric Li||Li cells, operating for 1200 h at a constant and low overvoltage of 54 mV and a current density of 0.2 mA cm-2. NMC622 | Al2O3_PCL | Li cells are cycled at rates of up to 1 C, achieving 140 cycles at >80% state of health. The straightforward synthesis and opportunity of upscaling as well as solvent-free polymerization render the Al2O3_PCL hybrid material as rather safe, potentially sustainable and affordable alternative to conventional polymer-based electrolytes.
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Herein, a mesoporous MnCo2O4/Co3O4 nanocomposite was fabricated using a polyvinylpyrrolidone (PVP)-assisted hydrothermal synthesis method by maintaining only the non-stoichiometric ratio of Mn and Co (2 : 6), leading to an extra phase of Co3O4 coupled with MnCo2O4. Microstructural analysis showed that the obtained sample has a uniform nanowire-like morphology composed of interconnected nanoparticles. The stoichiometric ratio (2 : 4) was maintained to synthesize pure MnCo2O4 for comparative analysis. However, the obtained structure of pure MnCo2O4 was found to be irregular and fragile. After their employment as anode-active materials, the nanocomposite electrode showed superior high rate capability (1043.8 mA h g-1 at 5C) and long-term cycling stability (773.6 mA h g-1 after 500 cycles at 0.5C) in comparison to the pure MnCo2O4 electrode (771.5 mA h g-1 at 5C and 638.9 mA h g-1 at 0.5C after 500 cycles). It was believed that the extra phase of Co3O4 may also participate in the electrochemical reactions due to its high electrochemically active nature. Benefiting from the appealing architectural features and striking synergistic effect, the integrated MnCo2O4/Co3O4 nanocomposite anode exhibits excellent electrochemical properties and high cycle stability for LIBs.
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Antibody combination therapies have become viable therapeutic treatment options for certain severe diseases such as cancer. The co-formulation production approach is intrinsically associated with more complex drug product variant profiles and creates more challenges for analytical control of drug product quality. In addition to various individual quality attributes, those arising from the interactions between the antibodies also potentially emerge through co-formulation. In this study, we describe the development of a widely applicable multi-dimensional liquid chromatography coupled to tandem mass spectrometry method for antibody homo- versus hetero-aggregate characterization. The co-formulation of trastuzumab and pertuzumab was used, a challenging model system, comprising two monoclonal antibodies with very similar physicochemical properties. The data presented demonstrate the high stability of the co-formulation, where only minor aggregate formation is observed upon product storage and accelerated temperature or light-stress conditions. The results also show that the homo- and hetero-aggregates, formed in low and comparable proportions, are only marginally impacted by the formulation and product storage conditions. No preferential formation of hetero-aggregates, in comparison to the already existing pertuzumab and trastuzumab homo-aggregates, was observed.
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Anticorpos Monoclonais , Espectrometria de Massas em Tandem , Cromatografia Líquida , Anticorpos Monoclonais/química , Trastuzumab/químicaRESUMO
Pre-lithiation via electrolysis, herein defined as electrolytic pre-lithiation, using cost-efficient electrolytes based on lithium chloride (LiCl), is successfully demonstrated as a proof-of-concept for enabling lithium-ion battery full-cells with high silicon content negative electrodes. An electrolyte for pre-lithiation based on γ-butyrolactone and LiCl is optimized using boron-containing additives (lithium bis(oxalato)borate, lithium difluoro(oxalate)borate) and CO2 with respect to the formation of a protective solid electrolyte interphase (SEI) on silicon thin films as model electrodes. Reversible lithiation in Si||Li metal cells is demonstrated with Coulombic efficiencies (CEff ) of 95-96% for optimized electrolytes comparable to 1 m LiPF6 /EC:EMC 3:7. Formation of an effective SEI is shown by cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). electrolytic pre-lithiation experiments show that notable amounts of the gaseous product Cl2 dissolve in the electrolyte leading to a self-discharge Cl2 /Cl- shuttle mechanism between the electrodes lowering pre-lithiation efficiency and causing current collector corrosion. However, no significant degradation of the Si active material and the SEI due to contact with elemental chlorine is found by SEM, impedance, and XPS. In NCM111||Si full-cells, the capacity retention in the 100th cycle can be significantly increased from 54% to 78% by electrolytic pre-lithiation, compared to reference cells without pre-lithiation of Si.
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Li-rich layered oxides are considered as one of the most promising cathode materials for secondary lithium batteries due to their high specific capacities, but the issue of continuous voltage decay during cycling hinders their market entry. Increasing the Ni content in Li-rich materials is assumed to be an effective way to address this issue and attracts recent research interests. However, a high Ni content may induce increased intrinsic reactivity of materials, resulting in severe side reactions with the electrolyte. Thus, a comprehensive study to differentiate the two effects of the Ni content on the cell performance with Li-rich cathode is carried out in this work. Herein, it is demonstrated that a properly dosed amount of Ni can effectively suppress the voltage decay in Li-rich cathodes, while over-loading of Ni, on the contrary, can cause structural instability, Ni dissolution, and nonuniform Li deposition during cycling as well as severe oxygen loss. This work offers a deep understanding on the impacts of Ni content in Li-rich materials, which can be a good guidance for the future design of such cathodes for high energy density lithium batteries.
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Effective electrolyte compositions are of primary importance in raising the performance of lithium-ion batteries (LIBs). Recently, fluorinated cyclic phosphazenes in combination with fluoroethylene carbonate (FEC) have been introduced as promising electrolyte additives, which can decompose to form an effective dense, uniform, and thin protective layer on the surface of electrodes. Although the basic electrochemical aspects of cyclic fluorinated phosphazenes combined with FEC were introduced, it is still unclear how these two compounds interact constructively during operation. This study investigates the complementary effect of FEC and ethoxy(pentafluoro)cyclotriphosphazene (EtPFPN) in aprotic organic electrolyte in LiNi0.5 Co0.2 Mn0.3 O ⥠SiOx /C full cells. The formation mechanism of lithium ethyl methyl carbonate (LEMC)-EtPFPN interphasial intermediate products and the reaction mechanism of lithium alkoxide with EtPFPN are proposed and supported by Density Functional Theory calculations. A novel property of FEC is also discussed here, called molecular-cling-effect (MCE). To the best knowledge, the MCE has not been reported in the literature, although FEC belongs to one of the most investigated electrolyte additives. The beneficial MCE of FEC toward the sub-sufficient solid-electrolyte interphase forming additive compound EtPFPN is investigated via gas chromatography-mass spectrometry, gas chromatography high resolution-accurate mass spectrometry, in situ shell-isolated nanoparticle-enhanced Raman spectroscopy, and scanning electron microscopy.
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The lifetime of lithium ion batteries (LIBs) decreases under continuous cycling due to various degradation processes, such as dissolution of transition metals (TMs) from the electrodes. Therefore, suitable methods to analyze the oxidation states of TMs are mandatory to better understand the dissolution mechanisms of TMs from positive and negative electrodes (LIBs). To investigate the dissolution of Mn2+ and Mn3+ in electrolytes of LIBs, a previously implemented capillary electrophoresis (CE) method with UV/Vis spectroscopy detection was further developed with the aim of higher sensitivities and additional detection of other dissolved divalent TMs such as Co2+ , Ni2+ , and Cu2+ . Therefore, inductively coupled plasma-mass spectrometry was applied instead of UV/Vis for detection. This also allows the use of Ga3+ instead of the previously used Cu2+ as an internal standard, which solves the limitation of this method for cycled LIBs due to copper dissolution from the copper-based current collector. The CE buffer based on sodium diphosphate as complexing agent for the stabilization of Mn3+ and cetyltrimethylammonium bromide as dynamic capillary wall modifier was optimized in terms of concentrations and pH. Finally, both manganese species and Co2+ , Ni2+ , and Cu2+ could be analyzed within 15 min. With this improved method, the dissolution of TMs in LIBs for positive electrode materials such as LiNi0.5 Mn1.5 O4 (LNMO) or LiNix Coy Mnz O2 (NCM, x + y + z = 1) can be studied in future in more detail.
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Cobre , Manganês , Cobre/análise , Espectrometria de Massas/métodos , Análise Espectral , Lítio , Eletroforese Capilar/métodosRESUMO
The state-of-charge (SOC) is an essential parameter for battery management systems to reflect and monitor the remaining capacity of individual battery cells. In addition to its application at the cell level, the SOC also plays an important role in the investigation of redox processes of cathode active materials (CAMs) in lithium ion batteries (LIBs) during electrochemical cycling. These processes can be influenced by a large variety of factors such as active material properties, inhomogeneities of the electrode, degradation phenomena and the charge/discharge protocol during cycling. Consequently, non-uniform redox reactions can occur, resulting in charge heterogeneities of the active material. This heterogeneity can translate into accelerated aging of the CAM and a reduction in reversible capacity of the battery cell, since the active material is not fully utilized. To understand and monitor the SOC heterogeneity at the mesoscale, a wide range of techniques have been implemented in the past. In this perspective an overview of current state-of-the-art techniques to evaluate charge heterogeneities of CAMs in LIBs is presented. Therefore, techniques which utilize synchrotron radiation like X-ray absorption near-edge structure (XANES) and transmission X-ray spectroscopy (TXM) are presented as well as Raman spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Next to these established techniques, classification single particle inductively coupled plasma optical emission spectroscopy (CL-SP-ICP-OES) as a new approach is also discussed in this perspective. For these techniques, the areas of application, advantages as well as drawbacks are highlighted and discussed.
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Linear poly(alkylene carbonates) such as polyethylene carbonate (PEC) and polypropylene carbonate (PPC) have gained increasing interest due to their remarkable ion transport properties such as high Li+ transference numbers. The cause of these properties is not yet fully understood which makes it challenging to replicate them in other polymer electrolytes. Therefore, it is critical to understand the underlying mechanisms in polycarbonate electrolytes such as PPC. In this work we present insights from impedance spectroscopy, transference number measurements, PFG-NMR, IR and Raman spectroscopy as well as molecular dynamics simulations to address this issue. We find that in addition to plasticization, the lithium ion coordination by the carbonate groups of the polymer is weakened upon gelation, leading to a rapid exhange of the lithium ion solvation shell and consequently a strong increase of the conductivity. Moreover, we study the impact of the anions by employing different conducting salts. Interestingly, while the total conductivity decreases with increasing anion size, the reverse trend can be observed for the lithium ion transference numbers. Via our holistic approach, we demonstrate that this behavior can be attributed to differences in the collective ion dynamics.
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In sub-surface drilling rigs, one key critical crisis is unwanted influx into the borehole as a result of increasing the influx rate while drilling deeper into a high-pressure gas formation. Although established risk assessments in drilling rigs provide a high degree of protection, uncertainty arises due to the behavior of the formation being drilled into, which may cause crucial situations at the rig. To overcome such uncertainties, real-time sensor measurements are used to predict, and thus prevent, such crises. In addition, new understandings of the effective events were derived from raw data. In order to avoid the computational overhead of input feature analysis that hinders time-critical prediction, EventTracker sensitivity analysis, an incremental method that can support dimensionality reduction, was applied to real-world data from 1600 features per each of the 4 wells as input and 6 time series per each of the 4 wells as output. The resulting significant input series were then introduced to two classification methods: Random Forest Classifier and Neural Networks. Performance of the EventTracker method was understood correlated with a conventional manual method that incorporated expert knowledge. More importantly, the outcome of a Neural Network Classifier was improved by reducing the number of inputs according to the results of the EventTracker feature selection. Most important of all, the generation of results of the EventTracker method took fractions of milliseconds that left plenty of time before the next bunch of data samples.
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Faradaic reactions including charge transfer are often accompanied with diffusion limitation inside the bulk. Conductive two-dimensional frameworks (2D MOFs) with a fast ion transport can combine both-charge transfer and fast diffusion inside their porous structure. To study remaining diffusion limitations caused by particle morphology, different synthesis routes of Cu-2,3,6,7,10,11-hexahydroxytriphenylene (Cu3 (HHTP)2 ), a copper-based 2D MOF, are used to obtain flake- and rod-like MOF particles. Both morphologies are systematically characterized and evaluated for redox-active Li+ ion storage. The redox mechanism is investigated by means of X-ray absorption spectroscopy, FTIR spectroscopy and in situ XRD. Both types are compared regarding kinetic properties for Li+ ion storage via cyclic voltammetry and impedance spectroscopy. A significant influence of particle morphology for 2D MOFs on kinetic aspects of electrochemical Li+ ion storage can be observed. This study opens the path for optimization of redox active porous structures to overcome diffusion limitations of Faradaic processes.
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Cobre , Estruturas Metalorgânicas , Lítio , Espectroscopia Dielétrica , Difusão , ÍonsRESUMO
In ionic-liquid (IL)-based electrolytes, relevant for current energy storage applications, ion transport is limited by strong ion-ion correlations, generally yielding inverse Haven ratios (ionicities) of below 1. In particular, Li is transported in anionic clusters into the wrong direction of the electric field, requiring compensation by diffusive anion fluxes. Here, we present a concept to exploit ion-ion correlations in concentrated IL electrolytes beneficially by designing organic cations with a Li-coordinating chain. 1H NMR and Raman spectra show that IL cations with seven or more ether oxygens in the side chain induce Li coordination to organic cations. An unusual behavior of an inverse Haven ratio of >1 is found, suggesting an ionicity larger than that of an ideal electrolyte with uncorrelated ion motion. This superionic behavior is consistently demonstrated in both NMR transport/conductivity measurements and molecular dynamics (MD) simulations. Key to this achievement is the formation of long-lived Li-IL cation complexes, which invert the Li drift direction, yielding positive Li+ ion mobilities for the first time in a single IL-solvent-based electrolyte. Onsager correlation coefficients are derived from MD simulations and demonstrate that the main contributions to the inverse Haven ratio, which induce superionicity, arise from enhanced Li-IL cation correlations and a sign inversion of Li-anion correlation coefficients. Thus, the novel concept of coordinating cations not only corrects the unfortunate anionic drift direction of Li in ILs but even exploits strong ion correlations in the concentrated electrolyte toward superionic transport.
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The formation of solid-electrolyte interphase (SEI) in "water-in-salt" electrolyte (WiSE) expands the electrochemical stability window of aqueous electrolytes beyond 3.0 V. However, the parasitic hydrogen evolution reaction that drives anode corrosion, cracking, and the subsequent reformation of SEI still occurs, compromising long-term cycling performance of the batteries. To improve cycling stability, an unsaturated monomer acrylamide (AM) is introduced as an electrolyte additive, whose presence in WiSE reduces its viscosity and improves ionic conductivity. Upon charging, AM electropolymerizes into polyacrylamide, as confirmed both experimentally and computationally. The in situ polymer constitutes effective protection layers at both anode and cathode surfaces, and enables LiMn2 O4 ||L-TiO2 full cells with high specific capacity (157 mAh g-1 at 1 C), long-term cycling stability (80% capacity retention within 200 cycles at 1 C), and high rate capability (79 mAh g-1 at 30 C). The in situ electropolymerization found in this work provides an alternative and highly effective strategy to design protective interphases at the negative and positive electrodes for high-voltage aqueous batteries of lithium-ion or beyond.
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Herein we report on an analytical study of dry-shredded lithium-ion battery (LIB) materials with unknown composition. Samples from an industrial recycling process were analyzed concerning the elemental composition and (organic) compound speciation. Deep understanding of the base material for LIB recycling was obtained by identification and analysis of transition metal stoichiometry, current collector metals, base electrolyte and electrolyte additive residues, aging marker molecules and polymer binder fingerprints. For reversed engineering purposes, the main electrode and electrolyte chemistries were traced back to pristine materials. Furthermore, possible lifetime application and accompanied aging was evaluated based on target analysis on characteristic molecules described in literature. With this, the reported analytics provided precious information for value estimation of the undefined spent batteries and enabled tailored recycling process deliberations. The comprehensive feedstock characterization shown in this work paves the way for targeted process control in LIB recycling processes.
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Solid polymer electrolytes (SPEs) have attracted considerable attention for high energy solid-state lithium metal batteries (LMBs). In this work, potentially ecofriendly, solid-state poly(ε-caprolactone) (PCL)-based star polymer electrolytes with cross-linked structures (xBt-PCL) are introduced that robustly cycle against LiNi0.6 Mn0.2 Co0.2 O2 (NMC622) composite cathodes, affording long-term stability even at higher current densities. Their superior features allow for sufficient suppression of dendritic lithium deposits, as monitored by 7 Li solid-state NMR. Advantageous electrolyte|electrode interfacial properties derived from cathode impregnation with 1.5 wt% PCL enable decent cell performance until up to 500 cycles at rates of 1C (60 °C), illustrating the high potential of PCL-based SPEs for application in high-voltage LMBs.
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Lítio , Polímeros , EletrólitosRESUMO
Electrically rechargeable zinc-air batteries attract extensive research interests due to their potentially high energy density and low cost but suffer from chemical instability and poor electrochemical reversibility caused by the corrosive nature of the conventional alkaline electrolyte. Here we demonstrate a non-alkaline zinc acetate electrolyte for electrically rechargeable zinc-air batteries with long-term operation stability (>600â hours) in ambient air without any special cell engineering. The unique battery chemistry with reversible formation/decomposition of zinc hydroxyacetate dihydrate is systematically revealed using diversified electrochemical and analytical techniques. Furthermore, the carbon-based air cathode is modified towards a hydrophilic surface to increase the energy efficiency. This work provides new insight on effective electrolyte design to achieve long-term operation zinc-air batteries.
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The chemical and structural complexity of lithium-ion battery electrodes and their constituting materials requires comprehensive characterization techniques to reveal degradation phenomena at the mesoscale. For the first time, application of single-particle inductively coupled plasma-optical emission spectroscopy enables the investigation of the chemomechanical interplay on the particle level of lithium transition-metal oxide [e.g., Li(Ni1/3Co1/3Mn1/3)O2] cathode materials. The sample-inherent polydisperse size distribution of particles ranging up to 10⯵m was effectively restricted with the use of a custom-made gravitational-counter-flow classifier to facilitate complete particle vaporization and excitation. After classification, the particles were transported directly to the plasma by means of an argon flow to prevent chemical alterations in aqueous media due to potentially occurring Li+-H+ exchange reactions. The size-separated particles were monitored online by flow cell particle analysis (FPA). The influence of different gas flow settings and plasma parameters on the peak emission intensity of Li and Mn was evaluated. A particle size detection limit of â¼0.5 µm was estimated based on the 3σ criterion of the baselines and the measured peak intensities for Li and Mn considering the particle size distribution as obtained by FPA. The corresponding analyte masses at the detection limits were â¼30 and â¼180 fg for Li and Mn, respectively. Furthermore, an approach for a matrix-matched external calibration with electrochemically delithiated lithium transition-metal oxides is presented.