Battery Interface Research Articles

Electroanalytical Exploration of Li Loss at the Solid Electrolyte-Anode Interface in Anode-Free Batteries with Polymer Electrolytes

Li loss during cycling at the solid electrolyte∣anode interface strongly determines the cycle life of anode-free solid-state batteries (SSBs). Here, this loss is probed electroanalytically for polymer electrolyte (PE)-based SSBs in anode-free coin cells with practical pressures. A wide range of parameters expected to impact the measured average coulombic efficiency (CE) were explored to estimate the expected range of performance. These factors include PE type, cycling profiles, current collector type, and the presence of a thin Li seed layer. Low CE values in the ∼50%–85% range are observed for all electrolytes and test conditions. Other than the electrolyte type, a strong dependence of the CE on the electrochemical cycling profile and the type of metallic current collector is observed. Compared to the anode-free setup, the presence of a thin (5 μm) Li seed layer did not improve the average CE for two out of three PEs, suggesting its presence to be a weak contributor in minimizing the Li loss. This work provides baseline data on the Li losses in low-pressure anode-free configuration cells with PEs.

Enhanced prelithiation performance of Li5FeO4 cathode additive and optimized solid electrolyte interface enabled by Mn substitution

In the pursuit of enhancing the energy density of lithium-ion batteries, cathode prelithiation emerges as a pivotal approach, introducing additional irreversible active lithium ions to augment performance. Li5FeO4 (LFO) stands out as an excellent option, boasting an impressive theoretical specific capacity and the additional advantages of cost-effectiveness in raw materials and low preparation cost. However, the impact of extra lithium incorporations on compositional changes at the electrode-electrolyte interface as well as on cell stability has impeded further researches. Herein, a Mn doping strategy is proposed and predicted by first-principles calculations to synthesize partially Mn-substituted Li5.125Fe0.875Mn0.125O4 (LFMO). And the prelithiation with LFMO improved the interfacial composition of LiFePO4 (LFP) batteries compared to LFO, achieving a charging capacity of 213 mAh∙g−1 in the first cycle at 0.05 C. The subsequent treatment demonstrated superior cycling stability, maintaining a discharge specific capacity as high as 155.3 mAh∙g−1 after 100 cycles at 0.2 C, and exhibiting a higher capacity retention in the full cell. These discoveries could contribute to enhancing the regulation of battery interface during the utilization of LFO, potentially promoting the development of cathode lithium additives.

Optimizing the Na/NASCION electrolyte interface for stable solid-state Na metal batteries

Na super ionic conductor (NASICON)-type Na3Zr2Si2PO12 (NZSP) electrolytes, with their excellent safety and high energy density, are a promising candidate material for all-solid-state sodium-ion batteries. However, poor sintering performance and interfacial issues have limited its practical application. Herein, we propose the addition of sintering aids to densify grain boundaries and fine-tune the grain to achieve the densest microstructure, improve interfacial contact with sodium, and realize stable Na plating/stripping cycles at room temperature. (CuO)2-(B2O3)3 (CBO) is selected to reinforce grain boundary densification, inhibit dendrite growth, and ensure interfacial stability upon sintering at the lower temperature of 1000 °C. The optimized NZSP-0.2CBO demonstrates an ion conductivity reaching 6.83×10−4 S cm−1 at room temperature, exhibiting a lower activation energy of 0.27 eV compared to bare NZSP. The interface impedance of Na/NZSP-0.2CBO (34.48 Ω cm²) is significantly lower than that of bare NZSP (373.43 Ω cm²). The corresponding Na/NZSP-0.2CBO/Na exhibits stable deposition/stripping cycles over 850 h at 0.1 mA cm−2 and room temperature, with a low polarization voltage of 65 mV. These superior performances can be attributed to the densification effect that enhances conductivity, enabling a uniform and enhanced Na+ flux across the electrode/electrolyte interface without dendrite formation. A Na/NZSP-0.2CBO/Na3V2(PO4)3 battery is assembled accordingly, exhibiting a capacity of 87.4 mAh g−1for 100 cycles with a capacity retention rate of 84.9% and a high average coulombic efficiency of 97.6% at room temperature.

In Situ Polymerization Derived from PAN-Based Porous Membrane Realizing Double-Stabilized Interface and High Ionic Conductivity for Lithium-Metal Batteries.

Polymer polyacrylonitrile (PAN), with exceptional mechanical strength and ionic conductivity, is considered a potential electrolyte. However, the huge interfacial impedance of PAN-derived C≡N polar nitrile groups and Li anode limited its application. In this study, a double-stabilized interface was integrated by in situ polymerization of DOL between electrodes and a three-dimensional (3D) porous PAN polymer matrix containing SN plasticizer and LLZTO ceramic fillers to optimize the challenge of interfacial instability. The fabricated PDOL-PAN(SN/LLZTO)-PDOL composite solid electrolyte (CSE) exhibited the maximum ionic conductivities of 1.9 × 10-3 S cm-1 at room temperature and 2.5 × 10-3 S cm-1 at 60 °C, an electrochemical stability window (ESW) of 4.9 V, and a high Li+ transference number (tLi+) of 0.65. In addition, the side reactions of the PAN/Li metal were effectively prevented by inserting PDOL between the 3D porous membrane and Li electrode. Benefiting from the superior interface compatibility and ion conductivity, the Li symmetric battery showed more than 2000 h of cyclability. The solid Li/LiFePO4 full battery delivered excellent cycling performance, showing an original specific capacity of 136.2 mAh g-1 with a capacity retention of 90.1% after 350 cycles at 1C and 60 °C. Furthermore, the cycling of solid-state Li/NCM622 batteries also proved their application potential. This work presents an effective approach to solving interface problems of the PAN electrolyte for solid lithium-metal batteries (LMBs).

In-situ construction of PDOL electrolyte with dual-reinforced stable interface for high-voltage lithium metal batteries

In-situ construction of PDOL electrolyte with dual-reinforced stable interface for high-voltage lithium metal batteries

Robust pseudocapacitive Na+ intercalation induced by MoS2 on active Mo2C current collector interface for high areal capacity sodium-ion batteries

Sodium-ion batteries (SIBs) have emerged as compelling alternatives in the realm of electrochemical energy devices, poised to substitute lithium-ion batteries (LIBs). The primary challenge encompasses not only the scarcity of anode materials exhibiting exceptional Na+ storage capacity but also the endeavor to achieve high areal capacity. To address this challenge, a comprehensive strategy is proposed that entails utilizing a highly conductive molybdenum dicarbide (Mo2C) current collector (denoted as CCM) as a supporting scaffold for the bottom-up growth of molybdenum disulfide nanosheets (MoS2, serving as the main active component) (denoted as CCM@MoS2). The CCM improves interfacial bonding with MoS2 nanosheets and offers additional capacity to accommodate the increased Na+ insertion activity. Both theoretical and kinetic analyses reveal that the enhanced Na+ storage properties primarily stem from favorable adsorption energy, reduced diffusion barrier, and intercalation pseudocapacitance due to the strong electronic interfacial interaction between active CCM and MoS2. Hence, the as-prepared optimized CCM@MoS2 electrode exhibits a superior areal capacity of 6.36 mAh cm−2 at 0.4 mA cm−2, excellent rate capability of 1.02 mAh cm−2 at 24 mA cm−2 and long cycle life up to 500 cycles at 4 mA cm−2. Interesting, our as-prepared CCM@MoS2 electrode shows better performance for Na+ storage than Li+ storage at higher current density, affirming the enhanced kinetics in our architecture. This work proposes a rational strategy to enhance the areal capacity and stability of MoS2-based anode for SIBs and beyond.

Single magnetic core based inductor integration for battery-friendly LCL-type interleaved interface

Interleaving operation of the two-phase Buck/Boost converter is beneficial for reducing current ripple and power sharing. It makes this converter considered an ideal battery interface. However, multiple inductors are required in this power interface. To overcome this issue, an inductor integration scheme is developed in this work to optimize the two-phase Buck/Boost converter. With this design, all inductors required in the converter are implemented by wounding three coils on one magnetic core, which effectively improves the utilization of magnetic cores and reduces the size and cost of the battery interface. Moreover, both phase current ripple and total current ripple are suppressed by this design. In addition to the design concept, the specific coil wounding scheme, magnetic flux analysis, air gap design, and active damping control are analyzed in detail. Finally, Maxwell simulation model of the integrated inductor and 240 V to 400 V prototype of the two-phase interleaved Buck/Boost converter are developed. Simulation and experimental results effectively verify the effectiveness of the design scheme and the correctness of the theoretical analysis.

Phosphoric Acid Activation of Titanium-Supported Lead Dioxide Electrodes for Bipolar Battery Applications

Titanium foil coated with doped tin dioxide is an attractive option for the positive current collector interface of bipolar lead batteries due its corrosion resistance and mechanical performance. The phosphoric acid and two of its derivatives, one inorganic (calcium hydrogen phosphate) and one organic (poly-vinylphosphonic acid), have been studied as additives with potential for improvement of the capacity retention of such positive electrodes. The results show that the jar-formation process of the electrodes in the sulfuric acid electrolyte containing phosphoric acid successfully overcomes the capacity retention problem at all studied cases. This leads also to considerable improvement of the lead dioxide utilization. The cycling ageing of the electrodes combined with periodic impedance spectroscopy measurements, indicate progressive capacity loss corresponding to the typical processes of degradation of the lead dioxide structure. Rather small changes in the electrode resistance prove the corrosion and the passivation resistance of the current collectors. It is concluded that the combined doping with phosphoric acid species in the electrolyte and in the positive paste offers a potential for further improvements of the electrodes cyclability.

Heteroionic Interfaces in Hybrid Solid-State Batteries─Current Constriction at the Interface between Different Solid Electrolytes.

The requirements for suitable electrolyte materials in solid-state batteries are diverse and vary greatly depending on their role as separator or as part of the composite cathode. Hybrid cell concepts that incorporate different types of solid electrolytes are considered a promising solution to overcome the limitations of single material classes. However, the kinetics at the heteroionic interface (i.e., charge transfer) substantially affects the cell performance. Moreover, non-ideal physical contacts hinder detailed electrochemical characterization of the interface properties. Thus, we use microstructure-resolved electric network computations to explore how the impedance response of a homogeneous bilayer system is influenced by the interface morphology and the material parameters of the single solid electrolyte layers. Porous interfaces and the resulting current constriction effects give rise to signatures in the impedance spectrum that resemble that of actual migration processes. This hinders unequivocal identification of the origin of the impedance contributions. The resistance and capacitance of this geometric interface signal depend strongly on the contact area and its spatial distribution, the pore capacitance, and the local conductivities around the interface. An experimental case study of an oxide-sulfide multilayer is considered to highlight the challenges in impedance analysis and the assessment of reliable material parameters. These findings are universal and apply to any heterojunction.

Role of Salt Concentration in Stabilizing Charged Ni-Rich Cathode Interfaces in Li-Ion Batteries.

The cathode-electrolyte interphase (CEI) in Li-ion batteries plays a key role in suppressing undesired side reactions while facilitating Li-ion transport. Ni-rich layered cathode materials offer improved energy densities, but their high interfacial reactivities can negatively impact the cycle life and rate performance. Here we investigate the role of electrolyte salt concentration, specifically LiPF6 (0.5-5 m), in altering the interfacial reactivity of charged LiN0.8Mn0.1Co0.1O2 (NMC811) cathodes in standard carbonate-based electrolytes (EC/EMC vol %/vol % 3:7). Extended potential holds of NMC811/Li4Ti5O12 (LTO) cells reveal that the parasitic electrolyte oxidation currents observed are strongly dependent on the electrolyte salt concentration. X-ray photoelectron and absorption spectroscopy (XPS/XAS) reveal that a thicker LixPOyFz-/LiF-rich CEI is formed in the higher concentration electrolytes. This suppresses reactions with solvent molecules resulting in a thinner, or less-dense, reduced surface layer (RSL) with lower charge transfer resistance and lower oxidation currents at high potentials. The thicker CEI also limits access of acidic species to the RSL suppressing transition-metal dissolution into the electrolyte, as confirmed by nuclear magnetic resonance (NMR) spectroscopy and inductively coupled plasma optical emission spectroscopy (ICP-OES). This provides insight into the main degradation processes occurring at Ni-rich cathode interfaces in contact with carbonate-based electrolytes and how electrolyte formulation can help to mitigate these.

A Stable Matrix Assisting Highly Compatible and Maintainable Lithium-Garnet Interface for Solid-State Batteries.

Solid-state Li metal batteries (SSLMBs) are attractive due to their capability to simultaneously offer high energy density and high-level safety when combining Li metal anodes, solid-state electrolytes (SSEs), and high-voltage cathodes together. However, SSLMBs may well incur short circuits caused by Li dendrites penetrations, which mainly originate from the instability and poor contact between Li metal and SSEs. Herein, by taking full advantage of the reaction products of Li and Li1.3Al0.3Ti1.7(PO4)3 (LATP), a lithium-LATP composite anode (Li-LATP) is obtained, in which a stable matrix is formed to enhance the contact between Li and the garnet-type SSEs, alleviating the volume change and preserving an intact interface during the charge/discharge process. Consequently, the Li-LATP/garnet/Li-LATP symmetric cell displays a fairly low interfacial resistance of 6Ωcm2 and stable cycling performance for over 2500h with a low overpotential. Furthermore, the LiCoO2/garnet/Li-LATP full cell also shows a high discharge capacity of 159mAhg-1 and great cycling performance.

The Influence of Cathode Degradation Products on the Anode Interface in Lithium-Ion Batteries.

Degradation of cathode materials in lithium-ion batteries results in the presence of transition metal ions in the electrolyte, and these ions are known to play a major role in capacity fade and cell failure. Yet, while it is known that transition metal ions migrate from the metal oxide cathode and deposit on the graphite anode, their specific influence on anode reactions and structures, such as the solid electrolyte interphase (SEI), is still quite poorly understood due to the complexity in studying this interface in operational cells. In this work we combine operando electrochemical atomic force microscopy (EC-AFM), electrochemical quartz crystal microbalance (EQCM), and electrochemical impedance spectroscopy (EIS) measurements to probe the influence of a range of transition metal ions on the morphological, mechanical, chemical, and electrical properties of the SEI. By adding representative concentrations of Ni2+, Mn2+, and Co2+ ions into a commercially relevant battery electrolyte, the impacts of each on the formation and stability of the anode interface layer is revealed; all are shown to pose a threat to battery performance and stability. Mn2+, in particular, is shown to induce a thick, soft, and unstable SEI layer, which is known to cause severe degradation of batteries, while Co2+ and Ni2+ significantly impact interfacial conductivity. When transition metal ions are mixed, SEI degradation is amplified, suggesting a synergistic effect on the cell stability. Hence, by uncovering the roles these cathode degradation products play in operational batteries, we have provided a foundation upon which strategies to mitigate or eliminate these degradation products can be developed.

Improvement of the Interface Contact between Solid Polymer Electrolytes and Electrodes via Ultrasonic-Press Fusion

All solid-state lithium batteries have high energy density, good safety, and broad prospects. However, the poor compatibility of the electrolyte/electrode interface limits its development. To improve the interface contact performance of batteries, this study proposes an ultrasonic-press fusion method. The electrolyte/electrode structure was pressed by an ultrasonic sonotrode, and fused tightly via thermal and mechanical effects produced by ultrasonic-press fusion. The results showed that the charge transfer impedance at the battery interface was reduced by 80.3% in AC impedance testing, and the battery interface impedance performance was significantly improved. By observing the surface and interface morphology of the electrolyte, it was found that ultrasonic-press fusion improved the electrolyte interface contact. The electrolyte melted and produced microscale rheological behavior under the action of ultrasonic-press fusion, ultimately filling the capillary structure of anode in the battery, improving contact performance of the interface. Furthermore, a molecular dynamics model of the interface was constructed to calculate the contact performance. It was found that ultrasonic-press fusion generates thermal and mechanical effects. The thermal effect facilitates the electrolyte melts, and the mechanical effect causes the melt to vibrate, which coordinate and act on the electrolyte and cause the electrolyte to solder to the anode.

Constructing a Robust Cathode Electrolyte Interface for Aqueous Hybrid Lithium-Ion Batteries Via Regulating the Solvent–Solute Interaction in a Locally Concentrated Electrolyte

Constructing a Robust Cathode Electrolyte Interface for Aqueous Hybrid Lithium-Ion Batteries Via Regulating the Solvent–Solute Interaction in a Locally Concentrated Electrolyte

Construction of Selective Ion Transport Polymer at Anode-Electrolyte Interface for Stable Aqueous Zinc-Ion Batteries.

Rampant dendrite formation and serious adverse parasitic reactions induced by migration of dissolved V/Mn cathode ions on Zn anode have hampered the high performance of aqueous zinc-ion batteries (AZIBs). Inspired by the coordination chemistry between functional groups of polymer and electrolyte ions, a freestanding layer consisting of dopamine-functionalized polypyrrole (DA-PPy) nanowires served as a selective ion transport layer at the anode-electrolyte interface to address these two issues, which could simultaneously avoid polarization caused by the introduction of an additional interface. On the one hand, the DA-PPy layer displays excellent zinc ion and charge transfer ability, as well as provides chemical homochanneling for zinc ions at the interface, which endow the DA-PPy layer with properties as a chemical guider and physical barrier for dendrite inhibition. On the other hand, the DA-PPy layer can trap excess transition metal ions fleeing from the cathodes, thus serving as a chemical barrier, preventing the formation of Vx+/Mnx+-passivation on the surface of the zinc anode. Consequently, the AZIBs based on V2O5 and MnO2 cathodes involving the DA-PPy functional layer show a great improvement in the capacity retention.

Constructing Stable Zinc-Metal Anodes by Synergizing Hydrophobic Host with Zincophilic Interface for Aqueous Zinc Ions Batteries.

Aqueous zinc (Zn) ions battery is promising for future large-scale applications of energy storage due to the abundant reserves, high capacity of metallic Zn. However, dendritic growth, severe side reactions have limited the development of Zn-metal anodes. A single skeleton structure or interface protection is difficult to simultaneously mitigate these issues. Here, a novel composite design based on the synergistic interaction between the hydrophobic host, the zincophilic interface is reported. On the one hand, the 3D substrate reduces the local current density, inhibits dendritic growth. On the other hand, the protective interface homogenizes the nucleation due to the formation of the ZnAu3 alloy layer. More importantly, the collaborative construction of the hydrophobicity, zincophilicity for the electrode alleviates the aggravated hydrogen evolution reaction (only 2.5mmol h-1 ), simultaneously enables a low nucleation overpotential (31.7mV) during cycling. Consequently, a high Coulombic efficiency of ≈98.25% after 300 cycles is harvested for the composite electrode. The pouch cells assembled by this anode, LiMn2 O4 cathode maintain 82 mAh g-1 capacity retention after 140 cycles. This research shows an innovative Zn-based structural design for aqueous Zn-ion batteries.

Practical relevance of charge transfer resistance at the Li metal electrode|electrolyte interface in batteries?

AbstractThe theoretically possible energy and power densities of rechargeable batteries are practically limited by resistances as these lead to overvoltages, particularly pronounced at kinetically harsher conditions, i.e., high currents and/or low temperature. Charge transfer resistance (Rct), being a major type of resistance alongside with Ohmic (RΩ) and mass transport (Rmt), is related with the activation hindrance of electrochemical reactions. Its practical relevance is discussed within this work via analyzing $$\mathrm{Li}\mid \,\, \mid\mathrm{Li}$$ Li ∣ ∣ Li cells with the galvanostatic/constant current (CC) technique. Rct at Li|electrolyte interfaces is shown to be relevantly impacted by electrode–electrolyte interphases; implying the electrolyte type, as well. While solid polymer electrolytes (SPEs), e.g., based on poly(ethylene) oxide (PEO), show negligible Rct, it is evident for commercial liquid electrolytes and readily increase during storage. Given the asymptotic overvoltage vs. current behavior of Rct, obeying Butler-Volmer equation, Rct gets less relevant at enhanced currents, as experimentally validated, finally pointing to the dominance of RΩ and (depending on system) Rmt in the overall resistance. Graphical Abstract

A Review of the Synthesis of Biopolymer Hydrogel Electrolytes for Improved Electrode–Electrolyte Interfaces in Zinc-Ion Batteries

The market for electric vehicles and portable and wearable electronics is expanding rapidly. Lithium-ion batteries currently dominate the market, but concerns persist regarding cost and safety. Consequently, alternative battery chemistries are investigated, with zinc-ion batteries (ZIBs) emerging as promising candidates due to their favorable characteristics, including safety, cost-effectiveness, theoretical volumetric capacity, energy density, and ease of manufacturing. Hydrogel electrolytes stand out as advantageous for ZIBs compared to aqueous electrolytes. This is attributed to their potential application in flexible batteries for wearables and their beneficial impact in suppressing water-induced side reactions, zinc dendrite formation, electrode dissolution, and the risk of water leakage. The novelty of this review lies in highlighting the advancements in the design and synthesis of biopolymer hydrogel electrolytes in ZIBs over the past six years. Notable biopolymers include cellulose, carboxymethyl cellulose, chitosan, alginate, gelatin, agar, and gum. Also, double-network and triple-network hydrogel electrolytes have been developed where biopolymers were combined with synthetic polymers, in particular, polyacrylamide. Research efforts have primarily focused on enhancing the mechanical properties and ionic conductivity of hydrogel electrolytes. Additionally, there is a concerted emphasis on improving the electrochemical performance of semi-solid-state ZIBs. Moreover, some studies have delved into self-healing and adhesive properties, anti-freezing characteristics, and the multifunctionality of hydrogels. This review paper concludes with perspectives on potential future research directions.

Application of metal-organic frameworks to the anode interface in metal batteries

Metal batteries have attracted considerable attention from researchers because of their low reduction voltage and high specific capacity. However, the reduction in the capacity and lifespan of batteries caused by the dendrite growth of metal anode limits the development of metal batteries. Metal-organic frameworks (MOFs) can be used to protect metal anodes owing to their advantages of ideal specific surface area, tunable porosity, and physiochemical stability in electrolytes. Therefore, MOFs have been extensively investigated in metal batteries. The introduction of MOFs to the metal anode interface can greatly improve the performance of batteries. In this review, the synthesis methods of typical MOFs and their derivatives, their protective mechanism on the metal anode, including Li, Na, K, Zn, and Mg, and their effects on the performance of metal batteries were elucidated. This review would help to design and apply MOFs to the anode interface in metal batteries.

Tailoring the interface of lithium metal batteries with an in situ formed gel polymer electrolyte

In situ formed gel polymer electrolyte with wide electrochemial stability window is obtained with an amide group covalently cross-linked polymer matrix. It can stabilize lithium metal anode and inhibit liquid electrolyte decomposition on the cathode.