Microstructural engineering of zinc anodes: Expediting the fabrication and industrial-scale deployment of high-performance batteries

To meet the requirements of flexibility and high performance for energy storage devices in flexible wearable electronic equipment, the MnO2/acetylene black composite flexible cathodes is fabricated via 3D printing technology and the aqueous manganese-based zinc-ion flexible batteries are assembled. Based on bending and torsion mechanical tests, and the electrochemical tests, the optimal 3D printing electrode structure was determined. The micromorphology of the electrode after mechanical tests shows that when the printed lines of the upper and lower layers form a 30° angle, the electrode sheet exhibits the least damage. Electrochemical tests indicated that it had an ohmic resistance of 2.052 Ω, an interfacial charge transfer resistance of 141.1 Ω, a specific capacity of 103 mAh/g at 50 mA/g, and a specific capacity of 65 mAh/g at 500 mA/g. Compared with traditional coated electrodes, the 3D-printed electrode showed significantly improved diffusion coefficient, conductivity, and cycle stability. The assembled 3D-printed flexible battery could stably power a 1.5 V LED bulb under flat, bent, and twisted states. It provides a feasible solution for the development of high-performance flexible energy storage devices.

Despite striking advantages in terms of cost and safety, penetration of rechargeable Mg batteries into the commercial market is still hampered by major technical challenges, including intrinsic hypersensitivity of Mg metal to moisture, which readily forms a compact ion-insulating film on the surface. To unlock this critical constraint, a moisture-tolerant Mg electrode is developed that is capable of efficient Mg plating-stripping even in the highly moist electrolytes. Here we show that short immersion of Mg metal in trimethyl phosphate creates a sacrificial protection layer containing dimethyl magnesium in magnesium dimethyl phosphate, which synergistically scavenges water molecules from the electrolytes instantly, enabling manufacturing of Mg-ion cells under moist and/or atmospheric conditions. This simple and scalable strategy provides a practical route to reducing the manufacturing costs of rechargeable Mg batteries, thereby expediting their early commercialization.

The fabrication of solid-state batteries (SSBs) without the need for high-temperature sintering significantly requires less energy. The powder aerosol deposition (PAD) method enables direct film formation at room temperature, bypassing the conventional thermal densification step. This study presents an overview of recent advancements in the cycling properties of SSBs fabricated via PAD. Employing LiNi 0.82 Mn 0.07 Co 0.11 O 2 (NMC) as cathode active material (CAM) and Li 7 La 3 Zr 2 O 12 (LLZO) as solid electrolyte, a capacity of 141 mAh g −1 with 90 % capacity retention over 25 cycles is demonstrated with no thermal post-treatment applied after film fabrication. Based on these results, the role of LLZO as catholyte in the cathode layer is investigated. The findings suggest an electrochemical instability between nickel-rich NMC and LLZO during cycling. To enhance the capacity, the aggregated results are used to discuss various strategies for optimizing cathode layer design, particularly with respect to the composition and choice of the CAM.

ABSTRACT Solid‐state battery fabrication requires the densification of solid electrolytes to achieve optimal cycling performance and high energy density. However, the underlying compaction mechanisms of these electrolytes remain poorly understood. Here, we investigate the effect of pressure consolidation on the ionic conductor Li 6 PS 5 Cl with particle size distributions (PSD) ranging from 4 to 40 µm. Heckel analysis reveals that samples with smaller PSDs exhibit higher compressibility at lower pressures. X‐ray diffraction peak profiling shows that applied pressure induces lattice strain, leading to peak broadening, while pair distribution function analysis demonstrates a reduction in coherence length upon pressing. Dark‐field X‐ray microscopy further provides spatially resolved orientation maps, uncovering intragranular structural variations within individual Li 6 PS 5 Cl agglomerates after compression. To better understand the origin of stress fluctuations, we performed discrete element method simulations using the experimental PSDs. The results indicate that smaller particles and broader PSDs experience higher stresses, whereas monodisperse systems do not exhibit significant stress fluctuations with position or particle size. This suggests that the high strain observed cannot be attributed solely to smaller particles, but rather to size inhomogeneity. Overall, these findings highlight that both particle size and its distribution play a critical role in processing solid electrolytes for solid‐state batteries.

Sacrificial sodium-rich salts pre-sodiation is a safe and promising approach to supplement sodium-ion batteries with additional capacity for energy density enhancement. However, high-cost from additional solvent and low-utilization-ratio caused by loose electrical contact limit its practical application in slurry-coated electrodes. Herein, we demonstrate a dry-processing method to enable complete sodium oxalate decomposition and solvent-free production of thick electrodes. Distinct to particle aggregation in slurry-coated electrodes, a homogenous mixture of Na2C2O4 and conductive agents is generated and wraps Na3V2(PO4)3 particles after high-speed shear-mixing and hot-calendaring of dry-processing method, constructing intimate and durable electronic pathways, thus realizing theoretical decomposition capacity of Na2C2O4 in thick electrodes (54 mg cm-2). This strategy increases the lifespan by 200 cycles and energy density by 82.5% for all-dry-processing sodium-ion batteries with areal capacity of 5.4 mAh cm-2, which highlights the vital role of exploiting mechanical and thermal effects of dry-processing method in sustainable fabrication of high-energy sodium-ion batteries.

As the global demand for energy continues to rise, there is a greater need for low-cost, high energy density batteries. One approach to decrease cost is to improve the manufacturing process, and dry electrode processing has recently been explored as a way to eliminate solvent costs and minimize material waste. We developed a dry cathode processing method by first spray coating a cathode powder mixture onto aluminum foil, and then using a laser to melt the polymer binder particles and adhere the electrode to the current collector. Extra unattached powder was then collected and recycled to minimize waste. We investigated laser/material interactions by XRD, SEM, and XPS and optimized laser parameters (speed, power, etc.) and wavelengths to melt the binder without significantly damaging the cathode active material. In addition to providing cost benefits, this laser processing technique also enables rapid fabrication of architected electrodes (since the laser melting can easily be patterned in any shape), which can facilitate mass transport and significantly improve performance at high charge/discharge rates or through thick electrodes. These transport benefits can lead to batteries with higher energy densities, since the use of thick electrodes decreases the number of inactive current collector and separator layers necessary during cell assembly. Overall, laser processing is a promising next-generation manufacturing technique for battery fabrication that provides increased versatility and decreased waste and solvent costs.Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.

Solid electrolytesare critical to enabling safe and high-energy-densitybatteries; yet, their practical deployment is impeded by poor electrochemicalstability, inadequate interfacial contact, and challenging manufacturingprocesses. Here, we introduce a novel “solid-in-solid”electrolyte architecture comprising a porous Li zeolite electrolyte(LiX) infiltrated with a melt-processable plastic crystal electrolyte(PCE). This LiX–PCE electrolyte achieves an ionic conductivityof 0.55 mS/cm at 20 °C, alongside improved electrochemical stabilityover pure PCE. Solid-state nuclear magnetic resonance reveals threeLi+ transport pathways: through LiX, through PCE, and viaion exchange at phase boundaries. Leveraging the melt-processabilityof the PCE, we proposed a roll-to-roll-compatible melt infiltrationstrategy for scalable solid-state battery (SSB) fabrication with theLiX–PCE electrolyte. The SSBs demonstrate excellent rate performance(up to 10 C), 93% capacity retention after 200 cycles at 2C, and 4.5V compatibility. This work elucidates critical design principles forhigh-performance solid-state electrolytes and presents a viable pathtoward practical, fast-charging, high-power SSBs.

Abstract This work introduces nickel (II) tetraphenylporphyrin (NiTPP) as a multifunctional electrolyte additive to simultaneously address polysulfide shuttle and uncontrolled lithium dendrite growth in lithium–sulfur (Li–S) batteries. Mobile NiTPP species act as homogeneous catalysts with Ni–N 4 centers for rapid polysulfide redox mediation to suppress migration, while planar molecules featuring lithium‐affinity capability migrate to the lithium metal surfaces, enabling uniform lithium flux and anode protection. NiTPP‐modified electrolytes significantly enhance Li–S battery performance, demonstrated by 634.9 mAh g −1 at 4C, 758.3 mAh g −1 after 100 cycles at 0.2 C (83.4% retention), and 757.5 mAh g −1 under high sulfur loading (2.9 mg cm −2 ) with lean electrolyte ( E / S = 5 μL mg −1 ), all with high Coulombic efficiency. Crucially, NiTPP, acting as a soluble dual‐functional mediator enabling homogeneous operation in electrolytes, simplifies Li–S battery fabrication while demonstrating the commercial viability of molecularly engineered mobile active sites for stabilizing both electrodes in high‐energy‐density Li–S batteries.

ABSTRACT Sodium carboxymethyl cellulose (CMC) and polyacrylic acid (PAA) are state‐of‐the‐art binders in aqueous‐processed anodes for lithium‐ion batteries. Binders act as dispersing agents and rheology modifiers in aqueous slurries, while also providing mechanical integrity of dry electrodes during battery fabrication and operation. However, despite their low concentration, they may have detrimental effects on the conductivity and electrochemical performance of batteries, for example, due to their adsorption on active material particles, which is supposed to limit Li + insertion and extraction, but also affect electrode microstructure and adhesion to the current collector. Here, a commercially available, cross‐linked acrylate binder (Carbopol® Ultrez10, x‐PAA) with high thickening efficiency is applied for graphite anodes. At lower polymer content, anode slurries based on x‐PAA exhibit high‐shear viscosities similar to those of the CMC reference and provide a yield stress, which is advantageous for slurry stability. Furthermore, SBR content could be reduced without loss of adhesion strength compared to the CMC reference, since x‐PAA does not adsorb onto graphite. Thus, the total binder content could be lowered by about 40% in comparison to reference anodes comprising CMC. The substantial reduction in total binder amount resulted in slightly lower long‐term stability compared to the reference cell including CMC. Cells incorporating x‐PAA, however, outperformed references under fast‐charging conditions (up to 5C) presumably since x‐PAA does not adsorb on graphite, thus enabling more effective Li + insertion and extraction. Further refinement of crosslinking microstructure may enable fabrication of electrodes with higher energy density and higher capacity retention during cycling, irrespective of cycling rate.

Anode-free sodium batteries (AFSBs) guarantee enhanced energy density and safety; however, their practical applications are hindered by uncontrolled dendritic growth and fragile solid electrolyte interphase formation. Hence, a novel interface engineering strategy is adopted in the present work to construct an in situ 3D porous interphase with dual ion/electron conductive channels on aluminum (Al) foil. The interphase consisting of a fast ion-conducting sodium aluminate (NaAlO2)framework, a highly conductive carbon nanotube network, and a flexible carboxymethyl cellulose binder is fabricated through a simple in situ chemical etching method. The unique architecture of the as-prepared interface synergistically regulates the sodiophilic nature and the ion/electron flux distribution, dramatically reducing the sodium nucleation overpotential from 35mV for bare Al to 15mV, and enabling ultra-stable sodium plating/stripping in the half cells for over 6000 h at 1mAcm-2 with a low polarization of 30mV. When the resultant anode-free full cell is paired with a sodium vanadium phosphate (Na3V2(PO4)3) cathode, it yields impressive high-rate cyclic stability with a retention capacity of 90.7% after 100 cycles at 1 C and a remarkable energy density of 314Whkg-1. This work presents a scalable and effective method for stabilizing anode-free configurations and offers valuable insights for next-generation metal-based battery fabrication.

Durable and highly active oxygen electrocatalysts are crucial to the large-scale application of rechargeable zinc-air batteries. Here we utilize the N4 unit in phthalocyanine molecule to trap the tungsten atoms scratched off from the tungsten carbide milling balls and place the obtained W-N4 unit adjacent to the Fe-N4 units from iron (Ⅱ) phthalocyanine, resulting in highly active Fe-N4/W-N4 diatomic sites with well-pronounced 3d−5d hybrid for efficient and durable oxygen electrocatalysis. The electron distribution of the Fe-N4 site is optimized by the neighboring W-N4 site, which facilitates the O2 activation and the desorption of *OH and enhances the catalytic activity of the Fe-N4 site. Meanwhile, the unsaturated 5 d orbitals and tunable valence of the W atoms could modulate the electronic state of the Fe species, prevent leaching, and further enhance the catalytic stability. The resulting zinc-air battery with Fe,W-N-C air cathode exhibits notable cycling stability and repeatability for over 10,000 h. This enhanced stability highlights the possibility of developing 5 d metal-boosted 3 d metal active sites for the fabrication of efficient oxygen electrocatalysts and stable zinc-air batteries.

Recently, sulfide-based electrolytes, including the argyrodite family (Li6PS5X, X = Cl, Br, I), are considered promising candidates for all-solid-state battery fabrication due to their high ionic conductivity. However, from the industrial point of view, other parameters such as the chemical and electrochemical stability toward current collectors are equally important, but often neglected. Although many efforts have been directed toward the investigation, optimization and testing of sulfide electrolytes into a press device (10 MPa) with a stainless-steel current collector, the investigation of the current collector's behavior in contact with sulfide solid electrolytes in coin cell (0.2 MPa) or pouch cell (0.1-0.2 MPa) formats is still an open question. In this work, the systematic physicochemical and electrochemical analyses of copper, nickel, stainless steel, aluminum, and aluminum-carbon current collectors in contact with the Li6PS5Cl electrolyte in coin cell format configuration is reported, enabling the understanding of the reaction mechanisms. While SS, Ni, Al and Al/C show good chemical stability, Cu, Li, and Cu/Li have high corrosion susceptibility in sulfide electrolytes. Therefore, this study supports the selection of appropriate current collectors for fabricating sulfide-based components, especially via the wet chemistry process which is a promising approach for the industrialization of solid-state batteries with sulfide electrolyte.

Photocuring, including photopolymerization and photocrosslinking, has emerged as a transformative manufacturing paradigm that enables the precise, rapid, and customizable fabrication of advanced battery components. This review first introduces the principles of photocuring and vat photopolymerization and their unique advantages of high process efficiency, non-contact fabrication, ambient-temperature processing, and robust interlayer bonding. It then systematically summarizes photocured battery components, involving electrolytes, membranes, anodes, and cathodes, highlighting their design strategies. This review examines the impact of photocured materials on the battery’s properties, such as its conductivity, lithium-ion transference number, and mechanical strength, while examining how vat-photopolymerization-derived 3D architectures optimize ion transport and electrode–electrolyte integration. Finally, it discusses current challenges and future directions for photocuring-based battery manufacturing, emphasizing the need for specialized energy storage resins and scalable processes to bridge lab-scale innovations with industrial applications.

Abstract In this work, a flexible battery structure is fabricated using soft lithography and three-dimensional (3D) printing technology. Ga52.5Sn39.5Zn8 anode material, Bi67In33 cathode material, and alkaline hydrogel electrolyte are introduced to form the flexible battery. A variety of circuit structures are fabricated to realize the series-parallel integration of different numbers of single cells and achieve the fabrication of batteries with different voltages and powers, with a maximum open-circuit voltage (OCV) of 4.6 V and a maximum output power of 1.193 mW. A reconfigurable soft battery group is proposed, and the regulation of the battery voltage has been realized through the microfluidic perfusion process without the need for an external variable-voltage circuit. We have also fabricated an EGaIn-NaOH microfluidic switch to achieve the control of the light emitting diode (LED). In addition, a wristband with a flexible battery is demonstrated to realize power supply to a liquid crystal display (LCD) with a clock or a temperature sensor.

Rapidly growing technology of batteries demands high-stability and energy-efficient batteries for their applications in the everyday utility of mankind, which is strongly motivating researchers to rapid innovation of battery materials that include electrolytes as one of the primary components. Besides fast ionic transportation and stable electrochemical performance of the electrolytes, enormous efforts must be made in order to eliminate the safety problem due to the flammability, leakage, and thermal instability. These benefits can only be achieved by inventing new types of electrolytes for energy storage systems (ESS). Though much work is going on in the field of solid polymer electrolytes, these are yet lagging for the practical applications. Presently, ionic liquids are considered one of the most promising types of electrolytes for the fabrication of advanced and much safer lithium-ion batteries. In the last few decades, ionic liquids (ILs) have created much interest as electrolytes in Li-ion batteries, fuel cells, and supercapacitor applications, which probably will become an important pathway toward breakthroughs in next-generation ESS. The review mainly focused on ILs exhibiting high ionic conductivity, with a melting point lower than 100°C, a wide electrochemical potential window of up to 5 to 6 V vs. Li+/Li, good thermal stability, and nonflammability with low volatility, obtained through appropriate cation-anion combinations; an attempt has been made to illustrate the status of the art of recent development of ILs, advantages, and challenges. Figure 1

Na batteries have been proposed as ideal complementary alternatives to LIBs for EVs and large-scale energy storage applications because of the high abundance, low cost, and suitable redox potential of Na. The liquid-based Na batteries process similar drawbacks to liquid-based LIBs, such as flammability, volatility, poor thermal, chemical, and electrochemical stability at high temperatures, etc. These drawbacks of liquid electrolytes have encouraged further research to develop solid-state Na batteries (SSNBs) [1]. The major component of SSNBs is the SSE, which acts as both an ionic conductor and separator between the cathode and anode. The ideal SSEs should possess high ionic conductivity, high chemical stability, wide electrochemical windows, good air stability, and good processability for battery fabrication. In this presentation, I will introduce our research that contributed to the design of materials and interfaces for the next-generation solid-state Na batteries.i) The cation and anion co-doping approach for sulfide-based solid-state Na electrolytes. The WCl6 was chosen as the doping precursor to introduce both W cation and Cl anion at the same time during the synthesis process. The optimized W and Cl co-doping NAS present a significantly enhanced room temperature ionic conductivity of 6.4 mS cm-1. In addition, as prepared W/Cl co-doped NAS SSEs have been used for solid-state Na-S batteries with remarkable electrochemical performances, especially at high current density [2].ii) Earth-abundant solid electrolyte for low-cost, high-performance and long-life solid-state sodium-sulfur battery. We successfully developed a new glassy-ceramic earth-abundant SSEs with good electrochemical stability, low cost, and superior long-cycling stability for SSNSBs. The edge-sharing tetrahedral AlS4 crystal frame structure and metal-sulfide local chemical structure in glassy-ceramic Na-Al-S have been studied in detail via various characterization techniques. The SSNSBs with Na-Al-S SSEs present remarkable performances with a high reversible capacity of 1027 mAh g-1 over 800 cycles, which is at the top of the reported literature for SSNSBs.iii) A new family of Na oxychlorides solid-state electrolytes. We demonstrated a new sodium superionic glass, Na-Ta-O-Cl, based on a dual-anion sublattice of oxychlorides. The unique local structures with abundant bridging and non-bridging oxygen atoms contribute a highly disordered Na-ion distribution as well as a low Na ion migration barrier within Na-Ta-O-Cl, enabling an ultra-high ionic conductivity of 4.62 mS cm-1 at 25 ℃ [3-4].iv) Self-sacrifice of sulfide electrolytes facilitating solid-state sodium-sulfur batteries. we have overturned and re-investigated the application of Na3SbS4 in solid-state Na-S batteries. Unlike the traditional understanding, we first reveal the novel mechanism of self-sacrificed and decomposition of sulfide SE for achieving high-performance and stable solid-state Na-S batteries. Benefiting from decompositions, the NAS-aided solid-state Na-S batteries can deliver an ultra-high initial specific capacity of 1975.7 mAh g-1 with a capacity retention of 1294.6 mAh g-1 after 140 cycles, at a current density of 0.127 mA cm-2 .v) Interface engineering for sulfide-based solid-state Na batteries. A molecular layer deposition alucone film is employed to stabilize the active Na anode/electrolyte interface in the SSNBs, limiting the decomposition of the sulfide-based electrolytes and Na dendrite growth. Such a strategy effectively improves the room-temperature full battery performance as well as cycling stability in Na-Na symmetric cells [5].[1] Chemical Reviews, 2022, 122, 3763–3819[2] Nano Energy, 2024, 128, 109871[3] Angewandte Chemie International Edition, 2024, 63, e202314181[4] Nature Materials, 2024, 10.1038/s41563-024-02011-x[5] Advanced Functional Materials, 2020, 30, 2001118

Development and characterization of anode filaments for fused filament fabrication of sodium-ion batteries

Anodes containing Si and SiOx are promising candidates for the fabrication of high energy density Li-ion batteries (LIBs).However, despite their specific capacity advantages, maintaining a sustainable cycling performance remains challenging due to their significant volume expansion and contraction.To enhance the interfacial stability of SiOx, this study uses an electrolyte containing 1,1,2,2-tetrafluoroethyl-2,2,3,3tetrafluoropropyl ether (D2) as an electrolyte additive and focuses on the solid electrolyte interphase (SEI) formed on the electrode surface.The reduction of D2 forms a robust LiFbased SEI along with a D2-specific fluoroalkyl component, which sufficiently stabilizes the SiOx interface.Therefore, the electrolyte containing D2 contributes not only to improving the charge-discharge cycle life and reducing resistance but also to suppressing gas generation within the battery system.To elucidate the mechanism of performance enhancement by D2, this study employs a wide range of analytical techniques, such as AC impedance spectroscopy, scanning electron microscopy (SEM), energy dispersive Xray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and time of flight secondary ion mass spectrometry (TOF-SIMS), along with density functional theory (DFT) calculations to predict the reaction pathways of D2.These experimental and theoretical analyses demonstrate that D2 is an excellent additive for anode materials ACCEPTED MANUSCRIPT 4 containing SiOx.

3D printing, an advanced additive technology, shows promise for battery fabrication. Due to its high design flexibility, cost-effectiveness, and minimal waste generation, 3D printing has been used to create different battery components such as cathode and anode materials, solid-state electrolytes, and battery packages. Recent studies have demonstrated promising battery performances in using 3D-printed materials, benefiting from the enhanced ion/electron transport abilities. However, the practical application of 3D printing for different battery materials and fully integrated batteries is still a topic of debate. This is primarily due to the challenges to overcome the limitations of electrode materials and maximize their benefits. The effectiveness of 3D printing techniques can vary depending on the materials and printing process used. Variations in material structure and properties may require unique design structures or processing additives, so traditional 3D printing may not be suitable for addressing some materials' issues. Different 3D printing techniques can impact battery material performance, emphasizing the importance of selecting appropriate inks or structures to maximize benefits. This paper concentrates on how 3D printing can offer solutions for powder electrodes, metal electrodes, and solid-state electrolytes. It also discusses the unique capabilities of different 3D printing technologies for battery manufacturing, post-treatment processes, battery configurations, and packaging considerations. We also analyse the characteristics and limitations of 3D printing in addressing challenges with various battery materials. It aims to provide insights for advancing 3D printed batteries, paving the way for 3D printing to become an essential part of the future manufacturing industry.