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At least 163 records · Page 9

Fabrication of films and coatings used to activate shear thickening, impact resistant electrolytes

A method of making a passively impact resistant composite electrolyte and separator layer includes providing a suspension composition including electrically non-conducting particles that enable shear thickening. The particles can have a polydispersity index of no greater than 0.1, an average particle size in a range of from 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV. A particle suspension solvent is provided for suspending the particles. The suspension composition is applied to a porous separator material. A portion of the particles and suspension solvent penetrate the pores and the remainder of the particles in the suspension composition are distributed across the surface of the separator material. The suspension solvent is evaporated from the separator material to provide a shear thickening particle loaded separator. A separator assembly and a passivated battery are also disclosed.

25 ENERGY STORAGE↗

Optimizing the Fabrication of Electrospun Nanofibrous Membrane Using Fractional Factorial Design

Electrospinning, a simple and easily tunable technique that utilizes the force balance between the electrostatic force and the solution surface tension to fabricate membranes out of 1D nanostructured fibers, has garnered much interest especially from the nanotechnology community. Depending on the morphology of the fibers, electrospun membrane has found its way in a wide range of applications, such as oil-water separation, desalination, tissue engineering, and batteries. During an electrospinning process, many factors can affect the morphology of the products, such as viscosity of the solution, voltage supply, discharge distance, feed rate of the solution, and electrospinning time. In this work, we investigated the impacts of the most important parameters on the morphology of electrospun fibrous membrane based on the fractional factorial design. We evaluated the electrospun fibrous membrane morphology using scanning electron microscopy (SEM) and capillary flow porometry. Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was chosen for the current study due to its interesting and versatile functionalities including superior hydrophobicity, high free volume, and piezoelectricity. This work provides valuable insight for the fabrication of electrospun membranes, especially for tailoring membrane properties in accordance with any targeted applications.

Zhao, Yajing↗

Fabrication of films and coatings used to activate shear thickening, impact resistant electrolytes

A method of making a passively impact resistant composite electrolyte and separator layer includes providing a suspension composition including electrically non-conducting particles that enable shear thickening. The particles can have a polydispersity index of no greater than 0.1, an average particle size in a range of from 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV. A particle suspension solvent is provided for suspending the particles. The suspension composition is applied to a porous separator material. A portion of the particles and suspension solvent penetrate the pores and the remainder of the particles in the suspension composition are distributed across the surface of the separator material. The suspension solvent is evaporated from the separator material to provide a shear thickening particle loaded separator. A separator assembly and a passivated battery are also disclosed.

Armstrong, Beth L.↗

VTO_2021_APR_LLNL_Ye

Traditional batteries are composed of two-dimensional films that are stacked and/or rolled. Thin film batteries display high power density while their thick film counterparts show good energy density, but it has proven difficult to concurrently achieve both within these planar form factors. In addition, conventional Li-ion batteries based on liquid organic electrolytes or gel polymer electrolytes have raised severe safety concerns due to the intrinsic flammable properties of the organic electrolytes. They are also not ideal for the use of high energy density metallic lithium (Li) anodes due to Li dendrite growth, or sulfur cathodes due to shuttling effects that result in fast capacity fade. There is an urgent need to develop safe, high-performance solid-state batteries (SSBs) with advanced electrolyte and separator technologies. Although in recent years a series of superionic conductors have been developed for electrolytes and separators, their performance does not satisfy demanding criteria due to large impedance from poor solid electrolyte-electrode contact and questionable electrochemical and mechanical stability. Unlike the well-established roll-to-roll fabrication of conventional Li-ion batteries, the processing of SSBs is unique due to the brittleness of solid-state electrolytes (SSEs). The commercially available or lab-developed SSE discs are usually very thick (hundreds of micrometers to millimeters) to overcome their brittle nature, which unfortunately increases the cell impedance and accounts for the majority of the overall cell weight and volume, leading to dramatically decreased power and energy densities. In this project, we will investigate 3D printing techniques to overcome safety, fabrication, mechanical, and electrochemical issues in SSBs. 3D printing builds complex structures in a layer-by-layer fashion, which allows rapid production of hierarchical architectures, gradient and multi-material structures, and multi-component assemblies. 3D printing is an emerging area that could fundamentally transform energy storage devices. For example, 3D printing can produce batteries with arbitrary form factors to fit a product’s specific volume requirements and can create interwoven electrode arrangements over a wide range of length scales to improve transport and increase power density for a given energy density. For SSBs, 3D printing may dramatically reduce the separator thickness from ~1 mm (by hydraulic pressing) to tens of micrometers or less. In addition, the interfacial contact area between the electrolyte and the electrode may be increased via 3D interdigitated designs. Hence, we expect a significant reduction of the overall cell impedance and enhancement of both energy and power densities of SSBs by harnessing an array of 3D printing technologies being developed at Lawrence Livermore National Laboratory (LLNL).

25 ENERGY STORAGE↗

Evaluation of bio-inspired flow fields in a mediated Li-S flow battery for grid energy storage

Lithium-sulfur is a redox flow battery with high energy density for applications in safe, reliable, and lasting scaling of energy. However, lithium-based batteries often encounter platting as a problem thanks to poor Li-ions deposition after cycling. Aiming to reduce this impact, a uniform and continuous flow of ions is needed. On this work, novel bio-inspired flow fields in the electrochemical cell were tested to improve ions flowability and lithium platting control, ultimately enhancing battery performance and life. To secure Li-S efficient, low-cost, and secure energy storage capabilities, we chose a configuration with decamethylferrocene and cobaltocene acting as redox mediators, Li metal as anode and sulfur kept in a separate catholyte reservoir. Flow test and battery results insinuated a beneficial influence of bio-inspired designs in flowing electrolyte uniformly with less pressure and pump power in comparison to other conventional designs used in the industry, with an encouraging ability to approach a cheap, safe, and reliable Li-S grid energy storage.

25 ENERGY STORAGE↗

Scalable High-Throughput Open-Air Spray-Plasma Manufacturing of Solid-State Lithium Batteries

This final technical report presents a comprehensive analysis of a novel plasma-based in-line manufacturing process for large-area, LLZO-separator-based, solid-state lithium-ion batteries, demonstrating both technical feasibility and economic advantages over conventional vacuum deposition methods. The technical validation shows that spray-deposition with plasma curing achieves comparable electrode and separator quality to vacuum techniques while enabling continuous processing of components and industrially relevant film areas. Critical material interfaces maintain low porosity and high ionic conductivities, which confirm the process's ability to overcome the primary limitation of conventional methods - the trade-off between deposition quality and economically-viable production scale.

25 ENERGY STORAGE↗

Battery Life Prediction Using Reduced-Order Physics Models and Machine Learning (CRADA Final Report)

Phase 1 (Original CRADA, plus no-cost extension modifications #1-3, 6/1/2017 to 3/13/2021): The Australian Department of Defence (AUDoD) is performing accelerated aging tests of Li-ion batteries to benchmark their reliability and degradation characteristics. Using its previously developed battery lifetime predictive model framework, the National Laboratory of the Rockies (NLR) will develop analytical models based the AUDoD data to predict lifetime of the multiple Li-ion battery chemistries under real-world use scenarios of interest to AUDoD. The NLR model is based on physical degradation mechanisms encountered by Li-ion batteries and has been previously validated. Phase 2 (CRADA modification #4, plus no-cost extension modification #5, 2/22/2021 to 3/30/2025): Train and support Australian Department of Defence personnel to use NLR software for model-based estimation of Li-ion battery lifetime using accelerated battery aging data collected by the Australian Department of Defence. Under separate DOE funding from 2019 to 2021, NLR enhanced its battery life-prediction software using machine learning algorithms to automate portions of the model-fitting process, requiring significantly less labor and expert judgment and also adding uncertainty quantification, increasing statistical rigor. Under Phase 2, NLR will customize NLR Software and provide it to AuDoD. NLR will enhance its NLR Model to capture aging modes of AuDoD's multi-cell modules, including cell-balancing effects. NLR will develop example single-cell and multi-cell models based on one AuDoD battery aging dataset. NLR will train AuDoD personnel on NLR Software. By the conclusion of the project, NLR will have provided AuDoD the training materials, a user manual and software needed to perform their own analysis of additional and/or future battery aging datasets.

33 ADVANCED PROPULSION SYSTEMS↗

Understanding and Manipulating Counterion Condensation within Charged Polymer Electrolytes for Selective and Low Resistant Membrane Separations

Polymeric ion-exchange membranes are found at the heart of numerous electrochemical systems spanning separations (electrodialysis and membrane capacitive deionization) and energy conversion and storage (flow batteries, fuel cells, and electrolyzers). The ion-exchange membrane separators need to be ion conducting but electron insulating, and in many scenarios selective for a particular ion to conduct. Because of their polymeric nature, the molecular architectures of ion-exchange membranes lack the molecular precision found in many inorganic materials. Plus, they contain numerous structural defects that impede ionic transport. As a result of their poor structure, it has been difficult to carefully probe the underlying physics that governs ion transport in ion-exchange membranes. We investigated counterion condensation phenomena in ion-exchange membranes and correlated it to bulk ionic charge transport and selectivity in precisely defined and long-range ordered materials afforded through the principles of directed self-assembly. A multi-faceted approach spanning i.) advanced metrology, two-dimensional atomic force microscopy, x-ray scattering, and ion-exchange equilibria, and ii.) molecular simulations (classical molecular dynamics and ab-inito molecular dynamics) that bridge multiple time and length scales, were employed to correlate the extent of counterion condensation to ionic conductivity and selectivity. After uncovering the extent of the condensation phenomena in this project, new macromolecular chemistries were employed to manipulate the ion pairing interactions of the condensed counterions to tethered ions on the polymer backbone so more facile and selective conduction rates can be attained. The research has aided in the rational design of polymeric ion-exchange membrane separators with high current density for electrochemical systems and subsequently better energy efficiency.

36 MATERIALS SCIENCE↗

Nano- and Earth-Science-inspired Electric Vehicle Battery Recycling to Secure Battery Supply Chain

With the expected growth of electric vehicles (EV) in the transportation sector, recycling or upcycling spent battery materials will be required to reduce EV costs, lessen waste, and ease critical material supply chain pressure for EV battery applications. “Direct” recycling or upcycling is an alternative to current industrial approaches. Many challenges remain for viable direct battery upcycling, including upgrading the transition metal ratio in the costliest component (cathode oxide); separation of transition metal ions in the exit stream; battery disassembly; improving cathode exfoliation which can lead to a new way of direct recycling; and lithium metal anode recycling -- including safety concerns. We devise and deploy a suite of methods to deal with these challenges. The results pave the way to future work on battery recycling, in areas of technological/commercial readiness level ranging from basic research to large-scale commercialization.

25 ENERGY STORAGE↗

Selenium-doped sulfur cathodes for rechargeable batteries

An electrochemical device includes an anode, a separator, a cathode comprising a selenium-doped sulfur/carbon composite that includes a conductive carbon matrix and nano-sized selenium-doped sulfur particles of formula SxSey, where a ratio of x:y is from 2.5 to 1000, and an electrolyte comprising a salt and a non-aqueous fluorinated ether solvent.

25 ENERGY STORAGE↗

A review of thermal physics and management inside lithium-ion batteries for high energy density and fast charging

Traditionally it has been assumed that battery thermal management systems should be designed to maintain the battery temperature around room temperature. That is not always true as lithium-ion battery (LIB) R&D is pivoting towards the development of high energy density and fast charging batteries. Therefore, it is necessary to have a comprehensive review of thermal considerations for LIBs targeted for high energy density and fast charging, i.e., the optimal thermal condition, thermal physics (heat transport and generation) inside the battery, and thermal management strategies. As the energy density and charge rate increases, the optimal battery temperature can shift to be higher than room temperature. In the first part of the review various sources of heat generation inside LIBs and various approaches to minimizing battery heat generation are summarized. The importance of heat of mixing due to ion diffusion during fast charging is also highlighted. To improve the temperature uniformity and avoid excessive internal temperature rise, heat transfer inside the battery needs to be enhanced, and reducing the thermal contact resistance between the electrodes and separator can significantly increase the effective thermal conductivity of batteries. In the second part of the review various challenges and latest developments related to thermal transport and properties of LIBs are discussed. Finally, a summary of latest advancement on smart control of internal temperature of LIBs is discussed as depending on the ambient temperature and the optimal temperature; the battery heat needs to be retained or dissipated to elevate or avoid temperature rise.

25 ENERGY STORAGE↗

Direct regeneration of degraded LiFePO4 cathodes via a separator-enabled prelithiation strategy

A persistent challenge in lithium-ion batteries is the loss of active lithium due to the solid electrolyte interphase (SEI) formation and associated side reactions. While prelithiation employing lithium replenishment separator (LRS) has been proven effective in compensating for lithium loss, previous studies have largely been accompanied by gas evolution or solid residue formation during the prelithiation process. To surmount this challenge, we present a LRS based on 4-fluoro-1,2-dihydroxybenzene lithium salt (LiDF), capable of mitigating lithium loss while producing decomposition products that integrate directly into the electrolyte as functional additives which can assist with the stability of the SEI, free from gas or solid formation, thus establishing a sustainable and environmentally benign strategy for lithium compensation. Incorporation of the LRS enables the pristine LiFePO4||graphite (Gr) full cell to achieve 10.8% higher capacity than the cell with a polypropylene separator (PPS) after 200 cycles at 0.5C. Remarkably, the degraded LiFePO4 (D-LFP)||Gr full cell with the LRS exhibits a 135.8% capacity improvement over the PPS-based cell after 500 cycles. These findings establish the LRS as a powerful approach for both boosting high-performance lithium-ion batteries and recovering the capacity of degraded batteries.

Tao, Fujun↗

Discharge intermittency considerably changes ZnO spatial distribution in porous Zn anodes

Porous Zn anodes are ubiquitous in primary batteries and are under development for low-cost rechargeable batteries. Spatial distribution of ZnO discharge product is a critical factor in these, because it can passivate the active material. In rechargeable cells this is related to a major failure mechanism called shape change, in which ZnO is relocated to inactive locations. In this work we demonstrate rest steps during discharge of primary Zn anodes dramatically alter the placement of ZnO in the anode. In alkaline electrolyte, ZnO discharge product is typically modeled as precipitating close to Zn particles, forming a porous ZnO shell around the Zn core. Further, anodes discharged continuously at low-rate are compared to anodes similarly discharged intermittently, using in situ computed tomography from a synchrotron source. Zn–ZnO core-shell structures are produced during continuous discharge but are not found in cells discharged intermittently. Continuously discharged cells showed that ZnO was formed most strongly near the separator, in agreement with Zn anode battery models. In pulse-discharged cells, ZnO was more radially distributed and was in large formations not physically connected to Zn particles. Thus, discharge intermittency changes spatial distribution of ZnO in ways that are unpredicted by Zn anode models.

25 ENERGY STORAGE↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration (FY2020 Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Established methods that typify R2R processing include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating, and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier and membrane materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, the means must be available to enable manufacture of these products in a cost-competitive manner that is affordable. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations and the coating and drying processes to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product. To solve the problems associated with these challenges, the R2R Collaboration is executing a research program with outcomes that will ultimately link modeling, processing, metrology and defect detection tools, thereby directly relating the properties of constituent particles and processing conditions to the performance of final devices. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy materials development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this project leverages the capabilities and expertise at each of five National Laboratories to further the development of multilayer technologies that will enable high-volume, cost-competitive platforms. A typical R2R process has three steps: (1) mixing of particles and various constituents in a slurry, (2) coating of the ink/slurry mixture on a substrate, and (3) drying/curing and processing of the coating. Final performance of devices made via R2R processes is dependent on the active materials (e.g., electrochemical particles in battery or fuel cell electrodes) and the device structure that stems from the governing component interactions within the various steps. However, a fundamental understanding of the underlying mechanisms and phenomena is still lacking, which is why industrial-scale R2R process development and manufacturing is still largely empirical in nature. The FY 2019 through FY 2021 program addresses aspects of the following two targets from the AMO Multi-Year Program Plan: (1) Target 8.1 Develop technologies to reduce the cost per manufactured throughput of continuous R2R manufacturing processes. (A) Increasing throughput of R2R processes by 5 times for batteries (to 50 square feet per minute (50 ft 2 /min)) and capacitors and 10 times for printed electronics and the manufacture of other substrates and MEs used in support of these products. (B) Developing resolution capabilities to enable registration and alignment that will detect, align, and co-deposit multiple layers of coatings and print < 1-micron (1 µm) features using continuous process scalable for commercial production. (C) Developing scalable and reliable R2R processes for solution deposition of ultra-thin (<10 nm) films for active and passive materials. (D) Develop in-line multilayer coating technology on thin films with yields greater than 95%. (2) Target 8.2 Develop in-line instrumentation tools that will evaluate the quality of single and multilayer materials in-process. (A) Developing in-line QC technologies and methodologies for real-time identification of defects and expected product properties “in-use/application” during continuous processing at all size-scales with a focus on the “micro” and “nano” scale traces, lines, and devices, i.e., <1 μm at 300 ft./min for R2R processing in air and <10 nm at 20 ft./min for vacuum (B) Developing technologies to increase the measurement frequency of surface rheology without significant cost increases with a goal of a 10-nanometer in-line profilometry at a production rate of 100,000 square millimeters per minute (100,000 mm 2 /min).

42 ENGINEERING↗

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.

Zhou, Qiongyu↗