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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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3D LiMn 2 O 4 nThin Film Deposited by ALD: A Road toward High-Capacity Electrode for 3D Li-Ion Microbatteries

Miniaturized electronics suffer from a lack of energy autonomy. In that context, the fabrication of lithium-ion solid-state microbatteries with high performance is mandatory for powering the next generation of portable electronic devices. Here, the fabrication of a thin film positive electrode for 3D Li-ion microbatteries made by the atomic layer deposition (ALD) method and in situ lithiation step is demonstrated. The 3D electrodes based on spinel LiMn 2 O 4 films operate at high working potential (4.1 V vs Li/Li + ) and are capable of delivering a remarkable surface capacity (approximate to 180 mu Ah cm -2 ) at low C-rate while maintaining more than 40 mu Ah cm -2 at C/2 (time constant = 2 h). Both the thickness of the electrode material and the 3D gain of the template are carefully tuned to maximize the electrode performance. Further, advanced characterization techniques such as transmission electron and X-ray transmission microscopies are proposed as perfect tools to study the conformality of the deposited films and the interfaces between each layer: no interdiffusion or segregation are observed. This work represents a major issue towards the fabrication of 3D-lithiated electrode by ALD-without any prelithiation step by electrochemical technique-making it an attractive solution for the fabrication of 3D Li-ion solid-state microbatteries with semiconductor processing methods.

3D Li-ion micro-batteries↗

High energy density picoliter-scale zinc-air microbatteries for colloidal robotics

The recent interest in microscopic autonomous systems, including microrobots, colloidal state machines, and smart dust, has created a need for microscale energy storage and harvesting. However, macroscopic materials for energy storage have noted incompatibilities with microfabrication techniques, creating substantial challenges to realizing microscale energy systems. Here, we photolithographically patterned a microscale zinc/platinum/SU-8 system to generate the highest energy density microbattery at the picoliter (10 −12 liter) scale. The device scavenges ambient or solution-dissolved oxygen for a zinc oxidation reaction, achieving an energy density ranging from 760 to 1070 watt-hours per liter at scales below 100 micrometers lateral and 2 micrometers thickness in size. The parallel nature of photolithography processes allows 10,000 devices per wafer to be released into solution as colloids with energy stored on board. Within a volume of only 2 picoliters each, these primary microbatteries can deliver open circuit voltages of 1.05 ± 0.12 volts, with total energies ranging from 5.5 ± 0.3 to 7.7 ± 1.0 microjoules and a maximum power near 2.7 nanowatts. We demonstrated that such systems can reliably power a micrometer-sized memristor circuit, providing access to nonvolatile memory. We also cycled power to drive the reversible bending of microscale bimorph actuators at 0.05 hertz for mechanical functions of colloidal robots. Additional capabilities, such as powering two distinct nanosensor types and a clock circuit, were also demonstrated. The high energy density, low volume, and simple configuration promise the mass fabrication and adoption of such picoliter zinc-air batteries for micrometer-scale, colloidal robotics with autonomous functions.

Robotics↗

Three-Dimensional Microbatteries beyond Lithium Ion

Ubiquitous implementation of microelectronics in microelectromechanical systems requires stable power supplies and necessitates development of on-chip miniature power sources, such as microbatteries. However, conventional thin-film batteries exhibit limited surface area and sluggish diffusion kinetics with insufficient energy and power density. In contrast, three-dimensional (3D) beyond-lithium (sodium, zinc, aluminum, etc.) battery architectures can significantly enhance the areal energy and power and meanwhile maintain the low-cost mass production. Despite this, the future of beyond-lithium systems is being questioned as they each present shortcomings. In this Comment, we discuss scientific advancements in reaction kinetics control, electrochemical stability improvements, and reaction mechanism understandings in 3D beyond-lithium battery systems, and finally, call for intensive research effort to address the challenges and develop strategies that can pave the way toward their commercialization.

25 ENERGY STORAGE↗

Plasma enhanced atomic layer deposition of thin film Li 1+x Mn 2-x O 4 for realization of all solid-state 3D lithium-ion microbatteries

Here, the plasma enhanced atomic layer deposition (PEALD) process for MnO 2 was demonstrated, exhibiting self-limiting growth as well as stable composition and stable growth rate over a temperature window of 205–265 °C. The PEALD process for MnO 2 was combined with the thermal ALD process for LiOH to synthesize Li 1+x Mn 2-x O 4 thin film cathodes, where the stoichiometry was effectively controlled to allow for crystallization in the electrochemically active spinel phase. A 3D nanostructure consisting of an Li 1+x Mn 2-x O 4 cathode layer, ALD Li x Al y Si z O solid electrolyte, and SiGe nanowire anode was fabricated and characterized via TEM. The Li 1+x Mn 2-x O 4 thin films maintained 66% of the areal capacity upon a 100× increase in the rate (4–360 μ A cm -2 ) as well as 97% capacity retention over 100 cycles at ~5C. The ALD Li 1+x Mn 2-x O 4 thin films exhibited a volumetric capacity of 52 μ Ah cm -2 μ m -1 at a C-rate of ~0.5C and, coupled with the high operating voltage (4.0 V), offer some of best areal energy densities for ALD thin film cathodes, making it a viable material for integration with 3D lithium-ion microbatteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion conductive inks and solutions for additive manufacturing of lithium microbatteries

A separator made of ion conductive ink is produced by additive manufacturing. A micro-battery is produced with the separator made of ion conductive ink located between the battery's anode and cathode. The separator functions to keep the anode and cathode apart and to facilitate the transport of ions to produce an operative micro-battery.

25 ENERGY STORAGE↗

Cylindrical battery design app

Software that delivers optimal design parameters and performance predictions for cylindrical cells, which can range in size from microbatteries to EV batteries, is developed. The software utilizes machine learning and includes a graphical user interface to enable rapid prototyping and to accelerate energy storage research, development, and manufacturing. The Cylindrical battery design V1.0 comprises of three types of cylindrical batteries, Microbattery (Primary), Microbattery (Secondary) and 18650/21700/xxxxx Cylindrical battery. The software was developed in MATLAB. The software has the capability to output the cell design with the capacity ranges from several mAh to several million Ah.

Xiao, Jie↗

High-Performance Solid-State Lithium-Ion Battery with Mixed 2D and 3D Electrodes

It is well established that the miniaturization of batteries has not kept pace with the miniaturization of electronics. Three-dimensional (3D) batteries, which were developed with the intent of improving microbattery performance, have had limited success because of fabrication challenges and material constraints. Solid-state, 3D batteries have been particularly susceptible to these shortcomings. In this paper we demonstrate that the incorporation of a high conductivity, solid electrolyte is the key to achieving a non-planar solid-state battery with high areal-capacity and high power-density. The model, 2.5D platform used in this study is a modification of the more typical 3D configuration in that it is comprised of a cathode array of pillars (3D) and a planar (2D) anode. This 2.5D geometry exploits the use of a high conductivity, ionogel electrolyte (10 -3 S cm -1 ) which interpenetrates the 3D electrode array. The 2.5D battery offers high areal energy densities from the post array while the high-conductivity, solid electrolyte enables high power densities (3.7 mWh cm -2 at 2.8 mW cm -2 ). Here, the reported solid-state 2.5D device exceeds the energy and power densities of any 3D solid-state system and the derived multiphysics model provides guidance for achieving significantly higher energy and power densities.

2.5D batteries↗

Viability of Additively Manufactured Electrodes for Lithium-Ion Batteries

As the global economy becomes increasingly electrified, the demand for batteries and energy storage is expected to rise significantly, particularly in the transportation and electricity sectors. Lithium-ion batteries (LIBs) are currently the most advanced and widely used technology in this field. Traditionally, LIBs are manufactured using simple 2D planar geometries to maximize production efficiency and minimize costs. However, this approach limits energy density due to the restricted design flexibility of the electrodes. Additive manufacturing (AM) offers a promising solution to enhance the energy density and efficiency of LIBs by enabling the design of architectures that reduce diffusive losses and allow for a greater amount of active material to be incorporated within the same device footprint, thereby minimizing the use of inactive materials. Different AM techniques come with their own set of limitations, including printing speed, material compatibility, and scale, which must be considered when designing electrodes. Scalable and cost-effective methods are particularly important for electric vehicle batteries, while achieving higher energy densities in microbatteries is crucial for the miniaturization of wearable electronics and medical devices. Here, in this study, we simulate various 3D porous electrode designs for LIBs using graphite and nickel manganese cobalt oxide (NMC) electrodes. These designs are selected to represent structures that could be produced using different AM techniques, such as direct ink writing, fused deposition modeling, and stereolithography. Our results indicate that at higher charging rates and increased areal mass loading, 3D structures can outperform traditional 2D electrodes, although the benefits may diminish with more complex designs that are harder to manufacture. The observed gains in energy density are attributed to improved electrode utilization and reduced diffusive energy losses. This comprehensive analysis of structure–performance relationships will provide valuable insights to guide future research on 3D designs, material selection, and AM techniques for additively manufactured battery electrodes.

25 ENERGY STORAGE↗

Synthesis and Crystallization of Atomic Layer Deposition β-Eucryptite LiAlSiO 4 Thin-Film Solid Electrolytes

Atomic layer deposition (ALD) was used to control the stoichiometry of thin lithium aluminosilicate films, thereby enabling crystallization into the ion-conducting β-eucryptite LiAlSiO 4 phase. Here, the rapid thermal annealed ALD film developed a well-defined epitaxial relationship to the silicon substrate: β-LiAlSiO4 ($1\bar{21}0$)||Si (100) and β-LiAlSiO 4 ($10\bar{10}$)||Si (001). The extrapolated room temperature ionic conductivity was found to be 1.2 × 10 –7 S/cm in the [$1\bar{21}0$] direction. Because of the unique 1-D channel along the c axis of β-LiAlSiO 4 , the epitaxial thin film has the potential to facilitate ionic transport if oriented with the c axis normal to the electrode surface, making it a promising electrolyte material for three-dimensional lithium-ion microbatteries.

25 ENERGY STORAGE↗

Giant energy storage and power density negative capacitance superlattices

Dielectric electrostatic capacitors, because of their ultrafast charge-discharge, are desirable for high-power energy storage applications. Along with ultrafast operation, on-chip integration can enable miniaturized energy storage devices for emerging autonomous microelectronics and microsystems. Moreover, state-of-the-art miniaturized electrochemical energy storage systems-microsupercapacitors and microbatteries-currently face safety, packaging, materials and microfabrication challenges preventing on-chip technological readiness, leaving an opportunity for electrostatic microcapacitors. Here, in this study, we report record-high electrostatic energy storage density (ESD) and power density, to our knowledge, in HfO 2 -ZrO 2 -based thin film microcapacitors integrated into silicon, through a three-pronged approach. First, to increase intrinsic energy storage, atomic-layer-deposited antiferroelectric HfO 2 -ZrO 2 films are engineered near a field-driven ferroelectric phase transition to exhibit amplified charge storage by the negative capacitance effect, which enhances volumetric ESD beyond the best-known back-end-of-the-line-compatible dielectrics (115 J cm -3 ). Second, to increase total energy storage, antiferroelectric superlattice engineering scales the energy storage performance beyond the conventional thickness limitations of HfO 2 -ZrO 2 -based (anti)ferroelectricity (100-nm regime). Third, to increase the storage per footprint, the superlattices are conformally integrated into three-dimensional capacitors, which boosts the areal ESD nine times and the areal power density 170 times that of the best-known electrostatic capacitors: 80 mJ cm -2 and 300 kW cm -2 , respectively. This simultaneous demonstration of ultrahigh energy density and power density overcomes the traditional capacity-speed trade-off across the electrostatic-electrochemical energy storage hierarchy. Furthermore, the integration of ultrahigh-density and ultrafast-charging thin films within a back-end-of-the-line-compatible process enables monolithic integration of on-chip microcapacitors, which can unlock substantial energy storage and power delivery performance for electronic microsystems.

25 ENERGY STORAGE↗

Optimization and Commercialization of the Juvenile Eel/Lamprey Acoustic Transmitter and Micro-battery (CRADA 477)

Through collaboration with partners under this CRADA, we continued to optimize the Eel/Lamprey Acoustic Transmitter (ELAT) of the Juvenile Salmon Acoustic Telemetry System (JSATS) to enhance its capability to track sensitive species and early life stages of fish with 3D and sub-meter accuracy. The transmitter firmware was improved to offer new functionalities, and the circuit design was revised to provide significantly more accurate frequency transmission. The transmitter's transducer was replaced with a shorter, more energy-efficient model. Additionally, the manufacturing processes for the transmitter and the microbattery used in it were improved. The outcomes of this work help advance understanding of migration timing and behaviors, habitat use, and survival rates of these species, supporting more informed management decisions for new and existing hydroelectric facilities and better designs for new hydropower systems that minimize or avoid environmental impacts.

13 HYDRO ENERGY↗