Gallium-based Liquid Metal Research Articles

Gallium-Based Liquid Metal Flexible Electronics Prepared by Solid–Liquid Phase Transition

Gallium-Based Liquid Metal Flexible Electronics Prepared by Solid–Liquid Phase Transition

CuGa2 transition phase anchored liquid GaSn achieves high-performance liquid metal battery cathode

Severe volume expansion will cause the gallium-based liquid metal cathode material to detach from the collector thus deteriorating performance. Here, we propose a strategy for preparing electrodes by anchoring the liquid metal with an intermetallic compound transition phase to avoid the problem of liquid metal shedding during cycling. The good reactive wetting between the CuGa2 transition phase and gallium can firmly anchor the liquid metal to prevent the electrode material exfoliating from the collector. On the other hand, the unique two-dimensional layer structure of CuGa2 can also limit the lithiation volume expansion of liquid gallium. Density functional theory (DFT) reveals the anchoring mechanism of the CuGa2 transition layer to liquid gallium and the reaction mechanism of Li with CuGa2 during the electrochemical reaction. As a result, O-GaSn/CF cathodes exhibit low resistance, fast ion diffusion, high reversible capacity, excellent rate performance and outstanding cycling stability.

On the effective thermal conductivity of gallium-based liquid metal filled elastomers

Gallium based alloys are liquid at ambient temperature, combining both metal-like high thermal conductivity and fluidity characteristics, which contributes to their applications in thermal management, soft robotics, stretchable electronics and etc. A great number of experimental researches have been performed in preparing Ga-based liquid metal filled elastomers (LMFEs) with various constituent systems, processing techniques, droplet morphology and filler sizes in attempt to obtain the best thermal conductive efficiency. The thermal conductive mechanisms in these LMFEs are still lacking a comprehensive understanding up to date, and therefore the present work aimed to conduct a thorough analysis on this topic using both theoretical models and finite element method (FEM) simulations. The predictability of four classic micromechanics models was compared with the experiments and FEM simulations, and their relevant thermal conductive principles were identified from the simulated thermal flux evolution. Some deficiencies of these analytical models are identified and amended by reconsidering their special architectures. This work is favorable for establishing a general and quantitative relationship between the effective thermal conductivity and microstructures for most of the synthesized LMFEs available in the literatures.

Mechanism behind the Controlled Generation of Liquid Metal Nanoparticles by Mechanical Agitation.

The size-controlled synthesis of liquid metal nanoparticles is necessary in a variety of applications. Sonication is a common method for breaking down bulk liquid metals into small particles, yet the influence of critical factors such as liquid metal composition has remained elusive. Our study employs high-speed imaging to unravel the mechanism of liquid metal particle formation during mechanical agitation. Gallium-based liquid metals, with and without secondary metals of bismuth, indium, and tin, are analyzed to observe the effect of cavitation and surface eruption during sonication and particle release. The impact of the secondary metal inclusion is investigated on liquid metals' surface tension, solution turbidity, and size distribution of the generated particles. Our work evidences that there is an inverse relationship between the surface tension and the ability of liquid metals to be broken down by sonication. We show that even for 0.22 at. % of bismuth in gallium, the surface tension is significantly decreased from 558 to 417 mN/m (measured in Milli-Q water), resulting in an enhanced particle generation rate: 3.6 times increase in turbidity and ∼43% reduction in the size of particles for bismuth in gallium liquid alloy compared to liquid gallium for the same sonication duration. The effect of particles' size on the photocatalysis of the annealed particles is also presented to show the applicability of the process in a proof-of-concept demonstration. This work contributes to a broader understanding of the synthesis of nanoparticles, with controlled size and characteristics, via mechanical agitation of liquid metals for diverse applications.

Injectable composite hydrogels embedded with gallium-based liquid metal particles for solid breast cancer treatment via chemo-photothermal combination

Photothermal therapy (PTT) holds great promise as a cancer treatment modality by generating localized heat at the tumor site. Among various photothermal agents, gallium-based liquid metal (LM) has been widely used as a new photothermal-inducible metallic compound due to its structural transformability. To overcome limitations of random aggregation and dissipation of administrated LM particles into a human body, we developed LM-containing injectable composite hydrogel platforms capable of achieving spatiotemporal PTT and chemotherapy. Eutectic gallium–indium LM particles were first stabilized with 1,2-Distearoyl-sn‑glycero-3-phosphoethanolamine (DSPE) lipids. They were then incorporated into an interpenetrating hydrogel network composed of thiolated gelatin conjugated with 6-mercaptopurine (MP) chemodrug and poly(ethylene glycol)-diacrylate. The resulted composite hydrogel exhibited sufficient capability to induce MDA-MB-231 breast cancer cell death through a multi-step mechanism: (1) hyperthermic cancer cell death due to temperature elevation by near-infrared laser irradiation via LM particles, (2) leakage of glutathione (GSH) and cleavage of disulfide bonds due to destruction of cancer cells. As a consequence, additional chemotherapy was facilitated by GSH, leading to accelerated release of MP within the tumor microenvironment. The effectiveness of our composite hydrogel system was evaluated both in vitro and in vivo, demonstrating significant tumor suppression and killing. These results demonstrate the potential of this injectable composite hydrogel for spatiotemporal cancer treatment. In conclusion, integration of PTT and chemotherapy within our hydrogel platform offers enhanced therapeutic efficacy, suggesting promising prospects for future clinical applications. Statement of significanceOur research pioneers a breakthrough in cancer treatments by developing an injectable hydrogel platform incorporating liquid metal (LM) particle-mediated photothermal therapy and 6-mercaptopurine (MP)-based chemotherapy. The combination of gallium-based LM and MP achieves synergistic anticancer effects, and our injectable composite hydrogel acts as a localized reservoir for specific delivery of both therapeutic agents. This platform induces a multi-step anticancer mechanism, combining NIR-mediated hyperthermic tumor death and drug release triggered by released glutathione from damaged cancer populations. The synergistic efficacy validated in vitro and in vivo studies highlights significant tumor suppression. This injectable composite hydrogel with synergistic therapeutic efficacy holds immense promise for biomaterial-mediated spatiotemporal treatment of solid tumors, offering a potent targeted therapy for triple negative breast cancers.

Conversion of CO2 into fibrous carbon materials using Ga-based liquid alloys

This study investigates the catalytic reduction of CO2 using various ratios of Ga-based liquid alloys under different conditions. We explored the alloying of liquid gallium with metals like indium (In) and magnesium (Mg) through mechanical stirring and heating. The alloys, once prepared, were exposed to CO2 in a reactor, with the Ga-In-Mg alloy demonstrating optimal reaction effects. In an exemplary synthesis, 1 g of Ga was combined with 30 wt% In and 7 wt% Mg, yielding a 7 wt% Ga-In-Mg alloy. This alloy, when reacted with CO2 for 10 h, exhibited a maximum weight gain of 445 mg. Elemental analysis showed a carbon content increase from 4.56 % to 72.56 % post-reaction. The reacted alloy, post-acid washing and electron microscopy examination, revealed the production of fibrous carbon materials approximately 7 μm wide. The primary objectives of this research were to identify the optimal temperature for CO2 reduction by the alloy and to determine the most efficient alloy catalyst using orthogonal experimental methods. Furthermore, we aimed to elucidate the catalytic mechanism of gallium-based liquid metal in CO2 reduction. The study also involved analyzing the adsorption and reaction processes by fitting the adsorption and reaction kinetic curves of the liquid metal with CO2. Achieving these objectives could enable the conversion of CO2 into solid carbon products, aligning with current environmental and sustainable development goals. This research offers new insights and innovative approaches to tackling energy-related challenges, highlighting the potential of liquid metal alloys in carbon capture and reduction applications.

Lubrication properties of gallium-based liquid metals by doping bismuth

Ga-based liquid metal (GLM) is a promising high temperature lubricant but its lubricating properties still need to be further improved. In this work, the lubrication properties of bismuth doped Ga-base liquid metal in a vacuum environment were studied in a wide temperature range from room temperature (RT) to 600 °C, where the self-mated Inconel 625 alloy sliding-pairs were selected. The results indicate that the addition of a small amount of bismuth (0.5 wt%) in GLM can enhance its lubricating performance by suppressing the oxidation of gallium within the temperature range of 200 °C to 600 °C, thereby decreasing the wear of Inconel 625 alloy.

Liquid metal-enhanced thermoelectric generator for high-temperature thermal harvesting

It is a challenge to achieve high output power of the thermoelectric generator (TEG) for high-temperature waste heat recovery due to the working fluids with low thermal conductivity (such as air) or low tolerance of temperature (water or oil). In this paper, the gallium-based liquid metal (LM) with a high boiling point (>1000 ℃) and thermal conductivity (>20 W/mK) are introduced to significantly enhance heat charging and discharging at the hot/cold sides of TEG. We also developed an electromagnetic induction pumping method for the effective LM-driven flow at high temperatures. A three-dimensional coupling multi-parameter optimization simulation model of LM-based TEG was developed to reveal the internal heat transfer and power generation mechanism for clarifying the impact factors of the performance. The results have shown that the power generation capacity can be effectively improved by increasing the inlet temperature (Thot-in). It is worth noting that the temperature difference (ΔT) of the TEG module is severely limited by the thermal resistance (Rcapacity) of the LM heat capacity, such as, when the flow rate of 2 L/min, the Rcapacity accounts for 90.6 % (0.020 ℃/W). It is easier to achieve a larger open circuit voltage by increasing the height of the thermoelectric leg, but the Pmax is constantly weakened. Compared with Xceltherm 600 and Solar salt, LM heat transfer fluid has more obvious advantages in enhancing the power generation performance of the system. The LM-based TEG experiment platform was established to study heat transfer and power generation characteristics. The results have demonstrated that good consistency was proved by comparing experimental and numerical data. And the Pmax of the LM-based TEG system is 0.16 W/cm2 at ΔT of 136 ℃. LM-based TEG can open new perspectives for broad applications in high-temperature waste heat recovery.

Experimental investigation on optimization of the performance of gallium-based liquid metal with high thermal conductivity as thermal interface material for efficient electronic cooling

Effective thermal conduction between solid interfaces has emerged as a major bottleneck in heat dissipating heat from new-generation high-performance electronics. Gallium-based liquid metals (LMs), known for their high thermal conductivity, are gaining significant traction as thermal interface materials (TIMs) for enhanced thermal management. In this work, to address the key issues facing the application of gallium-based LMs as TIMs, including the lack of composition ratio data, poor coating performance and the need for improved thermal conductivity, two types of gallium-based LM-TIMs (Ga-In binary LM-TIMs and Ga-In-Sn ternary LM-TIMs) with different composition ratios were experimentally prepared, investigated and optimized. The thermal conductivities of the LM-TIMs at different temperatures (80 - 120 ℃) were tested, and the application reliability of the LM-TIMs was optimized by continuously destructing the oxide layer and filling micro copper particles. The influence of optimization parameters such as the duration of the destruction of oxide layer, the filling ratios of the particles and the particle size on the operation performance of the LM-TIMs was studied and analyzed. The results showed that the LM-TIMs exhibited excellent thermal conductivities of 29.6 - 38.5 W/(m·K), and the thermal conductivity increased with indium mass fraction and decreased with tin mass fraction. Significant improvements in coating performance were observed with the increase of the duration of destructing oxide layer, but it led to a reduction in thermal conductivity. Balancing coating performance and thermal conductivity, it was found that 30 min was the ideal duration. The filling of micro particles made up for the reduced thermal conductivity, and higher filling ratios and smaller particle sizes achieved better enhancement. In the experiment, a filling ratio of 5 % was appropriate because solidification occurred in LM-TIMs at higher filling ratios which weakened the thermal conductivity. This work provided valuable reference for the application and optimization of high thermal conductive gallium-based LM-TIMs.

Stretchable and recyclable In3SnBi/PU nanofiber composite as flexible sensors for human motion monitoring

Abstract Low-melting-point metal alloys (LMMAs) have great potential for application in soft sensors. However, the high cost limits the application of gallium-based liquid metals. In this paper, LMMA In3SnBi has been designed and prepared through a facile melt-mixing process followed by an ultrasonic dispersion technique. To overcome the fragility of low-melting-point alloys, flexible electrospun polyurethane (PU) matrix is used as structural support. When used as a sensor, the composite film exhibits a response time of 54.37 ms within a strain range of 15%. In addition, the composite film exhibits self-healing properties, and cracks generated by cyclic stretching can be repaired through a hot-pressing process. The current work presents a versatile fabrication strategy for LMMA-based flexible sensors, which holds great promise in the field of wearable electronic devices.

Printing of liquid metal by electrically modulating of interface tension in liquid environment

In recent years, gallium-based liquid metal has emerged as a prominent research material in the realm of flexible electronics, owing to its exceptional electrical conductivity and deformability. The crux of developing flexible electronic devices using liquid metal as a conductive material lies in the patterning of the liquid metal. Inkjet printing technology possesses the capability to efficiently craft functional patterns by printing any inkable material. However, due to the facile oxidation of the gallium-based liquid metal surface in ambient air, leading to the formation of oxide films and the presence of high surface tension, conventional inkjet printing techniques are incapable of directly rendering liquid metal prints. This manuscript introduces a refined and remarkably efficient approach to inkjet printing utilizing the liquid metal. By deftly adjusting the interfacial tension of the liquid metal at the nozzle with ultra-low potentials, falling within the 2-V range, the achievement of on-demand, micron-scale liquid metal microdroplet ejection printing surpassing 3 kHz is brought to fruition. This article delves into unraveling the mechanisms of potential modulation on the interfacial tension of the liquid metal at the nozzle, as well as the fundamental theories pertaining to the formation and migration of liquid metal microdroplets. These insights establish a theoretical and technical foundation for the application of liquid metals in the field of electronic printing.

Liquid Metal-Polymer Conductor-Based Conformal Cyborg Devices.

Gallium-based liquid metal (LM) exhibits exceptional properties such as high conductivity and biocompatibility, rendering it highly valuable for the development of conformal bioelectronics. When combined with polymers, liquid metal-polymer conductors (MPC) offer a versatile platform for fabricating conformal cyborg devices, enabling functions such as sensing, restoration, and augmentation within the human body. This review focuses on the synthesis, fabrication, and application of MPC-based cyborg devices. The synthesis of functional materials based on LM and the fabrication techniques for MPC-based devices are elucidated. The review provides a comprehensive overview of MPC-based cyborg devices, encompassing their applications in sensing diverse signals, therapeutic interventions, and augmentation. The objective of this review is to serve as a valuable resource that bridges the gap between the fabrication of MPC-based conformal devices and their potential biomedical applications.

Thermal Performance and Reliability of Liquid Metal Pastes with Solid Metal Particles as Thermal Interface Materials for the Cooling of Computing Electronics

In recent years, we have developed a series of gallium-based liquid metal pastes containing low content solid metal particle additives (LMPMPs) to enhance thermal performance and control bondline thickness (BLT) of prepared liquid metal composites as thermal interface materials (TIMs). This new material is synthesized via in-situ by introducing gallium oxide into liquid metal alloys. In our recent research, we intensively investigated thermal properties of different primary liquid metal alloys containing small amounts of metal additives, and ran extensive reliability tests including power cycling, thermal cycling, and aging tests on the synthesized LMPMPs. In this paper, the thermal properties of the synthesized LMPMPs with different liquid metal alloys are studied with reliability tests that focus on power cycling by monitoring thermal resistance of LMPMPs over time using a custom power cycler. We have found power density, BLT, and different liquid metal alloys have a significant impact on thermal properties and reliability of LMPMPs. We also conducted thermal aging tests on Cu-LMPMPs-Cu sandwich specimens at 85°C in an ambient atmosphere to study the deterioration of thermal conductivity of LMPMPs over time, measured by laser flash analyzer using the layered structure method. Highly accelerated stress test (HAST) with a profile of 110°C, 85RH%, and 264 hours was used to study the decomposition of liquid metal alloys. Thermal cycling test with a profile of -40 to 125°C was employed to investigate the pump-out of LMPMPs. It has been proven that LMPMPs have much better thermal performances than polymer-based thermal grease.

Effects of metal element doping on the lubrication behaviors and mechanisms of gallium-based liquid metals

Gallium-based liquid metals (GLMs) are a novel high-end lubricant with low friction coefficient and excellent load-carrying capacity. This paper aims to improve the lubrication properties of GLMs by regulating the frictional interfaces. Six types of GLMs doped with Zn, Mg, Bi, Cu, Ti, or Sc elements are prepared respectively, and the effects of metal element doping on the lubrication behaviors and mechanisms for AISI 440C steel self-mated pairs are investigated in the mixed lubrication regime with a ball-on-three-plate setup. Doping 1 wt% Zn or Cu elements can improve the lubrication properties, with the friction coefficient reduced by 20.3 % and the wear rate reduced by 55.1 % compared with those under eutectic Ga/In/Sn lubrication. However, doping Ti, Sc, Mg, or Bi all reduce the lubrication properties. Doping Zn improves the lubrication properties of GLMs by promoting the adsorption of gallium on the frictional interfaces. Conversely, doping Bi inhibits the adsorption of gallium. The improvement in the lubrication properties of Cu-doped GLM is attributed to the formation of low-hardness CuGa2 particles. The doping of Ti or Sc generates high-hardness TiGa3 or ScGa3 particles, causing three-body abrasive wear. The doping of Mg generates a large number of Mg2Ga5 particles, seriously disrupting the stable lubrication.

Gallium-Based Liquid Metals in Rechargeable Batteries: From Properties to Applications.

Gallium-based (Ga-based) liquid metals have attracted considerable interest due to their low melting points, enabling them to feature both liquid properties and metallic properties at room temperature. In light of this, Ga-based liquid metals also possess excellent deformability, high electrical and thermal conductivity, superior metal affinity, and unique self-limited surface oxide, making them popular functional materials in energy storage. This provides a possibility to construct high-performance rechargeable batteries that are deformable, free of dendrite growth, and so on. This review primarily starts with the property of Ga-based liquid metal, and then focuses on the potential applications in rechargeable batteries by exploiting these advantages, aiming to construct the correlation between properties and structures. The glorious applications contain interface protection, self-healing electrode construction, thermal management, and flexible batteries. Finally, the opportunities and obstacles for the applications of liquid metal in batteries are presented.

Laser manufactured-liquid metal nanodroplets intercalated Mxene as oil-based lubricant additives for reducing friction and wear

Two-dimensional (2D) material MXene is a research hotspot in lubricating materials because of its unique layered structure, which provides weak interlayer interaction and easy shear ability. Herein, the liquid metal nanodroplets intercalated MXene were successfully prepared via pulsed laser treatment and self-assembly method. First, zero-dimensional (0D) nano gallium-based liquid metal (GLM) was synthesized by pulsed laser irradiation of bulk Ga80In20 in acetone. Then, the GLM nanodroplets were loaded onto 2D MXene nanosheets via the effect of electrostatic adsorption to prepare MXene@GLM composite material. The as-obtained GLM not only widens the interlayer distance between MXene nanosheets, making it more susceptible to interlayer shear, but also enhances its lipophilicity. The friction test results showed that the MXene@GLM has the best lubrication performance with 1.0 wt% additive. The coefficient of friction (COF) of base oil PAO-6 can decrease from 0.79 to 0.097, the wear volume is reduced by 90.3 %, and the maximum load sustained reaches 950 N. The good tribological properties are mainly owing to the synergistic lubrication of GLM and MXene, which can form a continuous and firm tribofilm on the friction contact surface and avoid the direct contact of the friction pair.

Interface of gallium-based liquid metals: oxide skin, wetting, and applications.

Gallium-based liquid metals (GaLMs) are promising for a variety of applications-especially as a component material for soft devices-due to their fluidic nature, low toxicity and reactivity, and high electrical and thermal conductivity comparable to solid counterparts. Understanding the interfacial properties and behaviors of GaLMs in different environments is crucial for most applications. When exposed to air or water, GaLMs form a gallium oxide layer with nanoscale thickness. This "oxide nano-skin" passivates the metal surface and allows for the formation of stable microstructures and films despite the high-surface tension of liquid metal. The oxide skin easily adheres to most smooth surfaces. While it enables effective printing and patterning of the GaLMs, it can also make the metals challenging to handle because it adheres to most surfaces. The oxide also affects the interfacial electrical resistance of the metals. Its formation, thickness, and composition can be chemically or electrochemically controlled, altering the physical, chemical, and electrical properties of the metal interface. Without the oxide, GaLMs wet metallic surfaces but do not wet non-metallic substrates such as polymers. The topography of the underlying surface further influences the wetting characteristics of the metals. This review outlines the interfacial attributes of GaLMs in air, water, and other environments and discusses relevant applications based on interfacial engineering. The effect of surface topography on the wetting behaviors of the GaLMs is also discussed. Finally, we suggest important research topics for a better understanding of the GaLMs interface.

Gallium-based liquid metals as reaction media for nanomaterials synthesis.

Gallium-based liquid metals (LMs) and their alloys have gained prominence in the realm of flexible and stretchable electronics. Recent advances have expanded the interest to explore the electron-rich core and interface of LMs to synthesize various nanomaterials, where Ga-based LMs serve as versatile reaction media. In this paper, we delve into the latest developments within this burgeoning field. Our discussion begins by elucidating the unique attributes of LMs that render them suitable as reaction media, including their high metal solubility, low standard reduction potential, self-limiting oxidation and ultra-smooth and "layer" surface. We then provide a comprehensive categorized summary of utilizing these features to fabricate a variety of nanomaterials, including pure metallic materials (metal alloys, metal crystals, porous metals, high-entropy alloys and metallic single atoms), metal-inorganic compounds (2D metal oxides, 2D metallic inorganic compounds and 2D graphitic materials), as well as metal-organic composites (metal-organic frameworks). This paper concludes by discussing the current challenges in this field and exploring potential future directions. The versatility and unique properties of Ga-based LMs are poised to play a pivotal role in the future of nanomaterial science, paving the way for more efficient, sustainable, and innovative technological solutions.

Magnetic and injectable Fe-doped liquid metals for controlled movement and photothermal/electromagnetic therapy.

As a multifunctional material, gallium-based liquid metal (LM) mixtures with metal particles dispersed in the LM environment display many excellent and intriguing properties. In this study, biomaterials were prepared by mixing Fe particles with LM for easily manageable photothermal or electromagnetic therapy and evaluated. Clinically, the fabricated 5%Fe/LM sample was injectable and radiopaque, which allowed its smooth delivery through a syringe to the target tissues, where it could help achieve clear imaging under CT. Meanwhile, because of the loading of Fe particles, the 5%Fe/LM possessed a magnetic property, implying a high manipulation capability. According to the experiments, the capsule containing 5%Fe/LM when placed in an isolated pig large intestine could move as desired to the designated position through an external magnet. Further, the biosafety and low toxicity of the 5%Fe/LM were confirmed by cytotoxicity tests in vitro, and the temperature changes at the interface between the 5%Fe/LM and intestinal tissue after near-infrared (NIR) laser irradiation were determined through theoretical modeling and numerical simulation data analysis. Due to the excellent photothermal and magnetothermal effects of LM, the temperature of the 5%Fe/LM injected into the rabbit abdominal cavity could significantly increase under NIR laser or alternating magnetic field (AMF) administration. As a novel functional biomaterial, the 5%Fe/LM exhibited promising potential for designated position movement and photothermal or magnetothermal therapy in the near future.

Electrokinetic behavior of an individual liquid metal droplet in a rotating electric field

The interfacial tension gradient forms tangential stress that drives fluid flow at a liquid–liquid interface, known as the Marangoni convection. In this study, we report on the electrocapillary-driven Marangoni flow at the polarizable interface between a gallium-based liquid metal droplet (LMD) and electrolytes, activated by the rotating electric field. When the electric field frequency exceeds 50 Hz, the amplitude of the oscillatory movement of LMD decays to zero, resulting in a stationary droplet. Utilizing micrometer-resolution particle image velocimetry (micro-PIV), we investigate the flow patterns around the LMD in detail. The visualized flow fields reveal two distinct flow patterns in the surrounding fluid at the central cross section of LMD, which vary with changes in frequency: normal flow (50–200 Hz) and tangential flow (300–1000 Hz). To reveal this flow mechanism, we first analyzed the fluid configuration in a linear electric field. Subsequently, we employ the stream functions to theoretically derive the slip velocity of the Marangoni flow in a rotating electric field. By combining this with the numerical simulations, we arrive at the following conclusions: At high frequencies (f≥50 Hz), the time-averaged part of the interfacial tension gradient dominates the in-phase Marangoni flow, leading to normal flow; while the frequency increases (f≥300 Hz), the electrorotation due to the out-of-phase charging accounts for the transformation of the flow pattern. Our work systematically studied the Marangoni flow under linear and rotating electric fields, which is vital in electrokinetic flows and of fundamental interest for the fluid dynamics society.