Thin Lithium Research Articles

Tailored Pre-Lithiation of Carbon Anodes Using Melt Deposited Thin Lithium

The user demands for Lithium ion batteries in mobile applications and electric vehicles request steady improvement in terms of capacity and cycle life. State-of-the-art lithium ion batteries irreversibly loose about 10 % of the capacity during the first cycles due to SEI formation. Therefore, 10 % of the cathode material is not used during the rest of the cells life which results in a waste of cathode material and leads to a lowered range of battery electric vehicles. Therefore, these losses must be compensated to ensure efficient resource utilization and to further increase the capacity of the lithium ion battery.We have developed a method to compensate these capacity losses by pre-lithiation: A fast and simple approach of electrolyte-free direct contact pre-lithiation leads to targeted degrees of pre-lithiation in a range of 7-50 % for state-of-the-art graphite electrodes. The parameters pressure (0-40 MPa), temperature (20-150°C) and time (0-60 min) are used to transfer lithium from a temporary substrate to the graphite anode. This process uses 1-5 µm thin lithium films made by the Fraunhofer IWS lithium melt deposition process as a lithium source.[1] The degree of pre-lithiation can be controlled by the lithium loading of the temporary substrate. NCM full cells built with pre-lithiated graphite electrodes where electrochemically evaluated in comparison to unlithiated electrodes. They show 6.5 % capacity increase after the first cycles using the additional lithium to form the SEI during the first cycles. The parameter influence of the pre-lithiation process on the initial coulomb efficiency of cells with pre-lithiated graphite electrodes is examined in half cells showing an ICE of 99.91 % for the best parameters.This method of electrolyte-free direct contact pre-lithiation shows an efficient way to further increase the capacity of state-of-the-art LIBs with graphite electrodes by increasing the cathode material utilization. It can potentially be scaled up to a roll-to-roll process using a heated calender nip. The temporary substrates with tailored lithium loading can be processed by lithium melt deposition in an efficient way with high lithium yield and high precision.[1] K. Schönherr, B. Schumm, F. Hippauf, R. Lissy, H. Althues, C. Leyens, S. Kaskel, Chemical Engineering Journal Advances 2022, 9, 100218. Figure 1

High-Energy Li−S Batteries Achieved by Compact S Cathode and Polysulfide Adjoining Interface Engineering

To maximize the energy density of Li−S batteries, it is crucial to increase the loading level of sulfur cathode and minimize the electrolyte content. However, excessive amounts of lithium polysulfides (LiPSs) generated in the high loading Li-S batteries limit the stable cycling. In this study, a high-loading S cathode with a three-dimensional (3D) network structure is fabricated using a simple pelletizing method, and the exhausting overcharging phenomenon, which occurs in the high loading Li−S cell, is successively prevented by pre-treating the lithium metal anode. Moreover, adding a diluent to the electrolyte containing viscous LiPSs enables the facile conversion between S species during the cycling of high-loading Li−S cells under lean electrolyte conditions. Finally, a prototype Li−S pouch cell with high energy density (427 Wh kg−1) was realized by combining a compacted 3D cathode with a high-loading, pretreated thin lithium metal and diluent-modified electrolyte. We believe that the results reported herein will be a good guideline to establish proper strategies to achieve high energy density Li−S batteries.

(Invited) Processability of Solid-State Batteries

Solid-state batteries are promising energy storage alternatives that can achieve high energy densities be enabling Li metal anode and high voltage cathodes. When combined with long cycle life, improved safety, and low cost (<$100/kWh) the value proposition of solid-state lithium metal battery becomes more and more relevant. There are, however, significant materials and processing challenges that disrupt the materialization of working SSBs at present. Recent reviews clearly informed that the energy and power densities of the reported SSBs fall short in comparison with the state-of-the-art Li-ion batteries. The technical barriers to be addressed in the long-term include achieving areal capacities in the range of 3-10 mAh cm-2 with less than 10% excess Li anode, and more than 70% active that material loading in solid-state composite cathodes that are assembled against thin electrolytes which can withstand current densities higher than 1 mA cm-2, and yet enables higher coulombic efficiencies. Cell design calculations show that solid electrolytes with <100 µm thicknesses and Li metal anode with <50 µm thickness are necessary to achieve energy densities comparable or higher than the state-of-the-art lithium-ion batteries. The processability and integration of thick composite cathodes, thin solid electrolytes, and thin lithium metal anode into cell configurations in scalable fashions are of utmost significance to improve the value proposition of near market SSBs.

Experimental characterization of the flowline of a lithium film formed using an electromagnetic thruster for a RAON prototype charge stripper

This paper describes the variable optimization of a lithium charge-stripper device for the Rare isotope Accelerator complex for ON-line experiences (RAON) and the experimental characterization of a lithium film formed for the charge removal of uranium using a magnetohydrodynamic liquid metal circulation system. To this end, liquid lithium charge stripper was fabricated to form a thin lithium film flow through collisions between a liquid lithium jet and a planar deflector. The flow characteristics of the lithium film were analyzed through simulation and waterjet experiments in terms of the liquid lithium film thickness. To circulate the liquid lithium, a mechanically safe electromagnetic thruster with precise pressure control was designed by analyzing its electromagnetic and hydraulic parameters through finite element simulation. The analysis of the geometrical arrangement of the permanent magnet and input current of the thruster revealed that compared to existing electromagnetic thrusters, the nominal input current of the newly-constructed thruster was reduced to 57% and its weight reduced to 6%, while facilitating easy maintenance. The optimized nozzle diameter and angle of the lithium charge stripper was 0.7 mm and 34°, respectively. Further, the formation of a 22-µm thick liquid lithium thin film required to obtain the 79+ charge state of uranium was confirmed at an input current of 107 A.

Combining Solid Solution Strengthening and Second Phase Strengthening for Thinning Li Metal Foils.

Thin lithium (Li) metal foils have been proved to be indispensable yet elusive for practical high-energy-density lithium batteries. Currently, the realization of such thin foils (<50 μm) is impeded by the inferior mechanical processability of metallic Li. In this work, we demonstrate that the combination of solid solution strengthening and second phase strengthening, achieved by the addition of silver fluoride (AgF) to Li metal, can substantially enhance both the strength and ductility of metallic Li. Benefiting from the improved machinability, we succeed in fabricating an ultrathin (down to 5 μm), freestanding, and mechanically robust Li-AgF composite foil. More interestingly, the in situ-formed LixAg-LiF skeleton in the composite facilitates Li diffusion kinetics and uniform Li deposition, where the thin Li-AgF electrode displays a prolonged cycle life over 500 h at 1 mA cm-2 and 1 mAh cm-2 in a carbonate electrolyte. Coupled with a commercial LiCoO2 cathode (3.4 mAh cm-2), the LiCoO2||Li-AgF cell delivers a notable capacity retention of ∼90% over 100 cycles at 0.5 C with a low negative/positive ratio of 2.5.

Weakly coordinated Li ion in single-ion-conductor-based composite enabling low electrolyte content Li-metal batteries

The pulverization of lithium metal electrodes during cycling recently has been suppressed through various techniques, but the issue of irreversible consumption of the electrolyte remains a critical challenge, hindering the progress of energy-dense lithium metal batteries. Here, we design a single-ion-conductor-based composite layer on the lithium metal electrode, which significantly reduces the liquid electrolyte loss via adjusting the solvation environment of moving Li+ in the layer. A Li||Ni0.5Mn0.3Co0.2O2 pouch cell with a thin lithium metal (N/P of 2.15), high loading cathode (21.5 mg cm−2), and carbonate electrolyte achieves 400 cycles at the electrolyte to capacity ratio of 2.15 g Ah−1 (2.44 g Ah−1 including mass of composite layer) or 100 cycles at 1.28 g Ah−1 (1.57 g Ah−1 including mass of composite layer) under a stack pressure of 280 kPa (0.2 C charge with a constant voltage charge at 4.3 V to 0.05 C and 1.0 C discharge within a voltage window of 4.3 V to 3.0 V). The rational design of the single-ion-conductor-based composite layer demonstrated in this work provides a way forward for constructing energy-dense rechargeable lithium metal batteries with minimal electrolyte content.

Rational Design of a High-Loading Polysulfide Cathode and a Thin-Lithium Anode for Developing Lean-Electrolyte Lithium-Sulfur Full Cells.

Lithium-sulfur cells are attractive energy-storage systems because of their high energy density and the electrochemical utilization rates of the high-capacity lithium-metal anode and the low-cost sulfur cathode. The commercialization of high-performance lithium-sulfur cells with high discharge capacity and cyclic stability requires the optimization of practical cell-design parameters. Herein, a carbon structural material composed of a carbon nanotube skeleton entrapping conductive graphene is synthesized as an electrode substrate. The carbon structural material is optimized to develop a high-loading polysulfide cathode with a high sulfur loading capacity (6-12mg cm-2 ), rate performance (C/10-C/2), and cyclic stability for 200 cycles. A thin lithium anode based on the carbon structural material is developed and exhibits long lithium stripping/plating stability for ≈2500h with a lithium-ion transference number of 0.68. A lean-electrolyte lithium-sulfur full cell with a low electrolyte-to-sulfur ratio of 6µL mg-1 is constructed with the designed high-loading polysulfide cathode and the thin lithium anode. The integration of all the critical cell-design parameters endows the lithium-sulfur full cell with a low negative-to-positive capacity ratio of 2.4, while exhibiting stable cyclability with an initial discharge capacity of 550 mAh g-1 and 60% capacity retention after 200 cycles.

Locally Concentrated Ionic Liquid Electrolytes Enabling Low‐Temperature Lithium Metal Batteries

AbstractLithium metal is a promising anode material for next‐generation high‐energy‐density batteries but suffers from low stripping/plating Coulombic efficiency and dendritic growth particularly at sub‐zero temperatures. Herein, a poorly‐flammable, locally concentrated ionic liquid electrolyte with a wide liquidus range extending well below 0 °C is proposed for low‐temperature lithium metal batteries. Its all‐anion Li+ solvation and phase‐nano‐segregation solution structure are sustained at low temperatures, which, together with a solid electrolyte interphase rich in inorganic compounds, enable dendrite‐free operation of lithium metal anodes at −20 °C and 0.5 mA cm−2, with a Coulombic efficiency of 98.9 %. As a result, lithium metal batteries coupling thin lithium metal anodes (4 mAh cm−2) and high‐loading LiNi0.8Co0.15Al0.05O2 cathodes (10 mg cm−2) retain 70 % of the initial capacity after 100 cycles at −20 °C. These results, as a proof of concept, demonstrate the applicability of locally concentrated ionic liquid electrolytes for low‐temperature lithium metal batteries.

Locally Concentrated Ionic Liquid Electrolytes Enabling Low-Temperature Lithium Metal Batteries.

Lithium metal is a promising anode material for next-generation high-energy-density batteries but suffers from low stripping/plating Coulombic efficiency and dendritic growth particularly at sub-zero temperatures. Herein, a poorly-flammable, locally concentrated ionic liquid electrolyte with a wide liquidus range extending well below 0 °C is proposed for low-temperature lithium metal batteries. Its all-anion Li+ solvation and phase-nano-segregation solution structure are sustained at low temperatures, which, together with a solid electrolyte interphase rich in inorganic compounds, enable dendrite-free operation of lithium metal anodes at -20 °C and 0.5 mA cm-2 , with a Coulombic efficiency of 98.9 %. As a result, lithium metal batteries coupling thin lithium metal anodes (4 mAh cm-2 ) and high-loading LiNi0.8 Co0.15 Al0.05 O2 cathodes (10 mg cm-2 ) retain 70 % of the initial capacity after 100 cycles at -20 °C. These results, as a proof of concept, demonstrate the applicability of locally concentrated ionic liquid electrolytes for low-temperature lithium metal batteries.

Overview of nuclear data production system at RAON

Nuclear Data Production System (NDPS), a fast neutron facility for nuclear science and applications, was constructed at the Rare Isotope Accelerator complex for ON-line experiments (RAON) in Korea. NDPS is designed to provide both white and quasi-monoenergetic neutrons using 98 MeV deuteron and 20 – 83 MeV proton beams with thick graphite and thin lithium targets, respectively. Neutron energy is determined by employing the Time-Of-Flight (TOF) technique, along with a pulsed deuteron (or proton) beam with a repetition rate of less than 200 kHz. Fast neutrons are produced in the target room and are guided to the TOF room through a 4 m long neutron collimator consisting of iron and 5% borated polyethylene. The neutron beam is monitored using a parallel plate avalanche counter (PPAC) and a micro-mesh gaseous (MICROMEGAS) detector installed in the TOF room, so as to measure the energy and the position of neutrons.

Efficient Second- and Third-Harmonic Generations in Er3+/Fe2+-Doped Lithium Niobate Single Crystal with Engineered Surficial Cylindrical Hole Arrays.

Herein, significant enhancement of second- and third-harmonic generation efficiencies in a 1 mol% Er3+ and 0.07 mol% Fe2+-doped lithium niobate single-crystal plate were achieved after ablating periodic cylindrical pit arrays on the surface. Enhanced absorption and reduced transmittance of light were measured when the incident light signal passed through the patterned sample. Enhanced photoluminescence and two-photon-pumped upconversion emission spectra were also explored to obtain more details on the efficiency gains. The excitation-energy-dependent second-harmonic generation efficiency was measured, and an enhancement as high as 20-fold was calculated. The conversion efficiency of second-harmonic generation is 1 to 3 orders higher than that from other lithium niobite metasurfaces and nanoantennas. This work provides a convenient and effective method to improve the nonlinear conversion efficiency in a thin lithium niobite plate, which is desirable for applying to integrated optical devices.

Final Color of CAD-CAM Produced Thin Lithium Disilicate Ceramics Cemented with Different Colored Resin Cements on Darker Backgrounds

Aim: The aim of the present study was to evaluate the final color of CAD-CAM produced thin lithium disilicate ceramics cemented with A2, opaque, and bleach resin cements on darker backgrounds. Materials and Method: Nine different experimental groups (n=10) were generated according to the colors of resin backgrounds (ND3:A3, ND4:A3.5, and ND8:A4) and cements (A2, opaque, and bleach). Target specimen was prepared by cementing lithium disilicate ceramic layer onto ND2 (A2) background by using translucent resin cement. The color difference values between experimental groups and target specimen were calculated according to CIEDE2000 formula. The data were statistically analyzed by using Kruskall Wallis test (α=0.05). Results: The results showed that most of the experimental groups had higher color difference values than acceptability threshold (1.8) except ND3-A2 and ND3-opaque groups. It was observed that when the background got darker, the color difference values increased. Conclusion: The darker backgrounds (A3, A3.5, and A4) and resin cement color (A2, opaque, and bleach) affected the final color of the lithium disilicate ceramics in 1 mm thickness. Color difference values were found in clinically acceptable limits for cementing lithium disilicate ceramics with A2 and opaque resin cements on A3 background.

Measurement of 6Li burn-up reaction rate using a single crystal CVD diamond detector under fast neutron irradiation environment

The study aimed to develop a technique for measuring the 6Li burn-up rate using a single crystal diamond (SCD) detector (SDD) made by chemical vapor deposition (CVD) with a thin lithium fluoride foil. The method relied on pulse shape discrimination (PSD) to separate pulses by nuclear reaction products of 6Li from pulses due to fast neutrons and gamma-rays.By applying the PSD method, the rectangular shape pulses induced by events occurred at the specific depth positions of the SCD, i.e., the incident surface, the ballistic center region (BCR), and the rear surface, were extracted. Thereafter, pulses occurred each specific depth position of the SCD were discriminated according to the pulse width.Due to a short range of nuclear reaction products in the SCD, pulses at the incident surface should be induced by both fast neutrons and nuclear reaction products, although pulses at the BCR are caused by fast neutron only. The study demonstrated that quantitative measurements of nuclear reaction products in the 6Li burn-up reaction under fast neutron irradiation can be achieved using only one SDD by analyzing event rates at the incident surface and in the BCR region.

Solvation Engineering Enables High‐Voltage Lithium Ion and Metal Batteries Operating Under −50 and 80 °C

AbstractExtreme temperatures (&lt;‐20 °C or &gt;50 °C) would seriously impair the performance of lithium batteries through deteriorating bulk ion transport and electrode interfaces. Here, a rational design of weak solvent and anti‐solvent combination is presented for wide‐temperature electrolytes. The weak solvent provides accelerated desolvation kinetics of Li+ around the anode region, while the anti‐solvent not only functions as an antifreeze agent for smooth ion migration at low temperatures but also interacts with the weak solvent to boost the formation of ionic aggregates. The weak and anti‐solvent electrolyte (WAE) exerts excellent compatibility with both lithium metal and graphite. Under −40 °C, Li anode delivers 98.5% Coulombic efficiency and graphite outputs capacity over 230 mAh g‐1. Lithium‐ion/metal batteries by pairing graphite anode with LiCoO2 cathode with a negative to positive capacity ratio of 0.75 can realize steady operation at −50 °C with an average coulombic efficiency of 99.9%. Lithium metal batteries with 4.2 mAh cm‐2 high LiCoO2 cathode loading and 50 µm thin lithium anode deliver 73.8% capacity output at −40 °C. Besides, the cells are stable up to 80 °C with an average coulombic efficiency of 99.7%. This research demonstrates a relatively loose Li+ solvation environment in WAE systems and provides wide‐temperature electrolyte for high‐performance lithium ion and metal batteries.

Mitigating Concentration Polarization through Acid-Base Interaction Effects for Long-Cycling Lithium Metal Anodes.

Lithium (Li) metal has attracted great attention as a promising high-capacity anode material for next-generation high-energy-density rechargeable batteries. Nonuniform Li+ transport and uneven Li plating/stripping behavior are two key factors that deteriorate the electrochemical performance. In this work, we propose an interphase acid-base interaction effect that could regulate Li plating/stripping behavior and stabilize the Li metal anode. ZSM-5, a class of zeolites with ordered nanochannels and abundant acid sites, was employed as a functional interface layer to facilitate Li+ transport and mitigate the cell concentration polarization. As a demonstration, a pouch cell with a high-areal-capacity LiNi0.95Co0.02Mn0.03O2 cathode (3.7 mAh cm-2) and a ZSM-5 modified thin lithium anode (50 μm) delivered impressive electrochemical performance, showing 92% capacity retention in 100 cycles (375.7 mAh). This work reveals the effect of acid-base interaction on regulating lithium plating/stripping behaviors, which could be extended to developing other high-performance alkali metal anodes.

A 700 W⋅h⋅kg−1 Rechargeable Pouch Type Lithium Battery

High-energy-density rechargeable lithium batteries are being pursued by researchers because of their revolutionary potential nature. Current advanced practical lithium-ion batteries have an energy density of around 300 W⋅h⋅kg−1. Continuing to increase the energy density of batteries to a higher level could lead to a major explosion development in some fields, such as electric aviation. Here, we have manufactured practical pouch-type rechargeable lithium batteries with both a gravimetric energy density of 711.3 W⋅h⋅kg−1 and a volumetric energy density of 1653.65 W⋅h⋅L−1. This is achieved through the use of high-performance battery materials including high-capacity lithium-rich manganese-based cathode and thin lithium metal anode with high specific energy, combined with extremely advanced process technologies such as high-loading electrode preparation and lean electrolyte injection. In this battery material system, the structural stability of cathode material in a widened charge/discharge voltage range and the deposition/dissolution behavior of interfacial modified thin lithium electrode are studied.

Mathematical modeling of the parameters of an electro-optic modulator in the Mach–Zehnder interferometer configuration based on thin lithium niobate films

Subject of study. An electro-optic modulator in a Mach–Zehnder interferometer configuration based on ridge waveguides made of a thin lithium niobate film was studied. Aim of study. The study aimed to mathematically model the parameters of an electro-optic modulator in a Mach–Zehnder interferometer configuration based on ridge waveguides made of a thin lithium niobate film. Method. The dependence of the optical losses introduced by a Y-branch splitter on the angle of the splitter was investigated using a beam propagation method based on the fast Fourier transform. Main results. The results of mathematical simulation of the parameters of the electro-optic modulator in the Mach–Zehnder interferometer configuration based on thin lithium niobate films were presented. The dependence of the optical losses, introduced by the Y-splitter, on the waveguide separation angle was obtained. Images of interference patterns occurring in the output waveguide were examined. A comparison revealed that the effectiveness of the proposed interferometer configuration was higher than that of the alternative solutions available in the literature. The novelty of the results is that the configuration of the electro-optic modulator investigated in this study was fabricated in the form of an integrated optical circuit based on ridge waveguides of thin-film lithium niobate. Such a solution enables a reduction in the dimensions of the final device and increases the sensitivity compared with that of existing analogs based on bulk electro-optic crystals. Additionally, owing to the use of a semiconductor substrate, an electronic circuit can possibly be integrated into the substrate, which enables the implementation of an electro-optic sensor system on a single chip. Practical significance. The method for interference pattern analysis proposed in this study provides information on the magnitude of the voltage applied to the arm of the interferometer and enables the development of requirements for its further modernization for increasing the accuracy of measurements and developing optoelectronic devices based on thin lithium niobate films, including integrated optical electric-field sensors.

Magnetoelectric MEMS Magnetic Field Sensor Based on a Laminated Heterostructure of Bidomain Lithium Niobate and Metglas.

Non-contact mapping of magnetic fields produced by the human heart muscle requires the application of arrays of miniature and highly sensitive magnetic field sensors. In this article, we describe a MEMS technology of laminated magnetoelectric heterostructures comprising a thin piezoelectric lithium niobate single crystal and a film of magnetostrictive metglas. In the former, a ferroelectric bidomain structure is created using a technique developed by the authors. A cantilever is formed by microblasting inside the lithium niobate crystal. Metglas layers are deposited by magnetron sputtering. The quality of the metglas layers was assessed by XPS depth profiling and TEM. Detailed measurements of the magnetoelectric effect in the quasistatic and dynamic modes were performed. The magnetoelectric coefficient |α32| reaches a value of 492 V/(cm·Oe) at bending resonance. The quality factor of the structure was Q = 520. The average phase amounted to 93.4° ± 2.7° for the magnetic field amplitude ranging from 12 to 100 pT. An AC magnetic field detection limit of 12 pT at a resonance frequency of 3065 Hz was achieved which exceeds by a factor of 5 the best value for magnetoelectric MEMS lead-free composites reported in the literature. The noise level of the magnetoelectric signal was 0.47 µV/Hz1/2. Ways to improve the sensitivity of the developed sensors to the magnetic field for biomedical applications are indicated.

Y-Z cut lithium niobate longitudinal piezoelectric resonant photoelastic modulator.

The capability to modulate the intensity of an optical beam has scientific and practical significance. In this work, we demonstrate Y-Z cut lithium niobate acousto-optic modulators with record-high modulation efficiency, requiring only 1.5 W/cm2 for 100% modulation at 7 MHz. These modulators use a simple fabrication process; coating the top and bottom surfaces of a thin lithium niobate wafer with transparent electrodes. The fundamental shear acoustic mode of the wafer is excited through the transparent electrodes by applying voltage with frequency corresponding to the resonant frequency of this mode, confining an acoustic standing wave to the electrode region. Polarization of light propagating through this region is modulated at the applied frequency. Polarization modulation is converted to intensity modulation by placing the modulator between polarizers. To showcase an important application space for this modulator, we integrate it with a standard image sensor and demonstrate 4 megapixel time-of-flight imaging.

Insights into the Importance of Native Passivation Layer and Interface Reactivity of Metallic Lithium by Electrochemical Impedance Spectroscopy.

Lithium-metal batteries offer substantial advantages over lithium-ion batteries in terms of gravimetric and volumetric energy densities. However, their widespread practical use is hindered by safety concerns, often attributed to the poor stability of the metallic lithium interface, where electrochemical impedance spectroscopy (EIS) can provide crucial information. The EIS spectra of metallic lithium electrodes proved to be more complex than expected, especially when studying thin lithium metal foils. Here, it is identified that charge-transfer impedance becomes one of the main components of the EIS spectra, the magnitude of which is found to be strongly dependent on the native passivation layer of metallic lithium and on the nature of electrolyte. "Asymmetricity" of the EIS spectra in symmetric cells when separated the working and counter electrode contributions to the total impedance using three-electrode cells is also identified.