Lithium Loading Research Articles

Advances in the Application of Graphene in Lithium-ion Batteries

The search for effective energy storage options has escalated due to the rising global energy demands and environmental concerns. Lithium-ion batteries (LIBs) emerge as a key technology. However, the performance of traditional LIBs still needs to be improved. Therefore, choosing new nanomaterials for the modification of LIBs has become an effective solution. Graphene, as a nanomaterial, is an excellent candidate material for modification. This paper delves into the application of graphene in enhancing the performance of LIBs. Graphene, with its superior electrical conductivity and substantial specific surface area, offers the potential to enhance the performance of both anode and cathode materials in LIBs. This can lead to significant improvements in the overall cycle life, energy density, and power density of these batteries. This work emphasizes the application of graphene in cathode and anode materials. In cathode materials, the layered structure of graphene enables lithium-ion with high theoretical capacity. Meanwhile, graphene helps improve the electron and lithium ion mobility of anode materials. Despite the promising developments, challenges such as lithium loading capacity and coulombic efficiency still remain. The continued exploration of graphene applications is expected to drive LIBs to unprecedented performance metrics. This is in line with the global quest for sustainable and efficient energy storage technologies.

Li-doped transition metal high-entropy oxides (Li/TM-HEOs) as Li-Ion batteries cathodes: a first report on capacity fading and cycling stability

High-Entropy Oxides (HEOs) have gained significant attention for their wide range of compositions and potential applications across various sectors, including rechargeable batteries. This study explores the characterization of two distinct HEO systems as potential cathode materials for Lithium-ion batteries (LIBs). A series of rock salt structured HEOs with varying Li loadings (16Li/RS-HEO, 25Li/RS-HEO, 33Li/RS-HEO, and 41Li/RS-HEO) and a spinel-structured HEO with 16 mol% of Li loading (16Li/SP-HEO) were firstly synthesized through co-precipitation. Electrochemical analyses via cyclic voltammetry revealed stark differences in the behavior of these structures. The Li/SP-HEO sample displayed broad and strongly irreversible hysteresis cycles, while the Li/RS-HEO series manifested thin, narrow hysteresis cycles with single oxidation peaks between 0.5 V and 0.7 V. As the lithium content increases in the RS-HEO system, the cycling stability of the cell decreases, most likely due to the reduced ratio of transition metal cations to lithium ions. Although there was a noticeable decrease in capacity under higher current rates, the higher lithium loadings positively impact the cell capacity, albeit with notable capacity fading under higher current rates. Li-doped rock salt structured high entropy materials show potential for LIB cathodes in terms of high specific capacities; the observed stability issues at medium and high current densities indicate a rapid electrode degradation.

Lithium-loaded GelMA-Phosphate glass fibre constructs: Implications for astrocyte response.

Combinations of different biomaterials with their own advantages as well as functionalization with other components have long been implemented in tissue engineering to improve the performance of the overall material. Biomaterials, particularly hydrogel platforms, have shown great potential for delivering compounds such as drugs, growth factors, and neurotrophic factors, as well as cells, in neural tissue engineering applications. In central the nervous system, astrocyte reactivity and glial scar formation are significant and complex challenges to tackle for neural and functional recovery. GelMA hydrogel-based tissue constructs have been developed in this study and combined with two different formulations of phosphate glass fibers (PGFs) (with Fe3+ or Ti2+ oxide) to impose physical and mechanical cues for modulating astrocyte cell behavior. This study was also aimed at investigating the effects of lithium-loaded GelMA-PGFs hydrogels in alleviating astrocyte reactivity and glial scar formation offering novel perspectives for neural tissue engineering applications. The rationale behind introducing lithium is driven by its long-proven therapeutic benefits in mental disorders, and neuroprotective and pronounced anti-inflammatory properties. The optimal concentrations of lithium and LPS were determined in vitro on primary rat astrocytes. Furthermore, qPCR was conducted for gene expression analysis of GFAP and IL-6 markers on primary astrocytes cultured 3D into GelMA and GelMA-PGFs hydrogels with and without lithium and in vitro stimulated with LPS for astrocyte reactivity. The results suggest that the combination of bioactive phosphate-based glass fibers and lithium loading into GelMA structures may impact GFAP expression and early IL-6 expression. Furthermore, GelMA-PGFs (Fe) constructs have shown improved performance in modulating glial scarring over GFAP regulation.

Zinc oxide nanoparticles intercalated with porous carbon as a separator coating for improving the stability of lithium metal anodes.

Metal lithium negative electrodes are considered the "holy grail" of lithium battery negative electrodes due to their ultra-high energy density and low overpotential. However, the arbitrary growth of lithium dendrites during the cycling process hindered its industrialization process. We prepared porous carbon doped with zinc oxide nanoparticles (ZNC-MOF-5) by high-temperature carbonization of MOF-5, and coated ZNC-MOF-5 on the surface of commercial membranes (ZNC-MOF-5@PP). Used to improve the cycling stability of metal lithium negative electrodes. Zinc oxide nanoparticles in ZNC-MOF-5 have good lithium affinity and can promote Li+ deposition. The porous structure with a high specific surface area endows the electrode with high lithium loading capacity, reduces local current density, and obtains a dendrite-free metal lithium negative electrode. The electrochemical cycling performance of Li/Cu batteries indicates that, ZNC-MOF-5@PP. The separator can prevent the growth of dendrites and improve cycling stability, proving that ZNC-MOF-5 can effectively guide the deposition of Li and solve dendrite problems.

Liovix® Printable Lithium Technology for Controlled and Scalable Prelithiation of Silicon Anodes

Loss of active lithium in the first cycle permanently lowers the lithium-ion cell energy density. Prelithiation employs an external, sacrificial source of lithium to offset these losses allowing more efficient use of lithium from the cathode and raising the cell energy density.LIOVIX®printable lithium technology is comprised of stabilized lithium metal powder (SLMP®) dispersed in a compatible solvent along with other rheology and performance modifiers to create a formulation that is chemically stable and not prone to separation for extended periods of time. The technology is easily scalable using industry standard coating and printing equipment to apply the formulation to the surface of a prefabricated anode. LIOVIX® can be used in anodes with a range of silicon content, because lithium loading can be accurately controlled based on the applications’ requirements.In this presentation, we will compare LIOVIX® to other prelithiation methods. The electrochemical results will be discussed as well.

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

Electronic signatures of Lorentzian dynamics and charge fluctuations in lithiated graphite structures

Lithium graphite intercalation compounds (Li-GICs) are essential materials for modern day portable electronics and obtaining insights into their atomic structure and thermodynamics is of fundamental interest. Here we explore the electronic and atomic states of Li-GICs at varying degrees of Lithium loading (i.e., “staging”) by means of ab-initio molecular dynamics simulations and simulated X-ray adsorption spectroscopy (XAS). We analyze the atomic correlation functions and shows that the enhancements of the Li-ion entropy with increased staging result from Lorentzian lithium-ion dynamics and charge fluctuations, which activate low-energy phonon modes. The associated electronic signatures are modulations of the unoccupied π*/σ* orbital energy levels and unambiguous fingerprints in Carbon K-edge XAS spectra. Thus, we extend the canonical view of XAS, establishing that these “static” measurements in fact encode the signature of the thermodynamic response and relaxation dynamics of the system. This causal link between atomic structure, spectroscopy, thermodynamics, and information theory can be generally exploited to better understand stability in solid-state electrochemical systems.

Li+ intercalation current generation in amorphous and crystalline MoS2: Experiment and theory

In this work, crystalline and amorphous nano-MoS2 materials for effective Li+-intercalation current generation have been synthesized. The effect of disordering on the structural and electrochemical properties of nano-MoS2 has been systematically investigated by multiple characterizations: transmission electron microscopy (TEM), X-ray diffraction method and electrochemical measurements. Thermodynamic and kinetic peculiarities of intercalation processes have been studied. Dependences of the change in Gibbs’ free energy of the intercalation reaction on the extent of ‘guest’ lithium loading are analyzed. The distinctive feature of disordered structures is their ability to show colossal lithium ‘guest’ load, which ensures the specific capacity of the material in cathode processes up to ~2500 mAh·g-1 under the discharge not less than 2.6 V relative to lithium. The diffusion coefficient of lithium cations in the structure of disordered nano-MoS2 is two orders of magnitude higher than that in the crystalline MoS2. A quantum-mechanical model of the observed phenomena is suggested.

Multifunctional surface-engineering of 3D-lithiophilic nanocarbon scaffold for high-voltage anode-minimized lithium metal batteries

A lithium metal anode (LMA) offers the lowest negative potential and a high specific/volumetric capacity; however, it promotes the decomposition of electrolyte and leads to poor Coulombic efficiency, particularly in a conventional carbonate-based electrolyte which is electrochemically stable at high voltage; >4 V (vs Li+/Li). Herein, we report the development of a catalytic support to realize a high-performance LMA, suitable for use in carbonate-based electrolyte systems, consisting of a 3D carbon nanofiber scaffold (3D-CNS) coated with LiNO3. The lithium-rich inorganic coating preferentially decomposes on the surface of the 3D-CNS during initial lithiation, forming an inorganic compound–rich, solid–electrolyte interface (SEI) layer before any electrolyte decomposes. The LiNO3-derived SEI layer not only inhibits side reactions that consume electrolyte but also improves lithium-ion transport kinetics, leading to LMAs with high CE and superior rate capability. In addition, residual LiNO3 promotes the uniform deposition/dissolution of lithium during cycling, facilitating stable cycling over 300 cycles. Moreover, a lithium metal battery featuring a high-voltage NCM811 cathode and a LMA based on the proposed support with minimal excess lithium loading demonstrates significantly improved cycling performance with high energy and power densities of ∼ 570 Wh kg−1 and ∼ 690 W kg−1, respectively.

Conductive Iodine-Doped Red Phosphorus Enabled Dendrite-Free Lithium Deposition on MXene Matrix.

The highest theoretical capacity and lowest redox potential of lithium metal make lithium-based batteries the "holy grail" of the next-generation batteries. However, the uncontrollable dendrite growth and infinite volume change of lithium seriously hinder the real-world implementation of lithium-based batteries. Herein, a flexible MXene@iodine-doped red phosphorus (MXene@RP) paper with iodine-doped red phosphorous particles evenly distributed on the surface and interlayer of MXene matrix is designed by a simple vapor condensation reduction approach. The MXene@RP paper can be used as an efficient matrix to enable dendrite-free lithium deposition. On the one hand, the iodine doping alleviates the low conductivity shortcoming of red phosphorus, making it facilitate homogeneous lithium nucleation, thus promoting uniform lithium deposition and suppressing dendrite growth. On the other hand, the unique layered structure of conductive MXene paper provides ion transport channels and free spaces for lithium loading, alleviating the volume change induced structural damage. As a result, the MXene@RP paper with preloaded lithium exhibits long-term cycling stability. Particularly, a full cell based on Li-MXene@RP anode can maintain 81.4% of the initial capacity after 600 cycles at 4 C. The MXene@RP-based anode increases the potential applications of MXene and provides a guide for the design of dendrite-free lithium hosts.

Industrial Perspectives on Innovation: Sustainability, Safety, Scalability, and Advanced Performance

Industry continues to look forward to innovative and to sustainable solutions that can improve battery performance, safety, and manufacturing efficiency. Livent is looking forward to bringing LIOVIX™ to the market as a product to help meeting these growing requirements while opening pathways for the development of next generation battery technology.LIOVIX™, proprietary lithium metal product, is a unique printable formulation of lithium metal and other specialty materials that can improve the performance of lithium-ion batteries, reduce manufacturing costs, and enable the next generation of battery technology, all while enhancing safety and sustainability.LIOVIX™ can be printed on a battery’s anode during electrode manufacturing in a process called pre-lithiation. Pre-lithiation employs an external, sacrificial source of lithium to offset the first cycle loss of lithium due to SEI formation allowing more efficient use of lithium from the cathode and raising the cell energy density. However, pre-lithiation techniques that are scalable at giga-factory throughput speeds have yet to be demonstrated. LIOVIX™ technology is easily scalable using industry standard coating and printing equipment and is adaptable to any anode or cathode chemistry where an independent source of lithium is required. LIOVIX™ can be used in anodes with a range of silicon content, because lithium loading can be accurately controlled based on the applications’ requirements. Incorporation of this technology has led to higher columbic efficiency at the first cycle, better cell capacity, and longer life batteries. In fact, the application of LIOVIX™ has been demonstrated to improve a battery’s output and to extend its useful life for a variety of battery chemistries (Figure 1).LIOVIX™ is an important technology for the development and commercialization of solid-state batteries using lithium metal. These next generation batteries will address many of the challenges and limitations of today’s liquid electrolyte-based battery systems. LIOVIX™ can be directly printed on current collectors and can act as an anode in solid state batteries. It can also be printed on other anode material to improve the first cycle columbic efficiency and cell performance. It can reduce the interface resistance between anode and solid electrolyte layer.Commercialization of battery systems that use metallic lithium anodes is strongly dependent on the industry’s ability to manufacture these anodes cost effectively at scale. Using LIOVIX printable lithium technology thin lithium foils in the range of 10um – 30um have been demonstrated at the desired width. Figure 1

Printable Lithium - LIOVIXTM Assisted All Solid-State Lithium-Ion and Lithium-Metal Batteries for Enhanced Electrochemical Properties

All solid-state lithium-ion and lithium-metal batteries, which utilize a solid electrolyte in place of liquid electrolytes, are considered next-generation devices for energy storage due to their advantages in safety and potentially higher energy density. However, currently many solid-state lithium-ion and lithium-metal batteries are limited by their low Coulombic efficiency, poor power performance, and short cycling life due to the high resistance at the solid-state interfaces. Because of the diverse physical, chemical, and mechanical properties of various solid components in all solid-state batteries as well as the nature of solid-solid contact, many types of interfaces are present in a solid-state battery that can result in loose physical contact, formation of grain boundaries, and undesired chemical and electrochemical side reactions. All of these contribute to increasing resistance at the interface, which diminishes the cell performance, making solid state batteries not suitable for practical application.LIOVIXTM is a unique printable formulation of lithium metal and other specialty materials, which can be used in both lithium-ion and lithium metal-based rechargeable batteries. In the case of lithium-ion batteries, it can be printed on a range of anode materials including silicon-containing anodes for the pre-lithiation process to improve the first cycle columbic efficiency and cell performance. In the case of lithium metal-based batteries, LIOVIXTM can be printed directly onto the current collectors or solid electrolyte separators to fabricate all solid-state batteries utilizing printed lithium metal anodes. This approach has the potential to enable improved performance, safety, recyclability, and lower cost compared to the current advanced lithium-ion systems. In both categories, printable lithium formulation can reduce the interface resistance between the anode and solid electrolyte layer, which enhances the cell performance enabling practical application. The printable lithium formulation is easily scalable using industry standard coating and printing equipment and is adaptable to any anode or cathode chemistry where an independent source of lithium is required. In addition, the lithium loading can be accurately controlled based on the applications’ requirements. We have demonstrated improved electrochemical performance of silicon containing anodes with liquid electrolytes in a full cell format. The present work will demonstrate the concept of all solid-state batteries incorporating printable lithium with enhanced electrochemical properties compared to conventional solid-state batteries.

Lithium promotion of Pt/m-ZrO2 catalysts for low temperature water-gas shift

Low temperature water-gas shift (LTS) is an important reaction occurring in a fuel processor for producing and purifying hydrogen. Platinum supported on m-ZrO2 belongs to a family of catalysts consisting of metal nanoparticles and an active partially reducible oxide, with the catalysis proposed to occur at the boundary between metal particles and the support. In this investigation, increasing the loading of lithium dopant increased the LTS rate up to 0.54 wt % lithium, where conversion was 2.4 times that of the unpromoted catalyst at 260 °C. Further increases in lithium loading up to 1.5 wt % decreased the rate, although it remained higher than that of the unpromoted catalyst. Infrared spectroscopy and CO2 temperature programmed desorption experiments showed three effects with increasing lithium loading: (1) lithium promoter weakened the C–H bond of formate, the proposed rate limiting step of the interfacial surface formate mechanism; (2) high levels of lithium suppressed the platinum site capacity required for hydrogen transfer; and (3) high levels of lithium increased catalyst basicity. Aspects (2) and (3) tended to inhibit desorption of product CO2, an acidic molecule the removal of which is metal-catalyzed. XANES and XPS experiments revealed that electron transfer to enrich Pt nanoparticles is unlikely the root cause of C–H bond weakening in formate. However, other electronic effects (e.g., electrostatic effects or molecular rearrangement due to enhanced basicity) were not ruled out.

Printed Lithium for Next Generation Battery Technologies

Next generation lithium ion batteries will need to utilize anode materials that offer higher energy density and faster charging rates compared to graphite anode. However, widespread commercialization of anodes containing more than a few percent of high energy density materials such as silicon and tin has been hindered by issues such as high first cycle inefficiency and poor cycle life. Loss of active lithium from cathode materials due to SEI formation permanently lowers the cell energy density. Pre-lithiation employs an external, sacrificial source of lithium to offset active lithium losses during the first cycle, allowing more efficient use of lithium from the cathode and therefore raising the cell energy density1,2,3.Livent has developed a proprietary approach to pre-lithiation called Printable Lithium Technology (PLT) that incorporates SLMP into a stable printable formulation. Printable Lithium Formulation (PLF) is comprised of SLMP dispersed in a compatible solvent along with other rheology and performance modifiers to create a formulation that is chemically stable and not prone to separation for extended periods of time. The technology is scalable using industry standard equipment to apply the formulation to the surface of a prefabricated anode. Printable Lithium Technology (PLT) is anode and cathode chemistry agnostic4,5,6. PLT can be used in anodes with a range of silicon content, because lithium loading could be accurately controlled based on the applications’ requirements. Lithium loading control is achieved through the print head designed for pattern printing. We will also discuss safety benefits of using our approach.Figure 1a shows the dQ/dV curve of for baseline SiO/Li half-cell compared to a half-cell with PLF treated SiO. Figure 1a shows the absence of solvent reduction peak in the 0.4V – 0.2V range for the cell incorporating PLT, indicating PLF eliminate the irreversible capacity loss. The voltage vs. capacity curve on the right shows that the first cycle efficiency (FCE) has been improved from 69% in the baseline cell to 87% in the cell with PLT incorporated. Initial voltage is lowered from 1.6V to 0.2V in the cell with treated anode.It can be seen in Figure 2 that PLT can be used in a variety of cell chemistries to improve the cell FCE. Figure 1

Anthraquinone functionalized pseudocalixarene for high lithium loading and chromogenic ion-pair recognition in DMSO

The [2 + 2] condensation between 1,8-dihydroxyanthraquinone diester and 1,3-diamino-2-propanol in ethanol affords pseudocalixarene macrocyclic L2 in high yield. Heating L2 to 200 °C in DMSO can generate much smaller [1 + 1] macrocycle L1. Crystal structure of L1 shows that all non-hydrogen atoms are coplanar except one carbon from 1,3-diamino-2-propanol. L1 is quite inert, but L2 can interact with alkaline, alkaline-earth, as well as Zn2+, Cu2+, Fe3+ and Al3+ cation (chloride) evidenced by their CV and 1H NMR. With a L2:M (1:2), there are discernable UV–vis spectrum/1H NMR changes in the presence Cu2+, Fe3+, Al3+. Anion plays a key role in the cation binding process as the chromogenic response to Li+, Na+, K+, Ba2+ and TBA+ hydroxide. L2 forms 1:1 complex with TBAOH and 2:3 complex with NaOH, KOH, Ba(OH)2 in DMSO. L2 reacts with LiOH in 1:4 stoichiometric and is one of the highest lithium loading ligand. The reaction is second-order with t1/2 ~ 30 min for 0.25 mM L2 in the presence of 4.0 eq. LiOH. Besides hydroxide, L2 can interact with TBAF to form 1:1 host–guest complexes evidenced by their color and NMR change. With bulky cation, TBAOH shifts Ep(II) more negative, while other cations shift Ep(II) to positive. L2 is an ion pair acceptor that binds hydroxide and fluoride salt chromogenic.

Piperazine-based two-dimensional covalent organic framework for high performance anodic lithium storage

The controllably spatial and chemical structures and abundantly elemental reserves of covalent organic frameworks (COFs) endow them the potential of being applied in next generation of electrochemical lithium-ions storage with high performances. Here, a piperazine-based two-dimensional covalent organic framework (PTDCOF) is designed and synthesized. PTDCOF is constructed by triphenylene units through irreversible piperazine linkages to afford the regular in-plane pores sized ~11 Å. PTDCOF is charactered with few-layered features, which is crystalized through eclipsed (AA) and staggered (AB) stacking modes together. And the synthesized framework exhibits excellent stability upon harsh chemical environments. As the active material of anodic lithium storage, the guest-eliminated product derived by PTDCOF demonstrates remarkable lithiation (1644.3 mAh g − 1 capacity contribution at 0.1 A g − 1), rate and cycling performances. The abundant active sites lead to a high and reversible lithium loading of at least 14 lithium atoms per triphenylene unit (Li14(C18N3H9)). Such product presents superior anodic lithiation capability comparing with previously reported carbonaceous materials. This study provides a possible and attractive path for hunting the high performances of lithium or other metal ions storage systems.

Deep hydrothermal and shallow groundwater borne lithium and boron loadings to a mega brine lake in Qinghai Tibet Plateau based on multi-tracer models

Brine lakes are good natural laboratories to investigate groundwater influences on the hydrologic and chemical evolutions in arid environments, and the mineralization processes under intensive evaporation. Lacustrine groundwater discharge (LGD) is the vital conveyor for the loadings of resource elements in the brine lakes. Da Qaidam Lake, located in the Qaidam basin of the Qinghai–Tibet Plateau (QTP), is one of the largest brine lakes for boron and lithium resources in China. Lithium and boron in the lake are considered to be dominantly sourced from deep hydrothermal groundwater and shallow groundwater, but the partitioning of deep and shallow components to the lake and the derived lithium and boron loadings remain unknown, LGD derived boron and lithium provide the primary source of the salt lake. vitally regulates the formation, evolution and mineralization of Li and B resources in the brine lake. This study performs systematical investigations of radium isotopes (226Ra, 228Ra, 224Ra and 223Ra), lithium, boron, and other hydrogeochemical parameters in different water endmembers around the brine lake. The results indicate that radium isotopes are significantly enriched in the hydrothermal groundwater and will be removed by co-precipitation with barite precipitates in the lake water. The multi-tracer models coupled radium bass balance, conservative tracer buildup and water budget were deployed to precisely constrain radium co-precipitation rates, and to quantify the deep and shallow LGD (total LGD = LGDD + LGDS) and the derived lithium and boron loadings. Radium co-precipitation coefficient is obtained to be 4.7–6.1 y−1. LGDD and total LGD are estimated to be 8.8 × 106 and 3.3 × 107 m3 y−1, respectively, which account for 11.9% and 57.2% of the total water input. LGDD and total LGD derived lithium/boron loadings constitute up to 70.2/60.1%, and 79.0/77.7% of the total loadings, respectively, indicating the significance of disproportionate LGDD in delivering resource elements into the brine lake. This study presents the first attempt to partition the deep hydrothermal and shallow LGD to a mega the QTP brine lake by multi-tracer models and the findings contribute to the understanding of lithium and boron budgets in the brine lakes of the QTP and worldwide.

Printable Lithium Technology for Pre-Lithiation and Solid-State Battery Applications

The need for pre-lithiation has become more important due to the commercialization of anodes containing silicon for high energy density batteries. When Si / Graphite mixtures are used, there can be 10-20% or higher active lithium loss on the first charge depending on the amount of Si used. Pre-lithiation can introduce sacrificial lithium into a lithium ion cell which will off-set the irreversible lithium loss. There are many proposed pre-lithiation techniques such as roll-to-roll electrochemical baths, sacrificial salts, vacuum deposition and lithium sputtering. (1) None of these pre-lithiation methods have been scaled beyond the laboratory or pilot scale due to safety, cost, manufacturing inefficiencies or cell performance issues. Currently, the pre-lithiation method that has shown the most promise is the addition of lithium metal to the prefabricated anode (2), (3), (4). Because of its high capacity, lithium metal causes a negligible increase in cell mass and volume. In comparison, when sacrificial salts are used, the energy density can decrease due inactive phases remaining after lithium extraction.One solution has been to use stabilized lithium metal powder (SLMP®) to pre-lithiate silicon-based anodes (5), (6). The use of Livent’s advanced material, Lectro® Max Powder (SLMP) has been demonstrated worldwide as an effective and efficient pre-lithiation material (7). SLMP can deliver capacity close to the theoretical lithium capacity of 3860 mAh/g and, after addition of the electrolyte, it intercalates or alloys with the anode material in-situ, and; therefore, exists in the lithium ion form in the cell. By incorporating this sacrificial source of lithium in the anode to compensate for first cycle irreversible losses, the lithium provided by the cathode can be fully utilized.The use of dry SLMP in large scale deployments presents challenges that have delayed wide-spread adoption of the technology. To this end, Livent has developed a proprietary technology that incorporates SLMP into a stable printable formulation. Printable Lithium Technology (PLT) is uniquely positioned to address challenges associated with handling of a high surface area reactive powder; thus, allowing to mitigate both industrial hygiene and process safety issues. Printable Lithium Formulation (PLF) is comprised of SLMP dispersed in a compatible solvent along with other rheology and performance modifiers to create a formulation that is chemically stable and not prone to separation for extended periods of time. The solvent used is compatible with commercial electrode slurry solvent removal and recovery practices and is less toxic than NMP. The technology is easily scalable using industry standard coating and printing equipment to apply the formulation to the surface of a prefabricated anode. PLT is adaptable to any anode or cathode chemistry where an independent source of lithium is required. PLT can be used in anodes with a range of silicon content, because lithium loading can be accurately controlled based on the applications’ requirements. Lithium loading control is achieved through modification of the print head to print stripes of various width and spacing on the electrode surface. The patterns can range from narrow stripes spaced evenly across the electrode to a monolithic lithium layer. F igure 1. Cycle performance for commercially available electrode materials with anode loading > 4mAh/cm2. A) NMC811/Graphite-10% SiO; B) NCA/Graphite-10% SiO, C) LCO/80% SiO Composite; D) LFP/Hard carbon. Cycling condition: A and B: CCCV (0.5C rate with charge current cut off 0.1C), 2.8-4.2V at RT. Every 50th cycle is at C/10 rate. C: 2.8-4.45V, 0.1C-0.1C at RT. D: 2.5-3.5V, 0.1C-0.1C at RT. References Florian Holtstiege, Peer Bärmann, Roman Nölle, Martin Winter, and Tobias Placke, Pre-Lithiation Strategies for Rechargeable Energy Storage Technologies: Concepts, Promises and Challenges, Batteries 2018, (491), 4Sa Li, Yunhui Huang, Ju Li et al., Roll-to-roll prelithiation of Sn foil anode suppresses gassing and enables stable full-cell cycling of lithium ion batteries. Energy Environ. Sci., 2019,12, 2991Chengxu Shen, Rusheng Fu, Yonggao Xia and Zhaoping Liu, New perspective to understand the effect of electrochemical prelithiation behaviors on silicon monoxide. RSC Adv.,2018,8, 14473Michael W. Forney, Matthew J. Ganter, Jason W. Staub, Richard D. Ridgley and Brian J. Landi, Prelithiation of Silicon−Carbon Nanotube Anodes for Lithium Ion Batteries by Stabilized Lithium Metal Powder (SLMP). doi.org/10.1021/nl401776d, NanoLett.R. Jarvis, M.J. Lain, Y. Gao, and M. Yakovleva, J. Power Sources, 146, 331 (2005).Li, B. Fitch, Electrochem. Commun., 13, (2011) 664.Guo Ai, Zhihui Wang, Hui Zhao, Wenfeng Mao, Yanbao Fu, Vincent Battaglia, Sergey Lopatin, and Gao Liu, Scalable process for application of stabilized lithium metal powder in Li-ion batteries. Journal of Power Sources, (2016). Figure 1

Functionalization of Nitrogen-Doped Carbon Nanofibers with Polyamidoamine Dendrimer as a Freestanding Electrode with High Sulfur Loading for Lithium–Polysulfides Batteries

Lithium sulfur (Li–S) batteries have been considered as promising energy storage devices because of their superiority in energy density. However, the sulfur loading, low active material utilization...

Localized High Concentration Electrolytes for High Voltage Lithium-Metal Batteries: Correlation between Salt, Solvent, and Diluent Contents, and Reductive Stability of the Electrolytes

The quest for energy storage devices with high energy densities leads researches to drift away from conventional electrodes for novel architectures able to withstand high lithium loadings and deliver high discharge voltages. Two of the most promising electrode architectures to achieve these goals are the lithium metal anodes and the so-called high-Ni LiNixCoyMn1-x-yO2 (x ≥ 0.6) (NMC) cathodes based on mixed transition metal oxides. These electrodes, however, produce strong reducing/oxidizing environments at the interface with the electrolyte. Dilute electrolyte formulations (dominant in conventional lithium-ion batteries) are inadequate to resist uncontrolled electrolyte decomposition, triggering Li dendritic growth, and prompting low Coulombic efficiency (CE).There is an urgent need to work on new electrolyte formulations. In this sense, high concentrated electrolytes (HCE) gained attention due to their enhanced reductive and oxidative stability and high carrier density but still suffer from low ionic conductivity, high viscosity, and poor wettability. A promising strategy to overcome these drawbacks is diluting the electrolyte without affecting the original lithium salt – solvent coordination from the HCE, which has proven effective in increasing the CE and producing thinner lithium deposition patterns on the anode compared to dilute electrolytes.In this work, we examine the liquid structure and electronic properties in dilute, HCE, and localized high concentration electrolytes (LHCE), in an attempt to uncover changes in the solvated complexes based on salt, solvent, and diluent contents, focusing on an electrolyte formulation proven effective in experiments with lithium bis(fluorosulfonyl)imide (LiFSI), dimethyl carbonate (DMC), and bis(2,2,2-triflouroethyl) ether (BTFE) as the diluent. In our calculations, we modeled the liquid electrolytes within a unit cell with periodic boundaries along the x-, y-, and z-coordinates, and followed the formation of solvated structures performing ab-initio molecular dynamics (AIMD).Examining the dilute and the HCE formulations, besides the depletion of free solvent DMC molecules, we found a change in the coordination behavior of the FSI- anions that trigger the formation of a three-dimensional solution structure. Each FSI- anion coordinates with multiple lithium-ions, shifting the anion LUMO levels lower than the solvent molecules, which explains the improved reductive stability of the HCE formulation and the salt-dominant composition of the SEI films in experiments. Different from previous explanations, however, we do not attribute this improvement to the depletion of free solvent molecules but to lithium-salt pairing mechanisms modified in HCE electrolytes.For the LHCE formulations, we found that dilution does not influence the three-dimensional solution structure from the equivalent HCE. However, we found there should be a limit beyond which the solvation complexes that exist in the equivalent HCE formulation disappear. In summary, our approach allows for the development of a screening methodology that allows finding a correlation between the salt, solvent, and diluent contents, and the reductive properties of the electrolyte formulation. We believe this methodology constitutes an effective tool to explore further LHCE electrolyte formulations for a new generation of high energy density rechargeable batteries.