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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Status and prospects of lithium iron phosphate manufacturing in the lithium battery industry

Abstract Lithium iron phosphate (LiFePO 4 , LFP) has long been a key player in the lithium battery industry for its exceptional stability, safety, and cost-effectiveness as a cathode material. Major car makers (e.g., Tesla, Volkswagen, Ford, Toyota) have either incorporated or are considering the use of LFP-based batteries in their latest electric vehicle (EV) models. Despite LFP’s well-researched status as a cathode material, it is expected to fulfill additional demands in electric vehicle applications, such as fast-charging capabilities, wide temperature range adaptability, and higher energy density. This perspective examines the LFP supply chain, synthetic approaches, manufacturing processes, market trends, recent advancements, and evolving demands to better understand its future role in the EV market. Graphical abstract

Lu, Yanying↗
DOE OSTI2020

Lithium-sulfur battery with lithium polysulfide catholyte

A liquid catholyte for a Li-S battery comprises a non-aqueous solution of at least one lithium polysulfide of formula Li 2 S x (wherein x is selected from 4, 6, and 8) and an anion receptor compound capable of complexing with polysulfide anion. The non-aqueous solution typically is composed of the Li 2 S x and the anion receptor compound dissolved in a non-aqueous solvent (e.g., one or more organic ether or fluorinated ether solvents). The anion receptor compound typically is present in the catholyte at a concentration of about 0.1 M to about 4 M. Li-S batteries comprise a metallic lithium anode; a porous conductive substrate; a separator membrane between the anode and the porous conductive substrate; and the liquid catholyte composition within pores of the substrate.

25 ENERGY STORAGE↗
DOE OSTI2020

Cobalt-stabilized lithium metal oxide electrodes for lithium batteries

An electrode material comprising a composite lithium metal oxide, which in an initial state has the formula: y[xLi2MO3.(1−x)LiM′O2].(1−y)Li1+dMn2−z−dM″zO4; wherein 0≤x≤1; 0.75≤y<1; 0<z≤2; 0≤d≤0.2; and z−d≤2. M comprises one or more metal ions that together have an average oxidation state of +4; M′ comprises one or more metal ions that together have an average oxidation state of +3; and M″ comprises one or more metal ions that together with the Mn and any excess proportion of lithium, “d”, have a combined average oxidation state between +3.5 and +4. The Li1+dMn2−z−dM″zO4 component comprises a spinel structure, each of the Li2MO3 and the LiM′O2 components comprise layered structures, and at least one of M, M′, and M″ comprises Co. Cells and batteries comprising the electrode material also are described.

25 ENERGY STORAGE↗
DOE OSTI2022

Understanding Solid-Electrolyte Interphase Formation at the Lithium Metal Anode of Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are one of the most promising chemistries for the next generation of energy storage devices. In a standard Li-S cell, the metallic lithium anode is an essential component of the battery due to its low density, extremely high theoretical specific capacity, and very low negative electrochemical potential. However, several challenges related to the use of Li metal have prevented this battery technology from becoming commercially available. For instance, Li-anodes are highly reactive, which results in the continuous decomposition of the electrolyte and the formation of the solid-electrolyte interphase (SEI) layer. This, combined with the non-uniform deposition of Liions during plating at the anode surface, can seriously affect the performance, cycling, and safety of the battery. In addition, it has been suggested that a controlled SEI formation at the metallic Li anode can yield enhanced battery performance. Hence, a comprehensive understanding of how the SEI layer is formed can help elucidate improvements in this battery technology. In this work, the formation of the SEI layer in Li-S batteries is investigated using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The stability of liquid organic-based electrolyte components, salt concentration, electron-rich environments, and the use of inorganic solid-state electrolyte (SSE) materials are explored in order to provide molecular-level fundamental insights into how the nature and composition of the electrolyte can alter the initial stages of the SEI formation. The products of electrolyte decomposition and electro-/chemical reaction pathways of liquid electrolyte component such as solvent and salts are predicted from AIMD simulations of electrolyte-anode interfaces. Energetics of reactions from DFT ground-state optimizations are also presented to confirm the decomposition mechanisms. Some significant differences are then drawn regarding the use of low and high salt concentrations. Simulations under electron-rich environments show additional multielectron electrochemical reactions of solvent and salt decomposition taking place due to the excess of electrons and the presence of radical anions in the solution. Finally, the initial stages of formation, stability, and main constituents of interfaces between Li-metal and Sbased electrodes with sulfide-based SSEs are characterized in detail.

25 ENERGY STORAGE↗
DOE OSTI2022

High Current-Density-Charging Lithium Metal Batteries Enabled by Double-Layer Protected Lithium Metal Anode

The practical application of lithium (Li) metal anode (LMA) is still hindered by non-uniformity of solid electrolyte interphase (SEI), formation of "dead" Li, and continuous consumption of electrolyte although LMA has an ultrahigh theoretical specific capacity and a very low electrochemical redox potential. Herein, we report a facile protection strategy for LMA using a double layer (DL) coating that consists of a polyethylene oxide (PEO)-based bottom layer which is highly stable with LMA and promotes uniform ion flux, and a cross-linked polymer-based top layer which prevents solvation of PEO layer in electrolytes. Li deposited on DL-coated Li (DL@Li) exhibits a smoother surface and much larger size than that deposited on bare Li. The LiF/Li 2 O enriched SEI layer generated by the salt decomposition on top of DL@Li further suppresses the side reactions between Li and electrolyte. Driven by the abovementioned advantageous features, the DL@Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 cells demonstrate capacity retention of 92.4% after 220 cycles at a current density of 2.1 mA cm -2 (C/2 rate) and stability at a high charging current density of 6.9 mA cm -2 (1.5C rate). These results indicate that the DL protection is promising to overcome the rate limitation of LMAs and high energy-density Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Optimization of Magnesium-Doped Lithium Metal Anode for High Performance Lithium Metal Batteries through Modeling and Experiment

Lithium (Li)-magnesium (Mg) alloy with limited Mg amount, which can also be called Mg-doped Li (Li-Mg), has been considered as a potential alternative anode for high energy density rechargeable Li metal batteries. However, the optimum doping-content of Mg in Li-Mg anode and the mechanism of the improved performance are not well understood. In this study, density functional theory (DFT) calculations are used to investigate the effect of Mg amount in Li-Mg anode. The Li-Mg with about 5 wt. % Mg (abbreviated as Li-Mg5) has the lowest absorption energy of Li, thus all the surface area can be “controlled” by Mg atoms, leading to the smooth and continuous deposition of Li on the surface around the Mg center. A localized high concentration electrolyte enables Li-Mg5 to exhibit the best cycling stability in Li metal batteries with high-loading cathode and lean electrolyte under 4.4 V high-voltage, which is approaching the demand of practical application. This electrolyte also helps generate an inorganic-rich solid electrolyte interphase, which leads to smooth, compact and less corrosion layer on the Li-Mg5 surface. Both theoretical simulations and experimental results prove that Li-Mg5 has optimum Mg content and gives best battery cycling performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High–Nickel NMA: A Cobalt–Free Alternative to NMC and NCA Cathodes for Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) are the cathode materials of choice for next-generation high-energy lithium-ion batteries. Both NMC and NCA contain cobalt, an expensive and scarce metal generally believed to be essential for their electrochemical performance. Herein, a high-Ni LiNi 1–x–y Mn x Al y O 2 (NMA) cathode of desirable electrochemical properties is demonstrated benchmarked against NMC, NCA, and Al–Mg-codoped NMC (NMCAM) of identical Ni content (89 mol%) synthesized in-house. Despite a slightly lower specific capacity, high-Ni NMA operates at a higher voltage by ≈40 mV and shows no compromise in rate capability relative to NMC and NCA. In pouch cells paired with graphite, high-Ni NMA outperforms both NMC and NCA and only slightly trails NMCAM and a commercial cathode after 1000 deep cycles. Further, the superior thermal stability of NMA to NMC, NCA, and NMCAM is shown using differential scanning calorimetry. Here, considering the flexibility in compositional tuning and immediate synthesis scalability of high-Ni NMA very similar to NCA and NMC, this study opens a new space for cathode material development for next-generation high-energy, cobalt-free Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Lithium Manganese Spinel Cathodes for Lithium-Ion Batteries

Spinel LiMn 2 O 4 , whose electrochemical activity was first reported by Professor John B. Goodenough’s group at Oxford in 1983, is an important cathode material for lithium-ion batteries, which attracts continuous academic and industrial interests. It is cheap and environmentally friendly, and has excellent rate performance with 3-dimensional (3D) Li + diffusion channels. However, it suffers from severe degradations, especially under extreme voltages and during high-temperature operations. In this review, the current understanding and future trends of the spinel cathode and its derivatives with cubic lattice symmetry (LiNi 0.5 Mn 1.5 O 4 that shows high-voltage stability, and Li-rich spinels that show reversible hybrid anion- and cation-redox activities) shall be discussed. Special attention is given to the degradation mechanisms, further development of spinel cathodes, and concepts of utilizing the cubic spinel structure to stabilize high-capacity layered cathodes and as robust framework for high-rate electrodes. Lastly, “Good spinel” surface phases like LiNi 0.5 Mn 1.5 O 4 are distinguished from “bad spinel” surface phases like Mn 3 O 4 .

25 ENERGY STORAGE↗
DOE OSTI2021

In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries

A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.

degradation mechanisms↗
DOE OSTI2023

Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes

Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li0, with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. Using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.

25 ENERGY STORAGE↗
DOE OSTI2023

Anion-tethered Single Lithium-ion Conducting Polyelectrolytes through UV-induced Free Radical Polymerization for Improved Morphological Stability of Lithium Metal Anodes

Single Li + ion conducting polyelectrolytes (SICs), which feature covalently tethered counter-anions along their backbone, have the potential to mitigate dendrite formation by reducing concentration polarization and preventing salt depletion. However, due to their low ionic conductivity and complicated synthetic procedure, the successful validation of these claimed advantages in lithium metal (Li 0 ) anode batteries remains limited. In this study, we fabricated a SIC electrolyte using a single-step UV polymerization approach. The resulting electrolyte exhibited a high Li + transference number (t + ) of 0.85 and demonstrated good Li + conductivity (6.3×10 -5 S/cm at room temperature), which is comparable to that of a benchmark dual ion conductor (DIC, 9.1×10 -5 S/cm). Benefitting from the high transference number of SIC, it displayed a three-fold higher critical current density (2.4 mA/cm 2 ) compared to DIC (0.8 mA/cm 2 ) by successfully suppressing concentration polarization-induced short-circuiting. Additionally, the t + significantly influenced the deposition behavior of Li 0 , with SIC yielding a uniform, compact, and mosaic-like morphology, while the low t + DIC resulted in a porous morphology with Li 0 whiskers. In conclusion, using the SIC electrolyte, Li 0 ||LiFePO 4 cells exhibited stable operation for 4500 cycles with 70.5 % capacity retention at 22 °C.

25 ENERGY STORAGE↗
DOE OSTI2023

Review on Low-Temperature Electrolytes for Lithium-Ion and Lithium Metal Batteries

Abstract Among various rechargeable batteries, the lithium-ion battery (LIB) stands out due to its high energy density, long cycling life, in addition to other outstanding properties. However, the capacity of LIB drops dramatically at low temperatures (LTs) below 0 °C, thus restricting its applications as a reliable power source for electric vehicles in cold climates and equipment used in the aerospace. The electrolyte engineering has proved to be one of the most effective approaches to mitigate LIB performance degradation at LTs. In this review, we summarize the important factors contributing to the deterioration in Li + transport and capacity utilization at LTs while systematically categorize the solvents, salts and additives reported in the literature. Strategies to improve the Li + transport kinetics, in the bulk electrolyte and across the interphases, are discussed. In particular, the formation mechanism of solid electrolyte interphase and its functionality for LT electrolytes are analyzed. Perspectives on the future evolution of this area are also provided. Graphical abstract

25 ENERGY STORAGE↗
DOE OSTI2021

Zinc-Doped High-Nickel, Low-Cobalt Layered Oxide Cathodes for High-Energy-Density Lithium-Ion Batteries

High-Ni layered oxides with Ni contents greater than 90% are promising cathode candidates for high-energy-density Li-ion batteries. However, drastic electrode-electrolyte reactions and mechanical degradation issues limit their cycle life and practical viability. We demonstrate here that LiNi 0.94 Co 0.04 Zn 0.02 O 1.99 (NCZ), obtained by incorporating 2 mol% Zn 2+ into an ultrahigh-Ni baseline cathode material LiNi 0.94 Co 0.06 O 2 (NC), delivers superior cell performance. NCZ retains 74% of the initial capacity after 500 cycles in full cell assembled with graphite anode, outperforming NC (62% retention). NCZ also possesses a higher average discharge voltage relative to NC with an outstanding average voltage retention of over 99% after 130 cycles in half cells. Bulk structural investigations unveil that Zn doping promotes a smoother phase transition, suppresses anisotropic lattice distortion, and maintains the mechanical integrity of cathode particles. Furthermore, NCZ shows an enhanced interphase stability after long-term cycling, in contrast to the seriously degraded surface chemistry in NC. Finally, this work provides a practically viable approach for designing higher-energy-density high-Ni layered oxide cathodes for lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Influence of Calendering on the Electrochemical Performance of LiNi 0.9 Mn 0.05 Al 0.05 O 2 Cathodes in Lithium-Ion Cells

Electrode calendering is a necessary process used in industry to improve the volumetric capacity of lithium-ion batteries. However, calendering high-nickel cathodes leads to electrode particle pulverization, raising concerns of a reduced cycle life due to parasitic side reactions. We present here an investigation of the impact of calendering on the morphology and electrochemical performance of the cobalt-free layered oxide cathode LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA-90). We find that secondary particle pulverization and fusion simultaneously occur at sufficiently high pressures. The initial surface area of the cathode is shown to increase with the degree of calendering, despite the higher likelihood of secondary particle fusion. Long-term cycling of full coin cells assembled with the NMA-90 cathode and the graphite anode indicates that cells with higher degrees of cathode calendering exhibit lower capacity fade compared to uncalendered cathodes. Hybrid pulse-power tests demonstrate that the usable capacity range of cells with calendered cathodes far exceeds those with uncalendered cells after long-term cycling. The improved capacity retention and pulse-power performance are attributed to the enhanced mechanical properties of the electrode after calendering that prevents loss of the primary particle contact during long-term cycling. As a result, we find that calendering high-nickel NMA-90 to industrially relevant densities does not have a detrimental effect on capacity fade, marking an important step toward commercial adoption.

25 ENERGY STORAGE↗
DOE OSTI2022

Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Solid-state lithium metal batteries (SSLMBs) that utilize novel solid electrolytes (SEs) have garnered much attention because of their potential to yield safe and high-energy-density batteries. Sulfide-based argyrodite-class SEs are an attractive option because of their impressive ionic conductivity. Recent studies have shown that LiF at the interface between Li and SE enhances electrochemical stability. However, the synthesis of F-doped argyrodites has remained challenging because of the high temperatures used in the state-of-the-art solid-state synthesis methods. In this work, for the f irst time, we report F-doped Li 5+y PS 5 F y argyrodites with a tunable doping content and dual dopants (F-/Cl- and F-/Br-) that were synthesized through a solvent-based approach. Among all compositions, Li 6 PS 5 F 0.5 C l0.5 exhibits the highest Li-ion conductivity of 3.5 x 10 -4 S cm -1 at room temperature (RT). Furthermore, Li symmetric cells using Li 6 PS 5 F 0.5 Cl 0.5 show the best cycling performance among the tested cells. X-ray photoelectron spectroscopy and ab initio molecular dynamics simulations revealed that the enhanced interfacial stability of Li 6 PS 5 F 0.5 C l0.5 SE against Li metal can be attributed to the formation of a stable solid electrolyte interphase (SEI)-containing conductive species (Li 3 P), alongside LiCl and LiF. These findings open new opportunities to develop high-performance SSLMBs using a novel class of F-doped argyrodite electrolytes.

25 ENERGY STORAGE↗