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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Sulfur Polymers as Flexible Interfacial Additives for Low Stack-Pressure Solid-State Lithium-Ion Batteries

Solid-state batteries (SSBs) fabricated using sulfide solid electrolytes (SSEs) typically require cell stack-pressures in the range of tens to hundreds of megapascals to maintain effective interfacial contact and lithium-ion mobility across the full cell stack. These relatively high cell stack-pressures necessarily require additional cell components that reduce the delivered volumetric and gravimetric capacities of SSBs. This work has developed a novel sulfur polymer (polyS) that improves lithium-ion conductivity in SSBs at low cell stack-pressures, thereby directly targeting this technological limitation. Specifically, this work shows that polyS can be combined with the argyrodite Li6PS5Cl (LPSC) to form a stable composite SSE. By combining LPSC particles with a flexible additive that enhances interfacial contact at low pressures, this new polyS LPSC composite SSE material greatly improves ionic conductivity at cell stack-pressures below 2.0 MPa in comparison to conventional LPSC composites. Furthermore, this polyS LPSC composite can be used to fabricate a full SSB that cycles reversibly at only 1.6 MPa. Finally, this composite SSE exhibits self-healing behavior when combined with a lithium metal electrode, wherein lithium dendrites are oxidized to form passivating Li2S species that recover the cell from shorting.

ENERGY STORAGE↗
DOE OSTI2023

Unraveling Li growth kinetics in solid electrolytes due to electron beam charging

Revealing the local structure of solid electrolytes (SEs) with electron microscopy is critical for the fundamental understanding of the performance of solid-state batteries (SSBs). However, the intrinsic structural information in the SSB can be misleading if the sample’s interactions with the electron beams are not fully understood. In this work, we systematically investigate the effect of electron beams on Al-doped lithium lanthanum zirconium oxide (LLZO) under different imaging conditions. Li metal is observed to grow directly on the clean surface of LLZO. The Li metal growth kinetics and the morphology obtained are found to be heavily influenced by the temperature, accelerating voltage, and electron beam intensity. We prove that the lithium growth is due to the LLZO delithiation activated by a positive charging effect under electron beam emission. Our results deepen the understanding of the electron beam impact on SEs and provide guidance for battery material characterization using electron microscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ion transport in composites of binary electrolyte and single ion conductor—A chronoamperometry study

Composite electrolytes for lithium batteries typically combine materials with very different mechanical properties and ionic transport mechanisms and the degree to which these two phases affect each other is not well understood. In this work we used numerical simulations and experiments to investigate the transport in composite electrolytes consisting of polyethylene oxide (PEO) with Lithium bis-triuoromethanesulfonimide (LiTFSI) and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) lithium ion conducting glass-ceramic particles. In particular we are interested in how the introduction of a single ion conductor (SIC) changes the salt concentration gradients in the polymer electrolyte (PE) under applied potential. To study this, we performed numerical simulations and chronoamperometry experiments in electrolytes with different arrangements of the SIC and PE phases, i.e. layers and particulate composites. The results show that the particulate composites have the highest concentration gradients and take the longest time to reach steady state current. Furthermore, the high concentration gradient can be exacerbated by a high SIC/PE interfacial resistance. Finally, the best arrangement appears to have a layer of SIC impenetrable to anions in the polymer phase within the electrolyte membrane.

25 ENERGY STORAGE↗
DOE OSTI2022

Application of GO anchored mediator in a polymer electrolyte membrane for high-rate solid-state supercapacitors

Here, we synthesized a novel polymer electrolyte membrane by combining poly (vinylidene fluoride) (PVDF) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with graphene oxide (GO) nanosheets and a lithium salt of tungstosilicic acid (Li 4 SiW 12 O 40 , hereafter, referred to SiWLi). The impact of the addition of GO/SiWLi on the microstructure and morphology of the membrane were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). We found that adding the GO/SiWLi to the PVDF/LiTFSI polymer electrolyte membrane significantly reduced the pore size. Furthermore, the addition of the GO/SiWLi resulted in not only an increase of the ionic conductivity from 0.87 $\times$ 10 –2 to 3.12 $\times$ 10 –2 Scm –1 but also an increase in the lithium-ion transference number from 0.52 to 0.87. The polymer electrolyte membranes with and without GO/SiWLi were utilized to fabricate solid-state supercapacitors. The supercapacitors fabricated with the membrane containing GO/SiWLi displayed 37.2% lower equivalent series resistance and 88.2% greater specific capacitance than those fabricated using the membrane without GO/SiWLi at 200mVs –1 .

42 ENGINEERING↗
DOE OSTI2025

Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

High-nickel oxide cathodes, LiNi x M 1−x O 2 (x ≥ 0.8), are preferred in automotive lithium batteries, but they face thermal instability challenges. Inconsistent literature reports and unstandardized testing protocols further complicate quantitative assessments of the thermal stability of these cathodes. Here, we present here a statistical thermal analysis based on the differential scanning calorimetry measurements of 15 representative cathode materials with different compositions, morphologies and states of charge. The findings reveal that each cathode has a critical state of charge that defines its safe operating limit, which is affected by the metal–oxygen bond strength and surface reactivity. The thermal runaway temperature is dictated by the layered Li 1−x NiO 2 to LiNi 2 O 4 spinel-like phase transition, which is thermodynamically determined by the metal–oxygen bond covalency and kinetically influenced by the cation mixing and particle size. Raman spectroscopy is used to predict the thermal runaway temperature on the basis of the linear relationship between them. Finally, we propose a thermal stability index to quantify cathode thermal stability as a guide for developing safer high-nickel cathodes.

batteries↗
DOE OSTI2020

Layered-spinel electrodes for lithium batteries

An electrode for a lithium-ion cell comprising a ‘layered-spinel’ composite oxide material is disclosed. The ‘layered-spinel’ can be a material of formula xLiMO2.(1−x)LiyM′zO4, wherein 0 < x < 1; LiMO2 is a lithium metal oxide having a layered structure in which M comprises one or more transition metals and optionally lithium, and has a combined average oxidation state of +3; and LiyM′zO4 is a lithium metal oxide having a spinel structure, 1≤y≤1.33, 1.66≤z≤2, and M′ comprises one or more transition metals, and has a combined average metal oxidation state in the range of about +3.5 to about +4.

25 ENERGY STORAGE↗
DOE OSTI2024

Regulating the Electron Distribution of Metal-Oxygen for Enhanced Oxygen Stability in Li-rich Layered Cathodes

Li-rich Mn-based layered oxides (LLO) hold great promise as cathode materials for lithium-ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)-oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TM—O bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TM—O framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface-to-interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.

25 ENERGY STORAGE↗
DOE OSTI2020

Facile and scalable dry surface doping technique to enhance the electrochemical performance of LiNi 0.64 Mn 0.2 Co 0.16 O 2 cathode materials

Lithium nickel manganese cobalt oxide (NMC) is one of the dominant cathode materials in lithium-ion batteries. In this study a simple, efficient and scalable surface doping technique is successfully demonstrated, which can be readily used in mass production of cathode materials. For the first time neodymium oxide (Nd 2 O 3 ) has been employed as the surface doping agent. The Nd-doped NMC shows greatly improved cycling and rate performance, and the enhanced cycling stability has been demonstrated in full pouch cells, with a 17.5% increase in capacity retention after 300 cycles. Fewer cracks have been observed in the doped NMC after cycling, and in situ X-ray diffraction reveals the suppressed lattice collapse by Nd doping. Greatly suppressed surface phase change has been confirmed by HR-TEM and EELS. The result suggests great promise in using this dry doping technique to enhance the electrochemical performance of NMC cathodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Bayesian learning for rapid prediction of lithium-ion battery-cycling protocols

Advancing lithium-ion battery technology requires the optimization of cycling protocols. A new data-driven methodology is demonstrated for rapid, accurate prediction of the cycle life obtained by new cycling protocols using a single test lasting only 3 cycles, enabling rapid exploration of cycling protocol design spaces with orders of magnitude reduction in testing time. We achieve this by combining lifetime early prediction with a hierarchical Bayesian model (HBM) to rapidly predict performance distributions without the need for extensive repetitive testing. The methodology is applied to a comprehensive dataset of lithium-iron-phosphate/graphite comprising 29 different fast-charging protocols. HBM alone provides high protocol-lifetime prediction performance, with 6.5% of overall test average percent error, after cycling only one battery to failure. Here, by combining HBM with a battery lifetime prediction model, we achieve a test error of 8.8% using a single 3-cycle test. In addition, the generalizability of the HBM approach is demonstrated for lithium-manganese-cobalt-oxide/graphite cells.

25 ENERGY STORAGE↗
DOE OSTI2025

Ultra-high efficient lithium recovery via terephthalic acid from spent lithium-ion batteries

The recovery of lithium from spent lithium-ion batteries (LIBs) is a critical step in advancing sustainability within the battery industry. Traditional lithium extraction methods from end-of-life LIBs predominantly rely on chemical leaching techniques. However, these methods often involve the excessive use of acids, leading to substantial environmental concerns. Additionally, their non-selective nature can compromise the purity of the recovered lithium salt. To achieve battery-grade purity, further purification and recovery processes are necessary. In this study, we introduce a universal and eco-friendly process for lithium recovery, employing terephthalic acid to selectively extract lithium prior to the recycling of other valuable metals. This innovative method achieves lithium recovery rates exceeding 98.53% from layered oxide cathodes and 98.53% from lithium iron phosphate cathodes, delivering an exceptional purity level of 99.95%. By demonstrating applicability across a variety of cathode materials, this approach establishes a universal, sustainable and efficient solution for LIB recycling. The high-purity lithium extraction enabled by this process supports the comprehensive utilization of valuable resources, contributing significantly to the development of a circular economy for battery materials.

Hou, Jiahui [Worcester Polytechnic Institute, MA (↗
DOE OSTI2024

(CrMnCoNiZn) 3 O 4 @PPy core-shell nanocomposite with excellent electrochemical performance as lithium-ion battery anode

High entropy oxides (HEOs) have an excellent potential for use as electrode materials in lithium-ion batteries (LIBs) due to their high theoretical specific capacity. In this work, spinel-structured (CrMnCoNiZn) 3 O 4 HEO nanoparticles with five elements in equal molar ratio is first generated by solution combustion method. (CrMnCoNiZn) 3 O 4 @polypyrrole (PPy) nanocomposites are prepared by in-situ polymerization method. As an anode for lithium-ion batteries, the electrochemical performance of the (CrMnCoNiZn) 3 O 4 @PPy composite outperforms that of (CrMnCoNiZn) 3 O 4 nanoparticles. The capacity is 802 mAh/g after 100 cycles at a current density of 100 mA/g, 416 mAh/g after 1000 cycles at a high current density of 1 A/g, and 360 mAh/g rate capacity at 2 A/g. The excellent electrochemical performance of the composites is mainly due to the fact that the conductive and flexible PPy is encapsulated on the high-entropy oxides, which can alleviate the volume change triggered by extraction-insertion of lithium ions process, as well as enhance the electrical conductivity and reduce the occurrence of some side reactions. Finally, this method of compositing materials can also be used in other HEOs and conductive polymers, providing a new idea to enhance the electrochemical properties of HEOs.

25 ENERGY STORAGE↗
DOE OSTI2020

Task 12 PV Sustainability - Environmental Life Cycle Assessment of Residential PV and Battery Storage Systems

Using a life cycle assessment (LCA), the environmental impacts from generating 1 kWh of electricity for self-consumption via a photovoltaic-battery system are determined. The system includes a 10 kWp multicrystalline-silicon photovoltaic (PV) system (solar irradiation about 1350 kWh/m2/year and annual yield 1000 kWh/kWp), an iron phosphate lithium-ion (LiFePO4) battery, and other components such as the control system, battery housing, and two inverters (one for the PV system and one for the battery system). Three options for the AC-coupled system with changing battery capacities (5, 10, or 20 kWh nominal capacity) are investigated. The environmental impacts are assessed using the indicators greenhouse gas emissions and cumulative energy demand (separated into total and non-renewable cumulative energy demand). In addition, the four most important impact categories for PV electricity - respiratory inorganics (particulate matter), acidification, energy carrier resource use, and minerals and metals resource use - are assessed according to the environmental footprint (EF) method. Data are drawn from the DETEC data DQRv2:2018, recent literature, and product details provided by manufacturers. The results show larger environmental impacts of PV-battery systems with increasing battery capacity; for capacities of 5, 10, and 20 kWh, the cumulative greenhouse gas emissions from 1 kWh of electricity generation for self-consumption via a PV-battery system are 80, 84, and 88 g CO 2- eq/kWh, respectively. The cumulative greenhouse gas emissions of PV electricity consumed directly or fed into the grid are 54 g CO 2 -eq/kWh. The corresponding total cumulative energy demands are 5.27, 5.40, and 5.50 MJ oil-eq/kWh, with non-renewable energy carriers contributing 1.16, 1.22, and 1.29 MJ oil-eq/kWh. In the investigated EF impact categories, we similarly observe a larger environmental burden with increasing battery capacity, except in the use of minerals and metals. Our sensitivity analyses show that using a nickel cobalt manganese oxide (NCM) lithium-ion battery, instead of an LiFePO 4 battery, leads to a comparable environmental impact in terms of greenhouse gas emissions and cumulative energy demand. However, the NCM battery increases the impact in the EF categories of acidification and respiratory inorganics by 7 and 10%, respectively, whereas energy carrier resource use decreases by 4% and minerals and metals resource use decrease by 1%. Using a copper indium selenium (CIS) PV panel instead of a multicrystalline-silicon decreases greenhouse gas emissions by 24%, non-renewable cumulative energy demand by 13%, and particulate matter emissions by 60% (the largest decrease). Furthermore, the calculated environmental impacts are sensitive to the assumed battery lifetime. A decrease from 5000 to 3000 charge cycles increases non-renewable cumulative energy demand by 24% and greenhouse gas emissions by 16%. Increasing from 5000 to 7000 charge cycles decreases the environmental impacts by 6% and 7% in terms of non-renewable cumulative energy demand and greenhouse gas emissions, respectively. A utility-scale battery system case study shows that using batteries to store PV electricity overproduction reduces greenhouse gas emissions compared to using natural gas backup electricity generation.

14 SOLAR ENERGY↗
DOE OSTI2022

Oxygen Vacancy Introduction to Increase the Capacity and Voltage Retention in Li‐Excess Cathode Materials

Li‐rich rocksalt oxides are promising cathode materials for lithium‐ion batteries due to their large capacity and energy density, and their ability to use earth‐abundant elements. The excess Li in the rocksalt, needed to achieve good Li transport, reduces the theoretical transition metal redox capacity and introduces a labile oxygen state, both of which lead to increased oxygen oxidation and concomitant capacity loss with cycling. Herein, it is demonstrated that substituting the labile oxygen in Li‐rich cation‐disordered rocksalt materials with a vacancy is an effective strategy to inhibit oxygen oxidation. It is found that the oxygen vacancy in cation‐disordered lithium manganese oxide favors high Li coordination thereby reducing the concentration of unhybridized oxygen states, while increasing the theoretical Mn capacity. It is shown that in the vacancy‐containing compound, synthesized by ball milling, the Mn valence is lowered to less than +3, providing access to more than 300 mAh g −1 capacity from the Mn 2+ /Mn 4+ redox reservoir. The increased transition metal redox and decreased O oxidation are found to improve the capacity and voltage retention, indicating that oxygen vacancy creation to remove the most vulnerable oxygen ions and reduce transition metal valence provides a new opportunity for the design of high‐performance Li‐rich rocksalt cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Can Cobalt Be Eliminated from Lithium-Ion Batteries?

Following the discovery of LiCoO 2 (LCO) as a cathode in the 1980s, layered oxides have enabled lithium-ion batteries (LIBs) to power portable electronic devices that sparked the digital revolution of the 21st century. Since then, LiNi x Mn y Co z O 2 (NMC) and LiNi x Co y Al z O 2 (NCA) have emerged as the leading cathodes for LIBs in electric vehicle (EV) application and have become crucial components in the fight against global warming. However, the surging demand for LIBs has led to an extremely tight supply. The EV sector has already dominated the LIB market, even though EV sales were only 2–3% of total passenger vehicle sales in 2020. EV sales are expected to grow 10-fold by the end of this decade, and close to 90% of the total LIB demand will come from the EV sector. As a result, LIB manufacturers must aggressively ramp up cell production to keep pace with the immense growth of the EV market, a quest that brings scrutiny to the cost and sustainability of current LIB manufacturing practices. Here, cathodes are a critical component that largely determines the energy density and 40–50% of the total cell cost in LIBs. Rigorous consideration of the cathode performance and material cost is crucial in sustaining EV adoption. In this Viewpoint, we discuss why using cobalt in cathodes is unsustainable in the long run and highlight the features of cobalt-free cathodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Lattice Oxygen Redox Reversibility Modulation in Enhancing the Cycling Stability of Li-Rich Cathode Materials

The practical application of lithium-rich layered oxides is prohibited by the drawbacks such as severe capacity and voltage degradation resulting from unstable oxygen redox environment and the accompanied irreversible oxygen release. In this report a facile and effective strategy is proposed to regulate the oxygen redox chemistry via foreign Fe doping and its induced intrinsic transition metal (TM) doping as well as the in situ constructed spinel surface layer. The Fe doping, together with the induced intrinsic TM dual doping, can stabilize the lattice oxygen in the bulk due to the formed stronger Fe—O bond, and restrain the irreversible TM migration and then the undesirable phase transformation. More importantly, thermodynamical energy barrier of oxygen activation is dramatically decreased by the O 2p–Fe 3d charge-transfer, allowing stable oxygen redox activity. And the pre-constructed spinel layer can effectively stabilize the surface lattice oxygen and suppress harmful interfacial side-reactions. Such a simple optimizing method make the modified cathode exhibit a high specific capacity of 298 mAh g -1 at 0.2 C, outstanding cycling stability with a superior capacity and voltage retentions of 92.5% and 90.8%, respectively, after 400 cycles at 1 C. This study provides a new direction for developing advanced Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Uncovering the Critical Role of Ni on Surface Lattice Stability in Anionic Redox Active Li 1.2 Ni 0.2 Mn 0.6 O 2

Anionic redox reaction (ARR) can provide extra capacity beyond transition metal (TM) redox in lithium-rich TM oxide cathodes. Practical ARR application is much hindered by the structure instability, particularly at the surface. Oxygen release has been widely accepted as the ringleader of surficial structure instability. However, the role of TM in surface stability has been much overlooked, not to mention its interplay with oxygen release. Herein, TM dissolution and oxygen release are comparatively investigated in Li 1.2 Ni 0.2 Mn 0.6 O 2 . Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn, facilitating subsequent oxygen release of the ARR process. Intriguingly, surface reorganization occurs following regulated Ni dissolution, enabling the stabilization of the surface and elimination of oxygen release in turn. Accordingly, a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure. Battery performance can be effectively improved, with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle, and cycle stability improved from 66.77% to 90.01% after 100 cycles. This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.

25 ENERGY STORAGE↗
DOE OSTI2025

An Oxygen‐Scavenger Sulfide Coating Enabling Long‐Term Stable Nickel‐Rich Cathodes

Oxygen release is a major issue associated with layer-structured metal oxide cathodes in lithium batteries, which can further cause a series of problems, such as irreversible phase transition, microcracking, and electrolyte decomposition. Eventually, these issues jointly result in cell performance degradation and safety hazards. Thus, it is very significant to tackle oxygen release for achieving long-term stable cyclability, but very challenging. Although intensive efforts have been invested to date, there still lacks a feasible solution. In this study, nanoscale ZrS 2 coatings are applied on prefabricated LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes directly via atomic layer deposition (ALD). Very encouragingly, we reveal that this ALD-deposited conformal ZrS 2 nanocoating can serve as an exceptional oxygen scavenger and then convert into a stable sulfate (Zr(SO 4 ) 2 ) coating. Such an in situ conversion is very beneficial and effective for protecting the electrolyte from decomposition. In addition, the resultant Zr(SO 4 ) 2 coating further inhibits undesirable reactions, stabilizes the interface between NMC811 and the electrolyte, suppresses microcracking, mitigates transition metal dissolution, and maintains the structural stability of the NMC811 cathode. Consequently, the ZrS 2 -coated NMC811 cathode has demonstrated extraordinary performance. Thus, this study advances the understanding of interface engineering while paving a new technical pathway for commercializing NMC811 cathodes.

Nickel-rich cathodes↗
DOE OSTI2022

Understanding slurry formulations to guide solution-processing of solid electrolytes

Scalable processing of thin solid electrolytes is crucial for engineering solid-state batteries with practical energy densities. To leverage existing battery production infrastructure, pathways for solution processing of solid electrolyte films must be investigated. Here, roll-to-roll compatible film preparation of aluminum-doped lithium lanthanum zirconate oxide was studied. Four slurry configurations accounting for different solvent properties and solid loadings were evaluated to investigate the ternary interactions within the dispersions. Rheological and coating stability analyses were carried out on the processed slurries. The analysis and characterization indicated that improved component interactions within the ethanol/toluene system result in homogenized distribution of the particles, binder, and plasticizer, and enable the extraction of free-standing thin films with thicknesses of 20 μm and large area (>15 in. 2 ). The drawbacks and opportunities of several protocols for high temperature sintering of the dried green films were investigated. This study highlights the importance of engineering dispersions during the development of processing protocols for solid electrolytes and provides guidelines for the best practices that can be leveraged for solution processing–based fabrications for a wide range of solid electrolyte materials.

25 ENERGY STORAGE↗