Nickel Manganese Cobalt Oxide Research Articles

Conversion of Lithium Chloride into Lithium Hydroxide Using a Two-Step Solvent Extraction Process in an Agitated Kühni Column

A significant consequence of the green transition is the growing demand of lithium-ion batteries (LIBs), as they are essential for electrical vehicles. In turn, the demand for the raw materials that are needed to produce LIBs is increasing. A common LIB cathode type for electrical cars is lithium nickel manganese cobalt oxide (NMC). Since cobalt is currently considered as a critical raw material, nickel-rich NMC cathodes are now designed with lower cobalt contents. The synthesis of these new NMC types requires LiOH instead of Li2CO3, which was used for Co-richer NMC materials in the past. Most production routes of LiOH start from Li2CO3 or Li2SO4. However, LiCl could also be a potential precursor for LiOH, as it could be obtained from various lithium sources. A two-step solvent extraction process (SX) was developed for direct conversion of LiCl into LiOH, using a phenol (butylhydroxytoluene or BHT) and a mixture of quaternary ammonium chlorides (Aliquat 336) in an aliphatic diluent (Shellsol D70) as the solvent. The SX process was validated in counter-current mode using a rotary agitated Kühni extraction column. The use of a column instead of mixer-settlers reduced the CO2 uptake by the final product (LiOH), which prevented the partial conversion of LiOH to Li2CO3. A total of 75 L of LiCl feed solution was processed in the Kühni column to obtain a solution of LiOH with a final purity of more than 99.95%, at a yield of 96%.Graphical

Overcoming low initial coulombic efficiencies of Si anodes through prelithiation in all-solid-state batteries

All-solid-state batteries using Si as the anode have shown promising performance without continual solid-electrolyte interface (SEI) growth. However, the first cycle irreversible capacity loss yields low initial Coulombic efficiency (ICE) of Si, limiting the energy density. To address this, we adopt a prelithiation strategy to increase ICE and conductivity of all-solid-state Si cells. A significant increase in ICE is observed for Li1Si anode paired with a lithium cobalt oxide (LCO) cathode. Additionally, a comparison with lithium nickel manganese cobalt oxide (NCM) reveals that performance improvements with Si prelithiation is only applicable for full cells dominated by high anode irreversibility. With this prelithiation strategy, 15% improvement in capacity retention is achieved after 1000 cycles compared to a pure Si. With Li1Si, a high areal capacity of up to 10 mAh cm–2 is attained using a dry-processed LCO cathode film, suggesting that the prelithiation method may be suitable for high-loading next-generation all-solid-state batteries.

The practical utility of ternary nickel-cobalt-manganese oxide-supported platinum catalysts for room-temperature oxidative removal of formaldehyde from the air

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel–cobalt-manganese oxide–supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h−1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir–Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO–, and CO32–. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

High Precision Nail‐Penetration Setup for the Controlled Thermal Runaway Initiation of Lithium‐Ion Cells at Very Low Temperatures

A high precision nail‐penetration (NP) tool for characterizing the mechanically induced thermal‐runaway (TR) of lithium‐ion battery (LIB) cells in a defined range of temperatures down to −140 °C was developed. To understand the cell specific behavior at low temperatures aiming at the determination of safe handling conditions, different scenarios are analyzed. First, accuracy tests of the NP‐tool regarding motion and penetration depth are conducted with cylindrical cells at different temperatures. Thus, postmortem computer tomographic (CT) images are compared to the data measured with the newly integrated 3‐axis force sensor which is further combined with a high‐resolution position sensor. The herein developed setup allows evaluation of the NP‐metrics at an accuracy of ±1 pierced electrode layer without CT‐scans. Further NP examinations at 20 °C of fully charged cylindrical lithium nickel manganese cobalt oxide cells reveal a reproducible minimum damage as a reliable TR‐trigger. Moreover, NP‐tests at low temperature disclose a relation of the short circuit conductivity and TR‐reactions during subsequent rethermalization to room temperature. Finally, the implementation of a novel fixture for a controlled very fast cooling of LIB‐cells during critical damage opens the way to investigate the individual steps during a TR and, thus, to gain important information of the specific TR‐mechanism of different LIB‐cells.

Round‐robin test of all‐solid‐state battery with sulfide electrolyte assembly in coin‐type cell configuration

AbstractThe replacement of conventional lithium‐ion batteries with solid‐state batteries is currently under investigation by many players both from academia and industry. Sulfide‐based electrolytes are among the materials that are regarded as most promising, especially for application in the transport sector. The performance of anode, cathode, and solid electrolyte materials of this type of solid electrolyte is typically evaluated using manually assembled cells such as Swagelok cells, EL‐CELLs, and in‐house built pressure devices. Coin cells, however, are often disregarded. Though coin cells cannot accurately predict how a material will perform in an end‐use application battery cell format, they are easy to assemble and can provide reproducible data compared to the other cell types, which make them an interesting option for testing the materials under conditions more relevant for their envisioned application. The coin cell preparation method presented in this work has been evaluated interlaboratory for reproducibility and, in addition, can be modified depending on the optimization parameters of the solid electrolyte, cathode material, bilayer comprised on cathode and solid electrolyte, lithium metal anode, and cell in general. Besides, an interlab round‐robin test (RRT) is carried out between four laboratories, measuring defined electrochemical tests of sulfide solid‐state batteries in coin cell configuration. This RRT for the preparation of coin cell solid‐state batteries with sulfide solid electrolyte, lithium nickel manganese cobalt oxides cathode, and lithium metal anode is intended for academic researchers and provides guidelines of research in this field.

Development of dual polarization battery model with high accuracy for a lithium-ion battery cell under dynamic driving cycle conditions

Lithium-ion batteries are a key technology for electric vehicles. They are suitable for use in electric vehicles as they provide long range and long life. However, Lithium-ion batteries need to be controlled by a Battery Management System (BMS) to operate safely and efficiently. The BMS continuously controls parameters, such as current, voltage, temperature, state of charge (SoC), and state of health (SoH), and protects the battery against overcharging and discharging, imbalances between cells, and thermal runaways. The battery models and several prediction algorithms that the BMS uses to carry out these checks are essential to the system's performance. This research assesses the Dual Polarization (DP) model's ability to mimic actual battery performance in different dynamic driving conditions. In the study, a battery model for a Lithium–Nickel–Manganese–Cobalt-Oxide (Li-NMC) cell with a nominal capacity of 2 Ah is developed. A DP model was used in the study. Modeling and parameter estimation were performed in MATLAB Simulink/Simscape. Firstly, the model parameters are estimated depending on the SoC using the current and voltage data obtained from the Hybrid Pulse Power Characterization (HPPC) test. A further validation study of the model for low dynamic and high dynamic driving cycles is then presented. Dynamic Stress Test (DST), the US06 Supplemental Federal Test Procedure (SFTP) and Worldwide harmonized Light vehicles Test Procedure (WLTP) cycles were used for model validation. As a result of the study, the model's Root Mean Square (RMS) error values were obtained as 0.0053 V for DST, 0.0059 V for US06, and 0.008 V for WLTP. The obtained model is particularly successful for simulating a battery under dynamic current conditions and for use in control and prediction algorithms.

Thermal runaway of Li-ion battery with different aging histories

Safety issues associated with thermal runaway (TR) in batteries have attracted extensive research attention. However, understanding and predicting TR encounter significant challenges due to the complexities of chemical reactions, venting events, thermal stratification, multiphase interactions, and variable boundary conditions. These challenges are further complicated by intrinsic battery degradation, a phenomenon often insufficiently characterized and governed by multiple mechanisms. These primarily include the depletion of electrolyte and active materials, thickening of the solid-electrolyte-interphase (SEI), and formation of lithium plating and dendrites. Such degradation alters the battery's materials and structure, directly causing electrochemical performance penalties and potentially affecting its TR behavior. This study examines the TR behavior of commercial 18,650 cells with lithium nickel manganese cobalt oxide (NMC) cathodes, focusing on degradation associated typical usage scenarios: long-term cycling, low-temperature cycling, dynamic cycling with calendar aging. We employ Electrochemical Impedance Spectroscopy (EIS) to probe internal changes in the electrochemical properties of aged cells compared to fresh counterparts. The EIS results reveal pronounced SEI impedance and substantially increased charge transfer impedance in long-term cycled cells. TR tests were conducted using an Accelerating Rate Calorimeter (EV+ ARC, Thermal Hazard Technology) following the heat-wait-seek (HWS) strategy. Our findings indicate a significant impact of aging mechanisms on second-life battery safety. Specifically, cells subjected to low-temperature cycling demonstrated a considerably lower onset temperature for exothermic reactions, and shorter TR delay time, despite all aged cells showing similar state of health (SOH). Furthermore, the temperature corresponding to the cell voltage drop is consistently much lower for aged cells with dynamic cycling and calendar aging.

Recovery of metal ions in lithium iron phosphate powder and lithium nickel-cobalt-manganate powder by electrochemical oxidation

In recent years, lithium-ion batteries have been increasingly used in electric and hybrid vehicles. It is anticipated that the first lithium-ion batteries will be discarded at the height of their useful lives in 2025, so developing an effective and ecologically friendly recycling process is essential. In this study, an electrochemical cathode synergism is proposed for the electro-catalyzed oxidation of lithium nickel cobalt manganese oxide powder and lithium iron phosphate powder to extract metal. The oxidation of Fe2+ and the release of Li+ (98 %) in LiFePO4 and the leaching of Ni (92 %), Co (91 %), Mn (94 %) and Li (97 %) from its NCM523 were mainly triggered by the rapid attack of a large amount of OH during advanced oxidation. The leaching kinetic analysis showed that the leaching system for electrochemical leaching of binary and ternary cathode materials was a chemical reaction control model, and the leaching thermodynamic analysis showed that the dissolution of each metal ion was feasible in this leaching environment. The suggested recycling technique utilizes fewer chemicals and generates less waste when compared to previous recycling techniques. The method offers a fresh approach to environmentally friendly recycling for spent lithium-ion battery leaching and recycling.

Utilization of lithium sulphate electrodialysis for closed-loop LIB recycling: Experimental study and process simulation

The hydrometallurgical recycling of spent lithium-ion batteries (LIBs) frequently relies on sodium hydroxide and sodium carbonate. This process generates a sodium-enriched solution, requiring treatment prior to safe discharge. This study focuses on a closed-loop recycling process for spent Lithium Nickel Manganese Cobalt Oxide (NMC) cathode material, eliminating sodium ions from conventional hydrometallurgical methods and regenerating acid and precipitant from disposal slurry. It employs lithium hydroxide (LiOH) as the precipitating reagent, while lithium recovery is conducted employing electrodialysis (ED) to regenerate LiOH and sulfuric acid (H2SO4) from the lithium sulfate solution. A part of the LiOH and H2SO4 reagents are subsequently used for the leaching and precipitation steps, creating a closed-loop recycling process. An experimental setup was developed to study the leaching, impurity removal, and metal extraction processes. The closed-loop recycling process was further investigated by simulation of this process. This involved the development of the ED module in both continuous and batch configurations using the Aspen Custom Modeler. This ED module is incorporated into Aspen Plus to integrate with the recycling process under experimental operational conditions. The minimal deviations of 3.34% and 2.38% within the precipitation and co-precipitation processes indicated the accuracy and validity of this work. Utilizing multiple batch-mode ED cells yields a 25% higher recovery of LiOH solution compared to continuous ED cells in the same operation conditions, i.e., employing 48 cells for 96 min under a current density of 1100 A·m−2. Furthermore, increasing the leaching temperature by 60°C yields a 53% increase in lithium leaching efficiency.

Boosting the performance enhancement of short-process regenerated Ni-rich cathode via antimony doping and modification

Currently, the short-process regeneration of cathode materials in spent lithium-ion batteries has attracted wide attention from researchers because of its short process flow, less waste liquid discharge and the cascade utilization of recycled materials. However, the performance of short-process regenerated electrode materials is generally difficult to comparable with the commercial materials, especially for lithium nickel cobalt manganese oxide (NCM). Herein, antimony (Sb) doping, and modification is proposed to boost the performance enhancement of short-process regenerated NCM in our work. Spent NCM is first selectively leached by oxalic acid, and then directly dried to obtain the precursor without separation and filtration. Finally, NCM is regenerated by lithium supplement and Sb doping modification. The regenerated NCM with optimal Sb doping modification (R-Sb10) has better electrochemical performance and cycle stability. It delivers an initial specific discharge capacity of 152.3 mAh/g, and the capacity retention maintains 86.3 % after 200 cycles at 0.5C, which can be comparable to the commercial NCM. The Sb element can be evenly distributed in the interior of short-process regenerated NCM, especially with a protective Li3SbO4 film on the surface. Through theoretical calculation, the R-Sb10 has a lower energy for material formation, higher energy barrier for cation disorder and decreasing diffusion energy barrier for Li+. The doping modification method provides a new idea to improve the performance of regenerated materials and is expected to meet the needs of industrial applications in the future.

Research Progress and Optimization Strategies of Cathodes, Anodes and Electrolytes for Lithium-ion Batteries

The importance of lithium-ion batteries is becoming increasingly clear as the world's need for clean energy grows. However, the challenges of realizing their higher energy density, stability and safety remain to be overcome. This paper discusses the working principle of Li-ion batteries and the importance of their core components, then explores the research significance of cathode, anode materials and electrolytes, respectively, and describes the current mainstream materials and their current challenges and optimization strategies. In terms of positive electrode materials, this paper introduces mainstream materials such as Nickel Manganese Cobalt Oxide (NMC), Nickel Cobalt Aluminum Oxide (NCA), and Lithium Iron Phosphate (LFP), and puts forward strategies to improve energy density and enhance stability; in terms of negative electrode materials, this paper lists core materials such as graphite and silicon, and discusses the issues of volume change and how to improve stability, etc. In the electrolyte section, it not only introduces the mainstream electrolytes such as organic liquid electrolytes and solid electrolytes, but also analyzes and discusses the problems of how to improve their ionic conductivity. By synthesizing these reviews and strategies, this paper aims to promote the progress and development of lithium-ion battery technology and bring new research perspectives and values.

Business Model Design for Cathode Material Manufacturer Startup Case Study: PT Polimikro Berdikari Nusantara

Startups often offer innovations in solving problems, but if these innovations have a business model, they will be protected from entering the valley of death. Polimikro Berdikari Nusantara is one of the startups recently facing risk. Polimikro Berdikari Nusantara’s main product, Lithium Nickel Manganese Cobalt Oxide (NMC), had Technological Readiness Level (TRL) 7 Demonstration System. However, the Market Readiness Level (MRL) is level MRL 4 Small Scale Early Adopter Campaign. Therefore, several activities need to be done to increase MRL to save Polimikro from the valley of death. This study aims to provide a design model and business strategy for Polimikro Berdikari Nusantara. This qualitative research uses analytical techniques using an interactive analysismodel by Miles and Huberman. Data collection was done by observation, documentation, andinterviews. The results obtained in this study are business models in the form of Business ModelCanvas (BMC) and Lean Canvas (LC) integration

Bioleaching of valuable metals from three cathode active materials comprising lithium nickel cobalt manganese (NCM) oxide using indigenous microorganisms

Recently, bioleaching has been studied for the metal recovery of lithium (Li), nickel (Ni), cobalt (Co), and manganese (Mn) from spent lithium-ion batteries. However, further work should be conducted to improve the metals recovery using efficient microorganisms and to investigate the effects of metal composition on black mass due to its heterogeneity. Our study reports bioleaching-mediated recovery of valuable metals Li, Ni, Co, and Mn from three typical LiNixCoyMn1−x−yO2 (NCM) cathode active materials with different compositions (NCM111, NCM523, and NCM622) using five bacterial strains (N10, P6, P7, N4, and F-O5) isolated from abandoned mines. Compared with the control (Acidithiobacillus ferrooxidans, KCTC4516) and blank conditions, the metal leaching efficiency of Li, Ni, Co, and Mn from NCM111 reached above 95 % using the N10 and P7 strains for 24 h at a pulp density of 10 g/L. Moreover, the lower leaching efficiency of metals using NCM523 and NCM622 was observed. A higher concentration of nickel in the leachate negatively influenced the bacterial activities. This study elucidates the bioleaching potential of isolated single strains for the extraction of metals from NCM. Additionally, it emphasizes the crucial role of Ni-adapted microorganisms in efficiently extracting metals from NCM with high Ni-content.

On the Influence of Li3InCl6−PEDOT:PSS Hybrids in Solid‐State Batteries Prepared via an Aqueous One‐Pot Approach

AbstractSolid‐state batteries (SSBs) utilizing halide solid electrolytes (SE) have garnered attention due to their enhanced stability when paired with oxide‐based cathode active materials. However, the dynamic interparticle contact during cycling in SSBs poses challenges to their stability and performance. To mitigate this problem, in this study, we present a one‐pot, aqueous synthesis of composites that integrate ion conductivity, electron conductivity, and mechanical stability into a single material. The developed composites consist of a halide SE, lithium indium chloride (Li3InCl6), and a conductive polymer (CP), poly(3,4‐ethylendioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS). The successful synthesis was verified using spectroscopic, thermal, scattering, and microscopy methods, with Kelvin Probe Force Microscopy (KPFM) demonstrating the distribution of PEDOT:PSS at the grain boundaries between Li3InCl6 particles. Upon incorporating our composite material with lithium nickel manganese cobalt oxide (NMC) cathode active material (CAM) as catholyte, an increase in the partial electronic transport was observed with increasing CP content. A direct correlation between the partial electronic transport of the catholytes and the initial discharge capacities was demonstrated. This study lays the groundwork for the preparation of multi‐functional catholytes under more sustainable conditions, without the need for organic solvents, extremely high temperatures, or special environments.

Direct flotation separation of active materials from the black mass of lithium nickel cobalt manganese oxides-type spent lithium-ion batteries

Batteries based on lithium nickel cobalt manganese oxides (NCM), which have not been extensively studied, were considered for this study. A black mass (BM) derived from a diverse mix of NCM-type batteries was pyrolyzed at three different temperatures before flotation. The optimum pyrolysis temperature was determined via X-ray spectrometry, contact angle measurements, thermogravimetry, X-ray diffraction, and X-ray photoelectron spectroscopy as 400 °C at which the active materials in the BM were successfully liberated without generating new phases on the material surfaces. This is crucial for recovering materials from the BM using flotation and their potential subsequent application in battery manufacturing, which requires high-purity materials. After optimal pretreatment, the flotation of the treated BM was conducted to separate active materials. At the laboratory scale, the optimal conditions were an impeller speed of 1600 rpm, a collector dosage of 150 g/t, a frother dosage of 150 g/t, and a pulp density of 20 g/L. Furthermore, the initial anode and cathode grades of 84 % and 92 % were further enhanced to 97 % and 95 %, respectively, by employing additional cleaning and scavenging stages. Therefore, this study offers a promising method for recovering high-purity active materials from the BM through systematic pyrolysis pretreatment and subsequent flotation.

Upcycling of lithium cobalt oxide to LiNi1/3Mn1/3Co1/3O2

Upcycling of lithium cobalt oxide (LCO) into lithium nickel manganese cobalt oxide (NMC111) cathode material using acetone antisolvent crystallization of citrate leachate followed by sol–gel synthesis with complementary metal acetate or sulfate salts.

Mitigating hydrogen gas evolution in high nickel cathodes using single-crystalline NCM particles

Single-crystal nickel cobalt manganese oxide cathodes significantly reduce hydrogen gas evolution due to their smaller specific surface area and enhanced structural stability.

Sustainable regeneration of a spent layered lithium nickel cobalt manganese oxide cathode from a scrapped lithium-ion battery

Direct regeneration, representing the most advanced technique, is capable of healing spent cathodes under nondestructive condition. This review aims at pushing forward the technical progress of direct regeneration for spent LiNixCoyMnzO2 cathodes.

Challenges and opportunities using Ni-rich layered oxide cathodes in Li-ion rechargeable batteries: the case of nickel cobalt manganese oxides

Doping, coating, surface modification, formation of composites and control of crystalline orientation can control the capacity retention of Ni-rich cathodes. Furthermore, the design of Co-free Ni-rich cathodes may provide a cost-effective solution.

Performance Enhancement of Nickel Manganese Cobalt Oxide Cathodic Material for Solid-State Battery Technology by Surface Engineering

Batteries as any other electronic devices are affected by parasitic phenomena including physical processes and chemical reactions occurring within the battery materials as well as their interfaces. The phenomena lead to degradation in performance, impose operation restrictions and potentially make devices unsafe.Solid-state, lithium-metal-based, batteries show promise to meet electric vehicle market requirements, but technical challenges to overcome rapid degradation and cost-effective processing remains. Cathode/electrolyte interfacial side reactions can lead to passivating layer formation, thus increasing cell resistance, unwanted additional overvoltage, and ultimately capacity loss. These phenomena are exacerbated in solid-to-solid contact between solid state electrolytes, active materials, and electronic conductive agents. Therefore, electrode manufacturing design is required to mitigate these issues.Within this work we have evaluated Spray Drying (SD) and Atomic Layer Deposition (ALD) coating processes to engineer the cathode/ electrolyte interface of SSBs, thus improving performance and overall cell cycle life. Cathode materials coating is utilised as an effective strategy to mitigate the degradation of the interface. SD is classically utilised in the food and pharma industries, and it has recently been expanded to include the synthesis/shaping of battery electrode materials as a versatile and robust methodology that can be easily scaled up. ALD is a widely exploited technique in the semiconductor (SC) industry based on self-limiting chemical reactions to deposit stoichiometrically-fixed, defect-free and nanometric-thick materials on surfaces. As such, the application of ALD to coat powders in the battery community is innovative and currently under development.Cathodic materials such as NMC (Nickel Manganese Cobalt Oxides) have been investigated, as the need for improving the capacity retention is strong for high-content (>80%) nickel cathodes. Indeed, ALD utilised to coat NMC powder provides a nanometric thick layer of a dielectric but ionic conductive metal oxide. Optimisation of aluminium oxide shell on a core of polycrystalline high nickel material has been investigated with surface engineering. In parallel, we have been exploring the benefit of SD to create an NMC811 powder showing a decorated structure using two different approaches. Indeed, we have either used preformed metal oxide nanoparticles dispersed in an NMC suspension or synthesised a metal oxide layer on top of the NMC in-situ by a chemical reaction during the spray process.Morphological and chemical characterisation of the products have been crucial to develop the coating processes. Electrochemical Impedance Spectroscopy (EIS) probed the engineered cathode/ electrolyte interface within half- and full-coin cell configuration. Rate performance and long-term cycling evaluation has driven the design of an oxide-based lithium metal solid state battery.Alumina coated powder NMC showed longer capacity retention than raw materials when tested in coin cell batteries. The cells were assembled using thin lithium metal anode, Lithium-Lanthanum Zirconium Oxide (LLZO) electrolyte, and surface-engineered NMC811 supported by aluminium current collector. Key words:Surface Engineering, Coatings, Solid-State Batteries (SSB), Spray Dry, Atomic Layer Deposition (ALD), Preformed Nanoparticles, Nickel Manganese Cobalt Oxide (NMC), NMC811, Lithium Lanthanum Zirconium Oxide (LLZO), Interfaces.