Nickel Manganese Cobalt Oxide Research Articles

Decarboxylative - Dimerization of levulinic acid using spent Li-ion battery electrode material with lithium nickel cobalt manganese oxide as a catalyst

A low cost catalyst prepared by pyrolyzing electrode coating material from spent Li-ion battery cells was shown as an effective catalyst for the decarboxylative - dimerization of levulinic acid to a mixture of C6 and C9 fuel precursors. The highest levulinic acid conversion of 94% was observed with 10% (w/w) catalyst loading under 1.24 MPa H2 at 140 °C, 15 h. A reaction scheme was proposed to explain the novel transformation producing C9 lactone products and C6 unsaturated alcohol product through a decarboxylative pathway followed by the aldol dimerization of levulinic acid.

Life cycle assessment of electric vehicles' lithium-ion batteries reused for energy storage

Energy storage batteries are part of renewable energy generation applications to ensure their operation. At present, the primary energy storage batteries are lead-acid batteries (LABs), which have the problems of low energy density and short cycle lives. With the development of new energy vehicles, an increasing number of retired lithium-ion batteries need disposal urgently. Retired lithium-ion batteries still retain about 80 % of their capacity, which can be used in energy storage systems to avoid wasting energy. In this paper, lithium iron phosphate (LFP) batteries, lithium nickel cobalt manganese oxide (NCM) batteries, which are commonly used in electric vehicles, and lead-acid batteries, which are commonly used in energy storage systems were taken as the research objects. The environmental impacts of their full life cycles were compared, and the sensitivity analysis of the key parts in the battery production phase and the data with major contributions were carried out through the life cycle assessment (LCA) method. The results show that the environmental impacts of lithium-ion batteries in the production phase are higher than lead-acid batteries. However, they have lower environmental impacts in the use phase because of their higher charging and discharging efficiency. In general, the environmental performance of LFP batteries is better, especially in carbon emission, soil acidification, and abiotic resource depletion. Lead-acid batteries have more advantages in ozone loss, ecotoxicity, and eutrophication. The production phase contributes the most to various environmental impacts, which can be alleviated through recycling. The recycling of NCM batteries has better environmental benefits. The physical recycling technology of LFP batteries is better than hydrometallurgy in terms of ecotoxicity and eutrophication, but it has negative effects on some environmental indicators. Secondary utilization can avoid the high energy consumption and high emission process of battery production and achieve the purpose of environmental protection. According to the results, discarded lithium-ion batteries can be reused to maximize the value of batteries, which will also promote the development of clean electricity to a certain extent and further reduce the burden on the environment.

Surface Modification on Nickel Rich Cathode Materials for Lithium-Ion Cells: A Mini Review.

Nickel-rich (Ni-rich) layered oxides are considered as the most promising cathode candidates for lithium-ion cells owing to their high theoretical specific capacity. However, the higher nickel content endows structural deformation through unwanted phase transitions and parasitic side reactions that lead to capacity fading upon prolonged cycling. Hence, a deep understanding of the chemistry and structural behaviour is essential for developing Ni-rich Lithium Nickel Cobalt Manganese oxide (NCM) cathode-based high-energy batteries. The present review focuses on the different challenges associated with Ni-rich NCM materials and surface modification as a strategy to solve the issues associated with NCM materials, assessment of several coating materials, and the recent developments in the surface modification of Ni-rich NCMs, with an in-depth discussion on the impact of coating on the degradation mechanism.

Thermal explosion energy evaluation on LCO and NCM Li-ion polymer batteries using thermal analysis methodology

An advanced lithium-ion polymer battery (LIPB) has higher energy density, long-life cycle, and flexible configuration that can be arbitrarily shaped. It is the mainstream candidate for electronics products as energy storage device. However, an energetic LIPB will generate an abnormal electrochemistry reaction and will even cause spontaneous ignition to the battery pack in case cells fail, such as a short circuit or thermal runaway. Two commercial 603450 LIPBs, whose cathodes include lithium cobalt oxide (LiCoO₂, LCO) and lithium nickel cobalt manganese oxide (LiNixCoyMnzO2, NCM), were examined for their thermophysical data. Enhanced calorimetry methods are modified to analyse an LIPB’s heat capacity and enthalpy. In case thermal runaway the heat capacity and enthalpy are 0.99 kJ g–1 K–1 and 11.76 kJ for an LCO cell and 0.96 kJ g–1 K–1 and 10.68 kJ for an NCM cell, respectively. Furthermore, TNT equivalency mass is 7.62 g for an LCO and 7.01 g for an NCM cell. An LIPB is examined to identify the fire-explosion behaviour and thermokinetic data for enhancing battery thermal management.

Targeting new ways for large-scale, high-speed surface functionalization using direct laser interference patterning in a roll-to-roll process

Direct Laser Interference Patterning (DLIP) is used to texture current collector foils in a roll-to-roll process using a high-power picosecond pulsed laser system operating at either fundamental wavelength of 1064 nm or 2nd harmonic of 532 nm. The raw beam having a diameter of 3 mm @ 1/e 2 is shaped into an elongated top-hat intensity profile using a diffractive so-called FBS®-L element and cylindrical telescopes. The shaped beam is split into its diffraction orders, where the two first orders are parallelized and guided into a galvanometer scanner. The deflected beams inside the scan head are recombined with an F-theta objective on the working position generating the interference pattern. The DLIP spot has a line-like interference pattern with about 15 μm spatial period. Laser fluences of up to 8 J cm−2 were achieved using a maximum pulse energy of 0.6 mJ. Furthermore, an in-house built roll-to-roll machine was developed. Using this setup, aluminum and copper foil of 20 μm and 9 μm thickness, respectively, could be processed. Subsequently to current collector structuring coating of composite electrode material took place. In case of lithium nickel manganese cobalt oxide (NMC 622) cathode deposited onto textured aluminum current collector, an increased specific discharge capacity could be achieved at a C-rate of 1 °C. For the silicon/graphite anode material deposited onto textured copper current collector, an improved rate capability at all C-rates between C/10 and 5 °C was achieved. The rate capability was increased up to 100% compared to reference material. At C-rates between C/2 and 2 °C, the specific discharge capacity was increased to 200 mAh g−1, while the reference electrodes with untextured current collector foils provided a specific discharge capacity of 100 mAh g−1, showing the potential of the DLIP technology for cost-effective production of battery cells with increased cycle lifetime.

Life cycle economic viability analysis of battery storage in electricity market

Battery storage is essential to enhance the flexibility and reliability of electric power systems by providing auxiliary services and load shifting. Storage owners typically gains incentives from quick responses to auxiliary service prices, but frequent charging and discharging also reduce its lifetime. Therefore, this paper embeds the battery degradation cost into the operation simulation to avoid overestimated profits caused by an aggressive bidding strategy. Based on an operation simulation model, this paper conducts the economic viability analysis of whole life cycle using the internal rate of return(IRR). A clustering method and a typical day method are developed to reduce the huge computational burdens in the life-cycle simulation of battery storage. Our models and algorithms are validated by the case study of two mainstream technology routes currently: lithium nickel cobalt manganese oxide (NCM) batteries and lithium iron phosphate (LFP) batteries. Then a sensitivity analysis is presented to identify the critical factors that boost battery storage in the future. We evaluate the IRR results of different types of battery storage to provide guidance for investment portfolio.

Effective Thermal Conductivity of Lithium‐Ion Battery Electrodes in Dependence on the Degree of Calendering

The thermal conductivity represents a key parameter for the consideration of temperature control and thermal inhomogeneities in batteries. A high‐effective thermal conductivity will entail lower temperature gradients and thus a more homogeneous temperature distribution, which is considered beneficial for a longer lifetime of battery cells. Herein, the impact of the microstructure within the porous electrode coating obtained by different compression rates and its thermal contact to the current collector is investigated as both factors significantly determine the overall conduction through the electrode. The effective thermal conductivity of two graphite anodes and two lithium nickel manganese cobalt oxide cathodes is evaluated at different compression rates. It is found that the thermal conductivity does not have a monotone dependence on the porosity with changing compression rates. The results show a strong correlation with the adhesion strength, thus a significant impact of the thermal contact resistance between the coating and current collector is assumed.

Environmental Benefit Assessment of Second-Life Use of Electric Vehicle Lithium-Ion Batteries in Multiple Scenarios Considering Performance Degradation and Economic Value.

Second-life use of electric vehicle lithium-ion batteries (LIBs) is an inevitable trend; however, battery performance degradation increases environmental loads. This study evaluated the life cycle environmental impacts of second-life use of LIBs in multiple scenarios, considering performance degradation and economic value. The results showed that a component replacement rate of retired LIBs below 50% made the batteries worthy of repurposing. Reusing whole packs of retired LIBs was better than using only cells or modules owing to the environmental loads from diagnosis, disassembly, replacement, and test processes. The battery energy density and performance degradation significantly affect the maximum return on the environmental input. Compared with lithium iron phosphate (LFP) batteries, new lithium nickel manganese cobalt oxide (NMC) batteries, or lead-acid batteries, using retired NMC-811 batteries with capacities as low as 60.7% for energy storage systems to store wind electricity rather than hybrid or photovoltaic electricity, had substantial environmental benefits, including a low global warming potential. Considering the costs of battery recycling, labor, and electricity, using whole packs of retired LIBs could simultaneously achieve high economic and environmental values in energy storage and peak shaving scenarios.

The Effect of Doping Process Route on LiNiO2 Cathode Material Properties

The pursuit of higher energy density in lithium-ion batteries has driven the increase of the nickel content in lithium nickel cobalt manganese oxide cathode active materials (CAMs), ultimately approaching LiNiO2 (LNO). The downside of the high specific capacity of LNO is more severe degradation of the CAM during battery operation. A common approach to increase structural stability is the introduction of dopants. Various dopants are discussed and compared with each other when integrated into the CAM and tested against undoped materials in the literature, but little attention is given to the role of the process route of their introduction. In this work, we demonstrate with a series of nominally equally Zr-doped LNO samples that effects on various physico- and electrochemical properties are due not to the dopant itself, as one would assume in comparison to an undoped sample, but to the process route and the resulting particle morphology. Dopant, concentration and process routes (co-precipitation, impregnation and co-calcination) were chosen based on their significance for industrial application.

Osmotically Delaminated Silicate Nanosheet-Coated NCM for Ultra-Stable Li+ Storage and Chemical Stability Toward Long-Term Air Exposure.

To ensure the safety and performance of lithium-ion batteries (LIBs), a rational design and optimization of suitable cathode materials are crucial. Lithium nickel cobalt manganese oxides (NCM) represent one of the most popular cathode materials for commercial LIBs. However, they are limited by several critical issues, such as transition metal dissolution, formation of an unstable cathode-electrolyte interphase (CEI) layer, chemical instability upon air exposure, and mechanical instability. In this work, coating fabricated by self-assembly of osmotically delaminated sodium fluorohectorite (Hec) nanosheets onto NCM (Hec-NCM) in a simple and technically benign aqueous wet-coating process is reported first. Complete wrapping of NCM by high aspect ratio (>10000) nanosheets is enabled through an electrostatic attraction between Hec nanosheets and NCM as well as by the superior mechanical flexibility of Hec nanosheets. The coating significantly suppresses mechanical degradation while forming a multi-functional CEI layer. Consequently, Hec-NCM delivers outstanding capacity retention for 300 cycles. Furthermore, due to the exceptional gas barrier properties of the few-layer Hec-coating, the electrochemical performance of Hec-NCM is maintained even after 6 months of exposure to the ambient atmosphere. These findings suggest a new direction of significantly improving the long-term stability and activity of cathode materials by creating an artificial CEI layer.

Impact of heating and cooling loads on battery energy storage system sizing in extreme cold climates

Efficient operation of battery energy storage systems requires that battery temperature remains within a specific range. Current techno-economic models neglect the parasitic loads heating and cooling operations have on these devices, assuming they operate at constant temperature. In this work, these effects are investigated considering the optimal sizing of battery energy storage systems when deployed in cold environments. A peak shaving application is presented as a linear programming problem which is then formulated in the PYOMO optimization programming language. The building energy simulation software EnergyPlus is used to model the heating, ventilation, and air conditioning load of the battery energy storage system enclosure. Case studies are conducted for eight locations in the United States considering a nickel manganese cobalt oxide lithium ion battery type and whether the power conversion system is inside or outside the enclosure. The results show an increase of 42% to 300% in energy capacity size, 43% to 217% in power rating, and 43% to 296% increase in capital cost dependent on location. This analysis shows that the heating, ventilation, and air conditioning load can have a large impact on the optimal sizes and cost of a battery energy storage system and merit consideration in techno-economic studies.

Enhanced Energy Storage in Lithium-Metal Batteries via Polymer Electrolyte Polysulfide-Polyoxide Conetworks.

The present article entails a novel concept of storing extra energy in a multifunctional polymer electrolyte membrane (PEM) beyond the storage capacity of a cathode, which is achieved by so-called "prelithiation" upon simply deep discharging to a low potential range of a lithium-metal electrode (i.e., -0.5 to 0.5 V). This unique extra energy-storage capacity has been realized recently in the PEM consisting of polysulfide-co-polyoxide conetworks in conjunction with succinonitrile and LiTFSI salt that facilitate complexation via ion-dipole interaction of dissociated lithium ions with thiols, disulfide, or ether oxygen of the conetwork. Although ion-dipole complexation may increase the cell resistance, the prelithiated PEM provides excess lithium ions during oxidation (or Li+ stripping) at the Li-metal electrode. Once the PEM network is fully saturated with Li ions, the remaining excess ions can move through the complexation sites at ease, thereby affording not only facile ion transport but also extra ion-storage capacity within the PEM conetwork. Of particular interest is that the lithiated polysulfide-co-polyoxide polymer network-based PEM exhibits a high conductivity of 1.18 × 10-3 S/cm at ambient, which can also store extra energy with a specific capacity of about 150 mAh/g at a 0.1C rate in the PEM voltage range of 0.01-3.5 V in addition to 165 mAh/g at 0.2C of an NMC622 (nickel manganese cobalt oxide) cathode (i.e., 2.5-4.6 V) with a Coulombic efficiency of approximate unity. Moreover, its Li-metal battery assembly with an NMC622 cathode exhibits a very high specific capacity of ∼260 mAh/g at 0.2C in the full battery range of 0.01-5 V, having a higher Li+ transference number of 0.74, suggestive of domination by the lithium cation transport relative to those (0.22-0.35) of organic liquid electrolyte lithium-ion batteries.

The Effect of Lithium Excess on NMC-721 using Oxalate Co-precipitation

Lithium Nickel Manganese Cobalt Oxide (Li-NMC) has been regarded as preferred cathode material for Lithium-ion battery (LIB), compared to other materials such as Lithium Cobalt Oxide (LCO) and Lithium Manganese Oxide (LMO). Ni-rich content displays severe cycling performance and needs to be addressed to improve its performance of electric vehicle. This research focused on synthesis NMC-721 precursors with the oxalate co-precipitation. Furthermore, a variation of lithium hydroxide with the excess of 3% and 5% were added into the precursors, then calcined at temperature 800 ℃ for 12 hours. The product of precursor was analyzed by X-Ray Fluorescence (XRF) and Particle Size Analysis (PSA) to analyze elemental composition and particle size, respectively. Meanwhile, the NMC-721 cathodes were characterized by an X-Ray Diffraction. The XRF data of precursor shows the ratio of transition metals at 7.5:1.5:1 identifying that more Ni content and less Mn content in the NMC-721, due to oxalate co-precipitation. The PSA shows that the average diameter of the precursor was 9.19 ± 0.31 (µm). The XRD result shows that the crystal structure of NMC-721 cathode belongs to hexagonal structure. It can be concluded that the NMC-721 were successfully synthesized and can be applied for lithium-ion battery.

An Evolving Quantum Fuzzy Neural Network for online State-of-Health estimation of Li-ion cell

With the rapid advancement in the battery industry, more accurate and advanced state estimation methods are required to meet the performance requirements. The State of Health (SOH) estimation is performed in the battery management system (BMS), which provides the qualitative measure of the capability of a lithium-ion battery (LIB), in terms of capacity or internal resistance. Theoretically, the cell capacity is obtained by complete charge and discharge of the cell but in practical scenario, complete charge or discharge is never the case. To address this issue of dynamic discharge, this paper presents an evolving model-based SOH estimation, predicting the capacity fade of the cell extracted from the incomplete discharge conditions as in the case of dynamic driving scenarios. The evolving algorithm uses Neural Network, which features an interval fuzzy set, with conjectural jump positions. For better identification of overlaps between the classes, the quantum fuzzy set uses graded membership function. The number of rules are automatically adjusted and evolved, in the quantum fuzzy set using Decoupled Extended Kalman Filter (DEKF) for parameter estimation. The proposed method uses voltage, current and sampling time data to estimate the capacity, over a period of 600 charging-discharging cycles of Nickel Manganese Cobalt Oxide (NMC) chemistry batteries. The dynamic discharge voltage data is obtained from the periodic characterization tests and is used for predict the complete discharge voltage. The full voltage profile has been forecasted using Long-Short Term Memory (LSTM) network and the subsequent capacity has been estimated using evolving Quantum Fuzzy Neural Network (eQFNN) with an RMSE of less than 5% making it suitable for on-board applications. The results are simulated in MATLAB 2020b and are validated using experimental verification in Battery Testing Lab (BTL), IIT Delhi.

Comparative Study of High-Temperature Cycling and Thermal Stability of LLOs and NCMs under Medium–High Voltage

Lithium-rich layered oxides (LLOs) are considered as one of the most potential layered cathode materials due to their high discharge specific capacity, low cost, and environmental friendliness. However, the decomposition of electrolytes at high voltages (4.7 V) limits the commercial application of LLOs. Furthermore, to meet the demand for high energy density, lithium nickel cobalt manganese oxides (NCMs) need to improve their working voltage. In limited conditions, all LLOs and NCMs need to be used under the medium–high (4.4–4.6 V) cutoff voltage. Herein, we compare the performance of LLOs and NCMs in the voltage window with a medium–high cutoff voltage. Results show that after 100 cycles at high temperature (45 °C), the capacity retention rate of LLO is 98.68%, while that of NCMs is 78.15–96.93%. Differential scanning calorimetry reveals that the exothermic temperature of LLO is increased by 60–100 °C, and thermal release is reduced by 33–93%. LLOs have obvious advantages under medium–high voltages and a promising application prospect. This work systematically analyzes and compares LLOs and NCMs under medium–high voltage, providing guidance for the industrialization of LLOs.

Sputtered silver on the current collector for anode-less NMC111 gel polymer electrolyte lithium batteries

The anode-less lithium battery with the structure of lithium nickel manganese cobalt oxide (LiNi0.33Mn0.33Co0.33O2, NMC111) /gel polymer electrolyte (GPE)/silver (Ag)/ conductive carbon black (CCB) coated aluminum current collectors has been proposed for high energy density in this research. The results indicate that the anode-less lithium battery on Ag/CCB-coated aluminum current collector has a sufficient discharge capacity of 0.935 mAh/cm2 and exhibited capacity retention of 86.1 % after 30 cycles of the charge–discharge test. This 1st lower coulombic efficiency (discharge capacity/charge capacity × 100 %) only goes to 46.8 % due to the Li-Al alloying reaction, and part of the lithium ions reacted with the GPE, CCB, and aluminum current collector during the 1st cycle of the anode-less NMC111 lithium battery. These accompanying reactions consumed the Li ions and resulted in the irreversible capacity in the 1st cycle. However, the coulombic efficiency has increased to about 96.2 % after the 1st cycle test. This result indicates that most of the charge–discharge cycles reacted in a reversible capacity, and the anode-less NMC111 lithium battery has the potential for high energy density application.

Characterization and recycling of lithium nickel manganese cobalt oxide type spent mobile phone batteries based on mineral processing technology

Characterization and recycling of lithium nickel manganese cobalt oxide type spent mobile phone batteries based on mineral processing technology

Research on thermal runaway process of 18650 cylindrical lithium-ion batteries with different cathodes using cone calorimetry

The complex chemical reactions and the safety properties of lithium-ion batteries (LIBs) with different cathode materials are various from each other. In this article, a cone calorimeter was used to measure the mass change, heat generation and gas release characteristics of three types of 18650 cylindrical LIBs with lithium iron phosphate (LFP), lithium cobalt oxide (LCO) or lithium nickel manganese cobalt oxide (NMC) as the positive electrode material. All samples were tested under 9 kinds of conditions combined state of charge (SOC) of 33 %, 66 %, 100 % with heat flux of 30 kW/m2, 45 kW/m2, 60 kW/m2, respectively. Especially, the principal component analysis (PCA) method was applied to further analyze the difference of thermal runaway (TR) behavior for the three kinds of batteries. Moreover, the influence of SOC and heat flux on the safety features of 18650-cylinder LIBs was analyzed. After comparing parameters such as mass loss rate (MLR), gas generation/consumption, heat release, toxicity among the tested 18650 cylindrical LIBs, the results displayed that the influence of external heat flux on the intensity of battery TR reactions was lower than that of SOC. The TR risk of LCO and NMC batteries with relatively high SOC was higher than that of LFP ones in large fire scenarios. When the fire scale was relatively small, the main factor that determined the risk of battery fire was the type of cathode, while which became SOC under the opposite situation of large-scale fire. PCA results showed that LFP and NMC batteries presented almost completely different TR characteristics, which could provide important references for battery design, corresponding fire investigation and attack.

Fast Charging Behaviour of High-Power Li-Ion Cell at Different Temperatures and Effect on Capacity and Internal Resistance

Lithium-Ion Batteries (LIBs), which have already proven to be a reliable power source in consumer electronics devices, are being considered a viable option for powering Electric Vehicles (EVs). Fast charging of EVs is one of the key challenges that is preventing a wide range of adoption of EVs. In this study, a lithium-ion cell with Lithium Titanium Oxide (LTO)-lithium Nickel Manganese Cobalt oxide (NMC) chemistry of 30 Ah has been used to study the fast charging capabilities at different temperatures and C-rates. Various parameters such as temperature rise, nominal and exponential capacity, and internal resistance have been studied for different C-rates (C/3, 1C, and 2C) and at different temperatures (25 °C, 40 °C, and -10 °C). The ΔV values along with the charge and discharge characteristics have been analyzed, and the experimental results are compared with the simulation results.

Li[Ni0.6Mn0.2Co0.2]O2 Made From Crystalline Rock Salt Oxide Precursors

Layered lithium nickel manganese cobalt oxide or NMC type cathode materials dominate the lithium-ion battery market. However, the production of their precursor involves the use of large amounts of water and can create waste. All-dry synthesis methods are attractive as they are potentially cheaper and greener. However, it remains a challenge to achieve atomic scale mixing of the precursor elements by dry methods. Here, we report an alternative route to achieve atomic scale mixing by employing thermal interdiffusion to produce a phase pure rock salt structure precursor for NMC cathode materials, which can significantly shorten the preparation time and may further reduce cost. The complications and applicability of using a thermally synthesized precursor to make layered cathode material are presented in detail.