Metal Oxide Cathode Materials Research Articles

Investigating the Effects of Modified Interlayer Spacing within Mixed Metal Oxide Cathode Materials for Next-Generation Aqueous Rechargeable Zinc-Ion Batteries

Aqueous rechargeable zinc-ion batteries (ZIBs) are a promising addition to the current energy storage landscape, particularly supporting the decarbonization of the power sector as a low-cost, high safety alternative to lithium-ion batteries. Unfortunately, the relative infancy of ZIBs means that there are a limited number of reported cathode materials, and a divisive understanding of the operating principles for those which have been reported including Mn- and V-oxides. The large solvation shell of the working cation (Zn2+) imparts several design requirements for cathode material development, specifically the need for sufficient void space for Zn2+ intercalation, further limiting the materials which have been reported. Looking to other well-established battery chemistries, we considered the use of layered mixed metal oxides (MMOs) with Mn due to its known electrochemical activity within the operating voltage of aqueous ZIBs. We developed several MMO cathodes with tuned interlayer distance to achieve the larger void spacing capable of accommodating Zn2+. We investigated the impact of composition on the structural and electrochemical properties of 15+ different MMO materials. We determined that interlayer spacing plays critical role in electrochemical performance and that there is an optimal composition to provide enhanced specific capacity to the battery. Considering the narrow range of reported ZIBs cathodes, in this study we proposed several new materials that expand the scope of viable cathodes for next generation ZIBs and provides direction for future researchers to accelerate new material development for this technology.

Recent Advances on F-Doped Layered Transition Metal Oxides for Sodium Ion Batteries.

With the development of social economy, using lithium-ion batteries in energy storage in industries such as large-scale electrochemical energy storage systems will cause lithium resources to no longer meet demand. As such, sodium ion batteries have become one of the effective alternatives to LIBs. Many attempts have been carried out by researchers to achieve this, among which F-doping is widely used to enhance the electrochemical performance of SIBs. In this paper, we reviewed several types of transition metal oxide cathode materials, and found their electrochemical properties were significantly improved by F-doping. Moreover, the modification mechanism of F-doping has also been summed up. Therefore, the application and commercialization of SIBs in the future is summarized in the ending of the review.

Three dimensional nickel foam carried sea urchin-like copper-cobalt-cerium cathode for enhanced tetracycline wastewater purification in photocatalytic fuel cell

Photocatalytic fuel cells (PFCs) regarded as a potential sustainable technique, have been broadly reported. In this work, the carbon quantum dot-loaded TiO2 photoanode and sea urchin-like CuCoCe ternary metal oxide cathode materials are successfully synthesized and used to construct PFC systems for efficient tetracycline (TC) degradation (45 mg/L) and simultaneous electricity generation. The results demonstrate that the CQDs-modified TiO2 photoanode has improved absorption intensity in both the UV and visible regions, and the photocurrent density at 1.23 V vs RHE reached 1.31 mA cm−2, which is 1.3 times higher than that of the original TiO2 photoanode. The established PFC system achieves the highest removal ratio of 96.9 % for TC in 60 min with a maximum power density of 0.77 mW cm−2. The PFC system can operate efficiently over a wide pH range (3.0–9.0). Furthermore, quenching experiments and ESR spectra show that the main reactive oxygen species in the degradation process are •O2−, 1O2 and •OH. This study provides meaningful way to develop multiple metal oxides as cathode of PFC system for efficient organic pollutant degradation and energy recovery.

In Operando Strain Evolution in Sodium Chromium Oxide Cathode for Na-Ion Batteries during Battery Cycling

Layer-structured Na intercalation compounds such as NaxMO2 (M=Co, Mn, Cr) have attracted much attention as cathode materials for sodium-ion batteries due to their high volumetric and gravimetric energy densities. Among them, NaCrO2 with layered rock salt structure is one of the promising cathodes since NaCrO2 has a desirable flat and smooth charge/discharge voltage plateau.1 In addition, NaCrO2 has the highest thermal stability at charged state which makes it a potentially safer cathode material.2 The NaCrO2 exhibits a reversible capacity of 110 mAh g-1 with good cycling performance.3 However, the transition metal oxide (TMO) cathode materials in NIBs undergo severe chemo-mechanical deformations which leads to capacity fade and poor cycling and is the limiting factor of NIBs. The electrochemical characterization and examination of the electrode structure were the primary focus of several investigations. To improve the lifespan and performance of electrode materials for Na-ion batteries, it is vital to comprehend how Na ions impact the chemo-mechanical stability of the electrodes.In this talk, we will discuss the driving forces behind the structural and interfacial deformations on NaCrO2 cathodes. Digital image correlation measurements were conducted to probe strain evolution in the electrode during cycling. The free-standing composite NaCrO2 electrode was used for stain measurements in custom-cell assembly. The battery was cycled against Na metal in 1 M NaClO4 in PC. The first part of the study involves structural and interfacial deformations in the lower voltage range of 2.3 V to 3.5 V where x<0.5 in NaxCrO2. And the second part focuses on the structural and interfacial deformations in the voltage range of 2.3 V to 4.7 V where x>0.5 in NaxCrO2. In the preliminary studies, we observed that the initial insertion of Na ions leads to negative strain evolution (contraction) in the electrode, followed by expansions in the electrode at a higher state of discharge. Similar phenomena are also observed during charge cycles, where extraction of Na results in an initial contraction in the electrode, followed by expansion at a higher state of charge. Understanding the mechanisms behind chemo-mechanical deformations will allow to tune structure & material property for better electrochemical performance.Acknowledgement: This work is supported by National Science Foundation’s (NSF) Faculty Early Career Development (CAREER) Program, 2142726.

Insights into layered–tunnel dynamic structural evolution based on local coordination chemistry regulation for high‐energy‐density and long‐cycle‐life sodium‐ion oxide cathodes

AbstractThe pursuit of high energy density while achieving long cycle life remains a challenge in developing transition metal (TM) oxide cathode materials for sodium‐ion batteries (SIBs). Here, we present a concept of precisely manipulating structural evolution via local coordination chemistry regulation to design high‐performance composite cathode materials. The controllable structural evolution process is realized by tuning magnesium content in Na0.6Mn1−xMgxO2, which is elucidated by a combination of experimental analysis and theoretical calculations. The substitution of Mg into Mn sites not only induces a unique structural evolution from layered–tunnel structure to layered structure but also mitigates the Jahn–Teller distortion of Mn3+. Meanwhile, benefiting from the strong ionic interaction between Mg2+ and O2−, local environments around O2− coordinated with electrochemically inactive Mg2+ are anchored in the TM layer, providing a pinning effect to stabilize crystal structure and smooth electrochemical profile. The layered–tunnel Na0.6Mn0.95Mg0.05O2 cathode material delivers 188.9 mAh g−1 of specific capacity, equivalent to 508.0 Wh kg−1 of energy density at 0.5C, and exhibits 71.3% of capacity retention after 1000 cycles at 5C as well as excellent compatibility with hard carbon anode. This work may provide new insights of manipulating structural evolution in composite cathode materials via local coordination chemistry regulation and inspire more novel design of high‐performance SIB cathode materials.image

Synthesis of Cu‐Doped Layered Transition Metal Oxide Cathode Materials Directly from Metal‐Organic Frameworks for Sodium‐Ion Batteries

Comprehensive SummaryMn‐based layered transition metal oxides are promising cathode materials for sodium‐ion batteries (SIBs) because of their high theoretical capacities, abundant raw materials, and environment‐friendly advantages. However, they often show insufficient performance due to intrinsic issues including poor structural stability and dissolution of Mn3+. Atomic doping is an effective way to address these structural degradation issues. Herein, we reported a new synthesis strategy of a Cu‐doped layered cathode by directly calcinating a pure metal‐organic framework. Benefiting from the unique structure of MOF with atomic‐level Cu doping, a homogeneous Cu‐doped layered compound P2‐Na0.674Cu0.01Mn0.99O2 was obtained. The Cu substitution promotes the crystal structural stability and suppresses the dissolution of Mn, thus preventing the structure degradation of the layered cathode materials. A remarkably enhanced cyclability is realized for the Cu‐doped cathode compared with that without Cu doping, with 83.8% capacity retention after 300 cycles at 100 mA·g–1. Our findings provide new insights into the design of atomic‐level doping layered cathode materials constructed by MOFs for high‐performance SIBs.

Optimizing Electrochemical Performance in Sodium-Ion Batteries using O3-type Na0.90Cu0.22Fe0.30Mn0.48O2 and Hard Carbon

Sodium-ion batteries (SIBs) are being viewed as a prime alternative to lithium-ion batteries (LIBs) due to their resource availability, cost-effectiveness, safety, and superior power performance. Layered transition metal oxide cathode materials, in particular, have garnered interest for their high theoretical capacity and extended cycle life. This study focuses on the O3-type Na0.90Cu0.22Fe0.30Mn0.48O2(NCFMO), synthesized using the polyvinylpyrrolidone combustion method, showcasing notable specific capacity and capacity retention of over 80% after 200 cycles at 1C. Hard carbon has been identified as a potential candidate for commercialization among various anode materials, due to its high reversible capacity and stable structure. We assembled and evaluated a coin SIB full cell comprised of an NCFMO cathode and hard carbon anode (HC), which demonstrated optimal electrochemical performance at a positive-to-negative capacity ratio of 0.9. The study also explored the influence of the electrolyte on electrochemical performance, with NaClO4 (0.1 M NaClO4 in PC = 100 Vol% with 2.0%FEC) found to deliver the best results. Further, we assessed the heat generation characteristics of the NCFMO/HC full cell, revealing higher total heat generation during charging compared to discharging. This comprehensive study contributes significantly to the ongoing efforts towards commercialization of SIBs.

Antioxidant layer enables chemically stable cathode-electrolyte interface towards durable and safe Li-ion batteries

Although nickel-rich layered lithium transition metal oxides are one of the most promising candidates for high energy-density Li-ion batteries in electric vehicle applications, they yet suffer from irreversible capacity fading and poor safety properties due to the unstable cathode-electrolyte interphase (CEI), especially at high voltage and high temperature. This instability is mainly caused by the attack of free radicals generated from electrolyte decomposition and active oxygen species (especially singlet oxygen) released from the surface lattice. Here, we propose a novel modification method to construct a protective antioxidant layer on the surface of LiNi0.8Co0.1Mn0.1O2 (NCM). By scavenging free radicals and singlet oxygen, the antioxidant layer greatly reduces the interfacial side reactions and significantly suppresses irreversible rock-salt phase transitions and the associated oxygen species release, leading to the stabilization of the interface. As a result, superior electrochemical performance and enhanced thermal stabilities are achieved. Specifically, the modified NCM exhibits a capacity retention of 92.0% over 1000 cycles in full cells and a dramatic increase of onset temperature (T1) from 75.2 °C to 114.2 °C. This antioxidant layer modification by scavenging free radicals and singlet oxygen provides a new strategy for addressing challenges of CEI design, which is theoretically applicable to all layered transition metal oxide cathode materials.

Application of high energy X-ray diffraction and Rietveld refinement in layered lithium transition metal oxide cathode materials

Application of high energy X-ray diffraction and Rietveld refinement in layered lithium transition metal oxide cathode materials

Application of Electron Paramagnetic Resonance in an Electrochemical Energy Storage System

The improvement of our living standards puts forward higher requirements for energy storage systems, especially rechargeable batteries. Unfortunately, phenomena such as capacity failure, etc. have been major difficulties in the field of energy storage. Therefore, we need some advanced means to explore the reaction process and mechanisms of the cell. Electron paramagnetic resonance (EPR) has the advantages of a high sensitivity to electrons, lack of damage to samples, quantitative analysis, etc., which can make for a more in-depth exploration of most paramagnetic electrode materials and metal electrode materials. After a brief description of the principle of EPR, this review briefly summarizes the application of EPR to the characterization of transition metal oxide cathode and lithium metal anode electrode materials in recent years, such as showing how to study electrode materials by using EPR in situ and operando .

Ti, F Codoped Sodium Manganate of Layered P2-Na 0.7 MnO 2.05 Cathode for High Capacity and Long-Life Sodium-Ion Battery

Ti, F Codoped Sodium Manganate of Layered P2-Na _0.7 MnO _2.05 Cathode for High Capacity and Long-Life Sodium-Ion Battery

Halide Solid‐State Electrolytes: Stability and Application for High Voltage All‐Solid‐State Li Batteries

AbstractOver the past few years, halide solid‐state electrolytes (HSSEs) have attracted the attention of researchers, and many reports about HSSEs have been published. Their wide electrochemical window (ECW) and a quite good compatibility with the popular oxide cathode materials make them attractive for practical applications. As a result, HSSEs are exciting candidates for the future generation of all‐solid‐state Li batteries (ASSLBs). In recent years, noticeable efforts have been made to develop novel HSSEs and utilize them in ASSLBs. Herein, a comprehensive update on the progress of HSSEs development and their application in ASSLBs is provided. First, a brief summary of the conductivity of HSSEs and potential synthesis approaches is provided. Next, the moisture and phase stabilities of HSSEs are reviewed separately, and the techniques proposed in the recently published reports to achieve sufficient stabilities are summarized. In addition, the electrochemical stabilities of HSSEs with Li metal anode and oxide cathode materials, from experimental and theoretical points of view, are provided in parallel. Furthermore, the application and progress of HSSEs in high‐voltage ASSLBs are discussed. Finally, new research directions are suggested for the development of scalable HSSEs‐based ASSLBs.

Synergistic Effect of Bis(2,2,2-trifluoroethyl) Carbonate and Succinonitrile in Suppressing the Dissolution of Nickel for Performance Improvement of Nickel-Rich Lithium Metal Batteries

Nickel-rich layered transition metal (TM) oxide cathode materials become the prospective candidates for high-energy lithium-ion batteries on account of their significant role in improving specific energy and power density. However, the decomposition of the electrolyte caused by the catalytic reaction of highly active Ni4+ ions together with the deposition of TM ions dissolved into the electrolyte upon the anode surface eventually deteriorates the capacity and cycling stability of nickel-rich lithium metal batteries. Herein, the effectively synergistic effect of a bis(2,2,2-trifluoroethyl) carbonate (BTFC) and succinonitrile (SN) electrolyte in suppressing the TM nickel ion dissolution in a nickel-rich lithium metal battery by building a reliable and protective electrode/electrolyte interface was reported. While SN was used to improve the electrochemical stability of the electrolyte, the oxidation products of BTFC can form a dense and stable passivated layer covering up the surface of the electrode. With the strong coordination ability of F bonding to the high-valence Ni ions, the continued TM nickel ion dissolution in the hybrid electrolyte was prevented. Thus, the NCA||Li cell with the designed electrolyte demonstrates an obvious improvement of capacity retention from 53.3% to 82.1% after 100 cycles compared with a conventional electrolyte. The remarkable rate performance is witnessed with high specific capacity over 120 mAh g–1 at the rate of 1000 mA g–1. The results provide insight into improving the performance of Ni-rich lithium metal batteries by the electrolyte manipulation strategy. The fundamental mechanism understanding of this synergistic effect in this study may facilitate the development of cooperative electrolytes with an advanced nickel-rich cathode for next-generation batteries.

Ion-Migration Mechanism: An Overall Understanding of Anionic Redox Activity in Metal Oxide Cathodes of Li/Na-Ion Batteries.

The anionic redox reaction (ARR) has attracted extensive attention due to its potential to enhance the reversible capacity of cathode materials in Li/Na-ion batteries (LIBs/SIBs). However, the understanding of its activation mechanism is still limited by the insufficient mastering of the underlying thermodynamics and kinetics. Herein, a series of Mg/Li/Zn-substituted Nax MnO2 and Lix MnO2 cathode materials are designed to investigate their ARR behaviors. It is found that the ARR can be activated in only Li-substituted Lix MnO2 and not for Mg- and Zn-substituted ones, while all Mg/Li/Zn-substituted Nax MnO2 cathode materials exhibit ARR activities. Combining theoretical calculations with experimental results, such a huge difference between Li and Na cathodes is closely related to the migration of substitution ions from the transition metal layer to the alkali metal layer in a kinetic aspect, which generates unique Li(Na)-O-□TM and/or □Li/ Na -O-□TM configurations and reducing reaction activation energy to trigger the ARR. Based on these findings, an ion-migration mechanism is proposed to explain the different ARR behaviors between the Nax MnO2 and Lix MnO2 , which can not only reveal the origin of ARR in the kinetic aspect, but also provide a new insight for the development of high-capacity metal oxide cathode materials for LIBs/SIBs.

0D Physics-Based Modeling of High Energy Lithium Metal Batteries with Pulsing Requirements

Lithium metal batteries are promising candidates for high energy storage solutions. To further increase capacity, electrolyte components can have a secondary function of storing charge through electrochemical reactions. This work focuses on modeling high-energy lithium metal anode and metal oxide cathode material and potentially other materials with additional capacity from electrolyte components. Physics-based modeling can be utilized to explore design space and predict battery performance under various conditions. This work utilizes a zero-dimensional model with thermodynamics, kinetics, transport, and morphology changes of the solution and solid-phase species. The effect of the additional electrolyte components on the transport, capacity, and voltage behavior will be explored. Pulse power will also be discussed, and this talk may include comparisons to experimental data.

Molybdenum-Doped Li/Mn-Rich Layered Transition Metal Oxide Cathode Material Li1.2Mn0.6Ni0.1Co0.1O2 with High Specific Capacity and Improved Cyclic Stability for Rechargeable Li-Batteries

Molybdenum-Doped Li/Mn-Rich Layered Transition Metal Oxide Cathode Material Li_1.2Mn_0.6Ni_0.1Co_0.1O₂ with High Specific Capacity and Improved Cyclic Stability for Rechargeable Li-Batteries

Spray-drying Al onto hydroxide precursors to prepare LiNi0.855Co0.095Al0.05O2 as a highly stable cathode for lithium-ion batteries

The very high specific discharge capacities of Ni> 90% cathodes are often undone by their extremely poor cycle life and thermal stability. Herein, Ni-poor, and Al-rich particle with double concentration gradients is fabricated by synthesizing particles of the Ni-rich hydroxide Ni0.9Co0.1(OH)2 in a highly efficient Taylor flow (TF) reactor and then depositing Al onto their surfaces using three methods: spray-drying and conventional wet and dry chemical coating. The uniformity of the surface distribution of Al on the Ni-rich transition metal oxide cathode materials affected the overall structural and electrochemical stability. Among our three systems, the cathode material prepared with the spray-dried Al exhibited the best performance, with an initial discharge capacity of 196.9 mA h g–1 and capacity retention of 93% after 100 cycles at a rate of 1 C. It also demonstrated superior electrochemical performance at higher C-rates. For example, at 10 C, it delivered an initial discharge capacity of 134.4 mA h g–1, compared with 56.8 mA h g–1 for the Al-free LiNi0.9Co0.1O2. We attribute this enhanced electrochemical performance to the presence of Al and its uniform distribution (through spray-drying processing) on the outer layer of the active material, with the Ni and Co elements remaining mainly within the core.

Structural Stabilization of Cation-Disordered Rock-Salt Cathode Materials: Coupling between a High-Ratio Inactive Ti4+ Cation and a Mn2+/Mn4+ Two-Electron Redox Pair

Cation-disordered rock-salt cathode materials are featured by their extraordinarily high specific capacities in lithium-ion batteries primarily contributed by anion redox reactions. Unfortunately, anion redox reactions can trigger oxygen release in this class of materials, leading to fast capacity fading and major safety concern. Despite the capability of absorbing structural distortions, high-ratio d0 transition-metal cations are considered to be unfavorable in design of a new cation-disordered rock-salt structure because of their electrochemically inactive nature. Herein, we report a new cation-disordered rock-salt compound of Li1.2Ti0.6Mn0.2O2 with the stoichiometry of Ti4+ as high as 0.6. The capacity reducing effect by the low-ratio active transition-metal center can be balanced by using a Mn2+/Mn4+ two-electron redox couple. The strengthened networks of strong Ti–O bonds greatly retard the oxygen release and improve the structural stability of cation-disordered rock-salt cathode materials. As expected, Li1.2Ti0.6Mn0.2O2 delivers significantly improved electrochemical performances and thermal stability compared to the low-ratio Ti4+ counterpart of Li1.2Ti0.4Mn0.4O2. Theoretical simulations further reveal that the improved electrochemical performances of Li1.2Ti0.6Mn0.2O2 are attributed to its lower Li+ diffusion energy barrier and enhanced unhybridized O 2p states compared to Li1.2Ti0.4Mn0.4O2. This concept might be helpful for the improvement of structural stability and electrochemical performances of other cation-disordered rock-salt metal oxide cathode materials.

Probing Crossover Degradation Effects in Nickel-Rich LiNixMnyCozO2 Lithium-Ion Battery Cathodes with Ultrasensitive on-Chip Electrochemistry Mass Spectrometry

Performance improvements in electric vehicle batteries are needed in order to reduce their cost and encourage greater use.1 This improvement is dependent on the properties (e.g. specific capacity and stability) of the cathode active material in the electric vehicle’s lithium ion battery.1 Lithium Nickel Cobalt Manganese Oxide (NMC) is a layered transition metal oxide that shows great promise as an electrode in lithium ion batteries for electric vehicles, with a high theoretical specific capacity and good stability in the layered structure.2 As the nickel content of the cathode material increases, so does the discharge capacity, however this increase comes at the cost of significantly decreased capacity retention.1 The mechanisms that contribute to this degradation are complex and interlinking and many of them are accompanied by some form of gas evolution. For example, the solid electrolyte interphase (SEI) formation at the cathode evolves CO2, which is able to crossover and contribute to solid electrolyte interphase formation at the anode.1 Similarly, upon electrochemical cycling a reactive form of oxygen can be evolved from the NMC lattice, resulting in a cascade of parasitic reactions within a lithium-ion battery.2 Herein, we probe these gas evolving degradation mechanisms through the development and use of a novel type of electrochemistry mass spectrometry (EC-MS) with unprecedented time resolution and sensitivity.3,4 The new technique, known as on-chip EC-MS, employs a microfabricated membrane chip to precisely control the transfer of volatile species from an electrochemical cell to a mass spectrometer. Its design also allows instantaneous gas exchange, particularly useful to simulate cross talk phenomena. This work demonstrates the first application of this technique to the study of lithium-ion batteries; this study uses a new cell design to facilitate operando measurements of gas evolution in lithium-ion batteries to provide important insight into these complex mechanisms.4 More specifically, the effect of transition metal dissolution on the stability of the anodic SEI is investigated by monitoring ethylene evolution. Isotopic labelling studies are also performed to probe the evolution and consumption of CO2 that is evolved from the cathode. Complementary and correlative ex situ surface sensitive analysis (such as x-ray photoelectron spectroscopy and secondary ion mass spectrometry) are carried out in order to develop a holistic understanding of the complex reactivity and chemistry evolution of lithium-ion batteries during operation.References(1) Jung, R.; Metzger, M.; Maglia, F.; Stinner, C.; Gasteiger, H. A. Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon. J. Phys. Chem. Lett. 2017, 8 (19), 4820–4825.(2) Wandt, J.; Freiberg, A. T. S.; Ogrodnik, A.; Gasteiger, H. A. Singlet Oxygen Evolution from Layered Transition Metal Oxide Cathode Materials and Its Implications for Lithium-Ion Batteries. Mater. Today 2018, 21 (8), 825-833.(3) Trimarco, D. B.; Scott, S. B.; Thilsted, A. H.; Pan, J. Y.; Pedersen, T.; Hansen, O.; Chorkendorff, I.; Vesborg, P. C. K; Stephens, I. E. L. Enabling Real-Time Detection of Electrochemical Desorption Phenomena with Sub-Monolayer Sensitivity. Electrochim. Acta 2018, 268, 520–530.(4) Thornton D. B.; Cavalca F.; Aguadero A.; Ryan M.; Stephens I.E.; UK Patent filed 17 September 2021

Aqueous Processed Thick-Film Li(Ni0.6Mn0.2Co0.2)O2 Electrodes with 3D Architectures

The development of high areal energy density electrodes with layered metal oxide cathode materials is currently worldwide a main topic in research and industry. Water-based binders were applied in the presented work for the manufacturing of NMC 622 (Li(Ni0.6Mn0.2Co0.2)O2) cathodes in order to achieve environmental friendly and cost-reduced production, replacing the conventional organic PVDF binder and the toxic and volatile NMP solvent. However, the pH value of aqueous processed cathode slurries increases to over 12 due to the reaction between NMC 622 particles and water, which decreases the specific discharge capacity of the cells and on the other side results in the chemical corrosion of the current collector during casting. In order to avoid the damage of the current collector and protect the cathode material, different acids could be applied during mixing process to adjust the slurry pH value. In addition, the energy density at battery level can be increased with increasing electrode film thickness which corresponds to an enhanced areal capacity. However, capacity fading of thick-film electrodes at C-rates above C/2 is mainly due to a limited lithium-ion diffusion kinetics and crack formation in cathode particles. 3D electrode architectures produced by ultrafast laser ablation are proven to improve the capacity retention at high discharge rates and the electrolyte wettability of electrodes as reported in our previous works.In this work, NMC 622 electrodes with a film thickness of 150 µm (5.8 mAh/cm2) were manufactured with aqueous binders TRD 202A and CMC, and were subsequently laser structured. With increasing film thickness from 70 µm to 150 µm, the mass loading of cathodes increased from 17 mg/cm2 to 36 mg/cm2. The slurry pH values were adjusted between 9 - 10 with citric acid (CA), phosphoric acid (PA), and acetic acid (AC). The dried electrodes were characterized using XPS and SEM. The unstructured and structured electrodes with different thicknesses were afterwards assembled versus lithium in coin cells. Rate capability test and cyclic voltammetry (CV) were performed in order to investigate the electrochemical performance of the electrodes. Cells containing 70 µm cathodes with PA and CA+PA showed about 10 mAh/g higher capacity at C/20 to C/5 compared to cells with PA, while at 1C to 3C cells with CA showed the lowest capacities With increasing electrode film thickness, cells with PA and PA+CA retained 5-10 mAh/g more capacity than cells with CA at C/20 to C/5. The cells with PA maintained about 120 mAh/g discharge capacity at C/2, while cells with PA+CA and CA showed about 80 mAh/g and 45 mAh/g, respectively. In comparison to cells with unstructured electrodes, laser structuring increased the discharge capacity of cells with 70 µm electrodes from 1C to 3C, regardless of the type of added acid. As for cells with thick-film electrodes, the discharge capacity of cells containing structured electrodes with CA+PA increased to 120 mAh/g, which is about 40 mAh/g higher compared to cells with unstructured electrodes. Finally, CV proved that the addition of acids had no effect on the redox reaction of NMC 622.