Study of Water-Based Lithium Titanate Electrode Processing: The Role of pH and Binder Molecular Structure.
ABSTRACT: This work elucidates the manufacturing of lithium titanate (Li₄Ti₅O12, LTO) electrodes via the aqueous process using sodium carboxymethylcellulose (CMC), guar gum (GG) or pectin as binders. To avoid aluminum current collector dissolution due to the rising slurries' pH, phosphoric acid (PA) is used as a pH-modifier. The electrodes are characterized in terms of morphology, adhesion strength and electrochemical performance. In the absence of phosphoric acid, hydrogen evolution occurs upon coating the slurry onto the aluminum substrate, resulting in the formation of cavities in the coated electrode, as well as poor cohesion on the current collector itself. Consequently, the electrochemical performance of the coated electrodes is also improved by the addition of PA in the slurries. At a 5C rate, CMC/PA-based electrodes delivered 144 mAh·g-1, while PA-free electrodes reached only 124 mAh·g-1. When GG and pectin are used as binders, the adhesion of the coated layers to the current collector is reduced; however, the electrodes show comparable, if not slightly better, electrochemical performance than those based on CMC. Full lithium-ion cells, utilizing CMC/PA-made Li[Ni0.33Mn0.33Co0.33]O₂ (NMC) cathodes and LTO anodes offer a stable discharge capacity of ~120 mAh·g-1(NMC) with high coulombic efficiencies.
Project description:This work presents an alternative method for fabricating Li-ion electrodes in which the use of aluminum/copper current collectors and expensive binders is avoided. Low-cost natural cellulose fibers with a 2-mm length are employed as binder and support for the electrode. The objective of this method is to eliminate the use of heavy and inactive current collector foils as substrates and to replace conventional costly binders with cellulose fibers. Moreover, no harmful solvents, such as N-methylpyrrolidone, are employed for film fabrication. Water-soluble carbons are also utilized to reduce the preparation time and to achieve a better repartition of carbon in the electrode, thus improving the electrochemical performance. Flexible and resistant LiFePO4 (LFP), Li4Ti5O12 (LTO), organic 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), and graphite electrodes are obtained with active mass loadings similar to those obtained by the current casting method. The initial discharge capacity of approximately 130 mAh·g-1 at 2?C is obtained for an LFP/LTO paper battery with an approximately 91.6% capacity retention after 1000 cycles. An all-organic prelithiated PTCDA/graphite cell without a transition metal is prepared and electrochemically tested. It is one of the first self-standing batteries that is composed of organic redox active molecules and biodegradable components reported in literature.
Project description:The electrochemical performances of Li4Ti5O12 (LTO) and Li4Ti5O12-rutile TiO2 (LTO-RTO) composite electrodes at low temperatures were evaluated. The electrochemical performance of both electrodes decreased at low temperatures; regardless, the LTO-RTO electrode performed better than the LTO electrode. First, high viscosity and low ion conductivity of liquid electrolytes at low temperatures significantly reduce electrochemical performance. Second, cycling at low temperatures changes the crystal structure of LTO-based electrodes, impeding lithium ion diffusion and even causing the diffusion path to change from easy to difficult. However, changes in the crystal structure of the LTO-RTO electrode were not sufficient to change this path; thus, diffusion continued along the 8a-16c-8a pathway. Finally, from the perspective of dynamics, aggravation of a side reaction, increase in charge transfer resistance and polarization, and decrease in lithium ion diffusion at low temperatures reduce the electrochemical performance of LTO-based anode materials. However, the activation energy based on lithium ion diffusion is lower in the LTO-RTO electrode than the LTO electrode. The results confirmed that the electrochemical performance of the LTO-RTO electrode was better than that of the LTO electrode at low temperatures.
Project description:Resistive interfaces within the electrodes limit the energy and power densities of a battery, for example, a Li-ion battery (LIB). Typically, active materials are mixed with conductive additives in organic solvents to form a slurry, which is then coated on current collectors (e.g., bare or carbon-coated Al foils) to reduce the inherent resistance of the active material. Although many approaches using nanomaterials to either replace Al foils or improve conductivity within the active materials have been previously demonstrated, the resistance at the current collector active material interface (CCAMI), a key factor for enhancing the energy and power densities, remains unaddressed. We show that carbon nanotubes (CNTs), either directly grown or spray-coated on Al foils, are highly effective in reducing the CCAMI resistance of traditional LIB cathode materials (LiFePO4 or LFP and LiNi0.33Co0.33Mn0.33O2 or NMC). Moreover, the CNT coatings displace the need for currently used toxic organic solvents (e.g., N-methyl-2-pyrrolidone) by providing capillary channels, which improve the wetting of aqueous dispersions containing active materials. The vertically aligned CNT-coated electrodes exhibited energy densities as high as (1) ?500 W h kg-1 at ?170 W kg-1 for LFP and (2) ?760 W h kg-1 at ?570 W kg-1 for NMC. The LIBs with CCAMI-engineered electrodes withstood discharge rates as high as 600 mA g-1 for 500 cycles in the case of LFP, where commercial electrodes failed. The CNT-based CCAMI engineering approach is versatile with wide applicability to improve the performance of even textured active materials for both cathodes and anodes.
Project description:The state-of-the-art aqueous binder for supercapacitors is carboxymethyl cellulose (CMC). However, it limits the mass loading of the coatings owing to shrinkage upon drying. In this work, natural polymers, that is, guar gum (GG), wheat starch (WS), and potato starch (PS), were studied as alternatives. The flexibility and adhesion of the resulting coatings and electrochemical performance was tested. The combination of 75:25 (w/w) ratio PS/GG showed a promising performance. Electrodes were characterized by SEM, thermal, adhesion, and bending tests. Their electrochemical properties were determined by cyclic voltammetry, electrochemical impedance spectroscopy, and cycling experiments. The PS/GG mixture conformed well to criteria for industrial production, enabling mass loadings higher than CMC (7.0?mg?cm-2 ) while granting the same specific capacitance (26?F?g-1 ) and power performance (20?F?g-1 at 10?A?g-1 ). Including the mass of the current collector, this represents a +45?% increase in specific energy at the electrode level.
Project description:LTO (Li?Ti?O12) has been highlighted as anode material for next-generation lithium ion secondary batteries due to advantages such as a high rate capability, excellent cyclic performance, and safety. However, the generation of gases from undesired reactions between the electrode surface and the electrolyte has restricted the application of LTO as a negative electrode in Li-ion batteries in electric vehicles (EVs) and energy storage systems (ESS). As the generation of gases from LTO tends to be accelerated at high temperatures (40?60 °C), the thermal stability of LTO should be maintained during battery discharge, especially in EVs. To overcome these technical limitations, a thin layer of Al?O? (~2 nm thickness) was deposited on the LTO electrode surface by atomic layer deposition (ALD), and an electrochemical charge-discharge cycle test was performed at 60 °C. The capacity retention after 500 cycles clearly shows that Al?O?-coated LTO outperforms the uncoated one, with a discharge capacity retention of ~98%. TEM and XPS analyses indicate that the surface reactions of Al?O?-coated LTO are suppressed, while uncoated LTO undergoes the (111) to (222) phase transformation, as previously reported in the literature.
Project description:The commercial uptake of lithium-sulfur (Li-S) batteries is undermined by their rapid performance decay and short cycle life. These problems originate from the dissolution of lithium polysulfide in liquid electrolytes, causing charge and active material to shuttle between electrodes. The dynamics of intractable polysulfide migration at different length scales often tend to escape the probing ability of many analytical techniques. Spatial and temporal visualization of Li in Li-S electrodes and direct mechanistic understanding of how polysulfides are regulated across Li-S batteries starting from current collector and active layer coating to electrode-electrolyte interface are still lacking. To address this we employ neutron depth profiling across Li-S electrodes using the naturally occurring isotope, 6Li, which yields direct spatial information on Li-S electrochemistry. Using three types of Li-S electrodes, namely, carbon-sulfur, carbon-sulfur with 10% lithium titanium oxide (LTO), and carbon-sulfur with LTO membrane, we provide direct evidence for the migration, adsorption, and confinement of polysulfides in Li-S cells at work. Our findings further provide insights into the dynamics of polysulfide dissolution and re-utilization in relation to Li-S battery capacity and longevity to aid rational electrode designs toward high-energy, safe, and low-cost batteries.
Project description:The industrial lignin used here is a byproduct from Kraft pulp mills, extracted from black liquor. Since lignin is inexpensive, abundant and renewable, its utilization has attracted more and more attention. In this work, lignin was used for the first time as binder material for LiFePO₄ positive and graphite negative electrodes in Li-ion batteries. A procedure for pretreatment of lignin, where low-molecular fractions were removed by leaching, was necessary to obtain good battery performance. The lignin was analyzed for molecular mass distribution and thermal behavior prior to and after the pretreatment. Electrodes containing active material, conductive particles and lignin were cast on metal foils, acting as current collectors and characterized using scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge cycles. Good reversible capacities were obtained, 148 mAh·g-1 for the positive electrode and 305 mAh·g-1 for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAh·g-1 and the negative electrode with 160 mAh·g-1 at 1C. Low ohmic resistance also indicated good binder functionality. The results show that lignin is a promising candidate as binder material for electrodes in eco-friendly Li-ion batteries.
Project description:The effect of particle size and electronic percolation on low-temperature power performance in the lithium titanate (LTO) cell is reported. Particle size and carbon contents in negative electrodes are systematically controlled to understand ionic and electronic contribution. The LTO cell with a small particle size, that is, high surface area, showed superior power performance, while additional electronic percolation did not improve the performance at ?30 °C when coupled with a lithium manganese spinel cathode. The results are supported by electrochemical impedance spectroscopy measurements, which indicate that smaller LTO particles exhibit lower charge transfer-related impedance and guide rational design and fabrication of electrode architectures at low temperature.
Project description:We investigated the effect of carboxymethyl cellulose (CMC) and the particulate fluorine/acrylate hybrid polymer (FAHP) on the flow behavior of LiFePO4-based cathode slurries as well as on electrical and mechanical properties of the corresponding dry layers. CMC dissolves in water and partly adsorbs on the active particles. Thus, it has a strong impact on particle dispersion and a critical CMC concentration distinguished by a minimum in yield stress and high shear viscosity is found, indicating an optimum state of particle dispersion. In contrast, the nanoparticulate FAHP binder has no effect on slurry rheology. The electrical conductivity of the dry layer exhibits a maximum at a CMC concentration corresponding to the minimum in slurry viscosity but monotonically decreases with increasing FAHP concentration. Adhesion to the current collector is provided by FAHP, and the line load in peel tests strongly increases with FAHP concentration, whereas CMC does not contribute to adhesion. The electrical conductivity and adhesion values obtained here excel reported values for similar aqueous LiFePO4-based cathode layers using alternative polymeric binders. Both CMC and FAHP contribute to the cohesive strength of the layers; the contribution of CMC, however, is stronger than that of FAHP despite its lower intrinsic mechanical strength. We attribute this to its impact on the cathode microstructure since high CMC concentrations result in a strong alignment of LiFePO4 particles, which yields superior cohesive strength.
Project description:The preparation of redox-active coatings is a key step in fabricating electrochemical biosensors. To this goal, a variety of coating materials have been used in combination with redox-active compounds. In this study, alizarin red S (ARS) was confined in layer-by-layer (LbL) films composed of poly(ethyleneimine) (PEI) and carboxymethylcellulose (CMC) to study the redox properties. A gold (Au) disc electrode coated with PEI/CMC LbL film was immersed in an ARS solution to uptake ARS into the film. ARS was successfully confined in the LbL film through electrostatic interactions. The cyclic voltammogram (CV) of ARS-confined PEI/CMC film-coated electrodes thus prepared exhibited redox waves in the potential range from -0.5 to -0.7 V originating from 9,10-anthraquinone moiety in ARS, demonstrating that ARS preserves its redox activity in the LbL film. An additional oxidation peak appeared around -0.4 V in the CV recorded in the solution containing phenylboronic acid (PBA), due to the formation of a boronate ester of ARS (ARS-PBA) in the film. The oxidation peak current at -0.4 V decreased upon addition of 3,4-dihydroxyphenylalanine (L-dopa) to the solution. Thus, the results suggest a potential use of the ARS-confined PEI/CMC films for constructing voltammetric sensors for L-dopa.