Introducing lignin as a binder material for the aqueous production of NMC111 cathodes for Li-ion batteries

By enabling water-based cathode processing, the energy-intensive N-methyl-2-pyrrolidone (NMP) recovery step can be eliminated, reducing the cost and environmental impact of LIBs. Aqueous processing of high capacity Ni-containing LiNixMn1−x−yCoyO2 (NMC) cathodes is problematic due to lithium-ion(Li+) leaching, corrosion of the aluminum (Al) current collector, and the lack of aqueous soluble bio-derived binders. The present study investigates the potential of substituting and fully replacing the commonly used polyvinylidene fluoride (PVDF) and carboxymethyl cellulose (CMC) binders with abundant, bio-derived kraft lignin. This paper gives a holistic overview of the optimal conditions when employing these binders. For the first time, we demonstrate that NMC111 cathodes of comparable specific capacities to NMP/PVDF-based ones over 100 cycles or at high C-rates (5C) can be formulated in water using lignin or CMC/lignin as binder materials. Cyclic voltammetry (CV) revealed that kraft lignin undergoes a redox reaction with the electrolyte between 2.8 and 4.5 V, which diminishes upon subsequent cycles. Differential scanning calorimetry (DSC) revealed that lignin is thermally stable up to 152 °C. Rheology measurements showed that replacing NMP with water allows for a solvent reduction. The cathodes fabricated using an aqueous slurry should be dried at 50 °C, as extensive surface cracks detected using scanning electron microscopy (SEM) diminish. Li+ leaching from NMC111 and NaOH species from kraft lignin caused an increase in pH during aqueous slurry fabrication. A carbon-coated Al foil (C-Al) prevented Al corrosion and increased the lignin cathode's mechanical strength revealing lignin's exceptional binding abilities to carbon. The electrolyte wettability decreased for calendered lignin-containing cathodes with low porosity and a large carbon black/lignin matrix

Structured aqueous processed lignin-based NMC cathodes for energy-dense LIBs with improved rate capability

The cost and environmental impact of lithium-ion batteries (LIBs) can be reduced substantially by enabling the aqueous processing of cathode materials. For the first time, we fabricate high-density, thick NMC111 cathode coatings using water as a solvent, and bio-derived kraft lignin as a binder material. The performance deterioration at high discharge currents is amplified by high mass loading and low bulk porosity. At porosities higher than 60%, the electronic conductivity limits the rate capability of the cathode, while for porosities lower than 30%, ionic conduction causes significant ionic polarization and consequently diminishes rate performance. The underlying lithium-ion diffusion limitation at current densities higher than 0.2 C is mitigated by creating line structures on the surface of the cathode. Structuring the half-dried cathode surface with ceramic blades is preferred over a stamp-like silicon wafer, and the line structures are easier to produce with high mechanical stability in comparison to pit structures. The lignin/water cells investigated herein restore after undergoing rate capability tests (5C), except those with pit structures or ultra-high thickness (>200 μm), due to the extensive crack formation during water evaporation which causes poor mechanical stability. Mechanical and laser structuring methods are compared on the surface of a PVDF/NMP-based cathode. Concerning the implementation in a large-scale battery factory, mechanical structuring is currently considered a processing of choice as it has no surface residuals or waste material. However, laser structuring with ultra-short pulses technique has the potential of outperforming mechanical structuring if the process is optimized to high precision to reduce residual and waste material, due to reproducibility and lower operational costs