Water-soluble Polypyrrole-Polybis(4-oxy benzene sulfonic acid)phosphazene Composites and Investigation of Their Performance as Cathode Binder in Li-ion Batteries.

Current electric storage systems eagerly focus on high-power and energy-dense Lithium-ion batteries to cope with increasing energy storage demands. Since cathode materials are one of the bottlenecks of these batteries, there is much interest in layered lithium-rich manganese oxide-based (LLMO) cathodes which can develop this technology. However, Initial Coulombic Efficiency (ICE) loss, poor rate performance and cycling instability issues are still persistent as problems to be solved for these materials. Recent research shows that water-soluble binders are effective in improving the performance of LLMO materials. Herein, we describe the synthesis, characterisation, and application of a series of water-soluble composites as a binder for LLMO cathodes. The PPy is introduced as part of the binder to improve the electronic conductivity and two different oxidants and various PPy to PSAP ratios were used to optimise the final properties. The electrochemical performance and morphology of the cathodes before and after cycling were investigated and compared with the conventional PVDF binder. The LLMO-2c electrode showed excellent charge-discharge performance, especially at 5 C and 10 C rates, and high cycling stability at 0.2 C whilst maintaining a final capacity of 184 mAh/g after 200 cycles, which is equal to 89.3 % capacity retention.

Polymeric Binder Design for Sustainable Lithium-Ion Battery Chemistry.

The design of binders plays a pivotal role in achieving enduring high power in lithium-ion batteries (LIBs) and extending their overall lifespan. This review underscores the indispensable characteristics that a binder must possess when utilized in LIBs, considering factors such as electrochemical, thermal, and dispersion stability, compatibility with electrolytes, solubility in solvents, mechanical properties, and conductivity. In the case of anode materials, binders with robust mechanical properties and elasticity are imperative to uphold electrode integrity, particularly in materials subjected to substantial volume changes. For cathode materials, the selection of a binder hinges on the crystal structure of the cathode material. Other vital considerations in binder design encompass cost effectiveness, adhesion, processability, and environmental friendliness. Incorporating low-cost, eco-friendly, and biodegradable polymers can significantly contribute to sustainable battery development. This review serves as an invaluable resource for comprehending the prerequisites of binder design in high-performance LIBs and offers insights into binder selection for diverse electrode materials. The findings and principles articulated in this review can be extrapolated to other advanced battery systems, charting a course for developing next-generation batteries characterized by enhanced performance and sustainability.

In Situ Hydrogel Polymerization to Form a Flexible Polysaccharide Synergetic Binder Network for Stabilizing SiOx/C Anodes.

Today, the commercial application of silicon oxides (SiOx, 1 < x < 2) in lithium-ion batteries (LIBs) still faces the challenge of rapid performance degradation. In this work, by integrating hydrothermal and physicomechanical processes, water-soluble locust bean gum (LBG) and xanthan gum (XG) are utilized to in situ form an LBG@XG binder network to improve the performance of SiOx/C anodes. As a synergy of LBG and XG polysaccharides in hydrogel polymerization, LBG@XG can tightly wrap around SiOx/C particles to prevent plate damage. The flexible SiOx/C anode with the LBG@XG binder exhibits capacity retentions of 74.1% and 76.4% after 1000 cycles at 0.5 A g-1 and 1 A g-1, respectively. The full battery capacity remains stable for 100 cycles at 1 C and the rate performance is excellent (103 mAh g-1 at 3 C). This LBG@XG is demonstrated to be highly electronegative and has a strong attraction to SiOx/C particles, thereby reducing the expansion and increasing the stability of the SiOx/C anodes when coupled with the flexible binder network. In addition to the promising LBG@XG binder, this work also provides a research idea for developing green water-based binders suitable for application in the SiOx/C anodes of LIBs.

New Partially Water-Soluble Feedstocks for Additive Manufacturing of Ti6Al4V Parts by Material Extrusion.

In this work, a process chain for the realization of dense Ti6Al4V parts via different material extrusion methods will be introduced applying eco-friendly partially water-soluble binder systems. In continuation of earlier research, polyethylene glycol (PEG) as a low molecular weight binder component was combined either with poly(vinylbutyral) (PVB) or with poly(methylmethacrylat) (PMMA) as a high molecular weight polymer and investigated with respect to their usability in FFF and FFD. The additional investigation of different surfactants' impact on the rheological behaviour applying shear and oscillation rheology allowed for a final solid Ti6Al4V content of 60 vol%, which is sufficient to achieve after printing, debinding and thermal densification parts with densities better than 99% of the theoretical value. The requirements for usage in medical applications according to ASTM F2885-17 can be fulfilled depending on the processing conditions.

Cathode-Electrolyte Interface Modification by Binder Engineering for High-Performance Aqueous Zinc-Ion Batteries.

A stable cathode-electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO- from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+ ; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn-Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.

Sulfated Alginate as an Effective Polymer Binder for High-Voltage LiNi0.5Mn1.5O4 Electrodes in Lithium-Ion Batteries.

Although the increasing demand for high-energy-density lithium-ion batteries (LIBs) has inspired extensive research on high-voltage cathode materials, such as LiNi0.5Mn1.5O4 (LNMO), their commercialization is hindered by problems associated with the decomposition of common carbonate solvent-based electrolytes at elevated voltages. To address these problems, we prepared high-voltage LNMO composite electrodes using five polymer binders (two sulfated and two nonsulfated alginate binders and a poly(vinylidene fluoride) conventional binder) and compared their electrochemical performances at ∼5 V vs Li/Li+. The effects of binder type on electrode performance were probed by analyzing cycled electrodes using soft/hard X-ray photoelectron spectroscopy and scanning transmission electron microscopy. The best-performing sulfated binder, sulfated alginate, uniformly covers the surface of LNMO and increased its affinity for the electrolyte. The electrolyte decomposition products generated in the initial charge-discharge cycle on the alginate-covered electrode participated in the formation of a protective passivation layer that suppressed further decomposition during subsequent cycles, resulting in enhanced cycling and rate performances. The results of this study provide a basis for the cost-effective and technically undemanding fabrication of high-energy-density LIBs.

Crosslinked Chitosan Binder for Sustainable Aqueous Batteries.

The increased percentage of renewable power sources involved in energy production highlights the importance of developing systems for stationary energy storage that satisfy the requirements of safety and low costs. Na ion batteries can be suitable candidates, specifically if their components are economic and safe. This study focuses on the development of aqueous processes and binders to prepare electrodes for sodium ion cells operating in aqueous solutions. We demonstrated the feasibility of a chitosan-based binder to produce freestanding electrodes for Na ion cells, without the use of organic solvents and current collectors in electrode processing. To our knowledge, it is the first time that water-processed, freestanding electrodes are used in aqueous Na ion cells, which could also be extended to other types of aqueous batteries. This is a real breakthrough in terms of sustainability, taking into account low risks for health and environment and low costs.

Sodium Alginate Binders for Bivalency Aqueous Batteries.

Environmental friendly sodium alginate (SA) cannot be used as a binder in aqueous batteries due to its high solubility in water. A water-insoluble polyvinylidene difluoride (PVDF) binder has been widely applied for an aqueous battery, in which the toxic and expensive organic solvent of N-methy-2-pyrrolidone (NMP) is required during the coating process. Herein, we report that the water-soluble SA can be utilized as a binder in aqueous Zn batteries because SA could cross-link with the Zn2+ ion to form a water-insoluble and mechanically super strong binder for electrodes. Aqueous Zn||LiFePO4 cells are assembled to demonstrate the performance of the SA binder for LiFePO4 cathodes. Due to the high adhesion strength of cross-linked Zn-SA, LiFePO4 with the SA binder displays a high capacity retention of 93.7% with a high Coulombic efficiency of nearly 100% after 100 cycles at a 0.2 C rate, while the capacity of LiFePO4 with the PVDF binder quickly decays to 84.7% after 100 cycles at 0.2 C. In addition, the LiFePO4 cathode with the SA binder also has smaller redox polarization, faster ion diffusion rate, and more favorable electrochemical kinetics than that with the PVDF binder.

A Modified Natural Polysaccharide as a High-Performance Binder for Silicon Anodes in Lithium-Ion Batteries.

A modified natural polysaccharide (carboxymethylated gellan gum) is investigated as a water-soluble high-performance binder for silicon anodes in lithium-ion batteries to improve poor cycle life and fast capacity fade of silicon anodes due to dramatic volume expansion during lithiation/delithiation process. The numberof carboxyl and acetyl groups distributed homogeneously in the modified polysaccharide polymer chain can form strong hydrogen bonds with the surface of Si particle and copper current collector, thus effectively restricting the volume change of silicon and maintaining electronic integrity of Si electrodes during repeated charge/discharge cycles. As a result, Si anodes with carboxymethylated natural polysaccharide polymer present high capacity performance, excellent rate capability, and stable cycling.

Poly-γ-glutamate Binder To Enhance Electrode Performances of P2-Na2/3Ni1/3Mn2/3O2 for Na-Ion Batteries.

P2-Na2/3Ni1/3Mn2/3O2 (P2-NiMn) is one of the promising positive electrode materials for high-energy Na-ion batteries because of large reversible capacity and high working voltage by charging up to 4.5 V versus Na+/Na. However, the capacity rapidly decays during charge/discharge cycles, which is caused by the large volume shrinkage of ca. 23% by sodium deintercalation and following electric isolation of P2-NiMn particles in the composite electrode. Serious electrolyte decomposition at the higher voltage region than 4.1 V also brings deterioration of the particle surface and capacity decay during cycles. To solve these drawbacks, we apply water-soluble sodium poly-γ-glutamate (PGluNa) as an efficient binder to P2-NiMn instead of conventional poly(vinylidene difluoride) (PVdF) and examined the electrode performances of P2-NiMn composite electrode with PGluNa binder for the first time. The PGluNa electrode shows Coulombic efficiency of 95% at the first cycle and capacity retention of 89% after 50 cycles, whereas the PVdF electrode exhibits only 80 and 71%, respectively. The alternating current impedance measurements reveal that the PGluNa electrode shows a much lower resistance during the cycles compared with the PVdF one. From the surface analysis and peeling test of the electrodes, the PGluNa binder was found to cover the surface of the P2-NiMn particles and suppresses the electrolyte decomposition and surface degradation. The PGluNa binder further enhance the mechanical strength of the electrodes and suppresses the electrical isolation of the P2-NiMn particles during sodium extraction/insertion. The efficient binder with noticeable adhesion strength and surface coverage of active materials and carbon has paved a new way to enhance the electrochemical performances of high-voltage positive electrode materials for Na-ion batteries.

Mechanochemical Synthesis of PEDOT:PSS Hydrogels for Aqueous Formulation of Li-Ion Battery Electrodes.

Water-soluble binders can enable greener and cost-effective Li-ion battery manufacturing by eliminating the standard fluorine-based formulations and associated organic solvents. The issue with water-based dispersions, however, remains the difficulty in stabilizing them, requiring additional processing complexity. Herein, we show that mechanochemical conversion of a regular poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) water-based dispersion produces a hydrogel that meets all the requirements as binder for lithium-ion battery electrode manufacture. We particularly highlight the suitable slurry rheology, improved adhesion, intrinsic electrical conductivity, large potential stability window and limited corrosion of metal current collectors and active electrode materials, compared to standard binder or regular PEDOT:PSS solution-based processing. When incorporating the active materials, conductive carbon and additives with PEDOT:PSS, the mechanochemical processing induces simultaneous binder gelation and fine mixing of the components. The formed slurries are stable, show no phase segregation when stored for months, and produce highly uniform thin (25 µm) to very thick (500 µm) films in a single coating step, with no material segregation even upon slow drying. In conjunction with PEDOT:PSS hydrogels, technologically relevant materials including silicon, tin, and graphite negative electrodes as well as LiCoO2, LiMn2O4, LiFePO4, and carbon-sulfur positive electrodes show superior cycling stability and power-rate performances compared to standard binder formulation, while significantly simplifying the aqueous-based electrode assembly.

Graphite//LiNi0.5 Mn1.5 O4 Cells Based on Environmentally Friendly Made-in-Water Electrodes.

The performance of graphite//LiNi0.5 Mn1.5 O4 (LNMO) cells, both electrodes of which are made using water-soluble sodium carboxymethyl cellulose (CMC) binder, is reported for the first time. The full cell performed outstandingly over 400 cycles in the conventional electrolyte ethylene carbonate/dimethyl carbonate-1 m LiPF6 , and the delivered specific energy at the 100th, 200th, 300th, and 400th cycle corresponded to 82, 78, 73, and 66 %, respectively, of the initial energy value of 259 Wh kg-1 (referring to the sum of the two electrode-composite weights). The good stability of high-voltage, LNMO-CMC-based electrodes upon long-term cycling is discussed and the results are compared to those of LNMO-composite electrodes with polyvinylidene fluoride (PVdF). LNMO-CMC electrodes outperformed those with PVdF binder, displaying a capacity retention of 83 % compared to 62 % for the PVdF-based electrodes after 400 cycles at 1 C. CMC promotes a more compact and stable electrode surface than PVdF; undesired interfacial reactions at high operating voltages are mitigated, and the thickness of the passivation layer on the LNMO surface is reduced, thereby enhancing its cycling stability.