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Register a new userScalable Solvent-Based Fabrication of Thermo-Responsive Polymer Nanocomposites for Battery Safety Regulation
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Mingqian Li
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Improving lithium-ion batteries (LIBs) safety remains in a challenging task when compared with the tremendous progress made in their performance in recent years. Embedding thermo-responsive polymer switching materials (TRPS) into LIB cells has been proved to be a promising strategy to provide consistent thermal abuse protections at coin-cell level. However, it is unrealistic to achieve large-scale applications without further demonstration in high-capacity pouch cells. Here, we employed tungsten carbide (WC) as a novel conductive filler, and successfully overcame the intrinsic processing difficulty of polyethylene (PE) matrix in a scalable solvent-based method to obtain ultra-thin, uniform, highly conductive TRPS. Moreover, by integrating TRPS directly into LIB electrodes, no extra fabrication facilities or processes are required for making the cells. As a result, multi-layer pouch cells with consistent electrochemical performance and thermal abuse protection function were fabricated using industry relevant manufacturing techniques, which brings TRPS one step further to the real application scenarios.
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The paper presents a comprehensive analysis of elastic properties of polystyrene-based nanocomposites filled with different types of inclusions: small spherical particles (SiO2 and Al2O3), alumosilicates (montmorillonite, halloysite natural tubules and Mica) and carbon nanofillers (carbon black and multi-walled carbon nanotubes). Composites were fabricated by melt technology. The analysis of composite melts showed that the introduction of Montmorillonite, Multi-walled carbon nanotubes, and Al2O3 particles provided an increase in melt viscosity by an average of 2 to 5 orders of magnitude over the pure polystyrene. Block samples of composites with different filler concentrations were prepared, and their linear and nonlinear elastic properties were studied. The introduction of more rigid particles led to a more profound increase in the elastic modulus of the composite, with the highest rise of about 80% obtained with carbon fillers. Carbon black particles provided also an enhanced strength at break of about 20% higher than that of pure polystyrene. The nonlinear elastic moduli of composites were shown to be more sensitive to addition of filler particles to the polymer matrix than the linear ones. The nonlinearity coefficient $beta$ comprising the combination of linear and nonlinear elastic moduli of a material demonstrated considerable changes correlating with changes of the Youngs modulus. The absolute value of $beta$ showed rise in 1.5-1.6 times in the CB- and HNT-containing composites as compared to that of pure PS. The changes in nonlinear elasticity of fabricated composites were compared with measurements of the parameters of bulk nonlinear strain waves in them. Variations of wave velocity and decay decrement correlated with observed enhancement of materials nonlinearity.
We study two thermo-electrochemical models for lithium-ion batteries. The first is based on volume averaging the electrode microstructure whereas the second is based on the pseudo-two-dimensional (P2D) approach which treats the electrode as a collection of spherical particles. A scaling analysis is used to reduce the volume-averaged model and show that the electrochemical reactions are the dominant source of heat. Matched asymptotic expansions are used to compute solutions of the volume-averaged model for the cases of constant applied current, oscillating applied current, and constant cell potential. The asymptotic and numerical solutions of the volume-averaged model are in remarkable agreement with numerical solutions of the thermal P2D model for (dis)charge rates up to 2C, and reasonable agreement is found at 4C. Homogenisation is then used to derive a thermal model for a battery consisting of several connected lithium-ion cells. Despite accounting for the Arrhenius dependence of the reaction coefficients, we show that thermal runaway does not occur in the model. Instead, the cell potential is simply pushed closer to the open-circuit potential. We also show that in many cases, the homogenised battery model can be solved analytically, making it ideal for use in on-board thermal management systems.
For a wide range of modern soft functional materials the selective transport of sub-nanometer-sized molecules (`penetrants) through a stimuli-responsive polymeric membrane is key to the desired function. In this study, we investigate the diffusion properties of penetrants ranging from non-polar to polar molecules and ions in a matrix of collapsed Poly(N-isopropylacrylamide) (PNIPAM) polymers in water by means of extensive molecular dynamics simulations. We find that the water distributes heterogeneously in fractal-like cluster structures embedded in the nanometer-sized voids of the polymer matrix. The nano-clustered water acts as an important player in the penetrant diffusion, which proceeds via a hopping mechanism through `wet transition states: the penetrants hop from one void to another via transient water channels opened by rare but decisive polymer fluctuations. The diffusivities of the studied penetrants extend over almost five orders of magnitude and thus enable a formulation of an analytical scaling relation with a clear non-Stokesian, exponential dependence of the diffusion coefficient on the penetrants radius for the uncharged penetrants. Charged penetrants (ions) behave differently as they get captured in large isolated water clusters. Finally, we find large energetic activation barriers for hopping, which significantly depend on the hydration state and thereby challenge available transport theories.
Among the several flexible thermoelectric modules in existence, sintered Bi-Te-based modules represent a viable option because of their high output power density and flexibility, which enables the use of arbitrary heat sources. We have fabricated Bi-Te-based modules with a large-scalable fabrication process and improved their output performance. The reduction in the interconnection resistance, using thick electrodes of the flexible printed circuit, significantly improves the modules output power to 87 mW/cm$^{2}$ at $Delta T$ = 70 K, which is 1.3-fold higher than a previous prototype module. Furthermore, the establishment of the fabrication for the top electrodes by using the surface mount technology makes it possible to realize a high-throughput manufacturing of the module. Our durability tests reveal that there is no significant change in the internal resistance of the module during 10000 cycles of mechanical bending test and 1000 cycles of thermal stress test.
We demonstrate the fabrication of large-scale arrays of single photon emitters (SPEs) in hexagonal boron nitride (hBN). Bottom-up growth of hBN onto nanoscale arrays of dielectric pillars yields corresponding arrays of hBN emitters at the pillar sites. Statistical analysis shows that the pillar diameter is critical for isolating single defects, and diameters of ~250 nm produce a near-unity yield of a single emitter at each pillar site. Our results constitute a promising route towards spatially-controlled generation of hBN SPEs and provide an effective and efficient method to create large scale SPE arrays. The results pave the way to scalability and high throughput fabrication of SPEs for advanced quantum photonic applications.
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