Embedded distributed temperature sensing enabled multi-state joint observation of smart lithium-ion battery

Accurate monitoring of the internal statuses are highly valuable for the management of lithium-ion battery (LIB). This paper proposes a thermal model-based method for multi-state joint observation, enabled by a novel smart battery design with embedded and distributed temperature sensor. In particular, a novel smart battery is designed by implanting the distributed fiber optical sensor (DFOS) internally and externally. This promises a real-time distributed measurement of LIB internal and surface temperature with a high space resolution. Following this endeavor, a low-order joint observer is proposed to co-estimate the thermal parameters, heat generation rate, state of charge, and maximum capacity. Experimental results disclose that the smart battery has space-resolved self-monitoring capability with high reproducibility. With the new sensing data, the heat generation rate, state of charge, and maximum capacity of LIB can be observed precisely in real time. The proposed method validates to outperform the commonly-used electrical model-based method regarding the accuracy and the robustness to battery aging

Wiskott-Aldrich syndrome gene as a prognostic biomarker correlated with immune infiltrates in clear cell renal cell carcinoma

IntroductionThe abnormal expression of the Wiskott-Aldrich syndrome protein (WASP) encoded by the Wiskott-Aldrich syndrome (WAS) gene has been implicated in tumor invasion and immune regulation. However, prognostic implications of WAS and its correlation tumor infiltrating in renal clear cell carcinoma (ccRCC) is not clear cut.MethodsThe correlation between WAS expression, clinicopathological variables and clinical outcomes were evaluated using The Cancer Genome Atlas (TCGA), Gene Expression Omnibus (GEO), Tumor Immune Estimation Resource (TIMER), UALCAN, Gene Expression Profiling Interaction Analysis (GEPIA), Kaplan-Meier (KM) plotter and other databases. Furthermore, we assessed the transcription expression of WAS in renal cancer tissues, various renal carcinoma cell lines and human renal tubular cells (HK2) using quantitative polymerase chain reaction (qPCR). A comprehensive analysis of multiple databases including TIMER, GEPIA, TISIDB, ESTIMATE algorithm, and CIBERSORT algorithm were performed to determine the correlation between WAS and tumor infiltrating immune cells in ccRCC.ResultsThe results displayed an increase in WAS mRNA level in ccRCC compared to normal tissue. WAS protein level was found highly expressed in cancer tissues, particularly within renal tumor cells via the human protein atlas (HPA). Interestingly, we found that elevated WAS expression was significantly positively correlated with the infiltration of CD8+ T cells, B cells, Monocytes, Neutrophils, Macrophages, T cell regulation, NK cells, and Dendritic cells in ccRCC. Bioinformatics demonstrated a strong correlation between WAS expression and 42 immune checkpoints, including the T cell exhaustion gene PD-1, which is critical for exploring immunotherapy for ccRCC. We revealed that patients with high WAS expression were less sensitive to immunotherapy medications.ConclusionIn conclusion, our study identified that WAS was a prognostic biomarker and correlated with immune infiltrates in ccRCC

Insertion Homo- and Copolymerization of Diallyl Ether

The previously unresolved issue of polymerization of allyl monomers CH2=CHCH2X is overcome by a palladium-catalyzed insertion polymerization of diallyl ether as a monomer. An enhanced 2,1-insertion of diallyl ether as compared to mono-allyl ether retards the formation of an unreactive five-membered cyclic O-chelate (after 1,2-insertion) that otherwise hinders further polymerization, and also enhances incorporation in ethylene polymers (20.4 mol %). Cyclic ether repeat units are formed selectively (96 %–99 %) by an intramolecular insertion of the second allyl moiety of the monomer. These features even enable a homopolymerization to yield polymers (poly-diallyl ether) with degrees of polymerization of DPn≈44.publishe

Insertion Polymerization of Divinyl Formal

Copolymerization of ethylene and divinyl formal by [{κ²-<i>P</i>,<i>O-</i>(2-MeOC₆H₄)₂PC₆H₄SO₃}­PdMe­(dmso)] (<b>1)</b> by a coordination–insertion mechanism affords highly linear polyethylenes with a high (12.5 mol %) incorporation of divinyl formal. This significantly exceeds the thus far relatively low incorporation (6.9 mol %) and activity with vinyl ether monomer in insertion polymerization. The resulting ethylene–divinyl formal copolymers exclusively (>98%) contain five-membered (<i>trans</i>-1,3-dioxolane) and six-membered (<i>cis</i>-/<i>trans</i>-1,3-dioxane) cyclic acetal units in the main chain, and also in the initiating ends of this functionalized polyethylene. Comprehensive NMR analysis of the microstructure of these copolymers revealed that under pressure reactor conditions consecutive 2,1–1,2-insertion of divinyl formal into a Pd–H bond is preferred, but consecutive 1,2–1,2-insertion of divinyl formal into more bulky Pd–alkyls (growing polymer chain) is favored. Moreover, homopolymerization of divinyl formal yielded a non-cross-linking poly­(divinyl formal) with degrees of polymerization of DP_n ≈ 26

Unsymmetrical Strategy on α-Diimine Nickel and Palladium Mediated Ethylene (Co)Polymerizations

Among various catalyst design strategies used in the α-diimine nickel(II) and palladium(II) catalyst systems, the unsymmetrical strategy is an effective and widely utilized method. In this contribution, unsymmetrical nickel and palladium α-diimine catalysts (Ipty/iPr-Ni and Ipty/iPr-Pd) derived from the dibenzobarrelene backbone were constructed via the combination of pentiptycenyl and diisopropylphenyl substituents, and investigated toward ethylene (co)polymerization. Both of these catalysts were capable of polymerizing ethylene in a broad temperature range of 0–120 °C, in which Ipty/iPr-Ni could maintain activity in the level of 106 g mol−1 h−1 even at 120 °C. The branching densities of polyethylenes generated by both nickel and palladium catalysts could be modulated by the reaction temperature. Compared with symmetrical Ipty-Ni and iPr-Ni, Ipty/iPr-Ni exhibited the highest activity, the highest polymer molecular weight, and the lowest branching density. In addition, Ipty/iPr-Pd could produce copolymers of ethylene and methyl acrylate, with the polar monomer incorporating both on the main chain and the terminal of branches. Remarkably, the ratio of the in-chain and end-chain polar monomer incorporations could be modulated by varying the temperature

Short-Chain Branched Polar-Functionalized Linear Polyethylene via “Tandem Catalysis”

Cationic Pd^II complex <b>1</b> chelated by an <i>N</i>-fixed phosphine sultam has been synthesized and structurally characterized. Exposure of <b>1</b> to ethylene resulted in the formation of short-chain olefins (1-butene: 2-butene: 1-hexene: 1-octene = 86:7:6:1) with a high catalytic activity of 10⁵ mol_E mol_Pd^–1 h^–1. By combination of <b>1</b> and one of the well-known phosphinesulfonato Pd^II catalyst precursors <b>2</b>–<b>5</b>, linear polyethylenes containing methyl, ethyl, and <i>n</i>-butyl branches of up to 100 per 1000 C were generated from the polymerization of ethylene alone in a “tandem catalysis” one-pot approach. In further exploitation of this concept, linear polyethylenes with both various short-chain branches and a choice of different polar functional groups incorporated into the main chain were obtained for the first time from the copolymerization of ethylene and polar vinyl monomers (methyl acrylate, <i>N</i>-isopropylacrylamide, methyl vinyl sulfone, acrylonitrile, ethyl vinyl ether, vinyl acetate, and allyl bromide). All these apolar and polar branches are incorporated into the linear polyethylene backbones to varying degrees, while the type of initiating and terminating chain ends of the resulting polyethylenes depends significantly on the nature of polar vinyl monomer

Short-Chain Branched Polar-Functionalized Linear Polyethylene via “Tandem Catalysis”

Cationic Pd^II complex <b>1</b> chelated by an <i>N</i>-fixed phosphine sultam has been synthesized and structurally characterized. Exposure of <b>1</b> to ethylene resulted in the formation of short-chain olefins (1-butene: 2-butene: 1-hexene: 1-octene = 86:7:6:1) with a high catalytic activity of 10⁵ mol_E mol_Pd^–1 h^–1. By combination of <b>1</b> and one of the well-known phosphinesulfonato Pd^II catalyst precursors <b>2</b>–<b>5</b>, linear polyethylenes containing methyl, ethyl, and <i>n</i>-butyl branches of up to 100 per 1000 C were generated from the polymerization of ethylene alone in a “tandem catalysis” one-pot approach. In further exploitation of this concept, linear polyethylenes with both various short-chain branches and a choice of different polar functional groups incorporated into the main chain were obtained for the first time from the copolymerization of ethylene and polar vinyl monomers (methyl acrylate, <i>N</i>-isopropylacrylamide, methyl vinyl sulfone, acrylonitrile, ethyl vinyl ether, vinyl acetate, and allyl bromide). All these apolar and polar branches are incorporated into the linear polyethylene backbones to varying degrees, while the type of initiating and terminating chain ends of the resulting polyethylenes depends significantly on the nature of polar vinyl monomer

Disturbance-Immune and Aging-Robust Internal Short Circuit Diagnostic for Lithium-Ion Battery

The accurate diagnostic of internal short circuit (ISC) is critical to the safety of lithium-ion battery (LIB), considering its consequence to disastrous thermal runaway. Motivated by this, this paper proposes a novel ISC diagnostic method with a high robustness to measurement disturbances and the capacity fading. Particularly, a multi-state-fusion ISC diagnostic method leveraging polarization dynamics instead of the conventional charge depletion is proposed within a model-switching framework. This is well proven to eliminate the vulnerability of diagnostic to battery aging. Within this framework, the recursive total least squares method with variant forgetting (RTLS-VF) is exploited, for the first time, to mitigate the adverse effect of measurement disturbances, which contributes to an unbiased estimation of the ISC resistance. The proposed method is validated both theoretically and experimentally for high diagnostic accuracy as well as the strong robustness to battery degradation and disturbance

Polar-Functionalized Polyethylenes Enabled by Palladium-Catalyzed Copolymerization of Ethylene and Butadiene/Bio-Based Alcohol-Derived Monomers

Polar-functionalized polyolefins are high-value materials with improved properties. However, their feedstocks generally come from non-renewable fossil products; thus, it requires the development of renewable bio-based monomers to produce functionalized polyolefins. In this contribution, via the Pd-catalyzed telomerization of 1,3-butadiene and three types of bio-based alcohols (furfuryl alcohol, tetrahydrofurfuryl alcohol, and solketal), 2,7-octadienyl ether monomers including OC8-FUR, OC8-THF, and OC8-SOL were synthesized and characterized, respectively. The copolymerization of these monomers with ethylene catalyzed by phosphine–sulfonate palladium catalysts was further investigated. Microstructures of the resultant copolymers were analyzed by NMR and ATR-IR spectroscopy, revealing linear structures with incorporations of difunctionalized side chains bearing both allyl ether units and polar cyclic groups. Mechanical property studies exhibited better strain-at-break of these copolymers compared to the non-polar polyethylene, among which the copolymer E-FUR with the incorporation of 0.3 mol% displayed the highest strain-at-break and stress-at-break values of 940% and 35.9 MPa, respectively