Norbornene-Functionalized Plant Oils for Biobased Thermoset Films and Binders of Silicon-Graphite Composite Electrodes

Abstract

We herein report the functionalization of plant oil with norbornene (NB) and subsequent polymerization to prepare biobased thermoset films and biobased binders for silicon/mesocarbon microbead (MCMB) composite electrodes for use in lithium-ion batteries. A series of NBfunctionalized plant oils were prepared as biobased thermoset films via ringopening metathesis polymerization (ROMP) in the presence of a secondgeneration Grubbs catalyst with tunable thermomechanical properties. Increasing the catalyst loading and cross-linking agent increased cross-link density, storage modulus (E′), and glass transition temperature (T g ), while the numbers of unreacted or oligomeric components in the films were reduced. High number of NB rings per triglyceride in the plant oil encouraged monomer incorporation to form a polymer network, therefore accounting for the high T g and E′ values. Furthermore, the NB-functionalized plant oil and 2,5-norbornadiene (NBD) were copolymerized as bioderived binders for silicone/MCMB composite electrodes of lithium-ion batteries via ROMP during electrode preparation. Cell performance investigation showed that the silicone/MCMB composite electrode bearing the NBD-cross-linked NB-functionalized plant oil binder exhibited a higher C-rate and cycle-life performance than that using a conventional poly(vinylidene fluoride) (PVDF) binder. Finally, the electrode based on the bioderived binder exhibited a high specific charge capacity of 620 mA h g −1 at 0.5 C.

Synthesis of Bio-Based Aliphatic Polyesters from Plant Oils by Efficient Molecular Catalysis: A Selected Survey from Recent Reports

“…As described above, ADMET polymerization has been employed for synthesis of aliphatic bio-based polyesters. − ,− However, the resultant polymer contained internal olefinic double bonds, which have to be hydrogenated to obtain saturated aliphatic polyesters, which should possess high melting temperature in semicrystalline polymers in addition to better stability. As exemplified in Scheme , and also exemplified above (Schemes , , and ), ,,, the (exhaustive) hydrogenation of ADMET polymers generally requires rather harsh conditions. − For sample preparation in the laboratory, we often use p -toluenesulfonyl hydrazide for the purpose (not in catalytic amount), − even with ROMP polymers. , …”

“…In particular, as focused on in this Perspective, development of advanced polyesters, which display tunable mechanical properties and biodegradability, from so-called bio-based monomers by precise polymerization techniques attracts considerable attention. − Plant oils, ,− ,− generally obtained as fatty acids or fatty acid methyl esters by chemical modifications, have been considered as a useful renewable feedstock especially for synthesis of the (semicrystalline) aliphatic polyesters, whereas many studies have thus been known for synthesis of polyesters from the other renewable resources such as lignin, sugars, ,,− and terpenes. ,, As described below, study on efficient conversion of plant oils, such as isomerization alkoxycarbonylation, olefin metathesis (including so-called ethenolysis) routes, or new catalysts for the transesterification, attracts considerable attention.…”

Digital Light Processing 3D Printing of Isosorbide- and Vanillin-Based Ester and Ester–Imine Thermosets: Structure–Property Recyclability Relationships

“…Using a similar approach, Schen et al synthesized biobased epoxy thermosets by curing epoxidized vanillic acid, epoxidized plant-based phenolic acids, or epoxidized soybean oil with an anhydride curing agent, achieving degradation in NaOH solution in duration dependent on the epoxide content, monomer structure, degree of hydrophilicity, cross-linking density, and glass transition temperature. More recently, Le et al proposed the ring-opening metathesis polymerization of norbornene-functionalized epoxidized soybean oil . Thanks to the presence of ester bonds, the resulting thermosets were degradable into small oligomers in NaOH or KOH solutions.…”

“…More recently, Le et al proposed the ring-opening metathesis polymerization of norbornene-functionalized epoxidized soybean oil. 21 Thanks to the presence of ester bonds, the resulting thermosets were degradable into small oligomers in NaOH or KOH solutions.…”