Radiolysis effect on Eu(III)-superplasticiser interactions in artificial cement and squeezed cement pore waters.

In the framework of the French deep geological repository for radioactive waste, cement-based materials are envisaged to immobilize radionuclides and/or provide protection from radiation to the environment. Superplasticisers (SPs) are added to these materials to increase their workability. SPs will undergo degradation by coupled radiolytic and hydrolytic effects in the pore solution leading to the formation of potentially complexing degradation products. The objective was to study the potential effect of radiolyzed superplasticizers contained in cement-based materials on radionuclide uptake. The Eu speciation and solubility with organic ligands resulting from the degradation of SPs were studied for the two solutions and the results were compared. Two different SPs were selected, a polycarboxylate ether and a polynapthalene sulfonate. Two different protocols were followed: direct irradiation of the solution containing the superplasticizer, and irradiation of the compacted cement sample followed by extraction of the pore water. Solubility enhancements observed in artificial cement waters are not representative of real cement pore water interactions, in agreement with other studies. Finally, the effects of alkaline hydrolysis and radiolysis of SPs on Eu solubility in pore water are limited.

Electrolytes Ageing in Lithium-ion Batteries: A Mechanistic Study from Picosecond to Long Timescales.

The ageing phenomena occurring in various diethyl carbonate/LiPF6 solutions are studied using gamma and pulse radiolysis as a tool to generate similar species as the ones occurring in electrolysis of Li-ion batteries (LIBs). According to picosecond pulse radiolysis experiments, the reaction of the electron with (Li(+), PF6(-)) is ultrafast, leading to the formation of fluoride anions that can then precipitate into LiF(s). Moreover, direct radiation-matter interaction with the salt produces reactive fluorine atoms forming HF(g) and C2H5F(g). The strong Lewis acid PF5 is also formed. This species then forms various R(1)R(2)R(3) P=O molecules, where R is mainly -F, -OH, and -OC2H5. Substitution reactions take place and oligomers are slowly formed. Similar results were obtained in the ageing of an electrochemical cell filled with the same model solution. This study demonstrates that radiolysis enables a description of the reactivity in LIBs from the picosecond timescale until a few days.

Radiolysis as a solution for accelerated ageing studies of electrolytes in Lithium-ion batteries.

Diethyl carbonate and dimethyl carbonate are prototype examples of eco-friendly solvents used in lithium-ion batteries. Nevertheless, their degradation products affect both the battery performance and its safety. Therefore, it is of paramount importance to understand the reaction mechanisms involved in the ageing processes. Among those, redox processes are likely to play a critical role. Here we show that radiolysis is an ideal tool to generate the electrolytes degradation products. The major gases detected after irradiation (H2, CH4, C2H6, CO and CO2) are identified and quantified. Moreover, the chemical compounds formed in the liquid phase are characterized by different mass spectrometry techniques. Reaction mechanisms are then proposed. The detected products are consistent with those of the cycling of Li-based cells. This demonstrates that radiolysis is a versatile and very helpful tool to better understand the phenomena occurring in lithium-ion batteries.

Stability of [MeBu3N][Tf2N] under gamma irradiation.

The stability of the ionic liquid [MeBu3N][Tf2N], dry or after contact with water (where [MeBu3N]+ is the methyltributylammonium cation and [Tf2N](-) is the bistriflimide anion), was studied under 137Cs gamma irradiation in argon and in air. In a quantitative study with an absorbed dose of 2 MGy this ionic liquid was highly stable regardless of the radiolysis conditions. The radiolytic disappearance yields determined by ESI-MS were -0.38 and -0.25 micromol J(-1) for the cation and anion, respectively. ESI-MS, NMR, and liquid chromatography coupled with ESI-MS identified a large number of degradation products in very small quantities for the same dose. The cation radicals were formed by the loss of a Bu group, the Me group, or two H atoms to form a double bond with the butyl chain. Radiolysis of the anion produced mainly F and CF3 radicals. The anion radicals recombined with the cation to form a wide range of secondary degradation products regardless of the radiolysis conditions.