Implications of the BATTERY 2030+ AI-Assisted Toolkit on Future Low-TRL Battery Discoveries and Chemistries

Funder: Swedish national Strategic e‐Science programmeFunder: Deutsche Forschungsgemeinschaft; Id: http://dx.doi.org/10.13039/501100001659BATTERY 2030+ targets the development of a chemistry neutral platform for accelerating the development of new sustainable high-performance batteries. Here, a description is given of how the AI-assisted toolkits and methodologies developed in BATTERY 2030+ can be transferred and applied to representative examples of future battery chemistries, materials, and concepts. This perspective highlights some of the main scientific and technological challenges facing emerging low-technology readiness level (TRL) battery chemistries and concepts, and specifically how the AI-assisted toolkit developed within BIG-MAP and other BATTERY 2030+ projects can be applied to resolve these. The methodological perspectives and challenges in areas like predictive long time- and length-scale simulations of multi-species systems, dynamic processes at battery interfaces, deep learned multi-scaling and explainable AI, as well as AI-assisted materials characterization, self-driving labs, closed-loop optimization, and AI for advanced sensing and self-healing are introduced. A description is given of tools and modules can be transferred to be applied to a select set of emerging low-TRL battery chemistries and concepts covering multivalent anodes, metal-sulfur/oxygen systems, non-crystalline, nano-structured and disordered systems, organic battery materials, and bulk vs. interface-limited batteries

Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4

Classical electrodes for Li-ion technology operate by either single-phase or two-phase Li insertion/de-insertion processes, with single-phase mechanisms presenting some intrinsic advantages with respect to various storage applications. We report the feasibility to drive the well-established two-phase room-temperature insertion process in LiFePO4 electrodes into a single-phase one by modifying the material's particle size and ion ordering. Electrodes made of LiFePO4 nanoparticles (40 nm) formed by a low-temperature precipitation process exhibit sloping voltage charge/discharge curves, characteristic of a single-phase behaviour. The presence of defects and cation vacancies, as deduced by chemical/physical analytical techniques, is crucial in accounting for our results. Whereas the interdependency of particle size, composition and structure complicate the theorists' attempts to model phase stability in nanoscale materials, it provides new opportunities for chemists and electrochemists because numerous electrode materials could exhibit a similar behaviour at the nanoscale once their syntheses have been correctly worked out

Blended Positive Electrodes for Li‐Ion Batteries: From Empiricism to Rational Design

Physical mixtures (i. e. blends) of two or more active materials are often used in commercial batteries to achieve better performance than what can be attained with a single component. This approach has been empirically driven and found to result in relevant synergistic improvements that are unfortunately poorly understood at a fundamental level. Indeed, internal redox processes (which induce structural changes in the components) can take place in blended electrodes that are severely influenced by electrode kinetics. These are in turn affected by temperature and also electrode formulation. Despite difficulties ahead, efforts to understand such issues are needed to pave the way for a rational electrode design enabling optimized performance which ideally could be tuned to match specific application requirements.Authors are grateful to ALISTORE‐ERI colleagues for helpful discussions. ICMAB‐CSIC members thank the Spanish Ministry for Economy, Industry and Competitiveness Severo Ochoa Programme for Centres of Excellence in R&D (CEX2019‐000917‐S) and funding through grant MAT2017‐86616‐R. MCC is also grateful to Spanish Ministry for Economy, Industry and Competitiveness for funding through grant PID2019‐107106RB‐C33.Peer reviewe

Carbon dioxide sensing properties of bismuth cobaltite

Bismuth cobaltite with sillenite-type structure was prepared from Co(OH)2 and Bi(NO3)3·6H2O through solid state reaction at 600 °C. Neutron powder diffraction (NPD) data and X-ray absorption spectroscopy revealed the existence of mixed oxidation states for cobalt in this compound, the chemical formula being Bi 12(Bi0.55Co0.45)O19.6. The gas sensing properties of Bi12(Bi0.55Co0.45)O 19.6 were characterized by alternating current, at 200, 300 and 400 °C. The optimal response was observed at 400 °C, using a frequency of 100 kHz. © 2011 Elsevier B.V

Microstructural analysis of nickel hydroxide: Anisotropic size versus stacking faults

11 pages.-- PACS: 61.72.Nn; 61.10.Nz; 61.72.Ff; 68.37.LpTwo different approaches for studying sample's contributions to diffraction-line broadening are analyzed by applying them to several nickel hydroxide samples. Both are based in the refinement of powder diffraction data but differ in the microstructural model used. The first one consists in the refinement of the powder diffraction pattern using the FAULTS program, a modification of DIFFaX, which assigns peak broadening mainly to the presence of stacking faults and treats finite size effects by convolution with a Voigt function. The second method makes use of the program FULLPROF, which allows the use of linear combinations of spherical harmonics to model peak broadening coming from anisotropic size effects. The complementary use of transmission electron microscopy has allowed us to evaluate the best approach for the Ni(OH)2 case. In addition, peak shifts, corresponding to reflections 10l (l0) were observed in defective nickel hydroxide samples that can be directly correlated with the degree of faulting.Peer reviewe

Defect chemistry and catalytic activity of nanosized Co3O 4

Nanometric cobalt oxide Co3O4 powders made of 4 nm isotropic particles, directly precipitated from Co2+ aqueous solutions under alkaline and oxidizing conditions, are found to exhibit abnormal X-ray diffraction intensities, mainly in (111) and (220) reflections, because of a significant amount of displaced Co atoms from ideal 8a and 16d positions to interstitial 48f and 16c sites. Upon heating, the Co/O stoichiometry is maintained and the delocalized atoms progressively migrate to stable positions through empty neighboring sites. Despite the presence of such defects, the order of reaction (n ̃ 1) and the activation energy (Ea ̃ 60 ± 5 kJ/mol) versus the decomposition of diluted solutions of hydrogen peroxide solutions is found to be similar to bulk nonfaulted Co3O4 materials, but the intrinsic rate constants k20 °C are found to be proportionally enhanced by both the defect and microstrains levels. Last, a careful selection of monolithic samples, so as to keep away the catalytic influence of the intercrystallites reactive grainboundaries, has enabled us to precisely study and isolate the role of the structural characteristics on the catalytic activity of Co3O4 toward H2O 2 decomposition. The catalytic activity of such divided oxides toward this reaction is also put forward as a fast selection tool for catalysts in Li-oxygen secondary cells. © 2009 American Chemical Society

Existence of superstructures due to large amounts of Fe vacancies in the LiFePO4-type framework

LiFePO4 has been under intense scrutiny over the past decade because it stands as an attractive positive electrode material for the next generation of Li-ion batteries to power electric vehicles and hybrid electric vehicles, hence the importance of its thermal behavior. The reactivity of LiFePO4 with air at moderate temperatures is shown to be dependent on its particle size. For nanosized materials, a progressive displacement of Fe from the core structure leading to a composite made of nanosize Fe 2O3 and highly defective, oxidized LixFe yPO4 compositions, among which the 'ideal' formula LiFe2/3PO4. Herein we report, from both temperature-controlled X-ray diffraction and electronic diffraction microscopy, that these off-stoichiometry olivine-type compounds show a defect ordering resulting in the formation of a superstructure. Such a finding shows striking similarities with the temperature-driven oxidation of fayalite Fe 2SiO4 (another olivine) to structurally defective laihunite, reported in the literature three decades ago. © 2010 American Chemical Society