Microbially Induced Mineralization of Layered Mn Oxides Electroactive in Li Batteries

Abstract

Nanoparticles produced by bacteria, fungi, or plants generally have physicochemical properties such as size, shape, crystalline structure, magnetic properties, and stability which are difficult to obtain by chemical synthesis. For instance, Mn(II)oxidizing organisms promote the biomineralization of manganese oxides with specific textures under ambient conditions. Controlling their crystallinity and texture may offer environmentally relevant routes of Mn oxide synthesis with potential technological applications, e.g., for energy storage. However, whereas the electrochemical activity of synthetic (abiotic) Mn oxides has been extensively studied, the electroactivity of Mn biominerals has been seldom investigated yet. Here we evaluated the electroactivity of biologically induced biominerals produced by the Mn(II)-oxidizer bacteria Pseudomonas putida strain MnB1. For this purpose, we explored the mechanisms of Mn biomineralization, including the kinetics of Mn(II) oxidation, under different conditions. Manganese speciation, biomineral structure, and texture as well as organic matter content were determined by a combination of X-ray diffraction, electron and X-ray microscopies, and thermogravimetric analyses coupled to mass spectrometry. Our results evidence the formation of an organic-inorganic composite material and a competition between the enzymatic (biotic) oxidation of Mn(II) to Mn(IV) yielding MnO 2 birnessite and the abiotic formation of Mn(III), of which the ratio depends on oxygenation levels and activity of the bacteria. We reveal that a subtle control over the conditions of the microbial environment orients the birnessite to Mn(III)-phases ratio and the porosity of the assembly, which both strongly impact the bulk electroactivity of the composite biomineral. The electrochemical properties were tested in lithium battery configuration and exhibit very appealing performances (voltage, capacity, reversibility, and power capability), thanks to the specific texture resulting from the microbially driven synthesis route. Given that such electroactive Mn biominerals are widespread in the environment, our study opens an alternative route for the synthesis of performing electrode materials under environment-friendly conditions.

Forced Biomineralization: A Review

“…Recently, it was hypothesized [ 129 ] that Mn biominerals, which are widespread in the environment, could be used for the synthesis of new electrode materials.…”

Biologically Assisted One-Step Synthesis of Electrode Materials for Li-Ion Batteries

“…Continuous wave (CW) measurements were performed with an X-band Bruker Elexsys E580 spectrometer operating at 9.6 GHz at room temperature, with a modulation frequency of 100 kHz, modulation amplitude of 2 gauss and 2 mW (for powders) or 10 mW (for solutions) of microwave power. Before EPR analyses, powder samples (H 0.5 MnO 2 , planktonic-MnO 2 [ 22 ] and biofilm-MnO x ) were filled into 3 mm quartz tubes, whereas 2 mm quartz tubes were used to analyze the liquid samples.…”

“…To do this, our approach has comprised using microbial biomineralization to synthesize a Mn-oxide-based electrode. Microbial biomineralization proceeding under soft conditions, i.e., at ambient temperature and in aqueous media, offers a possible abatement of the energetic cost for making electrode materials, as already reported for Fe-phosphates [ 16 ], Fe-oxides [ 17 ], Co 3 O 4 [ 18 , 19 ], MnO x /C [ 20 ], MnO 2 [ 21 , 22 ] and CuO [ 23 ].…”

Mineralogical Characterization of Manganese Oxide Minerals of the Devonian Xialei Manganese Deposit

“…Compared with other TMOs, Mn oxide has a lower conversion reaction potential, especially MnO (standard potential is 1.03 V); it is widely available, and it is environmentally friendly. It is a multi-electron reaction with great potential for anode material [28]. The synthetic material K-OMS-2 has been designed to manufacture high-energy-density batteries [29,30].…”