PED304_EN

PED304

Project Name
High-performance nanocomposites for Li-ion battery anodes based on Sn, Si, Ge nanoalloys and single-walled carbon nanohorns (SWCNHs) / reduced graphene oxide nanosheets (RGOs)

Contract nr. 304PED/2020

Programme: Priority 2 - Enhancement of the romanian economy competitivity by research, development and innovation

Project type: Demonstrative-Experimental Project

Project Director: Fleacă Claudiu Teodor
Coordinator: National Institute for Lasers, Plasma and Radiation Physics (INFLPR Magurele)
Partner: National Research and Development Institute for Cryogenic and Isotopic Technologies  (ICSI Rm. Vâlcea)

Financing source: Executive Unit for Funding Higher Education, Research, Development and Innovation (UEFISCDI)

Project Abstract:

The project aims to obtain, characterize and test advanced nanostructured hybrid materials that can be used for anodes in modern Li-ion batteries that require both a high mass storage capacity of energy (well above the value of ~300 mAh/g characteristic of graphite) as well as maintaining this performance over hundreds of loading-unloading cycles. To achieve these performances we will combine the elements of the main group IV - Sn, Si, Ge (which has a very high capacity to incorporate Li) in the form of alloy nanoparticles obtained by laser pyrolysis or laser ablation with carbon nanostructures that possess a large specific surface - single-walled carbon nanohorns (SWCNHs) also synthesized by laser ablation and reduced graphene oxide nanosheets obtained from hydrophilic graphene oxide by reduction. Thus, the large volume variation characteristic of the litiation-delitiation process of Si, Sn and Ge can be damped, ensuring a good electrical conductivity and avoiding the degradation of the anode. Obtaining SWCNHs-nanoparticle nanocomposites will be done either by surface oxidation (hydrophilization) of nanohorns followed by suspension mixing with nanoparticles and drying, or directly by the simultaneous ablation of two adjacent targets, one graphite and the other metal / metalloid (Sn, Si , Ge in various proportions). The ternary composite will also be obtained in suspension by reducing the aqueous mixture suspended by SWCNHs-nanoparticles and graphene oxide chemically or by irradiating the mixture suspended in liquid nitrogen with the infrared laser. For the battery tests, the nanocomposites will be mixed with auxiliary materials, resulting in anodes that will be encapsulated in half-cells with metallic Li cathode and LiPF6 electrolyte in a mixture of organic carbonates and will be subjected to a series of loading-unloading cycles.

First phase - 31/12/2020

Synthesis, characterization and testing on anodes for Li-ion batteries of the reference nanocomposites.

Phase I duration: 03/08/2020-31/12/2020

The value allocated to the project from the state budget for 2020:  198.000 RON

Dissemination of the results

Manuscript entitled “From coffee rings” to thick colloidal crystals, through drop spread inhibition by the substrate edge” (authors I. Sandu, C.T. Fleacă, F. Dumitrache, B. Sava, I. Urzică, M. Dumitru)   submitted to  Colloids and Surfaces Journal

Second phase - 31/12/2021

Synthesis, characterization and anode testing for Li-ion batteries for nanocomposites containing Si-Ge, Si-Sn or Sn-Ge nanoalloys and SWCNHs/RGO.

Phase II duration: 01/01/2021-31/12/2021

The value allocated to the project from the state budget for 2021:  300.000 RON

Dissemination of the results

Posters presented at International Conferences

C. Fleaca, F. Dumitrache, M. Buga, A. Spinu-Zaulet, C. Ungureanu, S. Enache, A.-M. Banici, E. Dutu, M. Dumitru, Laser pyrolysis Silicon nanoparticles and their nanocomposites with Reduced Graphene Oxide (RGO) sheets for Li-ion battery anodes, 2021 EMRS Fall Meeting Virtual Conference, 20-23 september 2021 (previous in  Warsaw, Poland)

F. Dumitrache, C. Fleaca, D. Craciun, L. Gavrila-Florescu, E. Goncearenco, I.P.  Morjan, I. Sandu, M. Buga, S. Enache, G. Prodan, Composite nanoparticles containing silicon and tin phases synthesized by Laser pyrolysis for Li-ion battery anodes, 2021 EMRS Fall Meeting Virtual Conference, 20-23 september 2021 (previous in Warsaw, Poland)

C. Fleaca, F. Dumitrache, M. Buga, A. Spinu-Zaulet, C. Ungureanu, S. Enache, A.-M. Banici, E. Dutu, M. Dumitru, Laser  pyrolysis SnOx nanoparticles - characterization and testing for Li-ion battery anodes, XXIIIrd International (Virtual) Conference New Cryogenic and Isotope Technologies for Energy and Environment – EnergEn 2021, 26-29 oct. 2021 (previous in Băile Govora, Romania)

Scientific articles published in ISI-quoted journals

G. Huminic, A. Huminic, C. Fleacă, F. Dumitrache, I. Morjan, Experimental study on contact angle of water based Si-C nanofluid, J. Molec. Liquids 332 (2021) 115833. DOI: 10.1016/j.molliq.2021.115833

M.-R. Buga, A.A. Spinu-Zaulet, C.G. Ungureanu, R.-A. Mitran, E. Vasile, M. Florea, F. Neatu, Carbon-Coated SiO₂ Composites as Promising Anode Material for Li-Ion Batteries, Molecules 2021, 26, 4531. DOI: 10.3390/molecules26154531

I. Sandu, C.T. Fleaca, F. Dumitrache, B.A. Sava, I. Urzica, I. Antohe, S. Brajnicov, M. Dumitru, Shaping in the Third Direction; Synthesis of Patterned Colloidal Crystals by Polyester Fabric-Guided Self-Assembly, Polymers 2021, 13, 4081. DOI: 10.3390/polym13234081

The manuscript entitled From thin “coffee rings” to thick colloidal crystals, trough drop spreading inhibition by the substrate edge – authors  I. Sandu, C.T. Fleacă, F. Dumitrache, B. Sava, I.Urzică and M. Dumitru – initially submitted  in 2020 to Colloids and Surfaces A journal and reported at Phase I  was finally published in Applied Physics A   127 (2021) 325 (9 pag.),  DOI: 10.1007/s00339-021-04447-3

Third phase  - 03/08/2022

Synthesis, characterization and anode testing for Li-ion batteries of nanocomposites containing ternary Si-Ge-Sn nanoalloys and carbonaceous 3D/2D SWCNHs/RGO nanostructures

Phase III duration: 01/01/2022-03/08/2021

The value allocated to the project from the state budget for 2021:  102.000 RON

Dissemination of the results

Posters presented at International Conferences

C. Fleaca, F. Dumitrache, V. Craciun, M. Dumitru, L. Gavrila-Florescu,  M. Buga, A. Spinu-Zaulet, C. Ungureanu, Laser-pyrolysis Ge-Si based nanoparticles and their composites with reduced Graphene oxide for Li-ion battery anodes, 2022 EMRS Spring Meeting Virtual Conference, 30 may - 3 june 2022

C.T. Fleaca, F. Dumitrache, V. Craciun, E. Goncearenco, E. Dutu, I.P. Morjan, L. Gavrila-Florescu, M. Dumitru, V.A. Maraloiu, M. Buga, Ternary Si-Ge-Sn Based Nanopowders Synthesized by Single-Step Laser Pyrolysis, Int. Conf. on Laser, Plasma and Radiation - Science and Technology ICLPR-ST, 7-10 june 2022, Bucharest, Parliament Palace, Romania

Scientific articles published in ISI-quoted journals

I.P. Morjan, E. Dutu, C.T. Fleaca, F. Dumitrache, I. Morjan,  N. Mihailescu, M. Demian, V.S. Teodorescu, M. Scarisoreanu, Effect of annealing on the structural, optical and electrical properties of (F, Zn) double doped SnO₂ nanoparticles obtained by the laser pyrolysis method,  Mater. Sci. Semicond. Proc. 142 (2022) 106511

G. Huminic, A. Vardaru, A. Huminic, C. Fleaca, F. Dumitrache, I. Morjan, Water-Based Graphene Oxide - Silicon Hybrid Nanofluids - Experimental and Theoretical Approach, Int. J. Mol. Sci. 2022, 23, 3056 (16 pag.). DOI:10.3390/ijms23063056

I. Sandu, C.T. Fleacă, F. Dumitrache, B.A. Sava, I. Urzică, I. Antohe, S. Brajnicov, M. Dumitru, Shaping in the Third Direction; Fabrication of Hemispherical Micro-Concavity Array by Using Large Size Polystyrene Spheres as Template for Direct Self-Assembly of Small Size Silica Spheres,  Polymers2022, 14, 2158 (15 pag.).  DOI:10.3390/polym14112158

A. Vardaru, G. Huminic, A. Huminic, C. Fleaca, F. Dumitrache, I. Morjan, Synthesis, characterization and thermal conductivity of water based graphene oxide–silicon hybrid nanofluids: An experimental approach, Alexandria Eng. J. 61 (2022) 12111–12122

Patent proposals submitted to OSIM

A100455/28.iul.2022  - Procedeu de obținere de nanoparticule Ge-Si ca material activ pentru anozi ai bateriilor reîncărcabile cu ioni de Li ,  autori C. Fleaca, F. Dumitrache, L. Gavrila-Florescu, M. Dumitru, E. Goncearenco,  M. Scarisoreanu, M.R. Buga, G.C. Ungureanu

Brief presentation of the results obtained in the framework of PROJECT PED 304/2020

Nanoparticles (NPs) based on Si, Sn  (fig.2 left) and/or Ge were synthesized by infrared laser pyrolysis from  gas/vapor phase presursors (fig.1). These NPs were combined with Reduced Graphene Oxide (RGO) and/or Single-walled Carbon Nanohorns (SWCNHs) to obtain active composites for energy storage in high-performance Li-ion rechargeable battery anodes. The best performing anode with such composites (SiSn9-RGO, fig. 2 right) presented after a charge/discharge protocol repeated 5 times at the rate of C/2 and 200 times at a rate of 1C an excellent 100% Coulombic Efficiency and a Discharge Capacity of 889 mAh/g (fig.3), more than twice the theoretical graphite of 372 mAh/g widely used in commercial Li-ion battery anodes.

Fig.1 Laser pyrolysis installation sketch used for the synthesis of Si, Sn and/or Ge nanoparticles

Fig.2 SEM images of SiSn9 nanoparticles  (left) and SiSn9-RGO  nanocomposite (right)

Fig.3 Cyclic stability profile (5 cycles at C/2 and 200 cycles at 1C) for SnSi9-RGO anode