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Microwave-Assisted Nonaqueous Synthesis of Nanocrystalline Lithium Transition Metal Phosphates for Battery Applications

English title Microwave-Assisted Nonaqueous Synthesis of Nanocrystalline Lithium Transition Metal Phosphates for Battery Applications
Applicant Niederberger Markus
Number 124632
Funding scheme Project funding (Div. I-III)
Research institution Departement Materialwissenschaft ETH Zürich
Institution of higher education ETH Zurich - ETHZ
Main discipline Material Sciences
Start/End 01.04.2009 - 31.07.2012
Approved amount 185'775.00
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All Disciplines (2)

Discipline
Material Sciences
Inorganic Chemistry

Keywords (6)

nanoparticles; lithium metal phosphates; microwave chemistry; battery applications; electrochemistry; Lithium iron phosphate

Lay Summary (English)

Lead
Lay summary
Energy storage based on rechargeable lithium batteries is of greatest technological importance due to the rapidly increasing number of portable electronic devices such as cell phones, laptops, digital cameras, or music players. The need for clean and efficient energy storage is immense, and nanomaterials are expected to play a critical role in this development. Nanoparticulate lithium transition metal phosphates, and especially LiFePO4, represent a promising alternative to other well-studied oxide-based lithium intercalation compounds, because they are environmentally benign, cheap, and provide high thermal and chemical stability. In spite of the growing interest in lithium metal phosphate nanoparticles, most of the syntheses still involve high-temperature solid-state routes, which do not allow any size and shape control. An interesting, relatively recent approach for the synthesis of inorganic nanoparticles involves the use of microwave irradiation. The microwave heating technique allows precise control of the temperature, fast thermal ramping, and the direct energy transfer suppresses the wall effect, which is responsible for thermal gradients and inhomogeneous reactions.The objective of the proposed research is directed towards the development of nonaqueous liquid-phase synthesis routes to lithium transition metal phosphates LiMPO4 (M=Mn, Fe, Co, Ni) using microwave irradiation as heating tool, and study of the electrochemical properties with respect to their application as cathode material in lithium ion batteries. The first part of the research project deals with the elaboration of synthesis routes to phospho-olivine nanoparticles involving the microwave-mediated reaction of various molecular precursors in organic solvents at temperatures less than 200 °C. Systematic variation of precursor-solvent combinations will make it possible to prepare lithium transition metal phosphates with different particle sizes and shapes. In a next step the electrochemical properties will be studied at the Electrochemistry Laboratory of the Paul Scherrer Institute in Villigen in close collaboration with the group of Dr. Petr Novak. Another integral part of the project is the chemical modification of the lithium transition metal phosphate nanoparticles to increase the electronic conductivity, either by doping with supervalent ions or by coating with a conductive phase.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Formation Mechanism of LiFePO4 Sticks Grown by a Microwave-Assisted Liquid-Phase Process
Carriazo D, Rossell MD, Zeng GB, Bilecka I, Erni R, Niederberger M (2012), Formation Mechanism of LiFePO4 Sticks Grown by a Microwave-Assisted Liquid-Phase Process, in SMALL, 8(14), 2231-2238.
Microwave-Assisted Nonaqueous Sol-Gel Chemistry for Highly Concentrated ZnO-Based Magnetic Semiconductor Nanocrystals
Bilecka I, Luo L, Djerdj I, Rossell MD, Jagodic M, Jaglicic Z, Masubuchi Y, Kikkawa S, Niederberger M (2011), Microwave-Assisted Nonaqueous Sol-Gel Chemistry for Highly Concentrated ZnO-Based Magnetic Semiconductor Nanocrystals, in JOURNAL OF PHYSICAL CHEMISTRY C, 115(5), 1484-1495.
Microwave-assisted solution synthesis of doped LiFePO4 with high specific charge and outstanding cycling performance
Bilecka I, Hintennach A, Rossell MD, Xie D, Novak P, Niederberger M (2011), Microwave-assisted solution synthesis of doped LiFePO4 with high specific charge and outstanding cycling performance, in JOURNAL OF MATERIALS CHEMISTRY, 21(16), 5881-5890.
Simultaneous formation of ferrite nanocrystals and deposition of thin films via a microwave-assisted nonaqueous sol-gel process
Bilecka I, Kubli M, Amstad E, Niederberger M (2011), Simultaneous formation of ferrite nanocrystals and deposition of thin films via a microwave-assisted nonaqueous sol-gel process, in JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, 57(3), 313-322.
Microwave chemistry for inorganic nanomaterials synthesis
Bilecka I, Niederberger M (2010), Microwave chemistry for inorganic nanomaterials synthesis, in NANOSCALE, 2(8), 1358-1374.
Microwave-Assisted Nonaqueous Sol-Gel Deposition of Different Spinel Ferrites and Barium Titanate Perovskite Thin Films
Kubli M, Luo L, Bilecka I, Niederberger M (2010), Microwave-Assisted Nonaqueous Sol-Gel Deposition of Different Spinel Ferrites and Barium Titanate Perovskite Thin Films, in CHIMIA, 64(3), 170-172.
New developments in the nonaqueous and/or non-hydrolytic sol-gel synthesis of inorganic nanoparticles
Bilecka I, Niederberger M (2010), New developments in the nonaqueous and/or non-hydrolytic sol-gel synthesis of inorganic nanoparticles, in ELECTROCHIMICA ACTA, 55(26), 7717-7725.
Efficient microwave-assisted synthesis of LiFePO4 mesocrystals with high cycling stability
Bilecka I, Hintennach A, Djerdj I, Novak P, Niederberger M (2009), Efficient microwave-assisted synthesis of LiFePO4 mesocrystals with high cycling stability, in JOURNAL OF MATERIALS CHEMISTRY, 19(29), 5125-5128.
Kinetic and Thermodynamic Aspects in the Microwave-Assisted Synthesis of ZnO Nanoparticles in Benzyl Alcohol
Bilecka I, Elser P, Niederberger M (2009), Kinetic and Thermodynamic Aspects in the Microwave-Assisted Synthesis of ZnO Nanoparticles in Benzyl Alcohol, in ACS NANO, 3(2), 467-477.

Collaboration

Group / person Country
Types of collaboration
Paul Scherrer Institute Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Fall Meeting of the Swiss Chemical Society Talk given at a conference 16.09.2010 Zurich, Switzerland Niederberger Markus; Bilecka Idalia;
11th International Conference on Ceramic Processing Science Talk given at a conference 29.08.2010 Zurich, Switzerland Bilecka Idalia; Niederberger Markus;
MRS Spring Meeting Poster 05.04.2010 San Francisco, United States of America Niederberger Markus; Bilecka Idalia;
Euromat Talk given at a conference 07.09.2009 Glasgow, Great Britain and Northern Ireland Niederberger Markus; Bilecka Idalia;
XVth International Sol-Gel Conference Poster 23.08.2009 Porto de Galinhas, Brazil Niederberger Markus; Bilecka Idalia;
EMRS Spring Meeting Talk given at a conference 08.06.2009 Strasbourg, France Niederberger Markus; Bilecka Idalia;


Associated projects

Number Title Start Funding scheme
144437 Microwave-assisted preparation of composite cathodes for lithium ion batteries 01.01.2013 Project funding (Div. I-III)
144437 Microwave-assisted preparation of composite cathodes for lithium ion batteries 01.01.2013 Project funding (Div. I-III)
119741 Development of Concepts for the Size- and Shape-Controlled Synthesis of Metal Oxide Nanoparticles in Surfactant-Free Reaction Systems 01.04.2008 Project funding (Div. I-III)

Abstract

The objective of the proposed research is directed towards the development of nonaqueous liquid-phase synthesis routes to lithium transition metal phosphates LiMPO4 (M=Mn, Fe, Co, Ni) using microwave irradiation as heating tool, and study of the electrochemical properties with respect to their application as cathode material in lithium ion batteries.Lithium transition metal phosphates are one of the most promising candidates to replace the expensive and oxidatively unstable LiCoO2 in cathodes of secondary lithium batteries. LiFePO4 for example has a discharge voltage of about 3.4 V vs. lithium, shows no obvious fading even after several hundred cycles, exhibits high power capabilities, and its theoretical energy density is 550 W h/kg, which is higher than obtained in commercial LiCoO2 cells. Moreover, it is very stable during discharge/recharge, can be produced from low-price components and is non-toxic. Remaining challenges are how to make these materials by a low-cost process, ideally involving no energy intensive high temperature firing, and how to increase its electronic conductivity.The first part of the research project deals with the elaboration of synthesis routes to phospho-olivine nanoparticles involving the microwave-mediated reaction of various molecular precursors in organic solvents at temperatures less than 200 °C. Preliminary results (see Section 2.3) have already proven that it is possible to directly produce nanocrystalline LiFePO4 in benzyl alcohol at 200 °C after just a few minutes of microwave irradiation. However, these synthesis protocols have to be reproduced, optimized and extended to other phospho-olivines such as LiMnPO4, LiCoPO4, and LiNiPO4. Systematic variation of precursor-solvent combinations will make it possible to prepare lithium transition metal phosphates with different particle sizes and shapes.In a next step the electrochemical properties of these nanopowders have to be studied. These investigations will be performed at the Electrochemistry Laboratory of the Paul Scherrer Institute in Villigen in close collaboration with the group of Dr. Petr Novak. If the electrochemical properties exhibit size- and shape-dependent behaviour, the morphology of the nanoparticles will be optimized with respect to their performance as cathode material.Another integral part of the project is the chemical modification of the lithium transition metal phosphate nanoparticles to increase the electronic conductivity. We foresee two possibilities, namely doping with supervalent ions or including a conductive phase. Although these ideas are not new, we know from our experience with metal oxides that microwave irradiation is particularly suitable for the preparation of doped materials, as well as for the synthesis of core-shell-like structures.In summary, the proposed research will target the following goals:i)Development of synthesis routes to nanocrystalline lithium transition metal phosphates with high crystallinity using microwave irradiation as heating toolii)Systematic variation of precursor-solvent combination to achieve different particle sizes and shapesiii)Fabrication of electrodes and study of the electrochemical propertiesiv)Modification of the electrical conductivity of the lithium metal phosphate nanoparticles, either by doping with supervalent ions or by coating with a conducting layer (e.g. metal or metal oxides)
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