Направленная модификация катодных материалов со структурой трифилина / Three-dimensional modification of triphylite-type cathode materials тема диссертации и автореферата по ВАК РФ 00.00.00, кандидат наук Назаров Евгений Евгеньевич

• Назаров Евгений Евгеньевич
• кандидат наук
• 2024

Оглавление диссертации кандидат наук Назаров Евгений Евгеньевич

Table of contents

Chapter 1. Introduction

Chapter 2. Literature review

2.1. Li-ion batteries, their application and motivation

2.2. Crystal structure and defect chemistry of LiFePO4

2.3. Substitution of Fe by higher redox potential 3d metals

2.4. Application of conductive carbon coatings

2.5. Synthesis of triphylite-type cathodes

2.6. Motivation and objectives

Chapter 3. Methodology

3.1. Synthesis methods

3.1.1. Solvothermal synthesis

3.1.2. Carbon coating application technique

3.1.3. Co-precipitation synthesis

3.2. Characterization techniques

3.2.1. Chemical composition estimation

3.2.2. Synchrotron X-ray, X-ray and neutron powder diffraction

3.2.3. 57Fe Mossbauer spectroscopy

3.2.4. Fourier transform infrared spectroscopy

3.2.5. Raman spectroscopy

3.2.6. Low-temperature nitrogen adsorption

3.2.7. Thermogravimetry

3.2.8. Tap density measurements

3.2.9. Scanning electron microscopy

3.2.10. Transmission electron microscopy

3.2.11. Electrochemical measurments

Chapter 4. Crystal structure modification

4.1. Characterization of Li-rich LFMP

4.2. Phase transformations during operation of the cathode material

Chapter 5. The surface modification and influence of carbon coating on the electrochemical properties of Lii+s(Fe0.5Mn0.5)1-sPO4

5.1. Characterization of Li-rich LFMP/C composites

5.2. Electrochemical properties of Li-rich LFMP/C composites

Chapter 6. Microstructure modifications of LFMP

6.1. Development of dittmarite precursor synthesis process

6.2. Dittmarite-LFMP-LFMP/C transformation

6.3 Upscaling of the precursor synthesis process

6.4 Electrochemical properties of microspherical LFMP

Chapter 7. Summary and outlook

Chapter 8. Conclusions

Bibliography

List of Figures

List of Tables

Acknowledgments

Введение диссертации (часть автореферата) на тему «Направленная модификация катодных материалов со структурой трифилина / Three-dimensional modification of triphylite-type cathode materials»

Chapter 1. Introduction

Modern trends in automotive and large grid storage systems dictate new requirements for active components: the materials should be stable during operation, have a high energy density in order to give an energy output necessary for the process, and more importantly - safety. Li ion batteries (LIBs) are considered as a predominant energy source for the above-mentioned applications. Among all known cathode materials for LIBs, lithium transition metal phosphates also referred as to triphylites meet most of the necessary requirements for the implementation in the described industries.

The thesis topic is relevant since the present research is focused on the modification of one of the most attractive cathode materials, LiFe0.5Mn0.5PO4 (LFMP) for the utilization in the area of electric transportation and large grid storage systems capable of replacing the conventional LiFePO4 (LFP). The materials modification includes the crystal structure design and the formation of Lh+a(Fe0.5Mn0.5)1-aPO4 (Lirich LFMP), surface modification and utilization of PAN as a carbon-coating agent, and morphology control with the application of dittmarite-type precursors. The outlined modifications not only allow reducing the impact of the materials drawbacks on its electrochemical performance, but also create a solid basis for semi-industrial production of the material.

The aim of the work is to investigate the influence of the outlined modifications on the key operational properties of LFMP: electrochemical performance, cycling stability, and kinetics. In order to fulfill the thesis goal, the following objectives should be addressed:

1. Solvothermal synthesis of Li-rich LFMP using lithium phosphate as a precursor, detailed description of the materials crystal structure and investigation of its Li+ de/intercalation mechanism.

2. Optimization of the carbon-coating technique with the utilization of PAN as a carbon-coating agent, description of the PAN-derived carbon-coated Li-rich LFMP operational properties and comparison of the obtained results with glucose-derived Li-rich LFMP/C.

3. Development of the dittmarite-type precursor (NH4Fe0.5Mn0.5PO4'H2O) by co-precipitation synthesis route with the production of spherical morphology particles. Investigation of the dittmarite-triphylite transformation process, characterization of the electrochemical properties of the produced LFMP.

A set of modern physicochemical methods was applied including powder x-ray diffraction (XRD), neutron powder diffraction, synchrotron powder and operando diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron diffraction (ED), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), electron energy loss spectroscopy (EELS),

Mossbauer spectroscopy, Raman spectroscopy, dynamic light scattering, inductively coupled plasma optical emission spectroscopy (ICP-OES), cycling voltammetry (CV), galvanostatic cycling, potentiostatic intermittent titration (PIT), impedance spectroscopy was used to characterize the materials under study.

The following statements to be defended disclose the scientific novelty of the present thesis work:

1. The joint neutron and synchrotron data-based crystal structure refinement reveals the presence of 7% of excess Li+. The refined chemical composition coincides well with Mossbauer spectroscopy results, indicating the occurrence of Fe3+ ions in the crystal lattice. According to operando X-ray diffraction and PIT data analysis the total Li+ solid-solution-type de/intercalation process covers 57% and 61% of the total charge and discharge respectively.

2. PAN as a carbon-coating precursor was applied for the surface modification of Li-rich LFMP cathode material. The obtained LFMP/C composite with PAN-derived carbon nanocoating was compared to the LFMP/C with glucose-decomposed carbon nanolayer. The utilization of PAN results in less charge transfer resistance during Mn2+ ^ Mn3+ transition affecting the overall cycling stability of the material. Capacity retention of the material after 1000 cycles at 5C-10C current density is 78±2%. As a comparison, the conventional glucose-derived carbon coating demonstrates only 43±3% in the same conditions.

3. The designed synthesis route involving the usage of dittmarite-type precursors for the production of LFMP results in the formation of microspherical powder with tap density of 1.44 g-cm-3. The produced material demonstrates more than 138 mAh-g-1 at C/10 and 90 mAh-g-1 at 5C current density and retains more than 85% and 86% of its initial capacity after 250 cycles at 5C and 1C rate respectively.

The achieved results of the discussed modifications implementation for the technology of triphylite-type cathode materials form the practical value of the thesis. The additional Li ions introduction in the crystal structure allows influencing the materials de/intercalation mechanism and potentially leads to the production of high-power cathode materials capable of withstanding increased current densities without severe degradation. The thoroughly investigated carbon-coating process grants the possibility of a targeted production of whether high-power or high-energy cathode materials depending on the carbon precursor type and its concentration. The developed strategy of LFMP microspherical production using dittmarite as a precursor could be treated as an alternative industrial route for manufacturing triphylite-type cathodes materials.

The validity and reliability of the obtained results are proved by the application of modern physico-chemical techniques with high reproducibility of the experimental results, most of the experiments were run multiple times in order to exclude any uncertainties in the interpretation. Additional confirmation comes

from the results publication in peer-reviewed scientific journals and presentation at international and national conferences.

Author's personal contribution includes aims settings, experiment design, literature review and analysis, results published in peer-reviewed journals, and presentations of the results at conferences. The author developed the methodology for the solvothermal production of Li-rich LFMP. Crystal structure description and microstructure characterization were performed by the author as well as functional groups distribution by IR. The sample preparation for the neutron and synchrotron powder diffraction, and Mossbauer spectroscopy was processed by the applicant. Electrochemical cells for galvanostatic cycling, impedance spectroscopy, CV, PIT, and operando synchrotron diffraction experiment were assembled by the author. The carbon-coating technique with the application of PAN as a carbon-coating agent was modified by the author, all the samples with different carbon content were produced by the author. The carbon content, functional groups distribution, and graphitization degree for all the samples were determined by the applicant. The electrochemical tests were performed by the author. The synthesis route for the production of LFMP using dittmarite-type precursors was developed by the applicant. The experiments concerning the description of crystal structure, morphology characterization and electrochemical performance of the material were performed by the author.

The PhD research was conducted in the Center for Energy Science and Technology of Skolkovo Institute of Science and Technology (Skoltech) under supervision of Prof. S.S. Fedotov and Prof. E.V. Antipov Dr. O.A. Tyablikov (Skolkovo Institute of Science and Technology) and T.V. Ivanova. (Mendeleev University of Chemical Technology of Russia, Skolkovo Institute of Science and Technology) were assisting with the development and technical aspects of the synthesis of cathode materials mentioned in the thesis. The precise crystal structure refinement of Li-rich LFMP based on joint XRD and NPD data was performed by Dr. I.A. Trussov (Skolkovo Institute of Science and Technology), operando synchrotron diffraction results were treated together with A.D. Dembitskiy (Skolkovo Institute of Science and Technology). Neutron diffraction experiment was conducted in the FRM II neutron facility of the Technical University of Munich with assistant of Dr. A. Senyshyn Mossbauer spectroscopy experiment was conducted at Lomonosov Moscow State University by Dr. I.A. Presnyakov, Dr. I.S. Glazkova, and Dr. A.V. Sobolev. The PIT and impedance experiments were planned and discussed together with Prof. V.A. Nikitina Transmission microscopy experiments were conducted by Dr. A.V. Morozov the obtained results were discussed together with Dr. A.V. Morozov and Prof. A.M. Abakumov.

The thesis experimental results were published in 8 pieces including 3 research papers in peer-reviewed scientific journals and were presented at 5 conferences. The results were presented in the following conferences during oral talks and poster sessions: the III school of young scientists: Electrochemical devices, processes, materials, and technologies, Novosibirsk, Russia, September 9-13 2023, IV Baikal material science forum, Ulan-Ude, Russia, July 1-7 2022, X national crystal chemistry conference Terskol, Kabardino-Balkar republic, Russia, July 5-9 2021, XII scientific conference for young scientists "Mendeleev 2021", Saint-Petersburg, Russia, September 6-10 2021, XXI Mendeleev congress on general and applied chemistry, Saint-Petersburg, Russia, September 9-13 2019. List of Conferences:

1. E. E. Nazarov, O. A. Tyablikov, E. V. Antipov, Mild hydrothermal synthesis of LiFe1-xMnxPO4: investigation the influence of synthesis parameters on structure and electrochemical properties of the material // 21st Mendeleev congress on general and applied chemistry, book of abstracts, 2019, V. 6, p. 395

2. Е. Е. Назаров, О. А. Тябликов, С. С. Федотов, Е. В. Антипов, Синтез, структура и свойства катодного материала на основе обогащенного литием Li1+5(Fe0.5Mn0.5)1-sPO4 // X национальный кристаллохимический конгресс, сборник тезисов, 2021, с. 266-267

3. E. E. Nazarov, S. S. Fedotov, E. V. Antipov, carbon coating precursor' influence on electrochemical properties of LiFe0.5Mn0.5PO4/C // XII international conference on chemistry for young scientists "Mendeleev 2021", book of abstracts, 2021, p.292

4. Е. Е. Назаров, О. А. Тябликов, С. С. Федотов, Е.В. Антипов, Современные методы модификации катодных материалов со структурой трифилина // IV Байкальский материаловедческий форум, 2022 c. 126-127

5. Е. Е. Назаров, Т. В. Иванова, Е. В. Антипов, С. С. Федотов. Применение прекурсора со структурой диттмарита для производства катодных материалов LiFexMn1-xPO4 с повышенной насыпной плотностью // III школа молоды ученых "Электрохимические устройства: процессы, материалы, технологии", 2023, с. 71

Заключение диссертации по теме «Другие cпециальности», Назаров Евгений Евгеньевич

Chapter 8. Conclusions

A novel Li-rich LFMP (Lh.072(2)Mn0.456(3)Fe0.473(2)PO4) was synthesized via a facile solvothermal route. The material's crystal structure refinement based on the joint neutron and synchrotron diffraction data revealed 7% Li+ at the M2 site, which corroborates with the results of 57Fe Mossbauer spectroscopy clearly identifying the presence of a matching amount of Fe3+. According to HAADF-STEM, IR and Mossbauer spectroscopy neither Fe(Mn)/Li antisite nor hydrotriphylite-type (phosphorus deficiency) defects were detected.

It was shown that designing the defect structure with Li ions at the M2 site significantly extends Li+ solid solution de/intercalation regions for both charge and discharge processes, positively influencing the power capabilities of the material. Based on operando synchrotron diffraction, the solid solution mechanism covers 57% and 61% of the material's de/intercalation process during charge and discharge respectively. Comparing the obtained results with the previously published data on LFMP, additional Li+ introduction leads to the total solid solution region extension of 6% during charge and 10% during discharge.

The utilization of PAN as a carbon-coating source enabled boosting capacity retention of the material at 5C-10C rates up to 78±2% after 1000 cycles as compared with only 43±3% for the glucose-derived carbon-coated samples due to the decreased charge transfer resistance in the Mn2+ ^ Mn3+ electrochemical activity region by one order of magnitude.

A co-precipitation synthesis technique for producing the dittmarite-type precursor NH4Fe0.5Mn0.5PO4'H2O with spherical morphology and mean particles diameter of 32 pm was developed. The macro- and microstructure evolution during the dittmarite-triphylite transformation was investigated by means of BET, SEM and ED. An 8% tap density decrease from 1.56 to 1.44 g-cm-3 for the precursor and LFMP material correspondingly was observed, with the specific surface area increasing 20 times due to the NH4+ and H2O substitution by Li+ leading to the precursor's primary particles fracturing and formation of radially aligned elongated individual particles of LFMP stacked along the 001 direction of the unit cell.

Despite higher charge transfer resistance of the agglomerated LFMP in contrast to Glu- and PAN-derived carbon-coated nanomaterials, the dittmarite-derived microspherical LiFe0.5Mn0.5PO4-based electrode material demonstrates decent electrochemical performance and exhibits 138 mAh-g-1 and 90 mAh-g-1 with volumetric energy density of 720 Wh-l-1 and 447 Wh-l-1at C/10 and 5C current densities. The material retains 85±4% and 86±2% of its initial discharge capacity after 250 cycles at 1C and 5C current loads.

Список литературы диссертационного исследования кандидат наук Назаров Евгений Евгеньевич, 2024 год

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