リケラボ論文検索は、全国の大学リポジトリにある学位論文・教授論文を一括検索できる論文検索サービスです。

リケラボ 全国の大学リポジトリにある学位論文・教授論文を一括検索するならリケラボ論文検索大学・研究所にある論文を検索できる

リケラボ 全国の大学リポジトリにある学位論文・教授論文を一括検索するならリケラボ論文検索大学・研究所にある論文を検索できる

大学・研究所にある論文を検索できる 「フッ化物イオン電池正極材料の熱力学的性質の研究」の論文概要。リケラボ論文検索は、全国の大学リポジトリにある学位論文・教授論文を一括検索できる論文検索サービスです。

コピーが完了しました

URLをコピーしました

論文の公開元へ論文の公開元へ
書き出し

フッ化物イオン電池正極材料の熱力学的性質の研究

朱, 尚萍 ZHU, SHANGPING シュ, ショウヘイ 九州大学

2023.03.20

概要

九州大学学術情報リポジトリ
Kyushu University Institutional Repository

Study for Thermodynamic Properties of Fluoride
Ion Battery Cathode Materials
朱, 尚萍

https://hdl.handle.net/2324/6787643
出版情報:Kyushu University, 2022, 博士(工学), 課程博士
バージョン:
権利関係:

(様式3)Form 3





:朱

尚萍

Name

論 文 名 :Study for Thermodynamic Properties of Fluoride Ion Battery Cathode
Materials
(フッ化物イオン電池正極材料の熱力学的性質の研究)




:甲

Category















Thesis Summary
High-energy density storage devices are urgently required to meet the increasing demand for
battery-operated electric vehicles, electric trains, and airplanes, which may become the future of
mobility. Hence, the demand for efficient and sustainable systems is increasing drastically. Therefore,
fluoride-ion batteries (FIBs), which works through a chemical reaction that shunts F-ions between
anode and cathode, have been studied. FIBs show higher ion mobility and energy density than most
multivalent ion batteries because monovalent F- ions have a small ion radius, and the theoretical energy
density of FIBs are eight times that of current lithium-ion batteries owing to the movement of several
charged anions per reaction step. Numerous combinations of cathode and anode materials have been
explored for FIBs based on monovalent anions and multivalent cations. Several active materials, such
as Bi, Cu, and Sn, have been used for the development of FIBs. CuF2 exhibits unique capacity and a
high theoretical conversion potential as a cathode material. However, most CuF2 cathodes cannot reach
their theoretical capacity values because of the low F- ion diffusion rate in CuF2.
In terms of utilization rate for active material Cu of FIBs, the cathode material CuPb2F6 was
reported and demonstrated a capacity exceeding that of the conventional CuF2 cathode in previous
studies, in which dispersion of nano Cu and super ion conductor PbF2 improved the utilization of
Cu. However, the deterioration of cathode material was occurred during charge/discharge process,
because of the coarsening of Cu grains during discharging process. In this study, we focus on
thermodynamics properties of Cu-Pb-F ternary system, which is helpful to understand the chemical
reaction during discharge process of CuPb2F6. The thermodynamical properties were investigated
by CALPHAD (Calculation of Phase Diagrams) method, in which the binary, ternary compounds
were assessed by first principal calculation and the optimization of calculated phase diagram was

implemented using experimental data. Especially, the discrepancy of stability between calculated
phase diagram and experimental data was discussed by experimental methods, including atomic
pair distribution function (PDF) analysis of neutron powder diffraction (ND), in which the analysis
of discrepancy is helpful to improve the accuracy of calculated phase diagram and the understanding
of thermodynamics properties.
To investigate the deterioration of cathode and reaction during the discharging process, the MultiPhase-Field (MPF) method coupling with CALPHAD database we calculated above was
implemented to simulate the decomposition and discharge reaction of CuPb2F6 cathode material.
Because of the conservation restriction for all elements during simulation, it is difficult to simulate
discharging process, in which the amounts of F element keep decreasing along with every time step.
Novel model, which splits discharging process into some simulation with small time step, was used
to evaluate microstructure evolution during discharging process by different parameters of
simulation. The grain growth of Cu nanoparticles is considered to be an important cause of
deterioration, and simulations are performed among parameters such as discharge rate, nucleation
ratio and diffusion coefficient.
For the viewpoint of Cu-La-F ternary system, since the ternary compounds does not exist, we
focused on the microstructure of Cu-La alloy in which La can form the fluoride ion conductor LaF3.
Owing to thin-film (2.3 nm) Cu almost accomplished the theoretical capacity in previous studies,
rapid solidification method was used to synthesize Cu-La alloys with fine lamella microstructure,
in which Cu-enrich phases and La-enriched phases were dispersed and expected to be fluorinated
as reported LaNi5 cathode material. Besides, we evaluated the microstructures processed by
different compositions and cooling speed to obtain finest lamella structure. After fluorination, the
finest lamella structure was expected that the dispersed finer Cu and ion conductor LaF3 could
shorten the diffusion path of F- ions.
For investigating the unknown ternary compounds of Cu-La-F and Cu-Pb-F ternary systems,
which is possible to be promising cathode materials as CuPb2F6. the phase stability among these
compounds of Cu-La-F and Cu-Pb-F ternary systems was calculated by Density Functional Theory
(DFT) calculation method and the existence of ternary compounds was predicted by evolutionary
algorithm. Furthermore, the predicted energy curve of Cu-La-F and Cu-Pb-F ternary systems were
evaluated by comparing with reported crystal structure.
Chapter 1 introduced the general information of fluoride ion batteries, fluoride ion conductors,
research methods about thermodynamics properties and the objectives of this study.
Chapter 2 discussed the thermodynamic assessment of Cu-Pb-F system, in which the compounds
in the Cu-Pb-F system were assessed by first principal calculation. The Cu-Pb-F ternary phase
diagram was calculated by CALPHAD method. Moreover, the crystal structure of CuPb2F6 was
refined by ND method and PDF analysis.

Chapter 3 discussed microstructure evolution simulation of promising cathode material CuPb2F6
by Multi-Phase-Field (MPF) method coupling with the database calculated in the Chapter 2. The
decomposition of CuPb2F6 was simulated at high temperature. Moreover, to evaluate discharging
process of CuPb2F6 cathode material, novel model was stablished to investigate the effects of
different parameters, which was helpful to analyze the deterioration of cathode material CuPb2F6.
Chapter 4 discussed the synthesis of Cu-La alloys, as an alternative cathode material in FIBs.
Based on Cu-La phase diagram, the formation of the lamellar structure and Cu-La alloys near
eutectic point were investigated by rapid solidification method. To investigate the effect of cooling
rate, composition of Cu-La alloys was fixed at 24.5 at% La and synthesized at different cooling
speed. Besides, for the detailed observations of microstructure, the alloys, with composition fixed
at 24.5 at% La and cooling speed of 500 and 1000 rpm, were observed by Electron Backscatter
Diffraction (EBSD) and Transmission Electron Microscope (TEM).
Chapter 5 discussed the phase stability of compounds in Cu-La-F and Cu-Pb-F ternary systems.
In order to search for a wider range of stable structures, we used both an evolutionary algorithm and
first-principles calculations to search for stable structures without any restrictions on crystal
structures.
Chapter 6 summarized the general results of thermodynamic properties for Cu-La-F, Cu-Pb-F
systems.
In general, according to study the thermodynamical properties of Cu-La-F, Cu-Pb-F systems, the
approaches, which could improve the utilization of Cu in the cathode materials of FIBs, were
investigated.

この論文で使われている画像

参考文献

1.

N. Nitta, F. Wu, J. T. Lee, G. Yushin, Li-ion battery materials: present and future. Materials Today

18, 252-264 (2015).

2.

M. Sawicki, L. L. Shaw, Advances and challenges of sodium ion batteries as post lithium ion

batteries. RSC Advances 5, 53129-53154 (2015).

3.

J. W. Choi, D. Aurbach, Promise and reality of post-lithium-ion batteries with high energy

densities. Nature Reviews Materials 1, 1-16 (2016).

4.

Y. Shao et al., Highly reversible Mg insertion in nanostructured Bi for Mg ion batteries. Nano

letters 14, 255-260 (2014).

5.

A. M. Melemed, A. Khurram, B. M. Gallant, Current Understanding of Nonaqueous Electrolytes

for Calcium‐Based Batteries. Batteries & supercaps 3, 570-580 (2020).

6.

H. Jiao, C. Wang, J. Tu, D. Tian, S. Jiao, A rechargeable Al-ion battery: Al/molten AlCl3–

urea/graphite. Chemical Communications 53, 2331-2334 (2017).

7.

E. Levi, Y. Gofer, D. Aurbach, On the Way to Rechargeable Mg Batteries: The Challenge of New

Cathode Materials. Chemistry of Materials 22, 860-868 (2010).

8.

O. Mizrahi et al., Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable

Magnesium Batteries. Journal of The Electrochemical Society 155, A103 (2008).

9.

J. Muldoon et al., Electrolyte roadblocks to a magnesium rechargeable battery. Energy &

Environmental Science 5, 5941 (2012).

10.

N. Jayaprakash, S. K. Das, L. A. Archer, The rechargeable aluminum-ion battery. Chem Commun

(Camb) 47, 12610-12612 (2011).

11.

G. Kamath, B. Narayanan, S. K. Sankaranarayanan, Atomistic origin of superior performance of

ionic liquid electrolytes for Al-ion batteries. Phys Chem Chem Phys 16, 20387-20391 (2014).

12.

H. Wang et al., Anion-effects on electrochemical properties of ionic liquid electrolytes for

rechargeable aluminum batteries. Journal of Materials Chemistry A 3, 22677-22686 (2015).

13.

F. Gschwind, H. Euchner, G. Rodriguez ‐ Garcia, Chloride ion battery review: theoretical

calculations, state of the art, safety, toxicity, and an outlook towards future developments.

European Journal of Inorganic Chemistry 2017, 2784-2799 (2017).

14.

X. Zhao, S. Ren, M. Bruns, M. Fichtner, Chloride ion battery: A new member in the rechargeable

battery family. Journal of Power Sources 245, 706-711 (2014).

15.

X. Zhao et al., Magnesium Anode for Chloride Ion Batteries. ACS Applied Materials & Interfaces

6, 10997-11000 (2014).

16.

P. Gao et al., Vanadium Oxychloride/Magnesium Electrode Systems for Chloride Ion Batteries.

ACS Applied Materials & Interfaces 6, 22430-22435 (2014).

17.

M. Anji Reddy, M. Fichtner, Batteries based on fluoride shuttle. Journal of Materials Chemistry

21, (2011).

119

18.

F. Gschwind et al., Fluoride ion batteries: Theoretical performance, safety, toxicity, and a

combinatorial screening of new electrodes. Journal of Fluorine Chemistry 182, 76-90 (2016).

19.

F. Gschwind, Z. Zao-Karger, M. Fichtner, A fluoride-doped PEG matrix as an electrolyte for anion

transportation in a room-temperature fluoride ion battery. J. Mater. Chem. A 2, 1214-1218 (2014).

20.

T. Liu et al., Insight into anion storage batteries: Materials, properties and challenges. Energy

Storage Materials 42, 42-67 (2021).

21.

M. A. Nowroozi et al., Fluoride ion batteries – past, present, and future. Journal of Materials

Chemistry A 9, 5980-6012 (2021).

22.

C. Rongeat, M. Anji Reddy, T. Diemant, R. J. Behm, M. Fichtner, Development of new anode

composite materials for fluoride ion batteries. J. Mater. Chem. A 2, 20861-20872 (2014).

23.

M. A. Nowroozi, K. Wissel, J. Rohrer, A. R. Munnangi, O. Clemens, LaSrMnO4: Reversible

Electrochemical Intercalation of Fluoride Ions in the Context of Fluoride Ion Batteries. Chemistry

of Materials 29, 3441-3453 (2017).

24.

S. V. Gopinadh, P. V. R. L. Phanendra, B. John, T. D. Mercy, Fluoride-ion batteries: State-of-theart and future perspectives. Sustainable Materials and Technologies 32, e00436 (2022).

25.

W. Bollmann, Ionic conductivity of pure and doped BaF2 crystals. physica status solidi (a) 18,

313-321 (1973).

26.

W. Bollmann, H. Henniger, Concentration and mobility of fluorine ion vacancies in CaF2. physica

status solidi (a) 11, 367-371 (1972).

27.

P. Hagenmuller, J.-M. Réau, C. Lucat, S. Matar, G. Villeneuve, Ionic conductivity of fluorite-type

fluorides. Solid State Ionics 3-4, 341-345 (1981).

28.

A. G. MacDiarmid, L. S. Yang, W. S. Huang, B. D. Humphrey, Polyaniline: Electrochemistry and

application to rechargeable batteries. Synthetic Metals 18, 393-398 (1987).

29.

F. Gschwind, Z. Zao-Karger, M. Fichtner, A fluoride-doped PEG matrix as an electrolyte for anion

transportation in a roomerature fluoride ion battery. Journal of Materials Chemistry A 2, 12141218 (2014).

30.

V. K. Davis et al., Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for

high-energy fluoride ion cells. Science 362, 1144-1148 (2018).

31.

C. Rongeat, M. Anji Reddy, R. Witter, M. Fichtner, Solid Electrolytes for Fluoride Ion Batteries:

Ionic Conductivity in Polycrystalline Tysonite-Type Fluorides. ACS Applied Materials &

Interfaces 6, 2103-2110 (2014).

32.

M. Leblanc, V. Maisonneuve, A. Tressaud, Crystal Chemistry and Selected Physical Properties of

Inorganic Fluorides and Oxide-Fluorides. Chemical Reviews 115, 1191-1254 (2015).

33.

M. A. Nowroozi et al., High cycle life all-solid-state fluoride ion battery with La2NiO4+d high

voltage cathode. Communications Materials 1, 27 (2020).

34.

L. Zhang, M. Anji Reddy, M. Fichtner, Development of tysonite-type fluoride conducting thin film

120

electrolytes for fluoride ion batteries. Solid State Ionics 272, 39-44 (2015).

35.

D. Zhang et al., Understanding the reaction mechanism and performances of 3d transition metal

cathodes for all-solid-state fluoride ion batteries. Journal of Materials Chemistry A 9, 406-412

(2021).

36.

M. Anji Reddy, M. Fichtner, Batteries based on fluoride shuttle. Journal of Materials Chemistry

21, 17059-17062 (2011).

37.

K.-i. Okazaki, Y. Uchimoto, T. Abe, Z. Ogumi, Charge–Discharge Behavior of Bismuth in a Liquid

Electrolyte for Rechargeable Batteries Based on a Fluoride Shuttle. ACS Energy Letters 2, 14601464 (2017).

38.

C. Rongeat, M. A. Reddy, R. Witter, M. Fichtner, Nanostructured Fluorite-Type Fluorides As

Electrolytes for Fluoride Ion Batteries. The Journal of Physical Chemistry C 117, 4943-4950

(2013).

39.

C. Rongeat, M. Anji Reddy, T. Diemant, R. J. Behm, M. Fichtner, Development of new anode

composite materials for fluoride ion batteries. Journal of Materials Chemistry A 2, 20861-20872

(2014).

40.

G. G. Amatucci, N. Pereira, Fluoride based electrode materials for advanced energy storage

devices. Journal of Fluorine Chemistry 128, 243-262 (2007).

41.

X. Hua et al., Comprehensive Study of the CuF2 Conversion Reaction Mechanism in a Lithium

Ion Battery. The Journal of Physical Chemistry C 118, 15169-15184 (2014).

42.

J. Lin et al., Self-Templated Formation of Hollow Yolk-Like Spheres Iron Fluoride as Cathode

Material for High-Performance Li-Ion Batteries. Journal of The Electrochemical Society 166,

A2074 (2019).

43.

S. Dey et al., Structural Evolution of Layered Manganese Oxysulfides during Reversible

Electrochemical Lithium Insertion and Copper Extrusion. Chemistry of Materials 33, 3989-4005

(2021).

44.

N. Yamakawa, M. Jiang, C. P. Grey, Investigation of the Conversion Reaction Mechanisms for

Binary Copper(II) Compounds by Solid-State NMR Spectroscopy and X-ray Diffraction.

Chemistry of Materials 21, 3162-3176 (2009).

45.

D. T. Thieu et al., CuF2 as Reversible Cathode for Fluoride Ion Batteries. Advanced Functional

Materials 27, 1701051 (2017).

46.

Y. Morita et al., Redox Behavior of a CuF2/Cu Electrode for an All-Solid-State Fluoride Shuttle

Battery. ECS Meeting Abstracts MA2020-01, 71 (2020).

47.

S. S. FLASCHEN, P. D. GARN, Inorganic Electrical Insulating Coatings on Aluminum and

Copper. Journal of the American Ceramic Society 42, 641-642 (1959).

48.

H. Nakano et al., Fluoride-Ion Shuttle Battery with High Volumetric Energy Density. Chemistry

of Materials 33, 459-466 (2021).

121

49.

H. Stephen, Superionics: crystal structures and conduction processes. Reports on Progress in

Physics 67, 1233 (2004).

50.

G. Dénès, G. Milova, M. C. Madamba, M. Perfiliev, Structure and ionic transport of PbSnF4

superionic conductor. Solid State Ionics 86-88, 77-82 (1996).

51.

L. N. Patro, K. Hariharan, Fast fluoride ion conducting materials in solid state ionics: An overview.

Solid State Ionics 239, 41-49 (2013).

52.

T. Tojigamori et al., Reversible Charge/Discharge Reaction of a Ternary Metal Fluoride, Pb2CuF6:

A Highly Conductive Cathode Material for Fluoride-Ion Batteries. ACS Applied Energy Materials

5, 1002-1009 (2022).

53.

M. Murakami et al., High Anionic Conductive Form of PbxSn2–xF4. Chemistry of Materials 31,

7704-7710 (2019).

54.

K. Mori et al., Experimental Visualization of Interstitialcy Diffusion Pathways in Fast-FluorideIon-Conducting Solid Electrolyte Ba0.6La0.4F2.4. ACS Applied Energy Materials 3, 2873-2880

(2020).

55.

J. Chable et al., Fluoride solid electrolytes: investigation of the tysonite-type solid solutions

La1−xBaxF3−x (x < 0.15). Dalton Transactions 44, 19625-19635 (2015).

56.

C. E. Derrington, A. Navrotsky, M. O'Keeffe, High temperature heat content and diffuse transition

of lead fluoride. Solid State Communications 18, 47-49 (1976).

57.

R. Bachman, H. Schulz, Crystal structure and anion disorder in β-PbF2. Solid State Ionics 9-10,

521-523 (1983).

58.

V. M. Carr, A. V. Chadwick, R. Saghafian, The electrical conductivity of PbF2 and SrCl2 crystals

at high temperatures. Journal of Physics C: Solid State Physics 11, L637 (1978).

59.

A. Holleman, E. Wiberg, N. Wiberg, Inorganic chemistry. (Academic press, 2001).

60.

M. T. Hutchings et al., Investigation of thermally induced anion disorder in fluorites using neutron

scattering techniques. Journal of Physics C: Solid State Physics 17, 3903 (1984).

61.

M. J. Gillan, Dynamics of defects in superionic fluorites. Journal of the Chemical Society, Faraday

Transactions 86, 1177-1182 (1990).

62.

H. Zhang, X. Wang, A. Chremos, J. F. Douglas, Superionic UO2: A model anharmonic crystalline

material. The Journal of Chemical Physics 150, 174506 (2019).

63.

C. Rambaut, H. Jobic, H. Jaffrezic, J. Kohanoff, S. Fayeulle, Molecular dynamics simulation of

the lattice: dynamic properties. Journal of Physics: Condensed Matter 10, 4221 (1998).

64.

M. Castiglione, P. A. Madden, P. Berastegui, S. Hull, The crystal structure of α-PbSnF4 and its

anion diffusion mechanism. Journal of Physics: Condensed Matter 17, 845 (2005).

65.

T. Eguchi, H. Amasaki, T. Suzuki, J. Kuwano, Y. Saito, Towards Fluoride-Based Oxygen Gas

Sensors Operating at Room Temperature: Effects of the Whisker Materials Incorporated in the

Sensing Electrode on Response Time. Analytical Sciences 13, 295-298 (1997).

122

66.

A. Wakagi, J. Kuwano, Amperometric PbSnF4-based oxygen sensors: rapid response at room

temperature in the operating pressure range 10 kPa–7.2 MPa. Journal of Materials Chemistry 4,

973-975 (1994).

67.

E. Murray, D. F. Brougham, J. Stankovic, I. Abrahams, Conductivity and Fluoride Ion Dynamics

in α-PbSnF4; 19F Field-Cycling NMR and Diffraction Studies. The Journal of Physical Chemistry

C 112, 5672-5678 (2008).

68.

V. Y. Kavun et al., NMR and impedance spectroscopy data on the ionic mobility and conductivity

in PbSnF4 doped with alkali metal fluoride. Journal of Structural Chemistry 53, 290-294 (2012).

69.

N. I. Sorokin, B. P. Sobolev, Nonstoichiometric fluorides—Solid electrolytes for electrochemical

devices: A review. Crystallography Reports 52, 842-863 (2007).

70.

B. Sobolev, A. Golubev, P. Herrero, Fluorite M1− xRxF2+ x phases (M= Ca, Sr, Ba; R= rare earth

elements) as nanostructured materials. Crystallography Reports 48, 141-161 (2003).

71.

B. Ruprecht, M. Wilkening, S. Steuernagel, P. Heitjans, Anion diffusivity in highly conductive

nanocrystalline BaF2:CaF2 composites prepared by high-energy ball milling. Journal of Materials

Chemistry 18, 5412 (2008).

72.

M. Heise, G. Scholz, A. Düvel, P. Heitjans, E. Kemnitz, Mechanochemical synthesis, structure,

and properties of solid solutions of alkaline earth metal fluorides: Ma1− xMbxF2 (M: Ca, Sr, Ba).

Solid State Sciences 60, 65-74 (2016).

73.

A. Düvel, B. Ruprecht, P. Heitjans, M. Wilkening, Mixed Alkaline-Earth Effect in the Metastable

Anion Conductor Ba1–xCaxF2 (0 ≤ x ≤ 1): Correlating Long-Range Ion Transport with Local

Structures Revealed by Ultrafast 19F MAS NMR. The Journal of Physical Chemistry C 115,

23784-23789 (2011).

74.

A. Düvel, J. Bednarcik, V. Šepelák, P. Heitjans, Mechanosynthesis of the Fast Fluoride Ion

Conductor Ba1–xLaxF2+x: From the Fluorite to the Tysonite Structure. The Journal of Physical

Chemistry C 118, 7117-7129 (2014).

75.

K. J. Kim, M. Yoshimura, S. Sōmiya, Hydrothermal crystal synthesis of solid solutions in the

system SrF2-LaF3. International Journal of High Technology Ceramics 3, 231-241 (1987).

76.

J. Chable et al., Fluoride solid electrolytes: investigation of the tysonite-type solid solutions

La1−xBaxF3−x (x ≤ 0.15). Dalton Transactions 44, 19625-19635 (2015).

77.

B. Dieudonné et al., Exploring the Sm1–xCaxF3–x Tysonite Solid Solution as a Solid-State

Electrolyte: Relationships between Structural Features and F– Ionic Conductivity. The Journal of

Physical Chemistry C 119, 25170-25179 (2015).

78.

A. Privalov et al., Distribution of motional correlation times in Superionic conductors: 19F NMR

on tysonite-like LaF3. Journal of Physics Condensed Matter 9, 9275-9287 (1997).

79.

A. Roos, F. C. M. van de Pol, R. Keim, J. Schoonman, Ionic conductivity in tysonite-type solid

solutions La1−xBaxF3−x. Solid State Ionics 13, 191-203 (1984).

123

80.

B. Dieudonné et al., The key role of the composition and structural features in fluoride ion

conductivity in tysonite Ce1− xSrxF3− x solid solutions. Dalton Transactions 46, 3761-3769 (2017).

81.

L. Patro, K. Hariharan, Fast fluoride ion conducting materials in solid state ionics: An overview.

Solid State Ionics 239, 41-49 (2013).

82.

V. Y. Kavun et al., Ion mobility and transport in β-PbF2 doped with alkaline-earth fluorides.

Inorganic materials 43, 301-309 (2007).

83.

S. Achary, A. Tyagi, Synthesis and characterization of mixed fluorides with PbF2 and ScF3. Powder

diffraction 20, 254-258 (2005).

84.

M. Samouël, P. Gredin, A. de Kozak, Powder diffraction data for copper hexafluorides: Ba2CuF6

and Pb2CuF6. Powder Diffraction 10, 221-222 (1995).

85.

M. Samouël, Equilibres de cristallisation dans onze sysemes de deux fluorures simples. Syntheses

dans l’eta solide et identifications cristallographiques des fluorures doubles rencontres. Revwe de

Chimie minerale 8, 1 (1971).

86.

K. Nakayama et al., Fluoride-ion conversion alloy for fluoride-ion batteries. Journal of Materials

Chemistry A 10, 3743-3749 (2022).

87.

Z. Du, Y. Xu, W. Zhang, Thermodynamic assessment of the Cu–La system. Journal of alloys and

compounds 289, 88-95 (1999).

88.

I. Vaajamo, H. Johto, P. Taskinen, A thermodynamic assessment of the Cu-Fe-Pb ternary system.

4, 1283-1302 (2011).

89.

B. G. Müller, F. Schrötter, Zur Kristallstruktur ternärer Cu(II)-Fluoride CuMIVF6 (MIV = Sn, Pb,

Ti, Mn, Pd). 196, 261-268 (1991).

90.

N. Saunders, A. P. Miodownik, CALPHAD (calculation of phase diagrams): a comprehensive

guide. (Elsevier, 1998).

91.

H. Johto, P. Taskinen, Phase stabilities and thermodynamic assessment of the system Cu–Pb–S.

Minerals Engineering 42, 68-75 (2013).

92.

R. Kobayashi, Modeling and numerical simulations of dendritic crystal growth. Physica D:

Nonlinear Phenomena 63, 410-423 (1993).

93.

I. Steinbach, Why solidification? Why phase-field? Jom 65, 1096-1102 (2013).

94.

H. W. Kerr, J. Cisse, G. F. Bolling, On equilibrium and non-equilibrium peritectic transformations.

Acta Metallurgica 22, 677-686 (1974).

95.

M. Hillert, Solidification and casting of metals. The Metals Society, London 81, (1979).

96.

M. Tang et al., Model for the particle size, overpotential, and strain dependence of phase transition

pathways in storage electrodes: application to nanoscale olivines. Chemistry of Materials 21,

1557-1571 (2009).

97.

Y.-H. Kao et al., Overpotential-Dependent Phase Transformation Pathways in Lithium Iron

Phosphate Battery Electrodes. Chemistry of Materials 22, 5845-5855 (2010).

124

98.

P. Bai, D. A. Cogswell, M. Z. Bazant, Suppression of phase separation in LiFePO4 nanoparticles

during battery discharge. Nano letters 11, 4890-4896 (2011).

99.

A. R. Oganov, Y. Ma, C. W. Glass, M. Valle, Evolutionary crystal structure prediction: overview

of the USPEX method and some of its applications. Psi-k Newsletter 84, 142-171 (2007).

100.

C. W. Glass, A. R. Oganov, N. Hansen, USPEX—Evolutionary crystal structure prediction.

Computer physics communications 175, 713-720 (2006).

101.

A. O. Lyakhov, A. R. Oganov, H. T. Stokes, Q. Zhu, New developments in evolutionary structure

prediction algorithm USPEX. Computer Physics Communications 184, 1172-1182 (2013).

102.

A. R. Oganov, C. W. Glass, S. Ono, High-pressure phases of CaCO3: crystal structure prediction

and experiment. Earth and Planetary Science Letters 241, 95-103 (2006).

103.

W. Zhang et al., Unexpected stable stoichiometries of sodium chlorides. Science 342, 1502-1505

(2013).

104.

Q. Zhu et al., Stability of xenon oxides at high pressures. Nature chemistry 5, 61-65 (2013).

105.

H. Zhang, B. Gilbert, F. Huang, J. F. Banfield, Water-driven structure transformation in

nanoparticles at room temperature. Nature 424, 1025-1029 (2003).

106.

M. W. Terban et al., Early stage structural development of prototypical zeolitic imidazolate

framework (ZIF) in solution. Nanoscale 10, 4291-4300 (2018).

107.

T. Egami, S. J. Billinge, Underneath the Bragg peaks: structural analysis of complex materials.

(Newnes, 2012).

108.

R. L. McGreevy, Reverse monte carlo modelling. Journal of Physics: Condensed Matter 13, R877

(2001).

109.

C. Farrow et al., PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals.

Journal of Physics: Condensed Matter 19, 335219 (2007).

110.

A. A. Coelho, TOPAS and TOPAS-Academic: an optimization program integrating computer

algebra and crystallographic objects written in C++. Journal of Applied Crystallography 51, 210218 (2018).

111.

P. Juhás, C. L. Farrow, X. Yang, K. R. Knox, S. J. Billinge, Complex modeling: a strategy and

software program for combining multiple information sources to solve ill posed structure and

nanostructure inverse problems. Acta Crystallographica Section A 71, 562-568 (2015).

112.

K. Parlinski, Z. Q. Li, Y. Kawazoe, First-Principles Determination of the Soft Mode in Cubic ZrO2.

Physical Review Letters 78, 4063-4066 (1997).

113.

S.-L. Chen et al., The PANDAT software package and its applications. Calphad 26, 175-188

(2002).

114.

G. Kresse, J. Furthmüller, Bayesian optimization for calibrating and selecting hybrid-density

functional models. Phys. Rev. B 54, 11169-11186 (1996).

115.

G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method.

125

Physical Review B 59, 1758-1775 (1999).

116.

J. P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made Simple [Phys.

Rev. Lett. 77, 3865 (1996)]. Physical Review Letters 78, 1396-1396 (1997).

117.

M. Yonemura et al., Development of SPICA, New Dedicated Neutron Powder Diffractometer for

Battery Studies. Journal of Physics: Conference Series 502, 012053 (2014).

118.

A. T. Dinsdale, SGTE data for pure elements. Calphad 15, 317-425 (1991).

119.

C. T. Heycock, F. H. Neville, Complete Freezing-Point Curves of Binary Alloys Containing Silver

or Copper Together with Another Metal. Philosophical Transactions of the Royal Society of

London. Series A, Containing Papers of a Mathematical or Physical Character 189, 25-69 (1897).

120.

D. Chakrabarti, D. Laughlin, The Cu− Pb (Copper-Lead) system. Bulletin of Alloy Phase

Diagrams 5, 503-510 (1984).

121.

C. T. Heycock, F. H. Neville, XXXIX.—The freezing points of alloys containing zinc and another

metal. Journal of the Chemical Society, Transactions 71, 383-422 (1897).

122.

J. Eiken, A Phase-Field Model for Technical Alloy solidification. RWTH Aachen University,

(2009).

123.

I. Steinbach, Phase-field models in materials science. Modelling and Simulation in Materials

Science and Engineering 17, 073001 (2009).

124.

J.-O. Andersson, T. Helander, L. Höglund, P. Shi, B. Sundman, Thermo-Calc & DICTRA,

computational tools for materials science. Calphad 26, 273-312 (2002).

125.

B. Böttger, J. Eiken, M. Apel, Phase-field simulation of microstructure formation in technical

castings–A self-consistent homoenthalpic approach to the micro–macro problem. Journal of

Computational Physics 228, 6784-6795 (2009).

126.

J. Eiken, B. Böttger, I. Steinbach, Multiphase-field approach for multicomponent alloys with

extrapolation scheme for numerical application. Physical review E 73, 066122 (2006).

127.

B. Sundman, H. Lukas, S. Fries, Computational thermodynamics: the Calphad method.

(Cambridge university press Cambridge, 2007).

128.

P. Galenko, D. Jou, Rapid solidification as non-ergodic phenomenon. Physics Reports 818, 1-70

(2019).

129.

A. Sasaki, A. Himeda, H. Konaka, N. Muroyama, Ab initio crystal structure analysis based on

powder diffraction data using PDXL. Rigaku J 26, 10-14 (2010).

130.

K. Momma, F. Izumi, VESTA: a three-dimensional visualization system for electronic and

structural analysis. Journal of Applied crystallography 41, 653-658 (2008).

131.

N. Khrapov, V. Roizen, M. Posypkin, A. Samtsevich, A. Oganov, Volunteer computing for

computational materials design. Lobachevskii Journal of Mathematics 38, 926-930 (2017).

132.

A. R. Oganov, C. W. Glass, Crystal structure prediction using ab initio evolutionary techniques:

Principles and applications. The Journal of chemical physics 124, 244704 (2006).

126

133.

A. R. Oganov, A. O. Lyakhov, M. Valle, How Evolutionary Crystal Structure Prediction Works

and Why. Accounts of chemical research 44, 227-237 (2011).

134.

J. P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made Simple.

Physical Review Letters 77, 3865-3868 (1996).

135.

R. Allmann, R. Hinek, The introduction of structure types into the Inorganic Crystal Structure

Database ICSD. Acta Crystallographica Section A 63, 412-417 (2007).

136.

N. Rybin, D. Y. Novoselov, D. M. Korotin, V. I. Anisimov, A. R. Oganov, Novel copper fluoride

analogs of cuprates. Physical Chemistry Chemical Physics 23, 15989-15993 (2021).

127

128

Achievement

Paper

1.

Zhu, S.; Akamine, H.; Nagahata, Y.; Tojigamori, T.; Miki, H.; Zhang, Y.;Tokunaga,

T.; Iikubo, S., Microstructure control and its observation of rapid solidification Cu–

La alloy for the development of fluoride-ion batteries. Journal of Alloys and

Compounds 2023, 930, 167447.

2. Zhu, S.; Harada, H.; Kawano, S.; Yamamoto, K.; Miki, H.; Tojigamori, T.; Noi, K.;

Iikubo, S., Thermodynamic properties of Cu–Pb–F ternary system for the

development of fluoride-ion batteries. Engineering Sciences Reports, Kyushu

University 2023, 44, 11.

3. Chen, Y.; Liu, H.; Guo, X.; Zhu, S.; Zhao, Y.; Iikubo, S.; Ma, T., Bimetallic Sulfide

SnS2/FeS2 Nanosheets as High-Performance Anode Materials for Sodium-Ion

Batteries. ACS Applied Materials & Interfaces 2021, 13 (33), 39248-39256.

Conference

1. Zhu, S.; Akamine, H.; Nagahata, Y.; Tojigamori, T.; Miki, H.; Zhang, Y.;Tokunaga,

T.; Iikubo, S., Microstructure observation of CuLa alloys as cathode material for

fluoride shuttle battery. The Japan institute of metals and materials, online, March

2022(oral).

2.

Nagahata, Y.; Zhu, S.; Akamine, H.; Tojigamori, T.; Miki, H.; Zhang, Y.;Tokunaga,

T.; Iikubo, S., Simulation of Microstructure Evolution for Fluoride Shuttle Battery,

The Japan institute of metals and materials, online, March 2022.

129

130

Acknowledgment

The thesis marks the end of a long and memorable journey that I could not have

completed without the dedicated support of my supervisors and peer colleges. My

heartfelt thanks go to my supervisor prof. Satoshi Iikubo for his consistent and helpful

support throughout my PhD studies. I would want to thank him for his patience, help,

empathy, and academic professions. He provided me with excellent chances and advice

in writing papers, and he also spent significant amount of time reviewing my papers and

proving me with constructive feedback to help me better my work.

I would like to express my gratitude to Assistant Professor Hiroshi Akamine, and

Assistant Professor Qin Wang of Kyushu University for their helpful discussions

throughout this study.

I would also like thank Prof. Miki Inada of Kyushu University, Prof. Yuki shirosaki of

Kyushu Institute of Technology, and students from their laboratory for their helpful

feedback and advice, which have help me develop solid arguments in my thesis.

I would also like thank Prof. Tatsuya Tokunaga and Dr. Yichen Zhang of Kyushu

Institute of Technology, who support me for synthesis of Cu-La alloys.

I would also like thank Mr. Takeshi Tojigamori, Hidenori Miki, and Mr. Kousuke Noi

of Toyota motor corporation for their helpful discussions throughout this study.

I would also like thank the support from The Ultramicroscopy Research Center of

Kyushu university.

I would also like thank students and staffs in the same laboratory for their kindness and

obliging.

I would also like to thank my dear parents for their encouragement and support.

December 2022 Shangping Zhu

131

...

参考文献をもっと見る

全国の大学の
卒論・修論・学位論文

一発検索!

この論文の関連論文を見る