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Title Page

Contents

Abstract 7

1. Research Background 12

1.1. Lithium ion batteries (LiBs) 12

1.2. All-solid-state batteries 15

1.3. Prussian Blue Analogues 19

2. Prussian Blue Analogues based all-soild-state batteries 22

2.1. Experimental 22

2.2. Results and Discussion 26

2.2.1. Characterization 26

2.2.2. Electrolyte properties 28

2.2.3. Electrochemical stability window 31

2.2.4. Cell fabrication 35

Conclusion 43

References 44

List of Tables

Table 1. True density of five PBAs. 24

Table 2. Pellet density of five PBAs. 25

Table 3. Relativie density of five PBAs. 27

List of Figures

Figure 1. Development of LiBs for the electronic devices and energy storage system. 12

Figure 2. Scheme of LiBs (LiCoO₂,Electrolyte / Separator, graphite). 13

Figure 3. a) Battery energy density and electric vehicles range on the rise. b) Fire explosition due to flammable organic liquid electrolytes. 14

Figure 4. a) Scheme of all-solid-state battery systems. b) Prospects of next-generation batteries for high energy density of lithium metal battery systems. 15

Figure 5. a) Lithium consumption in the annual and total from 2015 to 2050. b) Histogram showing the number of published papers on SIBs and full cell of SIBs. c) The abundance of main elements in... 16

Figure 6. a) Ionic conductivity of solid electrolytes in sodium ion batteries. b) Electrochemical stability windows of solid electrolytes in sodium ion batteries. 17

Figure 7. Radar plots of each solid electrolyte candidate which are being mostly studied. 18

Figure 8. a) Schematic image of Prussian blue analogues. b) Large channel size which accommodates various alkali metal ions. c) Various PBAs can be synthesized by combining two... 19

Figure 9. Characteristics of Prussian Blue analogues. a) Tunable diffusion properties of PBAs as the concentration of sodium ions various in the lattice. b) Tunable redox properties of PBAs as the... 21

Figure 10. a) High Power X-ray diffraction of five PBAs. b) Two octahedrally coordinated metals M(NC)₆ and Fe(CN)₆ share a common corner. c) SEM images of morphology of PBAs. MnHCF,... 26

Figure 11. a) Cross-sectional SEM images for a compressed pellet. b) Optical image of compressed pellets. MnHCF, FeHCF, CoHCF, NiHCF, CuHCF from left to right. 27

Figure 12. a) Ionic conductivity of PBAs changes as the NaCl concentration varies during the synthetic condition. b) Ionic conductivity of PBAs at room temperature. c) Nyquist plot of PBAs. d) Ionic... 28

Figure 13. a) Arrhenius plot of PBAs for activation energy b) Electronic conductivity of PBAs by DC polarization. 29

Figure 14. TGA analysis to measure the contents of water and material stability. 30

Figure 15. Electrochemical stability window of five PBAs. 32

Figure 16. CV profiles with GCPL voltage curves to measure the oxidation and reduction. a,b) MnHCF CV profiles. c) MnHCF GCPL voltage profiles. d,e) FeHCF CV profiles. f) GCPL voltage profiles.... 33

Figure 17. a) The electrochemical stability windows of PBAs with reference Na₃PS₄ sulfide solid electrolyte. b) The electrochemical stability windows of sodium ion solid electrolytes. 34

Figure 18. Sodium metal symmetric cell of PBAs. The electrochemical performances were poor that the overpotential was around from 2 V to 4 V for all the materials. 35

Figure 19. a) Electrochemical voltage plateaus of Na-Sn alloy. b) Phase diagram of the Na-Sn system. 36

Figure 20. a-e) Na₃Sn symmetric cell of PBAs. f) Overall symmetric cell of PBAs. MnHCF showed the lowest over-potential of about 0.45 V and the most stable voltage profiles among the other PBAs. 37

Figure 21. MnHCMn voltage profiles. The operating voltage can be below the oxidation stability of PBAs. 38

Figure 22. a-e) MnHCMn symmetric cell of PBAs. f) Overall symmetric cell of PBAs. MnHCF showed the lowest over-potential of about 0.1 V which is comparable to other types of solid... 39

Figure 23. a) Voltage profiles as a function of specific capacity of full cell with MnHCF solid electrolyte. MnHCF shows the best performances among the other PBA materials. b) Discharge... 40

Figure 24. a) Nyquist plots for Na₃Sn/MnHCF/Na₃Sn symmetric cell for every 5 hours. b) Powder X-ray diffraction after mixing MnHCF and Na₃Sn with aging 1 day. 41

Figure 25. a) Cross-sectional SEM images of the interface between MnHCF and Na₃Sn. b) EDS analysis at the interface between MnHCF and Na₃Sn. c) SE image of the inteface. d) BSE image of... 42

초록보기

 All-solid-state sodium-ion batteries (ASNBs) are promising and attracting attention due to its low cost versus lithium, high energy density and safety. Sulfide, oxide, and boro-hydride solid electrolytes have great potential due to their high ionic conductivities.

However, sulfide solid electrolytes have poor electrochemical stability against common electrodes and require extra coating materials for high-voltage oxide cathodes. On the other hand, oxide solid electrolytes are mechanically robust which makes it difficult to fabricate pellets without sintering process and require high temperature heat treatment for synthesis. Boro-hydride solid electrolytes have poor oxidation stability and high cost which make it challenging for solid electrolytes. Therefore, the development of all-round solid-state electrolytes(SSEs) should be needed for the next-generation batteries.

Here, we report Prussian blue analogues (PBAs) as new solid-state electrolyte materials and explore appropriate PBA materials that satisfy the requirements of solid electrolytes. We select five PBAs which are mostly studied in the battery fields and changed N-coordinated transition metal ions while C-coordinated Fe ion is fixed. The high power X-ray diffraction reveals that all five materials have cubic phase and three-dimensional framework structure. The sodium-ion conductivities of cold-pressed manganese hexacyanoferrate (MnHCF) powders exhibits the highest ionic conductivity among the other PBAs of about 0.13 mS/cm at 30℃ which is practically available to be applied for a solid electrolyte. Manganese hexacyanomanganate (MnHCMn) / MnHCF / Na₃Sn ASNBs exhibit 71.8 mAhg-1 discharge capacities for the first cycle at 0.4 C at 30℃ and maintain over 100 cycles with 70.8% capacity retention. This results demonstrate that PBAs have potential as a next generation solid electrolyte candidate materials.

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