[논문]고성능 이차 전지용 하이브리드 에너지 저장 메커니즘을 위한 고용체 화학

하시온; 김경호

doi:10.4313/jkem.2024.37.1.2

[국내논문] 고성능 이차 전지용 하이브리드 에너지 저장 메커니즘을 위한 고용체 화학
Hybrid Energy Storage Mechanism Through Solid Solution Chemistry for Advanced Secondary Batteries

전기전자재료학회논문지 = Journal of the Korean Institute of Electrical and Electronic Material Engineers, v.37 no.1, 2024년, pp.11 - 25

하시온 (부경대학교 재료공학과) , 김경호 (부경대학교 재료공학과)

Abstract ▼ AI-Helper

Lithium-ion batteries (LIBs) have attracted great attention as the common power source in energy storage fields of large-scale applications such as electrical vehicles (EVs), industries, power plants, and grid-scale energy storage systems (ESSs). Insertion, alloying, and conversion reactions are the main electrochemical energy storage mechanisms in LIBs, which determine their electrochemical properties and performances. The electrochemical reaction mechanisms are determined by several factors including crystal structure, components, and composition of electrode materials. This article reviews a new strategy to compensate for the intrinsic shortcomings of each reaction mechanism by introducing the material systems to form a single compound with different types of reaction mechanisms and to allow the simultaneous hybrid electrochemical reaction of two different mechanisms in a single solid solution phase.

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표/그림 (12)

표 Table 1. Three different types of anode materials based on the lithium storage mechanism and their advantages and common issues.
그림 Fig. 1. Specific capacities and working potentials (V vs. Na/Na⁺) for different classes of anode materials for SIBs.
그림 Fig. 2. (a) Crystal structure, ionic radius of transition metal (TM), and formation enthalpy of various 1st row transition metal monophosphides (TM = Ti - Ni). Schematic illustration of three main energy storage mechanism as (b) insertion, (c) alloying, and (d) conversion reactions.
그림 Fig. 3. (a) Refined lattice parameters, (b) galvanostatic discharge/charge profiles, and (c) corresponding differential capacity plots (DCPs) of Mn1-xFexP (x=0.0, 0.5, 0.75, and 1.0) electrodes [☆ in (a) is the lattice parameter from ICDD] [11].
그림 Fig. 4. Cycling performance at a current density of (a) 2 A g^-1 for Mn_1-xFe_xP and CoP electrodes and (b) schematic illustration for the discharged state of MnP, FeP, and Mn1-xFexP electrodes [11].
그림 Fig. 5. (a) Crystal structures of VP and MnP, (b) Rietveld refined lattice parameters, and (c) prismatic site parameters of Mn_1-xV_xP (x=0, 0.25, 0.5, 0.75, and 1.0) [12].
그림 Fig. 6. (a) Galvanostatic discharge/charge voltage profiles and (b) corresponding differential capacity plots, and ex-situ XRD patterns for (i) pristine, (ii) fully lithiated (0.01 V vs. Li/Li⁺), and (iii) delithiated (2.0 V vs. Li/Li⁺) states of Mn_1-xV_xP (x = 0, 0.25, 0.50, 0.75, and 1.0) electrodes [12].
$Fig. 7. (a) HAADF STEM image, (b) corresponding FFT pattern, and (c) EDS mapping images of combination of Mn, V, and P K for fully lithiated Mn0.75V0.25P electrode. (d) Crystal structure illustration and diffraction pattern of aligned along the [100] direction for Li-inserted Mn0.75V0.25P, Li3MnP2, and hybrid alloying/insertion phases, respectively [12].$ 그림 Fig. 7. (a) HAADF STEM image, (b) corresponding FFT pattern, and (c) EDS mapping images of combination of Mn, V, and P K for fully lithiated Mn_0.75V_0.25P electrode. (d) Crystal structure illustration and diffraction pattern of aligned along the [100] direction for Li-inserted Mn_0.75V_0.25P, Li₃MnP₂, and hybrid alloying/insertion phases, respectively [12].
그림 Fig. 8. (a) Long-term cycle performance of Mn_1-xV_xP (x=0.25), MnP/VP (3:1), and commercial graphite electrodes at 1 A g^-1, (b) cross sectional SEM images before cycle and fully lithiated state for (b,c) MnP, (d,e) VP, and (f,g) Mn_0.75V_0.25P electrodes, respectively, and (h) schematic illustration for the cycling behavior of MnP/VP mixture and Mn_0.75V_0.25P solid solution electrodes [12].
그림 Fig. 9. (a) XRD patterns, (b) cycling performance at a current density of 500 mA g^-1 with activation of 3 cycles at 50 mA g^-1, and (c) nyquist plots after 50 cycles (inset figure for pristine state) for MnP₄ and Mn_0.75TM_0.25P₄ (TM = V and Fe) electrodes, respectively [The reference peaks for MnP4 (ICDD # 01-072-0949, black dash line), VP₄ (ICDD # 01-077-0262, green dash line), and FeP₄ (ICDD # 01-079-0486, brown dash line) are included in (a)] [13].
그림 Fig. 10. (a) XRD patterns of NiP_2-xS_x (x = 0, 0.5, 1.0, 1.5 and 2.0) nanopowders and (b) enlargement of the patterns in 2 theta range of 50~60° [The reference peaks for NiP₂ (ICDD # 01-073-0436, red dash line) and NiS₂ (ICDD # 01-078-4702, orange dash line) are included], and (c) 1st cycle dQ/dV plots of NiP_2-xS_x (x = 0, 0.5, 1.0, 1.5 and 2.0) at 50 mA g^-1 [14].
그림 Fig. 11. (a) The 1st cycle galvanostatic discharge/charge voltage profiles, (b) corresponding dQ/dV plots at 50 mA g^-1 and (c) the 1st discharge capacities at different current densities of the NiP_2-xS_x (x = 0, 0.5, and 2.0) and NiP₂/NiS₂ (3:1) electrodes. (d) Schematic illustration for the sodiation/desodiation process of the NiP_2-xS_x solid solution [14].

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