Magnified STEM images of the outer (location A) and inner (location B) surfaces and associated FFT patterns are also shown. The EDS mapping and spectrum data of the (a) LCO and (b) M-LCO cathode after full cell test. Micro- and atomic structure of the LCO surface after cycling. a) TEM images of the LCO after 500 whole-cell cycles.
Surface micro and atomic structure of M-LCO after cycling. a) TEM images of M-LCO after 50 full cell cycles. SEM images of graphite anode in (a) LCO/Gr and (b) M-LCO/Gr full cell after 500 cycles. EDS mapping and spectral data of graphite anode in (a) LCO/Gr and (b) M-LCO/Gr full cell after 500 cycles.
Introduction
Layered LiCoO 2 cathode material
In the LCO crystal structure, cobalt and lithium ions alternately occupy the octahedral site in the cubic close-packed oxygen atom array. This is because a cut-off voltage of the LCO cell is limited to 4.4 V (vs Li/Li+) and the active material undergoes severe degradation at higher voltages. Many researchers have revealed breakdown mechanisms at high voltages, including phase transition from the hexagonal to a monoclinic phase, 5-6 dissolution of Co ions, 7-8 formation of the spinel or rock salt phase at the surface, 9-10 and various side reactions with electrolytes. 11-12 Notably, the transition towards the monoclinic phase is irreversible, resulting in only partially reversible intercalation and deintercalation of Li ions and eventually significant capacity fading.
Recently, the increasing cost of the cobalt source and the ever-increasing demand for LIBs with higher energy density have led to the replacement of LCO with LiNixCoyMnzO2 (x + y + z = 1) cathode materials. Nevertheless, LCO is still one of the most attractive LIB cathode materials for portable electronics due to its extensive synthetic capability, high electrode density (≥4.0 g cm−3), high redox potential (~ 4 V vs. Li/Li+) with decent performance and excellent moisture stability.13 Accordingly, extensive research efforts have been made to increase the energy density of LCOs, resulting in a higher threshold voltage by modifying the surface and bulk properties. However, the specific practical performance is still limited, which requires other better achievements. a) Crystal structure of LiCoO2.
High voltage operation of layered cathode materials
- Degradation mechanisms of layered cathode materials in high voltage environment
- Previous strategies for high voltage operation of layered cathode materials
- Objective of this work
The cathode-electrolyte reactions cause not only a loss of the active material and Li ions, but also an increase in internal resistance due to the accumulation of the side reaction products at the cathode-electrolyte interphase. As mentioned above, the electrolyte becomes thermodynamically unstable at high voltages due to a change in the electrochemical potential of the cathode. In addition, nucleophilic surface oxygen in the highly delithiated cathode materials can attack the electrophilic carbonate solvent molecules of the electrolyte solution.
The breakdown of the electrolyte can be accelerated by acidic substances resulting from the hydrolysis of the LiPF6 salts.23. Reduction and dissolution of the TM of the cathode surface have been widely accepted as one of the main degradation mechanisms of layered cathode materials at high voltages. TM ions must remain in the crystal lattice of the cathode material and participate in redox reactions during cycling.
Recently, most advanced Ni-based cathode materials have been synthesized through the co-precipitation method, whereby the secondary particles are constructed. This type of cracking is termed an intergranular crack, which has been well known as one of the main degradation mechanisms for Ni-based cathode materials. More seriously, the intragranular cracking is related to the structural degradation and mechanical failure of the active materials.
The high electrochemical reversibility of Ni-rich materials was believed to be attributed to the screen effect of the migrated TM ions at the Li site. As mentioned above, the electrolyte containing carbonate solvents inevitably decomposes at high voltages, which deteriorates the electrochemical properties of the cell. For example, vinyl carbonate (VC) is well known as one of the most effective additives in the commercial phase.
Each component of the LCO/graphite full cell was thoroughly analyzed to find the main degradation mechanism in the high voltage environment. Interestingly, the cross-linking of Co ions did not affect the capacity fading of the LCO/graphite full cell, which is inconsistent with previous findings. This led to a significant improvement in the electrochemical properties of LCO in an extended voltage window (from 3.0 to 4.5 V compared to Li/Li+).
Experimental detail
The charge level and electrode density of the full-cell cathode electrode were adjusted to 13.60 mg cm-2 and 3.6 g cm-3, respectively. The same electrolyte with the cathode half-cell was used in the full-cell test. To investigate the crystallographic structure of the cathode materials, the X-ray diffraction (XRD) patterns were obtained using Rigaku D/MAX 2500 V/PC X-ray diffractometer with Cu-Kα radiation.
The morphology of the cathode active materials was observed with a scanning electron microscope (SEM, Verios 460, FEI). Atomic-scale structural and elemental analysis was performed by a high-resolution transmission electron microscope (HR-TEM, ARM300, JEOL) at 300 kV. To measure the amount of Co dissolution, coin-type half-cells were fabricated with Li metal anodes, and initially charged to 4.5 V.
Then the cells were disassembled in a glove box and the cathode materials were stored in the electrolyte at 60 °C for 4 weeks. After the first, second and fourth week, the amount of Co ions in the electrolyte was examined using inductively coupled plasma (ICP). The same amount of cathode materials (69.4 mg) and the electrolyte (10 ml) were used for the test.
Results and discussion
Electrochemical results
LCO and M-LCO showed almost the same reversible capacity of ~190 mAh g−1 and coulombic efficiency of ~98% in the formation cycle, as shown in Figure 17a. As shown in Figure 17b, the capacity retention of the LCO cathode was significantly improved with the introduction of magnesium ions. Surprisingly, M-LCO exhibits an excellent capacity retention of 96.6% after 50 cycles even at elevated temperature, which is ∼40% higher than that of LCO ( Figure 17d ).
This indicates that the introduction of magnesium ions on the LCO surface can significantly improve the phase reversibility of the bulk structure. Next, the rate capabilities of LCO and M-LCO were compared with different C discharge rates ranging from 0.2 to 5.0C and a fixed C loading rate of 0.2C (Figure 19a). Thus, we performed EIS analysis to investigate the charge transfer resistance of LCO and M-LCO (Figure 19b, Table 2).
After the formation cycle, the interfacial resistance of M-LCO was slightly higher than that of LCO. However, the charge transfer resistance of M-LCO was kept stable, whereas that of LCO showed a drastic growth during 50 cycles. The values of IR drop and overpotential for LCO increased approx. 5 times after the 50th cycle, whereas no significant change was observed for M-LCO. a) Speed test of LCO and M-LCO.
Constant loading rate C (0.2C) was applied and discharging rate C was increased from 0.2 to 5.0C every four cycles. b) EIS measurements of LCO and M-LCO recorded after formation, 25th and 50th cycle. Moreover, M-LCO/Gr showed very stable retention in Coulombic efficiency over 500 cycles, compared to that of LCO/Gr (Figure 21c). As expected, the amount of dissolved Co ions for the LCO electrode was ~2 times that of M-LCO after 4 weeks.
The content of Co ions in the electrolyte for the LCO and M-LCO after the storage at 60 °C for 4 weeks, measured by ICP.
Structural analysis
This implies that the surface damage of the LCO cathode was not too severe considering the very poor capacity retention of the LCO/Gr full-cell, which is consistent with the EDX results. Therefore, we could conclude that the serious deterioration of the electrochemical performance in the LCO cathode stems from the significant damage in the micro- and nanostructure. This damaging structural damage can be suppressed by the incorporation of the Mg ions into the LCO structure.
This results in the suppression of the structural breakdown and cracking, leading to the excellent capacity retention of M-LCO. In addition, some peak changes, including the disappearance of the (006) peak, showed the severe structural change of LCO. As mentioned in Section 1.2.3, there has been no direct evidence showing that the Co-ion junction causes capacity fading of the anode and LCO/Gr full-cell.
Thus, we observed the anode surface of the disassembled LCO/Gr and M-LCO/Gr whole cells in order to investigate the effect of Co ion crosslinking in the whole cells (Figure 30). In fact, the amount of Co ions deposited on the anode of the LCO/Gr whole cell was approximately 1% of that of carbon (Figure 31a). This apparently indicates that the Co-ion junction on the anode surface hardly affects the capacity fading of the graphite anode and the LCO/Gr full cell.
In addition, it can be concluded that the severe performance reduction in the LCO/Gr full cell mainly originated from the cathode degradation, as the LCO/Gr anode had similar performance to the M-LCO/Gr full cell anode after reassembly. The reassembled LCO/Gr full cell cathode had an initial capacity of ∼98 mAh g-1, half of the original reversible capacity of LCO. In the LCO/Gr separator, severe pore clogging and accumulation of surface deposits were observed (Figure 33a, b).
This work showed the main breakdown mechanism of bulk LCO at high voltage of 4.5 V (compared to Li/Li+) by investigating each component of LCO/Gr full cell after 500 cycles. The severe degradation of the LCO/Gr solid cell was mainly due to the severe irreversible structural change and the formation of cracks. This led to a significantly improved electrochemical performance of the LCO cathode, especially in a full-cell system, which can reach high levels of commercial standards in LIBs.
Conclusion
