Surficial structure retention mechanism for LiNi0.8Co0.15Al0.05O2 in

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Surficial structure retention mechanism for LiNi Co Al O in a full gradient cathode 0.8

0.15

0.05

2

Chaodeng Liu, Guoqin Cao, Zhihao Wu, Junhua Hu, Haoyang Wang, and Guosheng Shao ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b10160 • Publication Date (Web): 13 Aug 2019 Downloaded from pubs.acs.org on August 13, 2019

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ACS Applied Materials & Interfaces

Surficial structure retention mechanism for LiNi0.8Co0.15Al0.05O2 in a full gradient cathode Chaodeng Liu1,2, Guoqin Cao1,2, Zhihao Wu1,2, Junhua Hu1,2*, Haoyang Wang1,2, Guosheng Shao1,2** 1. School

of Materials Science and Engineering, Zhengzhou University, Zhengzhou

450001, China 2. State

Center for International Cooperation on Designer Low-carbon &

Environmental Materials (CDLCEM), Zhengzhou University, 100 Kexue Avenue, Zhengzhou 450001, China Corresponding author: *[email protected]; ** [email protected] Abstract A LiNi0.8Co0.15Al0.05O2 (NCA) solid battery was assembled by coupling an NCA cathode with a polyvinylidene fluoride (PVDF) / Li6.75La3Z1.75Ta0.25O12 (LLZTO) composite polymer electrolyte and a Li anode. A NiO-like phase transition is regarded as the reason for interface impedance, which leads to drastic capacity fading during cycling. A gradient cathode with an excessive addition of Li6.75La3Zr1.75Ta0.25O12 was fabricated at the cathode/electrolyte interface to overcome the increased impedance. Using high-resolution transmission electron microscopy and electron energy loss spectra, the formation of a unique localized cation migration (LCM) region was confirmed on the NCA surface. The formation of an LCM region hindered further distortion and enhanced the capacity retention of the spinel lattice. Keywords: LiNi0.8Co0.15Al0.05O2; gradient cathode; cation mixing; phase 1 / 19

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transition, solid state battery 1. Introduction Rising fuel costs and increasing environmental issues have boosted the research and development of electric vehicles in recent years. There is a strong need to improve their safety with solid-state electrolyte techniques, which can reduce the flammability of the battery pack.1,2,3 Emerging solid electrolytes enable the production of batteries with an increased power density.4-8 LiNi0.8Co0.15Al0.05O2 (NCA), a Ni-based cathode material, has potential application in electronic vehicles due to its low cost and high mileage capability.9 However, this material exhibits significant power fading and an increase in the interfacial impedance during cycling. Such power attenuation originates from the structural degradation of the layered — —

— —

structure (space group R 3 m) upon cycling to the spinel structure (Fd 3 m) first and — —

then to the rock-salt structure (Fm 3 m).10-13 In addition, the unexpected phase transition also induces micro-crack formation at the grain boundaries of the NCA particles, causing an interruption in the electronic and ionic conduction. Various approaches are used to address this challenge, including core–shell structure and surface gradient doping, to enhance the cycling ability and improve the structural stability of layered Ni-rich oxide cathodes. Cells with Al gradient-doped LiNi0.815Co0.15Al0.035O2 exhibit excellent cycling stability due to the electrochemically inactive

Al3+-rich

surface.14

Gradient

boric

polyanion-doped

Li(Ni0.8Co0.15Al0.05)(BO3)x(BO4)yO2-3x-4y (x=0, 0.01, 0.015, 0.02) was also synthesized to decrease the Ni-O bond around the outer layers, which improved the structural 2 / 19


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stability and prevented the generation of cracks during cycling.15 Although the phase transition mechanism of NCA is still under investigation16-18, it is accepted that both the state and rate of the charging govern the stability of the crystallographic and electronic structures. Especially, solid-state batteries always work at a low rate. The phase evolution and optimization approaches for NCA cathodes should be further investigated. In this work, a surficial structure retention mechanism for LiNi0.8Co0.15Al0.05O2 in a full gradient cathode was proposed based on a unique localized cation migration (LCM), which was specified by high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectra (EELs). The formation of an LCM region hindered further distortion and enhanced the capacity retention of the spinel lattice. 2. Result and discussion 2025-type coin cells were assembled with an NCA cathode (Supporting Info and Fig. S1). The cathodes were grouped as gradient cathodes (GC), reverse gradient cathodes (R-GC), and uniform doped cathodes (UDC). A polyvinylidene fluoride (PVDF) / Li6.75La3Z1.75Ta0.25O12 (LLZTO) composite polymer electrolyte (CPE, Fig. S2, S3) and a Li anode were assembled with these NCA cathode. To study the effect of the gradient on Li1-xNi0.8Co0.15Al0.05O2 structural changes during the first charging process (to 4.3 V), we measured the X-ray diffraction (XRD) patterns at different charging potentials. The crystalline structure changed with the charging state (Fig. S4). The peaks in the XRD spectra were indexed to a hexagonal phase,19 where L and S correspond to layered and spinel structures, respectively. The (0 0 3) peak shifted as 3 / 19



the

lithium

ions

were

removed.

The

XRD

patterns

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show

a

typical

expansion-contraction process along c-axis11. These structural evolutions correspond to the repulsive force of neighboring oxygen layers after delithiation and TM-O2 layers gliding toward the adjacent Li planes.20 The lattice parameters of the c-axis obtained from least-squares refinement are shown in Fig. 1a, which also demonstrate expansion and contraction along the c-axis. Both the expansion and contraction of the lattice were alleviated on the surface of GC. In contrast, the R-GC had a pronounced expansion and a subsequent drastic contraction along the c-axis. To evaluate the cycling ability, the cells underwent a charge/discharge process at a high rate of 0.5 C (100mA.g-1) for the solid battery. The cycling range of 2.5-4.0 V was selected according to the stability of the CPE (Fig. S2, S3). Each cell maintained a high and stable coulombic efficiency (~97%) during cycling. Fig. 1b compares the cycle performance of the GC, R-GC, and UDC for 50 cycles, and their charge-discharge curves are shown in Fig. S5. The discharge capacities of the R-GC and UDC cells decreased to 45% and 58.6% of their initial capacity after 50 cycles, respectively. As expected, the GC cell shows a capacity retention of 89% after 50 cycles. To explore the cycling degradation, the interface impedance was investigated. For comparison, the EIS at the initial state was shown in Fig.S6. Before cycling, the interface kept healthy contact with electrolyte. The electrochemical impedance spectra (EIS) after the 15th and 50th cycles are shown in Fig. 1c and 1d, respectively. The semicircle observed in the medium frequency is attributed to the interface impedance of the cathode/electrolyte interface.21 After 15 cycles, the GC cells had the lowest interfacial 4 / 19


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resistance among all tested cathodes. After 50 cycles, the GC cathode maintained the healthiest interface contact during cycling. As a result, the charge-discharge curves also show different polarization. In Fig.S5, the crossing point at the charge/discharge curves for three kinds of cathodes are very different, indicating big polarization for R-GC case, then UDC case and GC cases. The EIS result (Fig.1c and d) is consistent with that of charge-discharge curves (Fig.S5)

Figure 1. (a) Lattice parameters of LiNi0.8Co0.15Al0.05O2 particles on the surface of the GC, R-GC, and UDC during the first charge at the C/2 rate. (b) Cycle performance of the solid-state batteries with a GC, R-GC, and UDC at 0.5 C with a cut-off potential of 4.0-2.5 V at 50 oC. EIS plots of batteries after (c) 15 and (d) 50 cycles. The values in the figures correspond to the interfacial resistance. The optimization of interface contact originates from the suppression of NCA 5 / 19



microstructural degradation. XRD patterns from the NCA cathode surface in contact with CPE after cycling for 15 and 50 cycles are compared in Fig. 2a. After cycling, the structure of the NCA on the surface of the GC showed a moderate change, while the R-GC showed the most pronounced shift due to a disordered structure. After 15 cycles, the (0 0 3) peak of the spinel phase shifted to a lower 2θ angle. Expansion along the c-axis occurred, and the NCA structure in the GC was the closest to the initial state. As shown in Fig.S7 (a), the layer structure of splitted (108)/ (110) can be observed after 15 cycles, which also proves the structure retention on GC surface. The Rietveld refinement result of XRD in Fig.S7 was shown in Fig.S8. It is noted that the XRD was recorded from the interfacial particles (Fig.2a). The contribution of surface structure and intermediate state cannot be ignored, which makes the Rietveld refinement difficult to get good match. The surfacial structure was analysed further. After the 50th cycle, phase separation occurred. O GC demonstrated a single-phase spinel structure, which illustrated the enhanced reversibility on the surface of GC. The formation of a rock-salt phase indicated by a shoulder labeled as R can be observed in the UDC and R-GC samples (also in Fig.S7b).11 It should be noted that the charge/discharge curve (Fig.S5) are similar upon cycling. The interfacial phase transition is definitely different with that in cathode bulk. 22-24 The phase evolution on the surface at the end of the cycling was also confirmed by the diversity in the Ni chemical states (X-ray photoelectron spectroscopy, Fig. 2b). Nickel with a low bonding energy after cycling indicates a decrease in the bond state of the nickel-oxygen compound, corresponding to the formation of an 6 / 19


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oxygen-deficient surface.25, 26 In figure 2b, Ni 2p3/2 peaks are located at 857.0, 856.4 and 855.5 eV, respectively. Apparently, the suppression of the rock-salt phase transition on the surface of the GC contributed to healthy interface conditions and a high capacity retention (Fig. 1b).

Figure 2. (a) XRD (0 0 3) peaks from the LiNi0.8Co0.15Al0.05O2 on the surface of the GC, R-GC, and UDC after 15 and 50 cycles. L, S and R denote the layered phase, spinel and rock salt, respectively. The full patterns are available in Fig.S7. (b) XPS spectra of Ni 2p taken from the surface of the pristine particles, GC and R-GC surface after 50 cycles. The XRD and XPS indicate the average structural information from numerous particles. However, the phase separation of the rock-salt phase and chemical state change indicate typical surface and localized issues on the surface of NCA particles.27 The NCA particles collected from the surface of the electrodes were characterized by TEM and EELS (Fig. 3 and 4).

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Figure 3. (a) HRTEM of region II on NCA surface. The inset displays the image of the whole particle desquamated from the surface of the R-GC. From core to surface, areas a-1, a-2, and a-3 show the phase transition process from spinel to rock salt. (b) EELS of the oxygen K-edge from corresponding areas I (core) and II (surface region) in the inset in (a). Fig. 3a shows an image of a particle surface (region II) after the transition to an irreversible rock-salt phase. A core-shell configuration of spinel@rock-salt NCA was formed. In the different regions away from the particle core, a typical transition process from spinel to rock-salt can be seen. In Fig. 3(a-1), the faint but distinguishable lattice contrast between the (0 4 0) planes indicated that the Li layer was subjected to a certain degree of cation mixing, as indicated by a yellow circle. Then, the periodic bright spots on the Li layers became more distinct during the 8 / 19


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second step (Fig. 3a-2), which indicates a critical state of the phase transition from spinel to rock salt. At the outermost part of the R-GC particle (Fig. 3a-3), a well-defined rock salt structure appeared. This series of transitions agrees well with that in the literature.28 The electronic states of oxygen in the core and shell were recorded by EELS (Fig. 3b). As EELS spectra were normalized to the intensity of the main peak, the shrinking pre-edge peak (II) of the R-GC proved that the oxygen on the surface was relatively poor. The loss of oxygen is also consistent with the reduced state of Ni, which helps keep the electric neutrality on the lattice. The oxygen content increased with the depth into the particles. A similar structural evolution was also reported for UDC samples.12, 28

Figure 4. (a) HRTEM of NCA surface region II. The inset (in Fig. 4a) displays the whole particle separated from the surface of the GC. From the core to the surface, (a-1) 9 / 19



shows the lattice fringes of the spinel and (a-2) shows the localized cation migration (LCM) region on the surface of the NCA particle. (b-1) Details of the structure of the LCM region and (b-2) elongated atom images of ○1 ○2 ○3 ○4 in b-1. (c) EELS of the oxygen K-edge from corresponding areas in (a). The original images of (a-2) and (b-1) were shown in Fig.S9. In the HRTEM image (Fig. 4a) of the NCA particles on the surface of the GC, the surface contained the lattice fringes of the spinel (particle surface region II). This indicates that a considerable portion of the surface underwent the transition back to a spinel structure upon cycling (Fig. 4a-1). In marked contrast to Fig. 3a, there was no long-range cation mixing observed on the surface. In Fig. 4a-2, the distance of 2.05 Å is consistent with that of the (0 4 0) planes in the spinel structure. However, the localized expansion to 2.51 Å for the d (0 4 0) was observed. As indicated by the dotted square (Fig. 4a-2), the atom configuration of the (0 4 0) planes became wavy due to the expansion. In Fig. 4b-1, the TMs glided to the adjacent Li layers, which resulted in an elongation of the diffraction spots of the TM atoms within 3-5 atom layers (○1 -○4 in Fig. 4b-1 and b-2). The existence of a localized cation migration (LCM) region was confirmed. As compared with that in figure 3(a-1), (a-2), the shrinkage of d (0 4 0) was obviously suppressed with LCM region. It indicated that LCM region kept a structure similar to spinel structure and has alleviated structure degradation compared with R-GC. In the unmixed region of LCM, the lattice spacing was consistent with that of the (0 4 0) in spinel structure (Fig. 4b-1), which confirmed the existence of residual Li atoms in the interstitial sites of the (0 4 0) planes. It is understood that the transition to 10 / 19


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an irreversible rock-salt phase is triggered by the loss of oxygen on the surface.29,30 The EELS (Fig. 4c) of the LCM region confirmed that the content and chemical state of the oxygen was almost identical to that in the core area. A loss of oxygen on the “shell” layer was not observed. The formation of an LCM region and its contribution to retaining the structure are illustrated in Fig. 5a. The excessive incorporation of a fast ion conductor on the surface of the GC enhanced Li+ diffusion. The insufficient delithiation always occurred when the Li+ had a high migration rate during the charging process of the NCA.31 In the Li vacancy region, cation mixing occurred locally (Fig. 5a-2), which was thermodynamically driven. The residual Li limited the cation migration within LCM regions. As indicated in Fig. 1a and Fig. S4, the alleviated lattice changes during the charging process proved that residual Li can act as obstacles for the further distortion of the spinel lattice. As illustrated in Fig. 5a, the TM atoms can glide to the Li vacancies and to form a TM neighbor on one side (type I). After relaxing, the localized expansion of the (0 1 0) interplanar spacing was caused by the static repulsion between the dangling oxygen atoms (indicated by ↔ ).32 The formation of the elongated atom images from ○1 ○2 ○3 ○4 in Fig. 4(b-1) was elucidated as two adjoining TM atoms. If the TM atoms glide to Li vacancies separately on two sides, an edge-like defect (indicated by ┸ ) on the (0 1 0) plane would be formed. Both conditions (Fig. 5a-2) would generate unique wavy planes (Fig. 4a-2). Conversely, more Li vacancies formed over a wide range on the R-GC surface during charging and cation mixing occurred, as shown in Fig. 5b.

33-35

Therefore, the mixing was in a wider range, and the rock-salt phase was irreversibly 11 / 19



generated. The result provided direct evidence that residual Li acted as an obstacle for further distortion of the spinel lattice due to the LCM regions. 3. Conclusion In summary, NCA-based solid-state batteries with different cathode constitutions were studied. The interface impendence after cycling was responsible for the capacity fading. A gradient cathode with excessive addition of LLZTO on the surface enhanced the cycling performance. The insufficient extraction of Li generated a unique localized cation migration region in the NCA on the GC surface that suppressed the widespread cation mixing. EELS also demonstrated that there was no evident oxygen loss on the surface of the GC. A battery with a gradient cathode would maintain a relatively high capacity retention rate during cycling. This work provides direct evidence about how the kinetic factor functions in the structure retention in an all-solid NCA battery.

Figure 5. Schematic of the phase evolution on the surface of a GC and R-GC. (a-1) 12 / 19


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——

Original lattice with the incident direction of [1 0 3]. (a-2) Formation of the LCM region. (b) A typical process from spinel (b-1) to cation mixing (b-2) to rock salt structure (b-3). Supporting Information. Fabrication process of electrodes and batteries; XRD patterns in the 1st cycle; Charge-discharge curves of solid-state Li batteries; Electrochemical impedance spectra (EIS) in the initial state; Full XRD patterns; Original figures of LCM. Acknowledgements We acknowledge financial support from the National Natural Science Foundation of China [51571182, 51001091], Fundamental Research Program from the Ministry of Science and Technology of China [2014CB931704] and Program for science & talents in Henan Province [18HASTIT009,182102310815, 2017GGJS001]. References 1 Gao, Z.; Sun, H.; Fu, L.; Ye, F.; Zhang Y.; Luo, W.; Huang Y. Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries. Adv. Mater. 2018, 30, 17057021-17057027. 2 Yin, J.; Yao, X.; Peng, G.; Yang, J.; Huang Z.; Liu, D.; Tao, Y.; Xu, X. Influence of the Li-Ge-P-S Based Solid Electrolytes on NCA Electrochemical Performances in All-Solid-State Lithium Batteries. Solid State Ionics 2015, 274, 8-11. 3 Fan, L.; Wei, S.; Li, S.; Li, Q.; Lu, Y. Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries. Adv. Energy Mater. 2018, 8 (11), 13 / 19



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30

Bellharouak,

I.;

Vissers,

D.;

Amine,

K.

Thermal

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Stability

of

the

Li(Ni0.8Co0.15Al0.05)O2 Cathode in the Presence of Cell Components. J. Electrochem. Soc. 2006, 153 (11), A2030-A2035. 31 Zou, L.; Zhao, W.; Liu, Z.; Jia, H.; Zheng, J.; Wang, G.; Yang, Y.; Zhang, J.; Wang, C. Revealing Cycling Rate Dependent Structure Evolution in the Ni-rich Layered Cathode Materials. ACS Energy Lett. 2018, 3, 2433-2440. 32 Wang, P.; Yao, H.; Liu, X.; Yin, Y.; Zhang, J.; Wen, Y.; Yu, X.; Gu, L.; Guo, Y. Na+ / Vacancy Disordering Promises High-Rate Na-Ion Batteries. Sci. Adv. 2018, 4, eaar60181-60189. 33. Q.B. Zhang, H.X. Chen, L.L. Luo, B.T. Zhao, H. Luo, X. Han, J.W. Wang, C.M .Wang, Y. Yang, T. Zhu, ML Liu. Harnessing the concurrent reaction dynamics in active Si and Ge to achieve high performance lithium-ion batteries. Energy & Environmental Science , 2018,11(3), 669-681. 34.Huiping Yang, Hong‐Hui Wu, Mingyuan Ge, Lingjun Li, Yifei Yuan, Qi Yao, Jie Chen, Lingfeng Xia, Jiangming Zheng, Zhaoyong Chen, Junfei Duan, Kim Kisslinger, Xiao Cheng Zeng, Wah ‐ Keat Lee, Qiaobao Zhang, Jun Lu. Simultaneously Dual Modification of Ni ‐ Rich Layered Oxide Cathode for High ‐ Energy Lithium ‐ Ion Batteries. Adv. Funct. Mater. 2019, 29(13), 18088251-18088259. 35.Longze Zhao, Hong-Hui Wu, Chenghao Yang, Qiaobao Zhang, Guiming Zhong, Zhiming Zheng, Huixin Chen, Jinming Wang, Kai He, Baolin Wang, Ting Zhu, Xiao Cheng Zeng, Meilin Liu, and Ming-Sheng Wang, Mechanistic Origin of the High Performance of Yolk@Shell Bi2S3@N-Doped Carbon Nanowire Electrodes. ACS 18 / 19


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Surficial structure retention mechanism for LiNi0.8Co0.15Al0.05O2 in

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