Site-Selective and Element-Selective Analysis of Nickel Substituted Li-Rich Layered Material Using By X-Ray Diffraction and Absorption Spectroscopy
Authors: Komatsu Hideyuki , Minato Taketoshi , Matsunaga Toshiyuki , Shimoda Keiji , Kawaguchi Tomoya , Fukuda Katsutoshi , Nakanishi Koji , Arai Hajime , Uchimoto Yoshiharu , Matsubara Eiichiro , Ogumi Zempachi 
Published: February 2020

1. Introduction

Li-rich type (manganese) oxides are one of the most featured cathodes for lithium ion batteries in recent years, owing to their high capacity and cyclability. In these cathodes, partial substitution of manganese by other transition metals such as Ni and Co has been proposed and shown to be effective in improving the performance, [1] however, the role of such metals in the battery performance has not been clarified in detail.
We have synthesized Ni ion substituted Li excess manganese oxides (Li2Mn1-xNixO3) as a simple model of Li2MeO3 phase in solid solution cathode to understand the effect of introduced Ni by using the combination of in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction spectroscopy (XDS) analysis. Diffraction anomalous fine structure (DAFS) spectra are achieved by XDS analysis, that there were quantitatively showed potential-dependent transbilayer migration of nickel and manganese and their reversibility.

2. Experimental procedure

The active material of nickel substituted Li2MnO3 (Li2Mn1-x
NixO3, x = 0 ~ 0.25) was prepared from solid phase calcination at 1173 K for 12 h in air. The working electrode consisted of active material (80 wt.%), acetylene black (10 wt.%) and polyvinylidene difluoride (PVdF) binder (10 wt.%), coated on aluminum current foil.
The electrochemical measurements of the electrode were employed using aluminum pouch type cells, metallic lithium as counter and reference electrodes, 1 mol dm-3 LiPF6 in a 3:7 mixture of EC/DMC, and a polyolefin film as a separator. The electrochemical charge and discharge tests were performed at room temperature and the potential range was between 2.0 and 4.8 V.
XAS measurements were performed by the three-electrode cell with charging and discharging processes (in Operando). The XAS measurements of the Ni-K and Mn-K edge region were performed using a solid-state detector at beamlines BL28XU in SPring-8 (Hyogo, Japan).
The XDS measurements were conducted at beamline BL28XU, SPring-8, Japan. A two-dimensional Pilatus detector (Dectris Co., Ltd.) was mounted onto an arm of a multi-axis goniometer and was used to measure the diffraction profile, and two ionization chamber was used for the absorption correction of the DAFS spectra.

3. Results and Discussion

The obtained X-ray absorption near edge structure (XANES) region spectra at N-K energy region of Li2Mn1-x
NixO3 (x = 0.25) in the 1st charging and discharging processes are shown in Fig. 1. The edge energy was shifted to high energy, which is suggested that Ni element function as a charge compensation species. However the end of charging region around 4.7 V to 4.8 V was shifted to low energy as seen in previous XAS report [2], which means the reduction of nickel on average in this region.
As our group have published before,[3] XANES-like spectra only from selected sites (i.e. DAFS spectra) can be extracted from the XDS analysis. Fig. 2 shows the DAFS spectra of initial sample. The Ni-K edge XANES-like spectra shows that there was cation mixing in the lithium layer of the pristine material. In contrast, Mn-K edge XANES-like spectra shows that manganese mostly occupied in transition metal layer. XDS analysis of the fully charged sample indicated that Ni element further migrated to the lithium layer.
These analytical approaches are important to understand the metal migration behavior as a function of operation potential together with the charge compensation mechanism during electrochemical charging and discharging.

References

[1] Thackeray, M. M.et al., J. Mater. Chem.
2007, 17, 3112.
[2] Ito, A. et al., J. Power Sources
2011, 196, 6828.
[3] Kawaguchi, T. et al., J. Synchrotron Rad. 2014, 21, 1247.

Acknowledgement

This work was supported by RISING of NEDO.

Fig. 1 In situ Ni-K edge XAS spectra at 1st charging to 4.5V (a), irreversible plateau region (b), end of charging region 4.7-4.8 V (c), discharging to 2.0 V (d).
Fig. 2 DAFS spectra of Ni-K edge XANES-like spectra (a) and Mn-K edge XANES-like spectra (b).

Figure 1