Supporting Information

Improvement of the Cathode Electrolyte Interphase

on P2-Na2/3Ni1/3Mn2/3O2 by Atomic Layer
Deposition

Judith Alvaradoa,b‡, Chuze Mab‡, Shen Wangb, Kimberly Nguyenb, Moses Kodurb, Ying Shirley Mengb*

a. Materials Science and Engineering Program, University of California San Diego, La Jolla
CA 92093, USA
b. Department of NanoEngineering, University of California, San Diego, 9500 Gilman Drive, La Jolla,
CA 92093, USA

* E-mail (Y.S.M.) shirleymeng@ucsd.edu

S-1
Figure S1. Normalized XRD pattern of pristine-uncycled-uncoated P2-Na2/3Ni1/3Mn2/3O2 and (b)
the corresponding Rietveld refinement results. Lattice parameters are: a = b = 2.8878Å and c =
11.1596 Å. The Rwp is 2.37 and Rp is 6.07.

Table S1. Rietveld refinement results (lattice parameters, Na

sites, and R-factors)

S-2
 Figure S2. (a) SEM image of ALD coated P2-NaNiMnO particle, (b) SEM image coated
P2-NaNiMnO electrode without conductive additive, (c) EDS elemental detection of SEM
image b, and its corresponding (d) EDS elemental percentage table.

SEM images (a) and (b) demonstrate the morphology of the uncycled uncoated electrodes.

Furthermore, the ALD coating did not affect the morphology of the electrode. EDS was used to

determine the atomic percentage of the Al2O3 and its effectiveness to coat the electrode.

S-3
Figure S3. Preparation of electrode by Focused Ion Beam(FIB) (a)Platinum protecting layer
deposited on P2-NaNiMnO electrode, (b) After Milling, (c) TEM picture of sample on Omni
Probe, the red circle indicates where the TEM image are taken. (d) Dark field TEM image and
(e) bright field TEM image of electrode. Image (f) demonstrates the TEM image without FIB
preparation.

S-4
 Figure S4. High resolution TEM image of ALD coated P2-
NaNiMnO particle with a d spacing of 1.86 Ǻ, equivalent
to the (104) plane.

In the early stages of experiments, the coating thickness was measured by scrapping off the

electrode from the aluminum current collector and loaded on the TEM grid. It became apparent

that is would be difficult to determine the coating thickness of the ALD coating because both the

ALD coating and the conductive additive are amorphous (highlighted in the figure). Therefore,

focused ion beam was used to cut a piece of the coated electrode and loaded on to the TEM grid,

allowing us to properly see and determine the coating thickness (Figure S4). Figure S5 shows the

coated P2-NaNiMnO in the (104) plane.

S-5
 (a) (b)

(c)

Figure S5. (a) EIS of the uncycled first cycle Nyquist plot of the full cell, cathode, Na metal.
(b) Fitted Nyquist plot of the cathode using the equivalent circuit in (c). Equivalent circuit and
table describes the symbol of the equivalent circuit.

Figure S5 demonstrates the effectiveness of using a 3 electrode cell to determine the impedance

of the working electrode (P2-NaNiMnO), counter electrode (Na) and of the “full cell”, which

takes into consideration the resistance of the Na metal and P2-NaNiMnO. Figure S5 (a) shows

the Nyquist plot of the uncoated P2-NaNiMnO after one cycle discussed in the paper. Here one

can see the impedance of the full cell, P2-NaNiMnO, and Na metal. To our surprise, the Na

metal contributes significantly to the impedance of the full cell. Both of the Na metal and P2-

NaNiMnO impedance add up to the impedance of the “full cell”. The equivalent circuit used to

fit the Nyquist plot of the P2-NaNiMnO electrode as described in the paper and the table defines

the symbols.

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Figure S6. Elemental atomic percentage of the uncoated and ALD coated cycled electrodes at first
charge 4.1V, 4.5V, 5 cycles, and 100 cycles.

S-7
Figure S7. Manganese 2p region scan and fits of (a) uncoated P2-NaNiMnO and (b) ALD
Al2O3 coated P2-NaNiMnO. Nickel 2p region scan and fits (c) uncoated and (d) coated
electrode.

S-8