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Article
LiNi Co Al O (NCA) Cathode Material: New
0.8 0.15 0.05 2

Insights via Li and Al MAS NMR Spectroscopy

7 27

Nicole Leifer, Onit Srur-Lavi, Irina Matlahov, Boris Markovsky, Doron Aurbach, and Gil Goobes
Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.6b01412 • Publication Date (Web): 13 Sep 2016
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Page 1 of 15 Chemistry of Materials

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2 LiNi0.8Co0.15Al0.05O2 (NCA) Cathode Material: New Insights via 7Li and
3
4 27
5 Al MAS NMR Spectroscopy
6
7
8
9 Nicole Leifer, Onit Srur-Lavi, Irina Matlahov, Boris Markovsky, Doron Aurbach, Gil Goobes*
10
Department of Chemistry, Bar Ilan University, Ramat Gan 5290002, Israel.
11
12
13 ABSTRACT: Aluminum doped mixed metal oxides are popular positive electrode materials for Li-ion batteries. They are used
14 extensively in many applications yet their operation and limitations are not entirely understood. This work shows the ad-
7 27
15 vantage of using solid-state Li and Al NMR for monitoring the electrochemical properties of the doped nickel-cobalt oxide
16 cathode material, LiNi0.8Co0.15Al0.05O2 (NCA), particularly during the first few charge/discharge cycles. The changes in the
17 state of the material as lithium ions are intercalated and de-intercalated during discharge and charge respectively, are high-
18 lighted via the Li nuclei as a dynamic reporter and the Al nuclei as a static, material-embedded reporter. In particular, the NMR
view of the cyclic change of Ni ions between paramagnetic and diamagnetic oxidation states is enhanced by monitoring both
19 nuclei. Two protocols of cycling the NCA electrode are compared: one employing a smaller voltage window, cycled against
20 graphite as anode, and one using a wider voltage window, cycled against a lithium metal anode. The NMR analysis unveils
21 notable differences in the reversibility of the changes in the Ni oxidation states as charge carriers are shuttled in and out of the
27
22 cathode material. The Al NMR data of the pristine material shows the existence of at least two distinct configurations of Ni
23 ions around the Al dopant ions, suggesting co-existence of two disparate phases, which remain intact upon cycling. The pro-
24 tocol employing slower cycling versus Li anode delivers better cathode performance in the sense that more extensive re-
25 lithiation occurs and here it is shown that the return of the local environments to their pristine electronic configurations is more
27 7
26 complete. The Al and Li NMR results are integrated into a simple scheme exemplifying how better understanding of the
local electronic changes in paramagnetic electrode materials can be gained using this approach.
27
28
29
30 INTRODUCTION choice of dopant for many different transition metal oxide
31 Lithium battery research today is highly driven by con- systems. Aluminum has a thermal stabilization effect due
32 sumer demand for longer-lasting and better performing to partial substitution for nickel.2 The aluminum ions, hav-
33 energy storage systems for use in many devices, from ing similar radii to Ni and Co (rCo+3=0.545 Å, rNi+3=0.56
34 portable electronics to electric cars. Transition metal Å, rAl+3=0.53 Å)3, occupy the TM sites in the layered R-
35 (TM) layered oxide materials, particularly of the form Li- 3m crystal structure.4
36 MO2 (M=Mn, Ni, Co), exhibit the most appropriate cath- First-principles calculations suggest that at room
37 ode properties in terms of specific capacity, energy den- temperature Li(Ni,Al)O2 is in the form of a solid solution5,
38 sity, relative safety and cost. This body of materials, ini- meaning that Al and Ni are spread evenly in the TM lay-
39 tially proposed in 1980 starting with LiCoO2, has evolved er. Additional studies have shown that aluminum substi-
40 to include the huge variety of transition metal oxide com- tution up to 15%, and in some cases up to 30% in the
41 binations that exists today. nickel layers indeed results in the formation of a solid
42 The main drawbacks of the initially developed lay- solution.6-8
43 ered LiCoO2 cathodes are their high price and cobalt tox- In contrast, in LiNiO2 with aluminum content of 10-
44 icity, but the primary limitation is their limited practical 50%, x-ray diffraction (XRD) measurements have indi-
45 capacity due to oxygen loss in the partially de-lithiated cated that dopant aluminum ions are distributed inhomo-
46 cathodes. Consequently, the capacity consequently geneously.9 Further support for the segregation tendency
achieved, 140 mA, is only half of the theoretical value. of nickel and aluminum in the layered lithium nickel ox-
47
The addition of nickel to the cobalt oxide system (e.g. ides was inferred from a more recent study utilizing syn-
48 LiNixCo1-xO2) serves to reduce the cost of the material chrotron XRD, electron diffraction, energy-dispersive x-
49 and increase the capacity to 180-200 mAh/g, in part be- ray diffraction (EDX) and electron energy loss spectros-
50 cause these cathodes do not appear to lose oxygen until copy analyses.10
51 the lithium stoichiometry falls below 0.3. However, the Aluminum serves to reduce oxygen release from
52 substitution of cobalt for nickel introduces a structural the system by suppressing the exothermic reactions of
53 instability under mild heat due to the migration of the the nickel-oxides with the electrolyte.16 This reduction of
54 nickel ions from the nickel plane (3a) to the lithium plane material breakdown has also been suggested to be a
55 (3b), which can lead to a subsequent transformation to result of the stabilizing effect of aluminum on the cath-
56 spinel structure.1 ode's charge-transfer impedance.17
57 One successful way that this issue is addressed is
58 by doping the cathode with aluminum cations, a common
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3 A related consequence of the presence of alumi- materials, mainly, but not limited to transition metal oxide
4 num in these systems is the reduced variation in the unit cathodes and carbon-based anodes. Due to its ability to
5 cell c-parameter in the crystal lattice. In a study of probe the immediate environment of the nucleus, NMR is
6 LiNi0.8Co0.16Al0.04O2 cycled to 4.5V, the lateral cell param- applicable even in the case of highly disordered systems.
7 eters (a,b) were unaffected, but the c-parameter indicat- NMR is very sensitive to the electronic surrounding of the
8 ed a 0.7% change, versus a 3.5% change in the Al-free nuclei probed including the influence of neighboring ions.
9 analog. 14,15 It enables the monitoring of the effects of electrochemical
10 In all cases, the Al3+ ions remain electrochemically cycling on the ions directly and indirectly involved in the
11 inactive throughout cycling8,11 while maintaining high electrochemical processes. (in this case, 6,7Li & 27Al).31
12 practical capacity.8,12,13 The NMR properties of lithium nuclei in transition
13 Overall, the NCA system is currently an important metal oxide-based cathode materials are markedly af-
14 material for commercial use. The most commonly used fected by a strong interaction with TM ions containing
15 form of NCA is LiNi0.8Co0.15Al0.05O2, with an aluminum unpaired electrons in their orbital structure (i.e. paramag-
16 content limited to 5%. Its main advantages are relatively netic). The electronic environment around the Li nuclei
17 high specific energy, reasonably good specific power and becomes highly de-shielded due to hyperfine coupling, or
18 a long life-span. The exact reasons for the favorable ef- Fermi contact interaction, in which the paramagnetic spin
fects of the aluminum are only partly understood and density on the transition metal (in this case, Ni) ions is
19
further investigations may lead to improvement in cath- transferred to the Li 1s orbital via the overlapping oxygen
20 2p orbitals. The resultant Li NMR spectra are then char-
21 ode performance.
acterized by heavily shifted resonance lines.32,33
22 As typical of most of the nickel-based systems, the
first charge/discharge cycle of NCA is characterized by a Paramagnetic effects in 27Al NMR have been re-
23
large irreversible specific charge loss, with subsequent ported as well, both from direct contact with a neighbor-
24 ing paramagnetic ion and through-bond TM--O--Al spin-
25 cycles showing very stable capacity.11,15,18,19 This phe-
nomenon has been investigated in several studies, in polarization mechanisms.34-38 However, these reports are
26 much less common than Li NMR, presumably due to the
both the Al-free20 and Al-doped systems.19,21,22
27 larger quadrupolar interactions in 27Al which make the
28 Because of the importance of the first cycle in the-
NMR measurements and data interpretation much more
29 se systems, the cycling parameters, particularly in the
challenging. Several NMR studies have been conducted
30 voltage window used (3.0V – 4.1V) were carefully con-
specifically on the family of Ni/Co/Al lithium-intercalation
sidered. Several studies have concluded that above
31 compounds.4,39-45 Insights have been gleaned from NMR
4.1/4.2V, the Ni-based materials undergo some irreversi-
32 studies of the Al-free and/or Co-free analogs of the NCA
ble phase transitions, such as a drastic increase in defect
33 material as well, but only a handful focused on the
sites,23 nickel ion leaching, and/or a two-phase reaction,
34 standard NCA material itself. These are discussed in
which severely degrade the rechargeability of the materi-
35 context, below.
al.8
36 In this study, two different electrochemical cycling
The use of aluminum as a dopant at moderate
37 protocols were performed in order to investigate different
percentages helps reduce some of these undesired ef-
38 aspects of the NCA cathode material. The first protocol
fects.8,12,13 Additional reported effects of high voltage cy-
39 was performed on full cells (NCA vs. graphite), in ac-
cling (above 4.2V) in the LiNiO2 system include the
40 cordance with the PNGV Battery Test Manual.46 The se-
breaking of cathode particles and associated loss of elec-
cond protocol focused exclusively on the cathode by us-
41 trical connection,15 which in the NCA material leads to a
ing a half-cell configuration (vs. Li metal) and charging to
42 faster material degradation.24 Therefore, the two cycling
a lower voltage to ensure a more complete lithium inter-
43 protocols used in this study were set with voltage win-
calation upon discharge.
44 dows of 3.0-4.1V and 2.7-4.2V. Other studies have been 27
conducted in this more limited voltage range9,25 using Al and 7Li NMR were conducted on the cathode
45
various current densities (C rates) during cycling.17,26,27 materials extracted from disassembled cells that were
46
terminated at different states of charge (SOC) throughout
47 The uncycled material was initially thought to con-
the two above-mentioned cycling protocols. As outlined
48 tain the nickel as Ni3+. A later study reported an addition-
above, the surrounding paramagnetic Ni ions induced
49 al minor population of Ni2+ in the layered nickel-oxide
large shifts in the probed nuclei, whose resonance fre-
50 materials28. This was further corroborated using NEXAFS
quencies are then a function of the SOC of the NCA ma-
51 measurements showing that Ni2+ ions are found on the
terial.
52 surface of the NCA electrode.29,30 However, the relative
fraction of Ni2+ ions in NCA cathode material was not yet In contrast to the usual large positive shifts in the
53 7
Li spectra of lithiated NCA due to surrounding paramag-
determined, therefore, it is not known whether they have
54 netic Ni ions, unusually large negative shifts are ob-
an important role electrochemically.
55 served in 27Al spectra. This is demonstrated below and
56 Solid state nuclear magnetic resonance (NMR)
discussed in terms of the hyperfine interaction with the
has been employed very usefully in the last two decades
57 paramagnetic Ni ions. The 27Al nuclei are shown to serve
to probe many different types of electrochemically-active
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3 as a valuable static probe of the changes occurring in the in the voltage window used. It is also reasonable, given
4 layered material at various SOC and through different the moderate cycling conditions employed, to neglect
5 cycles. The results obtained complement the information side reactions, which otherwise may have affected calcu-
6 obtained from the 7Li nuclei of charge-carrying Li ions, lations of the Ni oxidation states.
7 which de-intercalate and re-intercalate into the cathode MAS NMR measurements
8 during each battery cycle. 7
Li and 27Al MAS NMR spectra were recorded on a
9 EXPERIMENTAL Bruker AvanceIII 200MHz spectrometer with respective
10 Preparation of sample cells Larmor frequencies of 77.73 and 52.11 MHz equipped
11 with a 4 mm VTN CPMAS probe. Additional 27Al MAS
The LiNi0.8Co0.15Al0.05O2 (NCA) studied in this work is a
12 cathode material used by Tadiran Batteries in N-type NMR spectra were recorded on a Bruker AvanceIII
13 cells. This material was used as the positive electrode in 500MHz spectrometer at a Larmor frequency of 130.32
14 the preparation of the electrochemical cells. The elec- MHz. The spectra were collected with no external tem-
15 trodes comprised 88% NCA, and the remainder polyvinyl perature control. All 27Al measurements were externally
16 difluoride (PVDF) and carbon black. The electrodes were referenced to Al(NO3)2(aq). All 7Li measurements were
17 double-side coated on aluminum foil with an average externally referenced to LiCl(aq)
18 loading of 9.8 mg/cm2 and a total thickness of approxi- 7
Li spectra were recorded using a spinning rate of
19 mately 80 µm. Prior to cell assembly, the electrodes were 12.5kHz and 27Al spectra were recorded at spinning rates
20 dried in a vacuum oven overnight at 120°C. Pouch-cells of 9, 10, 10, 15, 15, 15, and 12.5 kHz for samples 1A,
21 were used in which the cathode and the anode were 2A, 3A, 4A, 5A, 6A, 7A respectively and at 12.5 kHz for
22 separated by polypropylene separators (Celgard). samples 1B-6B. The 7Li spectra were collected using
23 The cells were filled with an electrolyte solution of single-pulse and rotor-synchronized Hahn-echo (90x-τ-
24 1M LiPF6 in EC:EMC=3:7 (by weight) and sealed in an 180y-τ-acquire) sequences, employing a recycle delay of
25 argon-filled glove-box. We assembled two types of cells 1 s and a π/2 = 1.9 µs. The 27Al spectra were collected
comprising NCA cathodes, one with a graphite anode using a rotor-synchronized solid-echo (90x-τ-90y-τ-
26
(full-cells) and one with a lithium metal anode (half-cells). acquire) sequence, a recycle delay of 0.3s, a π/2 = 2.0µs
27
The full cells were cycled between 3.0 and 4.1V at a C/5 and processed using exponential multiplication with 1000
28 Hz line broadening.
rate for the first cycle and a C/3 rate for subsequent cy-
29
30
cles (protocol A). The half-cells were charged to 4.2V at The uncycled NCA material 27Al solid-echo spec-
a C/15 rate for the first cycle, and cycled between 2.7 tra, acquired at 130.32 MHz, were collected using fre-
31 and 4.2V at a C/10 rate in subsequent cycles (protocol quency stepping of 1000 ppm (from -2000 to 2000 ppm),
32 B). a 90° pulse of 5.5 µs, spinning rate of 12 kHz, 9k scans,
33 echo delay period of 83.3 µs equal to the rotor period and
Seven NCA electrode samples were prepared un-
34 a recycle delay of 0.3 s. The signal was acquired with a
der protocol A, and six samples under protocol B, for
35 analysis by 7Li and 27Al MAS NMR. The samples, collect- dwell time of 1.6 µs and processing included a left shift of
36 ed at subsequent stages of cycling, are annotated by 202 points followed by exponential multiplication using a
37 cycle number and protocol type (see Figure 1). The 4000 Hz line broadening. The uncycled NCA material 27Al
38 uncycled electrode was also analyzed for comparison solid-echo spectrum, acquired at 52.11 MHz, employed a
39 (samples 1A and 1B). The experiments were conducted 90° pulse of 2.0 µs, a spinning rate of 12.5 kHz, 196k
40 ex-situ. For each sample, a cell was prepared and cycled scans, a transmitter frequency offset of -1000 ppm, an
41 separately in the constant current-constant voltage mode echo delay period of 80 µs equal to the rotor period, and
42 to the cut-off voltage labelled on the profile. The cells a recycle delay of 0.3 s. The signal was acquired with a
43 were then each held potentiostatically for five hours at dwell time of 1.6 µs and processing included a left shift of
44 the specified potentials (see Figures 1a and b; constant 180 points followed by exponential multiplication using a
45 voltage steps are not shown) to reach quasi-equilibrium 4000 Hz line broadening.
46 before disassembly inside an oxygen-free dry box. The Solid-echo measurements of delithiated material
47 samples were then extracted from the cells, rinsed with sample 5B (Figure 4 bottom) were done at 130.32 MHz
dimethyl carbonate and dried under vacuum. The sam- and 52.11 MHz using π/2 pulses of 5.5µs and 2.0µs re-
48
ples were then packed inside the box into airtight NMR spectively and an inter-pulse delay of one rotor period. In
49 rotors for analysis. both measurements spinning rate was adjusted to
50
The values for the Ni oxidation states at each elec- 12.5kHz, recycle delay was 0.3s and exponential multi-
51
trode state of charge are reported in Tables 1a & b and in plication with 400 Hz line broadening was used in pro-
52 cessing.
Figure 5. They were calculated by subtracting the equiva-
53
lents of remaining intercalated Li+ ions from the un- The 7Li NMR data were processed and fitted using
54 changed oxidation states of the O (-2 x 2 = -4), the Co the MestReNova program version 7.1.2-10008, from
55 (+3 x 0.15) and the Al (+3 x 0.05) and dividing by the MestreLab Research. The 27Al NMR data were pro-
56 number of equivalents of Ni (0.8). These calculations cessed using the Bruker software, TopSpin, version 3.2.
57 assumed no change in the Co or O oxidation states with- The 7Li single-pulse experiments were processed using
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3 no left shift, in order to capture the maximum amount of boratory cycling procedure. Protocol A employed cyclic
4 signal. charging to 4.1V and discharging to 3.0V, and protocol B
5 The sample signal was recorded after a standard employed charging to 4.2V and discharging to 2.7V, as
6 6.5 µs dead time delay to avoid overlap with the ring- shown in the figure. Additional differences in C-rates and
7 down, therefore, some baseline distortions in the spectra counter electrodes in the two protocols are given in the
8 were encountered. These distortions were removed us- experimental section.
9 ing a standard polynomial baseline correction algorithm Because of the differences in cycling conditions in
10 in most case and using a spline function in few spectra. the two protocols (the voltage window, cycling rates and
11 7
Li Hahn-echo experiments conducted on these the counter electrode used) valid comparisons can be
12 samples (Figures S3a & b) exhibited differences in rela- made as long as appropriate considerations are taken of
13 tive signal intensities from Li in diamagnetic environ- the differences expected for each cycling procedure. De-
14 ments and Li in paramagnetic environments, as com- tailed descriptions of these measurements are given in
15 pared to the single-pulse data.45 The signal intensities the Experimental section.
16 from surface versus bulk Li species in the samples are It is evident from the potential profile in Figure 1b
17 affected by disparate anisotropic bulk susceptibilities and that the electrochemically active voltage window contrib-
18 T2 (spin-spin relaxation) times which make any reliance uting to nearly all of the capacity is from 4.2V to 3.5V and
19 on intensity challenging. in the range from 3.4V to 2.7V the number of Li-ions de-
20 intercalated or intercalated is negligible. The latter phe-
21 nomenon is represented in the curve by the constant
22 vertical regions. The differences in content of charge car-
riers along similar steps in the two cycling profiles are
23
generally due to two main reasons. One is the anode
24 used, Li metal vs. graphite. The other is the C-rate used.
25 The slower rate in protocol B allows for more efficient
26 and therefore more complete re-lithiation. The voltage
27 window used is large enough to have an insignificant
28 effect on the Li content in the cathode.
29 In terms of the cells’ de-intercalation steps
30 (charge), the anodes used (graphite or Li metal) play a
31 minor role. The different upper charge voltages used and
32 the different currents applied dictate the amount of lithi-
33 um de-intercalated from the cell. Therefore, the cells from
34 the two protocols can be compared on that basis alone.
35 Since it is only the NCA material that is under investiga-
36 tion in this study, it is only the amount of Li remaining in
37 the material that is of relevance to our analysis.
38 The cycling profile in protocol B is similar to previ-
39 ously reported NCA cathode cycling profiles.19,47 The cy-
40 cling profile in protocol A exhibits some differences from
41 Figure 1: a, b) Potential profiles measured from these reported profiles due to the changes in the dynam-
42 NCA electrodes using cycling protocols A and B, ics of lithiation when cycling is performed against graph-
43 respectively. Protocol A entailed a first charge at a ite with relatively high C-rates. The calculated number of
C/5 rate and subsequent cycles at a C/3 rate. Pro- Li equivalents and average nickel oxidation state (OS) at
44 tocol B entailed, a first charge at a C/15 rate and each state-of-charge (Table 1) were derived from the
45 subsequent cycles at a C/10 rate. The dots indicat- capacity value at each state. The OS was calculated as
46 ed on the curves are the points during cycling at described in the Experimental section.
47 which the cells were terminated and samples taken
48 for NMR measurements. In protocol A, sample 2A was charged to 4.1V and
49 only 56.0 ± 2.8% of the lithium was extracted. Sample 2B
50 RESULTS AND DISCUSSION was charged to 4.2V resulting in 78.6 ± 3.9% of the Li de-
Electrochemical cycling intercalated. The latter sample reached near complete
51
de-lithiation of the material, since 20% of the lithium must
52
Cycling profiles of NCA cathode material are shown in remain intercalated within the material at full charge due
53 to the presence of 5% of Al and 15% cobalt, which are
Figure 1 with points along the charge-discharge curves at
54 electrochemically inactive in this voltage range.
which samples were taken for NMR analysis. These pro-
55 files represent comparison between two protocols, proto-
56 col A matching standard requirements in commercial
57 cycling tests, and protocol B chosen to follow typical la-
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Table 1: Details of lithium percentage in the NCA cathode samples at each voltage, as calculated from the
4
capacity data (not shown), and the corresponding average oxidation state of the nickel ions calculated from the
5 7
electrochemical results, and calculated from the Li NMR shifts for protocols A and B, as shown in Figure 1.
6
7
8 Average Ni oxidation state
9 Sample Final voltage % Li in cathode
10 calculated from capacity calculated from 7Li NMR shift
11
12 1A -- 100 3.00 --
13
14 2A 4.10 44.0 ± 2.8 3.70 ± 0.04 3.63
15
3A 3.60 61.0 ± 3.1 3.49 ± 0.04 3.31
16
17 4A 3.00 79.0 ± 4.0 3.26 ± 0.05 3.01
18
19 5A 4.10 43.0 ± 2.9 3.71 ± 0.04 3.66
20 6A 3.00 79.0 ± 4.0 3.26 ± 0.05 3.06
21
22 7A 3.00 77.5 ± 3.9 3.28 ± 0.05 3.06
23
1B -- 100 3.00 --
24
25 2B 4.20 21.4 ± 3.9 3.98 ± 0.05 3.92
26
3B 3.75 62.2 ± 3.1 3.47 ± 0.04 3.17
27
28 4B 2.70 99.8 ± 5.0 3.00 ± 0.06 --
29
5B 4.20 24.8 ± 2.8 3.94 ± 0.04 3.81
30
31 6B 2.70 86.0 ± 4.3 3.18 ± 0.05 --
32
Note that the partially discharged samples (3A and The corresponding differences in the 7Li and 27Al
33
3B), despite their different states of charge (maximum NMR results of these samples will be described below.
34 final voltages of 3.6V and 3.75V, respectively), resulted The differences in Li content and average Ni oxidation
35 in nearly equal percentages of Li (partial) re-intercalation: state are used in conjunction with NMR measurements in
36 61.0 ± 3.1% and 62.2 ± 3.1%, respectively. The larger a semi-quantitative manner to show different partitioning
37 differences in lithium re-insertion appear after one cycle of Ni ions between diamagnetic (Ni4+) and paramagnetic
38 in samples 4A and 4B and are a consequence of the an- (Ni3+, Ni2+) states at different cycling stages in the two
39 odes used (graphite vs. lithium metal, respectively). protocols.
40 Cathode samples 5A and 5B were taken at the
41 end of the second and fifth charge to their cut-off voltag- NMR studies of pristine and cycled material – 7Li NMR
42 es respectively (4.1V for 5A vs 4.2V for 5B). The per-
43 The 7Li spectra of the samples from protocols A and B
centages of remaining lithium charge carriers in the cath-
are shown in Figure 2 with spectra representing analo-
44 odes at these states relative to the values after the first
gous points along the cycling profiles shown in parallel,
45 charge were: 43.0 ± 2.9% in 5A vs 44.0 ± 2.8% in 2A and and colored similarly. The peak at 0 ppm (marked with a
46 24.8 ± 3.8% in 5B vs 21.4 ± 3.9% in 2B. This indicates dashed vertical line) of lithium in diamagnetic environ-
47 that in each protocol separately, Li ions intercalated and ments is attributed to unreacted precursor salts on the
48 de-intercalated quite reversibly as the cycling proceeded. surface of the cathode or Li surrounded solely by Co and
49 Samples 7A and 6B similarly reflect the state of Al neighbors in the first and second coordination
50 the NCA material in the discharged state at the end of spheres, suggesting inhomogeneous TM ion distribution.
51 the fifth cycle. They both showed the expected decrease The differences in the 0 ppm peak intensities in
52 in reversible lithiation. A larger drop of 22.5 ± 3.9% was the spectra of the uncycled materials, 1A and 1B, are
53 observed for the full cell in protocol A, compared to 14.0 due to the presence of unreacted lithium-containing pre-
54 ± 4.3% for the half-cell in protocol B. The former value cursor materials (e.g. LiOH) indicating slight differences
55 reflects the partial discharge already noted above. The in sample preparation. The differences in the paramag-
56 decrease in protocol B was slightly higher than expected netically shifted peak are due to the different spinning
57 for the material after only five cycles. rates used in the NMR experiments causing differences
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3 in the sample temperatures, which have an inverse effect broad spectra of the pristine and re-lithiated samples
4 on the paramagnetic shift.48,49 were fitted crudely, in order to determine an approximate
5 In the cycled samples, with Ni4+ forming, the 0 value for the main line intensity. These fittings are indi-
6 ppm peak can result from either lithium surrounded by cated in Figure S1. The changes observed in the line
7 diamagnetic TM ions (Ni4+, Al3+, Co3+) or Li-containing width of the main (non-zero) peak include a narrowing
8 surface breakdown products such as LiOH, LiF and oth- from ~15 kHz to ~7 kHz and are also the result of neigh-
9 ers forming the solid electrolyte interphase (SEI). boring paramagnetic Ni ions.
10 The diamagnetic peaks in the various spectra ex- The dipolar broadening mechanism is known to af-
11 hibit broad spinning sideband manifolds (marked by *) fect the 7Li signal50 and as the cycled (fully charged and
12 which span up to 2000 ppm in some samples. These partially discharged) samples contain less of the para-
13 very broad patterns are the result of the through-space magnetic species Ni3+ and Ni2+, they exhibit less of this
14 interactions of the Li nuclei with unpaired electrons of broadening phenomenon as indicated earlier for the NCA
15 Ni3+/Ni2+ ions that are distant (beyond the second coordi- material27 and for the Al-free analog.40 The shift values of
16 nation sphere) and therefore are not causing a Fermi these resonances for the different samples are given in
17 contact shift. The breadth of the manifold reflects the Tables S1 and S2.
18 strength of the effective dipolar-like interaction, which The upfield shift typically occurring upon succes-
19 depends on the number of Ni3+/Ni2+ ions and their dis- sive Li de-intercalation was observed, as a result of the
20 tances from the Li nucleus.42 oxidation of the Ni2+/Ni3+ to Ni4+, as was the subsequent
21 In both protocols, these sideband manifolds nar- downfield shift which occurs upon Li re-intercalation dur-
22 rowed substantially with each de-lithiation step (2A, 3A, ing each discharge cycle and its associated conversion
5A and 2B, 3B, 5B) as the amount of paramagnetic Ni of the nickel back to low oxidation states. The largest
23
decreased and the distances to the Li nuclei increased shifts were seen for the pristine samples 1A and 1B, for
24 which the average oxidation state of the Ni ions is 3.00,
25 with charge carrier extraction. The manifolds broadened
again with each re-lithiation step (4A, 6A, 7A, 4B, 6B) as and for the discharged samples 4A, 4B and 6B. Changes
26 in the resonance shifts were observed in the electrode
charge carriers were inserted back into the NCA material
27 material with progressive cycling. The partially charged
and Ni was reduced.
28 (de-lithiated) samples 3A and 3B show intermediate
29 Apart from the sharp line at 0 ppm common to all
shifts and the charged samples 2A, 5A and 2B, 5B exhib-
30 spectra, at least one other prominent line was observed
it the lowest shift values.
that varied in position and line width between different
31 The cycling conditions used in protocol A are very
samples. To determine the resonance shifts, careful line
32 deconvolutions were conducted on all samples. Samples similar to those used in a previous 7Li NMR study of
33 2A, 3A, 5A, 2B, 3B and 5B were fitted reliably. The very NCA.27 The resonance shifts measured (see Table S1)
34 are also comparable to shifts reported for samples similar
35
36
37 1A 1B
38
39
2A 2
40 B
41 3A 3B
42
43 4A 4B
44
45 5A
46 5B
47 6A
48
49
7A 6B
50
51
52
53
54 7
55 Figure 2: Li single-pulse MAS NMR spectra for (left) samples 1A-7A run at a spinning rate of 15 kHz, and (right)
56 samples 1B-6B (data not normalized) run at a spinning rate of 10 kHz. Approximate peaks of paramagnetically
shifted Li species are marked by empty diamonds and circles, diamagnetic Li signals (at ~0 ppm) by the dashed
57
line, and spinning-sidebands of 0 ppm peaks by asterisk.
58
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3 in both state-of charge and capacity fade.27 since they involve either inhomogeneous distribution of
4 ions or existence of divalent Ni ions, the average OS of
When the cells are fully charged, and all Ni ions
5 nominally oxidize to diamagnetic Ni4+, the remaining lithi- these samples does not appear in Table 1.
6 um is not expected to exhibit a shift at all, and instead is Sample 2A, charged to 4.1V, indicates a peak at
7 expected to resonate at or around 0 ppm. In the maxi- 171 ppm. Assuming now that all Ni2+ ions have oxidized
8 mally charged samples from protocol B (2B and 5B) the at this voltage meaning that the shift depends only on the
9 lithium remaining in the system does not resonate at 0 Ni3+ amount. Then, the 171 ppm corresponds to 3.6 n.n.
10 ppm. In the maximally charged samples from protocol A Ni3+ ions, and therefore 6 n.n. Ni4+ ions, giving an aver-
11 (2A and 5A) complete delithiation was not reached and a age Ni OS of 3.63, which is almost within error of the OS
12 significant Li shift is observed instead, reflecting the rela- derived from the capacitance (3.70 ± 0.04). Sample 2B,
13 tive quantity of Ni2+/3+ that remains in reduced form. The charged to 4.2V, indicates a peak at 36 ppm, corre-
14 shifts correlate to the difference in the average nickel sponding to a nearly fully discharged state. Using similar
15 oxidation states in the cells (further elaborated below), argument, the calculated average Ni OS from the NMR
16 and highlight the marked differences upon charging to shift gives 3.92, also slightly outside of the error of the
17 4.1V (protocol A) vs. charging to 4.2V (protocol B). electrochemically calculated value.
7
18 Li NMR studies of similar LiNiO2 materials have After multiple cycles, the resonance shift of the
19 shown that the large Li resonance shifts are the result of lithium retained in the cathode changes. After two cycles
20 cumulative individual shifts imparted by nearest neighbor under protocol A, the shift decreases from 171 (2A) to
21 (n.n.) paramagnetic nickel ions in either the first or se- 155ppm (5A), corresponding to the decrease in calculat-
22 cond coordination shell around the lithium ion. The differ- ed lithium (44.0% to 43.0%), while in protocol B, after five
ences between Ni2+ and Ni3+ paramagnetism (with d8 and cycles, the peak increases from 36 (2B) to 84 ppm (5B),
23
d7 electron configurations, respectively), result in Fermi in correspondence with the increase in lithium from
24 contact shifts that are twice as large in the former.51 21.4% to 24.8%. Again no Ni2+ is expected to remain at
25 Thus, each Ni3+ ion in the first coordination shell (1st n.n., this voltage, and thus the Ni OS is calculated from the
26 a 90o Ni-O-Li interaction) shifts by -15 ppm the reso- NMR shifts by Ni3+ ions as 3.66 (5A) and 3.81 (5B). The
27 nance and each Ni3+ in the second coordination shell (2nd value for 5A is within error of the electrochemically calcu-
28 n.n., a 180o Ni-O-Li interaction) by +110 ppm. Each n.n. lated value, while the 5B value is somewhat lower. It was
29 Ni2+ ion in the 1st shell shifts by -30 ppm and each n.n. suggested earlier that in cycled NCA, regions that are
30 Ni2+ in the 2nd shell by +170 ppm.40,51 electrochemically less active are formed30. These regions
31 However, a discrete distribution of the different with Ni ions in reduced state would be invisible to the
32 lithium environments is mostly not seen, because, as the electrochemical measurement, but would still contribute
33 Ni3+ and Ni2+ ions are oxidized to Ni4+, electron hopping is to the shifted Li resonance and lead to the lower Ni OS
34 enabled between the nickel states, and this occurs on a obtained from the NMR.
35 time-scale faster than the NMR sampling rate; therefore Spectra from samples 2A and 5A both indicate
36 'average' shifts are observed.33,42 small shoulder peaks. Sample 2A indicates a shoulder at
37 Assuming a defect-free layered structure, each 111 ppm constituting ~8.3% of the integrated intensity of
38 lithium ion is surrounded by six 1st shell n.n. TM ions and the main peak, which translates into a Ni OS of 3.76.
39 six 2nd shell n.n. TM ions. Since nickel ions constitute Sample 5A indicates a shoulder at 102 ppm that is 5% of
40 80% of the TM ions, this translates into an average of 9.6 the total intensity corresponding to a Ni OS of 3.78. The-
Ni ions, half in the 1st and the other half in the 2nd shell se data are indications of segregated regions within the
41
surrounding the Li ion. Then, 7Li shifts can be calculated bulk material, which have oxidized differently. The de-
42
for the pristine materials. Assuming all Ni ions are triva- crease in this ratio from 2A to 5A may suggest a reduc-
43 tion of these segregated regions, i.e., a homogenization
44 lent, the average value of the 1st and 2nd nearest neigh-
bor shifts would result in a 456 ppm shift (4.8 x 110 + 4.8 of the material over the course of the 2nd dis-
45 charge/charge cycle.
x -15 ppm).
46
However, the shifted peaks in the pristine materi- Samples 3A and 3B, which have nearly equal
47 amounts of lithium, both indicate shifts reflective of their
48 als are centered at a somewhat higher value, i.e. ~500
ppm. The additional shift can possibly be explained either partially discharged state. The difference in their shifts,
49 313 vs. 376 ppm, is mainly attributed to the disparate
by an overall 0.8:0.2 partitioning of Ni3+/Ni2+ (0.8x456 +
50 spinning rates used in the measurements. These sam-
0.2x672) or by existence of biphasic distribution of Ni3+ in
51 material, with 39% in a Co/Al free phase and 61% in a ples are similar to the 40% SOC sample in the Kerlau
52 stoichiometric NCA phase (0.61x456 + 0.39x570). Differ- study27, which underwent two cycles during preparation
53 ent scenarios with mix of several phases and other frac- before the final (partial) discharge, and indicated a 7Li
54 tions of divalent Ni, off course, can explain the resonance shift at 330 ppm. Again, neglecting Ni2+ in relithiated
55 shift obtained. The difficulty in accurately determining state, the NMR calculated average Ni OS of these sam-
56 experimentally this resonance shift from the 7Li spectra ples are 3.31 and 3.17, respectively. Both of these values
57 leaves this figure as an estimated value only. Moreover, fall below the Ni OS derived from the electrochemical
58 data. This undershoot of NMR calculated Ni OS, as
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3 aforementioned, may result from existence of an electro- similar to each other, but very different from the pristine
4 chemically inactive phase. state.
5 The spectra of the re-lithiated samples having sim- Additional relevant information about the changes
6 ilar SOC, i.e. 4A vs. 4B, as well as 6A, 7A vs. 6B are in- to the bulk spectra were revealed in the Hahn echo data
7 teresting to compare vis-a-vis. In the 'A' series, the collected (shown in Figures S3a & b). In protocol A, while
8 21.0% decrease in reversible lithiation is evident in the a large signal centered around 450 ppm is seen in the
9 NMR spectra, where the main bulk shift is reduced in pristine sample (1A) almost no bulk signal is seen in the
10 intensity reflecting less lithium ions re-intercalated in the re-lithiated samples (4A, 6A and 7A). In contrast, the re-
11 bulk material. However, the spectra of 6A and 7A are lithiated samples in protocol B (4B & 6B) exhibit signifi-
12 almost identical to that of 4A. In terms of the signal inten- cant intensity, equivalent to approximately 80 and 65%,
13 sity, this is expected, because the amount of lithium does respectively, of the original intensities. The explanation
14 not change considerably. Also, no additional resonance for these differences is due to the mobility of the 7Li ions
15 shift is seen, indicating that the system has reached an in the bulk material42.
16 invariant state and so the lithium environment remains Because of the changes induced in the spin sys-
17 unchanged. In the 'B' series, a shift is not seen in spec- tem during the time between the echo pulses (τ), highly
18 trum of 4B as compared to that of the pristine material. mobile 7Li ions may not recover by the echo. Thus the re-
This is expected because the re-lithiation is 99.8 ± 5.0%. lithiated samples from protocol A exhibit charge carriers
19
However, in the spectrum of 6B, fully discharged after that are more mobile, as compared to those from proto-
20
five cycles, the lithiation is only 86.0 ± 4.3%, yet the 7Li col B. Increased motions of Li ions in layered oxide mate-
21
NMR spectrum, while lower in intensity, has practically rials is generally expected upon de-lithiation, as the
22 the same resonance shift as in the spectrum of the pris- number of holes available for ion-hopping is increased.
23 tine material. Thus some differences in the samples with 99.8 % lithi-
24 um versus 79.0 % are to be expected. But, it is quite sur-
An overlay of these spectra, normalized to equal
25 prising to compare the signals of 6A and 6B, whose lithi-
intensity, renders them indistinguishable (see Figure
26 S2b). This suggests, then, that even with 86% re- um contents are 79.0 ± 4.0 % and 86.0 ± 4.3 %, respec-
27 intercalation in the fifth cycle, in protocol B, the Li ions re- tively, differing by only 7.0 ± 5.8 %, but whose respective
28 attain the same environment as in the pristine state. This 7
Li NMR responses may indicate very different Li mo-
29 is in contrast to the data from protocol A (see Figure S2a) tions. Relaxation measurements are required to further
30 in which the spectra of the re-lithiated samples are very assess that explanation.
31
32 
33 
34
35
 
36
37

38
39 
40
41 

42
43
44 

45
46
47  
48 
49
50 

51
52
53
54
27
55 Figure 3: Al solid-echo MAS NMR spectra recorded at spinning rates given in the experimental section for
56 samples 1A-7A (left), and for samples 1B-6B (right). Open circles and squares indicate approximate locations
57 of isotropic resonances, asterisks (*) indicate spinning-sidebands, data 1B-6B were not normalized.
58
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3 cond-order quadrupolar term. While this interaction can
4 NMR studies of pristine and cycled material – 27Al NMR potentially reveal further information on bond structure
5 While the 7Li signal followed a predicted pattern, the 27Al around the nucleus, the extra shift and reduced resolu-
6 NMR results of the material over the course of the first tion add further complication to interpretation of the 27Al
7 few charge/discharge cycles were in some cases unex- signals. In the presence of another large interaction e.g.
8 pected and potentially illuminating in terms of the local the Fermi-contact coupling, it is challenging to isolate and
9 changes occurring over the course of the cell cycling. determine individual contributions.
10 All of the prepared samples showed a peak in their The rotor-synchronized solid-echo pulse sequence
11 27
Al spectra at approximately 1640 ppm (not shown) (θ1 = 90ox, θ2 = 90oy) was employed to measure the 27Al
12 which was the signal from metallic aluminum shifted spectra of the NCA samples shown in Figure 3. The se-
13 downfield by Knight shift,52 a contamination originating quence, which serves to refocus some of the quadrupolar
14 from scraping off the electrode from its Al foil current col- broadening and suppress the broadening from quadru-
15 lector. pole satellite transitions, generated sensitive spectra and
16 showed the off-resonant signals of the bulk aluminum
The 27Al NMR spectra of the pristine NCA material
17 barely discernible in the single pulse experiments. The
exhibited extremely large negative shifts (-770 to -1150
18 line widths in the spectra were about 10-40 kHz. Due to
ppm), suggesting that a strong electron-shielding interac-
19 tion is affecting the 27Al nuclei (see Figure 3). A recent
20 study of NCA materials reported 27Al spectra with similar-
21 ly large negative shifts.45 Several 6/7Li NMR studies on
22 LiNi(1-y)CoyO2 materials indicated negative shifts from
23 through-bond hyperfine interactions with nickel
24 ions.40,42,55 In one study, the 6Li MAS NMR of La4LiMnO8
25 and La3SrLiMnO8 indicated resonances with large nega-
26 tive hyperfine shifts of -491 and -500 ppm, respectively.57
In a 119Sn NMR study of a series of lanthanide stannates
27
(Ln2Sn2O7), negative Fermi contact shifts as large as -
28 4150ppm were reported.55
29
30 The resonance shift is associated with a hyperfine
(Fermi-contact) coupling similar to the 7Li nuclei. Howev-
31
er, since the Al ions occupy TM positions in the layered
32 structure, its orbital overlap with vicinal Ni assumes a 90o
33 Ni-O-Al configuration. In this form of interaction, the Ni
34 electrons induce a net negative spin density on the elec-
35 tronic orbitals of the Al ion. The latter is reflected by a
36 substantial shielding effect on the nuclei and a large
37 negative shift.53-55 These shifts are larger than observed
38 for Li nuclei in similar electronic configuration (90o Ni-O-
39 Li). A more in-depth explanation of these interactions and
40 their calculations from first principles based on the
41 Goodenough-Kanamori super exchange rules can be
42 found elsewhere.42,53,56
43 To corroborate that the hyperfine interaction is the
44 predominant factor causing these large shifts, the sample
45 was run at elevated temperatures, and at two different
46 magnetic fields. The elevated temperature (data not
47 shown) caused a clear downfield shift, in accordance
48 with the inverse temperature dependence of the Fermi
49 contact shift. The measurements at 11.7 T and 4.7 T
were used to explore quadrupolar vs. paramagnetic 27
50 Figure 4: Al solid-echo spectra recorded at
mechanisms of line broadening.
51 27
130.3 MHz (11.7 T) (black) and 52.1 MHz (4.7 T)
52 Al nuclei (I = 5/2) have a significant quadrupole (blue) of (top) uncycled NCA material and
53 moment Cq = 14.66 Q/fm2, resulting in a large coupling (bottom) de-lithiated material (sample 5B). In
interaction that markedly affects the spectra of aluminum the top spectra of the pristine material, the
54
found in non-symmetric electronic environments. The experiment at 11.7 T was collected using
55 quadrupole coupling in 27Al is typically 100 kHz to 2 MHz. frequency stepping, and at 4.7 T was recorded
56 Therefore, the NMR central transition (-1/2 to 1/2) reso- normally, using a transmitter frequency offset
57 nance is shifted and broadened by a non-negligible se- of -1000 ppm.
58
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3 the limited resolution of samples 1A and 1B, the reso- Coming back to the spectra in Figure 3, another
4 nance shifts listed in Tables S2a & b and plotted in Fig- prominent feature of the 27Al data is that the pristine ma-
5 ure 5 have a substantial degree of uncertainty. terial exhibits at least two distinguishable resonances, at
6 To examine the contributions of hyperfine versus approximately –980 and -1070 ppm, indicative of two
7 the quadrupolar couplings to line width, solid-echo different configurations of 1st and 2nd n.n. Ni ions around
8 measurements were performed on the pristine NCA 1B the Al3+ ion. These isotropic shifts in the pristine material
9 sample (Figure 4 top) and on the cycled, charged 5B were determined via measurements at different spinning
10 sample (Figure 4 bottom) at 4.7 T and at 11.7 T. The rates. In their recent 27Al measurements of the NCA ma-
11 spectrum of 1B at 11.7 T is a panoramic reconstruction of terial Dogan et al.45 suggested a quantitative analysis of
12 four spectra measured at four different resonance fre- similar large negative shifts. The Al ion, occupying an
13 quencies as explained in the Experimental section.60 octahedral site in the TM layer, is in a 90o Ni-O-Al orbital
configuration thus experiencing a negative spin-
14 The 27Al spectra of the pristine sample indicate a
polarization interaction. This interaction was assigned a
15 similar resonance frequency for the negatively shifted shift of the Al resonance by ~ -100 ppm.45
16 line at around -1000 ppm. The spectrum recorded at 4.7
17 T (blue) appears broader on the ppm scale, but narrower The cumulative shift is obtained by adding up all
18 on an absolute frequency scale (see Figure S4). This interactions with the n.n. Ni3+ ions. Neglecting possible
increase in line width with field strength points to the hy- effects of the presence of Ni2+ (which would likely cause
19
perfine coupling (which grows with the field) as the main a larger shift, as seen for the 7Li), and assuming 12 inter-
20 actions with the 6 surrounding ions, this could explain the
21 source of line broadening in the pristine material spec-
trum. Line width dominated by the second order quadru- two shifts, i.e. –980 and -1070 ppm, as two phases in the
22 NCA. Non-distorted phase of homogeneously distributed
polar interaction (which scales inversely with the field)
23 Ni/Co/Al would result in a shift of -960 ppm (80% of the
would be expected to decrease going to higher magnetic
24 field. 12 nearest neighbors being Ni3+), explaining the -980
25 ppm resonance observed in our data. While a phase
For sample 5B, the 27Al spectra indicate a shift in
26 completely devoid of Co ions, e.g. with only Ni3+ ions sur-
the main peak from 1.3 ppm (at 4.7 T) with linewidth of
27 rounding the Al dopant would predict a peak at around -
4.5 kHz to 47.4 ppm (at 11.74 T) with linewidth of ~4.2
28 1200 ppm. The -1070 ppm peak seen herein, therefore
kHz (see also Figure S5). The field independent line
29 would correspond to partial (~50%) cobalt segregation,
width implies mutual cancelation of the opposite effects approximately 10.5 n.n. Ni3+, meaning ~ 87%.
30 of the hyperfine and the quadrupolar couplings on lin-
31 ewidth. In turn, it suggests that the resonance shift de- This existence of the Ni-rich second phase, in turn,
32 pends on the two interactions and precludes the use of implies partial cobalt segregation, a phenomenon report-
33 the two shift values measurements in the two fields for ed in the Al-free alloy of such materials and could explain
34 extraction of the quadrupole coupling constant using Eq. diamagnetic Al line in the pristine material spectra in Fig-
35 1.61 ure 3. Unlike in the lithium case, the 27Al shifts in the de-
36 
lithiated samples could not employed, based on this pro-

  
Eq. 1
 
  1
 1    posed value, to extract calculated Ni OS therefore their
37  ,   

analysis is left out. However, noteworthy is that in the re-
38 Interestingly, the contribution from quadrupolar coupling lithiated (re-charged) samples, these two distinct peaks
39 to the spectra could not be separated out from the para- (NCA and cobalt-depleted NCA) re-appear, implying that
40 magnetic one even for the extensively charged (mostly these phases remain intact even after several
41 diamagnetic) sample. charge/discharge cycles. These two regions may corre-
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56 27 7
57 Figure 5: Progressive Al (left) and Li (right) resonance shift plots as a function of cycling, showing the
reversible/non-reversible changes in the spectra of the NCA material subjected to cycling protocol A (blue) and B
58 (red) and demonstrating the larger shift values spanned by the latter protocol.
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3 spond to the phases identified in the pristine material
4 from XRD62 and XANES measurements,19,30 though the
5 issue of having divalent Ni ions and their ability to shift
6 the Al resonance further needs further examinations.
7 Upon electrochemical charging of the NCA mate-
8 rial, the 27Al signals shift downfield to less negative reso-
9 nance values (see Figure 3). As with the gradual shift
10 seen in the 7Li NMR measurements, the change in the
11 shift of the 27Al signal also reflects the gradual oxidation
12 of Ni2+/3+ to diamagnetic Ni4+. In contrast to the 7Li data,
13 almost no intensity was seen at 0 ppm in the 27Al data of
14 the pristine material, indicating that all of the aluminum is
15 in the bulk; no unreacted aluminum salts remain, nor do
16 they form upon cycling. This is unlike results reported in
17 a recent study on the NCA cathode where prominent
18 diamagnetic species were observed in the 27Al spectra.45
19 A few comparisons of the samples from the two
20 different protocols are worth noting. It is important to
21 point out that most of the variations seen in the spectra,
22 particularly with respect to the extra peaks seen in proto-
col B samples compared to the spectra from protocol A,
23
are due to the decrease in the spinning rate used, so that
24 more spinning sidebands are visible, and anisotropic in-
25 teractions are less efficiently averaged out.
26
Samples 2A and 2B both indicate a positive reso-
27
nance shift value of 15 and 222 ppm, respectively, and a
28 substantial reduction in peak width. The sizable decrease
29 in peak width suggests that it is mostly diamagnetic Ni4+
30 ions that are located in the two nearest coordination
31 shells of the 27Al nuclei in these samples. The major
32 downfield shift to a slightly de-shielded environment may
33 suggest that residual paramagnetic ions found in the Al
34 coordination shells in these samples are in a different
35 TM-O-M+ configuration so as to induce a positive spin
36 polarization on the nuclei. The incomplete charge asso-
37 ciated with protocol A and the subsequent limited oxida-
38 tion of paramagnetic Ni ions result in a larger fraction of
39 residual Ni2+/Ni3+ in this sample versus 2B.
40 The spectra of samples 3A and 3B are similar, as
was the case with the 7Li data. One noticeable difference
41
42 is that sidebands are unresolvable in 3A due to an addi-
43 tional broadening process. Both spectra indicate a nega-
44 tive shift reflecting re-lithiation and subsequent reduction
of the Ni4+ to its paramagnetic state. However, both spec-
45
tra also indicate some remaining intensity at 0 ppm, sug-
46
gesting a non-homogeneous re-lithiation in the vicinity of
47 the Al3+ ions.
48
Samples 4A and 4B indicate results that are anal-
49
ogous to their 7Li NMR counterpart spectra. As expected,
50
and in correlation with the extent of reversible lithium
51 intercalation under the two charging conditions, the shift
52
of the signal indicated in the sample from protocol A simi-
53 larly does not return to its pristine state upon a full cycle
54 of the material, while the signal from protocol B does.
55 Samples 6A and 7A separated by three cycles ex-
56 hibited similar 27Al spectra, demonstrating that the alumi-
57 num environment is nearly unchanged in the discharged
58
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state from the end of the second cycle forward, although
this state is of partial discharge compared to the pristine
material as judged by their smaller shift in absolute
terms. Samples 7A and 6B exhibited interesting varia-
tions from the lithium. The 27Al signal in sample 7A (and
6A, in fact) did not show the same shift as in sample 4A,
although the amount of Li is the same. This further sug-
gests the inhomogeneous re-lithiation of the cells under
protocol A.
In contrast, the 27Al data of the re-lithiated cells in
protocol B exhibited similar behavior to the 7Li results: the
five-times-cycled sample is almost identical to the data
after only one cycle, demonstrating that the NCA material
cycles back to a similar state as observed from both the
dynamic charge carrier spectra (7Li) and dopant spectra
(27Al).
The NMR results and the respective effect on the
resonance shift of the different paramagnetic Ni environ-
ments experienced by the charge carrier (7Li) and dopant
nuclei (27Al) as a function of the two cycling protocols
performed in this paper are summarized in Figure 5. This
form of progressive chart is used to represent some of
the effects seen in the NMR spectra and is suggested as
a useful tool to illustrate the performance of the battery
material. It also shows the reversibility or irreversibility of
the changes imposed by the electrochemical cycling on
the NCA material in terms of the changes to the partition-
ing of Ni ions between the different oxidation states.
It underscores the larger span of resonance shifts
obtained for protocol B in accordance with a larger varia-
tion in Ni OS imposed by a larger potential difference and
other cycling conditions and the deviation of sample 3B
from the overall trend of the samples in protocol B. It also
shows that within the limited cycling window used in pro-
tocol A, aluminum serves as a better proxy of the pro-
gressive changes in the material than Li. Similar plots
can be constructed for other cathode materials in order to
infer concise informative data from the NMR on the cy-
cling behavior of the oxide material that relates to its per-
formance.
CONCLUSIONS
This work offers some novel insights into the commercially
important NCA cathode material, which may be useful in
improving its long-term performance in lithium-ion batteries.
One of the findings is that despite its inactivity, the Al
27
serves as a distinct, static marker of the changes in the local
electronic environments in the bulk material, analogous to
6,7 27
the way Li has been used as a dynamic probe. The Al
NMR data of the pristine material also indicates the exist-
ence of at least two distinct configurations of Ni ions around
the Al dopant ions, which are not averaged out by electron
hopping. These two configurations, approximately equal in
magnitude, can be explained by significant cobalt segrega-
2+
tion, and/or the presence of a significant amount of Ni . It is
furthermore indicated that these distinct domains remain
intact upon cycling, even after several charge cycles. It is
possible that the existence of these regions corresponds to
11
 Chemistry of Materials Page 12 of 15

1
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3 the biphasic scenario suggested to exist in the pristine mate- LixNi1.02O2 and LixNi0.89Al0.16O2. Chem. Mater. 2003, 15, 4484–
30
4 rial via EXAFS. 4493.
5 +
Neither the pristine configurations around the Li nor 3. Shannon, R. D. Revised Effective Ionic Radii and Systematic
6 3+
around the Al environments are recovered in the charge- Studies of Interatomic Distances in Halides and Chalconides
7 discharge cycle in protocol A, reflecting the irreversibility, on Acta Crystallogr. 1976, A32, 751-767.
8 the electronic level, in samples cycled under these specific 4. Aurbach, D.; Srur-Lavi, O.; Ghanty, C.; Dixit, M.; Haik, O.;
9 conditions. In contrast, the results from the slower cycling Talianker, M.; Grinblat, Y.; Leifer, N.; Lavi, R.; Major, D. T.;
+ 3+ Goobes, G.; Zinigrad, E.; Erickson, E. M.; Kosa, M.; Markovsky,
10 used in protocol B indicate that both the Li and Al envi-
ronments return to their pristine configurations upon subse- B.; Lampert, J.; Volkov, A.; Shin, J.-Y.; Garsuch, A. Studies of
11 Aluminum-Doped LiNi0.5Co0.2Mn0.3O2: Electrochemical Behavior,
quent discharge to low voltage.
12 Aging, Structural Transformations, and Thermal Characteristics.
13 It was significant that in correspondence with the J. Electrochem. Soc. 2015, 162, A1014–A1027.
changes in nickel oxidation states occurring during cycling,
14 27
the Al NMR signal followed a similar (but opposite in sign)
5. Buta, S.; Morgan, D.; Van der Ven, A.; Aydinol, M. K. ; Ceder,
15 7 G. Phase Separation Tendencies of Aluminum-Doped Transi-
pattern of resonance shift variation typically seen in Li NMR
16 tion-Metal Oxides (LiAl1−xMxO2) in the α-NaFeO2 Crystal Struc-
of such materials. More so, comparative analysis under- ture. J. Electrochem. Soc. 1999, 146, 4335-4338.
17 scored, the differences that Al and Li ions are experiencing
6. Zhong, Q.; Sacken, U. von. Crystal Structures and Electro-
18 in terms of their electronic environments throughout the
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22 presentation, immediately expressing the variation with cy- chargeable Lithium Batteries. Solid State Ionics 1999, 116,
23 cling in various electrodes in a compact form. 271–277.
24 8. Ohzuku, T.; Ueda, A.; Kouguchi, M. Synthesis and Character-
25 ASSOCIATED CONTENT ization of LiAl1/4Ni3/4O2 (R3m) for Lithium-Ion (Shuttlecock) Bat-
26 teries J. Electrochem. Soc. 1995, 142, 4033–4039.
Supporting Information
27 9. Guilmard, M.; Rougier, A.; Grüne, M.; Croguennec, L.; Del-
Tables with 7Li and 27Al resonance shift values for all mas, C. Effects of Aluminum on the Structural and Electrochem-
28
samples, Line deconvolutions of samples 2A, 3A, 5A, 2B, ical Properties of LiNiO2. J. Power Sources 2003, 115, 305–314.
29 3B & 5B, 7Li single pulse and Hahn echo spectra of pris- 10. Croguennec, L.; Shao-Horn, Y.; Gloter, A.; Colliex, C.;
30 tine and re-lithiated samples, 27Al solid-echo spectra of Guilmard, M.; Fauth, F.; Delmas, C. Segregation Tendency in
31 samples 1B and 5B measured at 11.74 T and 4.7 T “This Layered Aluminum-Substituted Lithium Nickel Oxides. Chem.
32 material is available free of charge via the Internet at Mater. 2009, 21, 1051–1059.
33 http://pubs.acs.org.” 11. Guilmard, M.; Pouillerie, C.; Croguennec, L.; Delmas, C.
34 Structural and Electrochemical Properties of
35 LiNi0.70Co0.15Al0.15O2. Solid State Ionics 2003, 160, 39–50.
36 AUTHOR INFORMATION 12. Zhou, F.; Zhao, X.; Lu, Z.; Jiang, J.; Dahn, J. R. The Effect
37 of Al Substitution on the Reactivity of Delithiated
Corresponding Author LiNi1/3Mn1/3Co(1/3−z)AlzO2 with Non-Aqueous Electrolyte. Electro-
38
*Email: gil.goobes@biu.ac.il chem. Commun. 2008, 10, 1168–1171.
39
13. Croguennec, L.; Bains, J.; Bréger, J.; Tessier, C.; Biensan,
40 Ph.; Levasseur, S.; Delmas, C. Effect of Aluminum Substitution
41 Notes on the Structure, Electrochemical Performance and Thermal
42 The authors declare no competing financial interests. Stability of Li1+x(Ni0.40Mn0.40Co0.20−zAlz)1−xO2. J. Electrochem.
43 Soc. 2011, 158, A664-A670.
44 ACKNOWLEDGMENT 14. D'Epifanio, A; Croce, F.; Ronci, F.; Rossi Albertini, V.; Tra-
45 versa, E.; Scrosati, B. Thermal, Electrochemical and Structural
The authors thank Dr. Ronit Lavi for fruitful data discussions
46 Properties of Stabilized LiNiyCo1-y-zMzO2 Lithium-Ion Cathode
and Dr. Keren Keinan-Adamsky for assistance in operating
Material Prepared by a Chemical Route. Phys. Chem. Chem.
47 the NMR spectrometers. Phys 2001, 3, 4399–4403.
48
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