Al Doped NMC

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Article
Direct Observation of Lattice Aluminum Environments in Li-ion
Cathodes NCA and Al-doped NMC via Al MAS NMR Spectroscopy
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Fulya Dogan, John T. Vaughey, Hakim Iddir, and Baris Key

ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b04516 • Publication Date (Web): 14 Jun 2016
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Page 1 of 31 ACS Applied Materials & Interfaces
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Direct Observation of Lattice Aluminum Environments in Li-ion Cathodes NCA and
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5 Al-doped NMC via 27Al MAS NMR Spectroscopy
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12 Fulya Dogana,*, John T. Vaughey a, Hakim Iddirb and Baris Keya
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Chemical Sciences and Engineering Division,
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Materials Science Division,
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17 Argonne National Laboratory, Argonne, IL, 60439
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19 *: fdogan@anl.gov
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21 Abstract
22 Direct observations of local lattice aluminum environments have been a major
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24 challenge for aluminum bearing Li-ion battery materials such as LiNi1-y-zCoyAlzO2 (NCA)
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26 and aluminum doped LiNixMnyCozO2 (NMC). Al magic angle spinning (MAS) nuclear
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28 magnetic resonance (NMR) spectroscopy is the only structural probe currently available
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that can qualitatively and quantitatively characterize lattice and non-lattice (i.e. surface,
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31 coatings, segregation, secondary phase etc.) aluminum coordination and provide
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33 information that helps discern its effect in the lattice. In the present study, we use NMR to
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35 gain new insights into transition metal (TM)-O-Al coordination and evolution of lattice
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37 aluminum sites upon cycling. With the aid of first principles DFT calculations, we show
38 direct evidence of lattice Al sites, non-preferential Ni/Co-O-Al ordering in NCA, and the
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40 lack of bulk lattice aluminum in aluminum “doped” NMC. Aluminum coordination of
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42 paramagnetic (lattice) and diamagnetic (non-lattice) nature is investigated for Al-doped
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44 NMC and NCA. For the latter, the evolution of the lattice site(s) upon cycling is also
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studied. A clear re-ordering of lattice aluminum environments due to nickel migration is
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47 observed in NCA upon extended cycling.
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51 Keywords NCA, NMC, lattice Al, Al segregation, transition metal migration, Al MAS
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NMR, DFT
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ACS Applied Materials & Interfaces Page 2 of 31
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5 Introduction
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Rechargeable lithium batteries have a major role in the growing number of electric
10 vehicles (EV) reaching the market. This demand for high energy systems has highlighted
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12 the importance of identifying and understanding stable and safe lithium ion battery cathode
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14 materials. Aluminum-based coatings and partial aluminum substitution for transition metals
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16 (doping) are commonly used in lithium ion batteries to improve electrochemical
17 performance and chemical stability of the cathode systems by modifying the surface of
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19 cathode materials, increasing the operating voltages, enhancing thermal stability of the
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21 material, and reducing metal dissolution.1-7 Li1.0Ni0.8Co0.15Al0.05O2 (NCA) type cathode
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23 materials have achieved significant commercial use in the last decade due to its cost and
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safety advantages with high energy and power. To this end, Tesla’s Model S electric
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26 vehicle utilizes an NCA battery chemistry for on-board energy storage. Despite their
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28 widespread applications as positive electrodes in lithium ion batteries, the majority of
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30 characterization studies are on electrochemical performance and long range order of the
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material. However, there is a need for better understanding of local ordering, the
33 homogeneity of aluminum cations and possible segregation as well as understanding of the
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35 surface versus bulk aluminum species, as many of these factors play a role in the materials
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37 performance. The NCA class of materials have been extensively studied primarily by
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39 Delmas et al. and it has been reported that for a homogeneous aluminum distribution
40 (where nickel and aluminum ions are randomly distributed in the 3a sites) in nickel rich
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42 layered oxides (Li(NiAl)O2) the aluminum substitution should be limited to 5%. At higher
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44 aluminum concentrations, aluminum rich phases (such as γ-LiAlO2 and Li5AlO4) have been
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46 observed as impurities. Furthermore, optimum aluminum and transition metal compositions
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were previously reported and tentatively ascribed to aluminum local order.2-4
49 On the other hand, NMC type materials with LiMO2 composition where M is a
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51 combination Ni, Mn and Co have received major attention and are currently being used in
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53 commercial EVs. Mitigation of thermal and electrochemical instabilities often has involved
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55 several strategies including coating and/or doping aluminum into NMC. However, there is
56 very limited information on the lattice incorporation of the aluminum particularly in the
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case of dopings, the nature of the coating and the interface between the bulk and the
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5 coating for NMC type of cathodes.5, 7-9
In many cases, the substitution of aluminum in
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7 NMC type cathodes have been characterized by long range order techniques such as X-ray
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9 diffraction (observing indirect changes via cell parameters) and electron microscopy
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techniques with Al mapping. It is unclear at this point whether aluminum substitution is
12 effective or aluminum bearing species exist only as secondary phases in NMC.
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14 Solid state nuclear magnetic resonance (NMR) is a powerful local probe that has
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16 found increasing use over the last decades in battery chemistries. For paramagnetic battery
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18 systems, it is generally used to characterize bulk local structures. Due to hyperfine (or
19 Fermi-contact) interaction which is a measure of the unpaired spin density that is
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21 transferred from paramagnetic transition metals ions to lithium s-orbital, the NMR shift of
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23 Li nucleus in bulk is significantly shifted from that in diamagnetic surface environments.
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25 Fermi contact shifts and electron-nucleus dipolar interactions have been extensively studied
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for 6Li and 7Li MAS NMR providing useful information on lithium local ordering,
28 structural defects and changes in lithium environments upon cycling.10-13 However,
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30 hyperfine interactions of other nuclei in paramagnetic battery systems have not been
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32 extensively studied. 12, 14-16 Aluminum nuclei are especially challenging to study with solid
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34 state NMR in paramagnetic systems as it is generally deemed invisible to NMR mainly due
35 to the quadrupolar nature of the nuclei with very few exceptions.17 Whereas 27
Al MAS
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37 NMR has been widely used to study diamagnetic (surface coatings, impurity phases)
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39 species, its applications on bulk paramagnetic metal oxide cathodes have yet to be
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41 explored.
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In this study we show for the first time that 27Al MAS NMR can be used to directly
44 probe lattice (paramagnetic) and non-lattice (diamagnetic) aluminum environments for Al
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46 doped NCM and NCA and study the evolution of lattice aluminum sites upon cycling. The
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48 study focuses on three main aspects: (i) the effect of nickel and cobalt content in NCA on
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50 bulk Al coordination, and its evolution upon extended cycling, (ii) the effect of Mn on Al
51 segregation in the Al doped NCM structure, (iii) the effect of Al content on formation of
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53 secondary diamagnetic Al-bearing phases in NCA and Al doped NCM. Here we show that
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55 the use of an Al specific local structural probe is crucial to effectively study the presence of
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57 lattice aluminum in aluminum doped layered oxides for specific aluminum contents and
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synthesis conditions, especially as shown in this study when the intended dopant is not
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5 always incorporated into the layered oxide structure but stay as secondary species.
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9 Experimental
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12 Material Synthesis
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14 All materials (except TODA NCA and NCM 523 commercial powders) were
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16 synthesized by the direct reaction of Li(OH)•H2O with a mixed metal hydroxide of with the
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18 correct stoichiometric ratio of cations. The mixed metal hydroxides were synthesized by
19 mixing the appropriate amounts of metal nitrates in water, adding a slight excess of
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21 Li(OH)•H2O to precipitate the hydroxide precursor. After mixing for several hours, the
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23 precipitate was filtered and dried. This material was then washed with distilled water and
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25 centrifuged several times to remove any residual nitrate anions. Reports by the groups
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Chiang and Dahn on similar materials had stressed the importance of removing the nitrate
28 as any residual nitrate species strongly influenced the sintering properties of the isolated
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30 product.18-19 Once isolated, the hydroxides were mixed and fired at 500o C for 3 h then 900
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32 C for 3 h before cooling to room temperature.
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35 Electrochemical Testing
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37 Cathodes for the electrochemical tests were prepared by coating Al foil with a
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39 slurry containing 82 wt% of the oxide powder, 8wt% Super P carbon, and 10 wt%
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41 polyvinylidene difluoride (PVDF) binder in NMP and assembled in coin cells (size 2032).
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The electrolyte was a 1 M solution of LiPF6 in a 1:1 mixture of ethylene carbonate (EC)
44 and dimethyl carbonate (DMC). Cells were cycled between 3-4.5V with a C/5 rate. 20
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46 cycle sample discussed in section 2 was cycled against lithium and 120th cycle was cycled
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48 against graphite. Cycling tests were performed in a temperature-controlled oven at 30°C.
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50 After electrochemical testing the cells were immediately disassembled in an Ar filled
51 glovebox with an oxygen and water content both below 0.5 ppm. The cathodes were rinsed
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53 with anhydrous DMC to remove electrolyte and dried in Ar before NMR characterization.
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Structural Characterization
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5 XRD Powder X-ray diffraction (XRD) patterns for the synthesized samples were
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7 obtained using Bruker D8 diffractometer equipped with Cu-Kα radiation source (λ =
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9 1.5418 Å).
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Al MAS NMR spectra were acquired at two different fields, 7.02 Tesla (300
12 MHz) on a Bruker Avance III HD spectrometer operating at a Larmor frequency of 78.204
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14 MHz, and 11.7 Tesla (500 MHz) on Bruker Avance III spectrometer at a Larmor frequency
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16 of 130.25 MHz. A rotor synchronized echo pulse sequence (π/2 - τ -π - acq.), where τ= 1/νr
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18 (spinning frequency), was used to acquire the spectra with a 1.3 mm probe at varying
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spinning speeds of 60-67kHz (except the spectra in supporting information (Figure S1) and
21 300MHz data where only 67kHz was used). Pulse widths of 0.75 µs and 0.65 us were used
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23 at 11.7 and 7.02 Tesla magnetic fields, respectively. The pulse delay times varied between
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25 0.5s and 2s. The relaxation measurements on NCA compositions have shown that 0.5s is a
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27 sufficiently long pulse recycle delay to study the lattice aluminum environments (with T1
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29 relaxation time in the order of µs). For studies on diamagnetic aluminum species, variable
30 pulse delay experiments have performed (with 0.01s, 0.1s, 2s and 10s) and 2s was found
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32 sufficient enough to quantitatively study diamagnetic species (Figure S2). All spectra were
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34 collected at a constant temperature of 283 ± 0.1 K. The spectra were referenced to 1M
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36 Al(NO3)3 at 0 ppm .
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Li MAS-NMR experiments were performed at 7.02 Tesla (300 MHz) on a Bruker
39 Avance III HD spectrometer operating at a Larmor frequency of 44.21 MHz, using a 1.3
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41 mm MAS probe. All spectra were acquired at 67 kHz with a rotor synchronized echo pulse
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43 sequence (90°-τ-180°-τ-acq), where τ= 1/νr. A π/2 pulse width of 1.5 µs was used with
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45 sufficiently long pulse recycle delays of 0.2 s. All spectra were collected at a constant
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temperature of 283 ± 0.1 K. The spectra were referenced to 1M LiCl at 0 ppm.
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50 Theoretical Calculations
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52 Simulations were performed to investigate possible atomic arrangements Co and Al
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54 dilute dopants in LiNiO2 layered oxides. We employ first principles density functional
55 theory in the PAW representation, as implemented in the VASP code,20-21 the Heyd–
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57 Scuseria–Ernzerhof (HSE06) screened hybrid functional is used.22-24 Compared to the GGA
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+ U method,25 the hybrid functional improves the transferability of calculations across
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5 compounds by treating all orbitals on the same footing, thus improving the accuracy of
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7 defect formation energies. Most of the simulations were performed with only a single k-
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9 point, owing to the large cell size.
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All calculations are performed with a 6×8×1 super cell containing 48 formula units (f.u.)
12 (48Li, 48Ni and 96O), a total of 192 atoms. . In the absence of (Al or Co) dopants, Ni ions
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14 adopt a paramagnetic state in the 3+ charge state.
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18 Results and Discussion
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21 (i) Observation of Lattice Al sites in a Paramagnetic Lattice
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25 1) Pristine LiNi1-y-zCoyAlzO2 (NCA)
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To the best of our knowledge, the role of aluminum in layered cathode oxides have
28 been investigated mostly by diffraction and synchrotron methods. 6-7 Structural information
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30 on the layered structure of NCA suggests Ni, Co and Al to share the same lattice sites in the
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32 transition metal layers (Figure 1a). It is worth mentioning here that very little is known
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34 about the local coordination of Al in the pristine material. i.e. the first and second
35 coordination shells, let alone changes upon cycling for aluminum stabilized commercial
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37 material. In addition, the so-called role of Al incorporation into the “lattice” for alumina
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39 coated NMC materials annealed at high temperatures, as well as Al doped NMC has not
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41 been studied in detail by local structure characterization tools. Here, we use 27Al solid state
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NMR as a direct probe to monitor all the aluminum lattice sites and local coordination for
44 NCA and Al-doped NMC cathode materials.
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37 Figure 1 a) Graphic representation of 1st and 2nd coordination shell of an octahedral
38 aluminum (in blue) and transition metal sites in Al doped NMC and NCA lattices.
39 Arrangement of the 12 neighboring atoms around the central aluminum is highlighted.
40 Yellow highlights show 180o Al-O-Li and 90o Al-O-TM interactions. b and c are,
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schematic representations showing honeycomb (light blue) ordering with 35% and 10% Co
43 (with 5%Al) in the lattice, respectively. Blue and red dots are cobalt and aluminum atoms,
44 respectively in the transition metal layers within the nickel sub-lattice.
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47 Figure 2 shows 27Al MAS NMR spectra comparison of aluminum doped NMC and
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49 pristine commercial NCA. Consistent with the 27Al shifts reported previously on aluminum
50 oxides26 typical 4-6 coordinate diamagnetic aluminum environments have been observed
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52 for aluminum doped NMC. Furthermore, line-shapes and shifts of these cation
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54 coordinations are consistent with aluminum oxides and discussed in more detail in section
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56 3. Traditionally, any aluminum directly coordinated to the transition metal lattice, i.e.
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lattice aluminum, is expected to be non-diamagnetic and has often been deemed invisible in
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various Al NMR studies.17 On the other hand, the spectrum for the typical NCA is
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5 entirely different. In addition to the sharp diamagnetic aluminum resonances observed
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7 between 0-120ppm, very broad and highly shifted new Al resonance(s) have been
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9 observed at low frequencies. Similar shifts, on higher frequencies have regularly been
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observed for battery materials in 6Li and 7Li solid state NMR.11, 27 The shift is governed for
12 these systems due to d-orbital spin density transfer from paramagnetic transition metals via
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14 empty oxygen p-orbitals to nuclei under observation and is called the Fermi contact shift.
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16 In a recent study, a similar shift mechanism has been reported for aluminum doped iron
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18 oxides and oxyhydroxides by 27Al NMR as well.17 The resonance observed at -1214 ppm in
19 the NCA spectrum is due to the Fermi contact shift, and is accompanied with a set of
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21 spinning sidebands which is manifested by the MAS experiment. The origin of these
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23 spinning sidebands is partly from quadrupolar interaction of the spin 5/2 27Al nuclei which
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25 is the result of the interaction of the quadrupolar nucleus with the electric field gradient
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(EFG) at the nucleus due to the satellite transitions and partly due to electron-nuclear
28 dipolar coupling to nearby paramagnetic metal centers (dipolar interaction).
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30 In addition to the paramagnetic Al environments, a minor set of diamagnetic
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32 environments likely representing oxides can also be observed. These species could be
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34 either due to the formation of aluminum oxides, stabilized on the surface or aluminum
35 oxide phase segregation. Absolutely no paramagnetic aluminum resonances are observed
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37 for any of the NMC samples ran between 25000 to -10000 ppm range (Figure 2). Instead,
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39 major diamagnetic aluminum peaks with large sideband envelopes have been observed
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41 which account for all the aluminum in the composition in an integrated NMR peak
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intensity comparison including the spinning sidebands (Figure 2).
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36 Figure 2 Effect of metal composition on Al local structure: 27Al MAS NMR for, Al doped
37 NMC and NCA. The inset shows zoom-in spectra for diamagnetic shifts. The arrow
38 indicates lattice aluminum environment. The stars mark the spinning sidebands for
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40 diamagnetic aluminum peaks.
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42 In order to understand the nature of ordering for the paramagnetic Al environments
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44 in NCA materials, a set of samples of varying nickel and cobalt ratios have been
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46 synthesized while keeping the aluminum concentration constant at 5%. While decreasing
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48 the nickel content from 80%, to 60 and 40%, it is possible to quantify specific Al-O-TM
49 coordinations. Figure 3a shows a clear trend to higher frequencies in paramagnetic 27
Al
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51 resonance(s) with decreasing Ni and increasing Co content. The decrease in the Fermi
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53 contact is directly correlated with increased coordination of non-paramagnetic transition
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55 metals to aluminum sites, in the NCA system case; cobalt. With a maximum of 12xNi-O-
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Al coordination’s possible (see Figure 1 for 1st and 2nd coordination shell) which can result
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in maximum Fermi Contact or in other words the most negative shift, the shift observed at -
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5 1214 ppm is tentatively ascribed to Al-6Ni coordination’s in the TM layer honeycomb
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7 arrangement (Figure 1 b and c) for LiNi0.8Co0.15Al0.05O2. This tentative assignment is
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9 studied via theoretical calculations; first we investigated whether Co and Al substituted for
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two Ni atoms in LiNiO2 (Li48Ni46CoAlO96 cell composition) would prefer to cluster or be
12 far from each other (spaced configuration). The DFT calculations suggest rather similar
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14 energies for the spaced and clustered configurations, with Co being in the more stable 3+
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16 diamagnetic state. Therefore the theory does not show any driving force for Co-Al
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18 clustering in a Ni rich matrix, correlating well with the NMR shift assignment. According
19 to the assignment, each Al-O-Ni+3 90o coordination is associated with approximately -100
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21 ppm shift. Note that since aluminum atoms are assumed to be only in transition metal layer,
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23 the only possible Al-TM coordination is through a 90o interaction. Therefore, this negative
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25 shift is expected, considering the sign of hyperfine shift observed in an analog system; Li-
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O-Ni interactions in lithium metal oxides.12-13 The magnitude of the shift is an order of
28 magnitude larger compared to Li systems, which is in fact similar to the large shift range
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30 changes observed when moving from Li+ to Mg+2 ion paramagnetics in references13 and 15-
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34 Similarly, we have also investigated the case of Al dopants only. The DFT results
35 show that the clustered configuration (1.57 eV/cell, 33 meV/f.u.) is favored over the spaced
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37 configuration. HSE seems to be strongly sensitive to the atomic arrangements of Al
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39 dopants. As expected, Ni and Al are found to be in the 3+ charged state (magnetization 1
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41 and 0, respectively). In summary theory suggests that Al segregation would be favored in
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Ni rich matrix. This correlates well with formation of diamagnetic Al environments in NCA.
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Figure 3. Effect of nickel content on Al local structure of NCA : 27Al MAS NMR for
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5 LiAlCoO2, and NCA with varying Ni/Co composition, a and b show diamagnetic and
6 fermi contact shift, respectively. Sample marked with purple asterisks marks the
7 commercial NCA sample. Black stars mark the spinning sidebands for diamagnetic
8 aluminum peaks.
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Figure 4b shows Al NMR collected at a lower magnetic field (7.04T). Coupled
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13 with fast spinning and due to lower electron-nuclear dipolar interaction at lower magnetic
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15 fields, sufficient sideband separation is achieved to detect a minor resonance at -1000 ppm
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for LiNi0.8Co0.15Al0.05O2. This resonance corresponds to an aluminum cation surrounded by
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18 5 Ni’s and a Co cation, also written as Al-5Ni1Co coordination based on the shift
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20 assignments (10 x Al-O-Ni+3; 10 x -100ppm = -1000 ppm). When Ni content is decreased
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22 from 80% to 60%, the Al shift moves to higher frequencies, observed at ~ -600ppm (Figure
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5a) and significant disorder is introduced as evidenced by broadening of the Al
25 resonance(s) and sidebands. This broadening is suggestive of convolution of multiple
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27 aluminum local environments; Al-6Ni, Al-5Ni1Co, Al-4Ni2Co, Al-3Ni3Co, Al-2Ni4Co,
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29 Al-1Ni5Co. However, the prominent center of mass of resonance(s) which is at ~ -600ppm
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31 (half of -1200) indicates a significant concentration of Al-3Ni3Co local coordination
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present in LiNi0.60Co0.35Al0.05O2 based on the shift assignments (6 x Al-O-Ni+3; 6 x -
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34 100ppm = -600 ppm, as shown in Figure 3b and 4b). These experimental observations
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36 again correlate well with theoretical calculations; findings for non-selective aluminum
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38 cobalt clustering in NCA where the driving force of any possible Al-Co clustering is driven
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solely by the ratios of Ni and Co in the lattice. When compared to 60% Ni content, 40% Ni
41 content NCA (Figure 4b) spectrum has significantly more local order and slight shift to
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43 higher frequencies resonance(s). Figure 4b clearly shows three distinct resonances for
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45 LiNi0.40Co0.55Al0.05O2 composition at -184, -405 and -614 ppm. These resonances point to
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47 significant concentrations of Al-1Ni5Co, Al-2Ni4Co, Al-3Ni3Co based on the shift
48 assignments [(2,4,6) x Al-O-Ni+3; (2,4,6) x -100ppm = (-200,-400,-600 ppm)], respectively.
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50 It must be noted that there is a clear increase of the diamagnetic peak intensities at 80ppm,
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52 64ppm, 56ppm and at 13 ppm (Figure 3a) with increasing Co content in the NCA,
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54 indicative of increasing Li(CoAl)O2 local order and some 6-coordinate Al2O3, respectively.
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50 Figure 4 Effect of nickel content on local structure of NCA. a and b are 6Li MAS
51 NMR and 27Al MAS NMR at 7.04 Tesla, respectively. Stars mark the spinning
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sidebands for diamagnetic aluminum peaks.
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55 The lattice aluminum sites and the basis of paramagnetic 27
Al resonances are further
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57 investigated with 6Li NMR. Figure 4a shows 6Li MAS NMR spectra of NCA samples
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discussed in Figure 3b. Two main broad resonances can be identified at 700 and 600ppm
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5 with a center of mass around 600ppm for LiNi0.8Co0.15Al0.05O2 composition. These
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7 resonances are ascribed to Li in Li layers in coordination with nickel, cobalt and aluminum
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9 with varying ratios (mostly nickel rich) as shown in Figure 1. The broad resonance
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distribution is found to be more symmetric and Gaussian-like for LiNi0.60Co0.35Al0.05O2
12 with a center of mass at 400ppm. A sharper resonance at 100ppm and broader shoulder
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14 peaks up to 600ppm with an overall center of mass around 200ppm can be observed for
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16 LiNi0.40Co0.55Al0.05O2 –as diamagnetic cobalt content increases. These shift trends have also
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18 previously been observed and ascribed to decreasing paramagnetic shift contributor (Ni+3)
19 and increase of diamagnetic transition metal concentration (Co+3).10 However, the trend to
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21 lower frequencies and more interestingly, the distinct shapes of resonances correlate
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23 directly with Al environments observed which were discussed above. As lithium shifts
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25 decrease with increasing Co concentration, aluminum shifts increase in frequency.
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Specifically, two main groups of resonances were observed for LiNi0.80Co0.10Al0.05O2 in
28 both 6Li (Figure 4a) and 27Al NMR (Figure 3b and 4b) and can now be ascribed to the same
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30 Ni-Co clusters. Interestingly, a similarly broad, slightly symmetric and Gaussian-like
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32 distribution observed in 27Al NMR (Figure 3b and 4b) of LiNi0.6Co0.35Al0.05O2 is seen in 6Li
33
34 NMR (Figure 4a) as well, which largely agrees the statistical distribution of Ni-Co clusters
35 in this composition. Furthermore, the cobalt rich distribution of 27
Al resonances for
36
37 LiNi0.40Co0.55Al0.05O2 correlates very well with the 6Li resonances at 200 and 100ppm
38
39 (Figure 4a). It has to be noted that no such trend is observed with varying the composition
40
41 of paramagnetic transition metals (Ni+3 and Mn+3) for NMC. The center of mass of 6Li
42
43
resonances and peak shapes were found to be identical for LiNi0.5Co0.1Mn0.3Al0.1O2 (except
44 for 1450 and 750ppm sharp Li2MnO3-like ordering13 and LiNi0.6Co0.1Mn0.2Al0.1O2, when
45
46 compared to LiNi0.5Co0.2Mn0.3O2, in agreement with total lack of lattice aluminums.
47
48
49
50 2) Evolution of local structure and lattice Al sites in NCA upon cycling
51
52
53
The presence of Al in NCA lattice is crucial for electrochemical stability and
54 27
performance, therefore the evolution of paramagnetic Al resonances reported above for
55
56 NCA has been further investigated via an ex-situ study of cycled electrodes from both full
57
58
59
60 14
1
2
3
and half cells, between 3.0 to 4.5V up to 120 cycles. The electrochemical profile of the full
4
5 cell at 2nd and 119th cycle is shown in Figure 5. The initial capacity observed is around
6
7 200mAh/g and is dropped to 175mAh/g at the end of 119th cycle. Besides this gradual
8
9 capacity loss, a similar voltage profile has been observed for the fresh vs. the extensively
10
11
cycled NCA electrode.
12 The 27
Al MAS NMR of electrodes harvested from cells collected at 20th and 120th
13
14 cycles are compared with pristine NCA sample in Figure 6a. No major changes in Al order
15
16 has been observed between pristine material and the electrode sample collected after 20
17
18 cycles, suggesting no significant structural changes during early cycles. However, a shift of
19
center of mass of NMR peaks to higher frequencies were observed for the electrode
20
21 collected after 120 cycles, indicative of Al local structure change.
22
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45 Figure 5. Voltage versus capacity plot for cycled NCA
46
47
48 Due to the similar ionic radius of Ni and Li, the likelihood of Al local order change
49
50 upon extensive cycling is investigated via a Ni vacancy migration mechanism. In the case
51
52 of dilute Al and Co dopants, our DFT calculations show that Ni vacancy formation is most
53
54 favorable near Co and Al when second nearest neighbors, with the Ni vacancy located in-
55 between Al and Co in a non-linear configuration. When Al and Co are in the spaced
56
57 configuration (not adjacent), Ni vacancy formation is favorable near Co (by 5 meV/f.u.)
58
59
60 15
1
2
3
compared to being near Al. The strong Co-O hybridization allows for better charge
4
5 compensation mechanism than with Al-O bond. These results suggest that in these systems
6
7 (NCA), Co-Al segregation is the result of Co rather than Al migration, a mechanism
8
9 mediated by Ni vacancy migration. This, in turn, could be expected to generate a statistical
10
11
distribution of Al-Co and Al-Ni local order in the transition metals after 120 cycles.
12 Therefore the theory does show a driving force for Co-Al clustering in the presence of Ni
13
14 vacancies (resulting from Ni migration to the Li layer), correlating well with the NMR shift
15
16 changes upon extensive cycling. Furthermore, 6Li NMR of the cycled samples is also
17
18 compared with pristine powder in Figure 6b. The formation of a statistical distribution of
19 6
Li resonances for the 120 cycle sample supports the discussions on the Ni migration
20
21 theory and change of Al local order in the transitional metal layers from 27Al NMR results
22
23 above. It must be noted that due to ~ 12.5% lithium loss after 120 cycles, a small
24
25 percentage of the shifts observed after extended cycling may be due to presence of
26
27
diamagnetic Ni+4.
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52 Figure 6 Effect of cycling on local structure of NCA (LiNi0.80Co0.10Al0.05O2): 27Al MAS
53 NMR for NCA pristine, 20 cycles, 120 cycles a and b are 27Al MAS NMR and 6Li MAS
54 NMR, respectively. The inset shows 27Al MAS NMR of 120 cycle sample at 7.04 Tesla
55 Magnetic Field. Stars mark the spinning sidebands for diamagnetic aluminum peaks.
56
57
58
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60 17
1
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3
ii) Demonstration of Al Segregation from LiNixMnyCozO2 (NMC) Lattice; Effect
4
5 of Manganese
6
7
8 Aluminum substitution in NCM structure have been widely studied with varying Al
9 compositions and previous studies have shown that aluminum substitution should be
10
11 limited to 5-10% for an homogeneous distribution in the layered structure.3, 6 The structural
12
13 characterization studies with XRD Rietveld refinement have shown larger ahex. and chex.
14
15 cell parameters for aluminum substituted NCM compositions than that of the non-
16
substituted material.
17
18 On the contrary, in this study, no lattice aluminum coordination has been observed for
19
20 Li1.0Ni0.5Co0.1Mn0.3Al0.1 or Li1.0Ni0.6Co0.1Mn0.2Al0.1 compositions via 27Al solid state NMR
21
22 (Figure 2). The experiments performed at varying excitation frequencies (scanning wide
23
24
spectrum width) and pulse delays (studying relaxation effects), did not show any
25 paramagnetic shifted aluminum peaks as observed for NCA samples with similar aluminum
26
27 content. In order to study the effect of diamagnetic aluminum species formation and
28 27
29 correlate Al signal observed with dopant concentration: 2%, 5% and 10 % Al doped
30
31 NCM 523 materials were synthesized. The comparison of the three samples not only
32
provides information on the effect of aluminum content on surface segregation but also the
33
34 degree of aluminum substitution in the lattice and how lattice aluminum effects local
35
36 layered structure. As shown in Figure 7, none of the compositions show aluminum
37
38 resonances affected by hyperfine interactions. The integration of the aluminum peaks
39
40
(diamagnetic phases) observed for all three compositions gives roughly 1:0.58:0.2 ratios for
41 10, 5 and 2% aluminum addition to material, respectively. This mainly shows that the
42
43 aluminum atoms within the structure do not contain paramagnetic metal centers (Ni and
44
45 Mn) in their first and second coordination shell and mostly present as aluminum oxide or
46
47 separate aluminum clusters (mostly on the surface or interface) as a diamagnetic phase.
48 Note that aluminum substitutions (or presence of lattice aluminum) below 1% may not be
49
50 observed and can be invisible to solid state NMR. The effect of aluminum substitution on
51
52 lithium local environments was studied by 6Li MAS NMR. Both Li1.0Ni0.6Co0.1Mn0.2Al 0.1
53
54 and Li1.0Ni0.5Co0.1Mn0.3Al0.1 compositions show mostly solid solution like behavior
55
56
observed by lithium-6 MAS NMR similar to commercial Li1.0Ni0.5Co0.2Mn0.3 material.
57 Figure 8 shows the 6Li MAS NMR spectra of natural abundance LiNixMnyCozAlO2 /
58
59
60 18
1
2
3
LiNixMnyCozO2 samples with different compositions. All compositions show a broad
4
5 resonance centered around 600 ppm due to the distribution of different lithium
6
7 environments, which interact with nearby paramagnetic nickel and manganese.
8
9 Unsubstituted commercial NCM 523 material shows a broad small peak around 1360 ppm
10
11
due to lithium atoms in the transition metal layer which shows roughly 2% Li-Ni exchange.
12 Interestingly synthesized aluminum doped NCM 523 sample does not show any lithium
13
14 peaks due to Li-Ni exchange. On the other hand slight formation Li2MnO3 like ordering is
15
16 observed for this sample with the formation of lithium-6 peaks at around 716 and 1460
17
18 ppm.13 The formation of Li2MnO3, is most likely the result of increased Mn clustering,
19
resulting from Al doping, as suggested by the DFT results.
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48
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50
51
52 Figure 7 Effect of aluminum content on Al local structure of NCM 523: Normalized 27Al
53 MAS NMR data for Li1.0Ni0.5Co0.2Mn0.3with varying aluminum composition. a, b and c are
54
Li1.0Ni0.5Co0.18Mn0.3Al0.02, Li1.0Ni0.5Co0.15Mn0.3Al0.05 and Li1.0Ni0.5Co0.1Mn0.3Al0.1,
55
56 respectively. The inset shows diamagnetic region (non-normalized). Stars mark the
57 spinning sidebands for diamagnetic aluminum peaks.
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60 19
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32
33 Figure 8. Effect of aluminum on local structure of NCM: 6Li MAS NMR for pristine
34 (commercial) NCM 523 and Al doped NCM523 and NCM 622 compositions.
35
36
37 Both synthesized samples have signatures of diamagnetic lithium bearing species such as
38
39 surface LiAlO2 or impurities from the synthesis such as Li2CO3 species with a sharp peak
40 at 0 ppm (Figure 8). Although the main focus of the lithium experiments was the lattice
41
42 lithium environments (hyperfine shifted), intensity comparison of the diamagnetic lithium
43
44 peak of the two samples shows that the Al doped NCM 622 has more surface lithium
45
46 bearing species than Al doped NCM 523 which can be correlated with higher concentration
47
of surface aluminum species in the material. 6Li MAS NMR data for Al doped NCM
48
49 samples with varying aluminum content (2,5 and 10%) have shown same lithium local
50
51 environments for the lattice lithium atoms (data not shown).
52
53 From the theory perspective, a similar approach was used to sample the affinity of Mn
54
55
and Al to cluster within the Ni matrix, and the results (HSE) show that Mn and Al prefer to
56 be in a spaced configuration by 36 (meV/f.u.) rather than cluster within the Ni matrix. The
57
58
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60 20
1
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3
energetics favor Mn4+ states (charge compensated with Ni2+) which occur for Mn-Mn
4
5 clustering, not the Jahn-Teller active Mn3+; which occur when Mn-Al are next nearest
6
7 neighbors (NNN). In the case where we have 2Mn and 1Al dopants in the same cell, we
8
9 also find Mn-Mn clustering to be more favorable over Mn-Al clustering by 25 (meV/f.u.).
10
11
Therefore the theory does show a driving force for Mn-Al avoidance in a Ni rich matrix.
12 (This also correlates well with the observation of Li2MnO3-like ordering in Li1.0Ni0.5Co
13
14 0.1Mn0.3Al0.1 composition by 6Li MAS NMR). In this case Mn is 4+, and Al is 3+ in both
15
16 situations, however, Ni electronic configuration differs between the two configurations: we
17
18 obtained 3xNi2+ and 1xNi4+ for Mn-Al NNN, and 2xNi2+ and 1xNi3+ in antiferromagnetic
19 state for Mn-Mn NNN configuration. In summary theory suggests that Al segregation due
20
21 to any significant concentration Mn in a Ni rich matrix would be favored. This correlates
22
23 well with experimentally observed near total exclusion Al from an NMC lattice.
24
25
26
27
iii) Analysis of Trends in Diamagnetic Aluminum Components in NCA and Al-
28 doped NMC
29
30 27
31 Our Al solid state NMR studies have shown that whether the composition is
32
lithium nickel cobalt oxide or lithium nickel manganese cobalt oxide, aluminum doping in
33
34 the structure always results in formation of surface aluminum species (which might work as
35
36 more of a coating rather than dopant). Under the same synthesis conditions, the extent of
37
38 these surface species formation depends on the composition of the material such as nature
39
40
of transition metal, their distribution and aluminum content.
41 For lithium nickel cobalt oxide composition we have studied two different
42
43 approaches; the effect of increasing Al content in 80% Ni rich NCA and the effect of Ni/Co
44 27
45 ratio with 5% aluminum in the structure. Figure 9 compares Al NMR of 5%, 10% and
46
47 20% Al content NCA synthesized at the expense of Ni content. No major change is
48 observed for paramagnetic Al resonances (lattice aluminum environments) except an
49
50 expected slight shift to higher frequencies with slightly decreasing Ni content. On the other
51
52 hand, a major increase in the diamagnetic Al resonances at 90, 76 and 10ppm is seen for
53
54 20% aluminum sample suggesting that added Al is not incorporated at all into the lattice as
55
56
but found to form an excluded amorphous/disordered domains that are not captured in X-
57 ray diffraction data (Figure 10).
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36 Figure 9 Effect of aluminum content on Al local structure of NCA: 27Al MAS NMR for
37 NCA with varying aluminum composition, the inset shows diamagnetic region. Stars mark
38
39 the spinning sidebands for diamagnetic aluminum peaks.
40
41
42 For diamagnetic / surface species , 6-coordinate aluminum environments in Al2O3
43 and Al(OH)3 resonate between 0-10 ppm whereas 4- and 5- coordinated aluminum atoms
44
45 27
of aluminum oxides show distinct Al NMR peaks within 50-80 and 30 ppm regions,
46
47 respectively.26 Studies on LiAlxCo1-x O2 have shown a distribution of lattice aluminum
48
49 chemical shifts between 30 to 60 ppm with varying the cobalt contents as shown in Figure
50
51
3 and previously studied.8-10 LiAlO2 has two phases α-LiAlO2 and γ-LiAlO2 with
52 octahedral and tetrahedral aluminum coordination giving aluminum -27 peaks at around, 10
53
54 and 76 ppm, respectively. The former phase generally converts to γ-LiAlO2 phase at higher
55
56 temperatures ( > 500oC). AlN4 and AlOxN4-x compositions give aluminum -27 resonances
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60 22
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within 80-100 ppm range.26 The 27Al MAS NMR data for commercial LiAlO2 sample (data
4
5 not included) shows two main resonances (10 and 76 ppm) for both environments.
6
27
7 Considering these Al MAS NMR signatures of Al2O3, LiAlO2 and LiAlxCo1-xO2 we can
8
9 conclude that there is no major surface segregation of LiAlxCo1-x O2 phase for 20%
10
11
aluminum NCA sample. The peak at 76 ppm can be assigned as the tetrahedral aluminum
12 species in LiAlO2 and the 14 ppm peak with a shoulder at 8 ppm is due to the octahedral
13
14 aluminum environments in the octahedral sites of LiAlO2 and Al2O3, respectively (Figure
15
16 9, inset). The peak at 90ppm is unique to Al doped NCM and commercial NCA sample and
17
18 it is not observed in the lab synthesized 5 and 10% aluminum NCA samples which mostly
19 have 4- and 6-coordinate Al2O3 with peak formations at ~68 and 8 ppm, respectively. This
20
21 suggests that the commercial sample may have initially more aluminum concentration in
22
23 the starting material and goes through a higher temperature process. Our NMR studies on
24
25 high temperature treated AlNO3+LiOH mixtures show formation of a 90 and 76 ppm peaks
26
27
which is a proof of segregated AlOxN4-x and LiAlO2 formation, respectively regardless of
28 presence of transition metals in the composition.
29
30 Changing Ni/Co ratio in NCA has more dramatic effects on formation of surface
31
32 species as shown in Figure 3. Ni/Co 60/40 sample has similar environments with regular
33
34 NCA (mostly 4- and 6- coordinate Al2O3 whereas distribution of different aluminum sites
35 is observed for Ni/Co:40/60 sample. The new aluminum peaks observed at 77 and 55 ppm
36
37 can be associated with formation of LiAlO2 and LiAlxCo1-x O2 phase. These results show
38
39 that the two surface aluminum rich compositions for lithium nickel cobalt oxide are
40
41 aluminum rich and (20% Al) and cobalt rich (Ni/Co:40/60) compositions where the former
42
43
case results in high lithium aluminate segregation (with mostly tetrahedral aluminum
44 environments) whereas the latter forms lithium cobalt aluminate rich (mostly octahedral
45
46 aluminums) .
47
48 As discussed in the previous section, lattice aluminum in LiNixMnyCozO2 (NMC)
49
50 composition is limited due to Al-Mn incompatibility and mostly, aluminum is pushed out
51 of the lattice to form surface species. Figure 2 and 7 insets show 27Al MAS NMR data for
52
53 Al doped NCM with varying transition metal and aluminum concentrations. Different from
54
55 the NCA samples, Al doped NCM samples show new aluminum environments at 110-130
56
57 ppm region with a broad aluminum peaks. These aluminum environments - which are
58
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60 23
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formed with aluminum content higher than 2% (Figure 7, inset) can be tentatively assigned
4
5 to aluminum oxide/ lithium aluminum oxide/ aluminum oxynitride clusters at the interface
6
7 and might be due to large distortions of tetrahedral aluminum environments affected by
8
9 manganese rich clusters. The samples also show aluminum peaks at ~90, 75 ppm 10 ppm
10
11
that overlap with peaks observed in NCA samples. Similar with NCA case, these
12 resonances can be assigned as AlOxN4-x, 4- and 6- coordinated Al-O environments within
13
14 lithium aluminate clusters, respectively and the aluminum oxynitride species are mostly
15
16 formed with higher aluminum concentrations.
17
18 The X-ray diffraction patterns of the synthesized aluminum doped NCM and NCA
19 composition with varying aluminum content are shown in Figure 10 along with the
20
21 diffraction patterns of the commercial samples. All the diffraction lines can be indexed in
22
23 R-3m space group for with no major secondary phases or impurity peaks. An increase in
24
25 the c-lattice parameter is observed with 003 reflection as “aluminum content” increases
26 3, 6-7
27
(Figure S3) which agrees with references . Also we see changes related to ab-plane
28 from reflections 104 and 113 similar to previous reports (Figure S3). A peak splitting is
29
6
30 also observed in 113 reflection analogous to reference (Figure S3). Based on the
31
32 quantitative aluminum segregation observed with NMR analysis, the changes in the lattice
33
34 parameters observed from X-ray diffraction can therefore be ascribed to transition metal
35 composition changes due to aluminum loss from the bulk material instead of lattice
36
37 alumination, effectively changing transition metal composition to cobalt poor and
38
39 nickel/manganese rich. Studies in the literature have clearly shown a clear increase in c-
40
41 lattice parameter when Co composition is decreased in NMC: NMC 3-3-3, 5-3-2, 4.5-4.5-
42
43
1.0 compositions have c-lattice parameters of 14.22, 14.24 and 14.28Å, clearly agreeing
44 with our findings (from references 19, 7 and 6, respectively). However, it must be noted that
45
46 these observation are inherent to the samples synthesized with specific conditions listed
47
48 above and low level lattice aluminations may be achieved with different synthesis
49
50 conditions and/or with dilute manganese concentrations in the lattice.
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56 Figure 10. X-ray Diffraction data for the synthesized samples with a) 5-20% Al in NCA b)
57
58 10% to 55% Co in NCA and c) pristine (commercial) and Al doped NCM.
59
60 25
1
2
3
Summary
4
5
6
27
7 In this study Al MAS NMR spectroscopy has been used for the first time to provide
8
9 structural information on local lattice aluminum environments in pristine LiNi1-y-z CoyAlzO2
10
11
(NCA) and aluminum “doped” LiNixMnyCozO2 (NMC) as well as transition metal (TM)-O-
12 Al coordinations and evolution of lattice aluminum sites upon cycling of NCA. The NMR
13
14 results show that:
15
16 1. For NCA composition: with high nickel content, lattice Al prefers to coordinate
17 27
18 with 6Ni in Aloct honeycomb sites with a unique Al NMR peak at ~ -1200ppm.
19 Increasing cobalt content increases Al site disorder facilitating Aloct-3Ni3Co site
20
21 formation in honeycombs with aluminum-27 resonances at ~-600ppm. Increasing
22
23 aluminum content forms large amounts of diamagnetic aluminum peaks that shows
24
25 segregation tendency for aluminates (aluminum oxides, lithium aluminates and
26
27
aluminum oxynitrides), confirming that maximum lattice Al occupancy in NCA is
28 ~5% within the lattice.
29
30 2. For NMC composition: 27Al NMR has not shown any paramagnetic aluminum peak
31
32 and direct evidence of significant lack of lattice aluminum sites in aluminum doped
33
34 NMC materials synthesized in this study. Furthermore, DFT calculations have
35 shown Al-Mn incompatibility and favored aluminum segregation due to any
36
37 27
significant concentration Mn in a Ni rich matrix. Al solid state NMR studies have
38
39 shown formation of segregated aluminum species such as lithium aluminates,
40
41 aluminum oxides and aluminum oxynitrides acting as more of a coating/composite
42
43
rather than a dopant.
44 3. For cycled NCA: Both 6Li and 27Al MAS NMR data show aluminum local structure
45
46 change and lithium reordering after 120 cycles. The new peak positions for
47
48 aluminum-27 NMR of the extended cycle sample suggest aluminum environments
49
50 are mostly in the vicinity of cobalt suggesting Al-Co segregation and/or formation
51 of nickel vacancies around aluminums. DFT calculations also show that Ni
52
53 vacancy formation is most favorable near Co and Al when second nearest
54
55 neighbors, in other words when there is Al-Co clustering.
56
57
58
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60 26
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3
Acknowledgements
4
5
6
7 Support from the Vehicle Technologies Program, Hybrid and Electric Systems, in
8
9 particular, David Howell, Tien Duong, and Peter Faguy, at the U.S. Department of Energy,
10
11
Office of Energy Efficiency and Renewable Energy are gratefully acknowledged. The
12 submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne
13
14 National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of
15
16 Science laboratory, is operated under Contract No. DE-AC02-06CH11357. Dr. Daniel
17
18 Abraham is acknowledged for valuable discussions and Dr. Eungje Lee is acknowledged
19 for experimental support. Computer time allocations at the Fusion Computer Facility,
20
21 Argonne National Laboratory and at EMSL Pacific Northwest National Laboratory are
22
23 gratefully acknowledged.
24
25
26
27
Supporting Information
28
29
27
30 Al MAS NMR with varying spinning frequencies and varying pulse delay times for
31
32 commercial TODA NCA, XRD 003, 104, 113 reflection comparison for Al doped NCM
33
34 523. This material is available free of charge via the Internet at http://pubs.acs.org.
35
36
37
38
39 References:
40
41
42
43 1. Hu, S.-K.; Chou, T.-C.; Hwang, B.-J.; Ceder, G., Effect of Co Content on Performa
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45
nce of LiAl1/3-xCoxNi1/3Mn1/3O2 Compounds for Lithium-Ion Batteries. Journal of Pow
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47
48 er Sources 2006, 160 (2), 1287-1293.
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50 2. Croguennec, L.; Shao-Horn, Y.; Gloter, A.; Colliex, C.; Guilmard, M.; Fauth, F.; D
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elmas, C., Segregation Tendency in Layered Aluminum-Substituted Lithium Nickel Oxides
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55 . Chemistry of Materials 2009, 21 (6), 1051-1059.
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57 3. Croguennec, L.; Bains, J.; Breger, J.; Tessier, C.; Biensan, P.; Levasseur, S.; Delma
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60 27
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s, C., Effect of Aluminum Substitution on the Structure, Electrochemical Performance and
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6 Thermal Stability of Li1+x(Ni0.40Mn0.40Co0.20-zAlz)(1-x)O-2. Journal of the Electroch
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8 emical Society 2011, 158 (6), A664-A670.
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4. Guilmard, M.; Pouillerie, C.; Croguennec, L.; Delmas, C., Structural and Electroche
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13 mical Properties of LiNi0.70Co0.15Al0.15O2. Solid State Ionics 2003, 160 (1-2), 39-50.
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15 5. Myung, S. T.; Izumi, K.; Komaba, S.; Sun, Y. K.; Yashiro, H.; Kumagai, N., Role o
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18 f Alumina Coating on Li-Ni-Co-Mn-O Particles as Positive Electrode Material for Lithium-
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20 Ion Batteries. Chemistry of Materials 2005, 17 (14), 3695-3704.
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22 6. Conry, T. E.; Mehta, A.; Cabana, J.; Doeff, M. M., Structural Underpinnings of the
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25 Enhanced Cycling Stability upon Al-Substitution in LiNi0.45Mn0.45Co0.1-yAlyO2 Positiv
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27 e Electrode Materials for Li-ion Batteries. Chemistry of Materials 2012, 24 (17), 3307-331
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29
7. Aurbach, D.; Srur-Lavi, O.; Ghanty, C.; Dixit, M.; Haik, O.; Talianker, M.; Grinblat
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32 , Y.; Leifer, N.; Lavi, R.; Major, D. T.; Goobes, G.; Zinigrad, E.; Erickson, E. M.; Kosa, M.
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34 ; Markovsky, B.; Lampert, J.; Volkov, A.; Shin, J.-Y.; Garsuch, A., Studies of Aluminum-
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37 Doped LiNi0.5Co0.2Mn0.3O2: Electrochemical Behavior, Aging, Structural Transformatio
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39 ns, and Thermal Characteristics. Journal of the Electrochemical Society 2015, 162 (6), A10
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41 14-A1027.
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44 8. Gaudin, E.; Taulelle, F.; Stoyanova, R.; Zhecheva, E.; Alcantara, R.; Lavela, P.; Tir
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46 ado, J. L., Cobalt(III) Effect on Al-27 NMR Chemical Shifts in LiAlxCo1-xO2. Journal of
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48 Physical Chemistry B 2001, 105 (34), 8081-8087.
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51 9. Alcantara, R.; Lavela, P.; Relano, P. L.; Tirado, J. L.; Zhecheva, E.; Stoyanova, R.,
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53 X-ray Diffraction, EPR, and Li-6 and Al-27 MAS NMR Study of LiAlO2-LiCoO2 Solid S
54
55
56
olutions. Inorganic Chemistry 1998, 37 (2), 264-269.
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Fulya Dogan, John T. Vaughey, Hakim Iddir, and Baris Key

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