High Performance LiNiO2 Cathodes with Practical Loading Cycled

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High Performance LiNiO2 Cathodes with Practical Loading Cycled with Li metal anodes in Fluoroethylene Carbonate Based Electrolyte Solution. Elena Markevich, Gregory Salitra, Yosef Talyosef, Un-Hyuck Kim, Hoon-Hee Ryu, Yang-Kook Sun, and Doron Aurbach ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b00304 • Publication Date (Web): 14 May 2018 Downloaded from http://pubs.acs.org on May 16, 2018

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ACS Applied Energy Materials

High Performance LiNiO2 Cathodes with Practical Loading Cycled with Li metal anodes in Fluoroethylene Carbonate Based Electrolyte Solution. Elena Markevich,a Gregory Salitra, a Yosef Talyosef, a Un-Hyuck Kim, b Hoon-Hee Ryu, b YangKook Sun, b Doron Aurbach*, a a

Department of Chemistry Bar-Ilan, University, Ramat Gan 52900, Israel

b

Department of Energy Engineering, Hanyang University, Seoul 133-791, South Korea

KEYWORDS Li batteries, LiNiO2 cathodes, Li metal anodes, Li| LiNiO2 cells, fluoroethylene carbonate, high areal capacity, surface chemistry

ABSTRACT: LiNiO2 is one of the most promising cathode materials for high energy density Li ion batteries because of its high theoretical capacity (275 mAh g-1) and reasonable cost. However, cathodes comprising pure LiNiO2 suffer from intrinsic instability problems which lead to their capacity fading during cycling. We report herein on highly stable Li (metal) - LiNiO2 prototype cells with practical areal loading of the electrodes due to the quality of the cathode material and the use of a suitable electrolyte solution in which both the Li metal anodes and the LiNiO2 cathodes are stabilized. The electrolyte solution contains 1M LiPF6 in 1:4 (by volume) mixture of fluoroethylene carbonate (FEC) and dimethyl carbonate (DMC)). The cells with

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practical cathode loading (4 mAh cm-2), low amount of the electrolyte solution (33 µl cm-2) and Li metal anodes were cycled at 0.8÷1 mA cm-2 for more than 700 cycles with excellent capacity retention. We attribute these results to the combination of optimal structure and morphology of the synthesized LiNiO2 and the formation of highly passivating surface films, which behave as a stable solid electrolyte interphase (SEI) on the surfaces of the Li anodes and the LiNiO2 cathodes. Reactions of FEC at low and high potentials induce favorable surface chemistry induce favorable surface chemistry on both negative and positive electrodes in Li batteries.

1. INTRODUCTION LiNiO2 with high theoretical capacity of 275 mAh g−1 is considered as one of the most promising cathode material for Li batteries.1 This material is especially attractive due to the low cost and abundance of Ni and its reasonable environmental compatibility. However, it has not been commercialized because of its insufficient reversibility and cycling stability.2-4 Capacity fading of LiNiO2 is associated with phase transformations at high states-of-charge and surface instability.5-8 The rapid capacity fading of this cathode material is attributed to several detrimental processes. One of them are surface reactions of the particles in which unstable Ni4+ are involved leading to the formation of more stable but insulating (inactive) Ni oxide phases.8-11 Another important reason for the capacity loss for Ni rich cathodes is the formation and propagation of micro-cracks upon cycling arising from the anisotropic lattice volume change, which leads to grain separation and intensive reactions of the active mass with components of the standard electrolyte solutions used in Li ion batteries. 9, 12-14 Hence, effective passivation of Ni rich cathode materials that avoids continuous detrimental surface reactions of the active mass is essential for their cycling stability.


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The performance of LiNiO2 as a cathode material depends also on the synthesis conditions. The synthesis of stoichiometric LiNiO2 is difficult, as lithium loss and migration of Ni to the lithium layers leads to lithium deficient Li1-xNi1+xO2. The presence of Ni ions in Li sites blocks Li diffusion pathways and adversely affects the electrochemical performance (both capacity and kinetic problems). 7, 15, 16 Different approaches were applied to stabilize LiNiO2 and Ni-rich cathodes. Substituting part of the Ni by Co, Mn and Al, thus preparing Li[NiCoMo]O2 (NCM) or Li[NiCoAl]O2 (NCA) cathode materials enables to obtain stable cathode materials on the expense of high specific capacity. Other approaches involve preparation of particles with core shell structures9,

17, 18

or

gradient concentration of the transition metals in the NCM active mass19 where the surface is rich with Mn while most of the Ni is in the core of the particles. In such a way the surface of the particles which is depleted in Ni concentration, is much less reactive with solution species. Other methods include coating and doping of Ni rich cathode materials, which require the addition of only small amount of supporting substances (thereby do not require pronounced substitution of Ni by other elements and subsequent compromise on capacity). There are many reports on useful coating NCM cathode materials by carbon/ or metal oxide layers that allow Li ion transport and serving as an interphase that avoid detrimental contacts and side reactions between the active mass and solution species.15,

20, 21

Doping Ni rich NCM cathode materials by small amounts

(around 1% or less) of Zr, Al, Mg has a pronounced stabilization effect that was explored and explained in recent years.21 Preparation of LiNiO2 with low Ni content in the 3a sites and Ni defect formation in the 3b sites leads to highly reversible LiNiO2.22 Cycling results for pure LiNiO2 presented in the literature are characterized by very limited cycling life of several dozens of cycles.3, 6, 7, 22, 23 In Ref.18 Jun et al. demonstrated 1000 cycles of


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graphite|LiNiO2 with capacity fading of about 50% for pure LiNiO2 material, whereas the use of core-shell Ni rich cathode materials exhibited much better performance. However, in all of these works the loading of active cathode LiNiO2 material was impractically low or undefined. Dahn et al. showed stable cycling of carbon| LiNiO2 cells with high loading of the electrode materials during 300 cycles. Nevertheless, the capacity of the cathode was only 80 mAh g-1.24 Typically, ethylene carbonate (EC) based and LiPF6 containing electrolyte solutions were used for cycling cells with Ni rich cathodes. It is known that chemical and electrochemical reactions on the lithiated transition metal oxide cathode materials with components of the standard electrolyte solutions used in Li batteries cause degradation of the cathode surface.25, 26 Such surface reactions accompanied by electrolyte solution decomposition and gas generation deteriorate the performance of Li batteries. The problem of gas evolution is especially important for Ni-rich materials, as the increase of Ni content in the cathode increases also the amount

LiOH and Li2CO3 residues on the particles.

LiOH reacts nucleophilically with alkyl carbonates while Li2CO3 decomposes to form CO2 gas.27 Due to unavoidable strains and stresses developed in the particles during repeated Li insertion/de-insertion cycling, micro-cracks are formed in them. In the absence of effective passivation, electrolyte solution can penetrate into the cathode particles through the micro-cracks formed during cycling, reacting with a fresh cathode material, thereby expediting the degradation of the cathode’s active mass.3, 9, 14, 28, 29 Thus, the choice of electrolyte solutions which induce favorable surface chemistry is very important to attain stable cycling of cathodes comprising the very reactive LiNiO2. In our previous works we showed that the use of fluoroethylene carbonate (FEC)-based electrolyte solution ensures better passivation of the surface of Li batteries cathodes compared to


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EC-based electrolyte solutions.30-37 Besides, recently we demonstrated very stable lithium-metal stripping/plating at a high rate and high areal capacity in FEC-based electrolyte solutions exhibiting more than thousand cycles of symmetric Li|Li cells.37 Replacement of the conventional graphite anode by high capacity Li metal (specific capacity of 3,860 mAh g-1) can increase pronouncedly the energy density of cells comprising high capacity LiNiO2 cathodes. It is important to note that while the use of Li metal anodes in rechargeable batteries may provide high energy density, it is impossible to reach with such batteries the high fidelity, excellent safety features and prolonged cycle life of Li ion batteries. The latter batteries reach nearly zero fault situation, at a level < ppb. Thereby they can power all kinds of portable electronic devices for billions of users and can be promoted to propel electric vehicles. It is hard to believe that Li metal based batteries can ever reach the level of safety and high fidelity of Li ion batteries. Thereby, their use has to be limited to applications in which one can compromise on high energy density vs. more limited safety features. There are no questions that there are applications in which Li metal based rechargeable batteries may be useful and thereby their development is important. Discussion about appropriate applications of rechargeable batteries with Li metal anodes is beyond the scope of this paper. In the present work we report on a stable performance of the cells containing LiNiO2 composite cathodes and Li metal anodes with practical loading, low amount of electrolyte solution and high current density (definitely practical values) cycled in FEC-based electrolyte solution (1M LiPF6 in FEC:DMC 1:4). 2. RESULTS AND DISCUSSION


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Fiigure 1a, c and e shows SEM images of pristine LiNiO2 composite cathodes prepared from LiNiO2 particles synthesized by lithiation of the Ni(OH)2 with LiOH·H2O.8 The LiNiO2 particles used herein are spherical with a particle diameter of ̴ 10 µm. Each particle, in turn, is composed of nanosized secondary particles which are packed compactly into a spherical geometry. This secondary structure minimizes the contact surface between the electrolyte solution and the cathode thus reducing side parasitic reactions of the electrolyte on the electrode surface.8 The XRD patterns of pristine LiNiO2 electrodes in Figure 2 indicate that LiNiO2 particles have R3̅m layered structure with no impurity phases. Typical galvanostatic cycling results obtained for Li| LiNiO2 cells with areal charge/discharge capacity of about 4 mAh cm-2 cycled in FEC-based electrolyte solution are shown in Figure 3. A very stable cycling of the cells with about 100% efficiency for 540 cycles was observed at a current density of 1 mA cm-2 (Figure 3a, b red curves). The cells demonstrate voltage profile typical for LiNiO2 cathodes1 (Figure 3c). The black curves shown in Figure 3a relate to the cells cycled with different current densities and reflect a very good rate capability of LiNiO2 cathodes with high areal loading. The cells underwent more than 700 cycles without pronounced capacity fading. It is seen that the capacity of about 250 mAh g-1 extracted from LiNiO2 cathodes during the initial cycles at a current density of 0.12 mA cm-2 did not change markedly after the increase of the current density A moderate capacity fading observed up to about 150 cycles was followed by a stabilization with very low capacity loss per cycle. It is remarkable that very stable cycling behavior of LiNiO2 cathodes was observed during cycling in a full potential range of 2.8 – 4.3 V, whereas in Ref.8 it was shown that cycling of LiNiO2 cathodes with upper cutoff voltage higher than 4.1 V led to capacity loss because of structural damage due to H2 → H3 phase transition accompanied by micro-cracking. The blue curve in Fig. 3a demonstrates cycling performance of


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a

b

c

d

e

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Figure 1. SEM images of pristine LiNiO2 cathode (a, c, e) and LiNiO2 cathode cycled in Li| LiNiO2 cell for 540 cycles (b, d, f) at different magnifications. Li| LiNiO2 cells with EC-based electrolyte solution. It is seen that FEC-based solution significantly outperforms EC-based solution. Obviously, FEC provides more effective stabilization for both the cathodes and the anodes in Li batteries due to the formation of more effective protective surface films.36 The significantly higher Coulombic efficiency that was


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Pristine LNO electrode

021 116

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108/110

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101 006/102

60000 40000

LNO electrode after 540 cycles

Graphite

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Intensity, a.u.

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Al

20000 *

*

*

0 10

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70

2Ɵ Figure 2. XRD patterns of pristine LiNiO2 electrodes and LiNiO2 electrodes in fully lithiated state from Li| LiNiO2 cell after 540 cycles with a current density of 1 mA cm-2 in 1M LiPF6 FEC/DMC electrolyte solution. Peaks marked with asterisks relate to Kapton film. measured for Li|Cu cells with FEC-based compared to EC-based electrolyte solution supports this conclusion.37 Typical Nyquist plots measured with Li|LiNiO2 cells before cycling and after 13 and 540 cycles are presented in Figure 3d. The decrease in the surface films and chargetransfer resistance of the cells reflected by the impedance spectra due to cycling is obviously mainly relates to the changes in the morphology of the Li metal electrodes with increase in the effective surface area of Li anodes, since the LiNiO2 cathodes do not change pronouncedly during cycling.37 SEM images of LiNiO2 cathodes cycled in Li|LiNiO2 cell for 540 cycles are shown in Figure 1b, d and f. It is seen that LiNiO2 particles remained undamaged without any signs for micro-cracks


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formation. We could not observe cathodes’ particles with visible damages after prolonged cycling. Typical particles related to the cycled cathode (Figure 1f) are almost indistinguishable in their morphology from that of pristine electrode (Figure 1e). XRD patterns of cycled LiNiO2

Figure 3. (a) Cycling performance of Li| LiNiO2 cells cycled in FEC-based electrolyte solution with current densities as indicated (red and black curves) and EC-based electrolyte solution (blue curve). (b) Coulombic efficiency of Li| LiNiO2 cells (c) Voltage profile measured for Li| LiNiO2 cells cycled with a current density 1 mA/cm2. (d) Nyquist plots measured at 3.0V for Li|NMC cells before cycling, after 13 cycles and after 540 cycles, as indicated. The 1st cycle was performed with a current density of 0.12 mA/cm2 and the 2nd – at 0.24 mA/cm2 Diameter of electrodes 14 mm. The amount of the electrolyte solution 33 µl cm-2. 30°C.


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cathodes presented in Figure 2 did not reveal the formation of new phases, as well as the ratio of the intensities of the peaks remained unchanged. These observations confirm structural stability of the material during prolonged cycling. Obviously, an excellent stability of high capacity stoichiometric LiNiO2 cathodes in FEC-based electrolyte solutions is achieved due to the formation of effective protective surface films. XPS analysis was performed for the examination of the composition of SEI formed on the cycled electrodes. Survey XPS spectra of pristine LiNiO2 electrodes and LiNiO2 electrodes after 13 and 540 cycles are presented in Figure 4. It is seen that during cycling the ratio of the intensity of F 1s to O 1s and of F 1s to C 1s peaks decreases, revealing the formation of C and O-containing species on the surface. Indeed, the intensities of the signals of graphite (a conducing additive in the cathode) at 284.4 eV and PVdF at 290.7 eV in the C 1s spectra and at 688 eV in the F 1s spectra of pristine electrodes (Figure 5) decreases substantially due to the attenuation by SEI which is formed during cycling. As is seen from C 1s and O 1s (Figure 6) spectra of LiNiO2 electrodes, the main C- and Ocontaining species which are formed on the surface of the electrodes are Li2CO3, Li alkyl carbonates and polyethylene oxide (PEO)-like polymer species.38-40 In turn, a drastic increase of LiF fraction is observed in the composition of F-containing compounds. The surface films formed on the cathodes contains also LixPFy and POxFy species which are the products of LiPF6 decomposition.41, 42 It should be emphasized that these results are fully in line with our previous work in which we demonstrated excellent performance of prototype cells comprising lithiated Si anodes,43, 44 LiMn1.5Ni0.5O2, LiCoPO4 and Li and Mn rich NCM high voltage cathodes.30-33 In these previous studies we already showed that the prolonged stability of these high voltage Li ion cells result from the formation of protective surface films on the cathodes, due to oxidation of


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Figure 4. Survey XPS of pristine LiNiO2 electrodes and LiNiO2 electrodes after 13 and 540 cycles, as indicated.


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Figure 5. C 1s and F 1s XPS of pristine and cycled for 13 and 540 cycles LiNiO2 electrodes, as indicated. FEC. The reason for the high stability of Li metal and Li-Si anodes was also discussed in depth in our previous publications.43 A major reason for electrodes stabilization in Li cells achieved by the use of FEC is the formation of flexible protective matrices which contain


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Figure 6. O 1s, P 2p and Li 1s spectra of pristine LiNiO2 electrodes and LiNiO2 electrodes after 13 and 540 cycles, as indicated. polymeric/oligomeric species, formed by reduction and oxidation of FEC. These flexible matrices can accommodate morphological changes such as volume expansion (Si anodes), surface roughening (Li anodes) and cracking (all kinds of cathodes). We found that the cycling stability of Li | LiNiO2 cells was lower than that of symmetric Li | Li cells cycled in similar conditions, because the Li anodes degrade much faster in the former case (easily inspected visually by post-mortem analysis of Li| LiNiO2 cells). This observation is in line with the conclusion that the major source of the capacity fading of Li batteries is negative electrodes45 and in the case of Li| LiNiO2 cells arises from detrimental reactions of the Li anodes with species formed on the cathode side by reactions of the electrolyte solutions therein. The


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reflection between the surface chemistries of anodes and cathodes in Li batteries may be a major reason for degradation of all kinds of Li ion and Li batteries during cycling.46,

47

Study and

discussion of these phenomena are beyond the scope of this paper. 3. CONCLUSION In summary, very stable cycling of the cells comprising stoichiometric LiNiO2 cathodes with practical loading of 17 mg cm-2 (around 4 mAh cm-2) and Li metal anodes in FEC-based electrolyte solutions was demonstrated. After 540 cycles the cells cycled with a current density of 1 mA cm-2 demonstrated an areal capacity of about 2.4 mAh cm-2. The cells cycled with a current density of 0.8 mA cm-2 for the most part of their cycle life exhibited more than 700 cycles without pronounced capacity fading. Note that these cycling results were obtained with an amount of the electrolyte solution of 33 µl cm-2 of electrodes area (about 1.9 µl g -1 of LiNiO2). Remarkable, after 540 cycles with a charging cut-off up to 4.3V, the spherical LiNiO2 particles preserved their integrity and morphology without any signs for micro-cracking. These results are very promising from a practical point of view and may promote the use of high specific capacity LiNiO2 cathodes with optimal structure and morphology and FEC-based electrolyte solutions. The use of these electrolyte solutions ensures a stable behavior of both LiNiO2 cathodes and Li metal anodes, due to the favorable surface chemistry which is developed on both types of electrodes in them. 4. EXPERIMENTAL SECTION Synthesis of LiNiO2 and composite cathodes preparation. Stoichiometric LiNiO2 was synthesized using spherical Ni(OH)2 and LiOH·H2O precursors mixed with molar ratio Li/Ni = 1.01:1 and calcined at 650 °C for 10 h under an oxygen atmosphere. Detailed description of the synthesis


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presented in [8]. For composite electrodes preparation LiNiO2 powder was mixed with conducting agent and poly(vinylidene fluoride) in a weight ratio of 90:5.5:4.5 in Nmethylpyrrolidinone. The conducting agent was a mixture of graphite KS-6 and carbon black in a weight ratio of 6: 4. The slurry was spread onto Al foil, dried, and roll-pressed. Characterization of Pristine and Cycled Electrodes. SEM images were obtained with Environmental Scanning Electron Microscope, Ouanta FEG 250 (FEI). X-ray diffraction (XRD) patterns were obtained with a D8 Advance system (Bruker Inc.) using Cu Ka radiation operated at 40 mA and 40 kV. To prevent the contact of NMC electrodes with the ambient atmosphere they were protected with Kapton film of 20 µm (Goodfellow). X-ray photoelectron spectroscopy (XPS) was used for the surface analysis of the electrodes. Photoelectron spectra were obtained with a Kratos Axis-HS spectrometer (England) at a residual gas pressure of ∼5 × 10−10 Torr using monochromatized Al Kα radiation (hν = 1486.68 eV). High resolution spectra were recorded with pass energy of 40 eV (0.05 eV step). During the measurements, the vacuum in the analysis chamber was 2 × 10−9 Torr. Binding energies (BEs) were corrected with respect to the BE value of the C1s peak at 284.8 eV. Air sensitive electrodes after cycling were transferred from the glove box to X-ray photoelectron spectrometer without contact with ambient air. Electrochemical Testing. For galvanostatic and impedance tests of Li| LiNiO2 cells Li-metal foil disk electrodes (thickness 0.25 mm, diameter 14 mm) and LiNiO2 cathodes (27 mg of active material, diameter 14 mm) were assembled with a polyethylene separator (Tonen) in twoelectrode configurations using coin-type cells (2325, NRC, Canada). The electrolyte solutions were 1M LiPF6 in FEC:DMC 1:4 and 1M LiPF6 in EC:DMC 1:1. The amount of the electrolyte solution used was 33 µl cm-2 of electrodes. Li| LiNiO2 cells were cycled with a current density of 0.4 – 1.6 mA cm-2 and cutoff voltage 2.8-4.3 V. The upper cutoff voltage corresponds to the


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value when no transition metals dissolution from the cathode active material was observed for Ni rich cathodes.48 AUTHOR INFORMATION Corresponding Author *E-mail Doron Aurbach : [email protected] ACKNOWLEDGMENT A partial support for this work was obtained by the Israel High Committee of High Education and the Prime Ministry office in the framework of INREP (Israel National Research center for Electrochemical Propulsion). REFERENCES (1) Ohzuku, T.; Ueda, A.; Nagayama, M. Electrochemistry and Structural Chemistry of LiNi02 (R3m) for 4 Volt Secondary Lithium Cells. J. Electrochem. Soc. 1993, 140, 1862–1870. (2) Kalyani, P.; Kalaiselvi, N. Various Aspects of LiNiO2 Chemistry: A Review. Science and Technology of Advanced Materials 2005, 6, 689–703. (3) Yoon, C. S.; Choi, M. H.; Lim, B.-B.; Lee, E.-J.; Sun Y.-K. Review—High-Capacity Li[Ni1-xCox/2Mnx/2]O2 (x = 0.1, 0.05, 0) Cathodes for Next-Generation Li-Ion Battery. J. Electrochem. Soc. 2015, 162, A2483-A2489. (4) Myung, S.-T.; Maglia, F.; Park, K.-J.; Yoon, C. S.; Lamp, P.; Kim, S.-J.; Sun, Y.-K. Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives. ACS Energy Lett. 2017, 2, 196−223.


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300

5 4 3 2 1 0

Li | LiNO2

200

1 mA cm-2

100 0 0

200 400 Cycle number

Capacity, mAh cm-2

Table of Contents

Capacity, mAh g-1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


600


23

High Performance LiNiO2 Cathodes with Practical Loading Cycled

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