Molecular Surface Modification of NCM622 Cathode Material Using

Subscriber access provided by Kaohsiung Medical University

Energy, Environmental, and Catalysis Applications

Molecular Surface Modification of NCM622 Cathode Material Using Organophosphates for Improved Li-Ion Battery Full-Cells Sven Neudeck, Felix Walther, Thomas Bergfeldt, Christian Suchomski, Marcus Rohnke, Pascal Hartmann, Jürgen Janek, and Torsten Brezesinski ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04405 • Publication Date (Web): 29 May 2018 Downloaded from http://pubs.acs.org on May 29, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 29 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

ACS Applied Materials & Interfaces

Molecular Surface Modification of NCM622 Cathode Material Using Organophosphates for Improved Li-Ion Battery Full-Cells Sven Neudeck,†,* Felix Walther,‡ Thomas Bergfeldt,§ Christian Suchomski,‡ Marcus Rohnke,‡ Pascal Hartmann,†,# Jürgen Janek,†,‡,* and Torsten Brezesinski†,* †

Battery and Electrochemistry Laboratory, Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 EggensteinLeopoldshafen, Germany ‡

Institute of Physical Chemistry & Center for Materials Research, Justus-LiebigUniversity Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany §

Institute for Applied Materials, Karlsruhe Institute of Technology, Hermann-vonHelmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany #

BASF SE, 67056 Ludwigshafen, Germany

Keywords Lithium-Ion Battery, Lithium Nickel Cobalt Manganese Oxide, Phosphate Ester, Molecular Coating, Surface Shell, ToF-SIMS Imaging

1 ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 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

Abstract Surface coating is a viable strategy for improving the cyclability of Li1+x(Ni1–y–zCoyMnz)1–xO2 (NCM) cathode active materials for lithium-ion battery cells. However, both gaining synthetic control over thickness and accurate characterization of the surface shell, which is typically only few nm thick, are considerably challenging. Here, we report on a new molecular surface modification route for NCM622 (60% Ni) using organophosphates, specifically tris(4-nitrophenyl) phosphate (TNPP) and tris(trimethylsilyl) phosphate (TMSP). The functionalized NCM622 was thoroughly characterized by state of the art surface and bulk techniques such as attenuated total reflection infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to name a few. The comprehensive ToF-SIMS based study comprised surface imaging, depth profiling, and 3D visualization. In particular, tomography is a powerful tool to analyze the nature and morphology of thin coatings, and is applied, to our knowledge for the first time, to a practical cathode active material. It provides valuable information about relatively large areas (over several secondary particles) at high lateral and mass resolution. The electrochemical performance of the different NCM622 materials was evaluated in long-term cycling experiments of full-cells with a graphite anode. The effect of surface modification on the transition-metal leaching was studied ex situ via inductively coupled plasma-optical emission spectroscopy. TNPP@NCM622 showed reduced transition-metal dissolution and much improved cycling performance. Taken together, with this study, we contribute to optimization of an industrially relevant cathode active material for application in high-energy-density lithium-ion batteries.


Page 2 of 29

Page 3 of 29 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


Introduction Apart from LiNi0.80Co0.15Al0.05O2 (NCA), layered lithium nickel cobalt manganese oxides (NCMs) of the general formula Li1+x(Ni1–y–zCoyMnz)1–xO2 are the most relevant cathode active materials in rechargeable lithium-ion batteries (LIBs) for electric vehicles at present. In particular, Ni-rich NCMs such as NCM622 (60% Ni) and NCM811 (80%) are either already being used or have the potential to be used in automotive applications.1-6 To further improve these materials, the deactivation and capacity fading pathways in full-cells need to be better understood and, then, strategies developed to suppress them. Structural changes, mechanical degradation, and surface reactions are considered the main issues in NCM based cells.5,7 Structural transformations lead to impedance rise during cycling operation and, therefore, eventually to capacity decay. Mechanical degradation such as secondary particle fracture and pulverization results in electronic contact losses and continuous exposure of fresh surface material to the electrolyte. Surface reactions at the positive electrode/liquid electrolyte interface comprise those that involve residual lithium compounds such as Li2CO3, electrolyte decomposition (oxidation), and transitionmetal dissolution from the active material. Increases in pressure and cell impedance as well as irreversible lithium losses are inevitable results of these adverse side reactions. Note that the different processes are not separated phenomena, but rather are interrelated.5,7-13 Bulk-doping and coating of the material’s surface have been shown to be effective strategies to mitigate most of the deactivation pathways.5,7,10,14,15 While doping mainly addresses the structural stability, coating tackles the problem of surface reactions. A robust surface shell acts as a physical barrier between the highly reactive cathode active material, especially when in charged state, and the electrolyte solution. Ideally, it should be electronically insulating, but Li-ion conducting (and ‘soft’ enough to allow direct contact of secondary particles after electrode fabrication and calendaring). However, the synthesis of coating layers of uniform thickness and composition that fulfill these requirements is complicated. An additional problem is the characterization of the coating material since the thickness is usually well below 10 nm. Thus, new synthesis protocols and a variety of special characterization techniques are required. Highly stable oxides such as aluminum oxide are common coating materials in the area of LIBs.16-20 Besides their protective function, they may also act as an HF scavenger.21-23 HF is believed to be responsible, at least partly, for the leaching of transition metals at the cathode side.16 Furthermore, in recent years, Li-ion conducting materials like Li3PO4 have been employed.24-26 Other efforts with phosphate-type coatings concentrated on using (lithium) transition-metal phosphates, including Co3(PO4)2 and LiCoPO4.27-29 Because of the covalent P-O bonds, these polyanionic compounds exhibit high stability, as known for example for olivine materials.4 Only few studies (patents) reported on the use of organic molecules containing POx groups.30,31 In contrast, phosphonates (OPR1(OR2)2) are widely used for anchoring molecules on solid supports.32 The anchoring occurs through reaction 3 ACS Paragon Plus Environment


between surface hydroxy groups (-OH) and the phosphonate. In fact, phosphonates have already been used for modification of LiFePO4 (LFP), however, mainly aiming at improving the electronic charge transfer.33,34 Despite being few, these examples clearly demonstrate that organic phosphonates are well suited for surface functionalization of battery materials. Major advantages of molecular coating strategies are the high degree of control over both structure and thickness of the surface shell. In this context it is also important to note that molecular coatings are considered robust because of covalent attachment to the surface. In general, precursor routes are scarce, and they mostly make use of the reduction of diazonium salts.35 Here, we describe the surface modification of NCM622 using organophosphates (OP(OR)3), with the objective of improving its cycling performance in LIB full-cells. NCMs naturally contain reactive OH-groups and, thus, are prone to surface functionalization (targeted deactivation of these groups is thought to increase the cell performance).36-38 In particular, two different phosphate esters were tested as potential coating agents, namely, tris(4-nitrophenyl) phosphate (TNPP) and tris(trimethylsilyl) phosphate (TMSP). TMSP is a common electrolyte additive for LIB applications, and the available studies suggest formation of a TMSP derived protective film on the cathode surface.39-42 Consequently, pre-coating of the cathode active material using TMSP might help to achieve a uniform surface layer, while TNPP, with its chromophoric nitrophenolate group, can be used to optimize the reaction conditions. Furthermore, we demonstrate the application of time-of-flight secondary ion mass spectrometry (ToF-SIMS) to obtain detailed molecular information with spatial resolution from the samples. Different modes of operation allowed imaging the top surface, depth profiling, and 3D reconstruction of secondary particles. Overall, we show that ToF-SIMS is a unique and powerful tool for characterizing battery materials, even though its use in this particular field of research is still rather limited.

Experimental Materials NCM622 (60% Ni) was obtained from BASF SE (Ludwigshafen, Germany). Tris(4nitrophenyl) phosphate (TNPP, ≥98.0%) was purchased from TCI (Tokyo Chemical Industry Co., Ltd.; Tokyo, Japan). Tris(trimethylsilyl) phosphate (TMSP, ≥98%), anhydrous dimethyl carbonate (DMC, ≥99%), and anhydrous diethyl carbonate (DEC, ≥99%) were obtained from Sigma-Aldrich. Deuterochloroform (99.80% D, 0.03% tetramethylsilane, H2O < 0.01%) was purchased from Euriso-Top (Saint-Aubin, France) and N-methyl-2-pyrrolidone (NMP, >99.5%) from Merck. All reactions were routinely performed using standard Schlenk techniques.


Page 4 of 29

Page 5 of 29 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


Synthesis of TNPP@NCM622 and TMSP@NCM622 A mixture of NCM622 (20.8 g) and either TNPP (810 mg, 1.76 mmol) or TMSP (1.42 g, 4.51 mmol) in DMC (50 mL) was heated to reflux for 10.5 h under argon (5.0, ≥99.999%, Air Liquid). The solid product was filtered off and, subsequently, washed using DMC (4 × 10 mL). After drying in vacuum at 120 °C overnight, the product was obtained as a black powder (19.8 g for TNPP@NCM622 and 20.0 g for TMSP@NCM622). In the case of TNPP@NCM622, the filtrate was collected and the solvent was removed under reduced pressure. The remaining white solid was dried prior to further analysis.

Preparation of Electrodes Slurries for electrode fabrication were prepared by dispersing binder (Solef5130 PVDF, 3 wt.-%) in NMP (7.5 wt.-% solution), graphite (SFG6L, 2 wt.-%), and carbon black (Super C65, 1 wt.-%) in NMP. The quantity of NMP was chosen such to achieve a total solid content of 65% in the final slurry (including NCM622). The suspension was mixed for 3 min at 2000 rpm and for additional 3 min at 400 rpm using a planetary centrifugal mixer (ARE 250, Thinky Corp.; Tokyo, Japan). After addition of cathode active material (94 wt.-%), the slurry was mixed twice at the conditions described above, followed by coating onto aluminum foil using a doctor blade (UA3000, MTV Messtechnik oHG; Erftstadt, Germany) on a film applicator (Coatmaster 510, Erichsen GmbH & Co. KG; Hemer, Germany). The electrodes were dried at 120 °C in a vacuum oven (VDL 53, Binder GmbH; Tuttlingen, Germany) and, then, they were calendared at 10 N mm–1 using a laboratory calendar (CA 5/200, Sumet Systems GmbH; Denklingen, Germany). The NCM622 loading was in the range between 10.5 and 11.0 mg cm–2.

Coin Cell Assembly and Electrochemical Testing Coin cells (CR2032, Hohsen Corp.; Osaka, Japan) were assembled in an argon-filled glovebox (MBraun) and sealed using a crimping tool (MSK-160D, MTI Corp.; Richmond, CA, USA). Prior to use, all materials were dried at 100 °C in vacuum overnight. Half-cells were assembled using NCM622 cathode (Ø14 mm), lithiummetal anode (99.9%, Ø15 mm, Gelon LIB Co.; Linyi, China), and glass fiber separator (GF/D, Whatman, GE Healthcare Life Sciences) soaked with electrolyte solution (200 µL of LP47, 1 mol L–1 LiPF6 in 3:7 by weight ethylene carbonate/DEC, BASF SE). For full-cells, NCM622 cathode (Ø14 mm), graphite anode (Ø15 mm, 6.8 mg cm–2 active material loading, BASF SE), and glass fiber separator (GF/A, Whatman) soaked with electrolyte solution (100 µL of LP472, LP47 containing 2 wt.-% vinylene carbonate, BASF SE) were used. Electrochemical testing was performed at 25 °C using a multichannel battery cycler (Series 4000, MACCOR Inc.; Tulsa, OK, USA). After 2 h of equilibration, half-cells 5 ACS Paragon Plus Environment


were cycled between 3.0 and 4.3 V with a potentiostatic step at the upper cutoff voltage. This constant voltage (CV) step was limited either by time (1 h) or by residual current (0.01C). After two cycles at 0.1C were completed, the cycling was performed at 0.25C charge and discharge at different rates from 0.1 to 3C. Half-cell cycling data are averaged from three to four cells. The standard deviation of the average initial specific discharge capacities was ≤0.3 mAh g–1NCM. Full-cells were equilibrated for 6 h, followed by cycling between 2.8 and 4.2 V with a CV step at 4.2 V. The CV step was also limited either by time (1 h) or by residual current (0.02C). After three formation cycles at 0.1C were completed, the cells were cycled at 1C, with a rate capability test every 100 cycles. Long-term cycling data are averaged from two cells. The standard deviation of the average initial discharge capacities was ≤0.4 mAh g–1NCM.

Instrumentation Nuclear magnetic resonance (NMR) spectra were recorded on a Bruker Avance III 500 in CDCl3 (δ = 7.26 ppm). Ultraviolet-visible (UV-vis) spectra were collected on a Cary 500 Scan (Varian) instrument using crown glass cuvettes (d = 1 cm). Attenuated total reflection-infrared (ATR-IR) spectra were recorded on an ALPHA FT-IR spectrometer (Bruker) equipped with an ECO-ATR sampling module with a germanium crystal in an argon-filled glovebox. The spectra were background corrected using the OPUS software (Bruker). Thermogravimetric analysis-mass spectrometry (TGA-MS) data were acquired on a Netzsch STA 409 PC coupled to a Balzers QMG 421 quadrupole mass spectrometer. The ionization energy was 70 eV. Both the phosphorus content of the different materials and the amount of transitionmetal species deposited on the anode were determined via inductively coupled plasma-optical emission spectroscopy (ICP-OES) on both a PerkinElmer Optima 4300 DV and a Thermo Scientific iCAP 7600. As for the latter, the cells were discharged to 2.8 V and, then, transferred to an argon-filled glovebox, followed by opening using a decrimping tool for the crimping machine (MSK-160D, MTI Corp.). The cathode was separated and washed using DEC (4 × 250 µL). Both separator and anode were soaked in DEC (500 µL). After removal of the separator, the anode was washed using DEC (2 × 250 µL). All electrodes were dried in vacuum. The data presented are averaged from measurements conducted on two different anodes. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) in positive and negative ion modes was performed on a ToF.SIMS 5 instrument (IONTOF GmbH; Muenster, Germany) equipped with a Bi cluster primary ion gun and a dual source column for depth profiling. The spectrometry mode was applied to investigate the fragmentation of both coatings and to draw conclusions about the composition. Bi3+ ions (25 keV) 6 ACS Paragon Plus Environment

Page 6 of 29

Page 7 of 29 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


were used for analysis. The analysis area was (150 × 150) µm2 and the primary ion beam was rastered with (128 × 128) pixels at 1 shot per pixel. The data shown are based on a single measurement per sample. To demonstrate the reproducibility of results, ToF-SIMS data with error bars from two different measurements conducted on TNPP@NCM622 are shown in the Supporting Information. The mass resolution (m/∆m) achieved was >5000 for the masses 62.97 (PO2–) and 78.96 (PO3–). Depth profiling in fast imaging mode was combined with delayed extraction to allow 3D tomography studies. The latter measurements were performed in negative ion mode with Bi3+ (25 keV) as primary ion species and O2+ (1 keV) for sputtering and in noninterlaced mode with 3 s low energy electron flooding per cycle for charge compensation. The analysis area was (20 × 20) µm2 and centered in the (100 × 100) µm2 sputter crater. The analysis area was rastered with (128 × 128) pixels at 5 shots per pixel. Using delayed extraction enabled a mass resolution of >6000 for the masses 62.97 (PO2–) and 78.96 (PO3–). X-ray photoelectron spectroscopy (XPS) was performed using a PHI5000 Versa Probe II XPS (Physical Electronics GmbH; Ismaning, Germany) equipped with a monochromatic Al Kα radiation source (1486.6 eV). The power of the X-ray source was 50 W at a voltage of 15 keV. The analytical beam had a diameter of 200 µm. Sputtering using Ar+ ions (0.5 keV) was performed by rastering over a (2 × 2) mm2 area. All spectra were calibrated to the signal of adventitious carbon at 284.8 eV, and Shirley background was applied.

Results and Discussion For the modification of NCM622 (referred to as TNPP@NCM622 and TMSP@NCM622 hereafter), a reaction between native M-OH groups at the top surface and OP(OR)3 is considered (reminiscent of a transesterification process). Ultimately, this leads to incorporation of M-O-P binding units, accompanied by release of R-OH species, as shown in Scheme 1. Depending on various parameters such as distance of M-OH groups, reactivity of reactants etc., the triester can react once, twice, or three times with the surface species, leading to mono, bi, or tridentate binding modes and corresponding release of one, two, or three equivalents of R-OH. In practice, both NCM622 and phosphate triester were heated in DMC. DMC is a common electrolyte solvent and, therefore, believed to not undergo reaction with either NCM622 or phosphate ester. The reaction conditions were optimized by analyzing the hydrolysis of TNPP@NCM622, as described below. Different analytical techniques were applied to characterize the modified NCM622 materials and estimate the amount of surface coating.



Page 8 of 29

Scheme 1. Reaction scheme of the surface modification of NCM622 using phosphate triester. ‘M’ represents any of the three transition metals present in NCM622. Only monodentate and tridentate binding modes are shown for clarity.

NMR spectroscopy of the reaction solution after filtration provided a first indication as to whether the synthesis was successful. In the case of TNPP, the released alcohol, 4-nitrophenol (R-OH in Scheme 1), is found by 1H NMR (Figure S1), thereby clearly demonstrating that a reaction with the triester took place. More importantly, partially or fully hydrolyzed phosphate species are not detected in the filtrate via 31P NMR (Figure S2). Consequently, the phosphate is indeed incorporated into the surface structure. The phosphorus content of pristine NCM622, TNPP@NCM622, and TMSP@NCM622 was determined by means of ICP-OES. As indicated in Table 1, TNPP@NCM622 and TMSP@NCM622 reveal similar quantities, while the phosphorus content of pristine NCM622 is negligible.

Table 1. Phosphorus content of TMSP@NCM622 from ICP-OES.

pristine

NCM622,

TNPP@NCM622,

Sample

P / µmol g–1NCM

NCM622

99.98% during the first 200 cycles (Figure 7b); no differences are observed between pristine NCM622 and TNPP@NCM622. However, the Coulombic efficiency is slightly lower in the case of TMSP@NCM622, which is in agreement with the observed faster capacity degradation. In addition, for TMSP@NCM622, the cell impedance, which is, in part, reflected in the evolution of the average charge voltage, is found to strongly increase over the first 200 cycles. In general, it is much higher compared to that of pristine NCM622 and TNPP@NCM622 (Figure 7c), both of which show similar behavior with respect to impedance build-up. Thus, the impedance rise only does not provide full explanation of the difference in cycling performance between TNPP@NCM622 and pristine NCM622. In the case of TMSP@NCM622, it seems that competing side reactions during synthesis such as formation of Si-O-Si binding units lead to a notably higher overall cell impedance. Besides, the relatively lower Coulombic efficiency strongly suggests (deleterious) reactions of the TMSP derived coating during cycling operation. Finally, the rate capability of the materials was evaluated. TNPP@NCM622 exhibits better performance than pristine NCM622 for discharge rates ≥1C (Figure 7d). The specific discharge capacity of TNPP@NCM622 in the early cycles is lower by 12.8 and 22.2 mAh g–1NCM at 2C and 3C, respectively, relative to that delivered at a rate of 0.5C. The overall decrease in capacity with increasing C-rate is much more pronounced for pristine NCM622 (2C: 14.0 mAh g–1NCM, 3C: 25.2 mAh g–1NCM) and TMSP@NCM622 (2C: 15.2 mAh g–1NCM, 3C: 28.6 mAh g–1NCM). However, after 900 cycles, both pristine NCM622 and TNPP@NCM622 show similar discharge kinetics, which is still superior to that of TMSP@NCM622 (Figure S11). Overall, this result suggests that either the TNPP derived coating is not long-term stable or other effects determined the rate performance in the later cycles. The different cycling performance of TNPP@NCM622 and TMSP@NCM622 demonstrates that the improvement seen for the former material is in fact caused by the surface shell, rather than a kind of activation of the actual NCM622 during the synthesis process. Also, it is evident that a larger coating thickness or surface coverage does not necessarily result in a more protective film and TMSP apparently functions differently when used as an electrolyte additive.39-42 As for the latter, the beneficial effect is probably more related to its reactivity in solution.



Figure 7. Capacity retention based on the discharge capacity at 1C rate in the fifth cycle (a), Coulombic efficiency (b), average charge voltage (c), and rate performance in early cycles (d) of graphite based full-cells using pristine NCM622, TNPP@NCM622, and TMSP@NCM622. For better comparison, the difference in specific discharge capacity relative to that at 0.5C in the 15th cycle is given in part d. The asterisks in parts a and c indicate the rate capability test every 100 cycles.

One of the deactivation pathways in full-cells is the dissolution of transition-metal species from the cathode and subsequent deposition at the anode side. This process is believed to result in continuous poisoning/destruction (and rebuilding) of the solid electrolyte interphase (SEI) on graphite and, therefore, loss of active lithium.7 The amounts of Co, Mn, and Ni on the graphite anode were determined via ICP-OES, aiming at studying the effect of surface coating on the transition-metal leaching. To this end, discharged cells were disassembled inside an argon-filled glovebox, followed by rinsing the anode using DEC. Regardless of the type of transition metal, the lowest quantity is found when TNPP@NCM622 is used as the cathode material (Figure 8); the total amount of transition metals is lower by about 25% compared to pristine NCM622 and TMSP@NCM622. The proportion of Mn is much more than expected from the NCM622 stoichiometry. In the case of pristine NCM622, Co, Mn, and Ni account for roughly 10, 30, and 60% of the total amount of transition metals 20 ACS Paragon Plus Environment

Page 20 of 29

Page 21 of 29 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


on the anode. For both coated samples, even larger proportions of Mn are observed. It is known that the dissolution of Mn, especially from charged NCMs, is much higher than for Co and Ni species. However, there are contradictory reports as to whether Co or Ni exhibits higher dissolution rates.64,65 Larger quantities of Mn species were also found on the anode of NCM111 (33% Ni) and NCM523 (50% Ni) full-cells after cycling.66,67 Collectively, the ICP-OES results demonstrate that while phosphate ester coatings, in general, affect the transition-metal leaching from the cathode, only TNPP is capable of preventing the dissolution to a greater extent.

Figure 8. Amounts of Co, Mn, and Ni species deposited after 963 cycles at 1C rate on the graphite anode of full-cells using pristine NCM622, TNPP@NCM622, and TMSP@NCM622. Error bars are highlighted in orange.

The amount of transition metals found on the graphite anode accounts for around 0.6% of all the transition metals in the as-made cathode active material in the case of pristine NCM622. Consequently, the capacity fading can be attributed not only to loss of active material but also to loss of active lithium at the anode side. The reduced leaching (and subsequent deposition on graphite) is certainly one of the reasons for the superior cycling performance of TNPP@NCM622. However, it should be noted that the anode contribution to the rise in cell impedance with cycling is usually small compared to that of the cathode.68,69 This is likely also why there are no significant differences in the average charge/discharge voltages between pristine NCM622 and TNPP@NCM622, even though the capacity retention is much improved for the latter material. Taken together, we conclude from the data shown above that the TNPP derived coating mainly affects the cathode transition-metal dissolution. However, we cannot rule out that other adverse effects such as gassing play a major role, too.70

Conclusions Two different phosphate esters, namely, tris(4-nitrophenyl) phosphate (TNPP) and tris(trimethylsilyl) phosphate (TMSP) have been successfully used for formation of molecular coatings on NCM622. The presence of phosphate ester species on the top surface was confirmed by detection of characteristic P-O, N-O, and Si-O vibrational 21 ACS Paragon Plus Environment


bands via ATR-IR spectroscopy. Besides, for TNPP@NCM622, the presence of nitrophenyl groups was demonstrated in hydrolysis and TGA-MS experiments. The surface shells were also thoroughly characterized by means of ToF-SIMS. Among others, PO2– and PO3– fragments were clearly detected for both materials. Depth profiling in fast imaging mode combined with delayed extraction allowed characterization at high lateral and mass resolution. 3D reconstructions made from NiO2– and PO2–/PO3– signals revealed the spherical nature of the secondary cathode particles and, more importantly, provided evidence that the NCM622 material is uniformly coated by a thin shell, with minor inhomogeneities in the case of TNPP. The characterization using XPS supported the successful incorporation of phosphate ester onto the NCM622. Electrochemical testing was performed in graphite based full-cells. TNPP@NCM622 showed superior cycling performance, followed by pristine NCM622 and TMSP@NCM622. Although there were no significant differences in measures for cell impedance between TNPP@NCM622 and pristine NCM622, ICP-OES indicated much reduced transition-metal dissolution (and deposition at the anode side) in the case of TNPP@NCM622 which partly explains the improved longevity. Ultimately, our results demonstrate that molecular coating is a useful option for surface modification of cathode active materials, in addition to the more common coating with thin ceramic films.

Associated Content Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Details of the calculation of coating amount together with experimental results, 1H and 31P NMR spectra, UV-vis data and analysis, TGA-MS curves, positive and negative ToF-SIMS data and depth profiling results, and additional cycling data of half-cells and full-cells.

Author Information Corresponding Authors *Phone: +49 721 60828907, E-mail: [email protected] *Phone: +49 721 60828827, E-mail: [email protected] *Phone: +49 721 60828827, E-mail: [email protected] ORCID Marcus Rohnke: 0000-0002-8867-950X Jürgen Janek: 0000-0002-9221-4756 22 ACS Paragon Plus Environment

Page 22 of 29

Page 23 of 29 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


Torsten Brezesinski: 0000-0002-4336-263X Notes The authors declare no competing financial interest.

Acknowledgements This study is part of the projects being funded within the BASF International Network for Batteries and Electrochemistry. The work was partially carried out with the support of the Karlsruhe Nano Micro Facility (KNMF, www.knmf.kit.edu), a Helmholtz research infrastructure at Karlsruhe Institute of Technology (KIT, www.kit.edu).

References [1] [2]

[3]

[4] [5] [6]

[7]

[8]

[9]

Blomgren, G. E. The Development and Future of Lithium Ion Batteries. J. Electrochem. Soc. 2017, 164, A5019–A5025. Rozier, P.; Tarascon, J. M. Review-Li-Rich Layered Oxide Cathodes for NextGeneration Li-Ion Batteries: Chances and Challenges. J. Electrochem. Soc. 2015, 162, A2490–A2499. 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. Nitta, N.; Wu, F.; Lee, J. T.; Yushin, G. Li-Ion Battery Materials: Present and Future. Mater. Today 2015, 18, 252–264. Kim, J.; Lee, H.; Cha, H.; Yoon, M.; Park, M.; Cho, J. Prospect and Reality of Ni-Rich Cathode for Commercialization. Adv. Energy Mater. 2018, 8, 1702028. de Biasi, L.; Kondrakov, A. O.; Geßwein, H.; Brezesinski, T.; Hartmann, P.; Janek, J. Between Scylla and Charybdis Balancing Among Structural Stability and Energy Density of Layered NCM Cathode Materials for Advanced LithiumIon Batteries. J. Phys. Chem. C 2017, 121, 26163–26171. Radin, M. D.; Hy, S.; Sina, M.; Fang, C.; Liu, H.; Vinckeviciute, J.; Zhang, M.; Whittingham, M. S.; Meng, Y. S.; der Ven, A. V. Narrowing the Gap between Theoretical and Practical Capacities in Li-Ion Layered Oxide Cathode Materials. Adv. Energy Mater. 2017, 7, 1602888. Ryu, H.-H.; Park, K.-J.; Yoon, C. S.; Sun, Y.-K. Capacity Fading of Ni-Rich Li[NixCoyMn1-x-y]O2 (0.6 < x < 0.95) Cathodes for High-Energy-Density LithiumIon Batteries: Bulk or Surface Degradation? Chem. Mater. 2018, 30, 1155– 1163. Kim, U.-H.; Lee, E.-J.; Yoon, C. S.; Myung, S.-T.; Sun, Y.-K. Compositionally Graded Cathode Material with Long-Term Cycling Stability for Electric Vehicles Application. Adv. Energy Mater. 2016, 6, 1601417.



[10]

[11]

[12]

[13]

[14] [15] [16]

[17]

[18]

[19]

[20] [21]

Liu, W.; Oh, P.; Liu, X.; Lee, M.-J.; Cho, W.; Chae, S.; Kim, Y.; Cho, J. NickelRich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries. Angew. Chem. Int. Ed. 2015, 54, 4440–4457. Schipper, F.; Erickson, E. M.; Erk, C.; Shin, J.-Y.; Chesneau, F. F.; Aurbach, D. Review - Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes. J. Electrochem. Soc. 2017, 164, A6220–A6228. Kondrakov, A. O.; Schmidt, A.; Xu, J.; Geßwein, H.; Mönig, R.; Hartmann, P.; Sommer, H.; Brezesinski, T.; Janek, J. Anisotropic Lattice Strain and Mechanical Degradation of High- and Low-Nickel NCM Cathode Materials for Li-Ion Batteries. J. Phys. Chem. C 2017, 121, 3286–3294. Kondrakov, A. O.; Geßwein, H.; Galdina, K.; de Biasi, L.; Meded, V.; Filatova, E. O.; Schumacher, G.; Wenzel, W.; Hartmann, P.; Brezesinski, T.; Janek, J. Charge-Transfer-Induced Lattice Collapse in Ni-Rich NCM Cathode Materials during Delithiation. J. Phys. Chem. C 2017, 121, 24381–24388. Mauger, A.; Julien, C. Surface Modifications of Electrode Materials for LithiumIon Batteries: Status and Trends. Ionics 2014, 20, 751–787. Chen, Z.; Qin, Y.; Amine, K.; Sun, Y. K. Role of Surface Coating on Cathode Materials for Lithium-Ion Batteries. J. Mater. Chem. 2010, 20, 7606–7612. Myung, S.-T.; Amine, K.; Sun, Y.-K. Surface Modification of Cathode Materials from Nano- to Microscale for Rechargeable Lithium-Ion Batteries. J. Mater. Chem. 2010, 20, 7074–7095. Han, B.; Paulauskas, T.; Key, B.; Peebles, C.; Park, J. S.; Klie, R. F.; Vaughey, J. T.; Dogan, F. Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes. ACS Appl. Mater. Interfaces 2017, 9, 14769– 14778. Wise, A. M.; Ban, C.; Weker, J. N.; Misra, S.; Cavanagh, A. S.; Wu, Z.; Li, Z.; Whittingham, M. S.; Xu, K.; George, S. M.; Toney, M. F. Effect of Al2O3 Coating on Stabilizing LiNi0.4Mn0.4Co0.2O2 Cathodes. Chem. Mater. 2015, 27, 6146–6154. Mohanty, D.; Dahlberg, K.; King, D. M.; David, L. A.; Sefat, A. S.; Wood, D. L.; Daniel, C.; Dhar, S.; Mahajan, V.; Lee, M.; Albano, F. Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries. Sci. Rep. 2016, 6, 26532. Cho, J.; Kim, Y. J.; Kim, T.-J.; Park, B. Zero-Strain Intercalation Cathode for Rechargeable Li-Ion Cell. Angew. Chem. Int. Ed. 2001, 40, 3367–3369. Myung, S.-T.; Izumi, K.; Komaba, S.; Yashiro, H.; Bang, H. J.; Sun, Y.-K.; Kumagai, N. Functionality of Oxide Coating for Li[Li0.05Ni0.4Co0.15Mn0.4]O2 as Positive Electrode Materials for Lithium-Ion Secondary Batteries. J. Phys. Chem. C 2007, 111, 4061–4067.


Page 24 of 29

Page 25 of 29 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


[22]

[23]

[24]

[25]

[26]

[27]

[28]

[29]

[30] [31] [32]

[33]

[34]

Oh, Y.; Ahn, D.; Nam, S.; Park, B. The Effect of Al2O3-Coating Coverage on the Electrochemical Properties in LiCoO2 Thin Films. J. Solid State Electrochem. 2009, 14, 1235–1240. Myung, S.-T.; Izumi, K.; Komaba, S.; Sun, Y.-K.; Yashiro, H.; Kumagai, N. Role of Alumina Coating on Li–Ni–Co–Mn–O Particles as Positive Electrode Material for Lithium-Ion Batteries. Chem. Mater. 2005, 17, 3695–3704. Jo, C.-H.; Cho, D.-H.; Noh, H.-J.; Yashiro, H.; Sun, Y.-K.; Myung, S. T. An Effective Method to Reduce Residual Lithium Compounds on Ni-Rich Li[Ni0.6Co0.2Mn0.2]O2 Active Material Using a Phosphoric Acid Derived Li3PO4 Nanolayer. Nano Res. 2015, 8, 1464–1479. Lee, Y.; Lee, J.; Lee, K. Y.; Mun, J.; Lee, J. K.; Choi, W. Facile Formation of a Li3PO4 Coating Layer During the Synthesis of a Lithium-Rich Layered Oxide for High-Capacity Lithium-Ion Batteries. J. Power Sources 2016, 315, 284– 293. Lee, S.-W.; Kim, M.-S.; Jeong, J. H.; Kim, D.-H.; Chung, K. Y.; Roh, K. C.; Kim, K.-B. Li3PO4 Surface Coating on Ni-Rich LiNi0.6Co0.2Mn0.2O2 by a Citric Acid Assisted Sol-Gel Method: Improved Thermal Stability and High-Voltage Performance. J. Power Sources 2017, 360, 206–214. Min, K.; Park, K.; Park, S. Y.; Seo, S.-W.; Choi, B.; Cho, E. Improved Electrochemical Properties of LiNi0.91Co0.06Mn0.03O2 Cathode Material via LiReactive Coating with Metal Phosphates. Sci. Rep. 2017, 7, 7151. Kim, J.; Lee, J.; Ma, H.; Jeong, H. Y.; Cha, H.; Lee, H.; Yoo, Y.; Park, M.; Cho, J. Controllable Solid Electrolyte Interphase in Nickel-Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium-Ion Batteries. Adv. Mater. 2018, 30, 1704309. Cho, W.; Kim, S.-M.; Lee, K.-W.; Song, J. H.; Jo, Y. N.; Yim, T.; Kim, H.; Kim, J.-S.; Kim, Y.-J. Investigation of New Manganese Orthophosphate Mn3(PO4)2 Coating for Nickel-Rich LiNi0.6Co0.2Mn0.2O2 Cathode and Improvement of its Thermal Properties. Electrochim. Acta 2016, 198, 77–83. Ewald, B.; Lampert, J. K.; Schulz-Dobrick, M. Process for Preparing Electrode Materials. Eur. Pat. EP 2 619 139 B1, 2015. Ewald, B.; Lampert, J. K.; Schulz-Dobrick, M. Process for Preparing Modified Transition Metal Mixed Oxides. Eur. Pat. EP 2 619 141 B1, 2014. Queffélec, C.; Petit, M.; Janvier, P.; Knight, D. A.; Bujoli, B. Surface Modification Using Phosphonic Acids and Esters. Chem. Rev. 2012, 112, 3777–3807. Yassin, A.; Jimenez, P.; Lestriez, B.; Moreau, P.; Leriche, P.; Roncali, J.; Blanchard, P.; Terrisse, H.; Guyomard, D.; Gaubicher, J. Engineered Electronic Contacts for Composite Electrodes in Li Batteries Using ThiopheneBased Molecular Junctions. Chem. Mater. 2015, 27, 4057–4065. Wang, Q.; Evans, N.; Zakeeruddin, S. M.; Exnar, I.; Grätzel, M. Molecular Wiring of Insulators: Charging and Discharging Electrode Materials for High-



[35]

[36]

[37] [38]

[39]

[40]

[41]

[42]

[43]

[44]

[45]

[46]

[47]

Energy Lithium-Ion Batteries by Molecular Charge Transport Layers. J. Am. Chem. Soc. 2007, 129, 3163–3167. Anothumakkool, B.; Guyomard, D.; Gaubicher, J.; Madec, L. Interest of Molecular Functionalization for Electrochemical Storage. Nano Res. 2017, 10, 4175–4200. Xu, S.; Luo, G.; Jacobs, R.; Fang, S.; Mahanthappa, M. K.; Hamers, R. J.; Morgan, D. Ab Initio Modeling of Electrolyte Molecule Ethylene Carbonate Decomposition Reaction on Li(Ni,Mn,Co)O2 Cathode Surface. ACS Appl. Mater. Interfaces 2017, 9, 20545–20553. Moses, A. W.; Flores, H. G. G.; Kim, J.-G.; Langell, M. A. Surface Properties of LiCoO2, LiNiO2 and LiNi1-xCoxO2. Appl. Surf. Sci. 2007, 253, 4782–4791. Tebbe, J. L.; Fuerst, T. F.; Musgrave, C. B. Degradation of Ethylene Carbonate Electrolytes of Lithium Ion Batteries via Ring Opening Activated by LiCoO2 Cathode Surfaces and Electrolyte Species. ACS Appl. Mater. Interfaces 2016, 8, 26664–26674. Yan, G.; Li, X.; Wang, Z.; Guo, H.; Wang, C. Tris(trimethylsilyl)phosphate: A Film-Forming Additive for High Voltage Cathode Material in Lithium-Ion Batteries. J. Power Sources 2014, 248, 1306–1311. Wang, K.; Xing, L.; Zhu, Y.; Zheng, X.; Cai, D.; Li, W. A Comparative Study of Si-Containing Electrolyte Additives for Lithium Ion Battery: Which One Is Better and Why Is It Better. J. Power Sources 2017, 342, 677–684. Zhang, J.; Wang, J.; Yang, J.; NuLi, Y. Artificial Interface Deriving from Sacrificial Tris(trimethylsilyl)phosphate Additive for Lithium Rich Cathode Materials. Electrochim. Acta 2014, 117, 99–104. Rong, H.; Xu, M.; Xie, B.; Huang, W.; Liao, X.; Xing, L.; Li, W. Performance Improvement of Graphite/LiNi0.4Co0.2Mn0.4O2 Battery at High Voltage with Added Tris (trimethylsilyl) Phosphate. J. Power Sources 2015, 274, 1155– 1161. Bowers, G. N.; McComb, R. B.; Christensen, R. G.; Schaffer, R. High-Purity 4Nitrophenol: Purification, Characterization, and Specifications for Use as a Spectrophotometric Reference Material. Clin. Chem. 1980, 26, 724–729. Koike, T.; Kimura, E. Roles of Zinc(II) Ion in Phosphatases. A Model Study with Zinc(II)-Macrocyclic Polyamine Complexes. J. Am. Chem. Soc. 1991, 113, 8935–8941. Larkin, P. J. Infrared and Raman Spectroscopy: Principles and Spectral Interpretation. [Online]; Elsevier: Amsterdam, 2011; http://lib.myilibrary.com/detail.asp?id=311412 (accessed August 25, 2017). Ishida, H.; Koenig, J. L. Effect of Hydrolysis and Drying on the Siloxane Bonds of a Silane Coupling Agent Deposited on E-Glass Fibers. J. Polym. Sci. Polym. Phys. Ed. 1980, 18, 233–237. McElwee, J.; Helmy, R.; Fadeev, A. Y. Thermal Stability of Organic Monolayers Chemically Grafted to Minerals. J. Colloid Interface Sci. 2005, 285, 551–556. 26 ACS Paragon Plus Environment

Page 26 of 29

Page 27 of 29 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


[48]

[49]

[50]

[51]

[52]

[53]

[54]

[55]

[56]

[57]

[58]

[59]

Roobottom, H. K.; Jenkins, H. D. B.; Passmore, J.; Glasser, L. Thermochemical Radii of Complex Ions. J. Chem. Educ. 1999, 76, 1570– 1573. Franzmann, E.; Khalil, F.; Weidmann, C.; Schröder, M.; Rohnke, M.; Janek, J.; Smarsly, B. M.; Maison, W. A Biomimetic Principle for the Chemical Modification of Metal Surfaces: Synthesis of Tripodal Catecholates as Analogues of Siderophores and Mussel Adhesion Proteins. Chem. Eur. J. 2011, 17, 8596–8603. Li, W.; Dolocan, A.; Oh, P.; Celio, H.; Park, S.; Cho, J.; Manthiram, A. Dynamic Behaviour of Interphases and Its Implication on High-Energy-Density Cathode Materials in Lithium-Ion Batteries. Nat. Commun. 2017, 8, 14589. Börner, M.; Horsthemke, F.; Kollmer, F.; Haseloff, S.; Friesen, A.; Niehoff, P.; Nowak, S.; Winter, M.; Schappacher, F. Degradation Effects on the Surface of Commercial LiNi0.5Co0.2Mn0.3O2 Electrodes. J. Power Sources 2016, 335, 45– 55. Gilbert, J. A.; Bareño, J.; Spila, T.; Trask, S. E.; Miller, D. J.; Polzin, B. J.; Jansen, A. N.; Abraham, D. P. Cycling Behavior of NCM523/Graphite LithiumIon Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes. J. Electrochem. Soc. 2016, 164, A6054–A6065. Hwang, J.-Y.; Myung, S.-T.; Choi, J. U.; Yoon, C. S.; Yashiro, H.; Sun, Y.-K. Resolving the Degradation Pathways of the O3-Type Layered Oxide Cathode Surface Through the Nano-Scale Aluminum Oxide Coating for High-Energy Density Sodium-Ion Batteries. J. Mater. Chem. A 2017, 5, 23671–23680. Holzer, S.; Krivec, S.; Kayser, S.; Zakel, J.; Hutter, H. Large O2 Cluster Ions as Sputter Beam for ToF-SIMS Depth Profiling of Alkali Metals in Thin SiO2 Films. Anal. Chem. 2017, 89, 2377–2382. Henss, A.; Otto, S.-K.; Schaepe, K.; Pauksch, L.; Lips, K. S.; Rohnke, M. High Resolution Imaging and 3D Analysis of Ag Nanoparticles in Cells with ToFSIMS and Delayed Extraction. Biointerphases 2018, 13, 03B410. Morgan, W. E.; Wazer, J. R. V.; Stec, W. J. Inner-Orbital Photoelectron Spectroscopy of the Alkali Metal Halides, Perchlorates, Phosphates, and Pyrophosphates. J. Am. Chem. Soc. 1973, 95, 751–755. Chen, Z.; Wang, J.; Chao, D.; Baikie, T.; Bai, L.; Chen, S.; Zhao, Y.; Sum, T. C.; Lin, J.; Shen, Z. Hierarchical Porous LiNi1/3Co1/3Mn1/3O2 Nano/Micro Spherical Cathode Material: Minimized Cation Mixing and Improved Li + Mobility for Enhanced Electrochemical Performance. Sci. Rep. 2016, 6, 25771. Biesinger, M. C.; Payne, B. P.; Grosvenor, A. P.; Lau, L. W.; Gerson, A. R.; Smart, R. S. Resolving Surface Chemical States in XPS Analysis of First Row Transition Metals, Oxides and Hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 2011, 257, 2717–2730. Kanamura, K.; Tamura, H.; Takehara, Z. XPS Analysis of a Lithium Surface Immersed in Propylene Carbonate Solution Containing Various Salts. J. Electroanal. Chem. 1992, 333, 127–142. 27 ACS Paragon Plus Environment


[60]

[61]

[62]

[63]

[64]

[65]

[66]

[67]

[68]

[69]

[70]

Moulder, J. F.; Stickle, W. F.; Sobol, P. E.; Bomben, K. D. Handbook of X-ray Photoelectron Spectroscopy; A Reference Book of Standard Spectra for Identification and Interpretation of XPS Data; Physical Electronics, Inc, 1995. Kosova, N.; Devyatkina, E.; Kaichev, V. Optimization of Ni2+/Ni3+ Ratio in Layered Li(Ni,Mn,Co)O2 Cathodes for Better Electrochemistry. J. Power Sources 2007, 174, 965–969. Talaie, E.; Bonnick, P.; Sun, X.; Pang, Q.; Liang, X.; Nazar, L. F. Methods and Protocols for Electrochemical Energy Storage Materials Research. Chem. Mater. 2017, 29, 90–105. Koyama, Y.; Yabuuchi, N.; Tanaka, I.; Adachi, H.; Ohzuku, T. Solid-State Chemistry and Electrochemistry of LiCo1/3Ni1/3Mn1/3O2 for Advanced LithiumIon Batteries. J. Electrochem. Soc. 2004, 151, A1545–A1551. Zheng, H.; Sun, Q.; Liu, G.; Song, X.; Battaglia, V. S. Correlation Between Dissolution Behavior and Electrochemical Cycling Performance for LiNi1/3Co1/3Mn1/3O2-Based Cells. J. Power Sources 2012, 207, 134–140. Gallus, D. R.; Schmitz, R.; Wagner, R.; Hoffmann, B.; Nowak, S.; CekicLaskovic, I.; Schmitz, R. W.; Winter, M. The Influence of Different Conducting Salts on the Metal Dissolution and Capacity Fading of NCM Cathode Material. Electrochim. Acta 2014, 134, 393–398. Zheng, H.; Qu, Q.; Zhu, G.; Liu, G.; Battaglia, V. S.; Zheng, H. Quantitative Characterization of the Surface Evolution for LiNi0.5Co0.2Mn0.3O2/Graphite Cell during Long-Term Cycling. ACS Appl. Mater. Interfaces 2017, 9, 12445– 12452. Evertz, M.; Horsthemke, F.; Kasnatscheew, J.; Börner, M.; Winter, M.; Nowak, S. Unraveling Transition Metal Dissolution of Li1.04Ni1/3Co1/3Mn1/3O2 (NCM 111) in Lithium Ion Full Cells by Using the Total Reflection X-Ray Fluorescence Technique. J. Power Sources 2016, 329, 364–371. Liu, T.; Garsuch, A.; Chesneau, F.; Lucht, B. L. Surface Phenomena of High Energy Li(Ni1/3Co1/3Mn1/3)O2/Graphite Cells at High Temperature and High Cutoff Voltages. J. Power Sources 2014, 269, 920–926. Abraham, D. P.; Poppen, S. D.; Jansen, A. N.; Liu, J.; Dees, D. W. Application of a Lithium-Tin Reference Electrode to Determine Electrode Contributions to Impedance Rise in High-Power Lithium-Ion Cells. Electrochim. Acta 2004, 49, 4763–4775. Berkes, B. B.; Schiele, A.; Sommer, H.; Brezesinski, T.; Janek, J. On the Gassing Behavior of Lithium-Ion Batteries with NCM523 Cathodes. J. Solid State Electrochem. 2016, 20, 2961–2967.


Page 28 of 29

Page 29 of 29 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


Table of Contents Graphic


Molecular Surface Modification of NCM622 Cathode Material Using

Recommend Documents