Tetrathiafulvalene as a Conductive Film-Making Additive on High

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Tetrathiafulvalene as a conductive filmmaking additive on high-voltage cathode Yoon-Sok Kang, Min Sik Park, Insun Park, Dong Young Kim, Junho Park, Kwangjin Park, Meiten Koh, and Seok Gwang Doo ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b11991 • Publication Date (Web): 06 Jan 2017 Downloaded from http://pubs.acs.org on January 10, 2017

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ACS Applied Materials & Interfaces

Tetrathiafulvalene as a conductive film-making additive on high-voltage cathode Yoon-Sok Kang*1, Min Sik Park2, Insun Park1, Dong Young Kim1, Jun-Ho Park1, Kwangjin Park1, Meiten Koh1, and Seok-Gwang Doo1 1

Energy Laboratory, Samsung Advanced Institute of Technology, Samsung Electronics Co. Ltd.,

130, Samsung-ro, Yeongtong-gu, Suwon-Si, Gyeonggi-do, 16678, South Korea 2

Computer-Aided Engineering Group, Samsung Advanced Institute of Technology, Samsung

Electronics Co. Ltd., 130, Samsung-ro, Yeongtong-gu, Suwon-Si, Gyeonggi-do, 16678, South Korea KEYWORDS: lithium ion battery, electrolyte additive, tetrathiafulvalene, cathode passivation, overlithiated layered oxide

ABSTRACT: Tetrathiafulvalene (TTF) is investigated as a conductive film-making additive on overlithiated layered oxide (OLO) cathode. When the OLO/graphite cell is cycled at high voltage, carbonate-based electrolyte without the additive decomposes continuously to form a thick and highly resistant surface film on the cathode. In contrast, TTF added into the electrolyte becomes oxidized before the electrolyte solvents, creating a thinner film on the cathode surface. This film inhibits further electrolyte decomposition through cycling, and stabilizes the interface between

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the cathode and electrolyte. The cells containing the OLO cathode with TTF-added electrolyte afforded enhanced capacity retention and rate capability, making TTF a prospective electrolyte additive for higher energy density lithium ion cells.

1. INTRODUCTION

The rechargeable lithium-ion cell has been widely employed in mobile phones and laptops due to its many advantages, such as high energy density, reasonable price, and insignificant selfdischarge rate. While it is also the most promising candidate power source for electric vehicles, it needs further enhancement to meet the specifications of advanced electric vehicles1-4. For example, the driving distance of an electric vehicle on a single charge is becoming more and more important, which requires batteries with ever higher energy density. An effective method to enhance the energy density is to raise the average voltage and specific capacity of the cathode materials5,6. For this purpose, overlithiated layered oxides (OLO) have been developed7-10. Nevertheless, there are a few limitations that need to be surmounted before high energy density batteries containing OLO can be mass produced. In particular, significant deterioration of the cycle performance (capacity fading) has been observed with high-voltage cathodes such as OLO, because of the increased surface reactivity between the charged cathode and the electrolyte11-15. The electrolyte usually decomposes to make a solid electrolyte interphase (SEI) on the graphite anodes, which reduces the subsequent reaction between the electrolyte and the anodic surface16-22. Functional electrolyte additives such as fluoroethylene carbonate (FEC), vinylene carbonate, lithium difluoro(oxalate)borate, lithium bis(oxalate)borate, and succinic anhydride


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have been investigated to deliberately control the SEI film formed on the anode23-38. Meanwhile, film-making additives for the cathode surface have been examined for overcharge protection39,40. A few cathode passivation additives that form lithium ion-permeable films on the cathode have been studied, such as biphenyl, thiophene, 1,3,5-trihydroxybenzene, 5-hydroxy- 1H-indazole, tris(trimethylsilyl) phosphite, and lithium alkyl trimethyl borates41-48. They are oxidized before electrolyte decomposition to passivate the cathode surface. The film is expected to act like a surface coating on the cathode, thereby suppressing the irreversible crystal structural change, dissolution of transition metal ions, and electrolyte decomposition49,50. Calculated oxidation potentials can be used to screen organic compounds for their feasibility as film-making additives on the positive electrode51-54. The oxidation potential of 2H-1,3-dithiole calculated using density functional theory (DFT) is 3.56 V (vs. Li/Li+)52. Tetrathiafulvalene (TTF), because of its structural similarity to 2H-1,3-dithiole (Figure 1), might have lower oxidation potential than carbonate-based electrolytes. Therefore, TTF is anticipated to oxidize on the cathode before the decomposition of the electrolyte.

S

S

S

S

S ,

S

Figure 1. Chemical structures of tetrathiafulvalene (left) and 2H-1,3-dithiole (right).

TTF can be oxidized at relatively low voltages due to its nonaromatic 14-π electron structure, and it can sequentially and reversibly form a cation radical and a dication. Therefore, it is an organic mixed-valence compound. High electrical conductivity has been observed in its oxidized


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form with various salts55-57. For example, TTF+ Cl- is known as an outstanding organic semiconductor; its conductivity is 12 orders of magnitude higher than that of neutral TTF at room temperature. Therefore, significant research has been conducted on TTF and its derivatives in charge transfer complexes, nonlinear optics, and Langmuir-Blodgett films58,59. However, to the best of our knowledge, it has never been used as a functional electrolyte additive in lithiumion cells. In this study, we found that the modification of the cathode surface by TTF produced significantly superior cycle/rate performances, indicating the development of a highly conductive film on the OLO surface.

2. EXPERIMENTAL SECTION We preformed ab initio calculations of the redox potentials for organic molecules by using Gaussian 03 package, in which the B3LYP/6-311+G (d,p) basis sets and polarized continuum model (PCM) was employed60. For an effective description of the experimental electrolyte environment, the dielectric constant was set to be 25.7 corresponding to the average value of those of FEC and dimethyl carbonate (DMC) (3:7 v/v) used in the subsequent experiments61. The following reactions were used for calculating the oxidation and reduction potentials, respectively: TTF (electrolyte) → TTF+ (electrolyte) + e- (gas) TTF (electrolyte) + e- (gas) → TTF- (electrolyte) We also employed the following equations for direct comparison of the theoretical values with experimental ones, in which the physical (eV) scale was converted to the electrochemical one (V) by subtracting 1.39 V from the former62.


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For the oxidation potential (Eox), Eox(V vs. Li/Li+) = [Etot(TTF+, eV → joule) – Etot(TTF, eV → joule)]/e – 1.39 V where Etot(TTF+) and Etot(TTF) denote the total energies (unit conversion: eV → joule) of oxidized and neutral TTF, respectively, and e is the elementary charge. For the reduction potential (Erd), Erd(V vs. Li/Li+) = [Etot(TTF, eV → joule) – Etot(TTF-, eV → joule)]/e – 1.39 V where Etot(TTF-) denotes the total energy of reduced TTF. The electrolyte was 1.3 M LiPF6 dissolved in FEC/DMC (3:7 v/v), which hereafter is mentioned as a TTF-free electrolyte. The TTF-added electrolyte contained 0.1 wt% TTF. The OLO investigated in this study (Li1.17Mn0.50Co0.17Ni0.17O2) was synthesized by a co-precipitation method45. The cathode slurry was mixed with the OLO powder, Denka black, and poly(vinylidene fluoride) (PVdF, Solef) at a 90:5:5 weight ratio in 1-methyl-2-pyrrolidinone (NMP). Then, it was coated on an aluminum foil in the thickness of 8.5 mg cm-2 of OLO. The anode slurry comprised blended graphite powder and a carboxymethyl cellulose-styrene-butadiene rubber (CMC-SBR) binder in water, and it was coated on a copper foil. An Al2O3-coated polyethylene film (Teijin) was inserted between the cathode and the anode to prevent any direct contact of the electrodes. The capacity of the cell was 3 mA·h and the N/P ratio was 1.15. In order to make a stable surface film on both electrodes, the cells were initially charged and discharged twice at 25 mA·g1

(0.1C) over the voltage range of 2.5–4.65 V at 25 °C. The full cells were cycled at galvanostatic


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charge (1C)/discharge (1C) in the same potential range at 45 °C. At the end of each charging step, a constant-voltage step was added that indicated the completion of charging. In order to study the influence of TTF on the rate performance of the OLO cathodes, OLO half-cells were assembled with TTF-free or TTF-added electrolyte and cycled at 25 °C with various C rates: 0.2C–5C. After 300 cycles, the OLO/graphite full cells were disassembled in an Ar-filled glove box, and the electrodes were washed with DMC, and then dried at room temperature in a vacuum oven overnight for further analysis by scanning electron microscopy (SEM, Hitachi S4500) and X-ray photoelectron spectroscopy (XPS, Sigma probe, Thermo, UK). The C 1s peak at 285 eV originating from the C–C single bond was used for calibrating the binding energy of XPS.

3. RESULTS AND DISCUSSION TTF was tested as a cathode passivating additive to stabilize the OLO-electrolyte interface at high voltages. It should be noted the TTF is prone to lose electrons in electrochemically oxidative environments, because its highest occupied molecular orbital (HOMO) level is higher than those of the carbonate solvents. The calculated oxidation potential of TTF (Eox = 2.90 V vs. Li/Li+) is much lower than those of the carbonate solvents (6.78 and 7.51 V for DMC and FEC, respectively), and also lower than the upper voltage limit of conventional electrolytes (~4.3 V). Therefore, it is anticipated that the TTF oxidizes before the carbonate solvents on the cathode. Furthermore, the calculated reduction potential of TTF (0.26 V) is far below that of FEC (~1.2 V). Therefore, it is not expected to greatly affect the morphology of the SEI on the anode surface of the full cell.


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The 1st charge-discharge curves of the full cells (potential range: 2.5–4.65 V, current density: 0.1C (25 mA/g)) are presented in Figure 2a. OLO cathodes composed of Li(Ni0.33Mn0.33Co0.33)O2 and Li2MnO3 showed two voltage plateaus (~4.0 and 4.5 V) during initial charging, and displayed a large discharge capacity of approximately 260 mAh/g. The 1st cycle Coulombic efficiency of the cell with the TTF-added electrolyte (80.4%) was slightly lower than that without TTF (81.3%), which might be due to the additional decomposition of TTF at the cathode during charging. Figure 2b clearly shows that using even an infinitesimal amount of TTF (0.1 wt%) improved the cycle performance at 45 °C: the capacity retention after the 300th cycle was increased from 67% to 77%. This improvement with the TTF additive could be explained to protect the active sites on the OLO particle during initial charging by film making, which improved the average Coulombic efficiency of the cell (Figure 2c).

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Figure 2. Effects of TTF as an electrolyte additive (a) Voltage profiles of the OLO/graphite full cells at 25 °C, 1st cycle. (b) Capacity retention ratio and (c) averaged Coulombic efficiency of the full cells at 45 °C cycling.

The high rate cycling stability of OLO was investigated to examine the suitability of the TTF-derived film for promoting charge transfer on the OLO (Figure 3). Note that the experiment was performed just after the cell formation process at room temperature. In this case, the passivation film on the cathode in the TTF-free cell was not yet thickly stacked. Nevertheless, the TTF-added cell delivered a better discharge capacity (138 mAh/g) at 5C, whereas that of the reference cell was only 130 mAh/g at the same discharging rate. Therefore, the addition of TTF promoted the rate capability of the OLO/Li cell, as the TTF-derived surface film led to better cycle and rate performances than the carbonate-derived one. This could be partly attributed to the enhanced conductivity of TTF in its oxidized form, as mentioned earlier. The effects of additional parameters, such as the film thickness and composition, will be discussed later in the context of XPS analysis.


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In order to explore the surface morphology of the OLO cathodes during 300 cycles at 45 °C, SEM was employed. The sharp edges of the primary particles of OLO are evident in the SEM images of the pristine OLO composite electrode, as shown in Figure 4a. The cathodes cycled in electrolyte without and with TTF (Figure 4b and 4c, respectively) showed no significant damage such as particle cracking. In spite of the marginal difference in the surface morphology, passivation films were deposited on the cathode surface in both case. Therefore, both films were strong enough to withstand the prolonged cycling at high temperature and high voltage. We speculated that TTF can operate as a good passivation additive for the positive electrode by stabilizing the electrode surface, as it is an electron-rich system. Its derivatives have been used as basic units for the polymer network, even though oxidized TTF is soluble in electrolyte6366

. Indeed, we found experimentally that TTF does change the interface of the positive electrode

and improved the cell performance.


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(a)

300nm (b)

(c)

Figure 4. SEM images of OLO particles: a) pristine electrode and after 300 cycles in b) TTFfree electrolyte and c) TTF-added electrolyte.

The impact of TTF on the chemistry of the cycled OLO surface was examined by XPS measurement. Figures 5a and 5b display the C 1s and S 2p spectra of the cathode after 300 cycles, respectively. PVdF binder usually shows two C 1s peaks at 285 eV and 290 eV. The shoulder peak at 289 eV observed for TTF-free electrolyte is attributed to the CO3 functional group of carbonate derivatives, whereas this peak is nearly invisible for the OLO in the TTF-added electrolyte. Therefore, the surface passivation film made in the latter case contained less carbonate compounds. The C 1s spectra of both electrodes also showed new carbonaceous species at the electrode/electrolyte interface (284.5 eV). In Figure 5b, the peaks at around 169 eV


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for both electrodes may be attributed to SO42- from the transition metal precursor used during OLO synthesis. However, another peak at 164 eV only appeared for the TTF-added electrolyte, and it comes from the C-S bond from thiophene-like rings. Therefore, this peak could be assigned to TTF derivatives (five-membered ring with sulfur). These spectra showed that the cathode surface film formed in TTF-added electrolyte contained mainly TTF derivatives. Therefore, TTF displays specific reactivity towards the electrode surface, possibly due to its preferential decomposition compared to the electrolyte solvent. The peaks of Mn 2p (Figure 5c), and F 1s (Figure 5d) were also recorded for the cycled OLO. The Mn 2p photoelectron peak is stronger in the OLO cathode cycled in the TTF-added electrolyte, indicating a thinner deposited surface film. A thick surface film may hamper the transfer of electrons and lithium ions to/from the cathode, and thereby impede the delithiation/lithiation kinetics of the cathode upon prolonged cycling. The F 1s peak at 688 eV can originate from LiPF6 or CF2 of the PVdF binder. The peak at the lower binding energies (around 685 eV) can be designated to lithium fluoride (LiF), which has been reported to be much less conductive than carbonate-based surface films for lithium ion conduction33, 45, 67-70. Importantly, the cycled cathode surface with the TTF-added electrolyte has much less LiF. When the electrode undergoes prolonged cycling with TTF, it shows more rapid kinetics because the TTF-derived thin surface film with low resistance contains a lower concentration of LiF. Therefore, the TTF-derived film has excellent passivating ability, and consequently the additional electrolyte decomposition, LiF formation, and film growth are not severe.


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Figure 5. XPS data of the OLO cathode cycled in two electrolytes: (a) C 1s, (b) S 2p, (c) Mn 2p, and (d) F 1s peaks.

Figure 6 summarizes the different passivation films developed on the cycled OLO cathode in the two electrolytes. The high-voltage cycling leads to violent reaction between the TTF-free electrolyte and OLO surface. Therefore, thick and highly resistive LiF-dominant film is created on the OLO particle. In the presence of TTF, TTF oxidation occurs quickly at the beginning of the first charge, and the products act as a passivation film that protects further electrolyte decomposition. As a result, a thin/conductive film is formed on the OLO, thus preserving the electrochemical performance of the battery.


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Figure 6. A schematic representation of the enhanced conductivity of the surface film on OLO particles cycled in TTF-added electrolyte.

4. CONCLUSIONS Tetrathiafulvalene (TTF) is examined as a film-making electrolyte additive in high-voltage lithium ion batteries using an OLO cathode. The additive considerably enhanced the poor electrochemical performance of the cathode in carbonate-based electrolyte. Ex situ analysis of the OLO cathode shows that the film formed on the OLO surface without the additive is thick and contains mainly carbonate solvents with high LiF content. In contrast, TTF is electrochemically oxidized prior to the electrolyte on the OLO particle, resulting into a surface passivation film. This film inhibits further electrolyte decomposition and the film growth, and reduces the formation of highly resistive LiF to improve the ionic conduction. Therefore, the TTF-derived surface film is thinner and more conductive than that derived from the carbonatebased electrolyte. Consequently, the capacity retention and rate property of the cell are enhanced.


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AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] Author Contributions The manuscript was written through the contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The authors acknowledge Dr. Anass Benayad and In-Yong Song for their support in surface analysis of the electrodes. ABBREVIATIONS Tetrathiafulvalene (TTF), Solid Electrolyte Interphase (SEI), Overlithiated Layered Oxide (OLO)


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REFERENCES (1) Armand, M.; Tarascon, J.-M. Building Better Batteries. Nature 2008, 451, 652–657 (2) Tollefson, J. Car industry: Charging up the Future. Nature 2008, 456, 436-440 (3) Scrosati. B; Garche, J. Lithium Batteries: Status, Prospects and Future. J. Power Sources 2010, 195, 2419-2430 (4) Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries. Chem. Mater., 2010, 22, 587-603 (5) Hu, M.; Pang, X.; Zhou, Z. Recent Progress in High-Voltage Lithium Ion Batteries. J. Power Sources, 2013, 237, 229-242 (6) Manthiram, A.; Knight, J.C.; Myung, S.-T.; Oh, S.-M.; Sun, Y.-K. Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives. Adv. Energy Mater., 2016, 6, 1501010 (7) Thackeray, M.; Kang, S.; Johnson, C.S.; Vaughey, J.T.; Benedek, R.; Hackney, S. A. Li2MnO3-stabilized LiMO2 Electrodes for Lithium Ion Batteries. J. Mater. Chem., 2007, 17, 3112-3125 (8) Yabuuchi, N.; Yoshii, K.; Myung, S. T.; Nakai, I.; Komaba, S. Detailed Studies of a Highcapacity Electrode Material for Rechargeable Batteries, Li2MnO3-LiCo1/3Ni1/3Mn1/3O2. J. Am. Chem. Soc., 2011, 133, 4404-4419


15


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Page 16 of 25

(9) Li, Y.; Bettge, M.; Polzin, B.; Zhu, Y.; Balasubramanian, M.; Abraham, D. P. Understanding Long-term Cycling Performance of Li1.2Ni0.15Mn0.55Co0.1O2–graphite Lithium-Ion Cells. J. Electrochem. Soc., 2013, 160, A3006-A3019 (10) Yu, S.-H.; Yoon, T.; Mun, J.; Park, S.; Kang, Y.-S.; Park, J.-H.; Oh, S.M.; Sung, Y.-E. Continuous Activation of Li2MnO3 Component upon Cycling in Li1.167Ni0.233Co0.1Mn0.467Mo0.033O2 Cathode Material for Lithium Ion Batteries. J. Mater. Chem. A., 2013, 1, 2833-2839 (11) Aurbach, D.; Markovsky, B.; Salitra, G.; Markevich, E.; Talyossef, Y.; Koltypin, M.; Nazar, L.; Ellis, B.; Kovacheva, D. Review on Electrode–electrolyte Solution Interactions, related to Cathode Materials for Li-Ion Batteries. J. Power Sources, 2007, 165, 491-499 (12) Yang, L.; Ravdel, B.; Lucht, B. L. Electrolyte Reactions with the Surface of High Voltage LiNi0.5Mn1.5O4 Cathodes for Lithium-Ion Batteries. Electrochem. Solid-State Lett., 2010, 13, A95-A97 (13) Martha, S. K.; Nanda, J.; Veith, G. M.; Dudney, N. J. Surface Studies of High Voltage Lithium Rich Composition: Li1.2Mn0.525Ni0.175Co0.1O2. J. Power Sources, 2012, 216, 179-186 (14) Li, J.; Downie, L.E.; Ma, L.; Qiu, W.; Dahn, J.R. Study of the Failure Mechanism of LiNi0.8Mn0.1Co0.1O2 Cathode Material for Lithium Ion Batteries. J. Electrochem. Soc., 2015, A1401-A1408 (15) Kim, D.Y.; Park, M.S.; Lim, Y.; Kang, Y.-S.; Park, J.-H.; Doo, S.-G. Computational Comparison of Oxidation Stability: Solvent/Salt Monomers vs Solvent-solvent/Salt Pairs. J. Power Sources, 2015, 288, 393-400


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Page 17 of 25

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(16) Peled, E.; Golodnisky, D.; Ardel, G. Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes. J. Electrochem. Soc., 1997, 144, L208-L210 (17) Buqa, H.; Golob, P.; Winter, M.; Besenhard, J. O. Modified Carbons for Improved Anodes in Lithium Ion Cells. J. Power Sources, 2001, 97-98, 122-125 (18) Jeong, S.-K.; Inaba, M.; Mogi, R.; Iriyama, Y.; Abe. T.; Ogumi, Z. Surface Film Formation on a Graphite Negative Electrode in Lithium-Ion Batteries: Atomic Force Microscopy Study on the Effects of Film-forming Additives in Propylene Carbonate Solutions. Langmuir, 2001, 17, 8281-8286 (19) Aurbach, D.; Markovsky, B.; Rodkin, A.; Cojocaru, M.; Levi, E.; Kim, H.-J. An Analysis of Rechargeable Lithium-Ion Batteries after Prolonged Cycling. Electrochim. Acta, 2002, 47, 1899-1911 (20) Markovsky, B.; Rodkin, A.; Cohen, Y. S.; Palchik, O.; Levi, E.; Aurbach, D.; Kim, H.-J.; Schmidt, M. The Study of Capacity Fading Processes of Li-Ion Batteries: Major Factors that Play a Role. J. Power Sources, 2003, 119-121, 504-510 (21) Xu, K. Nonaqueous Liquid Electrolytes for Lithium-based Rechargeable Batteries. Chem. Rev., 2004, 104, 4303-4417 (22) Verma, P.; Maire, P.; Novak, P. A Review of the Features and Analyses of the Solid Electrolyte Interphase in Li-Ion Batteries. Electrochim. Acta, 2010, 55, 6332-6341


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Page 18 of 25

(23) Aurbach, D.; Gamolsky, K.; Markovsky, B.; Gofer, Y.; Schmidt, M.; Heider, U. On the Use of Vinylene Carbonate (VC) as an Additive to Electrolyte Solutions for Li-Ion Batteries. Electrochim. Acta, 2002, 47, 1423-1439 (24) Herstedt, M.; Stjerndahl, M.; Gustafsson, T.; Edstrom, K. Anion Receptor for Enhanced Thermal Stability of the Graphite Anode Interface in a Li-Ion Battery. Electrochem. Commun., 2003, 5, 467-472 (25) Xu, K.; Zhang, S.; Jow, T.R. LiBOB as Additive in LiPF6-based Lithium Ion Electrolytes. Electrochem. Solid State Lett., 2005, 8, A365-A368 (26) Zhang, S.S. A Review on Electrolyte Additives for Lithium-Ion Batteries. J. Power Sources, 2006, 162, 1379-1394 (27) Choi, N.-S.; Yew, K.H.; Lee, K.Y.; Sung, M.; Kim, H.; Kim, S.-S. Effect of Fluoroethylene Carbonate Additive on Interfacial Properties of Silicon Thin-film Electrode. J. Power Sources, 2006, 161. 1254-1259 (28) Chen, L.; Wang, K.; Xie, X.; Xie, J. Effect of Vinylene Carbonate (VC) as Electrolyte Additive on Electrochemical Performance of Si Film Anode for Lithium Ion Batteries. J. Power Sources, 2007, 174, 538-543 (29) Liu, J.; Chen, Z.; Busking, S.; Amine, K. Lithium Difluoro(Oxalato)Borate as a Functional Additive for Lithium-Ion Batteries. Electrochem. Commun., 2007, 9, 475-479 (30) Qin, Y.; Chen, Z.; Lu, W.; Amine, K. Electrolyte Additive to Improve Performance of MCMB/LiNi1/3Co1/3Mn1/3O2 Li-Ion Cell. J. Power Sources, 2010, 195, 6888-6892


18

Page 19 of 25

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


(31) Han, G.-B.; Ryou, M.-H.; Cho, K.Y.; Lee, Y.M.; Park, J.-K. Effect of Succinic Anhydride as an Electrolyte Additive on Electrochemical Characteristics of Silicon Thin-Film Electrode. J. Power Sources, 2010, 195, 3709-3714 (32) Dalavi, S.; Guduru, P.; Lucht, B. Performance Enhancing Electrolyte Additives for Lithium Ion Batteries with Silicon Anodes. J. Electrochem. Soc., 2012, 159, A642-646 (33) Lin, Y.-M.; Kalvetter, K.C.; Abel, P.R.; Davy, N.C.; Snider, J.L.; Heller, A.; Mullins, C.B. High Performance Silicon Nanoparticle Anode in Fluoroethylene Carbonate-Based Electrolyte for Li-Ion Batteries. Chem. Commun., 2012, 48, 7268-7270 (34) Ushirogata, K.; Sodeyama, K.; Okuno, Y.; Tateyama, Y. Additive Effect on Reductive Decomposition and Binding of Carbonate-Based Solvent toward Solid Electrolyte Interphase Formation in Lithium-Ion Battery. J. Am. Chem. Soc., 2013, 135, 11967-11974 (35) Xu, K. Electrolytes and Interphase in Lithium Ion Batteries and Beyond. Chem. Rev., 2014, 114, 11503-11618 (36) Ma, L.; Xia, J.; Dahn, J.R. Ternary Electrolyte Additive Mixtures for Lithium Ion Battery that Promote Long Lifetime and Less Reactivity with Charged Electrodes at Elevated Temperature. J Electrochem. Soc., 2015, 162, A1170-A1174 (37) Haregewoin, A.M.; Wotango, A.S.; Hwang, B.-J. Electrolyte Additives for Lithium Ion Battery Electrodes: Progress and Perspectives. Energy Environ. Sci., 2016, 9, 1955-1988 (38) Lindgren, F.; Xu, C.; Niedzicki, L.; Marcinek, M.; Gustafsson, T.; Björefors, F.; Edström, K.; Younesi, R. SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based


19


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

Page 20 of 25

Electrolyte with FEC and VC Additives for Li-Ion Batteries. ACS Appl. Mater. Interfaces, 2016, 8, 15758-15766 (39) Xiao, L.; Ai, X.; Cao, Y.; Yang, H. Electrochemical Behavior of Biphenyl as Polymerizable Additive for Overcharge Protection of Lithium Ion Batteries. Electrochim. Acta, 2004, 49, 4189-4196 (40) Watanabe, Y.; Morimoto, H.; Tobishima, S. Electrochemical Properties of Aryladamantanes as New Overcharge Protection Compounds for Lithium Cells. J. Power Sources, 2006, 154, 246-254 (41) Abe, K.; Takaya, T.; Yoshitake, H.; Ushigoe, Y.; Yoshio, M.; Wang, H. Functional Electrolyte: Additives for Improving the Cyclability of Cathode Materials. Electrochem. Solidstate Lett., 2004, 7, A462-A465 (42) Lee, K.; Sun, Y.; Noh, J.; Song, K.; Kim, D. Improvement of High Voltage Cycling Performance and Thermal Stability of Lithium–Ion Cells by Use of a Thiophene Additive. Electrochem. Commun., 2009, 11, 1900-1903 (43) Tarnopolskiy, V.; Kalhoff, J.; Nadherna, M.; Bresser, D.; Picard, L.; Fabre, F.; Rey, M.; Passerini, S. Beneficial Influence of Succinic Anhydride as Electrolyte Additive on the SelfDischarge of 5 V LiNi0.4Mn1.6O4 Cathodes. J. Power Sources, 2013, 236, 39-46 (44) Kang, Y.-S.; Yoon. T.; Lee, S.S.; Mun, J.; Park, M.S.; Park, J.-H.; Doo, S.-G.; Song, I.-Y.; Oh, S.-M. 1,3,5-Trihydroxybenzene as a Film Forming Additive for High Voltage Positive Electrode. Electrochem. Commun., 2013, 27, 26-28


20

Page 21 of 25

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


(45) Kang, Y.-S.; Yoon. T.; Mun, J.; Park, M.S.; Song, I.-Y.; Benayad, A.; Oh, S.-M. Effective Passivation of a High Voltage Positive Electrode by 5-Hydroxy-1H-Indazole Additives. J. Mater. Chem. A., 2014, 2, 14628-14633 (46) Perea, A.; Zaghib, K.; Belanger, D. Characterization of LiNi0.5Mn1.5O4 Spinel Electrode in the Presence of 1,3,5-Trihydroxybenzene as Additive. J. Mater. Chem. A., 2015, 3, 2776-2783 (47) Han, J.-G.; Lee, S.J.; Lee, J.; Kim, J.-S.; Lee, K.T.; Choi, N.-S. Tunable and Robust Phosphite Derived Surface Film to Protect Lithium Rich Cathodes in Lithium Ion Batteries. ACS Appl. Mater. Interfaces, 2015, 7, 8319-8329 (48) Xu, M.; Zhou, L.; Dong, Y.; Chen, Y.; Demeaux, J.; MacIntosh, A.D.; Garsuch, A.; Lucht, B.L. Development of Novel Lithium Borate Additives for Designed Surface Modification of High Voltage LiNi0.5Mn1.5O4 Cathodes. Energy and Environ. Sci., 2016, 9, 1308-1319 (49) 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, 70747095 (50) Zhang, H. Z.; Qiao, Q. Q.; Li, G. R.; Ye, S. H.; Gao, X. P. Surface Nitridation of Li-Rich Layered Li(Li0.17Ni0.25Mn0.58)O2 Oxide as Cathode Material for Lithium-ion Battery. J. Mater. Chem., 2012, 22, 13104-13109 (51) Abe, K.; Ushigoe, Y.; Yoshitake, H.; Yoshio, M. Functional Electrolytes: Novel Type Additives for Cathode Materials, Providing High Cycleability Performance. J. Power Sources, 2006, 153, 328-335


21


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

Page 22 of 25

(52) Park, M.S.; Kang, Y.-S.; Im, D.; Doo, S.-G.; Chang, H. Design of Novel Additives and Nonaqueous Solvents for Lithium-Ion Batteries Through Screening of Cyclic Organic Molecules: An ab initio Study of Redox Potentials. Phys. Chem. Chem. Phys., 2014, 16, 22391-22398 (53) Park, M.S.; Kang, Y.-S.; Im, D. A High Speed Screening Method by Combining a HT Method And a Machine Learning Algorithm for Developing Novel Organic Electrolytes in Rechargeable Batteries. ECS Trans., 2015, 68, 75-81 (54) Park, M.S.; Park, I.; Kang, Y.-S.; Im, D.; Doo, S.-G. A Search Map for Organic Additives and Solvents Applicable in High-voltage Rechageable Batteries. Phys. Chem. Chem. Phys., 2016, 18, 26807-26815 (55) Wudl, F.; Wobschall, D.; Hufnagel, E. J. Electrical Conductivity by the Bis(1,3-Dithiole)bis(1,3-Dithiolium) System. J. Am. Chem. Soc., 1972, 94 (2): 670–672 (56) Ferraris, J.; Cowan, D. O.; Walatka, V. V., Jr.; Perlstein, J. H. Electron Transfer in a New Highly Conducting Donor-Acceptor Complex. J. Am. Chem. Soc., 1973, 95 (3): 948-949 (57) Hasegawa, H. Tetrathiafulvalene-based Nanocrystals: Site-Selective Formation, Device Fabrication, and Electrical Properties, J. Mater. Chem. C, 2015, 3, 8986-8991 (58) Segura, J.L; Martín, N. New Concepts in Tetrathiafulvalene Chemistry. Angew. Chem. Int. Ed., 2001, 40, 1372-1409 (59) Frere, P.; Skabara, P. J. Salts of Extended Tetrathiafulvalene Analogues: Relationships between Molecular Structure, Electrochemical Properties and Solid State Organization. Chem. Soc. Rev., 2005, 34 (1): 69–98


22

Page 23 of 25

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


(60) Frisch, M.J; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery Jr.; J. A.; Vreven, T.; Kudin, K..N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R., Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A., Gaussian 03. (61) Tomasi, J.; Mennucci, B.; Cammi, R. Quantum Mechanical Continuum Solvation Models. Chem. Rev., 2005, 105, 2999-3093 (62) Trasatti, S. The Absolute Electrode Potential: an Explanatory Note. Pure Appl. Chem., 1986, 58, 955–966 (63) Dougherty, D. A. Cation-pi Interactions in Chemistry and Biology: A New View of Benzene, Phenylalanine, Tyrosine, and Tryptophan. Science, 1996, 271, 163-168 (64) Muller, H.; Salhi, F.; Divisia-Blohorn, B.; Genoud, F.; Narayanan, T.; Lorenzen, M.; Ferroro, C. Poly[(dibenzylidene)tetrathiapentalene]—the First Linearly Extended TTF Polymer. Chem. Commun., 1999, 1407-1408


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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

Page 24 of 25

(65) Inatomi, Y.; Hojo, N.; Yamamoto, T.; Watanabe, S.-I.; Misaki, Y. Construction of Rechageable Batteries Using Multifused Tetrathiafulvalene Systems as Cathode Materials ChemPlusChem, 2012, 77, 973-976 (66) Bildirir, H.; Paraknowitsch, J. P.; Thomas, A. A Tetrathiafulvalene(TTF)-Conjugated Microporous Polymer Network. Chem. Eur. J., 2014, 20, 9543-9548 (67) Zaban, A.; Zinigrad, E.; Aurbach, D. Impedance Spectroscopy of Li Electrodes. 4. A General Simple Model of the Li-Solution Interphase in Polar Aprotic Systems. J. Phys. Chem., 1996, 100, 3089-3101 (68) Herstedt, M.; Stjerndahl, M.; Gustafsson, T.; Edstrom, K. Anion Receptor for Enhanced Thermal Stability of the Graphite Anode Interface in a Li-Ion Battery. Electrochem. Commun., 2003, 5, 467-472 (69) Aurbach, D.; Markovsky, B.; Salitra, G.; Markevich, E.; Talyossef, Y.; Koltypin, M.; Nazar, L.; Ellis, B.; Kovacheva, D. Review on Electrode–Electrolyte Solution Interactions, Related to Cathode Materials for Li-Ion Batteries. J. Power Sources, 2007, 165, 491-499 (70) Yildirim, H.; Kinaci, A.; Chan, M. K. Y.; Greenley, J. P. First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF. ACS Appl. Mater. Interfaces, 2015, 7, 18985-18996


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Tetrathiafulvalene as a Conductive Film-Making Additive on High

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