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Li-Sulfur Batteries: State of the Art and Future Directions

Teyeb Ould Ely, Dana Kamzabek, Dhritiman Chakraborty, and Michael F. Doherty
ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.7b00153 • Publication Date (Web): 17 Apr 2018
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Page 1 of 150 ACS Applied Energy Materials
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7 Li-Sulfur Batteries: State of the Art and Future
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Directions
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15 Teyeb Ould Ely,1,2* Dana Kamzabek1†, Dhritiman Chakraborty,1††
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18 Michael F. Doherty2*
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[1] Department of Chemistry, School of Science and Technology, Nazarbayev University,
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27 Astana, 010000, Kazakhstan, Ouldely00@ucsb.edu.
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29 Office: 7.107, Phone: +7 (7172) 70 62 86,
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31 [2] Department of Chemical Engineering, University of California Santa Barbara, CA
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33 93106-5080, USA email: mfd@ucsb.edu, phone: (805) 893-5309, fax: (805) 893-4731
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60 ACS Paragon Plus Environment
ACS Applied Energy Materials Page 2 of 150
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5 ABSTRACT.
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7 Sulfur remains in the spotlight as a future cathode candidate for the post Lithium ion age.
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This is primarily due to its low cost and high discharge capacity, two critical requirements
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12 for any future cathode material that seeks to dominate the market of portable electronic
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14 devices, electric transportation and electric-grid energy storage. However, before Li-S
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16 batteries replace lithium ion batteries several technical challenges need to be solved.
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18 Among these challenges polysulfide containment, the increase of sulfur loading (which
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20 must be ≥4-6 mg cm −2
), the increase of sulfur fraction ≥70%, the increase of sulfur
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utilization ≥80%, the decrease of the electrolyte/sulfur weight ratio (which must be in the
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25 range of 3:1 or lower), and the stability of lithium anode material. Beside traditional
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27 carbon coating strategies, recent novel strategies addressing each of these challenges have
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29 been reported. The main purpose of this article is to review the state of the art, summarize
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31 and shed light on the most promising recent discoveries related to each challenge. The
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33 review also addresses the role of the electrolyte systems and electrocatalytic additives.
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49 KEYWORDS
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51 Lithium Sulfur Batteries, Batteries Beyond Lithium, Electrocatalytic Polysulfides
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53 Conversion, Sulfur Cathode Coating, Lithium Anode Protecton, Solid State Electrolytes.
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5 1. INTRODUCTION
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7 Lithium sulfur batteries are poised to play an important role in the future of energy
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storage. This is primarily due to their high discharge capacity and low cost of sulfur. The
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12 run time of all electronic devices depends on the discharge capacity of their batteries 1-2 .
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14 Conventional Li ion batteries use lithiated transition metals such as LiCoO2 and LiFePO4
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16 as lithium insertion cathode materials 3. These transition metals are neither cheap nor
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18 abundant and are toxic to the environment. Furthermore, the main limitation of these
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20 cathodes is their small energy capacity that does not allow them to be practical for energy
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intensive applications such as public transportation 2-4 . Doping these oxides with low cost
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25 nickel and manganese transition metals improved the capacity specially for he lithium-
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27 rich transition metal oxide with the general formula of xLi2MnO3·(1−x)LiMO2(M = Mn,
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29 Co, Ni) however, the growing demand for high capacity batteries necessitates the
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31 development of new chemistries beyond current lithium ion batteries . The theoretical
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33 specific energy for conventional lithium ion batteries is 387 Whkg-15. Their
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competitiveness on the market is further affected by the cost associated with lithium
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38 metal and lithium ion cell packaging. Magnesium ion and sulfur are poised to compete
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40 with lithiated transition metal cathode materials. Magnesium ion batteries provide better
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42 energy per unit volume, yet the closest to the market are lithium-sulfur batteries2.
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46 The theoretical capacity of the sulfur cathode is 1675 mAhg-1 and the Li-S battery itself
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48 is expected to give 500 Wh kg-1 of gravimetric energy, in comparison to the gravimetric
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51 energy of Li ion cell of∼243 Wh kg-16-7, Figure 1.
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19 Figure 1. Commercialized Li-ion cells (e.g., Panasonic NCR18650B) have twice the
20 volumetric energy density of prototype Li–S cells which, by contrast, can have a higher
21 gravimetric energy density. Adapted with permission from 8.
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25 The challenges facing the commercialisation of LiS batteries are inherent to the
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27 physical and chemical properties of sulfur. Sulfur has the largest number of allotropes
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(~30 allotropes) compared to any other element, with the most stable form at room
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32 temperature (orthorhombic, α-S8) having 8 sulphur atoms arranged into a puckered ring.
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34 The most common allotropes are displayed in Figure 2. Gradual heating of sulfur is
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36 accompanied by an interesting viscosity change 9. Near 119 °C sulfur starts to melt and it
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becomes a yellow liquid; its viscosity sharply decreases until approximately 155 °C,
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41 further heating results in viscosity increase. Above 159°C the liquid pours very
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43 sluggishly. At high temperatures (> 200° C) the viscosity starts decreasing and the liquid
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45 sulfur becomes reddish. These viscosity changes are related to the tendency of sulfur S-S
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bond to break and reform leading to linear S8 chains and ultimately to longer linear
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50 chains such as S16, S24 and so on. These long chains can also be formed and intertwined
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52 during oxidation reaction processes and cause a dramatic increase of viscosity.
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19 Figure 2. Most common allotropes of sulfur. Reproduced with permission from reference
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24 There are multiple advantages of using sulfur as a cathode material. Among them low
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26 prices, relative nontoxicity, high gravimetric capacity, high energy density and low
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28 operating voltage. However, there are also a number of disadvantages such as the
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shuttling effect (i.e., polysulfide migration), low volumetric density, limited cyclability
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33 and poor safety that need to be considered and amended to make Li-S cells more widely
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35 usable . Moreover, Li-S batteries should be useful for oil producing countries, due to
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37 their large stocks of pure sulfur accumulated as a result of oil purification and refining.
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41 The remainder of this review is divided into five main sections. The first section
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addresses the concept of lithium sulfur batteries and their fundamental problem; that is
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46 polysulfides shuttling. In the third and fifth, we review the most promising state of the art
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48 strategies to prevent polysulfide migration. These techniques can be divided into: (1)
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50 containment techniques (whereby a functional coating and/or an interlayer separator are
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52 used to confine polysulfides) and (2) destruction techniques (whereby an electrocatalyst is
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54 used to autocatalytically destroy or precipitate polysulfides and disable their shuttling
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abilities). In the fourth section, we review recent progress in LiS electrolyte systems, and
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3 whenever data are available we highlight the electrolyte/sulfur ratio and sulfur utilization.
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5 This sheds light on the most promising electrolyte systems with additives to solve
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7 polysulfide challenges. In the final section (section 6), we address the challenges related
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to the use of a lithium metal anode and the most promising remedies reported in the
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12 recent literature.
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16 2. Li-S CELLS AND THE POLYSULFIDES SHUTTLING PROBLEMS
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18 As outlined in Figure 3, a typical Li-S battery consists of two electrodes: an anode that is
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20 made of lithium metal, and a cathode with sulfur as the main component supplemented
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with a separator and conductive electrolyte between the electrodes. The electrolyte can be
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Figure 3. a) Scheme and typical charge-discharge curves for lithium sulfur batteries. b)
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First discharge and charge profiles of a Li–S cell between 1.5 and 2.8V vs. Li+/Li. Graph
46 b is reproduced with permission from Angulakshmi et al.12
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49 The energy is produced by the battery during the discharge process. The starting cathode
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51 material is octasulphur – S8 the most stable conformation of sulfur. S8 is reduced to
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53 produce multiple highly soluble polysulfides (Li2Sx, 4 < x < 8). Li ions move to the
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55 positive electrode (cathode) and react with those polysulphides to finally form Li2S or
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3 Li2S2 while electrons move through the external circuit producing energy. The overall
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5 formula for the discharge process is depicted in Figure 3a.
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Polysulfides are indispensable in lithium-sulfur batteries since both S and Li2S are poor
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12 electronic and ionic conductors. Nonetheless, polysulfides (Li2S8, Li2S6, Li2S4, Li2S3) are
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14 highly soluble in liquid electrolytes which compromises the functioning of the battery in
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16 two significant ways: (1) the dissolution of polysulfides, beside creating voids in the
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18 cathode, increases the viscosity of the electrolyte making it less conductive, (2) upon
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20 dissolution polysulfides tend to shuttle back and forth to the anode side and precipitate in
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the form of insoluble and insulating low order Li2Sx. These species contribute to self-
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25 discharge and an overall poor cycle life with low specific capacity. An electrolyte with
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27 high polysulfide solubility and low viscosity, and most importantly, with ability to oppose
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29 shuttling is highly desirable for best performance of Li/S cells.
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33 The voltage profile of the first LiS battery discharge/charge (Figure 3b) shows the
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presence of soluble S82- and S62- species in the electrolyte following two successive
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38 reductions characterized by a solid to liquid plateau S8→S82- (a-b), and a steep capacity
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40 decrease S82- →S62- (b-c). These solid to liquid and liquid to liquid transformations
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42 increase the electrolyte viscosity drastically and are responsible of the sharp decrease of
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44 the overall cell voltage and self-discharge. The third reduction step (b-c) is characterized
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46 by a lower voltage plateau between 1.9 to 2.1 V which contributes predominantly to the
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48 capacity of Li/S cell. In this liquid to solid plateau other polysulfides of the general
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formula Li2S8-n and Li2Sn ions and radicals are produced as the result of
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53 disproportionation reactions and continue to be reduced to low order polysulfides such as
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55 the highly insoluble and insulating Li2S or Li2S2 species12-13, 4. Upon charging, these
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3 highly soluble in the electrolyte but tend to shuttle through the separator to the anode
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5 where they get reduced into low order species such as Li2S or Li2S2. The precipitation of
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contribute to the capacity fading, self-discharge and an overall poor cycle life, low
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12 specific capacity and lower efficiency.
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16 It is worth noting that the anode side has its own intrinsic challenges independent of the
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18 polysulfides shuttling problem. In fact, the lithium metal anode tends to react with, and
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20 deplete, the electrolyte forming a thick and unstable SEI layer that pulverizes upon
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repeated cycling, generating active sites for dendrites nucleation. The latter leads to
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25 internal short and in some cases explosion and fire. The precipitation of an insulating
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31 One possible solution to polysulfides shuttling is to introduce an ion selective
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33 membrane. Recently, hybrid (liquid-solid) electrolyte concept that shield the lithium
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metal from direct contact with the electrolyte and prevent polysulfide migration was
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38 reported 14. We will review this promising hybrid electrolyte approach in the electrolyte
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44 The next problem with sulfur is its poor volumetric packing and tendency to expand
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46 upon cycling by approximately 80%15,16 upon reduction to Li2S. This results in nonlinear
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to mechanical stress. To handle the stress, improve the conductivity and maintain the
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53 cathode integrity, durable carbon based cathode composites need to be developed17.
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55 Sulfur loading of the cathode should be at least 70% by weight or higher. Recently, a
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can be avoided if smaller allotropes of sulfur (S2, S3 and S4) are used. The confined sulfur
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12 molecules prevent the transition between S8 and S42- while charging/discharging leading
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14 to a LiS cells with high charge/discharge capacities and cyclability. A recent promising
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16 approach uses electrocatalysts to render polysulfides insoluble and less prone to shuttling
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20 In the next section, we discuss the best carbon materials used for sulfur cathode
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modifications to restrain polysulfides migration, increase volumetric packing of sulfur
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29 3. SULFUR CATHODE MODIFICATIONS WITH VARIOUS CARBON
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Carbon-sulfur modification is the most investigated strategy to stabilize sulfur cathodes
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38 and led to higher capacities and cyclabilities compared to bare sulfur. Extensive body of
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40 literature is available and will be briefly reviewed in this section. Nan et al.21 obtained
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42 high initial discharge capacity of 1394 mAhg-1 prior to adding carbon to enhance
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44 conductivity, however upon limited cycling the capacity fade. Upon carbon coating using
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46 CVD an initial specific capacity of 972 mAhg-1 was obtained at 0.2C for 1 µm spheres, at
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48 high C-rate this capacity drops further to 821 mAh g−1at the 0.5C rate, and 793 mAh g−1
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at the 1C rate. After 100 cycles, the 1 µm particles achieved a high specific capacity of
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53 737 mAh g−1 at the 0.2C rate, 683 mAh g−1 at the 0.5C rate, and 634 mAh g−1 at the 1C
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55 rate with a sulfur content of 60 wt % in the electrodes.
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3 In the upcoming paragraphs, we will review and compare the effect of Sulfur cathode
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Nanofibers, and (4) Mesoporous Carbons. At the end of each section we will present a
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12 summary of the best performances achieved in the course of the last decade (2006-2016).
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16 3.1. Graphene and Graphene oxide
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18 Graphene has been used for Li-S batteries as a cathode complement due to its physical
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conductivity of graphene compensates the insulating nature of sulfur and the hardness and
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25 compliance of graphene provides resistance to mechanical stress from sulfur expansion
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31 Ji et al. 27
reduced polysulfide dissolution by immobilizing sulfur and polysulfides on
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33 graphene oxide (GO). They prepared cathode composite in two steps: firstly, they
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deposited sulfur on graphene oxide and then applied low temperature thermal treatment
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38 (155°C) to get rid of excess sulfur. Melted sulfur has strong attraction to graphene oxide
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40 and it seeps into the composite. This process helped to achieve a unique cathode
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42 structure: extremely thin (tens of nanometers) sulfur flake layer on graphene oxide.
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44 Functional groups on the surface of GO aided in trapping sulfur and polysulfides. The
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46 new cathode composite was tested with several electrolytes under different conditions and
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48 maintained high capacity of near 1000 mAhg-1 at rate of 0.1C during more than 50 cycles.
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The GO-S nanocomposite was efficient in preventing the leakage of polysulfides and
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3 Qiu and co-workers have improved the efficiency of graphene-sulfur composite by
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7 sulfur and polysulfides. The new sulfur/nitrogen-doped graphene (S-NG) composite
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exhibited cycling of 120 cycles with initial discharge capacity of around 1200 mAh g-1
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12 and 760 mAh g-1 retention at 0.2C rate.
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16 Lin et al 29 used graphene sheets as a cathode additive and observed reversible capacity
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18 of 570 mAhg-1 after 100 cycles at high 2C current rate with sulfur content of 73 wt.%. Xu
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synthesized S/3D-graphene composite and obtained an initial discharge capacity
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of 1260 mAh g-1 and reversible capacity of 700 mAh g-1 after 100 cycles at 0.1C rate. The
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25 highly porous 3D structure of graphene provides conductive paths for electron and ion
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also used nitrogen-doped graphene (NG), but with higher sulfur loading
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33 (5 mg cm-2) which is critical to obtain energy density close to that of available Li-ion
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batteries. The authors attempted to mitigate structural changes in graphene that have
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38 adverse effect on the performance of the battery. The composite retained high discharge
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40 capacity (920 mAh g-1) after 300 cycles at current density of 0.2C rate. NG composite has
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42 shown excellent results, because it allows for high sulfur loading (up to 90 wt% of sulfur)
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48 Graphene is also frequently used as additive to sulfur/polymer cathode composite 11, 32-
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. For instance, Zhang et al.36 obtained reversible capacity of up to 450 mAh g-1 after
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3 Liu et al.211 proposed new nitrogen doped graphene using one-step self-supporting
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5 solid-state pyrolysis (OSSP) to produce graphene-like oxygenated carbon nitride (OCN)
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7 host material that contains tens of micrometer scaled two-dimensional (2D) rippled
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sheets. Remarkably, this material gave high initial specific capacity of 1407.6 mAh g−1 at
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12 C/20 rate with 84% S loading and retain improved reversible capacity during long-term
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14 cycles (> 2000 cycles) at high current density. In Figure 4 we summarize the best
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32 Figure 4. Recent literature survey of the highest capacity of Li-S batteries coated with graphene or graphene oxides and cycled at 0.2C rate. The
33 survey is narrowed from 630 non-review articles (light orange) dealing with “lithium sulfur and graphene”. To exclude cases where graphene is
34 used as interlayer, separator coating or blended with other material to increase conductivity, the search was narrowed to 129 using the term
35 “coating” (deep orange bars). Within these articles we reviewed articles providing 100 cycles or more at 0.2 C. The maximum value is listed on
36 top of each bar. The data was extracted from the following references; 201138, 2012 39-41, 201336, 42-44, 2014 45-50, 201534, 37, 51-65, 2016 31, 66-79.
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3 Graphene and Graphene oxides are the most investigated carbon coating as a laminate
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Yu et al.107 reported an interesting role of coating although they used titanium oxide
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12 deposited by atomic layer deposition (ALD). This coating, beside leading to strong
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14 capacity retention of 61 % higher than the retention of bare NG/S which was only 42%,
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16 can confine the lithium polysulfides and avoid their dissolution, maintaining the integrity
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18 and stability of the electrodes during the redox process. TiO2 was also suggested to
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20 reduce the polarization of the S cathodes at high rates. The rate performances of ALD
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TiO2 modified electrodes became worse at any current density with 5 or 40 TiO2 cycles.
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25 This indicates that the coating should not be too thin (< 1 nm) whereby it degrades upon
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27 cycling, or too thick to hinder lithium ion diffusivity and cause poor electronic
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29 conductivity. These effects offset the advantage of the TiO2 layer.107
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31 Recently, a composite made from calcium fluoride and graphene oxide (CaF2/GO)
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33 coated onto the separator of an LiS cell produced an in situ LiF SEI layer upon cycling.
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This layer inhibited the shuttle effect and precluded the precipitation of insulating
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38 Li2S2/Li2S on the lithium anode surface yielding good cyclic performance with a high
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40 discharge capacity of 1205 mA h g−1 at a current density of 0.2 C and capacity decay of
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42 only 0.043% per cycle during 400 cycles108. However, upon increasing sulfur loading
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44 from ≈1.3 mg cm−2 to ≈2.6 mg cm−2 the capacity retention drops to 700 mA h g−1.
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48 3.2.Carbon Nanotubes
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Sulfur-CNT are believed to be a good cathode composite due to their unique structure
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53 which can accommodate polysulfides and reduce shuttling effect, also they are cheaper
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3 research on sulfur cathodes-CNT modification, however, overall, CNT-Sulfur was found
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Ahn et al. reported the use of 70% of sulfur-MWCNT cathode and compared its
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12 performance with sulfur-MWCNT composite. The initial discharge capacity of the latter
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14 was 1355 mAhg-1 but it decreased rapidly to 854 mAh g-1 over 30 cycles. Unconfined
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16 sulfur might have accelerated the cathode degradation which resulted in sharp decrease in
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18 capacity and possible leakage of polysulfides. Su et al. 111
showed that MWCNT paper
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20 layer inserted between the positive electrode and separator contributed to an unexpectedly
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high initial charge capacity: 1446 mAh g-1 and good cycling life as the capacity remained
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25 at 962 mAh g-1 over the 50 cycles. Such effect was caused by the ability of the layer to
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27 catch migrating polysulfides, thus stopping the shuttling effect. However, the capacity
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29 faded after low number of cycles112. In Figure 5 we summarize the best performances
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29 Figure 5. Recent literature survey of the highest capacity of Li-S batteries coated with CNTs, and cycled at 0.2C rate. The survey is narrowed
30 from 359 non-review articles (deep orange) dealing with “lithium sulfur and CNT” to 69 using the term coating (light orange bars). Within these
31
articles we searched articles providing 100 cycles or more at 0.2 C. The best performances are listed on top of each bar. The best performances
32
are listed on top of each bar. There were no reports with cyclability higher than 100 cycles in 2006, 2009 and 2010. The data were extracted
33
34 from the following references; 2007113, 2011114, 2012115, 2013116, 2014117, 2015118, 2016119
35
36
37
38
39
40
41
42
43
44
46
47
17
1
2
120
3 More promising results were obtained by Liang et al. who used S/polypyrrole-
4
5 MWCNT as a cathode composite and reported a discharge capacity of 725.8 mAhg-1
6
7 which was retained over 100 cycles. These authors tested composites with different PPy
8
9
content and concluded that 25 wt.% of Ppy is optimal to ensure homogeneous dispersion
10
11
12 of sulfur. Higher PPy content reduced the conductivity of the cell and caused lower
13
14 discharge capacities. Similar experiment was conducted by Zhang et al 121 , who obtained
15
16 high capacity for S/PPy and suggested that PPy coating retains polysulfides in CNT
17
18 pores, yielding a capacity of 960.7 mAhg-1 on average for up to 40 cycles at a discharge
19
20 rate of 0.1C. These authors found that an increase in current rate from 0.25C to 0.5C leads
21
22
to rapid capacity fading from 971.7 mAh g-1 to 492.4 mAh g-1. The ability of Ppy to
23
24
25 reduce shuttling significantly improved the efficiency of the cell 122 .
26
27 Ahn et al. improved the capacity considerably by coating the separator with
28
29 montmorillonite, which was found to act as an ion selective ceramic that effectively
30
31 suppress polysulfides diffusion while enabling lithium diffusion123. This cathode
32
33 displayed a discharge capacity of 1382 mAhg-1 at a current density of 100 mAg-1 and
34
35
maintain 924 mAhg-1 after 200 cycles.
36
37
38
39
40 3.3. Hollow Carbon Nanofibers
41
42 HCNF’s are usually one atom thick, 200-300nm width and 60 µm long hollow tubes
43
44 with sulfur deposited only inside the tube (Figure 6) 124
. They have a number of
45
46 advantages that make them a good cathode component. Firstly, they encapsulate sulfur
47
48
49
with polysulfides and thus minimize the shuttling effect. Secondly, because of the thin
50
51 walls they provide short pathways for lithium cations to reach the sulfur. Thirdly, they
52
53 create a conductive network that increases the charge density of the cell. Fourthly, they
54
55 are able to provide enough space for sulfur expansion and consequently pulverization of
56
57
58
59
18
1
2
3 sulfur is avoided. Hollow carbon fibres have also been used in conjunction with other
4
5 nanomaterials to increase discharge capacity, such as MnO, TiO2 125-127.
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22 Figure 6. Hollow carbon nanofiber.
23
24
25
26 Zheng et al. 128
prepared hollow carbon nanofibers by using membrane of anodic
27
28
29
aluminum oxide (AAO). AAO served a dual function: it acted as a template and also
30
31 made it possible to incorporate melted sulfur exclusively inside the tubes, thus the
32
33 sulfur/electrolyte contact was limited. Sulfur to carbon ratio in these cathodes was of 3:1
34
35 which indicates a high sulfur percentage of 75%. The reverse capacities were 630 mAhg-1
36
37 and 730 mAhg-1 after 150 cycles at current rates 0.5C and 0.2C respectively. These
38
39 authors suggested the removal of AAO would improve the capacity, although this may
40
41
42
compromise the cycling stability. Upon using LiNO3 as an electrolyte additive 1560 mAh
43
44 g-1 of initial capacity was obtained, the specific cyclability is not provided, but it was
45
46 claimed to be similar to the samples without additives. Finally, coulombic efficiency with
47
48 LiNO3 was highly improved (~ 98%).
49
50
51
52 Li et al. 129 , reported another approach based on sublimation of sulfur into a DMF/CS2
53
54
organic solution (DMF: N,N-Dimethylformamide, CS2: carbon disulfide). Then Hollow
55
56
57
58
59
19
1
2
3 Carbon Nanofibers (HCNFs) were added to the prepared sulfur containing DMF/CS2.
4
5 After heating and stirring sulfur crystallized and the cathode was formed. The initial
6
7 discharge capacity was 1090 mAh g-1 with reversible capacity of 600 mAh g-1 after 100
8
9 130
cycles at 1C rate. To enhance the ability of HCNF’s to trap polysulfides Zhang et al.
10
11
12 decorated them with polyaniline. The obtained structure was examined by numerous
13
14 techniques and it was revealed that polyaniline coats homogeneously the surface of the
15
16 cathode. The reversible capacity of 535 mAh g-1 was observed after 200 cycles at a rate of
17
18 0.5C. Despite the fact that sulfur was exposed to the electrolyte, the performance of the
19
20 HCNF with PANI-S is relatively good, possibly due to the ability of polyaniline coating
21
22
to limit polysulfides shuttling.
23
24
25
26
27 In addition to polymer coating, two additional strategies to improve the performance of
28
29 S-HCNF cathode have been investigated. The first strategy is dealing of nitrogen doping
30
31 which improves the overall conductivity of the HCNF. The second strategy is the
32
33 inclusion of layered oxides within the HCNF to prevent polysulfides migration and
34
35
leakage.
36
37
38
39 126
40 Li et al. have optimized hollow carbon nanofibers/sulfur composite by nitrogen
41
42 doping and obtained reversible capacities of 625 mAh g-1 and 513 mAh g-1 after 100
43
44 cycles at 0.2C and 0.5C current rates. The superior performance of the new composite
45
46 compared to performance of undoped HCNF/S composite can be attributed to the ability
47
48 of nitrogen doping to improve conductivity and bind sulfur and polysulfides, providing
49
50
51
homogenous sulfur dispersion. Another successful nitrogen doping of HCNFs was
52 127
53 performed by Zhou et al . They obtained excellent cyclability with high current rate.
54
55 The reversible capacity of 600 mAhg-1 was retained after 600 cycles at 0.6C rate.
56
57
58
59
20
1
2
3
4
5 Li et al. 125
filled HCNFs with manganese dioxide nanosheets (Figure 7, 8) and
6
7 observed a reversible capacity up to 600 mAhg-1 after 300 cycles at 0.05C current rate.
8
9
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11
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27
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29
30
31
32
Figure 7: a) Synthesis of the MnO2@HCF/S composite. b) Advantages of the
33
MnO2@HCF/S composite over HCF/S, reproduced with permission from reference 125.
34
35
36
37
38 These various hollow carbon nanofibers/sulfur composites are a promising solution to
39
40 the issue of shuttling and capacity fading in Li-S batteries. Unlike MWCNT, HCNF’s do
41
42 not have an external sulfur layer nor require polysulfide coating. This leads to reduced
43
44 shuttle effect in comparison with CNT and gives more cycles with high discharge
45
46
capacity.
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48
49
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51
52
53
54
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59
21
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27
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30
31
32
33 Figure 8: a) Cycle capacity and Coulombic efficiency of MnO2@HCF/S in comparison
34 with HCF/S at a current density of 0.2 C. b) Voltage profiles during cycling at 0.1 C. c)
35 Discharge capacities. d) Voltage profiles at various rate capabilities from 0.05 to 1 C. e)
36 Prolonged cycling performance of MnO2@HCF/S at 0.5 C and the corresponding
37 Coulombic efficiency. Areal capacity values were calculated based on the specific
38 capacity and areal mass loading of sulfur, reproduced with permission from reference 125.
39
40
41 75, 131
The use of metal oxides in the cathode reduces sulfur loading. Liang et al were
42
43
44 able to increase the loading from 1.5 mgcm−2 to 2.8 mgcm−2 and 4.1 mgcm−2 while
45
46 maintaining good cyclability and an overall capacity of 780 mAhg-1. A free standing
47
48 carbon nanofiber interlayer combined with a sulfur cathode loaded at 4.4 mgcm−2 showed
49
132
50 remarkable reversible capacity retention of 79.98 % after 100 cycles . The capacity at
51
52 0.2 C was above 1214 mAh/g, however the capacity continues fading above 100 cycles.
53
54 The carbon nanofiber mats used were fabricated by electrospinning and directly used as
55
56
57
58
59
22
1
2
3 an interlayer between the separator and the cathode to create an additional electron
4
5 pathway and to trap polysulfides without any further modification or surface treatment on
6
7 other cell components. Recently, Chung et al 18
achieved an exceptional loading of 61.4
8
9
mg cm−2 and sulfur content (80 wt %) using carbon cotton fibers. These authors
10
11
12 demonstrated the highest areal capacity (56 mAhcm−2) ever reported, and a volumetric
13
14 capacity (1121 mAhcm−3), and a stable gravimetric capacity (724 mAhg−1) that was
15
16 retained after 200 cycles. In Figure 9 we summarize the best performances of Li-
17
18 S/carbon fibers (capacity, cyclability and sulfur loading) reported in the last decade
19
20 (2006-2016).
21
22
23
24
25
26
27
28
29
30
31
32
33
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2 23
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13
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17
18
19
20
21
22
23
24
25
26
27
Figure 9. Recent literature survey of the highest capacity of Li-S batteries coated with HCNF, and cycled at 0.2C rate. The survey is narrowed
28
29 from 82 non-review articles (deep orange) dealing with “lithium sulfur and CNT”. The search was narrowed further to 27 using the term coating
30 (light orange bars). Within these 27 articles we reviewed articles providing 100 cycles or more at 0.2 C. The best performances are listed on top
31 of each bar. There were no substantial reports between 2006-2011. The data were extracted from the following references; 201618, 2015132,
32 2014133, 2013134, 2011135.
33
34
35
36
37
38
39
40
41
42
43
44
46
47
24
1
2
3
4
5 3.4. Mesoporous Carbon
6
7 Another carbon-based material that is actively being investigated for sulfur cathode
8
9 31, 56, 67, 97, 103, 136-177
coating is mesoporous carbon . Mesoporous carbon is used as both a
10
11 136-139, 178
12 separator (interlayer to trap polysulfide) and a coating material (to stabilize
13 143
14 sulfur cathode) . The large surface area, mechanical stability and ability to
15
176
16 accommodate large amount of sulfur are among the advantages of this material .
17
18 Mesoporous carbon material seems to be able to cope with multiple problems of Li-S
19
20 cells. Firstly, mesoporous carbon is a conductor, thus it compensates the insulating nature
21
22
of sulfur. Secondly, its pores are small enough to keep polysulfides inside and at the same
23
24
25 time they allow Li metal to migrate to sulfur. Thirdly, the amount of sulfur impregnated
26
27 can be controlled to avoid the problem of its expansion. Furthermore, mesoporous carbon
28
29 is more efficient compared to nano-sized and submicro-sized cathode materials in terms
30
31 of durability of the cathode 179
. Numerous articles have reported that mesoporous carbon
32
33 in conjunction with sulfur greatly increases the stability and the capacity of Li-S batteries
34
35 164, 179-188
.
36
37
38
39 15
40 Yang et al. synthesized CMK-3 mesoporous C/S composite, and ultimately coat it
41
42 with polymer poly(3,4-еthylеnеdioxythiophеnе)-poly(styrеnеsulfonate) (PEDOT:PSS)
43
44 (Figure 10). The coating was adjusted by the dispersion and sonication of the cathode
45
46 material. Beside the coating, the PEDOT:PSS polymer led to the adhesion between the
47
48 particles, thus it acted like a binder.
49
50
51
52
53
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23 Figure 10. Schematic of PEDOT:PSS-coated CMK-3/sulfur composite (a) In bare
24 CMK-3/S particles (gray: CMK-3, yellow: sulfur), polysulfides (green) still diffuse out of
25 the carbon matrix during lithiation/delithiation. (b) With conductive polymer coating
26 layer (blue), polysulfides could be confined within the carbon matrix. Lithium ions and
27 electrons can move through this polymer layer. Figure and caption are reproduced with
28
permission from reference 15.
29
30
31
32 The PEDOT:PSS film, as in this case, not only serves as a soft buffer to restrict
33
34 polysulfides migration, but also provides increased active surface to capture and reuse
35
36 polysulfides. The polymer coated cathode cell exceeded the bare mesoporous carbon-
37
38 sulfur composite cathode in initial discharge capacity by 9%, yielding a capacity of 1140
39
40 mAhg-1 and 1049 mAhg-1 respectively. These authors [51] also reported final discharge
41
42
capacity of 600 mAhg-1 for the coated sample after 150 cycles.
43
44
45
46 183
47 Wang et al. prepared one dimensional mesoporous carbon fibers (OMCF) using an
48
49 electrospinning technique and mixed it with sulfur to create OMCF-S cathode. They
50
51 obtained the reversible capacity of 690 mAhg-1 after 300 cycles at 0.3C rate. The
52
53 exceptional cyclability is explained by the ability of mesoporous fibers to maintain
54
55
56
57
58
59
26
1
2
3 physical stability of the electrode and enhance conductivity of the system. This procedure
4
5 successfully achieved high sulfur loading (63%).
6
7
8
9
Multiple reports investigated the use of mesoporous carbon in conjunction with other
10
11 180
12 materials to increase the efficiency of the cell. Jin and co-workers , for instance,
13
14 combined mesoporous carbon/sulfur composite with polyaniline coating. PANI coating
15
16 served as a barrier for polysulfides diffusion and it was proved to improve utilization of
17
18 sulfur and conductivity of the cell. The results show that CMK3/S-PANI composite gives
19
20 high initial discharge capacity of 1103 mAh g-1 which gradually drops to 649 mAh g-1
21
22
after 100 cycles at 1C rate. In comparison, CMK3/S composite without coating is capable
23
24
25 of giving the highest discharge capacity of approximately 600 mAh g-1 which eventually
26
27 drops to 200 mAh g-1 after 100 cycles at the same rate. Ma et al.189 used polypyrrole
28
29 (PPY) to coat CMK-8/S and obtained stable capacity of 860 mAh/g after 100 cycles at
30
31 0.2C.
32
33
34
35
Xu et al. 179 obtained good cyclability and capacity retention by incorporation of carbon
36
37
38 nanotubes into porous spherical carbon-sulfur composite. New PSC-CNT-S composite
39
40 have shown initial discharge capacity of 1100 mAh g-1 which fell to 700 mAh g-1 after
41
42 200 cycles. In comparison, PSC-S alone can give reversible capacity of only around 500
43
44 mAh g-1 which was maintained during 75 cycles. Higher cyclability and capacity retention
45
46 can be attributed to decrease in electrical resistivity provided by the addition of CNT to
47
48 the composite.
49
50
51
52 182
53 Wang et al. coated mesoporous carbon-sulfur composite with a titanium (IV) oxide
54
55 layer which improved the performance of the cell by preventing the leakage of
56
57
58
59
27
1
2
3 polysulfides. Their results show that the coated cathode composite has higher reversible
4
5 capacity compared to carbon-sulfur composite: 608 mAh g-1 versus 450 mAh g-1 at 0.2C
6
7 rate after 120 cycles. These authors mention that C-S-TiO2 generally show lower initial
8
9
discharge capacities due to higher resistivity caused by TiO2 coating. However, in the
10
11
12 long term TiO2 coating improves trapping of polysulfides especially upon coupling with
13
14 mesoporous carbon.
15
16
17
18 Wang et al.181 have developed the S-MC-4-60 composite cathode material. This
19
20 material displayed a high initial discharge capacity of 1388 mAhg-1 and a good cycling
21
22
stability of 857 mAhg-1 after 100 cycles at 0.2C, the pore sizes were around 3-30 nm. Qu
23
24
25 et al. 190 used waste material to develop a novel highly ordered nitrogen-rich mesoporous
26
27 carbon (HNMC), which was prepared by the pyrolysis of biomass waste. These authors
28
29 obtained high initial discharge capacity of 1209 mAh g-1, and reversible capacity of 600
30
31 mAh g-1 after 200 cycles at 1C rate. In addition, their cathode demonstrated excellent
32
33 cycling stability up to 300 cycles at high 3C current rate. Balach and co-authors 184
34
35
observed high discharge capacity of 1015 mAh g-1 at 0.2C rate after 200 cycles in the cell
36
37
38 with mesoporous carbon interlayer placed between separator and sulfur cathode.
39
40
41
42 Yang et al.191 obtained high specific energy by incorporating Li2S/mesoporous carbon
43
44 (CMK-3) instead of bare sulfur as the active cathode material and silicon nanowires as the
45
46 anode to avoid using potentially unsafe lithium metal anodes (Figure 11).
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48
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28
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27
Figure 11. Schematic representation and capacities of mesoporous carbon-embedded
28
29
Li2S/silicon nanowire battery. (a) A schematic of a CMK-3 mesoporous carbon-
30 embedded Li2S/silicon nanowire battery. (b) The voltage profile of a CMK-3/Li2S
31 cathode versus a lithium anode. (c) The cycling performance of a CMK-3/Li2S cathode
32 compared to a commercial 10 mm-sized Li2S particle electrode. (d) Typical capacity
33 delivery in multiple charge–discharge cycles (1 blue, 2 red, 3 green) of a Li2S/C electrode
34 in a polymer electrolyte. Lithium metal counter and reference electrode. The operating
35 temperature is 60 º C and the cycling rate is C/20 (C = 2.2 mA cm-2). The upper and
36 bottom axes represent capacity based on the mass of Li2S and Li2S–carbon, respectively.
37 Reproduced with permission from reference124.
38
39
40 192
Schuster showed that double coating Li2S/mesoporous carbon with thin layer of
41
42
43 SiOx lead to better cyclability and a higher reversible capacity of 830 mAh/g was
44
45 obtained at high current density 1C for 100 cycles. Lee et al. confirmed that SiOx coating
46
47 retards the dissolution of polysulfides and alleviates both problems of the loss of active
48
49 mass, and polarization resulting from the deposition of insolulible sulphides, and results
50
51 in enhanced performance of the active sulfur material 193. Nitrogen doping of mesoporous
52
53
carbon was used to suppress the shuttling phenomenon194, possibly via an enhanced
54
55
56
surface interaction between the basic nitrogen functionalities and polysulfide species and
57
58
59
29
1
2
3 yielded high discharge capacity of 758 mA h g-1 at a 0.2 C rate and 620 mA h g-1 at a 1 C
4
5 rate after 100 cycles195. An even higher discharge capacity of 1200 mA h g-1 after 200
6
7 cycles was achieved by Song et al194. A record rate capability of 887 mAh g-1 at 5C was
8
9
observed by Tao et al.20 upon integrating an electrocatalyst (Nb2O5) that renders
10
11
12 polysulfides insoluble and less prone to shuttling. Lanthanum Oxide (La2O3), Alumina
13
14 (Al2O3) and Mg0.6Ni0.4O have been investigated for similar adsorptive and electrocatalytic
15
16 purposes and yielded excellent rate capability196. Multichannel carbon nanofibers that are
17
18 composed of parallel mesoporous channels connected with micropores are found to act as
19
20 containment trap for sulfur and led to stable reversible capacity as high as ≈1100 mAhg-1
21
22
with higher sulfur loading of 4.6 mg cm-2.197. In Figure 12, we summarize the best
23
24
25 performances of Li-S/mesoporous carbon (capacity, cyclability and sulfur loading)
26
27 reported in the last decade (2006-2016).
28
29
30
31
32
33
34
35
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37
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2 30
3
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5
6
7
8
9
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12
13
14
15
16
17
18
19
20
21
22 Figure 12. Recent literature survey of the highest capacity of Li-S batteries coated with mesoporous carbon, and cycled at 0.2C rate. The survey
23 is narrowed from 230 non-review articles (deep orange) dealing with “lithium sulfur and and mesoporous carbon”. The search was narrowed
24 further to 44 entries using the term coating (light orange bars). Within these 27 articles we searched articles providing 100 cycles or more at 0.2
25 C. The best performances are listed on the top of each bar. Other than reference [2009]198 and [2010]191 that reported limited cyclability, there
26 were no substantial reports between 2006-2010. The data were extracted from the following references [2009]198 and [2010]191, [2011]199,
27 [2012]192, [2013]195, [2014]47,[ 2015]200, [2016]20.
28
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32
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34
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47
31
1
2
3 3.5. Sulfur Cathode with Hybrid Carbon Coating
4
5
6 We have seen previously that polymer coating of mesoporous carbon, or halo fibers
7
8 yield better performance. In this section we investigate further whether combination of
9
10 different types of carbon additives, which work successfully by their own, further
11
12
13
improve the efficiency and rate-capability of lithium-sulfur batteries.
14
15
16
17 3.5.a. Graphene/Mesoporous Carbon Hybrid Coating
18
19
Mesoporous carbon has proved to be a good modifier for sulfur cathode composite,
20
21
22 but it still needs improvement, as it cannot efficiently cope with polysulfide dissolution
23
24 and allows for their leakage through the pores. Graphene coating coupled with
25
26 mesoporous carbon is expected to give better results in polysulfides trapping 201-204
.
27
28
29 For instance, Zhou and colleagues 204 observed reversible capacity of 734 mAhg-1 at 0.5
30
203
31 rate after 100 cycles with only 53 wt.% of sulfur. Zhao et al. obtained 650 mAhg-1
32
33 after 100 cycles at 0.1C rate with 60.6% of sulfur by weight. Better resistance to fading
34
35 201
36
was reported by Bao et al. upon coupling graphene oxide with mesoporous carbon
37
38 (GO@Meso-C) using metal-organic framework hybrid materials (GO@MOF-5) as
39
40 both the template and precursor, they obtained a capacity of 820 mAh g-1 after 100
41
42
cycles at 0.2C rate. Peng et al. 202 observed high reversible capacity of 900 mAhg-1 after
43
44
45 150 cycles at 0.1C current rate with 40 wt.% of sulfur.
46
47
48
49 3.5.b. Mesoporous Carbon/CNT Hybrid Coating
50
51
52 Mesoporous carbon can also be successfully coupled with carbon nanotubes for
53
54 higher Li-S battery efficiency 164, 194, 205. Sun et al. 164 206 have reported a novel aligned
55
56
57
58
59
32
1
2
3 and laminated sulfur-coated mesoporous carbon/CNT cathode with high capacity of
4
5
6 1226 mAh g-1 that retains up to 75% of capacity after 100 cycles at 0.1C rate (Figure
7
8 13).
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44 Figure 13. Electrochemical performance of the aligned and laminated nanostructured
45 carbon hybrid cathode with a sulfur load of 1 mg cm−2. a) Cyclic voltammograms at 0.1
46 mV s−1. b) Voltage profiles at 0.1 C. c) Rate capability. d) Cyclic performance at 0.1 C
47
48
for 100 cycles. e) Cyclic performance at 2 C for 1000 cycles. Reproduced with
49 permission from reference 206.
50
51
52 These authors claim that capacity of 900 mAhg-1 can be obtained for extremely high
53
54
(20 mg cm-2) sulfur loading. The aligned and laminated hybrid cathode endows the
55
56
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59
33
1
2
3 battery with extreme flexibility (Figure 14), and allows it to maintain operation of the
4
5
6 cell after being folded 500 times (Figure 15).
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31 Figure 14. a, b) Photographs of hybrid electrodes being lifted up by a flower and
32
33
being bent into a curved structure, respectively. c, d) Scanning electron microscopy
34 (SEM) images of aligned CNT sheets before and after deposition of CMK-3@S
35 particles, respectively. e, f) Transmission electron microscopy (TEM) images of a bare
36 CMK-3 particle and a CMK-3@S particle with weight ratio of 1:3, respectively.
37 Reproduced with permission from reference 206.
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43
44 Figure 15. Merits of the lithium–sulfur battery. a) Cyclic performance of the batteries
45 with sulfur loads of 1, 5, 10 and 20 mg cm−2 at 0.1 C. b) A comparison on the specific
46 capacity and sulfur load between this battery and the reported lithium–sulfur batteries.
47 c) Cyclic performance of the battery at 0.1 C after bending for 500 times with bending
48 angles of 60° and 180°. d) Voltage profiles at 0.1 C at a bent state with bending angles
49
of 60° and 180°. e) Cyclic performance at 0.5 C and 1 C at a bent state with bending
50
51 angles of 60° and 180°. f) Real-time monitoring of the voltage of the battery when
52 undergoing bending and recovering. reproduced with permission from reference 206.
53
54
55
56
57
58
59
35
1
2
3 3.5.c. CNT/Graphene Hybrid Coating
4
5
6 Carbon nanotubes are effective in improving the conductivity and capacity of lithium
7
8 sulfur batteries. However, Li-S cells with sulfur-carbon nanotubes cathode composites
9
10 generally show high discharge capacities that rapidly decrease over a small number of
11
12 110-111
13
cycles . To enhance the stability of the cathode S/CNT composites are modified
14 59, 207-211
15 with graphene . These three-dimensional (3D) CNT/graphene-Li2S cathodes
16
17 were realized through solvothermal reaction and a subsequent sulfur liquid-infiltration-
18
19
evaporation coating method. These constructs were loaded with 81.4 wt % Li2S
20
21
22 loading. The concept of the hybrid CNT/Graphene/S cathode is nicely illustrated by
23
24 the sketch in Figure 16.
25
26
27
28
29
30
31
32
33
34
35
36
37
38 Figure. 16. Schematic of hybrid CNT/graphene-Li2S cathode, reproduced with
39 permission from reference 131
40
41
42 131
43 He et al compared the efficiency of 3D-CNT-graphene and 3D-graphene
44
45 composites. These new 3DCG−Li2S composite demonstrated exceptionally high
46
47 reversible capacity of 1052.1mAh g−1 and 958.3 mAh g−1 (3.83 mAh cm−2) even after
48
49
50 300 cycles, with only 0.02% long-term capacity decay per cycle and a high-rate
51
52 capacity of 514 mAh g−1 at 4 C, with almost 100% Columbic efficiency, while the
53
54 3DG−Li2S delivers a low initial discharge capacity of 672 mAh g−1 (2.69 mAh cm−2),
55
56
57
58
59
36
1
2
3 that decays to 287.9 mAh g−1 (1.15 mAh cm−2) after 300 cycles. These performances
4
5
6 are attributed to limited shuttling effect.
7
8
9
10 Tang et al. 208 proposed new nitrogen doped aligned CNT/G hybrid and compared its
11
12
13
performance with bare S/CNT composite. The former clearly has shown superior
14
15 performance, proving that hybrid coatings are able to enhance the capacity of the
16
17 battery.
18
19
20
21 106
22 Li and co-workers proposed a pie-like structure of the cathode electrode with S-
23
24 3D core and thin layer of ethylenediamine (EDA)-functionalized with reduced
25
26 graphene oxide coating. The graphs in Figure 17 show that after 200 cycles the cell
27
28
29 maintains capacity close to 1100 mAh g-1 at 0.2C rate with high sulfur loading (3.6 mg
30
31 cm-2).
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Figure 17. Electrochemical performances of lotus root-like multichannel carbon
54 (LRC/S) and coated with a thin layer of ethylenediamine (EDA)-functionalized reduced
55 graphene oxide (EFG)LRC/S@EFG. a) Cycle performance of LRC/S@EFG in
56
57
58
59
37
1
2
3 comparison with LRC/S at a current density of 0.2 C. (b) Voltage profiles and (c)
4
discharge capacities at various current densities from 0.1 to 2 C. (d) Areal capacities of
5
6 layer-by-layer structured LRC/S@EFG electrodes during cycling at a current density of
7 1.2mAcm-2. Reproduced with permission from 106.
8
9
10 Lu et al 134
, developed hybrid coating of graphene and carbon nanofibers with
11
12
13
significantly improved cyclability (over 1500 cycles) and rate capability of Li−S using
14
15 coaxial graphene wrapping over sulfur-coated carbon nanofibers. The cell was able to
16
17 maintain ∼273 mA h g−1 C after 1500 cycle.
18
19
20
21
22 3.6. COMPARISONS OF VARIOUS FORMS OF CARBON COATINGS.
23
24 DATA SURVEYED (2006-2016).
25
26
27
28
29 A comparison of Li-S battery performance of various carbon coated sulfur cathode
30
31 materials was recently reported by Eftekhari et al.212. In this section, we compare and
32
33 summarize the maximum specific capacities for various forms of carbon coating of LiS
34
35
36
batteries based on our comprehensive survey of the last 10 years 2006-2016.
37
38
39
40 The best performances were reported by Wu et al79 using a graphene-Li2S-Carbon
41
42
Nanocomposite with a discharge capacity of 1300 mAhg−1 at 0.2C, after 200 Cycles,
43
44
45 and a remarkable capacity retention of ∼1040 mAhg–1 at C/2 after over 700 cycles
46
47 exceeding the state of the art. The electrolyte used was 2.4 M lithium LiTFSI in
48
49
distilled dimethoxyethane (DME)/1,3-dioxolane (DIOX) (1:1, by volume) with 0.24 M
50
51
52 LiI as additive. The loading ranges from 1.3-2.8mg/cm-2.
53
54
55
56
57
58
59
38
1
2
3 HCNFs generally show smaller discharge capacities, however, they show good
4
5
6 durability compared to graphene. This is due to their elongated structure that has the
7
8 ability to minimize electrolyte/sulfur interaction and successfully retain polysulfides
9
10 preventing the shuttling effect.
11
12
13
14
15 CNT coating alone dominates neither in capacity nor in durability. Although S/CNT
16
17 cathodes display large initial capacities, various reports show consistently that this does
18
19
not last for long due to the presence of sulfur on the outer layer of nanotubes causing
20
21
22 shuttling effect that rapidly causes capacity fading. Thus, among all carbon coating
23
24 materials Graphene (or Graphene Oxides), are the best in terms of their impact on
25
26 discharge capacity and the overall cell performance. This success can be attributed to
27
28
29 the fact that graphene (or graphene oxides), beside its ability to confine polysulfides
30
31 dissolution, has high electrical conductivity that compensates the insulating nature of
32
33 sulfur. Furthermore, its hardness and compliance provide resistance to mechanical
34
35
36
stress from sulfur expansion during the discharge process and effectively maintain the
37
38 cathode integrity yielding high discharge capacity and excellent life cycle.
39
40
41
42
Coating with mesoporous carbon comes in second place after graphene and presents
43
44
45 another promising coating approach to confine polysulfides and yield durable and
46
47 efficient Li-S batteries.
48
49 There appears to be a consistent, if not directly proportionate relation between the
50
51
52 pore size of the mesoporous structures and the overall discharge capacity of the cathode
53
54 material. The large pore volumes exhibit superior electrochemical performance,
55
56
57
58
59
39
1
2
3 probably due to better mass transport in the cathode213. This proportionality is lost
4
5
6 above a certain threshold loading214. Similarly, there appears to be a consistent relation
7
8 between the size of the pores, the width of the film and the thickness of the coatings on
9
10 the cathode and the overall discharge capacity of the cathode material 158. This suggests
11
12
13
the thinner the coating the greater the utilization of Sulfur and the overall discharge
14
15 capacity of the cathode material. Sahore et al.215 investigated the role of pore
16
17 size/volume and surface area on the discharge capacity of sulfur confined within
18
19
Hierarchical Porous Carbons (HPC). The physical characteristics of the four porous
20
21
22 carbon categories (I, II, III and VI) are described in the Table 1 below.
23
24
25
26 Table 1: Characteristics of the four porous carbon categories (I, II, III and VI). Carbons
27
marked with a star (*) were synthesized using colloidal silica of two different sizes
28
29 (values separated by a comma) taken in a weight ratio of 1:1. (reproduced with
30 permission from215).
31
32 Category Carbon a) S BET V Total Avg. pore Electrical loadi Actual
33 [m2g −1] [cm3g −1] size [nm] conductiv ng sulfur
34 ity [C:S] loading
35 [S cm −1 ] [wt%]
36 4-0.3-0 511 0.6 5 9.9 1:1 1:5
37 I
38 4-0.5-0 800 1.2 6 7.9 1:2 1:5
39 12-1-0 838 1.6 12 2.9 1:3 1:5
40 20-1-0 964 2.1 18 3.4 1:4 1:5
41
4-1-0 1110 2.1 7 6.5 1:4 1:4
42
II
43 4-0.5-3 1922 2.3 5 3.6 1:4 1:5
44 4-0.5-4 2336 2.5 5 3.5 1:5 1:5
45
12-2-0 1236 2.7 13 1.5 1:5 1:5
46
III
47 4-1-1 1473 2.8 7 7.8 1:5 1:4
48 20-2-0 1279 3.3 19 1.6 1:6 1:4
49 4,20-2-0* 1245 3.7 6,32 2.5 1:7 1:5
50 4-2-0 1263 3.7 21 2.1 1:7 1:5
51
52 20,140-2-0.5* 1290 5.0 21,84 2.9 1:9 1:4
53 20-1-2 2004 3.5 18 3.1 1:6 1:5
54 IV 4-1-2 2384 3.8 7 4.0 1:7 1:4
55 4,20-2-1* 2219 3.9 25 2.6 1:7 1:4
56
57
58
59
40
1
2
3 12-2-1.5 1604 4.1 12 1.8 1:7 1:4
4 4-2-0.5 2297 4.5 18 – 1:8 1:4
5
20-2-1.5 2270 4.6 16 1.7 1:8 1:4
6
7 4,20-2-0.5* 1909 4.8 30 2.0 1:9 1:4
8
9
10
11 The S/mesoporous carbons composites from carbons with both high surface area and
12
13 pore volume resulted in the highest capacities while the composites from carbons with
14
15 moderate pore volume led to moderate capacities. To achieve greater sulfur utilization
16
17
18 and maximize sulfur loadings, pore volume is more important than surface area.
19
20 Moderate surface area but high pore volume led to high capacities. When specific
21
22 capacity was plotted against primary mesopore size, no correlation was observed.
23
24
25
However, the carbons with the lowest surface area and smallest pore volume led to the
26
27 lowest capacities as expected (Figure 18).
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 Figure 18. Scatter plots correlating specific capacity obtained at the end of 100th
55 discharge cycle with (a) surface area, (b) pore volume, and (c) pore size, of hierarchical
56 porous carbons loaded with ≈80 wt% sulfur. Data points are color coded according to
57
58
59
41
1
2
3 HPC category: category I (black), category II (blue), category III (red), and category IV
4
(green). d) Capacity retention of all composites calculated from 20th–100th cycle.
5
6 (reproduced with permission from215).
7
8
9 A similar conclusion was obtained upon comparing the effect of porosity of SB-15 (7
10
11 nm), mesoporous carbon (2 nm) and MOF (2.9 nm, with dual oxygenated porous
12
13
14 architecture). These authors found that Cr trimesate MOF (MIL-100(Cr) has a
15
16 pronounced effect on enhancing the cycle performance.216 Furthermore, a recent study
17
18 by Hippauf et al.217 established a direct correlation between the pore size and the
19
20
21
polysulfide trapping. It was also confirmed that doping improved the fixation of
22
23 polysulfides within the pores and thus improved overall cycle life of the batteries.
24
25
26
27
4. Li-S BATTERIES ELECTROLYTE SYSTEMS
28
29
30 Electrolytes have a huge impact on the cyclability, safety, efficiency and capacity of
31
32 Li-S batteries. Electrolytes are also central to the problem of shuttling. Conventional
33
34 salts and solvents used in lithium ion batteries cannot be used in lithium sulfur batteries
35
36
37 due to their reactivity with polysulfides. Furthermore, the reactivity of the lithium metal
38
39 anode with liquid electrolytes leads to their depletion necessitating a higher electrolyte
40
41 to sulfur ratio. Four categories of electrolytes are used in Li-S batteries and will be
42
43
44
briefly reviewed: (1) liquid electrolytes, (2) ionic liquid electrolytes, (3) gel-polymer
45
46 electrolytes, and (4) solid state electrolytes
47
48
49
50
4.1. Liquid Electrolytes
51
52
53 Liquid electrolytes are composed of salts and solvents. The most common lithium
54
55 salts are LiClO4, LiPF6, or LiCF3SO3 while the most common solvents are: (1)
56
57
58
59
42
1
2
3 carbonates (such as ethylene carbonate (EC), propylene carbonate (PC) and diethyl
4
5
6 carbonate (DEC)), (2) ethers (such as 1,3-dioxolane (DOL), 1,2-dimethoxyethane
7
8 (DME), and tetra-(ethylene glycol) dimethyl ether (TEGDME)), (3) ethyl methyl
9
10 sulfone (EMS).
11
12
13
Gao et al218 found the salts to have no significant effects on electrochemical
14
15 performance of lithium sulfur batteries while the solvent plays a key role. Using in-situ
16
17 XAS at the sulfur K-edge, these authors show that unlike ethers, carbonate solvents are
18
19
subject to nucleophilic attack by polysulfides during the battery discharge leading to
20
21
22 low capacities. This reactivity increases with the nucleophilicity of polysulfides (short
23
24 chain length) (Figure 19, scheme a and b).
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 Figure 19: a) Reactivity of ethylene carbonates (EC) and diethyl carbonate (DEC)
53
54
with polysulfides. b) Discharge capacities of sulfur/carbon in various solvents with
55 1.0M of LiCF3SO3. Reproduced with permission from Gao et al.218
56
57
58
59
43
1
2
3 For these reasons, tetraethylene glycol dimethyl ether (TEGDME) and 1,3-dioxolane
4
5
6 with 1,2-dimethoxyethane (DOL/DME) are the most widely used solvents for Li-S
7
8 batteries. Calculations of the stability and reactivity shows that ethers are not
9
10 completely immune of nucleophilic attack by Li2S2 and Li2S3 species in solution, with
11
12
13
Li2S2 being more reactive in solution leading to poor longer-term stability.
14
15
16
17 Zhang et al219 improved storage capacities by using microporous carbon to restrain
18
19
polysulfides within ~ 1-2 nm microporous carbon. However, the large distribution and
20
21
22 the tendency of long chain polysulfides to dissolve led to imperfect sequestration. To
23
24 address this problem short-chain polysulfides, predominately S2, polysulfides were
25
26 covalently restrained in sub-nanometer microporous carbon and displayed remarkable
27
28 −1 −1
29 stability with ≈ 600mAh g capacity over 4020 cycles (0.0014% loss cycle ) at
30
31 ≈100% Coulombic efficiency220. Similarly, an outstanding coulombic efficiency is
32
33 obtained upon bonding short chain polysulfides to polyacrylonitrile (PAN) leading to
34
35
36
stable SEI layer. The redox reactions involved a separated Li+/S2− ion couple and
37
38 precluded Li2S compound formation. The redox reactions and their subsequent soluble
39
40 sulfur anions were efficiently confined within the carbonaceous conducting matrix, and
41
42
the host polymer prevented formation of S8 after complete oxidation during recharge of
43
44
45 the cell. These two sequestration approaches220,221 do not require usage of additives to
46
47 stabilize the anode, can be carried out in simple carbonate electrolytes and led to high
48
49 coulombic efficiency. The multielectron redox process in conductive polymers delivers
50
51
52 a large lithium storage capacity cf Figure 20292.The mechanism and the impact of
53
54 cycling on the backbone of the matrix still need some clarifications.221
55
56
57
58
59
44
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 20. A schematic of the multi-electron redox process inside the SPPY
24 electrode. Reproduced with permission from292
25
26
27
28 In the absence of complete physical sequestration of polysulfides the shuttle effect
29
30 occurs and easily propagates due to the low density of liquid electrolytes. Two types of
31
32 remedies can mitigate these effects; (1) the use of highly concentrated organic
33
34
35 electrolytes, (2) liquid ionic electrolytes with additives. Alternatively, (3) gel polymer
36
37 electrolyte and solid-state electrolytes (both polymer electrolytes and solid state
38
39 ceramic electrolytes) are reported and provide the safest and most promising approach.
40
41
42
43
44 4.1.a Highly Concentrated Electrolytes
45
46 As reported by Hagen et al8 57% of all Li–S batteries use lithium bis-
47
48 trifluoromethanesulfonimide (LiTFSI, LiN(CF3SO2)2) as an electrolyte mainly because
49
50
51 of its stability. The typical concentration of the electrolyte is ≈1.0 M, however recent
52
53 reports confirm that higher concentration limits polysulfides dissolution and
54
55 propagation and provides better stability 79, 222
. Shin et al.293 found that the viscosity
56
57
58
59
45
1
2
3 and the increased ionic strength of the highly concentrated solutions to contribute to
4
5
6 suppression of the shuttle reaction by reducing the common ion effect. The
7
8 combination of these factors suppresses the shuttle reaction, and decreases significantly
9
10 the overcharge that takes place during the charge reaction (cf Figure 21).
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 Fig. 21. (a) Discharge–charge curves at the 1st cycle, and (b) the discharge (&),
43 charge (J) capacities and overcharge (+) amounts of Li–sulfur cells made of electrolyte
44 with 1.5 M (red), 3.0 M (green), 4.0 M (grey), and 5.0 M (blue) concentration of
45 LiTFSI. The initial 3 cycles were tested at a 0.1 C rate and thereafter at a 0.5 C rate. (1
46
C = 1675 mA g-1 of sulfur).293
47
48
49
50 Furthermore, in most liquid electrolytes (whether organic or inorganic) polysulfides
51
52 dissolution can be regulated by the electrolyte/sulfur (E/S) ratio. The best Li/S cell
53
54
performances occur at an optimum E/S ratio and areal surface loading. Zhang et al223
55
56
57
58
59
46
1
2
3 investigated the role of E/S ratio using LiSO3CF3-M LiNO3 (0.25/0.25 M) dissolved in
4
5
6 a mixture of dimethyl ether (DME) and 1,3-dioxolane (DOL) (1:1 (wt:wt) and showed
7
8 that a Li/S cell with a cathode containing 72% sulfur and 2 mg cm−2 sulfur loading is
9
10 able to retain a specific capacity of 780 mAh g−1 after 100 cycles at 0.5 mA cm−2
11
12
13
between 1.7 V and 2.8 V. While a cell with an excess amount of electrolyte E/S = 13.3
14
15 mL g−1 shows high initial capacity that declines rapidly upon cycling due to
16
17 polysulfides dissolution and shuttling. In the case of low amount of the electrolyte the
18
19
cell is able to retain high specific capacity but display poor reproducibility and cycle
20
21
22 life due to the high accumulation of polysulfides causing dramatic increase of the
23
24 electrolyte viscosity. Furthermore, high sulfur loading (> 2.0 mg cm−2) tends to
25
26 decrease the capacity and the cell performance, in contrast with low loading. This is
27
28
29 attributed to the thickness of the electrode and its propensity to retain insulating
30
31 polysulfides species.223 The optimal E/S ratio is affected by several factors, such as the
32
33 type of solvent, the composition and thickness of the sulfur cathode, the specific
34
35
36
surface area, as well as the configuration of Li/S cells.
37
38
39
40 As discussed in section 2, upon employing highly concentrated electrolyte 2.4 M
41
42
lithium LiTFSI in distilled dimethoxyethane (DME)/1,3-dioxolane (DIOX) (1:1, by
43
44
45 volume) with 0.24 M LiI as additive and a loading ranges from 1.3-2.8mg/cm-1 Wu et
46
47 al79 obtained a discharge capacity of 1300 mAhg−1 at 0.2C, after 200 Cycles, and a
48
49 remarkable capacity retention of ∼1040 mAhg–1 at C/2 after over 700 cycles exceeding
50
51
52 the state of the art. High salt concentration can hinder polysulfides mobilities,
53
54
55
56
57
58
59
47
1
2
3 however, too high concentration may impact the overall ionic conductivity of the
4
5
6 electrolyte. 224
7
8 Beside the electrolyte concentration, a sulfur content of at least 70% by weight and a
9
10 reasonable sulfur loading equal to a specific capacity of 2-3 mAh cm-2 are required to
11
12
13
maintain the advantage of high density energy of sulfur cathodes. Remarkable loadings
14
15 of >5.0 mg cm-2, or even higher than 10 mgcm-2, have been reported (see section 1).
16
17 However, the cells still mostly show capacity decay, and their cycle life remains below
18
19
200 cycles. This is attributed to the inability of the substrate to provide effective
20
21
22 binding to highly-loaded sulfur electrodes. As a remedy, compact coatings that confine
23
24 sulfur loading in titanium oxide microcapsules while minimizing the amount of binder
25
26 is suggested.225
27
28
29
30
31 4.1.b Ionic liquids electrolytes
32
33 Ionic liquid electrolytes are attractive due to their ability to limit polysulfides
34
35
36
dissolution295, miscibility, conductivity, non-flammability and have been intensively
37
38 investigated for use in Li-S cells226-227. They have been used as an electrolyte, an
39
40 electrolyte co-solvent228 or as an additive to organic liquid electrolytes and showed
41
42
great potential in suppressing shuttling229. Wang et al. 230
used an ionic liquid
43
44
45 electrolyte composed of trifluoromethanesulfonimidate (LiTFSI) in 1-ethyl,3-
46
47 methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI) in conjunction with
48
49 mesoporous carbon-sulfur cathode composite and reported a better capacity retention
50
51
52 (550 mAh g-1 after 40 cycles) compared to the one with LiTFSI in a conventional
53
231
54 organic electrolyte. Yan and co-workers used n-Mеthуl-n-Allylpуrrolidinium
55
56
57
58
59
48
1
2
3 bis(trifluoromеthanеsulfonуl)imidе (P1A3TFSI) ionic liquid as an electrolyte. The
4
5
6 initial reversible capacity of 926.4 mAhg-1 was recorded and it remained as high as
7
8 670mAhg-1 over 50 cycles. Ionic liquid electrolyte based on
9
10 [Li(triglyme)][bis(trifluoromethanesulfonyl)amide] was reported to suppress
11
12
13
polysulfides dissolution and improve the life cycle for over 800 cycles.232 Solvate ionic
14
15 liquid electrolyte based on tetraglyme [Li(tetraglyme)]X (where X is [N(SO2C2F5)2] or
16
17 [N(SO2CF3)2]) were also found to stop shuttling and yield a capacity of 600−700
18
19
mAh·g−1 and a Coulombic efficiency of 98.5% over 100 cycles.233
20
21
22
23
24 4.2 Gel-polymer electrolytes
25
26 Non-miscible electrolytes such as gel/polymer electrolytes or solid state electrolytes,
27
28
29 have been proposed as a remedy to the issues facing liquid and ionic liquid
30
31 electrolytes234. Rao et al.235 investigated gel-polymer electrolytes (GPE) made from
32
33 pоlу(acrylonitrile)/poly(methyl methacrylate) (PАN/PММА) membranes and lithium
34
35
36
bis(trifluoromethylsulfonyl)imide in N-methyl-N-
37
38 butylpiperidiniumbis(trifluoromethanesulfonyl)imide (РРR14ТFSI) and poly(ethylene
39
40 glycol) dimethyl ether (РЕGDМЕ). A carbon nanofibers/sulfur composite was used as a
41
42
cathode material and these authors reported that the coupled effect of a modified
43
44
45 cathode and a gel electrolyte would increase the capacity of the battery. The discharge
46
47 capacity of 760 mAh g-1 was observed over 50 cycles at 0.15C.
48
49
50
51
52 Jeddi et al.236 observed highly stable discharge capacity (1050 mAhg-1) which was
53
54 maintained for 100 cycles. Zhang et al 237 used a gel-polymer electrolyte in conjunction
55
56
57
58
59
49
1
2
3 with a PEO-SiO2 composite coated separator and reported decreased charge density and
4
5
6 reduced polysulfides shuttling. The discharge capacity was approximately 600 mAhg-1
7
238
8 after the first 100 cycles. Another report by Zhang et al. showed high reversible
9
10 capacity of 1071 mAhg-1 after 100 cycles at 0.1C rate and the Coulombic efficiency of
11
12
13
the cell was close to 100%, which indicates their polymer electrolyte may potentially
14
15 solve the problem of polysulfide dissolution.
16
17
18
19
Gel-polymer electrolytes are safer, more robust, and simpler to manufacture. They
20
21
22 are usually made by mixing a large amount of liquid electrolyte with an organic
23
24 polymer susceptible to forming a stable gel such as poly (ethylene oxide) PEO and
25
26 polypropylene oxide (PPO). They display better ionic conductivity compared to solid
27
28
29 polymer electrolytes and they enable lower utilization of sulfur due to decreased
30
36, 235
31 polysulfide solubility in polymer electrolytes .They display good cyclability,
32
33 although the discharge capacities are generally low.
34
35
36
37
38 Another impressive performance was introduced by Chen et al.239 who used
39
40 polysulfide containing ether electrolytes and conventional C-S cathode. They proposed
41
42
that extra polysulfides present in solution would compensate the loss of active sulfur
43
44
45 and increase the capacity. Their results revealed that while conventional battery’s
46
47 capacity eventually fade, a battery with polysulfides in the electrolyte displays a slight
48
49 decrease in capacity that ultimately stabilizes. Moreover, the graph (Figure 22) shows a
50
51
52 dramatic difference between their initial capacities, around 1500 mAh g-1 for a
53
54 polysulfide containing sample and 975 mAhg-1 for a conventional one.
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16 Figure 22. Cyclability of Li-S batteries with and without addition of polysulfides into
17 the electrolyte. Graph reproduced with permission from239
18
19
20
The following table (Table-2) summarizes the most promising liquid electrolytes
21
22
23 strategies to limit polysulfides dissolution, transport and obtain high capacity and
24
25 cyclability.
26
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29
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31
32
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Table 2: Summary of the most promising electrolytes strategies to limit polysulfides dissolution and transport, obtain high capacity and
1 cyclability. All abbreviations are given in the abbreviation section.
2
3 Current Capacity Comment Refs
4
Electrolyte and additive composition Composition of the cathode
density
5 (mA.g-1) (mAh.g-1)/cycles
6
7 Strategy-1: Conventional carbonate electrolytes
8 1 MLiPF6 (solvent EC/DMC/EMC (1:1:1, v/v/v) SPPY material (S: 41%) 80 %, AcB, 20 (mA.g-1) ~700/100 These examples are obtained at [292]
9 10%, 10% PAN binder) various current densities and showed
that physical encapsulation of PS
10 enabled the use of conventional
11 1M LiPF6 in EC/DEC (1:1 (v/v) C/S2 (S:21.7 wt %))/CB/sodium alginate binder 80 (mA.g-1) ≈600/> 4000 carbonate electrolytes that are less [220]
12 (70:15:15 wt %), prone to depletion and reactivity
with Li metal
13
1M LiPF6 in EC/DEC 1:1 (v/v) SPAN4/CB/PVDF binder ratio : (70:15:15 wt%) 670 (mA.g-1) ≈400-500/>1000 [221]
14
15
16 Strategy-2: High concentration of the electrolytes
17 1M 1M LiTFSI, 0.2MLiNO3(Solvent DOL/DME, 1:1) SPAN4/carbon black /PVDF (70/15/15 wt %) 670 (mA.g-1) ≈400-500/ 1000 [221]
18 These reports show that high
electrolyte concentration limited the
19 dissolution and transport of PS, but
2.4 M 2.4 M LiTFSI in DME/DIOX (1:1,v/v) with 0.24 80% Li2S-Graphene (S ~55%)/CB (7 wt %) and 400 (or C/2) ~1040/700 [79]
20 did not interdict the phenomenon
M LiI (additive) PVP (3%) (based on sulfur)
21
22
5M 5 M LiTFSI in DME/DOL (1:1,v/v) with 0.24M Commercial Sulfur powder (200 mg) and carbon 167.5(or 0.1C) ~1300/first cycle [293]
23 LiI (additive) black (100 mg), PVDF (25 mg) (based on sulfur)
24
25 7M 7 M LiN(SO2CF3)2, LiTFSI) in (DME:DOL 1:1 C/S composite /CNT/ PVDF in 8:1:1 w/w/w 0.1 mA cm -2, 700 /100 [222]
26 v/v)
27
28 Strategy-3: Optimal E/S ratio
E/S = 6.5 mL.g-1 Sulfur/CB/KB/PANMMA (77/10/10/3 wt %) 0.5mA cm−2 < 600/80 Optimal E/S depends on various
29 parameters such as the loading and
30 E/S = 10 mL.g-1 Sulfur/CB/KB/PANMMA (77/10/10/3 wt %) 0.5 mA cm−2 780/100 the type of the electrolyte. For this [223]
31 case-study (ref [223]) the authors
used
32 E/S = 13.3 mL.g-1 Sulfur/CB/KB/PANMMA (77/10/10/3 wt %) 0.5 mA cm−2 <400/100 LISO3CF3-LINO3(0.25/0.25M)
33 (DME/DOL) (1:1, WT:WT).
34 Strategy-4: Ionic liquids
35 Mixed IL 1 M LiTFSI in EMITFSI C-S 50% sulfur powder, 40% carbon black, 50 (mA.g-1) 600−700 /> 40 As of 2018, ionic liquids succeeded [230]
36 and 10%, PVDF binder only partially in suppressing
dissolution and shuttling of PS.
37
0.5 M LiTFSI in P1A3TFSI) S/C/AcB/PvDF 80/10/10 167 (mA.g-1) 670/>50 [231]
38 Next generation electrolytes will be
39
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43
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Page 53 of 150 52 Materials
ACS Applied Energy
An all IL Li(G3)1TFSA] PE-S/KB/PVA (56.7/28.3/15) 92.9µA cm-2g-1- 459/800 based on solid and semi-solid [232]
1 S (or C/18) electrolytes, see strategy 5, 6, and 7
2
3 [Li(G4)][X, X: [N(SO2C2F5)2] S8/KB/PVA (60/30/10 wt %) 139 (mA.g-1) 600−700 />100 [226,
4 233]
5 Strategy-5: Gel polymer to improve safety and limit shuttling
6 (100 mg) of (-)-(S,S)-dodecyl-3-[2-(3- RT Conductivity Sulfur/CMK3 composite/super P/PVDF, 0.1C 337/100 Gel polymer electrolytes can form a [234]
7 dodecyl ureido)cyclohexyl] urea mixed 6.43(mScm-1) 70/15/15wt% physical protection for the anode by
with (500µl) of DOL and DME (v/v, 1/1) serving as a trap to shuttling
8 with 1M LiN(CF3SO2)2 polysulfides. However, their room
9 temperature conductivity is still low.
10 PAN/PMMA mixed with RT Conductivity CNFs-S/Super-P carbon/CMC and styrene 0.15 mA cm-2 750/50 Similarly, solid polymer electrolytes [235]
can inhibit polysulfides diffusion but
11 PPR14TFSI-PEGDME (1:1) 3.8 (mScm-1) butadiene rubber (SBR)(CMC:SBR=2:3, by
all known solid polymer electrolytes
weight) (70/20/10 w%)
12 PVdF-HFP/OMMT soaked in1M LiPF6 RT Conductivity (S/PAN/Mg0.6Ni0.4O)/KB/PVDF. 0.2 C 650-700/80 necessitate high temperature to [236]
13 dissolved in a (EC/DEC) 1:1 (v/v) 4–7 mScm−1 Ratio : 60/20/20 w% improve their conductivities
14
15 PEO-SiO2 (50/50 wt.%) gelled with gel RT Conductivity Sulfur/Super P/ Ketjenblack/ANMMA 0.5 mA cm−2 800/100 [237]
forming electrolyte made of 0.25molkg−1 77/10/10/3 wt %
16 LiTFSI-0.25molkg−1 LiNO3 dissolved in −3
4.2×10 Scm −1
17 a DME/DOL 1:1(wt %), then coated on Poor conductivity

18 Celgrad
19
Gel Polymer of Polyvinylidenefluoride- NA SPAN 70 wt.-% mixed with 20 wt.-% 0.2 mAcm-2 ~600 / 50 [294]
20 hexafluoropropylene, acetylene black and 10 wt.-% PTFE,
21 1 M LiPF6/ (EC/DMC) (1:1, v/v)
22 Polymer in salt ; PEO in 1 M LiTFSI in 1.67 ×10−3 S cm−1 S/C (7:3) composite, Super P, poly(vinylidene 100 mA.g-1 720/300 [240]
DOL:DME (1:1 v/v) difluoride) in weight ratio of 8:1:1.
23
24 Strategy-6: Solid State Electrolytes to discard PS and improve safety
25 Glass–ceramic 1.1×10−3 S cm−1 and 1.6 ×10−3 S Sulfur, Acetylene Black and Li2S–P2S5 glass– 333 mA.g-1 850/200 Inorganic solid electrolytes exhibit high Li+ [244]
26 electrolyte-Li2S–P2S5 cm−1, ceramic ion conductivity of over 10−3 S cm−1 at
27 25◦C. However, the contact resistances still
need improvement. In addition, the cells
28 Solid electrolyte 0.31 mS cm-1 0.82(Li1.5 PS3.3).0.18(LiI) 1.3 mA cm-2 1500/100
usually suffer from internal strains.
[68]
Li10GeP2S12
29 Inorganic solid electrolytes exhibit high Li+
30 ion conductivity of over 10−3 S cm−1 at
25◦C.
31 Strategy-7: Hybrid electrolytes to bypass the limitations of solid and liquid electrolytes
32 Dual electrolytes, separated by Li super ionic conductor RT conductivity Li2S 0.1C 800/50 The structure of the cell is as follows: [14]
33 membrane of Li1+x+y AlxTi2-y SiyP3-yO12 10-4Scm-1
34 “Li anode|electrolyte-1|LATP|electrolyte-2 |Li2S-cathode”
35 Electrolyte 1, Anode side: 1 M LiPF6 in EC/DMC/DEC
(1 :1 : 1 v/v/v), Al, and Graphite can be used as an anode . Since PS are confined in the cathode side,
36 carbonate can be used. Mass loading can be achieved by increasing the concentration
37 Electrolyte 2, cathode side:Li2S was dispersed in a 1 M of Li2S in the cathodic electrolyte. The rate capability is still low for this system, and
38 LiClO4 dissolved in tetrahydrofuran (THF) the manufacturability is more complex than traditional cells
39
40
41
42
43
44
46
47
53
1
2
3 4.3. Solid state electrolytes
4
5
6 Solid electrolytes provide another way of avoiding polysulfides formation and show promising
7
240
8 results for capacity retention . There are two major categories of solid state electrolytes:
9
10 inorganic solid electrolytes, and (2) organic solid polymer electrolytes. As of today, the organic
11
12 296, 297, 298, 299
13
solid polymer electrolytes have low room temperature conductivities, much lower
14
15 than liquid electrolytes. The inorganic electrolytes can be divided into two classes: (1) sulfide
16
17 solid state electrolytes and (2) oxide solid state electrolytes. We will limit our discussion to
18
19
sulfide solid state electrolytes owing to their high ionic conductivities, cold pressing
20
21
22 processability, good interfacial contact, and high ionic conductivities.
23
24
25
26 Sulfide solid state electrolytes can be divided into two main categories based on their crystal
27
28
29 structure: (1) glass and glass-ceramic Li2S-P2S5, (2) the crystalline thio-based-LISICON, and
30
31 anion-doped Li2S-P2S5. Table 3 provides the ionic conductivity of the most common solid state
32
33 electrolytes.
34
35
36
37
38 The thio-LISICON which can be represented by the formula Li4−x A1−y ByS4 (A=Si, Ge, B =
39
40 Zn, Al, Pt) are reported to have high ionic conductivities at their operating temperature. For
41
42
example the lithium superionic conductor Li10GeP2S12, has conductivities high than polymer
43
44
45 electrolytes and comparable to liquid electrolytes241. This superionic conductivity originates
46
47 from the electronic and ionic pathways in the crystal structure. The topology of the anionic
48
49 arrangement is the key factor in determining intrinsic Li-ion mobility (Figure 23)242-243.
50
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22
23
24
25
26
27
28
29
30
31
32 Figure 23. a, The framework structure and lithium ions that participate in ionic conduction. b,
33 Framework structure of Li10GeP2S12. One-dimensional (1D) chains formed by LiS6 octahedra
34 and (Ge0:5P0:5)S4 tetrahedra, which are connected by a common edge. These chains are connected
35
by a common corner with PS4 tetrahedra. c, Conduction pathways of lithium ions. Zigzag
36
37 conduction pathways along the c axis are indicated. Lithium ions in the LiS4 tetrahedra (16h site)
38 and LiS4 tetrahedra (8f site) participate in ionic conduction. Thermal ellipsoids are drawn with a
39 30% probability. The anisotropic character of the thermal vibration of lithium ions in three
40 tetrahedral sites gives rise to 1D conduction pathways.243
41
42
43
Most solid-state electrolytes suffer from high interfacial impedances and are hardly used at
44
45
46 room temperature. To reduce interfacial impedance conductive additives are often required.
47
48 Nagao et al. 244 prepared sulfur cathode composites by grinding the constituting materials using a
49
50 planetary ball milling apparatus. The electrode consisted of sulfur, acetylene black and Li2S–P2S5
51
52
53 glass–ceramic. Milling provided close contact between the cathode constituents and improved
54
55 the performance of the battery. An outstanding reversible capacity of 850 mAh g-1 was achieved
56
57 and it was maintained over 200 cycles.
58
59
55
1
2
3 Table 3. Ion conductivities of different sulfide solid electrolytes. Reproduced with permission
4
from Zhang et al.241
5
6 Composition Classification Conductivity at 25 °C (S cm−1)
7
8 70Li2S· 30P2S5 Glass 5.4×10−5
9
10 75Li2S·25P2S5 Glass 2.0×10−4
11
12 80Li2S·20P2S5 Glass 2.0×10−4
13
14 80(0.7Li2S·0.3P2S5)·20LiI Glass 5.6×10−4
15
16 95(0.8Li2S·0.2P2S5)·5LiI Glass 2.7×10−3
17
18 56Li2S·24P2S5·20Li2O Glass >1.0×10−4
19
20 75Li2S·21P2S5·4P2O5 Glass >1.0×10−4
21
22 67.5Li2S·7.5Li2O·25P2S5 Glass 1.1×10−4
23
24 33(0.7B2S3·0.3P2S5)·67Li2S Glass 1.4×10−4
25
26 67(0.75Li2S·0.25P2S5)·33LiBH4 Glass 1.6×10−3
27
28 70Li2S·30P2S5 Glass-Ceramic 3.2×10−3
29
30 80Li2S·20P2S5 Glass-Ceramic 9×10−4
31
33
34 Li7P3S11-z Glass-Ceramic 5.4×10−3
35
36 Li7P3S11 Glass-Ceramic 1.7×10−2
37
38 Li3.25P0.95 S4 Glass-Ceramic 1.3×10−3
39
40 γ-Li3PS4 Crystalline 3.0×10−7
41
42 β-Li3PS4 Crystalline 1.6×10−4
43
44 Li3.25Ge0.25P0.75S4 Crystalline 2.2×10−3
45
46 Li10GeP2S12 Crystalline 1.2×10−2
47
48 Li10SnP2S12 Crystalline 4.0×10−3
49
50 Li11Si2PS12 Crystalline >1.2×10−2
51
52 Li7P2S8I Crystalline 6.3×10−4
53
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56
57
58
59
56
1
2
3 Volume change is another challenge facing, all-solid-state batteries with inorganic solid-state
4
5 245
6 electrolytes . Repeated cycling tends to destroy both the electron pathway and the ion
7
8 diffusion channels that are responsible for Li superionic conductivity. Furthermore, the absence
9
10 of a high order soluble redox intermediate decreases the overall ionic and electronic conductivity
11
12
13
of the cathode
14
15
16
17 4.4. Hybrid-electrolytes
18
19
So far all-solid-state Li-S batteries displayed unsatisfactory performance, especially in terms of
20
21
22 rate capability, sulfur-cathode utilization and cyclability 246.The scientific community is facing a
23
24 hard choice of either a solid electrolyte with poor conductivity but good mechanical properties or
25
26 good conductivity and poor mechanical properties. For example; plastic crystal electrolytes
27
28
29 (PCEs), such as succinonitrile (SN)/lithium salt-based PCEs exhibit a high ionic conductivity of
30
31 more than 10−3 Scm−1 at room temperature, excellent thermal stability and nonflammability, but
32
33 display poor mechanical properties that limit their application in an all-solid-state battery.
34
35
36
In order to escape this conundrum a concept of dual electrolyte (or hybrid-electrolyte) was
37 14
38 investigated . This promising concept revolves around the use a dual-phase-nonaqueous
39
40 electrolyte, in which two types of electrolyte are used and separated by a protective lithium super
41
42
ionic conductor glass film (LISICON) of Li1+x+yAlxTi2−xSiyP3−yO12 (LTAP) that is permeable to
43
44
45 Li-ions while impermeable to polysulfide-anions. This hybrid electrolyte succeeded in
46
47 eliminating parasitic reactions associated with the polysulfide shuttle effect (cf Scheme of the
48
49 cell in Figure 24):
50
51
52
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54
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57
58
59
57
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Figure 24: Schematic of the architecture for the Li–S battery composed of (−) Cu foil/Li
17
18
metal/organic electrolyte-1/ceramic separator (LATP)/organic electrolyte-2/Li2S cathode/Super P
19 carbon/Ti foil (+) from top to bottom. (reproduced with permission from reference 14).
20
21
22 The unique features of this hybrid electrolyte are that it confines the polysulfides to one side of
23
24
the electrode, shields lithium metal from the electrolyte, and prevents electrolyte depletion. This
25
26
27 cell architecture (based on a hybrid electrolyte) is scalable and flexible as it allows the use of a
28
29 variety of electrolytes and anode materials other than metallic lithium. Furthermore, other types
30
31 of conductive membrane have been recently investigated such as NaSICON-type Li+-ion
32
33
34 conductive membranes that delivered an initial discharge capacity of ≈1000 mAhg−1 (based on
35
36 the active sulfur material) and retains ≈ 90% of the initial capacity after 150 cycles with a low
37
38 capacity fade-rate247.
39
40
41
To summarize this section; an ideal liquid electrolyte for Li–S batteries should be selected
42
43 based on its ability to prevent shuttling and form a solid electrolyte interphase (SEI) on the Li
44
45 surface to protect the anode from reacting with polysulfides. Lithium metal is currently the major
46
47
bottle-neck of Li-S batteries due to its reactivity with most liquid and semi-liquid electrolytes as
48
49
50 we will discuss in section 5. However, the progress of lithium ionic superconductor materials
51
52 holds great promise for an all-solid-state battery with high safety and discharge capacity. Still the
53
54 interfacial impedances between lithium metal and solid state electrolytes need to be solved by
55
56
57 integrating an efficient interface layer.
58
59
58
1
2
3
4
5
6 Solid polymer electrolytes are easier to process, have low interfacial resistance due to
7
8 improved contact, and are conformal, unlike inorganic solid-state electrolytes. However, their
9
10 narrow electrochemical stability windows and low ionic conductivity still prevent their adoption
11
12
13
in an all polymer-based all-solid-state battery.
14
15
16
17 5. ELECTROCATALYTIC POLYSULFIDES CONVERSION
18
19
One of the newest and most promising directions for dealing with polysulfides shuttling is
20
21 248
22 their conversion into harmless species . This approach uses both noble metals and earth
23
24 abundant electrolcatalysts and has the potential to be cheaper and more scalable than other
25
26 approaches. The advantages of this strategy include: (i) unlike physical containment of
27
28
29 polysulfides, the rate capability of lithium ions is not hindered; (ii) a large number of catalysts
30
31 from earth abundant metals are available (for example transition metal dichalcogenide such as
32
33 MS2, where M : Mo, W, Co, Re, and some metal oxides such as Al2O3 and Nb2O5 among others),
34
35
36
therefore the low cost advantage of sulfur batteries is retained; (iii) the technique is easily
37
38 scalable. In this section, we will highlight the most promising electrocatalytic approaches.
39
40
41
42
5.1. Noble Metal Electrocatalysts
43
44
45 Platinum is one of the most promising electrocatalysts as it has been proven to convert
46
47 polysulfides into harmless species leading to an increase of 40% of the discharge capacity
48
49 compared to the discharge capacity obtained without platinum. Furthermore, it leads to high
50
51 248
52 cyclability and high coulombic efficiency (99.3%) . A recent study shows that an electrode
53
54 with 2 wt% Pt added delivers a 61 % enhancement in the discharge specific capacity compared
55
56 to the control electrode after 200 cycles at 0.5 C, with a coulombic efficiency of 98.3 % 249
.
57
58
59
59
1
2
3 Among the remaining noble-metals gold has been coated on current collectors and used as an
4
5 250
6 electrocatalyst but showed less promising results as the capacity fades rapidly . More efforts
7
8 are needed to probe the effect of gold nanoparticles since it is well known that gold catalytic
9
10 activities are strongly size dependent 251.
11
12
13
Ruthenium was used as an electrocatalyst albeit in its oxide form RuO2 that is highly
14
15 conductive (104 Scm-1), chemically very stable and a very active for oxidation catalysis processes
16
17 such as chlorine production. Balach et al.252 embedded RuO2 nanoparticles into a mesoporous
18
19
carbon-coated separator and tested its electrocatalytic performance vis-à-vis polysulphides
20
21
22 retention, to improve sulfur utilization and boost the electrochemical performance of lithium–
23
24 sulphur batteries. Silver and palladium were not reported due to their poor electrochemical
25
26 stability and chemical instabilities vis-à-vis most electrolytes.
27
28
29
30
31 5.2. Non-Noble Metal Electrocatalysts
32
33 Transition metals offer several potential polysulfides electrocatalysts that are much cheaper than
34
35
36
noble metal catalysts. Arguably, nickel is one of the most promising transition metal
37
38 electrocatalysts due to its low cost and relative stability in LiS battery electrochemical cell
39
40 environments. It has been used in the form of a nanoparticles suspension248, or in the form of a
41
42 250
film electroplated on current collectors . Furthermore, a pie-like electrode that consists of an
43
44
45 electrocatalytic nickel-foam as a filling to adsorb and store polysulfide catholytes and an outer C
46
47 shell as a crust for facilitating high-loading S cathodes with superior electrochemical properties
48
49 and structural stabilities was reported by Manthiram et al.253. Other non-noble transition metals
50
51
52 have been mostly used in their oxide or sulphide form. A brief survey of these two types of
53
54 electrocatalysts is presented below.
55
56
57
58
59
60
1
2
3 5.2.a Metal Oxide Electrocatalysts
4
5
6 Owing to their natural abundance and low-cost, metal oxides and metal chalchogenides are
7
8 promising electrocatalysts for polysulfides fixation and conversion. Nazar and co-workers have
9
10 extensively used manganese and titanium transition metal oxides to trap and convert polysulfides
11
12 254-256
13
. The mechanism of binding of polysulfide on 3d transition metal oxides and their
14
15 dependence on the metal element identity across the periodic table was recently investigated.
16
17 The Li-O interactions dominate polysufides binding to the oxides (Mn3O4, Fe2O3, and Co3O4),
18
19
with increasing strength from Mn, to Fe to Co. In terms of binding selectivity Co3O4 appears to
20
21
22 have the strongest affinity to polysulfides entrapment 257.
23
258
24 A recent promising work found that α-Fe2O3 nanoparticles not only interact strongly with
25
26 sulfur and polysulfide species, but also promote their transformation into insoluble products in
27
28
29 both charge and discharge processes, effectively suppressing the shuttling of poly-sulfides and
30
31 improving sulfur utilization. These findings were corroborated by theoretical calculation where
32
33 the catalytic surface of iron shows strong bonding owing to the affinity of Lithium to Oxygen
34
35
36
and Iron to Sulfur ions, which is quite different from the dipole-dipole interaction between the
37
38 Li2S4 and graphene.258 The α-Fe2O3 nano-particles increased the rate performance and the
39
40 discharge capacity yielding 565 mAh g-1 at a high rate of 5 C relative to 1571 mAh g-1 at 0.3 C)
41
42
as well as long cyclic stability (an ultralow capacity fading rate of 0.049% per cycle over 1000
43
44
45 cycles at the high current rate of 5 C) 258.
46
47
48
49 A more recent approach uses a cooperative interface composed of “lithiophilic” nitrogen-
50
51
52 doped graphene (NG) and “sulfiphilic” multimetallic layered hydroxides is proposed as a novel
53
54 concept to mimic the fine-tuned molecular machinery for bacterial sulfur metabolism. This
55
56 cooperative coating led to outstanding battery performance both in terms of high discharge
57
58
59
61
1
2
3 capacity and extended life cycle 151
. Among other transition metal oxides that are worth
4
5
6 mentioning niobium oxides showed remarkable electrocatalytic performance with high initial
7
8 capacity of 1289 mAh g-1 at 0.5C with a reversible capacity of 913 mA h g-1 after 200 cycles.
9
10
11
12
13
5.2.b Metal Chalcogenide Electrocatalysts
14
15 Metal chalcogenides represent a new direction in dealing with polysulfides electrocatalysts.
16
17 This is due to their great affinity to adsorb polysulfides and thus reduce the overall electrode
18
19
polarization, and enhance the specific capacity and cycle life 259-260. For example, WS2 electrodes
20
21
22 exhibited stable electrochemical performance with a specific capacity of 590 mAhg–1 with
23
24 excellent Coulombic efficiency (99%) over 350 discharge−charge cycles. Furthermore, WS2
25
26 showed similar catalytic surfaces to platinum, however, its catalytic mechanism is purely based
27
28
29 on charge transfer rather than direct bond formation 260.
30
31 The advantages of metal sulfides electrocatalytic properties stems from their flat 2D molecular
32
33 structure that adsorb instead of encapsulate leading to improved rate capability of lithium ion
34
35
36
insertion and deinsertion260. Several other low-cost promising transition metal dichalcogenides
37 261
38 have been investigated such as MoS2 , ReS2 262, CoS2 97, and ZnS2 263
and showed interesting
39
40 results. For example, ReS2 on carbon nanofibers led to high specific capacity of 750 mA h g−1,
41
42
that was retained for 300 cycles with only ∼0.063% capacity fade per cycle decay (Figure 25),
43
44
45 much better than the baseline battery (without ReS2). This improvement is related to the strong
46
47 interaction of sulfur in the ReS2 with electron deficient lithium cation of LixSy species 262.
48
49
50
51
52
53
54
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62
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3
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5
6
7
8
9
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16
17
18
19
20
21
22
23 Figure 25: Electrochemical performance comparison of Li−S batteries with PS−ReS2@CNF
24 and PS−CNF electrodes. (a) Specific capacity at different current densities (1 C = 1675 mA g−1).
25 (b) Galvanostatic charge−discharge profiles of the second cycle at ∼0.2 C within a potential
26 window of 1.5−2.8 V vs Li+ and Li0. c) Cycling stability and coulombic efficiency of the
27
28
PS−ReS2@CNF and baseline PS−CNF. Reproduced with permission from 262.
29
30
31 6. CHALLENGES FACING THE Li-S ANODE SIDE
32
33 In the previous sections we discussed improvement of the efficiency and capacity of Li-S
34
35
36
batteries with the use of advanced carbon coating materials in conjunction with appropriate
37
38 electrolyte systems. We also highlighted the role of electrocatalysts and the advantages and
39
40 limitations of certain type of electrolytes in terms of their reactivity with polysulfides. These
41
42
strategies led to excellent performance, in terms of polysulfides control as well as capacity, rate
43
44
45 capability and life span. However, most of these reports must be placed in the context that the
46
47 lithium and the electrolyte are present in large excess, 1500% and 200%, respectively, compared
48
49 to normal lithium ion cells13. This excess is required since lithium metal displays an intense
50
51
52 reactivity towards most, if not all, known liquid electrolytes leading to quick electrolyte
53
54 depletion and formation of a thick, irregular and unstable SEI layer. Under these circumstances
55
56 dendrites form and short-circuit the cell, and in some circumstances lead to fire and explosion 13.
57
58
59
63
1
2
3 In addition, the vast majority of these reports deal with coin cells which are not appropriate for
4
5
6 high energy and high-power density applications such as for electric vehicles, drones, and smart
7
8 phones. For these applications cylindrical, prismatic or pouch cell geometries are typically
9
10 required Figure 26.
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 Figure 26: The most common commercial cell structures. a. Cyclindrical, b. Prismatic, and c.
28 Pouch cell. Reproduced with permission from 264
29
30
31
32
However, these planar geometries tend to have large areal current that cannot distribute
33
34 uniformly favouring dendrite formation and lithium powdering 13, 265.
35
36 Dendrite formation is generally induced by the four following parameters: (1) low surface
37
38
energy of lithium, (2) high diffusion energy, (3) appropriate nucleation site mediated either by
39
40
41 the roughness of the surface of the electrode or the nature of the current collector, (3) very large
42
43 space charge and electric field near the electrode/electrolyte interfaces. Each of these parameters
44
45 is proposed based on both empirical and theoretical observation13, 266-267. Our aim in this section
46
47
48 is to summarize and briefly review the best strategies to protect lithium anodes from both
49
50 polysulfides attack and reactivity with the electrolytes.
51
52
53
54
55
6.1. Protection of lithium anode by in situ passivation
56
57
58
59
64
1
2
3 Beside the electrocatalytic role of inorganic additive on ploysulfides destruction (reviewed in
4
5
6 section 4), some liquid electrolytes and additives generate sacrificial in-situ layer that protects
7
8 and passivates lithium anode. However, this passivating coating layer must be thin and made of
9
10 materials that are insoluble in liquid electrolytes, chemically inert vis-à-vis of lithium metal and
11
12
13
the incoming polysulfides. This layer should also be highly Li ion conductive.
14
15 Lithium nitrate, lithium fluoride and ammonium salts and phosphorous pentasulfides (P2S5)268-
16
17 269,270
are the most common chemical additives that are used for in situ passivation of lithium
18
19
anode. Liang et al.271 successfully improved the specific capacity and capacity retention of Li/S
20
21
22 cells by addition of small amount of P2S5. In addition, LiNO3 additive was found to effectively
23
24 suppress the shuttling and contribute to the formation of an SEI layer protecting lithium anode162,
25
26 272,209
and enhancing the solubility and stability of polysulfides in liquid electrolytes. Canas et al.
27
28 273
29 reported that addition of LiNO3 additive to the electrolyte helped to maintain discharge
30
31 capacity up to 800 mAh g-1 after 50 cycles at 0.18C rate. In some cases, combining multiple
32
33 additive yields an optimum result in terms of dendrite suppression and SEI layer thickness. The
34
35
36
synergetic effect of lithium polysulfide (Li2S8) and lithium nitrate (LiNO3) suppressed dendrites
37
38 formation and led to the formation of stable and uniform SEI layer. Among other materials that
39
40 can protect the anode fluorinated solvents and polymers electrolytes and have a limited reactivity
41
42
with lithium and generate an in-situ passivating layer of LiF protecting lithium and enhancing the
43
44
45 cycling efficiency 108, 162, 272 however fluorinated solvent and polymers are vulnerable to attacks
46
47 by polysulfides.
48
49
50
51
52 6.2. Protection of lithium anode by ex situ coating
53
54 Ex situ coating seems to be the most reliable strategy in terms of shielding lithium metal from
55
56 redox shuttle. Various coating methods are employed and nearly all of them suppress Li dendrite
57
58
59
65
1
2
3 growth under certain conditions. Among the most common coating materials are
4
5
6 Al2O3,274carbon275, some polymers276-277and some alloys278. The Li−S battery with a thin Li−Al
7
8 alloy coating layer on the Li anode exhibits a better cycling performance than the one with pure
9
10 Li anode279. These coatings prevent direct contact between lithium metal and lithium
11
12
13
polysulfides, reinforce the SEI layer and retard dendritic growth. The alloy layer must be tightly
14
15 cured to the lithium metal to obtain best rate capability with lowest charge transfer resistance,
16
17 showing improvement over bare Li anode.280
18
19
Liu et al.281 protected lithium anodes by placing a lithiated graphite at the interface between
20
21
22 lithium metal and the electrolyte, this hybrid anode (graphite/lithium) suppresses the risk of
23
24 dendrites as the lithium anode serves as a reservoir of lithium that feeds into the graphite anode,
25
26 while the graphite shields the lithium from reacting with polysulfides. Cui et al. coated a lithium
27
28
29 anode with a thin interfacial layer of interconnected hollow carbon nanospheres and obtained
30
31 stable Li metal anode cycling and a coulombic efficiency of ∼99% for more than 150 cycles.
32
33 The honeycomb morphology (Figure 27) of the coating layer isolates lithium deposit and
34
35
36
suppresses dendrites formation up to a practical current density of 1 mAcm–2.275
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 Figure 27. a, A thin film of SEI layer forms quickly on the surface of deposited Li (blue).
53
Volumetric changes during the Li deposition process can easily break the SEI layer, especially at
54
55
high current rates. This behavior leads to ramified growth of Li dendrites and rapid consumption
56 of the electrolyte. b, Modifying the Cu substrate with a hollow carbon nanosphere layer creates a
57 scaffold for stabilizing the SEI layer. The volumetric change of the Li deposition process is
58
59
66
1
2
3 accommodated by the flexible hollow-carbon-nanosphere coating. Reproduced with permission
4
from ref.275
5
6
7
8
9
10 6.3. Alternatives to lithium metal anode
11
12
13
Replacing the Li anode is certainly the most reliable approach in terms of safety282. The use
14
15 Li2S as the starting cathode material, and lithium-free anode material has received great
16
17 attention. In these cells, Li2S is oxidized through a series of polysulfide intermediates to sulfur or
18
19
soluble high-order polysulfides, whereas Li+ ions are reduced to form Li/M alloy on the anode.
20
21
22 These cells have an improved safety profile since only equal equivalents of Li alloys as the sulfur
23
24 and PS in the cathode can be formed.
25
26 Several other anode systems based on alkali and alkaline earth metals have been investigated
27
28
29 such as Na-S283, K-S284, Mg-S285, and Ca-S286. Recently, aluminum was found to be attractive as
30
31 a metallic anode for electrochemical systems owing to its light atomic weigh, trivalent oxidation
32
33 state and high theoretical gravimetric capacity of 2900 mAhg−1. Furthermore, considering its
34
35
36
relatively high density, aluminum offers a high theoretical volumetric capacity of 8040 mAhcm−3
37
38 , much higher than lithium. A recent report showed that coupling an aluminum anode with a
39
40 sulfur cathode using an ionic electrolyte may lead to a promising sulfur battery that bypasses the
41
42
use of a lithium anode. Further, investigation of this system and concept is worth pursuing287.
43
44
45
46
47
48 7. CONCLUSION
49
50
51
52 Lithium sulfur batteries are the energy storage media of choice for beyond current lithium ion
53
54 battery technologies. However, to make a practical LiS battery numerous problems need to be
55
56
57
58
59
67
1
2
3 solved. These problems can be categorized into three main categories: (1) Insulation problems,
4
5
6 (2) Volumetric loading problems, (3) Reactivity problems.
7
8
9
10 Insulation Problems; sulfur and lithium sulphides (Li2S and Li2S2) are insoluble and have poor
11
12
13
ionic and electronic conductivities leading to capacity fading with progressive dissolution and
14
15 precipitation of these species on both sides of the cell (due to the shuttle effect) as well as in the
16
17 electrolyte, rendering it highly viscous. Great progress has been achieved in addressing these
18
19
insulation issues using graphene or graphene oxide coated sulphur (GO-S) combined with
20
21
22 polymer coatings. These conductive cathode coating materials resulted in high discharge
23
24 capacities and long life-time.
25
26
27
Preventing shuttling by electrolyte design may have received the least attention until recently,
28
29
30 when high concentration of the electrolyte was found to limit the dissolution and transport of
31
32 polysulfides.
33
34
35
36
Volumetric Loading Problems: to obtain high volumetric cell energy densities, sulfur volumetric
37
38 loading and sulfur utilization should be higher than ≥4 mg cm-2 and high sulfur content (≥70 wt
39
40 %). However, poor volumetric packing of sulfur makes this objective challenging. Recently, a
41
42
record loading (61.4 mg/cm2) and sulfur content (80 wt %) was achieved using a carbon-cotton
43
44
45 matrix. The cathode exhibited enhanced cycle stability with good dynamic capacity retention and
46
47 high static capacity retention of above 93% 18 . These carbon-cotton-sulfur cathodes along with
48
49 sulfur-coated mesoporous carbon/CNT 206 288
are certainly a promising new finding to increase
50
51
52 the loading and achieve practical LiS cathodes. Mao et al.288 developed very recently a foldable
53
54 interpenetrated metal-organic framework/carbon nanotube thin film for lithium–sulfur batteries
55
56
57
58
59
68
1
2
3 with sulfur loading as high as 4.57 mg cm-2. These cells exhibited low capacity decay rate
4
5
6 (0.019% per cycle over 1,500 cycles) with almost no capacity fading after the initial 100 cycles.
7
8
9
10 The Reactivity Problems: Sulfur tends to dissolve in most electrolytes leaving voids in the
11
12
13
cathode thus compromising the integrity of the battery. In addition, most liquid electrolytes are
14
15 unstable in the presence of polysulfides and are subject to nucleophilic attack and tend to react
16
17 with the anode. The overall result is depletion of the electrolyte, formation of an irregular SEI
18
19
layer and subsequent development of dendrites. Electrocatalytic conversion of polysulfides is a
20
21
22 promising and novel approach that inhibits polysulfides’ reactivity with various cell components
23
24 and renders them harmless. Furthermore, metal organic framework (MOF) and Covalent Organic
25
26 Framework (COF)-net are found to eliminate shuttling 289
. MOF-based separators can act as an
27
28
29 ionic sieve selectively sieving Li+ ions while efficiently suppressing undesired polysulfides
30
290
31 migration . The complete encapsulation/sequestration of short-chain polysulfides in
32
33 microporous carbon and polyacrylonitrile (PAN) provides a remarkable procedure that
34
35
36
suppressed shuttling and enabled the use of a variety of electrolytes including polycarbonate
37
38 electrolytes.
39
40
41 Our survey shows that the insulation, shuttling and reactivity of the cathode side can be brought
42
43
44 under control by a variety of techniques. The scientific community might consider refocusing its
45
46 efforts on the anode side to subdue lithium anode reactivity with liquid and semi-liquid
47
48 electrolytes. This reactivity causes both depletion of the electrolyte and dendrite formation. As of
49
50
today, safety and low coulombic efficiency of the lithium anode side of the LiS cells remain
51
52
53 unsolved. Numerous recent strategies have been developed to prevent dendrites formation and to
54
55 make lithium anodes reliable and safe for lithium sulfur batteries. The manufacturability and cost
56
57 effectiveness of these approaches is still far from the market. A glimpse of hope lies in the all-
58
59
69
1
2
3 solid-state battery where the safety of lithium and reactivity of polysulfides are less of a concern.
4
5
6 This is especially promising since the recent discovery of ion superconductor solid electrolytes
7
8 and solid polymer electrolytes. However, both electrolytes need further development; that is to
9
10 say ion superconductor solid electrolytes suffer from interfacial stresses and poor understanding
11
12
13
of interfacial transport mechanisms, while solid state polymer electrolytes still have low room-
14
15 temperature conductivity. An all-solid-state LiS batteries offer a great potential both in terms of
16
17 safety and gravimetric energy densities, however, interfacial impedances on both side of the cell
18
19
are still challenging.
20
21
22
23 The recent development of a dual-electrolyte (or hybrid-electrolyte) opens new possibilities for
24
25 an all-solid-state Li-S battery where the electrolyte insulates and separates the lithium-metal
26
27 14
anode and the sulfur cathode . This remarkable concept of hybrid electrolyte deserves further
28
29
30 attention as it solves both the problem of solid electrolyte (whether ceramic or polymer) and
31
32 inhibits lithium dendrite formation.
33
34
35
36
Until an all-solid-state battery with room temperature highly conductive dry polymer, conformal
37
38 solid state ceramic or a hybrid (with dual electrolyte) becomes feasible, lithium-free anodes
39
40 continue to be regarded as a viable option. Lithium sulfide (Li2S) presents opportunities291 to be
41
42
coupled with other than Li metal anode materials such as silicon, tin, aluminium and so on.
43
44
45 These anodes need to be nano-engineered to avoid volume expansion during charge and
46
47 discharge which causes mechanical stress with subsequent electrode pulverization and failure. In
48
49 the near future, nano-engineered lithium-free anodes coupled with layered oxides, in particular
50
51
52 Lithium Manganese Nickel Cobalt Oxides, will dominate the market. However, LiS batteries
53
54 represent a very active and exciting field of investigation that may provide performance beyond
55
56 that of current Li-ion battery technology.
57
58
59
70
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3
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10
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13
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19 286. See, K. A.; Gerbec, J. A.; Jun, Y.-S.; Wudl, F.; Stucky, G. D.; Seshadri, R., A high
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287. Yu, X.; Manthiram, A., Electrochemical Energy Storage with a Reversible Nonaqueous
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29 Room-Temperature Aluminum-Sulfur Chemistry. Advanced Energy Materials 2017, 7 (18), n/a.
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32 288. Mao, Y.; Guo, Y.; Peng, X.; Li, G.; Li, Z.; Liang, C.; Lin, Z., Foldable interpenetrated
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34 metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries. Nat Commun
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40 289. Yoo, J.; Cho, S.-J.; Jung, G. Y.; Kim, S. H.; Choi, K.-H.; Kim, J.-H.; Lee, S.-Y.; Lee, C.
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42 K.; Kwak, S. K., COF-Net on CNT-Net as a Molecularly Designed, Hierarchical Porous
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44 Chemical Trap for Polysulfides in Lithium-Sulfur Batteries. Nano Lett 2016, 16 (5), 3292-300.
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290. Bai, S.; Liu, X.; Zhu, K.; Wu, S.; Zhou, H., Metal-organic framework-based separator for
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53 291. Lee, S.-K.; Lee, Y. J.; Sun, Y.-K., Nanostructured lithium sulfide materials for lithium-
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3 292. Wang, Li; He, Xiangming; Sun, Wenting; Li, Jianjun; Gao, Jian; Tian, Guangyu; Wang,
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6 Jianlong; Fan, Shoushan. Organic polymer material with a multi-electron process redox reaction:
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8 towards ultra-high reversible lithium storage capacity. RSC Adv. 2013, 3(10), 3227-3231
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11 293. Shin, Eon Sung; Kim, Keon; Oh, Si Hyoung; Cho, Won Il. Polysulfide dissolution
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13 control: the common ion effect. Chem. Commun., 2013, 49(20), 2004--2006
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294. Wang, Jiulin; Yang, Jun; Xie, Jingying; Xu, Naixin. A novel conductive polymer-sulfur
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24 295. Yuan, L. X.; Feng, J. K.; Ai, X. P.; Cao, Y. L.; Chen, S. L.; Yang, H. X. Improved
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dischargeability and reversibility of sulfur cathode in a novel ionic liquid electrolyte.
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29 Electrochem. Commun. 2006, 8(4), 610-614
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32 296. Hassoun, Jusef; Scrosati, Bruno. Moving to a Solid-State Configuration: A Valid
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34 Approach to Making Lithium-Sulfur Batteries Viable for Practical Applications. Adv. Mater.
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2010, 22 (45), 5198-5201
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40 297. Marmorstein, D.; Yu, T. H.; Striebel, K. A.; McLarnon, F. R.; Hou, J.; Cairns, E. J.
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42 Electrochemical performance of lithium/sulfur cells with three different polymer electrolytes., J.
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44 Power Sources, 2000, 89(2), 219-226
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298. Jeong, S. S.; Lim, Y. T.; Choi, Y. J.; Cho, G. B.; Kim, K. W.; Ahn, H. J.; Cho, K. K.,
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50 Electrochemical properties of lithium sulfur cells using PEO polymer electrolytes prepared under
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52 three different mixing conditions. J. Power Sources, 174 (2), 745-750
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3 299. Liang, Xiao; Wen, Zhaoyin; Liu, Yu; Zhang, Hao; Huang, Lezhi; Jin, Jun. Highly
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6 dispersed sulfur in ordered mesoporous carbon sphere as a composite cathode for rechargeable
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8 polymer Li/S battery. J. Power Sources, 2011, 196(7), 3655-3658
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Corresponding Authors.
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23 *T. Ould Ely; Ouldely00@ucsb.edu : orcid : 0000-0001-6619-2904
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25 *M.F. Doherty; mfd@ucsb.edu : orcid: 0000-0003-3309-3082
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27
28 .
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31 Present Addresses
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† Dana Kamzabek’s present address; École normale supérieure Paris-Saclay, 61 Avenue du
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35 Président Wilson, 94230 Cachan, France
36 ††
37 Dhritiman Chakraborty’s present address; Computational Nanotechnology Laboratory, School
38 of Engineering, University of Warwick.UK
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40
41
42 ACKNOWLEDGMENT
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44
45 The Authors thank the Ministry of Education of Kazakhstan and the Government of
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48 Kazakhstan for financial support under the MES NU joint Grant 180/077-2015 as well as
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50 partial support from the targeted program 0115CK03029, research projects 5687/GF4 and
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52 5097/GF4-1. We are also grateful for the U.S. National Science Foundation (Award No.
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55
CBET-1335694) for partial support.
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113
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3 Notes
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5
§ Whether sulfur batteries will be able replace lithium ion battery remains an open question. However, Li-S battery will be
6
7 part of the energy storage systems of the future. Furthermore, for many oil producing countries lithium sulfur batteries will
8
9 find their niche market and remain the best practical solution for recycling the huge deposits of sulfur resulting from
10
petrochemical refineries into high value products.
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ABBREVIATIONS
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28 Ethylene Carbonate (EC),
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30
Dimethyl Carbonate (DMC),
31 Ethylene Methyl Carbonate (EMC),
32 1, 3-Dioxolane (DOL),
33 1, 2 Dimethoxyethane (DME),
34 Sulfur Grafted on Poly(pyridinopyridine) (SPPY),
35 Microporous Carbon/Sulfur (C/S2),
36
Poly(acrylonitrile-Methyl Methacrylate)(PANMMA),
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38 Polyacrylonitrile (PAN), Sulfur/Polyacrylonitrile (SPAN),
39 Polyvinylidene Difluoride (PVDF),
40 Graphene, (G), Natural Graphite, (NG),
41 Graphene Oxides, (GO),
42 Carbon Nanotube, (CNT),
43 Polysulfides (PS),
44
Carbon Nanofibers (CNF),
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46 Carbon Black (CB),
47 Polytetrafluorethylene (PTFE),
48 Acetylene black (AcB),
49 Areal Sulfur Loading (ASL)
50 Ketjenblack (KB),
51 Polyvinylalcohol (PVA),
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53
Carboxyl methyl cellulose (CMC),
54 Poly(ethylene oxide) (PEO),
55 Diethyl Carbonate (DEC)
56 Poly(methyl methacrylate) (PMMA),
57 Organically Modified Montmorillonite (OMMT),
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59
114
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3 Hexafluoropropylene (HFP)
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Poly (ethylene glycol) dimethyl ether (PEGDME),
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6 Lithium bistrifluoromethanesulfonimidate (LiTFSI),
7 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI),
8 n-Methyl-n-Allylpyrrolidinium Chlorine (P1A3Cl),
9 [Li(triglyme)][bis(trifluoromethanesulfonyl)amide] ([Li(G3)1TFSA]),
10 N-methyl-N-butylpiperidinium bis(tri-fluoromethanesulfonyl)imide (PPR14TFS),
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36 TOC
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FIGURES CAPTION
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27 Figure 1. Commercialized Li-ion cells (e.g., Panasonic NCR18650B) have twice the volumetric
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29 energy density of prototype Li–S cells which, by contrast, can have a higher gravimetric energy
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32 density. Adapted with permission from 8.
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20 Figure 2. Most common allotropes of sulfur. Reproduced with permission from reference 10.
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46 Figure 3. a) Scheme and typical charge-discharge curves for lithium sulfur batteries. b) First
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49 discharge and charge profiles of a Li–S cell between 1.5 and 2.8V vs. Li+/Li. Graph b is
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51 reproduced with permission from Angulakshmi et al.12
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30 Figure 4. Recent literature survey of the highest capacity of Li-S batteries coated with graphene or graphene oxides and cycled at
31 0.2C rate. The survey is narrowed from 630 non-review articles (light orange) dealing with “lithium sulfur and graphene”. To exclude
32
33
cases where graphene is used as interlayer, separator coating or blended with other material to increase conductivity, the search was
34 narrowed to 129 using the term “coating” (deep orange bars). Within these articles we reviewed articles providing 100 cycles or more
35 at 0.2 C. The maximum value is listed on top of each bar. The data was extracted from the following references; 201138, 2012 39-41,
36 201336, 42-44, 2014 45-50, 201534, 37, 51-65, 2016 31, 66-79.
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32 Figure 5. Recent literature survey of the highest capacity of Li-S batteries coated with CNTs, and cycled at 0.2C rate. The survey is
33
narrowed from 359 non-review articles (deep orange) dealing with “lithium sulfur and CNT” to 69 using the term coating (light
34
35 orange bars). Within these articles we searched articles providing 100 cycles or more at 0.2 C. The best performances are listed on top
36 of each bar. The best performances are listed on top of each bar. There were no reports with cyclability higher than 100 cycles in
37 2006, 2009 and 2010. The data were extracted from the following references; 2007113, 2011114, 2012115, 2013116, 2014117, 2015118,
38 2016119
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22 Figure 6. Hollow carbon nanofiber
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31 Figure 7: a) Synthesis of the MnO2@HCF/S composite. b) Advantages of the MnO2@HCF/S
32 composite over HCF/S, reproduced with permission from reference 125.
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42 Figure 8: a) Cycle capacity and Coulombic efficiency of MnO2@HCF/S in comparison with
43 HCF/S at a current density of 0.2 C. b) Voltage profiles during cycling at 0.1 C. c) Discharge
44 capacities. d) Voltage profiles at various rate capabilities from 0.05 to 1 C. e) Prolonged cycling
45 performance of MnO2@HCF/S at 0.5 C and the corresponding Coulombic efficiency. Areal
46 capacity values were calculated based on the specific capacity and areal mass loading of sulfur,
47
reproduced with permission from reference 125.
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25 Figure 9. Recent literature survey of the highest capacity of Li-S batteries coated with HCNF, and cycled at 0.2C rate. The survey is
26 narrowed from 82 non-review articles (deep orange) dealing with “lithium sulfur and CNT”. The search was narrowed further to 27
27 using the term coating (light orange bars). Within these 27 articles we reviewed articles providing 100 cycles or more at 0.2 C. The
28 best performances are listed on top of each bar. There were no substantial reports between 2006-2011. The data were extracted from
29
the following references; 201618, 2015132, 2014133, 2013134, 2011135.
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28 Figure 10. Schematic of PEDOT:PSS-coated CMK-3/sulfur composite (a) In bare CMK-3/S
29 particles (gray: CMK-3, yellow: sulfur), polysulfides (green) still diffuse out of the carbon
30 matrix during lithiation/delithiation. (b) With conductive polymer coating layer (blue),
31
polysulfides could be confined within the carbon matrix. Lithium ions and electrons can move
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33
through this polymer layer. Figure and caption are reproduced with permission from reference
15
34 .
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Figure 11. Schematic representation and capacities of mesoporous carbon-embedded
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Li2S/silicon nanowire battery. (a) A schematic of a CMK-3 mesoporous carbon-embedded
42 Li2S/silicon nanowire battery. (b) The voltage profile of a CMK-3/Li2S cathode versus a lithium
43 anode. (c) The cycling performance of a CMK-3/Li2S cathode compared to a commercial 10
44 mm-sized Li2S particle electrode. (d) Typical capacity delivery in multiple charge–discharge
45 cycles (1 blue, 2 red, 3 green) of a Li2S/C electrode in a polymer electrolyte. Lithium metal
46 counter and reference electrode. The operating temperature is 60 º C and the cycling rate is C/20
47
(C = 2.2 mA cm-2). The upper and bottom axes represent capacity based on the mass of Li2S and
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49 Li2S–carbon, respectively. Reproduced with permission from reference124.
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21 Figure 12. Recent literature survey of the highest capacity of Li-S batteries coated with mesoporous carbon, and cycled at 0.2C rate.
22 The survey is narrowed from 230 non-review articles (deep orange) dealing with “lithium sulfur and and mesoporous carbon”. The
23 search was narrowed further to 44 entries using the term coating (light orange bars). Within these 27 articles we searched articles
24
providing 100 cycles or more at 0.2 C. The best performances are listed on the top of each bar. Other than reference [2009]198 and
25
26
[2010]191 that reported limited cyclability, there were no substantial reports between 2006-2010. The data were extracted from the
27 following references [2009]198 and [2010]191, [2011]199, [2012]192, [2013]195, [2014]47,[ 2015]200, [2016]20.
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Figure 13. Electrochemical performance of the aligned and laminated nanostructured carbon
42 hybrid cathode with a sulfur load of 1 mg cm−2. a) Cyclic voltammograms at 0.1 mV s−1. b)
43 Voltage profiles at 0.1 C. c) Rate capability. d) Cyclic performance at 0.1 C for 100 cycles. e)
44 Cyclic performance at 2 C for 1000 cycles. Reproduced with permission from reference 206.
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28 Figure 14. a, b) Photographs of hybrid electrodes being lifted up by a flower and being bent
29 into a curved structure, respectively. c, d) Scanning electron microscopy (SEM) images of
30 aligned CNT sheets before and after deposition of CMK-3@S particles, respectively. e, f)
31 Transmission electron microscopy (TEM) images of a bare CMK-3 particle and a CMK-3@S
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particle with weight ratio of 1:3, respectively. Reproduced with permission from reference 206.
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35 Figure 15. Merits of the lithium–sulfur battery. a) Cyclic performance of the batteries with
36 sulfur loads of 1, 5, 10 and 20 mg cm−2 at 0.1 C. b) A comparison on the specific capacity and
37 sulfur load between this battery and the reported lithium–sulfur batteries. c) Cyclic performance
38
of the battery at 0.1 C after bending for 500 times with bending angles of 60° and 180°. d)
39
40 Voltage profiles at 0.1 C at a bent state with bending angles of 60° and 180°. e) Cyclic
41 performance at 0.5 C and 1 C at a bent state with bending angles of 60° and 180°. f) Real-time
42 monitoring of the voltage of the battery when undergoing bending and recovering. reproduced
43 with permission from reference 206.
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18 Figure. 16. Schematic of hybrid CNT/graphene-Li2S cathode, reproduced with permission
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from reference 131
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Figure 17. Electrochemical performances of lotus root-like multichannel carbon (LRC/S) and
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45 coated with a thin layer of ethylenediamine (EDA)-functionalized reduced graphene oxide
46 (EFG)LRC/S@EFG. a) Cycle performance of LRC/S@EFG in comparison with LRC/S at a
47 current density of 0.2 C. (b) Voltage profiles and (c) discharge capacities at various current
48 densities from 0.1 to 2 C. (d) Areal capacities of layer-by-layer structured LRC/S@EFG
49 electrodes during cycling at a current density of 1.2mAcm-2. Reproduced with permission from
50 106
.
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7 Table 1: Characteristics of the four porous carbon categories (I, II, III and VI). Carbons marked
8 with a star (*) were synthesized using colloidal silica of two different sizes (values separated by
9 a comma) taken in a weight ratio of 1:1. (reproduced with permission from215).
10
11 Category Carbon a) S BET V Total Avg. pore Electrical loading Actual
12 [m2g −1] [cm3g −1] size [nm] conductiv [C:S] sulfur
13 ity loading
14 [S cm −1 ] [wt%]
15
4-0.3-0 511 0.6 5 9.9 1:1 1:5
16 I
17 4-0.5-0 800 1.2 6 7.9 1:2 1:5
18
12-1-0 838 1.6 12 2.9 1:3 1:5
19
20-1-0 964 2.1 18 3.4 1:4 1:5
20
21 4-1-0 1110 2.1 7 6.5 1:4 1:4
22 II 4-0.5-3 1922 2.3 5 3.6 1:4 1:5
23
4-0.5-4 2336 2.5 5 3.5 1:5 1:5
24
25 12-2-0 1236 2.7 13 1.5 1:5 1:5
26 III
4-1-1 1473 2.8 7 7.8 1:5 1:4
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28 20-2-0 1279 3.3 19 1.6 1:6 1:4
29 4,20-2-0* 1245 3.7 6,32 2.5 1:7 1:5
30
4-2-0 1263 3.7 21 2.1 1:7 1:5
31
32 20,140-2- 1290 5.0 21,84 2.9 1:9 1:4
33 0.5*
34 20-1-2 2004 3.5 18 3.1 1:6 1:5
35 IV 4-1-2 2384 3.8 7 4.0 1:7 1:4
36
37 4,20-2-1* 2219 3.9 25 2.6 1:7 1:4
38
39 12-2-1.5 1604 4.1 12 1.8 1:7 1:4
40 4-2-0.5 2297 4.5 18 – 1:8 1:4
41 20-2-1.5 2270 4.6 16 1.7 1:8 1:4
42 4,20-2-0.5* 1909 4.8 30 2.0 1:9 1:4
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Figure 18. Scatter plots correlating specific capacity obtained at the end of 100th discharge
36 cycle with (a) surface area, (b) pore volume, and (c) pore size, of hierarchical porous carbons
37 loaded with ≈80 wt% sulfur. Data points are color coded according to HPC category: category I
38 (black), category II (blue), category III (red), and category IV (green). d) Capacity retention of
39 all composites calculated from 20th–100th cycle. (reproduced with permission from215).
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38 Figure 19: a) Reactivity of ethylene carbonates (EC) and diethyl carbonate (DEC) with
39
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polysulfides. b) Discharge capacities of sulfur/carbon in various solvents with 1.0M of
41 LiCF3SO3. Reproduced with permission from Gao et al.218
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30 Figure 20. A schematic of the multi-electron redox process inside the SPPY electrode.
31 Reproduced with permission from292
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39 Fig. 21. (a) Discharge–charge curves at the 1st cycle, and (b) the discharge (&), charge (J)
40
capacities and overcharge (+) amounts of Li–sulfur cells made of electrolyte with 1.5 M (red),
41
42 3.0 M (green), 4.0 M (grey), and 5.0 M (blue) concentration of LiTFSI. The initial 3 cycles were
43 tested at a 0.1 C rate and thereafter at a 0.5 C rate. (1 C = 1675 mA g-1 of sulfur).293
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Figure 22. Cyclability of Li-S batteries with and without addition of polysulfides into the
24 electrolyte. Graph reproduced with permission from239
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Electrolyte and additive composition Composition of the Current Capacity Comment Refs
Page 141 of 150 cathode ACS Applied Energy Materials
density
(mA.g-1) (mAh.g-1)/cycles
1
2
3
4
5 Table 2: Summary of the most promising electrolytes strategies to limit polysulfides dissolution and transport, obtain high capacity and cyclability. All abbreviations
6 are given in the abbreviation section.
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1
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3 Strategy-1: Conventional carbonate electrolytes
4
5 1 MLiPF6 (solvent EC/DMC/EMC (1:1:1, v/v/v) SPPY material (S: 41%) 20 (mA.g-1) ~700/100 cycles These examples are obtained at various [292]
current densities and showed that physical
6 80 %, AcB, 10%, 10%
encapsulation of PS enabled the use of
7 PAN binder) conventional carbonate electrolytes that are
8 less prone to depletion and reactivity with Li
1M LiPF6 in EC/DEC (1:1 (v/v) C/S2 (S:21.7 wt %))/CB/sodium 80 (mA.g-1) ≈600/> 4000 cycles metal [220]
9 alginate binder (70:15:15 wt
10 %),
11
1M LiPF6 in EC/DEC 1:1 (v/v) SPAN4/CB/PVDF binder ratio : 670 (mA.g-1) ≈400-500/>1000 [221]
12 (70:15:15 wt%)
13
14 Strategy-2: High concentration of the electrolyte
15
16
1M 1M LiTFSI, 0.2MLiNO3(Solvent SPAN4/carbon black /PVDF 670 (mA.g-1) ≈400-500/ 000 [221]
17 DOL/DME, 1:1) (70/15/15 wt %)
18
19 2.4 M 2.4 M LiTFSI in DME/DIOX (1:1,v/v) with 80% Li2S-Graphene (S 400 (or C/2) ~1040/700 cycles [79]
These reports show that high electrolyte
20 0.24 M LiI (additive) ~55%)/CB (7 wt %) and PVP
concentration limited the dissolution and
(3%) (based on sulfur)
21 transport of PS, but did not interdict the
22 5M 5 M LiTFSI in DME/DOL (1:1,v/v) with Commercial Sulfur powder 167.5(or 0.1C) ~1300/first cycle
phenomenon
[293]
23 0.24M LiI (additive) (200 mg) and carbon black (100
24 mg), PVDF (25 mg) (based on sulfur)
25
7M 7 M LiN(SO2CF3)2, LiTFSI) in (DME:DOL C/S composite /CNT/ PVDF in 0.1 mA cm -2, 700 /100 cycles [222]
26 1:1 v/v) 8:1:1 w/w/w
27
28 Strategy-3: Optimal E/S ratio
29
30 E/S = 6.5 mL.g-1 Sulfur/CB/KB/PANMMA 0.5mA cm−2 < 600/80 cycles Optimal E/S depend on various parameters
(77/10/10/3 wt %) such as the loading and the type of electrolyte.
31 For this case-study (ref [223]) the authors
32 E/S = 10 mL.g-1 Sulfur/CB/KB/PANMMA 0.5 mA cm−2 780/100 cycles used LISO3CF3- LINO3 (0.25/0.25M)
33 (77/10/10/3 wt %) (DME/DOL) (1:1, WT:WT). [223]
34
E/S = 13.3 mL.g-1 Sulfur/CB/KB/PANMMA 0.5 mA cm−2 <400/100 cycles
35 (77/10/10/3 wt %)
36
37 Strategy-4: Ionic liquids
38
39 Mixed IL 1 M LiTFSI in EMITFSI C-S 50% sulfur powder, 40% carbon black, and 50 600−700 /> 40 As of 2018, ionic liquids succeeded only [230]
10%, PVDF binder (mA.g-1) partially in suppressing dissolution and
40
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1
2
3 0.5 M LiTFSI in P1A3TFSI) S/C/AcB/PvDF 80/10/10 167 670/>50 cycles shuttling of PS. [231]
4 (mA.g-1)
5 Next generation electrolytes will be based on
An all IL Li(G3)1TFSA] PE-S/KB/PVA (56.7/28.3/15) 92.9μA 459/800 cycles solid and semi-solid electrolytes, see strategy [232]
6 cm-2g-1-S 5, 6, and 7
7 (or C/18)
8
[Li(G4)][X, X: [N(SO2C2F5)2] S8/KB/PVA (60/30/10 wt %) 139 600−700 />100 [226,
9
(mA.g-1) 233]
10
11 Strategy-5: Gel polymer to improve safety and limit shuttling
12
13 (100 mg) of (-)-(S,S)-dodecyl- RT Conductivity Sulfur/CMK3 composite/super P/PVDF, 0.1C 337/100 Gel polymer electrolytes can form a physical [234]
3-[2-(3-dodecyl 70/15/15wt% protection for the anode by serving as a trap
14 ureido)cyclohexyl] urea mixed 6.43(mScm-1) to shuttling polysulfides. However, their
15 with (500µl) of DOL and DME room temperature conductivity is still low.
16 (v/v, 1/1) with 1M Similarly, solid polymer electrolyte can
LiN(CF3SO2)2 inhibit polysulfides diffusion but all known
17 solid polymer electrolytes necessitate high
18 PAN/PMMA mixed with RT Conductivity CNFs-S/Super-P carbon/CMC and styrene 0.15 mA cm-2 750/50 temperature to improve their conductivities [235]
19 butadiene rubber (SBR)(CMC:SBR=2:3, by
20 PPR14TFSI-PEGDME (1:1) 3.8 (mScm-1) weight) (70/20/10 w%)
21
PVdF-HFP/OMMT soaked RT Conductivity (S/PAN/Mg0.6Ni0.4O)/KB/PVDF. 0.2 C 650-700/80 [236]
22 in1M LiPF6 dissolved in a
23 (EC/DEC) 1:1 (v/v) 4–7 mScm−1 Ratio : 60/20/20 w%
24
25 PEO-SiO2 (50/50 wt.%) gelled RT Conductivity Sulfur/Super P/ Ketjenblack/ANMMA 0.5 mA cm−2 800/100 [237]
with gel forming electrolyte
26 made of 0.25molkg−1 LiTFSI- 4.2×10−3Scm−1 77/10/10/3 wt %
27 0.25molkg−1 LiNO3 dissolved Poor conductivity
28 in a DME/DOL 1:1(wt %),
then coated on Celgrad
29
30 Gel Polymer of NA SPAN 70 wt.-% mixed with 20 wt.-% 0.2 mAcm-2 ~600 / 50 [294]
31 Polyvinylidenefluoride- acetylene black and 10 wt.-% PTFE,
32 hexafluoropropylene, 1 M
LiPF6/ (EC/DMC) (1:1, v/v)
33
34 Polymer in salt ; PEO in 1 M 1.67 ×10−3 S cm−1 S/C (7:3) composite, Super P, poly(vinylidene 100 720/300 [240]
35 LiTFSI in DOL:DME (1:1 v/v) difluoride) in weight ratio of 8:1:1. mA.g-1
36
37 Strategy-6: Solid State Electrolyte to discard PS and improve safety
38
39 Glass–ceramic electrolyte- 1.1×10−3 S cm−1 Sulfur, Acetylene Black and Li2S–P2S5 glass– 333 mA.g-1 850/200 Inorganic solid electrolytes exhibit high Li+ [244]
Li2S–P2S5 and 1.6 ×10−3 S ceramic ion conductivity of over 10−3 S cm−1 at 25◦C.
40 cm−1, However, the contact resistances still need
41 improvement. In addition, the cells usually
42
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1
2
3 suffer from internal strains. Inorganic solid
4 electrolytes exhibit high Li+ ion conductivity
of over 10−3 S cm−1 at 25◦C.
5
6 Solid electrolyte Li10GeP2S12 0.31 mS cm-1 0.82(Li1.5 PS3.3).0.18(LiI) 1.3 mA cm-2 1500/100 [68]
7
8 Strategy-7: Hybrid electrolyte to bypass the limitations of solid and liquid electrolytes
9
10 Dual electrolytes, separated by Li super ionic conductor RT conductivity Li2S 0.1C 800/50 The structure of the cell is as follows:“Li [14
membrane of Li1+x+yAlxTi2-y SiyP3-yO12 Electrolyte 1, Anode 10-4Scm-1 anode|electrolyte1|LATP|electrolyte-2 |Li2S-cathode” Al, and Graphite can ]
11 side: 1 M LiPF6 in EC/DMC/DEC (1 :1 : 1 v/v/v), be used an anode . PS are confined in the cathode side, carbonate can be
12 Electrolyte 2, cathode:Li2S was dispersed in a 1 M LiClO4 used. Mass loading can be achieved by increasing the concentration of Li2S
13 dissolved in tetrahydrofuran (THF) in the cathodic electrolyte. The rate capability is still low for this system,
14 and the manufacturability is more complex than traditional cells
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39 Figure 23. a, The framework structure and lithium ions that participate in ionic conduction. b,
40 Framework structure of Li10GeP2S12. One-dimensional (1D) chains formed by LiS6 octahedra
41 and (Ge0:5P0:5)S4 tetrahedra, which are connected by a common edge. These chains are connected
42 by a common corner with PS4 tetrahedra. c, Conduction pathways of lithium ions. Zigzag
43 conduction pathways along the c axis are indicated. Lithium ions in the LiS4 tetrahedra (16h site)
44
and LiS4 tetrahedra (8f site) participate in ionic conduction. Thermal ellipsoids are drawn with a
45
46 30% probability. The anisotropic character of the thermal vibration of lithium ions in three
47 tetrahedral sites gives rise to 1D conduction pathways.243
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1
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3 Table 3. Ion conductivities of different sulfide solid electrolytes. Reproduced with permission from
4 Zhang et al.241
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7
8
Composition Classification Conductivity at 25 °C (S cm−1)
9
10 70Li2S· 30P2S5 Glass 5.4×10−5
11 75Li2S·25P2S5 Glass 2.0×10−4
12 80Li2S·20P2S5 Glass 2.0×10−4
13 80(0.7Li2S·0.3P2S5)·20LiI Glass 5.6×10−4
14 95(0.8Li2S·0.2P2S5)·5LiI Glass 2.7×10−3
15 56Li2S·24P2S5·20Li2O Glass >1.0×10−4
16 75Li2S·21P2S5·4P2O5 Glass >1.0×10−4
17 67.5Li2S·7.5Li2O·25P2S5 Glass 1.1×10−4
18 33(0.7B2S3·0.3P2S5)·67Li2S Glass 1.4×10−4
19 67(0.75Li2S·0.25P2S5)·33LiBH4 Glass 1.6×10−3
21 80Li2S·20P2S5 Glass-Ceramic 9×10−4
23 Li7P3S11-z Glass-Ceramic 5.4×10−3
24 Li7P3S11 Glass-Ceramic 1.7×10−2
25 Li3.25P0.95 S4 Glass-Ceramic 1.3×10−3
26 γ-Li3PS4 Crystalline 3.0×10−7
27 β-Li3PS4 Crystalline 1.6×10−4
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3 Li3.25Ge0.25P0.75S4 Crystalline 2.2×10−3
4 Li10GeP2S12 Crystalline 1.2×10−2
5 Li10SnP2S12 Crystalline 4.0×10−3
6
7 Li11Si2PS12 Crystalline >1.2×10−2
8 Li7P2S8I Crystalline 6.3×10−4
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48 Figure 24: Schematic of the architecture for the Li–S battery composed of (−) Cu foil/Li
49 metal/organic electrolyte-1/ceramic separator (LATP)/organic electrolyte-2/Li2S cathode/Super P
50 carbon/Ti foil (+) from top to bottom. (reproduced with permission from reference 14).
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53 Figure 25: Electrochemical performance comparison of Li−S batteries with PS−ReS2@CNF
54 and PS−CNF electrodes. (a) Specific capacity at different current densities (1 C = 1675 mA g−1).
55
(b) Galvanostatic charge−discharge profiles of the second cycle at ∼0.2 C within a potential
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1
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3 window of 1.5−2.8 V vs Li+ and Li0. c) Cycling stability and coulombic efficiency of the
4
PS−ReS2@CNF and baseline PS−CNF. Reproduced with permission from 262.
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50 Figure 26: The most common commercial cell structures. a. Cyclindrical, b. Prismatic, and c.
51 Pouch cell. Reproduced with permission from 264
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18 Figure 27. a, A thin film of SEI layer forms quickly on the surface of deposited Li (blue).
19 Volumetric changes during the Li deposition process can easily break the SEI layer, especially at
20 high current rates. This behavior leads to ramified growth of Li dendrites and rapid consumption
21 of the electrolyte. b, Modifying the Cu substrate with a hollow carbon nanosphere layer creates a
22 scaffold for stabilizing the SEI layer. The volumetric change of the Li deposition process is
23
accommodated by the flexible hollow-carbon-nanosphere coating. Reproduced with permission
24
25 from ref.275
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Li-Sulfur Batteries: State of the Art and Future Directions

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

17 a DME/DOL 1:1(wt %), then coated on Poor conductivity

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