Abstract
This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.
Introduction
The global warming and depletion of fossil fuel resources have accelerated immense research on energy storage devices unquestionably (Tarascon, ). In response to the modern society, it is now essential to develop new, low-cost and environmental friendly energy conversions and storage systems with new advanced materials (Arico et al., ; Bruce et al., ; Goodenough and Kim, ; Scrosati, ). Undoubtedly, lithium-ion battery is one of the great successes of modern electrochemistry due to its appealing properties such as high single cell voltage, no-memory effect, long cycle life, and high energy density. The fundamental aspects of lithium-ion batteries, working principles, and their limitations can be understood from numerous review articles (Whittingham, ) and dedicated books (Schalkwijk and Scrosati, ). The state-of-the-art lithium-ion batteries are composed of a carbonaceous anode and lithium transition metal oxide cathode separated by a polyolfine porous separator soaked in a non-aqueous liquid electrolyte (Manuel Stephan, ). The lithium-ion battery has become an inevitable power source not only for portable electronic devices such as laptop computers, cellular phones, and MP3 players but also find applications in satellites (Santoni et al., ) and in medical equipments (Bock et al., ). Nevertheless, with the existing insertion cathode materials (e.g., LiCoO2, LiFePO4, etc.), lithium-ion batteries have attained a maximum discharge capacity of approximately 250 mAh g−1 (with a theoretical energy density of 800 Wh kg−1), which is not sufficient to meet out the demand of key markets such as transport and power grid applications (Lee et al., ). Obviously, intense research has been accelerated to find alternative electrochemical lithium-based power systems across the world. Among the systems known today, both Li–S and Li–O2 are expected to fulfill the requirements of mankind with enhanced capacity and energy density. Nevertheless, so many technological and scientific problems remain unsolved in Li2O systems (Bruce et al., ). The Li–S batteries have inspired many researchers recently, because sulfur is electrochemically active and can accept up to two electrons per atom approximately at 2.1 V vs. Li/Li+. It has a high-theoretical capacity of 1675 mAh g−1, which corresponds to an energy density of 2600 Wh kg−1 or 2800 Wh l−1 based on weight or volume, respectively. However, their practical applications are impeded by several major issues (Cakan et al., ; Xia et al., ).
Unfortunately, sulfur undergoes a series of compositional and structural changes during cycling, which involves soluble polysulfides and insoluble sulfides (Cheon et al., ,; Mikhaylik and Akridge, ). The typical Li–S batteries are composed of a lithium metal anode, an organic liquid electrolyte, and a sulfur composite cathode as depicted in Figure 1.
Figure 1
Although the concept of elemental sulfur as positive electrode material was introduced almost five decades ago by Hebert and Ulam (
Lithium-ion reacts with elemental sulfur (S8) and produces lithium polysulfides of general formula Li2Sn, e.g., Li2S8, Li2S6. Upon discharge the length of the polysulfide is shortened as the sulfur is being further reduced. The overall reaction is
The elemental sulfur is a promising electrode material, which is available abundantly, cheap, non-toxic, and environmentally benign. Despite all these advantages sulfur suffers from poor electronic conductivity.
Figure 2 shows typical discharge–charge profile of a Li–S cell. The discharge process is generally divided into four reduction regions depending upon the phase changes of sulfur species.
Figure 2

First discharge and charge profiles of a Li–S cell between 1.5 and 2.8 V vs. Li+/Li [adopted from Barghamadi et al. (
According to Zhang (
In the second region, the cell voltage suddenly reduced with an increase in viscosity of electrolyte solution. The solution’s viscosity reaches a maximum value at the end of the discharge region, which corresponds to the equation;
The low voltage plateau, which occurs between 1.9 and 2.1 V offers majority of the total capacity of Li–S cell. In this third region, a liquid-solvent two-phase reduction takes place in which dissolved low-order polysulfide (PS) to insoluble Li2S2 or Li2S.
In the fourth region, a solid–solid reduction from insoluble Li2S2 to Li2S process takes place, which is kinetically slow and suffers from high polarization due to the non-conductive and insoluble natures of Li2S2 and Li2S.
According to Mikhaylik and Akridge (
The sulfur and lithium sulfides, which are strong insulators, will easily dissolve in common organic liquid electrolytes. Spontaneously, they diffuse through the liquid electrolyte and subsequently leads to self-discharge and thereby increasing the viscosity of the electrolyte solution. These drawbacks lead the lithium/sulfur batteries to poor cycle life, low specific capacity, and lower efficiency.
Non-Aqueous Liquid Electrolytes
In order to improve the electrochemical performance of Li–S batteries, different strategies have been adopted, which also include the optimization of the electrolyte compositions (Barchasz et al.,
In a pioneering work, Rauh et al. (
Generally, both DIOX and glyme solvents exhibit higher sulfur solubility (Peled et al.,
By employing electrochemical and in situ X-ray absorption spectroscopy, Gao et al. (
The electrochemical performance of LiClO4/DOL/DME as electrolyte was reported by Wang et al. (
The cycling behavior of Li/TEGDME/S cells was examined at low temperature by Rhu et al. (
Ionic Liquids as Electrolytes
Ionic liquids are identified as an electrolyte system for lithium-ion batteries due to their unique properties such as non-flammability, wide electrochemical stability, non-volatility, high ionic conductivity, and environmental friendliness (Galinski and Lewandowski,
Polymer Electrolytes
In the last three decades, extensive research has been devoted on the development of polymer electrolytes as they find applications not only in lithium batteries but also other electrochemical devices such as supercapacitors, fuel cells, and electrochromic devices (Manuel Stephan,
Marmorstein et al. (
According to Zhang and Tran (
Lécuyer et al. (
The cycling profile of Li–S cells with PEO-based gel electrolytes with LiClO4 and TEGDME. The cell delivered higher discharge capacity than the subsequent cycles and a flat discharge has been observed at 2.0 V. The capacity fading has been attributed to low utilization of sulfur, which arises to the aggregation of sulfur (polysulfide) upon cycling (Jeon et al.,
Superionic Conductors
The appealing properties such as high safety, non-flammability, high thermal stability, reliability, and prevention of polysulfide formation and migration qualify the ionically conducting solids as potential electrolytes for lithium sulfur batteries. Based on their properties they are classified as (i) sulfides, (ii) oxides, and (iii) phosphates (Fergus,
Nagao et al. (
Hayashi et al. (
In a similar way, Kobayashi et al. (
Electrolyte Additives
Electrolyte additives play an extraordinary role in lithium-ion batteries. Although the amount of additive in the electrolyte is around 5% either by volume or by weight it plays a significant role in the electrochemical performance of lithium-ion batteries. It significantly improves the solid-electrolyte interface on the surface of graphite, reduces irreversible capacity, enhances thermal stability, promotes physical properties of the electrolyte such as ionic conductivity, viscosity, and wettability of the polyolifine membrane (Zhang,
In a similar way, the electrolyte additives play a vital role in lithium/sulfur batteries. The polysulfides involve reactions with cathode and anode during cycling and therefore protection of lithium anode from chemical reactions is mandatory. This will significantly eliminate the shuttling of polysulfide and effectively promotes the columbic efficiency and cycling performance. Lithium nitrate (LiNO3) reacts with metallic lithium and forms a rigid passivation layer that prevents the chemical reactions of polysulfides with metallic lithium and is attributed to the decomposition of LiNO3 in the non-aqueous liquid electrolyte (Xiong et al.,
Summary and Future Outlook
Li–S batteries are considered as one of the ultimate power source by virtue of its appealing properties such as low cost, non-toxic, abundance, and above all higher discharge capacity (1640 mAh g−1) and energy density (2400 Wh kg−1) than lithium-ion batteries. Regarding the non-aqueous liquid electrolytes for lithium–sulfur batteries, no one system is found to be optimal in all aspects. In this area, more work is certainly needed. Although, extensive research work has been pursued on the development of cathode materials for lithium/sulfur batteries, reports on solid polymer electrolytes and superionic conductors are very scanty. A few reports illustrate the glass-ceramic electrolytes with ionic conductivity exceeding 10−3 Scm−1 at ambient temperature. However, attention should be focused on the major drawbacks such as fragility at low thickness, high cost, and poor interfacial property at electrode/electrolyte interfaces. Prevention of shuttling of polysulfides by suitable polymeric/solid electrolytes will be appreciable and exotic. Ionic liquids in conjunction with polymer electrolytes and sulfurized carbon electrodes may offer a safe, reliable, and polysulfide shuttle-free lithium–sulfur batteries.
Statements
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The Review Editor Jijeesh Ravi Nair declares that, despite having collaborated with author Natarajan Angulakshmi, the review process was handled objectively and no conflict of interest exists.
Abbreviations
AFM, atomic force microscope; CGPE, composite gel polymer electrolyte; DEC, diethyle carbonate; DIOX, 1,3-dioxolane; DMAc, dimethyl acetamide; DME, dimethyl ether; DMSO, dimethyl sulfoxide; EC, ethylene carbonate; EDX, energy dispersive X-ray; EMS, ethyl methane sulfonate; GPE, gel polymer electrolyte; Li2S, lithium sulfide; LiB(C2O4)2, lithium bis(oxalate)borate (LiBOB); LiBF2C2O4, lithium bid(difluoro oxalate)borate (LiDFOB); LiBF4, lithium tetrafluoroborate; LiClO4, lithium perchlorate; LiCF3SO3, lithium trifluoromethanesulfonate; LiPF6, lithium hexafluorophosphate; LiTFSI, lithium bis(trifluoromethylsulfonyl)imide; P2S5, phosphorous pentasulfide; PC, propylene carbonate; PEO, poly(ethylene oxide); PMMA, polymethylmethacrylate; PVDF, poly(vinylidene fluoride); PVDF-HFP, poly(vinylidene fluoride-co-hexafluoropropene); PYR14TFSI, N-methyl-n-butyl-pyrrolidinium-bis(trifluoromethylsulfonyl)imide; SEM, scanning electron microscope; TEGDME, tetra (ethylene glycol) dimethyl ether; TEOS, triethoxysilane; THF, tetrahydrofuran; XRD, X-ray diffraction.
References
1
AbrahamK. M.RauhR. D.BrummerS. B. (1978). A low temperature Na-S battery incorporating a soluble sulfur cathode. Electrochim. Acta23, 501–507.10.1016/0013-4686(78)85027-0
2
AgostiniM.LeeD.-J.ScrosatiB.SunY. K.HassounJ. (2014). Characteristics of Li2S8-tetraglyme catholyte in a semi-liquid lithium-sulfur battery. J. Power Sources265, 14–19.10.1016/j/jpowsour.2014.04.074
3
AkridgeJ. R.MikhaylikY. V.WhiteN. (2004). Li/S fundamental chemistry and application to high performance rechargeable batteries. Solid State Ionics.175, 243–245.10.1016/j.ssi.2004.07.070
4
AricoA. S.BruceP. G.ScrosatiB.TarasconJ.-M.SchalkwijkM. V. (2005). Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater.4, 366–377.10.1038/nmat1368
5
AurbachD.PollakE.ElazariR.SalitraG.KelleyC. S.AffinitoJ. (2009). On the surface chemical aspects of very high energy density, rechargeable Li-sulfur batteries. J. Electrochem. Soc.156, A694–A702.10.1149/1.3148721
6
BarchaszC.LeprêtreJ. C.AlloinF.PatouxS. (2012). New insight into the limiting parameters of the Li/S rechargeable cell. J. Power Sources199, 322–330.10.1016/j.jpowsour.2011.07.021
7
BarchaszC.LeprêtreJ.-C.PatouxS.AlloinF. (2013a). Electrochemical properties of ether-based electrolytes for lithium/sulfur rechargeable batteries. Electrochim. Acta89, 737–743.10.1016/j.electacta.2012.11.001
8
BarchaszC.LeprêtreJ.-C.PatouxS.AlloinF. (2013b). Revisiting TEGDME/DIOX binary electrolytes for lithium/sulfur batteries: importance of solvation ability and additives. J. Electrochem. Soc.160, A430–A436.10.1149/2.022303jes
9
BarghamadiM.BestA. S.BhattA. I.HollenkampA. F.MusamehM.RessR. J.et al (2014). Lithium-sulfur batteries – the solution is in the electrolyte, but is the electrolyte a solution?Energy Environ. Sci.7, 3902–3920.10.1039/C4EE02192D
10
BarghamadiM.KapoorA.WenC. (2013). A review on Li-S batteries as a high efficiency rechargeable lithium battery. J. Electrochem. Soc.160, A1256–A1263.10.1149/2.096308jes
11
BockD. C.MarchilokA. C.TakeuchiK. J.TakeuchiE. S. (2012). Batteries used to implantable biomedical devices. Electrochim. Acta84, 155–164.10.1016/j.electacta.2012.03.057
12
BresserD.PasseriniS.ScrosatiB. (2013). Recent progress and remaining challenges in sulphur-based lithium secondary batteries – a review. Chem. Commun. (Camb.)49, 10545–10562.10.1039/c3cc46131a
13
BruceP. G.FreunbergerS. A.HardwickL. J.TarasconJ. M. (2012). Li-O2 and Li-S batteries with high energy storage. Nat. Mater.11, 19–29.10.1038/nmat3191
14
BruceP. G.ScrosatiB.TarasconJ. M. (2008). Nanomaterials for rechargeable lithium batteries. Angew. Chem. Int. Ed. Engl.47, 2930–2946.10.1002/anie.200702505
15
BrücknerJ.Soren ThiemeS.GrossmannH. T.DeorflerS.AlthuesH.KaskelS. (2014). Lithium-sulfur batteries: influence of C-rate, amount of electrolyte and sulfur loading on cycle performance. J. Power Sources268, 82–87.10.1016/j/jpowsour.2014.05.143
16
BrummerS. B.RauhR. D.MsrstonJ. M.ShukerF. S. (1976). Low Temperature Alkali Metal-S Batteries. Annu Prog Rep. U.S. ERDA Contract No.Ey-76-c-02-2520.
17
CakanR.MorcretteM.TarasconJ.-M. (2013). Li-S batteries: simple approaches for superior performance. Energy Environ. Sci.6, 176–182.10.1039/C2EE23411D
18
CanasN. A.WolfS.WagnerN.FriedrichK. A. (2013a). In-situ X-ray diffraction studies of lithium-sulfur batteries. J. Power Sources226, 313–319.10.1016/j.jpowsour.2012.10.092
19
CanasN. A.HiroseK.PascucciB.WagnerN.FriedrichK. A.HiesgenR. (2013b). Investigations of lithium-sulfur batteries using impedance spectroscopy. Electrochim. Acta97, 42–51.10.1016/j.electacta.2013.02.101
20
ChangD. R.LeeS. H.KimS. W.KimH. T. (2002). Binary electrolyte based on tetra(ethylene glycol) dimethyl ether and 1,3-dioxolane for lithium-sulfur battery. J. Power Sources112, 452–460.10.1016/S0378-7753(02)00418-4
21
ChenS.DaiF.GordinM. L.WangD. (2013). Exceptional electrochemical performance of rechargeable lithium-sulfur batteries with a poysulfide containing electrolyte. RSC Adv.3, 3540–3543.10.1039/C3RA23070H
22
CheonS. E.KoK. S.ChoJ. S.KimS. W.ChinE. Y.KimH. T. (2003a). Rechargeable lithium sulfur battery: 1. Structural change of sulfur cathode during discharge and charge. J. Electrochem. Soc.150, A796–A799.10.1149/1.1571532
23
CheonS. E.KoK. S.ChoJ. S.KimS. W.ChinE. Y.KimH. T. (2003b). Rechargeable lithium sulfur battery: 2. Rate capability and cycle characteristics. J. Electrochem. Soc.150, A800–A805.10.1149/1.1571533
24
ChoiJ. W.CheruvallyG.KimD. S.AhnJ. H.KimK. W.AhnH. J. (2008). Rechargeable lithium/sulfur battery with liquid electrolytes containing toluene as additive. J. Power Sources183, 441–445.10.1016/j.jpowsour.2008.05.038
25
ChuM. Y.PeJongheL. C.ViscoS. J.KatyB. D. (2000). Liquid Electrolyte Lithium Sulphur Batteries. US Patent 08/948,969.
26
DiaoY.XieK.XiongS.HongX. (2013). Shuttle phenonmenon: the irreversible oxidation mechanism of sulphur active material in Li-S battery. J. Power Sources235, 181–186.10.1016/j.jpowsour.2013.01.132
27
ElazariR.SalitraG.TalyosefY.GrinblatJ.KelleyS. C.XiaoA.et al (2010). Morphological and structural studies of composite sulfur electrodes upon cycling by HRTEM, AFM and Raman spectroscopy. J. Electrochem. Soc.157, A1131–A1138.10.1149/1.3479828
28
FergusJ. W. (2010). Ceramic and polymeric solid electrolytes for lithium-ion batteries. J. Power Sources195, 4554–4569.10.1016/j.jpowsour.2010.01.076
29
FuY.SuY.-S.ManthiramA. (2012). Sulfur-carbon nanocomposite cathodes improved by anamphiphilic block copolymer for high rate lithium-sulfur batteries. ACS Appl. Mater. Interfaces4, 6046–6052.10.1021/am301688h
30
GalinskiM.LewandowskiA. (2006). Ionic liquids as electrolytes. Electrochim. Acta51, 5567–5580.10.1016/j.electacta.2006.03.016
31
GaoJ.LoweM. A.KiyaY.AbrunaH. D. (2011). Effects of liquid electrolytes on the charge-discharge performance of rechargeable Li/S batteries: electrochemical and in-situ X-ray absorption spectroscopic studies. J. Phys. Chem. C115, 25132–25137.10.1021/jp207714c
32
GoodenoughJ. B.KimY. S. (2010). Challenges for rechargeable lithium batteries. Chem. Mater.22, 587–603.10.1021/cm901452z
33
HagenM.SchiffelsP.HammerM.DörflerS.TübkeJ.HoffmannM. J.et al (2013). In-situ Raman investigation of polysulfide formation in Li-S cells. J. Electrochem. Soc.160, A1205–A1214.10.1149/2.045308jes
34
HassounJ.ScrosatiB. (2010). A high performance polymer tin sulfur lithium-ion battery. Angew. Chem. Int. Ed.49, 2371–2374.10.1002/anie.200907324
35
HassounJ.ScrosatiB. (2012). Moving to a solid-state configuration: a valid approach to making Li-S batteries viable for practical applications. Adv. Mater.22, 5198–5201.10.1002/adma.201002584
36
HayashiA.OhtomoT.MizunoF.TadanagaK.TatsumisagoM. (2003). All solid-state Li/S batteries with highly conductive glass-ceramic electrolytes. Electrochem. commun.5, 701–705.10.1016/S1388-2481(03)00167-X
37
HebertD.UlamJ. (1962). Electric Dry cells and Storage Batteries. U.S Patent 3,043, 896.
38
JeddiK.GhaznaviM.ChenP. (2013a). A novel polymer electrolyte to improve the cycle life of high performance Li-sulfur batteries. J. Mater. Chem. A1, 2769–2772.10.1039/C3TA01169K
39
JeddiK.ZhaoY.ZhangY.KunarovA.ChenP. (2013b). Fabrication and characterization of and effective nanocomposite electrolyte membrane for high performance lithium/sulfur batteries. J. Electrochem. Soc.160, A1052–A1060.10.1149/2.010308jes
40
JengS. S.LimY. T.ChoiY. J.ChoG. B.KimK. W.AhnH. J.et al (2007). Electrochemical properties of lithium sulfur cells using PEO polymer electrolytes prepared under three different mixing conditions. J. Power Sources174, 745–750.10.1016/j.jpowsour.2007.06.108
41
JeonB. H.YeonJ. H.KimK. M.ChungI. J. (2002). Preparation and electrochemical properties of lithium-sulfur polymer batteries. J. Power Sources109, 89–97.10.1016/S0378-7753(02)00050-2
42
JiX.LeeK. T.NazarL. F. (2009). A highly ordered nanostructured carbon-sulfur cathode for lithium-sulfur batteries. Nat. Mater.8, 500–506.10.1038/nmat2460
43
JiX.NazarL. (2010). Advances in lithium-sulfur batteries. J. Mater. Chem.20, 9821–9826.10.1039/b925751a
44
KimS.JungY.ParkS. J. (2007). Effect of imidazoliumcation on cycle life characteristics of secondary lithium-sulfur cells using liquid electrolytes. Electrochim. Acta52, 2116–2122.10.1016/j.electacta.2006.08.028
45
KimY.SaiengaJ.MartinS. W. (2006). Anamalous ionic conductivity increase in Li2S+GeS2+GeO2 glass. J. Phys. Chem. B110, 16318–16325.10.1021/jp060670c
46
KobayashiT.ImadeY.ShishiharaD.HommaK.NagaoM.WatanabeR.et al (2008). All solid-state battery with sulphur electrode and thio-LISICON electrolyte. J. Power Sources182, 621–625.10.1016/j.jpowsour.2008.03.030
47
KobayashiT.WatanabeR.YokoiT.TatsumiT.KannoR.NagaoM.et al (2013). All-solid-state Li/sulfur batteries with mesoporous electrode and thio-LISICON solid electrolyte. J. Power Sources222, 237–242.10.1016/j.jpowsour.2012.08.041
48
KockV. R.YoungJ. H. (1977). The Electrochemical Society Fall Meeting. Atlanta, GA: Electrochemical Society.
49
KolosnitsynV. S.KarasevaE. V. (2008). Lithium-sulfur batteries: problems and solutions. Russ. J. Electrochem.44, 506–509.10.1134/S1023193508050029
50
KolosnitsynV. S.Kuz’minaE. V.KarasevaE. V.MichalovS. E. (2011). Impedance spectroscopy studies of changes in the properties of lithium sulfur cells in the course of cycling. Russ. J. Electrochem.47, 793–798.10.1134/S1023193511070093
51
LécuyerM.GaubicherJ.DeschampsM.LestriezB.BrousseT.GuyomardD. (2013). Structural changes of a Li/S rechargeable cell in lithium metal polymer technology. J. Power Sources241, 249–254.10.1016/j.jpowsour.2013.04.119
52
LeeJ. S.KimS. T.CaoR.ChoiN. S.LiuM.LeeK. T.et al (2011). Metal-air batteries with high energy density: Li-air versus Zn-air. Adv. Energy Mater.1, 34–50.10.1002/aenm.201000010
53
LiangC. D.DudneyN. J.HoweJ. Y. (2009). Hierarchically structured sulfur/carbon nanocomposite materials for high energy lithium battery. Chem. Mater.21, 4724–4730.10.1021/cm902050j
54
LinZ.LiuZ.FuW.DudneyN. J.LiangC. (2013). Phosphorous pentasulfide as a novel additive for high performance lithium-sulfur batteries. Adv. Funct. Mater.23, 1064–1069.10.1002/adfm.201200696
55
MachidaN.YonedaY.ShigematsuT. (2004). Mechano-chemical synthesis of lithium ion conducting materials in the system Li2O-Li2S-P2S5. J. Jpn. Soc. Powder Powder Metall.51, 2.10.2497/jjspm.51.91
56
ManthiramA.FuY.SuY. S. (2013). Challenges and prospects of lithium-sulfur batteries. Acc. Chem. Res.46, 1125–1134.10.1021/ar300179v
57
Manuel StephanA. (2006). Review on gel polymer electrolytes for lithium batteries. Eur. Polym. J.42, 21–42.10.1016/j.eurpolymj.2005.09.017
58
Manuel StephanA.KumarT. P.NathanM. A. K.AngulakshmiN. (2009). Chitin-incorporated poly(ethylene oxide)-based nanocomposite electrolytes for lithium batteries. J. Phys. Chem. B113, 1963–1972.10.1021/jp808640j
59
MarmorsteinD.YuT. H.StriebelK. A.McLarnonF. R.HouJ.CairnsE. J. (2000). Electrochemical performance of lithium/sulfur cells with three different polymer electrolytes. J. Power Sources89, 219–226.10.1016/S0378-7753(00)00432-8
60
MikhaylikY.KovalevI.ScholckR.KumaresanK.XuJ.AffinitoJ. (2010). High energy rechargeable Li-S cells for EV application: status, remaining problems and solutions. ECS Trans.25, 23–25.10.1149/1.3414001
61
MikhaylikY. V. (2008). Lithium Sulfur Electrochemical Cell Including Insoluble Nitrogen-Containing Compound. US 2008/0193835 A1
62
MikhaylikY. V.AkridgeJ. R. (2004). Polysulfide shuttle study in the Li/S battery system. J. Electrochem. Soc.151, A1969–A1976.10.1021/ja508982p
63
NagaoM.HayashiM.TatsumisagoT. (2011). Sulfur/carbon composite electrode for allsolid-state lithium/sulfur battery with Li2S-P2S5 solid electrolytes. Electrochim. Acta56, 6055–6059.10.1016/j.electacta.2011.04.084
64
NazarL. F.EversS. (2013). New approaches for high energy density lithium sulfur battery cathodes. Acc. Chem. Res.46, 1135–1143.10.1021/ar3001348
65
ParkJ.-W.UenoK.TachikawaN.DokkoK.WatanabeM. (2013). Ionic liquid electrolytes for lithium-sulfur batteries. J. Phys. Chem. C117, 20531–20541.10.1002/cssc.201402800
66
PeledE.SternbergY.GorensteinA.LaviY. (1989). Lithium-sulfur battery: evaluation of dioxolane-based electrolytes. J. Electrochem. Soc.136, 1621–1625.10.1149/1.2096981
67
QuartaroneE.MustarelliP. (2011). Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives. Chem. Soc. Rev.40, 2525–2540.10.1039/C0CS00081G
68
RauhR. D.AbrahamK. M.PearsonG. F.SuprenantJ. K.BrummerS. B. (1979). A lithium/dissolved sulfur battery with an organic electrolyte. J. Electrochem. Soc.126, 523–527.10.1149/1.2129079
69
RauhR. D.ShukerF. S.MarstonJ. M.BrummerS. B. (1977). Formation of lithium polysulfides in aprotic media. J. Inorg. Nucl. Chem.39, 1761–1766.10.1016/0022-1902(77)80198-X
70
RhuH. S.AhnH.-J.KimK.-W.AhnJ.-H.ChoK. K.NamT. H.et al (2006). Discharge behavior of lithium/sulfur with TEGDME based electrolytes at low temperature. J. Power Sources163, 201–206.10.1016/j.jpowsour.2005.12.061
71
SantoniF.TortoraP.AlessandriniF.PasseriniS. (2002). Proceedings of the Sixth European Space Power Conference (ESPC) 6–10 May 2002, Porto, Portugal. European Space Agency, 653–658.
72
SchalkwijkV. K.ScrosatiB. (2002). Advances in lithium-Ion Batteries. New York, NY: Kluwer Academic/Plenum.
73
ScrosatiB. (2011). Review of bottled lightning: super batteries, electric cars, and the new lithium economy Seth Fletcher. Nature473, 448–449.10.1038/473448a
74
ShimJ.StriebelK.CairnsE. J. (2002). The lithium/sulfur rechargeable cell: effects of electrode composition and solvent on cell performance. J. Electrochem. Soc.149, A1321–A1325.10.1149/1.1503076
75
ShinJ. H.CairnsE. J. (2008). N-methyl-N-butylpyrrolidiniumBis (trifluoromethanesulfonyl)imide-LiTFSI-tetraethylene glycol dimethyl ether mixture as a lithium cell electrolyte. J. Electrochem. Soc.155, A368–A373.10.1149/1.2869876
76
ShinJ. H.KimK. W.AhnH. J. (2002). Electrochemical properties and interfacial stability of(PEO)10LiCF3SO3-/TinO2n-1 composite polymer electrolytes forlithium/sulfur battery. Mater. Sci. Eng. B95, 148–156.10.1016/S0921-5107(02)00226-X
77
TachikawaN.YamauchiK.TakashimaE.ParkJ. W.DokkoK.WatanabeM. (2011). Reversibility of electrochemical reactions of sulfur supported on inverse opal carbon in glyme-Li salt molten complex electrolytes. Chem. Commun.47, 8157–8159.10.1039/C1CC12415C
78
TarasconJ.-M. (2001). Issues and challenges facing rechargeable Lithium batteries. Nature414, 359–367.10.1038/35104644
79
UenoK.ParkJ. W.YamazakiA.MandaiT.TachikawaN.DokkoK.et al (2013). Anionic effect as solvate ionic liquid electrolytes in rechargeable lithium/sulfur batteries. J. Phys. Chem. C117, 20509–20516.10.1021/jp407158y
80
WangJ.ChewS. Y.ZhaoZ. W.AshrafS.WexlerD.ChenJ.et al (2008). Sulfur-mesoporous carbon composites in conjunction with a novel ionic liquid electrolyte for lithium rechargeable batteries. Carbon N. Y.46, 229–235.10.1016/j.carbon.2007.11.007
81
WangL.ByonH. R. (2013). N-methyl-N-propylpiperidiniumbis (trifluoromethanesulfonyl)imide-based organic electrolyte for high performance lithiumesulfur batteries. J. Power Sources236, 207–214.10.1016/j.jpowsour.2013.02.068
82
WangW.WangY.HuangY.HuangC.YuZ.ZhangH.et al (2010). The electrochemical performance of Li-sulfur batteries with LiClO4, DOL/DME electrolyte. J. Appl. Electrochem.40, 321–326.10.1007/s10800-009-9978-z
83
WhittinghamM. S. (2004). Lithium batteries and cathode materials. Chem. Rev.104, 4271–4302.10.1021/cr020731c
84
XiaY.XinS.GuoY.-G.WanL.-J. (2013). Li-S batteries: electrochemistry, materials and prospects. Angew. Chem. Int. Ed. Engl.52, 13186–13200.10.1002/anie.201304762
85
XiongS.XieK.DiaoY.HongX. (2012). Properties of surface film on lithium anode with LiNO3 as lithium salt in electrolyte solution for Li/S batteries. Electrochim. Acta83, 78–86.10.1016/j.electacta.2012.07.118
86
YaminH.PeledE. (1983). Electrochemistry of a non-aqueous lithium/sulfur cells. J. Power Sources9, 281–287.10.1016/0378-7753(83)87029-3
87
YangY.YuG.ChaJ. J.WuH.VosgueritchianM.YaoY.et al (2011). Improving the performance of lithium-sulfur batteries by conductive polymer coating. ACS Nano5, 9187–9193.10.1021/nn203436j
88
YeonJ.-T.JangJ.-Y.HanJ.-G.ChoJ.LeeK. T.ChoiN.-S. (2012). Raman spectroscopic and X-ray diffraction studies of sulfur composite electrodes during discharge and charge. J. Electrochem. Soc.159, A1308–A1314.10.1149/2.080208jes
89
YuanL.YuanH.QiuX.ChenL.ZhuW. (2009). Improvement of cycle property of sulphur-coated multi-walled carbon nanotubes composite cathode for lithium sulphur batteries. J. Power Sources189, 1141–1146.10.1016/j.jpowsour.2008.12.149
90
YuanL. X. (2006). Improved dischargeability and reversibility of sulfur cathode in a novel ionic liquid electrolyte. Electrochem. Commun.8, 610–614.10.1016/j.elecom.2006.02.007
91
ZhangS. S. (2006). A review on electrolyte additives for lithium-ion batteries. J. Power Sources162, 1379–1394.10.1016/j.jpowsour.2006.07.074
92
ZhangS. S. (2013a). Liquid electrolyte lithium/sulfur battery: fundamental chemistry, problems and solutions. J. Power Sources231, 153–162.10.1016/j.jpowsour.2012.12.102
93
ZhangS. S. (2013b). A concept for making PEO based composite gel polymer electrolyte lithium/sulfur battery. J. Electrochem. Soc.160, A1421–A1424.10.1149/2.058309jes
94
ZhangS. S. (2013c). New insight into liquid electrolyte of rechargeable lithium/sulfur battery. Electrochim. Acta97, 226–230.10.1016/j.electacta.2013.02.122
95
ZhangS. S.ReadJ. A. (2012). A new direction for the performance improved of rechargeable lithium/sulfur batteries. J. Power Sources200, 77–82.10.1016/j.jpowsour.2011.10.076
96
ZhangS. S.TranD. T. (2013d). How a gel polymer electrolyte affects performance of lithium/sulfur batteries. Electrochim. Acta114, 296–302.10.1016/j.electacta.2013.10.069
Summary
Keywords
lithium–sulfur batteries, poly sulfides, polymer electrolytes, charge–discharge studies, interfacial properties, ionic liquids, super ionic conductors, electrolyte additives
Citation
Angulakshmi N and Stephan AM (2015) Efficient Electrolytes for Lithium–Sulfur Batteries. Front. Energy Res. 3:17. doi: 10.3389/fenrg.2015.00017
Received
15 July 2014
Accepted
26 March 2015
Published
21 May 2015
Volume
3 - 2015
Edited by
Mariusz Walkowiak, Institute of Non-Ferrous Metals, Poland
Reviewed by
Xiqing Wang, Nanotek Instruments Inc., USA; Jijeesh Ravi Nair, Politecnico di Torino, Italy; Mariusz Walkowiak, Institute of Non-Ferrous Metals, Poland
Copyright
© 2015 Angulakshmi and Stephan.
This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) or licensor are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
*Correspondence: Arul Manuel Stephan, Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi 630 006, India e-mail: arulmanuel@gmail.com; amstephan@cecri.res.in
This article was submitted to Energy Storage, a section of the journal Frontiers in Energy Research.
Disclaimer
All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors and the reviewers. Any product that may be evaluated in this article or claim that may be made by its manufacturer is not guaranteed or endorsed by the publisher.