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Journal ofMaterials Chemistry A
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aResearch Institute of Chemical Defen
[email protected]; Fax: +86-010-6bSchool of Materials Science and Engineeri
Beijing, Beijing 100083, China
Cite this: DOI: 10.1039/c3ta13782a
Received 21st September 2013Accepted 16th October 2013
DOI: 10.1039/c3ta13782a
www.rsc.org/MaterialsA
This journal is © The Royal Society of
A new lithium secondary battery system: the sulfur/lithium-ion battery
Bochao Duan,ab Weikun Wang,*a Anbang Wang,a Zhongbao Yu,a Hailei Zhaob
and Yusheng Yangab
A new lithium secondary battery system, the sulfur/lithium-ion battery, has been constructed by employing
a lithium/Sn–C composite anode, a carbyne polysulfide cathode, and a carbonic ester electrolyte.
Compared with a lithium/sulfur battery, the use of a lithium/Sn–C composite anode ensures the high
safety of the new battery. Meanwhile, the novel battery possesses high-energy characteristics. It delivers
a reversible capacity of 500 mA h g�1 after 50 cycles at a current density of 200 mA g�1, which ensures
a stable specific energy of 410 W h kg�1. As all of the materials required for the new battery are readily
available and low-cost, and the techniques are simple, this new battery has a strong potential for use in
industry. Furthermore, there is considerable room for improvement of the energy density of the sulfur/
lithium-ion battery, and the new battery is one of the most promising candidates for the next generation
of high-performance rechargeable batteries.
1. Introduction
There has been a steady increase in the demand for powersources for portable electronic devices and electric vehicles, andthe common commercially-available lithium-ion batteries(LIBs) can no longer meet the requirements of modern societydue to their low energy density (150W h kg�1).1–3 In recent years,although a series of high-capacity anodes for LIBs (such as tin-based anodes4,5 and silicon-based anodes6,7) have been devel-oped, the cathodes (those based on transition metal oxides andphosphates) have not improved much in capacity due toinherent characteristics,8–10 which restrict signicant improve-ment of LIB energy density. In addition, any attempt to improveoutput voltage to increase the LIB energy density will pose asafety hazard if standard electrolytes are still used.11 Lithium/sulfur (Li/S) batteries possess great potential as advancedrechargeable batteries due to their high theoretical energydensity (2600 W h kg�1), environmental friendliness and richnatural reserves.12–14 Although sulfur-based cathodes presentproblems with respect to low electronic conductivity and thedissolution of lithium polysuldes in the electrolyte, manyimportant technological breakthroughs have taken place inrecent years, and sulfur-based cathodes with a high capacityand excellent cycle performance have been developed.15–20
However, the application of metal lithium anodes limits theindustrial development of Li/S batteries, because the Li dendrite
se, Beijing 100191, China. E-mail:
6705840; Tel: +86-010-66705840
ng, University of Science and Technology
Chemistry 2014
generated during long-term cycling oen leads to short cir-cuiting and even catastrophic failure.21,22 Therefore, we proposethat if a lithium secondary battery can be constructed byemploying a high-capacity intercalation anode and a sulfur-based cathode, the novel battery will possess both high-safetyand high-energy characteristics. On the basis of its workingmechanism, we have named the new battery system sulfur/lithium-ion batteries (S/LIBs). A diagrammatic representation ofthe sulfur/lithium-ion battery is shown in Fig. 1. We havecalculated and compared the theoretical specic energies ofsome lithium secondary batteries using the equation:
E ¼ Cc � Ca
Cc þ Ca
ðVc � VaÞ;
where C indicates the capacity and V indicates the averagepotential versus Li/Li+. The subscripts c and a represent thecathode and anode respectively. As shown in Table 1, the S/LIBshave a signicant advantage with respect to energy density.With the intercalation anode ensuring high safety, the S/LIB isone of the most promising candidates for the next generation ofhigh-performance rechargeable batteries.
Based on a similar concept, the new battery prototype hasbeen the subject of preliminary study by several researchgroups. Cui and co-workers,23 Aurbach and co-workers24 andScrosati and co-workers25 have constructed the new batterysystem by employing a silicon-based anode, a sulfur-basedcathode, and an ether electrolyte (which is commonly used inLi/S batteries), respectively. A method of introducing lithium tothe system is to use the prelithiated anode or Li2S cathode.Although the full cells could yield an initial specic energy of ca.600 W h kg�1 (based on the sulfur in the cathode), their cycle
J. Mater. Chem. A
Fig. 1 Diagrammatic representation of the sulfur/lithium-ion battery.
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performances were not good. This is because there is a limitedsupply of Li ions in full cells, but both of the electrodesconsume Li ions irreversibly during cycles, which severelyreduces the cycle life. Guo and co-workers11 used an ionic liquidelectrolyte and Hassoun and Scrosati26 used a gel-type polymermembrane electrolyte instead of an ether electrolyte to build thenew battery system, and both got a better cycle performance.Nonetheless, the technology for the new electrolytes is not quitefully developed and it is far from being production-ready.
Herein, we constructed a sulfur/lithium-ion battery byemploying a lithium/Sn–C composite anode, a carbyne poly-sulde cathode, and a carbonic ester electrolyte (which iscommonly used in LIBs). Most sulfur-based cathodes are onlysuitable for ether electrolytes, but the dissolution of lithiumpolysuldes in this electrolyte is inevitable, which results in apoor electrochemical performance.27–29 However, the carbynepolysulde prepared by us displays excellent cycle characteris-tics and a high reversible capacity in the carbonic ester elec-trolyte. In addition, as the Sn–C anode has ideal electrochemical
Table 1 Theoretical specific energies for some lithium secondary batter
Cathode/anodeCathode capacity(mA h g�1)
Anode c(mA h g
LiCoO2/graphite 155 372LiFePO4/graphite 170 372LiCoO2/silicon 155 4212LiFePO4/silicon 170 4212S/silicon 1675 4212S/tin 1675 994
J. Mater. Chem. A
properties and the carbonic ester electrolyte is technically well-developed, we have the basis to build a new outstanding batterysystem. Moreover, we introduce lithium into the system byusing a lithium/Sn–C composite anode, which is more easilymanipulated than a prelithiated anode, and conducive toreducing the initial irreversible capacity of the electrodes. Theas-assembled sulfur/lithium-ion battery exhibits superior elec-trochemical performance in terms of energy density and cyclestability.
2. Experimental2.1. Synthesis of carbyne polysulde cathode materials
Carbyne polysulde was prepared30 by co-heating a carbyneanalogue and elemental sulfur. The carbyne analogue wasprepared by dehydrochlorination of polyvinylidene chloride(PVDC) in a highly alkaline solution. Firstly, 10 g of PVDC wasdissolved in 200 ml of tetrahydrofuran (THF), and 800 ml of asaturated solution of potassium hydroxide (KOH) in ethanol
ies
apacity�1)
Voltage difference(V)
Specic energy(W h kg�1)
3.75 4103.3 3853.4 5082.95 4821.75 20941.9 1185
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and THF (1 : 1 v/v) was made. The two solutions were mixedaccompanied by mechanical agitation for 2 h at ambienttemperature. The black red product was the carbyne analogue,which was collected by ltration and washed to neutral withdistilled water and acetone several times. Carbon powder wasobtained aer drying under vacuum (0.1 MPa) at 60 �C for 24 h.The carbyne analogue was then mixed with the sublimed sulfur(the ratio of C to S atoms was about 1 : 5) by ball milling for 4 hto obtain uniformity. Finally, the mixture was heated at 350 �Cfor 3 h in a tube furnace under N2 atmosphere.
2.2. Preparation of the Sn–C anode material
The Sn–C anode material is a novel nano-Sn–mesoporouscarbon parasitic composite.31 The mesoporous carbon withabundant pores (30–70 nm in diameter) was prepared usingsucrose as a precursor and commercially available CaCO3
nanoparticles as the template. The prepared mesoporouscarbon was impregnated into a saturated solution ofSnCl2$2H2O at vacuum state with stirring for 1 h. The mixturewas then centrifuged and dried at 60 �C for 24 h in a vacuumoven. The obtained black powder was annealed in a tubefurnace under Ar (95 vol%)/H2 (5 vol%) atmosphere at 320 �Cfor 16 h.
2.3. Material characterization
The characterizations of carbyne polysulde were measured byelemental analysis (Vario EL III elemental analyzer, Elementar,Germany), fourier-transform infrared spectroscopy (FTIR,NICOLET6700), Raman spectra (Raman, Renishew-1000, thewavelength of the lamp-house is 632.8 nm), X-ray diffraction(XRD, Rigaku RINT2400 with Cu Ka radiation l ¼ 1.5418 A),scanning electron microscope (SEM, JEOL JSM 6360) andtransmission electron microscopy (TEM, FEI, Tecnai G2 F30),respectively.
The Sn–C anode material was characterized by inductively-coupled plasma atomic emission spectrophotometry (ICP-AES;Seiko Instruments, Chiba, Japan) and transmission electronmicroscopy (TEM, FEI, Tecnai G2 F30).
2.4. Electrode preparation and electrochemical tests
When preparing the carbyne polysulde cathode, carbyne pol-ysulde was mixed with acetylene black and a polytetrauoro-ethylene (PTFE) binder in a weight ratio of 70 : 20 : 10. Ethanolwas poured into the mixture as a dispersant, and the mixturewas then ground to a homogenous paste. The resultingslurry was then uniformly pasted onto aluminum foil and driedin a vacuum oven at 60 �C for 24 h. The Sn–C anode wasprepared by mixing the active material, acetylene black, and thePVDF binder at a weight ratio of 80 : 10 : 10 in the solvent N-methyl pyrrolidinone (NMP). The resulting slurry was thenuniformly pasted onto copper foil and dried in a vacuum oven at90 �C for 24 h. The electrolyte we used was a carbonic esterelectrolyte, 1 M LiPF6 dissolved in a mixture of ethylenecarbonate (EC) and diethyl carbonate (DEC) (in a volume ratio of1 : 1), and a Celgard 2320 microporous polypropylene lm wasused as a separator. The single-electrode electrochemical
This journal is © The Royal Society of Chemistry 2014
measurements were performed with R2032 coin-type cells, usinglithium foil as a counter electrode. The half-cells were assembledin an Ar-lled glove box (H2O < 0.5 ppm, O2 < 0.5 ppm).
The lithium/Sn–C composite anode was made by pressing aknown amount of thin lithium foil tightly on the surface of anas-prepared Sn–C anode in the glove box lled with argon gas.The full-cells were assembled as reported for the half-cells,except that the lithium metal foil was replaced by the lithium/Sn–C composite anode.
The half-cells for testing the Sn–C anode were galvanostati-cally discharged and charged in the voltage range of 0.01–1.5 Vvs. (Li/Li+) with the LANDCT-2001A testing system, and cyclicvoltammetry (CV) measurements were performed using anelectrochemical workstation (CHI 660C) at a scan rate of 0.1 mVs�1 between 0.01 and 2 V. The half-cells for testing the carbynepolysulde cathode and the full-cells were galvanostaticallydischarged and charged in the voltage range of 1–3 vs. (Li/Li+)/V,and the CV measurements were performed at a scan rate of 0.1mV s�1 between 1 and 3 V.
3. Results and discussion3.1. The cathode
Carbyne polysulde is a novel organic sulde, rather than asimple mixture of carbon and elemental sulfur.30 The structureof carbyne polysulde and its synthetic route are depicted inScheme 1. Carbyne polysulde has a unique and stable struc-ture consisting of a conducting sp2 hybrid carbon skeleton andenergy-storing sulfur side chains (Sm, 1 # m # 4). The Sm couldparticipate adequately in electrochemical reactions withoutdissolution, which ensured the excellent cycle performance ofcarbyne polysulde. In addition, the good conductivity meantthat the active sulfur could deliver a high reversible capacity.
For a comprehensive and objective description, character-ization of carbyne polysulde was carried out and the resultsare shown in Fig. 2. Fig. 2(a) shows the FTIR spectrum ofcarbyne polysulde. The characteristic peak at 1404 cm�1 isassigned to C]C bonds, which correspond to the sp2 hybridcarbon skeleton, and a peak assigned to the C–S bonds (618cm�1) is also visible.30,32 Raman spectroscopy was furtheremployed to conrm the structure of carbyne polysulde. Asshown in Fig. 2(b), there are four peaks appearing at 470, 789,1440 and 1548 cm�1.33,34 The peak at 470 cm�1 can be attrib-uted to the S–S bonds and the peak at 789 cm�1 can beattributed to the C–S bonds. It has been previously reportedthat peaks at 1580 cm�1 and 1360 cm�1 can be attributed to thecarbon vibration of graphite crystallites at the centers and edges,which were called the G and D vibration modes, respectively.30
The peaks shi to 1548 cm�1 and 1440 cm�1, respectively, whichsuggests that the carbon vibration is inuenced by the S atoms,probably resulting from the chaining of C with S. Taken incombination with the FTIR data, it can be concluded that smallsulfur molecules, the Sm (1 # m # 4), have linked to the carbonmatrix via sp2 hybridization (C]C bonds) in carbyne polysulde.For further characterization, elemental analysis, XRD, SEM andTEM were conducted on carbyne polysulde. According toelemental analysis, the organic sulde contains approximately
J. Mater. Chem. A
Scheme 1 The structure of carbyne polysulfide and its synthetic route.
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43.4 wt% C, 54.1 wt% S, 0.4 wt% H and 2.1 wt% O. The presenceof elemental oxygen indicates that the carbyne moieties aresufficiently active to interact with oxygen-containing functionalgroups. XRD patterns of elemental sulfur and carbyne polysuldeare shown in Fig. 2(c). Usually, elemental sulfur exists in acrystalline state with an orthorhombic structure (S8). Theas-prepared carbyne polysulde only shows a broad peak at ca.24�, indicating the formation of an amorphous phase, whichsuggests that it is not elemental sulfur but the Sm (1#m# 4) thatbind to the carbon skeleton in carbyne polysulde.35,36 Fig. 2(d)shows the morphology of carbyne polysulde. The SEM imageshows that the carbyne analogue has a porous structure withabundant pores ranging in diameter size from 80 nm to 300 nm.The TEM image (inset) of carbyne polysulde clearly reveals themicrostructure on a nanoscale. It also indicates that carbynepolysulde is in an amorphous state, and somemesopores with apore size less than 50 nm can be observed. Moreover, we testedthe electronic conductivity of carbyne polysulde by using thefour-point probe method, and the value was 2.5 � 10�4 S cm�1,which is much better than that of elemental sulfur (5 � 10�30 Scm�1). We also investigated the electrochemical performance ofcarbyne polysulde and the results are shown in Fig. 2(e) and (f).In a carbonic ester electrolyte, the capacity of carbyne polysuldeis high and fades very slowly with cycling (with the exception of
Fig. 2 FTIR spectrum (a) and Raman spectrum (b) for carbyne polysulfideimage of carbyne polysulfide (TEM image, inset). Electrochemical perfocharge profile, inset), (f) cyclic voltammogram.
J. Mater. Chem. A
the rst cycle). It delivers a reversible capacity of 520 mA h g�1
aer 50 cycles at a current density of 200 mA g�1, demonstratinga capacity retention of 96% based on the 2nd cycle dischargecapacity. The initial greater irreversible capacity could be mainlydue to two reasons. On one hand, the electrochemically activesurface groups in carbyne polysulde consume a part of the Liions, and on the other hand, a little inactivated Li2S is formed. Inaddition, the carbyne polysulde has only one sloping dischargeprole with an average voltage of 1.8V in carbonic ester electro-lyte, which is characteristic of a single-phase reaction, meaningthat there is no dissolution and following deposition occurringduring its discharge process.37 This is the main reason for itsoutstanding cycle performance. Some other sulfur-basedmaterials showed similar electrochemical characteristics,which were attributed to the unique characteristics of smallsulfur molecules, the Sm (1 # m # 4), by Guo et al.38 Carbynepolysulde should have a similar electrochemical mecha-nism: the Sm (1 # m # 4) can react directly with Li+ to formLi2S (and Li2S2) without dissolution in the electrolyte,meaning that the discharge–charge process here is in a solidphase and the structure of the electrodes remainsunchanged. However, as a result of this, the diffusion resis-tance of the Li ions on the carbyne polysulde/electrolyteinterface increases compared with that on the S8/electrolyte
, (c) XRD patterns of elemental sulfur and carbyne polysulfide, (d) SEMrmance of carbyne polysulfide: (e) cycling performance (discharge–
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interface, which leads to high electrochemical polarizationand a low discharge voltage. In addition, the effect ofchemical bonding between C and S atoms may decrease theGibbs free energy of its electrochemical reaction, leading to alow discharge voltage.
3.2. The anode
The Sn–C anode material is a novel nano-Sn/mesoporouscarbon parasitic composite.31 In the composite, as shown inFig. 3, tin nanoparticles with diameters of about 10 to 30 nm aregenerated and distributed uniformly in the pores of meso-porous carbon, and the weight ratio of Sn : C is about 47 : 53(tested by ICP-AES). As an anode material, this compositedisplays a high reversible capacity of 500 mA h g�1 aer50 cycles with a current density of 200 mA g�1, and its potentialplateau is at ca. 0.2 V. The special architecture of the nano-Sn/mesoporous carbon parasitic composite plays an important rolein ensuring its remarkable electrochemical performance.Firstly, the sufficiently small tin nanoparticles are generated insitu and distributed uniformly into the pores of the carbonmaterial, so that the nanoscale particles can mitigate the effectof volume change and shorten the diffusion length for lithiumions. Secondly, the mesoporous carbon buffers and provides anadequate void space to accommodate the large volume changecaused by the Sn active component, preventing electricalisolation aer a prolonged cycle time.
3.3. The sulfur/lithium-ion battery
The data above conrm that the Sn–C anode and the carbynepolysulde cathode may indeed be suitable electrodes for the
Fig. 3 (a) TEM observation of the Sn–C anode material (selected area eSn–C anode material: (b) cycling performance, (c) cyclic voltammogram
This journal is © The Royal Society of Chemistry 2014
development of sulfur/lithium-ion batteries. A further challengeis the introduction of lithium-ions into the system. Herein, wepressed a given amount of lithium foil onto the surface of an as-prepared Sn–C anode to form a composite anode in order tofabricate the full-cell with the carbyne polysulde cathode. Thisway of introducing lithium into the system allows greatermanipulation than using a prelithiated anode, and is conduciveto reducing the initial irreversible capacity of the electrodes.39
The mass ratio of lithium foil, the carbyne polysulde in thecathode and the Sn–C material in the anode is 1 : 4 : 2, whichensures that the capacity of the cathode is in excess of that ofthe anode, and that the amount of lithium-ions in the system issufficient (the amount of lithium is equivalent to the capacity ofthe cathode aer deducting the initial irreversible capacities ofboth electrodes). Aer the rst ve discharge–charge cycles, thefull-cell was disassembled in a glove box lled with argon gasand there was no thin lithium foil residue found on the surfaceof the Sn–C anode. This suggested that the lithium foil wascompletely changed into lithium-ions and that the batterysystem shied to the working mode of a lithium-ion battery.The lithium foil is therefore fully utilized and presents little riskin terms of cell safety. The electrochemical process of the newbattery system is as follows:
2Li + S / Li2S (1)
2.2Li2S + Sn 4 2.2S + Li4.4Sn (2)
The electrochemical performance of the sulfur/lithium-ionbattery was investigated and is shown in Fig. 4(a) and (b). It candeliver a high reversible charge capacity of 500 mA h g�1 aer 50cycles at a current density of 200 mA g�1, and the coulombic
lectron diffraction pattern, inset). Electrochemical performance of the(discharge–charge profile, inset).
J. Mater. Chem. A
Fig. 4 Electrochemical performance of the sulfur/lithium-ion battery: (a) cyclic voltammogram, (b) cycling performance with excess lithium inthe system (rate performance and discharge–charge profiles, inset), (c) cycling performance with a moderate amount of lithium in the system(discharge–charge profiles, inset).
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efficiency always approached �100% aer the initial cycle. It canalso be seen that the sulfur/lithium-ion battery outputs onedischarge plateau at about 1.6 V, which is consistent with thecombination of the carbyne polysulde (single plateau at 1.8 V)and the Sn–C composite (single plateau at 0.2 V) outputs. Basedon these data, we can obtain a battery system that has a stablespecic energy of 410W h kg�1 (based on the carbyne polysuldein the cathode) aer 50 cycles, which ismuch higher than what isobserved in similar systems that have been previously repor-ted.11,23–26 Furthermore, the sulfur/lithium-ion battery exhibits agood rate-capability, with a reversible capacity as high as 350 mAh g�1 being achieved when it is cycled at a 1000 mA g�1 currentrate. This is mainly due to the fact that both the anode andcathode materials have a good rate-capability in the carbonicester electrolyte.30,31 We also controlled the mass ratio of lithiumfoil, the carbyne polysulde in the cathode and the Sn–Cmaterialin the anode to give a 1 : 4 : 3 ratio, to ensure that optimumamounts of each are present. The electrochemical performanceof the full-cell is shown in Fig. 4(c). It can be seen that in thiscontext the capacity of the system showed a continuous decay,albeit by only a minimal amount. This might be due to the factthat when the Li-ions are nite in the system, continuousconsumption of lithium-ions by the two electrodes cannot besupported, which severely limits the cycle life of the full-cell.However, if we were to use an excess amount of the cathode toconstruct the new battery system in order to improve the cyclingperformance, it would essentially add extra weight to the battery,which would lower the specic energy. Therefore, the use of good
J. Mater. Chem. A
electrode materials is the basis on which to build a newoutstanding battery system.
In summary, we successfully constructed a sulfur/lithium-ion battery and the remarkable electrochemical performance ofthe new battery could be attributed to the combination of twofeatures. Firstly, both of the electrodes (the Sn–C anode and thecarbyne polysulde cathode) possess excellent electrochemicalproperties and the carbonic ester electrolyte shows goodcompatibility with them. Secondly, the safety of the new batterycould be signicantly improved by using a lithium/Sn–Ccomposite anode instead of a metal lithium anode. In addition,as all of the materials for the new battery are readily availableand low-cost, and the techniques used are simple, the newbattery has good potential for industrial use. Moreover, webelieve that there is considerable room for improvement withrespect to the energy density of sulfur/lithium-ion batteries. If,as suggested by previous reports, the capacity of the cathode canreach 800 mA h g�1 (ref. 17) and the capacity of the anode canreach 2500 mA h g�1,7 then using these to construct the newbattery will result in an impressive specic energy of 880 W hkg�1 (Vc ¼ 1.8 V, Va ¼ 0.3 V, according to the references).
4. Conclusion
A new lithium secondary battery system, which we have namedthe sulfur/lithium-ion battery, is successfully constructed byemploying a lithium/Sn–C composite anode, a carbyne polysuldecathode, and a carbonic ester electrolyte. The novel battery
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possesses both high-energy and high-safety characteristics. Itdelivers a reversible charge capacity of 500mA h g�1 aer 50 cyclesat a current density of 200 mA g�1, which gives a stable specicenergy of 410 W h kg�1. The use of a lithium/Sn–C compositeanode is effective in avoiding the intrinsic safety issues associatedwith the use of metallic lithium anodes in Li/S batteries. Inaddition, as the materials for the new battery are readily availableand low-cost, and the techniques used are simple, the new batteryhas good potential for industrial use. Furthermore, immensepotential exists with respect to improving the energy density ofsulfur/lithium-ion batteries, warranting extensive further work tooptimize this promising new battery system.
Acknowledgements
The authors would like to acknowledge nancial supportprovided by the 863 Program of the National High TechnologyResearch Development Project of China (no. 2011AA11A256, no.2012AA052202).
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