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Synthesis of Ionic Dendrimers and Their Potential Use as
Electrolytes for Lithium–Sulfur Batteries
Tim Lebherz, Dianne L. Weldin, Andreas Hintennach, and Michael R. Buchmeiser*
A series of ionic dendrimers is synthesized and used as conducting salt in
carbonate-based electrolytes for Li/S-cells. The resulting electrolytes display
increasing viscosity with increasing chain length of the side chains, both in
the first- and second-generation dendrimers. Higher conductivity is observed
for the first-generation dendrimers as compared to the second-generation
ones. While all cells show high cycle stability, the differences in dendrimer
structure also influence the electrochemical behavior of the Li–S cells. Thus,
discharge capacities of the corresponding Li–S cells correlate both with the
viscosity and the conductivity of the electrolytes. The best electrolyte system
is obtained with a first-generation dendrimer having a short side chain, D1-1,
having the lowest viscosity and the highest conductivity, which delivers dis-
charge capacities of 1150 mAh gsulfur−1 @ 0.5 C and 780 mAh gsulfur−1 @ 1 C.
1. Introduction
Because of a high specific capacity of 1672 mAh g−1 and an
energy density of 2600 Wh kg−1,[1,2] lithium–sulfur (Li–S) bat-
teries show attractive properties for commercial applications,
for example, for the automotive sector. In addition, sulfur is
highly abundant, non-toxic, and easily available. Also, in com-
parison with conventional lithium–ion batteries, higher energy
densities can be reached for Li–S batteries.[3,4] However, some
issues that are still not fully resolved are related to the insulating
nature of sulfur and the polysulfide shuttle. Polysulfides, which
are formed as intermediates during the reduction of elemental
sulfur, S8, to Li2S, are well soluble in common ether-based
electrolytes.[1] The dissolved polysulfides (Li2Sx) are finally
T. Lebherz, Dr. D. L. Weldin, Prof. M. R. Buchmeiser
Institute of Polymer Chemistry
University of Stuttgart
70569 Stuttgart, Germany
E-mail: michael.buchmeiser@ipoc.uni-stuttgart.de
T. Lebherz, Prof. A. Hintennach
Daimler AG, RD/EBT, HPC G012-BB
71034 Böblingen, Germany
Prof. M. R. Buchmeiser
German Institutes of Textile and Fiber Research (DITF) Denkendorf
73770 Denkendorf, Germany
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/macp.201900436.
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim. This is an open access article under the terms of the Creative
Commons Attribution License, which permits use, distribution and re-
production in any medium, provided the original work is properly cited.
DOI: 10.1002/macp.201900436
Macromol. Chem. Phys. 2019, 1900436 1900436 (1 of 6) © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
reduced to insoluble Li2S at the lithium
anode forming a passivating layer. This
results in poor cycle stability due to loss
of active material at the cathode side and a
passive layer on the anode side. One solu-
tion to address this issue is the usage of a
sulfur-poly(acrylonitrile) composite (SPAN)
as active material. The SPAN composite is
synthesized by the reaction of elemental
sulfur with poly(acrylonitrile) at tem-
peratures >300 °C. The reaction was first
described by Wang et. al. and involves the
dehydrogenation of the poly(acrylonitrile)
backbone by sulfur and its concomitant
integration into the polymeric structure up
to 55 wt%.[5–7] The result is a condensed,
polyaromatic backbone with covalently
bound sulfur units. We already showed that
the structure mainly contains phenylogous and vinylogous thio-
amides, which act as anchor groups for the sulfur species during
the reduction and oxidation of the SPAN-based cathode.[8–10]
There are a number of differences between the SPAN material
and materials based on elemental sulfur. The composite mate-
rial shows a high addressability of sulfur (up to 90%)[7] as well
as a high C-rate capability. Also, since there are no long chained
polysulfides, the material is compatible with carbonate-based
electrolytes.[11–14] However, SPAN has a comparably low sulfur
content of 40–55 wt%. One approach to address this drawback
is the use of electrochemically active additives, that is, catholytes
in the electrolyte like dimethyl trisulfide. The resulting hybrid
system delivers discharge capacities up to 4 mAh cm−².[15]
Besides the electrode material, separator, binder, and cell
configurations, electrolytes play a pivotal role in cell design[16]
and are also relevant in terms of safety. In the past, ionic liquids
(ILs) have been used as additives or solvents for Li–S batteries
to both suppress the polysulfide shuttle mechanism and lower
the vapor pressure of the electrolyte to increase safety.[17–20]
So far, the IL has been used as solvent or additive. Here, we
report on the use of ionic dendrimers as conductive salts as a
new approach to introduce ionic liquid-type compounds[21] into
the electrolyte. Ionic dendrimers can address two issues of Li–S
batteries. On the one hand, ionic dendrimers lower the vapor
pressure of the liquid electrolyte system and increase the safety
of the battery. On the other hand, the multivalent, branched cat-
ions should be able to avoid or suppress the poly(sulfide) shuttle
mechanism by forming a 3D network with the polysulfide
anions. Thus, the reversible formation of large ion clusters pre-
vents the passivating of the lithium anode by formation of Li2S.
Synthetic routes to dendrimers have been described by Vögtle
et. al.,[22] de Brabander-van den Berg et al.,[23] Moors et. al.,[24]
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Meier et al.[25] and Wörner et. al.[26] Preferably, acrylonitrile is
added to amines to build up new generations and enlarge the
dendritic structure. By this synthetic route, higher generations
can be easily built up and modified. It was therefore chosen
to synthesize different ionic dendrimers, which were used as
conducting salt in electrolytes for SPAN-based Li/S-cells.
2. Results and Discussion
The synthesis of the dendrimers is outlined in Figure S1,
Supporting Information. Tris(2-aminoethyl)amine was used as
starting material for all ionic dendrimers. It was either reacted
with formic acid and formaldehyde in an Eschweiler–Clarke
reaction to achieve the core molecule for the first-generation
dendrimers or reacted with acrylonitrile in a Michael-addition
followed by hydrogenation[23,26] and methylation[27] to achieve
the core molecule for the second-generation dendrimers. The
alkylating agents necessary for quaternization were prepared
via a Finkelstein reaction using ethylene glycol-based alkyl chlo-
rides/tosylates as starting material (Figure S2, Supporting Infor-
mation). Different ethylene glycol-based alkylating agents were
used to vary the chain length of the side chains of the dendrimers
and synthesize ionic dendrimers with different size. Quaterniza-
tion of the amines in the core molecules was carried out with an
excess of alkylating agents in N,N-dimethylformamide (DMF).
Once the iodide salt was obtained, it was immediately dissolved
in water and reacted with LiTFSI for anion metathesis. Due to
the hydrophobic properties of the bis(trifluoromethylsulfonyl)
imide (TFSI) salts, the ionic dendrimers precipitated from the
aqueous solution. Interestingly, the core nitrogen in all dendritic
structure remained unalkylated. As a result, all first-generation
ionic dendrimers carried three positive charges while all second-
generation dendrimers carried nine positive charges as evi-
denced by NMR- and mass spectroscopy as well as by elemental
analysis. After drying over molecular sieve and removal of the
solvent in vacuo (10−8 mbar), the ionic dendrimers were used as
conducting salt in electrolytes. An overview over the synthesized
dendrimers is given in Figure 1.
Since SPAN-based cathodes are compatible with carbonate-
based electrolytes,[12] a mixture of ethylene carbonate and
dimethyl carbonate (1:1, v/v) was used as solvent. The ionic
dendrimers were dissolved in the solvent mixture to achieve a
Figure 1. Structures of the first (D1-1 to D1-7) and second (D2-1 to D2-7) generation ionic dendrimers.
Macromol. Chem. Phys. 2019, 1900436 1900436 (2 of 6)
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[TFSI−] concentration of 1 mol L−1. All cells were cycled between
1 and 3 V (versus Li/Li+) with an initial formation cycle at C/30
followed by cycles with 0.5 C. The results of the cycle tests of
the cells with electrolytes based on ionic dendrimers of the first-
and second-generation are shown in Figure 2. Cells with D1-1
to D1-3 based electrolytes showed no significant difference in
electrochemistry. All cells displayed high cycle stability (<10%
capacity loss over 100 cycles) and discharge capacities in the
range of 1100–1150 mAh gsulfur−1 without any indication of a pol-
ysulfide shuttle. Only the cell based on the ionic dendrimer D1-7
showed a significant lower discharge capacity than the all other
first-generation ionic dendrimer-based cells. In order to iden-
tify even subtle differences in electrochemistry, cells containing
D1-1, D1-3, or D1-5 in the electrolyte were also cycled at 1 C. As
expected, discharge capacities were lower than in the cycle test
run at 0.5; nonetheless, cycle stability was still high and almost
no capacity fading was observed during 100 cycles (Figure 3).
This confirms the proposed capability of the dendritic electrolyte
to suppress the poly(sulfide) shuttle according to Figure 4. Differ-
ences in discharge capacity between cells based on D1-1, D1-3, or
D1-5 correlate with the structure of the ionic dendrimers in the
electrolyte. Thus, discharge capacities decreased with increasing
chain length of the rest R of the ionic dendrimer. In line with
that, cells based on ionic dendrimers of the second generation
showed pronounced differences in electrochemistry already at
discharge capacities of 0.5 C. Discharge capacities also decreased
with increasing length of the ethylene glycol side chains in the
dendritic structure. At 0.5 C, even a cell based on dendrimer
D2-1, which is the second-generation ionic dendrimer with the
shortest side chain, could not outperform any of the cells based
on ionic dendrimers of the first generation. Clearly, both the size
of the dendritic molecules as such and the length of the ethylene
glycols in the side chain do affect the electrochemical behavior
of the corresponding Li–S cells. We therefore measured both the
conductivity and viscosity of the electrolytes (Table 1) to deter-
mine their role in the electrochemical performance of the cells.
The conductivity of electrolytes based on first-generation ionic
dendrimers was higher (1.76–2.11 mS cm−1) than the one of
electrolytes based on the second-generation ionic dendrimers
(1.45–1.54 mS cm−1). The viscosity of the electrolytes strongly
also correlated with the structure of the ionic dendrimers for
both the first- and second-generation ionic dendrimers. While,
as expected, the increase in viscosity from the first- to the second
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Figure 2. Cycle test (1–3 V versus Li/Li+) with 0.5 C of SPAN-based cells with electrolytes based on dendrimers D1-1 to D1-7 and D2-1 to D2-7.

generation dendrimers was only marginal for a given R-group,
viscosity increased substantially with increasing chain length in
the side chains R. Accordingly, the electrolyte based on the ionic
dendrimer D1-1 had the lowest (0.00174 Pa∙s) viscosity, and the
electrolyte based on the ionic dendrimer D2-7 had the highest
viscosity (0.0031 Pa∙s). A linear correlation between the viscosity
of the electrolyte and the structure of the ionic dendrimers is
shown in Figure S3, Supporting Information. The fact that vis-
cosity can influence electrochemistry was already shown for
carbonate-based electrolytes containing LiTFSI as conducting
salt[12,16] and has now been found true for ionic dendrimer-based
electrolytes, too. Discharge capacities of the cells decreased with
increasing chain length of the rest R. Both first- and second-gen-
eration ionic dendrimers containing only a methyl side group
showed the lowest viscosity and, accordingly, the best cycle
behavior and the highest discharge capacities. In addition to
viscosity, the conductivity of the ionic dendrimer-based electro-
lytes had also an influence on the electrochemical behavior. This
becomes apparent when comparing the electrochemistry of cells
based on D1-5 and D2-1-containing electrolytes. Both electrolytes

Figure 3. Cycle test (1–3 V versus Li/Li+) at 1 C of SPAN-based cells with electrolytes based on dendrimers D1-1 to D1-5.

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opens the door for further developments in the area of ionic,

dendrimer-based electrolytes for the efficient suppression of the
polysulfide shuttle mechanism in Li–S cells.

4. Experimental Section
Synthesis of the Precursors: K1: Tris(2-aminoethyl)amine (0.027 mol,
4.0 g) was added dropwise to 40 mL formic acid at 0 °C. Afterward, 50 mL
of a 37% aqueous formaldehyde solution was added and stirred for
30 min at 0 °C. The mixture was refluxed for 48 h. After the solution was
allowed to cool to room temperature, NaOH was carefully added until
pH < 10. The aqueous phase was extracted with CHCl3 (4 × 150 mL).
The combined organic phases were dried over MgSO4 and the solvent
was removed in vacuo. The yellowish crude product was vacuum-
distilled (0.01 mbar, 120 °C) to yield a colorless oil (5.72 g, 92%). 1H-
NMR (400 MHz, CDCl3, δ): 2.58 (m, 6H, –CH2CH2N(CH3)2), 2.36 (m,
6H, –CH2CH2N(CH3)2), 2.20 (s, 18 H, CH3); 13C-NMR (101 MHz, CDCl3,
δ): 57.5, 53.0, 46.0; ESI m/z: [M + H]+ calcd for C12H30N4: 231.25; found:
231.25.
Figure 4. Proposed structure of the 3D network of ionic dendrimers and K2-CN: Tris(2-aminoethyl)amine (1 eq, 0.064 mol, 10.0 g) was
poly(sulfide)s. dissolved in 75 mL demineralized water. Freshly distilled acrylonitrile
(8 eq, 0.568 mol, 29 g) was added and the mixture was refluxed for 24 h.
The residual acrylonitrile was removed via distillation and the remaining
Table 1. Conductivities and viscosities of ionic dendrimer-based
aqueous phase was extracted with CH2Cl2 (3 × 100 mL). The combined
electrolytes. (1 m solution [TFSI−] in EC/DMC (1:1) for viscosity
organic phases were washed with demineralized water and dried over
measurements and 0.1 m solution [TFSI−] in EC/DMC (1:1), v/v) for
conductivity measurements). MgSO4. After the solvent was removed, the product was obtained as
a white, waxy solid (24.6 g, 82%). 1H-NMR (400 MHz, CDCl3, δ): 2.89
(t, 3J = 6.4 Hz, 12H, CH2CH2CN), 2.70–2.62 (m, 12H, NCH2CH2N),
Dendrimer Conductivity [mS cm−1] Viscosity [Pa s] 2.50 (t, 3J = 6.6 Hz, 12H, CH2CH2CN); 13C-NMR (101 MHz, CDCl3, δ):
D1-1 2.11 0.00174 119.1, 54.1, 52.4, 30.3, 17.3; Anal. calcd for C24H36N10: C 62.04, H 7.81,
N 30.15; found: C 61.98, H 7.88, N 29.92.
D1-3 2.04 0.00184
K2-NH2: NaOH (8.37 g) was dissolved in 150 mL of a water/ethanol
D1-5 1.87 0.00215 mixture (1:19; v/v). Raney-Ni (3.6 g) and K2-CN (0.01 mol, 4.77 g)
D1-7 1.76 0.00248
were added. The suspension was stirred for 24 h in an autoclave at
40 °C and a hydrogen pressure of 16 bar. The residual Raney-Ni was
D2-1 1.49 0.00210 removed by filtration and the solvents were removed in vacuo. The
D2-3 1.54 0.00223 residue was diluted with 100 mL CH2Cl2 and filtered over celite. All
solvent was removed and the product was obtained as colorless oil
D2-5 1.45 0.00272
(4.12 g, 84%). 1H-NMR (400 MHz, CDCl3, δ): 2.66 (t, 3J = 6.8 Hz, 12H,
D2-7 1.48 0.00331 CH2NH2), 2.53–2.43 (m, 12H, NCH2CH2N), 2.42 (t, 3J = 7.3 Hz,
CH2CH2CH2NH2, 1.53 (quint., 3J = 7.4 Hz, 12H, CH2CH2CH2NH2),
1.36 (s, 12H, NH2); 13C-NMR (101 MHz, CDCl3, δ): 53.3, 52.4, 52.3,
had similar viscosity (0.00215 vs 0.00210 Pa∙s) but showed dif- 40.7, 31.0; ESI m/z: [M + H]+ calcd for C24H60N10: 489.50; found:
ferent discharge capacities at 0.5 C (1100 vs 700 mAh∙g−1). This 489.51.
difference is attributed to the different conductivities (1.87 vs K2: K2-NH2 (1 eq, 8.2 mmol, 4.0 g) was dissolved in 250 mL of a
1.49 mS∙cm−1) of the electrolytes. 1 N aqueous NaH2PO3 solution. Formaldehyde solution (37% in water,
20 mL) and dioxane (250 mL) were added. The solution was stirred for
2 h at 65 °C. NaOH was added until pH > 10. The solution was extracted
with CH2Cl2 (3 × 200 mL). The combined organic phases were dried over
3. Conclusions MgSO4 and the solvent was removed in vacuo. The product was isolated
as a yellowish, viscous oil (3.87 g, 72%).1H-NMR (400 MHz, CDCl3, δ):
In summary, ionic dendrimers were synthesized and success- 2.55–2.45 (m, 12H, CH2N(CH3)2) 2.45–2.35 (m, 12H, NCH2CH2N)
fully used as conducting salt in carbonate-based electrolytes for 2.25–2.20 (m, 12H, CH2CH2CH2N(CH3)2) 2.16 (s, 36H, NCH3),
Li/S-cells. Increasing viscosity and decreasing conductivity with 1.60–1.50 (m, 12H, CH2CH2CH2); 13C-NMR (101 MHz, CDCl3, δ):
57.9, 53.5, 52.7, 52.6, 45.5, 25.4; ESI m/z: [M + H]+ calcd for C36H84N10:
increasing chain length of the side chains was observed for both 657.69; found: 657.69.
the first- and second-generation dendrimers. All cells showed A3: 1-Chloro-2-methoxyethane (1.0 eq, 0.085 mol, 8.0 g) was
high cycle stability, confirming the proposed ability of den- dissolved in 150 mL acetone. NaI (2.00 eq, 0.170 mol, 25.5 g) was added
dritic polycations to suppress the polysulfide shuttle. Discharge to the solution, which was then stirred for 24 h at room temperature.
capacities of the Li–S cells correlated both with the viscosity and NaCl was removed by filtration and the solvent was removed in vacuo.
the conductivity of the electrolytes. The best electrolyte system The residue was diluted with diethyl ether and filtered again to remove
residual NaCl. The organic phase was washed with demineralized water
obtained from a short side chain, first-generation dendrimer
and with a solution of sodium thiosulfate, then dried over MgSO4.
delivered discharge capacities of 1150 mAh gsulfur−1 @ 0.5 C Finally, the solvent was removed in vacuo to obtain the product as yellow
and 780 mAh gsulfur−1 @ 1 C. The observed correlation of the liquid (9.5 g, 65%). 1H-NMR (400 MHz, CDCl3, δ): 3.65 (t, 3J = 6.7 Hz,
structure of the ionic dendrimers with their electrochemistry 2H, CH2OCH3), 3.39 (s, 3H, OCH3), 3.25 (t, 3J = 6.7 Hz, 2H, CH2I);

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13C-NMR (101 MHz, CDCl3, δ): 73.2, 58.6, 2.9 ppm; EI m/z: calcd for
C3H7OI: 186.0; found: 186.0.
T5: Diethyleneglycol monomethyl ether (1.00 eq, 0.122 mol, 14.66 g)
and triethylamine (2.00 eq, 0.244 mol, 24.65 g) were dissolved in 100 mL
CH2Cl2. Tosyl chloride (0.98 eq, 0.120 mol, 23.4 g) was dissolved in
50 mL CH2Cl2 and added dropwise to the diethyleneglycol monomethyl
ether solution at 0 °C. After the mixture had been stirred for 2 h at room
temperature, 100 mL water were added. The organic phase was washed
with water (3 × 100 mL) and dried over MgSO4. After removing the
solvent, the product was obtained as colorless oil (30.18 g, 92%). 1H-
NMR (400 MHz, CDCl3, δ): 7.77 (d, 3J = 8.3, 2H, CH2CSO3), 7.31 (d,
3J = 8.3, 2H, CH CCH ), 4.14 (t, 3J = 5.0 Hz, 2H, CH SO ), 3.66 (t,
2 3 2 3
3J = 5.0 Hz, 2H, CH CH SO ), 3.56–3.53 (m, 2H, CH CH OCH ), 3.56–
2 2 3 2 2 3
3.53 (m, 2H, CH2CH2OCH3), 3.46–3.43 (m, 2H, CH2CH2OCH3), 3.32
(s, 3H, OCH3), 2.42 (s, 3H, Ph-CH3); C-NMR (101 MHz, CDCl3, δ):
13
144.9, 132.9, 129.9, 128.0, 71.8, 70.7, 69.3, 68.7, 21.7; ESI m/z: [M+H]+
calcd for C12H18O5S: 275.09; found: 275.09.
A5: 2-(2-Methoxyethoxy)ethyl 4-methylbenzenesulfonate T5 (1.0
eq, 0.037 mol, 10 g) was dissolved in 150 mL acetone. NaI (2.0 eq,
0.074 mol, 11.1 g) was added to the solution, which was then stirred
for 24 h at room temperature. The sodium tosylate was removed by
filtration and the solvent was removed in vacuo. The residue was diluted
with diethyl ether and again filtered to remove residual sodium tosylate.
The organic phase was washed with demineralized water and a solution
of sodium thiosulfate. It was then dried over MgSO4 and the solvent was
removed in vacuo to obtain the product as yellow liquid (5.36 g, 63%).
1H-NMR (400 MHz, CDCl δ): 3.76–3.73 (m, 2H, CH CH I), 3.66–3.61
3, 2 2
(m, 2H, CH2CH2OCH3), 3.56–3.52 (m, 2H, CH2CH2OCH3), 3.38 (s,
3H, OCH3), 3.27–3.24 (m, 2H, CH2I); 13C-NMR (101 MHz, CDCl3,
δ): 72.1, 71.9, 59.2, 2.8; ESI m/z: [M+Na]+ calcd for C5H11O2I: 252.98;
found: 252.97.
T7: Triethyleneglycol monomethyl ether (1.00 eq, 0.122 mol, 20.0 g)
and triethylamine (2.00 eq, 0.244 mol, 24.65 g) were dissolved in 100 mL
CH2Cl2. Tosyl chloride (0.98 eq, 0.120 mol, 23.4 g) was dissolved in 50 mL
CH2Cl2 and the solution was added dropwise to the diethyleneglycol
monomethyl ether solution at 0 °C. After stirring the mixture for 2 h at
room temperature 100 mL water were added. The organic phase was
washed with water (3 × 100 mL) and dried over MgSO4. After removing
the solvent, the product was obtained as colorless oil (34.9 g, 90%).
1H-NMR (400 MHz, CDCl δ): 7.71 (d, 3J = 8.4, 2H, CH CSO ), 7.25
3, 2 3
(d, 3J = 8.4), 2H, CH2CCH3), 4.07 (t, 3J = 5.0 Hz, 2H, CH2SO3), 3.59
(t, J = 5.0 Hz, 2H, CH2CH2SO3), 3.53–3.48 (m, 2H, CH2OCH3), 3.50
3 acetonitrile, and dried over molecular sieves (3 Å). The product was
(s, 4H, OCH2CH2O), 3.45–3.42 (m, 2H, CH2CH2OCH3), 3.28 (s, 3H,
OCH3), 2.35 (s, 3H, Ph-CH3); 13C-NMR (101 MHz, CDCl3, δ): 144.9,
133.0, 129.9, 128.1, 72.0, 70.8, 70.7, 70.6, 69.3, 68.7, 59.1, 21.7; ESI m/z:
[M+H]+ calcd for C14H22O6S: 319.11; found: 319.12.
A7: T7 (1 eq, 0.031 mol, 10 g) was dissolved in 150 mL acetone.
NaI (2.0 eq, 0.063 mol, 9.5 g) was added to the solution, which was
then stirred for 24 h at room temperature. The sodium tosylate was
removed by filtration and the solvent was removed in vacuo. The residue
was diluted with diethyl ether and filtered again to remove residual
sodium tosylate. The organic phase was washed with demineralized
water and a solution of sodium thiosulfate. It was dried over MgSO4
and the solvent was removed in vacuo to obtain the product as yellow
liquid (5.60 g, 66%). 1H-NMR (400 MHz, CDCl3, δ): 3.73 (t, 3J = 6.9 Hz,
2H, CH2CH2I), 3.65–3.61 (m, 2H, –CH2CH2OCH3), 3.65 (s, 4H,
OCH2CH2O), 3.53 (m, 2H, CH2CH2OCH3), 3.36 (s, 3H, OCH3),
3.24 (t, 3J = 6.9 Hz, 2H, CH2I); 13C-NMR (101 MHz, CDCl3, δ): 72.1,
72.0, 70.7, 70.3, 59.2, 3.0; ESI m/z: [M+Na]+ calcd. for C7H15O3I: 296.99;
found: 296.99.
Synthesis of D1-1 – D1-7: K1 (1.00 eq, 4.35 mmol, 1.00 g) and the
alkylating agent (A1–A7, 6.0 eq, 26 mmol) were dissolved in 10 mL
DMF and stirred for 3 days at 60 °C. The solvent was removed and the
residue was washed several times with acetone and dissolved in 10 mL
demineralized water. The solution was added dropwise to a solution
of LiTFSI (18.0 eq, 78.0 mmol, 22.4 g) in 50 mL demineralized water.
The precipitate was washed several times with water, dissolved in dry
acetonitrile and dried over molecular sieves (3 Å). The product was
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obtained after removing the solvent in vacuo. Yields: D1-1: 3.06 g, 63%;
D1-3: 3.31, 61%; D1-5: 3.60 g, 60%; D1-7: 3.68 g, 56%.
D1-1:1H NMR (400 MHz, CD3CN, δ): 3.31–3.25 (m, 6H,
CH2N(CH3)3), 3.07 (s, 27H, CH3), 2.95–2.88 (m, 6H,
NCH2CH2N); 13C NMR (101 MHz, CD3CN, δ): 125.3, 122.1, 118.9,
115.7, 63.0, 54.1, 47.5; 19F-NMR (376 MHz, CD3CN, δ) −80.13 ppm;
Anal. calcd for C21H39F18N7O12S6: C 22.60, H 3.52, N 8.79; found: C
22.80, H, 3.70, N 8.79.
D1-3: 1H-NMR (400 MHz, CD3CN, δ): 3.80–3.75 (m, 6H,
OCH2CH2OCH3), 3.48–3.44 (m, 6H, OCH2CH2OCH3), 3.36 (s,
9H, OCH3), 3.36–3.30 (m, 6H, CH2N(CH3)2), 3.07 (s, 18H,
N(CH3)2), 2.93–2.87 (m, 6H, (m, 6H, NCH2CH2N(CH3)2); 13C-
NMR (101 MHz, CD3CN, δ): 125.7, 122.5, 119.3, 116.1, 66.6, 65.0, 62.7,
59.3, 52.9, 47.6; 19F-NMR (376 MHz, CD3CN, δ) −80.15; Anal. calcd
for C27H51F18N7O15S6: C 25.98, H 4.12, N, 7.86; found: C 25.85, H 4.29,
N 7.96.
D1-5: 1H-NMR (400 MHz, CD3CN, δ): 3.90–3.85 (m, 6H,
OCH2CH2OCH3), 3.65–3.60 (m, 6H, OCH2CH2N), 3.54–3.50 (m,
6H, OCH2CH2N), 3.49–3.44 (m, 6H, OCH2CH2OCH3), 3.39–
3.33 (m, 6H, CH2N(CH3)2), 3.31 (s, 9H, OCH3), 3.09 (s, 18H,
N(CH3)2), 2.96–2.90 (m, 6H, NCH2CH2N(CH3)2); 13C-NMR
(101 MHz, CD3CN, δ): 125.3, 122.1, 118.9, 115.7, 71.7, 70.5, 64.7, 64.5,
62.5, 58.5, 52.5, 47.1; 19F-NMR (376 MHz, CD3CN, δ): −80.09 ppm;
Anal. calcd for C33H63F18N7O18S6: C 28.71, H 4.60, N 7.11; found: C
29.01, H 4.67, N 7.25.
D1-7: 1H-NMR (400 MHz, CD3CN, δ): 3.92–3.87 (m, 6H,
OCH2CH2OCH3), 3.65–3.61 (m, 6H, OCH2CH2N), 3.61–3.55
(m, 12H, CH2), 3.49–3.44 (m, 12H, CH2), 3.39–3.33 (m, 6H,
CH2N(CH3)2), 3.29 (s, 9H, OCH3), 3.10 (s, 18H, N(CH3)2),
2.96–2.90 (m, 6H, NCH2CH2N(CH3)2); 13C-NMR (101 MHz, CD3CN,
δ): 125.7, 122.5, 119.3, 116.1, 72.5, 70.9, 70.7, 70.5, 65.1, 64.9, 63.0,
58.8, 52.9, 47.6; 19F-NMR (376 MHz, CD3CN, δ): −80.13; Anal. calcd
for C39H75F18N7O21S6: C 30.97, H 4.99, N 6.48; found: C 30.53, H 4.97,
N 6.55.
Synthesis of D2-1–D2-7: K2 (1.00 eq, 1.36 mmol, 1.00.0 g) and the
alkylating agents A1–A7 (12 eq, 16.3 mmol) were dissolved in 10 mL
DMF and stirred for 5 days at 60 °C. The solvent was removed and the
residue was washed several times with acetone and dissolved in 10 mL
demineralized water. The solution was added dropwise to a solution
of LiTFSI (50.0 eq, 68.0 mmol, 19.5 g) in 50 mL demineralized water.
The precipitate was washed several times with water, dissolved in dry
obtained after removing the solvent in vacuo. Yields: D2-1: 2.70 g, 60%;
D2-3: 2.87 g, 57%; D2-5: 3.13 g, 56%; D2-7: 3.12 g, 51%.
D2-1: 1H-NMR (400 MHz, CD3CN, δ): 3.81–3.62 (m, 6H,
NCH2CH2N), 3.37–2.29 (93 H, m), 2.23–2.03 (m, 12H,
CH2CH2CH2); 19F-NMR (376 MHz, CD3CN, δ): −79.95 ppm; Anal.
calcd for C63H111F54N19O36S18: C 22.83, N 8.03, H 3.38; found C 22.61,
N 8.09, H 3.39.
D2-3: 1H-NMR (400 MHz, CD3CN, δ): 3.78–3.71 (m, 12H,
NCH2CH2N), 3.51–3.42 (m, 18H CH2), 3.35 (s, 18H, OCH3),
3.28–3.21 (m, 18H, CH2), 3.10 (s, 9H, -OCH3), 3.03 (s, 36H,
N+R(CH3)R), 2.57–2.45 (m, 24H, CH2CH2CH2), 1.85–1.75 (m,
12H, CH2CH2CH2); 19F-NMR (376 MHz, CD3CN, δ): -79.99; Anal.
calcd. for C81H147F54N19O45S18: C 26.22, N 7.18, H 4.00; found C 25.99,
N 7.64, H 3.71.
D2-5: 1H-NMR (400 MHz, CD3CN, δ): 3.94–3.82 (m, 12H,
-NCH2CH2N–), 3.70–3.57 (m, 24H, -OCH2CH2O-), 3.57–3.42 (m,
33H, OCH3 and OCH2CH2O), 3.39–3.19 (m, 54H, OCH3 and
–N+R(CH3)R) 3.17–3.02 (m, 48H, CH2CH2CH2 and OCH2CH2O),
2.26–2.03 (m, 12H, CH2CH2CH2); 19F-NMR (376 MHz, CD3CN, δ):
−80.03; Anal. calcd. for C99H183F54N19O54S18: C 28.95, N 6.48, H 4.49;
found: C 29.10, N 6.91, H 4.43.
D2-7: 1H-NMR (400 MHz, CD3CN, δ): 3.95–3.83 (m, 12H,
NCH2CH2N), 3.69–3.38 (m, 90H, CH2), 3.36–3.21 (m, 18H,
CH2), 3.29 (s, 18H, OCH3) 3.12–3.05 (m, 45H, OCH3 and
-N+R(CH3)R), 2.92–2.44 (m, 24H, CH2CH2CH2),1.90–1.74 (m, 12H,
CH2CH2CH2); 19F-NMR (376 MHz, CD3CN, δ): –79.92; Anal. calcd.
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
for C117H219F54N19O63S18: C 31.20, N 5.91, H 4.90; found: C 31.24, N
6.46, H 5.06.
Preparation of the Electrolytes: All electrolytes were freshly prepared in
an Ar-filled glove box. The ionic dendrimers were dissolved in a mixture
of ethylene carbonate/dimethyl carbonate (1:1, v./v.) to achieve a [TFSI−]
concentration of 1 mol L−1.
Synthesis of the Active Material: Poly(acrylonitrile) was converted into
SPAN via treatment with excess elemental sulfur at a temperature of
550 °C for 5 h under inert gas atmosphere. After the reaction, residual
sulfur was removed by Soxhlet extraction with toluene for 2 days. The
active material had a sulfur content of 40 wt%.
Electrochemistry: The active material was ground and sieved (average
particle size: <63 µm). A dispersion of SPAN/PVDF/Super C65
(70/15/15, wt%) in NMP was coated on a carbon-coated aluminum
foil via doctor blading (200 µmwet, sulfur loading: 0.6 mg∙cm−²).
After drying the cathode sheets, cathodes, 12 mm in diameter were
punched out. Elemental lithium chips, 12.5 mm in diameter, served
as anode material and Freudenberg FS 2190 membranes were used as
separators. Swagelok T-cells were built in an Ar-filled glovebox for the
electrochemical characterization of the ionic dendrimer-containing
electrolytes. All electrochemical measurements were performed on a
BasyTec XCTS-LAB battery test station. The specific capacity and charge/
discharge rates were calculated based on the mass of sulfur in the
cathode (1 C = 1672 mA h g−1).
Viscosity Measurements: The viscosity of the electrolytes was measured
on an Anton Paar Physica MCR 301 rheometer at 25 °C using a cone
geometry (CP50-1, diameter: 50 mm, angle 1°). All measurements were
carried out with 450 µL of electrolyte and a shear rate of 1000 s−1.
Conductivity Measurements: The conductivity of the ionic dendrimers
was measured with a Mettler Toledo 710 using 5 mL of a 0.1 m solution
([TFSI−]) of the dendrimers.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by the German Federal Ministry for
Economic Affairs and Energy (BMWi, project nr.: S50400).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
batteries, dendrimers, electrolytes, sulfurized poly(acrylonitrile)
Macromol. Chem. Phys. 2019, 1900436 1900436 (6 of 6)
www.mcp-journal.de
Received: October 2, 2019
Revised: November 12, 2019
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© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim