Single-ion diblock copolymers for solid-state polymer electrolytes

Article abstract of DOI:10.1016/j.polymer.2015.04.056

Li-ion battery technology is considered as the most efficient solution for the electrochemical energy storage. While standard liquid electrolyte - based configurations provide best performances, solid state electrolytes are developed as a safer alternative. Herein, we discuss a three step synthesis procedure of self-doped solid block copolymer electrolyte, combining a single-ion poly(lithium methacrylate-co-oligoethylene glycol methacrylate) ion conducting block (P(MALi-co-OEGMA)) and a structuring polystyrene block (PS). The macromolecular design allows the formation of a self-standing film with excellent mechanical properties provided by the PS anchoring nanodomains while attaining attractive ionic conductivities of up to 0.02 mS/cm at room temperature. Moreover, the single-ion configuration based on polyanionic backbone affords high transference numbers, close to unity, and alleviates the power limitation encountered in salt-doped solid polymer electrolyte (SPE). The electrolyte exhibits a wide electrochemical stability window up to 4.5 V vs. Li⁺/Li and promote the formation of stable interfaces at the electrodes.

Full text of DOI:10.1016/j.polymer.2015.04.056

Accepted Manuscript
Single-ion diblock copolymers for solid-state polymer electrolytes
Julien Rolland, Elio Poggi, Alexandru Vlad, Jean-François Gohy
PII:
S0032-3861(15)00393-6
10.1016/j.polymer.2015.04.056
JPOL 17808
DOI:
Reference:
To appear in: Polymer
Received Date: 9 November 2014
Revised Date: 11 February 2015
Accepted Date: 20 April 2015
Please cite this article as: Rolland J, Poggi E, Vlad A, Gohy J-F, Single-ion diblock copolymers for solid-
state polymer electrolytes, Polymer (2015), doi: 10.1016/j.polymer.2015.04.056.
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POLYMER 00 (2014) 000–000
Contents lists available at www.sciencedirect.com
Polymer
Journal homepage: www.elsevier.com/locate/polymer
Single-ion diblock copolymers for solid-state polymer electrolytes
Julien Rollanda, Elio Poggia, Alexandru Vlada,b, Jean-François Gohya*
aInstitute of Condensed Matter and nanosciences (IMCN), Université catholique de Louvain, Place Louis Pasteur 1, 1348 Louvain-la-Neuve, Belgium.
bInstitute of Information and Communication Technologies, Electronics and Applied Mathematics (ICTEAM), Université catholique de Louvain, Place du
Levant 3, 1348 Louvain-la-Neuve, Belgium.
A R T I C L E I N F O
A B S T R A C T
Article history:
Li-ion battery technology is considered as the most efficient solution for the electrochemical energy
storage. While standard liquid electrolyte - based configurations provide best performances, solid state
electrolytes are developed as a safer alternative. Herein, we discuss a three step synthesis procedure of
self-doped solid block copolymer electrolyte, combining a single-ion poly(lithium methacrylate-co-
oligoethylene glycol methacrylate) ion conducting block (P(MALi-co-OEGMA)) and a structuring
polystyrene block (PS). The macromolecular design allows the formation of a self-standing film with
excellent mechanical properties provided by the PS anchoring nanodomains while attaining attractive
ionic conductivities of up to 0.02 mS/cm at room temperature. Moreover, the single-ion configuration
based on polyanionic backbone affords high transference numbers, close to unity, and alleviates the power
limitation encountered in salt-doped solid polymer electrolyte (SPE). The electrolyte exhibits a wide
electrochemical stability window up to 4.5 V vs. Li+/Li and promote the formation of stable interfaces at
the electrodes.
Received 00 December 00
Received in revised form 00 January 00
Accepted 00 February 00
Keywords:
Single-ion electrolyte
Solid polymer electrolyte
Lithium-ion batteries
Block copolymer electrolyte
Atom transfer radical polymerization
© 2013 xxxxxxxx. Hosting by Elsevier B.V. All rights reserved.
10 liquid electrolyte exhibiting high ionic conductivities (>10-3 S/cm at room
11 temperature) and thus, the best power performances, despite safety issues
12 like leakage of corrosive and flammable constituents.2,4
1
1. Introduction
2
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With an ever-increasing demand for wireless technologies and portable
devices, Li-ion batteries (LIBs) have become widespread in our day life.1,2
Although many great advances have been made over the past two decades,
the challenge is still to design safer, longer lifespan, higher energy density
batteries able to power as well the electric vehicles of tomorrow. Tackling
this challenge requires the design of new materials at the cathode and at
the anode, as well as the development of new electrolyte chemistries.1,2,3
Currently, the large majority of commercial LIBs use carbonate-based
13 Gel polymer electrolyte have considerably reduced leakage hazard by
14 trapping the liquid electrolyte within a polymer gel matrix or a swollen
15 membrane.5,6 Many achievements have been made so far to attain a well
16 mature technology currently used in commercial lithium-polymer
17 batteries. The mechanical integrity of gel polymer electrolyte also ensures
18 original battery configurations such as flexible,7 stretchable,8 transparent9
19 and paintable batteries.10 The risks of fire and bursting are however
20 unavoidable due to the content of flammable liquid electrolyte.
* Corresponding author. Jean-François GOHY
E-mail address: Jean-François GOHY jean-francois.gohy@uclouvain.be
Peer review under responsibility of xxxxx.
xxxx-xxxx/$ – see front matter © 2013 xxxxxxxx. Hosting by Elsevier B.V. All rights reserved.
http://dx.doi.org/xxxx

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Solid-state electrolytes remain together with ionic liquids the best49 tethered onto the polymeric backbone (PEO or POEGMA) allowing only
alternatives to develop safe all-solid-state lithium cells.11,12 Dry polymers50 for Li+ motion (t+ ≈1).
and ceramic electrolytes developed over the years have been found to51
exhibit technologically relevant ionic conductivities.13 However, the52 Here, we discuss on the synthesis, characterization and performances of a
structural rigidity of ceramic membrane and limited deposition techniques53 series of single-ion block copolymers SPEs that combine i) high ionic
restrain their implementation only to niche batteries applications such as54 conductivity at room temperature due to the POEGMA conductive matrix,
micro-, thin-film and 3D batteries.14 By combining their lightweight,55 ii) mechanical strength thanks to the PS mechanical anchor and iii) single-
easier and conformal implementation, as well as their mechanical56 ion transport through the use of lithium carboxylate groups.
strength, solid polymer electrolyte (SPE) appears as an attractive
10 alternative to inorganic electrolytes.15 To enable both, mechanical strength
11 and high ionic conductivity at ambient temperature, various polymers
12 were studied.16 Amongst them, poly(ethylene oxide) (PEO) based
13 materials are by far the most implemented systems given their good Li+
14 solvation in the solid-state.17,18 The solid-state lithium ion transport in
15 PEO is enabled through an ion hopping mechanism mainly in the
16 amorphous regions.12 In the crystalline domains, the ion motion is
17 severely hampered and is responsible of poor ionic conductivities in PEO-
18 based electrolytes at ambient temperature (<10-6 S/cm).12 Relevant
19 performances are only attained at elevated temperatures. Thus, much
20 effort was devoted to lower the melting point at ambient temperature by
21 incorporating organic plasticizers, inorganic fillers and nanoparticles.17,19
22 Ionic conductivities were significantly improved but the mechanical
23 properties (film forming ability, dimensional stability, etc) were degraded.
24 Even worse, the ionic conductivity decreased in a matter of days because
25 of the rapid crystallization of metastable amorphous regions.15 Regarding
26 the charge transport, the anion mobility in PEO is usually higher than the
27 lithium cation. Transference numbers (t) of about 0.3 are typically
28 observed in PEO systems and are responsible for the electrode
29 polarization with deleterious effect on the power capabilities, dendrite
30 formation and the overall battery performances.20 An acceptable
31 compromise has to be found between high ionic conductivity, mechanical
32 strength, transference number (preferably tLi+ ≈ 1), as well as wide
33 electrochemical stability window.
57 2. Experimental section
58 Materials:
59 Lithium perchlorate, lithium bis(trifluoromethane)sulfonimide, lithium
60 trifluoromethanesulfonate, lithium bis(oxalato)borate (battery grade, 99.99
61 %, Aldrich); benzyl alcohol (99.8 %, Aldrich), α-bromo
62 isobutyrylbromide (98 %, Aldrich) 2,2’-bipyridyl (Bpy, 99%, Aldrich),
63 4,4’-dinonyl-2,2’-dipyridyl (dNbpy, 97 %, Aldrich), ethyl α-
64 bromoisobutyrate
(EBiB,
98%,
Aldrich),
N,N,N’,N”,N”-
65 pentamethyldiethylenetriamine (PMDETA, 99% Aldrich), copper(I)
66 bromide (CuBr, 99.999%, Aldrich), copper(I) chloride (CuCl, >99.995%,
67 Aldrich), were used as received. (Oligoethlene glycol) methyl ether
68 methacrylate (OEGMA, Mn: 500 Aldrich), tert-butyl methacrylate
69 (tBMA, >99%, Aldrich) and, styrene (>99%, Aldrich) were filtered
70 through activated basic alumina column prior to use. All other solvents
71 and reagents were analytical grade and were used without further
72 purification.
73 Instrumentation:
74 Proton nuclear magnetic resonance (1H NMR) spectra were acquired on a
75 300 MHz and 500 MHz Bruker Advance II. All conversions are
1
76 determined by H NMR by integration of the characteristics peaks. The
77 conversion of OEGMA-tBMA containing polymers are determined by
78 using trioxane as an internal reference. Molar mass (Mn) and dispersity
79 (Đ) of the polymers were measured on an Agilent gel permeation
80 chromatography (GPC) system equipped with an Agilent 1100/1200
81 pump (35 °C; eluent DMF; flow rate 1 mL/min), an Agilent differential
82 refractometer and two PSS GRAM columns. The calibration was
83 performed using polystyrene standards.
34 Poly(oligo (ethylene glycol)) methacrylate (POEGMA) was found as a
35 promising amorphous substitute to PEO raising the room temperature
36 ionic conductivity above 10-5 S/cm.21 In turn, mechanical reinforcement is
37 required to freeze the dimensional stability of the viscous liquid-like
38 polymer. Therefore, various block copolymer architectures have been
39 developed to combine the two antagonistic properties: high ionic
40 conductivity of POEGMA and mechanical stiffness of a structuring
41 block.21–25 For instance, by using high glass transition polystyrene, notable
42 performances were obtained for poly(styrene-block-oligo(ethylene glycol)
43 methacrylate) block copolymer offering good mechanical properties
44 without compromising on ionic conductivity.26 Nevertheless, a great deal
45 of work remains to be realized to overcome the power limitations caused
46 by the small current fraction carried by the lithium cation. The concept of
47 single-ion SPE (and self-doped electrolyte) has been proposed to
48 circumvent those limitations.20,23,27 In a single-ion SPE, the anion is
84 Synthesis of benzyl bromoisobutyrate (BnBiB):
85 Benzyl alcohol (6.21 mL, 0.06 mol, 1.2 eq.) was diluted in dry DCM (50
86 mL) and cooled down on ice bath. A solution of α-bromoisobutyryl
87 bromide (6.18 mL, 0.05 mol, 1 eq.) and triethylamine (8.3 mL, 0.06 mol,
88 1.2 eq.) in dry DCM (25 mL) was added dropwise over a period of 30
89 min. The mixture was stirred at room temperature for 2 h, and then
90 washed five times with acidic water (pH 2). The organic phase was dried
91 over Na2SO4 and the solvent removed under reduced pressure.
92 Purification was achieved by fractionated distillation under vacuum to
1
93 afford a clear oil (44 mg, 88 %). H NMR (300 MHz, CDCl3) δH (ppm):
94 1.9 (s, 6H, 2xCH3), 5.2 (s, 2H, CH2), 7.3 (br m, 5H, HAr).

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Typical synthesis of P(OEGMA-co-tBMA) macroinitiator:
48 cold hexane, filtered and dried in vacuo at 35 °C for 15 h, affording a
A solution of benzyl bromoisobutyrate (BnBiB) (6 ꢀL, 0.0314 mmol, 149 white powder. Mn (GPC) = 12.2 kg.mol-1; Đ (GPC) = 1.09; 1H NMR (500
eq.), OEGMA9 (828 µL, 1,882 mmol, 60 eq.), tBMA (306 µL, 1,882
mmol, 60 eq.), dNbpy (32 mg, 0.0784 mmol, 2.5 eq.) and absolute ethanol
(1 mL, 40 wt%) was degassed three times by freeze-pump-thaw cycles.
The degassed solution was introduced in a Schlenk flask under argon
atmosphere containing CuBr (5 mg, 0.0376 mmol, 1.2 eq.). The mixture
was degassed three times by freeze-pump-thaw cycles, filled with argon
and stirred in oil bath at 60 °C for 30 min. The polymerization was
50 MHz, CDCl3) δH (ppm): 7.3-6.3 (br m, 5 H, HAr), 2.3-1.2 (br m, 3H, CH-
51 CH2 backbone).
52 Typical procedure for PS-b-POEGMA block copolymer synthesis:
53 A solution of PS-Br (530 mg, Mn: 12.2 kg.mol-1, Đ: 1.09), OEGMA (3.1
54 mL, 7.1 mmol, 164 eq.), dNbpy (36 mg, 0.089 mmol, 2.05 eq.), and
55 anisole (3.4 mL, 50 wt%) was degassed three times by freeze-pump-thaw
56 cycling. The degassed solution was introduced in a Schlenk flask
57 containing CuCl (4 mg, 0.043 mmol, 1 eq.). The solution was degassed
58 three times by freeze-pump-thaw cycles, filled with argon and stirred in an
59 oil bath at 50 °C for 2h30. The polymerization was stopped by cooling
60 down the solution and exposing the catalyst to air. The reaction mixture
61 was diluted with CH2Cl2 and passed through neutral alumina column. The
62 solvent was removed under reduced pressure. The residue was diluted in
63 methanol and then purified by dialysis (SpectraPor membrane, cut off
64 6000-8000 Da) in methanol over 48 h. The solvent was removed under
65 reduced pressure and the residue dried under vacuum at 35 °C for 24h.
66 Unreacted PS macroinitiator was finally removed by stirring the residue in
67 ether/toluene (95:5 %vol) solution during 24h. The opalescent residue was
10 stopped by cooling down at room temperature the Schlenk tube and
11 exposing the catalyst to air. The reaction mixture was diluted in CH2Cl2
12 and filtered over neutral alumina. The solvent was removed under reduced
13 pressure. The residue was diluted in methanol and then purified by
14 dialysis (SpectraPor membranes cut off 6000-8000 Da) in methanol over
15 48 h. The solvent was finally removed under reduced pressure and the
16 residue dried under vacuum at 35 °C for 48 h, affording a clear viscous
17 liquid. Mn (GPC) = 13 kg.mol-1; dispersity, Đ, (GPC) = 1.16; H NMR
1
18 (500 MHz, CDCl3) δH (ppm): 7.4 (br m , 5H, HAr), 4.2 (br s, 23H, CH2
19 OEG side chain), 3.9-3.2 (br m, 483H CH2 oligo ethylene glycol side
20 chain), 2.2-0.8 (br m, 257H, CH3+CH2 backbone + CH3 tert-butyl).
21 Procedure for P(OEGMA-co-tBMA)-b-PS block copolymer synthesis: 68 recovered and dried at 60 °C over 24h. Mn (GPC) = 52 kg.mol-1; Đ (GPC)
22 A solution of P(OEGMA-co-tBMA) (325 mg, M : 13 kg.mol-1, Đ: 1.16),
69 = 1.25; 1H NMR (500 MHz, CDCl3) δH (ppm) 7.3-6.3 (br m, 720 H, HAr),
70 4.2 (br s, 228 H, CH2 oligo ethylene glycol side chain), 3.9-3.22 (br m,
71 4430 H, CH2 oligo ethylene glycol side chain), 2.0-0.7 (br m, 1250 H,
72 CHCH3-CH2 backbone).
n
23 styrene (2.7 mL, 23 mmol, 1000 eq.), PMDETA (6 µL, 0.0302 mmol, 1.2
24 eq.), and anisole (1.8 mL, 40 wt%) was degassed three times by freeze-
25 pump-thaw cycles. The degassed solution was introduced in a Schlenk
26 flask containing CuBr (4 mg, 0.0279 mmol, 1.2 eq.). The solution was
27 degassed three times by freeze-pump-thaw cycles, filled with argon,
28 stirred in oil bath at 100 °C for 24h. The polymerization was stopped by
29 cooling down the solution and exposing the catalyst to air. The reaction
30 mixture was diluted with CH2Cl2 and passed through neutral alumina
31 column. The solvent was removed under reduced pressure. The residue
32 was precipitated twice in cold hexane. The polymer was recovered and
73 Typical procedure for PS-b-P(OEGMA-co-tBMA) block copolymer
74 synthesis:
75 A solution of PS-Br (757 mg, Mn: 12.2 kg.mol-1, Đ: 1.09), OEGMA (1.9
76 mL, 4.293 mmol, 85 eq.), tBMA (700 µL, 4.293 mmol, 85 eq.), dNbpy
77 (43 mg, 0.106 mmol, 2.1 eq.), and anisole (2.7 mL, 50 wt%) was degassed
78 three times by freeze-pump-thaw cycling. The degassed solution was
79 introduced in a Schlenk flask containing CuCl (5 mg, 0.051 mmol, 1 eq.).
80 The solution was degassed three times by freeze-pump-thaw cycles, filled
81 with argon, stirred in oil bath at 60 °C for 2h30. The polymerization was
82 stopped by cooling down the solution and exposing the catalyst to air. The
83 reaction mixture was diluted with CH2Cl2 and passed through neutral
84 alumina column. The solvent was removed under reduced pressure. The
85 residue was diluted in methanol and then purified by dialysis (SpectraPor
86 membrane, cut off 6000-8000 Da) in methanol over 48 h. The solvent was
87 finally removed under reduced pressure and the residue dried under
88 vacuum at 35 °C for 24h, to afford a white viscous liquid. Mn (GPC) = 35
-1
1
33 dried at 35 °C for 48 h. Mn (GPC) = 37 kg.mol ; H NMR (500 MHz,
34 CDCl3) δH (ppm): 7.3-6.3 (br m, HAr), 4.2 (br s CH2 oligo ethylene glycol
35 side chain), 3.9-3.22 (br m CH2 oligo ethylene glycol side chain), 2.0-0.7
36 (br m, CH3+CH2 backbone + CH3 tert-butyl)).
37 Synthesis of PS macroinitiator:
38 A solution of EBiB (59 ꢀL, 0.243 mmol, 1 eq.), styrene (18.6 mL, 162
39 mmol, 400 eq.), PMDETA (51 ꢀL, 0.243 mmol, 0.6 eq.), and anisole (4.2
40 mL, 20 wt%) was degassed three times by freeze-pump-thaw cycles. The
41 degassed solution was introduced in a Schlenk flask containing CuBr (29
42 mg, 0.202 mmol, 0.5 eq.). The solution was degassed three times by
43 freeze-pump-thaw cycles, filled with argon, stirred in an oil bath at 90 °C
44 over 15 h. The polymerization was stopped by cooling down the solution
45 and exposing the catalyst to air. The reaction mixture was diluted with
46 CH2Cl2 and passed through neutral alumina column. The solvent was
47 removed under reduced pressure. The residue was precipitated twice in
1
89 kg.mol-1; H NMR (500 MHz, CDCl3) δH (ppm) 7.3-6.3 (br m, HAr), 4.2
90 (br s CH2 oligo ethylene glycol side chain), 3.9-3.22 (br m CH2 oligo
91 ethylene glycol side chain), 2.0-0.7 (br m, CHCH3-CH2 backbone + tert-
92 butyl).
93 Synthesis of PS-b-P(OEGMA-co-MALi):
94 PS-b-(POEGMA-co-PtBMA) (1.3 g, 10 g/L), butylated hydroxytoluene

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(BHT) (5 mg) was dissolved in chloroform (170 mL) in Ar atmosphere.49 Transference number measurement:
Trifuoroacetic acid (1.8 mL, 0.2 M) was added dropwise and the solution50 The ion transference numbers were determined by using the AC-DC
stirred in an oil bath at 60 °C for 12h. The reaction is cooled down at51 polarization experiment according to the Evans-Bruce protocol.28
room temperature and the solvent removed under reduced pressure. The52 Symmetrical Swagelock cell Li/PS-b-P(OEGMA-co-MALi)/Li were
residue was dissolved in a minimal amount of THF and purified by53 assembled by laminating the self-standing SPE film in between two Li-
dialysis (SpectraPor membrane, cut off 6000-8000 Da) in methanol over54 metal electrodes. The sandwich was sealed using a Swagelock cell inside
24 h. Single-ion functions were then generated by adding lithium55 an Ar-filled glove box. The cell was first heated at 90 °C in an Espec SH-
methoxide (2 mL, 2.2 M in methanol) to the dialysis solution and stirred56 261 oven followed by stabilization for at least 24
h prior any
during 12h. The polymer was then dialyzed in pure methanol for 24h. To57 measurement. Impedance spectra were recorded before and after DC cell
10 remove unreacted PS macroinitiator, the polymer was finally washed by58 polarization by using a CHI 660B electrochemical workstation in a
11 stirring the residue in ether/toluene (95:5 %vol) solution during 24h. The59 frequency range of 100 kHz - 1 Hz. An AC excitation voltage of 20 mV
12 resulting solid polymer was finally recovered and dried at 60 °C over 2460 was used. The cell was subsequently polarized at DC 20 mV and time-
1
13 h. Mn (GPC) = 33 kg.mol-1; H NMR (500 MHz, CDCl3) δH (ppm) 7.3-6.3
61 current dependence recorded until the steady state was reached.
14 (br m, 720 H, HAr), 4.2 (br s, 74 H, CH2 oligo ethylene glycol side chain),
15 3.9-3.22 (br m, 1422 H, CH2 oligo ethylene glycol side chain), 2.0-0.7 (br
16 m, 738 H, CHCH3-CH2 backbone).
62 Electrochemical stability window:
63 The electrochemical stability windows were determined by cyclic
64 voltammetry by using CHI 660B electrochemical workstation. Swagelock
65 cells consisting of a thick polymer film (≈ 300 µm) sandwiched between a
66 stainless steel working electrode and a lithium foil counter- and reference
67 electrode were used. The cells were cycled between 0 V to 6 V vs. Li/Li+
68 at 0.5 mV/s.
17 Thin-film preparation:
18 Thin-films were prepared by spin-coating a polymer solution onto silicon
19 substrates. The silicon substrates were first cleaned by piranha solution
20 (H2SO4 98 % : H2O2 35 % - 2/1 vol) and carefully rinsed with ultrapure
21 water. The substrates were then spun at 4000 rpm for 30 s. A filtered
22 (PTFE 0.2 µm) solution of PS-b-P(OEGMA-co-MALi) at 10 g/L in
23 THF/MeOH (50:50 vol%) was spin-coated at 2000 rpm for 40 s. Atomic
69 3. Results and discussion
70 Developing high performance solid state electrolytes requires high ionic
71 conductivities, combined with excellent mechanical strength. These two
72 features are usually in conflict (without considering further the
73 transference numbers). To reach high ionic conductivity, the used
74 polymers have to solubilize the lithium salt and the chain mobility has to
75 be very high to ensure rapid movement of ions through the matrix. Those
76 polymers exhibit usually low glass transition temperature (-60 °C for
77 PEO, -70 °C for POEGMA). Moreover, the polymers have to be fully
78 amorphous for the reasons mentioned above. As a result, their mechanical
79 strength is inevitably poor. To circumvent these drawbacks, block
80 copolymer electrolytes have been found to combine both antagonistic
81 properties: structural integrity and high ionic conductivity. In our
82 molecular design, the ionic conductive block is ensured by oligo(ethylene
83 glycol) chemically anchored to a methacrylic backbone (Figure 1a).
84 Oligo(ethylene glycol) oligomers exhibit excellent conductivities up to 10-
85 3 S/cm at room temperature, but behave like a liquid.29 Attaching OEG to
86 a methacrylic backbone results in a viscous liquid with no dimensional
87 integrity and thus requires further mechanical strengthening.26 The size of
88 the oligomers has to be considered carefully. For instance, OEG oligomers
89 with less than 15 units, exhibit the best performances given their liquid
90 form, low viscosity and good salt solubility.30 The trend is reversed to
91 some extent when the oligomers are attached to a methacrylic backbone.
92 Below 9 units, the chain motion is restricted and the ionic conductivities
93 are as low as 10-7 S/cm.31 Above 15 units, the oligomers tend to crystallize
94 at room temperature and the attained conductivities are also low, of the
95 order of 10-6 S/cm. POEGMA bearing oligomers with 9 units seemingly
24 Force Microscopy (AFM) imaging was performed on
a Digital
25 Instruments Nanoscope V scanning force microscope in tapping mode
26 using NCL cantilevers (Si, 48 N/m, 330 kHz, nanosensors).
27 Self-standing film preparation:
28 Self-standing films were prepared by casting a 10 wt% PS-b-P(MALi-co-
29 OEGMA) solution in THF/MeOH (50:50 vol%) onto Teflon film. The
30 film was first dried under air flux for 12h, and then further dried at 60 °C
31 under vacuum for 48 h. The obtained films with a thickness ranging from
32 300 µm to 1 mm were stored in a dry Argon glove box.
33 For BF3 doped films, all the following operations were carried into dry
34 argon glove box with dry polymer and solvent to prevent lewis acid
35 decomposition. To dope the polymer, an equimolar amount, with respect,
36 to MALi of BF3 in methanol is added to the PS-b-P(MALi-co-OEGMA)
37 THF/MeOH solution. The self-standing film is obtained by drop casting
38 of polymer solution onto Tefflon film, further dried under vacuum for 48
39 h.
40 Ionic conductivity:
41 Ionic conductivities were measured by electrochemical impedance
42 spectroscopy using a CHI 660 B analyzer. The electrolyte was first drop
43 casted (from a 50 g/L solution in MeOH/THF 50:50 vol%) onto a
44 stainless steel electrode, followed by drying under vacuum at 60 °C
45 during 48h. The set-up was capped with a second stainless steel electrode,
46 followed by annealing at 90 °C for 1h. The electrochemical response of
47 the electrolyte was measured in the 1 mHz-100 kHz frequency range with
48 an AC excitation voltage of 5 mV.

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provides the best compromise: totally amorphous and high ionic 5 electrolyte, the lithium cation is already bound to the polymer backbone.
conductivity, as high as 2 x 10-5 S/cm at room temperature.26
The carboxylate counterion is tethered and randomly distributed along the
6
In conventional SPE, the lithium source usually comes from lithium salt 7 methacrylic backbone, allowing thus only lithium mobility and high
dissolved in the conductive matrix. In our single-ion block copolymer 8 transference numbers (Figure 1a).
FIGURE 1: Electrolyte design. (a) Design at the molecular level of the tri-functional block copolymer bearing PS, POEGMA and, PMA-Li+ functions;
(b) Self-assembly leads to distinct functions: PS domains ensure mechanical anchor, POEGMA matrix is responsible for ionic transport at the solid state
whereas PMALi enables Li+ doping and anion immobilization. (c) Atomic force microscopy phase image revealing the nano-scale structure of the
electrolyte; (d) Robust self-standing films are obtained after solvent casting.
ecursor polymerization 1:
O
(a+b)
O
O
O
Br
Br
O
O
O
CuBr / CuBr2 / dNbpy
tBMA
a
b
CuBr / PMDETA
a
b
c
(a+b)
Br
+
O
O O
O
O
OO
O
O
Solvent 40 %wt
60 °C, 30 min
Solvent 50 %wt
100 °C, 24 h
O
B
O
O
O
9
Styrene
9
9
OEGMA
P(tBMA-co-OEGMA)
P(tBMA-co-OEGMA)-b-PS
macroinitiator
ecursor polymerization 2:
O
O
Br
x
Cl
z
y+z
O
CuCl / dNbpy
Solvent, T (°C), t (h)
O
O
CuBr / PMDETA
x
y
+
Br
O
O
O
O
Anisole 20 %wt
90 °C, 15 h
O
O
B
Styrene
O
+
PS-Br macroinitiator
O
O
9
O
OEGMA
tBMA
9
PS-b-P(tBMA-co-OEGMA)
drolysis & neutralization
O
O
Cl
z
y+z
Cl
z
y+z
1) TFA, CHCl3, 60 °C, 12h
2) MeOLi / MeOH
O
y
x
x
y
O
O
O
O
O
Li
O
O
O
-P(tBMA-co-OEGMA)
O
9
O
PS-b-P(MALi-co-OEGMA)
9
FIGURE 2: Single-ion SPE synthesis strategy. (a) First approach for P(tBMA-co-OEG9MA)-b-PS precursor polymerization, (b) Halogen exchange
strategy for precursor polymerization, (c) Hydrolysis step followed by neutralization to generate single-ion functions.

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POLYMER 00 (2013) 000–000
TABLE 1: Experimental conditions and results for ATRP polymerization of tBMA and OEG9MA
d
e
CuBr/CuBr2/dNbpy/OEGMA/tBMA
(molar ratio)
Conversionc
OEGMA/tBMA(%)
Mn th
Mn
Entrya
Solventb
Đe
(g.mol-1)
(g.mol-1)
1
1.0 / 0.1 / 2.4 / 60 / 60
1.0 / 0.1 / 2.4 / 60 / 60
1.1 / 0.1 / 2.4 / 60 / 60
1.2 / 0 / 2.4 / 120 / 0
1.1 / 0.1 / 2.4 / 120 / 0
1.1 / 0.2 / 2.6 / 60 / 60
1.1 / 0.1 / 2.4 / 60 / 60
1.1 / 0.1 / 2.4 / 60 / 60
1.2 / 0 / 2.4 / 60 / 60
Anisole
DMF
DMF
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
40 / 49
45 / 61
35 / 43
33 / -
16 000
18 000
13 600
19 000
29 000
12 200
10 500
13 200
11 300
16 000
16 500
13 200
22 000
29 000
14 700
12 000
13 000
10 000
1.24
1.23
1.21
1.25
1.22
1.20
1.19
1.16
1.18
2
3
4
5
51 / -
6
32 / 36
27 / 33
35 / 38
30 / 33
7
8f
9f,g
a Reactions initiated by EBiB and carried out at 60 °C during 30 min. b Solvent 40 wt%. c Conversion determined by 1H NMR. d Theoretical molecular
weight calculated on the basis of conversion data. e Mn and Đ measured by GPC using PS calibration. f Polymerization initiated by BnBiB. g Ligand
replaced by Bpy.
Finally, the integration of a polystyrene block induces the formation of
glassy nano-domains responsible of the mechanical reinforcement (Figure
1 b-c-d). Only small fraction of PS was necessary to confer the
dimensional stability of our electrolyte. As depicted in figure 1c, the
investigated diblock was designed to self-organize into a body-centered
cubic phase and form an optimized morphology for micrometer thick
electrode providing a continuous ion conductive matrix where the
tortuosity is limited to offer the best ionic conductivity performance and
mechanical stiffness provided by PS nanospheres.
relatively fast kinetics.33;34 Several parameters were screened such as the
solvent (anisole, DMF, ethanol), the addition of CuBr2, the ligand (dNbpy,
Bpy) and the initiator (EBib, BnBiB).
In each case, polymers with rather low dispersity, below 1.25, were
obtained in a relatively short time (30 min). The similar conversions of
both monomers, especially in EtOH, suggest that tBMA and OEGMA are
randomly incorporated in the resulting copolymer at the same amount as
the feed ratio. The relatively close reactivity of both methacrylic
monomers can be explained by the presence of bulky oligo(ethylene
glycol) side chain that increase steric constraint and favour random
incorporation of both monomers. Better dispersities were obtained by
performing the copolymerization in EtOH (Entries 6-8), instead of DMF
or anisole (Entries 1-3). The addition of 0.1 molar ratio of CuBr2 (Entries
4-6) and using BnBiB as an initiator further contributed to significantly
improve the dispersity values (Entries 8-9), leading to well-defined
macroinitiators.
Synthesis of single-ion block copolymers
The PS-b-P(MALi-co-OEGMA) single-ion block copolymer electrolytes
were synthetized via a three-step protocol (Figure 2). The first two steps
consist in the synthesis of a PS-b-P(OEGMA-co-tBMA) precursor by
atom transfer radical polymerization (ATRP). The carboxylate groups
(single-ion functions), are masked by tert-butyl groups, which prevent the
poisoning of the ATRP catalyst during the polymerization.32 In the final
step, the single-ion functions are released by hydrolysis of tert-butyl
protecting groups. The neutralization of the carboxylic acid functions with
a strong lithium base allows to generate the single-ion SPE.
In the next step, the polymerization of the structuring block was realized
by re-initiation from the P(tBMA-co-OEGMA) bromo end-chain. The
polymerization of styrene was performed by using CuBr/PMDETA
catalyst at 100 °C for 24 h. The block copolymerization was first
investigated in different solvents: anisole, dioxane, DMF (Table 2). For
each situation, low conversions were obtained after 24h. Re-initiation
efficiencies lower than 55 % were attained. GPC chromatograms of
dialyzed polymers clearly show two overlapping peaks corresponding to
diblock copolymer and unreacted macroinitiator at lower and higher
retention times, respectively (Figure 3).
In the first route, the ionic conductive block precursor is first produced by
copolymerization of OEGMA and tBMA (Figure 2a). The PS structuring
block is then polymerized starting from the P(OEGMA-co-tBMA)
macroiniator. Table 1 presents the results of a set of ATRP conditions for
POEG9MA
and
P(tBMA-co-OEG9MA)
polymerization.
The
copolymerizations were realized at 60 °C in presence of the CuBr/dNbpy
catalyst with the same comonomer feed (except entries 4, and 5). This
catalyst system was selected to generate polymers with a bromo end-
chain, known to ensure re-initiation of the second styrene block with

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POLYMER 00 (2013) 000–000
7
TABLE 2: Experimental conditions and results for styrene
polymerization starting from the P(tBMA-co-OEG9MA) macroinitiator
CuBr /
PMDETA
(molar
d
e
Convb
(%)
Mn th
Mn
Solvent
Entrya
(g.mol-1)
(g.mol-1)
ratio)
1
2
1.8 / 2.0
1.2 / 1.2
1.2 / 1.3
1.2 / 1.3
Anisole
Dioxane
DMF
< 5
5
-
37 000
38 000
77 000
85 000
21 000
26 000
29 000
3
11
4f
DMF
14
a Reactions conditions : P(tBMA-co-OEGMA) (Mn 13 kg.mol-1; Đ 1.16),
100 °C, 1000 equiv. styrene. b Solvent 50 wt%. c Conv = conversion
determined by 1H NMR. d Theoretical molecular weight calculated on the
basis of conversion data. e Mn and Đ measured by GPC using PS
calibration. f Reaction realized with preformed catalyst.
Figure 4: GPC chromatograms of PS-b-POEGMA, starting from
PS-Br (Table 3; entry 8).
see experimental section). Now, the PS macroinitiator can be
advantageously used as a platform to polymerize the POEGMA (Table 3)
or P(MALi-co-OEGMA) (Table 4) block. However the copolymerization
of a methacrylate block from a PS macroinitiator requires halogen
exchange methodology in ATRP.37,38 This strategy was successfully
applied here to the synthesis of PS-b-POEGMA and PS-b-P(tBMA-co-
OEGMA) copolymers, despite the incomplete re-initiation efficiency.
Pure PS-b-POEGMA was however recovered from the polymerization
mixture after ether/toluene washing step (Figure 4). In the case of PS-b-
P(tBMA-co-OEGMA), pure block copolymer was only obtained after the
hydrolysis step due to the solubility of P(tBMA-co-OEGMA) in ether
(Figure 5).
In practice, the experimental conditions were optimized for PS-b-
POEGMA and then applied for the PS-b-P(tBMA-co-OEGMA) synthesis.
The synthesis of PS-b-POEG9MA was carried out by using CuCl/dNbpy
catalyst. The effect of several parameters was screened such as the
solvent, the temperature and the concentration of monomer. Amongst
anisole, dioxane and DMF, only polymerizations performed in anisole led
to well-defined block copolymers with relatively narrow mass distribution
(Table 3; Entry 1-3). Looking at the temperature effect, the
polymerizations performed at 60 °C allow to get the best compromise
between efficient re-initiation and low dispersity (Table 3; Entry 1, 4-6).
Finally by lowering the concentration of the polymerization medium to 70
wt%, better control is achieved leading to well-defined block copolymers
with Đ=1.19 (Table 3; Entry 7-8). The optimized conditions presented in
the Entry 8 (Table 3) were transposed to the synthesis of the PS-b-
P(tBMA-co-OEGMA) copolymers with variable tBMA/OEGMA molar
ratio (Table 4).
Figure 3: GPC chromatograms of P(tBMA-co-OEG9MA)-b-PS
polymerized in different solvents and of the P(tBMA-co-
OEG9MA) starting macroinitiator.
As expected, incomplete re-initiation leads to a mixture of block
copolymer and unreacted macroinitiator after polymerization. However,
the re-initiation efficiency seems to be strongly dependent on the nature of
the solvent. Changing the solvent from DMF to dioxane improves the re-
initiation efficiency whereas with anisole poor re-initiation was
observed.These results suggest that some of the bromo chain-ends in the
macroinitiator are not able to reinitiate polymerization. A possible
explanation for this observation could lie in the conformation of the
macroinitiator polymer chain in solution.35,36 In this respect, the
accessibility of the bromo chain-end could be decreased or even totally
screened. Incomplete conversion of macromonomer or macroiniator
brushes is indeed usually reported in ATRP and in other controlled (or
living) polymerization, causing difficulties in purification.36
As encountered for the OEGMA/tBMA homopolymerization, the
conversion of both monomers is similar and is proportional to the molar
reactant feed. These results further support that tBMA and OEGMA are
randomly incorporated during the polymerization.
The synthetic strategy was thus adapted and the order of monomer
addition was reversed. As depicted in Figure 2b, the new approach
consists in the ATRP of the styrene block, followed by the
copolymerization of the second block. At the first step, a well-defined PS
macroinitiator was obtained with Đ=1.09 (for details on the PS synthesis
The PS-b-P(MALi-co-OEGMA) single-ion electrolytes were finally
obtained by the hydrolysis of tert-butyl groups. The hydrolysis is

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POLYMER 00 (2013) 000–000
performed in presence of a 10 fold excess of trifluoroacetic acid for 12 h
(reflux of chloroform).
TABLE 3: Experimental conditions and results for PS-b-POEG9MA polymerization
d
e
Temperature
(°C)
Reaction time
(h)
Conversionc
OEGMA (%)
Mn th
Mn NMR
Entrya
Solvent
Wt%b
Đf
(g.mol-1)
(g.mol-1)
1
Anisole
Dioxane
DMF
50
50
50
50
50
50
60
70
60
60
60
50
70
80
60
60
2.5
2.5
2.5
2.5
1.8
1.5
2.5
2.5
26
36
60
27
25
18
20
30
29 400
37 200
55 900
30 200
28 600
23 200
24 800
32 500
56 000
60 000
87 000
69 200
45 000
40 000
50 000
57 000
1.21
1.29
1.50
1.25
1.30
1.27
1.20
1.19
2
3
4
5
6
7
8
Anisole
Anisole
Anisole
Anisole
Anisole
a Reactions conditions: PS / CuCl / dNbpy / OEGMA = 1/1/2.05/160. b Solvent wt% c Conversion determined by 1H NMR. d Theoretical molecular weight.
e Mn determined by 1H NMR. f Đ measured by GPC.
TABLE 4: Experimental conditions and results for PS-b-P(MALi-co-OEGMA) synthesis
c
d
c
OEGMA/tBMA
(molar ratio)
Conversion
Mp
fMALi
Mn
Entrya
Đc
OEGMA/tBMA(%)b
(g.mol-1)
(%)
(g.mol-1)
1
2
3
4
85 / 85
85 / 85
23 / 25
25 / 27
24 / 25
25 / 26
34 000
35 000
33 500
44 000
76e
53
41
28
29 000
33 400
32 500
43 000
1.23
1.23
1.23
1.25
102 / 68
127 / 43
a Reaction conditions: PS / CuCl / dNbpy 1:1:2.05, anisole 70 wt%, 60 °C, 2h30. c Conversion determined by 1H NMR. c Mp, Mn and Đ are respectively
molar mass of PS-b-P(tBMA-co-OEGMA), molar mass of PS-b-P(PMALi-co-OEGMA) obtained after hydrolysis and dispersity measured by GPC using
PS calibration. d MALi fraction assessed by 1H NMR. e Higher fraction of MALi obtained after hydrolysis during 24 h.
The hydrolysis yield is assumed to be complete after the total
disappearance of the straight and characteristic peak of tert-butyl protons
on the 1H NMR spectra. The fraction of MALi is then determined by
integration of protons signal of the remaining OEG side-chain and the
protons corresponding to the polymer backbone. Reaction time has been
optimized to hydrolyze mainly the tBu protecting groups and to limit as
much as possible the hydrolysis of the OEG side chains. Increasing the
reaction time resulted in deeper OEGMA side chain hydrolysis (Table 4;
Entry 1). Subsequent neutralization with lithium base and ether/toluene
washing allow to separate unreacted macroinitiator from well-defined
block copolymer chains as shown on GPC chromatograms (Figure 5)
Conduction characteristics
The ionic conductivities of the single ion block copolymer SPE and
conventional salt-doped SPE are detailed in Figure 6. First, the effect of
MALi content was investigated.
Figure 5: GPC chromatograms of PS-b-P(MALi-co-OEGMA) at
different MALi/OEGMA ratio (Table 4).

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POLYMER 00 (2013) 000–000
9
Figure 6: Ionic conductivities (a) MALi content dependence for single-ion electrolyte and BF3 effect, (b) high performance salts-doped PS-b-POEGMA
electrolytes (EO/Li 20:1) at 20 °C.
The ionic conductivities versus OEGMA/MALi ratio are shown in Figure
6a and correlated with the EO/Li+ ratio. For every case, the single-ion BF3
free SPE displays very low ion transport, with conductivities of the order
10-8 - 10-11 S/cm at room temperature. The ionic conductivity has been
found to gradually increase with a decrease in the MALi content which is
consistent with previous report for POEGMA based electrolytes.26 Indeed,
increasing MALi load results in higher lithium concentration in the
electrolyte. Based on crown ether mechanism, the number of EO[Li+]
complexes increases with the concentration and consequently reduce the
segmental motion of OEG side chain crucial for ion diffusion. Even
worse, the ion-pair formation and salt clustering is usually formed at
EO/Li ratio below 8 thus, trapping and hindering the lithium cation
motion.39 Even if the salt concentration affects the ionic conductivity, only
slight variations have been reported.26 The salt concentration alone does
not explain the trend. For weakly entangled polymers like POEGMA, the
inter-chain ion hopping mechanism is expected to severely impact the
ionic conductivity.12 In the ion conductive block; the distance between
OEGMA units is spaced by MALi groups. The ion hopping distance is
thus increased and the ion motion lowered. This effect is more
pronounced for conductivities as the MALi content increases.
orders of magnitude, with a maximum of 2.10-5 S/cm reached. These
values compete with those obtained for high performances lithium salt
such as LiBOB, LiTFSI, LiTFS dissolved in PS-b-POEG9MA as reflected
in Figure 6b. It is worth mentioning that BF3 is particularly sensitive to
moisture traces. All electrolyte film process should be carried out under
stringent dry inert atmosphere.
The rise in the transference number as a result of the single-ion design
was confirmed by AC-DC polarization spectroscopy.28 Transport numbers
as high as 0.84 were obtained for the single-ion electrolytes, which is
much higher than 0.2-0.3 usually observed for standard salt-doped
systems.15 Thus, by combining the high ionic conductivity and
transference numbers close to unity, the single-ion PS-b-P(MALi-co-
OEGMA) electrolytes outperform the simple salt-doped systems.
Electrochemical stability
The electrochemical stability of PS-b-P(MALi-co-POEGMA) with and
without added BF3 were investigated by cyclic voltammetry. The results
are shown in Figure 7. The PS-b-P(MALi-co-POEGMA) exhibits a wide
electrochemical stability window up 5 V, even when complexed with BF3.
Both formulations exhibit an anodic peak above 4.5 V that can be
attributed either to polymer electrolyte degradation and to the stainless-
steel electrode corrosion. In the BF3 containing electrolyte, an anodic peak
appears only at the first cycle around 3.5 V. Upon incorporation of BF3,
the reactivity of the electrolyte is seemingly increased at anodic potentials
and promote the oxidation of the electrolyte.41 At the second scan, the
peak is less pronounced and suggests the formation of a stable electrolyte
interface at the electrode that prevents further electrolyte oxidation on the
subsequent cycle. At the cathodic potential below 2 V vs. Li+/Li, the
formation of solid electrolyte interface (SEI) is inevitable as demonstrated
by strong electrochemical response around 1.3 and 0.8V. At these
potentials, complex reduction reactions occur and promote the
degradation of the electrolyte at the interface with the electrode.42
However, as observed for the anodic processes, the cathodic response
Even if the macromolecular architecture has been optimized, the ionic
conductivities remain low, of about 10-8 S/cm. In fact, similar
performances are characteristic for
a wide range of single-ion
moieties.20,23,27 The poor performances are attributed to strong ion-pairing
with the carboxylic group.
The Li+ ions are thus trapped onto the polymeric backbone bearing the
counter ions and only weakly contribute to ionic current. Providing
satisfactory conductivities require a higher degree of dissociation. The
addition of lewis acid was therefore exploited here, the process being
known to induce charge delocalization of carboxylate groups and then
enhance the degree of dissociation.40 Remarkably, the addition of boron
trifluoride raises the ionic conductivity of all studied configuration by 3

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POLYMER 00 (2013) 000–000
diminishes on the following cycles and is almost suppressed at the 5th
cycle. Due to the solid form of the electrolyte, a stable SEI is generated at
the interfaces between the electrode and the electrolyte. Unlike the
situation of liquid or gel electrolytes, this interface is structurally robust
and cannot be stripped and reformed by supplying fresh electrolyte at each
cycles. A stable and protective SEI is thus formed and prevents further
electrolyte deterioration.
Figure 7: Cyclic voltammetry of (a) PS-b-P(MALi-co-OEGMA) single-ion electrolyte and (b) in presence of BF3 at a scan rate of 0.5 mV/s. The
curves are shifted for more clarity.
4. Conclusion
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Highlights:
•
•
We disclose a convenient 3 steps synthesis for high performance solid electrolyte.
The single-ion electrolyte design has been optimized to afford the mechanical and ion
transport performances
•
•
Single-ion electrolytes containing BF3 have attractive ionic conductivities as high as 0.02
mS/cm at room temperature.
The single-ion electrolyte promotes the formation of a stable SEI