pNTQS: Easily Accessible High-capacity Redox-active Polymer for

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pNTQS: Easily Accessible High-capacity Redoxactive Polymer for Organic Battery Electrodes Simon Muench, Jan Winsberg, Christian Friebe, Andreas Joachim Wild, Johannes C. Brendel, Alexandra Lex-Balducci, and Ulrich S. Schubert ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b00734 • Publication Date (Web): 10 Aug 2018 Downloaded from http://pubs.acs.org on August 13, 2018

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ACS Applied Energy Materials

pNTQS: Easily Accessible High-Capacity RedoxActive Polymer for Organic Battery Electrodes Simon Muench,1,2 Jan Winsberg,1,2 Christian Friebe,1,2 Andreas Wild,# Johannes C. Brendel,1,2 Alexandra Lex-Balducci,1,2 Ulrich S. Schubert.1,2* 1

Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller

University Jena, Humboldtstr. 10, 07743 Jena, Germany, Fax: (+)49 3641 948202, E-mail: [email protected], Homepage: www.schubert-group.de 2

Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller

University Jena, Philosophenweg 7a, 07743 Jena, Germany #

Current address: Evonik Creavis GmbH, Paul-Baumann-Straße 1, 45772 Marl, Germany

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ACS Applied Energy Materials 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract Despite a continuous effort to develop novel materials for organic polymer-based batteries, their commercial success is still hampered by the demanding synthesis and the high costs of these materials. To overcome these issues, we developed poly(naphthotriazolequinonestyrene) (pNTQS), the first redox-active polymer bearing naphthotriazolediones, and demonstrate its promising characteristics for an application in organic batteries. The polymer is effectively synthesized using a straightforward cycloaddition reaction followed by a free-radical polymerization. The electrochemical investigations of this new material reveal a two-electron storage capability, and an electrolyte system optimized for use in Li-organic batteries was established. Coin cells comprising pNTQS as active electrode material reveal an excellent capacity of 135 mAh g−1, which exceeds most of the commonly applied polymer-based materials, while a capacity loss of only 30% over 1000 cycles was observed.

Keywords: Energy Storage, Organic Batteries, Organic Electronics, Polymers, Redox-Active Materials, Electrodes


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The market for gadgets like active RFID tags, mobile sensor systems, smart packaging and clothing, and ubiquitous integrated circuits, in particular with regard to the Internet of Things (IoT), is constantly growing.1-2 The required tailor-made solutions for mobile energy supply are just as versatile as the powered devices and have to feature the demanded characteristics, like capacity and power values. Classical metal-based secondary batteries3-5 with high gravimetric and volumetric energy densities but limited power capabilities on the one hand, and capacitors6-8 with high power densities but only low capacities on the other hand are not able to satisfy the requirements of this upcoming market for lightweight, flexible, and lowcost mobile energy supplies. In this regard, active electrode materials based on organic polymers represent an aspiring and promising element in this field of application.9-13 Compared to present-day metal-based active materials for electrochemical energy-storage devices, organic compounds, in particular polymers, feature several explicit advantages. They are less toxic, mechanically flexible, and enable the application of straightforward and cheap manufacturing techniques like printing or roll-to-roll processing.14-17 Furthermore, they can be potentially prepared from renewable resources18 and easily disposed by incineration without the formation of toxic by-products such as critical metal oxides. Moreover, the electrode potentials and, therefore, the resulting cell voltage can be tailored by the choice of appropriate redox-active moieties and their chemical functionalization. To prevent the dissolution of the active molecules into the electrolyte and the related capacity loss, they are incorporated as side-chains into a polymeric architecture. Up to now, numerous different organic substance classes were investigated, such as conjugated polymers,19 organosulfur20-21 and carbonyl compounds,22 as well as stable radicals.12 Extended quinoid structures, such as anthraquinone23-25 and corresponding derivatives,26-28 are of particular interest due to their ability to store two electrons, resulting in good charge-to-mass ratios and, therefore, high theoretical capacities. There are already 3 Environment ACS Paragon Plus


promising scientific results published,9-13 but up to now no large-scale industrial application evolved, which is essentially due to the required elaborate and expensive syntheses of most of the materials. Therefore, the accessibility of organic active materials obtained via an easy synthesis route involving maximal three steps and using inexpensive starting materials is highly desirable. With regard to this, a new redox-active material based on naphthotriazolediones was prepared in a straightforward synthetic process. Naphthotriazolediones were, up to now, mainly applied in pharmacological research due to their antibacterial and cytotoxic properties29-31 and represent a potential anti-cancer agent.32-34 However, no application in the field of energy storage was reported so far. Here, we present the first naphthotriazoledione-based polymer and its utilization as active n-type electrode material for organic batteries. The monomer naphthotriazolequinonestyrene was synthesized in a straightforward cycloaddition and subsequently polymerized in a cost-efficient free radical polymerization under optimized conditions. The materials were electrochemically characterized by cyclic voltammetry (CV) as well as by charge/discharge experiments in Liorganic batteries over 1000 cycles. Synthesis. The repeating unit of pNTQS was designed to feature a high specific capacity as well as a straightforward synthesis route starting from low-cost commercially available materials. The redox-active structure is accessible in a single-step 1,3-dipolar cycloaddition of an organic azide and naphthoquinone, simultaneously introducing a polymerizable styrene functionality using p-vinylbenzylazide. The azide reagent is attained from a nucleophilic substitution reaction of p-vinylbenzylchloride (1) with sodium azide. The quantitative conversion was confirmed by TLC. Without isolation, the azide compound was subsequently utilized for the next reaction step, the [3+2] cycloaddition with naphthoquinone (2) (Scheme 1).35 The ring formation is followed by a reconstitution of the quinone structure by in situ


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oxidation with the excess of naphthoquinone. The compound was characterized by 1H and 13

C NMR (Figure S1) as well as elemental analysis.

Scheme 1: Schematic representation of the synthesis of pNTQS.

Due to its styrene functionality, the material provides a suitable vinyl group for various polymerization techniques (Scheme 1). Considering the costs, a free radical polymerization is favored. However, the radical scavenging behavior of the quinone functionality might inhibit or at least limit the chain propagation and the conversion of this technique. As a consequence, suitable polymerization conditions (initiator, solvent, etc.) had to be thoroughly evaluated to obtain polymers with suitable high molar masses (Table 1). In general, high initiator concentrations are required to overcome the inhibiting effect of the quinone structure. The application of other initiators than azobis(isobutyronitrile) (AIBN) or controlled radical techniques, like the nitroxide-mediated polymerization, resulted in no improvements. The highest molar masses and yields were reached with DMSO as solvent and 10 mol% AIBN as initiator, providing pNTQS in a yield of 39% after precipitation in cold acetonitrile. A molar mass of Mn = 3900 g mol−1 and a dispersity of Ð = 1.25 were determined by size-exclusion chromatography (SEC) using poly(styrene) standards (Figure S2). This polymer was used for further investigations.



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Table 1: Comparison of the effect of the solvent on the polymerization of monomer 3. Solvent (conc. [M])

AIBN [mol%]

Mn [g mol−1]

Ð

Yield [%]

DMSO (0.4)

5

3400

1.33

14

NMP (0.6)

5

3200

1.30

17

DMSO (0.4)

10

3900

1.25

39

NMP (0.6)

10

2800

1.28

25

1,2-dichloroethane (0.3)

10

3500

1.25

11

1,2-dichlorobenzene (0.2)

10

3600

1.15

7

Electrochemical characterization. To evaluate the applicability as electrode material in an electrochemical storage device, the redox behavior and the stability of pNTQS were investigated by conducting cyclic voltammetry (CV) of the monomer (3) and the polymer. In DMF with 0.1 M tetrabutylammonium perchlorate (NBu4ClO4) as supporting electrolyte, the monomer reveals two distinct redox processes at half-step potentials of −1.10 and −1.90 V vs. Fc+/Fc, which are ascribed to the two quasi-reversible one-electron reduction steps to the radical anion and the dianion, respectively (Figure 1a). In this setup, with a NBu4ClO4containing electrolyte, the two reduction steps occur with a difference of 800 mV. Such a large potential difference between the individual steps would lead to two distinct charge/discharge plateaus for a respective battery and, thus, to a voltage drop at half of the charging level. However, this characteristic changes upon the utilization of Li+- instead of NBu4+-based salts and the gap decreases to 420 mV. This behavior is favorable since the voltage slope of a battery is decreased, i.e. the discharge voltage is more stable. The CV characterization of the polymer pNTQS in DMF with 0.1 M LiClO4 reveals also two redox steps at −1.09 V and −1.35 V vs. Fc+/Fc (Figure 1b). Thus, the difference further decreases to 265 mV. The peak corresponding to the second process is significantly smaller, which can most likely be ascribed to a lower diffusion coefficient of the single-reduced 6 Environment ACS Paragon Plus

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polymer. Furthermore, CV experiments with different scan rates were conducted and revealed a square-root dependence of the peak current on the scan rate for the monomer (Figure S3) as well as the polymer (Figure S4).

a)

DMF, NBu4ClO4

0.04

DMF, LiClO4 0.02

current [mA]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


0.00

-0.02

-0.04 -2.5

-2.0

-1.5

-1.0

-0.5

0.0

potential [V] vs. Fc+/Fc

Figure 1: Cyclic voltammetry (in DMF, 500 mV s−1, 10 cycles) of a) 3 with different conducting salts and b) pNTQS with LiClO4.

As the specific capacity Cspec of a compound depends on the ratio of the molar mass M to the number of stored electrons n (Eq. 1; F is the Faraday constant), the two-electron storage capability of this molecule results in a high theoretical capacity of 170 mAh g−1. Therefore, it is superior to other common redox-active polymers, like PTMA or polyTCAQ with 111 and 162 mAh g−1, respectively.9, 28

∙

∙ .

170 ! "#

(Eq. 1)

Galvanostatic charge/discharge experiments. In order to evaluate the performance of pNTQS as active electrode material, charge/discharge experiments in Li-organic coin cells were conducted. The composite cathode was prepared by mixing pNTQS, PVdF and SuperP® (10/10/80) with NMP in a dissolver to yield a homogeneous slurry, which was subsequently coated on an aluminum current collector by doctor-blading and dried in an oven. As first tests 7 Environment ACS Paragon Plus


with a carbonate-based electrolyte (1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate 1/1) revealed a fast capacity decay (Figure S5), alternative electrolytes were investigated. The electrolyte of choice was found to be 1,3-dioxolane (DOL)/ dimethoxyethane (DME) 1/1 with 1 M Lithium bis(trifluoromethane)sulfonimide (LiTFSI), which shows a stable cell performance. The cells were charged up to a voltage of 2.75 V and discharged to 1.9 V (Figure 2). pNTQS constitutes an n-type material (capable of reversible reduction) and would, therefore, likely be applied as anode active material in all-organic batteries. However, in the Li-organic cell setup it acts as cathode and the organic electrode is in its charged (oxidized) state upon manufacturing. Thus, the cell is assembled “precharged” and in the first cycle, a charge of only 25 mAh g−1 (with respect to the mass of redox-active polymer) is necessary to charge the cell. This remaining capacity can most probably be attributed to a partly discharge of the cell during assembly. The two charging steps are visible at 2.55 and 2.35 V while the discharge occurs at 2.5 and 2.2 V (at 1C, i.e. charging/discharging in 1 h), which reveals a potential that is in the same range like anthraquinone-based materials with the utilized electrolyte system.3638

The two processes occur very close to each other, so that their profiles overlap and the

discharge curve declines constantly over a range of 550 mV with only a small step in the discharge curve, instead of two distinct plateaus with a steep voltage drop after half discharge. Nevertheless, charging and discharging occur over a wider voltage range than usual for organic systems with a single plateau.9


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b)

Qspec charge 120

coulombic efficiency 160

2.8 100 80

120 60 80

1C 5C 10C 1C

5C

40

40

20

cell voltage [V]

Qspec discharge

200

coulombic efficiency [%]

a)

Qspec [mAh g-1]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2.6

1C (2nd cycle) 5C (101st cycle) 10C (201st cycle) 1C (301st cycle) 5C (401st cycle)

2.4 2.2 2.0 1.8

0 0

200

400

600

800

0 1000

0

40

80

120

160

Qspec [mAh g-1]

cycle number

Figure 2: Galvanostatic charge/discharge experiments: pNTQS/PVdF/SuperP® 10/10/80 (m/m/m) vs. Li with 1 M LiTFSI in DOL/DME 1/1 (v/v); a) specific capacity and coulombic efficiency, every 10th cycle is displayed; b) voltage profiles.

At a charge/discharge rate of 1C, the cell reveals an initial discharge capacity of 135 mAh g−1, which corresponds to a material activity of 79%. After 100 cycles at 1C, the capacity still amounts to 130 mAh g−1, corresponding to only 4% capacity loss. The coulombic efficiency is constantly above 99.5%. Subsequently, the cell was charged/discharged at 5C and 10C, each for another 100 cycles. Upon switching to 5C, the capacity decreases by only 4 mAh g−1 and even at a very high rate of 10C, it remains at 121 mAh g−1, revealing an excellent performance at high charge/discharge rates. This also holds true for the voltage, which decreases by less than 100 mV at higher rates. When going back to 1C, the capacity increases again to the previous level, which further emphasizes the excellent stability of the material. The long-term cycling stability was investigated by further charging and discharging the cell at 5C to reach 1000 cycles in total, after which it still maintains 70% of its initial capacity. To estimate the contribution of double-layer capacitance to the capacity, cyclic voltammetry was measured in a coin cell (Figure S6). From the non-faradaic background current, a capacitance of about 3 mAh g−1 (related to the mass of the active polymer) was calculated, which amounts to 2 to 3% of the total capacity.



Moreover, electrodes with a higher amount of active material were investigated. Cells with 25 wt% of pNTQS show a specific capacity of 88 mAh g−1, which declines to 67 mAh g−1 after 100 cycles at 1C (Figure 3). Charging/discharging at 5C and 10C, respectively, results in a decrease of each 8 mAh g−1. After a total of 1000 consecutive cycles, 41% of the initial capacity is maintained. The lower capacity and faster decrease, compared to the electrodes with 10 wt% active material, can be ascribed to a facilitated dissolution of the polymer, caused by a weakened retention via π–π interactions to the carbon additive at higher ratios of pNTQS to SuperP®.39-40 The coulombic efficiency is not affected by the higher polymer loading, whereas, the voltage profiles reveal an increased ohmic drop at higher rates, as the conductivity of the composite electrode decreases with higher polymer contents. However, when the specific capacity is calculated based on the mass of the total composite instead of the redox-active polymer alone, it amounts to 22 mAh g−1, compared to 13.5 mAh g−1 for the 10 wt% electrodes. Qspec charge

a)

b)

Qspec discharge

200

120 2.8

80 120

1C 5C 10C 1C

5C

60

80 40 40

20

cell voltage [V]

100

coulombic efficiency [%]

coulombic efficiency 160

Qspec [mAh g-1]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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2.6

1C (2nd cycle) 5C (101st cycle) 10C (201st cycle) 1C (301st cycle) 5C (401st cycle)

2.4 2.2 2.0 1.8

0 0

200

400

600

800

0 1000

0

40

80

120

Qspec [mAh g-1]

cycle number

Figure 3: Galvanostatic charge/discharge experiments: pNTQS/PVdF/SuperP® 25/10/65 (m/m/m) vs. Li with 1 M LiTFSI in DOL/DME 1/1 (v/v); a) specific capacity and coulombic efficiency, every 10th cycle is displayed; b) voltage profiles.

The development of pNTQS represents a valuable step forward to overcome the major drawbacks of today’s organic battery materials. This new material combines a two-electron


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storage mechanism leading to a high capacity and a fast charge/discharge rate performance with a straightforward synthesis route from cost-efficient starting materials. The active polymer is synthesized in only three steps via a 1,3-dipolar cycloaddition and a cost-efficient free radical polymerization. The electrochemical investigations point out the two-electron storage ability at −1.09 and −1.35 V vs. Fc+/Fc, associated with an especially high theoretical capacity of 170 mAh g−1. Li-organic batteries with pNTQS as active cathode material reveal a specific capacity of up to 135 mAh g−1 (79% material activity) and a coulombic efficiency above 99%. Furthermore, the capacity retention after charging and discharging for 1000 cycles at rates between 1C and 10C was as high as 70%. The high rate performance enables full charging and discharging within six minutes with only a minor decrease in capacity and increase of ohmic drop. Its low redox potential and high specific capacity make it a promising object for further studies on applications as active anode material for all-organic batteries.

Acknowledgements: The authors thank the European Regional Development Fund (EFRE), the Thuringian Ministry for Economic Affairs, Science and Digital Society (TMWWdG), the Thüringer Aufbaubank (TAB), the Deutsche Forschungsgemeinschaft (DFG), and Evonik Industries AG for financial support.

Supporting information available: materials and equipment; syntheses; characterization techniques; NMR spectra; SEC spectrum; further cyclic voltammetry data; galvanostatic charge/discharge experiments with carbonate-based electrolyte.



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