Perylene-Based All-Organic Redox Battery with Excellent Cycling

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Letter

A new perylene-based all-organic redox battery with excellent cycling stability Adriana Iordache, Virginie Delhorbe, Michel Bardet, Lionel Dubois, Thibaut Gutel, and Lionel Picard ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b07591 • Publication Date (Web): 12 Aug 2016 Downloaded from http://pubs.acs.org on August 17, 2016

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ACS Applied Materials & Interfaces

A New Perylene-Based All-Organic Redox Battery with Excellent Cycling Stability Adriana Iordache, †,‡ Virginie Delhorbe, †,‡ Michel Bardet,†,§ Lionel Dubois,†,⊥ Thibaut Gutel†,‡* and Lionel Picard†,‡* †

Université Grenoble Alpes, F-38000 Grenoble, France

‡

Commisariat à l’Energie Atomique - Direction de la Recherche Technologique - Laboratoire

d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux - Département de l’Electricité et de l’Hydrogène pour les tranports - Service des Composants pour Générateurs Electrochimiques, 17 rue des martyrs, F-38054 Grenoble, France §

Commisariat à l’Energie Atomique - Direction de la Recherche Fondamentale - Institut

Nanosciences et Cryogénie - Modélisation et Exploration des Matériaux, UMR-E CEA-UJF, 17 rue des martyrs, F-38054 Grenoble, France ⊥

Commisariat à l’Energie Atomique - Direction de la Recherche Fondamentale - Institut

Nanosciences et Cryogénie - Systèmes Moléculaires et Nano-matériaux pour l’Energie et la Santé, UMR-E CEA-UJF, 17 rue des martyrs, F-38054 Grenoble, France

1 ACS Paragon Plus Environment


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ABSTRACT: Organic materials derived from biomass can constitute a viable option as replacements for inorganic materials in lithium-ion battery electrodes owing to their low production costs, recyclability, and structural diversity. Among them, conjugated carbonyls have become the most promising type of organic electrode material as they present high theoretical capacity, fast reaction kinetics, and quasi-infinite structural diversity. In this letter we report a new perylene-based all-organic redox battery comprising two aromatic conjugated carbonyl electrode materials, the pre-lithiated tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi6) as negative electrode material and the poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI) as positive electrode material. The resulting battery shows promising long-term cycling stability up to 200 cycles. In view of the enhanced cycling performances, the two organic materials studied herein are proposed as suitable candidates for the development of new allorganic lithium-ion batteries.

KEYWORDS: organic active material, perylene, greener compound, lithium-ion, all-organic battery

Organic electrode materials are composed of naturally abundant chemical elements (C, H, N, O, S) and if properly designed, they could be generated from renewable resources or low cost precursors. The richness of organic chemistry provides great opportunities for finding original electrode

materials

with

specific

properties

such

as

flexibility,

transparency

or

electrochromism.1,2 Other attractive advantages of these materials are both the possibility of tuning the redox potential and the promotion of reversible multi redox reactions.3 For these reasons, electro-active organic compounds are promising candidates as electrode materials for


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the next generation of greener and sustainable energy storage devices. At present, different families of organics such as conductive polymers, organic free radical, organosulfide and carbonyl compounds have been studied as electrode materials for ion batteries.4–9 The conjugated carbonyl class has emerged as one of the most promising organic electrode materials, as each carbonyl group may undergo reversible one-electron reduction than can be extended to more electrons if further carbonyl groups are in direct conjugation to form multivalent anions. Polyimides are part of conjugated carbonyl materials known as highly (electro-)chemically and thermally stable, insoluble compounds, being synthesized by polycondensation reaction of dianhydride with diamines. Aromatic polyimides are redox-active with only two out of the four carbonyls in one repeating unit taking part in reversible lithium complexation.10–13 The first two electron reduction is reversible and leads to a radical anion. The the second two electron reduction is irreversible due to the reaction of the resulting species with the electrolyte, producing the unstable protonated species followed by the opening of the ring.14 Their theoretical capacity of 100-250 mAh g−1 is competitive among polymeric carbonyl compounds. Polyimides bearing a perylene core linked via alkyl bridges show average potentials of ~2.5 V vs Li+/Li0, specific capacities >110 mAh g−1 with excellent cycling capabilities and are usually used as positive electrode materials.11,15,16 In 2009, Armand et al.17 proposed a new class of organic negative electrode materials based on two redox active lithium carboxylates separated by a conjugated system. Since then, the interest for this family of compounds has grown rapidly.18–23 Using as conjugated system a large πaromatic core, such as perylene unit, tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi4) can be prepared. This material show low redox potential of ~1.1 V vs Li+/Li0 and significant theoretical capacity of 118 mAh g−1 (calculated for 2 electrons reduction processes).24 Beside 3 ACS Paragon Plus Environment


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these remarkable properties, this class of small organics is insoluble in the common organic electrolytes making them very attractive for their use as negative electrode materials in lithium batteries. In this letter we present the study of two aromatic carbonyl as electrode materials, the prelithiated tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi6) as negative electrode material and the poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI) as positive electrode material. The two materials were first tested in half-cell batteries using lithium metal as counter electrode, followed by their assembly to a novel all-organic redox battery, using lithium as an exchange cation. The assembled all-organic lithium-ion battery showed long-term cycling stability up to 200 cycles, a significant improvement over the similar lithium-containing allorganic batteries.11,19,20,25 The use of insoluble active materials with large aromatic core such as perylene, results in improved charge stabilization, increased rate capability and cycling stability of the carboxylate and carbonyl functions. Both electrode materials were synthesized by one-step reactions from the same low-cost starting material, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). The PTCLi4 was successfully synthetized as an orange powder by one-pot hydrolysis/lithiation reaction of PTCDA following the procedure described by Fédèle et al.21 The positive material, PTCI was obtained as a burgundy powder by one-step polycondensation reaction of PTCDA with hexamethylenediamine as described by Niu et al.26 Figure 1a shows the syntheses of the two electrode materials.


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Figure 1. a) Syntheses (i. LiOH·H2O/H2O, 60 °C, 12h; ii. hexamethylenediamine, mcresol/isoquinoline, 200 °C, 20h), b) FT-IR, and c)

13

C SSNMR of PTCI (burgundy), PTCLi4

(orange) and PTCDA (red); SSNMR assignments are directly reported on the resonance (solidstate NMR = SSNMR). * spinning side bands. The structures of the resulted organic materials were confirmed by FT-IR and

13

C SSNMR

spectroscopy (Figure 1b and 1c). The intense band at ~1730 cm−1 (Figure 1b, red line) assigned to the asymmetric C=O stretching in the PTCDA starting material shifts at ~1660 cm−1 for the PTCI (burgundy line) and at ~1580 cm−1 for the PTCLi4 (orange line). The results from FT-IR are consistent with the previous reports,11,15,16,21,27,28 confirming the successful syntheses of the targeted products. High-resolution

13

C SSNMR is a powerful technique to characterize the

molecular structure of these electrode materials. The NMR lines of PTCDA (red) and PTCLi4 (orange) in Figure 1c are rather narrow indicating an ordered structure of the solid phase, which is consistent with their expected crystalline morphology. The opening of the di-anhydride function leads to drastic changes in the PTCLi4 structure, along with the shift of the quaternary carbonyl, C7 from 160 ppm to 180 ppm and in the chemical shifts of the carbons of polyaromatic 5 ACS Paragon Plus Environment


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core (C1 to C6), contrary to the previous assignments given in the literature and described elsewhere.24 The NMR features of PTCI (burgundy line) are consistent with its polymer structure having a higher structural disorder and leading to the broadening of the resonance. Note that the aliphatic side chains are clearly identified with resonances at ~40 and 28 ppm assigned to carbons N-CH2- and respectively to -CH2- (C8, Figure 1c). The FT-IR and SSNMR measurements revealed residual starting material in the PTCI sample, a highly insoluble organic compound which failed to be removed by washing with excess of organic solvents (see experimental section). The PTCDA can be used as active electrode material29 since holds a two-electron reduction process at 2.3-2.5 V vs Li+/Li0, but shows poor cycling stabilities due to the dissolution of the electrogenerated lithium enolates species.

Figure 2. Cyclic voltammetry curves of a) PTCLi4/SP/PVdF and b) PTCI/SP/PVdF, and c) electrochemical lithiation and delithiation mechanism expected of PTCLi4 and PTCI. Measurements performed on half cells using PTCLi4(PTCI)/SP/PVdF=40/40/20 (wt%) as positive

electrode,

lithium

metal

as

counter/negative

electrode

in

1M

LiPF6/EC:DMC:EMC=1:1:1 (vol), at 0.01 mV s−1, rt. 1st scan solid line and 2nd scan dashed line. 6 ACS Paragon Plus Environment

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The electrochemical activity of PTCLi4 and PTCI was first studied at room temperature (rt) vs lithium metal by cyclic voltammetry (CV) in a half cell using 1M LiPF6/EC:DMC:EMC = 1:1:1 as electrolyte (vol ratio, EC = ethylene carbonate, DMC = dimethyl carbonate, EMC = ethyl methyl carbonate). The CV performed with electrodes containing 40 wt% PTCLi4 or PTCI, 40 wt% Super P® (SP) and 20 wt% PVdF are shown in Figure 2 (PVdF = polyvinyldifluoride). This electrode composition is suitable for the organic active materials due to their low electronic conductivities. The working potential of both electrode materials allows the use of aluminum foil as current collectors which are a considerable cost advantage and lightweight compared with copper current collectors commonly used for negative electrodes materials. In the following all potentials are given vs Li+/Li0. Figure 2a and 2b show the CV curves of the PTCLi4 and PTCI composite electrodes. At the first scan (Figure 2a, solid line) the reversible reduction process at ~1 V of PTCLi4 is associated with the complexation of two Li+ which leads to the formation of PTCLi6, and its re-oxidation reaction at 1.27 V (Figure 2c). The small increase in the cathodic current at ~1.3 V and the irreversible redox reaction at 0.75 V can be correlated to a combination of the electrolyte decomposition which forms a passivation layer, known as solid electrolyte interphase (SEI), and to the potentially irreversible reactions of lithium with the absorbed molecules present on the surface of the amorphous carbon (SP).30 These two processes disappear at the following scans, therefore confirming the processes mentioned above. The dashed CV curve (second scan) shows the reduction process of the PTCLi4, shifted with ~70 mV towards higher potentials and its stable re-oxidation. The difference between the reduction and the oxidation peaks decreases from 220 mV in the first scan to 150 mV in the second scan indicating a more favored redox reaction. At lower potentials, between 1 and 0.5 V, we noticed an increase in the current with no defined



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peak. This phenomenon is assigned to the reversible lithiation of the disordered structure of the carbon black in the electronically non-equivalent insertion sites.30 Figure 2b (solid line) displays a large reduction process with low-resolved waves at ~2.42, 2.25 and 2 V, assigned to the reduction of two PTCI carbonyls to the corresponding lithium enolates, and one re-oxidation process at 2.53 V of the enolates back to carbonyls groups (Figure 2c). In the second scan (dashed curve), the reduction processes are better defined with two shifts at 2.42 V and 2.14 V. The re-oxidation is anodically shifted by 30 mV and appears now at 2.56 V. Figure 3a and 3b depict the charge/discharge behaviors of PTCLi4 and PTCI half-cells in 1M LiPF6/ EC:DMC:EMC = 1:1:1 (vol) at C/10 rate and using lithium metals as counter electrode. The first discharge curve of 156 mAh g−1 of the PTCLi4 electrode displays several slopes (Figure 3a). The first, from ~2.5 to 1.45 V (~10 mAh g−1) and the second slope, from ~1.45 to 1.15 V (~40 mAh g−1) are assigned to the irreversible reactions of lithium with the surface groups and/or absorbed on the amorphous carbon30 and a minor contribution of the SEI formation down to 1 V. These processes, also identified on the CV curve (Figure 2a, solid line), lead to their disappearance in the second discharge cycle. The plateau at ~1.1 V corresponds to the reduction processes of PTCLi4 material to PTCLi6 together with the complexation of two lithium cations (Figure 2c). From the second cycle until the 40th, a reversible capacity of ~120 mAh g−1 was measured (Figure 3c). It is important to note that the conductive carbon additive (40% of SP) contributes with ~20 mAh g−1 to the total capacity of the electrode cycled between 3 and 1 V (Figure S1). The electrochemical redox reactions observed in the range potential of 3 to 1 V vs Li+/Li0 correspond to a two-electron process,24 thereby giving theoretical capacity of 118 mAh g−1. Removing the SP contribution from the total reversible capacity of the electrode, the PTCLi4 material delivers 85 % of the expected two electron transfer process. According to previous


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studies,21,27 PTCLi4 may react with up to four lithium ions per formula unit, the reported specific capacities are about and more than 200 mAh g−1, when setting the discharge cut-off potential to 0.6 V or 0.4 V. We demonstrated that the discharge cut-off potential has a great impact on the achievable specific capacity.24 The additional low-potential capacity is related to the (de-)lithiation reaction involving the conductive carbon and not to the second reduction process, when cycling down to 0.1 V.

Figure 3. First five cycles charge/discharge of a) PTCLi4/SP/PVdF (3 to 1 V) and b) PTCI/SP/PVdF (1.5 to 3.5 V), and cycle-life of c) PTCLi4/SP/PVdF and d) PTCI/SP/PVdF. Measurements performed on coin cells using PTCLi4(PTCI)/SP/PVdF = 40/40/20 (wt%) as positive

electrode,

lithium

metal

as

counter/negative

electrode

in

1M

LiPF6/EC:DMC:EMC=1:1:1 (vol), at C/10, rt. The discharge-charge cycles of the PTCI electrode (Figure 3b) show the characteristic profile of the polyimide material, similar with the reduction and re-oxidation processes observed in the CV curve. The initial discharge capacity of ~75 mAh g−1 and representing 66 % of the theoretical specific capacity of 113 mAh g−1, decreases at 69 mAh g−1 over 40 cycles (Figure 3d). This



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capacity fading is assigned to the dissolution of the electrogenerated lithium enolates species of the residual PTCDA. Based on these stable cycling performances, we assembled an all-organic lithium-ion battery using as negative electrode the pre-lithiated PTCLi6 and the PTCI as positive electrode (Figure 4). Additionally, the combination of a negative material having a flat voltage profile (Figure 4a) with a positive material having a sloped profile (Figure 4b) and stable output voltage could be advantageously used in the determination of the state of charge in practical applications. Both materials, PTCLi4 and PTCI can be pre-lithiated, and our choice was to electrochemically lithiate the PTCLi4 electrode in order to overcome the irreversible redox reactions detected in the first discharge cycle. The lithiation of the negative material was performed electrochemically, in a coin cell vs Li metal, by one discharge step at slower rate and down to 0.95 V (C/50, Figure S2). The expected electrochemical processes at the negative and positive electrodes are depicted in Figure 4a. At the negative electrode, the PTCLi6 is oxidized to PTCLi4 together with the releasing of two Li+, which bind subsequently the positive electrode where the reduction reaction of PTCI to PTCILi2 takes place.


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Figure 4. a) The electrochemical processes involved in the full-organic lithium-ion battery PTCLi6/PTCI, b) firsts five cycles charge (in black)/discharge (in red) and c) cycle-life performances

performed

on

coin

cells

of

the

full

organic

battery,

1M

LiPF6/EC:DMC:EMC=1:1:1 (vol), at C/10, rt, between 0.5 and 2.2 V. Electrochemical performances of PTCLi6/PTCI full cell are demonstrated in Figure 4b and 4c using 1M LiPF6/EC:DMC:EMC electrolyte. As shown in Figure 4b, the all-organic cell is operating at an average voltage of ~1.2 V and has a slightly sloped voltage profile. As a positive electrode limited design, the reversible capacity of the cell was calculated using the mass of the positive material. The first discharging to 0.5 V and subsequent charging to 2.2 V exhibit capacities of 82 and respectively 78 mAh g−1 at C/10 rate, representing the full practical capacity measured for PTCI (referred to a specific current of 11.3 mA g−1). The following galvanostatic charge-discharge shows a slight decrease (dissolution of the electrogenerated lithium enolates species of the residual PTCDA) and stabilization of the capacity to 70 mAh g−1. After 200 cycles of charge/discharge at C/10, 81% of the cell capacity was maintained with high coulombic efficiencies of 99.6%. The energy density of the as-assembled cell is about 32 Whkg−1 based on the total weight of both positive and negative electrode materials. Currently, we are studying this all-organic cell using ex-situ and in-situ techniques such as FT-IR, SSNMR and EPR (electron paramagnetic resonance) to enable the increase of the practical capacities and exploring the lithium storage mechanism. In conclusion, we successfully assembled and tested a full-organic lithium-ion battery, using the poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI) as positive electrode material and the pre-lithiated tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi6) as negative electrode material. These materials were easily synthetized in one-step reactions from a 11 ACS Paragon Plus Environment


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commercially available pigment facilitating the large-scale implementation of the active materials in commercial all-organic redox batteries with a reduced environmental impact. SSNMR and FTIR studies confirmed the structures of these two materials. A combination of cyclic voltammetry, charge-discharge and cycle life studies revealed that these materials can be successfully used in full-organic lithium-ion battery. This all-organic Li-ion cell showed an average cell voltage of ~1.2 V and excellent cyclability over 200 cycles making these two organic materials promising candidates for the construction of all-organic rechargeable redox batteries. The performances of this new full-organic lithium-ion battery will be improved by in depth studies of the lithium storage mechanism.

Supporting Information Available Synthesis protocol of PTCLi4 and PTCI, description of FTIR experiments, Electrode preparation and cell test, description of NMR experiments, Discharge/charge cycles of lithium half cells using SP as active material and Voltage profile of the electrochemical lithiation of PTCLi4 to PTCLi6. This material is available free of charge via the Internet at http://pubs.acs.org.

Corresponding Author *E-mail: [email protected] (LP) *E-mail: [email protected] (TG)

Author Contributions 12 ACS Paragon Plus Environment

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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ACKNOWLEDGMENT The authors gratefully thank to the CEA for the financial support. AI deeply thank to Dominic Bresser for fruitful discussions. REFERENCES (1) (2) (3)

(4) (5) (6) (7) (8) (9)

(10)

(11) (12)

(13) (14)

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Due to their low production costs, recyclability, and structural diversity, many organic materials have been investigated as electrodes for battery applications. Conjugated carbonyls have become the most promising type of organic electrode material due to their high theoretical capacity, fast reaction kinetics, and structural diversity. In this communication two sustainable aromatic conjugated carbonyl electrode materials were assembled to an all-organic ion-lithium battery.


Perylene-Based All-Organic Redox Battery with Excellent Cycling

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