Enhancing the understanding of the redox properties of lithium-inserted anthraquinone derivatives by regulating molecular structure

doi:10.1016/j.jelechem.2021.115172

Journal of Electroanalytical Chemistry

Volume 887, 15 April 2021, 115172

https://doi.org/10.1016/j.jelechem.2021.115172 Get rights and content

Highlights

•
The effect of -CF₃ and -C₂F₅ on redox properties of AQ are firstly investigated by DFT.
•
Overall influence ability of substituents on redox potentials of AQ is -C₂F₅ > -CF₃ > -F > -Cl > -Br.
•
Full -C₂F₅ substituted EWGs on AQ exhibits the highest reductional potential in five types EWGs.

Abstract

Organic compounds, such as quinone compounds, are promising renewable electrode materials for lithium ion batteries (LIBs) with redox stability and structural diversity. However, quinone electrode materials (QEMs) have low redox potentials as cathode and high solubility. In particular, low redox potentials result in low energy density and power density of QEMs. In this work, the substituent influence on anthraquinone (AQ) are studied by density-functional theory calculations to predict redox properties of potential positive materials for LIBs. The calculated results indicate a positive correlation between the redox potentials and the number of substituent, and the full substitution groups with electron-withdrawing groups (EWGs) gain the highest redox potentials, which is borne out by lowest unoccupied molecular orbital (LUMO). Mono-substitution, however, bring the highest specific capacity. Also, the different substituent sites on AQ can influence the redox potentials of AQ. Moreover, the calculation of molecular electrostatic potential (MESP) reveal carbonyl groups with local minima of MESP easily tend to bind lithium. AQ with Li binding carbonyl groups is more stable than the bare AQ, which is confirmed by the calculation of nucleus-independent chemical shift. At the same time, lithium atoms also easily bind electronegative atoms of EWGs and form intramolecular lithium bonds, which improve the thermodynamic stabilization of the lithiation AQ. The present study provide the new understanding with guidelines to design potential organic cathode materials with efficiency for LIBs.

Graphical abstract

The reductional potentials of AQ is positive correlation with the number of EWGs, and the overall effect ability of substituents on redox potentials of AQ is -C₂F₅>-CF₃>-F>-Cl >-Br under the condition of the same number of EWGs.

Introduction

Currently, the new materials are widely explored and investigated in secondary batteries owing to their high energy densities and power densities [1], [2], [3], [4], [5]. Organic electrode materials represent new candidates for next green and sustainable lithium ion batteries (LIBs) because of processing, renewability, redox stability and structural diversity [6], [7], [8], [9], [10]. A variety of redox-active organic electrode materials, such as conducting polymers, radical compounds, organosulfur compounds, carbonyl-based compounds, have been widely investigated. Among those organic electrode materials, quinone electrode materials (QEMs), which is belong to the type of carbonyl-based electrode materials, attract widely attention owing to its high theoretical specific capacity and rapid reaction kinetics. However, QEMs face two challenges of low redox potentials as cathode and high solubility. In particular, low redox potentials result in low mass energy density and power density of QEMs. Therefore, some experimental strategies, such as the introduction of electron groups, were done to improve the redox performance of QEMs [11], [12], [13], [14], [15]. Experimental searching, however, bring a large challenge because it is extremely time-consuming and expensive to the identification of optimal redox couples of the large number of QEMs and its derivatives. A rapid screening with minimal cost, computational method, could be viable alternative approach [16], [17]. Some QEMs and its derivatives with the redox properties, such as different number carbonyl groups on different sites, the introduction of the electron groups and fused heteroatoms, were examined by computational investigation, which offer some understanding of electrochemical windows at the molecular level.

In order to investigate the redox propertied effect of different number carbonyl groups on different sites of QEMs, Chen et al used two new methods, vertical electron affinity with consideration of solvation effect about the number of electron accommodation for quinones during lithiation process, and ΔA_2Li about the relationship between aromaticity and redox potential, to calculate the redox potentials of 20 parent quinone isomers for LIBs. The calculated results exhibited an increasing order of redox potentials as para-quinones < discrete-quinones < orthoquinones [18]. At the same time, a new tool of Molecular Electrostatic Potential (MESP) was used by Chen et al to investigated lithiation process of seven QEMs for LIBs, such as (1,4-benzoquinone (1,4-BQ), 1,4-phenanthraquinone (1,4-PQ), 1,7-anthraquinone (1,7-AQ), 1,7-naphthoquinone (1,7-NQ), 5,7,12,14-pentacenetetrone (PT, C₂₂H₁₀O₄), and tetra-(phthalimido)-benzoquinone (TPB, C₃₈H₁₆N₄O₁₀), polyanthraquinonyl sulfide (PAQS). The smaller values of the local minima of MESP, the easier Li binding carbonyl groups, making the redox potentials of QEMs high [19]. Zhou et al used the Clar’s aromatic sextet theory to investigate the correlation between ΔC_2Li about characterizing aromaticity change during lithiation and redox potentials of nine QEMs, such as 2,7-Phenanthrenedione, 2,3,6,7-Phenanthrenetetrone, 2,3,6,7,10,11-Triphenylenehexone, which indicated the 2,7-Phenanthrenedione has the largest ΔC_2Li value and the highest work voltage (3.11 V), and 2,3,6,7,10,11-Triphenylenehexone has the largest theoretical energy density of 1386 Wh kg⁻¹ among nine QEMs [20]. For the influence of heteroatom on redox properties of QEMs, Yoshida et al investigated the effect of the replacement of the two and four CH moieties β to the carbonyl group of anthraquinone and its derivatives with nitrogen atoms for LIBs. Four N atoms fused heteroaromatic anthraquinone has high reductional potential with over 3.0 V by the theoretical calculation. Lithium could coordinate β N atom and carbonyl group simultaneously, which formed a five-membered rings [21]. The similar theoretical calculation also demonstrated CH moieties of the other quinones being replaced by N atoms formed fused heteroaromatic quinone significantly enhanced the work voltage of QEMs for LIBs [22], [23].

Except the different number carbonyl groups on different sites and the introduction of fused heteroatoms gained high redox potentials of QEMs for LIBs. The addition of electron groups, especially electron-withdrawing groups (EWGs), also can bring important effect on redox properties of QEMs for LIBs. Wang et al added different number EWGs of –NO₂, -SO₃H, -PO₃H₂, –COOH, –CN on different site fused N and S heteroaromatic anthraquinone and phenanthraquinone for LIBs. Theoretical calculation results showed the redox potentials increased with the number increase of EWGs, full substitution leaded to the highest redox potentials. However, single substitution is the best choice to gain the largest the mass energy density. The formation of intramolecular lithium bonds (ILBs) between Li atoms and the electronegative atoms of the substituent groups enhanced redox potentials and the stability of molecule structure [24]. The different number of -CF₃ groups from one to four were also introduced on benzoquinone and were studied by DFT calculations for sodium ion batteries (SIBs), respectively, which confirmed the redox potentials increased with the increase of -CF₃ groups. However, the four -CF₃ groups added on benzoquinone molecule structure resulted in the significantly decreases of gravimetric charge capacity [25]. At the same time, the different number of EWGs (Cl) and electron donating groups (EDGs) (–CH₃, –CH₂CH₃, -C(CH₃)₃, -Ph and so on) were introduced on different sites of anthraquinone for all-organic redox flow batteries by Assary et al. The theoretical calculation showed the EWGs could increase the redox potentials of anthraquinone. In particular, the full substitution of EWGs can be increased by 0.4 V for redox potentials of anthraquinone. Also, the substitution of different sites could influence the redox potentials of anthraquinone [26]. Er et al calculated redox potential influence of the R-groups as substituents on a total of 1,710 QEMs for all organic redox flow battery, such as –OH, -F, -Cl, -CF₃, –CN, –COOH, -PO₃H₂, -SO₃H, and –NO₂, which indicated the full substitution of electron groups greatly enhanced the redox potentials of QEMs compared with that of mono-substituted electron groups [27].

It can be seen from above reports that electron groups, substituted groups and substituted sites can change redox properties of QEMs. Although the effect of a variety of electron groups on electrochemical performance of QEMs were studied by density-functional calculations, the influence of EWGs of halogen, -CF₃ and -C₂F₅ on redox properties of anthraquinone are not systemically investigated. In this work, we performed density-functional calculations to determine the redox potentials, in combination of the structural stability, the electronic, thermodynamic and magnetic properties of anthraquinone molecules with those EWGs, which display a systematic study of families of anthraquinone with the goal of increasing gravimetric energy density of those cathode materials for LIBs. Typically, the effect of the different number of EWGs (-F, -Cl, -Br, -CF₃, -C₂F₅) and the different sites of EWGs on redox potentials of anthraquinone are explored in detail. Furthermore, the natures of lithium binding EWGs and forming intramolecular lithium bonds (ILBs) are investigated. Also, the stability of the lithium-inserted system are estimated by aromaticity obtained by using the nucleus independent chemical shift (NICS).

Section snippets

Computational details

All density functional theory (DFT) calculations presented in this work are performed using Gaussian 16 software [28]. Typically, the B3LYP/6–311 + G(d) level of theory is used to optimize the structure and calculate the energy of all molecules. In order to approximate the solvation effect, a single point energy calculation is performed by using propylene carbonate (PC) as the electrolyte solvent. Its static relative permittivity is 64.9, and its dynamic relative permittivity is 2.02 [23]. The

The choice of 9,10-anthraquinones (AQ) as research object

In order to investigated the ability of lithiation on anthraquinone isomers, molecular electrostatic potential (MESP) is used to assess the lithium binding sites on anthraquinone isomers, which reveals the electrostatic interaction between anthraquinone electrodes and lithium ions. Fig. 1 shows MESP plots of anthraquinone isomers obtained by calculating MESP with the combination method of Multiwfn [36] and VMD [37], and the red region and blue region represent positive electricity and negative

Conclusion

Five types of EWGs on different substituted sites of AQ were systematically designed by incorporating different numbers of EWGs. The theoretical performance parameters of AQ with EWGs were obtained, and the redox properties and thermodynamic properties were investigated by density-functional theory calculations to estimate their potential as cathodes for LIBs. The calculated results indicate that the addition of EWGs on AQ are favorable in the enhancement of redox potentials. The stronger the

Declaration of Competing Interest

The authors declare no conflict of interest.

Acknowledgments

The authors are grateful to the National Natural Science Foundation of China (Grant No. 21875076, 21673085), Science and Technology Planning Project of Guangdong Province (2018A05050677).

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View full text

Enhancing the understanding of the redox properties of lithium-inserted anthraquinone derivatives by regulating molecular structure

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Computational details

The choice of 9,10-anthraquinones (AQ) as research object

Conclusion

Declaration of Competing Interest

Acknowledgments

J. Electroanal. Chem.

Electrochim. Acta

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Angew. Chem. Int. Ed.

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Adv. Mater.

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Sci. Bull.

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Adv. Energy Mater.

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J. Phys. D: Appl. Phys.

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Chem. Rev.

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Adv. Energy Mater.

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Angew. Chem. Int. Ed.

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Adv. Energy Mater.

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Chem. Sci.

Rechargeable organic lithium-ion batteries using electron-deficient benzoquinones as positive-electrode materials with high discharge voltages

J. Mater. Chem. A

Structural modulation of anthraquinone with different functional groups and its effect on electrochemical properties for lithium-ion batteries

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Sci Data

The structure-electrochemical property relationship of quinone electrodes for lithium-ion batteries

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J. Phys. Chem. Lett.

Designing high-voltage carbonyl-containing polycyclic aromatic hydrocarbon cathode materials for Li-ion batteries guided by Clar's theory

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Energy Technol.