Highly reliable quinone-based cathodes and cellulose nanofiber separators: toward eco-friendly organic lithium batteries


Recently, organic compounds are considered as promising candidates for application in next-generation energy storage systems to overcome the disadvantages of conventional inorganic cathode materials, including their low specific capacity and poor disposal systems. In particular, pillar[5]quinone (P5Q) is very effective as it provides active sites that favor Li uptake and promote a high theoretical capacity. Herein, we propose P5Q-derived cathodes, which are enveloped in multi-walled carbon nanotubes and cellulose nanofibers (CNFs), fabricated by a simple vacuum-filtering method. The designed cathode solves the issues associated with organic materials, including their high solubilities in aprotic electrolytes and low conductivities. Furthermore, CNFs are introduced as alternatives to conventional polyolefin separators. CNF separators can effectively suppress the dissolution of active materials in liquid electrolytes. In addition, CNFs improve ionic conductivity (0.88 mS cm−1), electrolyte wettability (electrolyte uptake: 333.41%, porosity: 70 ± 5%), and thermal shrinkage in contrast to conventional polyolefin separators. The Li-ion battery, assembled with the suggested P5Q cathode and CNF separator, exhibits highly stable capacity retention (76.5% after 50 cycles at a 0.2 C rate) and good rate capability, although an organic electrolyte is used.

Graphic abstract


Rechargeable Li-based batteries are extensively utilized in portable devices, such as cellular phones and laptops (Armand et al. 2008; Kang et al. 2006; Li et al. 2014). These electronics are tending toward being multi-functional; consequently, energy storage devices with considerably high energy densities will be required for use within such electronics. Energy storage systems with high energy densities are also expected to dominate the market for application in large-scale power systems, particularly with the rapid development of electric vehicles (Dunn et al. 2011; Lee et al. 2016b). Therefore, enhancing the specific capacity of Li-ion batteries (LIBs) has become one of the most important objectives in battery research. Although LIBs can offer a high gravimetric capacity of 3862 mAh g−1 with Li as the anodic material (Khurana et al. 2014; Wang et al. 2013), most of the cathodic materials, which are represented as binary or ternary lithium metal (cobalt, nickel, manganese, aluminum) oxides, are mainly restricted in terms of their theoretical reversible capacities in contrast to the Li-metal anode. Thus, the cathode is the most vital component influencing the capacity of batteries. Commonly used inorganic lithium metal oxide materials, as cathodic materials, have drawbacks, such as low reversible specific capacities (< 200 mAh g−1) (Ellis et al. 2010; Scrosati et al. 2010), limited reserves of metals, and unstable price trends. Furthermore, cathodic active materials are environmentally unfriendly as their manufacturing and disposal processes are associated with large amounts of CO2 emissions (Ishiara 2002; Larcher et al. 2015; Wu et al. 2013).

To overcome these disadvantages, organic compounds have recently been considered as promising candidates for use in next-generation energy storage systems because they have many notable merits over inorganic materials, including their high theoretical capacities (> 400 mAh g−1), high safety, sustainability, environmental friendliness, and low cost (Chen et al. 2008; Liang et al. 2012; Mauger et al. 2019; Schon et al. 2016; Song et al. 2013; Wu et al. 2017). Inorganic compounds, based on intercalation reactions, depend on changes in the metal oxidation state and the charged structures of specific counter-ions, which are specific to the crystal structures of the inorganic materials; this inherently restricts the versatility of inorganic compounds. Conversely, organic compounds, based on conversion reactions, can be formulated and functionalized by various synthesis methods. This allows the optimization of the battery operating voltages by modulating the oxidation and reduction potentials. Furthermore, it is possible to change the capacity, electron-transfer rate, and crystal structure by modifying the chemical structure to match the specific requirements of the energy storage device. In addition, organic compounds are redox active toward Li metal as well as other metals, such as magnesium, zinc, and aluminum, owing to their Faradaic reactions (Levi et al. 2006).

Pillar[5]quinone (P5Q), which contains five quinone units linked by methylene bridges at the para positions, enable the achievement of a high theoretical capacity of 446 mAh g−1, and it is also highly effective as it provides active sites that favor Li-ion uptake with conversion reactions (Scheme 1a) (Ahmad et al. 2017; Chun et al. 2012; Huan et al. 2017; Zhu et al. 2014). However, these kinds of organic materials with low molecular weights have two critical issues. First, they dissolve easily in aprotic electrolytes such as carbonate-based solvents, leading to poor cyclability and rapid capacity fading (Zhu et al. 2014). Second, the low conductivities of their organic molecules limit their rate performance (Belanger et al. 2019; Lee et al. 2019; Walker et al. 2010). To address these problems, several approaches have been adpted to optimize the electrolyte. Examples of such approaches include utilizing a room-temperature ionic liquid (RTIL) (Hanyu et al. 2012, 2014), employing an all-solid-state electrolyte (Huang et al. 2013; Zhu et al. 2014), and modifying the electrode, which is analogous to the polymerization of organic compounds (Ahmad et al. 2017; Liu et al. 2011; Song et al. 2009; Yao et al. 2012; Zhan et al. 2008). However, these approaches are limited to solve the low electronic conductivity issues of organic active materials.

Scheme 1

a Structure and electrochemical redox reaction of pillar[5]quinone (P5Q), b schematic illustration of the structural features of organic-CNF batteries

To address these issues and promote the performance of organic LIBs, we utilized a nanocomposite electrode composed of P5Q as the active material, multi-walled carbon nanotubes (MWCNTs), and cellulose nanofibers (CNFs). This electrode composition was selected to enhance the electronic conductivity and to limit the solubility of organic materials in liquid electrolytes. Recently, CNFs are considered as promising sustainable materials for various applications, including in flexible electronic devices and displays (Paakko et al. 2008; Tobjörk et al. 2011). Here, we introduce CNFs, which are naturally abundant and sustainable mesoscopic materials, as binders in the electrode part and as separators. The advantages of CNFs in the cells include the following: (1) CNFs, as binders, bind securely to P5Q in the cathode to prevent the dissolution of active materials in the electrolyte and to afford a flexible substrate, thus facilitating film formation. Moreover, with CNFs, there is no ion-diffusion issue owing to their good wettability with electrolytes even with the tap density of the electrode increased to enhance the volumetric energy density. (2) CNFs, as separators, have nanoporous structures, high affinity toward liquid electrolytes, and good ionic conductivities; therefore, they exhibit superior electrochemical performances to conventional polyolefin separators, such as PP/PE/PP and PE (Chen et al. 2018, 2019; Du et al. 2017; Zhang et al. 2015). The CNF separator with a highly porous structure contributes to excellent capillary intrusion. When the electrolyte is introduced, the CNF separator absorbs the liquid electrolyte immediately thereby facilitating rapid ion transport. These characteristics of the CNF separator significantly affect its electrochemical performance (i.e., high initial capacity and stable cycle performance). (3) On the cathode side, CNF separators induce electrostatic repulsion with P5Qn− (n = 1–10). Both the deprotonation of β (1 → 4)-d-glucopyranose group of CNF and carbonyl group of quinone are negatively charged; thus they suppress the dissolution of P5Qs in liquid electrolytes and improve the cycling performances, in contrast to polyolefin separators (Huan et al. 2017). (4) On the Li-metal anode side, the uniform and unique nanoporous network channels of the CNF separators (i.e., labyrinth structures) promote a stable Li-metal surface and suppress Li dendrite formation due to their good ionic conductivity and homogeneous Li-ion flux (Chun et al. 2012; Lin et al. 2017). Furthermore, the MWCNTs with unique 3D network structures reduce the ability of P5Q to dissolve in the electrolyte by entangling with it. Furthermore, they provide pathways for efficient transportation of both electrons and ions; they act as current collectors and make direct contact with the active materials, which results in good electronic conductivities and fast charging/discharging of LIBs (Yin et al. 2018). For fabricating the P5Q/MWCNT/CNF (PMC) cathode, we suggest the vacuum-filtration method instead of the slurry-casting method to ensure a metallic current-collector-free and simple manufacturing process. Moreover, this method is cost effective, and it increases the tap densities of the electrodes. The PMC nanocomposite electrode having a CNF separator (Scheme. 1b) shows a high initial capacity of 427 mAh g−1 at a 0.2 C rate as well as highly stable capacity retention (76.5% after 50 cycles) and good rate capability.


Preparation of PMC nanocomposite electrodes and CNF separators

The PMC nanocomposite electrodes were fabricated via a vacuum-filtration method. P5Q, MWCNTs (CM-95, Hanwha Chemical Co., Ltd.), and aqueous gel CNFs (2.46 wt%, ANPOLY) were added to water with sodium dodecylbenzene sulfonate (Sigma-Aldrich) as the surfactant, and the mixture was tip-sonicated for 30 min. The composite dispersion was filtered using a cellulose acetate (CA) membrane (pore diameter: 0.2 μm, Advantec Toyo Roshi Kaisha, Ltd., Japan), and the PMC films were obtained. The contents of each material in the PMC electrode were determined by thermogravimetric analysis (TGA). The CNFs were dispersed in isopropyl alcohol (IPA) (Yan et al. 2012) by tip sonication (VC-750, Sonics & Materials, Inc.) for 20 min. The solution was poured on a CA filter paper, after which it was subjected to vacuum filtration. The CNF films were easily peeled from the filter paper to afford CNF separator.

Material characterization

The synthesized P5Q powder was characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy (500 MHz, Avance-500, Bruker), Fourier-transform infrared (FT-IR) spectroscopy, and liquid chromatography-mass spectrometry (LC–MS; 6530 Q-TOF, Agilent Technologies). The CNF separators were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), contact angles analysis, and Zeta potential analysis (ELSZ-2000, Otsuka Electronics Co., Ltd).

Electrochemical characterization

The electrochemical properties were evaluated using CR2032-type coin cells that were assembled in an argon-filled glove box. Electrochemical impedance spectroscopy (EIS) (VSP, BioLogic Science Instruments) was performed in the frequency range of 0.1 Hz to 1 MHz at room temperature with an amplitude of 5 mV rms. Galvanostatic charge/discharge test were conduccted at a 0.2 C rate using a battery cycler (WBCS 3000L, WonATech), and the full cells were analyzed in the potential range of 1.6–3.3 V vs. Li/Li+. Symmetrical cell tests (Li/Li) were performed with a current density of 1 mA cm−2 and 1 mAh. For the electrochemical tests, an ether-based electrolyte, 1 M lithium bis(trifluoromethanesulfonyl)imide(LiTFSI) in dimethyl ether (DME)/1,3-dioxolane (DOL) (volume ratio of 1/1) (PANAX ETEC) with 0.3 M lithium nitrate (LiNO3) as the additive (Fig. S1, Fig. S2) (Mauger et al. 2018). As a control device, a cathode composed of P5Qs, MWCNTs, and CNFs was prepared by the slurry-casting method. A carbonate-based electrolyte, 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC)/dimethyl carbonate (DMC)/diethyl carbonate (DEC) = 1/1/1(v/v/v), was used. The PP/PE/PP (Celgard 2325) and PE (NH616, Asahi Kasei) separators were compared with the CNF separators.

Results and discussion

Fabrication and characteristics of the PMC nanocomposite electrodes

The synthesis of P5Q was conducted in two steps as described in Fig. S3(a), which shows the overall synthesis procedure. NMR, FT-IR, and LC–MS were employed to identify each material (details in Supporting Information and Fig. S4). P5Q was obtained as a yellow powder and identified as a column-shaped particle by SEM (Fig. S3(c), Fig. S3(d)).

The cathodes, composed of P5Qs, MWCNTs, and CNFs, were fabricated via a simple vacuum-filtration method (Fig. S5(a)). The PMC cathodes were obtained as a freestanding membrane (Fig. S5(b)) and were equipped with bending capability (Fig. S5(c)). This electrode had the following advantages: (1)it benefits from the increased energy density by the elimination of the metallic current collector, which makes the electrode light and reduce the manufacturing cost (Kim et al. 2019); (2) it can increase the loading level of the cathode, in contrast to the electrode fabricated by the slurry-casting method, which has limitations due to cracking; (3) the MWCNTs with a 3D network structure are closely connected to the P5Q such that they promote the redox kinetics by promoting rapid electron transport and efficient ion diffusion (Yin et al. 2018); (4) the cathode can be used as a flexible electrode due to the CNF binder.

The SEM image shows that the MWCNTs and CNFs in the PMC electrode were physically entangled with the P5Qs (Fig. 1a); this was confirmed by the cross-sectional SEM image (Fig. S6). TGA was used to estimate the contents of each material in the PMC electrode (Fig. 1b). The ratio of P5Q to MWCNT in the PMC electrode was 1:1, and the CNF content was ~ 7%. The PMC electrode prepared by the vacuum-filtration method exhibited superior performances with an initial capacity of ~ 382 mAh g−1 and capacity fading of 60.1% between the 1st and 5th cycles, compared with the control electrode prepared by the slurry-casting method, which had an initial capacity of ~ 156 mAh g−1 and capacity fading of 77.9% between the 1st and 5th cycles in the potential range of 1.8–3.3 V vs. Li/Li+ (Fig. S7) (Zhu et al. 2014). The control cathode exhibited poor cycle performances, which is closely related to its limited reversible electrochemical redox reaction due to the high solubility of the organic active materials in the liquid electrolytes (Fig. S8(a)). Contrarily, the PMC electrode combined adequately with the MWCNTs and CNFs, trapped the active materials, and limited the solubility of the active materials in the liquid electrolytes (Fig. S8(b)). The 3D framework of the interconnected MWCNTs and CNFs exerts a confinement effect and also enhances the redox kinetics, thereby resulting in outstanding electrochemical performances (Yin et al. 2018). These results were obtained from the FT-IR spectra of the electrolytes in which the PMC electrode and the control electrode were each immersed for 48 h (Fig. S9). The dissolution of P5Qs in the liquid electrolyte was quantitatively analyzed by FT-IR spectroscopy. The band between 2800 and 2935 cm−1 was assigned to the –C-H stretching mode of the liquid electrolytes (1 M LiTFSI in DME/DOL (volume ratio of 1/1) (PANAX ETEC) with 0.3 M LiNO3 as the additive). The new peak at 1669 cm−1 was indicative of the presence of dissolved P5Qs with C=O groups (Pretsch et al. 2009). The largest peak indicated that a relatively large amount of P5Qs was dissolved from the slurry-casted control cathode contrary to the case with the vacuum-filtered PMC cathode. These results confirmed that the vacuum-filtration method is more effective for limiting the dissolution of P5Qs than the slurry-casting method, although the dissolution of active materials in the liquid electrolyte could not be completely prevented due to their intrinsically low molecular weights (He et al. 2016; Kong et al. 2009; Ma et al. 2015; Takamura et al. 2004).

Fig. 1

a SEM image of the PMC composite electrode, b TGA curves of P5Q, MWCNT, CNF, and the PMC cathode

Fabrication and characteristics of the CNF separators

The CNFs were uniformly dispersed in a high content of IPA (97% IPA and 3% water) because the porous structure varies according to the IPA/water composition ratio (Yan et al. 2012). IPA disassembles the CNFs and facilitates the creation of a nanoporous channel that promotes ion transport, whereas water enhances the packing density of the CNFs. This ratio was reasonable for the well-balanced characteristics of the CNF separators with a thickness of ~ 37 ± 0.5 μm and a density of ~ 0.20 g cm−3 (Table S1). The CNF separator, which was vacuum filtered, showed a highly porous structure composed of closely stacked CNFs (Fig. 2a), and well-distributed nanometer-scale pores were observed (dp,peak = 58.1 nm) throughout the separator (Fig. S10). These highly interconnected nanoporous networks of the CNF separator are expected to prevent thermal runaway by suppressing dendritic growth on the Li metal. In addition, the CNF separator exhibited a tensile strength of 26.2 MPa and Young’s modulus of 204 MPa; the corresponding elongation was about 12.8% (Fig S11). The CNF surface was slightly negatively charged (~ −10 mV, Fig. 2b) (Huang et al. 2016); thus, it could prevent the dissolution of active materials and the repeated electrolyte decomposition (Huan et al. 2017).

Fig. 2

a SEM image, b Zeta potentials of the CNF separators c Nyquist plot of the symmetrical cell. Stainless steel disks of the CR-2032 coin cells were used as electrodes with the liquid electrolytes (1 M LiTFSI in DME/DOL (volume ratio of 1/1) (PANAX ETEC) with 0.3 M LiNO3 as the additive) d Ionic conductivities, e DSC diagram, and f symmetrical cell tests (Li//Li) at a current density of 1 mA/cm2 and 1 mAh for CNF, PP/PE/PP, and PE separators

To characterize the wettability of polyolefin (PP/PE/PP and PE) and the CNF separators, the contact angles of each separator were measured using the same electrolyte (1 M LiTFSI in DME/DOL (volume ratio of 1/1) (PANAX ETEC) with 0.3 M LiNO3 as the additive). As shown in Fig. S12, the contact angle of the CNF separator could not be calculated because it was immersed immediately the electrolyte was introduced, whereas the contact angles of the PP/PE/PP and PE separators were calculated as 54° and 51°, respectively. The electrolyte uptakes of the PP/PE/PP, PE, and CNF separators were 138.94 wt%, 257.35 wt%, and 333.41 wt%, respectively. It was confirmed that the CNF separator had the most excellent electrolyte-philicity (Table. S1). In addition, this excellent wettability of the CNF separator with the electrolyte can be ascribed to its considerably higher porosity (70 ± 5%) compared to those of the PP/PE/PP (39%) and PE separators (46 ± 6%) (Ahn et al. 2015). It was proven that the polyolefin separators (PP/PE/PP and PE) have intrinsic hydrophobicity and a microporous structure, which is produced by stretching in the dry and wet processes (Fig. S13) (Knoche et al. 2016; Zhang et al. 2007). Conversely, the CNF separator has hydrophilic groups and a uniform and unique nanoporous structure (i.e., labyrinth structures). These characteristics of the CNF separator contribute to the capillary intrusion and rapid electrolyte absorption, which promote ionic mobility (Lee et al. 2016a). As displayed in Fig. 2c, d, the ionic conductivity of the CNF separator (0.88 mS cm−1) is higher than that of the polyolefin separators (PP/PE/PP: 0.76, PE: 0.68 mS cm−1) (Kim et al. 2018, Takamura et al. 2004). This implies that the CNF separator would exhibit better electrochemical characteristics, cycle performance, and rate capability by providing the conducting channels for Li-ions transport and accelerating the ion transport through electrolytes between the cathode and the anode.

To compare the thermal characteristics of each separator, DSC analysis was conducted to examine the melting points of the CNF and polyolefin separators; the results are shown in Fig. 2e. The spectra of the polyolefin separators showed endothermic peaks around 135 °C and 163 °C However, the spectrum of the CNF separator did not show any peak up to 250 °C; this confirms that the safety of batteries is ensured when CNFs are utilized as separators. Thermal shrinkage tests, which involve placing each separator inside a convection oven at 150 °C for 5 min, were also conducted to evaluate their thermal stabilities (Fig. S14). The results clearly showed that the CNF separators did not undergo any deformation and maintained their original dimension after being heated, whereas both the PP/PE/PP and PE separators were destroyed. This indicates that CNF separators ensure the safety of batteries at high temperatures up to 150 °C.

A symmetrical cell (Li//Li) test was carried out to examine the stability of the Li-metal surface with a current density of 1 mA cm−2 and 1 mAh, with repeated stripping and plating processes (Fig. 2f) (Pan et al. 2019). The polyolefin separators (PP/PE/PP and PE) showed unstable voltage profiles during the plating/stripping process and increased voltage difference because polyolefin separators with uneven structures and low porosities result in and inhomogeneous Li-ion distribution, which leads to the repeated undesirable formation of a solid electrolyte interphase (SEI) layer and uncontrolled Li dendrite growth (Zhang et al. 2007). On the contrary, the CNF separator showed very stable voltage profiles even after 600 h when it was used in the Li//Li symmetric cell configuration. The CNF separators, featuring highly nanoporous structures with unique pore tortuosity, exhibited good affinity toward the liquid electrolyte and a homogeneous Li+ ion flux. The nanostructures, comprising CNF, achieved enhanced reversibility of the Li plating/stripping process by forming a dense and uniform SEI layer between the Li metal and the electrolyte. The voltage hysteresis, which is the average of the voltage differences between the plating and stripping processes of each cycle, was calculated using the following equation:

$${\text{Voltage}}\,{\text{hysteresis}} = \frac{{Vmax_{stripping} - V min_{plating} }}{2}$$

with the PP/PE/PP and PE separators, the inactive layer, which acts as the resistance, was continuously accumulated on the Li-metal surface during the cycles; thus, an extremely increased ohmic potential drop was observed due to the thick SEI layer- (Kim et al. 2018). However, when the CNF separator was used as the separator, a stable profile was confirmed within the voltage range of 2 to 5 mV (Fig. S15).

Electrochemical performance of organic LIBs assembled with CNF separators

Figure 3 shows the electrochemical performance of organic LIBs, which are composed of the PMC electrode and the CNF separator. On the Nyquist plots (Fig. 3a) of the full cells in the frequency range of 1 MHz to 0.1 Hz, the CNF separator is observed to have a lower charge transfer resistance (Rct) of 49.2 Ω compared to those of the PP/PE/PP (59.1 Ω) and PE (59.0 Ω) separators. Figure S16(a) shows the cyclic voltammograms (CV) of a PMC electrode for various voltage ranges (1.8–3.3 V, 1.7–3.3 V, and 1.6–3.3 V) at a scan rate of 0.2 mV s−1. The sharpness of the redox peaks increased as the operating voltage range increased, and the PMC electrode operated stably even with 1.6–3.3 V. Thus, the electrochemical properties were analyzed in the range of 1.6–3.3 V to investigate the electrochemical characteristics with each separator. The cell with the CNF separator showed a high initial capacity of ~ 427 mAh g−1, corresponding to 95.7% of its theoretical capacity (446 mAh g−1), whereas the PP/PE/PP and PE separators exhibited initial capacities of ~ 390 mAh g−1 and ~ 387 mAh g−1, respectively (Fig. S16(b)). The PMC electrode displayed a plateau region from 2.9 to 2.5 V during the discharge step. This is related to the unique structure of the multi-carbonyl macrocyclic compound, with the multistep reduction of the carbonyl groups in the quinone units (Scheme 1a (Zhu et al. 2014)). A cyclic performance test was conducted in the voltage range of 1.6–3.3 V at a 0.2 C rate, as shown in Fig. 3b. After aging to stabilize the Li metal for five cycles, the PE/PP/PP and PP separators demonstrated specific capacity retentions of 71.6% and 62.6% for 50 cycles, respectively. Contrarily, the cell with the CNF separator showed a higher specific capacity and better cycle stability than the cell with the polyolefin separators, retaining 76.5% of its initial capacity despite considering that the liquid-type electrolyte was used. In Fig. 3c, 0.2, 0.5, 1.0, 2.0, and 0.2 C rates were applied to observe the rate capability. These results confirmed that the cell with the CNF separator was more reliable than that with the polyolefin separators, as it exhibited improved electrochemical performance. In Fig. S17, we observed the permeation of P5Qs through the PP/PE/PP, PE, and CNF separators over time. With the PP/PE/PP or PE separator, the color of the electrolyte was changed by the dissolution of P5Qs (Fig. S17 (a) and (b)), whereas no color change was observed with the P5Q permeation through the CNF separator (Fig. S17 (c)). Since the surface of the CNF separator has a slightly negative charge (~ − 10 mV) (Huang et al. 2016), it is expected to enable electrostatic repulsion with P5Qn− (n = 1–10) during the discharge process. The CNF separator prevented the migration of active materials to the anode part, which had a direct influence on the electrochemical performance. Further, the MWCNTs offered an interconnected 3D network between the P5Qs and MWCNTs in the PMC cathode. Even though the pure P5Q limits the utilization of the cathode and Li+ ion diffusion because of its electrical insulating characteristic and microrod shape, the MWCNTs enabled high specific capacities and improved the cycle/rate performance by enhancing the electronic conductivity and trapping the P5Q (Yan et al. 2012; Yin et al. 2018; Zhang et al. 2015).

Fig. 3

a Electrochemical impedance spectra of the full cells in the frequency range of 1 MHz to 0.1 Hz, b cycle performance at 0.2 C, c rate capability test between 1.6 and 3.3 V with various current densities (0.2–0.5–1.0–2.0–0.2 C) using the PMC electrode as the cathode, Li metal as the anode, and each separator (CNF, PP/PE/PP and PE)


In conclusion, we have developed eco-friendly organic LIBs with CNF separators and P5Q as the active material. Organic materials are promising candidates for use in next-generation energy storage systems because of their high theoretical capacities, high safety, sustainability, environmental friendliness, and low cost. CNF is an outstanding material not only as a binder for flexible electrodes but also as a separator for ensuring the safety of batteries; it exhibited good ionic conductivity (0.88 mS cm−1), electrolyte wettability (333.41%), porosity (70 ± 5%), and thermal stability. MWCNTs lowered the solubility of the organic cathodic materials in liquid electrolytes and solved the low conductivity problems associated with organic compounds by providing pathways for both electron and ion transport. Additionally, the PMC electrode, fabricated via the vacuum-filtration method, effectively addressed the issues of high solubility in aprotic electrolytes, in contrast to the control electrode prepared by the conventional slurry-casting method. The PMC electrode exhibited an initial capacity of ~ 382 mAh g−1 and capacity fading of 60.1% between the 1st and 5th cycles compared with the control electrode, which had an initial capacity of ~ 156 mAh g−1 and capacity fading of 77.9% between the 1st and 5th cycles. The cell composed of the PMC cathode and CNF separator showed an initial capacity as high as 427 mAh g−1 with a 76.5% capacity retention after 50 cycles at a 0.2 C rate. The proposed strategy is a promising method for fabricating other organic LIBs for use in next-generation advanced devices.


  1. Ahmad A et al (2017) A hierarchically porous hypercrosslinked and novel quinone based stable organic polymer electrode for lithium-ion batteries. Electrochim Acta 255:145–152

    CAS  Google Scholar 

  2. Ahn Y et al (2015) Enhanced electrochemical capabilities of lithium ion batteries by structurally ideal AAO separator. J Mater Chem A 3:10715–10719

    CAS  Google Scholar 

  3. Armand M et al (2008) Building better batteries. Nature 451:652–657

    CAS  PubMed  Google Scholar 

  4. Belanger RL et al (2019) Difusion control of organic cathode materials in lithium metal battery. Sci Rep 9:1213

    PubMed  PubMed Central  Google Scholar 

  5. Chen H et al (2008) From biomass to a renewable LiXC6O6 organic electrode for sustainable li-ion batteries. Chemsuschem 1:348–355

    CAS  PubMed  Google Scholar 

  6. Chen W et al (2018) Nanocellulose: a promising nanomaterial for advanced electrochemical energy storage. Chem Soc Rev 47:2837–2972

    CAS  PubMed  Google Scholar 

  7. Chen D et al (2019) An upgraded lithium ion battery based on a polymeric separator incorporated with anode active materials. Adv Energy Mater 9:1803627

    Google Scholar 

  8. Chun SJ et al (2012) Eco-friendly cellulose nanofiber paper-derived separator membranes featuring tunable nanoporous network channels for lithium-ion batteries. J Mater Chem 22:16618–16626

    CAS  Google Scholar 

  9. Du X et al (2017) Nanocellulose-based conductive materials and their emerging applications in energy devices—a review. Nano Energy 35:299–320

    CAS  Google Scholar 

  10. Dunn B et al (2011) Electrical energy storage for the grid: a battery of choices. Science 334:928–935

    CAS  PubMed  Google Scholar 

  11. Ellis BL et al (2010) Positive electrode materials for Li-ion and Li-batteries. Chem Mater 22:691–714

    CAS  Google Scholar 

  12. Hanyu Y et al (2012) Rechargeable quasi-solid state lithium battery with organic crystalline cathode. Sci Rep 2:453

    PubMed  PubMed Central  Google Scholar 

  13. Hanyu Y et al (2014) Multielectron redox compounds for organic cathode quasi-solid state lithium battery. J Electrochem Soc 161:A6–A9

    CAS  Google Scholar 

  14. He X et al (2016) Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes. Nat Nanotechnol 11:633–638

    CAS  PubMed  Google Scholar 

  15. Huan L et al (2017) Computational electrochemistry of pillar[5]quinone cathode material for lithium-ion batteries. Comput Mater Sci 137:233–242

    CAS  Google Scholar 

  16. Huang W et al (2013) Quasi-solid-state rechargeable lithium-ion batteries with a calix[4]quinone cathode and gel polymer electrolyte. Angew Chem Int Ed 52:9162–9166

    CAS  Google Scholar 

  17. Huang P et al (2016) A versatile method for producing functionalized cellulose nanofibers and their application. Nanoscale 8:3753–3759

    CAS  PubMed  Google Scholar 

  18. Ishiara K (2002) 5th ecobalance conference. Tsukuba

  19. Kang K et al (2006) Electrodes with high power and high capacity for rechargeable lithium batteries. Science 311:977–980

    CAS  PubMed  Google Scholar 

  20. Khurana R et al (2014) Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. Chem Soc 136:7395–7402

    CAS  Google Scholar 

  21. Kim H et al (2018) Highly stable lithium metal battery with an applied three-dimensional mesh structure interlayer. J Mater Chem A 6:15540–15545

    CAS  Google Scholar 

  22. Kim JH et al (2019) Nanomat Li–S batteries based on all-fibrous cathode/separator assemblies and reinforced Li metal anodes: towards ultrahigh energy density and flexibility. Energy Environ Sci 12:177–186

    CAS  Google Scholar 

  23. Knoche T et al (2016) Effect of annealing temperature on pore formation in preparation of advanced polyethylene battery separator membranes. Mater Today Commun 8:23–30

    CAS  Google Scholar 

  24. Kong BS et al (2009) Layer-by-layer assembly of graphene and gold nanoparticles by vacuum filtration and spontaneous reduction of gold ions. Chem Commun 16:2174–2176

    Google Scholar 

  25. Larcher D et al (2015) Towards greener and more sustainable batteries for electrical energy storage. Nat Chem 7:19–29

    CAS  PubMed  Google Scholar 

  26. Lee H et al (2016a) Structural modulation of lithium metal-electrolyte interface with three-dimensional metallic interlayer for high-performance lithium metal batteries. Sci Rep 6:30830

    CAS  PubMed  PubMed Central  Google Scholar 

  27. Lee JH et al (2016b) High-energy-density lithium-ion battery using a carbon-nanotube-Si composite anode and a compositionally graded Li[Ni0.85Co0.05Mn0.10]O2 cathode. Energy Environ Sci 9:2152–2158

    CAS  Google Scholar 

  28. Lee S et al (2019) The role of substituents in determining the redox potential of organic electrode materials in Li and Na rechargeable batteries: electronic effects vs. substituent-Li/Na ionic interaction. J Mater Chem A 7:11438

    CAS  Google Scholar 

  29. Levi MD et al (2006) Unusually high stability of a poly(alkylquaterthiophene-alt-oxadiazole) conjugated copolymer in its n and p-doped states. Chem Commun 31:3299–3301

    Google Scholar 

  30. Li L et al (2014) Advances and challenges for flexible energy storage and conversion devices and systems. Energy Environ Sci 7:2101–2122

    CAS  Google Scholar 

  31. Liang Y et al (2012) Organic electrode materials for rechargeable lithium batteries. Adv Energy Mater 2:742–769

    CAS  Google Scholar 

  32. Lin D et al (2017) Reviving the lithium metal anode for high-energy batteries. Nat Nanotechnol 12:194–206

    CAS  PubMed  Google Scholar 

  33. Liu K et al (2011) Poly(2,5-dihydroxy-1,4-benzoquinonyl sulfide) (PDBS) as a cathode material for lithium ion batteries. J Mater Chem 21:4125–4131

    CAS  Google Scholar 

  34. Ma CW et al (2015) A paper-like micro-supercapacitor with patterned buckypaper electrodes using a novel vacuum filtration technique. In: 28th IEEE international conference on micro electro mechanical systems (MEMS), pp 1067–1070

  35. Mauger A et al (2018) A comprehensive review of lithium salts and beyond for rechargeable batteries: progress and perspectives. Mater Sci Eng, R 134:1–21

    Google Scholar 

  36. Mauger A et al (2019) Recent progress on organic electrodes materials for rechargeable batteries and supercapacitors. Materials 12:1770

    CAS  PubMed Central  Google Scholar 

  37. Paakko M et al (2008) Long and entangled native cellulose I nanofibers allow flexible aerogels and hierarchically porous templates for functionalities. Soft Matter 4:2492–2499

    CAS  Google Scholar 

  38. Pan R et al (2019) Sandwich-structured nano/micro fiber-based separators for lithium metal batteries. Nano Energy 55:316–326

    CAS  Google Scholar 

  39. Pretsch E et al (2009) Structure determination of organic compounds tables of spectral data. Springer, Berlin

    Google Scholar 

  40. Schon TB et al (2016) The rise of organic electrode materials for energy storage. Chem Soc Rev 45:6345–6404

    CAS  PubMed  Google Scholar 

  41. Scrosati B et al (2010) Lithium batteries: status, prospects and future. J Power Sources 195:2419–2430

    CAS  Google Scholar 

  42. Song Z et al (2009) Anthraquinone based polymer as high performance cathode material for rechargeable lithium batteries. Chem Commun 45:448–450

    Google Scholar 

  43. Song Z et al (2013) Towards sustainable and versatile energy storage devices: an overview of organic electrode materials. Energy Environ Sci 6:2280–2301

    CAS  Google Scholar 

  44. Takamura T et al (2004) A vacuum deposited Si film having a Li extraction capacity over 2000 mAh/g with a long cycle life. J Power Sources 129:96–100

    CAS  Google Scholar 

  45. Tobjörk D et al (2011) Paper electronics. Adv Mater 23:1935–1961

    PubMed  Google Scholar 

  46. Walker W et al (2010) Ethoxycarbonyl-based organic electrode for Li-batteries. J Am Chem Soc 132:6517–186523

    CAS  PubMed  Google Scholar 

  47. Wang X et al (2013) An aqueous rechargeable lithium battery using coated Li metal as anode. Sci Rep 3:1401

    PubMed  PubMed Central  Google Scholar 

  48. Wu HP et al (2013) An organic cathode material based on a polyimide/CNT nanocomposite for lithium ion batteries. J Mater Chem A 1:6366–6372

    CAS  Google Scholar 

  49. Wu Y et al (2017) Quinone electrode materials for rechargeable lithium/sodium ion batteries. Adv Energy Mater 7:1700278–1700304

    Google Scholar 

  50. Yan J et al (2012) Advanced asymmetric supercapacitors based on ni(oh)2/graphene and porous graphene electrodes with high energy density. Adv Funct Mater 22(632):2641

    Google Scholar 

  51. Yao M et al (2012) Redox active poly(N-vinylcarbazole) for use in rechargeable lithium batteries. J Power Sources 202:364–368

    CAS  Google Scholar 

  52. Yin Z et al (2018) Copper nanowire/multi-walled carbon nanotube composites as all-nanowire flexible electrode for fast-charging/discharging lithium-ion battery. Nano Res 11:769–779

    CAS  Google Scholar 

  53. Zhan L et al (2008) PEDOT: cathode active material with high specific capacity in novel electrolyte system. Electrochim Acta 53:8319–8323

    CAS  Google Scholar 

  54. Zhang SS et al (2007) A review on the separators of liquid electrolyte Li-ion batteries. J Power Sources 164:351–364

    CAS  Google Scholar 

  55. Zhang H et al (2015) Preparation and characterization of a lithium-ion battery separator from cellulose nanofibers. Heliyon 1:e00032

    PubMed  PubMed Central  Google Scholar 

  56. Zhu Z et al (2014) All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode. J Am Chem Soc 136:16461–16464

    CAS  PubMed  Google Scholar 

Download references


This research was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT, Ministry of Science and ICT) - Nano-Material Technology Development Program (2016M3A7B4910458) and Basic Science Research Program (2019R1A2C1009239).

Author information




Writing—original draft preparation: [Gayeong Yoo], [Seonmi Pyo]; Formal analysis and investigation: [Gayeong Yoo], [Seonmi Pyo]; Methodology: [Gayeong Yoo], [Seonmi Pyo], [Youn Sang Kim]; Data curation and visualization: [Youn Jun Gong], [Jinil Cho], [Heebae Kim]; Conceptualization: [Youn Sang Kim], [Jeeyoung Yoo]; Writing- review and editing: [Jeeyoung Yoo]; Funding acquisition: [Youn Sang Kim], [Jeeyoung Yoo]; Supervision: [Youn Sang Kim], [Jeeyoung Yoo].

Corresponding authors

Correspondence to Youn Sang Kim or Jeeyoung Yoo.

Ethics declarations

Conflict of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 6899 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yoo, G., Pyo, S., Gong, Y.J. et al. Highly reliable quinone-based cathodes and cellulose nanofiber separators: toward eco-friendly organic lithium batteries. Cellulose 27, 6707–6717 (2020). https://doi.org/10.1007/s10570-020-03266-8

Download citation


  • Organic lithium batteries
  • Cellulose nanofibers
  • Carbon frame
  • Eco-friendly LIBs
  • Next generation batteries