Techno-Economical Feasibility of Biocellulose Membrane along with

Research Article Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

pubs.acs.org/journal/ascecg

Techno-Economical Feasibility of Biocellulose Membrane along with Polyethylene Film as a Separator for Lead-Acid Batteries Sung-Hee Roh,†,# Gowthami Palanisamy,†,# T. Sadhasivam,‡,§ Jae-Eun Jin,∥ Jin-Yong Shim,∥ and Ho-Young Jung*,‡,§,⊥ †

College of General Education, Chosun University, 309 Pilmoon- daero, Dong-gu, Gwangju 61452, Republic of Korea Department of Environment & Energy Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 61186, Republic of Korea § Center for Energy Storage System, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 61186, Republic of Korea ∥ Automotive Research and Development Division, HYUNDAI MOTOR GROUP, 150 Hyundaiyeonguso-ro, Namyang-eup, Hwaseong-si, Gyeonggi-do 445-706, Republic of Korea ⊥ Energy Planet Co. Ltd., 308, Venture Center, Techno Park, 333 Cheomdangwagi-ro, Buk-gu, Gwangju 61186, Republic of Korea

Downloaded via UNIV AUTONOMA DE COAHUILA on April 19, 2019 at 22:39:48 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡

S Supporting Information *

ABSTRACT: In this present investigation, we applied an ecofriendly bacterial cellulose (BC) membrane along with a polyethylene (PE) separator as a separator for lead-acid battery systems. The key factor of the research is to lower the cost of the lead-acid battery by introducing the BC membrane along with a thin PE separator. The specific surface areas of the BC membrane and the PE separator were 46.72 and 35.89 m2 g−1, respectively, with high porosity, which can enhance the electrolyte uptake and movement. The identified pore sizes of the BC membrane and the PE separator are 13.67 and 56.18 nm, respectively. The closely arranged microfibrils in the BC membrane with the smaller pore size can uptake a high amount of electrolyte, and it can hold it for a long period with the hydrogen interactions. In addition, the BC membrane and the PE separator exhibited higher thermal stabilities. The water uptake property of the BC membrane is 130% at 30 °C, which results in considerable electrolyte uptake. The ion exchange capacity of AGM, PE separator, and BC membrane are ∼0.0, ∼ 0.0, and 0.127 meq/g, respectively. The higher IEC is attributed to the presence of hydrophilic functional groups in the BC membrane, which increase the ion transportation in the membrane. The ion conductivity of the BC membrane is considerably higher than those of the AGM and PE separator. The charge and discharge performances of the AGM and BC-PE battery systems were analyzed using lead-acid battery cells. The exhibited discharge performances of both battery systems were considerably similar at 0.1 and 0.2 A discharge current. The final discharge capacities of the AGM battery and the BC-PE battery were 0.96 and 0.94 Ah, respectively, at 0.1 A under identical conditions. A considerable cyclic stability was observed in the BC-PE battery system during long-term operation. From our experimental analysis results, a cost-effective hybrid combination of a BC membrane along with a PE separator can be considered as an efficient separator for lead-acid battery systems. KEYWORDS: AGM separator, biocellulose membrane, polyethylene separator, lead-acid battery, hybrid membrane

■

INTRODUCTION With a focus on energy shortage issues in real-world applications and environmental concerns, the electrochemical energy storage system of batteries has gained more attention in recent years.1−3 To meet battery requirements, the lead-acid battery (LAB) has gained more consideration because of its low manufacturing cost compared to other battery systems.4−7 In addition, it possesses long cycle life with significant performance, and it can be effectively recycled (97%) at endof-life.8 A LAB is constructed with positive lead dioxide (PbO2) electrodes and negative lead (Pb) electrodes in series separated by separators including electrolyte solution. The © XXXX American Chemical Society

electrochemical reactions of the positive and negative electrodes are as follows9−11 In the positive electrode PbO2 + HSO4 − + 3H+ + 2e− ↔ PbSO4 + 2H 2O

(1)

In the negative electrode Pb + HSO4 − ↔ PbSO4 + H+ + 2e−

(2)

Received: February 2, 2019

A

DOI: 10.1021/acssuschemeng.9b00694 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

ACS Sustainable Chemistry & Engineering

■

The overall reaction is Pb + PbO2 + 2H 2SO4 ↔ 2PbSO4 + 2H 2O

Research Article

EXPERIMENTAL SECTION

Materials. The polyethylene separator was supplied by Ube Maxell Co., Ltd. Bacterial cellulose membrane was purchased from Hnb Vina Co., Ltd., Vietnam. Sulfuric acid (H2SO4, 98%) was purchased from Sigma-Aldrich. Lead electrode (Pb), lead dioxide (PbO2), and AGM separator were supplied by Sebang Global Battery Co. Ltd., South Korea. Material Structural and Microstructural Characterization. A Fourier transform infrared (FTIR) spectrometer (PerkinElmer Spectrum 400 and a Thermo Scientific Nicoleti S5) was used to identify the presence of functional groups in the samples. Nitrogen adsorption/desorption isotherm analysis using a BEL (Belsorp II) was performed for measuring specific surface area through the BET technique. The microstructural properties of the materials were observed using a scanning electron microscope (SEM, Hitachi SU70). The thermal stabilities of the samples were analyzed by thermal shrinkage measurement and TGA using a Shimadzu (DTG-60H). Before thermal stability analyses, the samples were dried to remove moisture content. For thermal shrinkage measurement, desired sizes (3 × 3 cm) of PE separator and BC membrane were cut into pieces and stored separately at 25, 60, and 80 °C for 30 min. For TGA analysis, sample pretreatment was performed by heating at 100 °C for 20 min in a N2 atmosphere. Then, the thermal stability was measured up to 800 °C at a constant heating rate of 10 °C/min in a N2 atmosphere. Water Uptake, Ion Exchange Capacity, and Ionic Conductivity. For WU (%) analysis, the separator/membrane was cut into 4 cm × 4 cm samples and then dried for 24 h in a hot-air oven. The weight of the dried samples was measured. Then, the samples were immersed in deionized (DI) water for 24 h at various fixed temperatures (30 °C, 50 °C, and 70 °C). Afterward, the samples were removed from the water, and the water drops on the sample surface were removed. The weight of the hydrated sample was measured. The WU properties of the samples were calculated as follows21

(3)

In LABs, microfiber-glass of absorptive glass mat (AGM) is widely used as the separator because of its higher electrolyte wicking properties.12−14 Furthermore, AGM exhibits the advantageous effect of stability in an acidic environment because of its zero contact angle with the acid.15,16 However, drawbacks are also associated with AGM separators includiong cost and thermal runaway.14 The AGM separator can produce heat in reduction reactions during constant-voltage overcharge.17 The generated heat can cause an undesirable temperature rise or thermal runaway in LAB cells.14,17−20 In addition, this condition is perhaps caused by the separator structure, acid stratification, and electrolyte drainage in the separator.13,14,17 In recent years, numerous efforts have been dedicated in the energy storage area to enhance the performance and lower the manufacturing cost of separator/ membranes.21−23 Among the various efforts, a new approach of eco-friendly and cost-effective biocellulose (BC) membranebased separators has gained significant consideration for many energy storage devices where membranes are used as separators to improve ion transportation.24−26 Cellulose membranes possess more advantages such as low cost, outstanding hydrophilicity (more wettability), high water holding capacity, improved thermal and chemical stability, and excellent mechanical stability,27,28 and they can meet the requirements of a separator for LAB. Furthermore, cellulose is renewable, abundant (from plants, bacteria, and other organisms), biodegradable, and biocompatible.27 The properties of BC membrane can be tuned on the basis of the production source, physical and chemical parameters for microbial growth, thickness, porosity, wettability, stability, and surface functional groups. The commercial separators produced from polyolefins (such as polyethylene, polyvinyl chloride, and polypropylene) have been used extensively as separators in different energy storage systems because of their high tensile strength and electrochemical stability.29,30 Among them, polyethylene (PE) separators possess unique properties such as cost-effective raw material and robustness against premature deterioration because of their excellent ductility, higher mechanical strength, and prevention of electrical short-circuits.31−33 In the present research work, we used a BC membrane along with a PE film as a separator for a LAB system. The main objective of the present investigation is to introduce the cost-effective separator and evaluate its possibilities on electrochemical performance for LAB. To the best of our intellectual awareness in the context of LAB system development, this is the first report using a hybrid system of BC membrane along with PE film as a separator for a LAB system. The structural, microstructural, and thermal properties, as well as specific surface area (SSA) properties, were examined through spectroscopy, microscopy, thermogravimetric analysis (TGA), and Brunauer−Emmett− Teller (BET; N2 adsorption/desorption) techniques. The physicochemical properties were analyzed through water uptake (WU), ion exchange capacity (IEC), and ionic conductivity (IC). A LAB unit cell was constructed with the hybrid separator (BC membrane with PE separator) for demonstration, and its electrochemical properties were measured through battery performance testing.

water uptake (%) =

Wwet − Wdry Wdry

× 100 (4)

where Wwet is the weight of the completely hydrated membrane and Wdry is the weight of the completely dehydrated membrane. For IEC analysis, acid−base titration was used. The desired amount of the samples was dried in a hot-air oven. Then, the sample weight was measured, and the samples were immersed in 1 M NaCl solution for 24 h to replace the H+ ions with Na+ ions. Finally, the exchanged protons in the solution were titrated against a 0.01 M NaOH solution using phenolphthalein as an indicator. The IEC values were calculated by the following equation34 IEC (mequiv g −1) =

C NaOH × VNaOH Wdry

(5)

where Wdry is the dried weight of the membrane, CNaOH is the molar concentration of the NaOH solution, and VNaOH is the consumed volume of the NaOH solution. For measuring the ion conductivity (IC), we used the AC impedance method from 1 MHz to 100 mHz with a SP-150 impedance spectroscopy (Biologic Science Instruments) to determine the resistance of the separator and the membrane. The separator/ membrane were cut (1 cm × 6 cm) and soaked for 24 h at room temperature. Then, the separator/membrane was fixed in an ion conductivity measurement cell (Teflon cell equipped with stainlesssteel electrodes), and it was placed in DI water to measure the conductivity. The ionic conductivity of the separator/membrane was calculated using the following equation35 proton conductivity (Scm−1) =

L R×A

(6)

where L is the exact distance between the two electrodes, R is the measured resistance from the impedance plot (Ω), and A is the separator/membrane cross-sectional area. B


Research Article

ACS Sustainable Chemistry & Engineering Construction of the Unit Cell and Electrochemical Characterization. A LAB was assembled with Pb as the negative electrode, PbO2 as the positive electrode, and a separator. The size of the positive and negative electrodes was 4.3 cm × 5.6 cm (height × length). The positive and negative electrodes were separated by the folded BC membrane sheets along with a PE separator sheet. Sulfuric acid (H2SO4, Sigma-Aldrich) with the specific gravity of 1.28 was used as an electrolyte. Before the cell was assembled, the electrolyte solution was introduced into the pores of the PE separator. In addition, the surface treated BC membrane was soaked in the electrolyte solution for 12 h. The construction and assembly of the LAB is shown in Figure 1. The charge and discharge characteristics of

Figure 2. FT-IR spectra of (a) AGM separator, (b) BC membrane, and (c) PE separator.

BC membrane and the PE separator were determined through BET measurements. Figure 3 and Figure S1 represent the nitrogen adsorption/desorption isotherm, pore size distribution analysis, and BET curves of the (a) AGM separator, (b) BC membrane, and (c) PE separator. The total SSAs of the BC membrane, PE separator, and AGM were 46.72, 35.89, and 1.36 m2 g−1, respectively. Compared to that of the AGM separator, the SSA is considerably higher for the BC membrane. The higher surface area in the BC membrane perhaps results from the higher porosity. The porosity properties of the samples were analyzed through Barrett− Joyner−Halenda (BJH) analysis. The identified pore size distributions of the AGM separator, BC membrane, and PE separator were 13.835, 13.673, and 56.184 nm, respectively. In the BC membrane, the porous structure influenced the higher surface area. The arrangement of cellulose fibrils influences the surface area and porosity of BC.39,40 Furthermore, the SSA and porosity of the BC membrane can be tuned by different media, bacterial strains, and physical parameters. In addition, the SSA and porosity can be altered to the PE separator through the addition of catalytic materials and polymerization processes. The microstructural morphologies of the AGM separator, BC membrane, and PE separator were determined through SEM analysis, as shown in Figure 4. Figure 4a shows a loose arrangement of fibers in AGM with varying diameters and without interconnection.41 These arrangements provide the numerous void spaces, which can influence electrolyte holding. As shown in Figure 4b, the highly porous and fibrous network structures were identified in the BC membrane. The BC membrane was found to be distributed with a higher amount of mesopores. The microfibrils were arranged in a random organization with large spaces between them. These resulted in a pore formation with different sizes and surface diameters throughout the entire BC membrane. The smaller pores in BC help to retain electrolyte for a longer time in the matrix.40 The closely arranged microfibrils in the BC membrane can uptake a large amount of electrolyte and hold it for a longer period by hydrogen bonding interactions.42 In the PE separator, a sheetlike structured morphology with porous structure was identified (Figure 4c). The porosity was uniformly patterned throughout the separator. The identified abundant open pores in the PE separator can provide a ionic diffusion path during the electrochemical reaction.

Figure 1. Schematic representation of lead-acid battery (BC membrane with PE separator and electrodes). the battery were determined through a Famtech Co. Ltd. battery testing system (model no. CT-4008-5V6A-S1-F). To measure the electrochemical activities, the battery was charged and discharged at different C-rates. To determine the starting discharge voltage, discharge performance, and capacity, the battery was charged at 0.1 A constant current for 10 h (maximum voltage limit: 2.33 V) and then the battery was discharged by 0.1 A current until the cutoff voltage reached 1.75 V. The similar voltage range and time were used to measure the battery at 0.2 A discharge current. For measuring the long-term cycle operation, the battery was charged to 50% State of Charge (SoC). Then, the long-term operation performances of the cells were tested (by HRPSoC cycling conditions) as charge at 0.1A for 15 s (upper voltage limit 2.33 V), rest for 3 s, discharge at 0.1A for 15 s, and rest for 3 s. The end of the discharge voltage was measured as cell voltage for each cycle.

■

RESULTS AND DISCUSSION FTIR analyses were carried out to recognize the presence of functional groups in the separators; the corresponding data of the PE separator, BC membrane, and AGM separator are shown in Figure 2. In the AGM separator spectrum, a major broad peak appeared at, approximately, 1015 cm−1, which corresponds to the Si−O−Si stretching vibration.36 In the BC membrane (as shown in Figure 2b), the characteristic peaks observed at 3339.38 cm−1 are associated with the O−H stretching vibration. The peak positioned at 2892 cm−1 corresponds to the C−H stretching vibration. In addition, the peaks at 1427, 1314, 1160, 1106, and 1055 cm−1 result from C−C stretching vibrations, skeletal vibrations, and ring vibrations in the BC membrane.37 For the PE separator, the characteristic peaks were observed at 2800−3000 cm−1 for C− H stretching vibrations and 1456 cm−1 for C−H bending vibration.38 The FTIR spectra successfully confirmed the structures of the AGM separator, BC membrane, and PE separator. The specific surface area (SSA) measurements of the C


Research Article


Figure 4. SEM micrograph images of (a) AGM separator, (b) BC membrane, and (c) PE separator. Figure 3. Nitrogen adsorption and desorption isotherms and the corresponding BJH pore size distribution (inset image) analyses of (a) AGM separator, (b) BC membrane, and (c) PE separator.

considerable thermal stability without thermal shrinkage related issues. Furthermore, the thermal stabilities of the separators were determined by TGA analysis. The TGA results of the BC membrane, PE separator, and AGM separator are represented in Figure 6. No degradation was observed in the AGM separator. For the BC membrane, the thermal decomposition began at ∼210 °C. A major weight loss of 60.33% was observed between ∼210 °C and ∼370 °C, which indicates the degradation of the main cellulose skeleton (dehydration and decomposition of glucose units), depolymerization, and dehydration due to pyrolysis resulting in carbonaceous char formation.46−48 The gradual decomposition factor began at ∼370 °C for the BC membrane. In this stage,

The thermal stability of the separator is also an important factor during the unit cell operation. To identify the thermal stabilities of the separators, thermal shrinkage behavior measurements at preferred temperature is a suitable method.43−45 Desired sizes of (3 cm × 3 cm) the PE separator and the BC membrane were stored separately at 25, 60, and 80 °C temperatures for 30 min under identical conditions. As shown in Figure 5, the thermal shrinkage of the PE separator and the BC membrane was approximately zero at 60 and 80 °C. The PE separator and the BC membrane showed D


Research Article


Figure 5. Thermal stability of (a−c) BC membrane and (d−f) PE separator at (a, d) 25 °C; (b, e), 60 °C; and (c, f) 80 °C for 30 min.

AGM.12 The WU values of the AGM separator were 838, 888, and 917.1% at 30, 50, and 70 °C. With increase in temperature, the WU properties increased for the AGM separator. In the PE separator, WU is poorer due to the absence of functional properties and lower thickness. However, a very small amount of WU was obtained because of the presence of water molecules inside the pores. For the BC membrane, the WU was considerably increased with increasing temperature. The WU values of the BC membrane were 130, 250, and 325.4% at 30, 50, and 70 °C, respectively. In the BC membrane, the WU ability may depend on the formation of hydrogen interactions with the hydroxyl group of cellulose.52 Initially, water molecules are adsorbed on the surface of the BC membrane which then enter into the matrix of cellulose fibrils.53 In addition, a large quantity of water can be adsorbed onto the membrane due to the presence of higher void spaces between the BC fibrils. Furthermore, the WU properties of the BC membrane can be increased by the arrangement of cellulose fibrils and hydrophilic functionalized groups in the BC membrane. Figure 7b represents the IEC of the AGM separator, the BC membrane, and the PE separator. There are no IEC properties for the AGM separator and the PE separator. However, the BC membrane showed efficient IEC performance. The determined IEC values were 0.0, 0.127, and 0.0 meq/g for AGM separator, BC membrane, and PE separator, respectively. The obtained higher IEC in the BC membrane is mainly due to the presence of a higher number of hydroxyl functional groups. To confirm ion transport in the separator and the membrane, ionic conductivity measurements were carried out, and the obtained data is shown in Figure 7c. Apart from the electrolyte holding properties and the separation of positive and negative electrodes, ion transport behavior in the separator is an additional advantage to the leadacid battery system during unit cell operation. The ionic conductivities of AGM separator, BC membrane, and PE separator were 0.14, 4.96, and 0.32 mS/cm, respectively. The lower ion transport in the separators and the membrane occurred due to the water molecules in the structure. Here, water molecules in the separator and membrane acted as

Figure 6. Thermogravimetric analyses of AGM, BC membrane, and PE separator.

cellulose decomposed into D-glucopyranose, and then a free radical was formed by further decomposition. In addition, factors such as molecular weight, crystallinity, and BC alignment influence the BC thermal degradation performance.46−49 For the PE separator, the onset of significant decomposition began at 300 °C, and the decomposition region of the polymer was observed between ∼300 and 481 °C. Furthermore, the thermal stability of the PE separator can be altered by the incorporation of inorganic additives or surface modifications.50,51 The WU properties of the AGM separator, BC membrane, and PE separator were measured at different temperatures (30, 50, and 70 °C) and the obtained data given in Figure 7a. Compared to the WU values of the BC membrane and the PE separator, the water holding or WU is significantly higher for the AGM separator. The AGM influences the wicking property (physical imbibition of a liquid by solid contact basis for electrolyte uptake), which significantly improves the WU in E


Research Article


Figure 7. (a) Water uptake, (b) ion exchange capacity, and (c) ion conductivity measurements of AGM, PE separator, and BC membrane.

Figure 8. Discharge performance characteristics (after 1C and 2C rate charge) of AGM battery and BC-PE battery system at (a) 0.1 A and (b) 0.2 A. Long-term cycle test performances at (c) 0.1 A and (d) 0.2 A current.

F



Research Article

■

CONCLUSION This research study confirmed the effectiveness and the advantages of a cost-effective BC membrane with a PE separator for LAB systems. The structural, microstructural, and physicochemical properties of the separator were evaluated, and high performance was achieved in the LAB. The determined SSA was 1.36, 35.89, and 46.72 m2 g−1 for the AGM separator, the PE separator, and the BC membrane, respectively. The BC membrane showed considerable WU (130% at 30 °C), IEC (0.127 meq/g), and IC (4.96 mS/cm), which is a major advantage in LAB systems. The high WU, IEC, and IC properties of BC may lead to improvements in electrochemical battery performance through higher electrolyte uptake and enhanced ion transportation during the unit cell operation. In addition, the PE separator showed outstanding supporting performance to the BC membrane because of its higher mechanical, thermal, and chemical stability properties. The battery with a BC-PE separator exhibited discharge performance comparable to that of the AGM battery system. At 0.1 A current, the discharge capacities of the AGM and BCPE batteries are approximately 0.96 and 0.94 Ah, respectively. Furthermore, the BC-PE battery showed stable performance during long-term operation. The results confirmed that the combined BC and PE separator is a promising candidate for LAB systems.

vehicles for the transport of ions. Comparatively, higher ion transport occurred in the BC membrane due to the presence of a large number of hydroxyl functional groups in the BC structure. This result suggests that the BC membrane can be helpful in transferring ions during the electrochemical reaction. Charge and discharge characteristic measurements of the AGM battery and the BC-PE battery were conducted to evaluate the battery performances under identical conditions. In unit cell operation, the batteries were charged at different Crates and the discharge performances of the batteries were evaluated at 0.1, and 0.2 A discharge current up to the cutoff voltage of 1.75 V under similar conditions. Figure 8 represents the discharge performances of the batteries at the different currents of (a) 0.1A and (b) 0.2A. As shown in Figure 8a,b, the open-circuit voltage (OCV) is similar for both the AGM battery and the BC-PE battery. It can be concluded that the open circuit voltage of the battery is not affected by the BC-PE separator, where the BC-PE separator is used instead of the AGM separator. In addition, both the batteries showed similar discharge characteristic performances. By using the BC-PE separator, the performance difference in discharge was not further varied. At 0.1 A discharge current, the discharge durations of the AGM and BC-PE batteries were 9.8928 and 9.6278 h, respectively. Hence, comparable discharge capacities were observed for the AGM and BC-PE batteries. The discharge capacities at 0.1A current were 0.938 and 0.962 Ah for the BC-PE and AGM battery systems, respectively (as shown in Figure S2). Moreover, a similar trend was observed at a discharge current of 0.2 A. In the BC-PE battery system, the PE provided synergetic advantages: (i) it acted as a separator between positive and negative electrodes, and (ii) it provided support to the BC membrane because of its higher mechanical and chemical stabilities. In addition, PE can prevent dendritelike formations between the electrodes, which is the main reason for short-circuits during long-term operation. The BC membrane enhanced the electrochemical reaction during unit cell operation. It can adsorb a large amount of electrolyte solution, which is a major advantage for long-term operation. The cycle life performance of a LAB was tested at different charge and discharge currents. The cycle life was measured by change of end of discharge voltage at 0.1 and 0.2 A current. Data was collected at every 100th cycle of charge and discharge, and the obtained data is represented in Figure 8c,d. The end of discharge voltage is slightly lower in the BC-PE battery compared to that in the AGM battery system. In both cases, the AGM battery and the BC-PE battery systems have showed stable performances after 5000 cycles also. In addition, the BC-PE battery system showed a nearly stable performance at 0.1 A current after 20000 cycles as shown in Figures S3−S5. This has clearly proved that the BC-PE battery system can be considered as a promising candidate for long-term operation. The BC-PE separator showed an effective performance in the low C-rates. In order to increase further development and performance enhancement of the BC-PE battery system at high C-rates, the following points need to be considered: varying thickness, porosity, surface modification, alteration of hydrophilicity/hydrophobicity, and stabilities of BC membrane and PE separator. On the basis of these experimental results, the cost-effective BC membrane with the PE separator can be effectively considered as a separator for advanced LAB systems.

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.9b00694. BET curves, discharge capacities of battery systems, long-term cycle test performances of BC-PE battery, cycle performances of BC-PE battery (PDF)

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]; [email protected]. Phone: +82-62-530-1865. Fax: +82-62-530-1859. ORCID

Ho-Young Jung: 0000-0002-3421-1055 Author Contributions #

These two authors (Sung-Hee Roh and Gowthami Palanisamy) contributed equally to this work and are considered as a cofirst authors.

Author Contributions

Sung-Hee Roh and Gowthami Palanisamy contributed equally to this work and are considered as a cofirst authors. Gowthami Palanisamy conducted the experimental research work, electrochemical measurements, and manuscript preparation under the supervision of Ho-Young Jung and Sung-Hee Roh. T. Sadhasivam supported the experimental work and manuscript preparation. Jae-Eun Jin and Jin-Yong Shim supported this research work and discussion. Ho-Young Jung is the corresponding author for this manuscript. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work was supported by the Korea Environment Industry & Technology Institute (KEITI) through the Advanced G


Research Article


(14) Ihmels, K.; Böhnstedt, W. Separator materials for valveregulated lead-acid batteries. Valve-Regulated Lead-Acid Batteries 2004, 183−205. (15) Zguris, G. C. A review of physical properties of separators for valve-regulated lead/acid batteries. J. Power Sources 1996, 59 (1−2), 131−135. (16) Zguris, G. C. Absorptive glass-mat separators for valveregulated lead/acid batteriesthoughts on compression. J. Power Sources 1997, 67 (1−2), 307−313. (17) Drenchev, B.; Dimitrov, M.; Boev, V.; Aleksandrova, A. Absorptive glass mat separator surface modification and its influence on the heat generation in valve-regulated lead-acid battery. J. Power Sources 2015, 280, 66−73. (18) Culpin, B. Thermal runaway in valve-regulated lead-acid cells and the effect of separator structure. J. Power Sources 2004, 133 (1), 79−86. (19) Hu, J.; Guo, Y.; Zhou, X. Thermal runaway of valve-regulated lead-acid batteries. J. Appl. Electrochem. 2006, 36 (10), 1083−1089. (20) Catherino, H. A. Complexity in battery systems: Thermal runaway in VRLA batteries. J. Power Sources 2006, 158 (2), 977−986. (21) Sadhasivam, T.; Kim, H. T.; Park, W. S.; Lim, H.; Ryi, S. K.; Roh, S. H.; Jung, H. Y. Low permeable composite membrane based on sulfonated poly (phenylene oxide)(sPPO) and silica for vanadium redox flow battery. Int. J. Hydrogen Energy 2017, 42 (30), 19035− 19043. (22) Mu, D.; Yu, L.; Liu, L.; Xi, J. Rice paper reinforced sulfonated poly (ether ether ketone) as low-cost membrane for vanadium flow batteries. ACS Sustainable Chem. Eng. 2017, 5 (3), 2437−2444. (23) Lu, W.; Yuan, Z.; Zhao, Y.; Zhang, H.; Zhang, H.; Li, X. Porous membranes in secondary battery technologies. Chem. Soc. Rev. 2017, 46 (8), 2199−2236. (24) Weng, B.; Xu, F.; Alcoutlabi, M.; Mao, Y.; Lozano, K. Fibrous cellulose membrane mass produced via force spinning® for lithiumion battery separators. Cellulose 2015, 22 (2), 1311−1320. (25) Zhang, L. C.; Sun, X.; Hu, Z.; Yuan, C. C.; Chen, C. H. Rice paper as a separator membrane in lithium-ion batteries. J. Power Sources 2012, 204, 149−154. (26) Zhang, J.; Liu, Z.; Kong, Q.; Zhang, C.; Pang, S.; Yue, L.; Cui, G. Renewable and superior thermal-resistant cellulose-based composite nonwoven as lithium-ion battery separator. ACS Appl. Mater. Interfaces 2013, 5 (1), 128−134. (27) Torres, F. G.; Commeaux, S.; Troncoso, O. P. Biocompatibility of bacterial cellulose based biomaterials. J. Funct. Biomater. 2012, 3 (4), 864−878. (28) Dayal, M. S.; Catchmark, J. M. Mechanical and structural property analysis of bacterial cellulose composites. Carbohydr. Polym. 2016, 144, 447−453. (29) Venugopal, G.; Moore, J.; Howard, J.; Pendalwar, S. Characterization of microporous separators for lithium-ion batteries. J. Power Sources 1999, 77 (1), 34−41. (30) Gwon, S. J.; Choi, J. H.; Sohn, J. Y.; Ihm, Y. E.; Nho, Y. C. Preparation of a new micro-porous poly (methyl methacrylate)grafted polyethylene separator for high performance Li secondary battery. Nucl. Instrum. Methods Phys. Res., Sect. B 2009, 267 (19), 3309−3313. (31) Jin, S. Y.; Manuel, J.; Zhao, X.; Park, W. H.; Ahn, J. H. Surfacemodified polyethylene separator via oxygen plasma treatment for lithium ion battery. J. Ind. Eng. Chem. 2017, 45, 15−21. (32) Xu, W.; Wang, Z.; Shi, L.; Ma, Y.; Yuan, S.; Sun, L.; Zhu, J. Layer-by-Layer Deposition of Organic−Inorganic Hybrid Multilayer on Microporous Polyethylene Separator to Enhance the Electrochemical Performance of Lithium-Ion Battery. ACS Appl. Mater. Interfaces 2015, 7 (37), 20678−20686. (33) Mu, D.; Yu, L.; Yu, L.; Xi, J. Toward Cheaper Vanadium Flow Batteries: Porous Polyethylene Reinforced Membrane with Superior Durability. ACS Appl. Energy Mater. 2018, 1 (4), 1641−1648. (34) Wei, Y.; Li, X.; Hu, Q.; Ni, C.; Liu, B.; Zhang, M.; Zhang, H.; Hu, W. Sulfonated nanocrystal cellulose/sulfophenylated poly (ether

Technology Program for Environmental Industry Program, funded by the Korea Ministry of Environment (MOE) (RE201805090), Republic of Korea. The research work was supported by the Energy Efficiency & Resources Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) which was granted financial resources from the Ministry of Trade, Industry & Energy (No. 20172420108550 and No. 20162020108400), Republic of Korea. This work was supported by Innopolis Foundation grant funded by the Korea government (MSIT) (No.2018-DD-RD-0096, Development of long life hybrid battery for ISG car).

■

REFERENCES

(1) Nayak, P. K.; Erickson, E. M.; Schipper, F.; Penki, T. R.; Munichandraiah, N.; Adelhelm, P.; Aurbach, D. Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li-and Mn-Rich Cathode Materials for Li-Ion Batteries. Adv. Energy Mater. 2018, 8 (8), 1702397. (2) Amirante, R.; Cassone, E.; Distaso, E.; Tamburrano, P. Overview on recent developments in energy storage: mechanical, electrochemical and hydrogen technologies. Energy Convers. Manage. 2017, 132, 372−387. (3) Palomares, V.; Serras, P.; Villaluenga, I.; Hueso, K. B.; CarreteroGonzález, J.; Rojo, T. Na-ion batteries, recent advances and present challenges to become low cost energy storage systems. Energy Environ. Sci. 2012, 5 (3), 5884−5901. (4) Palizban, O.; Kauhaniemi, K. Energy storage systems in modern gridsMatrix of technologies and applications. J. Energy Storage 2016, 6, 248−259. (5) Liu, J.; Zhang, J. G.; Yang, Z.; Lemmon, J. P.; Imhoff, C.; Graff, G. L.; Li, L.; Hu, J.; Wang, C.; Xiao, J.; Xia, G.; Viswanathan, V. V.; Baskaran, S.; Sprenkle, V.; Li, X.; Shao, Y.; Schwenzer, B. Materials science and materials chemistry for large scale electrochemical energy storage: from transportation to electrical grid. Adv. Funct. Mater. 2013, 23 (8), 929−946. (6) Luo, X.; Wang, J.; Dooner, M.; Clarke, J. Overview of current development in electrical energy storage technologies and the application potential in power system operation. Appl. Energy 2015, 137, 511−536. (7) Foudia, M.; Matrakova, M.; Zerroual, L. Effect of a mineral additive on the electrical performances of the positive plate of lead acid battery. J. Power Sources 2015, 279, 146−150. (8) Van der Kuijp, T. J.; Huang, L.; Cherry, C. R. Health hazards of China’s lead-acid battery industry: a review of its market drivers, production processes, and health impacts. Environ. Health 2013, 12 (1), 61. (9) Marom, R.; Ziv, B.; Banerjee, A.; Cahana, B.; Luski, S.; Aurbach, D. Enhanced performance of starter lighting ignition type lead-acid batteries with carbon nanotubes as an additive to the active mass. J. Power Sources 2015, 296, 78−85. (10) Pletcher, D.; Zhou, H.; Kear, G.; Low, C. J.; Walsh, F. C.; Wills, R. G. A novel flow battery-A lead-acid battery based on an electrolyte with soluble lead (II): V. Studies of the lead negative electrode. J. Power Sources 2008, 180 (1), 621−629. (11) Sadhasivam, T.; Dhanabalan, K.; Roh, S. H.; Kim, S. C.; Jeon, D.; Jin, J. E.; Shim, J.; Jung, H. Y. Preparation and characterization of Pb nanoparticles on mesoporous carbon nanostructure for advanced lead-acid battery applications. J. Mater. Sci.: Mater. Electron. 2017, 28 (7), 5669−5674. (12) Kumar, V.; Rao, P. K.; Rawal, A. Amplification of electrolyte uptake in the absorptive glass mat (AGM) separator for valve regulated lead acid (VRLA) batteries. J. Power Sources 2017, 341, 19− 26. (13) Culpin, B.; Peters, K. Saturation influences on the performance of valve-regulated lead−acid batteries. J. Power Sources 2005, 144 (2), 313−321. H


Research Article

ACS Sustainable Chemistry & Engineering ether ketone ketone) composites for proton exchange membranes. RSC Adv. 2016, 6 (69), 65072−65080. (35) Gindt, B. P.; Abebe, D. G.; Tang, Z. J.; Lindsey, M. B.; Chen, J.; Elgammal, R. A.; Zawodzinski, T. A.; Fujiwara, T. Nanoporous polysulfone membranes via a degradable block copolymer precursor for redox flow batteries. J. Mater. Chem. A 2016, 4 (11), 4288−4295. (36) Chen, J.; Zhao, D.; Jin, X.; Wang, C.; Wang, D.; Ge, H. Modifying glass fibers with graphene oxide: towards high-performance polymer composites. Compos. Sci. Technol. 2014, 97, 41−45. (37) Stoica-Guzun, A.; Stroescu, M.; Jinga, S.; Jipa, I.; Dobre, T.; Dobre, L. Ultrasound influence upon calcium carbonate precipitation on bacterial cellulose membranes. Ultrason. Sonochem. 2012, 19 (4), 909−915. (38) Lee, J. Y.; Lee, Y. M.; Bhattacharya, B.; Nho, Y. C.; Park, J. K. Separator grafted with siloxane by electron beam irradiation for lithium secondary batteries. Electrochim. Acta 2009, 54 (18), 4312− 4315. (39) Guo, J.; Catchmark, J. M. Surface area and porosity of acid hydrolyzed cellulose nanowhiskers and cellulose produced by Gluconacetobacter xylinus. Carbohydr. Polym. 2012, 87 (2), 1026− 1037. (40) Ul-Islam, M.; Khan, T.; Park, J. K. Water holding and release properties of bacterial cellulose obtained by in situ and ex situ modification. Carbohydr. Polym. 2012, 88 (2), 596−603. (41) Pavlov, D.; Naidenov, V.; Ruevski, S.; Mircheva, V.; Cherneva, M. New modified AGM separator and its influence on the performance of VRLA batteries. J. Power Sources 2003, 113 (2), 209−227. (42) Shah, N.; Ha, J. H.; Park, J. K. Effect of reactor surface on production of bacterial cellulose and water soluble oligosaccharides by Gluconacetobacter hansenii PJK. Biotechnol. Bioprocess Eng. 2010, 15, 110−118. (43) Chen, W.; Shi, L.; Zhou, H.; Zhu, J.; Wang, Z.; Mao, X.; Chi, M.; Sun, L.; Yuan, S. Water-based organic−inorganic hybrid coating for a high-performance separator. ACS Sustainable Chem. Eng. 2016, 4 (7), 3794−3802. (44) Mao, X.; Shi, L.; Zhang, H.; Wang, Z.; Zhu, J.; Qiu, Z.; Zhao, Y.; Zhang, M.; Yuan, S. Polyethylene separator activated by hybrid coating improving Li+ ion transference number and ionic conductivity for Li-metal battery. J. Power Sources 2017, 342, 816−824. (45) Jin, R.; Fu, L.; Zhou, H.; Wang, Z.; Qiu, Z.; Shi, L.; Zhu, J.; Yuan, S. High Li+ Ionic Flux Separator Enhancing Cycling Stability of Lithium Metal Anode. ACS Sustainable Chem. Eng. 2018, 6 (3), 2961−2968. (46) Pacheco, G.; Nogueira, C. R.; Meneguin, A. B.; Trovatti, E.; Silva, M. C.; Machado, R. T.; Ribeiro, S. J. L.; da Silva Filho, E. C.; Barud, H. D. S. Development and characterization of bacterial cellulose produced by cashew tree residues as alternative carbon source. Ind. Crops Prod. 2017, 107, 13−19. (47) Wang, S.; Liu, Q.; Luo, Z.; Wen, L.; Cen, K. Mechanism study on cellulose pyrolysis using thermogravimetric analysis coupled with infrared spectroscopy. Front. Energy. 2007, 1 (4), 413−419. (48) Ullah, M. W.; Ul-Islam, M.; Khan, S.; Kim, Y.; Park, J. K. Structural and physico-mechanical characterization of bio-cellulose produced by a cell-free system. Carbohydr. Polym. 2016, 136, 908− 916. (49) Du, R.; Zhao, F.; Peng, Q.; Zhou, Z.; Han, Y. Production and characterization of bacterial cellulose produced by Gluconacetobacter xylinus isolated from Chinese persimmon vinegar. Carbohydr. Polym. 2018, 194, 200−207. (50) Kaleel, S. H.; Bahuleyan, B. K.; Masihullah, J.; Al-Harthi, M. Thermal and mechanical properties of polyethylene/doped-TiO2 nanocomposites synthesized using in situ polymerization. J. Nanomater. 2011, 2011, 65. (51) Prasanna, K.; Subburaj, T.; Lee, W. J.; Lee, C. W. Polyethylene separator: stretched and coated with porous nickel oxide nanoparticles for enhancement of its efficiency in Li-ion batteries. Electrochim. Acta 2014, 137, 273−279.

(52) Mantanis, G. I.; Young, R. A.; Rowell, R. M. Swelling of compressed cellulose fiber webs in organic liquids. Cellulose 1995, 2 (1), 1−22. (53) Watanabe, K.; Tabuchi, M.; Morinaga, Y.; Yoshinaga, F. Structural features and properties of bacterial cellulose produced in agitated culture. Cellulose 1998, 5 (3), 187−200.

I


Techno-Economical Feasibility of Biocellulose Membrane along with

Recommend Documents