Although a large body of work regarding microbial fuel cell (MFC) technology is still at the laboratory stage, in the recent years, various attempts to evolve the technology towards commercialization have been made. Successful case studies of large-scale systems have been reported [1
] (total reactor volume of over 90 L) and an online biosensor based on MFC technology has been released to the market [5
]. Recently Trapero et al. claimed that MFC technology is economically feasible and sufficiently competitive when compared to conventional wastewater treatment processes such as activated sludge [6
]. As with every other technology, more effort needs to be made to improve the technology to be more cost-effective, reliable, and efficient. One of the major challenges for MFC commercialization is the cost of materials, especially separators [6
]. In MFCs, separators mediate ion transport and physically separate the anodes and cathodes. Separator-less systems have shown higher power outputs in some cases due to lower internal resistance [9
], thus being an attractive option to lower system costs. However, they have limitations in terms of low coulombic efficiency due to the occurrence of ionic species crossover and undesirable side reactions [10
]. Moreover, for the systems requiring anolyte/catholyte separation, separators are essential.
For efficient MFC operation, separators should have high proton transfer rate and low internal resistance. Chemical and mechanical strength is also an important requirement for long-term operation. One of the common issues related to MFC separators is membrane fouling, especially biofouling, which increases internal resistance of the system and leads to system failure. Koók et al. elucidated membrane biofouling mechanism and related membrane properties in their recent review paper [11
]. Separators used in MFCs can be classified in two groups, namely porous and non-porous separators. In-depth reviews on separators tested in MFCs can be found in [12
]. As an effort into seeking well-performing, cost-effective, and sustainable materials for the MFC separator, ceramics have drawn attention. The use of ceramic separators in MFCs has proven its comparable performance to that of selective ion exchange membranes with much less cost. Jana et al. built MFCs with cylindrical earthen ceramic separators which generated a maximum power output (PMAX
) of 14.6 W·m−3
]. Another study using much smaller cylindrical terracotta separators (internal volume of 10 mL) reported a PMAX
of 44.8 W·m−3
]. Besides the aforementioned advantages, ceramics are also thought to be suitable materials for MFC scaling up because of its structural durability and plasticity [17
]. Moreover, ceramic making capabilities exist around the world including ODA countries. Combining this with a ubiquitous fuel such as urine, could increase accessibility of MFC technology.
Ceramic separators are considered to be porous separators whose pores facilitate ion transport while separating anolyte and catholyte. Considering the pore size of common ceramic materials, they can be classified as ultra-filtration (UF, pore diameter of 10–100 nm) or micro-filtration (MF, pore diameter of 100–104
]. Not only the porosity affects MFC performance, but also clay composition, wall thickness, pore size distribution, and density may well play important roles in MFC performance, which in turn these parameters can be optimized for a specific target application [17
Winfield et al. compared earthenware and terracotta in cylindrical MFCs and reported that earthenware generated a 75% higher power than terracotta, which was a similar level of power produced from a cation exchange membrane (CEM) [20
]. Another study by Pasternak et al. also suggested earthenware is compatible to conventional ion exchange membranes for MFCs in terms of performance and cost after comparing four different types of ceramic: mullite, earthenware, pyrophyllite and alumina in cylindrical single-chamber MFCs [21
]. In that study, the highest performance was observed in ceramics with porosities ranging between 2 and 14%. Jimenez et al. investigated the effect of ceramic separator thickness on MFC performance [22
]. They tested cylindrical fine fire clay ceramic separators with different thicknesses (2.5, 5 and 10 mm) and reported the higher power and catholyte production was obtained from the thinnest separator of 2.5 mm. In a different study looking into the effect of thickness and porosity of ceramic separators, optimum ceramic separator thickness for MFC power generation depends on the porosity [23
]. For highly porous ceramics (porosity of 30.5%), power output was proportional to the thickness (highest power output of 321 mW·m2
obtained from 9 mm thick senators), whereas a thinner separator (thickness of 3 mm) was more favourable for less porous ceramics (porosity of 11.0%). If a separator is extremely porous such as tissue paper, then there is insufficient separation between the electrodes and a short circuit can occur [24
]. In less extreme cases, high porosity can result in anolyte crossover to the cathode chamber, both reducing the amount of available substrate for electrochemically active biofilms and promoting heterotrophic bacterial growth on the cathode. Oxygen transfer from the cathode to the anode can also be an issue in this case.
For successful implementation of ceramic separators in MFCs, understanding the relations between their properties and performance as MFC separators is crucial. Also testing long-term operation is required for practical applications. Nevertheless, there is still much need for comprehensive studies looking into these aspects in the field. The main objective of the present study was to investigate the effect of ceramic material properties on their performance as MFC separators. Three different clay-based ceramics with the same thickness of 3 mm were compared in terms of power output both in short-term and long-term operations. Not only porosity but also pore size of each test ceramic material was measured and its influence on the performance was analysed.
This piece of work is part of a bigger study into “Living Architecture” [25
], which is a field of work that investigates how smart homes and smart cities of the future could be developed. In particular, living technology such as the MFC can be integrated into bricks for households or other structures, thereby allowing on-site treatment and electricity generation in real time. This is the “living brick” context under which the ceramic samples were developed and tested.
2. Materials and Methods
2.1. Custom-Made Ceramics
The ceramic clays used in this study are a mixture of a plastic clay and 25% chamotte, which has a diameter ranging from 0 to 0.5 mm (Georg & Schneider, Siershahn, Germany). Three types of clay were used and named “brown” (product no.: 366), “red” (product no.: 364) and “white” (product no.: 264); the names were based on the resultant colour after kilning. Technical data of all three clay types are available from the manufacturer and are presented in Table S1
. All ceramics were fired at 960 °C for 20 min, at a rate of 150 °C·h−1
. This temperature is lower than the firing temperature recommended by the manufacturer, and was chosen to achieve a higher porosity by preventing the matrix from vitrifying and thus closing the majority of the interstices [26
]. The recommended firing temperatures are 1070–1120 °C for the brown, 1070–1240 °C for the red and white clay.
Ceramic separators were made in a cylindrical shape with one end sealed. Bottom sealed cylinders were 55 mm long, with inner diameter of 18 mm and thickens of 3 mm. The ceramic separators used for the study are shown in Figure 1
. As these were all hand made, and then fired, the dimensions vary by a few millimetres between samples.
As well as making separators from a single clay type (brown, red or white ceramic), combinations of the three raw materials were used to produce novel “spotty” separators. This type of ceramic separators was expected to offer additional benefits to the MFCs, resulting from the combination of the two clay types.
2.2. Microbial Fuel Cell Designs, Inoculation and Operation
Cylindrical MFCs were built to be tested as ceramic separators. For the anode, plain carbon fibre veil (20 g·m−2
carbon loading; PRF Composite Materials Poole, Dorset, UK) was cut into 270 cm2
(30 × 9 cm) and then folded to fit into the anode chambers. A hot-pressed activated carbon cathode, prepared as previously described [27
] with a total surface area of 35 cm2
, was placed onto the separator; this cathode was open to air. MFCs were inserted in 50 mL plastic containers, which was partially filled with water to keep the moisture of the cathodes. This allowed wetting of the air-cathodes, and improved the cathode performance. The schematic diagram of MFC design used in this study is shown in Figure 2
and the actual tested design is shown in Figure S2
Anaerobic sewage sludge from a local wastewater treatment plant (Wessex Water, Saltford, UK) was used to inoculate the MFCs, after being enriched with 1% tryptone and 0.5% yeast extract. MFCs were fed in batch (once every 1–3 days) with neat human urine, donated from consenting adults. Typically, the urine had a pH of 9.2–9.3, and conductivity of 28–30 mS·cm−1. In each feed, 5 mL of anolyte was replaced with fresh feedstock. The total volume of anolyte was 10 mL.
Throughout the work, variable external loads were connected to each MFC, which were determined based on polarisation runs that were carried out periodically. All tests were carried out in triplicates.
2.3. Polarisation Test and Data Logging
For polarisation experiments, various external resistances ranged from 4.8 kΩ to 4 Ω were loaded every 5 min and the potential between the anode and cathode was recorded every 30 s. Power output of the MFCs was monitored in real time in volts (V) against time using a multi-channel Agilent 34972A DAQ unit (Agilent Technologies, California, USA) every 5 min. All experiments were carried out in a temperature-controlled environment, at 22 ± 2 °C.
2.4. Physiochemical Property Analysis of Ceramic Separators
2.4.1. Porosity Investigation
Porosity investigation was carried out using both the ASTM (American Society for Testing and Materials) C373 procedure [28
] and mercury intrusion porosimetry (PASCAL 140, CE Instruments, Wigan, UK and CARLO ERBA Poro 2000, Science Exchange, Cobham, UK) methods. Prior to the analysis, single compound separator samples were thermally treated at 500 °C to remove even the very limited presence of organics and then subjected to thermal gravimetric analysis (TGA) to detect the presence of residues. The TGA results showed no evident weight loss, except for a very low amount at low temperature, probably corresponding to the evolution of humidity. The overall residue was below the sensitivity of the instrument (0.1%) and no thermal effects were noticed. Mercury intrusion tests were performed once for each sample to find surface area, porosity, pore size, and pore distribution data. ASTM tests were repeated on five different specimens for each sample, and the structural properties of a material such as bulk density, apparent porosity, and specific gravity to the precision of approx. ±0.1% were determined.
Scanning electron microscopy (SEM) analysis of the ceramic surface and cross-section was performed using Quanta FEG 650 (Thermo Fisher Scientific, Massachusetts, USA) and JSM-5500 (JEOL, Tokyo, Japan). The cross-section images were processed to find percentage porosity using MATLAB (MathWorks, Massachusetts, USA).
2.4.2. Composition Analysis
Energy dispersive X-ray Spectroscopy (EDXS) analysis was carried out to determine chemical compositions of the ceramics (Quanta FEG 650, Thermo Fisher Scientific, Massachusetts, USA).
2.5. Statistical Analysis
To evaluate if the differences between test ceramics in terms of power generation performance are statistically meaningful, analysis of variance (ANOVA: ordinary one-way) was performed using GraphPad Prism 8 (GraphPad Software, California, USA). Power produced in joules from 4 feeding cycles in days between 44 and 52 were calculated. This resulted in 108 data points for all 9 types of ceramic separator.
Commercially available ceramic materials with different compositions have been tested as MFC separators and as a (potential) chassis or vessel. Intensive physiochemical property analysis revealed that brown ceramic has lower porosity and larger pores in comparison to red and white ceramics. Single composition brown ceramic required cathode hydration due to its low porosity, which resulted in relatively poor performance initially. However, the brown ceramic separator is a more suitable choice for long-term operation, by outperforming other single composition ceramic types. This study confirms that pore size as well as porosity plays an important role in ceramic performance in MFCs.
Another important finding is the potential of spotty type ceramics. Although some of the spotty type ceramics had a leakage issue due to the nature of handmade ceramics and difference in extent of shrinkage of two materials during firing, in most cases spotty ceramics outperformed single composition types. Therefore, composite design could also be a way of enhancing the function of ceramic separators, as well as fine-tuning porosity and pore size. This may be particularly important in cases where the cathode is inside the cylinder (and the anode outside), which is an MFC topology that allows for catholyte synthesis [22
]; in this way, it is possible to combine high power performance and high catholyte quality.
Ceramic separators for MFCs are still very much a lab making and not subject to rigorous manufacturing and quality control procedures; this is by far the main consideration that anyone working in this field should take seriously into account. Fab labs or facilities, whose core competency is the fabrication of new structures from new materials, could be the first option for scientists, since ceramics manufacturers, whose (successful) business model is distant from research, will be unable to engage, unless such proposition made sense. In the case when scientific labs can employ a rigorous fabrication process, then physical parameters (thickness, density/porosity and pore size) should take priority before physicochemical parameters can become the focus.
Lastly, the use of low-cost, locally sourced ceramic separators of customisable shape for high performance MFCs would allow for the design and implementation of this technology into the built environment, integrated into a living architecture [25