Microbial fuel cell with activated carbon anode derived from waste coffee ground and method of manufacturing the same

Abstract

A microbial fuel cell and a method of manufacturing the same are provided. The microbial fuel cell includes a cathode, an anode, and a microbial community. The anode is made of an activated carbon prepared from waste coffee ground as an electrode material, and the microbial community is adhered to the surface of the activated carbon. Since the activated carbon prepared from waste coffee ground is beneficial for the adhesion of various microbial communities to form a biofilm, the electron transfer efficiency of the microbial fuel cell may be improved.

Claims

1. A microbial fuel cell, comprising: a cathode; an anode made from an activated carbon prepared from a waste coffee ground as an electrode material, wherein a sum of a volume of macropores of the activated carbon is greater than a sum of a volume of mesopores of the activated carbon, the mesopores refer to a pore diameter between 2 nm and 50 nm, and the macropores refer to a pore diameter greater than 50 nm; and a microbial community adhered to a surface of the activated carbon.

2. The microbial fuel cell of claim 1, further comprising a proton exchange membrane disposed between the cathode and the anode.

3. The microbial fuel cell of claim 1, wherein the anode further comprises a first conductive plate and an activated carbon material is coated on the first conductive plate, and the first conductive plate comprises a carbon cloth, a graphite felt, a carbon felt, a graphite paper, a carbon paper, a graphite brush, a carbon brush, a stainless steel mesh, or a foamed nickel.

4. The microbial fuel cell of claim 1, wherein the cathode comprises a second conductive plate and a carbon material coated on the second conductive plate, and the second conductive plate comprises a carbon cloth, a graphite felt, a carbon felt, a graphite paper, a carbon paper, a graphite brush, a carbon brush, a stainless steel mesh, or a foamed nickel, and the carbon material comprises a carbon nanotube or an activated carbon.

5. The microbial fuel cell of claim 1, wherein the microbial community comprises E. coli, Shewanella putrefaciens, or a diverse microbial system in wastewater sludge.

6. The microbial fuel cell of claim 1, wherein a power density of the microbial fuel cell is maintained at more than half of an initial power density under conditions of continuous five-day culture and no additional nutrients for next four days.

7. A method of manufacturing a microbial fuel cell, comprising: preparing an activated carbon using a waste coffee ground, wherein a sum of a volume of macropores of the activated carbon is greater than a sum of a volume of mesopores of the activated carbon, the mesopores refer to a pore diameter between 2 nm and 50 nm, and the macropores refer to a pore diameter greater than 50 nm; making the activated carbon into an anode; making a cathode; and culturing a microbial community to be adhered to a surface of the anode.

8. The method of manufacturing the microbial fuel cell of claim 7, wherein a method of preparing the activated carbon comprises a physical activation method or a chemical activation method.

9. The method of manufacturing the microbial fuel cell of claim 8, wherein the physical activation method comprises a water vapor activation method or a carbon dioxide activation method, and the chemical activation method comprises activating using a pore-forming agent.

10. The method of manufacturing the microbial fuel cell of claim 9, wherein the pore-forming agent comprises potassium hydroxide (KOH), zinc chloride (ZnCl), or sodium hydroxide (NaOH).

11. The method of manufacturing the microbial fuel cell of claim 9, wherein a weight ratio of the waste coffee ground to the pore-forming agent is 1:1 to 1:10.

12. The method of manufacturing the microbial fuel cell of claim 8, wherein a carbonization temperature of preparing the activated carbon is 700° C. to 1000° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure.

(2) FIG. 1 is a schematic of a microbial fuel cell according to an embodiment of the disclosure.

(3) FIG. 2 is a flowchart of the manufacturing process of a microbial fuel cell according to another embodiment of the disclosure.

(4) FIG. 3 is a graph of BET specific surface area of Preparation examples 1 to 3 and Comparative preparation example 1.

(5) FIG. 4A is a distribution curve of micropores in Preparation examples 1 to 3 and Comparative preparation example 1.

(6) FIG. 4B is a distribution curve of mesopores and macropores of Preparation examples 1 to 3 and Comparative preparation example 1.

(7) FIG. 5A is a cyclic voltammogram of Comparative preparation example 2.

(8) FIG. 5B, FIG. 5C, and FIG. 5D are cyclic voltammograms of Preparation examples 4 to 6, respectively.

(9) FIG. 6A is a scanning electron micrograph of Comparative preparation example 2.

(10) FIG. 6B, FIG. 6C, and FIG. 6D are scanning electron micrographs of Preparation examples 4 to 6, respectively.

(11) FIG. 7 is a graph of electrochemical impedance spectra (EIS) of Comparative preparation example 2 and Preparation examples 4 to 6.

(12) FIG. 8A is a graph of current density and open-circuit voltage of the microbial fuel cells of Experimental examples 1 to 3 and Comparative examples 1 and 2.

(13) FIG. 8B is a graph of current density and power density of the microbial fuel cells of Experimental examples 1 to 3 and Comparative examples 1 and 2.

(14) FIG. 9A is a graph of open-circuit voltage of the microbial fuel cell of Experimental example 2 changing with time.

(15) FIG. 9B is a graph of maximum power density of the microbial fuel cell of Experimental example 2 tested over a long period of time.

DESCRIPTION OF THE EMBODIMENTS

(16) In the following, exemplary embodiments of the disclosure are comprehensively described with reference to figures, but the disclosure may also be implemented in various different forms and should not be construed as limited to the embodiments of the specification. In the figures, for clarity, the size and thickness of each region, portion, and layer are not shown to actual scale. Moreover, similar or same reference numerals in each of the figures tend to indicate the presence of similar or same devices or features. Similar reference numerals in the figures represent similar devices and descriptions thereof are omitted.

(17) FIG. 1 is a schematic of a microbial fuel cell according to an embodiment of the disclosure.

(18) Referring to FIG. 1, a microbial fuel cell 100 of the present embodiment includes at least an anode 102, a cathode 104, and a microbial community. The anode 102 is made of a coffee-waste-derived activated carbon (CWAC) 106 as an electrode material, and the microbial community is adhered to an activated carbon surface 106a. The microbial community may be applied to a variety of single microbial systems, such as E. coli, Shewanella putrefaciens, etc., or a diverse microbial system in wastewater sludge. Moreover, in order to load an organic matter reacting with the microorganisms, a liquid 110 containing an organic matter is usually loaded using a container 108. The anode 102 further includes an activated carbon 106 and a first conductive plate 112. The activated carbon 106 is coated on the first conductive plate 112, and the first conductive plate 112 is, for example, a carbon cloth, a graphite felt, a carbon felt, a graphite paper, a carbon paper, a graphite brush, a carbon brush, a stainless-steel mesh, or a foamed nickel. The cathode 104 may include a second conductive plate 114 and a carbon material 116. The carbon material 116 is coated on the second conductive plate 114. The second conductive plate 114 is, for example, a carbon cloth, a graphite felt, a carbon felt, a graphite paper, a carbon paper, a graphite brush, a carbon brush, a stainless-steel mesh, or a foamed nickel. The carbon material 116 is, for example, a carbon nanotube or the activated carbon, including commercial activated carbon, waste coffee ground activated carbon, or activated carbon recovered from various biological wastes, etc. In addition, a proton exchange membrane 118 may further be disposed between the cathode 104 and the anode 102. However, the disclosure is not limited thereto. In another embodiment, the microbial fuel cell 100 may also adopt a proton-free exchange membrane design.

(19) In FIG. 1, a microbial community adhered to the activated carbon surface 106a performs biochemical reactions by consuming organic substance in the liquid 110 to produce carbon dioxide, protons, and electrons, wherein the electrons are transferred to the cathode 104 via an external circuit 120 to form a current and is supplied to an external device 122, and the protons reach the cathode 104 via the proton exchange membrane 118. The electrons and protons are combined with external oxygen at the cathode 104 to form water. It is experimentally confirmed that the power density of the microbial fuel cell 100 of the disclosure may be maintained at more than half of the initial power density under the condition of continuous culture for five days and no additional nutrients (i.e., organic matter) for the next four days. Therefore, the microbial fuel cell 100 of the disclosure may be further applied to industries and products such as (1) power supply of small electronic products, (2) power supply of biochips, and (3) wastewater treatment systems. Moreover, according to the International Coffee Organization (ICO) statistics, global coffee consumption reached 9.7 million metric tons in 2018, and the amount of coffee ground waste generated was considerable and even caused a serious environmental burden. Therefore, in the disclosure, waste coffee ground may be recycled and reused as an electrode raw material of the microbial fuel cell 100. Therefore, not only are environmental friendliness and waste recycling achieved, but electrical energy is also generated in combination with microbial technology, which is an important development of sustainable energy conforming to the main points of circular economy.

(20) FIG. 2 is a flowchart of the manufacturing process of a microbial fuel cell according to another embodiment of the disclosure.

(21) Referring to FIG. 2, step 200 is first performed to prepare activated carbon using waste coffee ground. The method of preparing activated carbon is, for example, a physical activation method or a chemical activation method. For example, the physical activation method includes a water vapor activation method or a carbon dioxide activation method, and the chemical activation method includes activating using a pore-forming agent. The pore-forming agent (also referred to as activator) is, for example, potassium hydroxide (KOH), zinc chloride (ZnCl), or sodium hydroxide (NaOH) or the like. In an embodiment, the weight ratio of the waste coffee ground to the pore-forming agent is between 1:1 and 1:10 (such as 1:5), and the carbonization temperature is about 700° C. to 1000° C. The activated carbon obtained in the present embodiment has a high surface area, a porous hole structure, and good electrical conductivity.

(22) Then, step 202 is performed to make the activated carbon prepared from the waste coffee ground into an anode. For example, a suitable proportion by weight of activated carbon, binder (such as a polymer material such as polyvinylidene fluoride (PVDF) and carboxymethyl cellulose (CMC)), and conductive additive (such as a highly conductive material such as carbon black, carbon nanotube, and conductive polymer) may be prepared, wherein the weight ratios of the binder and the conductive additive are similar. Thereafter, the prepared slurry is coated on a conductive plate to be dried and hot pressed to form an anode including the conductive plate and activated carbon, but the disclosure is not limited thereto. In another embodiment, a suitable weight ratio of activated carbon, binder, and conductive additive may be prepared and filled into a can, and the activated carbon obtained after drying may be directly used as an anode.

(23) Next, step 204 is performed to manufacture a cathode. It should be noted that the order of step 202 and step 204 is not limited, and step 202 may be performed first, step 204 may be performed first, or step 202 and step 204 may be performed simultaneously. Moreover, step 202 and step 204 may adopt a similar process. For example, first preparing a suitable weight ratio of carbon material, binder, and conductive additive, and then coating the prepared slurry on a conductive plate to dry to form a cathode including the conductive plate and carbon material. In another embodiment, a suitable weight ratio of carbon material, binder, and conductive additive may be prepared and filled into a can, and the carbon material obtained after drying may be directly used as a cathode. In still another embodiment, the cathode including the conductive plate and the carbon material may be placed on a proton exchange membrane, and a structure including the proton exchange membrane and the cathode may be formed via hot pressing.

(24) Then, step 206 is performed to culture a microbial community to be adhered to a surface of the anode. For example, the anode is placed in a suitable volume ratio of microorganisms, nutrient culture solution, and air for the co-culture of the microbial community. Since activated carbon prepared from waste coffee ground is a porous structure having a high surface area, it is suitable for the adhesion of a microbial community to form a biofilm. Taking E. coli as an example, the pore size distribution of activated carbon prepared from waste coffee ground gives the surface thereof a high degree of roughness. As a result, a greater amount of E. coli may be adhered than activated carbon prepared from other raw materials, which is beneficial to increasing the current density of the microbial fuel cell.

(25) Experimental examples are described below to verify the efficacy of the disclosure. However, the disclosure is not limited to the following content.

PREPARATION EXAMPLES 1 TO 3

(26) Using saturated KOH as a pore-forming agent, the weight ratio of waste coffee ground to pore-forming agent is 1:1, 1:5, and 1:10, and after filtering, carbonization is performed at a high temperature of 900° C. to form the activated carbons of Preparation examples 1 to 3 to produce pores of different ranges.

COMPARATIVE PREPARATION EXAMPLE 1

(27) As a comparative carbon material, a pore-forming agent was not used, but waste coffee ground of the same weight as in Preparation examples 1 to 3 was directly used for filtering and carbonized at 900° C. to obtain a carbon material.

(28) <BET Analysis>

(29) The surface structures of the activated carbons of Preparation examples 1 to 3 and the carbon material of Comparative preparation example 1 were analyzed to obtain the following Table 1, the BET specific surface area curve of FIG. 3, the micropore distribution curve of FIG. 4A, and the distribution curve of mesopores and macropores of FIG. 4B. In particular, micropores refer to pore diameter less than 2 nm, mesopores refer to pore diameter between 2 nm and 50 nm, and macropores refer to pore diameter greater than 50 nm.

(30) TABLE-US-00001 TABLE 1 Average pore S.sub.BET diameter V.sub.macro V.sub.meso V.sub.micro V.sub.total (m.sup.2/g) (nm) (cm.sup.3/g) (cm.sup.3/g) (cm.sup.3/g) (cm.sup.3/g) Comparative 18.97 23.21 0.00796 0.00734 0.00663 0.02193 preparation example 1 Preparation 428.00 7.95 0.01110 0.02239 0.14388 0.17737 example 1 Preparation 164.33 16.94 0.01118 0.01042 0.05861 0.08201 example 2 Preparation 3.58 15.43 0.00572 0.00516 0 0.01088 example 3 V.sub.macro refers to the sum of the volume of macropores. V.sub.meso refers to the sum of the volume of mesopores. V.sub.micro refers to the sum of the volume of micropores. V.sub.total refers to the sum of the volume of micropores, mesopores, and macropores.

(31) FIG. 3 shows that the activated carbon of Preparation example 1 has the largest specific surface area. FIG. 4A shows that the activated carbon of Preparation example 1 has more micropores. It may be seen from FIG. 4B that the activated carbon of Preparation example 2 has more large pores.

(32) <Component Analysis>

(33) The activated carbons of Preparation examples 1 to 3 and the carbon material of Comparative preparation example 1 were subjected to Raman analysis and X-ray photoelectron spectroscopy (XPS) analysis, and the results are shown in Table 2 below.

(34) TABLE-US-00002 TABLE 2 XPS Raman C 1s (%) C—C C═C C—O C═O O—C═O SP.sub.3/SP.sub.2 I.sub.D/I.sub.G Comparative 17.68 56.1 14.38 5.43 6.41 0.315 1.24 preparation example 1 Preparation 22.88 48.39 15.73 8.14 4.85 0.473 1.2 example 1 Preparation 17.61 63.19 8.74 6.03 4.42 0.279 0.96 example 2 Preparation 12.97 68.61 9.1 5.48 3.84 0.189 0.94 example 3

(35) Table 2 shows that the sp.sup.2 structure of Preparation examples 2 to 3 is greater than 60% and the peak intensity ratio is lower than I.sub.D/I.sub.G, meaning the graphite carbon structures of Preparation examples 2 to 3 are more. Therefore, it may be known from the cross-validation of the Raman test and the XPS test that the activated carbons of Preparation examples 2 to 3 have excellent electrical conductivity.

PREPARATION EXAMPLES 4 TO 6

(36) The activated carbon of Preparation example 1, a conductive additive (carbon black), and a binder (polyvinylidene fluoride (PVDF)) were mixed into a slurry at a weight ratio of 80:10:10. The slurry was coated on a 1 cm.sup.2 conductive plate, and the loading mass was 10 mg/cm.sup.2. The anode of Preparation example 4 was obtained after drying at 80° C. for 6 hours.

(37) The activated carbons of Preparation examples 2 to 3 were also made into the anodes of Preparation examples 5 to 6 in accordance with the above steps.

COMPARATIVE PREPARATION EXAMPLE 2

(38) The carbon material of Comparative preparation example 1 was subjected to the same steps as in Preparation example 4 to obtain the anode of Comparative preparation example 2.

(39) <Microbial Community Culture>

(40) The anodes of Comparative preparation example 2 and Preparation examples 4 to 6 were placed in different Erlenmeyer flasks respectively, and then E. coli DH5α and Lysogeny broth (LB) were placed in each Erlenmeyer flask. The mixing volume ratio of E. coli, LB, and air was 1:2000:8000, wherein E. coli was 20 μl of E. coli bacterial fluid that was pre-incubated for 16 hours. The incubator was kept at 37° C. and culture was performed by oscillating at 200 rpm for 16 hours.

(41) <Electrochemical Analysis>

(42) The anodes of Comparative preparation example 2 and Preparation examples 4 to 6 after culture, together with the E. coli and LB in the Erlenmeyer flask, were respectively placed in different containers. Electrochemical analysis before and after culture was performed via cyclic voltammetry to obtain the cyclic voltammogram of FIGS. 5A to 5D. At the same time, the surfaces of the anodes of Comparative preparation example 2 and Preparation examples 4 to 6 were observed via a scanning electron microscope to obtain the scanning electron micrographs of FIGS. 6A to 6D.

(43) FIGS. 5A to 5D show that the current density of Comparative preparation example 2 was increased by 24.8%, the current density of Preparation example 1 was increased by 10.5%, the current density of Preparation example 2 was increased by 53.9%, and the current density of Preparation example 3 was increased by 41.7%. It may be known by comparing with FIGS. 6A to 6D that the anodes of Preparation examples 5 to 6 (i.e., activated carbon prepared from waste coffee ground) have a greater amount of E. coli (i.e., dark black strips) adhered to the surface. Especially the surface of the activated carbon of Preparation example 5 has a large amount of E. coli. Compared to the activated carbon of Preparation example 2 of FIG. 4B, the adhesion of E. coli was promoted possibly because of the presence of more large pores.

(44) In addition, the following Table 3 and FIG. 7 were obtained via electrochemical impedance spectra (EIS) analysis. In FIG. 7, R.sub.s refers to equivalent series resistance, R.sub.ct refers to charge transfer impedance, C is capacitance, and Z.sub.w refers to Warburg impedance.

(45) TABLE-US-00003 TABLE 3 Comparative preparation Preparation Preparation Preparation example 2 example 4 example 5 example 6 R.sub.s (Ω) 21.25 19 12.22 9.57 R.sub.ct (Ω) 1.53 0.67 0.19 1.08

(46) Table 3 and FIG. 7 show that the equivalent series resistance of Preparation example 6 is the smallest, followed by Preparation example 5, and the equivalent series resistance of Comparative preparation example 2 is the largest, which is attributable to the amount of graphite carbon structures in the activated carbon. The charge transfer resistance of Preparation example 5 is the smallest, followed by Preparation example 4, and the charge transfer resistance of Comparative preparation example 2 is the largest, which confirmed that the biofilm composed of E. coli may enhance charge transfer efficiency.

EXPERIMENTAL EXAMPLE 1

(47) First, a commercial activated carbon (Homy graphite, G03-Y200-1K), a conductive additive (carbon black), and a binder (polyvinylidene fluoride (PVDF)) were mixed into a slurry at a weight ratio of 80:10:10. The slurry was coated on a 4 cm.sup.2 conductive plate, and the loading mass was 10 mg/cm.sup.2. The cathode after drying at 80° C. for 6 hours was placed on a proton exchange membrane (Nafion 117), and 100 μl of Nafion solution was added and hot pressing was performed at 110° C. for 3 minutes.

(48) Then, the resulting cathode and proton exchange membrane and the anode of Preparation example 4 were assembled into the microbial fuel cell of FIG. 1, wherein LB was used as an organic substance.

EXPERIMENTAL EXAMPLE 2

(49) A microbial fuel cell was manufactured in the same manner as in Experimental example 1, and the anode of Preparation example 4 was changed to the anode of Preparation example 5.

EXPERIMENTAL EXAMPLE 3

(50) A microbial fuel cell was manufactured in the same manner as in Experimental example 1, and the anode of Preparation example 4 was changed to the anode of Preparation example 6.

COMPARATIVE EXAMPLE 1

(51) A microbial fuel cell was manufactured in the same manner as in Experimental example 1, and the anode of Preparation example 4 was changed to the anode of Comparative preparation example 2.

COMPARATIVE EXAMPLE 2

(52) A microbial fuel cell was manufactured in the same manner as in Experimental example 1, and the anode of Preparation example 4 was changed to commercial activated carbon used as an anode.

(53) <Battery Efficiency Analysis>

(54) The microbial fuel cells of Experimental examples 1 to 3 and Comparative examples 1 and 2 were respectively subjected to linear sweep voltammetry (LSV) analysis to obtain FIG. 8A.

(55) Then, calculation was performed according to the numerical values of FIG. 8A to obtain the graph of current density and power density of FIG. 8B, wherein Power density (mW.Math.m.sup.−2)=Voltage (V)×Current density (mA.Math.m.sup.−2). The maximum power density values of the batteries of Experimental examples 1 to 3 and Comparative examples 1 and 2 are shown in Table 4 below.

(56) TABLE-US-00004 TABLE 4 Comparative Comparative Experimental Experimental Experimental example 1 example 2 example 1 example 2 example 3 Power density 1568 975 3445 3927 3399 (mW .Math. m.sup.−2)

(57) As may be seen from Table 4 and FIG. 8B, Experimental examples 1 to 3 all have a power density greater than 3000 mW.Math.m.sup.−2, and Experimental example 2 manufactured by the anode of Preparation example 5 having the most E. coli adhesion has the highest power density.

(58) <Long-Term Battery Testing>

(59) The microbial fuel cell of Experimental example 2 was discharged after the culture, and then the open-circuit voltage thereof was measured after two hours of rest, and the results are shown in FIG. 9A.

(60) FIG. 9A shows the microbial fuel cell of Experimental example 2 is one self-charging system.

(61) Then, the microbial fuel cell of Experimental example 2 was tested for maximum power density for a long period of time without continuing to replenish the nutrient solution, and the results are shown in FIG. 9B.

(62) FIG. 9B shows that the microbial fuel cell of Experimental example 2 may still maintain a power of about 2000 mW.Math.m.sup.−2 after 100 hours. That is, the power density of the microbial fuel cell of the disclosure may be maintained at more than half of the initial power density under the condition that the culture is continued for five days and no additional nutrients are added for the next four days.

(63) Based on the above, in the disclosure, an activated carbon electrode is prepared by recycling the waste of coffee ground and interacting the waste with microorganisms to generate energy. The activated carbon is applied to a microbial fuel cell and has the effects of low cost and high efficiency. Since the microbial fuel cell of the disclosure is low in cost and has high power density, it is expected to be applicable to (1) power supply of small electronic products; (2) power supply of biochips; and (3) wastewater treatment systems and the like.

(64) It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure covers modifications and variations provided that they fall within the scope of the following claims and their equivalents.