Development of High Capacity Periodate Battery with 3D-Printed

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Development of High Capacity Periodate Battery with 3DPrinted Casing Accommodating Replaceable, Flexible Electrodes Zhiqian Wang, Xianyang Meng, Kun Chen, and Somenath Mitra ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b05578 • Publication Date (Web): 17 Aug 2018 Downloaded from http://pubs.acs.org on August 18, 2018

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ACS Applied Materials & Interfaces

Development of High Capacity Periodate Battery with 3D-Printed Casing Accommodating Replaceable, Flexible Electrodes Zhiqian Wang, Xianyang Meng, Kun Chen and Somenath Mitra* Department of Chemistry and Environmental Science, New Jersey Institute of Technology, 161 Warren Street, Newark, NJ 07102, USA. *E-mail: [email protected]. KEYWORDS: periodate, reserve battery, 3D printing, carbon nanotube, flexible electrode

ABSTRACT: We present the development of a novel battery comprising of iron(III) periodate complex cathode and zinc anode. The periodate complex (H7Fe4(IO4)3O8) was prepared by a precipitation reaction between Fe(NO3)3 and NaIO4, and was used in battery development for the first

time.

The

periodate

complex

along

with

14%

carbon

nanotubes

and

a

polytetrafluoroethylene coating formed a stable flexible electrode, and the battery showed specific capacity as high as 300 mAh g-1. Compared to single-electron processes in conventional cathode reactions, the possibility to significantly enhancing cathode specific capacity via a multielectron process associated with valence change from I(VII) to I2 is demonstrated. A novel 3Dprinted reserve battery design comprising of replaceable electrodes and acetic acid electrolyte is also presented. 1 ACS Paragon Plus Environment

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Introduction Materials with higher energy density, electrode potential, specific capacity, as well as low solubility in electrolytes and low self-discharge rate have been of great interest to the battery industry. Most conventional batteries, especially aqueous ones such as MnO2-Zn, Ni-Cd, Ni-MH and Ag-Zn, are based on single-electron cathode processes 1. This makes the cathode specific capacity lower than the anode, especially when metal anodes are used. Cathode materials with high oxidation states can achieve multi-electron processes thus increasing specific capacity. Periodates (IO4-) are strong oxidants with the highest possible oxidation state for iodine. Periodic acid and its Na and K salts have been used in organic reactions 2-4. The iodine(VII) and iodine(V) compounds show positive electrode potentials, which makes them viable material for electrochemical storage

5-6

. Yet there have been few reports on periodate based electrodes

7-8

where Na and K periodate cathodes7 have shown two-electron reduction to IO3- in alkaline environment. There are also a few reports on IO3- based electrodes

5, 9

. A combination of KIO3

cathode and H2SO4 electrolyte has shown the reduction of IO3- to I2 5. However, the zinc anode reacted with H2SO4, making it a less effective battery. The oxidizing capability of IO4- is pH dependent and under the right conditions, iodine(VII) is expected to show multi-electron processes and can be reduced beyond iodine(V) to lower oxidation states, thus providing larger capacity. Another reported problem is that alkaline periodates are soluble in neutral and acidic environments, which makes electrode formation difficult. Moreover, periodate and iodates salts are nonconductive and require large amounts of conductive materials such as graphite and acetylene black which occupies space and adds to the electrode weight 5, 7. There has been much interest in conformal batteries that have different shapes and sizes. For example, flexible batteries have been made into thin-film

10-14

and cable

15-17

forms; and

2 ACS Paragon Plus Environment

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microscale 3D-printed batteries have been fabricated and zinc-air cells

18

18-21

. 3D-printed lithium-ion batteries

19, 22

have been fabricated using ink-dispensing systems. Although micro battery

electrode structures could be precisely controlled during 3-D printing, the electrode fabrication incorporating precise active component formulations poses major challenges. A proto-typing approach can be taken for 3D printing of batteries

23-24

where custom casing and packaging can

be printed using conventional polymer filaments. The casings can be reused whereas the electrodes, which can be prepared by conventional methods, can be replaced when consumed. Then the battery can be activated by the addition of electrolyte. This is also applicable to reserve batteries. The objective of this paper is to develop battery system based on periodate complex cathode. Yet another objective is to develop a prototype periodate reserve battery using 3D-printing technology.

Results and discussion The photographs and SEM images of synthesized periodate complexes and associated electrode prepared with iron periodate are shown in Figure 1. Unlike alkaline periodates which readily dissolve in water, the iron(III) periodate complex was insoluble, making solid electrode fabrication possible. The freshly prepared periodate complex showed dark yellow color, which turned orange upon heating to 100 ºC. This was used as the active cathode material. Scanning electron microscopy (SEM) images showed that the prepared sample comprised of sub-micron spherical particles. Energy-dispersive X-ray spectroscopy (EDX) showed that the complex contained Fe, I and O (Figure 2a). The iron(III) periodate complex contained 25.64% Fe and 43.65% I by mass 3 ACS Paragon Plus Environment


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and was determined to be H7Fe4(IO4)3O8, containing both adsorbed and lattice water. Thermal gravity analysis (TGA, Figure 2e) results were consistent with this; only Fe2O3 was left behind beyond 600 ºC. X-ray diffraction (XRD) patterns showed peaks at 20.70º (101), 36.08º (301), 53.76º (013) (ICSD 987-015-4674), but due to the sub-micron particle size, the sample was considered to be largely amorphous. For comparison, silver(I) periodate complex was synthesized using a similar method starting with AgNO3. EDX results showed that Ag and I had a molar ratio of 2:1, the rest being O. Yet TGA data indicated that only 35% of the original sample was Ag. Hence, the formula was inferred to be H5Ag2IO7·8H2O and the sample could be dehydrated under vacuum or by heating. Furthermore, the silver salt was more susceptible to hydrolysis in neutral aqueous environment, as the sample turned black slowly when soaked in DI water. Its XRD pattern is shown in Figure 2, whose peaks matched the reported structure of rhombohedral H3Ag2IO6 (ICDD 00-058-0524): major peaks were indexed as 20.97º (003), 22.24º (012), 30.10º (110), 36.95º (113), 39.51º (015), 50.41º (205), 53.38º (103), 67.95º (107) respectively. Electrolyte Selection: In aqueous battery systems, common anode candidates include zinc, aluminium, lead and magnesium. An active metal can provide higher potential but can also react with the acidic electrolyte to generate hydrogen. Zinc is moderately reactive, and has been extensively used in alkaline and mildly acidic systems and was selected for this battery. As mentioned before, the periodate cathode would be affected by the concentration of hydrogen ions and pH of the electrolyte. Several electrolytes were tested to check if they were practical for battery fabrication (Figure 3). Cells with potassium hydroxide showed relatively poor performance based on discharge voltage and discharge time

7-8

. 2 M phosphoric acid cell had a

relatively flat and stable discharge curve, though initially the voltage was lower than in 1 M 4 ACS Paragon Plus Environment

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sulfuric acid. This was attributed to the fact that the latter was a stronger acid providing higher concentration of hydrogen ions (Figure 3a). However, high H+ concentration led to reaction with metallic zinc and generated hydrogen. As a resulted, when concentration of sulfuric acid was increased to 4 M, the cell performance dropped. The direct reaction between electrolyte and anode not only consumed active materials but also generated hydrogen that inhibited discharge reaction and increased the pressure in a sealed battery, which is also a safety concern. Phosphoric acid corroded the zinc anode at a lower rate than sulfuric acid. Different concentrations of phosphoric acid were tested (Figure 3b). Higher acid concentration led to a higher discharge voltage at the beginning, which was in line with Nernst Equation. However, cells with 3 and 5 M acids experienced fast voltage drop as zinc corrosion consumed both electrolyte and anode. Lower acid concentration caused low discharge potential and cells reached cut-off voltage earlier. Acetic acid was also tested as an electrolyte. The direct reaction between acetic acid and zinc was significantly lower than phosphoric acid, although minor hydrogen generation was still observed. Different concentrations of acetic acid were tested (Figure 3c) and 6 M acetic, which showed longer discharge time than 2 M phosphoric acid was selected as the electrolyte of choice. Cyclic voltammetry (CV) was used to further study the electrochemical properties of iron(III) periodate complex (Figure 3d&e). An reduction peak shows at 0.36 V only at low scan rates, which was attributed to the periodate reduction

25

happening on solid particle

surfaces. As scan rate decreased, this peak would become more and more obvious compared to the oxidation peak. One interesting thing was that as the cycling continued, the cathode reduction peak got smaller and smaller, indicating the poor reversibility of this process; the anode peak got larger at first due to increased concentration of I2 at the beginning, and then dropped as I2 further dissolved into electrolyte (Figure 3e). Another observation was that the electrolyte turned yellow



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after multiple CV scans, as the I2 produced could not be oxidized back. Hence in acidic electrolyte this periodate was more suitable for a primary electrode. CV scans were also tried using 6 M acetic acid electrolyte. However no peak could be observed even using low scan rate of 0.1 mV s-1, possibly due to the fact that acetic acid was a very weak electrolyte. Electrolyte selection appeared to be critical. The acid should not be reducing as it might react with periodate, nor should it be oxidizing to avoid dissolution of the anode. A non-volatile, weak acid was deemed to be most suitable because it slowed down anode corrosion. The acid also should have adequate aqueous solubility to maintain a low pH to provide H+ for the cathode reaction. Organic acids such as benzoic acid were rejected due to low solubility. Because zinc is an active metal, even a weak acid could react with it, hence the periodate-zinc battery using an acid electrolyte is well suited as a reserve battery for longer storage time. In a previous study, it was reported that IO4- could be reduced to IO3- in an alkaline environment 7. While IO3- is still oxidizing in acidic environment, it can be further reduced to I2 5

. In the present periodate battery, the cathodic reaction was (1): 2H7Fe4(IO4)3O8(s) + 66HAc(aq) + 42e- → 3I2(aq) + 40H2O(l) + 8Fe3+(aq) +66Ac-(aq)

(1)

While the anodic reaction was (2): Zn(s) → Zn2+(aq) + 2e- (2) Starch solution was added to discharged cells and a dark blue color was observed, indicating a 7 e- process and production of I2. This was different from the IO4- to IO3- 2 e- process in alkaline system reported before 7. I2 was also extracted from the spent electrolyte using methylene chloride and quantified with using UV-visible spectrophotometry

26

(supporting


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information text and Figure S-1). The amount of I2 in the spent electrolyte was 35% of the original iodine in the electrode. It was estimated that some I2 could be adsorbed onto CNTs, current collectors and even the PET-EVA substrate, which lowered the overall extraction efficiency and the reported number may be on low side. Additional data and discussions regarding possible side reactions were presented in supporting information. Cathode Optimization. Because of the poor conductivity of periodates, conductive additives were needed. Typical battery conductive materials include graphite 5, 7, carbon black 11, 27, carbon cloth/foam

28-29

, graphene materials

22, 30

, carbon nanotubes (CNTs)

12, 31-32

and also the

combination of them 10, 13. Different carbon materials were tested in this research (Figure 4a&b). The sub-micron carbon particles performed better because they were easier to disperse. This is in line with previous reports

31, 33

. CNTs was found to be somewhat better than carbon black.

Different amount of CNTs were tested (Figure 4b). It was found that cell performance with 14%, 16% and 20% CNT had no obvious trend; while cells with lower or higher amount CNTs showed lower performance. The required amount of conductive carbon was much lower than previously reported values such as 42.9% graphite and acetylene black 5, and 25% graphite 7. The cations in periodates turned out to have a less significant impact on the final performance than expected. Ag(I) is has been used in batteries such as AgCl-Mg 34-35 and Ag2OZn

18, 36-37

. Yet the replacement of Fe(III) by Ag(I) did not show improvement in battery

performance (Figure 4c). This is because the silver complex had larger particle size, leading to slower reactions and larger molar mass, and lower periodate percentage dropped the overall performance. The reaction between Ag(I) and Zn had a lower actual potential than the cut-off voltage. Figure 1b-g also showed that CNTs distributed and formed better conductive networks in iron(III) periodate complex than in silver(I) partially due to its smaller particle size and 7 ACS Paragon Plus Environment


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spherical shape. Taking other factors including the costs into consideration, Fe(III) was more suitable than Ag(I). Anode: As has been mentioned above, H+ reacts with active metals like zinc and leads to anode corrosion. There have been various reports on the addition of inhibitor into electrolytes to slow down the process. Organic inhibitors adsorb onto the metal surface to inhibit corrosion

38-39

. In

this study, three organic inhibitors (at the concentration of 200 ppm) were tested (Figure 5a). Hydroxyethyl cellulose has been reported to be an efficient inhibitor for zinc corrosion and by suppressing the reaction with H+

38

. The discharge profile in presence of the cellulose showed

higher and more stable potential. However, cells became unstable and failed after some time. It was inferred that the oxidizing property of periodate and acidic environment caused this problem by oxidation and hydrolysis of cellulose molecules. Methylcellulose and hexadecylamine also caused drop in performance. Another way to inhibit the zinc corrosion is to alter the particle size. In traditional zincbatteries, either powdered zinc (alkaline systems) or zinc foil (acidic and neutral systems) are used as anodes. Here we found that surface area had a significant impact on lifetime and discharge voltage (Figure 5b). Different forms of Zn studied here are shown in Table 1. Though having the same mass, zinc foil electrodes showed lower lifetime due to its lower surface area compared with powdered zinc, and the discharge voltage was also lower. Zinc foil 2, which had larger mass but smaller surface area powdered zinc, performed better. Compared with powdered zinc, the zinc metal foil was more resistant to corrosion and had higher electric conductivity. Reserve Cells with 3D printed housing: Due to size/space limitation of Swagelok cells, only small amount of acids and electrode materials could be added. In order to further study the


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potential capacity of the iron(III) periodate complex, reserve cell prototypes which can accommodate more electrolyte and zinc anode were fabricated. Here both electrolyte and anode were designed to be in stoichiometrically excess. In the 3D printed batteries, zinc foils were used as both anode reagent and anode current collector. Figure 6 shows the fabrication process of the 3D printed cells. The housing was made with acrylonitrile butadiene styrene (ABS) plastic, a common 3D printing material. The flexible cathode was prepared as follows. The cathode ink was pasted onto the silver-PET current collector, dried and then thermally laminated with a hydrophilic polytetrafluoroethylene (PTFE) membrane. Then it was inserted into the electrode slots. The zinc foil anode was inserted before the electrolyte was injected into the housing. An optional cap was also added. The housing could be designed as a single-cell battery or a double-cell (or multi-cell) battery with different dimensions. Figure 6b and Table 2 show the performance of single reserve battery cells in 3D printed housings. As discharge rate increased, the cell capacity increased. This was due to the competition between the discharge and the hydrogen generation reaction. The corrosion rate of zinc was mostly constant at given acid concentration while higher discharge rate promoted the discharge reaction. Another possible undesired side reaction was the slow migration of cathode species (like Fe3+) into electrolyte that reacted with the anode. Generally the iron(III) periodate complex showed a specific capacity between 0.28 and 0.33 Ah g-1, which is similar to NiOOH (0.29 Ah g-1) and MnO2 (0.31 Ah g-1), but higher than Ag2O (0.23 Ah g-1) and AgCl (0.19 Ah g1 1

) . Yet at higher discharge rates the discharge voltage dropped, leading to lower energy output.

A demonstration of a double-cell battery with cap is shown in Figure 6c.



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Conclusions In summary, iron(III) periodate complex was prepared by precipitation reaction of Fe(NO3)3 and NaIO4 and used for the first time in battery applications. The complex used as a cathode using acid electrolytes and a zinc anode. A novel 3-D printed reserve battery design comprising of replaceable flexible electrodes was also developed. The iron(III) periodate complex, H7Fe4(IO4)3O8 showed a high specific capacity of 300 mAh g-1 demonstrating that solid form periodate compounds are promising cathode materials. Particle size, anode selection, electrolyte concentration and the pKa of the acid electrolyte were all important factors, and we believe that higher performance can be achieved with further optimization. It is conceivable that other types of electrochemical cells can be also developed based on periodate compounds presented here.

Experimental Section The iron(III) periodate composites were prepared via stoichiometric reaction between 0.1 M Fe(NO3)3 (Sigma Aldrich, nonahydrate, ≥ 98%) and 0.05 M NaIO4 (Sigma Aldrich, meta, ≥ 99.8%) solution, which was previously adjusted to the pH of 1 using nitric acid and with 0.01 g mL-1 polyvinylpyrrolidone (PVP, Sigma Aldrich, average mol wt. 10000) added. Dissolved Fe(NO3)3 was titrated into NaIO4 at the rate of 0.8 mL min-1. The solution was stirred during the process and stirring was continued for another 30 min. The resulting yellow precipitate was filtrated, washed with 0.01 M HNO3 and dried at 25 ºC under vacuum for 12 hours. For comparison, silver(I) periodate complex was also prepared by replacing Fe(NO3)3 with AgNO3.


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Typical cathode formulation was composed of periodate salt, conductive carbon additive and 6% PVP. Different conductive carbon additives were tested. They were used as received without further treatment. These were carbon nanotubes (CNTs, multiwalled, purity 95%, Cheap Tubes Inc. Brattleboro, VT, USA), synthetic graphite (Sigma Aldrich, < 20 micron), graphitized carbon black (Sigma Aldrich, < 500 nm), and activated charcoal (Sigma Aldrich, 100 mesh). Amount of conductive additives were also varied. Electrodes were made as follows: The dry powdered materials were mixed in DI water. Then electrode slurry was pasted onto a stainless steel current collector and dried. During cathode and electrolyte optimization, the anode was made with 6% PVP, 4% CNTs, 2% bismuth (III) oxide (Sigma Aldrich, 90-210 nm particle size, ≥ 99.8%), and 86% zinc powder (Sigma Aldrich, ≤10 µm, ≥ 98%), which would also be referred to as the standard anode. The anode was stoichiometrically in excess. The typical weights of the cathode and anode after drying were 0.016 and 0.057 g respectively, with 0.5 mL electrolyte for Swagelok cells. Optimization was carried out in Swagelok-type cells using stainless steel current collectors (MTI, Richmond, CA) and assembly was made with a PTFE film (5.0 µm, ANOW) and a glass fiber separator (Grade GF/A: 1.6 µm, Whatman) sandwiched between electrodes. Different electrolytes namely concentrated sulfuric acid, phosphoric acid, acetic acid and KOH were tested as electrolytes and were also purchased from Sigma Aldrich. 2-hydroxyethyl cellulose (Sigma Aldrich, average mol wt. 250,000), methylcellulose (Sigma Aldrich, average mol wt. 40,000) and hexadecylamine (Sigma Aldrich) were tested as inhibitors. Pure zinc foils were also tested as anodes.



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The casing of the prototype reserve battery was printed using ABS plastic in a Flashforge Creator Pro 3D Printer. In such a reserve cell, zinc foil (3 cm × 2 cm, in excess) was used as anode reagent and current collector. The final cathode formulation contained 14% CNT, 6% PVP and 80% periodate. Cathode current collectors were prepared by pasting silver ink onto on the adhesive side of ethylene vinyl acetate (EVA) resin coated polyethylene terephthalate (PET) sheets. Cathode ink was pasted onto the current collector and dried. Then a hydrophilic polytetrafluoroethylene (PTFE, 5.0 µm, ANOW) film was placed on cathode and laminated to form the cathode assembly. Cathode had an area of 2.4 cm × 1.4 cm and typical mass of 0.0194 g. Electrode plates were inserted into the slots before 15 mL 6 M acetic acid electrolyte was injected into the cell. The electrochemical performance of the cells was measured using an MTI Battery Analyzer. The assembled cells were discharged using constant resistance or constant current methods. Scanning electron microscope (SEM) with Energy-dispersive X-ray spectroscopy (EDS) were collected on an LEO 1530 VP Scanning Electron Microscope. Thermal gravity analysis (TGA) was done on PerkinElmer Pyris 1. The Brunauer, Emmett and Teller (BET) specific surface area of the samples were measured using Quantachrome Autosorb iQ-Chemisorption & Physisorption Gas Sorption Analyzer (Boynton Beach, FL) to calculate the surface area of powdered zinc electrode. X-ray Diffraction (XRD) patterns of periodates were taken on a PANalytical Empyrean XRD. Cyclic voltammetry (CV) was carried out on a Homiangz 320C electrochemical analyzer versus a standard Ag-AgCl electrode in 2 M H3PO4 electrolyte. UV-vis measurement were carried out on Shimadzu UV-1800.


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AUTHOR INFORMATION Corresponding Author *Corresponding Author: Somenath Mitra. E-mail address: [email protected]. Tel: +1 (973) 596-5611, Fax: +1 (973) 596-358 .Author contributions Z. Wang made the batteries and studied their properties. Z. Wang, K. Chen and X. Meng performed material preparation and characterization. Z. Wang and S. Mitra developed the different concepts and prepared the manuscript.

Conflict of Interest The authors declare no conflict of interest.

Supporting Information Supporting Information shows I2 quantitative analysis and iron(III) iodate complex as battery cathode.



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Figure 1. (a) Photographs of as prepared silver and iron periodate complexes; SEM images of (b) iron(III) periodate complex; (c) & (d) iron(III) periodate electrode; (e) silver(I) periodate complex; (f) & (g) silver(I) periodate electrode; and (h) pure carbon nanotubes.


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Figure 2. EDX of (a) iron(III) periodate complex; (b) silver(I) periodate complex; XRD of (c) iron(III) periodate complex; (d) silver(I) periodate complex; (e) TGA analysis of the periodates.



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Figure 3. Effect of electrolyte: (a) Strong acids and bases as electrolytes; (b) phosphoric acids as electrolyte; (c) Acetic acid as electrolytes (cathode: 82% iron(III) periodate complex, 12% CNT conductive additive, 6% PVP); (d) CV curves of periodate electrode in 2 M H3PO4 vs Ag-AgCl reference electrode; (e) iron(III) periodate complex cycling property at 5 mV s-1.


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Figure 4. (a) Cells with different conductive additives (cathode: 82% iron(III)periodate complex, 12% carbon conductive additive, 6% PVP; 1.85 M H3PO4 electrolyte; standard anode); (b) cells with different amounts of CNTs (cathode: iron(III) periodate complex, CNTs, 6% PVP; 1.85 M H3PO4 electrolyte; standard anode); (c) comparison of cations: Fe3+ vs Ag+ (cathode: 80% periodate complex, 14% CNTs, 6% PVP; 6 M acetic acid electrolyte; standard anode).



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Figure 5. (a) Influence of anode corrosion inhibitors in electrolyte; (b) zinc foil and powdered zinc as anode. In all experiments the cathode comprised of 80% iron(III)periodate complex, 14% carbon conductive additive, 6% PVP; 6 M acetic acid electrolyte; standard anode for (a); standard anode (zinc powder) and zinc foil anodes in (b).


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Figure 6. 3D printed reserve battery: (a) Steps in the fabrication of the reserve battery; (b) batteries discharged under different current (cathode: 80% iron(III) periodate complex, 14% CNTs, 6% PVP; 6 M acetic acid electrolyte; zinc foil anode); (c) flexible cathode; (d) demonstration of a 3D printed double-cell battery powering LED light.



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Table 1. Cell performance with different zinc anodes. Anode Mass [g]

Zinc Surface Area [cm2]

Cell Capacity [mAh]

Cell Energy

powdered zinc

0.057

155.5

2.82

2.86

Zinc foil 1

0.057

2.2

1.29

1.45

Zinc foil 2

0.480

17.1

3.58

4.00

Sample Name

[mWh]

Table 2. Performance of 3D-printed reserve battery. Specific Energy Discharge Rate Specific Discharge Rate Specific Capacity [mA] [mA g-1] [mAh g-1 periodate] [mWh g-1 periodate] 0.31

20

280.52

335.48

0.62

40

291.03

313.48

1.24

80

327.03

312.19


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The table of contents:

Development of High Capacity Periodate Battery with 3D-Printed Casing Accommodating Replaceable, Flexible Electrodes Zhiqian Wang, Xianyang Meng, Kun Chen and Somenath Mitra* Department of Chemistry and Environmental Science, New Jersey Institute of Technology, 161 Warren Street, Newark, NJ 07102, USA. E-mail: [email protected].

KEYWORDS: periodate, reserve battery, 3D printing, carbon nanotube, flexible electrode


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Development of High Capacity Periodate Battery with 3D-Printed

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