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Novel Cell Design for Electrochemical Characterizations of Metal-Ion Batteries in Organic and Aqueous Electrolyte Amir Bani Hashemi, and Fabio La Mantia Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.6b02138 • Publication Date (Web): 21 Jul 2016 Downloaded from http://pubs.acs.org on July 23, 2016

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Analytical Chemistry

Novel Cell Design for Electrochemical Characterizations of Metal-Ion Batteries in Organic and Aqueous Electrolyte Amir Bani Hashemi*,1,2, Fabio La Mantia*,1,2 1

Energiespeicher– und Energiewandlersysteme, Universität Bremen, 28359 Bremen, Germany

2

Semiconductor & Energy Conversion – Center for Electrochemical Sciences (CES), Ruhr-Universität Bochum, 44780 Bochum, Germany

* [email protected] (Amir Bani Hashemi), * [email protected] (Fabio La Mantia) ABSTRACT: Understanding the gas evolution in batteries, caused by decomposition of the electrolyte, is of fundamental importance for improving the long-time performances and cycle life of the battery systems. In general, this phenomenon causes simultaneously an irreversible energy and charge loss, as well as an increase of the internal resistance. Here, we introduce a new cell design capable of performing electrochemical impedance spectroscopy (EIS) and differential electrochemical mass spectroscopy (DEMS) with high resolution. Detailed aspects of the cell fabrication and the different components of the cell are extensively explained. Impedance measurements were validated by using symmetric electrodes. The possibility to perform long term DEMS measurements was tested on graphite electrodes in EC: DMC (1:1), 1M LiPF6 as an electrolyte. Finally, the cell was used to detect hydrogen evolution on the zinc negative electrode of a zinc-ion battery based on copper hexacyanoferrate. Keyword: cell design, differential electrochemical mass spectrometry, electrochemical impedance spectroscopy, zinc-ion batteries, lithium-ion batteries

The past two decades have seen the rapid development of electrochemical energy storage systems for electromobility and stationary application. Lithium-ion batteries, using organic electrolytes, are largely employed as storage devices for laptop, computers, smartphones, and electrical cars.1 However, they have shown some disadvantages in stationary applications, related to safety, environmental impact, and costs. As possible candidates for grid scale applications, aqueous metal-ion batteries have been recently introduced due to non-flammability, high ionic conductivity, solubility and thermal capacity of the electrolyte and possible low cost of the fabrication.2–5

EIS is a widely used electro-analytical technique, which popularity is related to the possibility to separate and quantify various phenomena in a large range of time constants, such as charge transfer resistance, charge accumulation at the interface, solid state and/or liquid diffusion.11 EIS is generally based on the superimposition of a small AC potential (typically smaller than 10 mV) to a constant DC potential. The response of the system is quasi-linear, and composed of an AC current and a DC current. The impedance, Z(ω), is a complex number, characterized by the magnitude |Z|, which is the ratio between the amplitude of the AC voltage and the AC current, and phase shift φ between the AC current and the AC potential. In order to access to the features of a single electrode based on EIS measurements in a battery system, it is necessary to use a three-electrode cell configuration, which involves the use of a reference electrode.12 Reproducibility, reversibility, and non-polarizability are the most important characteristics of an ideal reference electrode for EIS measuremnts.13 Mostly interesting, in the past decade there has been a continuous effort in developing dynamic impedance spectroscopy, which allows acquiring impedance spectra while the battery is cycled.14–18

One of the most important challenge in both types of electrochemical energy storage systems is gas evolution, which is caused by the decomposition of the electrolyte or other side reactions.6,7 This should be avoided for several reasons: it can cause a chemical short circuit, thus lowering the energy and charge efficiency of the storage system;6 it could start a bulk or surface degradation of the material, thus increasing the internal resistance of the device.8,9 Therefore, monitoring in-situ the impedance of the batteries by electrochemical impedance spectroscopy (EIS), and gas evolution, using differential electrochemical mass spectrometry (DEMS)10, in the same setup has the potential of giving a fundamental insight on the mechanism of aging of a battery.

The other useful analytical technique to study the mechanism of aging of the batteries is DEMS, which, by coupling mass spectrometry with an electrochemical technique (typically cyclic voltammetry), allows investi-

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without any further process. The graphite-based slurry was prepared by dispersing SFG6 (Timcal, Bodio, Switzerland) and PVdF in NMP by means of stirring machine for 30 minutes at 4000 rpm. The final composition of the electrode was 91-9 wt % of SFG6-PVdF. The slurry was painted on stainless steel and dried overnight, as recently described for the other electrodes. The cell is assembled inside a glove box in which the O2 and H2O impurities are less than 1 ppm. Cyclic voltammetry was performed outside the glovebox, starting from 1.5 V vs. Li+/Li down to 0.01 V vs. Li+/Li with scan rate 0.2 mV s-1 for the first cycle and between 1.0 and 0.1 V vs. Li+/Li for all subsequent cycles, using Gammry reference 600TM. During the measurement, argon was flown though the cell using a mass flow controller (Alicat Scientific, Inc., Tucson, USA). The outlet gases, containing argon plus the volatile compounds coming from the cell, are then detected by the mass spectrometer Thermostar (Pfieffer vacuum GmbH, Asslar, Germany) in which quadrupole mass spectrometer is used. The time delay between the gas evolution and detection is ~7 s. Temperature of the inlet and the capillary of the mass spectrometer is retained at 120 °C and 150 °C, respectively. Vacuum pressure is held around 7.65×10-7 mbar during experiment. DEMS measurements in an aqueous electrolyte were carried on a zinc-ion battery based on copper hexacyanoferrate in a two-electrode cell configuration. The copper hexacyanoferrate (CuHCF) was synthesized as described in reference.3 The CuHCF-based slurry was prepared by a mixture of CuHCF, binder (PVdF in NMP), C65 and SFG6 with the final ratio of 80-9-9-2 wt %. Zinc powder plus binder (PVdF in NMP) with the ratio of 96-4 wt % is used as negative electrode. 20 mM zinc sulfate with pH=6 is served as the electrolyte. Galvanostatic cycling is used to cycle the battery in the range of 1.4 V to 2.2 V at a current rate of 2C. Also in this case, the argon was flown though the cell and volatile compounds coming from the cell were detected by the mass spectrometer.

gating in-operando the formation of gaseous or volatile species.19 This method is vastly used for different application such as oxidation of ethanol and methanol on various substrates20–22, electro-oxidation of adsorbed CO on the surface of a catalyst22,23, and battery analysis.24–27 There are different kinds of DEMS setups; the most used setup to monitor gas evolution in batteries is by gas carrier6–8,28–30, where an inert gaseous compound (often argon) is continuously purging the atmosphere of the electrochemical cell, and bringing with it the volatile products. In this paper, we introduce a cell design where DEMS and EIS can be performed on the same electrode, for both organic and aqueous batteries. At this aim, it is important to show that the cell allows accessing correct values of impedance at high frequency as well as measuring small amount of evolved gaseous or volatile products. To the best of our knowledge, this cell is the first one that can be utilized for both DEMS and EIS measurements with reliable results.

EXPERIMENTAL SECTION EIS measurements. In order to validate the performance of the cell for EIS measurements, two electrodes based on lithium iron phosphate (LFP, MTI, Richmond, USA) were used as the working electrode (WE) and the counter electrode (CE) and half oxidized LFP was used as the reference electrode (RE). The electrode slurry was prepared by mixing of LFP, carbon black (C65, Timcal, Bodio, Switzerland) and polyvinylidene difluoride (PVdF) binder solution (Solef S5130, Solvay) in N-methyl pyrrolidone (NMP, Sigma-Aldrich), using stirring machine (ultra-turrax, Ika, Staufen, Germany) for 30 minutes at 4000 rpm. The final ratio of the compounds in the electrode was 80-10-10 wt % of LFP-C65-PVdF. Stainless steel meshes (Goodfellow, Bad Nauheim, Germany) were used as current collector: they were painted with the slurry and heated to 60 °C for five hours in air. To get rid of any trace of water, the electrodes were completely dried overnight at 120 °C in vacuum oven (Büchi, Essen, Germany). The reference electrode was prepared by oxidizing it completely, reducing it and finally oxidizing it again up to the half of its specific charge at a current rate of C/10 (nC means each oxidation or reduction step is completed in 1/n hours) against metallic lithium, following the procedure given in reference.31 EC: DMC (1:1), 1M LiPF6 was used as an electrolyte solution. EIS measurements were run in the frequency range from 100 kHz to 10 mHz and potential amplitude of 10 mV rms, using Gammry reference 600TM (Gammry Instruments, Warminster, USA). The DC potential was set to open circuit.

Figure 1. Schematic view of the DEMS-EIS cell. 1: cavity for the location of the electrodes; 2, 3, 4: stainless steel AISI 303 current connectors; 5, 6: gas inlet and outlet; 7: o-ring; 8: spring

DEMS measurements. To test the DEMS measurements in organic electrolytes, graphite, metallic lithium and LFP were used as WE, CE and RE, respectively. The reference LFP was prepared as described previously. Lithium metal sheet (Sigma-Aldrich) was used as the CE

RESULTS AND DISCUSSIONS

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Cell design. In Figure 1 a schematic drawing of the cell is reported. It was designed in order to perform high resolution EIS and DEMS measurements. The body of the cell is completely made of poly ether ether ketone (PEEK, Goodfellow, Bad Nauheim, Germany), which is inert in many organic solvents and aqueous solutions.32 The cell is composed by three main separated parts which are shown in Figure 1 by using the colors green, orange and brown. The space between the green and the orange part, which is marked with number 1, is used to allocate electrodes and separators. This area has a circular shape with diameter equal to 14 mm. CE, separator, RE, separator and WE are positioned in this space from down to top, respectively. Each separator (WhatmanTM, GE Healthcare, UK) was wetted with 150 µL of the appropriate electrolyte during the cell assembling. An o-ring (number 7 in Figure 1) is utilized around the intermediate part of the cell to attain proper sealing. PEEK nuts with double ferrule configuration are used (MACHEREY-NAGEL GmbH & Co. KG, Düren, Germany) to achieve a good sealing of the connections in the inlet and the outlet channels (number 5 and 6 in Figure 1). By using proper nuts, ferrules and o-ring, a sealing of 85% was achieved. This was calculated by using a 0.2 mL min-1 flow of argon, and measuring the output flow in an empty cell. In order to apply a constant external force on the electrodes during experiments, the middle part of the cell, which is indicated with orange color, is mechanically supported by a spring (number 8 in figure 1).

EIS measurements. The reliability of the cell in acquiring impedance spectra at high frequency is dictated by the cell geometry.11 This is often an important region of frequency to be explored, in order to understand the reaction mechanism of charge transfer between liquid and solid. In order to test our cell, we performed a set of impedance spectra on two similar electrodes based on lithium iron phosphate, called LFP1 and LFP2. A half oxidized LFP electrode, prepared as described in the experimental, was used as reference electrode. LFP1, RE and LFP2 were installed in the cell from top to down, respectively, using one separator between each of them. Three impedance spectra were acquired: the first one was obtained by connecting LFP1 as WE, and LFP2 as CE (LFP1RE); in the second one the role of LFP1 and LFP2 is inverted (LFP2-RE); in the third one the LFP1 is the WE, LFP2 is the CE, while the RE is short-circuited with the CE (LFP1LFP2, two-electrode configuration). The result of the impedance for these three different configuration is shown in Figure 2. The impedance spectra of LFP1 and LFP2 are identical, within the experimental error, apart for the starting resistance at high frequency, which is larger for LFP2-RE configuration. This is due to the contact of the electrode. The connector in Figure 1, indicated with number 2 and 3, are different, and this is causing the observed difference. We want to stress that, although a shifting of the spectra along the x-axis is observed, the shape of the spectra of the two LFP electrodes are almost the same, thus confirming that this cell is reliable for impedance spectra in the high frequency region. Moreover, the higher contact resistance of CE does not influence the current density distribution in the cell, thus it does not affect the impedance spectra recorded at WE. From Figure 2 it can be observed that the sum of the spectra of LFP1 and LFP2 coincides with the impedance of the whole cell, within the experimental error, thus confirming the reliability of the cell.

Current connectors (number 2 to 4 in figure 1) are made of polished stainless steel AISI 303, (Edelstahlhandel HARRY RIECK, Hilden, Germany). A reference electrode is located between the working and counter electrode. The reference electrode has a circular shape with an external segment, which allows the contact with the current connector (number 4 in Figure 1). The current connector of the WE enters 1 mm inside the cell. This 1 mm depth behind the WE is completely filled with polytetrafluoroethylene films (PTFE) (Goodfellow, Bad Nauheim, Germany), which prevent the electrolyte to approach to the outlet channel, but gaseous species can pass through the film and reach to the capillary of the mass spectrometer. It should be noticed that the mass spectrometer consumes a gas flow between 1 and 2 sccm (standard cubic centimeter per minute). In order to avoid rapid evaporation of the electrolyte, a low argon flow is sent to the cell via the main gas line. An auxiliary argon gas line is used to fulfill the requirements of the mass spectrometer. The ratio of the gas flow in the main and the auxiliary argon gas line is 1 to 5. For all connections between the experimental components, tubing, PEEK, 1/16 in. with 0.50 mm inner diameter (MACHEREY-NAGEL GmbH & Co. KG, Düren, Germany) is used. More detail about the cell design and the schematic of the setup are shown in figure S1 to S4. This cell is used in all the experiments shown in this manuscript.

Figure 2. Impedance spectra of two symmetric LFP electrodes. LFP1-RE indicate the configuration in which the WE is at the top, RE at the middle and the CE at the bottom of

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the cell. In configuration LFP2-RE, the WE is located at the bottom of the cell, while the CE is located at the top. LFP1LFP2 is two electrode configuration. LFP1-RE + LFP2-RE is the mathematical summation of the first and the second configuration.

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DEMS measurement. The difficulty in the design of a gas-carrier cell configuration for DEMS measurements lies on the ratio between the amounts of gas formed during the electrochemical process, the dead volume of the cell, and the flux of gas carrier (argon in our case): the larger is the dead volume of the cell and the larger is the flux of the gas carrier, the more diluted is the concentration of the gas released from the cell, and consequently the harder is to detect the gaseous species formed during the electrochemical experiment. In our case, the cell has a dead volume of circa 70 μL and the flow of gas carrier in the cell is 200 μL min-1. By assuming that the mass spectrometer can detect, in the best case scenario, a change in concentration equal to circa 10 ppm, this setup can detect a generation of 2.10-10 mol of volatile compounds in a time frame of 20 second. To prove the reliability of the cell for DEMS measurements, the gas evolution during the intercalation of lithium ions in graphite particles (SFG6) was monitored. Metallic lithium was used as CE and half-oxidized LFP as RE. Figures 3(c-e) shows the mass spectrometric signals during cyclic voltammetry performed at 200 μV s-1.

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From the analysis of the mass spectra, it could be concluded that the peak signal at I44 was generated by CO2 evolution, while the peak signal at I26 could be attributed to a fragment of ethylene generated during the formation of the solid-electrolyte interphase (SEI).33 These two signals are observed just in the first cycle and almost disappeared in the following cycles. It is not clear in a definitive way from which gas the mass signal m/z = 2 arose, although it could indicate hydrogen. This was coming at each cycle, with almost always the same intensity, as already observed previously. These results are very well matched with the previous studies27,28 and prove the reliability of the cell. We wish to stress again that such results were obtained in a cell where it was also possible to acquire impedance spectra, and with an electrode with an active mass on only circa 8 mg.

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Figure 3. (a-b) Potential and current profile in Cyclic voltammetry of SFG6 vs. lithium which is done from 1.5 V vs. + + -1 Li /Li down to 0.01 V vs. Li /Li with scan rate 0.2 mV s for + the first cycle and between 1.0 and 0.1 V vs. Li /Li for all subsequent cycles. (c-e) The mass spectrometric signals of mass -1 number m/z = 2, 26, 44 at 0.2 mV s of SFG6 electrode, using EC:DMC (1:1), 1 M LiPF6 as an electrolyte. Blue dash line indicates the point that SEI layer is electrochemically formed and the red dash lines show the lowest potential of each cycle.

Besides to the application of this cell in lithium-ion batteries with organic electrolyte, we wanted to show that it could be used also for characterization of gas evolution in aqueous metal-ion batteries. Here, we studied the hydrogen evolution in aqueous zinc-ion batteries based on copper hexacyanoferrate in neutral pH.

The average discharge voltage of this type of batteries is 1.73 V, which is the highest value among the other aqueous metal-ion batteries.3 One of the limiting factors of this new family of batteries is related to the zinc negative electrode, which potential is sufficiently cathodic to

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thermodynamically allow hydrogen evolution (see Figure S3 in supporting information for the Pourbaix diagram of zinc). Hydrogen evolution influences negatively the performance of the battery, hindering the energy density and efficiency, and could as well cause a safety issue, due to the increase of pressure inside the battery and accumulation of a very reactive gas. Thus, a direct observation of this phenomenon using DEMS measurement could be of very high importance, in order to understand which component of the cell should be improved and the optimization strategy.

on which half-oxidized active material is painted. Reliability of impedance spectra was confirmed by experiments involving two symmetric LFP electrodes. Reliable DEMS measurements were confirmed by the analysis of gas evolution during the lithium ion intercalation on graphite SFG6 particles. In order to show the flexibility of the cell, and the possible application also in aqueous metal-ion batteries, hydrogen evolution on the zinc negative electrode of a zinc-ion battery was shown. The experimental results confirm that the cell is suitable for simultaneous acquisition of impedance spectra and mass signals.

In Figure 4 the results of a galvanostatic mass cycles for the zinc negative electrode in 20 mM ZnSO4 aqueous solution is reported. Contrary to our recent hypothesis based on post-mortem analysis3, the hydrogen evolution was observed during all cycles. This phenomenon could be explained by the fact that zinc, upon contact with water, forms a thin layer of ZnO or Zn(OH)2 on the surface, which blocks the further hydrogen evolution. When the ZnO layer is reduced electrochemically, the hydrogen evolution starts again. To confirm this mechanism, it will be necessary to perform measurements at different value of pH, concentration and nature of the zinc salt, and zinc mass loading, as well as adding information from postmortem analysis. Also, it will be necessary to use an appropriate reference electrode, which was not yet identified. Being the main aim of this manuscript to show the flexibility of the cell setup, the specific case of H2 evolution in zinc-ion batteries will not be discussed further.

ASSOCIATED CONTENT Supporting Information Figure S1. Schematic view of the cell design Figure S2. Dimensions of the bottom part of the cell. Figure S3. Dimensions of the top part of the cell. Figure S4. Schematic setup for DEMS measurement. Figure S5. Pourbaix diagram of Zinc

AUTHOR INFORMATION Corresponding Author * [email protected] (Amir Bani Hashemi) * [email protected] (Fabio La Mantia)

ACKNOWLEDGMENT The financial support of the Federal Ministry of Education and Research (BMBF) in the framework of the project “Energiespeicher” (FKZ 03K3005) are gratefully acknowledged.

REFERENCES (1) (2) (3) (4) (5)

Figure 4. Seven cycle chronopotentiometry and mass spectrometric signals for m/z = 2 at 2C of zinc vs. CuHCF in 20 mM ZnSO4 as an electrolyte.

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CONCLUSION

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In this manuscript we wanted to present the design of cell geometry for performing reliable and accurate EIS and DEMS measurements, as well as more traditional electrochemical measurements, such as cyclic voltammetry and galvanostatic cycling. The cell geometry was designed in order to obtain the highest symmetry of current lines, with a reference electrode that consists of a mesh,

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Yoo, H. D.; Markevich, E.; Salitra, G.; Sharon, D.; Aurbach, D. Mater. Today 2014, 17 (3), 110–121. Pasta, M.; Wessells, C. D.; Huggins, R. a.; Cui, Y. Nat. Commun. 2012, 3 (May), 1149. Trócoli, R.; La, F. ChemSusChem 2015, 8 (3), 481–485. Dushina, A.; Stojadinović, J.; La Mantia, F. Electrochim. Acta 2015, 167, 262–267. Pasta, M.; Wessells, C. D.; Liu, N.; Nelson, J.; McDowell, M. T.; Huggins, R. A.; Toney, M. F.; Cui, Y. Nat. Commun. 2014, 5, 3007. Vetter, J.; Holzapfel, M.; Wuersig, A.; Scheifele, W.; Ufheil, J.; Novák, P. J. Power Sources 2006, 159, 277–281. Wuersig, A.; Scheifele, W.; Novák, P. J. Electrochem. Soc. 2007, 154 (5), A449. He, M.; Castel, E.; Laumann, A.; Nuspl, G.; Novak, P.; Berg, E. J. J. Electrochem. Soc. 2015, 162 (6), A870–A876. Aurbach, D.; Markovsky, B.; Weissman, I.; Levi, E.; Ein-Eli, Y. Electrochim. Acta 1999, 45 (1), 67–86. Baltruschat, H. J. Am. Soc. Mass Spectrom. 2004, 15 (12), 1693–1706. Klink, S.; Madej, E.; Ventosa, E.; Lindner, A.; Schuhmann, W.; La Mantia, F. Electrochem. commun. 2012, 22, 120–123. Song, J. Y.; Lee, H. H.; Wang, Y. Y.; Wan, C. C. J. Power Sources 2002, 111, 255–267. Newman, J.; Thomas-Alyea, K. Electrochemical Systems;

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Imhof, R.; Novak, P. J. Electrochem. Soc. 1999, 146 (5), 1702– 1706. La Mantia, F.; Rosciano, F.; Tran, N.; Novák, P. J. Appl. Electrochem. 2008, 38 (7), 893–896. Bernhard, R.; Meini, S.; Gasteiger, H. a. J. Electrochem. Soc. 2014, 161 (4), A497–A505. Seo, D. M.; Chalasani, D.; Parimalam, B. S.; Kadam, R.; Nie, M.; Lucht, B. L. ECS Electrochem. Lett. 2014, 3 (9), A91–A93. La Mantia, F.; Novák, P. Electrochem. Solid-State Lett. 2008, 11 (5), A84. La Mantia, F.; Rosciano, F.; Tran, N.; Novak, P. J. Electrochem. Soc. 2009, 156 (11), A823–A827. Liu, J.; Liu, J.; Wang, R.; Xia, Y. Chem. Mater. 2014, 161 (1), 160–167. La Mantia, F.; Wessells, C. D.; Deshazer, H. D.; Cui, Y. Electrochem. commun. 2013, 31, 141–144. Novák, P.; Goers, D.; Hardwick, L.; Holzapfel, M.; Scheifele, W.; Ufheil, J.; Würsig, a. J. Power Sources 2005, 146 (1-2), 15–20. Imhof, R.; Novák, P. Electrochem. Sci. Technol. 1998, 145 (10), 3313–3319.

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