High Specific Power Dual-Metal-Ion Rechargeable Microbatteries

Research Article www.acsami.org

High Specific Power Dual-Metal-Ion Rechargeable Microbatteries Based on LiMn2O4 and Zinc for Miniaturized Applications Rafael Trócoli,*,† Alex Morata,† Marcus Fehse,† Michel Stchakovsky,‡ Alfonso Sepúlveda,§ and Albert Tarancón*,† †

IREC, Catalonia Institute for Energy Research, Jardins de les Dones de Negre 1, 08930 SantAdrià de Besós, Spain HORIBA Scientific, Avenue de la Vauve, Passage Jobin Yvon, 91120 Palaiseau, France § Imec, Kapeldreef 75, B-3001 Leuven, Belgium ‡

S Supporting Information *

ABSTRACT: Miniaturized rechargeable batteries with high specific power are required for substitution of the large sized primary batteries currently prevalent in integrated systems since important implications in dimensions and power are expected in future miniaturized applications. Commercially available secondary microbatteries are based on lithium metal which suffers from several well-known safety and manufacturing issues and low specific power when compared to (super) capacitors. A high specific power and novel dual-metal-ion microbattery based on LiMn2O4, zinc, and an aqueous electrolyte is presented in this work. Specific power densities similar to the ones exhibited by typical electrochemical supercapacitors (3400 W kg−1) while maintaining specific energies in the range of typical Li-ion batteries are measured (∼100 Wh kg−1). Excellent stability with very limited degradation (99.94% capacity retention per cycle) after 300 cycles is also presented. All of these features, together with the intrinsically safe nature of the technology, allow anticipation of this alternative micro power source to have high impact, particularly in the high demand field of newly miniaturized applications. KEYWORDS: microbatteries, LiMn2O4, zinc, thin film, pulsed laser deposition

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INTRODUCTION Due to the ubiquitous presence of lithium ion batteries in portable applications and the excellent perspectives of their implementation in the transportation sector, the future cost and availability of lithium-based batteries is currently under debate.1 Consequently, several battery technologies based on alternative metals such as sodium,2−6 potassium,7−9 magnesium,10 aluminum,11,12 and zinc13−16 are receiving increasing attention as a low-cost substitute. Among them, aqueous zinc-ion batteries are considered as one of the best candidates because of their high theoretical capacity, low price, abundance of raw materials, cost-reduction of their fabrication processes (no need for operation and assembly under reducing atmospheres), and their inherently safe nature (absence of flammable organic electrolyte solutions and low toxicity). However, although their potential use is being studied for volume applications, the use of these alternative technologies is not yet explored for novel sectors involving miniaturization such as the Internet of Things © 2017 American Chemical Society

(IoT) for environmental monitoring, e-health, or smart metering of energy services.17 In this regard, most suitable rechargeable batteries for IoT applications can progressively substitute currently employed large sized primary batteries if miniaturization, safety, and specific energy and power issues are overcome. Commercially available all-solid-state secondary microbatteries are based on lithium metal which suffers from severe safety issues related to the formation of lithium dendrites through the grain boundaries of the solid electrolyte, and such microbatteries present low power densities18 due to the high internal resistances associated with large contributions from the solid electrolyte/electrodes interfaces.19 Even when the bestsuited ionic conductors based on sulfides are used, the potential Received: June 20, 2017 Accepted: September 8, 2017 Published: September 8, 2017 32713

DOI: 10.1021/acsami.7b08883 ACS Appl. Mater. Interfaces 2017, 9, 32713−32719

Research Article

ACS Applied Materials & Interfaces

LiMn2O4 cubic spinel phase (space group Fd3m ̅ , JCPDS 350782) with a preferential 111 orientation was the predominant phase in the films. Mn3O4 phase was also detected. This electrochemically inactive impurity is commonly found in LMO thin films due to the poor stoichiometric transference of lithium ions.25The displacement observed in peaks 222 and 331 is probably caused by the stress typically observed in thin films deposited onto rigid substrates. Scanning electron microscopy (SEM) images of the surface and cross sections of the films are shown in Figure 2. The

formation of toxic H2S (in the case of battery damage) or the formation of SO2 by oxidation of the solid electrolyte represent potential risks and imply a complete degradation of the electrolyte.20 To complement this, the use of three-dimensional (3D) electrode microstructures, to increase the specific active area enhancing the limited power density of the associated microbatteries, has been extensively reported.21However, although numerous electrodes, both positive and negative, have been developed, only a few examples have been reported of complete 3D cells, which, in general, still present insufficiently low power and poor stability.17 Regarding high-rate exchange electrodes which increase the specific power, the authors recently reported a half cell based on a LiMn2O4 (LMO) thin film with a unique microstructure fabricated via combinatorial Large Area Pulsed Laser Deposition (LA-PLD) and outstanding electrochemical cycling performance due to its pseudocapacitive lithium storage ability.22 This result, combined with the recently reported dual-metal-ion battery schemes based on metallic zinc,23 is developed in the current work to build the first dual-metal-ion microbattery based on LMO thin films. Remarkably, the system provides specific power similar to that exhibited by electrochemical supercapacitors and specific energies characteristic of Li-ion batteries, with excellent stability and potential scalability to an industrial level.

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Figure 2. SEM images of top and cross section of the LMO electrode. LMO400, top a); and cross section b); LMO1000, top c); and cross section d).

RESULTS AND DISCUSSION LMO thin films with thicknesses of c.a. 400 and 1000 nm (LMO400 and LMO1000, respectively) were deposited on Si/ TiN/Pt substrates by means of the industrially scalable LA-PLD under the conditions indicated in the Experimental Section. Although exceptional stoichiometry transference is typically expected for PLD deposition, Li-based compounds provide Lideficient layers due to the scattering of light species with the background gas.24To partially compensate for this deficiency, a multilayer combinatorial approach optimizing an intercalated deposition of LMO and Li2O was previously optimized to deposit near stoichiometric layers.22 Figure 1 shows the X-ray diffraction spectra of the as-deposited LMO films. An XRD spectrum on the clean substrate is included as a reference. The

samples were formed by stick-shaped grains randomly oriented, with larger dimension for the thicker LMO1000 film. The elongation of the grains seems to be related to faceted crystals being indicative of a preferential growth direction. Similar thicknesses measured by ellipsometry (Figure S3 of the Supporting Information, SI), in the range of 400 and 1000 nm, were observed for samples LMO400 and LMO1000, respectively. These electrodes were used to build a LMO/ Li2SO4:ZnSO4/Zn full battery using an aqueous electrolyte and a 1 μm-thick metallic foil of zinc. To simultaneously study the effect of the cycling in the cathode (LMO) and anode (Zinc) electrodes, the battery was initially tested in a three electrode configuration using a coaxial cell geometry26 with Ag/AgCl (3 M KCl) as reference electrode. The cyclic voltammetry measurements of the full cell using LMO400 or LMO1000 under low-medium scan rate, i.e., from 1 to 10 mV s−1, showed the two characteristic peaks associated with the (de-)intercalation of Li+ in the spinel structure (Figure 3a,c). In all of the cases, the peaks were shifted 1 V with respect to the potential referenced to the Ag/ AgCl (3 M KCl) electrode due to the contribution of the zinc anode (Figure S1 of the SI). The increment of the scan rate causes a higher polarization in the LMO1000 electrode shifting the second oxidation peak to values out of the potential window under study (Figure 3d). On the contrary, the classic two peaks profile was maintained for the LMO400 thin film under all of the scan rates used (Figure 3b) probably due to the shorter path for Li+ diffusion. It is worth mentioning that samples with the same or even lower thickness cycled in organic electrolytes (to the best of our knowledge, there are no equivalent experiments in aqueous electrolytes) suffer from this polarization already at lowmedium scan rates (10 mV s−1).27,28 This is a clear indicator of the excellent kinetics of the here presented LMO electrodes.

Figure 1. X-ray diffraction spectra of LMO400 and LMO1000 electrodes deposited on Si/TiN/Pt substrates. Reflection peaks corresponding to LiMn2O4 (JCPDS 35-0782) and Mn3O4 (JCPDS 01-080-0382) are labeled. For a better comparison, the intensity of the diffraction spectra was normalized to the intensity of the peak at 2θ = 46.4°, corresponding to the substrate, which can be approximately considered equal for all the samples. 32714


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Figure 3. Cyclic voltammetry measurements of full cells LMO/ Li2SO4:ZnSO4/Zn based on LMO400 a) and b), and LMO1000 c) and d) under different scan rates using a three electrode configuration cell. Figure 4. Charge/discharge profiles of LMO400 (a) and LMO1000 (c) and their respective zinc counter electrode (b) and (d) under different current densities in a three electrode configuration cell using Ag/AgCl (3 M KCl) as reference electrode and 1 M Li2SO4:0.2 M ZnSO4 as electrolyte.

The thicker sample provided currents around three times higher than those of the thinner electrode, in agreement with their thickness ratios. When these values are normalized by the thickness, the currents supplied for both cells were equivalent (Figure S4). The electrochemical behavior of both batteries were tested under different current densities, from 60 μA cm−2 to 2400 μA cm−2. These current densities are equivalent to the C-rates indicated in Figure 4 (a rate of nC represents a full charge or discharge in 1/n hours). For the calculation of the C-rates represented in the figure, thicknesses and porosities obtained by ellipsometry where used (Figures S1 and S2). Unlike Figure 3 where the profiles show the ΔE = ELMO − EZn, in Figure 4 the cathode and anode potentials are separated and referenced to the Ag/AgCl (3 M KCl) electrode. The classic two plateaus associated with the (de-)intercalation of Li+ in the spinel structure were observed

under all the current densities employed, even at high values of 104C when the battery is charged/discharged in less than 34 s, confirming the excellent kinetics observed by CV measurements (Figure 4). Remarkably, the fastest LMO thin film battery reported in the literature,29−33 shows a slope instead of the two plateau profile and capacities considerably lower than the ones reported here. Another evidence of the excellent kinetics of the LMO is the minimum polarization of the peaks under all the current rates explored, values lower than 50 mV are observed in all cases (Table S1). This kind of evaluation is not employed in the high 32715


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LMO400−Zn full battery at 104 C. It is important to highlight that the smaller thickness of the here presented layers provide at least 3 times more capacity per area, which is a clear evidence of the suitability of the LMO-Zn microbattery for high power microapplications. Finally, it is important to stress the fact that all these previously mentioned high power systems are half-cell batteries so a suitable anode electrode, i.e., carbon graphite, must still be incorporated for real applications. The stability of both Li−Zn cells, based on LMO400 and LMO1000, was additionally evaluated under a current density of 150 μAcm−2, equivalent to 6.6C and 2.6C, respectively (Figure S6). The cell operation was stopped after 150 cycles and disassembled for the evaluation of the LMO electrodes by SEM (Figure S7). The batteries were then reassembled using the same electrodes, and the SEM evaluation process was repeated after another 150 cycles (Figure S8). According to the SEM study, the morphology of the LMO400 film was not affected by the cycling, however in the case of LMO1000 sample, small cracks appeared after 150 cycles. These can be associated with the higher strain that thick samples suffer due to lithium (de)intercalation.36 Contrary to some examples in the literature where cracking induced a critical failure of the battery after tens of cycles,37,38 the capacity provided by the cell based on LMO1000 remained constant after the conditioning period. This limited effect of crack formation on the performance of the cells can be derived from the nanograined structure of the films that likely stops their propagation (Figure S8c). Although a three electrode cell is ideal for the accurate study of the cycling effects in both LMO and Zinc electrodes simultaneously, the design is not appropriate for commercial purposes. In order to prove the suitability of the proposed concept in a closer-to-market configuration, two batteries with a sandwich configuration based on LMO electrodes and 1-μm thick zinc foil were assembled using a 25-μm thick Celgard separator and aqueous electrolyte. They were submitted to cycles at 150 μA cm−2, providing charge/discharge profiles and specific charges equivalent to their three electrode counterparts (Figure 6) delivering close to 10 μAh cm−2 (LMO400 based cell) and 40 μAh cm−2 (LMO1000 based cell). After 300 cycles, they retained 83.1% and 74% of the initial capacity, respectively, which corresponded to retentions of capacities per cycle of 99.94% and 99.91%. Similar retention of capacities have been observed for the most stable thin films with similar thicknesses, as the LMO prepared by Rho et al. (1 μm in thickness, 200 cycles, 50 μA cm−2)28 and Ag-doped LMO reported by Wu et al. (260 nm in thickness, 50 cycles, 100 μA cm−2).36 It is important to remark that the current density used here is higher than the aforementioned studies. The Ragone plot of the samples is presented in Figure S9. The specific power and specific energy of the batteries under study are confronted with typical values corresponding to different energy storage technologies, namely, capacitor and electrochemical capacitors, state of the art Li-ion batteries, and Li primary batteries. The cells under study deliver specific energies characteristic of Li-ion batteries, due to the faradaic reaction associated with the (de-)intercalation of lithium in the spinel structure, while providing specific powers similar to the ones of electrochemical supercapacitors. Filled circles in the Ragone plot correspond to the LMO electrode alone, showing the reduction of the specific power of the battery (○) and energy due to the presence of the nonoptimized Zn electrode. In this regard, porous zinc could be implemented to reduce the mass of the device since its electrochemical oxidation/reduction

power LMO based batteries reported in literature,29−33 which hinders a proper comparison. However, without exception, a slope was presented in the charge/discharge profiles for C-rates higher than 10C. This suggests that a better reversibility under fast cycling is expected in our samples. During cycling, the maximum polarization reached a value of 121 mV for the zinc coupled with the LMO1000 at 41C (Figure 4b,d, Table S2). The plateau associated with the zinc oxidation remained practically constant for all scan rates, while just the reduction of Zn2+ presented a polarization. Further improvement of the zinc electrode can be achieved by the utilization of nanostructured zinc34 or additives35 but this optimization is out of the main scope of this article. Both cells showed an excellent retention of capacity (Figure 5). After increasing the scan rate 40 times, the capacity only

Figure 5. Evolution of capacity with the current density of full cells based on LMO400 (a) or LMO1000 (b) vs zinc under different current densities in a three electrode configuration cell using Ag/AgCl (3 M KCl) as reference electrodes and 1 M Li2SO4:0.2 M ZnSO4 as electrolyte.

decreased 30.9% and 27.9% for the cells based on LMO1000 and LMO400, respectively, the batteries were cycled under these conditions in less than 1.5 min and 34 s. The specific charges provided for the cell based on LMO1000 vary from 81.5% (1C) to 56.3% (41C) of the theoretical value (65 μAh cm−2μ−1). These values are on the order of the ones presented by the best performing conventionally sized batteries. Lee et al.31 presented high power LMO nanowires which showed 81% at 1C and 40.5% at 30C. Another example is the nano LMO reported by Tang et al.,32 which presented 67% at 1C and 48.6% at 50 C. Similar performances are also shown by the hollow nanocones prepared by Jiang et al. (77% at 1C and 60.8 at 50C).33 The cell based on LMO400, which was cycled under higher current rates, provided capacities from 47.1% to 34% of the theoretical values. The mesoporous LixMn2O 4 thin film pseudocapacitors developed by Lesel et al.29 (100 nm of thickness, four times thinner) reached 27% of the theoretical capacity at 100C, close to 1.25 times smaller than the capacity provided by our 32716


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drawbacks associated with organic solvents and lithium metal use and with a faster and simpler manufacturing.

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CONCLUSIONS A novel dual-ion microbattery based on LiMn2O4 and zinc electrodes is reported here for the first time. Microbatteries using LMO electrodes with thicknesses of 400 and 1000 nm were evaluated showing excellent rate capabilities while maintaining the classic E vs Q profile associated with the (de)intercalation of lithium in the LMO structure even after increasing the C rate 40 times. The cells showed specific energies of 16 and 81 Wh kg−1, respectively, comparable to typical Li-ion batteries and, more importantly, specific power densities of 3420 and 2640 W kg−1, respectively, comparable to typical electrochemical supercapacitors. LMO400 batteries were discharged in a minimum of 12 s while thicker LMO1000 electrodes discharged in 90 s increasing the specific energy 4.5 times. All in all, the current battery provided similar capacities at medium-to-fast scan rate as the most advanced “3D solid state half-battery”. Moreover, the batteries showed an excellent stability with retentions of capacities per cycle of 99.94% (cell based on LMO400) and 99.91% (LMO1000). This excellent electrochemical behavior, together with the intrinsically safe nature of the technology (aqueous electrolyte) and easy manufacture of the battery (using scalable techniques and commercial components), make this novel dual-ion microbattery an excellent candidate for substituting primary batteries in highly demanding applications where dimensions and rechargeability represent a high-added value, e.g., IoT for environmental monitoring, e-health, or smart metering of energy services.

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EXPERIMENTAL SECTION

LMO thin films were deposited using a Large Area PLD5000 by PVD Products, Inc. equipped with a KrF excimer laser with 248 nm wavelength by combinatorial deposition using LiMn2O4 and Li2O targets purchased from Neyco, France. Films were deposited onto Si/ TiN(10 nm)/Pt (80 nm) substrates provided by Imec. The substrates were cleaned prior to deposition subsequently with acetone, mili-Q water, and isopropanol. The laser fluency was fixed at 650 mJ cm−2 and an oxygen background pressure of 20 mTorr was applied. The deposition temperature, target-substrate distance, and frequency were 650 °C, 90 mm, and 10 Hz, respectively. LiMn2O4 and Li2O materials were deposited alternatively in a pulse ratio of 2:1 until the desired thicknesses were reached. The addition of lithium from the Li2O target permitted compensation for the losses of lithium from the LiMn2O4 target. XRD was carried out using Bruker-D8 Advance equipment using Cu Kα radiation with an Ni filter and Lynx Eye detector. The measurements were performed at room temperature in the range from 16° to 55° using an offset to avoid strong Si contribution from the substrate. The SEM equipment used is a Zeiss Auriga equipped with Inlens and back scattered electron detector. The spectroscopic ellipsometry measurements were recorded by a phase modulation system (UVISEL equipped with a Horiba spectrometer) at wavelengths ranging from 260 to 2100 nm (−4.77 to 0.59 eV). The ellipsometer beam angle of the incidence was fixed at 70.0°, and the spot size was fixed at 2 mm2. For the calculation of porosity, water was used as adsorbate. The thin films were measured at 0% relative humidity (RH), N2 gas flowing overnight, and at 100% RH, 100% RH water vapor in N2 as carried was flowed overnight. The RH was controlled by a Controller Evaporator Mixer Bronkhorst HI-TEC. Two different geometrics were used for the electrochemical evaluation: a three electrode cell with coaxial configuration14 to evaluate simultaneously working and counter electrodes with LMO, zinc foil (GoodFellow), and Ag/AgCl (3 M KCl) as working, counter, and reference electrodes, respectively, and 1 M Li2SO4:0.2 M ZnSO4 as

Figure 6. Evolution of capacity and efficiency with the number of cycles of two dual-metal-ion microbatteries based on LMO400 (a) and LMO1000 (c) and their selected charge/discharge profiles b) and d), respectively, in a sandwich configuration with LMO as working electrode, zinc foil as counter/reference electrode, and 1 M Li2SO4:0.2 M ZnSO4 soaked in a 25 μm thickness Celgard separator as electrolyte.

is a surface reaction where the bulk of the electrode does not contribute to the process. The high versatility of the Li−Zn microbattery, being cycled from less than 12 s to more than 1 h, makes it adequate for a variety of applications. Moreover, the combination of the excellent kinetics of the developed LMO, using an aqueous electrolyte, with higher conductivities than solid and organic electrolytes, and a 1 μm-thick zinc electrode, makes this dualion microbattery an ideal candidate for microenergy applications where high power and miniaturization are critical issues. In fact, the battery based on the LMO1000 film provided similar capacities at medium-to-fast scan rate as the most advanced “3D solid state half-battery” (from 42 μAh cm−2 to 60 μAh cm−2 at 2C),39 where lithium is used as counter electrode and Li(TFSI) in EC: DEC as electrolyte. This without the 32717


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ACS Applied Materials & Interfaces electrolyte. A sandwich configuration with LMO as working electrode, zinc foil as counter/reference electrode, and 1 M Li2SO4:0.2 M ZnSO4 soaked in a 25 μm thickness Celgard 3041 separator as electrolyte. The chips of LMO used as electrode have a total area of 1 cm2, including the Pt edge used for the contact. The active area changes slightly with the ring used for the assembly from 0.6 cm2 to 0.8 cm2. This area was calculated prior to every electrochemical measurement. All of the electrochemical measurements were performed using a Biologic VMP3 instrument at ambient temperature and in a range of potentials of 0.45−1.05 V vs Ag/AgCl (3 M KCl). Cyclic voltammetry was carried out at scan rates of 1, 5, 10, 25, 50, and 100 mV s−1 for the galvanostatic cycling current densities of 60, 150, 750, 1500, and 2400 μAcm−2.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b08883. Details of the ellipsometry and electrochemical measurements, ragone plots, and SEM images (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (R.T.). *E-mail: [email protected] (A.T.). ORCID

Rafael Trócoli: 0000-0001-8071-6882 Alfonso Sepúlveda: 0000-0003-4726-177X Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are thankful for the financial support of the European Commission who supported this work by FP7-NMP-2013SMALL-7, SiNERGY (Silicon Friendly Materials and Device Solutions for Microenergy Applications), Contract 604169, and CERCA Programme/Generalitat de Catalunya. A.S. would like to acknowledge the EU Horizon 2020 research and innovation programme under the MSCA grant agreement No. 658057.

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REFERENCES

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High Specific Power Dual-Metal-Ion Rechargeable Microbatteries

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