The authors acknowledge funding support for the development of all-solid-state batteries and in situ FIB and TEM holder development by U.S. Department of Energy, Office of Basic Energy Sciences, under award number DE-SC0002357. The collaboration with national laboratories is made possible with partial support of the Northeastern Centre for Chemical Energy Storage, an Energy Frontier Research Centre funded by the U.S. Department of Energy, Office of Basic Energy Sciences under the award number DE-SC0001294. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. This work was performed in part at the San Diego Nanotechnology Infrastructure (SDNI), a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (Grant ECCS-1542148). FIB work was performed in part at the UC Irvine Materials Research Institute (IMRI), using instrumentation funded in part by the National Science Foundation Center for Chemistry at the Space-Time Limit (CHE-082913). We thank Nancy Dudney, Oak Ridge National Laboratory for providing us the thin-film batteries. J.L. acknowledges support from the Eugene Cota-Robles Fellowship Program and D.S is thankful to SERB, India for Ramanujan Fellowship (SB/S2/RJN-100/2014).

1. Preparation of Sample and System
<ol>
	<li>Attain a complete thin film battery consisting of an Al2O3 substrate (500 &#181;m thick), a gold cathode current collector (100 - 150 nm thick, DC sputtered), a LiCoO2 cathode (2 &#181;m thick, RF sputtered), a LiPON electrolyte (1 &#181;m thick, RF sputtered), an amorphous silicon anode (80 nm thick, RF&#160;sputtered), and a Cu anode current collector (100 nm, DC sputtered)16,17.</li>
	<li>Mount a complete thin film battery on a 25-mm diameter aluminum SEM stub, and use a copper tape to electrically connect the cathode current collector to the SEM stub to minimize charging effects.</li>
	<li>Prior to pumping down the chamber, confirm a low-noise electrical pathway exists to the copper grid, which the nanobattery will be mounted on and will serve as the conductive pathway to the cathode (Figure 1).
	<ol>
		<li>Connect the cathode lead to the stage through a shielded electrical feedthrough, as is present in systems equipped for electron beam induced current (EBIC) measurements with the appropriate connection type. Internally, connect the feedthrough to the stage with a shielded wire with an exposed tip; the method of securing the exposed wire tip will depend on the sample stage type, and, here, it is held in place by an unused stage set screw.</li>
		<li>Alternatively, and depending on the configuration of the grounding circuit of the instrument&#39;s stage, connect the cathode lead of the potentiostat to the stage ground using a BNC cable as shown in Figure 1.</li>
		<li>Perform the low-current noise test using the potentiostat in constant current mode. Apply the current with which in situ cycling is to be performed, and observe the accuracy and precision of the measured current. 
		NOTE: Using the configuration described in 1.3.1, a measured current of 1 pA &#177; 0.1 pA was achieved.</li>
	</ol>
	</li>
	<li>Similarly, create a conductive pathway from the micromanipulator tip to the outside of the probe by connecting the anode lead of the potentiostat to the micromanipulator ground using a BNC cable or an alligator clip as shown in Figure 1.
	<ol>
		<li>As in step 1.3.3, perform the low-current noise test using the potentiostat in constant current mode. 
		NOTE: Using the connections described in step 1.4, the minimum stable current achieved was 10 pA &#177; 1 pA, due to unshielded grounds connected to the micromanipulator.</li>
	</ol>
	</li>
</ol>
2. Lift-out of the Nanobattery
<ol>
	<li>Load the sample into the SEM/FIB chamber and pump down to system specified high vacuum (&#8804;10-5 mbar) before turning on the electron beam and ion beam imaging.</li>
	<li>Focus the electron beam on the thin film battery surface and determine the eucentric height using standard SEM/FIB procedures1.</li>
	<li>Tilt the sample such that the ion beam is normal to the battery surface (here 52&#176; sample tilt), and deposit a 1.5 to 2 &#181;m thick layer of FIB-deposited organometallic platinum on the top current collector of the thin-film battery using an ion beam current of around 0.3 nA and dwell time of 200 ns over an area of 25 x 2 &#181;m (Figure 2).</li>
	<li>Set ion beam voltage to 30 kV and ion beam dwell time to 100 ns for the remainder of the experimental protocol.</li>
	<li>Use a step-pattern cross-sectional FIB milling option, as provided in the FIB software, to expose the nanobattery stack around the Pt-deposit, as in TEM lamella preparation1. Select a milling current &#8804;2.8 nA. Input a mill depth extending at least 1 &#181;m beneath the active thin film battery (Z = 5 &#181;m in this case), a cross-sectional width (X) of 25 &#181;m and a cross sectional height (Y) of 1.5 x Z (here, Y = 7.5 &#181;m). Afterwards, the battery cross-section is exposed, to be viewed in SEM (here, the electron beam is 52&#176; from surface normal) as in Figure 3. 
	NOTE: The actual milled depth is thin film battery dependent.</li>
	<li>Use a cross-section cleaning procedure, provided in the FIB software, where the ion beam incrementally rasters closer to the surface being cleaned, with an ion beam current &#8804;0.3 nA to clean off re-deposited material and clearly expose the layered structure (Figure 3).</li>
	<li>Perform a series of rectangle under-cuts (also called J-cuts or U-cuts) at a stage tilt of 0&#176; and beam current &#8804;2.8 nA to isolate the majority of the nanobattery2. Make under-cuts consisting of i) a lower rectangle 0.5 x 25 &#181;m below the Au current collector onto the Al2O3 substrate, ii) a vertical rectangle 0.5 &#181;m wide (X) and through the entirety of the nanobattery thickness (Y), and iii) a vertical rectangle 0.5 &#181;m wide (X) and with a height less than the nanobattery thickness (Y - 2.5 &#181;m) around the Pt-coated nanobattery as in Figure 4a. These three under-cuts should be performed in parallel mode (simultaneously milled), to prevent re-deposition of material within the under-cut regions.</li>
	<li>Rotate the sample 180&#176; and perform the same horizontal undercut as in step 2.5. This isolates the bottom and sides of the nanobattery except for the remaining connected region.</li>
	<li>Rotate the sample 180&#176;. Insert the micromanipulator to the park position specified in the control software, then slowly bring it in contact with the nanobattery using the x-y-z movement of the software.</li>
	<li>Fix the micromanipulator to the Pt region on top of the nanobattery by ion-beam depositing 0.5 &#181;m thick Pt using a 30 keV ion beam with a current of 10 pA over an area of 2 x 1 &#181;m.</li>
	<li>Ion mill the remaining connected portion of the nanobattery with a beam current around 1 nA, and raise the nanobattery vertically with the micromanipulator (Figure 4b).</li>
	<li>Mount the nanobattery on a Cu FIB lift-out grid with 2 &#181;m thick ion-beam deposited Pt using a 30 keV ion beam with a current of 0.28 nA over an area of 10 x 5 &#181;m.</li>
	<li>Ion mill away the connection between the micromanipulator and nanobattery using a 30 keV ion beam with a current of 0.28 nA over an area of 1 x 1 &#181;m to a depth of 2 &#181;m, leaving a freestanding section attached to the Cu grid (Figure 5)1. 
	NOTE: The Cu lift-out grid provides a flat base for mounting the nanobattery as well as serving as a conductive pathway between the stage and the nanobattery.</li>
</ol>
3. Cleaning and Cycling the Nanobattery
<ol>
	<li>Tilt the sample such that the ion beam is normal to the battery surface and use a cross-sectional cleaning procedure (see step 2.4) to remove re-deposited material over a 5 &#181;m wide section of the nanobattery near the Cu grid, leading to a clear view of individual layers of the nanobattery (Figure 6a). 
	NOTE: Re-deposited material from previous milling steps must be removed from the grid-mounted nanobattery to expose the electrochemically active core of the nanobattery and prevent shorting.</li>
	<li>Deposit 500 nm thick FIB-Pt using a 30 keV beam with a current of 0.1 nA over an area of 1 x 2 &#181;m to create an electrical contact between the cathode current collector and the metallic grid, which is electrically connected to the stage (Figure 6b).</li>
	<li>Tilt the sample to 0&#176; and, using an ion beam current of 1 nA, make a rectangular cut 3 &#181;m wide and deep enough (Z ~ 2 &#181;m) to completely remove the anode current collector and electrolyte, isolating the anode from the Cu grid (Figure 6c).</li>
	<li>Use the cross-section cleaning procedure (see step 2.4) with an ion beam current around 0.1 nA to remove the re-deposited material around all sides of the nanobattery cross-section until all the individual layers are distinctly visible as shown in Figure 6d.</li>
	<li>Insert the micromanipulator to the park position and, using the control software, bring the micromanipulator in contact with the Pt above the anode current collector. Ion beam deposit 0.2 &#181;m thick Pt using a 30 keV ion beam with a current of 10 pA over an area of 2 x 1 &#181;m to &#34;weld&#34; connect the micromanipulator and current collector ( Figure 6d)1.</li>
	<li>Run the potentiostat in galvanostatic cycling mode. Current parameters used depend on the ultimate cross-sectional area of the fabricated nanobattery and desired C-rate, but will generally be on the order of a few nA. We select charge and discharge currents such that the current density is on the order of tens of &#181;A/cm2. For LiCoO2-based thin film batteries, the voltage range is 2.0 and 4.2 V.</li>
</ol>

<ol>
	<li>Giannuzi, L. A., Stevie, F. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Introduction to focused ion beams: Instrumentation, theory, techniques and practice. , (2005).</li><li>Mayer, J., Giannuzi, L. A., Kamino, T., Michael, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=TEM+sample+preparation+and+FIB-induced+damage.">TEM sample preparation and FIB-induced damage.</a> MRS Bulletin. 32 (5), 400-407 (2007).</li><li>Pellerin, J. G., Griffis, D. P., Russeli, P. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Focused+ion+beam+machining+of+Si,+GaAs+and+InP.">Focused ion beam machining of Si, GaAs and InP.</a> J. Vac. Sci. Technol. B. 8, 1945-1950 (1990).</li><li>Rubanov, S., Munroe, P. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Investigation+of+the+structure+of+damage+layers+in+TEM+samples+prepared+using+a+focused+ion+beam.">Investigation of the structure of damage layers in TEM samples prepared using a focused ion beam.</a> J. Mater. Sci. Lett. 20 (13), 1181-1183 (2001).</li><li>Lugstein, A., Basnar, B., Bertagnolli, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Study+of+focused+ion+beam+response+of+GaAs+in+the+nanoscale+regime.">Study of focused ion beam response of GaAs in the nanoscale regime.</a> J. Vac. Sci. Technol. B. 20, 2238-2242 (2002).</li><li>Kato, N. I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reducing+focused+ion+beam+damage+to+transmission+electron+microscopy+samples.">Reducing focused ion beam damage to transmission electron microscopy samples.</a> J. Elect. Micro. 53 (5), 451-458 (2004).</li><li>Bals, S., Tirry, W., Geurts, R., Yang, Z., Schryvers, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+quality+sample+preparation+by+low+kV+FIB+thinning+for+analytical+TEM+measurements.">High quality sample preparation by low kV FIB thinning for analytical TEM measurements.</a> Microsc. Microanal. 13 (2), 80-86 (2007).</li><li>Miyajima, N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combining+FIB+milling+and+conventional+argon+ion+milling+techniques+to+prepare+high-quality+site-specific+TEM+samples+for+quantitative+EELS+analysis+of+oxygen+in+molten+iron.">Combining FIB milling and conventional argon ion milling techniques to prepare high-quality site-specific TEM samples for quantitative EELS analysis of oxygen in molten iron.</a> J. Elect. Microsc. 238 (3), 200-209 (2010).</li><li>Scahaffer, M., Schaffer, B., Ramasse, Q. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sample+preparation+for+atomic-resolution+STEM+at+low+voltages+by+FIB.">Sample preparation for atomic-resolution STEM at low voltages by FIB.</a> Ultramicroscopy. 114, 62-71 (2012).</li><li>Wang, Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effects+of+cathode+electrolyte+interfacial+(CEI)+layer+on+long+term+cycling+of+all-solid-state+thin-film+batteries.">Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries.</a> J. Power Sources. 324, 349-357 (2016).</li><li>Bates, J. B., Dudney, N. J., Gruzalski, G. R., Zuhr, R. A., Choudhury, A., Luck, C. F., Robertson, J. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fabrication+and+characterization+of+amorphous+lithium+electrolyte+thin+films+and+rechargeable+thin-film+batteries.">Fabrication and characterization of amorphous lithium electrolyte thin films and rechargeable thin-film batteries.</a> J. Power Sources. 43, 103-110 (1993).</li><li>Brazier, A., Dupont, L., Dantras-Laffont, L., Kuwata, N., Kawamua, J., Tarascon, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=First+cross-section+observation+of+an+all-solid-state+lithium+ion+"nanobattery"+by+transmission+electron+microscopy.">First cross-section observation of an all-solid-state lithium ion "nanobattery" by transmission electron microscopy.</a> Chem. Mater. 20 (6), 2352-2359 (2008).</li><li>Yamamoto, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dynamic+visualization+of+the+electric+potential+in+an+all-solid-state+rechargeable+lithium+battery.">Dynamic visualization of the electric potential in an all-solid-state rechargeable lithium battery.</a> Angew. Chem. Int. Ed. 49 (26), 4414-4417 (2010).</li><li>Santhanagopalan, D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Interface+limited+lithium+transport+in+solid-state+batteries.">Interface limited lithium transport in solid-state batteries.</a> J. Phys. Chem. 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B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lithium+silicon+tin+oxynitride+(LiySiTON):+high-performance+anode+in+thin-film+lithium+ion+batteries+for+microelectronics.">Lithium silicon tin oxynitride (LiySiTON): high-performance anode in thin-film lithium ion batteries for microelectronics.</a> J. Power Source. 81, 27-32 (1999).</li><li>Ziegler, J. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=SRIM-2003.">SRIM-2003.</a> Nucl. Instrum. Methods Phys. Res. B. 219, 1027-1036 (2004).</li><li>Bals, S., Tirry, W., Geurts, R., Yang, Z., Schryvers, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+quality+sample+preparation+by+low+kV+FIB+thinning+for+analytical+TEM+measurements.">High quality sample preparation by low kV FIB thinning for analytical TEM measurements.</a> Microsc. Microanal. 13 (2), 80-86 (2007).</li></ol>

We have nothing to disclose.

As demonstrated by our results, the technique described produces electrochemically active nanobatteries lifted out from a larger thin-film battery. Such techniques have enabled both ex situ and in situ STEM/EELS characterization of the buried interfaces by galvanostatically biasing the nanobattery. This allows unprecedented high-resolution characterization of quantitative chemical phenomena linked to the electrochemical state of charge. However, to achieve these results, a number of specific obstacles must be overcome.
Before beginning FIB processing, constant current testing should be conducted to ensure that there is a low-noise electrical pathway to the cathode and anode of the nanobattery. Cathode-side testing may be performed with the FIB chamber vented. Before pumping down the chamber for nanobattery fabrication, the positive terminal should be connected as if performing the experiment (either through a vacuum feedthrough or stage ground), and the negative terminal connected directly to the stage. Note that if using the touch alarm as a stage connection, the touch alarm capability of the instrument may be disabled, and the connection should only be made when no further tilting of the stage is necessary. However, here the test will require the system to be under vacuum, and the current will pass through both the micromanipulator and the stage circuit. The micromanipulator can be electrically adhered with Pt to the copper grid for constant current noise tests. If current resolution issues persist, contact your vendor for information on how to decouple the stage from the system ground.
For this technique to work, it is critical to use the provided ion beam specifications to minimize damage to the solid-electrolyte LiPON. LiPON is highly sensitive to prolonged exposure to (i) humid atmospheric conditions, (ii) electron beam, and (iii) ion beams. Hence the solid-state nanobattery fabrication process requires minimization of exposure to all three of these conditions. Pre- and post-fabrication exposure to atmospheric conditions should be absolutely minimized. The in situ FIB cycling process described was developed as a solution to minimize this exposure. During and after fabrication, electron beam imaging should be limited, as it damages the solid-electrolyte. Similarly, ion beam imaging should also be limited to avoid degradation of the electrolyte and other active components as well. The specific milling files and times are based on the equipment outlined in the table of materials/equipment for specific reagents, equipment, and manufacturers; this may vary between FIB instruments, and modifications may be required when using another instrument.
Of all parameters in the FIB fabrication of a nanobattery, the most critical considerations are the use of low beam current and dwell time to minimize damage14. Whenever required, imaging is performed with electrons at low pixel dwell times and with the ion beams at lower beam current (usually in pA) and low dwell time (100 ns). Most of the time, high dwell time electron beam imaging produces visible changes on the LiPON electrolyte. Figure 7a shows an undamaged LiPON and further imaging with an electron beam induces damage to the LiPON layer as shown in Figure 7b. This damage is irreversible resulting in a contrast change and will render the nanobattery electrochemically inactive.
Further, for electrochemical cycling, proper care must be taken to make electrical contact between the cathode current collector and the grid properly (Figure 6b). It is similarly important to maintain the micromanipulator contact to the anode (Figure 6); as seen in Figure 8a, at around 150 s, a spike in the electrochemical data corresponds to a vibration induced contact issue with the anode. Given the potential for instability of the micromanipulator-anode contact, the in situ testing time is minimized by limiting the nanobattery capacity, in turn reducing the charging time.
If the voltage profile is not consistent with the thin film battery, the cleaning procedure is repeated as there is likely some re-deposition causing shorting issues (Figure 10). The anode isolation step in particular is a large source of re-deposited material. This cleaning procedure decreases the nanobattery cross-section, so the current density should be corrected accordingly. It is noted that ion beam damage cannot be completely avoided and it is limited to between a few nm to a maximum of 25 nm into the surface, as calculated from ion scattering simulations SRIM program for 30 keV Ga+ into the electrode materials18. Low energy processing can reduce the damage to a large extent19. The FIB process demonstrated here is unique, and fabrication, manipulation, and in situ testing of nanodevices is enabled by FIB-SEM dual beam systems. It is possible to extend the process to any other battery chemistries and other nanoscale devices.
It is important to note that the specific parameters provided in this protocol may not directly transfer well to alternate electrochemical systems. LiPON was determined to be sensitive to thermal effects from the ion beam under high scanning rates. However, other electrolytes may suffer from other sensitivities. Similarly, although the material system tested in this protocol showed good electrochemistry after Ga+ ion milling, other materials systems may be more susceptible to ion straggle and implantation. As such, more exploration of the parameter space may be required for alternate material systems. More sensitive materials such as sulfides may perform poorly after ion milling, though this area of research is largely unexplored with advanced characterization techniques. Realistically, these parameters will translate to most material systems of interest, as modern solid electrolytes are generally crystalline and more robust than LiPON. Despite these potential limitations, the technique will be applied to new material systems, offering the potential to discover alternate interfacial phenomena, ultimately uncovering impedance mechanisms. A natural follow-up to this technique is the observation of electrochemical cycling in the TEM. This has been performed on the system described in this protocol, and uncovered previously unseen behavior at these interfaces. This technique will enable the observation of alternate forms of impedance.

Focused ion beams (FIB) have been used chiefly for transmission electron microscopy (TEM) specimen preparation and circuit editing1,2. Nanofabrication using FIB has progressed significantly during the last two decades with much focus on semiconductor materials3. Despite its importance to scientific advances, major concerns with FIB techniques remain, including surface damage, re-deposition, and preferential sputtering due to high current density4,5. There have been several articles on FIB damaging bulk materials during the preparation of TEM specimens and several methods to reduce this damage have been proposed6,7,8,9. However, FIB fabrication of active devices that consist of multiple layers with different functionality is still limited.
For solid-state devices, especially in the field of energy storage, interfaces play a crucial role, and the solid-solid interface is most often seen as a dominant source of impedance10. These interfaces are particularly difficult to characterize, due to a combination of their buried nature and data convolution in the presence of multiple interfaces in a single device. The fabrication of fully solid-state nanobatteries is critical to probe and understand the dynamic nature of these interfaces, which ultimately impact the electrochemical processes in batteries. Thin film batteries based on lithium phosphorous oxynitride (LiPON) were demonstrated more than two decades ago and are currently commercialized11. Although FIB fabrication of electrochemically active nanobatteries from a thin film battery is critical for enabling in situ evaluation of interfaces, most attempts to fabricate nanobatteries using FIB fail to retain electrochemical activity due to short-circuiting12. Initial attempts at in situ cycling thinned only a small portion of the nanobattery, to observe the lithium distribution by electron holography13.
More recent work has demonstrated the successful FIB fabrication of electrochemically active nanobatteries, which enabled both ex situ and in situ scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) characterization of interfacial phenomenon14,15. Important FIB fabrication parameters that help to retain electrochemical activity have been indicated by Santhanagopalan et al.14, and a detailed protocol is presented in this manuscript. This procedure is based on a model LiCoO2/LiPON/a-Si battery, but will ultimately enable the exploration of further thin film battery chemistries.

<table style="border-collapse:collapse;width:548pt" width="731">
	<colgroup>
		<col style="width:206pt" width="275" />
		<col style="width:128pt" width="170" />
		<col style="width:89pt" width="119" />
		<col style="width:125pt" width="167" />
	</colgroup>
	<tbody>
		<tr height="29" style="height:21.75pt">
			<td class="xl63" height="29" style="width:206pt;height:21.75pt" width="275">Biologic SP-200 Potentiostat</td>
			<td class="xl63" style="width:128pt" width="170">Biologic Science Instruments</td>
			<td class="xl63" style="width:89pt" width="119">SP-200</td>
			<td class="xl66" style="width:125pt" width="167">Ultra Low Current&#160; Option needed for pA current resolution</td>
		</tr>
		<tr height="21" style="height:15.75pt">
			<td class="xl63" height="21" style="width:206pt;height:15.75pt" width="275">FEI Scios DualBeam FIB/SEM</td>
			<td class="xl63" style="width:128pt" width="170">FEI</td>
			<td class="xl63" style="width:89pt" width="119"></td>
			<td class="xl66">Current noise improves with a shielded stage feedthrough</td>
		</tr>
		<tr height="42" style="height:31.5pt">
			<td class="xl63" height="42" style="width:206pt;height:31.5pt" width="275">SEM Stub: Large &#216;25.4mm x 9.5mm pin height</td>
			<td class="xl63" style="width:128pt" width="170">Ted Pella</td>
			<td align="right" class="xl63" style="width:89pt" width="119">16144</td>
			<td class="xl66">Or equivalent</td>
		</tr>
		<tr height="42" style="height:31.5pt">
			<td class="xl63" height="42" style="width:206pt;height:31.5pt" width="275">PELCO Colloidal Silver Paste, Conductive</td>
			<td class="xl63" style="width:128pt" width="170">Ted Pella, Inc.</td>
			<td class="xl68">16032</td>
			<td class="xl66">Or equivalent</td>
		</tr>
		<tr height="21" style="height:15.75pt">
			<td class="xl63" height="21" style="width:206pt;height:15.75pt" width="275">PELCO&#174;&#160;FIB Lift-Out TEM Grids</td>
			<td class="xl63" style="width:128pt" width="170">Ted Pella</td>
			<td class="xl63" style="width:89pt" width="119">10GC04</td>
			<td class="xl66">Or equivalent</td>
		</tr>
	</tbody>
</table>

focused ion beam fabrication of lipon-based solid-state lithium-ion nanobatteries for in situ testing

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

A representative solid-state Li-ion nanobattery fabrication process is shown step-by-step in the protocol referencing Figures 1-7.
Figure 8 shows in situ testing of the electrochemical charging profiles of two cells that were fabricated. Both profiles clearly show a 3.6 V plateau corresponding to LiCoO2-Si full cell chemistry and oxidation of Co3+ &#8594; Co4+. Cell-1 (Figure 8a) was tested at a lower current density (50 &#181;A/cm2) limiting the charge capacity to 12.5 &#181;Ah/cm2. Cell-2 (Figure 8b) presents a charging profile at a higher current density, 1.25 mA/cm2, that was limited by the upper cut-off voltage of 4.2 V. The capacity recorded was about 105 &#181;Ah/cm2, close to the theoretical capacity of Cell-2 (110 - 120 &#181;Ah/cm2). The first discharge capacity of the nanobatteries has been poor while the subsequent cycle capacities (both charge and discharge) were limited due to the first cycle irreversibility. The discharge process of nanobatteries is still not optimized, however, a representative charge-discharge profile at a current density of 60 &#181;A/cm2 is presented in Figure 9. The charge capacity was limited to 30 min and the discharge was limited to 2 V, and it is evident that the reversibility is about 35%. Though the reversibility is a lot better than what is reported in the literature14, further optimization is necessary.
If the voltage profile is not consistent with the thin film battery chemistry, this is likely due to either beam damage or shorting from re-deposited material. Figure 10 shows a voltage profile consistent with shorting where the voltage is constant and proportional to the applied current. The ion-beam image confirms that there is re-deposited material along the edge. The micromanipulator must be removed and further cross-sectional cleaning steps are needed to remove this material. This cleaning procedure decreases the nanobattery cross-section, so the current density should be corrected accordingly.
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56259/56259fig1.jpg" /> 
Figure 1: Electrical connection schematic. A potentiostat is connected to the FIB nanobattery via external connections: 1) the negative terminal of the potentiostat to the disconnected ground of the micromanipulator needle; 2) the cathode side to either an electrically shielded vacuum feedthrough or a direct connection to the stage ground such as a touch alarm circuit (shown). Internal connections are made between the tip of the micromanipulator and the anode, and between the cathode and stage through a copper TEM lift-out grid. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig1large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56259/56259fig2.jpg" /> 
Figure 2: Pt deposition. SEM image of the Pt protective cap deposited on the thin film battery surface to avoid damage and making contact. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig2large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56259/56259fig3.jpg" /> 
Figure 3:&#160;Nanobattery cross-section. SEM images of the nanobattery lamella after cross-sectional cutting at (a) 52&#176; cross-section view and (b) and 0&#176; top view. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig3large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56259/56259fig4.jpg" /> 
Figure 4:&#160;Nanobattery liftout. Ion-beam images of (a) the lamella with under-cut and (b) lift-out of the isolated nanobattery by the micromanipulator. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig4large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56259/56259fig5.jpg" /> 
Figure 5:&#160;Nanobattery mounting. (a) Ion-beam and (b) SEM image of welding the lifted nanobattery to the copper TEM grid. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig5large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56259/56259fig6.jpg" /> 
Figure 6:&#160;Nanobattery cleaning. Ion-beam images of (a) cleaning one of the nanobattery cross-sections, (b) electrically connecting the grid and cathode current collector by Pt deposition, (c) cut to isolate anode from the TEM grid, and (d) cleaning the cross-section of the front, back, and sides to remove all re-deposited material. Final contact is made to the anode using the micromanipulator for biasing. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig6large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56259/56259fig7.jpg" /> 
Figure 7:&#160;Nanobattery damage. SEM images of a nanobattery cross-section with (a) undamaged LiPON layer and (b) imaging at higher magnification induced damage in the LiPON layer indicated by the circle. High dwell time electron beam imaging produces visible changes in the LiPON electrolyte. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig7large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 8" class="xfigimg" src="/files/ftp_upload/56259/56259fig8.jpg" /> 
Figure 8:&#160;Nanobattery charging data. FIB fabricated nanobattery electrochemical charging profile at different current densities with (a) the capacity limited to 12.5 &#181;Ah/cm2 and (b) the voltage limited to a 4.2 V cut-off. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig8large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 9" class="xfigimg" src="/files/ftp_upload/56259/56259fig9.jpg" /> 
Figure 9: Nanobattery cycling profile. FIB fabricated nanobattery electrochemical charging and discharging profiles at a current density of 60 &#181;A/cm2. <a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig9large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>
<img alt="Figure 10" class="xfigimg" src="/files/ftp_upload/56259/56259fig10.jpg" /> 
Figure 10: Shorted nanobattery. (a) Voltage profile of a nanobattery that had not been cleaned properly resulting in shorting from re-deposited material and (b) the cross sectional ion-beam image.&#160;<a href="https://cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56259/56259fig10large.jpg" target="_blank">Please click here to view a larger version of this figure.</a>

Watch this Scientific Journal Video about Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing at JoVE.com

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of ...

focused-ion-beam-fabrication-lipon-based-solid-state-lithium-ion

Research

JoVE Journal

Engineering

10.0K Views.  University of California San Diego. A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

Video: Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

Construction and Testing of Coin Cells of Lithium Ion Batteries

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime. Lithium ion batteries have also been considered to be used in electric and hybrid vehicles1 or even electrical grid stabilization systems2. All these applications simulate a dramatic increase in the research and development of battery materials3-7, including new materials3,8, doping9, nanostructuring10-13, coatings or surface modifications14-17 and novel binders18. Consequently, an increasing number of physicists, chemists and materials scientists have recently ventured into this area. Coin cells are widely used in research laboratories to test new battery materials; even for the research and development that target large-scale and high-power applications, small coin cells are often used to test the capacities and rate capabilities of new materials in the initial stage. 
 In 2010, we started a National Science Foundation (NSF) sponsored research project to investigate the surface adsorption and disordering in battery materials (grant no. DMR-1006515). In the initial stage of this project, we have struggled to learn the techniques of assembling and testing coin cells, which cannot be achieved without numerous help of other researchers in other universities (through frequent calls, email exchanges and two site visits). Thus, we feel that it is beneficial to document, by both text and video, a protocol of assembling and testing a coin cell, which will help other new researchers in this field. This effort represents the "Broader Impact" activities of our NSF project, and it will also help to educate and inspire students.
In this video article, we document a protocol to assemble a CR2032 coin cell with a LiCoO2 working electrode, a Li counter electrode, and (the mostly commonly used) polyvinylidene fluoride (PVDF) binder. To ensure new learners to readily repeat the protocol, we keep the protocol as specific and explicit as we can. However, it is important to note that in specific research and development work, many parameters adopted here can be varied. First, one can make coin cells of different sizes and test the working electrode against a counter electrode other than Li. Second, the amounts of C black and binder added into the working electrodes are often varied to suit the particular purpose of research; for example, large amounts of C black or even inert powder were added to the working electrode to test the "intrinsic" performance of cathode materials14. Third, better binders (other than PVDF) have also developed and used18. Finally, other types of electrolytes (instead of LiPF6) can also be used; in fact, certain high-voltage electrode materials will require the uses of special electrolytes7.

A protocol to construct and test coin cells of lithium ion batteries is described. The specific procedures of making a working electrode, preparing a counter electrode, assembling a cell inside a glovebox and testing the cell are presented.

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime.  Lithium ion ...

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (&lt;80 &deg;C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 &deg;C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 &deg;C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

Lithium ion batteries employ flammable and volatile organic electrolytes that are suitable for ambient temperature applications. A safer alternative to organic electrolytes are solid polymer batteries. Solid polymer batteries operate safely at high temperatures (&gt;120 &deg;C), thus making them applicable to high temperature applications such as deep oil drilling and hybrid electric vehicles. This paper will discuss (a) the polymer synthesis, (b) the polymer conduction mechanism, and (c) provide temperature cycling for both solid polymer and organic electrolytes.

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (&lt;80 ...

Fabrication of VB2/Air Cells for Electrochemical Testing

A technique to investigate the properties and performance of new multi-electron metal/air battery systems is proposed and presented. A method for synthesizing nanoscopic VB2 is presented as well as step-by-step procedure for applying a zirconium oxide coating to the VB2 particles for stabilization upon discharge. The process for disassembling existing zinc/air cells is shown, in addition construction of the new working electrode to replace the conventional zinc/air cell anode with a the nanoscopic VB2 anode. Finally, discharge of the completed VB2/air battery is reported. We show that using the zinc/air cell as a test bed is useful to provide a consistent configuration to study the performance of the high-energy high capacity nanoscopic VB2 anode.

Fabrication of VB2/Air Cells for Electrochemical Testing

A protocol is presented to study multi-electron metal/air battery systems by using previous technology developed for the zinc/air cell. Electrochemical testing is then performed on fabricated batteries to evaluate performance.

A technique to investigate the properties and performance of new multi-electron metal/air battery systems is proposed and presented. A method for ...

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric vehicles.1,2 However, many challenges, such as energy density and battery lifetimes, need to be overcome before this particular battery technology can be widely implemented in such applications.3 This research is challenging, and we outline a method to address these challenges using in situ NPD to probe the crystal structure of electrodes undergoing electrochemical cycling (charge/discharge) in a battery. NPD data help determine the underlying structural mechanism responsible for a range of electrode properties, and this information can direct the development of better electrodes and batteries.
We briefly review six types of battery designs custom-made for NPD experiments and detail the method to construct the &#8216;roll-over&#8217; cell that we have successfully used on the high-intensity NPD instrument, WOMBAT, at the Australian Nuclear Science and Technology Organisation (ANSTO). The design considerations and materials used for cell construction are discussed in conjunction with aspects of the actual in situ NPD experiment and initial directions are presented on how to analyze such complex in situ data.

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

We describe the design and construction of an electrochemical cell for the examination of electrode materials using in situ neutron powder diffraction (NPD). We briefly comment on alternate in situ NPD cell designs and discuss methods for the analysis of the corresponding in situ NPD data produced using this cell.

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric ...

Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can potentially contribute to the exposure of biota and humans. The diffusive gradients in thin films technique is introduced here for in-situ measurements of Pu bioavailability and speciation. A diffusion cell constructed for laboratory experiments with Pu and the newly developed protocol make it possible to simulate the environmental behavior of Pu in model solutions of various chemical compositions. Adjustment of the oxidation states to Pu(IV) and Pu(V) described in this protocol is essential in order to investigate the complex redox chemistry of plutonium in the environment. The calibration of this technique and the results obtained in the laboratory experiments enable to develop a specific DGT device for in-situ Pu measurements in freshwaters. Accelerator-based mass-spectrometry measurements of Pu accumulated by DGTs in a karst spring allowed determining the bioavailability of Pu in a mineral freshwater environment. Application of this protocol for Pu measurements using DGT devices has a large potential to improve our understanding of the speciation and the biological transfer of Pu in aquatic ecosystems.

The technique of diffusive gradients in thin films (DGT) is proposed for speciation studies of plutonium. This protocol describes diffusion experiments probing the behavior of Pu(IV) and Pu(V) in presence of organic matter. DGTs deployed in a karstic spring allow assessment of the bioavailability of Pu.

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can ...

Ohmic Contact Fabrication Using a Focused-ion Beam Technique and Electrical Characterization for Layer Semiconductor Nanostructures

Layer semiconductors with easily processed two-dimensional (2D) structures exhibit indirect-to-direct bandgap transitions and superior transistor performance, which suggest a new direction for the development of next-generation ultrathin and flexible photonic and electronic devices. Enhanced luminescence quantum efficiency has been widely observed in these atomically thin 2D crystals. However, dimension effects beyond quantum confinement thicknesses or even at the micrometer scale are not expected and have rarely been observed. In this study, molybdenum diselenide (MoSe2) layer crystals with a thickness range of 6-2,700 nm were fabricated as two- or four-terminal devices. Ohmic contact formation was successfully achieved by the focused-ion beam (FIB) deposition method using platinum (Pt) as a contact metal. Layer crystals with various thicknesses were prepared through simple mechanical exfoliation by using dicing tape. Current-voltage curve measurements were performed to determine the conductivity value of the layer nanocrystals. In addition, high-resolution transmission electron microscopy, selected-area electron diffractometry, and energy-dispersive X-ray spectroscopy were used to characterize the interface of the metal&#8211;semiconductor contact of the FIB-fabricated MoSe2 devices. After applying the approaches, the substantial thickness-dependent electrical conductivity in a wide thickness range for the MoSe2-layer semiconductor was observed. The conductivity increased by over two orders of magnitude from 4.6 to 1,500 &#937;&#8722;1 cm&#8722;1, with a decrease in the thickness from 2,700 to 6 nm. In addition, the temperature-dependent conductivity indicated that the thin MoSe2 multilayers exhibited considerably weak semiconducting behavior with activation energies of 3.5-8.5 meV, which are considerably smaller than those (36-38 meV) of the bulk. Probable surface-dominant transport properties and the presence of a high surface electron concentration in MoSe2 are proposed. Similar results can be obtained for other layer semiconductor materials such as MoS2 and WS2.

We describe the approaches for the device fabrication and electrical characterization of molybdenum diselenide (MoSe2) layer semiconductor nanostructures with different thicknesses. In addition, the fabrication of ohmic contacts for MoSe2-layer nanocrystals by the focused-ion beam deposition method using platinum (Pt) as a contact metal is described.

Layer semiconductors with easily processed two-dimensional (2D) structures exhibit indirect-to-direct bandgap transitions and superior transistor ...

Non-aqueous Electrode Processing and Construction of Lithium-ion Coin Cells

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational analysis. Testing of lithium-ion batteries in an academic setting has taken on several forms, but at the most basic level lies the coin cell construction. In traditional LIB electrode preparation, a multi-phase slurry composed of active material, binder, and conductive additive is cast out onto a substrate. An electrode disc can then be punched from the dried sheet and used in the construction of a coin cell for electrochemical evaluation. Utilization of the potential of the active material in a battery is critically dependent on the microstructure of the electrode, as an appropriate distribution of the primary components are crucial to ensuring optimal electrical conductivity, porosity, and tortuosity, such that electrochemical and transport interaction is optimized. Processing steps ranging from the combination of dry powder, wet mixing, and drying can all critically affect multi-phase interactions that influence the microstructure formation. Electrochemical probing necessitates the construction of electrodes and coin cells with the utmost care and precision. This paper aims at providing a step-by-step guide of non-aqueous electrode processing and coin cell construction for lithium-ion batteries within an academic setting and with emphasis on deciphering the influence of drying and calendaring.

Non-aqueous electrode processing is central to the construction of coin cells and the evaluation of new electrode chemistries for lithium-ion batteries. A step-by-step guide to the basic practices needed as an electrochemical engineer working with batteries in an academic experimental setting is furnished.

Research into new and improved materials to be utilized in lithium-ion batteries (LIB) necessitates an experimental counterpart to any computational ...

Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and subsequent safety issues becomes increasingly important. In a Li-ion cell setup, the voltage measurement across the positive and negative terminals inherently includes the effect of the cathode and anode which are coupled and sum to the total cell performance. Accordingly, the ability to monitor the degradation aspects associated with a specific electrode is extremely difficult because the electrodes are fundamentally coupled. A three-electrode setup can overcome this problem. By introducing a third (reference) electrode, the influence of each electrode can be decoupled, and the electrochemical properties can be measured independently. The reference electrode (RE) must have a stable potential that can then be calibrated against a known reference, for example, lithium metal. The three-electrode cell can be used to run electrochemical tests such as cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Three-electrode cell EIS measurements can elucidate the contribution of individual electrode impedance to the full cell. In addition, monitoring the anode potential allows the detection of electrodeposition due to lithium plating, which can cause safety concerns. This is especially important for the fast charging of Li-ion batteries in electric vehicles. In order to monitor and characterize the safety and degradation aspects of an electrochemical cell, a three-electrode setup can prove invaluable. This paper aims to provide a guide to constructing a three-electrode coin cell setup using the 2032-coin cell architecture, which is easy to produce, reliable, and cost-effective.

Three-electrode cells are useful in studying the electrochemistry of lithium-ion batteries. Such an electrochemical setup allows the phenomena associated with the cathode and anode to be decoupled and examined independently. Here, we present a guide for construction and use of a three-electrode coin cell with emphasis on lithium plating analytics.

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and ...

Preparing an Isotopically Pure 229Th Ion Beam for Studies of 229mTh

A methodology is described to generate an isotopically pure 229Th ion beam in the 2+ and 3+ charge states. This ion beam enables one to investigate the low-lying isomeric first excited state of 229Th at an excitation energy of about 7.8(5) eV and a radiative lifetime of up to 104 seconds. The presented method allowed for a first direct identification of the decay of the thorium isomer, laying the foundations to study its decay properties as prerequisite for an optical control of this nuclear transition. High energy 229Th ions are produced in the &#945;&#160;decay of a radioactive 233U source. The ions are thermalized in a buffer-gas stopping cell, extracted and subsequently an ion beam is formed. This ion beam is mass purified by a quadrupole-mass separator to generate a pure ion beam. In order to detect the isomeric decay, the ions are collected on the surface of a micro-channel plate detector, where electrons, as emitted in the internal conversion decay of the isomeric state, are observed.

Preparing an Isotopically Pure 229Th Ion Beam for Studies of 229mTh

We present a protocol for the generation of an isotopically purified low-energy 229Th ion beam from a 233U source. This ion beam is used for the direct detection of the 229mTh ground-state decay via the internal-conversion decay channel. We also measure the internal conversion lifetime of 229mTh as well.

A methodology is described to generate an isotopically pure 229Th ion beam in the 2+ and 3+ charge states. This ion beam enables one to investigate the ...