Name: in situ neutron powder diffraction using custom-made lithium-ion batteries
Uploaded: 2014-11-10T15:00:00
Description: Watch this Scientific Journal Video about In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries at JoVE.com

We thank AINSE Ltd for providing support through the research fellowship and postgraduate award scheme.

1. Cell Components Required Prior to Construction
NOTE: A vanadium can is conventionally used for NPD experiments and it is a wholly-vanadium tube that is sealed at one end and open at the other. There is virtually no signal in NPD data from vanadium.
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	<li>Cut a piece of lithium metal-foil to dimensions matching the volume of the vanadium can. For example, cut a piece approximately 120 x 35 mm for a 9&#160;mm diameter vanadium can. In addition, use thinner lithium foil to minimize neutr...

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	<li>Winter, M., Besenhard, J. O., Spahr, M. E., Novak, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Insertion+electrode+materials+for+rechargeable+lithium+batteries.">Insertion electrode materials for rechargeable lithium batteries.</a> Adv. Mater. (Weinheim, Ger.). 10, 725-763 (1998).</li><li>Wakihara, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+developments+in+lithium+ion+batteries).">Recent developments in lithium ion batteries).</a> Mater. Sci. Eng., R. 33, 109-134 (2001).</li><li>Goodenough, J. B., Kim, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Challenges+for+Rechargeable+Li+Batteries.">Challenges for Rechargeable Li Batteries.</a> Chem. Mater. 22, 587-603 (2010).</li><li>Palomares, V., 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=Na-ion+batteries,+recent+advances+and+present+challenges+to+become+low+cost+energy+storage+systems.">Na-ion batteries, recent advances and present challenges to become low cost energy storage systems.</a> Energy Environ. Sci. 5, 5884-5901 (2012).</li><li>Masquelier, C., Croguennec, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polyanionic+(phosphates,+silicates,+sulfates)+frameworks+as+electrode+materials+for+rechargeable+Li+(or+Na)+batteries.">Polyanionic (phosphates, silicates, sulfates) frameworks as electrode materials for rechargeable Li (or Na) batteries.</a> Chem. Rev. (Washington, DC, U. S.). 113, 6552-6591 (2013).</li><li>Reddy, M. V., Subba Rao, G. V., Chowdari, B. V. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal+Oxides+and+Oxysalts+as+Anode+Materials+for+Li+Ion+Batteries.">Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries.</a> Chem. Rev. (Washington, DC, U. S.). 113, 5364-5457 (2013).</li><li>Goodenough, J. B., Kim, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Challenges+for+rechargeable+batteries.">Challenges for rechargeable batteries.</a> J. Power Sources. 196, 6688-6694 (2011).</li><li>Sharma, N., Peterson, V. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Overcharging+a+lithium-ion+battery:+Effect+on+the+LixC6+negative+electrode+determined+by+in+situ+neutron+diffraction.">Overcharging a lithium-ion battery: Effect on the LixC6 negative electrode determined by in situ neutron diffraction.</a> J. Power Sources. 244, 695-701 (2013).</li><li>Sharma, 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=Structural+changes+in+a+commercial+lithium-ion+battery+during+electrochemical+cycling:+An+in+situ+neutron+diffraction+study.">Structural changes in a commercial lithium-ion battery during electrochemical cycling: An in situ neutron diffraction study.</a> J. Power Sources. 195, 8258-8266 (2010).</li><li>Senyshyn, A., Muehlbauer, M. J., Nikolowski, K., Pirling, T., Ehrenberg, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-operando'+neutron+scattering+studies+on+Li-ion+batteries.">In-operando' neutron scattering studies on Li-ion batteries.</a> J. Power Sources. 203, 126-129 (2012).</li><li>Sharma, N., Yu, D., Zhu, Y., Wu, Y., Peterson, V. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Non-equilibrium+Structural+Evolution+of+the+Lithium-Rich+Li1+yMn2O4+Cathode+within+a+Battery.">Non-equilibrium Structural Evolution of the Lithium-Rich Li1+yMn2O4 Cathode within a Battery.</a> Chemistry of Materials. 25, 754-760 (2013).</li><li>Pang, W. K., Sharma, N., Peterson, V. K., Shiu, J. J., Wu, S. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-situ+neutron+diffraction+study+of+the+simultaneous+structural+evolution+of+a+LiNi0.5Mn1.5O4+cathode+and+a+Li4Ti5O12+anode+in+a+LiNi0.5Mn1.5O4+parallel+to+Li4Ti5O12+full+cell.">In-situ neutron diffraction study of the simultaneous structural evolution of a LiNi0.5Mn1.5O4 cathode and a Li4Ti5O12 anode in a LiNi0.5Mn1.5O4 parallel to Li4Ti5O12 full cell.</a> Journal of Power Sources. 246, 464-472 (2014).</li><li>Pang, W. K., Peterson, V. K., Sharma, N., Shiu, J. -. J., Wu, S. -. h. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Lithium Migration in Li4Ti5O12 Studied Using in Situ Neutron Powder. 26, 2318-2326 (2014).</li><li>Bergstom, O., Andersson, A. M., Edstrom, K., Gustafsson, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+neutron+diffraction+cell+for+studying+lithium-insertion+processes+in+electrode+materials.">A neutron diffraction cell for studying lithium-insertion processes in electrode materials.</a> J. Appl. Crystallogr. 31, 823-825 (1998).</li><li>Sharma, N., Du, G. D., Studer, A. J., Guo, Z. P., Peterson, V. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-situ+neutron+diffraction+study+of+the+MoS2+anode+using+a+custom-built+Li-ion+battery.">In-situ neutron diffraction study of the MoS2 anode using a custom-built Li-ion battery.</a> Solid State Ion. 199, 37-43 (2011).</li><li>Sharma, N., Peterson, V. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Current-dependent+electrode+lattice+fluctuations+and+anode+phase+evolution+in+a+lithium-ion+battery+investigated+by+in+situ+neutron+diffraction.">Current-dependent electrode lattice fluctuations and anode phase evolution in a lithium-ion battery investigated by in situ neutron diffraction.</a> Electrochim. Acta. 101, 79-85 (2013).</li><li>Dolotko, O., Senyshyn, A., Muhlbauer, M. J., Nikolowski, K., Ehrenberg, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Understanding+structural+changes+in+NMC+Li-ion+cells+by+in+situ+neutron+diffraction.">Understanding structural changes in NMC Li-ion cells by in situ neutron diffraction.</a> Journal of Power Sources. 255, 197-203 (2014).</li><li>Rodriguez, M. A., Ingersoll, D., Vogel, S. C., Williams, D. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Simultaneous+In+Situ+Neutron+Diffraction+Studies+of+the+Anode+and+Cathode+in+a+Lithium-Ion+Cell.">Simultaneous In Situ Neutron Diffraction Studies of the Anode and Cathode in a Lithium-Ion Cell.</a> Electrochem. Solid-State Lett. 7, (2004).</li><li>Wang, X. -. L., 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=Visualizing+the+chemistry+and+structure+dynamics+in+lithium-ion+batteries+by+in-situ+neutron+diffraction.">Visualizing the chemistry and structure dynamics in lithium-ion batteries by in-situ neutron diffraction.</a> Sci. Rep. 2, 00747 (2012).</li><li>Rodriguez, M. A., Van Benthem, M. H., Ingersoll, D., Vogel, S. C., Reiche, H. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+analysis+of+LiFePO4+batteries:+Signal+extraction+by+multivariate+analysis.">In situ analysis of LiFePO4 batteries: Signal extraction by multivariate analysis.</a> Powder Diffr. 25, 143-148 (2010).</li><li>Berg, H., Rundlov, H., Thomas, J. O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+LiMn2O4+to+lambda-MnO2+phase+transition+studied+by+in+situ+neutron+diffraction.">The LiMn2O4 to lambda-MnO2 phase transition studied by in situ neutron diffraction.</a> Solid State Ion. 144, 65-69 (2001).</li><li>Roberts, M., 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=Design+of+a+new+lithium+ion+battery+test+cell+for+in-situ+neutron+diffraction+measurements.">Design of a new lithium ion battery test cell for in-situ neutron diffraction measurements.</a> Journal of Power Sources. 226, 249-255 (2013).</li><li>Rosciano, F., Holzapfel, M., Scheifele, W., Novak, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+novel+electrochemical+cell+for+in+situ+neutron+diffraction+studies+of+electrode+materials+for+lithium-ion+batteries.">A novel electrochemical cell for in situ neutron diffraction studies of electrode materials for lithium-ion batteries.</a> J. Appl. Crystallogr. 41, 690-694 (2008).</li><li>Godbole, V. 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=Circular+in+situ+neutron+powder+diffraction+cell+for+study+of+reaction+mechanism+in+electrode+materials+for+Li-ion+batteries.">Circular in situ neutron powder diffraction cell for study of reaction mechanism in electrode materials for Li-ion batteries.</a> RSC Adv. 3, 757-763 (2013).</li><li>Colin, J. -. F., Godbole, V., Novak, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+neutron+diffraction+study+of+Li+insertion+in+Li4Ti5O12.">In situ neutron diffraction study of Li insertion in Li4Ti5O12.</a> Electrochem. Commun. 12, 804-807 (2010).</li><li>Bianchini, M., 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=A+New+Null+Matrix+Electrochemical+Cell+for+Rietveld+Refinements+of+In-Situ+or+Operando+Neutron+Powder+Diffraction+Data.">A New Null Matrix Electrochemical Cell for Rietveld Refinements of In-Situ or Operando Neutron Powder Diffraction Data.</a> Journal of the Electrochemical Society. 160, 2176-2183 (2013).</li><li>Liu, H. D., Fell, C. R., An, K., Cai, L., Meng, Y. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-situ+neutron+diffraction+study.">In-situ neutron diffraction study.</a> Journal of Power Sources of the xLi(2)MnO(3)center dot(1-x)LiMO2 (x=0, 0.5; M. 240 (2), 772-778 (2013).</li><li>Sharma, 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=Direct+Evidence+of+Concurrent+Solid-Solution+and+Two-Phase+Reactions+and+the+Nonequilibrium+Structural+Evolution+of+LiFePO4).">Direct Evidence of Concurrent Solid-Solution and Two-Phase Reactions and the Nonequilibrium Structural Evolution of LiFePO4).</a> J. Am. Chem. Soc. 134, 7867-7873 (2012).</li><li>Sharma, 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=Time-Dependent+in-Situ+Neutron+Diffraction+Investigation+of+a+Li(Co0.16Mn1.84)O4+Cathode.">Time-Dependent in-Situ Neutron Diffraction Investigation of a Li(Co0.16Mn1.84)O4 Cathode.</a> J. Phys. Chem. C. 115, 21473-21480 (2011).</li><li>Du, G., 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=Br-Doped+Li4Ti5O12+and+Composite+TiO2+Anodes+for+Li-ion+Batteries:+Synchrotron+X-Ray+and+in+situ+Neutron+Diffraction+Studies.">Br-Doped Li4Ti5O12 and Composite TiO2 Anodes for Li-ion Batteries: Synchrotron X-Ray and in situ Neutron Diffraction Studies.</a> Adv. Funct. Mater. 21, 3990-3997 (2011).</li><li>Marks, T., Trussler, S., Smith, A. J., Xiong, D., Dahn, J. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+Guide+to+Li-Ion+Coin-Cell+Electrode+Making+for+Academic+Researchers.">A Guide to Li-Ion Coin-Cell Electrode Making for Academic Researchers.</a> J. Electrochem. Soc. 158, 51-57 (2010).</li><li>Brant, W. R., 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=Rapid+Lithium+Insertion+and+Location+of+Mobile+Lithium+in+the+Defect+Perovskite+Li0.18Sr0.66Ti0.5Nb0.5O3.">Rapid Lithium Insertion and Location of Mobile Lithium in the Defect Perovskite Li0.18Sr0.66Ti0.5Nb0.5O3.</a> ChemPhysChem. 13, 2293-2296 (2012).</li><li>Richard, D., Ferrand, M., Kearley, G. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Analysis+and+Visualisation+of+Neutron-Scattering+Data.">Analysis and Visualisation of Neutron-Scattering Data.</a> J. Neutron Research. 4, 33-39 (1996).</li><li>Brant, W. R., Schmid, S., Du, G., Gu, Q., Sharma, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+simple+electrochemical+cell+for+in-situ+fundamental+structural+analysis+using+synchrotron+X-ray+powder+diffraction.">A simple electrochemical cell for in-situ fundamental structural analysis using synchrotron X-ray powder diffraction.</a> Journal of Power Sources. 244, 109-114 (2013).</li><li>Hu, C. -. W., 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=Real-time+investigation+of+the+structural+evolution+of+electrodes+in+a+commercial+lithium-ion+battery+containing+a+V-added+LiFePO4+cathode+using+in-situ+neutron+powder+diffraction.">Real-time investigation of the structural evolution of electrodes in a commercial lithium-ion battery containing a V-added LiFePO4 cathode using in-situ neutron powder diffraction.</a> J. Power Sources. 244, 158-163 (2013).</li><li>Cai, L., An, K., Feng, Z., Liang, C., Harris, S. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In-situ+observation+of+inhomogeneous+degradation+in+large+format+Li-ion+cells+by+neutron+diffraction.">In-situ observation of inhomogeneous degradation in large format Li-ion cells by neutron diffraction.</a> J. Power Sources. 236, 163-168 (2013).</li><li>Doeff, M. M., 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=Characterization+of+electrode+materials+for+lithium+ion+and+sodium+ion+batteries+using+synchrotron+radiation+techniques.">Characterization of electrode materials for lithium ion and sodium ion batteries using synchrotron radiation techniques.</a> J. Visualized Exp. , 50591-50594 (2013).</li></ol>

When designing and performing an in situ experiment, either with the &#8220;roll-over&#8221; neutron diffraction cell or another design, there are a number of aspects that must be carefully controlled to ensure a successful experiment. These include careful choice of the type and quantity of cell components, ensuring that the prepared electrode and final constructed cell are of high quality, choosing appropriate diffraction conditions, planning the electrochemical cycling steps to be performed in advance, and fi...

Rechargeable lithium-ion batteries provide portable energy for modern electronics and are important in high-energy applications such as electric vehicles and as energy storage devices for large-scale renewable energy generation.3-7 A number of challenges remain to achieve widespread use of rechargeable batteries in vehicular and large-scale storage, including energy densities and safety. The use of in situ methods to probe atomic and molecular-scale battery function during operation are becoming increasingly common as the information gained in such experiments can direct methods to improve existing battery materials, e.g. by identifying possible failure mechanisms,8-10 and by revealing crystal structures that could be considered for the next generation of materials.11
A primary goal of in situ NPD is to probe the crystal structure evolution of the components inside a battery as a function of charge/discharge. In order to measure the crystal structure evolution the components must be crystalline, which focuses such studies on crystallographically-ordered electrodes. It is at the electrodes that the charge carrier (lithium) is inserted/extracted and such changes are followed by NPD. In situ NPD offers the possibility to &#8220;track&#8221; not only the reaction mechanism and lattice parameter evolution of the electrodes, but also the insertion/extraction of lithium from the electrodes. Essentially the charge carrier in lithium-ion batteries can be followed. This gives a lithium-centered view of the battery function and has been recently demonstrated in only a few studies.11-13
NPD is an ideal technique to examine lithium-containing materials and lithium-ion batteries. This is because NPD relies on the interaction between a neutron beam and the sample. Unlike X-ray powder diffraction (XRD), where the interaction of the X-ray radiation is predominantly with the electrons of the sample and thus varies linearly with atomic number, in NPD the interaction is mediated by neutron-nuclei interactions that result in a more complex and apparently random variation with atomic number. Thus, in situ NPD is particularly promising for the study of lithium-ion battery materials due to factors such as the sensitivity of NPD towards lithium atoms in the presence of heavier elements, the non-destructive interaction of neutrons with the battery, and the high penetration depth of neutrons enabling the examination of the bulk crystal-structure of the battery components within whole batteries of the size used in commercial devices. Therefore, in situ NPD is particularly useful for the study of lithium-ion batteries as a result of these advantages. Despite this, the uptake of in situ NPD experiments by the battery-research community has been limited, accounting for only 25 publications since the first report of using in situ NPD for battery research in 1998.14 The limited uptake is due to some major experimental hurdles, such as the need to account for the large incoherent neutron-scattering cross section of hydrogen in the electrolyte solutions and separator in the battery, which is detrimental to the NPD signal. This is often overcome by substituting with deuterated (2H) electrolyte solutions and replacing the separator with alternate hydrogen-free or poor materials.15 Another hurdle is the need to have sufficient sample in the neutron beam, a requirement that often necessitates the use of thicker electrodes which in turn limits the maximum charging/discharging rate that can be applied to the battery. A more practical concern is the relatively small number of world-wide neutron diffractometers relative to X-ray diffractometers, and their capabilities &#8212; e.g. time and angular resolution. As new neutron diffractometers have come online and the abovementioned hurdles overcome, in situ NPD experiments have grown in number.
There are two options to conduct in situ NPD experiments, using either commercial or custom-built cells. Commercial cells have been demonstrated to reveal structural information, including the evolution of lithium content and distribution in electrodes.8-11,16-20 However, using commercial cells limits the number of electrodes that can be studied to those already commercially available, and where manufacturers or select research facilities are engaged to produce commercial-type cells with as yet un-commercialized materials. The production of the commercial-type cells is dependent on the availability of sufficient quantities of electrode material for cell manufacture, typically of the order of kilograms and significantly higher than that used in battery research, which can be a barrier to cell production. Commercial cells typically feature two electrodes that evolve during charge/discharge and the evolution of both electrodes will be captured in the resulting diffraction patterns. This is because the neutron beam is highly penetrating and can penetrate the single lithium-ion cells (e.g., the entire volume of 18,650 cells). The evolution of the two electrodes can make the data analysis complicated, but if sufficient Bragg reflections of both electrodes are observed these can be modeled using whole powder-pattern methods. Nonetheless, custom-made half cells can be constructed in which one electrode is lithium and should not structurally change during charge/discharge and therefore act as an (or another) internal standard. This leaves only one electrode that should exhibit structural change, simplifying data analysis. Care must also be taken to ensure that all electrode reflections of interest are not overlapping with reflections from other components undergoing structural change in the cell. The advantage of a custom-made cell is that components can be swapped to alter reflection positions in diffraction patterns. Furthermore, custom-made cells allow researchers the option to, in principle, improve signal-to-noise ratios and to investigate materials that are made in smaller-scale research batches and thereby permitting the in situ NPD study of a larger variety of materials.
To date there have been six electrochemical cell designs for in situ NPD studies reported, including three cylindrical designs,14,15,21,22 two coin-type cell designs23-26 and a pouch cell design.12,27 The first cylindrical cell design was limited in use to very low charging/discharging rates due to the large quantities of electrode materials used.14,21 The roll-over design,15 detailed below, and modified version of the original cylindrical cell,22 have overcome many of the problems associated with the first cylindrical design, and can be used for reliably correlating the structure of electrode materials with their electrochemistry. Coin-cell designs for in situ NPD also allow similar quantities of electrode materials to be probed relative to the roll-over cell, while featuring subtle differences in terms of construction, applicable charging rates, and cost.15 In particular, the coin-cell type was recently reported to have been constructed using a Ti-Zn alloy as the casing material (null-matrix) which produces no signal in the NPD patterns.26 This is similar to the use of vanadium cans in the roll-over design described below. A key factor that can influence applicable charge/discharge rates (and polarization) is electrode thickness, where typically thicker electrodes require the application of lower current. The cell designs that are now becoming more popular are the pouch cells with sheets of multiple individual cells connected in parallel, or sheets that are rolled in a similar manner to the construction of lithium-ion batteries found in mobile electronics.12,27 This cell is rectangular (a pouch) that can function at higher charge/discharge rates than the roll-over or coin-type cells. In this work, we focus on the &#8216;roll-over&#8217; cell design, illustrating the cell construction, use, and some results using the cell.
The electrode preparation for the roll-over design batteries is practically similar to the electrode preparation for use in conventional coin-cell batteries. The electrode can be cast onto the current collector by doctor blading, with the biggest difference being that the electrode needs to span dimensions larger than 35 x 120-150 mm. This can be hard to uniformly coat with every electrode material. Layers of the electrode on current collector, separator, and lithium metal-foil on current collector are arranged, rolled, and inserted into vanadium cans. The electrolyte used is LiPF6, one of the most commonly used salts in lithium-ion batteries with deuterated ethylene carbonate and deuterated dimethyl carbonate. This cell has been used successfully in four reported studies and will be described in greater detail below.15,28-30

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			<td height="21" style="height:21px;width:347px;">Name of Material/ Equipment</td>
			<td style="width:159px;">Company</td>
			<td style="width:119px;">Catalog Number</td>
			<td style="width:801px;">Comments/Description</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Slurry Preparation</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">PVDF</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-Lib-PVDF</td>
			<td>http://www.mtixtl.com/PVDFbinderforLi-ionbatteryelectrodes80g/bag-EQ-Lib-PVDF.aspx</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Active Electrode Material</td>
			<td style="width:159px;">Researcher makes*</td>
			<td style="width:119px;"></td>
			<td>This is dependent on the electrode under investigation, typically made in-house by the researcher and varies every time</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Carbon black</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-Lib-SuperC65</td>
			<td>http://www.mtixtl.com/TimicalSUPERC65forLithium-IonBatteries80g/bag-EQ-Lib-SuperC65.aspx</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">NMP</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-Lib-NMP</td>
			<td>http://www.mtixtl.com/N-Methyl-2-pyrrolidoneNMPsolventforPVDF 
			250g/bottleLib-NMP.aspx</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">Magnetic stirrer</td>
			<td style="width:159px;">IKA</td>
			<td style="width:119px;">C-MAG HS 7 IKAMAG</td>
			<td>http://www.ika.in/owa/ika/catalog.product_detail?iProduct=3581200</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:347px;"></td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Electrode Fabrication</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;">Doctor blade (notch bar)</td>
			<td style="width:159px;">DPM Solutions Inc.</td>
			<td style="width:119px;">100, 200, 300 &#38; 400 micron&#160; 4-Sided Notch Bar</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Al or Cu current collectors</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-bcaf-15u-280</td>
			<td>http://www.mtixtl.com/AluminumFoilforBatteryCathodeSub 
			strate-EQ-bcaf-15u-280.aspx</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Vacuum Oven</td>
			<td style="width:159px;">Binder</td>
			<td style="width:119px;">e.g. VD 53</td>
			<td>http://www.binder-world.com/en/vacuum-drying-oven/vd-series/vd-53/</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Flat-plate press</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-HP-88V-LD</td>
			<td>http://www.mtixtl.com/25THydraulicFlat 
			HotPress-EQ-HP-88V.aspx</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:347px;"></td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Roll-over cell construction</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">V can</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">electrode on Al/Cu</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-bcaf-15u-280</td>
			<td>http://www.mtixtl.com/AluminumFoilforBatteryCathodeSub 
			strate-EQ-bcaf-15u-280.aspx</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">polyethylene-based or PVDF membrane</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">EQ-bsf-0025-400C</td>
			<td>http://www.mtixtl.com/separatorfilm-EQ-bsf-0025-400C.aspx</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">LiPF6</td>
			<td style="width:159px;">Sigma-Aldrich</td>
			<td style="width:119px;">450227</td>
			<td>http://www.sigmaaldrich.com/catalog/product/aldrich/450227?lang=en&#38;region=AU</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">deuterated dimethyl carbonate</td>
			<td style="width:159px;">Cambridge Isotopes</td>
			<td style="width:119px;">DLM-3903-PK&#160;</td>
			<td>http://shop.isotope.com/productdetails.aspx?id=10032379&#38;itemno=DLM-3903-PK</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">deuterated ethylene carboante</td>
			<td style="width:159px;">CDN Isotopes</td>
			<td style="width:119px;">D-5489</td>
			<td>https://www.cdnisotopes.com/as/products/specifications/D-5489.php?ei=YWVraWmjoJ1i0lZ7nkr0RpwHr 
			Hxc9ornu14O4WUtZKbZWZrcq6j55 
			G0lOab3Wi0dMZ7xc+0Yse1leWVtZ 
			LnrGKvta7v591o4JrnkbRowHt/r</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Li metal foil</td>
			<td style="width:159px;">MTI Corporation</td>
			<td style="width:119px;">Lib-LiF-30M</td>
			<td>http://www.mtixtl.com/Li-Foil-30000mmL-35mmW-0.17mm 
			Th.aspx</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Rubber stopper cut to size</td>
			<td style="width:159px;">generic eraser</td>
			<td style="width:119px;"></td>
			<td>cut a generic eraser to size</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">dental wax</td>
			<td style="width:159px;">Ainsworth Dental</td>
			<td>AIW042</td>
			<td>http://www.ainsworthdental.com.au/catalogue/Ainsworth-Modelling-Wax-500g.html</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Copper wire (insulated)</td>
			<td style="width:159px;">generic</td>
			<td style="width:119px;"></td>
			<td>sheathed Cu wire that can be cut to size</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Aluminium rod (&#60;2mm diameter)</td>
			<td style="width:159px;">generic</td>
			<td style="width:119px;"></td>
			<td>cut to size as required</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Glovebox</td>
			<td style="width:159px;">Mbraun</td>
			<td style="width:119px;">UNILab</td>
			<td>http://www.mbraun.com/products/glovebox-workstations/unilab-glovebox/</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Scissors&#160;</td>
			<td style="width:159px;">generic</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Soldering iron</td>
			<td style="width:159px;">generic</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:347px;"></td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">In situ NPD</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Appropriate neutron diffractometer</td>
			<td style="width:159px;">ANSTO</td>
			<td style="width:119px;">Wombat</td>
			<td>http://www.ansto.gov.au/ResearchHub/Bragg/Facilities/Instruments/Wombat/</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Potentiostat/galvanostat</td>
			<td style="width:159px;">Autolab</td>
			<td style="width:119px;">PGSTAT302N</td>
			<td>http://www.ecochemie.nl/Products/Echem/NSeriesFolder/PGSTAT302N</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Connections to battery from potentiostat/galvanostat</td>
			<td style="width:159px;">generic</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Training of NPD instrument and use</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:347px;"></td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Data analysis</td>
			<td style="width:159px;"></td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Data visualisation and peak fitting, .e.g. LAMP suite</td>
			<td style="width:159px;">ILL</td>
			<td style="width:119px;">LAMP</td>
			<td>http://www.ill.eu/instruments-support/computing-for-science/cs-software/all-software/lamp/</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Rietveld analysis software, e.g. GSAS</td>
			<td style="width:159px;">APS</td>
			<td style="width:119px;">GSAS</td>
			<td>https://subversion.xray.aps.anl.gov/trac/EXPGUI</td>
		</tr>
	</tbody>
</table>

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.

We have demonstrated the versatility in using this roll-over cell in the literature15,28-30 and here we present an example with the Li0.18Sr0.66Ti0.5Nb0.5O3 electrode.32
Prior to attempting a sequential Rietveld refinement (Rietveld refinements as a function of state-of-charge), a single refinement of a multiphase model to the first data set was performed, with this data collected for the pristine cell prior to curren...

Watch this Scientific Journal Video about In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries at JoVE.com

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.

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 ...

Research

JoVE Journal

Engineering

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 ...

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. ...

Measuring Material Microstructure Under Flow Using 1-2 Plane Flow-Small Angle Neutron Scattering

A new small-angle neutron scattering (SANS) sample environment optimized for studying the microstructure of complex fluids under simple shear flow is ...

Using Neutron Spin Echo Resolved Grazing Incidence Scattering to Investigate Organic Solar Cell Materials

The spin echo resolved grazing incidence scattering (SERGIS) technique has been used to probe the length-scales associated with irregularly shaped ...

Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent ...

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 ...

Measuring Spray Droplet Size from Agricultural Nozzles Using Laser Diffraction

When making an application of any crop protection material such as an herbicide or pesticide, the applicator uses a variety of skills and information to ...

Characterization of Ultra-fine Grained and Nanocrystalline Materials Using Transmission Kikuchi Diffraction

One of the challenges in microstructure analysis nowadays resides in the reliable and accurate characterization of ultra-fine grained (UFG) and ...

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

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 ...

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic ...