|True Reference Electrode||Yes- drift rate less than 0.1 mV/min|
|True Counter Electrode||Yes|
|Counter Electrode Material||User’s choice of material|
|Electrolytes||Aqueous, Wide range of organics*|
|Spacer range||100nm to 2 um*|
|EELS/ EDS Compatible||Yes|
|TEM Compatibility||TFS/FEI, JEOL, Hitachi|
Model Baseline Electrochemistry – Ferrocyanide/Ferricyanide Redox
The Generation V liquid-electrochemistry in-situ TEM holder uses a completely newly developed hardware system and optimized electrochemistry chips with configuration of working electrode (WE), counter electrode (CE) and reference electrode (RE) that for the first time replicate bulk electrochemical conditions in-situ in the TEM . This was validated using several model electrochemical systems.
We performed cyclic voltammetry studies in a model 20 mM K3(Fe(CN)6/20 mM K4Fe(CN)6 in 0.1M KCl solutions. The redox reaction of 20 mM ferrocyanide/ 20 mM ferricyanide in 0.1M KCl at different voltage scans show reversible electrode reaction during both the forward and reverse scans, elucidating bulk behavior. The corresponding electrochemical impedance spectroscopy (EIS) measurements shows lower capacitive current, and better signal-to-noise ratio with the lower concentration of solution.
Left image: Top shows CV cycle performed at various potential scan rates – 20 mV/s and 100 mV/s. Bottom shows the corresponding EIS spectrum.
HBS internal data obtained in collaboration with William C. Chueh group at Stanford University.Edit
Model Baseline Electrochemistry – Cu Electrodeposition
To validate the performance of the Generation V Bulk Electrochemistry holder, we also perform TEM copper electrodeposition and compare the behavior with the beaker level bulk data.
A cyclic voltammetry (CV) study of a model compound 0.1 M CuSO4 showing plating and stripping of copper has been presented here. The copper plating and stripping occur at the Pt working electrode at distinct redox peaks and the result replicate the bulk electrochemical cells with large electrode areas and larger volume of electrolyte solution.
Image Left: Comparison of CV curves between in-situ TEM and bulk reference data.Edit
Hummingbird Scientific was the first to sell a commercial liquid-electrochemical TEM holder in 2008. With the release of the Generation V in-situ bulk electrochemical TEM specimen holder, we are now providing the first and only in-situ holder that can accurately replicate bulk electrochemistry behavior of a wide range of liquid-electrochemical systems in-situ. The holder can measure bulk level electrochemistry data in-situ using up to six electrodes, a wide range of bulk materials on the CE, and a variety of real reference electrode options for various electroanalytical modes of operation.
- Battery Materials
- Fuel Cell Materials
How It Works
The new Generation V liquid-electrochemistry holder is the first ever liquid solution for TEM with capabilities allowing true reference and counter electrodes performance for electroanalytical measurements. The stability of the electrodes with little or no interference with the working electrodes allows superior performance and accuracy in the readings during the electroanalytical measurements.
The comparison of cyclic voltammetry data between a typical standard liquid holder and newest generation of liquid-electrochemistry holder shows remarkable improvement in the latter with distinct and consistent redox peaks over two cycles in a plating experiment (Figure on the left). The quality of data in the Generation V liquid-electrochemistry holder matches the performance of the standard beaker electrochemistry.Read MoreEdit
Careful preparation of your samples and system are essential for effective use of environmental holders. A critical component of any holder system is a high-vacuum leak check station.
Our high-vacuum pumping station is a compact, all-in-one vacuum storage and seal-checking mechanism for TEM specimen holders. The station features short pumping and venting times, a low base pressure (<1e-6 mbar), and a glass viewing port for the holder tip.Read MoreEdit
Replicating bulk electrochemistry experiments in-situ in the TEM
Hummingbird Scientific’s newest Generation V Bulk in-situ liquid-electrochemistry holder allows researchers for the first time to fully replicate bulk-level electrochemical details inside the transmission electron microscope. A newly developed hardware system allows quantitative measurements of electrochemical processes with details showing the complete cycle of the bulk.
As an illustration, a cyclic voltammetry (CV) study of a model compound CuSO4 solution showing plating and stripping of copper from the active electrode has been presented here. The copper plating and stripping occurs at the working electrode, replicating actual bulk behavior.
The new Hummingbird Scientific’s liquid-cell hardware and cells allows, for the first time, for replication of bulk-level data in TEM.
Video Right: In-situ liquid cell TEM copper plating and stripping from CuSO4 solution. Inset shows corresponding CV curve representing the video.
HBS internal data obtained in collaboration with Rui Filipe Serra Maia and Eric Stach at the University of Pennsylvania.Edit
Customization & Service
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|Mei Sun, Xing Li, Zhiqiang Tang, Xianlong Wei and Qing Chen. “Constant-Rate Dissolution of InAs Nanowires in Radiolytic Water Observed by In situ Liquid Cell TEM.” Nanoscale (2018)||Abstract|
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|Jeung Hun Park, Tommy Watanabe, Ainsley Pinkowitz, David J. Duquette, Robert Hull, Daniel A. Steingart and Frances M. Ross. “In situ EC-TEM Studies of Metal Thin Film Corrosion in Liquid Solutions at Elevated Temperatures.” Microscopy & Microanalysis (2018)||Abstract|
|Feng Yan, Lili Liu, Tiffany R. Walsh, Yu Gong, Patrick Z. El-Khoury, Yanyan Zhang, Zihua Zhu, James J. De Yoreo, Mark H. Engelhard, Xin Zhang and Chun-Long Chen. “Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering,” Nature Communications (2018)||Abstract|
|Claudia Stauch, Christopher Hobbs, Aleksey Shmeliov, Valeria Nicolosi, Thomas Ballweg, Robert Luxenhofer, and Karl Mandel. “Colloidal Core–Satellite Supraparticles via Preprogramed Burst of Nanostructured Micro‐Raspberry Particles,” Particle & Particle Systems Characterization (2018)||Abstract|
|Chen Houa, Jiuhui Hanb, Pan Liua, Chuchu Yangb, Gang Huangb, Takeshi Fujitab, Akihiko Hiratab, and Mingwei Chen. “Operando observations of RuO2 catalyzed Li2O2 formation and decomposition in a Li-O2 micro-battery,” Nano Energy (2018)||Abstract|
|Pan Liu, Jiuhui Han, Xianwei Guo, Yoshikazu Ito, Chuchu Yang, Shoucong Ning, Takeshi Fujita, Akihiko Hirata and Mingwei Chen. “Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy,” Scientific Reports (2018)||Abstract|
|Jeung Hun Park, Nicholas M. Schneider, Daniel A. Steingart, Hariklia Deligianni, Suneel Kodambaka, and Frances M. Ross. “Control of Growth Front Evolution by Bi Additives during ZnAu Electrodeposition,” Nano Letters (2018)||Abstract|
|Trevor H. Moser, Hardeep Mehta, Chiwoo Park, Ryan T. Kelly, Tolou Shokuhfar, and James E. Evans. “The role of electron irradiation history in liquid cell transmission electron microscopy,” Science Advances (2018)||Abstract|
|Lili Liu, Shuai zhang, Mark E. Bowden, Jharna Chaudhuri, and James J. De Yoreo. “In-situ TEM and AFM investigation of morphological controls during the growth of single crystal BaWO4,” Crystal Growth & Design (2017)||Abstract|
|Edward R. White, Jared J. Lodico & B. C. Regan. “Intercalation events visualized in single microcrystals of graphite,” Nature Communications (2017)||Abstract|
|YuBo Wang, Shuai Wang, and Xing Lu. “In Situ Observation of the Growth of ZnO Nanostructures Using Liquid Cell Electron Microscopy,” The Journal of Physical Chemistry C (2017)||Abstract|
|See Wee Chee, Shu Fen Tan, Zhaslan Baraissov, Michel Bosman & Utkur Mirsaidov. “Direct observation of the nanoscale Kirkendall effect during galvanic replacement reactions,” Nature Communications (2017)||Abstract|
|Chuchu Yang, Jiuhui Han, Pan Liu, Chen Hou, Gang Huang, Takeshi Fujita, Akihiko Hirata, and Mingwei Chen. “Direct Observations of the Formation and Redox-Mediator-Assisted Decomposition of Li2O2 in a Liquid-Cell Li–O2 Microbattery by Scanning Transmission Electron Microscopy,” Advanced Materials (2017)||Abstract|
|. Jongwoo Lim, Yiyang Li, Daan Hein Alsem, Hongyun So, Sang Chul Lee, Peng Bai, Daniel A. Cogswell, Xuxhao Liu, Norman Jin, Young-sang Yu, Norman J. Salom, David A. Shapiro, Martin Z. Bazant, Tolek Tyliszczak, and William C. Chueh. “Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles,” Science (2017)||Abstract|
|Eli Fahrenkrug, Daan Hein Alsem, Norman Salmon, and Stephen Maldonado. “Electrochemical Measurements in In Situ TEM Experiments,” Journal of the Electrochemical Society (2017)||Abstract|
|Timothy S. Arthur, Per-Anders Glans, Nikhilendra Singh, Oscar Tutusaus, Kaiqi Nie, Yi-Sheng Liu, Fuminori Mizuno, Jinghua Guo, Daan Hein Alsem, Norman J. Salmon, and Rana Mohtadi. “Interfacial insight from operando sXAS/TEM for magnesium metal deposition with borohydride electrolytes,” Chemistry of Materials (2017)||Abstract|
|Jeung Hun Park, Daniel A. Steingart, Suneel Kodambaka, and Frances M. Ross. “Electrochemical electron beam lithography: Write, read, and erase metallic nanocrystals on demand,” Science Advances (2017)||Abstract|
|Jianbo Wu, Wenpei Gao, Hong Yang, and Jian-Min Zuo. “Dissolution Kinetics of Oxidative Etching of Cubic and Icosahedral Platinum Nanoparticles Revealed by in Situ Liquid Transmission Electron Microscopy,” ACS Nano (2017)||Abstract|
|Omid Sadeghi, Clément Falaise, Pedro I. Molina, Ryan Hufschmid, Charles F. Campana, Bruce C. Noll, Nigel D. Browning, and May Nyman. “Chemical Stabilization and Electrochemical Destabilization of the Iron Keggin Ion in Water,” Inorganic Chemistry (2016)||Abstract|
|R. R. Unocic, L. Baggetto, G. M. Veith, J. A. Aguiar, K. A. Unocic, R. L. Sacci, N. J. Dudneyb and K. L. Morea. “Probing battery chemistry with liquid cell electron energy loss spectroscopy,” Chem. Commun. Advance Article (2015)||Abstract|
|R.R. Unocic. “In-situ Liquid S/TEM: Practical Aspects, Challenges, and Opportunities,” Microscopy and Microanalysis (2015)||Abstract|
|W. Zhang, D.H. Alsem, F. Wang, N. Salmon. “In-Situ Liquid Cell TEM Studies of Electrochemical Reaction in Lithium-Ion Batteries,” Microscopy and Microanalysis (2015)||Abstract|
|J.P. Patterson, P. Abellan, M.S. Denny, C. Park, N.D. Browning, S.M. Cohen, J.E. Evans, N.C. Gianneschi. “Observing the Self-assembly of Metal-Organic Frameworks by In-Situ Liquid Cell TEM,” Microscopy and Microanalysis (2015)||Abstract|
|J.-M. Zuo, A. Yoon, W. Gao, J. Wu, H. Park. “Materials processes observed using dynamical environmental TEM at University of Illinois,” Microscopy and Microanalysis (2015)||Abstract|
|T.J. Woehal, S. Kashyap, E. Firlar, T. Perez-Gonzalez, D. Faivre, D. Trubitsyn, D. Bazylinski, T. Prozorov. “Correlative Electron and Fluorescence Microscopy of Magnetotactic Bacteria in Liquid: Toward In-Vivo Imaging,” Microscopy and Microanalysis (2015)||Abstract|
|T.J. Woehl, T. Prozorov. “Visualization of gold nanoparticle self-assembly kinetics,” Microscopy and Microanalysis (2015)||Abstract|
|N. Bhattarai, T. Prozorov. “In-situ STEM Investigation of Shape-Controlled Synthesis of Au-Pd Core-Shell Nanocube,” Microscopy and Microanalysis (2015)||Abstract|
|S.W. Chee, D. Loh, U Mirsaidov, P. Matsudaira, “Probing Nanoparticle Dynamics in 200 nm Thick Liquid Layers at Millisecond Time Resolution.” Microscopy & Microanalysis (2015)||Abstract|
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|P. J. M. Smeets, K. R. Cho, R. G. E. Kempen, N. A. J. M. Sommerdijk, and J. J. De Yoreo. “Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy”, Nature Materials Letters, Published Online 01/26/2015.||Abstract|
|E. Sutter, K. Jungjohann, S. Bliznakov, A. Courty, E. Maisonhaute, S. Tenney & P. Sutter. “In situ liquid-cell electron microscopy of silver–palladium galvanic replacement reactions on silver nanoparticles.” Nature Communications, 5, Article number: 4946 doi:10.1038/ncomms5946||Abstract|
|M.H. Nielsen, S. Aloni, J.J. De Yoreo. “In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways”, Science vol. 345 iss. 6201 (2014) pp. 1158-1162||Abstract|
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Probing the Degradation Mechanisms in Electrolyte Solutions for Li-Ion Batteries by in Situ Transmission Electron Microscopy” Nano Lett. 14:3 (2014) 1293-1299
|S.W. Chee, D.J. Duquette, F.M. Ross, and R. Hull. “Metastable Structures in Al Thin Films Before the Onset of Corrosion Pitting as Observed using Liquid Cell Transmission Electron Microscopy,” Micoscopy and Microanalysis 20:2 (2014) pp. 462‒468||Abstract|
|R.R. Unocic, X.G. Sun, R.L. Sacci, L.A. Adamczyk, D.H. Alsem, S. Dai, N.J. Dudney, and K.L. More. “Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy,” Microscopy and Microanalysis 20:4 (2014) pp.1029‒1037||Abstract|
|R.L. Sacci, N. Dudney, K. More, L.R. Parent, I. Arslan, N.D. Browning, and R.R. Unocic. “Direct Visualization of Initial SEI Morphology and Growth Kinetics During Lithium Deposition by In-Situ Electrochemical Transmission Electron Microscopy,” Chem. Commun. 50 (2014) pp. 2104‒2107||Abstract|
|D.A. Fischer, D.H. Alsem, B. Simon, T. Prozorov and N. Salmon. “Development of an Integrated Platform for Cross-Correlative Imaging of Biological Specimens in Liquid using Light and Electron Microscopies.” Microscopy and Microanalysis, 19 (Suppl. 2) , pp 476-477. (2013)||Abstract|
|M. Gu, L.R. Parent, B.L. Mehdi, R.R. Unocic, M.T. McDowell, R.L. Sacci, W. Xu, J.G. Connell, P. Xu, P. Abellan, X. Chen,Y. Zhang, D.E. Perea, J.E. Evans, L.J. Lauhon, J.G. Zhang, J. Liu, N.D. Browning, Y. Cui, I. Arslan, and C.M. Wang. “Demonstration of an Electrochemical Liquid Cell for Operando Transmission Electron Microscopy Observation of the Lithiation/Delithiation Behavior of Si Nanowire Battery Anodes.” Nano Lett. 13:12 (2013) pp. 6106‒6112||Abstract|
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|K.L. Jungjohann, S. Bliznakov, P.W. Sutter, E.A. Stach, E.A. Sutter. “In-Situ Liquid Cell Electron Microscopy of the Solution Growth of Au-Pd Core-Shell Nanostructures,” Nano. Lett. 13 (2013) pp. 2964–2970||Abstract|
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|T.J. Woehl , J. E. Evans, I. Arslan, W.D. Ristenpart , N.D. Browning “Direct in-situ determination of the mechanisms controlling nanoparticle nucleation and growth,” ACS Nano 6:10 (2012) pp. 8599–8610||Abstract|
|R.R. Unocic, L. Baggetto, K.A. Unocic, G.M. Veith, N.J. Dudney, and K.L. More. “Coupling EELS/EFTEM Imaging with Environmental Fluid Cell Microscopy.” Microscopy and Microanalysis 18 (Suppl 2), (2012) 1104-1105||Abstract|
|K.L. Jungjohann, J.E. Evans, I. Arslan, N.D. Browning. “Electron Energy Loss Spectroscopy for Aqueous in-Situ Scanning Transmission Electron Microscopy.” Microscopy & Microanaysis 17:S2 (2011) pp. 778–779.||Abstract|
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|R.R. Unocic, L.A. Adamczyk, N.J. Dudney, D.H. Alsem, N.J. Salmon, and K.L. More. “In-Situ Electron Microscopy of Electrical Energy Storage Materials,” ECS Fall Meeting 2010||Abstract|
|C.M. Wang, W. Xu, J. Liu, D.W. Choi, B. Arey, L.V. Saraf, J.G. Zhang, Z.G. Yang, S. Thevuthasan, D.R. Baer, and N. Salmon. “In-situ transmission electron microscopy and spectroscopy studies of interfaces in Li ion batteries: Challenges and opportunities,” J. Mater. Res. 25:8 (2010) pp. 1541–1547||Abstract|