Electrochemistry

Operando multi-modal imaging with bulk-level electrochemical data

Electrochemical characterization tool selector

		Nano-Manipulator	Biasing TEM	Tomography TEM	Liquid TEM	Cryo Biasing TEM	Liquid X-Ray	Liquid SEM
Battery Configuration	Individual nanowire/nanoparticle
Battery Configuration	Thin film
Imaging	Higher resolution and diffraction
	EDS/EELS compatibility
	3D reconstruction
	In-situ imaging
	Pre-and post-mortem analysis
	Transfer air-sensitive samples
	Temperature cycling
Beam Effects	Compatibility with volatile electrolytes
Beam Effects	Minimal beam damage
Quantitative Electrochemistry	Replicate bulk measurements
	Image all battery components
	Longer cycling

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特徴

Site-Specific Nano-Probing and Biasing

Hummingbird Scientific’s in-situ nano-manipulator probe can selectively charge or discharge individual nanomaterials such as nanowires and nanoparticles. This is a great tool for studying mechanics and kinetics of individual nanostructures, while allowing to manipulate and characterize their behavior in real-time. The piezo-driven probe carries the charge source (e.g. Li, Na, Mg or ionic liquid electrolyte). The sample containing TEM specimen is mounted to the fixed stage. A negative/positive bias is applied to the sample with respect to the probe source to initiate the reaction and study site-specific connections between material microstructure and performance.

The image on the left shows the lithiation/delithiation behavior of porous silicon nanorods, in which the void space allows free volumetric expansion during lithium intercalation and deintercalation processes.

Reference: Z. Yang, J. Sun, Y. Nia, Z. Zhao, J. Bao, S. Chen. “Facile synthesis and in situ transmission electron microscopy investigation of a highly stable Sb2Te3/C nanocomposite for sodium-ion batteries,” Energy Storage Materials 9 (2017) pp. 214-220. Abstract

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Electrical Biasing

Hummingbird Scientific’s in-situ electrical biasing holder can be used for electrochemically cycling thin film batteries while imaging the material microstructure. Representative battery cell can be thinned using FIB processing or attached to the substrate. The sample is a representative section of the real battery cell and the data obtained is representative of the real battery performance.

For example, a thin cross-section of a battery cell can be mounted, wire-bonded, and viewed in TEM while cycling. The image shown on the left is a 10 nm graphite flake folded onto itself after one complete intercalation/deintercalation cycle.

Reference: Edward R. White, Jared J. Lodico & B. C. Regan. “Intercalation events visualized in single microcrystals of graphite,” Nature Communications 8 (2017) pp. 1969. Abstract

Image (left) © 2017 Macmillan Publishers Limited, part of Springer Nature
Image (bottom right) © Materials Research Society 2010

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TEM Tomography

Hummingbird Scientific’s TEM Tomography holder is an important characterization tool in the electrochemistry suite that allows users to perform pre or post-mortem analyses of battery materials in great details. Because the system permits high tilt angles, the sample itself is the only contributor to the missing wedge. A range of removable tips are available for the system and can be customized for specific specimen support geometries. Specifically, any cycled samples on chips from the in-situ liquid/gas cell holders can be easily transferred and placed in the dedicated tomography tip for analyses.

Image on the left shows the porosity of silicon structure evaluated for battery materials using TEM tomography.

Reference: M. Ge, Y. Lu, P. Ercius, J. Rong, X. Fang, M. Mecklenburg, and C. Zhou “Large-Scale Fabrication, 3D Tomography, and Lithium-Ion Battery Application of Porous Silicon” Nano Letters 14 (2014) pp. 261–268. Abstract

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Liquid-electrochemistry

Hummingbird Scientific’s in-situ liquid holder allows researchers to image systems with volatile electrolytes enclosed in a cell in TEM. The flexibility of using any standard liquid electrolytes allows for the opportunity to mimic true electrochemistry in TEM. However, there are challenges associated with optimizing hardware suitable for small volume and limited diffusion cell geometries of liquid cell system. Our newest Generation V liquid cell system has the capability to observe and measure full-cycle bulk-level electroanalytical data in-situ in the TEM.

The image on the top left shows an example of cyclic voltammetry curve obtained during the copper deposition/stripping cycle in liquid cell TEM. This curve obtained in the liquid TEM cell mimics the bulk data from the large volumetric cell exactly and therefore can be used as a representative characterization tool of the relevant chemistries.

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TEM Sample Transfer and Biasing in Gas

Hummingbird Scientific’s in-situ Gas cell holders can be used as biasing holders of samples in gas environments that also allow encapsulation and transfer of air-sensitive battery materials in an inert gas from the glovebox to the TEM. Thin film battery materials can be loaded in the gas holder in the glove box and moved to the TEM in fully protected environmental conditions. The inlet and outlet are capped airtight enabling sample transfer to the TEM without exposure in air. Electrical biasing experiments can be conducted in-situ in the TEM in this protective environment or other relevant environmental conditions can be created around the sample by flowing in or removing gasses.

The TEM image of the top left shows the atomic scale redox dynamics of Ag/AgCl heterostructures studied using in-situ TEM gas holder.

Reference: Yimin A. Wu, Liang Li, Zheng Li, Alper Kinaci, Maria K. Y. Chan, Yugang Sun, Jeffrey R. Guest, Ian McNulty, Tijana Rajh, and Yuzi Liu. “Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution,” ACS Nano (2016) pp. 3738-3746. Abstract

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Cross-Correlative Microscopy

Our TEM liquid holder is compatible with most Synchrotron X-Ray beamlines and SEMs. System features include:

Don’t see what you’re looking for? We would also be happy to develop a custom solution for you.

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Multi-Modal Liquid X-Ray Microscopy

Designed for X-ray microscopes and synchrotron beamlines, Hummingbird Scientific’s X-ray environmental cell systems use the same removable tip design of our liquid TEM holder, allowing for multi-modal electrochemistry experiments across x-ray and electron microscope platforms

Using the operando x-ray microscopy platform shown here, William Chueh and his team at Stanford mapped the dynamics of the Li composition and insertion rate in LixFePO4, and found that nanoscale spatial variations in rate and in composition control the lithiation pathway at the subparticle length scale.

Reference: J. Lim,Y. Li, D. H. Alsem, H. So, S. C. Lee, P. Bai, D.A. Cogswell, X. Liu, N. Jin, Y. Yu, N. J. Salmon, D. A. Shapiro, M. Z. Bazant, T.Tyliszczak, W. C. Chueh, “Origin and Hysteresis of Lithium Compositional Spatiodynamics Within Battery Primary Particles,” Science 353 (2016) pp. 566-571. Abstract

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Biologic Potentiostat

We are proud to collaborate with Bio-Logic to offer the Biologic SP-200 potentiostat as our recommended potentiostat for electrochemistry experiments. Hummingbird Scientific’s multi-modal set of electrochemistry characterization tools and Bio-Logic’s potentiostat can be used in combination for corrosion experiments, electro-catalysis, electrolysis, and battery and photovoltaic research.

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Bulk Electrochemistry in TEM

Replicating bulk electrochemistry data in TEM

Hummingbird Scientific’s newest Generation V in-situ liquid-electrochemistry TEM holder allows researchers for the first time to fully replicate bulk-level electrochemical details inside the transmission electron microscope. A newly developed hardware and cells allows quantitative measurements of electrochemical processes with details showing the complete electrochemical cycle, replicating the data of bulk samples.

As illustrated, a cyclic voltammetry (CV) study of a model compound 01.M copper sulfate showing plating and deposition of copper has been presented here. The copper deposition and stripping occurs at the Pt working electrode, mimicking bulk behavior.

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Electrochemistry Video Spotlight

Origin of Li charging and discharging of primary particles

Using Hummingbird Scientific liquid cell technology, Dr. William Chueh and his team at Stanford University built a transparent nano-battery in the synchrotron liquid-electrochemistry x-ray platform, taking advantage of the modularity of the tip design.

The video shows the evolution of Li composition for particles during lithiation at a rate of 2C. The hue represents the Li composition X, where red indicate X=1 and green indicate X=0. The brightness represents thickness of material. The position of each particle (outlined in white) relative to each other, and the dashed line indicates divisions. These results highlight the crucial role of surface reaction rate for lithiation, observing these inconsistencies of ion insertion have implications for electrode engineering and battery management for future generation battery technology.

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Selected Electrochemistry Publications

Nikhilendra Singh, Timothy S. Arthur, Oscar Tutusaus, Jing Li, Kim Kisslinger, Huolin L. Xin, Eric A. Stach, Xudong Fan, and Rana Mohtadi. “Achieving High Cycling Rates via In-situ Generation of Active Nanocomposite Metal Anodes.” ACS Applied Energy Materials (2018)	Abstract
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
Khim Karki, Tyler Mefford, Daan Hein Alsem, Norman Salmon and William C. Chueh. “Replicating Bulk Electrochemistry in Liquid Cell Microscopy.” Microscopy & Microanalysis (2018)	Abstract
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
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
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
Mingyuan Ge, Ming Lu, Yong Chu & Huolin Xin. “Anomalous Growth Rate of Ag Nanocrystals Revealed by in situ STEM,” Scientific Reports (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
Eli Fahrenkrug, Daan Hein Alsem, Norman Salmon and Stephen Maldonado. “Electrochemical Measurements in In Situ TEM Experiments,” Journal of The Electrochemical Society (2017)	Abstract
Fei-Hu Du, Yizhou Ni, Ye Wang, Dong Wang, Qi Ge, Shuo Chen, and Hui Ying Yang. “Green Fabrication of Silkworm Cocoon-like Silicon-Based Composite for High-Performance Li-Ion Batteries,” ACS Nano (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
Karalee Jarvis, Chih-Chieh Wang, María Varela, Raymond R. Unocic, Arumugam Manthiram, and Paulo J. Ferreira. “Surface Reconstruction in Li-rich Layered Oxides of Li-ion Batteries,” Chemsitry of Materials (2017)	Abstract
Edward R. White, Jared J. Lodico & B. C. Regan. “Intercalation events visualized in single microcrystals of graphite,” Nature Communications (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
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
J. Lim,Y. Li, D. H. Alsem, H. So, S. C. Lee, P. Bai, D.A. Cogswell, X. Liu, N. Jin, Y. Yu, N. J. Salmon, D. A. Shapiro, M. Z. Bazant, T.Tyliszczak, W. C. Chueh, “Origin and Hysteresis of Lithium Compositional Spatiodynamics Within Battery Primary Particles,” Science (2016)	Abstract
Yimin A. Wu, Liang Li, Zheng Li, Alper Kinaci, Maria K. Y. Chan, Yugang Sun, Jeffrey R. Guest, Ian McNulty, Tijana Rajh, and Yuzi Liu. “Visualizing Redox Dynamics of a Single Ag/AgCl Heterogeneous Nanocatalyst at Atomic Resolution,” ACS Nano (2016)	Abstract
J.H. Park, N.M. Schneider, J.M. Grogan, M.C. Reuter, H.H. Bau, S. Kodambaka & F.M. Ross, “Control of Electron Beam-Induced Au Nanocrystal Growth Kinetics through Solution Chemistry,” Nano Letters (2015)	Abstract
Raymond R. Unocic, Loïc Baggetto, Gabriel M. Veith, Jeffery A. Aguiar, Kinga A. Unocic, Robert L. Sacci, Nancy J. Dudney and Karren L. More. “Probing battery chemistry with liquid cell electron energy loss spectroscopy,” Chemical Communications (2015)	Abstract
M. Ge, Y. Lu, P. Ercius, J. Rong, X. Fang, M. Mecklenburg, and C. Zhou “Large-Scale Fabrication, 3D Tomography, and Lithium-Ion Battery Application of Porous Silicon” Nano Letters (2014)	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,” Chemical Communication (2014)	Abstract
P. Abellan, B. L. Mehdi, L.R. Parent, M. Gu, C. Park, W. Xu, Y. Zhang, I. Arslan, J.G. Zhang, C.M. Wang, J.E. Evans, and N.D. Browning. “Probing the Degradation Mechanisms in Electrolyte Solutions for Li-Ion Batteries by in Situ Transmission Electron Microscopy,” Nano Letters (2014)	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 Letters (2013)	Abstract
E.R. White, S.B. Singer, V. Augustyn, W.A. Hubbard, M. Mecklenburg, B. Dunn, and B.C. Regan,“In-Situ Transmission Electron Microscopy of Lead Dendrites and Lead Ions in Aqueous Solution,” ACS Nano (2012)	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,” Journal of Materials Research (2010)	Abstract

	Nano-Manipulator HolderSee More Site specific biasing of samples
	Electrical Biasing HolderSee More Thin films and cross-sectioned battery cells
	Tomography HolderSee More Pre or post-mortem material analysis
	Liquid Flow HolderSee More Imaging in volatile battery electrolytes
	Cryo Biasing HolderSee More Electrical biasing and imaging at cryo temperatures
	X-Ray/Synchrotron Liquid HolderSee More A complete in-situ x-ray lab system

Instrumentation for Ion and Electron Microscopy

Electrochemistry

Operando multi-modal imaging with bulk-level electrochemical data

Electrochemical characterization tool selector