In situ visualization of Li/Ag
 2
 VP
 2
 O
 8
 batteries revealing rate-dependent discharge mechanism

Kirshenbaum, Kevin; Bock, David C.; Lee, Chia‐Ying; Zhong, Zhong; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

doi:10.1126/science.1257289

Cited by 110 publications

(67 citation statements)

References 30 publications

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“…This is a remarkable result, which was not at all achievable by the corresponding "as-prepared" spray deposited LiFePO 4 -based electrode described by Zolin et al [48]. This also clearly enlightens the specific role of pyrolysed nanocellulose fibres, which combine the functions of strong binder and conducting additive without negatively affecting cycling stability and rate performance [49,50]. It is worthy to note that the system does not show any performance decay;…”

Section: Accepted Manuscriptmentioning

confidence: 82%

A simple route toward next-gen green energy storage concept by nanofibres-based self-supporting electrodes and a solid polymeric design

Zolin

Nair

Beneventi

et al. 2016

Carbon

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Section: Accepted Manuscriptmentioning

confidence: 82%

A simple route toward next-gen green energy storage concept by nanofibres-based self-supporting electrodes and a solid polymeric design

Zolin

Nair

Beneventi

et al. 2016

Carbon

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“…S1. After Ag NPs immersed into Co-2TPABTz, there is no distinct change in the Co-2TPABTz diffraction pattern, and all the major peaks belonged to Ag NPs are clearly identified [42]. No Ag 2 O diffraction peaks are observed for composites 1-3, because Ag NPs is absolutely coated with the help of Co-2TPABTz [43].…”

Section: Characterizationmentioning

confidence: 95%

Silver nanoparticles-sensitized cobalt complex for highly-efficient photocatalytic activity

Huo

Zeng

2016

Applied Catalysis B: Environmental

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“…However, at C/170 V 5+ reduction is preferred and charge transfer resistance increases significantly. In other silver vanadium phosphorous oxide cathodes with different stoichiometry, such as Ag 2 VO 2 PO 4 7,11,12,15,30,34 and Ag 2 VP 2 O 8 , 9,13,29,30 an initial decrease in the charge transfer resistance coincides with the reduction of Ag + to form conductive metallic silver. An increase in charge transfer resistance associated with V 5+ reduction is reminiscent of the 5× increase in charge transfer resistance during the reduction of ε-VOPO 4 .…”

Section: Discussionmentioning

confidence: 99%

“…Specifically, for battery systems used to power implantable cardioverter defibrillators (ICD), silver vanadium phosphate (Ag w V x P y O z , SVOP) materials have been shown to minimize cathode dissolution compared to the commercially utilized silver vanadium oxide cathode, [4][5][6] creating the potential for improved ICD batteries with extended longevity. [7][8][9][10][11][12][13][14][15] However, a significant limitation of phosphate-based cathodes is their inherently poor electrical conductivity. Silver vanadium phosphates are able to overcome this issue due to the incorporation of silver.…”

mentioning

confidence: 99%

Rate Dependent Multi-Mechanism Discharge of Ag_0.50VOPO₄·1.8H₂O: Insights from In Situ Energy Dispersive X-ray Diffraction

Huie

Bock

Zhong

et al. 2016

J. Electrochem. Soc.

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Ag 0.50 VOPO 4 · 1.8H 2 O (silver vanadium phosphate, SVOP) demonstrates a counterintuitive higher initial loaded voltage under higher discharge current. Energy dispersive X-ray diffraction (EDXRD) from synchrotron radiation was used to create tomographic profiles of cathodes at various depths of discharge for two discharge rates. SVOP displays two reduction mechanisms, reduction of a vanadium center accompanied by lithiation of the structure, or reduction-displacement of a silver cation to form silver metal. In-situ EDXRD provides the opportunity to observe spatially resolved changes to the parent SVOP crystal and formation of Ag 0 during reduction. At a C/170 discharge rate V 5+ reduction is the preferred initial reaction resulting in higher initial loaded voltage. At a discharge rate of C/400 reduction of Ag + with formation of conductive Ag 0 occurs earlier during discharge. Discharge rate also affects the spatial location of reduction products. The faster discharge rate initiates reduction close to the current collector with non-uniform distribution of silver metal resulting in isolated cathode areas. The slower rate develops a more homogenous distribution of reduced SVOP and silver metal. This study illuminates the roles of electronic and ionic conductivity limitations within a cathode at the mesoscale and how they impact the course of reduction processes and loaded voltage. Polyanion-type materials such as LiFePO 4 have been heavily researched as battery cathodes because of their impressive stability and high operating voltage relative to oxide based materials.1-3 The thermal stability of the polyanion framework improves battery safety especially under demanding conditions. Furthermore, chemical stability of the polyanion can reduce cathode dissolution relative to oxides, extending the battery's lifetime. Specifically, for battery systems used to power implantable cardioverter defibrillators (ICD), silver vanadium phosphate (Ag w V x P y O z , SVOP) materials have been shown to minimize cathode dissolution compared to the commercially utilized silver vanadium oxide cathode, 4-6 creating the potential for improved ICD batteries with extended longevity.7-15 However, a significant limitation of phosphate-based cathodes is their inherently poor electrical conductivity. Silver vanadium phosphates are able to overcome this issue due to the incorporation of silver. As SVOP compounds are reduced, silver is reduced in-situ, forming a conductive network of silver nanoparticles that can improve electrical conductivity by ∼15,000 fold.14 In-situ energy dispersive X-ray diffraction (EDXRD) is a powerful technique that can be used to better understand the mechanisms of electrochemical discharge in SVOP materials. EDXRD utilizes white, collimated X-rays as the incident beam, which is scattered by the sample. 16 The resulting diffraction patterns are distributed in the selected energy range and captured by a detector held at a fixed angle. The light source is synchrotron based in order to emit the high-energy radiation n...

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In situ visualization of Li/Ag ₂ VP ₂ O ₈ batteries revealing rate-dependent discharge mechanism

Cited by 110 publications

References 30 publications

A simple route toward next-gen green energy storage concept by nanofibres-based self-supporting electrodes and a solid polymeric design

A simple route toward next-gen green energy storage concept by nanofibres-based self-supporting electrodes and a solid polymeric design

Silver nanoparticles-sensitized cobalt complex for highly-efficient photocatalytic activity

Rate Dependent Multi-Mechanism Discharge of Ag_0.50VOPO₄·1.8H₂O: Insights from In Situ Energy Dispersive X-ray Diffraction

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In situ visualization of Li/Ag 2 VP 2 O 8 batteries revealing rate-dependent discharge mechanism

Cited by 110 publications

References 30 publications

A simple route toward next-gen green energy storage concept by nanofibres-based self-supporting electrodes and a solid polymeric design

A simple route toward next-gen green energy storage concept by nanofibres-based self-supporting electrodes and a solid polymeric design

Silver nanoparticles-sensitized cobalt complex for highly-efficient photocatalytic activity

Rate Dependent Multi-Mechanism Discharge of Ag0.50VOPO4·1.8H2O: Insights from In Situ Energy Dispersive X-ray Diffraction

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Product

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In situ visualization of Li/Ag ₂ VP ₂ O ₈ batteries revealing rate-dependent discharge mechanism

Rate Dependent Multi-Mechanism Discharge of Ag_0.50VOPO₄·1.8H₂O: Insights from In Situ Energy Dispersive X-ray Diffraction