Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries

Zargouni, Yafa; Deheryan, Stella; Radisic, Aleksandar; Alouani, Khaled; Vereecken, Philippe M.

doi:10.3390/nano7060126

Cited by 9 publications

(9 citation statements)

References 79 publications

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“…[47,48] The MnO2 films are deposited by electrochemical deposition (ECD) where excellent conformality is obtained due to the resistive nature of the MnO2. [36,49] Alternatively, conformal MnO2 (and MnO) films can also be obtained by ALD. [50] Using 3D ECD MnO2 films converted to LiMn2O4, already a footprint capacity of 500 µAh cm -2 is shown for a 350 nm thin film.…”

Section: Cathodesmentioning

confidence: 99%

Advances in 3D Thin‐Film Li‐Ion Batteries

Moitzheim

Put

Vereecken

2019

Adv Materials Inter

102

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The status and progress toward solid‐state 3D thin‐film Li‐ion microbatteries is reviewed. Planar thin‐film batteries (TFBs) are commercially available. A major issue with planar TFBs, however, is that the total footprint capacity is limited, as only a relatively small electrode volume is available for energy storage. Coating of the complete battery thin‐film stack, i.e., cathode/solid electrolyte/anode, over a 3D microstructured current collector substrate can provide higher footprint capacity as a result of the surface area enhancement. However, thus far, no 3D TFB with footprint capacity exceeding the limit of ≈250 µAh cm−2 are achieved. The authors provide a status of the individual components: thin‐film cathodes, anodes, and thin‐film solid electrolyte conformally coated over 3D substrates with periodic microstructures. Guidance for designing a 3D TFB with optimum capacity is also provided.

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Section: Cathodesmentioning

confidence: 99%

Advances in 3D Thin‐Film Li‐Ion Batteries

Moitzheim

Put

Vereecken

2019

Adv Materials Inter

102

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“…Concerning the electron transfer between the semiconductive MnO 2 and the current collector, a few studies have reported on the poor adhesion and mechanical stability of MnO 2 on conductive substrates of various chemical composition and roughness. , Furthermore, because of the moderate electronic conductivity (10 –3 –10 –4 S·cm –1 ) of MnO 2 , , the ohmic drop is expected to rise together with the film thickness. All these issues can potentially be solved by using a 3D nanostructured current collector, with a high aspect ratio, well-suited for the conformal electrodeposition of thin films of MnO 2 to provide shorter ion diffusion distances and better electron harvesting paths. , Previously, such a strategy has been successfully exploited to improve the performances of MnO 2 -based supercapacitors − as well as MnO 2 cathodes toward reversible Li + insertion in organic electrolytes …”

Section: Introductionmentioning

confidence: 99%

Nanostructured Electrode Enabling Fast and Fully Reversible MnO₂-to-Mn²⁺ Conversion in Mild Buffered Aqueous Electrolytes

Mateos

Harris

Limoges

et al. 2020

ACS Appl. Energy Mater.

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On account of their low-cost, earth abundance, eco-sustainability, and high theoretical charge storage capacity, MnO 2 cathodes have attracted a renewed interest in the development of rechargeable aqueous batteries. However, they currently suffer from limited gravimetric capacities when operating under the preferred mild aqueous conditions, which leads to lower performance as compared to similar devices operating in strongly acidic or basic conditions. Here, we demonstrate how to overcome this limitation by combining a well-defined 3D nanostructured conductive electrode, which ensures an efficient reversible MnO 2-to-Mn 2+ conversion reaction, with a mild acid buffered electrolyte (pH 5). A reversible gravimetric capacity of 560 mA•h•g-1 (close to the maximal theoretical capacity of 574 mA•h•g-1 estimated from the MnO 2 average oxidation state of 3.86) was obtained over rates ranging from 1 to 10 A•g-1. The rate capability was also remarkable, demonstrating a capacity retention of 435 mA•h•g-1 at a rate of 110 A•g-1. These good performances have been attributed to optimal regulation of the mass transport and electronic transfer between the three process actors, i.e. the 3D conductive scaffold, the MnO 2 active material filling it, and the soluble species involved in the reversible conversion reaction. Additionally, the high reversibility and cycling stability of this conversion reaction is demonstrated over 900 cycles with a Coulombic efficiency > 99.4 % at a rate of 44 A•g-1. Besides these good performances, also demonstrated in a Zn/MnO 2 cell configuration, we discuss the key parameters governing the efficiency of the MnO 2-to-Mn 2+ conversion. Overall, the present study provides a comprehensive framework for the rational design and optimization of MnO 2 cathodes involved in rechargeable mild aqueous batteries.

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“…Similar deposition was also achieved with C-coated Si pillars as demonstrated in our earlier work. 26 Ability to conformally coat high-aspect ratio structures opens up a variety of new applications of EMD material, including Li-ion batteries with increased battery capacity due to surface microstructuring.…”

Section: Porosit Y = 100% · (1 − R B S F Ilm Thickness/s E M F Ilm Thmentioning

confidence: 99%

Electrodeposition of Adherent Submicron to Micron Thick Manganese Dioxide Films with Optimized Current Collector Interface for 3D Li-Ion Electrodes

Timmermans

Labyedh

Mattelaer

et al. 2017

J. Electrochem. Soc.

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Three-dimensional (3D) configuration of high-performance energy storage devices has been the subject of ongoing investigations targeting their integration in autonomous microelectronic systems. In this study we demonstrate a route toward the realization of high capacity cathode material for 3D thin-film lithium-ion (Li-ion) batteries. Electrolytic manganese dioxide (EMD) film can be applied as a Li-ion intercalation electrode upon its conversion to lithium manganese dioxide (LiMn 2 O 4 or LMO) by solid-state reaction. The main challenges of depositing thicker EMD film directly on the current collector often lay in achieving a good film adhesion and preventing oxidation of non-noble current collectors such as TiN, Ni. To improve the adhesion of the EMD films we modify the surface of the current collector by means of thin-film or seed layer coatings, which also prevent the oxidation of the underlying current collector substrate during the anodic deposition process. As a result submicron to micron thick EMD films with good adhesion were deposited on various current collectors. The acidity of the electrolyte solutions was varied depending on the type of the surface coating or current collector used. The mechanism of the EMD film growth and morphology on different substrates was examined. Compatibility of the proposed current collector interface modification for the electrodeposition of conformal thick EMD films on high-aspect ratio microstructures was demonstrated. A method of EMD film conversion to LMO at low-temperature on different substrates was shown as the path toward their application in 3D Li-ion batteries. Emerging electronic microsystems such as autonomous sensor systems for smart environments, body area networks, biomedical devices for lab-on-chip diagnosis and implants require onboard microstorage. For such applications the development of powerful, small and intrinsically safe batteries with sufficient storage capacity and long lifetime is critical. The key enabler to address the energy and power demands of footprint-limited autonomous devices is a three-dimensional (3D) configuration of energy storage devices such as lithium-ion (Li-ion) batteries and supercapacitors, where thin-film material is coated on a microstructured current collector.1-3 The surface area enhancement associated with 3D structuring not only provides more material for the same footprint, but also increases the interface between the active electrode material and the electrolyte, thus reducing the cell resistance and providing more surface for reversible insertion and extraction of Li ions. 4 As opposed to nanostructured electrode configuration, 3D microstructuring of energy storage devices allows to increase the thickness of active layers for improved areal capacitance. However, conformal deposition of films with good adhesion on industrially-relevant current collectors is an essential requirement and still remains a challenge.Manganese dioxide (MnO 2 ) has been widely explored for energy storage systems as a potential cathode materi...

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Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries

Cited by 9 publications

References 79 publications

Advances in 3D Thin‐Film Li‐Ion Batteries

Advances in 3D Thin‐Film Li‐Ion Batteries

Nanostructured Electrode Enabling Fast and Fully Reversible MnO₂-to-Mn²⁺ Conversion in Mild Buffered Aqueous Electrolytes

Electrodeposition of Adherent Submicron to Micron Thick Manganese Dioxide Films with Optimized Current Collector Interface for 3D Li-Ion Electrodes

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Electrolytic Manganese Dioxide Coatings on High Aspect Ratio Micro-Pillar Arrays for 3D Thin Film Lithium Ion Batteries

Cited by 9 publications

References 79 publications

Advances in 3D Thin‐Film Li‐Ion Batteries

Advances in 3D Thin‐Film Li‐Ion Batteries

Nanostructured Electrode Enabling Fast and Fully Reversible MnO2-to-Mn2+ Conversion in Mild Buffered Aqueous Electrolytes

Electrodeposition of Adherent Submicron to Micron Thick Manganese Dioxide Films with Optimized Current Collector Interface for 3D Li-Ion Electrodes

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Nanostructured Electrode Enabling Fast and Fully Reversible MnO₂-to-Mn²⁺ Conversion in Mild Buffered Aqueous Electrolytes