Energy Archives - The Nano Future https://www.thenanofuture.com/category/energy/ Featuring applied nanotechnologies and their potential Wed, 20 Oct 2021 09:00:23 +0000 en-GB hourly 1 /usercontent.one/wp/www.thenanofuture.com/wp-content/uploads/2020/08/Logo_blk-150x150.png Energy Archives - The Nano Future https://www.thenanofuture.com/category/energy/ 32 32 An Innovative Way to Enhance the PV Response of a Ferroelectric Material https://www.thenanofuture.com/an-innovative-way-to-enhance-the-pv-response-of-a-ferroelectric-material/ https://www.thenanofuture.com/an-innovative-way-to-enhance-the-pv-response-of-a-ferroelectric-material/#respond Wed, 20 Oct 2021 08:47:53 +0000 https://www.thenanofuture.com/?p=990 Photo by Andreas Gücklhorn on Unsplash In the recent paper: “Strongly enhanced and tunable photovoltaic effect in ferroelectric-paraelectric superlattices (Jun 2021)”, researchers found a way to engineer a superlattice of ferroelectric BaTiO3 sandwiched between paraelectric SrTiO3 and CaTiO3 resulting in 1000 times higher photovoltaic (PV) effect than measured in regular BaTiO3 of a similar thickness. […]

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Photo by Andreas Gücklhorn on Unsplash

In the recent paper: “Strongly enhanced and tunable photovoltaic effect in ferroelectric-paraelectric superlattices (Jun 2021), researchers found a way to engineer a superlattice of ferroelectric BaTiO3 sandwiched between paraelectric SrTiO3 and CaTiO3 resulting in 1000 times higher photovoltaic (PV) effect than measured in regular BaTiO3 of a similar thickness. The result is intriguing since neither SrTiO3 nor CaTiO3 has a PV effect, except for SrTiO3 under extremely large strain gradients.

The PV effect is what is used in solar cells to create electricity from the sunlight. Whether a material is paraelectric or ferroelectric has to do with its polarization curve.

Furthermore, the paper investigates the PV effect across different temperatures and over long time periods. It shows a persistent enhancement over these variations and thereby robustness. Perhaps this technique can be used for creating more efficient solar cells in the future and contribute to a greener energy grid.

The paper, including a STEM image of the structure, can be found here:

https://www.science.org/doi/10.1126/sciadv.abe4206

If you’d like to learn more about nanotechnology, please subscribe to our newsletter and stay tuned for upcoming posts. Credit to Thomas Conrad for bringing the scientific paper to our attention.

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Revolutionizing Solar Cells with Quantum Dots https://www.thenanofuture.com/revolutionizing-the-photovoltaic-industry-with-quantum-dots/ https://www.thenanofuture.com/revolutionizing-the-photovoltaic-industry-with-quantum-dots/#respond Wed, 30 Dec 2020 09:46:54 +0000 https://www.thenanofuture.com/?p=821 Introduction The great aspect of solar cells is that they are producing non-polluting renewable energy by absorbing photons i.e. sunlight, and by extension converting the energy  of the photon to electrical energy for applications or conservation.  One of the main challenges in the photovoltaic industry is the 33% efficiency limit for any traditional solar cell […]

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Introduction

The great aspect of solar cells is that they are producing non-polluting renewable energy by absorbing photons i.e. sunlight, and by extension converting the energy  of the photon to electrical energy for applications or conservation. 

One of the main challenges in the photovoltaic industry is the 33% efficiency limit for any traditional solar cell [1], which is where quantum dot solar cells (QDSCs) come into the spotlight as a solution to break the efficiency limit. 

The efficiency limit is due to excess energy lost to heat (thermalization loss), which could have been utilized [2]. The QDSC solves this issue with “quantum confinement” which will be elaborated further in the following.

What are quantum dot solar cells?

Quantum dot solar cells utilize crystalline nanoparticles known as quantum dots (QDs) as the absorbing photovoltaic material, and are investigated to replace common bulk materials such as silicon. QDs are typically in the size of 1-10 nanometers and are made from semiconductor materials or metals, e.g. cadmium selenide (CdSe) and lead sulfide (PbS). 

One of the biggest attractive attributes of QDSCs, is that they can cover the whole spectrum of wavelengths from sunlight. This is possible since the band gap i.e. the absorption spectrum is related to the size of QDs due to the quantum confinement effect. Therefore, the band gap can be tuned to match the solar radiation spectrum by adjusting the size of QDs, thereby providing great flexibility of light absorption and better efficiency in solar power generation [3]. 

Quantum dots made from lead sulfide are of most interest due to its great tunability [4]. In the case of bulk materials, the band gap is fixed in terms of what material is used, which makes thermalization loss inevitable.

Due to the very small size of QDs, it is also possible to print them into thin flexible sheets and make transparent solar cells more of a reality. These could possibly be incorporated into screens or windows as a form of electricity generation. The technology has also improved substantially in terms of efficiency, from 2.7% in 2010 to a reported 16.6% in 2020 [5].

Technical specifications of QDSCs

The QDSC is typically sandwich structured, with a photoanode, a counter electrode and an electrolyte. The photoanode consists of a transparent conducting electrode (TCE, typically indium tin oxide glass) and a metal oxide semiconductor (usually TiO2) coated with a layer of quantum dots [3]. 

The photoanode is where the sunlight is absorbed and as a result generates both positively charged electron vacancies (holes) and negatively charged electrons in the solar cell. The positive charges are transferred between the photoanode and the counter electrode with the use of an electrolyte. 

The purpose of the counter electrode is to transfer electrons from the external circuit (the electrical device) to the electrolyte, which results in catalyzing the redox reactions of the electrolyte [3]. A schematic of the QDSC is shown on Figure 1. 

Figure 1: A schematic of the quantum dot solar cell, which shows all the main components of a QDSC. The electrons transfer from the photoanode through the external circuit to the counter electrode. 

Outlook on Market

QDSCs are currently yet to be commercially viable in mass scale due to substantial challenges, such as reducing QD material cost and developing high-throughput deposition methods for mass production [6]. Although, several small companies have begun to produce QDSCs with the most notable ones being QD Solar, and Solterra Renewable Technologies, a subsidiary of the QD mass-manufacturer Quantum Materials Corp. 

Solterra gets a headstart in the immature market currently and has accordingly the proprietary technology to mass-produce QDSCs at hundreds of meters per minute using roll-to-roll printing technology. [7]

End note

QDSCs are currently seen as the next generation of photovoltaic devices, which has the most potential to break the thermodynamic efficiency limit of 33% with its excellent optoelectronic properties and the use of quantum confinement. QDSCs also have a maximum potential conversion efficiency of 66%, which is double the possible efficiency of traditional single junction solar cells [8], demonstrating that quantum dots could be the future of solar power.

If you’d like to learn more about nanotechnology, please subscribe to our newsletter and stay tuned for upcoming posts.

Sources

[1] Rühle, Sven “Tabulated values of the Shockley–Queisser limit for single junction solar cells”, published in ScienceDirect (2016).

[2]  Semalti, Pooja et. al.  “Advancements in Quantum Dot Solar Cells: Synthesis and Applications”, published in Sigma-Aldrich (2020). 

[3] Technical University of Denmark (DTU): Department of Chemistry. “Chemistry at the Nanoscale: Chapter 4”. (2020)

[4] Lutfullin, Marat et. al. (King Abdullah University of Science and Technology) . “Quantum Dots for Electronics and Energy Applications”, published in Sigma-Aldrich (2020)

[5] Hutchins, Mark. PV Magazine. “A quantum dot solar cell with 16.6% efficiency”. (2020)

[6] Jean, Joel. “Getting high with quantum dot solar cells”. Published in Nature (2020).

[7] Solterra. “Solterra: Business Objective”. (2020)

[8] NREL. “Quantum Dots Promise to Significantly Boost Solar Cell Efficiencies” (2013).

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Lithium Sulfur the Next-Gen Lithium Ion Battery? https://www.thenanofuture.com/lithium-sulfur-the-next-gen-lithium-ion-battery/ https://www.thenanofuture.com/lithium-sulfur-the-next-gen-lithium-ion-battery/#respond Wed, 16 Dec 2020 07:19:14 +0000 https://www.thenanofuture.com/?p=804 The lithium ion battery chemistries are reaching their theoretical limits. The transition to sustainable energy sources such as solar- and wind power requires large energy storage systems to counter their intermittency. Furthermore, the electrification of the transportation sector increases the demand for higher specific capacities i.e., the capacity to weight ratio. The needs are right […]

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The lithium ion battery chemistries are reaching their theoretical limits. The transition to sustainable energy sources such as solar- and wind power requires large energy storage systems to counter their intermittency. Furthermore, the electrification of the transportation sector increases the demand for higher specific capacities i.e., the capacity to weight ratio. The needs are right now being met by lithium ion batteries but as they approach their limit it is necessary to either improve the existing battery chemistries or develop new ones [i]. The former has been presented here. The latter is the subject of this article.

The lithium sulfur (Li-S) battery chemistry where sulfur, and lithium metal, are used as the cathode and anode, respectively, is very promising due to its high theoretical energy density of 2600 Wh kg-1. The sulfur is very attractive as cathode material due to its high theoretical specific capacity of 1675 mAh g-1 which is six times higher than that of the common LiCoO2 cathode. Likewise lithium metal is attractive as anode material because of its specific capacity of 3860 mAh g-1 which is about ten times that of graphite which is used in most commercial lithium ion batteries. [i, ii, iii]
     Some of the challenges that keep Li-S batteries from commercialization are trying to be solved by employing nanostructured graphene and sulfur particles. The results are promising and have led to significant improvements in the last ten years.

Content

–          The working principle of the Li-S battery

–          Challenges with Li-S batteries and possible solutions

–          Concluding remarks

The Inner Workings of the Li-S Chemistry

The lithium sulfur battery cells are commonly composed of a sulfur cathode, a lithium metal anode, a separator, and an organic liquid electrolyte. When the cell is in its charged state, the sulfur will mainly be on the form: Octasulfur since it is the most stable configuration at room temperature [ii]. As the cell discharges, lithium ions and electrons move internally and externally, respectively, from the anode to the cathode. The electrons are inhibited from flowing through the electrolyte because of the separator as it is electrically insulating. When the lithium ions and electrons approach the sulfur cathode, the cyclic octasulfur molecules undergo reduction reactions i.e., the octasulfur molecules accept the electrons which reduces their oxidation level. These reductions result in structural changes in the sulfur molecules which facilitate the formation of lithium polysulfides. At first, these polysulfides will in the early stages of the discharge be on the form Li2S8 and Li2S6, but as the cell discharges further, more lithium ions and electrons arrive at the cathode which reduces the lithium polysulfides to Li2S4 and Li2S3. When the cell is completely discharged the cathode will consist of Li2S molecules [i, ii, iv].
    The sulfur is a conversion cathode material since it converts from cyclic octasulfur to the linear Li2S molecules. This is different from the intercalation mechanism being utilized in the common commercial lithium ion batteries.

The Intrinsic Challenges of the Li-S Chemistry

The lithium sulfur chemistry is subject to several issues that must be overcome or at least mitigated before commercialization is possible. One of the issues is that both sulfur and Li2S are electrical insulating which lowers the amount of sulfur/Li2S that partakes in the charging/discharging of the battery. The result of this issue is a lower capacity. Another issue is that the intermediate compounds, Li2S8, Li2S6, Li2S4, and Li2S3 are soluble in the organic electrolyte and will therefore, alongside lithium, shuttle between the anode and cathode where they participate in side reactions. These side reactions deteriorate the anode and the cathode. A third issue is the change in volume when the cathode converts between sulfur and Li2S which may result in structural degradation of the cathode. [i]
    These issues can be solved by encapsulating the nanosized sulfur particles with a material that can enhance the electrical conductivity, trap the soluble lithium polysulfides, and buffer the volume changes. Graphene and graphene oxide (GO) have both been shown to meet these requirements.[i]
    Graphene is a sheet of carbon atoms arranged in a honeycomb lattice. Graphene oxide is obtained by treating graphene with oxidizers which introduces oxygen and hydrogen groups, and structural defects into the lattice. The oxygen and hydrogen form functional groups which increase the trapping capability of lithium polysulfides. However, the electrical conductivity of graphene and GO is reduced when defects and functional groups are introduced. Another approach is to enhance the physical trapping by constructing porous graphene or GO structures. The pores can be divided into micro- (<2 nm), meso- (2-50 nm), and macropores (>50 nm). Micropores inhibit the diffusion of the lithium polysulfides, while the mesopores trap the polysulfides and increase the amount of sulfur/Li2S that partakes in the charging/discharging. The macropores do not trap the lithium polysulfides but act as a buffer for the volume change instead. [i]

Sulfur and graphene can be combined into different nanostructures. Three of the possible structures are shown in the figure below. The first structure is the in plane configuration where sulfur is deposited onto a sheet of graphene. This structure does not facilitate a strong trapping of the soluble polysulfides. The entrapment can be enhanced by using a sandwich structure where the sulfur is deposited between layers of graphene. This also ensures great electrical conductivity. The polysulfides can however escape through the edges of the sandwich structure. This leakage can be overcome by wrapping the sulfur with a graphene sheet as seen in the core-shell structure. The last structure is very promising as it traps the polysulfides to a great extent, can buffer the volume changes, and provides high sulfur loadings. The electrical conductivity is however lower compared to the in plane- and sandwich structure. This is due to the larger sulfide particles.


Schematic of three configurations of Li2S and graphene. Lithium and sulfur are depicted as orange and yellow, respectively. 

Porous 3D foams of graphene oxide have also been utilized. They show great sulfur loading but due to the increased weight of the cathode, the specific capacity is reduced. The structure can also be combined to achieve e.g., high electrical conductivity and great entrapment of the polysulfides. This complicates the production process which in turn increases the cost. [i]

Besides the challenges with the cathode, the lithium metal anode also poses a serious issue. Lithium is highly reactive and will therefore participate in undesired side reactions some of which consume electrolyte. When the Li-S battery charges, lithium ions are shuttled from the cathode to the anode where they form dendrites that can grow through the separator and cause an internal short circuit.
    These issues can be solved in multiple ways. One technique is to coat the surface of the lithium metal with a carbonaceous material such as carbon nanotubes, carbon nanofibers, or graphite particles. Other techniques involve changing from a liquid electrolyte to a solid or gel polymer-based one, or modifying the separator such that it blocks the soluble lithium polysulfides. [i, v]

Conclusion

The Li-S battery chemistry is promising due to the high theoretical energy density of 2600 Wh kg-1, their low cost, and environmental friendliness, but some major issues must be overcome before they can be commercialized [i]. Graphene and graphene oxide are promising candidates to solve the issues.
    Before the way for commercialization is paved the issues with the lithium polysulfides, the sulfur loading, and the stability of the lithium anode must be solved. However, since 2010 the lifespan and the capacity fade per cycle has increased and decreased, respectively, for Li-S batteries significantly showing that progress is being made. [i]

If you’d like to learn more about nanotechnology, please subscribe to our newsletter and stay tuned for upcoming posts.

References

[i] Yunya Zhang et al., “Graphene and its derivatives in lithium-sulfur batteries”, Materials Today Energi, 9, 2018, pp. 319-335
https://www.sciencedirect.com/science/article/abs/pii/S2468606918300728?via%3Dihub 

[ii] Arumugam Manthiram, Yongzhu Fu, and Yu-Sheng Su, “Challenges and Prospects of Lithium-Sulfur Batteries”, Accounts of Chemical Research, 46, 2013, pp. 1125-1134
https://pubs.acs.org/doi/10.1021/ar300179v 

[iii] Wei Zhao, Woosung Choi, and Won-Sub Yoon, “Nanostructured Electrode Materials for Rechargeable Lithium-Ion Batteries”, Journal of Electrochemical Science and Technology, 11, 2020, pp. 195-219
https://www.jecst.org/journal/view.php?number=335

[iv] Seung-Ho Yu et al., “Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries”, 51, Accounts of Chemical Research, 2018, pp. 273-281
https://pubs.acs.org/doi/10.1021/acs.accounts.7b00487

[v] Xiaosong Xiong et al., “Methods to Improve Lithium Metal Anode for Li-S Batteries”, Frontiers in Chemistry, 7, 2019, 827
https://www.frontiersin.org/articles/10.3389/fchem.2019.00827/full

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Pushing the Boundaries of Lithium-Ion Batteries With Nanotechnology https://www.thenanofuture.com/pushing-the-boundaries-of-lithium-ion-batteries-with-nanotechnology/ https://www.thenanofuture.com/pushing-the-boundaries-of-lithium-ion-batteries-with-nanotechnology/#respond Wed, 25 Nov 2020 06:16:15 +0000 https://www.thenanofuture.com/?p=765 Note: Image adopted from UCL Faculty of Mathematical and Physical Sciences at http://www.ucl.ac.uk/maps-faculty/potw/potw/potw1313 Today it is hard to imagine a world where smartphones, laptops, smartwatches, and electric vehicles are not rechargeable. This indispensable attribute is thanks to the lithium-ion battery (LIB) which was first commercialized by Sony and Asahi Kasei in 1991 [i]. Our demand […]

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Note: Image adopted from UCL Faculty of Mathematical and Physical Sciences at http://www.ucl.ac.uk/maps-faculty/potw/potw/potw1313

Today it is hard to imagine a world where smartphones, laptops, smartwatches, and electric vehicles are not rechargeable. This indispensable attribute is thanks to the lithium-ion battery (LIB) which was first commercialized by Sony and Asahi Kasei in 1991 [i]. Our demand for LIBs does not seem to decrease or stagnate as more personal devices and especially electric vehicles are introduced to the market. The global electric vehicle stock increased exponentially from 1.18 million in 2016 to 4.79 million in 2019 [ii] and the trend is expected to continue. Therefore, continuous development and improvement of LIBs are of great importance.

Content

–          The working principle of lithium-ion batteries

–          Nanostructured anode and cathode materials

–          Outlook at commercial products and the successor to lithium-ion batteries

Working Principle of Lithium-Ion Batteries

The common present-day LIBs are similar to the ones commercialized in 1991 and are composed of two electrodes, a separator, and a liquid electrolyte, as seen in the figure below.

The positive electrode (cathode) is commonly a lithium metal oxide such as LiCoO2 while the negative electrode (anode) is made from graphite. When the LIB is charged the lithium ions shuttle from the cathode to the anode while electrons are moved away from the cathode and supplied at the anode.
    When the LIB is discharged the process is reversed and the lithium ions shuttle internally from the anode to the cathode where they intercalate. The electrons move externally from the anode to the cathode and as they move, they can be used to power a device such as a smartphone. The capacity of the LIB is hence limited by the amount of lithium that can be stored in the cathode and the anode structure. It can be increased by enlarging the batteries but since this is often not desired, much attention is given to increase the capacity per kilogram of battery i.e. the specific capacity.
    This can be done by creating new cathode and anode compounds which can accommodate more lithium per kilogram. However, this often comes with great challenges e.g. silicon as an anode material has about ten times higher specific capacity compared to graphite but it suffers from drastic volume changes during charge/discharge [iii]. Another way to increase the specific capacity is to optimize the structure of the anode and cathode material such that a larger portion of it participates in the intercalation process.

Nanostructured Anode and Cathode

The anode in commercial LIBs is based on graphite which is the same material used in pencils. It is used due to its price, availability, and relatively good theoretical specific capacity of 372 mAh g-1 [iv]. Despite the success graphite has had, it is still relevant to improve the anode in terms of e.g. the specific capacity. Some of the promising nanostructured carbon allotropes that could be used instead are: Carbon nanotubes (CNTs), graphene nanosheets, and carbon with nanosized pores. [iv]
    It has been demonstrated that the CNTs, which are rolled sheets of graphene, can accommodate lithium ions both on the inside and outside, and that they have excellent electronic conductivity. It was also reported that by introducing defects into the CNTs the capacity improved. [iv]
    Another option is graphene nanosheets, which can be prepared by exfoliation from bulk graphite since it is composed of stacked layers of graphene. Similar to the CNTs the surface area is greater compared to graphite and since both the plane and the edge of the nanosheets can accommodate lithium ions the theoretical specific capacity can reach 744 mAh g-1. Furthermore, it can be increased to over 1000 mAh g-1 by introducing defects. One of the difficulties with graphene is its low density and hence it requires a larger anode volume which ultimately leads to a larger battery. Another difficulty is that it participates in undesired reactions leading to irreversible loss of capacity. [iv]
    A third alternative is to create nanosized pores in carbonaceous materials. One approach is to make hollow spheres with a double-shelled nanostructure which increases the surface area and thus the specific capacity. The specific capacity for such a structure has been reported to reach 920 mAh g-1. However, the increased surface area inevitably results in obstacles and defects which may trap lithium ions which in turn causes an irreversible capacity loss. [iv]

While the anode material is based on carbon, the cathode material in common commercial LIBs is in general either a lithium metal oxide such as LiCoO2 (which was introduced by J. B. Goodenough and was the first commercial cathode) and LiNiMnCoO2,  or a phosphate-based compound such as LiFePO4. These cathode materials are used today along with multiple other types depending on the desired voltage and working environment. LiCoO2 and LiNiMnCoOare some of the most common cathode materials due to their great specific capacity of about 150 mAh g-1, and good cyclability. They, however, rely on cobalt which is expensive, toxic, and poses both environmental and health concerns due to the conditions in which it is mined and extracted.
    In order to lower the amount of cobalt and increase the specific capacity, it has been proposed to substitute some of the cobalt with manganese (Mn) and Nickel (Ni). It has been reported that a nanosheet structure of LiNi1/3Co1/3Mn1/3O2 with width and thickness of 0.7-1.5 µm and 10-100 nm, respectively, delivered an increased specific capacity of 193 mAh g-1. This is due to the high surface area of the nanosheets. [iv]

Outlook

Many of the nanostructured cathode and anode materials are still in the research phase but some have already been commercialized. An example is a LiFePO4/Graphite based LIB from LithiumWerks which utilizes their trademarked Lithium Nanophosphate technology [v]. Another example is the porous carbon material usable in both the anode and cathode developed by Graphene Batteries [vi].

Lithium-Ion batteries have and will be important for our transition to green energy but as our demand for inter alia higher capacities and higher power output keeps increasing we may have to look towards other materials for both the anode, cathode, and the electrolyte. This will give us new problems which we have to overcome, perhaps through nanostructuring?

If you’d like to learn more about nanotechnology, please subscribe to our newsletter and stay tuned for upcoming posts.

References    

[i] George Crabtree, Elizabeth Kócs, and Lynn Trahey, ”The energy-storage frontier: Lithium-ion batteries and beyond”, MRS Bulletin, 40, 2015, pp. 1067-1078
https://www.cambridge.org/core/journals/mrs-bulletin/article/energystorage-frontier-lithiumion-batteries-and-beyond/A0CE1F1D2F344EB6B362DA3C29DC2BD1/core-reader

[ii] International Energy Agency, “Global EV Outlook 2020 – Entering the decade of electric drive?”, Technology report, 2020
https://www.iea.org/reports/global-ev-outlook-2020

[iii] Xuefeng Song, Xiaobing Wang, Zhuang Sun, Peng Zhang, and Lian Gao, “Recent Developments in Silicon Anode Materials for High Performance Lithium-Ion Batteries”, Merck, [Accessed on: 08/11-2020]
https://www.sigmaaldrich.com/technical-documents/articles/materials-science/recent-developments-in-silicon-anode-materials.html

[iv] Wei Zhao, Woosung Choi, and Won-Sub Yoon, “Nanostructured Electrode Materials for Rechargeable Lithium-Ion Batteries”, Journal of Electrochemical Science and Technology, 11, 2020, pp. 195-219
https://www.jecst.org/journal/view.php?number=335

[v] LithiumWerks, [Accessed on: 08/11-2020]
https://lithiumwerks.com/

[vi] Graphene Batteries, [Accessed on: 08/11-2020]
https://www.graphenebatteries.no/

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Fuel cell electrocatalysts in nanoscale https://www.thenanofuture.com/nanocatalysts-in-hydrogen-fuel-cells/ https://www.thenanofuture.com/nanocatalysts-in-hydrogen-fuel-cells/#comments Wed, 14 Oct 2020 06:44:43 +0000 https://www.thenanofuture.com/?p=648 Hydrogen fuel cells (HFCs) are devices that use hydrogen as a fuel to generate electricity and have great potential for automotive applications and drones. Catalysts are used to power the reactions in the HFC and currently nanotechnology plays a major role in constructing cheaper electrocatalysts. Content What are hydrogen fuel cells? Nanoscale catalysts – Pt-dispersed […]

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Hydrogen fuel cells (HFCs) are devices that use hydrogen as a fuel to generate electricity and have great potential for automotive applications and drones. Catalysts are used to power the reactions in the HFC and currently nanotechnology plays a major role in constructing cheaper electrocatalysts.

Content

  • What are hydrogen fuel cells?
  • Nanoscale catalysts – Pt-dispersed on carbon nanotubes
  • Nanoscale catalysts – non-precious metal (NPMCs) and metal-free catalysts (MFCs)
  • Outlook on hydrogen fuel cells

What are hydrogen fuel cells? [i, ii, iii,iv]

HFCs utilize hydrogen as an energy carrier to produce electricity that can be used in various applications. The HFC is an electrochemical device that converts the chemical energy in hydrogen directly to electrical energy that can be used to power a motor without combustion. This makes the HFC a very attractive replacement to combustion engines, as the HFC only emits water vapor as a waste product. What makes HFCs very advantageous in automotive applications compared to purely electrical storage is the potential high ranges. This has been applied to drones, planes, trucks, and cars 

One of the most researched types of the HFC is the polymer electrolyte membrane fuel cell (PEMFC) due to its low operating temperature, very high efficiency, and low weight [i]. However, because of its low operating temperatures, the PEMFC needs a catalyst to generate useful currents due to sluggish kinetics [ii]. The most commonly used catalysts are made from platinum due to its high catalytic activity, but is expensive and of limited supply [iii], which makes it difficult for HFCs to be commercialized. Specifically, state-of-the-art platinum-based catalysts make around 25% of the overall fuel cell stack cost. [iv]

The solution to lowering costs is the use of nanotechnology. This is because most of the reactions in HFCs take place at the catalyst surface and by decreasing the size of it, you get a larger surface area per volume and therefore less material is used. 

Nanoscale catalysts – Pt-dispersed on carbon nanotubes [iii, v]

One of the most promising nanotechnologies to decrease the amount of Pt is the use of multi-walled carbon nanotube-graphene complexes (MWCNTs) atomically dispersed with Pt nanoparticles, which can overall increase the performance of catalysts. [iii] CNTs are cylinder-rolled graphene sheets i.e. carbon sheets with diameters in the range of a nanometer, in which MWCNTs consist of multiple rolled layers of graphene. The MWCNTs are used as catalyst supports in this case and have excellent electron conductivity, and with its high dispersion capability and surface area, less Pt is used and the large surface area ensures a high active site density. [v]

This nanotechnology can greatly reduce the amount of Pt used in the catalyst to 0.06 mg Pt per square meters from 0.125 mg Pt per square meters, a Pt reduction of 52%! [iii] However, MWCNTs do not exclude Pt totally, but they reduce the cost greatly and this is great for the commercialization of HFCs. 

Nitrogen doped on Pt-supported MWCNTs have also been introduced as a means to further increase performance by 8% in terms of maximum power density [iii], as nitrogen can enhance the properties of graphene. Additionally, there is currently research on whether Pt can be totally disregarded in catalysts, as to further reduce production costs of HFCs. 

Nanoscale catalysts – non-precious metal (NPMCs) and metal-free catalysts (MFCs) [vi, vii, viii, ix]

Current and past research shows that it is possible to build non-Pt solutions, which in favor avoids the cost of platinum altogether. However, catalyst activity and stability earlier were shown to be far more inferior compared to Pt-based catalysts in terms of kinetics. 

The earliest solutions utilized molecular catalysts such as iron-nitrogen complexes, but massive progress has been done with the introduction of N-doped carbon nanomaterials [vii, viii]. One of the most promising technologies is the transition metal-nitrogen-carbon catalyst due to it showing sufficient potential in durability and catalytic activity, in which iron is mostly used. [vi, vii]

However, the poor stability in PEMFC exhibits one of the greater challenges for NPMCs, which makes NPMCs not an ideal choice for PEMFCs currently. MFCs currently show interest and great promise in PEMFCs, as an N-doped CNT catalyst shows a stable PEMFC performance, though at a low activity [viii]. 

Outlook on hydrogen fuel cells 

Hydrogen fuel cells are slowly beginning to be commercialized and with solutions to the challenges of catalyst cost, the implementation can be accelerated. There are also other challenges to fuel cells than cost that affect their commercialization and attraction, such as carbon-monoxide poisoning, high energy cost of storage, and the use of mostly fossil fuels to produce hydrogen due to electrolysis having a kinetically sluggish oxygen evolution reaction (OER) [ix] etc. 

However, most of those challenges can be solved with nanotechnology, e.g. with electrolysis, the implementation of nanocatalysts can make electrolysis a more attractive option or the use of nanoparticles in photoelectrochemical water splitting can make hydrogen production more environmentally friendly [x]. While it is tempting to look at other energy options due to challenges of the HFC technology at present, the future advantages of the technology make it worth the investment in nano-solutions to solve them.

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References

[i] Dicks, Andrew L. Rand, David A. J.. (2018). Fuel Cell Systems Explained (3rd Edition). John Wiley & Sons. Retrieved from https://app.knovel.com/hotlink/toc/id:kpFCSEE01P/fuel-cell-systems-explained/fuel-cell-systems-explained 

[ii] Chen, Yuanjun et. al (2018). Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell. Retrieved from https://www.nature.com/articles/s41467-018-07850-2 

[iii] Lou, Chong et. al (2014). A Review of the Application and Performance of Carbon Nanotubes in Fuel Cells. Retrieved from https://www.hindawi.com/journals/jnm/2015/560392/ 

[iv] Technische Universität Darmstadt (2020). Investigation of the degradation process of non-precious metal catalysts (NPMC) for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEM-FC). https://www.mawi.tu-darmstadt.de/ekat/ekat/research_2/stabilization/index.en.jsp 

[v]  Gupta, Chanchal et. al (2016). Development of multiwalled carbon nanotubes platinum nanocomposite as efficient PEM fuel cell catalyst. Retrieved from https://link.springer.com/article/10.1007/s40243-015-0066-5

[vi] Shen, Yue et. al (2014). Pt Coated Vertically Aligned Carbon Nanotubes as Electrodes for Proton Exchange Membrane Fuel Cells. Retrieved from https://www.sciencedirect.com/science/article/pii/S1877705813018134 

[vii] Asset, Tristan et. al (2020). Iron-Nitrogen-Carbon Catalysts for Proton Exchange Membrane Fuel Cells. Retrieved from https://www.cell.com/joule/pdf/S2542-4351(19)30587-2.pdf 

[viii] Xei, Longfei et. al (2018). Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells. Retrieved from https://www.nature.com/articles/s41467-018-06279-x 

[ix] Cheng, Yi et. al (2015). Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes. Retrieved from https://www.sciencedirect.com/science/article/pii/S1002007115001264 

[x] Mao, Samuel S. (2012). Nanomaterials for renewable hydrogen production, storage and utilization. Retrieved from https://www.sciencedirect.com/science/article/pii/S1002007112001463

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