Robust iron nanoparticles with graphitic shells for high-performance Ni-Fe battery

doi:10.1016/j.nanoen.2016.09.029

Nano Energy

Volume 30, December 2016, Pages 217-224

https://doi.org/10.1016/j.nanoen.2016.09.029 Get rights and content

Highlights

•
Low-cost synthesis of iron nanoparticles coated with graphitic carbon shells by pyrolyzing a polymeric precursor.
•
The robust graphitic carbon shells protect the iron nanoparticles and improve the electrochemical performance.
•
Full Ni-Fe battery assembled from the as-prepared electrodes delivers high energy/power density and long cycling lifetime.

Abstract

Aqueous Ni-Fe battery with high safety and low cost is a promising candidate for large-scale electrical energy storage; their performance, however, has been limited by the poor performance of the Fe electrodes. We reported herein a facile synthesis of Fe particles coated with graphitic shell for high-performance Fe anodes. The anodes exhibit a high capacity of 224 mAh g⁻¹ at a high current density of 32 A g⁻¹, and a high capacity retention of 90% after 1000 cycles. When coupled with a cathode made from the composites of Ni(OH)₂ and nitrogen-doped graphene, the battery delivers a high energy density of 136.7 Wh kg⁻¹ at power density of 0.7 kW kg⁻¹ or 71.4 Wh kg⁻¹ at 11.7 kW kg⁻¹ (based on the total mass of active materials). This work provides highly promising materials towards better Ni-Fe batteries.

Graphical abstract

A robust Fe anode consists of Fe nanoparticles with graphitic shells is obtained by pyrolysis of homogenous polymeric complexes containing iron salts, which exhibits an excellent high-rate performance and long-term cycling stability. A high-performance full Ni-Fe battery is demonstrated by using the as-prepared Fe anode. This work provides highly promising materials towards better Ni-Fe batteries.

Introduction

There are increasing demands for electrochemical devices for electric vehicles, renewal energy storage and grid-energy storage [1], [2], [3], [4], [5], [6], [7], [8]. Particularly, for large-scale grid storage, it is of paramount importance to develop low-cost and non-flammable storage devices [2], [3], [4], [5]. In this context, aqueous-based batteries, such as Ni-Fe battery, hold the most promise [5], [9], [10], [11], [12]. Ni-Fe battery is also known as the Edison battery with a theoretical energy density of 267 Wh kg⁻¹, having the required characteristics (e.g., good safety and reliability, low cost, and a long service life with simple maintenance) [10], [11], [12], [13], [14], [15]. Commercial Ni-Fe batteries, however, generally show low energy/power density (e.g., ~30–50 Wh kg⁻¹ with ~3–50 W kg⁻¹) and low efficiencies (~60%), which are mainly due to the poor conductivity of the electrodes (e.g., Ni(OH)₂ and Fe(OH)₂) and hydrogen evolution in the anode, respectively [9], [11], [12], [13], [14], [15]. Developing Ni-Fe batteries with improved performance holds great promise for a broad range of applications [5], [10], [13], [14], [15], [16], [17].

Extensive work has been conducted to improve the performance by constructing carbon-based composites with better conductivity and mechanical robustness [10], [16], [17]. For example, composites of carbon nanotubes (CNTs) and Ni(OH)₂, as well as composites of FeO_x/graphene were synthesized by reacting the inorganic precursors in the presence of CNTs or graphene. The resulted cells could provide an energy density >120 Wh kg⁻¹ and power density >15 kW kg⁻¹. However, the capacity retention for the anode was only ~85% after 300 cycles, possibly due to the poor interface between the conducting moieties and the oxides [10]. Similar composites were also synthesized by direct growth of Ni(OH)₂ or Fe₂O₃ on the graphene foams/CNTs films, which resulted in cells with an energy density of 100.7 Wh kg⁻¹ at 287 W kg⁻¹ or 70.9 Wh kg⁻¹ at 1.4 kW kg⁻¹. This approach provided better interfaces between the conductive frameworks and the oxides, resulting in better capacity retention (~ 96% after 1000 cycles). However, the resulted anodes mainly consist of Fe₂O₃, which showed low capacity and rate performance (~109 mAh g⁻¹ at a current density of 4 A g⁻¹ and 278 mAh g⁻¹ at 1 A g⁻¹) [17].

Herein, we report the synthesis of high-performance Fe anode particles from homogenous polymeric complexes containing iron salts. As illustrated in Fig. 1, through mixing poly(acrylic acid) (PAA) and FeCl₃ in solution, electrostatic interaction between the negatively charged carboxylic groups (COO^-) of PAA and the positively charged iron cations (e.g., Fe(OH)²⁺, Fe(OH)₂⁺ or iron-chloride complexes) leads to the formation of gels with homogeneous distribution of the Fe salt [18]. Catalyzed by the Fe salt during the carbonization, PAA is converted to graphite-rich carbon. While the Fe-polymer complexes are gradually converted to Fe nanoparticles, during which the growth of Fe particles is limited by the carbon formation. This unique process leads to the formation of Fe nanoparticles uniformly coated with graphitic carbon. Such robust carbon coatings not only provide the Fe anodes with outstanding conductivity, but also retard the degradation of the Fe nanoparticles during charging/discharging process, leading to Fe anodes with high energy and power density, as well as high cycling stability.

Section snippets

Synthesis of carbon-coated Fe nanoparticles

Poly(acrylic acid) (PAA) was dissolved in water by stirring to achieve a concentration of 5 wt%. NaOH solution (1 M) was then added to the PAA solution and adjusted the pH to 7. After stirring the solution for 0.5 h, FeCl₃ was added with a PAA to FeCl₃ molar ratio of 2:1, and the PAA-FeCl₃ gel was formed. The gel was centrifugally washed for several times with water and dried at 80 °C in a drying oven. Then the product was annealed at 550 °C for 2 h followed by 900 °C for 3 h under nitrogen atmosphere

Materials characterizations

The X-ray diffraction (XRD) pattern in Fig. 2a confirms that the as-prepared sample contains Fe as the major phase, as well as Fe₃C and partly graphitized carbon. Fig. 2b shows Raman spectrum of the composite particles, in which three distinguishable peaks at about 1350 cm⁻¹, 1580 cm⁻¹ and 2690 cm⁻¹ are corresponding to D-band, G-band and 2D-band, respectively. The d-band is associated with defective graphitic structures, while the G-band is a characteristic feature of the graphitic layers and

Conclusion

In conclusion, a high-performance Fe anode is obtained through a facile and cost-effective route by pyrolysis of homogenous polymeric complexes containing iron salts. The resulting Fe-anode material consists of Fe nanoparticles fully coated and interconnected by graphitic carbon. The robust carbon shells can effectively restrain the deformation of the Fe nanoparticles, while the continuous carbon matrix serves as effective networks for facile electron transfer in the electrode. As a result,

Acknowledgments

This work was financially supported in part by the scholarship from China Scholarship Council (No. 201306770015), the Key Scientific Project of Wuhan City (No. 2013011801010598) and the Scientific Project of AQSIQ (No. 2013IK093).

Xu Wu is currently a Ph.D candidate under the supervision of Prof. Jisheng Chen and Zhihong Zhu in Central China Normal University. He joined Professor Yunfeng Lu's group as a visiting Ph.D candidate from 2013 to 2015 in the Department of Chemical and Biomolecular Engineering, University of California, Los Angeles. His research focuses on nanomaterials for electrochemical energy storage, especially rechargeable batteries and supercapacitors.

References (37)

Z. Chen et al.
Adv. Energy Mater.
(2011)
J. Liu et al.
Energy Environ. Sci.
(2014)
C. Chakkaravarthy et al.
J. Power Sources
(1991)
A.K. Shukla et al.
J. Power Sources
(1994)
Z.L. Liu et al.
Chem. Commun.
(2011)
C. Guan et al.
ACS Nano
(2015)
R. Li et al.
Adv. Funct. Mater.
(2015)
J.L. Liu et al.
Nano Lett.
(2014)
L.-Å. LINDÉN et al.
J. Appl. Polym. Sci.
(1993)
L. Öjefors
J. Electrochem. Soc.
(2012)
D. Lei et al.
(2016)
C. Long et al.
ACS Nano
(2013)
H.D. Liu et al.
Electrochim. Acta
(2014)
F.P. Pan et al.
(2013)

J. Yan et al.

Adv. Funct. Mater.

(2012)

H.B. Wu et al.

Energy Environ. Sci.

(2013)

M. Armand et al.

Nature

(2008)

B. Dunn et al.

Science

(2011)

L. Suo et al.

Science

(2015)

Z. Yang et al.

Chem. Rev.

(2011)

H.L. Wang et al.

Chem. Soc. Rev.

(2013)

W. Li et al.

Science

(1994)

K.T. Chau et al.

Energy Convers. Manag.

(1999)

Z. Chen et al.

Adv. Mater.

(2012)

Cited by (75)

A space-confined strategy towards stable α/β-Bi<inf>2</inf>O<inf>3</inf> heterojunction anode for high-energy aqueous battery
2023, Journal of Colloid and Interface Science
It is very necessary to design a high-capacity and stable Bi₂O₃ anode for nickel-bismuth (Ni//Bi) batteries. In this work, a stable α- and β- phase Bi₂O₃ heterojunction nanocomposite (α/β - Bi₂O₃) was successfully prepared via a simple “space-confined” strategy and it was used as a superior anode for nickel-bismuth (Ni//Bi) battery. The α/β-Bi₂O₃ obtained by using MCM-41 as a space-confined template possesses a stable structure and enhanced charge transfer capability. Such superior traits vest the designed α/β-Bi₂O₃ electrode with high specific capacity (235 mAh g⁻¹ at 1 A g⁻¹), extraordinary rate performance (137 mAh g⁻¹ at 40 A g⁻¹, and ∼58% capacity retention vs 1 A g⁻¹), and excellent cyclic durability (75% capacity retention after 5000 cycles). Such performances are far superior to that of mono-phase α-Bi₂O₃ and β-Bi₂O₃ electrodes. Furthermore, an excellent Ni//Bi battery with outstanding energy density (∼155 Wh kg⁻¹) and long cycle life was assembled using the obtained α/β-Bi₂O₃ electrode and a NiC₂O₄ electrode as anode and cathode, respectively (NiC₂O₄//α/β-Bi₂O₃). This work opens a new alternative strategy for the rational design of efficient electrodes for reliable aqueous rechargeable batteries.
Glucose pillared Ni-Co layered double hydroxide clay materials toward durable cathodes for alkaline zinc batteries
2023, Journal of Alloys and Compounds
Alkaline Ni-Zn batteries are gaining more and more attention because of their safety, environmental friendliness, low cost and excellent performance. However, the volume and structure of the cathode changes during the charging and discharging process, resulting in particle flaking and structural rupture during the cyclic charging and discharging process, thus reducing their cyclic stability and limiting wide application. Herein, NiCo Layered double hydroxides (LDHs)clay materials with a low crystallinity multilayer nanosheet structure are prepared by glucose intercalation as cathode materials for alkaline Ni-Zn batteries. Expanded NiCo LDH layer spacing through glucose intercalation reduces interlayer peeling and collapse, accelerates interlayer diffusion of ions, and thus improves electron transport performance. NiCo LDH-G1.5 electrode material provides a specific capacity of 224 mAh g^-1 and a capacity retention rate of 76% at a current density of 40 A g^-1, 2000 cycles to maintain 86% of maximum capacity. Alkaline NiCo LDH-G1.5//Zn battery, a specific capacity of 180 mAh g^-1 can be achieved at a high current density of 20 A g^-1 and still maintain 76% of their maximum capacity after 2000 cycles, a maximum energy density of 364 Wh kg^-1 and a maximum power density of 54 kW kg^-1. This work provides a viable cathode for the development of high specific capacity and stable alkaline Ni-Zn batteries.
Recent advances and challenges of anodes for aqueous alkaline batteries
2023, EnergyChem
The ongoing surge in demand for energy conversion and storage spurs the development of high-efficiency batteries. In recent decades, aqueous alkaline batteries (AABs) have been the focus point owing to the high safety, low cost, environmental benefits, impressive output voltage and theoretical energy density. However, the large-scale application of AABs is hindered by the poor cyclability and insufficient capacity utilization, especially in anodes. To circumvent the issues, great research efforts have been dedicated to the electrode design and electrolyte optimization. In this review, reaction mechanisms, modification strategies, application feasibility and existing challenges are systematically summarized and highlighted. Additionally, insightful perspectives and research orientations are proposed for further development of AABs anodes.
Rechargeable metal-metal alkaline batteries: Recent advances, current issues and future research strategies
2023, Journal of Power Sources
Over the past few decades, remarkable advancement has been attained in the field of rechargeable metal–metal alkaline batteries (RABs). In terms of safety, energy density, charge-discharge capacity, and long-term storage capability, metal-metal RABs (e.g., Ni–Zn, Ni–Fe, Ni–Bi, Ni–MH, Ag–Zn, Co–Zn, Cu–Zn, and Bi–Zn systems) are contemplated as the promising energy storage devices for the applications in electric vehicles (EVs), hybrid EVs, grid-scale energy storage, as well as various implantable and wearable electronic devices. Especially, Ni-MH batteries become competitive with Li-ion batteries for EVs and hybrid EVs applications due to their high tolerance against mechanical abuse, stability under wide temperature ranges, and considerable charge/discharge capacity. Meanwhile, earlier works reviewed only specific topics, so, as a rapidly growing research topic, providing a deep understanding on metal–metal RABs is timely and worthwhile. So, in this work, we discuss the electrochemistry of all metal-metal RABs, then full cell designing with their performance will be discussed thoroughly. Further, issues associated with the existing metal–metal RABs and corresponding improvement approaches will be provided for future advances in high-performance and reliable metal-metal RABs.
All-Iron Semi-Flow Battery Based on Fe<inf>3</inf>O<inf>4</inf>@CNTs 3-Dimensional Negative Electrode
2023, Electrochimica Acta
Low-cost large-scale electrochemical energy storage technology is of great significance for the efficient utilization of clean and renewable energy. In this work, a novel all-iron semi-flow battery is designed using a 3-dimensional Fe₃O₄/Carbon nanotubes (CNTs) negative electrode and K₄Fe(CN)₆/ K₃Fe(CN)₆ aqueous solution as the positive electrolyte. Fe₃O₄ is coated onto CNTs through the co-sedimentation method. It is revealed that two steps of redox reactions of Fe₃O₄ exist in the charge and discharge processes and hydrogen evolution happens along with the reaction of Fe(OH)₂ to Fe. It is proved to be effective to control hydrogen evolution by adjusting the capacity of the positive electrolyte. As a result, the coulombic efficiency and energy efficiency can achieve 99.3% and 73.1% at 10 mA·cm⁻², respectively. The specific capacity at 10 and 20 mA·cm⁻² reach 397.8 and 260.6 mA h·g⁻¹ with Bi₂S₃ as the additive to the negative electrode. Compared with previous works, the specific capacity and coulombic efficiency are notably improved. Moreover, benefiting from the low cost of the active materials (38.9 $·kw h⁻¹), the alkaline aqueous all-iron semi-flow battery could be promising as a low-cost battery technology for large-scale energy storage in the future.
High-Performance flexible Quasi-Solid-State aqueous Nickel-Iron battery enabled by MOF-Derived N-Doped carbon hollow nanowall arrays
2023, Chemical Engineering Journal
The development of portable, flexible and wearable electronic devices has accelerated ever-growing demand for high-performance power sources with high specific energy/power density, high-level safety, low cost, and highly flexible features. Herein, a flexible quasi-solid-state aqueous nickel–iron (QSSA Ni-Fe) battery with high energy and power densities is rationally developed using ultrathin Ni(OH)₂ nanoflakes and porous ɑ-Fe₂O₃ nanorods conformally deposited on vertically aligned MOF-derived N-doped carbon hollow nanowalls supported by carbon textiles (NC/CTs) as the cathode (Ni(OH)₂@NC/CTs) and anode (ɑ-Fe₂O₃@NC/CTs), respectively. The obtained flexible QSSA Ni-Fe battery delivers optimal electrochemical performance, including high energy density (155.4 Wh Kg⁻¹), high power density (14.0 KW Kg⁻¹) and excellent cycling stability (∼86.1 % retention after 10,000 cycles). Impressively, the flexible QSSA Ni-Fe battery delivers stable electrochemical performance even under different bending conditions. The excellent electrochemical properties may be attributed to the following reasons: (i) The ultrathin Ni(OH)₂ nanoflakes and porous ɑ-Fe₂O₃ nanorods deposited on 2D hollow NC arrays possess a high porosity and large specific surface area; (ii) The 2D hollow NC arrays on flexible CTs not only increase the electrical conductivity, but also function as a scaffold to hold the active materials (such as Ni(OH)₂ or ɑ-Fe₂O₃) and thus maintain the structural integrity of the composites. This work provides a novel approach to design and develop QSSA batteries with satisfactory electrochemical properties and excellent flexibility, and have greater potential for future flexible and wearable electronic devices.

View all citing articles on Scopus

Hao Bin Wu received his B.S. degree in chemistry from Fudan University (China) in 2010. He obtained his Ph.D degree in materials science from Nanyang Technological University (Singapore) under the supervision of Professor Xiong Wen (David) Lou in 2015. Currently he works with Professor Yunfeng Lu as a Postdoctoral Scholar at University of California, Los Angeles. His research interests focus on synthesis and applications of nanostructured and hybrid materials for electrochemical energy storage and conversion, including rechargeable batteries, electrochemical capacitors and electrocatalysis.

Wei Xiong received his B.S. degree from Shandong Normal University in 2013 and Master degree from Central China Normal University in 2016. Currently he is a Ph.D candidate in School of Advanced Materials, Peking University, Shenzhen. His research is focusing on supercapacitor, atomic layer deposition (ALD) and its applications.

Zaiyuan Le received his B.S. degree in Materials Science and Engineering from University of Toronto (Canada) in 2012. He is currently a Ph.D candidate under the supervision of Professor Yunfeng Lu in Chemical and Biomolecular Engineering at University of California, Los Angeles. His research interests lie in sodium-ion based energy storage, including rechargeable batteries and hybrid capacitors.

Fei Sun is currently a Ph.D candidate in School of Energy Science and Engineering, Harbin Institute of Technology under the supervision of Professor Jihui Gao. He was a visiting student in Professor Yunfeng Lu's group from 2013 to 2015 in the Department of Chemical and Biomolecular Engineering, University of California, Los Angeles. He received his Master and Bachelor's degrees in Harbin Institute of Technology, China, in 2012 and 2010, respectively. His research focuses on carbon- and graphene-based materials for energy storage and environmental pollution improvement.

Fang Liu is currently a Ph.D candidate in Chemical and Biomolecular Engineering at UCLA. She obtained her B.E. degree (2012) in polymer engineering from Jilin University in China. Her research is focused on high-energy-density sulfur cathode and metallic lithium protection.

Jisheng Chen obtained his Ph.D degree from Central China Normal University at 2001. He is a Professor at Central China Normal University. His research interest focused on theoretical condensed matter physics and statistical physics.

Zhihong Zhu obtained his Ph.D degree from Wuhan University at 2006 and worked as a Postdoctoral Scholar at Nanyang Technological University (Singapore) from 2008 to 2009. Currently he is an Associate Professor at Central China Normal University. His research interest focused on nanostructured and hybrid materials for energy storage, biosensor and biomaterial.

Yunfeng Lu obtained his Ph.D degree under the supervision of Professor C. Jeffrey Brinker in University of New Mexico at 1998. He became a Brown Chair Professor at Tulane University in 2005 and now he is a Professor at University of California, Los Angeles. His research interest focused on composition and architecture design towards energy storage and conversion, including supercapacitors, lithium-ion batteries, lithium-metal batteries, flow batteries, fuel cells, and effective methane conversion.

View full text

Robust iron nanoparticles with graphitic shells for high-performance Ni-Fe battery

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of carbon-coated Fe nanoparticles

Materials characterizations

Conclusion

Acknowledgments

Adv. Energy Mater.

Energy Environ. Sci.

J. Power Sources

J. Power Sources

Chem. Commun.

ACS Nano

Adv. Funct. Mater.

Nano Lett.

J. Appl. Polym. Sci.

J. Electrochem. Soc.

ACS Nano

Electrochim. Acta

Adv. Funct. Mater.

Energy Environ. Sci.

Nature

Science

Science

Chem. Rev.

Chem. Soc. Rev.

Science

Energy Convers. Manag.

Adv. Mater.