Preparation of NiO–Ni/natural graphite composite anode for lithium ion batteries

doi:10.1016/j.jallcom.2012.11.136

Journal of Alloys and Compounds

Volume 553, 15 March 2013, Pages 167-171

https://doi.org/10.1016/j.jallcom.2012.11.136 Get rights and content

Abstract

Natural graphite was introduced into NiO–Ni that prepared via a simple pyrogenation method to improve the electrochemical performance of the composite due to the advantages of natural graphite over other amorphous carbon materials in terms of fine electronic conductivity, abundance in nature, low cost and better performance of lithium ion storage. The electrochemical performance of the composite as anode for lithium ion battery was characterized via conventional charge/discharge test and cyclic voltammetric measurement. It shows initial discharge and charge capacity of 630 and 478 mAh g⁻¹ at charge/discharge rate of 0.15 C, maintaining of 532 and 522 mAh g⁻¹ after 100 cycles. It can deliver initial discharge and charge capacity of 508 and 504 mAh g⁻¹ at 0.25 C. After 40 cycles at various rates from 0.25 to 2.5 C, the electrode can restore discharge and charge capacity of 472 and 467 mAh g⁻¹ while lowering the charge/discharge rate to 0.25 C. The electrochemical performance of the NiO–Ni/natural graphite composite was compared with that of NiO–Ni/acetylene black, showing much improvement on cycle stability, specific capacity and rate capability.

Highlights

► We prepare NiO–Ni/natural graphite composite anode for lithium ion battery. ► The composite shows enhanced cycle stability and capacity than NiO–Ni/acetylene black. ► Enhanced cycle stability is due to the fine electronic conductivity of natural graphite. ► Improved capacity is due to the capacity contribution of natural graphite.

Introduction

Transition metal oxides are becoming one kind of promising anode materials for high performance lithium ion batteries owing to their high theoretical capacity (500–1000 mAh g⁻¹) that based on a novel reaction mechanism [1], [2], [3], [4], [5], [6], [7], [8]. Among them, NiO has a theoretical capacity of 718 mAh g⁻¹ when being used as anode material in lithium ion batteries, thus has been widely researched for many years [8], [9], [10], [11], [12], [13]. However, the electrochemical performance of NiO is not so satisfied due to its poor electronic conductivity and aggregation during cycling. Much effort such as fabrication of nano-sized NiO [8], [11], [13], optimization the structure design via directly growing of NiO on current collector [9], [10], and combining NiO with carbon material has been attempted, which shows impressive electrochemical performance [12], [14]. Among them, the combination of NiO and carbon is an efficient and facile way to improve the electrochemical performance of NiO, because carbon materials have the advantages of fine structure stability and electronic conductivity. However, amorphous carbon obtained from the carbonization of organic materials such as glucose [15], [16], sucrose [17] and citric acid [18] will impair the reversible capacity of composite material, resulting in depressed specific capacity. It is known that natural graphite has the advantages over amorphous carbon materials in terms of abundance in nature, low cost, high electronic conductivity and better performance of lithium ion storage, thus can be used as an ideal carbon component in metal oxides/carbon composite materials. It is desirable to research the electrochemical performance of metal oxides/natural graphite and to explore the large-scale synthesis and practical application of metal oxides/natural graphite in lithium ion batteries. Recently, Li et al. reported the preparation of NiO–Ni composite particles on Ni foam using a decomposition method, and the composite as anode for lithium ion battery shows good cycle stability [19]. This result inspires us to envision whether the electrochemical performance of NiO–Ni powders can be such fine as that of film structured NiO–Ni/Ni. Combining NiO–Ni powders with natural graphite may be a promising way to achieve ideal electrochemical performance. Here in this paper, we report the preparation of NiO–Ni/natural graphite as anode for lithium ion batteries. Electrochemical-inert Ni in NiO–Ni can improve the structure stability of NiO during charge and discharge process, and electrochemical-active natural graphite can improve the electronic conductivity and contribute to the specific capacity of the composite material. As a result, the NiO–Ni/natural graphite anode shows good electrochemical performance. To study the effect of natural graphite on the electrochemical performance of the composite, the electrochemical performance of NiO–Ni/acetylene black was contrastively researched, and NiO–Ni/natural graphite shows evident improvement on cycle performance, specific capacity and rate capability than those of NiO–Ni/acetylene black.

Section snippets

Experimental details

$Ni ({CH}_{3} COO)_{2} \cdot 4 H_{2} O$ was analytical grade and was purchased from Shanghai Chemical Reagents. Natural graphite was obtained from Yichang Hengda graphite company (99.9%). For preparation of NiO–Ni, $Ni ({CH}_{3} COO)_{2} \cdot 4 H_{2} O$ was treated by high energy mechanical milling at 1500 rpm for 1 h. Then the milled $Ni ({CH}_{3} COO)_{2} \cdot 4 H_{2} O$ were annealed in air atmosphere at 350 °C for 5 h. Natural graphite was subsequently introduced by mixing natural graphite and NiO–Ni with weight ratio of 1:1 $(m_{NiO – Ni :} m_{natural graphite} = 1 : 1)$ in

Results and discussion

XRD patterns of the as-synthesized NiO–Ni/natural graphite and NiO–Ni/acetylene black are shown in Fig. 1. Curve a is the XRD pattern of NiO–Ni/natural graphite. As shown, the diffraction peaks located at 37.2°, 43.2°, 62.9°, 75.4° and 79.3° can be ascribed to (1 0 1), (0 1 2), (1 1 0), (1 1 3) and (2 0 2) faces of hexagonal NiO, which are in good agreement with JCPDS, No. 44-1159. Four diffraction peaks located at 26.4°, 54.5°, 83.2° and 86.9° are attributed to (0 0 2), (1 0 1), (0 0 4) and (0 0 6) faces of

Conclusions

In summary, NiO–Ni/natural graphite composite was prepared and the electrochemical performance of the composite as anode for lithium ion battery was researched. It shows better cycle stability, enhanced capacity and improved rate capability than those of NiO–Ni/acetylene black. It is known that natural graphite has the advantages over amorphous carbon materials in terms of abundance in nature, high conductivity and low cost, thus can be expected to be used in metal oxides/carbon composite

Acknowledgements

We gratefully acknowledge the financial support from Natural Science Foundation of China (NSFC, 50972075), and key projects of Chinese Ministry of Education (D209083) and Education Office of Hubei Province (Q20111209). Moreover, the authors are grateful to Dr. Jianlin Li at Three Gorges University for his kind support to our research.

References (24)

X.Y. Yao et al.
J. Alloys Comp.
(2012)
Y. Qi et al.
J. Alloys Comp.
(2012)
G.H. Zhang et al.
Electrochim. Acta
(2012)
C. Wang et al.
J. Power Sources
(2010)
B. Wang et al.
Electrochem. Commun.
(2012)
S.B. Ni et al.
Mater. Chem. Phys.
(2012)
Y. Wu et al.
J. Alloys Comp.
(2012)
X.H. Huang et al.
Electrochim. Acta
(2007)
Q.M. Pan et al.
Electrochim. Acta
(2010)
M.Y. Cheng et al.
J. Power Sources
(2010)

M.M. Rahman et al.

Solid State Ionics

(2010)

X.F. Li et al.

J. Power Sources

(2011)

Cited by (47)

Graphitic nanostructure integrated NiO composites for high-performance lithium-ion batteries
2023, Journal of Energy Storage
So far, various graphite-Nickel Oxide (NiO) composites have been investigated as anodes for Li-ion batteries. However, developing an ideal composite that overcomes NiO's electrical conductivity limitations remains a significant challenge. The current study presents an in-situ one-step hydrothermal technique for integrating NiO into a 3D peony-like graphitic nanostructure (NiO-GNF), resulting in unique thin nanosheet arrays with porous, conductive channels. Notably, the composites endowed controlled aggregation and restacking of NiO, buffered electrode stress and improved electrical conductivity due to the expanded nature of graphite. In addition, the enlarged interlayer spacing of expanded graphite facilitated an improved Li-ion insertion. Overall, in comparison to pure NiO anodes, the NiO-GNF composite achieved an impressive electrochemical improvement exhibiting a highly reversible discharge capacity of 678.2 mAh/g after 370 cycles at a current density of 0.5 A g⁻¹, corresponding to a capacity retention of 60.7 %. The composite also demonstrated a capacity of 752 mAh/g at a high current density of 1.2 A g⁻¹.
Thermocatalytic partial oxidation of methane to syngas (H<inf>2</inf>, CO) production using Ni/La<inf>2</inf>O<inf>3</inf> modified biomass fly ash supported catalyst
2023, Results in Engineering
In this work, the biomass fly ash (BFA) supported Ni/La₂O₃ catalyst was synthesized for the first time to produce syngas, a mixture of CO and H₂ via the partial oxidation of methane (POM). The BFA support was modified using laboratory synthesized Ni/La₂O₃ through the wetness impregnation technique. The Ni/La₂O₃-BFA catalyst was characterized by several techniques to investigate its suitability for the POM reaction. The characterization results showed that the crystalline structure, better metal support interaction and enhanced thermal stability of Ni/La₂O₃-BFA make it suitable for the POM. The synthesized Ni/La₂O₃-BFA catalyst remained stable for 30 h on stream during POM at 850 °C. The addition of La₂O₃ promoter and active metal Ni to the BFA improved the CH₄ conversion from 55% to 85% and enhanced the H₂/CO ratio from 1.4 to 2.0 while maintaining a reactants stoichiometric ratio of (CH₄:O₂ = 2:1). The study of spent catalyst by using various techniques confirmed that the stable catalyst exhibited coke resistance in the POM even after 30 h time on stream. Thus, the performance of BFA supported Ni/La₂O₃ catalyst shows more potential for catalytic applications due to its suitable physiochemical properties as it is a combination of multiple oxides that synergistically participate in the reaction steps and increases syngas production. It also provides low-cost, abundant, greener, and waste based alternative to expensive metal oxide as supports for catalytic applications.
Neutron reactor dosimetry monitoring by optical, nanostructural, and morphological changes of NiO thin films
2023, Radiation Physics and Chemistry
The effect of mixed neutron-gamma (n/γ) irradiation on microstructural, morphological, and optical properties of nickel oxide (NiO) thin films has been studied using UV–visible spectrophotometry, photoluminescence (PL) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). (NiO) thin films were irradiated in a Minerve reactor core at a doses range between 100 and 1000 Gy. The fast neutron dose, mainly due to elastic neutron scattering interactions in the range of 1–5 MeV, represents around 70% of the total irradiation dose. The results obtained show that the irradiation of the NiO thin films lead to significant changes in the optical properties, in the structure and in the morphology of the materials. The optical analysis shows visible range activation, which resulted in an increase in the absorbance of the band, centered around 645 nm. Otherwise, the integrated area of the band presents a linear dose response from 85 to 115 at dose ranging from 0 to 500 Gy. Furthermore, the band gap energy of the samples was linearly decreased from 3.52 eV to 3.44 eV by increasing the dose from 100 to 500 Gy, reaching 3.62 eV at 1000 Gy of irradiation n/γ dose. Urbach energy exhibited the same linear behavior, hence increasing from 372 to 400 meV. The variability of the integrated area, band gap energy and Urbach energy did not exceed 3% during 25 days. XRD analysis demonstrates that the crystallite size and the peak intensity for each preferred orientation planes (111) change with neutron-gamma radiation dose. The lattice parameter of preferential orientation (111) plane from rises linearly from 4.171 to 4.199 Å ± 0.0021 Å. Its variability is low, not exceeding 2%. SEM picture of irradiated NiO thin films shows the pore formation whose distribution increases with a dose level up to 500 Gy. Overall, the obtained results suggest that NiO thin films could considered as new alternative mean in neutron dosimetry application in nuclear reactor.
Preparation of NiO/MWCNTs nanocomposite for the removal of cadmium ions
2022, Journal of Materials Research and Technology
In this work, a portable nanocomposite film made from nickel oxide nanoparticles (NiO NPs), multi-walled carbon nanotubes (MWCNTs), and polyvinyl alcohol (PVA) was prepared and investigated for the removal of Cd (II) from an aqueous solution. The preparation was carried out by eco-friendly pulsed laser ablation in liquid environmental technique to synthesize NiO NPs and to decorate MWCNTs to form NiO NPs/MWCNTs nanocomposites, followed by the formation of a portable nanocomposite film from the interaction between PVA and NiO NPs/MWCNTs nanocomposite. After that, the physicochemical properties of the prepared samples were investigated by XRD, SEM, EDX, TGA, and FT-IR. From structural analysis, the matrix nanocomposite film showed the presence of the hexagonal structure plane of NiO, PVA, and graphite, and its elemental analysis has just C, O, and Ni, which represent the constituent elements of the PVA matrix, MWCNTs, and NiO NPs. From morphological analysis, NiO NPs were loaded on the outer surface of the tubular structure of MWCNTs in a spherical shape. From optical analysis, the typical transmittance peaks of Ni–O–C and Ni–O were appeared. Also, the peaks related to the main functional groups of MWCNTs were shifted due to the interactions between MWCNTs and NiOs by non-covalent bonds. From thermal analysis, the thermal degradation is similar to that of pure PVA, but with higher percentage of decomposition due to presence of MWCNTs and NiO NPs. Furthermore, the effects of several parameters, such as pH, initial Cd (II) concentration, and adsorbent dosage, were studied in order to reach their maximum adsorption, representing the optimal conditions for the removal of Cd (II) from an aqueous solution. From these results, the adsorption of these heavy metal ions increased with pH and peaked at about pH 7–8. Also, their percentages of adsorption increased as the weight of the adsorbent dosage was raised. Based on these findings, it can be inferred that the produced nanocomposite might be an effective adsorbent for metal ions in aqueous solutions. So, these results showed the capability of using NiO NPs/MWCNTs/PVA nanocomposite film in a water treatment process and that it might be utilized to purify water before it is released into the natural environment.
Facile synthesis of a scale-like NiO/Ni composite anode with boosted electrochemical performance for lithium-ion batteries
2021, Journal of Alloys and Compounds
A scale-like NiO/Ni composite was developed via a facile solvothermal method. The NiO/Ni composite showed high capacity retention and superior rate capability, resulting from its unique scale-like structure and the presence of conductive metallic Ni. The composite delivered high initial discharge and charge capacities of 1224.4 and 782.7 mAh g⁻¹ at a current density of 200 mA g⁻¹, with a high capacity retention of 107.92% after 80 cycles, far higher than that of pure NiO (28.2%) prepared using a similar method. Even at an elevated current density of 500 mA g⁻¹, the NiO/Ni composite still maintained desirable cycling stability, with its discharge specific capacity remaining at 552.8 mAh g⁻¹ after 200 cycles. Moreover, the NiO/Ni composite also exhibited much higher rate performance than pure NiO. Our work provides a facile method for the fabrication of a NiO/Ni composite with an engineered structure and improved electrochemical performance. This shows further development potential for similar metal oxides/metal composites as anode candidates for lithium-ion batteries.
Propelling electrochemical kinetics of transition metal oxide for high-rate lithium-ion battery through in situ deoxidation
2021, Journal of Colloid and Interface Science
To engineer advanced anodes for high-rate lithium-ion battery, rational structural design with insightful understanding of rapid reaction kinetics is important and still highly desirable. In this work, a high-temperature in situ deoxidation strategy is used to propel electrochemical kinetics of NiO through incorporating an intrinsic Ni component. Both theoretical calculation and experimental study demonstrate that the Ni-NiO heterojunction significantly enhances the electronic conductivity and ion diffusion properties. Accordingly, the lithium-ion battery modified with the heterostructured Ni-NiO shows remarkably improved charge transfer efficiency and rate performance, substantially outperforming many reported NiO-based anodes. This work opens up the exploration of heterostructured metal compounds as kinetic regulators for high-rate lithium-ion battery and also enlightens the understanding of defect chemistry in propelling electrochemical reactions.

View all citing articles on Scopus

View full text

Preparation of NiO–Ni/natural graphite composite anode for lithium ion batteries

Abstract

Highlights

Introduction

Section snippets

Experimental details

Results and discussion

Conclusions

Acknowledgements

J. Alloys Comp.

J. Alloys Comp.

Electrochim. Acta

J. Power Sources

Electrochem. Commun.

Mater. Chem. Phys.

J. Alloys Comp.

Electrochim. Acta

Electrochim. Acta

J. Power Sources

Solid State Ionics

J. Power Sources