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Article

LiNi0.8Fe0.1Al0.1O2 as a Cobalt-Free Cathode Material with High Capacity and High Capability for Lithium-Ion Batteries

by
Elhoucine Elmaataouy
1,
Abdelwahed Chari
1,
Ayoub El Bendali
1,
Marwa Tayoury
1,
Rachid Amine
2,
Mohamed Aqil
1,
GuiLiang Xu
3,
Tongchao Liu
3,
Jones Alami
1 and
Mouad Dahbi
1,*
1
Department of Materials Science, Energy, and Nano-Engineering, Mohammed VI Polytechnic University (UM6P), Lot 660, Hay Moulay Rachid, Ben Guerir 43150, Morocco
2
Argonne National Laboratory, Department of Materials Science Division, 9700 S. Cass Avenue, Lemont, IL 60439, USA
3
Argonne National Laboratory, Department of Chemical Sciences and Engineering Division, 9700 S. Cass Avenue, Lemont, IL 60439, USA
*
Author to whom correspondence should be addressed.
Batteries 2023, 9(1), 23; https://doi.org/10.3390/batteries9010023
Submission received: 7 October 2022 / Revised: 19 November 2022 / Accepted: 25 November 2022 / Published: 28 December 2022
(This article belongs to the Section Battery Materials and Interfaces: Anode, Cathode, Separators and Electrolytes or Others)
Browse Figures
Versions Notes

Abstract

:
Obtaining cathode materials with high capacity and cycle stability is one of the main challenges regarding the success of electric vehicle technologies. However, most of the widely used materials with these properties involve the use of toxic and expensive cobalt as the active material. To overcome this challenge, this work proposes a novel cobalt-free cathode material, synthesized for the first time using a solid-state reaction, whose general formula is LiNi0.8Fe0.1Al0.1O2 (NFA). This class of materials offers high capacity and reduces the battery costs by removing cobalt, without jeopardizing the structural stability and safety of the NFAs. The morphology and the structural properties of the obtained NFA cathode material were characterized using different techniques, e.g., scanning electronic microscopy, X-ray diffraction, X-ray fluorescence, and infrared and Raman spectroscopies. The electrochemical activity and diffusivity of the Li-ion during lithium removal and its insertion into the bulk of the NFA cathode demonstrated high-yield specific capacities of ≈180 mAh g−1 at 0.1C, along with a reasonable rate capability and cycling stability, with a capacity retention of ≈99.6% after 100 charge/discharge cycles at a rate of C/2, and whose operando X-ray diffraction experiments have been used to study the crystallographic transitions during the lithiation–delithiation reaction.

Graphical Abstract

1. Introduction

Faced with the ethical and environmental challenges of cobalt mining, its high price, and supply uncertainty, [1,2] many battery material manufacturers are attempting to reduce the content of cobalt in their products. There are already several alternatives, but the strength of cobalt and the growing demand for batteries are likely to retain the use of this controversial mineral [3,4]. In the battery sector accompanying the electrification of the world, cobalt is utilized in LIBs to increase the stability of the cathode materials that largely dominate the portable electronic and electric car market. Until now, the first commercially manufactured Li-ion battery employed the layered oxide LiCoO2 as the positive electrode [5].
At this point, manufacturers are expanding their research to replace this controversial metal in their products with materials that offer better safety, higher capacity, high-rate capability, and which are also more abundant and affordable to meet needs of the consumer electronics and energy storage sectors [6].
Most of the widely used cathodes in lithium-ion batteries today contain cobalt in some form, e.g., LiNixMnyCozO2 (NMC) and LiNi0.8Co0.15Al0.05O2 (NCA) [7,8]. These materials provide a serious challenge to the low-cost and sustainability goals envisioned by the battery industry due to the negative socioeconomic impact of cobalt mining and refining, and they also suffer from capacity decay and thermal instability [9,10]. To overcome this challenge, a new class of cathode material such as LiNixFeyAlzO2 (NFA), which is good for the environment, human demand, and perhaps even for the performance of the LIBs, is a suitable candidate to replace the cobalt content in these cathode materials.
The rapid depletion of global cobalt reserves has created a constraint on the supply chain that is emerging as a threat to the future forecasts for the electric vehicle market. As the cost of cobalt has nearly tripled in recent years due to increased demand, the development of cathodes containing less cobalt is required [11].
In the search for the ideal booster cathode capable of fulfilling these requirements, an optimal candidate is the class of nickel-rich cathode materials including lithium-nickel oxide LiNiO2 (LNO). However, despite over 20 years of extensive study, LNO remains elusive due to its principal limitations, which may be classified into LNO surface instability during the delithiation process, and mechanical issues caused by significant volume changes and the diversity of phase transitions over cycling [12,13,14,15].
Consequently, to overcome these challenges and to simultaneously satisfy the cost and performance benefits, in this work, we highlight an alternative route using iron to replace cobalt in NCA structures, thereby yielding a new generation of cathode materials. This new class of cobalt-free cathode material, so far reported with sol-gel and coprecipitation as the synthesis method, with the general formula LiNixFeyAlzO2 (NFA) [16,17], reduces battery costs by removing cobalt without jeopardizing the structural stability and safety benefits, while delivering high energy density. LiNixMyO2 (With x > 80%) provides high capacity and allows for the replacement of Ni with trivalent elements (M) that have a similar ionic radius, such Al and Fe (0.54 Å for Al3+ and 0.55 Å for Fe3+ vs. 0.56 Å for Ni3+) resulting in better structural stability, increased safety, and improved life cycle compared to the primary structure [16,17,18,19].
There are several methods to synthesize NFA materials. However, they all differ from each other in the quality, reactivity, size, and purity of the final grains obtained, as well as in the time of the transformation and the cost. In this work, a solid-state approach has been used for the first time to prepare the NFA cathode material.

2. Materials and Methods

2.1. Synthesis

The LiNi0.8Fe0.1Al0.1O2 cathode material was obtained via a solid-state method. The starting precursors, NiO, Al2O3, FeO3, and Lithium hydroxide Li (OH), H2O, were purchased from Sigma-Aldrich, with a purity greater than 98.99%. The nominal composition of the oxide powder was weighed according to the desired stoichiometry to give a ratio of Li:Ni:Fe:Al as 1:0.8:0.1:0.1.
The obtained mixtures were ground and milled thoroughly using an agate mortar with a pestle until the mixture became homogeneous. The mixture was then placed in alumina crucibles and heated progressively from room temperature up to 400 °C for 6 h. In an effort to improve the homogeneity and intensify the kinetics of the solid-state reaction, the obtained powders were ground in a stochiometric manner and sintered at room temperature, then directly heated to 800 °C for 20 h. After each thermal treatment, the products were air quenched to room temperature. The monitoring protocol of the thermal treatment of each step was followed by the process visualized in Figure 1.

2.2. Structural and Morphological Observations

The morphology of the synthesized cobalt-free cathode material was studied using a high-resolution scanning electron microscope (SEM) (ZEISS 300). The images were recorded at different magnifications from 2 to 10 μm, respectively. The surface of the sample was coated with a layer of carbon, under high vacuum, for 20 min in a sputtering coater to improve the conductivity before SEM observation. The elemental composition was investigated using the X-ray fluorescence technique (XRF).
The crystal structure and phase purity of the prepared sample was evaluated using powder X-ray diffraction (XRD) in a scanning range of 10 and 80° (2θ) at a step scan of 0.02° (2θ)/min and 0.03 s/step on a Bruker D8 Discover ADVANCE diffractometer (30 kV, 10 mA) equipped with Cu Kα radiation (λ = 1.54059 Å). The crystal structure was also characterized by Raman spectroscopy. The Raman spectra were obtained by excitation with a green laser at 532 nm in a range of 150–1000 cm−1 at room temperature using a HORIBA LABRAM-HR Evolution instrument.
In order to determine the cation environment, the functional group identification of the NFA structure at room temperature was also investigated, which ranged from a wavenumber of 400 cm−1 to 4000 cm−1, recorded in transmittance mode, with KBr pellets using Fourier-transform infrared spectroscopy (FTIR).

2.3. Electrochemical Measurements

The electrochemical characteristics of the prepared sample were tested in a coin cell (2032). The coin cells were built within an argon-filled glove box with the synthesized cathode, Li metal, as an anode and a Whatman membrane as a separator. The electrolyte was 2 mol L−1 LiPF6 in a 1:1 v/v ethylene carbonate (EC): diethyl carbonate solution (DEC). The electrochemical measurements were performed at room temperature using a multichannel potentiostat (MPG-2, Bio-Logic SAS, 38170, Seyssinet-Pariset, France). The electrode consisted of 80 wt.% active material (NFA), 15 wt.% carbon black as the conducting agent and 5 wt.% polyvinylidene fluoride (PVDF) as the binder in N-methyl pyrrolidone solvent. The mixture was stirred overnight to form a viscous slurry, then coated in (5 cm × 10 cm) aluminum foil sheets and dried at 70 °C for 4 h before being cut into a (12.7 × 12.7 mm2) circular electrode sheet and finally dried in a vacuum oven at 80 °C for 14 h before assembly in an argon-filled glove box.
Cyclic volumetric measurements were carried out using a multi-scan rate from 0.01 to 1 mV s−1.The charge/discharge tests of the coin-type cells were performed on a Bcs-800 series battery testing system between 3.0–4.5 V vs. Li/Li+.

3. Results

3.1. Materials Characterization

The X-ray diffractogram of the NFA sample calcined at 800 °C in air is presented in Figure 2. All indexed reflections adopt the α-NaFeO2 structure, with an R-3m group and no obvious impurities or secondary phases confirmed, which indicates that our sample has a well-ordered crystal structure with the following lattice parameters, obtained using Rietveld refinement: a = 2.867 Å, and c = 14.218 Å, with reasonable values of Bragg R-factor = 4.59% and RF factor = 3.04%. In addition, the refined structure with the O-3 phase indicates that the lithium position has a high Biso-coefficient, which suggests high lithium mobility, giving the lithium ion the ability to move freely and intercalate very easily between the inter-layers.
Furthermore, to examine the degree of cationic mixing between Ni2+ and Li+1 in the layered structure, we investigated the intensity ratio of I (003)/I (104). In general, if this ratio is greater than 1.2, it is usually indicative of a small cationic mixture [20,21,22]. Thus, our material showed an intensity ratio (003)/(104) of 1.07, implying unfavorable levels of cation mixing, which was ~4%, confirmed using the Rietveld refinement of the diffractogram (Tables S1 and S2). These (110) and (108) lines are well separated (line width of ~0.55°), suggesting the formation of a lamellar structure.
The crystallite size was evaluated from XRD data using the Scherrer equation, Equation (1) (Table S3). The calculated average crystallite size (~33.41 nm) indicates a good effect regarding the electrochemical behavior for our cobalt-free cathode material (see Supporting information). However, in the solid-state method used to synthesize the NFA cathode material, many parameters affect the size of the crystallites, including heat treatment, particle size orientation, etc. In this context, every crystallite can be seen as an isolated microelectrode, and their entire cluster is streamlined as a network of similar microelectrodes [23].
Figure S1 presents the Raman-active modes of the pristine (uncycled cathode) NFA synthesized by solid-state reaction, with A1g and Eg derived from the R-3m space group, with a factor group analysis: D (5, 3d) of NFA crystal observed around (550–570) and (700–850) cm−1. However, these bands correspond to the M–O stretch (Eg) and symmetric O–M–O bend stretching vibration when MO6 unites with (A1g), respectively [24]. Additionally, small peaks above ~1000 are attributed to the D (disorder structure) mode of vibration, where the peaks below 370 correspond to LiO2 [24].
The structure was also studied by infrared spectroscopy to confirm the environment of the cations in the oxides, in particular the transition elements, as well as the distribution of lithium in the structure [25]. According to the group theoretic analysis of the D53d symmetry, as presented in [26], the vibrational spectra of the alpha-NaFeO2− type compounds with the R-3m space group yield four infrared active modes (2A2, +2E~). Figure S2 shows the FTIR absorption spectra of the NFA oxide powders synthesized by the solid-state method, fired at 800 °C under air atmosphere for 20 h.
The main spectrum of NFA contains the following main absorption bands: 670, 870, 1200, 1400, and 1750 cm−1. These results confirm the XRD and Raman spectroscopy observations, showing that the vibrational bands of the precursors have disappeared and that the vibrational bands of the oxide lattice have developed. In the far-infrared region, we identified a single well-resolved band at (400–670) cm−1.
The interval from 1200 to 1450 cm−1 can be attributed to the asymmetric stretching of the M-O bands in the M-O6 octahedron and others around 870 cm−1 corresponding to the O-M-O bonds [27].
However, the broadening of all IR bands in this study establishes that the layered structure of NFA is well conserved, even at the atomic level, and also demonstrates the high degree of cation ordering. In addition, the enlargement of the low-frequency band can be attributed to the random distribution of Li-ions persisting in the host matrix [26].
The chemical composition and morphology of the sample LiNi0.8Fe0.1Al0.1O2 were characterized using the SEM-EDS(Energy Dispersive Spectroscopy) EDS (Figure S3) and XRF methods. As shown in Figure 3, the material appears to be no-homogeneous; it is composed of aggregates of particles with a diameter ranging from ~5–10 μm, with individual crystallites of size ~1.5 μm. The smaller crystallite size and isotropic character of the NFA particles can be attributed to the specific characteristics of the synthesis process.
According to the XRF-analysis of the NFA sample, the deviation from the content set value of Ni, Al, and Fe of the synthesized NFA sample does not exceed 1% (Table S4).

3.2. Electrochemical Performances

Figure 4 shows that the NFA cobalt-free cathode material synthesis via the solid-state method exhibits a high discharge capacity of 154 mAh/g at a charge/discharge rate of C/2 in the 3 V–4.5 V range, with an excellent capacity retention of around 99.6% after 100 cycles (~150 mAh/g). This cobalt-free cathode material demonstrates properties comparable to those reported in commercial cobalt-containing layered oxide cathode materials NCMs and NCAs [28,29,30]—created using the same synthesis procedure reported so far—in terms of the lithiation–delithiation profile and stable cycling, with reasonable power capability. Moreover, the NFA material respect to the rate of the charge/discharge, as presented in the Figure S4, the process indicates a highly reversible lithiation–delithiation mechanism in the voltage range 3 V−4.5 V.
Cyclic voltammetry was used to assess the electrochemical properties of the NFA cathode during charge/discharge. Figure 5 shows the CV profile in a potential window of [3.0–4.5] V vs. Li/Li+ at different scan rates from 0.01 to 1 mVs−1. The I = f (V) profile (Figure 4a) shows one cathodic peak located at the E = 3.4 V potential corresponding to the oxidation of the Ni3+/Ni4+ [31]. The discharge is also characterized by one anodic peak of around E = 4.2 V, corresponding to the reduction of the Ni4+ ions.
The (4.2 V/3.4 V) cathodic and anodic peaks do not coincide in the same voltage, which shows a polarization. Nevertheless, the CV tests in the voltage window (3.0–4.5) V indicate that the NFA cathode shows good electrochemical reactivity in all at all the evaluated scan rates.
The diffusion coefficient of the Li+ ions was determined using Equation (1), which allows for the correlation between the peak currents vs. the square root of the scan rates, as shown in (Figure 4b). It assumes a semi-infinite diffusion that applies to electrochemical reactions controlled by diffusion [32].
ip = 2.69 × 105 × n3/2 × DLi1/2 × C × v1/2
where ip (A) is the maximum peak current, DLi+ is the diffusion factor of lithium ions, A is the area covered by the active material, n is the number of electrons, and C is the Li-ion concentration in the electrode.
Therefore, the DLi+ value of the NFA electrode in the electrolyte medium consisted of 2 mol L−1 LiPF6 in 1:1 v/v (EC): (DEC); with further delithiation, it grew steadily up to 4.025 V until reaching an almost constant value. Afterwards, depending on the lithium concentration, it gradually declined. The diffusivity values were clearly higher in the medium lithium concentration regions (≈4.025 to ≈4.3 V), suggesting that the two-dimensional ion transport channel provided by the layered structure improves the diffusion rate of the Li-ions and enables a better rate capability of NFA. The diffusivity values are significantly higher in the intermediate lithium concentration region (≈4.025 to ≈4.3 V), indicating that two-dimensional ion transport channels provided by the layered structure improved the diffusion rate of Li-ions, enabling a better rate capability of the NFA. The Li+ ion diffusion coefficients Ds,ca and Ds,pa in the electrode at the corresponding redox potentials are respectively 1.702 × 10−4 cm2·s−1 and 3.008 × 10−4 cm2 s−1. Inspired by these theoretical calculations, we can hypothesize that ionic diffusivity was not a limiting factor at lower cycling rates.
The rate capabilities of NFA were evaluated at different current rates in the 3 V–4.5 V voltage range, and the results are shown in Figure 6. The specific capacity decrease from rate to rate (C/10---C/8---C/5---C/2---C/10), with an average of 10.183 mAh/g, can explained by the structural and morphological degradation of the material (irreversible degradation) and the weak kinetics of the lithiation–delithiation process (lower diffusion coefficient) of the NFA cathode material at high current density.
The real-time phase transformations of the NFA during the lithiation–delithiation process were investigated by operando XRD. The index of lithium x in the structure LixNi0.8Fe0.1Al0.1O2 is based on the charge of the material in comparison to the capacity of the material, which is confirmed by the voltage profiles in the coin cells experiments. The results of the operando XRD are presented in (Figure 7): the position of the XRD (003), (006), (104), and (107) peaks of the material were tracked, and the movement of these peaks indicate the structural changes of the material during charge and discharge. At each XRD measurement, the peak positions were used to calculate the unit cell parameters, which are presented in (Figure 7b). The rectangular colorations specify the phases, which will be described in the discussion; clear disconnections in the unit cell parameter evolution indicate the phase changes of the material.
The XRD results (Figure 7) show that the NFA has a hexagonal-1, R-3m phase with unit cell parameters of a = b = 2.4353 Å; c = 14.0157 Å in the beginning of the charge; this phase remains dominant throughout the voltage rise to the of plateau at 3.92 V up to x ≈ 0.83; a slight increase in the unit cell volume caused by the increase in the c parameter is observed.Then, at the end of the plateau, the structure changes to another hexagonal-2 phase between x ≈ 0.83 and x ≈ 0.56, which exhibits a linear increase in volume upon delithiation because of the “c” parameter, even though the parameter “a” decreases slightly, compared to that in the hexagonal-1 phase. However, three steps are observed at x ≈ 0.75 and x ≈ 0.63, where the volume of the unit cell increases slightly before continuing linearly with the same rate of change; the steps are clear in the parameters: “a” jumps slightly, and “c” changes the rate of variation. The parameter “c” achieves 14.35 Å at the end of this phase. Then at x, between 0.56 and 0.48, the material converts to a monoclinic, C2/m space group phase (c = 5.0550; a = 4.8696). The appearance of this phase matches a small plateau and the change in the variation behavior of the material; the unit cell volume will begin to decrease with delithiation after this phase. At x lower than 0.48, the material returns to another hexagonal-3 phase, where the volume decreases linearly and also possesses two steps, where the volume jumps slightly at x ≈ 0.40 and x ≈ 0.25, then a final hexagonal-3 phase appears at the end of the charge, exhibiting a lower volume, which continues to decrease slightly.
In summary, Figure 8 demonstrates the phase transformation process of the NFA cathode during cycling, which indicates that the delithiation process is divided into five parts: two hexagonal phases for x between 1 and 0.56, a monoclinic phase, and two other hexagonal phases for x lower than 0.48 (H1-H2-M-H3-H4). Upon delithiation, the first two hexagonal phases, H1 and H2, have an increasing “c” parameter; however, the other two hexagonal phases show an opposite trend.
The same transformations were observed in the dQ/dV plot extracted from the 1st cycle charge–discharge curve of the NFA half-cell at C/10 in the voltage range between 3 and 4.5 V, which is also confirmed by the dV–dt curve of the operando XRD results, which is correlated with the cell parameters (see Supplementary materials, Figure S5). These results are similar to those from the transition phase process of the NMC cathode materials reported in the literature [20]. The process seems to be reversible, as these structural transitions were reversed during discharge.
However, Table 1 shows the reversible capacity of various cobalt-free-based positive electrodes for LIBs prepared using wet methods, such as sol-gel and co-precipitation. These methods may necessitate the use of some sophisticated instruments, harsh conditions, and organic materials such as citric acid, formic acid, polyvinyl alcohol, etc. [33]. The previously mentioned limitations make their use in industrial production difficult compared to the use of the solid-state reaction method. These methods also involve the use of complex processes and factors, such as stirring, flow rate, temperature, pH, and atmosphere, along with high production costs [33,34]. In contrast, due its simple synthesis parameters and cost-effectiveness, our cobalt-free cathode material, prepared via a solid-state reaction route, retains its industrial potential, as its commercialization is rapid, even if the process requires a high heating temperature for the precursors over a long time period, and particles of irregular shape and size are formed. Indeed, the capacities produced by our electrodes at various current rates were comparable, if not superior, to those in some previously published studies based on wet techniques. Moreover, it is expected that cobalt-free cathode materials will present abundant opportunities with high capacity, high capability, and low-cost electrodes, as Figure 9 demonstrates, for lithium-ion electronic systems over the next generation. On the other hand, and according to S&P Global Market Intelligence data for 23 September 2021, market intelligence analysts forecast that raw materials represent the bulk of the total cost of a battery—between 50 and 70%—and battery packs can represent 30% to 40% of an electric vehicle’s total cost; all these statistics favor the use of cobalt-free cathode materials for lithium-ion battery technology.

4. Conclusions

In this work, for the first time, a cobalt-free cathode material was successfully synthesized via solid-state reaction. XRD analysis shows a pure layered oxide without impurities or secondary phases, as confirmed by the various structural studies and FTIR, Raman, and XRF analyses. The NFA material demonstrated a relatively stable electrochemical performance, with a capacity of 180 mAh g−1 at C/10 current density within a 3.0 V–4.5 V potential window. Meanwhile, we attribute the use of Fe and Al in the NFA Co-free cathode to the stabilization of the M-O band and the suppression of irreversible phase transitions during cycling, despite the increase in Li/Ni disorder. Thus, these substitutions in Ni-rich cathodes might enable its operation at high voltages.
Here, we report a Co-free cathode material, represented as NFA, that exhibits encouraging performance and holds promise for use in long-cycle-life batteries and future commercial applications, resulting in higher specific energy (Wh kg−1) and lower cost (USD kWh−1), compared with various commercial cathodes including LiCoO2 (LCO), LiNi0.333Co0.333Mn0.333O2 (NMC111), and LiNi0.6Co0.2Mn0.2O2 (NMC622). This work opens the door for future work that could focus on doping and coating strategies which can be applied to a wide range of cathode chemistries to address key issues that limit energy density and cycle life.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/batteries9010023/s1: Figure S1: Raman spectra with a green laser at 532 nm in a range of 0 to 800 cm−1 at room temperature of NFA material; Figure S2: The function group identification of NFA structure at room temperature; Figure S3: Galvanostatic curve indicating the respect of rate at C/10 in the potential window of 3.0 V–4.5 V vs. Li/Li+; Figure S4: (a) the correlation between the c parameter and volume of the unit cell of NFA with the dV/dt variation; (b) the dQ/dV plot extracted from the 1st cycle charge–discharge curve at C/10 of the NFA half-cell in the range voltage between 3 and 4.5 V; Figure S5: (a) The correlation between the c parameter and volume of the unit cell of NFA with the dV/dt variation, (b) the dQ/dV plot extracted from the 1st cycle charge/discharge curve at C/10 of the NFA half-cell in the range voltage between 3V and 4.5V. Table S1: Ion site positions for NFA extracted from the X-ray diffraction data using the Rietveld refinement method; Table S2: Crystallographic data for NFA; Table S3: Average crystallite size (nm) of NFA material; Table S4: Surface composition in wt% for the NFA.

Author Contributions

Conceptualization and experimental design, E.E., A.C. and M.D.; writing—original draft preparation, E.E.; material synthesis and electrochemical tests E.E., A.C. and M.T.; XRD and operando-XRD measurement, E.E., A.E.B.; and M.A.; data analysis, E.E.; article review and validation of scientific content, R.A., G.X., T.L., J.A. and M.D. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Office Chérifien des Phosphates (OCP S.A.) and Mohammed VI Polytechnic University.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Acknowledgments

The authors would like to thank the Office Chérifien des Phosphates (OCP S.A.) and Mohammed VI Polytechnic University for their financial support.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Krutilla, K.; Good, D.; Toman, M.; Arin, T. Addressing Fundamental Uncertainty in Benefit–Cost Analysis: The Case of Deep Seabed Mining. J. Benefit Cost Anal. 2021, 12, 122–151. [Google Scholar] [CrossRef]
  2. Zeng, A.; Chen, W.; Rasmussen, K.D.; Zhu, X.; Lundhaug, M.; Müller, D.B.; Tan, J.; Keiding, J.K.; Liu, L.; Dai, T.; et al. Battery technology and recycling alone will not save the electric mobility transition from future cobalt shortages. Nat. Commun. 2022, 13, 1341. [Google Scholar] [CrossRef]
  3. Turcheniuk, K.; Bondarev, D.; Amatucci, G.G.; Yushin, G. Battery materials for low-cost electric transportation. Mater. Today 2020, 42, 57–72. [Google Scholar] [CrossRef]
  4. Lee, S.; Manthiram, A. Can Cobalt Be Eliminated from Lithium-Ion Batteries? ACS Energy Lett. 2022, 7, 3058–3063. [Google Scholar] [CrossRef]
  5. Choi, N.-S.; Chen, Z.; Freunberger, S.A.; Ji, X.; Sun, Y.-K.; Amine, K.; Yushin, G.; Nazar, L.F.; Cho, J.; Bruce, P.G. Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors. Angew. Chem. Int. Ed. 2012, 51, 9994–10024. [Google Scholar] [CrossRef] [PubMed]
  6. Liu, J.; Huang, Z.; Fan, M.; Yang, J.; Xiao, J.; Wang, Y. Future energy infrastructure, energy platform and energy storage. Nano Energy 2022, 104, 107915. [Google Scholar] [CrossRef]
  7. Manthiram, A. A reflection on lithium-ion battery cathode chemistry. Nat. Commun. 2020, 11, 1550. [Google Scholar] [CrossRef] [Green Version]
  8. Myung, S.-T.; Maglia, F.; Park, K.-J.; Yoon, C.S.; Lamp, P.; Kim, S.-J.; Sun, Y.-K. Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives. ACS Energy Lett. 2016, 2, 196–223. [Google Scholar] [CrossRef]
  9. Sun, Y.-K.; Lee, D.-J.; Lee, Y.J.; Chen, Z.; Myung, S.-T. Cobalt-Free Nickel Rich Layered Oxide Cathodes for Lithium-Ion Batteries. ACS Appl. Mater. Interfaces 2013, 5, 11434–11440. [Google Scholar] [CrossRef] [PubMed]
  10. Campbell, G.A. The cobalt market revisited. Miner. Econ. 2019, 33, 21–28. [Google Scholar] [CrossRef]
  11. Alves Dias, P.; Blagoeva, D.; Pavel, C.; Arvanitidis, N. Cobalt: Demand-supply balances in the transition to electric mobility. In EUR 29381 EN, Publications Office of the European Union; Publications Office of the European Union: Luxembourg, 2018; ISBN 978-92-79-94311-9. [Google Scholar] [CrossRef]
  12. Bianchini, M.; Roca-Ayats, M.; Hartmann, P.; Brezesinski, T.; Janek, J. There and Back Again—The Journey of LiNiO2 as a Cathode Active Material. Angew. Chem. Int. Ed. 2018, 58, 10434–10458. [Google Scholar] [CrossRef]
  13. Deng, T.; Fan, X.; Cao, L.; Chen, J.; Hou, S.; Ji, X.; Chen, L.; Li, S.; Zhou, X.; Hu, E.; et al. Designing In-Situ-Formed Interphases Enables Highly Reversible Cobalt-Free LiNiO2 Cathode for Li-ion and Li-metal Batteries. Joule 2019, 3, 2550–2564. [Google Scholar] [CrossRef]
  14. Chien, P.; Wu, X.; Song, B.; Yang, Z.; Waters, C.K.; Everett, M.S.; Lin, F.; Du, Z.; Liu, J. New Insights into Structural Evolution of LiNiO2 Revealed by Operando Neutron Diffraction. Batter. Supercaps 2021, 4, 1701–1707. [Google Scholar] [CrossRef]
  15. Mu, L.; Lin, F. Identifying Challenges and Methods for Mitigation in No-Cobalt LiNiO2 Cathode Materials. ECS Meet. Abstr. 2020, 45, 3726. [Google Scholar] [CrossRef]
  16. Muralidharan, N.; Essehli, R.; Hermann, R.P.; Amin, R.; Jafta, C.; Zhang, J.; Liu, J.; Du, Z.; Meyer, H.M.; Self, E.; et al. Lithium Iron Aluminum Nickelate, LiNixFeyAlzO2 —New Sustainable Cathodes for Next-Generation Cobalt-Free Li-Ion Batteries. Adv. Mater. 2020, 32, 2002960. [Google Scholar] [CrossRef]
  17. Muralidharan, N.; Essehli, R.; Hermann, R.P.; Parejiya, A.; Amin, R.; Bai, Y.; Du, Z.; Belharouak, I. LiNixFeyAlzO2, a new cobalt-free layered cathode material for advanced Li-ion batteries. J. Power Sources 2020, 471, 228389. [Google Scholar] [CrossRef]
  18. Shannon, R.D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst. 1976, 32, 751–766. [Google Scholar] [CrossRef]
  19. Ohzuku, T.; Ueda, A.; Nagayama, M. Electrochemistry and Structural Chemistry of LiNiO2 (R3m) for 4 Volt Secondary Lithium Cells. J. Electrochem. Soc. 1993, 140, 1862–1870. [Google Scholar] [CrossRef]
  20. Zhang, X.; Jiang, W.; Mauger, A.; Qilu, A.; Gendron, F.; Julien, C. Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material. J. Power Sources 2010, 195, 1292–1301. [Google Scholar] [CrossRef]
  21. Huang, Z.; Gao, J.; He, X.; Li, J.; Jiang, C. Well-ordered spherical LiNixCo(1−2x)MnxO2 cathode materials synthesized from cobolt concentration-gradient precursors. J. Power Sources 2011, 202, 284–290. [Google Scholar] [CrossRef]
  22. Zheng, J.; Liu, T.; Hu, Z.; Wei, Y.; Song, X.; Ren, Y.; Wang, W.; Rao, M.; Lin, Y.; Chen, Z.; et al. Tuning of Thermal Stability in Layered Li(NixMnyCoz)O2. J. Am. Chem. Soc. 2016, 138, 13326–13334. [Google Scholar] [CrossRef] [PubMed]
  23. Ivanishchev, A.V.; Ushakov, A.V.; Ivanishcheva, I.A.; Churikov, A.V.; Mironov, A.V.; Fedotov, S.S.; Khasanova, N.R.; Antipov, E.V. Structural and electrochemical study of fast Li diffusion in Li3V2(PO4)3-based electrode material. Electrochim. Acta 2017, 230, 479–491. [Google Scholar] [CrossRef]
  24. Zhu, S. Renovation of Lithium Cobalt Oxide from Spent Lithium Ion Batteries by an Aqueous Pulsed Discharge Plasma. Int. J. Electrochem. Sci. 2016, 11, 6403–6411. [Google Scholar] [CrossRef]
  25. Murali, N.; Margarette, S.; Rao, V.K.; Veeraiah, V. Structural, impedance, dielectric and modulus analysis of LiNi1-xy-0.02 Mg0.02Cox ZnyO2 cathode materials for lithium-ion batteries. J. Sci. Adv. Mater. Devices 2017, 2, 233–244. [Google Scholar] [CrossRef]
  26. Kalyani, P.; Kalaiselvi, N. Various aspects of LiNiO2 chemistry: A review. Sci. Technol. Adv. Mater. 2005, 6, 689–703. [Google Scholar] [CrossRef] [Green Version]
  27. Weber, D.; Tripković, D.; Kretschmer, K.; Bianchini, M.; Brezesinski, T. Surface Modification Strategies for Improving the Cycling Performance of Ni-Rich Cathode Materials. Eur. J. Inorg. Chem. 2020, 2020, 3117–3130. [Google Scholar] [CrossRef]
  28. Jiang, X.; Sha, Y.; Cai, R.; Shao, Z. The solid-state chelation synthesis of LiNi1/3Co1/3Mn1/3O2 as a cathode material for lithium-ion batteries. J. Mater. Chem. A 2015, 3, 10536–10544. [Google Scholar] [CrossRef]
  29. Hua, W.; Schwarz, B.; Azmi, R.; Müller, M.; Darma, M.S.D.; Knapp, M.; Senyshyn, A.; Heere, M.; Missyul, A.; Simonelli, L.; et al. Lithium-ion (de)intercalation mechanism in core-shell layered Li(Ni,Co,Mn)O2 cathode materials. Nano Energy 2020, 78, 105231. [Google Scholar] [CrossRef]
  30. Qiu, Z.; Zhang, Y.; Dong, P.; Xia, S.; Yao, Y. A facile method for synthesis of LiNi0.8Co0.15Al0.05O2 cathode material. Solid State Ion. 2017, 307, 73–78. [Google Scholar] [CrossRef]
  31. Manthiram, A.; Knight, J.C.; Myung, S.-T.; Oh, S.-M.; Sun, Y.-K. Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives. Adv. Energy Mater. 2015, 6, 1501010. [Google Scholar] [CrossRef]
  32. Wei, Y.; Zheng, J.; Cui, S.; Song, X.; Su, Y.; Deng, W.; Wu, Z.; Wang, X.; Wang, W.; Rao, M.; et al. Kinetics Tuning of Li-Ion Diffusion in Layered Li(NixMnyCoz)O2. J. Am. Chem. Soc. 2015, 137, 8364–8367. [Google Scholar] [CrossRef] [PubMed]
  33. Huo, Q.; Margolese, D.I.; Stucky, G.D. Surfactant Control of Phases in the Synthesis of Mesoporous Silica-Based Materials. Chem. Mater. 1996, 8, 1147–1160. [Google Scholar] [CrossRef]
  34. Bazito, F.F.C.; Torresi, R.M. Cathodes for lithium ion batteries: The benefits of using nanostructured materials. J. Braz. Chem. Soc. 2006, 17, 627–642. [Google Scholar] [CrossRef]
  35. Liu, T.; Yu, L.; Lu, J.; Zhou, T.; Huang, X.; Cai, Z.; Dai, A.; Gim, J.; Ren, Y.; Xiao, X.; et al. Rational design of mechanically robust Ni-rich cathode materials via concentration gradient strategy. Nat. Commun. 2021, 12, 6024. [Google Scholar] [CrossRef]
  36. Lin, H.; Liang, C.; Li, M.; Dai, C.; Xiong, Y. Effects of Aluminum Doping on Cobalt-Free Lithium-Iron-Nickel-Manganese-Oxygen Cathode Materials for Lithium-Ion Batteries. Energy Technol. 2017, 5, 1472–1483. [Google Scholar] [CrossRef]
  37. Darbar, D.; Self, E.C.; Li, L.; Wang, C.; Meyer, H.M.; Lee, C.; Croy, J.R.; Balasubramanian, M.; Muralidharan, N.; Bhattacharya, I.; et al. New synthesis strategies to improve Co-Free LiNi0.5Mn0.5O2 cathodes: Early transition metal d0 dopants and manganese pyrophosphate coating. J. Power Sources 2020, 479, 228591. [Google Scholar] [CrossRef]
  38. Hu, Y.; Liu, X. A novel method for preparing α-LiFeO2 nanorods for high-performance lithium-ion batteries. Ionics 2019, 26, 1057–1061. [Google Scholar] [CrossRef] [Green Version]
  39. Xu, H.; Sun, J.; Gao, L. Hydrothermal synthesis of LiMnO2 microcubes for lithium ion battery application. Ionics 2012, 19, 63–69. [Google Scholar] [CrossRef]
  40. Välikangas, J.; Laine, P.; Hietaniemi, M.; Hu, T.; Tynjälä, P.; Lassi, U. Precipitation and Calcination of High-Capacity LiNiO2 Cathode Material for Lithium-Ion Batteries. Appl. Sci. 2020, 10, 8988. [Google Scholar] [CrossRef]
  41. Shaari, H.R.; Sethuprakhash, V.; Basirun, W.J. Vanadium based lithium nickel aluminiumoxide system with good performance in lithium-ion batteries. J. Teknol. 2016, 78, 5–10. [Google Scholar] [CrossRef] [Green Version]
  42. Ram, P.; Gören, A.; Gonçalves, R.; Choudhary, G.; Ferdov, S.; Silva, M.M.; Singhal, R.; Costa, C.M.; Sharma, R.K.; Lanceros-Méndez, S. Improved electrochemical performance of rare earth doped LiMn1.5-xNi0.5RExO4 based composite cathodes for lithium-ion batteries. Compos. Part B: Eng. 2017, 139, 55–63. [Google Scholar] [CrossRef]
  43. Uzun, D.; Doğrusöz, M.; Mazman, M.; Biçer, E.; Avci, E.; Şener, T.; Kaypmaz, T.C.; Demir-Cakan, R. Effect of MnO2 coating on layered Li(Li0.1Ni0.3Mn0.5Fe0.1)O2 cathode material for Li-ion batteries. Solid State Ion. 2013, 249-250, 171–176. [Google Scholar] [CrossRef]
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Figure 1. Synthesis process of NFA material at 800 °C heat treatment.
Figure 1. Synthesis process of NFA material at 800 °C heat treatment.
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Figure 2. XRD patterns and the crystal structure of NFA material obtained at 800 °C.
Figure 2. XRD patterns and the crystal structure of NFA material obtained at 800 °C.
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Figure 3. SEM Micrographs (a–c) and EDS elemental compositions of NFA.
Figure 3. SEM Micrographs (a–c) and EDS elemental compositions of NFA.
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Figure 4. (a) Galvanostatic discharge–charge curves vs. Li/Li+ for NFA cycled at a rate of C/2 in 2 mol L−1 LiPF6 in 1:1 v/v ethylene carbonate (EC): dimethyl carbonate (DEC), cycle performance (First cycle (red line), 2 to 100 cycles (black line)); (b) Coulombic efficiency of NFA electrode cycled between 3.0 and 4.5 V vs. Li/Li+ at C/2 current rate.
Figure 4. (a) Galvanostatic discharge–charge curves vs. Li/Li+ for NFA cycled at a rate of C/2 in 2 mol L−1 LiPF6 in 1:1 v/v ethylene carbonate (EC): dimethyl carbonate (DEC), cycle performance (First cycle (red line), 2 to 100 cycles (black line)); (b) Coulombic efficiency of NFA electrode cycled between 3.0 and 4.5 V vs. Li/Li+ at C/2 current rate.
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Figure 5. Electrode process kinetics: (a) cyclic voltametric curves at various scan rates from 0.01 to 1.0 mV s−1; (b) relationships between the square root of scan rate (ν1/2) and the peak current (ip).
Figure 5. Electrode process kinetics: (a) cyclic voltametric curves at various scan rates from 0.01 to 1.0 mV s−1; (b) relationships between the square root of scan rate (ν1/2) and the peak current (ip).
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Figure 6. Galvanostatic charge–discharge profiles at different rates of (a) NFA; charge–discharge rate capability of (b) the NFA electrode at variant current rates from C/10 to C/2 (1C = 291 mA g−1).
Figure 6. Galvanostatic charge–discharge profiles at different rates of (a) NFA; charge–discharge rate capability of (b) the NFA electrode at variant current rates from C/10 to C/2 (1C = 291 mA g−1).
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Figure 7. (a) Operando XRD investigations to determine the different crystallographic transitions in the crystallographic planes (pattern) with a shift in lattice parameters as a function of the charge and discharge profiles. (b) the evolution of unit cell parameters upon the charge-discharge process. (These plots were recorded over the first 1.5 cycles from a cell containing a LiNi0.8Fe0.1Al0.1O2 cathode.)
Figure 7. (a) Operando XRD investigations to determine the different crystallographic transitions in the crystallographic planes (pattern) with a shift in lattice parameters as a function of the charge and discharge profiles. (b) the evolution of unit cell parameters upon the charge-discharge process. (These plots were recorded over the first 1.5 cycles from a cell containing a LiNi0.8Fe0.1Al0.1O2 cathode.)
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Figure 8. Schematic of structural changes when cycling between 3 and 4.5 V, based on the operando XRD test.
Figure 8. Schematic of structural changes when cycling between 3 and 4.5 V, based on the operando XRD test.
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Figure 9. (a) Raw materials represent increasing shares of battery and EV costs, according to S&P Global Market Intelligence, International Energy Agency (https://www.spglobal.com/ accessed on 31 December 2022); (b) a comparison of specific energy costs and cost per energy (kWh) of LCO, NMC111, NMC622, NFA811, and cobalt-free layered oxides.
Figure 9. (a) Raw materials represent increasing shares of battery and EV costs, according to S&P Global Market Intelligence, International Energy Agency (https://www.spglobal.com/ accessed on 31 December 2022); (b) a comparison of specific energy costs and cost per energy (kWh) of LCO, NMC111, NMC622, NFA811, and cobalt-free layered oxides.
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Table
Table 1. Comparison of the reversible capacity of cobalt-free-based positive electrodes for LIBs.
Table 1. Comparison of the reversible capacity of cobalt-free-based positive electrodes for LIBs.
Cobalt-Free Based ElectrodeSynthesis MethodCurrent RateReversible Capacity
(mAh g−1)		References
LiNi0.8Mn0.15Al0.05O2 (NMA)coprecipitation0.1 C210[35]
LiNi0.79Mn0.2Mg0.05O2 (NMM)coprecipitation0.1 C210[35]
LiNi0.79Mn0.2Ti0.01O2 (NMT)coprecipitation0.1 C210[35]
Li1.1[Fe0.2Ni0.2Mn0.6]0.9O2sol gel20 mA g−1175 (1st cycle)[36]
LiNi0.5Mn0.5O2sol gel20 mA g−1156[37]
α-LiFeO2 nanorodshydrothermal-assisted solid-state0.1 C165.85 (1st cycle)[38]
LiMnO2 microcubeshydrothermal1 C134[39]
LiNiO2 nanoparticlescoprecipitation0.1 C~135 (after 400 cycles)[40]
LiNixV1−x−y AlyO2carbon combustion method-~80.55
(for the first 10 cycles)		[41]
Li Ni0.5−x Al2x Mn1.5−x O4 (0 ≤ 2x ≤ 1.0)thermo-polymerization method10 C119[42]
Li(Li0.1Ni0.3Mn0.5Fe0.1)O2solid state0.1 C205[43]
LiNixFeyAlzO2 (x + y + z = 1)sol gel0.1 C160[16]
LiNixFeyAlzO2 (x + y + z = 1)coprecipitation0.2 C190[17]
LiNi0.8Fe0.1Al0.1O2solid-state0.1 C
0.2 C		180
160		This work
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Elmaataouy, E.; Chari, A.; El Bendali, A.; Tayoury, M.; Amine, R.; Aqil, M.; Xu, G.; Liu, T.; Alami, J.; Dahbi, M. LiNi0.8Fe0.1Al0.1O2 as a Cobalt-Free Cathode Material with High Capacity and High Capability for Lithium-Ion Batteries. Batteries 2023, 9, 23. https://doi.org/10.3390/batteries9010023

AMA Style

Elmaataouy E, Chari A, El Bendali A, Tayoury M, Amine R, Aqil M, Xu G, Liu T, Alami J, Dahbi M. LiNi0.8Fe0.1Al0.1O2 as a Cobalt-Free Cathode Material with High Capacity and High Capability for Lithium-Ion Batteries. Batteries. 2023; 9(1):23. https://doi.org/10.3390/batteries9010023

Chicago/Turabian Style

Elmaataouy, Elhoucine, Abdelwahed Chari, Ayoub El Bendali, Marwa Tayoury, Rachid Amine, Mohamed Aqil, GuiLiang Xu, Tongchao Liu, Jones Alami, and Mouad Dahbi. 2023. "LiNi0.8Fe0.1Al0.1O2 as a Cobalt-Free Cathode Material with High Capacity and High Capability for Lithium-Ion Batteries" Batteries 9, no. 1: 23. https://doi.org/10.3390/batteries9010023

APA Style

Elmaataouy, E., Chari, A., El Bendali, A., Tayoury, M., Amine, R., Aqil, M., Xu, G., Liu, T., Alami, J., & Dahbi, M. (2023). LiNi0.8Fe0.1Al0.1O2 as a Cobalt-Free Cathode Material with High Capacity and High Capability for Lithium-Ion Batteries. Batteries, 9(1), 23. https://doi.org/10.3390/batteries9010023

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