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Schematic density of states and Fermi energies for Li x Ni 0.5ÀyMn 1.5Ày Cr 2y O 4 spinel cathode. The Li permeable SEI layer formed on the electrode surface preserves the overall reversible reaction.
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The success of lithium-ion batteries in small-scale applications translates to large-scale applications, with an important impact in the future of the environment by improving energy efficiency and reduction of pollution. In this review, we present the progress that allows lithium-insertion compounds with the spinel structure to become the active c...
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Citations
... The spectra show fingerprints of a typical disordered spinel LNMO for both samples, as evidenced by the lack of a few extra peaks around 218 and 237 cm −1 , which are characteristic of the ordering of the Ni 2+ and Mn 4+ in the space group P43 32. 39 The peak at 630 cm −1 is attributed to Mn−O stretching mode in the octahedral MnO 6 groups, belonging to the A 1g mode, while the peak at 591 cm −1 (F 2g 1 ) is assigned to the Ni−O band. On the other hand, the peaks at 496 (F 2g 2 ) and 399 cm −1 (E g ) correspond to the Ni 2+ −O stretching mode in the structure. ...
There is an enormous drive for moving toward cathode material research in LIBs due to the proposal of zero-emission electric vehicles together with the restriction of cathode materials in design. LiNi0.5Mn1.5O4 (LNMO) attracts great research interests as high-voltage Co-free cathodes in LIBs. However, a more extensive study is required for LNMO due to its poor electrochemical performance, especially at high temperature, because of the instability of the LNMO interface. Herein, we design structural modifications using Mg and Zr to alleviate the above-mentioned drawbacks by limiting Mn dissolution and tailoring interstitial sites (which are shown by structural and electrochemical characterizations). This strategy enhances the cycle life up to 1000 cycles at both 25 and 50 °C. In addition, a thorough characterization by impedance spectroscopy is applied to give an insight into the electronic and ionic transport properties and the intricate phase transitions occurring upon oxidation and reduction.
... Among them, Li-ion batteries have high commercial interest due to their safety, lightweight, and appreciable gravimetric energy density of 250 Wh kg 1− . Olivines (e.g., LiFePO 4 ), 1 layered oxides (e.g., Li-Ni 0.8 Co 0.15 Al 0.05 O 2 (NCA), Li (Ni,Mn,Co)O 2 ) (NMC), 2−5 and spinels (e.g., LiMn 2 O 4 , i.e., LMO) 6,7 are commonly used as cathodes, along with graphite anodes. Graphite anodes were replaced by Si or Si-blended graphite anodes to increase the specific energy and energy density of Li-ion batteries. ...
Li metal secondary batteries known for their high energy and power density are the much-awaited energy storage systems owing to the high specific capacity of Li metal. However, due to the instability of Li metal with common Li-ion battery electrolytes, a combination with a polymer electrolyte seems to be an effective strategy to alleviate the safety issues of employing Li metal and provide design conformity to the system. Current trends show improvements in different aspects, such as improving ionic conductivity, single-ion conductivity, mechanical stability, and electrochemical stability. A combination of all these properties has been a bottleneck for the development of polymer electrolytes for safe and efficient operation of all solid-state batteries. Herein, a multifunctional polysalt has been synthesized from green and sustainable materials, namely, ethyl cellulose, plasticized with adiponitrile, that contributes to meeting the critical properties enabling high compatibility with Li metal and a quasi-single-ion-conducting property while simultaneously acting as a matrix/filler for efficient operation of the cells. This multifunctional polymer matrix inhibits further decomposition of nitrile-based plasticizers on Li metal anodes with the formation of a favorable Li metal anode interface, thus enabling the utilization of high-voltage stable nitrile-based plasticizers (4.2 V) to be implemented as an electrolyte component for realization of high-voltage Li metal anode polymer batteries.
... Several cathode materials based on layered oxides, spinel oxides, and polyanionic compounds (e. g., phosphates, silicates, sulfates, etc.) have been developed for high-voltage AMIBs. [6][7][8][9][10][11][12] However, developing a high-voltage electrolyte is still a challenge for researchers. For instance, electrolytes that are degraded/decomposed at high voltage cause crosstalk between the anode and cathode, leading to shorter battery life and raising a safety concern. ...
High‐voltage alkali metal‐ion batteries (AMIBs) require a non‐hazardous, low‐cost, and highly stable electrolyte with a large operating potential and rapid ion conductivity. Here, we have reported a halogen‐free high‐voltage electrolyte based on SiB11(BO)12⁻. Because of the weak π‐orbital interaction of −BO as well as the mixed covalent and ionic interaction between SiB11‐cage and −BO ligand, SiB11(BO)12⁻ has colossal stability. SiB11(BO)12⁻ possesses extremely high vertical detachment energy (9.95 eV), anodic voltage limit (∼10.05 V), and electrochemical stability window (∼9.95 V). Furthermore, SiB11(BO)12⁻ is thermodynamically stable at high temperatures, and its large size allows for faster cation movement. The alkali salts MSiB11(BO)12 (M=Li, Na, and K) are easily dissociated into ionic components. Electrolytes based on SiB11(BO)12⁻ greatly outperform commercial electrolytes. In short, SiB11(BO)12⁻‐based compound is demonstrated to be a high‐voltage electrolyte for AMIBs.
... Recently, high-energy active materials like lithium-and manganese-rich nickel-cobalt-manganese oxides (LMR-NCM), lithiumnickel-cobalt-aluminum oxides (NCA), and lithium-nickel-manganese oxides (LNMO) increased in popularity in comparison to stateof-the-art lithium-nickel-cobalt-manganese oxide (NCM) materials. [3][4][5][6] The materials facilitate higher energy densities while assuring low material costs due to their high nickel and low cobalt content. 7 For the anode, the partial replacement of graphite with silicon is desired due to the ten times higher specific capacity of silicon. ...
... 17 For nickel-rich, high-energy cathode materials, higher cut-off voltages are frequently chosen to maximize the retrievable cell capacity. 3 At high voltages, significant quantities of CO 2 are generated due to the release of reactive lattice oxygen species and subsequent oxidation of the electrolyte. 18 Electrolyte additives like vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are frequently used to stabilize the electrolyte and improve SEI formation. ...
Improving the energy density of lithium-ion batteries advances the use of novel electrode materials having a high specific capacity, such as nickel-rich cathodes and silicon-containing anodes. These materials exhibit a high level of gas evolution during formation, posing a safety hazard during operation. Analyzing the gas volume and the gassing duration is thus crucial to assess material properties and determine suitable formation procedures. We present a novel method for evaluating both gassing and swelling simultaneously to determine the operando gas evolution of pouch cells with volume resolutions below 1 µl. Dual 1D dilatometry is performed using a cell expansion bracket which applies a quasi-constant force on the cell, thus providing reproducible formation conditions. The method was validated using the immersion bath measurement and NCM/graphite pouch cells were compared to high-energy NCA/silicon-graphite pouch cells. Silicon-containing cells exhibited gas evolution higher by a factor of seven over ten successive cycles, thus demonstrating the challenges of high-silicon anodes. The concurrent dilation analysis further revealed a constant thickness increase over the formation, indicating continuous solid electrolyte interface growth and lithium loss. Consequently, the method can be used to select an ideal degassing time and to adjust the formation protocols with respect to gas evolution.
... The full realization of the theoretical possibilities corresponds to a specific energy of 622 W·h·kg −1 . This value is more than or comparable to commercially available cathode materials such as LiCoO 2 (518 W·h·kg −1 ), LiMn 2 O 4 (400 W·h·kg −1 ), LiFePO 4 (495 W·h·kg −1 ), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 (576 W·h·kg −1 ), and LiNi 0.5 Mn 1.5 O 4 (610 W·h·kg −1 ) [4,5]. LiCoVO 4 has the potential to provide an alternative to the electrode materials currently in use, as well as complementing a set of materials to choose from for specific applications and conditions. ...
... For lithium-ion cathode materials, the first process is lithium ion extraction during charging. Thus, the incomplete extraction of lithium ions from the structure of the material which are potentially capable of participating in the intercalation process is the only factor that limits the level of the specific charge-discharge capacity of LiCoVO 4 . The fact that the material has structural resolutions for the electrode process, a high electrochemical potential, and a high theoretical capacitance is undoubtedly a necessary condition for the manifestation of electrochemical activity. ...
The development of electrode materials for metal-ion batteries is a complex and resource-demanding process. The optimization of this development process requires a combination of theoretical and experimental methods. The former is used to predict the properties of materials and the latter to confirm them. Thus, it is very important to understand how the results of the modeling and experiment are related. In this study, we compare the results of determining the activation energies of lithium ion diffusion in cobalt(II)-lithium vanadate(V), which we obtained by calculations from first principles within the framework of density functional theory (DFT), with the experimental results, which we achieved by applying electrochemical methods such as cyclic voltammetry and galvanostatic and potentiostatic pulses. Based on the experimental and theoretical data obtained for LiCoVO4, we hypothesize that the limitation of the practically realizable capacity of the material at about 1/3 of the theoretical one is due to its structural limitations that lead to the impossibility of involving all lithium ions in the current-forming process. This reason is fixed by the simulation results, but is not detected by the experimental results.
... V (vs. Li/Li + ) in the redox reaction of Ni 2+ /Ni 3+ and Ni3+/Ni 4+ , increasing the energy density (650 Wh Kg −1 ) by around 20%-30% compared to that of conventional LiCoO 2 and LiFePO 4 materials (Scott et al., 2008;Liu et al., 2014). However, the presence of Mn 3+ ions in LNMO results in the dissolution of Mn 2+ ions (2Mn 3+ → Mn 4+ + Mn 2+ ) during lithiation/delithiation at high operating voltage (>4.5 V) and temperature (>40°C), as well as in Jahn-Teller distortion; as a result, a significant capacity reduction occurs Li et al., 2007;Liu et al., 2010;Shin et al., 2012;Manthiram et al., 2014). ...
LiNi0.5Mn1.5O4 (LNMO), a next-generation high-voltage battery material, is promising for high-energy-density and power-density lithium-ion secondary batteries. However, rapid capacity degradation occurs due to problems such as the elution of transition metals and the generation of structural distortion during cycling. Herein, a new LNMO material was synthesized using the Taylor-Couette flow-based co-precipitation method. The synthesized LNMO material consisted of secondary particles composed of primary particles with an octahedral structure and a high specific surface area. In addition, the LNMO cathode material showed less structural distortion and cation mixing as well as a high cyclability and rate performance compared with commercially available materials.
... More such quantitative comparison of electrochemical performance for different CAMs can be found in respective review works. Layered: NMC (LiNi x Mn y Co 1-x-y O 2 ) [13], NCA (LiNi x Co y Al 1-x-y O 2 ) [14], LNO (LiNiO 2 ) [15]; spinel: LMO (LiMn 2 O 4 ) [16], LNM (LiNi 0.5 Mn 1.5 O 4 ) [17,18]; olivine: LFP (LiFePO 4 ) [19,20], LCP (LiCoPO 4 ) [21], LMP (LiMnPO 4 ) [22,23]. ...
... Different compositions of Li 2 Fe 1−x Co x/2 Mn x/2 SiO 4 were prepared through rapid solid state synthesis [48]. Solid state synthesis is also employed to generate other promising CAMs such as layered: LNO [15], NCA [14], single crystal NMC622 [49]; spinel: LMO [16], LNM [17,18,50]; and tavorite: Li 2 CoPO 4 F [51], NaLiFePO 4 F [52]. ...
... After drying and heat treatment Li 2 FeSO 4 was obtained [55]. Molten salt synthesis has also been used for generating layered: single crystal NMC particles [27,56]; spinel: LNM [17,18,50]; and olivine: LFP/C composites [57]. ...
This work reviews different techniques available for the synthesis and modification of cathode
active material particles used in Li-ion batteries. The synthesis techniques are analyzed in terms
of processes involved and product particle structure. The knowledge gap in the process-particle
structure relationship is identified. Many of these processes are employed in other similar
industries; hence, parallel insights and knowledge transfer can be applied to battery materials.
Here, we discuss examples of applications of different mechanistic models outside the battery
literature and identify similar potential applications for the synthesis of cathode active materials.
We propose that the widespread implementation of such mechanistic models will increase the
understanding of the process-particle structure relationship. Such understanding will provide
better control over the cathode active material synthesis technique and open doors to the precise
tailoring of product particle morphologies favorable for enhanced electrochemical performance.
... Stoichiometric substitution of the Co in LCO results in LiNi x Co y Mn z O 2 (NCM; x + y + z = 1),LiNi x Co y Al z O 2 (NCA; x + y + z = 1), layered metal oxides with excess Li, or spinel-typeLiNi 0.5 Mn 1.5 O 4 (LMNO) and LiMn x Fe y PO 4 phosphates (x + y = 1). [8][9][10] A suitable arrangement in the stoichiometry of these systems can alter the energy band to push the redox end potentials up for achieving high-voltage positive electrodes. As recorded for Ni-rich NCA-type positive electrodes with a layered structure, for example, LiNi 0.80 Co 0.15 Al 0.05 O 2 for excellent gravimetric capacity and robust structure. ...
All‐solid‐state batteries with solid ionic conductors packed between solid electrode films can release the dead space between them, enabling a greater number of cells to stack, generating higher voltage to the pack. This Review is focused on using high‐voltage cathode materials, in which the redox peak of the components is extended beyond 4.7 V. Li−Ni−Mn−O systems are currently under investigation for use as the cathode in high‐voltage cells. Solid electrolytes compatible with the cathode, including halide‐ and sulfide‐based electrolytes, are also reviewed. Discussion extends to the compatibility between electrodes and electrolytes at such extended potentials. Moreover, control over the thickness of the anode is essential to reduce solid‐electrolyte interphase formation and growth of dendrites. The Review discusses routes toward optimization of the cell components to minimize electrode‐electrolyte impedance and facilitate ion transportation during the battery cycle.
... The strong peak~640 cm À 1 is assigned to the stretching vibration mode of MnÀ O, which corresponds to the vibrational stretching of the MnO 6 octahedral groups, while the peak around 600 cm À 1 is attributed to the NiÀ O band. [38,39] Meanwhile, the intensity of A 1g (640 cm À 1 ) is higher than the peak intensity of F 2g (1) (600 cm À 1 ) for all thin films, which confirms the existence of a disordered structure. [40] The strong peak around 500 cm À 1 (F 2g (2) ) and the weak spectral feature at~400 cm À 1 (E g ) correspond to Ni 2 + À O lattice bond vibrations. ...
The Cover Feature illustrates the magnetron sputtering process with variable ratio of Ar/N as process gas that leads to the formation of thin‐films of N‐containing LNMO high voltage cathodes. These results in improved electrochemical performance with respect to bare LNMO could be used to fabricate thin‐film high voltage Li‐ion batteries. More information can be found in the Research H. Darjazi et al.
... 15−19 The electrochemical performance of spinel LiNi 0.5 Mn 1.5 O 4 is attributed to Ni 4+ /Ni 2+ redox, with Mn 4+ remaining unchanged. 17,18 Thus, the large amount of Mn as a transition metal in the lattice is not utilized. In addition, LiNi 0.5 Mn 1.5 O 4 shows fast capacity decay at elevated temperatures. ...
... In addition, LiNi 0.5 Mn 1.5 O 4 shows fast capacity decay at elevated temperatures. 17,18 Fluorine incorporation into oxides has the potential to increase the redox potential of transition metals due to the high electronegativity of fluorine, 20 to tailor the crystal structure, 7,21−23 and to enable access to compositions rich in Li. Earlier success has been demonstrated for lithium transition-metal oxyfluorides such as Li 2 MO 2 F (M = Ni, Mn, V) with a disordered rocksalt (Fm3m) crystal structure. ...
... The correspond-ing differential capacity plots (dQ/dV) are shown in Figure S6b. Li 1. 25 18 Sloping potential profiles are usually considered as characteristic features of a single-phase Li + (de)intercalation mechanism, 26,39 consistent with ex situ XRD and Raman data presented later. A maximum discharge capacity of 219 mAh g −1 was observed at a broader potential range between 1.5 and 5 V. ...
