Improvement of electrochemical properties of MgO-coated LiNi0.4Co0.2Mn0.4O2 cathode materials for lithium ion batteries

The surface of LiNi_0.4Co_0.2Mn_0.4O₂ cathode is coated using MgO coating materials. The electrochemical properties of the coated materials are investigated as a function of the pH value of the coating solution and the composition of coating materials. Their microscopic structural features have been investigated using scanning electron microscopy and X-ray diffraction. The electrochemical properties of the samples were monitored using coin-cell by galvanostatic charge–discharge cycling test, EDS test, EIS test, and cyclic voltammetry. The coating solution with pH?=?10.5 is found to be favorable for the formation of stable coating layers, which enhances the electrochemical properties. In contrast, 2 % MgO-coated LiNi_0.4Co_0.2Mn_0.4O₂ shows better cycle performance and rate capability than the bare sample. Such enhancements are attributed to the presence of a stable MgO layer which acts as the interfacial stabilizer on the surface of LiNi_0.4Co_0.2Mn_0.4O₂.     

Influence of surface modification by vanadium oxide and carbon on the electrochemical performance of LiFePO4/C

Surface modification with metal oxides is an efficient method to improve the performance of LiFePO₄. Carbon and V₂O₃ co-coated LiFePO₄ is synthesized by carbothermal reduction method combined with star-balling technique, and vanadium oxide is produced in situ. The structure and pattern of LiFePO₄/C modified with different amounts of vanadium oxide (0–5 mol%) were studied by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and micro-Raman spectroscopy. The electrochemical performance of material electrodes was analyzed by constant current charge–discharge and electrochemical impedance spectra (EIS). Electrochemical test results show that sample B (1.0 mol%) exhibits the best electrochemical performance, whose discharge capacity is up to 160.1, 127.2, and 88.4 mAh?g^?1 at 1, 5, and 10 °C, respectively. It indicates that V₂O₃ modification efficiently improves specific capacity and rate capability. The EIS experiment demonstrates that catalytic activity and reversibility of the cathode electrode are obviously increased by the surface modification of vanadium oxide.     

Recent developments in the doping and surface modification of LiFePO4 as cathode material for power lithium ion battery

Lithium ion batteries have become attractive for portable devices due to their higher energy density compared to other systems. With a growing interest to develop rechargeable batteries for electric vehicles, lithium iron phosphate (LiFePO₄) is considered to replace the currently used LiCoO₂ cathodes in lithium ion cells. LiFePO₄ is a technically important cathode material for new-generation power lithium ion battery applications because of its abundance in raw materials, environmental friendliness, perfect cycling performance, and safety characteristics. However, the commercial use of LiFePO₄ cathode material has been hindered to date by their low electronic conductivity. This review highlights the recent progress in improving and understanding the electrochemical performance like the rate ability and cycling performance of LiFePO₄ cathode. This review sums up some important researches related to LiFePO₄ cathode material, including doping and coating on surface. Doping elements with coating conductive film is an effective way to improve its rate ability.     

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Nano-structured LiVPO₄F/Ag composite cathode material has been successfully synthesized via a sol–gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO₄F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO₄F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO₄F material exhibits high discharge capacity, good cycle performance (108.5 mAh g⁻¹ after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g⁻¹ for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (R_ct) of LiVPO₄F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO₄F for lithium-ion batteries cathode material.     

Effect of MoO3 surface coating on electrochemical performances of LiNi0.8Co0.1Mn0.1O2 cathode

In this paper, we synthesize the MoO 3 modified LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode (denoted as M-NCM81) and compare with pristine LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode (denoted as P-NCM81). The M-NCM81 cathode delivers good cation ordering and typical spherical form. The M-NCM81 cathode shows initial discharge capacity of 203.8 mAh g −1 at 0.1 C, capacity retention of 79.8% under the 5.0 C. In addition, the M-NCM81 cathode still retain a discharge capacity of 172.2 mAh g ⁻¹after 100 cycles. Such electrochemical performances are significantly improved compared to those of P-NCM81. It can be elucidated that MoO ₃ coating layer acts as a HF inhibitor/scavenger. The MoO ₃ modification plays an important role in inhibiting severe structural degradation, derived from a harmful side reaction with electrolyte. It effectively suppresses the increase in charge-transfer resistance, leading to superior electrochemical performances.     

Influence of NiCl2 modification on the electrochemical performance of LiV3O8 cathode for lithium ion batteries

The 5.0, 8.0, and 10.0 wt% NiCl₂-modified LiV₃O₈ materials are successfully prepared and the effects of NiCl₂ modification on the electrochemical performance of LiV₃O₈ cathode have been investigated. The structural and surface morphologic properties of synthesized materials are characterized by X-ray diffraction and scanning electron microscopy. The electrochemical properties are investigated by charge–discharge testing and cyclic voltammetry. It is found that 8.0 wt% NiCl₂-modified LiV₃O₈ shows excellent electrochemical properties. The initial discharge capacity of 8.0 wt% NiCl₂-modified LiV₃O₈ is much higher than that of pristine LiV₃O₈, and can attain 336.7 mAh g^?1 at the current rate of 0.5 C (300 mA g^?1 is assumed to be 1 C rate). Additionally, NiCl₂ modification significantly improves the cyclability of LiV₃O₈. The NiCl₂ modification is shown to be able to suppress the capacity fade of LiV₃O₈ without specific capacity expense by suppressing the characteristic phase transitions during cycling.     

Structural and electrochemical properties of Nd-doped LiFePO4/C prepared without using inert gas

To further improve the electrochemical performance of LiFePO₄/C, Nd doping has been adopted for cathode material of the lithium ion batteries. The Nd-doped LiFePO₄/C cathode was synthesized by a novel solid-state reaction method at 750 °C without using inert gas. The Li_0.99Nd_0.01FePO₄/C composite has been systematically characterized by X-ray diffraction, EDS, SEM, TEM, charge/discharge test, electrochemical impedance spectroscopy and cyclic stability. The results indicate that the prepared sample has olivine structure and the Nd³⁺ and carbon modification do not affect the structure of the sample but improve its kinetics in terms of discharge capacity and rate capability. The Li_0.99Nd_0.01FePO₄/C powder exhibited a specific initial discharge capacity of about 161 mAh g^− 1 at 0.1 C rate, as compared to 143 mAh g^− 1 of LiFePO₄/C. At a high rate of 2 C, the discharge capacity of Li_0.99Nd_0.01FePO₄/C still attained to 115 mAh g^− 1 at the end of 20 cycles. EIS results indicate that the charge transfer resistance of LiFePO₄/C decreases greatly after Nd doping.     

ZnO-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode material for lithium-ion batteries synthesized by a combustion method

ZnO-coated LiMn₂O₄ cathode materials were prepared by a combustion method using glucose as fuel. The phase structures, size of particles, morphology, and electrochemical performance of pristine and ZnO-coated LiMn₂O₄ powders are studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), galvanostatic charge-discharge test, and X-ray photoelectron spectroscopy (XPS). XRD patterns indicated that surface-modified ZnO have no obvious effect on the bulk structure of the LiMn₂O₄. TEM and XPS proved ZnO formation on the surface of the LiMn₂O₄ particles. Galvanostatic charge/discharge test and rate performance showed that the ZnO coating could improve the capacity and cycling performance of LiMn₂O₄. The 2 wt% ZnO-coated LiMn₂O₄ sample exhibited an initial discharge capacity of 112.8 mAh g^?1 with a capacity retention of 84.1 % after 500 cycles at 0.5 C. Besides, a good rate capability at different current densities from 0.5 to 5.0 C can be acquired. CV and EIS measurements showed that the ZnO coating effectively reduced the impacts of polarization and charge transfer resistance upon cycling.     

Enhanced electrochemical performances of LiNi0.5Co0.2Mn0.3O2 cathode material co-coated by graphene/TiO2

The electrochemical performances of LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) layered cathode material, such as poor rate capacity and cycling stability caused by undesirable intrinsic conductivity and low rate of lithium ion transportation, are not fairly good especially at elevated rate and cut-off voltage. To improve these properties, in this study, the co-coating layer of graphene and TiO₂ was constructed on NCM523 surface. The graphene/TiO₂ coating layer could effectively prevent hydrofluoric acid (HF) attacks, suppress the side reaction, accelerate the lithium ion diffusion and facilitate the electron migration. The enhancement of cycle performance and rate capacity was contributed to the uniform co-modified surface, interacting each other and thus exhibiting synergistic effects.     

Synthesis and characterization of pristine Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript> and Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C cathode materials for lithium ion batteries

The cathode materials, pristine Li₂MnSiO₄ and carbon-coated Li₂MnSiO₄ (Li₂MnSiO₄/C), were synthesized by the sol–gel method. Power X-ray diffraction and scanning electron microscopy analyses show that the presence of carbon during synthesis can weaken the formation of impurities in the final product and decrease the particle size of the final product. The effects of carbon coating on electrochemical characteristics were investigated by galvanostatic cycling test and electrochemical impedance spectroscopy. The galvanostatic cycling test results indicate that Li₂MnSiO₄/C cathode exhibits better electrochemical performance with an initial discharge capacity of 134.4 mAh g⁻¹ and a capacity retention of 63.9 mAh g⁻¹ after 20 cycles. Electrochemical impedance analyses confirm that carbon coating can increase electronic conductivity, which results in good electrochemical performance of Li₂MnSiO₄/C cathode. The two semicircles and the large arc obtained in this study can be attributed to the migration of lithium ions through the solid electrolyte interphase films, the electronic properties of the material, and the charge transfer step, respectively.     

Controllable Preparation of Nanosized LiMnPO4/C with Rod-Like Morphology by Hydrothermal Method with Excellent Electrochemical Performance

The nanosized rod-like LiMnPO₄/C cathode materials have successfully in situ synthesized on the surface of flaky structure MnPO₄ · H₂O self-sacrificing template by the hydrothermal method. The crystal microstructure, micro shape, and electrochemical parameters of LiMnPO₄/C are comprehensively studied by XRD, SEM, TEM, and electrochemical measurement methods. The physical and chemical properties analysis confirms that the vinyl acetate solution (VAc-H₂O) with a proper molar ratio is beneficial to generate orthorhombic olivine structure LiMnPO₄ with microporous structure and nanorod-shaped morphology. The electrochemical measurement results indicate that LMP-X1-AA sample delivers an initial discharge capacity of 148.1 mAh g⁻¹ at 0.05 C, the capacity retention rate still maintains at 89.2% after 200 cycles. As the discharge rate increases to 1 C, the discharge capacity still remains at 133.4 mAh g⁻¹. The results indicate that the synergistic effect of nanosized rod-like morphology and conductive carbon coating is beneficial to improving the lithium ions diffusivity and electrochemical properties of LiMnPO₄ materials.     

The preparation and characterization of olivine LiFePO4/C doped with MoO3 by a solution method

Composite Li_0.99Mo_0.01FePO4/C cathode materials were prepared by an easy solution method followed by heat-treating at various temperatures. XRD, SEM, TGA/DTA, EA, CV, XPS and charge–discharge cycles were used to evaluate the Li_0.99Mo_0.01FePO₄/C composite powders. The results indicate that mix-doping method does not affect the olivine structure of the cathode but considerably improves its capacity delivery and cycle performance. Among the prepared cathode materials, the sample heat-treated at 700 °C for 12 h shows best electrochemical performances. It shows initial specific discharge capacities of 161 and 124 mAh g^− 1 with C rates of 0.2C and 2C, respectively, which is ascribed to the enhancement of the electronic conductivity by ion doping and carbon coating.     

A review of recent developments in the surface modification of LiMn2O4 as cathode material of power lithium-ion battery

LiMn₂O₄ (LMO) is a very attractive choice as cathode material for power lithium-ion batteries due to its economical and environmental advantages. However, LiMn₂O₄ in the 4-V region suffers from a poor cycling behavior. Recent research results confirm that modification by coating is an important method to achieve improved electrochemical performance of LMO, and the latest progress was reviewed in the paper. The surface treatment of LMO by coating oxides and nonoxide systems could decrease the surface area to retard the side reactions between the electrode and electrolyte and to further diminish the Mn dissolution during cycling test. At present, LiMn₂O₄ is the mainstreaming cathode material of power lithium-ion battery, and, especially the modified LMO, is the trend of development of power lithium-ion battery cathode material in the long term.     

Influence of co-precipitation temperature on microstructure and electrochemical properties of Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript> cathode materials for lithium ion batteries

The layered Li-rich Mn-based cathode materials Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ were prepared by using co-precipitation technique at different temperatures, and their crystal microstructure and particle morphology were observed and analyzed by XRD and SEM. The electrochemical properties of these samples were investigated by using charge-discharge tests, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), respectively. The results indicated that all samples are of high purity. When the precursors were co-precipitated at 50 °C, their cathode materials have the most uniform and full particles and exhibit the highest initial discharge capacity (289.4 mAh/g at 0.1C), the best cycle stability (capacity retention rate of 91.2 % after 100 cycles at 0.5C), and the best rate performance. The EIS results show that the lower charge transfer resistance of 50 °C sample is responsible for its superior discharge capacity and rate performance.     

Enhanced rate performance of polypyrrole-coated sulfur/MWCNT cathode material: a kinetic study by electrochemical impedance spectroscopy

Lithium-sulfur batteries have a poor cyclability and inferior rate capability due to the shuttle effect of lithium polysulfides. To solve these problems, a sulfur-coated MWCNT composite (S/MWCNT) was coated with conductive polypyrrole (PPy) to trap the polysulfides and facilitate charge and lithium ion transport. From the contact angle measurement, it is found that the PPy coating improves the wettability of the S/MWCNT composite. Compared with the bare S/MWCNT composite, the PPy-coated S/MWCNT composite cathode exhibited improved cycle stability and high-rate performance. A reversible discharge capacity of 671 mAh g^?1 was maintained after 50 cycles at 3 C for the PPy-coated composite. The effect of PPy coating on kinetic property was investigated by electrochemical impedance spectroscopy (EIS). The electrolyte resistance, surface film resistance, charge transfer resistance, lithium ion diffusion coefficient, and exchange current density were evaluated from the EIS measurements. The EIS results reveal that the PPy coating increases both Li ion diffusion into the cathode and exchange current density. The as-prepared PPy-coated S/MWCNT composite can be considered to be a promising candidate for high capacity and high-rate performance cathode material.     

Vanadium Pentoxide‐Based Cathode Materials for Lithium‐Ion Batteries: Morphology Control,Carbon Hybridization,and Cation Doping

Vanadium pentoxide (V₂O₅) is a promising cathode material for high‐performance lithium‐ion batteries (LIBs) because of its high specific capacity, low cost, and abundant source. However, the practical application of V₂O₅ in commercial LIBs is still hindered by its intrinsic low ionic diffusion coefficient and moderate electrical conductivity. In the past decades, progressive accomplishments have been achieved that rely on the synthesis of nanostructured materials, carbon hybridization, and cation doping. Generally, fabrication of nanostructured electrode materials can effectively decrease the ion and electron transport distances while carbon hybridization and cation doping are able to significantly increase the electrical conductivity and diffusion coefficient of Li⁺. Implementation of these strategies addresses the problems that are related to the ionic and electronic conductivity of V₂O₅. Accordingly, the electrochemical performances of V₂O₅‐based cathodes are significantly improved in terms of discharge capacity, cycling stability, and rate capability. In this review, the recent advances in the synthesis of V₂O₅‐based cathode materials are highlighted that focus on the fabrication of nanostructured materials, carbon hybridization, and cation doping.     

An efficient process to fabricate spherical hierarchical LiFePO<Subscript>4</Subscript>/C cathode composites with controllable coating thickness

Hierarchical lithium iron phosphate/carbon (LiFePO₄/C) microspheres were fabricated successfully using a facile spray drying-assisted coprecipitation method. A relatively short calcination time and a relatively low calcination temperature were adopted to prepare the hierarchical LiFePO₄/C microspheres. The hierarchical microspheres consisted of nanoparticles with a uniform coating of amorphous carbon. The thickness of the carbon layer was controlled by the addition of glucose. The hierarchical LiFePO₄/C microspheres exhibited a high tap density and a large specific surface area. The electrochemical properties of the sample were investigated. The sample exhibited a better rate capability and a better cyclability than the coral-like LiFePO₄/C cathode material, and these were ascribed to the highly uniform carbon coating and the self-assembled nanoparticles.     

Electrochemical characterization of ionic liquid based gel polymer electrolyte for lithium battery application

High molecular weight polymer poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP), ionic liquid 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIMFSI), and salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based free-standing and conducting ionic liquid-based gel polymer electrolytes (ILGPE) have been prepared by solution cast method. Thermal, electrical, and electrochemical properties of 80 wt% IL containing gel polymer electrolyte (GPE) are investigated by thermogravimetric (TGA), impedance spectroscopy, linear sweep voltammetry (LSV), and cyclic voltammetry (CV). The 80 wt% IL containing GPE shows good thermal stability (~?200 °C), ionic conductivity (6.42?×?10^?4 S cm^?1), lithium ion conductivity (1.40?×?10^?4 S cm^?1 at 30 °C), and wide electrochemical stability window (~?4.10 V versus Li/Li⁺ at 30 °C). Furthermore, the surface of LiFePO₄ cathode material was modified by graphene oxide, with smooth and uniform coating layer, as confirmed by scanning electron microscopy (SEM), and with element content, as confirmed by energy dispersive X-ray (EDX) spectrum. The graphene oxide-coated LiFePO₄ cathode shows improved electrochemical performance with a good charge-discharge capacity and cyclic stability up to 50 cycles at 1C rate, as compared with the without coated LiFePO₄. At 30 °C, the discharge capacity reaches a maximum value of 104.50 and 95.0 mAh g^?1 for graphene oxide-coated LiFePO₄ and without coated LiFePO₄ at 1C rate respectively. These results indicated improved electrochemical performance of pristine LiFePO₄ cathode after coating with graphene oxide.     

A facile pyrolysis method to prepare vanadium oxides for high performance aqueous Zn-ion battery

Vanadium oxides, as one of the most promising cathode materials for zinc ion batteries, have attracted extensive attention in recent years. Different from the generally used hydrothermal and solvothermal methods to adjust the composition, structure, morphology and electrical properties of vanadium oxides, we firstly adopt a simple pyrolysis method to synthesize a series of vanadium oxides and use them as cathode materials for aqueous Zn-ion battery, whose electrochemical performances is superior to most state-of-the-art vanadium oxides. The as-obtained V₄O₇ under the calcination temperature of 700 °C exhibits excellent zinc ion storage performance with maximum specific capacity of 367.2 mAh g⁻¹ at the current density of 1 A g⁻¹, about 84.9% capacity retention after 100 cycles, excellent rate performance, high capacity. In addition, a series of structural and electrochemical characterization are used to reveal the possible mechanism of charge and discharge.     

Improvement of electrochemical performance for AlF<Subscript>3</Subscript>-coated Li<Subscript>1.3</Subscript>Mn<Subscript>4/6</Subscript>Ni<Subscript>1/6</Subscript>Co<Subscript>1/6</Subscript>O<Subscript>2.40</Subscript> cathode materials for Li-ion batteries

Li-rich layered-layered-Spinel structure spherical Li_1.3Mn_4/6Ni_1/6Co_1/6O_2.40 particles was successfully prepared and coated with a uniform layer by a two-step co-precipitation method and evaluated in lithium cells. The structures and electrochemical properties of pristine Li_1.3Mn_4/6Ni_1/6Co_1/6O_2.40 and AlF₃-coated Li_1.3Mn_4/6Ni_1/6Co_1/6O_2.40 were characterized. When the coating amount was 2 wt%, the cathode showed the best cycling performance and rate capability compared to others. The AlF₃-coated Li_1.3Mn_4/6Ni_1/6Co_1/6O_2.40 Li-ion cell cathode had a capacity retention of 90.07 % after 50 cycles at 0.5 C over 2.0–4.8 V, while the pristine Li_1.3Mn_4/6Ni_1/6Co_1/6O_2.40 exhibited capacity retention of only 80.73 %. Moreover, the rate capability and cyclic performance also improved. Electrochemical impedance spectroscopy testing revealed that the improved electrochemical performance might attribute to the AlF₃ coating layer which can suppress the increase of impedance during the charging and discharging process by preventing direct contact between the highly delithiated active material and electrolyte.