Hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@C hollow microspheres with high capacity as an anode material for lithium-ion batteries

Three-dimensional hierarchical Co₃O₄@C hollow microspheres (Co₃O₄@C HSs) are successfully fabricated by a facile and scalable method. The Co₃O₄@C HSs are composed of numerous Co₃O₄ nanoparticles uniformly coated by a thin layer of carbon. Due to its stable 3D hierarchical hollow structure and uniform carbon coating, the Co₃O₄@C HSs exhibit excellent electrochemical performance as an anode material for lithium-ion batteries (LIBs). The Co₃O₄@C HSs electrode delivers a high reversible specific capacity, excellent cycling stability (1672 mAh g^?1 after 100 cycles at 0.2 A g^?1 and 842.7 mAh g^?1 after 600 cycles at 1 A g^?1), and prominent rate performance (580.9 mAh g^?1 at 5 A g^?1). The excellent electrochemical performance makes this 3D hierarchical Co₃O₄@C HS a potential candidate for the anode materials of the next-generation LIBs. In addition, this simple synthetic strategy should also be applicable for synthesizing other 3D hierarchical metal oxide/C composites for energy storage and conversion.     

Preparation of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> hollow microsphere/graphene/carbon nanotube flexible film as a binder-free anode material for lithium-ion batteries

A flexible Co₃O₄ hollow microsphere/graphene/carbon nanotube hybrid film is successfully prepared through a facile filtration strategy and a subsequent thermally treated process. The composition, morphology, and structure of the as-prepared film are characterized by X-ray diffraction, X-ray photoelectron spectrometer, scanning electron microscopy, and transmission electron microscopy. Based on the morphology characterizations on the hybrid film, the Co₃O₄ hollow microspheres are uniformly and closely attached on three-dimensional (3D) graphene/carbon nanotubes (GR/CNTs) network, which decreases the agglomeration of Co₃O₄ microspheres effectively. In this hybrid film, the 3D GR/CNT network which enhances conductance as well as prevents aggregation is a benefit to help Co₃O₄ to exert its lithium storage capabilities sufficiently. When used as a binder-free anode material for lithium-ion batteries, the hybrid film delivers excellent electrochemical properties involving reversible capacity (863 mAh g^?1 at a current density of 100 mA g^?1) and rate performance (185 mAh g^?1 at a current density of 1600 mA g^?1).     

Dandelion-like mesoporous Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for lithium ion batteries

A dandelion-like mesoporous Co₃O₄ was fabricated and employed as anode materials of lithium ion batteries (LIBs). The architecture and electrochemical performance of dandelion-like mesoporous Co₃O₄ were investigated through structure characterization and galvanostatic charge/discharge test. The as-prepared dandelion-like mesoporous Co₃O₄ consisted of well-distributed nanoneedles (about 40 nm in width and about 5 μm in length) with rich micropores. Electrochemical experiments illustrated that the as-prepared dandelion-like mesoporous Co₃O₄ as anode materials of LIBs exhibited high reversible specific capacity of 1430.0 mA h g^?1 and 1013.4 mA h g^?1 at the current density of 0.2 A g^?1 for the first and 100th cycle, respectively. The outstanding lithium storage properties of the as-prepared dandelion-like mesoporous Co₃O₄ might be attributed to its dandelion-like mesoporous nanostructure together with an open space between adjacent nanoneedle networks promoting the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. The enhanced capacity as well as its high-rate capability made the as-prepared dandelion-like mesoporous Co₃O₄ to be a good candidate as a high-performance anode material for LIBs.     

Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres and their lithium storage properties

High-quality monodisperse multiporous hierarchical micro/nanostructured ZnCo₂O₄ microspheres have been fabricated by calcinating the Zn_1/3Co_2/3CO₃ precursor prepared by urea-assisted solvothermal method. The as-prepared products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) measurement to study the crystal phase and morphology. When tested as anode material for lithium ion batteries, the multiporous ZnCo₂O₄ microspheres exhibit an initial discharge capacity of 1,369 mAh g^?1 (3,244.5 F cm^?3) and retain stable capacity of 800 mAh g^?1 (1,896 F cm^?3) after 30 cycles. It should be noted that the good electrochemical performances can be attributed to the porous structure composed of interconnected nanoscale particles, which can promote electrolyte diffusion and reduce volume change during discharge/charge processes. More importantly, this ZnCo₂O₄ 3D hierarchical structures provide a large number of active surface position for Li⁺ diffusion, which may contribute to the improved electrochemical performance towards lithium storage.     

Improving the electrochemical performance of Li-rich Li<Subscript>1.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>O<Subscript>2</Subscript> cathode material by LiF coating

To suppress the capacity fade of Li-rich Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ material as cathode materials for lithium-ion battery, we introduce a LiF coating layer on the surface to improve the cycling performance of Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ material. The modified sample shows a capacity of 163.2 mAh g^?1 with a capacity retention of 95% after 100 cycles at a current density of 250 mA g^?1, while the pristine sample only delivers a capacity of 129.9 mAh g^?1 with a capacity retention of 82%. Compared with the pristine material, the LiF-modified sample exhibits an obvious enhancement in the electrochemical performance, which will be very beneficial for this material to be commercialized on the new energy vehicles and other related areas.     

Hexagonal-like NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> nanostructure based high-performance supercapacitor electrodes

A novel approach of double hydroxide-mediated synthesis of nickel cobaltite (NiCo₂O₄) electro-active material by the hydrothermal method is reported. The obtained NiCo₂O₄ electro-active material displays the spinel cubic phase and hexagonal-like morphology. Thermogravimetry analysis confirms the thermal stability of the electrode material. The functional groups and phase formation of NiCo₂O₄ have been confirmed by FT-IR and Raman spectral analysis. The modified NiCo₂O₄ electrode exhibits the highest specific capacitance of 767.5 F g^?1 at a current density of 0.5 A g^?1 in 3 M KOH electrolyte and excellent cyclic stability (94 % capacitance retention after 1000 cycles at a high current density of 5 A g^?1). The excellent electrochemical performance of the electrode is attributed to the hexagonal-like morphology, which contributes to the rich surface electro-active sites and easy transport pathway for the ions during the electrochemical reaction. The attractive Faradic behavior of NiCo₂O₄ electrode has been ascribed to the redox contribution of Ni²⁺/Ni³⁺ and Co²⁺/Co³⁺ metal species in the alkaline medium. The symmetrical two-electrode cell has been fabricated using the NiCo₂O₄ electro-active material with excellent electrochemical properties for supercapacitor applications.     

Improved electrochemical properties of YF<Subscript>3</Subscript>-coated Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> as cathode for Li-ion batteries

Yttrium fluoride YF₃ layer with different coating contents is successfully covered on the surface of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ via a common wet chemical approach. The XRD, SEM, TEM, and charge-discharge tests are applied to investigate the influence of YF₃ layer on the micro-structural, morphology, and electrochemical properties of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂. And the electrochemical test results demonstrate that the YF₃-coated LMNCO samples exhibit the improved electrochemical properties. The 2wt.%YF₃-coated LMNCO delivers a discharge capacity of 116.6 mAh g^?1 at 5 C rate, much larger than that (95.6 mAh g^?1) of the pristine one. Besides, the electrochemical impedance spectroscopy (EIS) and cyclic voltammetric results indicate that the YF₃ coating layer can promote the optimization formation of SEI film and reversibility of the electrochemical redox.     

Hierarchical porous ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> synthesized by the sucrose-assisted combustion method for high-rate supercapacitors

A simple sucrose-assisted combustion and subsequent high-temperature calcination route have been employed to prepare hierarchical porous ZnMn₂O₄ nanostructure. When used as an electrode for supercapacitor, the ZnMn₂O₄ electrode displays a high specific capacitance of 411.75 F g^?1 at a current density of 1 A g^?1, remarkable capacitance retention rate of 64.28 % at current density of 32 A g^?1 compared with 1 A g^?1, as well as excellent cycle stability (reversible capacity retention of 88.32 % after 4000 cycles). The outstanding electrochemical performances are mainly attributed to its hierarchical porous architecture, which provides large reaction surface area, fast ion and electron transfer, and good structure stability. All these impressive results demonstrate that ZnMn₂O₄ shows promise for its application in supercapacitors.     

Effects of doping Al on the structure and electrochemical performances 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

The Li-rich cathode material Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ had been successfully synthesized by a carbonate coprecipitation method. The effects of substituting traces of Al element for different transitional metal elements on the crystal structure and surface morphology had been investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy. The results revealed that all the materials showed similar XRD patterns and surface morphology. It was demonstrated that LNCMAl1 exhibited the superior electrochemical performance. The discharge capacity was 265.2 mAh g^?1 at 0.1 C and still maintained a discharge capacity of 135.6 mAh g^?1 at 5.0 C. The capacity retention could still be 58.2 and 66.8% after 50 cycles at 1.0 and 2.0 C, respectively. Electrochemical impedance spectra results proved that the remarkably improved rate capability and cycling performance could be ascribed to the low charge transfer resistance and enhanced reaction kinetics.     

Electrospinning preparation of one-dimensional Co<Superscript>2+</Superscript>-doped Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers for high-performance lithium ion battery

One-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofibers with a diameter of approximately 500 nm have been synthesized via a one-step controllable electrospinning method. The Co²⁺-doped Li₄Ti₅O₁₂ nanofibers were systematically characterized by XRD, ICP, TEM, SEM, BET, EDS mapping, and XPS. Based on the cubic spinel structure and one-dimensional effect of Li₄Ti₅O₁₂, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers exhibit the enlarged lattice volume, reduced particle size and enhanced electrical conductivity. More importantly, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers as a lithium ion battery anode electrode performs superior electrochemical performance than undoped Li₄Ti₅O₁₂ electrode in terms of electrochemical measurements. Particularly, the reversible capacity of Co²⁺-doped Li₄Ti₅O₁₂ electrode reaches up to 140.1 mAh g^?1 and still maintains 136.5 mAh g^?1 after 200 cycles at a current rate of 5 C. Therefore, one-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofiber electrodes, showing high reversible capacity and remarkable recycling property, could be a potential candidate as an anode material.     

Synthesis and electrochemical properties of Li<Subscript>1.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>O<Subscript>2</Subscript> cathode material for lithium-ion battery

The layered Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ lithium-rich manganese-based solid solution cathode material has been synthesized by a simple solid-state method. The as-prepared material has a typical layered structure with R-3m and C2/m space group. The synthesized Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ has an irregular shape with the size range from 200 to 500 nm, and the primary particle of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ has regular sphere morphology with a diameter of 320 nm. Electrochemical performances also have been investigated. The results show that the cathode material Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ prepared at 900 °C for 12 h has a good electrochemical performance, which can deliver a high initial discharge capacity of 233.5, 214.2, 199.3, and 168.1 mAh g^?1 at 0.1, 0.2, 0.5, and 1 C, respectively. After 50 cycles, the capacity retains 178.0, 166.3, 162.1, and 155.9 mAh g^?1 at 0.1, 0.2, 0.5, and 1 C, respectively. The results indicate that the simple method has a great potential in synthesizing manganese-based cathode materials for Li-ion batteries.     

Parallelepipedally shaped ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> particles with a hierarchical porous structure as an anode for lithium-ion batteries

The micrometer-sized ZnCo₂O₄ parallelepipeds with a hierarchical porous structure have been fabricated by a simple two-step procedure, i.e., the synthesis of the Zn_1/3Co_2/3CO₃ parallelepipeds and the subsequent calcination. When tested in lithium-ion batteries (LIBs), the hierarchical porous ZnCo₂O₄ parallelepipeds could exhibit a reversible capacity of >860 mAh g^?1 at a current density of 0.1 C. This clearly demonstrates the potential use of the hierarchical porous ZnCo₂O₄ parallelepipeds in LIBs. The high electrochemical performance of the hierarchical porous ZnCo₂O₄ parallelepipeds might originate from the unique porous structure which consists of the secondary ZnCo₂O₄ particles. First, the porous structure allows for a better accessibility of the active material to the Li⁺ ion storage, favoring easier diffusion of electrolyte in and out of electrode material. Second, the presence of the secondary particles shortens a pathway of Li⁺ diffusion in ZnCo₂O₄, facilitating the better utilization of the active material.     

NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> polyhedra with controllable particle size as high-performance anode for lithium-ion battery

Different particle sizes of dodecahedron precursors are synthesized by controlling the polarity of the solution. Through the results of scanning electron microscope (SEM) images, it can be found that different particle sizes of precursors present obvious edge angles and their morphology can be well retained after annealing. X-ray diffraction (XRD) measurements suggest that the annealed polyhedral products are pure single-phase NiCo₂O₄. When tested as lithium-ion battery anode, 0.5 μm NiCo₂O₄ polyhedra exhibits a specific capacity of 1050 mAh g^?1 at 0.1 C at the 60th cycle, which was higher than theoretical capacity of single metal oxide (NiO 718 mAh g^?1 and Co₃O₄ 890 mAh g^?1). It also exhibits the highest rate capability with an average discharge capacity of 890, 700, 490, 330, and 300 mAh g^?1 at 0.5, 2, 4, 8, and 10 C, respectively. Those advantages are attributed to that small-sized particle with great surface areas decrease the actual current density at the surface and inner of the prepared electrode.     

Improvement in rate capability of lithium-rich cathode material Li[Li<Subscript>0.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>]O<Subscript>2</Subscript> by Mo substitution

Lithium-rich cathode material Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D _Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g^?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g^?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.     

Preparation of carbon encapsulated Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode material for lithium ion battery through pre-coating method

Carbon encapsulated Li₄Ti₅O₁₂ (C/Li₄Ti₅O₁₂) anode material for lithium ion battery was prepared by using the pre-coat method of two steps, and the TiO₂ was pre coated before the reaction with Li₂CO₃. The structure and morphology of the resultant C/Li₄Ti₅O₁₂ materials were characterized by X-ray diffraction (XRD) and scanning microscopy (SEM). Electrochemical tests showed that at 0.1 C, the initial discharge capacity was 169.9 mAh g^?1, and the discharge capacity was 80 mAh g^?1 at 5 C. After 100 cycles at 2 C, the discharge specific capacity was 108.5 mAh g^?1. Compare with one step coating method, results showed the C/Li₄Ti₅O₁₂ prepared by pre-coat method can reduce the particle’s size and effectively improve the electrochemical performance.     

S/N dual-doped carbon nanosheets decorated with Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> nanoparticles as high-performance anodes for lithium-ion batteries

In this work, we have successfully synthesized the S/N dual-doped carbon nanosheets which are strongly coupled with Co _x O _y nanoparticles (SNCC) by calcinating cobalt/dithizone complex precursor following KOH activation. The SNCC as anode shows the wonderful charge capacity of 1200 mAh g^?1 after 400th cycles at 1000 mA g^?1 for Li-ion storage. The superior electrochemical properties illustrate that the SNCC can be a candidate for high-performance anode material of lithium-ion batteries (LIBs) because of the facile preparation method and excellent performance. Significantly, we also discuss the mechanism for the SNCC from the strong synergistic effect perspective.     

Advanced LiTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C anode by incorporation of carbon nanotubes for aqueous lithium-ion batteries

Inferior rate capability is a big challenge for LiTi₂(PO₄)₃ anode for aqueous lithium-ion batteries. Herein, to address such issue, we synthesized a high-performance LiTi₂(PO₄)₃/carbon/carbon nanotube (LTP/C/CNT) composite by virtue of high-quality carbon coating and incorporation of good conductive network. The as-prepared LTP/C/CNT composite exhibits excellent rate performance with discharge capacity of 80.1 and 59.1 mAh g^?1 at 10 C and 20 C (based on the mass of anode, 1 C = 150 mA g^?1), much larger than that of the LTP/C composite (53.4 mAh g^?1 at 10 C, and 31.7 mAh g^?1 at 20 C). LTP/C/CNT also demonstrates outstanding cycling stability with capacity retention of 83.3 % after 1000 cycles at 5 C, superior to LTP/C without incorporation of CNTs (60.1 %). As verified, the excellent electrochemical performance of the LTP/C/CNT composite is attributed to the enhanced electrical conductivity, rapid charge transfer, and Li-ion diffusion because of the incorporation of CNTs.     

Synthesis and lithium-ion storage performances of LiFe<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>PO<Subscript>4</Subscript>/C nanoplatelets and nanorods

Carbon-coated olivine-structured LiFe_0.5Co_0.5PO₄ solid solution was synthesized by a facile rheological phase method and applied as cathode materials of lithium-ion batteries. The nanostructure’s properties, such as morphology, component, and crystal structure for the samples, characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer, Emmett, and Teller (BET) determination, X-ray photoelectron spectroscopy (XPS), and the electrochemical performances were evaluated using constant current charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results indicate that nanoplatelet- and nanorod-structured LiFe_0.5Co_0.5PO₄/C composites were separately obtained using stearic acid or polyethylene glycol 400 (PEG400) as carbon source, and the surfaces of particles for the two samples are ideally covered by full and uniform carbon layer, which is beneficial to improving the electrochemical behaviors. Electrochemical tests verify that the nanoplatelet LiFe_0.5Co_0.5PO₄/C shows a better capacity capability, delivering a discharge specific capacity of 133.8, 112.1, 98.3, and 74.4 mAh g^?1 at 0.1, 0.5, 1, and 5 C rate (1 C?=?150 mA g^?1); the corresponding cycle number is 5th, 11th, 15th, 20th, and 30th, respectively, whereas the nanorod one possesses more excellent cycling ability, with a discharge capacity of 83.3 mAh g^?1 and capacity retention of 86.9% still maintained after cycling for 100 cycles at 0.5 C. Results from the present study demonstrate that the LiFe_0.5Co_0.5PO₄ solid solution nanomaterials with favorable carbon coating effect combine the characteristics and advantage of LiFePO₄ and LiCoPO₄, thus displaying a tremendous potential as cathode of lithium-ion battery.     

Thermoeletrochemical study on LiNi<Subscript>0.8</Subscript>Co<Subscript>0.1</Subscript>Mn<Subscript>0.1</Subscript>O<Subscript>2</Subscript> with in situ modification of Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript>

To improve the electrochemical performance of Nickel-rich cathode material LiNi_0.8Co_0.1Mn_0.1O₂, an in situ coating technique with Li₂ZrO₃ is successfully applied through wet chemical method, and the thermoelectrochemical properties of the coated material at different ambient temperatures and charge-discharge rates are investigated by electrochemical-calorimetric method. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests demonstrate that the Li₂ZrO₃ coating decreases the electrode polarizatoin and reduces the charge transfer resistance of the material during cycling. Moreover, it is found that with the ambient temperatures and charge-discharge rates increase, the specific capacity decreases, the amount of heat increases, and the enthalpy change (ΔH) increases. The specific capacity of the cells at 30 °C are 203.8, 197.4, 184.0, and 174.5 mAh g^?1 at 0.2, 0.5, 1.0, and 2.0 C, respectively. Under the same rate (2.0 C), the amounts of heat of the cells are 381.64, 645.32, and 710.34 mJ at 30, 40, and 50 °C. These results indicate that Li₂ZrO₃ coating plays an important role to enhance the electrochemical performance of LiNi_0.8Co_0.1Mn_0.1O₂ and reveal that choosing suitable temperature and current is critical for solving battery safety problem.     

Facile synthesis of hierarchical porous Ni-rich LiNi<Subscript>0.6</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode material with superior high-rate capability

A hierarchical porous nickel-rich LiNi_0.6Co_0.2Mn_0.2O₂ cathode is successfully prepared for the first time using a facile ammonia-induced method, wherein ammonia molecules play a key role in fabricating the complex architecture, and neither templates nor precipitants are employed. Hierarchical flower-like precursor with ultra-thin nanosheets is formed during the ammonia-induced reaction, and then, the porous product is obtained during the sintering process. The X-ray diffraction pattern demonstrates that the sample has a well-defined α-NaFeO₂ structure with very low-cation disorder. The peculiar hierarchical porous morphology and ideal structure endow this material-enhanced electrochemical performance. It delivers discharge capacities of 173, 138, 111, 97, and 82 mAh g^?1 at 0.1 C, 1 C, 5 C, 10 C, and 20 C, respectively, and maintains 91 % of its initial discharge capacity after 100 cycles at 1 C. The results reveal that this method is facile and feasible to synthesize high-rate Nickel-rich material.