Pouch-typed cell from Li-rich LiFePO<Subscript>4</Subscript> prepared by low-cost carbothermal reduction method

Lithium iron phospho-olivine cathode material with optimized lithium amount for lithium-ion batteries was successfully prepared from low cost Fe₂O₃ as raw materials by thermal reduction method. The as-obtained material showed a reversible discharge capacity of 153.8 mAh g^–1 in the voltage window of 2.0–4.2 V at half-cell level. The pouch-typed cells with prepared Li_1.05FePO₄ were assembled to investigate electrochemical performance at level of full-cell. The results show that the assembled pouch-typed full-cells present better rate capability and cycle life. The low-cost approach reported here firstly sheds light on application of mass production of olivinestructured LiFePO₄ at level of full-cell.     

Carbon nanotubes as a conductive additive in LiFePO<Subscript>4</Subscript> cathode material for lithium-ion batteries

The electrochemical properties and cyclic performances of commercial LiFePO₄ cathode material with different ratio of carbon black (CB) and carbon nanotubes (CNTs) as conductive material were tested in this study. Compared with other samples, the sample with 3 wt % CNTs exhibited the best electro-chemical and cyclic performances at various discharging rate at room temperature; and adhesion strength of electrode was improved by adding CNTs. The enhanced electrode performance may due to the unique natures of CNTs and the contact area of CNTs with active material or current collector.     

Electrochemical performance of LiFePO<Subscript>4</Subscript>/C doped with F synthesized by carbothermal reduction method using NH<Subscript>4</Subscript>F as dopant

The effect of fluorine doping on the electrochemical performance of LiFePO₄/C cathode material is investigated. The stoichiometric proportion of LiFe(PO₄)_1−x F_3x /C (x = 0.01, 0.05, 0.1, 0.2) materials was synthesized by a solid-state carbothermal reduction route at 650 °C using NH₄F as dopant. X-ray diffraction, scanning electron microscope, energy-dispersive X-ray, and X-ray photoelectron spectroscopy analyses demonstrate that fluorine can be incorporated into LiFePO₄/C without altering the olivine structure, but slightly changing the lattice parameters and having little effect on the particle sizes. However, heavy fluorine doping can bring in impurities. Fluorine doping in LiFePO₄/C results in good reversible capacity and rate capability. LiFe(PO₄)_0.95 F_0.15/C exhibits highest initial capacity and best rate performance. Its discharge capacities at 0.1 and 5 C rates are 156.1 and 119.1 mAh g⁻¹, respectively. LiFe(PO₄)_0.95 F_0.15/C also presents an obviously better cycle life than the other samples. We attribute the improvement of the electrochemical performance to the smaller charge transfer resistance (R _ct) and influence of fluorine on the PO₄³⁻ polyanion in LiFePO₄/C.     

A novel method with low-cost Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> to synthesize small size LiFePO<Subscript>4</Subscript> by carbothermal reduction method

The phase-pure LiFePO₄/C cathode materials have been successfully fabricated by precursor containing Fe₂O₃ coated with polyaniline through carbothermal reduction method. The polyaniline coating at Fe₂O₃ could restrict the growth of crystal and subsequently become electric carbon at higher synthesis temperature. Compared with conventional carbothermal reduction method, the sample showed a better capacity and less than 3% capacity fading after 30 cycles at various charge and discharge rate.     

Nearly monodispersed LiFePO<Subscript>4</Subscript>F nanospheres as cathode material for lithium ion batteries

Tavorite-structured lithium transition metal fluorophosphates have been considered as a good alternative to olivine-type cathode for lithium-ion batteries due to its exceptional ionic conductivity and excellent thermal stability. In this work, nearly monodisperse LiFePO₄F nanospheres with high purity are successfully synthesized by a solid-state route associated with chemically induced precipitation method for the first time. The synthesized LiFePO₄F presents nearly monodisperse nanospheres particles with average particle size of ~?500 nm. Cyclic voltammetry data exhibit a clear indication of the Fe³⁺/Fe²⁺ redox couple that involves a two-phase transition. Its electrochemical behaviors are examined by galvanostatic charge-discharge. The results show that the initial discharge capacity is 110.2 mAh g^?1 at 0.5 C, after 200 cycles is still retained 104.0 mAh g^?1 with the retention rate of 94.4%. The excellent cycle performance is mainly attributed to the uniform nanospheres-like morphology which is not only beneficial to shorten the transport distance of ions and electrons, but also improve the interface area between electrode and electrolyte, and thus improve the kinetics of Li ions.     

LiFePO<Subscript>4</Subscript> synthesized via melt synthesis using low-cost iron precursors

LiFePO₄/C material has been prepared using fast-melt synthesis method followed by grinding and carbon coating. The low-cost iron ore concentrate (IOC) and purified iron ore concentrate (IOP) were used as iron precursors in the melt process to reduce significantly the cost of LiFePO₄/C. The same product was also synthesized using pure Fe₂O₃ under similar conditions as reference. The physical-chemical and electrochemical properties of samples were investigated. The X-ray Diffraction (XRD) results confirm the formation of an olivine structure of LiFePO₄ with a minor amount of Li₃PO₄ and Li₄P₂O₇ impurities for all the samples but no Fe₂P. The power performances of LiFePO₄/C using low-cost iron precursors were close to the sample using pure Fe₂O₃ precursor although capacity in mAh g^?1 is somewhat lower. With the inherent presence of silicon and other metals species, multi-substitution may take place when using IOC as source of iron leading to a Li(Fe_1-yM_y)(P_1-xSi_x)O₄ general composition. Multi-substitution, however, allows a better cycling stability. Therefore, these iron precursors present a promising option in this field to reduce the cost of a large-scale synthesis of LiFePO₄/C for Li-ion batteries application.     

Synthesis of high-energy-density LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode through surficial Nb doping for lithium-ion batteries

LiMn₂O₄ is one of the most promising cathode materials due to its high abundance and low cost. However, the practical application of LiMn₂O₄ is greatly limited owing to its low volumetric energy density. Therefore, increasing its energy density is an urgent problem to be resolved. Herein, using the simple and mass production preferred solid-state reaction, surficial Nb-doped LiMn₂O₄ composed of the truncated octahedral or spherical-like primary particles are successfully synthesized. Auger electron spectroscopy (AES) and X-ray diffraction (XRD) characterizations confirm that most of Nb⁵⁺ enrich in the surficial layer of the particles to form a LiMn_2-xNb_xO₄ phase. This kind of doping can increase the specific discharge capacity of LiMn₂O₄ materials. Contrast with the pristine LiMn₂O₄, the discharge capacity of LiMn_1.99Nb_0.01O₄-based 18650R-type battery increases from 1497 to 1705 mAh with the volumetric energy density increasing by ~?13.9%, benefiting from the joint increments of the specific discharge capacity from 119.5 to 123.7 mAh g^?1 and the compacted density from 2.81 to 3.10 g cm^?3. Furthermore, the capacity retention after 500 cycles at 1 C (1500 mA) is also improved by 17.1%.

Open image in new window

Graphical abstract ?

     

Facile synthesis of single-crystalline Co<Subscript>3</Subscript>O<Subscript>4</Subscript> cubes as high-performance anode for lithium-ion batteries

Transition metal oxides have great potential as anode for lithium-ion batteries (LIBs), owing to their high theoretical capacity and low cost. However, the poor cycling stability and electron conductivity have limited the widely expected application of transition metal oxides. In this work, highly single-crystalline Co₃O₄ cubes with 400 nm in the average side length are successfully synthesized by a facile hydrothermal method. When used as anode for LIBs, the Co₃O₄ single-crystalline cubes exhibit highly stable and substantial discharge capacities of the amount to 877 mA h g^?1 at 200 mA g^?1 after 110 cycles with remarkable capacity retention of 98%, and 576 mA h g^?1 even at a high rate of 2000 mA g^?1. The scalability of the preparation method and the impressive results achieved here demonstrate the potential for the application to the future development of transition metal oxides anodes. These results suggest that the single-crystalline Co₃O₄ is a promising electrode material for the high-performance energy storage devices.     

Mn<Subscript>3</Subscript>O<Subscript>4</Subscript>/carbon nanotubes nanocomposites as improved anode materials for lithium-ion batteries

Mn₃O₄ and Mn₃O₄ (140)/CNTs have been investigated as high-capacity anode materials for lithium-ion batteries (LIBs) applications. Nanoparticle Mn₃O₄ samples were synthesized by hydrothermal method using Mn(Ac)₂ and NH₃·H₂O as the raw materials and characterized by XRD, TG, EA, TEM, and SEM. Its electrochemical performances, as anode materials, were evaluated by galvanostatic discharge-charge tests. The Mn₃O₄ (140)/CNTs displays outstanding electrochemical performances, such as high initial capacity (1942 mAh g^?1), stable cycling performance (1088 mAh g^?1 and coulombic efficiency remain at 97% after 60 cycles) and great rate performance (recover 823 mAh g^?1 when return to initial current density after 44 cycles). Compared to pure Mn₃O₄ (140), the improving electrochemical performances can be attributed to the existence of very conductive CNTs. The Mn₃O₄ (140)/CNTs with excellent electrochemical properties might find applications as highly effective materials in electromagnetism, catalysis, microelectronic devices, etc. The process should also offer an effective and facile method to fabricate many other nanosized metallic oxide/CNTs nanocomposites for low-cost, high-capacity, and environmentally benign materials for LIBs.     

Effect of carbon sources on the morphology of LiFePO<Subscript>4</Subscript> cathode materials for lithium ion batteries

The LiFePO₄ materials were prepared by incorporating conductive carbon from pyrolysising three different carbon sources (acetylene black, glucose and phonetic resin). The morphology LiFePO₄/C was investigated by the SEM. Results revealed that the carbon precursor has much effect on the morphology of the samples. The carbon coated LiFePO₄ showed much better performance in terms of the discharge capacity and rate capability than the bare LiFePO₄. Among the carbon coated LiFePO₄, the particles coated with phonetic resin residual carbon exhibited better electrochemical properties than others and a proper mechanism was proposed.     

Preparation and electrochemical properties of Li<Subscript>0.97</Subscript>Er<Subscript>0.01</Subscript>FePO<Subscript>4</Subscript>/C composite for lithium-ion batteries

Li_0.97Er_0.01FePO₄/C composite was prepared by solid-state reaction, using particle modification with amorphous carbon from the decomposition of glucose and lattice doping with supervalent cation Er³⁺. All samples were characterized by X-ray diffraction, scanning electron microscopy, multi-point Brunauer Emmett and Teller methodes. The electrochemical tests show Li_0.97Er_0.01FePO₄/C composite obtains the highest discharge specific capacity of 154 mAh g⁻¹ at C/10 rate and the best rate capability. Its specific capacity reaches 131 mAh g⁻¹ at 2C rate. Its capacity loss is only 14.9 % when the rate varies from C/10 to 2C.     

Chelation-assisted method for the preparation of cathode material LiFePO<Subscript>4</Subscript>

LiFePO₄/C composite cathode material is prepared by ball milling with the assistance of EDTA chelation with using water as the media of ball mill procedure. FePO₄ and LiOH are used as starting materials; a certain amount of glucose is used as carbon sources and reduction agent. The structure and morphology of the composite are characterized by X-ray diffraction and scanning electron microscopy. Cyclic voltammetry, AC impedance measurements, and galvanostatic charge–discharge and cycling performances are used to characterize its electrochemical properties. The results indicate that the performances of composites prepared by chelation-assisted method are much better than common ball milling method which using alcohol or acetone as the media of ball mill procedure. The stable discharge capacity of the prepared composite is 150 and 105 mAh g⁻¹ at 1 and 10 C rate, respectively.     

Green fabrication of sandwich-like and dodecahedral C@Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@C as high-performance anode for lithium-ion batteries

Sandwich-structured C@Fe₃O₄@C hybrids with Fe₃O₄ nanoparticles sandwiched between two conductive carbon layers have attracted more and more attention owing to enhanced synergistic effects for lithium-ion storage. In this work, an environment-friendly procedure is developed for the fabrication of sandwich-like C@Fe₃O₄@C dodecahedrons. Zeolitic imidazolate framework (ZIF-8)-derived carbon dodecahedrons (ZIF-C) are used as the carbon matrix, on which iron precursors are homogeneously grown with the assistance of a polyelectrolyte layer. The subsequent polydopamine (PDA) coating and calcination give rise to the formation of sandwiched ZIF-C@Fe₃O₄@C. When being evaluated as the anode material for lithium-ion batteries, the obtained hybrid manifests a high reversible capacity (1194 mAh g^?1 at 0.05 A g^?1), good high-rate behavior (796 mAh g^?1 at 10 A g^?1), and negligible capacity loss after 120 cycles.     

Effect of starting materials on electrochemical performance of sol-gel-synthesized Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials for lithium-ion batteries

In this study, the effect of the sol-gel starting materials with different particle sizes on the sol-gel-synthesized spinel Li₄Ti₅O₁₂ (LTO) was systematically investigated. The physical and electrochemical properties of the synthesized materials were characterized by X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller-specific surface area analyses, galvanostatic charge/discharge tests, cyclic voltammetry, and electrochemical impedance spectroscopy. It was found that the initial particle size of sol-gel starting material played a crucial role on the properties of as-prepared LTOs. The LTO synthesized with the relatively finer particle size of starting materials possessed relatively smaller particle size and larger specific surface area and therefore resulted in the superior electrochemical properties. The initial discharge capacity of the as-prepared LTO exhibited 168.2, 150.6, and 142.7 mAh g^?1 at current densities of 1, 5, and 10 C, respectively, and up to 95, 95, and 90 % of the corresponding initial discharge capacity was retained after 50 cycles.     

Influence of manganese ions dissolved from LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode on the degradation of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>-based lithium-ion batteries

A systematic investigation is conducted to evaluate the influence of dissolved manganese ions from LiMn₂O₄ cathode on the degradation of Li₄Ti₅O₁₂-based lithium-ion batteries. Worse capacity fading is found in Li₄Ti₅O₁₂-based full cells with increasing manganese ion addition. The interfacial film covered on Li₄Ti₅O₁₂ anode is affected by the manganese ion contamination during cycling, which becomes thicker but more non-uniform, and is composed by less ratio of compact components and more ratio of loose components compared with that free of contamination. Such flawed passivation film cannot restrain the further penetration of electrolyte and inhibit the contact between electrolyte and Li₄Ti₅O₁₂ anodes efficiently, thus triggering more interfacial reactions and that should be the reason for the more severe capacity degradation. Accordingly, we suggest that in addition to optimizing the chemistry and microstructure of Li₄Ti₅O₁₂ electrode, more attention should also be paid to minimizing the destructive effect imposed on the passivation film of Li₄Ti₅O₁₂ electrode by the transition metal ion contaminations.     

A procedure for specific charge and cycling performance measurements on LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> spinels for lithium-ion batteries

Ohne Zusammenfassung     

Electrochemical and magnetic characterization of LiFePO<Subscript>4</Subscript> and Li<Subscript>0.95</Subscript>Mg<Subscript>0.05</Subscript>FePO<Subscript>4</Subscript> cathode materials

A series of lithium iron phosphates was synthesized via the sol–gel route. Iron phosphides, which are electronic conductors, were formed when sintered at 850°C. Magnetic susceptibility measurements on the samples show antiferromagnetic behaviour with T _N=50±2 K for LiFePO₄ and Li_0.95Mg_0.05PO₄ sintered at temperatures below 850°C. The LiFePO₄ and Li_0.95Mg_0.05FePO4 cathodes show a stable electrochemical capacity in the range of 150–160 mA h/g on cycling. The cyclability deteriorates with increasing sample sintering temperature due to the increased crystal size and impurities.     

A new charging mode of Li-ion batteries with LiFePO<Subscript>4</Subscript>/C composites under low temperature

Li-ion batteries with LiFePO₄/C composites are difficult to be charged at low temperatures. In order to improve the low temperature performance of LiFePO₄/C power batteries, the charge–discharge characteristics were studied at different temperatures, and a new charging mode under low temperature was proposed. In the new charging mode, the batteries were excited by current pulses with the charge rates between 0.75 C and 2 C, while the discharge rates between 3 and 4 C before the conventional charging (CC–CV). Results showed that the surface temperature of Li-ion battery ascended to 3 °C at the end of pulse cycling when the environment temperature was −10 °C. Comparing with the conventional charging, the whole charge time was cut by 36 min (23.4%) and the capacity was 7.1% more at the same discharge rate, respectively.     

BiFeO<Subscript>3</Subscript>-coated spinel LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> with improved electrochemical performance as cathode materials for lithium-ion batteries

Spinel LiNi_0.5Mn_1.5O₄ cathode material is a promising candidate for next-generation rechargeable lithium-ion batteries. In this work, BiFeO₃-coated LiNi_0.5Mn_1.5O₄ materials were prepared via a wet chemical method and the structure, morphology, and electrochemical performance of the materials were studied. The coating of BiFeO₃ has no significant impact on the crystal structure of LiNi_0.5Mn_1.5O₄. All BiFeO₃-coated LiNi_0.5Mn_1.5O₄ materials exhibit cubic spinel structure with space group of Fd3m. Thin BiFeO₃ layers were successfully coated on the surface of LiNi_0.5Mn_1.5O₄ particles. The coating of 1.0 wt% BiFeO₃ on the surface of LiNi_0.5Mn_1.5O₄ exhibits a considerable enhancement in specific capacity, cyclic stability, and rate performance. The initial discharge capacity of 118.5 mAh g^?1 is obtained for 1.0 wt% BiFeO₃-coated LiNi_0.5Mn_1.5O₄ with very high capacity retention of 89.11% at 0.1 C after 100 cycles. Meanwhile, 1.0 wt% BiFeO₃-coated LiNi_0.5Mn_1.5O₄ electrode shows excellent rate performance with discharge capacities of 117.5, 110.2, 85.8, and 74.8 mAh g^?1 at 1, 2, 5, and 10 C, respectively, which is higher than that of LiNi_0.5Mn_1.5O₄ (97.3, 90, 77.5, and 60.9 mAh g^?1, respectively). The surface coating of BiFeO₃ effectively decreases charge transfer resistance and inhibits side reactions between active materials and electrolyte and thus induces the improved electrochemical performance of LiNi_0.5Mn_1.5O₄ materials.     

Sol-assisted spray-drying synthesis of porous Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C microspheres as high-activity cathode materials for lithium-ion batteries

Herein, porous Li₃V₂(PO₄)₃/C microspheres made of nanoparticles are obtained by a combination of sol spray-drying and subsequent-sintering process. Beta-cyclodextrin serves as a special chelating agent and carbon source to obtain carbon-coated Li₃V₂(PO₄)₃ grains with the size of ca. 30–50?nm. The unique porous structure and continuous carbon skeleton facilitate the fast transport of lithium ion and electron. The Li₃V₂(PO₄)₃/C microspheres offer an outstanding electrochemical performance, which present a discharge capacity of 122?mAh?g^?1 at 2?C with capacity retention of 96% at the end of 1000 cycles and a high-rate capacity of 113?mAh?g^?1 at 20?C in the voltage window of 3.0–4.3?V. Moreover, the Li₃V₂(PO₄)₃/C microspheres also give considerable cycling stability and high-rate reversible capacity at a higher end-of-charge voltage of 4.8?V.

Open image in new window