A novel battery-supercapacitor system with extraordinarily high performance

In this paper, a battery-supercapacitor system is developed and its electrochemical performance is investigated. The battery-supercapacitor system is composed of a separated LiFePO₄/activated carbon cathode and a separated Li₄Ti₅O₁₂/activated carbon anode onto both sides of a piece of aluminum foil. We demonstrated the superior electrochemical performance of this battery-supercapacitor system, such as its energy density of 4.9–48.5 Wh/kg, power density of 167.7–5243.2 W/kg, rate capability of 73.9% at a current density of 20 A and cycle life (91.5% after 1800 cycles) which outperforms that of a hybrid supercapacitor. This can be explained by the synergistic effect of a Faradaic and non-Faradaic system in a single cell. The results clearly show that the battery-supercapacitor system, including a LiFePO₄ cathode/Li₄Ti₅O₁₂ anode and an activated carbon anode/activated carbon cathode, has great potential for use in advanced energy storage devices.     

A high rate,high capacity and long life (LiMn2O4 + AC)/Li4Ti5O12 hybrid battery–supercapacitor

A hybrid battery–supercapacitor (LiMn₂O₄ + AC)/Li₄Ti₅O₁₂ using a Li₄Ti₅O₁₂ anode and a LiMn₂O₄/activated carbon (AC) composite cathode was built. The electrochemical performances of the hybrid battery–supercapacitor (LiMn₂O₄ + AC)/Li₄Ti₅O₁₂ were characterized by cyclic voltammograms, electrochemical impedance spectra, rate charge–discharge and cycle performance testing. It is demonstrated that the hybrid battery–supercapacitor has advantages of both the high rate capability from hybrid capacitor AC/Li₄Ti₅O₁₂ and the high capacity from secondary battery LiMn₂O₄/Li₄Ti₅O₁₂. Moreover, the electrochemical measurements also show that the hybrid battery–supercapacitor has good cycle life performance. At 4C rate, the capacity loss in constant current mode is no more than 7.95% after 5000 cycles, and the capacity loss in constant current–constant voltage mode is no more than 4.75% after 2500 cycles.     

Effect of capacity matchup in the LiNi0.5Mn1.5O4/Li4Ti5O12 cells

The effect of the capacity matchup between cathode and anode in the LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ cell system on cycling property, choice of electrolyte, high voltage and overcharge tolerances was investigated by comparing the cells with Li₄Ti₅O₁₂ limiting capacity with the cells with LiNi_0.5Mn_1.5O₄ limiting capacity. The former exhibits better cycling performance and less limitation of electrolyte choice than the latter. Furthermore, the Li₄Ti₅O₁₂-limited cell exhibits better tolerance to high voltage and overcharge than the LiNi_0.5Mn_1.5O₄-limited cell, owing to taking advantage of the extra capacity of Li₄Ti₅O₁₂ below 1 V. It is thus recommended that the LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ cell whose capacity is limited by Li₄Ti₅O₁₂ anode should be used to extend the application of the state-of-the-art lithium-ion batteries.     

Nano Li4Ti5O12–LiMn2O4 batteries with high power capability and improved cycle-life

We report the effects of electrode thickness, cathode particle size and morphology, cathode carbon coating matching ratio and laminate structure on the electrochemical characteristics of nanosized Li₄Ti₅O₁₂–LiMn₂O₄ batteries. We show that a correct adjustment of these parameters resulted in significant improvements in power capability and cycle-life of such devices, making them competitive, low-cost and safe battery chemistry for next generation Li-ion batteries. In addition, Li₄Ti₅O₁₂ reversible specific capacity beyond three Li-ions intercalation is reported.     

Li4Ti5O12/Sn composite anodes for lithium-ion batteries: Synthesis and electrochemical performance

Li₄Ti₅O₁₂/tin phase composites are successfully prepared by cellulose-assisted combustion synthesis of Li₄Ti₅O₁₂ matrix and precipitation of the tin phase. The effect of firing temperature on the particulate morphologies, particle size, specific surface area and electrochemical performance of Li₄Ti₅O₁₂/tin oxide composites is systematically investigated by SEM, XRD, TG, BET and charge-discharge characterizations. The grain growth of tin phase is suppressed by forming composite with Li₄Ti₅O₁₂ at a calcination of 500 °C, due to the steric effect of Li₄Ti₅O₁₂ and chemical interaction between Li₄Ti₅O₁₂ and tin oxide. The experimental results indicate that Li₄Ti₅O₁₂/tin phase composite fired at 500 °C has the best electrochemical performance. A capacity of 224 mAh g⁻¹ is maintained after 50 cycles at 100 mA g⁻¹ current density, which is still higher than 195 mAh g⁻¹ for the pure Li₄Ti₅O₁₂ after the same charge/discharge cycles. It suggests Li₄Ti₅O₁₂/tin phase composite may be a potential anode of lithium-ion batteries through optimizing the synthesis process.     

Insight into effects of graphene and zinc oxide in Li4Ti5O12 as anode materials for Li-ion full-cell battery

Programmable design of nanocomposites of Li₄Ti₅O₁₂ (LTO) conducted through hydrothermal route in the presence of ethylenediamine as basic and capping agent. In this work, effect of ZnO and Graphene on the Li₄Ti₅O₁₂ based nanocomposites as anode materials investigated for Li-Ion battery performances. The full cells battery assembled with LTO based nanocomposites on Cu foil as the anode electrode and commercial LMO (LiMn₂O₄) on aluminum foil as cathode electrode. X-Ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectroscopy (FT-IR), along with Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission electron microscopy (TEM) images was applied for study the composition and structure of as-prepared samples. The electrochemical lithium storage capacity of prepared nanocomposites was compared with pristine LTO via chronopotentiometry charge-discharge techniques at 1.5–4.0 V and current rate of 100 mA/g. As a result, the electrode which is provided by LTO/TiO₂/ZnO and LTO/TiO₂/graphene nanocomposites provided 765 and 670 mAh/g discharge capacity compared with pristine LTO/TiO₂ (550 mAh/g) after 15 cycles. Based on the obtained results, fabricated nanocomposites can be promising compounds to improve the electrochemical performance of lithium storage.     

Power-ion battery: bridging the gap between Li-ion and supercapacitor chemistries

A 40 Wh/kg Li-ion battery using a Li₄Ti₅O₁₂ nanostructured anode and a composite activated carbon LiCoO₂ cathode was built using plastic Li-ion processing based on PVDF-HFP binder and soft laminate packaging. The specific power of the device is similar to that of an electrochemical double-layer supercapacitor (4000 W/kg). The high power is enabled by a combination of a nanostructured negative electrode, an acetonitrile based electrolyte and an activated carbon/LiCoO₂ composite positive electrode. This enables very fast charging (full recharge in 3 min). The effect of electrode formulation and matching ratio on energy, power and cycle-life are described. Optimization of these parameters led to a cycle-life of 20% capacity loss after 9000 cycles at full depth of discharge (DOD).     

High-density spherical Li4Ti5O12/C anode material with good rate capability for lithium ion batteries

Li₄Ti₅O₁₂ is a very promising anode material for lithium secondary batteries. To improve the material's rate capability and pile density is considered as the important researching direction. One effective way is to prepare powders composed of spherical particles containing carbon black. A novel technique has been developed to prepare spherical Li₄Ti₅O₁₂/C composite. The spherical precursor containing carbon black is prepared via an “outer gel” method, using TiOCl₂, C and NH₃ as the raw material. Spherical Li₄Ti₅O₁₂/C powders are synthesized by sintering the mixture of spherical precursor and Li₂CO₃ in N₂. The investigation of TG/DSC, SEM, XRD, Brunauer–Emmett–Teller (BET) testing, laser particle size analysis, tap-density testing and the determination of the electrochemical properties show that the Li₄Ti₅O₁₂/C composite prepared by this method are spherical, has high tap-density and excellent rate capability. It is observed that the tap-density of spherical Li₄Ti₅O₁₂/C powders (the mass content of C is 4.8%) is as high as 1.71 g cm⁻³, which is remarkably higher than the non-spherical Li₄Ti₅O₁₂. Between 1.0 and 3.0 V versus Li, the initial discharge specific capacity of the sample is as high as 144.2 mAh g⁻¹, which is still 128.8 mAh g⁻¹ after 50 cycles at a current density of 1.6 mA cm⁻².     

Nonflammable electrolyte for 3-V lithium-ion battery with spinel materials LiNi0.5Mn1.5O4 and Li4Ti5O12

The compatibility between dimethyl methylphosphonate (DMMP)-based electrolyte of 1 M LiPF₆/EC + DMC + DMMP (1:1:2 wt.) and spinel materials Li₄Ti₅O₁₂ and LiNi_0.5Mn_1.5O₄ was reviewed, respectively. The cell performance and impedance of 3-V LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ lithium-ion cell with the DMMP-based nonflammable electrolyte was compared with the baseline electrolyte of 1 M LiPF₆/EC + DMC (1:1 wt.). The nonflammable DMMP-based electrolyte exhibited good compatibility with spinel Li₄Ti₅O₁₂ anode and high-voltage LiNi_0.5Mn_1.5O₄ cathode, and acceptable cycling performance in the LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ full-cell, except for the higher impedance than that in the baseline electrolyte. All of the results disclosed that the 3 V LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ lithium-ion battery was a promising choice for the nonflammable DMMP-based electrolyte.     

Electrochemical performance of all-solid-state lithium secondary batteries improved by the coating of Li2O-TiO2 films on LiCoO2 electrode

All-solid-state lithium secondary batteries using LiCoO₂ particles coated with amorphous Li₂O-TiO₂ films as an active material and Li₂S-P₂S₅ glass-ceramics as a solid electrolyte were fabricated; the electrochemical performance of the batteries was investigated. The interfacial resistance between LiCoO₂ and solid electrolyte was decreased by the coating of Li₂O-TiO₂ films on LiCoO₂ particles. The rate capability of the batteries using the LiCoO₂ coated with Li₂Ti₂O₅ (Li₂O·2TiO₂) film was improved because of the decrease of the interfacial resistance of the batteries. The cycle performance of the all-solid-state batteries under a high cutoff voltage of 4.6 V vs. Li was highly improved by using LiCoO₂ coated with Li₂Ti₂O₅ film. The oxide coatings are effective in suppressing the resistance increase between LiCoO₂ and the solid electrolyte during cycling. The battery with the LiCoO₂ coated with Li₂Ti₂O₅ film showed a large initial discharge capacity of 130 mAh/g and good capacity retention without resistance increase after 50 cycles at the current density of 0.13 mA/cm².     

Electrochemical performance of Li4Ti5O12/carbon nanotubes/graphene composite as an anode material in lithium-ion batteries

A three-dimensional Li₄Ti₅O₁₂/carbon nanotubes/graphene composite (LTO-CNT-G) was prepared by ball-milling method, followed by microwave heating. The as-prepared LTO-CNT-G composite as anode material in lithium-ion battery exhibited superior rate capability and cycle performance under relative high current density compared with that of Li₄Ti₅O₁₂/CNTs (LTO-CNT) and Li₄Ti₅O₁₂/graphene (LTO-G) composites. Graphene nanosheets and CNTs were used to construct 3D conducting networks, leading to faster electron transfer and lower resistance during the lithium ion reversible reaction, which significantly enhanced the electrochemical activity of LTO-CNT-G composite. The synergistic effect of graphene and CNTs can greatly improve the rate capability and cycling stability of Li₄Ti₅O₁₂-based anodes. The LTO-CNT-G composite exhibited a high initial discharge capacity of 172 mAh g^?1 at 0.2 C and 132 mAh g^?1 at 20 C, as well as an excellent cycling stability. The electrochemical impedance spectroscopy demonstrated that the LTO-CNT-G composite has the smallest charge-transfer resistance compared with the LTO-CNT and LTO-G composites, indicating that the fast electron transfer from the electrolyte to the LTO-CNT-G active materials during the lithium ion intercalation/deintercalation owing to the three-dimensional networks of graphene and CNTs.     

Nanosized Li4Ti5O12/graphene hybrid materials with low polarization for high rate lithium ion batteries

We report a simple strategy to prepare a hybrid of lithium titanate (Li₄Ti₅O₁₂, LTO) nanoparticles well-dispersed on electrical conductive graphene nanosheets as an anode material for high rate lithium ion batteries. Lithium ion transport is facilitated by making pure phase Li₄Ti₅O₁₂ particles in a nanosize to shorten the ion transport path. Electron transport is improved by forming a conductive graphene network throughout the insulating Li₄Ti₅O₁₂ nanoparticles. The charge transfer resistance at the particle/electrolyte interface is reduced from 53.9 Ω to 36.2 Ω and the peak currents measured by a cyclic voltammogram are increased at each scan rate. The difference between charge and discharge plateau potentials becomes much smaller at all discharge rates because of lowered polarization. With 5 wt.% graphene, the hybrid materials deliver a specific capacity of 122 mAh g⁻¹ even at a very high charge/discharge rate of 30 C and exhibit an excellent cycling performance, with the first discharge capacity of 132.2 mAh g⁻¹ and less than 6% discharge capacity loss over 300 cycles at 20 C. The outstanding electrochemical performance and acceptable initial columbic efficiency of the nano-Li₄Ti₅O₁₂/graphene hybrid with 5 wt.% graphene make it a promising anode material for high rate lithium ion batteries.     

Fabrication and electrochemical properties of lithium-ion batteries for power tools

204056-Type prismatic lithium-ion battery for power tools was developed by using LiMn₂O₄ as cathode and CMS (carbonaceous mesophase spheres) as anode. The performance of batteries and their electrodes were characterized by SEM, ac impedance and electrochemical tests. The bulk density of cathode after pressing was selected as a main factor and it effects on high current rate capability and discharge plateau distinctly, which were investigated in details. Being charged/discharged in the voltage range of 2.5–4.2 V, the normal LiMn₂O₄ battery with cathode bulk density of 2.7 g cm⁻³ shows excellent electrochemical performances. The discharge capacity at 20C rate is 94.1% of that at 1C rate, and the capacity retention ratio charged at 1C and discharged at 5C is 91.7% after 100 cycles at 25 °C. While modified LiMn₂O₄ is used as the cathode material, the cycling performance of batteries is better than that of batteries made from normal LiMn₂O₄. The capacity retention ratios of modified LiMn₂O₄ batteries after 100 cycles at 25 °C and 55 °C are 95.0% and 85.3%, respectively. The discharge capacity at low temperature was tested both at 1C rate and 5C rate, and the capacities discharged at −20 °C were 96.3% and 94.2% of that at 1C at 25 °C. Furthermore, the batteries also show good safety in the test of short circuit, overcharge, and nail penetration.     

Investigation of new types of lithium-ion battery materials

This paper reports part of the activities in progress in our laboratory in the investigation of electrode and electrolyte materials which may be of interest for the development of lithium-ion batteries with improved characteristics and performances. This investigation has been directed to both anode and cathode materials, with particular attention to convertible oxides and defect spinel-framework Li-insertion compounds in the anode area and layered mixed lithium–nickel–cobalt oxide and high voltage, metal type oxides in the cathode area. As for the electrolyte materials, we have concentrated the efforts on composite polymer electrolytes and gel-type membranes. In this work we report the physical, chemical and electrochemical properties of the defect spinel-framework Li-insertion anodes and of the high voltage, mixed metal type oxide cathodes, by describing their electrochemical properties in cells using either “standard” liquid electrolytes and “advanced” gel-type, polymer electrolytes.The results illustrated here demonstrate that the spinel-framework anodes of the Li[Li_1/3Ti_5/3]O₄ type can be combined with high voltage cathodes of the Li₂M_xMn_(4−x)O₈ family for the fabrication of new types of lithium-ion battery systems cycling around 3.5 V. The development of this interesting concept is however still limited by the availability of highly stable electrolytes.     

A novel high-performance cylindrical hybrid supercapacitor with Li4−xNaxTi5O12/activated carbon electrodes

A cylindrical hybrid supercapacitor was fabricated using Li_4−xNa_xTi₅O₁₂ as an anode and activated carbon as a cathode. Li_4−xNa_xTi₅O₁₂ (0 ≤ x ≤ 0.6) powder was successfully crystallized, and the grain size of Li_4−xNa_xTi₅O₁₂ decreased with increasing Na content. This indicated that Na can enhance the electrochemical performance due to smaller grain size and ionic conductivity. However, excessive Na content causes a distortion of the original Li₄Ti₅O₁₂ structure during cycling. The hybrid supercapacitor with the Li_3.7Na_0.3Ti₅O₁₂ anode shows similar electrochemical performance to Li_3.4Na_0.6Ti₅O₁₂, and approximately 92% of the maximum cycle performance is retained, even after 5000 cycles at 2.5 Ag⁻¹.     

Template-assisted synthesis of high packing density SrLi2Ti6O14 for use as anode in 2.7-V lithium-ion battery

SrLi₂Ti₆O₁₄ has been prepared by using mesoporous TiO₂ brookite as a template and reactant. The prepared particles retained the rounded shape of the precursor, leading to high dispersivity and high packing density. The material has been further electrochemically characterized in both half and full cells. It shows good cycling stability and rate capability. A 2.7-V cell has been built by combining a SrLi₂Ti₆O₁₄ anode with a 4-V spinel cathode of LiMn₂O₄. This cell has a higher voltage compared to the 2.5-V LiMn₂O₄/Li₄Ti₅O₁₂ system.     

Performance of Li-ion secondary batteries in low power,hybrid power supplies

Small, portable electronic devices need power supplies that have long life, high energy efficiency, high energy density, and can deliver short power bursts. Hybrid power sources that combine a high energy density fuel cell, or an energy scavenging device, with a high power secondary battery are of interest in sensors and wireless devices. However, fuel cells with low self-discharge have low power density and have a poor response to transient loads. A low capacity secondary lithium ion cell can provide short burst power needed in a hybrid fuel cell–battery power supply. This paper describes the polarization, cycling, and self-discharge of commercial lithium ion batteries as they would be used in the small, hybrid power source. The performance of 10 Li-ion variations, including organic electrolytes with Li_xV₂O₅ and Li_xMn₂O₄ cathodes and LiPON electrolyte with a LiCoO₂ cathode was evaluated. Electrochemical characterization shows that the vanadium oxide cathode cells perform better than their manganese oxide counterparts in every category. The vanadium oxide cells also show better cycling performance under shallow discharge conditions than LiPON cells at a given current. However, the LiPON cells show significantly lower energy loss due to polarization and self-discharge losses than the vanadium and manganese cells with organic electrolytes.     

Li4Ti5O12/poly(methyl)thiophene asymmetric hybrid electrochemical device

Electrochemically prepared poly(methyl)thiophene is characterized by cyclic voltammetry and galvanometry with an activated carbon counter-electrode. It is then used as a cathode in a laminated plastic asymmetric hybrid electrochemical device with a nano-structured Li₄Ti₅O₁₂ anode. This device displays the specific power of a supercapacitor, with a higher specific energy of 10 Wh/kg, and better cycle-life than a Li-ion battery. The matching ratio of the active materials was found to strongly influence cycle-life.     

Preparation and characterization of high-density spherical Li4Ti5O12 anode material for lithium secondary batteries

Li₄Ti₅O₁₂ is a very promising anode material for lithium secondary batteries. A novel technique has been developed to prepare Li₄Ti₅O₁₂. The spherical precursor is prepared via an “inner gel” method by TiCl₄ as the raw material. Spherical Li₄Ti₅O₁₂ powders are synthesized by sintering the mixture of spherical precursor and Li₂CO₃. The investigation of XRD, SEM and the determination of the electrochemical properties show that the Li₄Ti₅O₁₂ powders prepared by this method are spherical, and have high tap-density and excellent electrochemical performance. It is tested that the tap-density of the product is as high as 1.64 g cm⁻³, which is remarkably higher than the non spherical Li₄Ti₅O₁₂. Between 1.0 and 3.0 V versus Li, a reversible capacity is as high as 161 mAh g⁻¹ at a current density of 0.08 mA cm⁻².     

Development of coin-type lithium-ion rechargeable batteries

We developed coin-type lithium-ion rechargeable batteries made of crystalline V₂O₅ for the cathode and pitch-based carbon for the anode. We optimized the capacity balance of cathode and anode materials. The batteries have a high operating voltage of about 2.7 V and excellent charge/discharge cycle characteristics. We also designed the batteries whose cathode potential is over 3 V versus lithium when the batteries are overdischarged to 0 V. Therefore, the batteries have excellent recovery characteristics even after overdischarge. The batteries have high energy density (about 100 Wh/l) which is about two times that of the coin-type NiCd batteries. It can serve as a memory backup power source with a single battery.