Physical and Electrochemical Characterization of LiCo0.8M0.2O2 （M=Ni,Zr） Cathode Films for All-solid-state Rechargeable Thin-film Lithium Batteries

LiCo0.8M0.2O2 （M=Ni,Zr） films were fabricated by radio frequency sputtering deposition combined with conventional annealing methods. The strtuctures of the films were characterized with X-ray diffraction （XRD）, Raman spectroscopy and scarming electron microscopy （SEM） techniques. It was shown that the 700 ℃- annealed LiCo0.8M0.2O2 has an α-NaFeO2 like layered structure. All-solid-state thin-film batteries （TFBs） were fabrieated with these films as the cathode and their eleetroctemical performances were evaluated. It was found that doping of electrochemically active Ni and inactive Zr has different effects on the structural and elcctrochemical properties of the LiCoO2 cathode films. Ni doping increases the discharge capacity of the film while Zr doping improves its cycling stability.

In situ investigation of atmospheric corrosion behavior of PCB-ENIG under adsorbed thin electrolyte layer

The effects of relative humidity (RH) on a printed circuit board finished with electroless nickel immersion gold (PCB-ENIG) under an adsorbed thin electrolyte layer (ATEL) were investigated in situ via the measurement of cathodic polarization curves, electrochemical impedance spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to clearly elaborate the corrosion behavior of PCB-ENIG in the atmospheric environment. Results indicated that the cathodic process of PCB-ENIG under ATEL was dominated by the reduction of dissolved oxygen, corrosion products, and H2O. The cathodic current density of PCB-ENIG increased progressively with increasing RH. Moreover, its cathodic current density in the solution was greater than that under ATEL. This result demonstrated that the diffusion process was not the controlling step during the limiting reduction of cathodic oxygen. When the polarization potentials were located in a more negative region, the cathodic polarization current density gradually decreased under 75% and 85% RH. Notably, the anodic process became the controlling step in the extremely thin liquid film during the remainder of the experiment.

Effect of TiB_2 content on resistance to sodium penetration of TiB_2/C cathode composites for aluminium electrolysis

TiB2/C cathode composites with various contents of TiB2 were prepared and their characterizations were observed and compared. The expansion of samples due to sodium and bath penetration was tested with a modified laboratory Rapoport apparatus and the appearances of the cut sections of specimens after electrolysis were studied. The results show that the mass of TiB2/C cathode composites with mass fraction of TiB2 less than 70% appreciably increases, but that of the composites with mass fraction of TiB2 more than 70% decreases slightly after being baked. The resistance to sodium and bath penetration of TiB2/C cathode composites increases with the increase of TiB2 content, especially in the composites with high TiB2 content. TiB2/C cathode composites have high resistance to the penetration of sodium and bath as well as good wettability by molten aluminum, and keep integrality and have little change of appearance after electrolysis, which indicates that TiB2/C cathode composites can be used as inert wettable cathode for aluminum electrolysis.

Synthesis and characterization of triclinic structural LiVPO_4F as possible 4.2 V cathode materials for lithium ion batteries

A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.

Synthesis and electrochemical characterization of LiNi_(0.78)Co_(0.2)Al_(0.02)O_2 cathode material in a novel co-precipitation method

LiNi0.78 Co0.2 Al0.02O2 cathode materials were prepared with a novel co-precipitation method followed by heat-treating. The properties of the materials were characterized. XRD patterns showed that no secondary phase appeared and the hexagonal lattice parameter c of LiNi0.rsCoo.2AI^0202 was larger than that of LiNi0.8Co0.2O2. The SEM images indicated that the powders of the material were submicron size. The results of the ICP-AES analysis proved that elemental compositions of the material were similar to those of the targeted one. Cyclic voltammetry （3.0- 4. 2 V） illustrated that the new material had good lithium-ion intercalation/de-intercalation performance. The results of galvanostatic cycling showed that the initial specific discharge capacity of the prepared material was 181.4 mAh/g, and the specific discharge capacity was 177.3 mAh/g after 100 cycles （0. 2C, 3.0 - 4. 2 V, vs. Li^＋/Li） with the capacity retention ratio of 97.7%.

Preparation of LiFePO_4 for lithium ion battery using Fe_2P_2O_7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.

Effects of Na content on structure and electrochemical performances of Na_xMnO_(2+δ) cathode material

Sodium manganese oxides,NaxMnO2+δ(x = 0.4,0.5,0.6,0.7,1.0;δ = 0-0.3),were synthesized by solid-state reaction routine combined with sol-gel process.The structure,morphology and electrochemical performances of as-prepared samples were characterized by XRD,SEM,CV,EIS and galvanostatic charge/discharge experiments.It is found that Na0.6MnO2+δ and Na0.7MnO2+δ have high discharge capacity and good cycle performance.At a current density of 25 mA/g at the cutoff voltage of 2.0-4.3 V,Na0.6MnO2+δ gives the second discharge capacity of 188 mA·h/g and remains 77.9% of second discharge capacity after 40 cycles.Na0.7MnO2+δ exhibits the second discharge capacity of 176 mA·h/g and shows better cyclic stability;the capacity retention after 40 cycles is close to 85.5%.Even when the current density increases to 250 mA/g,the discharge capacity of Na0.7MnO2+δ still approaches to 107 mA·h/g after 40 cycles.

Physical Properties and Electrochemical Performance of Solid K_2FeO_4 Samples Prepared by Ex-situ and in-situ Electrochemical Methods

K2FeO4 powders were synthesized by the ex-situ and in-situ electrochemical methods, respectively, and characterized by infrared spectrum （IR）, scanning electron microscopy （SEM）, X-ray powder diffraction （XRD） and BET. Their electrochemical performances were investigated by means of galvanostatic discharge and electrochemi-cal impedance spectroscopy （EIS）. The results of physical characterization showed that the two samples have simi-lar structural features, but their surface morphologies and oriented growth of the crystals are different, which results in smaller specific surface area and lower solubility of the ex-situ electrosynthesized K2FeO4 sample. The results of discharge experiments indicated that the ex-situ electrosythesized K2FeO4 electrode has much larger discharge ca-pacity and lower electrode polarization than the in-situ electrosynthesized K2FeO4 electrode. It was found from the results of EIS that lower electrochemical polarization might be responsible for the improvement on the discharge performance of the ex-situ electrosynthesized K2FeO4 electrode.

Electrochemical performance of LiFePO_4/(C+Fe_2P) composite cathode material synthesized by sol-gel method

A LiFePO4/（C＋Fe2P） composite cathode material was prepared by a sol-gel method using Fe（NO3）3.9H20, LiAc·H2O）, NHaH2PO4 and citric acid as raw materials, and the physical properties and electrochemical performance of the composite cathode material were investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） and electrochemical tests. The Fe2P content, morphology and electrochemical performance of LiFePOa/（C＋Fe2P） composite depend on the calcination temperature. The optimized LiFePO4/（C＋FeeP） composite is prepared at 650 ~C and the optimized composite exhibits sphere-like morphology with porous structure and Fe2P content of about 3.2% （mass fraction）. The discharge capacity of the optimized LiFePO4/（C＋FeRP） at 0.1C is 156 and 161 mA.h/g at 25 and 55 ℃, respectively, and the corresponding capacity retentions are 96% after 30 cycles; while the capacity at 1C is 142 and 149 mA.h/g at 25 and 55 ℃, respectively, and the capacity still remains 135 and 142 mA-h/g after 30 cycles at 25 and 55℃, respectively.

Effect of cooling modes on microstructure and electrochemical performance of LiFePO_4

LiFePO4 was prepared by heating the pre-decomposed precursor mixtures sealed in vacuum quartz-tube. Three kinds of cooling modes including nature cooling, air quenching, and water quenching were applied to comparing the effects of cooling modes on the microstructure and electrochemical characteristics of the material. The results indicate that the water quenching mode can control overgrowth of the grain size of final product and improve its electrochemical performance compared with nature cooling mode and air quenching mode. The sample synthesized by using water quenching mode is of the highest reversible discharge specific capacity and the best cyclic electrochemical performance, demonstrating the first discharge capacity of 138.1 mA·h/g at 0.1C rate and the total loss of capacity of 3.11% after 20 cycles.

Technical optimization of LiFePO_4 preparation by water quenching treatment

A technique of combination of vacuum firing and water quenching was applied to the synthesis of LiFePO4 powder. The sample was prepared by heating the pre-decomposed precursor mixtures sealed in vacuum quartz-tube, followed by water quenching at the sintering temperature. The synthetic conditions were optimized by orthogonal experiment. The results indicate that the fast quenching treatment can avoid the overgrowth of single crystal and improve its availability ratio of active material. The sintering temperature has the greatest effect on the electrochemical performance of sample. Next is the molar ratio of Li to Fe and the sintering time, respectively. The samples prepared in the optimized technical condition has the highest reversible discharge specific capacity of 149.8 mA·h/g.

Effect of Carbon Content on Electrochemical Properties of LiFePO4/C Composite Cathode

Olivine-type LiFePO4/C composite cathode materials were synthesized by a solid-state reaction method in an inert atmosphere. The glucose was added as conductive precursors before the formation of the crystalline phase. The effects of glucose content on the properties of as-synthesized cathode materials were investigated. The crystal structure and the electrochemical performance were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, laser particle-size distribution measurement and electrochemical performance testing. The material has a single crystal olivine structure with grain-sizes ca. 100-200 nm. SEM micrographs and the corresponding energy dispersive spectrometer （EDS） data confirm that the carbon particulates produced by glucose pyrogenation are uniformly dispersed among the LiFePO4 grains, ensuring a good electronic contact. Impedance spectroscopy was used to investigate the ohmic and kinetic contributions to the cell performance. It is found that increasing the carbon content leads to a reduction of the cell impedance due to the reduction of the charge transfer resistance. The galvanostatically charge and discharge tests show that the material obtained by adding 10% C （by mass） gives a maximum discharge capacity of 140.8mA·h·g^-1 at the same rate （C/10）. The material also displays a more stable cycle-life than the others.

Preparation and electrochemical performance of Li_2Mn_(0.5)Fe_(0.5)SiO_4 cathode material with sol-gel method for lithium ion batteries

Li2Fe0.5Mn0.5SiO4 material was synthesized by a citric acid-assisted sol-gel method. The influence of the stoichiometric ratio value of n(citric acid) to n(Fe2+-Mn2+) on the electrochemical properties of Li2Fe0.5Mn0.5SiO4 was studied. The final sample was identified as Li2Fe0.5Mn0.5SiO4 with a Pmn21 monoclinic structure by X-ray diffraction analysis. The crystal phases components and crystal phase structure of the Li2Fe0.5Mn0.4SiO4 material were improved as the increase of the stoichiometric ratio value of n(citric acid) to n(Fe2+-Mn2+). Field-emission scanning electron microscopy verified that the Li2Fe0.5Mn0.5SiO4 particles are agglomerates of Li2Fe0.5Mn0.5SiO4 primary particles with a geometric mean diameter of 220 nm. The Li2Fe0.5Mn0.5SiO4 sample was used as an electrode material for rechargeable lithium ion batteries, and the electrochemical measurements were carried out at room temperature. The Li2Fe0.5Mn0.5SiO4 electrode delivered a first discharge capacity of 230.1 mAh/g at the current density of 10 mA/g in first cycle and about 162 mAh/g after 20 cycles at the current density of 20 mA/g.

Synthesis and electrochemical performance of Li_2Mg_(0.15)Mn_(0.4)Co_(0.45)SiO_4/C cathode material for lithium ion batteries

The synthesis, structure and performance of Li2Mg0.15Mn0.4Co0.45SiO4/C cathode material were studied. The Li2Mg0.15Mn0.4Co0.45SiO4/C solid solution with orthorhombic unit cell （space group Pmn21） was synthesized successfully by combination of wet process and solid-state reaction at high temperature, and its electrochemical performance was investigated primarily. Li2Mg0.15Mn0.4Co0.45SiO4/C composite materials deliver a charge capacity of 302 mA-h/g and a discharge capacity of 171 mA.h/g in the first cycle. The discharge capacity is stabilized at about 100 mA-h/g after 10 cycles at a current density of 10 mA/g in the voltage of 1.5-4.8 V vs Li/Li^＋. The results show that Mg-substitution for the Co ions in Li2Mn0.4Co0.6SiO4 improves the stabilization of initial structure and the electrochemical nerformance.

Microporous bamboo biochar for lithium-sulfur batteries

Being simple, inexpensive, scalable and environmentally friendly, microporous biomass biochars have been attracting enthusiastic attention for application in lithium-sulfur （Li-S） batteries. Herein, porous bamboo biochar is activated via a KOH/annealing process that creates a microporous structure, boosts surface area and enhances electronic conductivity. The treated sample is used to encapsulate sulfur to prepare a microporous bamboo carbon-sulfur （BC-S） nanocomposite for use as the cathode for Li-S batteries for the first time. The BC-S nanocomposite with 50 wt.% sulfur content delivers a high initial capacity of 1,295 mA-h/g at a low discharge rate of 160 mA/g and high capacity retention of 550 mA-h/g after 150 cycles at a high discharge rate of 800 mA/g with excellent coulombic efficiency （995%）. This suggests that the BC-S nanocomposite could be a promising cathode material for Li-S batteries.

Hollow-in-hollow carbon spheres with hollow foam-like cores for lithium-sulfur batteries

Lithium-sulfur batteries have attracted increasing attention because of their high theoretical capadty. Using sulfur/carbon composites as the cathode materials has been demonstrated as an effective strategy to optimize sulfur utilization and enhance cycle stability as well. In this work hollow-in-hollow carbon spheres with hollow foam-like cores （HCSF@C） are prepared to improve both capability and cycling stability of lithium-sulfur batteries. With high surface area and large pore volumes, the loading of sulfur in HCSF@C reaches up to 70 wt.%. In the resulting S/HCSF@C composites, the outer carbon shell serves as an effective protection layer to trap the soluble polysulfide intermediates derived from the inner component. Consequently, the S/HCSF@C cathode retains a high capacity of 780 mAh/g after 300 cycles at a high charge/discharge rate of 1 A/g.

Reduced CoNi2S4 nanosheets decorated by sulfur vacancies with enhanced electrochemical performance for asymmetric supercapacitors

Nowadays,it is a matter of great concern to design electrode materials with excellent electrochemical performance for supercapacitors by a safe,efficient and simple method.And these characteristics are usually related to the vacancies and impurities in the electrode.To investigate the effect of the vacancies on the electrochemical properties of the supercapacitor cathode material,the uniform reduced CoNi2S4(r-CoNi2S4)nanosheets with sulfur vacancies have been successfully prepared by a one-step hydrothermal method.And the formation of sulfur vacancies are characterized by Raman,X-ray photoelectron spectroscopy and other means.As the electrode for supercapacitor,the r-CoNi2S4 nanosheet electrode delivers a high capacity of 1918.9 Fg-1 at a current density of 1 A g-1,superior rate capability(87.9%retention at a current density of 20 A g-1)and extraordinary cycling stability.Compared with the original CoNi2S4 nanosheet electrode(1226 F g-1at current density of 1 A g-1),the r-CoNi2S4 nanosheet electrode shows a great improvement.The asymmetric supercapacitor based on the r-CoNi2S4 positive electrode and activated carbon negative electrode exhibits a high energy density of 30.3 Wh kg-1 at a power density of 802.1 W kg-1,as well as excellent long-term cycling stability.The feasibility and great potential of the device in practical applications have been successfully proved by lightening the light emitting diodes of three different colors.

Nanostructuring the electronic conducting La_(0.8)Sr_(0.2)MnO_(3-δ) cathode for high-performance in proton-conducting solid oxide fuel cells below 600℃

Proton-conducting oxides offer a promising electrolyte solution for intermediate temperature solid oxide fuel cells（SOFCs） due to their high conductivity and low activation energy. However, the lower operation temperature leads to a reduced cathode activity and thus a poorer fuel cell performance. La_（0.8）Sr_（0.2）MnO_（3-δ）（LSM） is the classical cathode material for high-temperature SOFCs, which lack features as a proper SOFC cathode material at intermediate temperatures.Despite this, we here successfully couple nanostructured LSM cathode with proton-conducting electrolytes to operate below600℃ with desirable SOFC performance. Inkjet printing allows depositing nanostructured particles of LSM on Y-doped Ba ZrO_3（BZY） backbones as cathodes for proton-conducting SOFCs, which provides one of the highest power output for the BZY-based fuel cells below 600 ℃. This somehow changes the common knowledge that LSM can be applied as a SOFC cathode materials only at high temperatures（above 700 ℃）.

Ln_2MO_4 cathode materials for solid oxide fuel cells

One of the major challenges to develop "intermediate temperature" solid oxide fuel cells is finding a novel cathode material, which can meet the following requirements: (1) high electronic conductivity; (2) chemical compatibility with the electrolyte; (3) a matched thermal expansion coefficient (TEC); (4) stability in a wide range of oxygen partial pressure; and (5) high catalytic activity for the oxygen reduction reaction (ORR). In this short review, a survey of these requirements for K2NiF4-type material with the formula Ln2MO4, Ln = La, Pr, Nd, Sm; M = Ni, Cu, Fe, Co, Mn, is presented. The composition-dependent TEC, electrical conductivity and oxygen transport property are considered. The Ln2MO4 materials exhibit improved chemical stability and compatibility with most of the traditional electrolytes. The complete fuel cells integrated with Ln2MO4 materials as cathodes show promising results. Furthermore, these materials are considered as cathodes of protonic ceramic fuel cell (PCFC), and/or anodes of high temperature steam electrolysis (HTSE). First results show excellent performances. The versatility of these Ln2MO4 materials is explained on the basis of structural features and the ability to accommodate oxygen non-stoichiometry.