Synthesis and characterization of metastable Li–Mn–O spinels from Mn(V)

Li₃MnO₄ Mn(V) was synthesized from LiOH and LiMnO₄, and characterized by gravimetric, X-ray, and XPS analysis. This precursor was used to improve the calcination time required for the low temperature solid state synthesis of highly oxidized spinels, Li₂Mn₄O_8+x. TG calculations were used to show the effect of calcination conditions on phase purity. The effect of a second phase on cycling performance was evaluated.     

Synthesis and electrochemical characterization of Li1.02Mg0.1Mn1.9O3.99S0.01 using sol–gel method

To improve the cycle performance of spinel LiMn₂O₄ as the positive electrode of 4 V lithium secondary batteries, the spinel oxysulfide Li_1.02Mg_0.1Mn_1.9O_3.99S_0.01 is synthesized by a sol–gel method using adipic acid as a chelating agent. The structural and electrochemical properties of the synthesized material are examined. Highly crystallized Li_1.02Mg_0.1Mn_1.9O_3.99S_0.01 is synthesized at 750°C in an oxygen atmosphere. Both cation and anion doping of spinel lithium manganese oxides are very effective for improving the cycle performance of lithium batteries.     

Microstructure and electrochemical properties of Zr–Ti–V–Ni–Mn–LM alloys for application in Ni–MH secondary battery

A series of multi-component Zr_1−xTi_xV_0.4Ni_1.2Mn_0.4LM_y (x=0.3, 0.4; y=0.0,0.02,0.05,0.1,0.2,0.3, LM; lantanum-rich-mischmetal) alloys are prepared and their crystal structure and P–C–T curves are analyzed. The alloys have been modified by adding LM and their gaseous and electrochemical hydrogenation properties are studied to find out the effect of LM elements. Also, the second phase and initial activation performance are investigated. The Zr_1−xTi_xV_0.4Ni_1.2Mn_0.4LM_y (x=0.3,0.4; y=0.0,0.02,0.05,0.1,0.2,0.3) alloys have C14 Laves phase hexagonal structure, so the volume expansion ratio of lattice parameters with LM has increased. As the amount of LM in alloy has increased, correspondingly the second phase is also increased. The second phase is LM, Ti and V-rich. The second phase improve the activation of La-rich misch-metal, and also the concentration of elements Ti, V〉LM〉 matrix in alloys.The addition of LM in Zr_1−xTi_xV_0.4Ni_1.2Mn_0.4LM_y (x=0.3, 0.4) alloys have increased the activation rate and hydrogen storage capacity significantly, but the plateau pressure and the discharge capacity have been decreased due to the formation of second phase. For more Zr in electrode alloys, the activation of rate becomes slow.     

Synthesis and electrochemical characteristics of Li(Ni · M)O2 (M = Co,Mn) cathode for rechargeable lithium batteries

The synthesis and electrochemical characteristics of LiNiO₂ and Li(Ni · M)O₂ (M = Co or Mn) as the cathode materials for rechargeable lithium batteries were investigated. It was clarified from these investigations that LiNiO₂ has been produced from crystalline NiO, which was derived from Ni(OH)₂ and LiOH, and that the property of NiO had some influence on the LiNiO₂ preparation. It was assumed that the formation of the layered structure has been inhibited by the existence of the Ni vacancy and Ni³⁺ ion in NiO. The synthesis of a solid solution of Li(Ni · Co)O₂ suggested that a part of the Ni replacement by Co might inhibit the formation of the Ni vacancy of NiO and promote the formation of the layered structure. The capacity fading with increase in cycle number was suppressed by the replacement of a part of Ni with Co. We considered that the capacity fading was suppressed by the development of the layered structure wherein formation of Ni vacancy was suppressed by replacement with Co. LiNi_0.8Co_0.2O₂ prepared under the stream of oxygen gas showed a small irreversible capacity at first cycle and higher cycling capacity of ∼ 180 mA h g⁻¹.     

Synthesis and electrochemical properties of lithium cobalt oxides prepared by molten-salt synthesis using the eutectic mixture of LiCl–Li2CO3

Lithium cobalt oxide powders have been successfully prepared by a molten-salt synthesis (MSS) method using a eutectic mixture of LiCl and Li₂CO₃ salts. The physico-chemical properties of the lithium cobalt oxide powders are investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), particle-size analysis and charge–discharge cycling. A lower temperature and a shorter time (∼700°C and 1 h) in the Li:Co=7 system are sufficient to prepare single-phase HT-LiCoO₂ powders by the MSS method, compared with the solid-state reaction method. Charge–discharge tests show that the lithium cobalt oxide prepared at 800°C has an initial discharge capacity as high as 140 mA h g⁻¹, and 100 mA h g⁻¹ after 40 cycles. The dependence of the synthetic conditions of HT-LiCoO₂ on the reaction temperature, time and amount of flux with respect to starting oxides is extensively investigated.     

Hydrogenation and electrochemical studies of La–Mg–Ni alloys

La–Mg–Ni alloys are potential candidates for hydrogen storage materials. In this study, mechanical alloying with subsequent annealing under an argon atmosphere at 973 K for 0.5 h, were used to produce La_2-xMg_xNi₇ alloys (x = 0, 0.25, 0.5, 0.75, 1). Shaker type ball mill was used. An objective of the present study was to investigate an influence of amount of Mg in alloy on electrochemical, hydrogenation and dehydrogenation properties of La–Mg–Ni materials. X-ray diffraction analyses revealed formation of material with multi-phase structure. Obtained materials were studied by a conventional Sievert's type device at 303 K. It was observed that electrochemical discharge capacity and gaseous hydrogen storage capacity of La–Mg–Ni alloys increases with Mg content to reach maximum for La_1.5Mg_0.5Ni₇ alloy. Moreover, all of La–Mg–Ni alloys were characterized by improved hydrogen sorption kinetics in comparison to La–Ni alloy.     

Preparation and electrochemical properties of lithium–sulfur polymer batteries

The lithium/sulfur (Li–S) batteries consist of a composite cathode, a polymer electrolyte, and a lithium anode. The composite cathode is made from elemental sulfur (or lithium sulfide), carbon black, PEO, LiClO₄, and acetonitrile. The polymer electrolyte is made of gel-type linear poly(ethylene oxide) (PEO) with tetra ethylene glycol dimethyl ether. Cells based on Li₂S or sulfur have open-circuit voltages of about 2.2 and 2.5 V, respectively. The former cell shows two reduction peaks and one oxidation peak. It is suggested that the first reduction peak is caused by the change from polysulfide to short lithium polysulfide, and the second reduction peak by the change from short lithium polysulfide to lithium sulfide (Li₂S, Li₂S₂). The cell based on sulfur has the same reduction mechanism as that of Li₂S, which is caused by the multi process (first and second reduction) of lithium polysulfide. On charge–discharge cycling, the first discharge has a higher capacity than subsequent discharges and the flat discharge voltage is about 2.0 V. As the current load is increased, the discharge capacity decreases. One reason for this fading capacity and low sulfur utilization is the aggregation of sulfur (or polysulfide) with cycling.     

Nanocrystalline structure and electrochemical hydrogen storage properties of the as-milled Mg–V–Ni–Fe–Zn-based materials

Among the electrode materials for Ni-MH batteries, the Mg alloy electrodes such as MgNi, Mg₂Ni, REMg₁₂, La₂Mg₁₇ are considered the most suitable anode materials due to their high discharge capacity and low cost. However, the poor electrochemical cycling stability prevents its practical application. In this paper, Mg_50-xV_xNi₄₅Fe₃Zn₂ (x = 0, 1, 2, 3, 4) + 50 wt% Ni alloys were prepared by partially replacing Mg with V and using mechanical ball milling techniques with amorphous and nanocrystalline structures. Electrochemical tests showed that the ball-milled alloy had good electrochemical uptake and release performance. The maximum release performance is achieved in the first cycle. After that, the discharge level and cycle stability increased significantly with increasing ball grinding time and V content.     

Synthesis and hydrogenation properties of Mg–La–Ni–H system by reactive mechanical alloying

We have synthesized Mg–30 mass%LaNi_2.28 composite material and investigated its hydrogenation behaviour. The reactive mechanical alloying process of the mixture of Mg and LaNi_2.28 was studied. It is found that a composite of _MgH2${\mathrm{MgH}}_2$, _La4H12.9${\mathrm{La}}_4{\mathrm{H}}_{12.9}$ and _Mg2NiH4${\mathrm{Mg}}_2{\mathrm{NiH}}_4$ formed after 80 h ball-milling under 3.0 MPa hydrogen. Scanning electron microscopic analysis indicated that these new phases are distributed homogeneously. This composite shows excellent hydriding properties even at moderate temperature. Under 3.0 MPa hydrogen pressure it absorbed more than 80% of its full capacity in the temperature range of 473–553 K within less than 1 min. The maximum hydrogen absorption capacity at 553 K is 5.4 mass%. The enhanced hydriding properties could be attributed to the fine and uniform particles and a synergeticly catalytic effect generated by mechanical milling.     

Structure and electrochemical hydrogen storage properties of A2B-type Ti–Zr–Ni alloys

Elemental substitution of part Ti by Zr has been carried out for Ti₂Ni alloy to form Ti_2−xZr_xNi (x = 0, 0.2, 0.4) alloys. Mechanical milling and subsequent heat treatment have been used to prepare non-equilibrium Ti–Zr–Ni alloys. The effects of Zr addition on the structure and discharge properties of Ti₂Ni alloy were investigated. The addition of Zr could enhance the discharge capacity of the non-equilibrium Ti₂Ni alloy at electrolyte temperatures of 313 and 333 K. For instance, the non-equlibrium Ti_1.6Zr_0.4Ni alloy had a stable discharge capacity of about 210 mAh/g at 313 K. However, the protective surface layer formed during heat treatment was destroyed at a high electrolyte temperature of 333 K, and thus a severe capacity loss during cycling.     

Synthesis and physicochemical properties of LiAl0.05Mn1.95O4 cathode material by the ultrasonic-assisted sol–gel method

Spinel LiAl_0.05Mn_1.95O₄ has been successfully synthesized by a new ultrasonic-assisted sol–gel (UASG) method. The structure and physicochemical properties of this as-prepared powder compared with the pristine LiMn₂O₄ and LiAl_0.05Mn_1.95O₄ synthesized by the traditional sol–gel method were investigated by differential thermal analysis (DTA) and thermogravimetery (TG), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), cyclic voltammetry (CV), and galvanostatic charge–discharge testing in detail. The results show that all samples have high phase purity, and ultrasonic process plays an important role in controlling morphology; LiAl_0.05Mn_1.95O₄ has higher Mn oxidation state, and the absorption peak of Mn(III)O and Mn(IV)O bonds has blue shift because of the doped Al. CV confirms that the LiAl_0.05Mn_1.95O₄ sample (UASG) has a good reversibility and its structure is very advantageous for the transportation of lithium ions. The charge–discharge tests indicate that LiAl_0.05Mn_1.95O₄ (UASG) has nearly equal initial capacity with LiMn₂O₄ (sol–gel) at 1C discharge rate, but LiAl_0.05Mn_1.95O₄ (UASG) has higher discharge potential than that of LiMn₂O₄ (sol–gel). In addition, LiAl_0.05Mn_1.95O₄ (UASG) has higher discharge potential and capacity than that of LiAl_0.05Mn_1.95O₄ (sol–gel) at 1C discharge rate, and LiAl_0.05Mn_1.95O₄ (UASG) has high capacity retention at C/3 and 1C discharge rate among three samples after 50 cycles, which reveals that the sample obtained via UASG method, has the best electrochemical performance among three samples.     

Electrochemical properties of Co3O4, Ni–Co3O4 mixture and Ni–Co3O4 composite as anode materials for Li ion secondary batteries

By varying the synthetic temperature and time, Co₃O₄ with highly optimized electrochemical properties was obtained from the solid state reaction of CoCO₃. As a result, Co₃O₄ showed a high capacity around 700 mAh/g and stable capacity retention during cycling (93.4% of initial capacity was retained after 100 cycles). However, its initial irreversible capacity reached about 30% of capacity. Several phenomenological examinations in our previous results told us that the main causes of low initial coulombic efficiency, that is, large initial irreversible capacity, were solid electrolyte interphase (SEI) film formation on surface and incomplete decomposition of Li₂O during the first discharge process. SEI film formation cannot be restrained without the development of a special electrolyte, and there has been little research on the proper electrolyte composition, whereas in our research, Ni had the catalytic activity to facilitate Li₂O decomposition. Thus, in order to improve the low initial coulombic efficiency of Co₃O₄ (69%), Ni was added to Co₃O₄ using two methods like physical mixing and mechanical milling. When adding the same amount of Ni, the mechanical milling showed the improvement in initial coulombic efficiency, 79%, but physical mixing had no effect. Finally, when the charge–discharge mechanism of Co₃O₄ was considered and the morphologies of Ni–Co₃O₄ mixture obtained by physical mixing and Ni–Co₃O₄ composite prepared by mechanical milling were compared, it was revealed that the initial coulombic efficiency of Ni–Co₃O₄ composite depends on the contact area between the Ni and the Co₃O₄.     

The preparation and properties of Mn–Co–O spinel coating for SOFC metallic interconnect

To meet the performance requirements of solid oxide fuel cell (SOFC) metallic interconnect, the Mn–Co–O spinel coating is prepared on the surface of AISI430 by pack cementation method to reduce the growth kinetics of oxides and inhibit the outward diffusion of Cr. The microstructural characterization shows that a dense, uniform, defect-free spinel coating is successfully fabricated on the surface of AISI430. Under the simulated SOFC cathode environment, the weight gain of coated steel (0.608 mg cm⁻²) after oxidation at 800 °C for 800 h is significantly lower than that of uncoated (1.586 mg cm⁻²). In addition, the area specific resistance (ASR) of the coated steel oxidized for 500 h is 17.69 mΩ cm², much smaller than that of the bare steel, indicating that the oxidation resistance and electrical conductivity of AISI430 are significantly improved by Mn–Co–O spinel coating. Cross-sectional observations of the Mn–Co–O spinel coating are conducted to assess the compatibility of substrate with the adjacent coating and its effectiveness in reducing the growth of the Cr₂O₃ layer.     

Synthesis and electrochemical properties of binary MgTi and ternary MgTiX (X = Ni,Si) hydrogen storage alloys

Mg-based hydrogen storage alloys are promising candidates for many hydrogen storage applications because of the high gravimetric hydrogen storage capacity and favourable (de)hydrogenation kinetics. In the present study we have investigated the synthesis and electrochemical hydrogen storage properties of metastable binary Mg_yTi_1?y (y = 0.80–0.60) and ternary Mg_0.63Ti_0.27X_0.10 (X = Ni and Si) alloys. The preparation of crystalline, single-phase, materials has been accomplished by means of mechanical alloying under controlled atmospheric conditions. Electrodes made of ball-milled Mg_0.80Ti_0.20 powders show a reduced hydrogen storage capacity in comparison to thin films with the same composition. Interestingly, for a Ti content lower than 30 at.% the reversible storage capacity increases with increasing Ti content to reach a maximum at Mg_0.70Ti_0.30. The charge transfer coefficients (α) and the rate constants (K₁ and K₂) of the electrochemical (de)hydrogenation reaction have been obtained, using a theoretical model relating the equilibrium hydrogen pressure, electrochemically determined by Galvanostatic Intermittent Titration Technique (GITT), and the exchange current. The simulation results reveal improved values for Mg_0.65Ti_0.35 compared to those of Mg_0.80Ti_0.20. The addition of Ni even more positively affects the hydrogenation kinetics as is evident from the increase in exchange current and, consequently, the significant overpotential decrease.     

Crystallographic and electrochemical characteristics of melt-spun Ti–Zr–Ni–Y alloys

Ti₄₅Zr₃₀Ni₂₅Y_x (x = 1, 3, 5 and 7) alloys were prepared by melt-spinning at wheel velocity of 20 m s⁻¹. The effect of additive Y on phase structure and electrochemical performance of melt-spun alloys was investigated. Ti₄₅Zr₃₀Ni₂₅Y_x melt-spun alloys were composed of I-phase and amorphous phase. The amorphous phase increased with increasing x value, indicating amorphous forming ability improved with increasing Y content. The maximum discharge capacity and high-rate dischargeability decreased with increasing x value, which may be ascribed to the decrease of nickel content. Cycling stability first increased with increasing x from 1 to 3, and then decreased when x increased to 7, which was resulted from the combined effect of the decrease of nickel content and the increase of amorphous phase.     

Preparation and electrochemical properties of composite LaNix/Ni–S–Co alloy film

The composite LaNi_x/Ni–S–Co film with considerable stability and high HER activity (η₁₅₀ = 70 mV, 353 K) was obtained by molten salt electrolysis combined with aquatic electrodeposition. LaNi_x film was prepared by galvanostatic electrolysis at 100 mA cm⁻² under 1273 K. The results showed that the La³⁺ ions could be reduced on the nickel cathode and the LaNi_x film could form, i.e. La³⁺ + 3e + xNi = LaNi_x (x = 5 or 3) at ca. −0.6 V, which is much lower than that of the decomposition potential of lanthanum, due to the strong depolarization effect of nickel. Furthermore, compared with the traditional amorphous Ni–S film, the composite LaNi_x/Ni–S–Co film could absorb large amount of H atoms, which would be oxidized and avoid the dissolution of the Ni–S–Co film under the state of open-circuit effectively and increase the HER activity.     

Crystallographic and electrochemical characteristics of Ti–Zr–Ni–Pd quasicrystalline alloys

Ti₄₅Zr₃₅Ni_20−xPd_x (x = 0, 1, 3, 5 and 7, at%) alloys were prepared by melt-spinning. The phase structure and electrochemical hydrogen storage performances of melt-spun alloys were investigated. The melt-spun alloys were icosahedral quasicrystalline phase, and the quasi-lattice constant increased with increasing x value. The maximum discharge capacity of alloy electrodes increased from 79 mAh/g (x = 0) to 148 mAh/g (x = 7). High-rate dischargeability and cycling stability were also enhanced with the increase of Pd content. The improvement in the electrochemical hydrogen storage characteristics may be ascribed to better electrochemical activity and oxidation resistance of Pd than that of Ni.     

Thermophysical properties and thermal simulation of Bridgman crystal growth process of Ni–Mn–Ga magnetic shape memory alloys

Ni–Mn–Ga magnetic shape memory alloys (MSMA) are well-known smart materials for actuation applications, due to their large magnetic field-induced shape change of up to 10%. The production of larger amounts of single-crystalline material from these alloys with reproducible and homogeneous properties is demanding and calls for optimization of the corresponding crystal growth process. In order to support this optimization, sensitive process parameters are varied in simulations and their effects are studied.Here, we report on thermal field simulations in a Bridgman–Stockbarger furnace. The lab furnace is equipped with liquid metal cooling (LMC) to achieve high and homogeneous thermal gradients at the crystallization front during crystal growth of cylindrical Ni–Mn–Ga-rods. The calibration of the thermal simulation model requires (i) the knowledge/measurement of the relevant thermophysical properties of the Ni–Mn–Ga alloy as functions of temperature and (ii) thermal data from a reference benchmark experiment in the lab furnace using the same alloy.The calibrated simulation model is used for the simulation of a specific virtual Bridgman-experiment and for the determination of the temperature distributions. Moreover, the influence of the type of liquid metal coolant on the simulation results is investigated.     

Synthesis,characterization and electrochemical properties of La2-xEuxNiO4+δ Ruddlesden-Popper-type layered nickelates as cathode materials for SOFC applications

Eu doped La₂NiO₄ powders, with the general formula La_2-xEu_xNiO_4+δ denoted as LENO_x (for x = 0, 0.2, 0.4, 0.6 and 0.8), were synthesized via the mechanical milling reaction method. The Eu³⁺ doping content has a remarkable influence on structural and electrochemical properties. The phase identification and morphology were studied by X-ray diffraction (XRD), Raman spectroscopy, Infrared spectroscopy (IR), A laser size analyzer and scanning electron microscopy (SEM). Lattice parameters were calculated using the Rietveld method. It was observed that the lattice parameter values in LENO_x systems varied with the amount of Eu³⁺. The latter was symmetrically deposited by spin coating on both surfaces of an Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte and studied using AC impedance spectroscopy. The electrochemical properties were studied using two-probe impedance spectroscopy and results showed that the ASR of LENO_x was enhanced by the Eu³⁺ dopant content x. Results also showed that LNEO_0.2 had the lowest Area specific resistance (ASR) at 700 °C and it was therefore concluded that doping with the appropriate amount of Eu³⁺ can further improve the properties of a nickelate cathode.