Study on High Power MH/Ni Battery for Hybrid Electric Vehicles

Metal hydride-nickel cell is one of the best choices for hybrid electric vehicle for its high specific energy density,security,reliability and renewability.However,its poor capability under high temperature and low specific power restrict its applications.Our studies on the metal hydride-nickel cell with different loading densities show that Ni（OH） 2 with CoOOH has good oxidation and reduction properties and proton spread rate when the loading density is 0.617 kg/m2.The power density and energy density can be as high as 1 250 W/kg and 49.4 W·h/kg respectively when Ni（OH） 2 with CoOOH was used in high power battery with the nickel foam.

Surface Modification for Metal Hydride Electrode of Ni/MH Battery

A novel method was applied to the surface modification of the metal hydride (MH) electrode of the Ni/MH battery. The electrode was plated with a thin silver film by using plasma technology and its effect on the performance of the Ni/MH battery was examined. Charge-discharge test proved that the battery with modified electrode exhibits a better high-rate dischargeability and chargeability than the battery with untreated electrode. The battery with modified electrode exhibits satisfactory durability. After 500 cycles, the capacities of the batteries with modified and unmodified electrode are 90.1% and 82.3% of their original capacities. The inner pressure test shows that the battery with modified electrode displays a much lower inner gas pressure on charging. The experimental results demonstrate that this method is an effective way for the surface modification of the electrode of the Ni/MH battery.

Microstructure and electrochemical characteristics of nonstoichiometric La-rich AB_5-type alloy for Ni/MH battery electrode

The nonstoichiometric La-rich mischmetal (designated by MI)-based hydrogen storage alloy with a composition of MI(Ni0.64Co0.2Mn0.12Al0.04)(4.76) was prepared by arc melting and annealed at 1173 K for 10 h to investigate the effect of annealing treatment on the microstructure and electrochemical characteristics of the alloy. X-ray diffraction analysis showed that annealing can cause a release of the crystal lattice strain and an increase in amounts of the La2Ni7-type second phase in MI(Ni0.64Co0.20Mn0.12Al0.04)(4.76) alloy. Scanning electron microscopy and electron probe microanalysis examinations indicated that annealing leads to disappearance of the dendrite structure in the as-cast alloy, growth of crystal grain, and decrease of composition segregation. The annealing at 1173 K for 10 h flattened and extended the potential plateau and increased the maximum discharge capacity to 328 mA center dot h/g from 310 mA center dot h/g and the cycling life. The mechanism of the improvement in electrochemical characteristics was discussed based on the alloy microstructure change induced by annealing.

Experiment Study on the Ending Criteria of Charge and Discharge of Nickel-Hydride Battery

Charge and discharge characteristics of Ni/MH batteries are investigated with experiments. During battery’s working, the voltage, capacity, temperature and internal resistance were recorded, corresponding curves were depicted. Variations of the aforementioned four parameters are differently obvious. Ending criteria of charge and discharge of Ni/MH batteries are discussed on the basis of the curves. Voltage, capacity and temperature of a battery can be used as ending criteria during charge. When discharge takes place, voltage, capacity and internal resistance can be chosen as ending criteria. As a whole, capacity is more suitable for being used as ending criteria of charge and discharge than the other three parameters. At last, the capacity of a battery is recommended to be ending criteria of charge and discharge. The conclusions will provide references to different capacity Ni/MH batteries for electric vehicles.

Study on Degradation and Recovery of AB_5-Type Hydrogen Storage Alloy Used in Ni-MH Batteries

The influences of deeply overdischarge on the negative electrode alloy of Ni/MH battery were studied. After overdischarge, La(OH) 3 and Al(OH) 3 are found to form in the negative electrode through XRD analysis. The hydrogen storage alloy powder from spent Ni/MH batteries was recovered by chemical and melting method according to degradation mechanism. The structure of recovered alloy was measured by XRD. The experimental results demonstrate that the alloy structure is CaCu 5 type. The constant current charge/discharge test was carried out to the original alloy and the recovered alloy. It is found that their discharge capacities are almost the same, but the discharge potential of the recovered alloy is higher than that of the original alloy. The results of cyclic lifetime test demonstrate that the capacity degradation of the recovered alloy is slower than that of the original one.

Changes of Some Capacities and Failure Mode of Ni/MH Batteries During Cycling

The changes of capacities of positive and negative electrodes, reserve capacities of charging and discharging, and the weight of batteries during cycling have been determined. The increase of the discharging reserve capacity due to the conjugated electrochemical reactions of the oxidation of hydrogen storage alloy is estimated. The results show that the failure mode of Ni/MH batteries developed is as follows: during the increase of cycles, the hydrogen storage alloy is oxidized continuously and the charging reserve capacity is decreased rapidly while the discharging reserve capacity is increased gradually, thus the internal pressure is increasing, first H 2 leaks out from the battery, then the mixture of H 2 and O 2. The leakage of gases and the total reaction of oxidation of the alloy consume H 2O, and the surface oxides on the alloy increase, so that the internal resistance of the battery increases.

Effect of praseodymium substitution for lanthanum on structure and properties of La_(0.65-x)Pr_xNd_(0.12)Mg_(0.23)Ni_(3.4)Al_(0.1)(x=0.00–0.20) hydrogen storage alloys

In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system （AB3.5-type） hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（x=0, 0.10, 0.15, 0.2） hydrogen storage alloys were prepared. X-ray diffraction （XRD）, scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS） analyses revealed that two alloys （x=0.0 and 0.10） were composed of （La,Mg）2（Ni,Al）7 phase, La（Ni,A1）5 phase and （La,Mg）Ni2 phase, while other alloys （x=0.15 and 0.20） consisted of （La,Mg）2（Ni,A1）7 phase, La（Ni,A1）5 phase, （La,Mg）Ni2 phase and （La,Mg）（Ni,A1）3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Electrochemical studies showed that the discharge capacity decreased from 360 mAh/g （x=-0.00） to 335 mAh/g （x=-0.20） as x increased. But the high-rate dischargeability （HRD） of alloy electrodes increased from 26% （x=0.00） to 56% （x=-0.20） at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.

Effects of spinning rate on structures and electrochemical hydrogen storage performances of RE-Mg-Ni-Mn-based AB_2-type alloys

La was partially substituted by Ce with the aim of improving the electrochemical hydrogen storage performances ofLa1–xCexMgNi3.5Mn0.5 (x=0, 0.1, 0.2, 0.3, 0.4) alloys, and melt spinning technology was adopted to fabricate the alloys. Theidentification of XRD and SEM reveals that the experimental alloys consist of a major phase LaMgNi4 and a secondary phase LaNi5.The growth of spinning rate results in that the lattice constants and cell volume increase and the grains are markedly refined. Theelectrochemical measurement shows that the as-cast and spun alloys can obtain the maximum discharge capacities just at the firstcycle without any activation needed. With the increase of spinning rate, the discharge capacities of the alloys first increase and thendecline, whereas their cycle stabilities always grow. Moreover, the electrochemical kinetic performances of the alloys first increaseand then decrease with spinning rate growing.

Bioleaching of Nickel and Cobalt from Spent Nickel Metal Hydride Batteries by Acidithiobacilli spp

The Acidithiobacillus ferrooxidans （At. f） and Acidithiobacillus thiooxidans （At. t ） were used in bio-dissolution experiments of heavy metals in spent MH/Ni batteries. The influences of the initial pH value, the concentration of electrode materials, the temperature and substrate concentration on the leaching rate of heavy metal Ni, Co have been investigated. The obtained results indicate that the efficiency of nickel extrac- tion and cobalt extraction is dependent on all of the mentioned factors. Especially, the initial pH value and the temperature have more effect than other factors for these microorganisms. In addition, the results show that the optimal leaching rate of Ni and Co in the spent MH/Ni batteries reaches to 95.7 % and 72.4 % respectively after 20 days under the conditions of the initial pH value 1.0, concentration of electrode materials 1.0 %, temperature 30°C and substrate（sulfur） concentration 4.0 g＇L^-1.

Electrochemical performance of nickel hydroxide doped with multi-wall carbon nanotubes

Nickel hydroxide doped with multi-wall carbon nanotubes(MCNTs)was synthesized by chemical coprecipitation method. The MCNTs doped nickel hydroxide was used as the electrochemical active material in the positive electrodes of rechargeable alkaline batteries.The powder X-ray diffraction(XRD)analysis shows that the addition of MCNTs induces more structural defect within the crystal lattice of the nickel hydroxide.The cyclic voltammetry(CV)and electrochemical impedance spectroscopy(EIS) tests demonstrate the better reaction reversibility and lower electrochemical impedance of MCNTs doped nickel hydroxide as compared with the pure nickel hydroxide.The charge/discharge tests show that MCNTs addition can improve the specific discharge capacity and increase the discharge voltage of the nickel hydroxide electrode.

Structure improvement and electrochemical studies of bipolar nickel metal hydride batteries for hybrid electric vehicles

Nickel metal hydride battery in bipolar design offers some advantages for its application as a power storage system for electric and hybrid vehicles. This paper deals with the structure design and electrochemical studies of bipolar Ni/MH batteries for hybrid vehicles. An improvement is applied in bipolar battery design, and such bipolar Ni/MH batteries with 5 sub-cells have been assembled and investigated. Testing results show that bipolar batteries with improved structure have better compression tolerance and cycle performance than conventional ones. In addition, the improved bipolar batteries display excellent large current discharge ability and high power density. As simulating working conditions for hybrid vehicles, the batteries show good stability during pulse cycles, which verifies the possibility of being used as a power storage device on hybrid vehicles.

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed . The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.

Effects of Annealing Temperature on Microstructure and Electrochemical Properties of Perovskite-type Oxide LaFeO3 as Negative Electrode for Metal Hydride/Nickel（MH/Ni） Batteries

We reported the effects of annealing temperatures on microstructure and electrochemical properties of perovskite-type oxide LaFeO3 prepared by stearic acid combustion method. X-Ray diffraction（XRD） patterns show that the annealed LaFeO3 powder has orthorhombic structure. Scanning electron microscopy（SEM） and transmission electron microscopy（TEM） images show the presence of homogeneously dispersed, less aggregated, and small crystals（30--40 nm） at annealing temperatures of 500 and 600 ℃. However, as the annealing temperature was increased to 700 and 800 ℃, the crystals began to combine with each other and grew into further larger crystals（90--100 nm）. The electrochemical performance of the annealed oxides was measured at 60 ℃ using chronopotentiometry, potentiodynamic polarization, and cyclic voltammetry. As the annealing temperature increased, the discharge capacity and anti-corrosion ability of the oxide electrode first increased and then decreased, reaching the optimum values at 600 ℃, with a maximum discharge capacity of 563 mA-h/g. The better electrochemical performance of LaFeO3 annealed at 600℃ could be ascribed to their smaller and more homogeneous crysals.

Electrochemical Properties of Sn Doped AB_5 Non-Stoichiometric Hydrogen Absorbing Alloys-Ⅱ

The effects of some substituting elements on the specific discharge capacity, activation and cycling life of AB 5 non stoichiometric hydrogen absorbing alloys were studied electrochemically. Results show that the characteristics of hydrogen absorbing alloys under low current density are greatly improved through the substitution of Ni by Sn, Co, and Mn. Three hydrogen storage alloys, i.e., La(NiSn) 5.14 , La(NiSnCo) 5.12 and La(NiSnMn) 5.12 have the higher specific capacity and easy activation. However, Al in the alloy shows the opposite effect on the electrochemical properties. Under high current density, the discharge capacity and potential of La(NiSn) 5.14 is superior to La(NiSnCo) 5.12 and La(NiSnMn) 5.12 , but the cycling life of La(NiSn) 5.14 is very short. The addition of Mn, Co and Al to the alloys improves the cycling characteristics. In all these alloys, La(NiSnCo) 5.12 is considered as an ideal hydrogen storage alloy.

Improved Electrochemical Performance of Surface-Modified Metal Hydride Electrodes

A novel plating process was applied to the surface modification of the metal hydride （MH） electrode of the MH/Ni batteries. The electrode was plated with a thin nickel film about 0.1 μm thick by using multi-arc ion plating technique. The X-ray diffraction （XRD）, X ray photoelectron spectroscopy （XPS） and scanning electron microscope （SEM） were used to analyze the electrodes. Influence of the surface modification on the performance of the MH/Ni batteries was studied. It is shown that the surface modification could enhance the electrode eondue tivity and decrease the batteries ohimie resistance by 28.2 %. After surface modification, the discharge capacity of the batteries at 5C （8.5 A） is increased by 212 mA· h and discharge voltage is increased by 0.09 V. The surface modification also improves the cyclic durability of the batteries. The inner pressure of the batteries with modified electrode during overcharging is much lower than that with unmodified electrode. The experimental results demonstrate that this process is an effective way for the surface modification of the electrode of MH/Ni batteries.

Structure of Sn Doped AB_5 Non-Stoichiometric Hydrogen-Absorbing Alloys-Ⅰ

Five non stoichiometric alloys, i.e., LaNi 5.15 , La(NiSn) 5.14 , La(NiSnCo) 5.12 , La(NiSnMn) 5.12 , and La(NiSnCoMnAl) 5.10 were studied. It is shown that the second minor phase does not exist in the major phase through the X ray diffraction analysis. By the measurements of the crystal lattice constant, the volume of crystal lattice decreases with the increasing of the amount of atom B in AB 5. It is more obvious when the element nickel in B is partially subsituted by other elements. For non stoichiometric alloys, the lattice volume greatly increases when Ni is partially substituted by Sn. The lattice constant is also effected by the addition of Mn, Co, and Al. By means of electrochemical measurements, the plateau pressure of hydrogen absorption/desorption is measured with the results that Sn, Co, Mn and Al decrease the plateau pressure.

Structure and electrochemical characteristics of LaNi_5-Ti_(0.10)Zr_(0.16)V_(0.34)Cr_(0.10)Ni_(0.30) composite alloy electrode

Composite LaNi5+x wt.% Ti0.10Zr0.16V0.34Cr0.10Ni0.30 (x=0, 1, 5, 10) alloys were prepared by two-step re-melting. X-ray diffractometer (XRD), scanning electron microscopy (FESEM), energy dispersive spectrometry (EDS), inductively coupled plasma (ICP) and electrochemical impedance spectroscopy (EIS) analyses showed that the matrix phase of LaNi5 alloy with CaCu5 structure remained unchanged after additive alloy was added, the amount of the second phase increased with increasing x. The synergetic effect withi...

Effect of carbon coating on electrochemical properties of AB_(3.5)-type La-Y-Ni-based hydrogen storage alloys

The superlattice La-Y-Ni-based hydrogen storage alloys have high discharge capacity and are easy to prepare.However,there is still a gap in commercial applications because of the severe corrosion of the alloys in electrolyte and poor high-rate dischargeability(HRD).Therefore,(LaSmY)(NiMnAl)_(3.5) alloy was prepared by magnetic levitation induction melting,and then the alloy was coated with different contents(0.1 wt%-1.0 wt%) of nano-carbons by low-temperature sintering with sucrose as the carbon source in this work.The results show that the cyclic stability and HRD of the alloy first increase and then decrease with the increase of carbon contents.The kinetic results show that the electrocatalytic activity and conductivity of the alloy electrodes can be enhanced by carbon coating.The electrochemical properties of the alloy are the best when the carbon coating content is 0.3 wt%.Compared with the uncoated alloy,the maximum discharge capacity(C_(max)) improves from 354.5 to 359.0 mAh/g,the capacity retention rate after 300 cycles(S_(300)) enhances from 73.15% to 80.01%,and the HRD_(1200) of the alloy enhances from 74.39% to 74.39%.

Phase structure and electrochemical properties of non-stoichiometric La_(0.7)Ce_(0.3)(Ni_(3.65)Cu_(0.75)Mn_(0.35)Al_(0.15)(Fe_(0.43)B_(0.57))_(0.10))_x hydrogen storage alloys

Phase structure and electrochemical characteristics of Co-free La0.7Ce0.3（Ni3.65Cu0.75Mn0.35Al0.15（Fe0.43B0.57）0.10）x （0.90≤x≤1.10） alloys were investigated. When x was 0.90, the alloy was composed of LaNi5, La3Ni13B2 and Ce2Ni7 phases. The Ce2Ni7 phase disappeared, and the abundant of La3Ni13B2 phase decreased when x increased to 0.95. When x was 1.00 or higher the alloys consisted of LaNi5 phase. The lattice parameter a and the cell volume V of the LaNi5 phase decreased, and the c/a ratio of the LaNi5 phase increased with x value increasing. Maximum discharge capacity of the alloy electrodes first increased and then decreased with x value increasing from 0.90 to 1.10, and the highest value was obtained when x was 1.00. High-rate dischargeability at the discharge current density of 1200 mA/g increased from 50.7% （x= 0.90） to 64.1% （x=1.10）. Both the charge-transfer reaction at the electrode/electrolyte interface and the hydrogen diffusion in the alloy were responsible for the high-rate dischargeability. Cycling capacity retention rate at 100^th cycle （$10o） gradually increased from 77.3% （x= 0.90） to 84.6% （x= 1.10）, which resulted from the increase in Ni content and the c/a ratio of the LaNi5 phase with x value increasing.

Microstructure and electrochemical characteristics of La_(0.7)Ce_(0.3)Ni_(3.75)Mn_(0.35)Al_(0.15)Cu_(0.75-x)(V_(0.81)Fe_(0.19))_x hydrogen storage alloys

Microstructure and electrochemical characteristics of La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x（V0.81Fe0.19）x hydrogen storage alloys were investigated. XRD indicated that La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x（V0.81Fe0.19）x alloys consisted of a single phase with CaCus-type structure, and the lattice parameter a and cell volume V increased with increasing x value. The maximum discharge capacity first increased from 319.0 （x=0） to 324.0 mAh/g （x=0.05）, and then decreased to 307.0 mAh/g （x=0.20）. The high-rate dischargeability at the discharge current density of 1200 mA/g first increased from 52.1% （x=0） to 59.1% （x=0.15）, and then decreased to 55.4% （x=0.20）. The hydrogen diffusion in the bulky alloy was responsible for the high-rate dischargeability. Cycling stability first increased with increasing x from 0 to 0.10 and then de- creased when x increased to 0.20, which was resulted fi＇om the synthesized effect of the improvement of the pulverization resistance and the decrease of corrosion resistance.