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 Ml)-based hydrogen storage alloy with a composition of Ml(Ni0.64Co0.20Mn0.12Al0.04)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 Ml(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 inprovement in electrochemical characteristics was discussed based on the alloy microstructure change induced by annealing.

Thermal behavior simulation of Ni/MH battery

Thermal behavior of overcharged Ni/MH battery is studied with microcalorimeter. The battery is in-stalled in a special device in a microcalorimeter with a quartz frequency thermometer. Quantity of heat and heat capacity of the battery charged at different state of charge (SOC) at different rates are meas-ured by the microcalorimeter. Based on a series of assumputions, heat transfer equation is set up. Ex-pression of heat generation is attained by curve fitting instead of theoretical calculation. Thermal model is used to simulate thermal behavior of the battery in charging period , results of calculation and ex-periment match very well. The temperature distribution is non-uniform because the poor conductivity limits the heat transfer during charging process. It is difficult to greatly improve the heat conductivity of the battery because it is related to materials inside the battery including electrodes, separators and so on. Therefore, high rate charge should be avoided in actual use. It may cause some damage to the battery.

Research of heat treatment of low-Co AB_5 type hydrogen storage alloys for MH-Ni batteries

The effects of low-Co AB5 type hydrogen storage alloys prepared by quenching and annealing on the performances of MH-Ni batteries were investigated, and the characteristics of the low-Co AB5 type hydrogen storage alloys were compared with those of the high-Co AB5 type hydrogen storage alloy as well. The results showed that the faster the cooling of the low-Co hydrogen storage alloy is, the better homogeneity of the chemical composition for the alloy and the longer cycle life of the battery are, but the electrochemical discharge capacity and high-rate discharge ability are reduced. The high-rate discharge ability and charge retention of MH-Ni batteries for the conventional as-cast annealed low-Co hydrogen storage alloy were superior to those for the rapidly quenched low-Co hydrogen storage alloy and the high-Co hydrogen storage alloy, but a little inferior in the cycle life.

Effects of iron phthalocyanine on performance of MH/Ni battery

Oxygen evolution causes a high inner pressure during charge and overcharge for MH/Ni battery, and an inappropriate eliminating way of the oxygen in the battery results in accumulation of heat. This is the main obstacle to develop and apply high capability and high power battery. How to reduce the ratio of the chemical catalysis rate to the electric catalysis rate in MH/Ni battery is considered as an urgent question. Iron phthalocyanine(FePc) was chosen as an electrochemical catalyst. The batteries were prepared by adding iron phthalocyanine with different dosages. The inner pressure, the capacity attenuation, the discharge voltage and capacity at high current of these three batteries were compared. The battery with 1 mg FePc in the negative electrode exhibits a good performance.

Effect of Electrode Constitution on the Discharge Properties of Ni-MH Battery

The discharge capacities for Ni-MH batteries with different electrode constitutions are analyzedby chemical pattern recognition method, and some criteria for improving synthetical dischargeproperties are obtained. The results show that the thicknesses of positive and negative electrodeare significant in influencing the discharge capacities at both of low and high discharge current,the influence of resistance of positive electrode on discharge capacity is less significant comparedwith other factor5 in electrode constitution and the effect of electrolyte on discharge capacity atlow discharge current is more significant than that at high discharge current.

Enhanced electrochemical properties of LaFeO_3 with Ni modification for MH–Ni batteries

In this work,we synthesized LaFeO_3–xwt%Ni(x=0,5,10,15)composites via a solid-state reaction method by adding Ni to the reactants,La_2O_3 and Fe_2O_3.Field-emission scanning electron microscopy(FE-SEM)and energy-dispersive X-ray spectroscopy(EDS)results revealed that Ni powders evenly dispersed among the LaFeO_3 particles and apparently reduced their aggregation,which imparted the composites with a loose structure.Moreover,the Ni formed a conductive network,thus improving the conductivity of the composites.The maximum discharge capacity of the LaFeO_3 electrodes remarkably increased from 266.8 mAh·g^(–1)(x=0)to 339.7 mAh·g^(–1)(x=10).In particular,the high-rate dischargeability of the LaFeO_3–10wt%Ni electrode at a discharge current density of 1500 mA·g^(-1) reached 54.6%,which was approximately 1.5 times higher than that of the pure LaFeO_3.Such a Ni-modified loose structure not only increased the charge transfer rate on the surface of the LaFeO_3 particles but also enhanced the hydrogen diffusion rate in the bulk LaFeO_3.

Effect of surface modification of metal hydride electrode on performance of MH/Ni batteries

A novel method was applied to the surface modification of the metal hydride(MH)electrode of MH/Ni batteries.Both sides of the electrode were plated with a thin silver film about 0.1μm thick using vacuum evaporation plating technology,and the effect of the electrode on the performance of MH/Ni batteries was examined.It is found that the surface modification can enhance the electrode conductivity and decrease the battery ohimic resistance.After surface modification,the discharge capacity at 5C(7.5A)is increased by 212 mA.h and the discharge voltage is increased by 0.11 V,the resistance of the batteries is also decreased by 32%.The batteries with modified electrode exhibit satisfactory durability.The remaining capacity of the modified batteries is 89%of the initial capacity even after 500 cycles.The inner pressure of the batteries during overcharging is lowered and the charging efficiency of the batteries is improved.

Microstructure and electrochemical properties of low-temperature hydrogen storage alloy used in Ni/MH batteries

AB5 hydrogen storage alloys La0.54Ce0.28Pr0.18Ni4-xCo0.6Mn0.35Alx(x=0.1,0.2,0.3) were prepared by arc melting method under an Ar atmosphere. The results show that the contents of Ni and Al have obvious influences on the microstructure and electrochemical properties of the alloys. Both the lattice parameters and the cell volumes decrease with decreasing x value. Moreover,the discharge capacity at different temperatures,the high rate discharge property,and the cycling life of the alloy electrode are also in close relationship with the x value. When x value increases from 0.1 to 0.3,the discharge capacities with a discharge current density of 60 mA/g slightly decreases at 25 ℃,but evidently deteriorates at -40 ℃,the high-rate property gravely decreases,and the cycle life of the alloy electrode is improved in some extent. Therefore,it is meaningful to control Al content for the AB5 hydrogen storage alloys used in Ni/MH batteries.

Low-Temperature Hydrogen Storage Alloy and Its Application in Ni-MH Battery

Rare earth compositions, La, Ce and Pr in Mm（NiCoMnAl）5 hydrogen storage alloy, were arranged by uniform design method. The discharge performances and kinetics parameters including capacity, exchange current density, symmetry factor and hydrogen diffusion coefficient of the alloy at -40 ℃, were tested in standard tri-electrode cell. And linear regression method was used to analyze the effect of rare earth compositions on the performances of hydrogen storage alloys. The results show that the capacities of the alloys are positively correlative to the square of Ce content at -40 ℃ and under both 0.4 and 0.2C rate. The kinetics parameters and hydrogen diffusion coefficient indicate that the low-temperature performances of the alloys are mainly controlled by hydrogen diffusion process, and the surface electrochemical reaction affects the low-temperature performances to a certain extent. The low-temperature discharge capacities of the battery were also tested. The results show excellent low-temperature performances.The battery delivers 69.6% of its room-temperature capacity at -40 ℃ and 0.2C rate, 77.7% at -40 ℃ and 0.4C rate, 59.1% at -45 ℃ and 0.2C rate.

Application of Nanocrystalline LaNi_5-type Hydrogen Absorbing Alloys in Ni-MH_x Batteries

The structure and electrochemical properties of nanocrystalline LaNi5-type alloys were studied. These materials were prepared by mechanical alloying （MA） followed by annealing. The properties of hydrogen host materials can be modified substantially by alloying to obtain the desired storage characteristics. It was found that the partial substitution of Ni by Al or Mn in LaNi5-xMx alloy leads to an increase in discharge capacity. The alloying elements such as Al, Mn and Co greatly improved the cycle life of LaNi5 material. For example, in the nanocrystalline LaNi3.75Mn0.75Al0.25Co0.25 powder, discharge capacity up to 258 mAh·g-1 was measured (at 40 mA·g-1 discharge current). Furthermore, the effect of the graphite coating on the structure of some nanocrystalline alloys and the electrodes characteristics were investigated. The mechanical coating with graphite effectively reduced the degradation rate of the studied electrode materials. The combination of a nanocrystalline LaNi5-type hydride electrodes and a nickel positive electrode to form a Ni-MH battery, was successful.

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.

Prospect of MH-Ni Batteries Development

The development trend and promising application prospects of high-power MH-Ni battery were reviewed by studying and comparing the current high-power batteries research area.High-power MH-Ni batiery has good performlife with 500 ～ 1000 times, abundant material resource, especially abundant rare earth resource in China, high-rate discharging, rapid charging, good safety as well as no pollution, etc., which is regarded as the most promising storage battery for electric vehicles.The performance of high power MH-Ni battery can be brought into play fully and ensure electric vehicles performance if it is equipped with appropriate chargers, controlling system and electric motors.Facing opportunities and challenges, MH-Ni battery has promising application prospects on hybrid electric automobile, electric bicycle and a variety of small sized electric vehicles by improving its technology constantly and developing market actively.

Improvement of Low OCV in MH/Ni Battery

In MH/Ni high power battery production, a large percent of batteries were found with an open circuit voltage lower than 1.18 V after formation, open circuit voltage of another large percent of batteries could be even as low as1.00 ～ 1.10 V after one month sitting.In this situation, we analysed the causes of the problem, and provided some efficient solution based on many experiments.It was proved that these solutions are working very well to prevent the low open circuit voltage and being used in real production.

Research on catalysis of sodium-metallochlorophylls in Ni/MH battery

The effects of sodium-metallochlorophylls including sodium-iron chlorophyllin, sodium-copper chlorophyllin and sodium-magnesium chlorophyllin on performance of Ni/MH battery were investigated. The results show that sodium-iron chlorophyllin can effectively activate the gases produced during charge in Ni/MH battery, therefore reducing the reduction potential of oxygen and the oxidation potential of hydrogen, and the increased speed of inner pressure of battery is decreased significantly. With the aid of DMol3 software, the activation process of oxygen and hydrogen by sodiummetallochlorophylls was simulated and analyzed. It was found that the catalysis behavior is in agreement with the experimental results, and the activation process also gets a reasonable explanation from the calculated results.

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.

Electrochemical Properties and Crystal Structure of Rare Earth AB_(3.5)-Type Alloy as Negative Electrode Material in MH-Ni Battery

The electrochemical characteristics and crystal structure of metal hydride electrode of AB3.5-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperature and -30 ℃. The partial substitution of Ni by Al element causes an expansion of the lattice cell and increases the specific capacity and rate discharge ability of the alloy.

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.

Effects of erbium additions on high temperature performance of high power Ni-MH batteries

The Co(Ⅲ)-coated spherical nickel hydroxide powder is optimum as positive electrode of high power Ni-MH battery because of its excellent property. But the performances at high temperature(above 50 ℃) is still not satisfied. In the present paper,the effect of element erbium,used as additive by different methods to prepare positive electrode,on the high temperature performances of the Ni-MH batteries is studied. It is found that the charge acceptance ability of the spherical Ni(OH)2 electrode with element erbium as additive is improved. The discharge capacities of Ni(OH)2 coated with 1%(atomic fraction) Er(OH)3 and mechanically added with 1%(atomic fraction) Er2O3 at 1C are 12.6% and 11.7%,respectively,higher than those of the samples without erbium at 70 ℃.

La-Y-Ni体系储氢合金的电化学性能的研究

主要研究了La_(0.5)Nd_(0.5)Y_(2)Ni_(9.5)Mn_(0.5)Al_(0.5)贮氢合金的结构及其电化学性能。使用真空电弧熔炼法制备合金,通过X射线衍射测试(XRD测试)测试其结构,用DC-5型电池测试仪测定合金的电化学性能。合金电极的放电容量最大可达到265.5 mAh·g^(-1)。由La_(0.5)Nd_(0.5)Y_(2)Ni_(9.5)Mn_(0.5)Al_(0.5)合金的循环关系曲线可以清楚地看出,当循环达到第60个周期时,此合金电极的电容量保持率S60仍能达到70.5%,这说明了此种储氢合金在303 K的温度下,有着良好的循环稳定性。储氢合金电极的高倍率性能随着温度的升高逐渐降低。高倍率放电性能在303 K时La_(0.5)Nd_(0.5)Y_(2)Ni_(9.5)Mn_(0.5)Al_(0.5)储氢合金的表现最为突出。尽管随着温度的升高,合金电极的高倍率放电性能在逐渐降低,但是减缓的程度也在逐渐降低。结果说明,La_(0.5)Nd_(0.5)Y_(2)Ni_(9.5)Mn_(0.5)Al_(0.5)合金具有较高的研究意义,在低成本La-Y-Ni系储氢合金成功应用并大量投入生产后,其应用前景将非常广阔。