CoO AS ADDITIVE IN POSITIVE ELECTRODE OF NICKEL-METAL HYDRIDE BATTERY

A series of positive electrodes for Ni/MH battery were fabricated by addition of CoO.The morphology and microstructure of the electrodes were examined by SEM and EDS, and electrochemical behavior was investigated in three-compartment appliances at room temperature.The electrochemical performance of the positive electrodes with CoO was improved. Under the same charge-discharge cycle, the electrodes with CoO showed higher specific capacity, lower charge mean voltage and higher discharge mean voltage. But ...

Understanding the catalysis of chromium trioxide added magnesium hydride for hydrogen storage and Li ion battery applications

This study explores how the chemical interaction between magnesium hydride(MgH_(2))and the additive CrO_(3) influences the hydrogen/lithium storage characteristics of MgH_(2).We have observed that a 5 wt.%CrO_(3) additive reduces the dehydrogenation activation energy of MgH_(2) by 68 kJ/mol and lowers the required dehydrogenation temperature by 80℃.CrO_(3) added MgH_(2) was also tested as an anode in an Li ion battery,and it is possible to deliver over 90%of the total theoretical capacity(2038 mAh/g).Evidence for improved reversibility in the battery reaction is found only after the incorporation of additives with MgH_(2).In depth characterization study by X-ray diffraction(XRD)technique provides convincing evidence that the CrO_(3) additive interacts with MgH_(2) and produces Cr/MgO byproducts.Gibbs free energy analyses confirm the thermodynamic feasibility of conversion from MgH_(2)/CrO_(3) to MgO/Cr,which is well supported by the identification of Cr(0)in the powder by X ray photoelectron spectroscopy(XPS)technique.Through high resolution transmission electron microscopy(HRTEM)and energy dispersive spectroscopy(EDS)we found evidence for the presence of 5 nm size Cr nanocrystals on the surface of MgO rock salt nanoparticles.There is also convincing ground to consider that MgO rock salt accommodates Cr in the lattice.These observations support the argument that creation of active metal–metal dissolved rock salt oxide interface may be vital for improving the reactivity of MgH_(2),both for the improved storage of hydrogen and lithium.

Electrode Characteristics of MmNi_5-based Alloys for Nickel-Metal Hydride Batteries

Negative electrodes of the Ni-metal hydride battery were made from hydrogen storage alloy Mm0.9Ti0. 1Ni3. 9Mn0.4Co0.4Al0.3 mod fied by coating with Ni or mixing with Co powder. The cell volume expansion of hexagonal structure was about 12 % after coating with 11 % Ni on the alloy Surface,When this alloy was mixed with Co powder. the discharge capacity and the utilization efficiency of the hydrogen storage alloy increased. When the alloy was coated with 11 wt-% Ni and also mixed with 10 wt-% Co powder. the capacity decay for a small sealed cylindrical cell (AA size. 1 Ah) was only about 4 % after 200 cycles

Electrode Characteristics of MmNi_5－type Alloys for Nickel－metal HydrideBatteries

Negative electrodes of the nickel-metal hydride battery were made from hydrogen storage alloy Mm0.9Ti0.1Ni3.9Mn0.4Co0.4Al0.3 modified by coating with nickei and mixing with cobalt powder. When the 10wt% cobalt powder was mixed with this alloy, the discharge capacity increased from 262 mAh/g to 300 mAh/g at 300K. When the alloy was coated with 11wt% nickel and mixed with 10wt% cobalt powder, the discharge capacity decay for a sealed cell (AA size, 1 Ah) was only about 4% after 200 cycles.

Preparation and Electrochemical Performances of Nickel Metal Hydride Batteries with High Specific Volume Capacity

Cylindrical nickel metal hydride （Ni-MH） battery with high specific volume capacity was prepared by using the oxyhydroxide Ni（OH）2 and AB5 type hydrogen storage alloy and adjusting the designing parameters of positive and negative electrodes. The oxyhydroxide Ni（OH）2 was synthesized by oxidizing spherical β-Ni（OH）2 with chemical method. The X-ray diffraction （XRD） patterns and the Fourier transform infrared （PT-IR） spectra indicated that 7-NiOOH was formed on the oxyhydroxide Ni（OH）2 powders, and some H2O molecules were inserted into their crystal lattice spacing. The battery capacity could not be improved when the oxyhydroxide Ni（OH）2 sample was directly used as the positive active materials. However, based on the conductance and residual capacity of the oxyhydroxide Ni（OH）2 powders, AA size Ni-MH battery with 2560 mA.h capacity and 407 W·h·L^-1 specific volume energy at 0.2C was obtained by using the commercial spherical β-Ni（OH）2 and AB5-type hydrogen-storage alloy powders as the active materials when 10% mass amount of the oxyhydroxide Ni（OH）2 with 2.50 valence was added to the positive active materials and subsequently the battery designing parameters were adjusted as well. The as-prepared battery showed 70% initial capacity after 80 cycles at 0.5C. The possibility for adjusting the capacity ratio of positive and negative electrodes from 1 ： 1.35 to 1 ： 1.22 was demonstrated preliminarily. It is considered the as-prepared battery can meet the requirement of some special portable electrical instruments.

The electrochemical characteristics of AB_(4)-type rare earth-Mg-Ni-based superlattice structure hydrogen storage alloys for nickel metal hydride battery

Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.

Magnesium hydride nanoparticles anchored on MXene sheets as high capacity anode for lithium-ion batteries

Magnesium hydride, with high specific capacity, favorable voltage profile and low voltage hysteresis properties, is regarded as a promising anode for lithium storage. However, the rapid fading of capacity caused by huge volume change, low electron/ion conduction, and spontaneous agglomeration of active materials during cycling greatly limit its practical application in lithium-ion batteries. Herein, we report the synthesis of monodisperse MgH2 nanoparticles with an average particle size of <20 nm homogeneously anchored on Ti3C2 MXene sheets by bottom-up self-assembly strategy. The unique nanoarchitectures are able to efficiently enhance the lithium insertion/extraction kinetics, accelerate the electron/lithium ion transfer and buffer the strain of volume changes. More importantly, the formed F–Mg bounding between MgH2 and MXene could avoid the shedding of MgH2 nanoparticles to electrolyte during cycling, which significantly enhance the capacity, cyclability, and rate performance of magnesium hydride. Moreover, due to the high density of MXene and the synergistic effect between the MgH2 and MXene matrix, the MgH2/MXene composite with 60 wt% MgH2 delivers a superior volumetric capacity of 1092.9 mAh cm−3 at a current density of 2000 mA g^(−1) after 1000 cycles. These results highlight the great promising of MgH2/MXene composite for high performance lithium-ion batteries.

Room temperature operation of all-solid-state battery using a closo-type complex hydride solid electrolyte and a LiCoO_(2) cathode by interfacial modification

We report on an all-solid-state battery that employs a closo-type complex hydride solid electrolyte and a LiCoO2 cathode.Interfacial modification between the solid electrolyte and cathode with a LiNbO3 buffer layer enables reversible charge-discharge cycling with a cell voltage of 3.9V (vs.Li^+/Li) at room temperature.Electrochemical analyses clarify that the given modification effectively suppresses side reactions at the cathode/solid electrolyte interface.The interfacial resistance is lowered by ca.10 times with a 5 nm thick LiNbO3 buffer layer compared to that without a buffer layer,so that a discharge capacity of 109 mAh g^-1 is achieved.These results suggest that interfacial modification can be a viable approach to the development of high-voltage all-solid-state batteries using closo-type complex hydride solid electrolytes and oxide cathodes.

Effect of Overcharge on Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride（Ni/MH） batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.

Recovery of rare earths from acid leach solutions of spent nickel-metal hydride batteries using solvent extraction

The extraction of rare earths from acid leach solutions of spent nickel-metal hydride batteries using a primary amine ex- tractant of N 1923 was studied. The effects of feed pH, temperature, agitation rate and time on the extraction of rare earths, as well as stripping agent composition and concentration, phase ratio on the stripping were investigated. In addition, the extraction isotherm was determined. The pilot plant test results showed that the extraction of rare earths reached 99.98% after a five-stage counter current extraction. The mixed rare earths oxalates with the 99.77% purity of rare earth elements and impurity content less than 0.05% were obtained by the addition of oxalic acids in loaded strip liquors. The extractant exhibited good selectivity of rare earths over base metals of iron, nickel, copper and manganese.

Separation and recovery of rare earth from waste nickel-metal hydride batteries by phosphate based extraction-precipitation

A novel type of extraction-precipitation strategy based on phosphate was developed to recover rare earth(RE,i.e.,La,Ce,Nd,and Pr)from waste nickel-metal hydride(NiMH)batteries.This method does not require saponification and organic solvents.The novel phosphates,i.e.,dibenzyl phosphate(DBP),diphenyl phosphate(DPP),triphenyl phosphate(TPP)were studied as extraction-precipitants.DBP has high precipitation efficiencies for RE^(3+),which can reach 97.84%,100%,100%and 99.77%,respectively.In addition,the precipitation efficiencies of Mn^(2+),Co^(2+)and Ni^(2+)are less than 1.75%.DBP-RE has the largest particle size(D10=52.6μm,D50=135.35μm,D90=296.08μm),which is much larger than the precipitations formed by NH_(4)HCO_(3),H_(2)C2O_(4),CaO and MgO.The larger precipitation particle sizes contribute to improving the solid-liquid separation efficiency.With 3 mol/L hydrochloric acid,the stripping efficiency of DBP-RE reaches 98.60%,and the purity of recovered RE is 99.85%.The regenerated DBP can be directly used for the recycling extraction.Therefore,the novel extraction-precipitation strategy is a green and sustainable separation method.

动力氢镍电池市场现状与前景

金属氢化物镍(氢镍)电池在新能源汽车领域占据重要地位。分析氢镍电池在新能源汽车市场的竞争力,探讨技术特点、市场规模、发展前景及面临的机遇与挑战。通过技术创新提升氢镍电池的性能,可满足市场的需求。氢镍电池面临着原材料价格波动及其他类型电池的挑战,虽具有经济竞争力,但仍需持续创新,以应对未来新能源汽车市场的需求。

基于翻转课堂的混合式教学质量提高的探索与实践——以“镍氢电池及材料”课程为例

“镍氢电池及材料”课程是新能源材料与器件专业的一门理论和实践性都很强的专业课程,因其知识点较多且枯燥,学生很难理解课本理论知识,想要激发学生的学习兴趣和自主学习的能力较难。随着混合式教学模式(线上+线下)在“镍氢电池及材料”课程中的实施,翻转课堂得以实现。研究结果表明:这种教学方式提高了学生的学习积极性和主动性,教师的教学质量和教学效果也得到了一定的改善。

High critical current density in Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12) electrolyte via interfacial engineering with complex hydride

Garnet-type solid-state batteries(SSBs)are considered to be one of the most promising candidates to realize next-generation lithium metal batteries with high energy density and safety.However,the dendrite-induced short-circuit and the poor interfacial contact impeded the practical application.Herein,interface engineering to achieve low interfacial resistance without high temperature calcination was developed,which Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)was simply coated with complex hydride(Li_(4)(BH_(4))_(3)I(3L1L))in various mass ratios n(Li_(4)(BH_(4))_(3)I)-(100−n)LLZTO(10≤n≤40).The interfacial conductivity increases by more than three orders of magnitude from 8.29×10^(−6)S·cm^(−1)to 1.10×10^(−2)S·cm^(−1).Symmetric Li cells exhibit a high critical current density(CCD)of 4.0 mA·cm^(−2) and an excellent cycling stability for 200 h at 4.0 mA·cm^(−2).SSBs with polymeric sulfur-polyacrylonitrile(SPAN)cathode achieve a high discharge capacity of 1149 mAh·g^(−1) with a capacity retention of 91%after 100 cycles(0.2 C).This attempt guides a simple yet efficient strategy for obtaining a stable Li/LLZTO interface,which would promote the development of solid-state batteries.

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。

Microstructural analyses of all-solid-state Li–S batteries using LiBH4-based solid electrolyte for prolonged cycle performance

Complex hydride materials have been widely investigated as potential solid electrolytes because they have good compatibility with the lithium metal anodes used in all-solid-state batteries. However, the development of all-solid-state batteries utilizing complex hydrides has been difficult as these cells tend to have short cycle lives. This study investigated the capacity fading mechanism of all-solid-state lithium–sulfur(Li–S) batteries using Li4(BH4)3I solid electrolytes by analyzing the cathode microstructure. Crosssectional scanning electron microscopy observations after 100 discharge–charge cycles revealed crack formation in the Li4(BH4)3I electrolyte and an increased cathode thickness. Raman spectroscopy indicated that decomposition of the Li4(BH4)3I solid electrolyte occurred at a constant rate during the cycling tests.To combat these effects, the cycle life of Li–S batteries was improved by increasing the amount of solid electrolyte in the cathode.

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 AB_(3.5)-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.

Consistency Research of Negative Electrode Pasting for MH/Ni High Power Battery

It is discovered that the consistency of negative electrode is one of the main influences on battery performance, since the main raw material in negative electrode is metal hydride powder, ingredients, particle distribution and density of the powder could influence the pasting consistency in some aspects.With the study of MH powder characteristics, through the modification of the coating die, the consistency of negative electrode is improved efficiently.

Hydrogen ion beam assisted preparation of metal halide electrodes for batteries

A new method of preparing thin film metal-hydride electrodes for metal-hydride batteries is described. The method consists of simultaneous deposition of multi-component metallic species onto a substrate while bombarding the growing, deposited thin film electrode with a low energy hydrogen ion beam An amorphous LaNi4 hydride thin film electrode has been prepared by this Hydrogen Ion Beam Assisted Deposition （HIBAD） technique. The electrochemical discharge capacity and cycle life of this electrode in a 6 M KOH solution surpass previously reported values for La-Ni thin film electrodes prepared by other deposition methods.

先进镍氢电池负极材料的研究进展

Ni/MH二次电池由于具有安全性和优异的综合性能等优势而被广泛用于日常生活和航空航天等领域,其中负极材料的迭代推动了镍氢电池的发展。本文详细综述了目前在市场需求推动下负极材料的研究进展,解释了涉及金属氢化物的电化学反应基本原理,重点介绍了常温、高温和低温环境下AB5合金以及高容量超晶格AB_(3)、A_(2)B_(7)、A_(5)B_(19)和AB_(4)合金的研究进展和相转变机制,最后,在新能源大力发展的背景下,讨论了镍氢电池及负极材料面临的挑战和机遇。