Accurate estimation of Li/Ni mixing degree of lithium nickel oxide cathode materials

Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.

A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode

Ultra-high nickel cobalt-free lithium layered oxides are promising cathode material for lithium-ion batteries(LIBs)because of their relatively high capacity and low cost.Nevertheless,the high nickel content would induce bulk structure degradation and interfacial environment deterioration,and the absence of Co element reduces the lithium diffusion kinetics,severely limiting the performance liberation of this kind of cathodes.Herein,a multifunctional Ti/Zr dual cation co-doping strategy has been employed to improve the lithium storage performance of LiNi_(0.9)Mn_(0.1)O_(2)(NM91)cathode.On the one hand,the Ti/Zr co-doping weakens the Li^(+)/Ni^(2+)mixing through magnetic interactions due to the inexistence of unpaired electrons for Ti^(4+)and Zr^(4+),increasing the lithium diffusion rate and suppressing the harmful coexistence of H1 and H2 phases.On the other hand,they enhance the lattice oxygen stability because of the strong Ti-O and Zr-O bonds,inhibiting the undesired H3 phase transition and lattice oxygen loss,improving the bulk structure and cathode-electrolyte interface stability.As a result,the Ti/Zr co-doped NM91(NMTZ)exhibits a 91.2%capacity retention rate after 100 cycles,while that of NM91 is only82.9%.Also,the NMTZ displays better rate performance than NM91 with output capacities of 115 and93 mA h g^(-1)at a high current density of 5 C,respectively.Moreover,the designed NMTZ could enable the full battery to deliver an energy density up to 263 W h kg^(-1),making the ultra-high nickel cobaltfree lithium layered oxide cathode closer to practical applications.

Removal of nickel from spent electroless nickel-plating bath with nickel foam cathode

The electrochemical method was used to remove nickel ion from spent electroless nickel plating bath (pH=5 3). An electrolytic cell was composed of a porous nickel foam cathode and an inert RuO 2/Ti anode. Nickel ions were reduced and deposited on the surface of the nickel foam cathode. The effect of current density (i), linear velocity of wastewater(v), gap between cathode and anode(d C/A) and reaction time(t) on nickel removal rate and current efficiency were studied. As reaction time prolonged, nickel removal rate increased while current efficiency decreased. And larger v and smaller d C/A can enhance nickel removal rate and increase current efficiency by promoting mass transfer and dropping concentration polarization. The effect of current density on nickel removal by electrochemistry was related to other parameters. After three hours’ electrolysis with i=1 0 A/dm2, v=18 5 cm/min and d C/A=0 5 cm, nickel removal rate and current efficiency reached 85 6% and 29 1%, respectively.

A critical review on nickel-based cathodes in rechargeable batteries

The 3d transition-metal nickel(Ni)-based cathodes have long been widely used in rechargeable batteries for over 100 years,from Ni-based alkaline rechargeable batteries,such as nickel-cadmium(Ni-Cd)and nickel-metal hydride(Ni-MH)batteries,to the Ni-rich cathode featured in lithium-ion batteries(LIBs).Ni-based alkaline batteries were first invented in the 1900s,and the well-developed Ni-MH batteries were used on a large scale in Toyota Prius vehicles in the mid-1990s.Around the same time,however,Sony Corporation commercialized the first LIBs in camcorders.After temporally fading as LiCoO_(2) dominated the cathode in LIBs,nickel oxide-based cathodes eventually found their way back to the mainstreaming battery industry.The uniqueness of Ni in batteries is that it helps to deliver high energy density and great storage capacity at a low cost.This review mainly provides a comprehensive overview of the key role of Ni-based cathodes in rechargeable batteries.After presenting the physical and chemical properties of the 3d transition-metal Ni,which make it an optimal cationic redox center in the cathode of batteries,we introduce the structure,reaction mechanism,and modification of nickel hydroxide electrode in Ni-Cd and Ni-MH rechargeable batteries.We then move on to the Ni-based layered oxide cathode in LIBs,with a focus on the structure,issues,and challenges of layered oxides,LiNiO_(2),and LiNi_(1−x−y)Co_(x)Mn_(y)O_(2).The role of Ni in the electrochemical performance and thermal stability of the Ni-rich cathode is highlighted.By bridging the“old”Ni-based batteries and the“modern”Ni-rich cathode in the LIBs,this review is committed to providing insights into the Ni-based electrochemistry and material design,which have been under research and development for over 100 years.This overview would shed new light on the development of advanced Ni-containing batteries with high energy density and long cycle life.

Electrochemical performance of a nickel-rich LiNi0.6Co0.2Mn0.2O2 cathode material for lithium-ion batteries under different cut-off voltages

A spherical-like Ni0.6Co0.2Mn0.2(OH)2precursor was tuned homogeneously to synthesize LiNi0.6Co0.2Mn0.2O2as a cathode material for lithium-ion batteries. The effects of calcination temperature on the crystal structure, morphology, and the electrochemical performance of the as-prepared LiNi0.6Co0.2Mn0.2O2were investigated in detail. The as-prepared material was characterized by X-ray diffraction, scanning electron microscopy, laser particle size analysis, charge–discharge tests, and cyclic voltammetry measurements. The results show that the spherical-like LiNi0.6Co0.2Mn0.2O2material obtained by calcination at 900°C displayed the most significant layered structure among samples calcined at various temperatures, with a particle size of approximately 10 μm. It delivered an initial discharge capacity of 189.2 mAh•g−1at 0.2C with a capacity retention of 94.0% after 100 cycles between 2.7 and 4.3 V. The as-prepared cathode material also exhibited good rate performance, with a discharge capacity of 119.6 mAh•g−1at 5C. Furthermore, within the cut-off voltage ranges from 2.7 to 4.3, 4.4, and 4.5 V, the initial discharge capacities of the calcined samples were 170.7, 180.9, and 192.8 mAh•g−1, respectively, at a rate of 1C. The corresponding retentions were 86.8%, 80.3%, and 74.4% after 200 cycles, respectively. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

Spray pyrolysis synthesis of nickel-rich layered cathodes LiNi_(1-2x)Co_xMn_xO_2(x = 0.075, 0.05, 0.025) for lithium-ion batteries

In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are submicron-sized particles and the particle sizes increase with the increase of Ni content.LiNi0.85Co0.075Mn0.075O2 delivers a discharge capacity of 174.9 mAh g-1 with holding 93% reversible capacity at 1 C after 80 cycles, and can maintain a discharge capacity of 175.3 mAh g-1 at 5 C rate. With increasing Ni content, the initial specific capacity increases while the cycling and rate performance degrades in some extent. These satisfying results demonstrate that spray pyrolysis is a powerful and efficient synthesis technology for producing Ni-rich layered cathode（Ni content 〉 80%）.

Effects of chromium doping on performance of LiNi_(0.5)Mn_(1.5)O_4 cathode material

In order to improve the cycle and rate performance of LiNi0.5Mn1.5O4, LiCr2 Ni0.5 Mn1.5 O （0≤Y≤0.15） particles were Y -Y -Y 4 synthesized by the sucrose-aided combustion method. The effects of Cr doping in LiNi0.5Mn1.5O4 on the structures and electrochemical properties were investigated. The samples were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, galvanostatic charge-discharge test and electrochemical impedance spectrum （EIS）. The results indicate that the LiCr2 Ni0.5 Mn1.5 O possess a spinel structure and small particle size, and LiCr0.2Ni0.4Mn1.4O4exhibits Y -Y -Y 4 the best cyclic and rate performance. It can deliver discharge capacities of 143 and 104 mA·h/g at 1C and 10C, respectively, with good capacity retention of 96.5% at 1C after 50 cycles.

Atomic Layer Deposition-Assisted Construction of Binder-Free Ni@N-Doped Carbon Nanospheres Films as Advanced Host for Sulfur Cathode

Rational design of hybrid carbon host with high electrical conductivity and strong adsorption toward soluble lithium polysulfides is the main challenge for achieving high-performance lithium-sulfur batteries(LSBs).Herein,novel binder-free Ni@N-doped carbon nanospheres(N-CNSs)films as sulfur host are firstly synthesized via a facile combined hydrothermal-atomic layer deposition method.The cross-linked multilayer N-CNSs films can effectively enhance the electrical conductivity of electrode and provide physical blocking“dams”toward the soluble long-chain polysulfides.Moreover,the doped N heteroatoms and superficial NiO layer on Ni layer can work synergistically to suppress the shuttle of lithium polysulfides by effective chemical interaction/adsorption.In virtue of the unique composite architecture and reinforced dual physical and chemical adsorption to the soluble polysulfides,the obtained Ni@N-CNSs/S electrode is demonstrated with enhanced rate performance(816 mAh g?1 at 2 C)and excellent long cycling life(87%after 200 cycles at 0.1 C),much better than N-CNSs/S electrode and other carbon/S counterparts.Our proposed design strategy offers a promising prospect for construction of advanced sulfur cathodes for applications in LSBs and other energy storage systems.

Improving Interfacial Electrochemistry of LiNi0.5Mn1.5O4 Cathode Coated by Mn3O4

In this work the surface of LiNi0.5Mn1.5O4(LMN)particles is modified by Mn3O4 coating through a simple wet grinding method,the electronic conductivity is significantly improved from 1.53×10^-7 S/cm to 3.15×10^-5 S/cm after 2.6 wt%Mn3O4 coating.The electrochemical test results indicate that Mn3O4 coating dramatically enhances both rate performance and cycling capability(at 55℃)of LNM.Among the samples,2.6 wt%Mn3O4-coated LNM not only exhibits excellent rate capability(a large capacity of 108 m Ah/g at 10 C rate)but also shows 78%capacity retention at 55 ℃ and 1 C rate after 100 cycles.

Synthesis and electrochemical characterization of layered Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 cathode materialfor Li-ion batteries

Layered LiNi1/3Co1/3Mn1/3O2 materials were synthesized using a nickel-cobalt-manganese carbonate precursor obtained by chemical co-precipitation. The [Ni1/3Co1/3Mn1/3]CO3 precursor and the LiNi1/3Co1/3Mn1/3O2 powders were characterized by X-ray diffraction（XRD） and scanning electron micrograph（SEM）. The SEM analysis shows that these particles possess uniform and spherical morphology. The electrochemical properties of the (LiNi1/3-)(Co1/3Mn1/3O2) cathode material for rechargeable lithium-ion batteries such as the galvanostatic charge-discharge performance and cyclic voltammetry（CV） were measured. The results show that an initial discharge capacity of 190.29mA·h·g-1 is obtained in the voltage range of 2.54.6V and at a current rate of 0.1C at 25℃.The discharge capacity increases linearly with the increase of the upper cut-off voltage limit.

CHARACTERISTICS OF NEW CATHODE MATERIAL FOR LTSOFC INVESTIGATED BY IMPEDANCE SPECTROSCOPY

The characteristics of a new Li-NiO cathode were investigated. The crystal structure of Li-NiO was explored by XRD. Electrochemical behaviors of Li-NiO composite cathode were revealed by impedance spectroscopy from 400℃ to 650℃. The diameter of deformed arc increased with the decrease of temperature. Above the melting point of the eutectic salt in composite electrolyte, the Li-NiO curves are similar with two deformed semicircular arcs at high frequency which partially overlaps each other and corresponds...

A novel,environmentally friendly and facile method for oxidative energy storage in nickel hydroxide film electrodes

The oxidative energy storage behaviors of a designed novel system comprising a nickel hydroxide film electrode and an oxygen-reducing platinum cathode were investigated by various electrochemical techniques. The structure and morphology of samples were characterized by scanning electron microscopy （SEM） and X-ray diffraction （XRD） analysis. It is found that the oxidative energy storage in the Ni（OH）2 electrodes can be obviously enhanced in the coupling system containing the cathode electrolytes with higher oxygen content or lower pH value. The results of the oxidation-discharge cycle tests show that the Ni（OH）2 film electrode oxidized in the coupling system with 1.0 mol/L Na2SO4 （pH=2） as cathode electrolyte for 600 s presents discharge capacities of 79.0 mC/cm2 at the first cycle and 97.9 mC/cm2 at the 12th cycle, suggesting the excellent reversibility of the investigated oxidative energy storage and conversion system.

Electrochemical ageing study of mixed lanthanum/praseodymium nickelates La2-xPrxNiO4+δ as oxygen electrodes for solid oxide fuel or electrolysis cells

The chemical and electrochemical stability of lanthanide nickelates La2 NiO4+δ(LNO),Pr2 NiO4+δ(PNO)and their mixed compounds La(2-x)PrxNiO4+δ(LPNOs)with x=0.5,1 or 1.5 is reported.The aim is to promote these materials as efficient electrodes for solid oxide fuel cell(SOFC)and/or solid oxide electrolysis cell(SOEC).La2 NiO4+δand La1.5Pr0.5NiO4+δcompounds are chemically very stable as powders over one month in the temperature range 600-800℃,while the other materials rich in praseodymium progressively decompose into various perovskite-deriving components with additional Pr6 O11.Despite their uneven properties,all these materials are quite efficient and sustainable as electrodes on top of gadolinium doped ceria(GDCBL)//yttrium doped zirconia(8 YSZ)electrolyte,for one month at 700℃without polarization.Under polarization(300 mA·cm-2),the electrochemical performances of LNO,PNO and La1.5Pr0.5NiO4+δ(LP5 NO)quickly degrade in SOFC mode,i.e.for the oxygen reduction reaction,while they show durability in SOEC mode,i.e.for the oxide oxidation reaction.

Effects of additives on nickel electrowinning from sulfate system

In order to eliminate the pitting and improve the surface morphology of cathode nickel,the influence of additives of boric acid and dodecyl sodium sulfate(SDS)on the process of nickel electrowinning from sulfate system was studied by cathode polarization tests and nickel electrodeposition experiments.The experimental results show that the addition of boric acid can increase the cathode polarization while SDS can decrease the cathode polarization.Both boric acid and SDS are useful to eliminate the pitting on nickel deposits and improve the morphology of surface.Good deposit morphology with rare pitting and high current efficiency is favored by adding 10 g/L boric acid and 40 mg/L SDS in the electrolyte under the condition of nickel ion concentration of 80 g/L, sodium ion concentration of 10 g/L,pH of 3,current density of 220 A/m 2 and temperature of 70℃.

Improvement of thickness deposition uniformity in nickel electroforming for micro mold inserts

Thickness deposition is a crucial issue on the application of electroformed micro mold inserts. Edge concentration effect is the main source of the non-uniformity. The techniques of adopting a non-conducting shield, a secondary electrode and a movable cathode were explored to improve the thickness deposition uniformity during the nickel electroforming process. Regarding these techniques, a micro electroforming system with a movable cathode was particularly developed. The thickness variation of a 16 mm×16 mm electroformed sample decreased respectively from 150% to 35%, 12% and 18% by these three techniques. Combining these validated methods, anickelmold insert for microlens array was electroformed with satisfactory mechanical properties and high replication precision. It could be applied to the following injection molding process.

Nickel electrodeposition from novel citrate bath

A new type of electroplating bath suitable for nickel electrodeposition was developed. Trisodium citrate was used as a complexing agent and a buffer in the bath. The buffering capacity between trisodium citrate and boric acid were compared. The effects were investigated under different conditions of bath composition, current density, pH and temperature on the potentiodynamic cathodic polarization curves, cathodic current efficiency and throwing index, as well as the electrical conductivity of these baths. The optimum conditions for producing sound and satisfactory nickel deposits were: NiSO4·6H2O 350 g/L, NiCl2·6H2O 45 g/L and Na3C6H5O7 30 g/L at pH=4 and 55 ℃. The surface morphology of the as-plated Ni deposit was examined by SEM. The results reveal that the nickel deposition obtained from the optimum conditions are composed of compact, non-porous fine grains covering the entire surface. X-ray analysis shows that nickel deposits obtained from the citrate bath have a fine crystal structure compared with deposits from the Watts bath.

Concentrated ternary ether electrolyte allows for stable cycling of a lithium metal battery with commercial mass loading high-nickel NMC and thin anodes

A new concentrated ternary salt ether-based electrolyte enables stable cycling of lithium metal battery(LMB)cells with high-mass-loading(13.8 mg cm^(−2),2.5 mAh cm^(−2))NMC622(LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2))cathodes and 50μm Li anodes.Termed“CETHER-3,”this electrolyte is based on LiTFSI,LiDFOB,and LiBF4 with 5 vol%fluorinated ethylene carbonate in 1,2-dimethoxyethane.Commer-cial carbonate and state-of-the-art binary salt ether electrolytes were also tested as baselines.With CETHER-3,the electrochemical performance of the full-cell battery is among the most favorably reported in terms of high-voltage cycling stability.For example,LiNi_(x)Mn_(y)Co_(1-x-y)O_(2)(NMC)-Li metal cells retain 80%capacity at 430 cycles with a 4.4 V cut-off and 83%capacity at 100 cycles with a 4.5 V cut-off(charge at C/5,discharge at C/2).According to simulation by density functional theory and molecular dynamics,this favorable performance is an outcome of enhanced coordination between Li^(+)and the solvent/salt molecules.Combining advanced microscopy(high-resolution transmission electron microscopy,scanning electron microscopy)and surface science(X-ray photoelectron spectroscopy,time-of-fight secondary ion mass spectroscopy,Fourier-transform infrared spectroscopy,Raman spectroscopy),it is demonstrated that a thinner and more stable cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)are formed.The CEI is rich in lithium sulfide(Li_(2)SO_(3)),while the SEI is rich in Li_(3)N and LiF.During cycling,the CEI/SEI suppresses both the deleterious transformation of the cathode R-3m layered near-surface structure into disordered rock salt and the growth of lithium metal dendrites.

黄铜集流体在无负极锂金属电池中的应用研究

虽然无负极锂金属电池(AF-LMBs)具有能量密度高、结构简单等优势,但是金属锂在负极集流体界面不可逆的沉积/剥离过程以及与电解液之间的副反应会大量消耗电池中有限的活性锂,导致电池容量迅速衰减。开发高性能的负极集流体是提升AF-LMBs循环寿命的有效策略之一。因此,本文研究了商业黄铜箔(F-Cu-Zn)作为负极集流体在AF-LMBs中的电化学性能,并且结合多种表征技术揭示了F-Cu-Zn电极在循环过程中的结构演变。结果表明:与商业铜箔(F-Cu)相比,F-Cu-Zn含有丰富的亲锂位点,诱导金属锂均匀成核与生长,所组装的Cu-Zn||NCM712软包全电池的室温循环寿命从75次增加至117次。此外,F-Cu-Zn电极中的Zn元素会在循环过程中不断溶解,最终在电极表层形成三维多孔结构。

阴极电阻分布对电镀泡沫镍电流密度影响的研究

采用挂镀和阴极移动连续镀两种模式,研究泡沫镍平面电流密度分布规律。结果表明:挂镀模式使电流密度分布呈四周高中央低,阴极移动连续镀模式受接触点和液下电镀沉积量的影响,电流密度分布有上高下低、中部高两头低等几种形式。

锂离子电池高镍三元正极材料表面改性研究进展

高镍三元材料存在表面结构不稳定、锂镍混排、晶间裂纹等问题,导致材料的循环性能降低以及高比容量无法充分发挥,表面包覆是解决上述问题的主要手段。目前的包覆材料主要有电化学惰性材料、离子/电子电导性材料和复合包覆材料,从这三个方面综述了高镍三元材料的表面改性研究。介绍了不同类型包覆材料的界面改善稳定机制、离子在固液界面的迁移率提升机理、界面副反应抑制机制以及对材料电化学性能的影响,并对高镍三元正极材料包覆改性的发展方向进行了展望。