The electrochemical performance of lithium-ion batteries,i.e.specific capacity and cyclability,is primarily determined by chemical reversibility and structural stability of the electrodes in cycling.Here we have inves...The electrochemical performance of lithium-ion batteries,i.e.specific capacity and cyclability,is primarily determined by chemical reversibility and structural stability of the electrodes in cycling.Here we have investigated the fundamental reaction behaviors of nickel sulfide(NixSy)as lithium-ion battery anodes by in-situ TEM.We find that Ni_(3)S_(2)is the electrochemically stable phase,which appears in the first cycle of the NixSyanode.From the second cycle,conversion between Ni_(3)S_(2)and Li_(2)S/Ni is the dominant electrochemical reaction.In lithiation,the NixSynanoparticles evolve into a mixture of Ni nanocrystals embedded in Li_(2)S matrix,which form a porous structure upon full lithiation,and with the recrystallization of the Ni_(3)S_(2)phase in delithiation,a compact and interconnected network is built.Structural stability in cycles is susceptible to particle size and substrate restraint.Carbon substrate can certainly improve the tolerance for size-dependent pulverization of NixSynanoparticles.When NixSynanoparticle exceeds the critical size value,the morphology of the particle is no longer well maintained even under the constraints of the carbon substrate.This work deepens the understanding of electrochemical reaction behavior of conversiontype materials and helps to rational design of high-energy density battery anodes.展开更多
Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li util...Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.展开更多
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 ...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.展开更多
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 indu...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.展开更多
Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield w...Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield with more than 50%.The obtained CQDs are further used as structure-directing and conductive agents to synthesize novel N,S-CQDs/NiCo2S4 composite cathode materials,manifesting the enhanced electrochemical properties resulted from the synergistic effect of highly conductive N,S-codoped CQDs offering fast electronic transport and unique micro-/nanostructured NiCo2S4 microspheres with Faradaic redox characteristic contributing large capacity.Moreover,the nitrogen-doped reduced graphene oxide(N-rGO)/Fe2O3 composite anode materials exhibit ultrahigh specific capacity as well as significantly improved rate property and cycle performance originating from the high-capacity prism-like Fe2O3 hexahedrons tightly wrapped by highly conductive N-rGO.A novel alkaline aqueous battery assembled by these materials displays a specific energy(50.2 Wh kg^−1),ultrahigh specific power(9.7 kW kg^−1)and excellent cycling performance with 91.5%of capacity retention at 3 A g^−1 for 5000 cycles.The present research offers a valuable guidance for the exploitation of advanced energy storage devices by the rational design and selection of battery/capacitive composite materials.展开更多
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 hyd...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.展开更多
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 posi...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.展开更多
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 suppos...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.展开更多
Simultaneous recovery of rare earth,nickel and cobalt resources from the anode material of hydrogen-nickel battery was performed through a hydrometallurgical process. Most of rare earth elements are separated from nic...Simultaneous recovery of rare earth,nickel and cobalt resources from the anode material of hydrogen-nickel battery was performed through a hydrometallurgical process. Most of rare earth elements are separated from nickel and cobalt in the form of sulfates when the anode material is firstly leached with sulfuric acid. Then,the precipitated rare earth sulfates are dissolved with sodium hydroxide to form rare earth hydroxides. The rare earth element,zinc and manganese ions in the lixivium are also separated from nickel and cobalt by using PC-88A extractant system,and the organic phase loaded rare earth is stripped with hydrochloric acid. By neutralizing the stripping solution with rare earth hydroxide,the rare earth chloride is obtained. Under the suitable leaching conditions of sulfuric acid 3 mol/L,leaching time 4 h and temperature 95 ℃,94.5% of rare earth in the anode material is transformed into the sulfate precipitates,and the leaching ratios of nickel and cobalt can approach 99.5%. When the pH value of the extractive system is controlled in the range of 3.0-3.5,the rare earth elements in the lixivium can be extracted completely into the organic phase,and the stripping recovery of the rare earth can reach 98% in the extraction stage. The total recoveries of rare earth,nickel and cobalt are 98.9%,98.4% and 98.5%,respectively.展开更多
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 su...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%).展开更多
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 ...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.展开更多
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 betw...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.展开更多
Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their a...Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.展开更多
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 t...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 ...展开更多
Zirconia separator is one of the key materials of nickel-hydrogen battery,thereby zirconia separators are prepared by precursor process in which cellulose textiles immersed with zirconium salts are oxidized,infrared s...Zirconia separator is one of the key materials of nickel-hydrogen battery,thereby zirconia separators are prepared by precursor process in which cellulose textiles immersed with zirconium salts are oxidized,infrared spectra show that viscose textile is an excellent precursor for preparing zirconia separator. The dominant factors in immersion are studied,it is revealed that the solution concentration and the temperature are the most important factors with regard to the area density of zirconia separator. The main reactions of immersed textiles during heat treatment are investigated by TG-DSC. The prepared zirconia separators are analyzed by SEM,XRD and infrared spectroscopy,which lead to kown that the separators maintain the same morphology of precursor textiles and contain little organic components,the main phase of the separators is tetragonal zirconia,the rate and the amount of alkaline absorption are about 5 cm/min and 220% respectively.展开更多
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 ...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.展开更多
A technique for recycling spent nickel-cadmium batteries, which makes separaion of cadmium and nickel possible, is developed by laboratory-scale experiments. NH3-H2CO3 aqueous solution was used in this leaching techni...A technique for recycling spent nickel-cadmium batteries, which makes separaion of cadmium and nickel possible, is developed by laboratory-scale experiments. NH3-H2CO3 aqueous solution was used in this leaching technique. Since neutralization and/or solvent extraction were not required in the separation procedure of nickel and cadmium, the closed systemizaion of the process becomespossible. Experimental results show that, (1) if the NH3 concentraion of leaching solution is sufficiently high and the ratio of H2CO3 toNH3 is properly adjusted, both Ni(OH)2 and Cd(OH)2 react with NH, and quickly dissolve into leaching solution, and (2) Ni(OH)2 can beconverted into insoluble NiO by calcination at 500℃, and CdO from Cd(OH)2 by calcination maintains good solubility in NH3-H2CO3aqueous solution. As a conclusion, the recycling technique characterized by two step leaching can be developed based on such changesin dissolution behavior by calcination. Meanwhile, the yields of 99.8% for nickel and 97.6% for cadmium are obtained, and the puritiesof Recycling of Spent Nickel-Cadmium BatterieRecycling of Spent Nickel-Cadmium Batteries Recycling of Spent Nickel-Cadmium Batteriesrecovered nickel and cadmium are 99.9% and 98.6%, respectively.展开更多
基金the support by the National Natural Science Foundation of China(11972219 and 11902185)the support of Shanghai Sailing Program(19YF1415100)+2 种基金the Young Elite Scientist Sponsorship Program by CAST(2019QNRC001)the support of the National Natural Science Foundation of China(52090022)the Natural Science Foundation for Distinguished Young Scholars of Hebei Province(E2020203085)。
文摘The electrochemical performance of lithium-ion batteries,i.e.specific capacity and cyclability,is primarily determined by chemical reversibility and structural stability of the electrodes in cycling.Here we have investigated the fundamental reaction behaviors of nickel sulfide(NixSy)as lithium-ion battery anodes by in-situ TEM.We find that Ni_(3)S_(2)is the electrochemically stable phase,which appears in the first cycle of the NixSyanode.From the second cycle,conversion between Ni_(3)S_(2)and Li_(2)S/Ni is the dominant electrochemical reaction.In lithiation,the NixSynanoparticles evolve into a mixture of Ni nanocrystals embedded in Li_(2)S matrix,which form a porous structure upon full lithiation,and with the recrystallization of the Ni_(3)S_(2)phase in delithiation,a compact and interconnected network is built.Structural stability in cycles is susceptible to particle size and substrate restraint.Carbon substrate can certainly improve the tolerance for size-dependent pulverization of NixSynanoparticles.When NixSynanoparticle exceeds the critical size value,the morphology of the particle is no longer well maintained even under the constraints of the carbon substrate.This work deepens the understanding of electrochemical reaction behavior of conversiontype materials and helps to rational design of high-energy density battery anodes.
基金supported by the National Natural Science Foundation of China(31870570)the Science and Technology Plan of Fujian Provincial,China(2020H4026,2022G02020 and 2022H6002)+1 种基金the Science and Technology Plan of Xiamen(3502Z20203005)the Scientific Research Start-up Funding for Special Professor of Minjiang Scholars。
文摘Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.
基金National Natural Science Foundation of China,Grant/Award Numbers:21905265,52072322,U1930402,61974042National Science Foundation,Civil,Mechanical and Manufacturing Innovation,Grant/Award Number:1911905+3 种基金Fundamental Research Funds for the Central Universities,Grant/Award Number:WK2060140026Department of Science and Technology of Sichuan Province,Grant/Award Numbers:2019‐GH02‐00052‐HZ,2019YFG0220Scientific and Technological Innovation Foundation of Shunde Graduate School,Grant/Award Number:BK19BE024National Key Research and Development Program of China,Grant/Award Number:2017YFA0303403。
文摘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.
基金funded by the Key R&D Program of Jilin Province(20220201132GX)the Key R&D Program of Hubei Province(2022BAA084)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(RERU2023008)。
文摘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.
基金financially supported by National Natural Science Foundation of China(21601057)Hunan Provincial Natural Science Foundation of China(2018JJ3116)Excellent Youth Fund of Hunan Provincial Education Department(18B298)
文摘Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield with more than 50%.The obtained CQDs are further used as structure-directing and conductive agents to synthesize novel N,S-CQDs/NiCo2S4 composite cathode materials,manifesting the enhanced electrochemical properties resulted from the synergistic effect of highly conductive N,S-codoped CQDs offering fast electronic transport and unique micro-/nanostructured NiCo2S4 microspheres with Faradaic redox characteristic contributing large capacity.Moreover,the nitrogen-doped reduced graphene oxide(N-rGO)/Fe2O3 composite anode materials exhibit ultrahigh specific capacity as well as significantly improved rate property and cycle performance originating from the high-capacity prism-like Fe2O3 hexahedrons tightly wrapped by highly conductive N-rGO.A novel alkaline aqueous battery assembled by these materials displays a specific energy(50.2 Wh kg^−1),ultrahigh specific power(9.7 kW kg^−1)and excellent cycling performance with 91.5%of capacity retention at 3 A g^−1 for 5000 cycles.The present research offers a valuable guidance for the exploitation of advanced energy storage devices by the rational design and selection of battery/capacitive composite materials.
基金financially supported by NSAF(No.U1530155)Ministry of Science and Technology(MOST)of China,US–China Collaboration on Cutting-edge Technology Development of Electric Vehicle,the Nation Key Basic Research Program of China(No.2015CB251100)Beijing Key Laboratory of Environmental Science and Engineering(No.20131039031)
基金financially supported by the China Postdoctoral Science Foundation(No.2021M700396)the National Natural Science Foundation of China(No.52102206)。
文摘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.
基金Supported by the Natural Science Foundation of Department of Education (05Z008) and the Science and Technology Projects of Guangdong Province (2007B030101007).
文摘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.
基金financially supported by the Natural Science Foundation of Hebei Province(Nos.E2019203414,E2020203081 and E2019203161)the National Natural Science Foundation of China(Nos.51701175 and 51971197)+1 种基金the Innovation Fund for the Graduate Students of Hebei Province(No.CXZZBS2020062)the Doctoral Fund of Yanshan University(No.BL19031)
文摘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.
基金Projects(50674060, 50734005) supported by the National Natural Science Foundation of ChinaProjects(20051070103, 2008B030302014) supported by the Development of Science and Technology of Guangdong Province, ChinaProject(2008BAC46B03) supported by the National Key Technology R&D Program
文摘Simultaneous recovery of rare earth,nickel and cobalt resources from the anode material of hydrogen-nickel battery was performed through a hydrometallurgical process. Most of rare earth elements are separated from nickel and cobalt in the form of sulfates when the anode material is firstly leached with sulfuric acid. Then,the precipitated rare earth sulfates are dissolved with sodium hydroxide to form rare earth hydroxides. The rare earth element,zinc and manganese ions in the lixivium are also separated from nickel and cobalt by using PC-88A extractant system,and the organic phase loaded rare earth is stripped with hydrochloric acid. By neutralizing the stripping solution with rare earth hydroxide,the rare earth chloride is obtained. Under the suitable leaching conditions of sulfuric acid 3 mol/L,leaching time 4 h and temperature 95 ℃,94.5% of rare earth in the anode material is transformed into the sulfate precipitates,and the leaching ratios of nickel and cobalt can approach 99.5%. When the pH value of the extractive system is controlled in the range of 3.0-3.5,the rare earth elements in the lixivium can be extracted completely into the organic phase,and the stripping recovery of the rare earth can reach 98% in the extraction stage. The total recoveries of rare earth,nickel and cobalt are 98.9%,98.4% and 98.5%,respectively.
基金financial support of the National Basic Research Program of China (2014CB643406)the National Natural Science Foundation of China (51674296, 51704332)+1 种基金the National Postdoctoral Program for Innovative Talents (BX201700290)the Fundamental Research Funds for the Central Universities of Central South University (2017zzts125)
文摘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%).
基金Sponsored by the National Basic Research Program of China (2002CB211800)
文摘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.
文摘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.
基金financial support from the National Natural Science Foundation of China(21878270,21878267,21922811,21978258 and 21961160742)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2019R01006)+3 种基金the Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Fundamental Research Funds for the Central Universities(2020XZZX002-09)the Startup Foundation for Hundred-Talent Program of Zhejiang Universitythe Zhejiang Key Laboratory of Marine Materials and Protective Technologies(2020K10)。
文摘Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.
基金supported by the National High Technology Development Program of China (No. 2003AA302420)the National Major Basic Research Project (No. GT20000264-06) of MOST, China
文摘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 ...
文摘Zirconia separator is one of the key materials of nickel-hydrogen battery,thereby zirconia separators are prepared by precursor process in which cellulose textiles immersed with zirconium salts are oxidized,infrared spectra show that viscose textile is an excellent precursor for preparing zirconia separator. The dominant factors in immersion are studied,it is revealed that the solution concentration and the temperature are the most important factors with regard to the area density of zirconia separator. The main reactions of immersed textiles during heat treatment are investigated by TG-DSC. The prepared zirconia separators are analyzed by SEM,XRD and infrared spectroscopy,which lead to kown that the separators maintain the same morphology of precursor textiles and contain little organic components,the main phase of the separators is tetragonal zirconia,the rate and the amount of alkaline absorption are about 5 cm/min and 220% respectively.
文摘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.
文摘A technique for recycling spent nickel-cadmium batteries, which makes separaion of cadmium and nickel possible, is developed by laboratory-scale experiments. NH3-H2CO3 aqueous solution was used in this leaching technique. Since neutralization and/or solvent extraction were not required in the separation procedure of nickel and cadmium, the closed systemizaion of the process becomespossible. Experimental results show that, (1) if the NH3 concentraion of leaching solution is sufficiently high and the ratio of H2CO3 toNH3 is properly adjusted, both Ni(OH)2 and Cd(OH)2 react with NH, and quickly dissolve into leaching solution, and (2) Ni(OH)2 can beconverted into insoluble NiO by calcination at 500℃, and CdO from Cd(OH)2 by calcination maintains good solubility in NH3-H2CO3aqueous solution. As a conclusion, the recycling technique characterized by two step leaching can be developed based on such changesin dissolution behavior by calcination. Meanwhile, the yields of 99.8% for nickel and 97.6% for cadmium are obtained, and the puritiesof Recycling of Spent Nickel-Cadmium BatterieRecycling of Spent Nickel-Cadmium Batteries Recycling of Spent Nickel-Cadmium Batteriesrecovered nickel and cadmium are 99.9% and 98.6%, respectively.