Mitigating the Jahn-Teller distortion driven by the spin-orbit coupling of lithium manganate cathode

Spinel LiMn_(2)O_(4)is recognized as one of the most competitive cathode candidates for lithium-ion batteries ascribed to environmentally benign and rich sources.However,the wholesale application of LiMn_(2)O_(4)is predominately plagued by its severe capacity degradation,mainly associated with the innate Jahn-Teller effect.Herein,single-crystalline LiMn_(2)O_(4)with Eu^(3+) doping is rationally designed to mitigate the detrimental Jahn-Teller distortion by tuning the chemical environment of MnO_(6) octahedra and accommodating localized electron,based on the unique aspheric flexible 4f electron orbit of rare-earth metal ions.Notably,the stretching of MnO_(6) octahedron stemmed from the Jahn-Teller effect in Eu-doped LiMn_(2)O_(4)is effectively suppressed,confirmed by theoretical calculation.Meanwhile,the structural stability of the material has been significantly enhanced due to the robust Mn–O band coherency and weakened phase transition,proved by synchrotron radiation absorption spectrum and operando X-ray diffraction.The corresponding active cathode manifests superior long-cycle stability after 300 loops at 2C and displays only a 0.011%capacity drop per cycle even at 5C.Given this,this modification tactic sheds new light on achieving superior long-cycle performances by suppressing distortion in various cathode materials.

Preparation of sodium manganate from low-grade pyrolusite by alkaline predesilication-fluidized roasting technique

Low concentration alkaline leaching was used for predesilication treatment of low-grade pyrolusite. The effects of initial NaOH concentration, liquid-to-solid ratio, leaching temperature, leaching time and stirring speed on silica leaching rate were investigated and the kinetics of alkaline leaching process was studied. The results show that silica leaching rate reached 91.2% under the conditions of initial NaOH concentration of 20%, liquid-to-solid ratio of 4：1, leaching temperature of 180 ℃, leaching time of 4 h and stirring speed of 300 r/min. Shrinking-core model showed that the leaching process was controlled by the chemical surface reaction with activation energy Ea of 53.31 k J/mol. The fluidized roasting conditions for preparation of sodium manganate were optimized by the orthogonal experiments using the desiliconized residue. The conversion rate of sodium manganate was obtained to be 89.7% under the conditions of silica leaching rate of 91.2%, NaOH/MnO2 mass ratio of 3：1, roasting temperature of 500 ℃ and roasting time of 4 h, and it increased with the increase of silicon leaching rate.

Study on mineral structural stability of marine 1nm manganate

In order to study the phase transformation between 1nm manganate and 0.7nm manganate, a series of Slum Me^(2+) manganates were made after the synthetic 1nm Na^+ manganate substituted with different kinds of divalent cations. The X-ray diffraction analysis of wet S1nm Me^(2+) manganates after 24 h room temperature dry showed that their basal d-spacing had been changed, indicating that there was phase transformation between 1nm and 0.7nm manganates. Take 1nm manganates with unstable structure collapsed into 0. 7nm manganate by losing one interlayer OH-H_2O, while those with stable structure still retained the 1nm d-spacing. This factor reminds us that the manganese nodule samples must be kept in wet condition to avoid the misleading results. The structural stabdity of 1nn manganate is mainly controlled by the interlayer divalent cations. There is a possitive correlation between the amount of cations in the interlayer and the structural stability, while the capacity of different canons in stabilizing the structure of 1nm manganate is as follows: Ni > Cu > Co > Zn > Ca>Mg > Na.

Study on the cation substitution capacity of synthetic 1nm manganate

Synthetic Ium manganate has been made in the laboratory at low temperature. The d-spaciug of which shows 1. 002 nm, 0. 501 nm and 0. 34 nm respectively. As the analogue of natural 1nm manganate, it has been used for a serieS of experiments of divalent cations substitution. The results indicate that the 1nm manganate has very strong cation substitution capacity, which probable is the reason of the valuable metal such as Cu, Ni and Co enriched in the manganese nodules. The preference of canons substituting into S 1nm manganate is Cu>Co>Zn≥Ni>Ca>Mg. In the manganese nodules, the content of Ni is usually higher than that of Cu and Co, but in the cation substitution, the latter two are more preference than the former. One can infer from this differentiation that the post-deposition cation substitution is not the sole mechanism by which the valuable metals enter the manganese nodules. It could be the results of combined effects of both original formation and the post-deposition substitution of canons,which leads to the enrichment of valuable metal in the manganese nodules.

Core level excitation spectra of La and Mn ions in LaMnO3

Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.

Effect and mechanism of manganate preoxidation for organics removal

The performance and mechanism of manganate preoxidation process for organics removal were investigated in the present paper.The results showed that manganate was a potentially powerful oxidizing agent and could make the natural organic matter(NOM)concentration of sample solution increase.The process of manganate in combination with ferrous sulphate(FeMnO)was effective for organics removal and with the highest removal rate of 89%when the FeMnO dose was 0.18 mmol/L.The fluorescence analysis showed that the fluorescence intensity values related to hydrophobic acids and model humic acid polymers were the highest and the relative position of the main peak fluorescence intensity was shifted towards lower emission wavelengths,which indicated the reduction in the degree of aromaticity of residual organic matter fraction.

Spinel Li Mn_(2)O_(4)integrated with coating and doping by Sn self-segregation

The development of high-performance and low-cost cathode materials is of great significance for the progress in lithium-ion batteries.The use of Co and even Ni is not conducive to the sustainable and healthy development of the power battery industry owing to their high cost and limited resources.Here,we report LiMn_(2)O_(4)integrated with coating and doping by Sn self-segregation.Auger electron energy spectrum and soft X-ray absorption spectrum show that the coating is Sn-rich LiMn_(2)O_(4),with a small Sn doping in the bulk phase.The integration strategy can not only mitigate the Jahn–Teller distortion but also effectively avoid the dissolution of manganese.The as-obtained product demonstrates superior high initial capacities of 124 mAh·g^(-1)and 120 mAh·g^(-1)with the capacity retention of 91.1%and 90.2%at 25℃and55℃after 50 cycles,respectively.This novel material-processing method highlights a new development direction for the progress of cathode materials for lithium-ion batteries.

Electrochemical process for recovery of metallic Mn from waste LiMn_(2)O_(4)-based Li-ion batteries in NaCl−CaCl_(2)melts

new method is proposed for the recovery of Mn via the direct electrochemical reduction of LiMn_(2)O_(4) from the waste of lithium-ion batteries in NaCl−CaCl_(2) melts at 750°C.The results show that the LiMn_(2)O_(4) reduction process by the electrochemical method on the coated electrode surface occurs in three steps:Mn(IV)→Mn(III)→Mn(II)→Mn.The products of this electro-deoxidation are CaMn2O4,MnO,(MnO)x(CaO)1−x,and Mn.Metal Mn appears when the electrolytic voltage increases to 2.6 V,which indicates that increasing the voltage may promote the deoxidation reaction process.With the advancement of the three-phase interline(3PI),electric deoxygenation gradually proceeds from the outer area of the crucible to the core.At high voltage,the kinetic process of the reduction reaction is accelerated,which generates double 3PIs at different stages.

Hexagonal and Orthorhombic Perovskite Phases of ErMnO_3 and TmMnO_3 from Hydrothermal Systems

The powder crystals of RMnO3（R=Er, Tm） with hexagonal and orthorhombic structures were prepared under hydrothermal conditions. The different structural phases of the title compounds were controllably formed from different kinds of precursors at different reaction temperatures. All of the samples were characterized by powder X-ray diffraction, scanning electron microscopy, inductively coupled plasma analysis, and variable temperature magnetic susceptibility. Their structures were refined by Rietveld method from powder X-ray diffraction data. The measurement of magnetic behavior shows antiferromagnetic orderings at Neel temperatures around 80 and 40 K for the hexagonal and orthorhombic phases, respectively.

Transport properties and magnetoresistance in La_(0.8)Te_(0.2)MnO_3/ZrO_2 composites

The transport properties and magnetoresistance of electron-doped manganate / insulator composites （Lao.sTeo.2MnO3）l-x/（ZrO2）x （x = 0, 0.3, and 0.5） are investigated. It is found that the metal-insulator transition temperature of this system shifts to a lower value as the ZrO2 content increases. The introduction of ZrO2 enhances both the domain scattering and electron relative scattering in the metal transport region. In the adiabatic small polaron hopping transport region, the thermal activation energy seems invariable regardless of the ZrO2 content. The applica- tion of a magnetic field promotes the charge transportation capabilities of the composites, and the magnetoresistance is enhanced with an increase of the ZrO2 content. This could be attributed to the more remarkable modification effect of magnetic field on ordering degree in the composites than in pure Lao.sTe0.2MnO3.

Subacute toxicity of exogenous manganese on rat hippocampal neurons Examination by MRI and optical microscopy

BACKGROUND： Manganism may cause learning and memory impairment by influencing the normal function of the hippocampus, however, this effect requires further examination. OBJECTIVE： To investigate the effects of manganism on the rat hippocampus using immunohistochemistry and MRI examination. DESIGN, TIME AND SETTING： A randomized controlled study, performed in the School of Medicine and Life Science, Jianghan University and the State Key Laboratory of Atomic ＆ Molecular Physics and Spectroscopy, Chinese Academy of Science, from July to September 2005. MATERIALS： Fourteen healthy SD rats aged two months were selected for this study. MnCl2 4H2O （BHD, UK） （batch number： 9791325）; glial fibrillary acidic protein （GFAP） staining kit （Beijing Zhongshan Biotechnology）; Biospec 4.7T/30 animal MRI formatter （Bruker, Germany）. METHODS： Fourteen rats were randomly divided into a control group （n =7） and a manganism group （n = 7）. Rats in the manganism group received intraperitoneal injection of MnCl2 · 4H2O （50 mg/kg）, once a day, for four successive days. Rats in the control group were injected according to the manganism regimen, but using saline instead of manganese solution. MAIN OUTCOME MEASURES： Twenty-four hours after the last injection, rats were examined using MRI. Immunohistochemically stained GFAP and hematoxylin-eosin stained hippocampal sections were observed under optical microscopy. RESULTS： Fourteen rats were included in the final analysis. After manganese treatment, T1 weighted image and inversion recovery MR1 demonstrated that the signal intensity was significantly enhanced in hippocampus, compared to controls. Neuronal necrosis was not observed in the hippocampus after HE staining. As compared to the control group, GFAP expression was markedly enhanced in the hippocampus of the manganism group. CONCLUSION： Within the rat brain, manganese preferentially localizes to the hippocampus and can induce astroctye activation.

Synthesis and Biodegradation of St-g-poly(MMA-co-VAc) Initiated by Manganic Pyrophosphate

Methyl methacrylate(MMA) and vinyl acetate(VAc) were grafted onto corn starch with manganic pyrophosphate{[Mn(H 2P 2O 7) 3] 3-} as the initiator and water as the reaction medium. The influences of reaction conditions, including pH value, initiator concentration, monomer concentration and its composition, on percent grafting and grafting efficiency were investigated. The graft copolymer was characterized by means of IR spectroscopy, scanning electron micrograph(SEM) and 1H NMR spectroscopy. The biodegradation experiment showed that the degradation of corn starch-g-poly(MMA-co-VAc) was mainly from starch. However, after poly VAc in the side chain was transformed into poly vinyl alcohol(PVA), both starch and the grafted side chain could be degraded completely.

Challenges and modification strategies of high-voltage cathode materials for Li-ion batteries

Li-ion batteries(LIBs)have gained wide recognition as effective energy storage devices and power supply sources due to their exceptional volumetric energy density,mass energy density and cycling performance.The cathode materials,a key component of LIBs,play a crucial role in determining the electrochemical performance of these batteries.Therefore,there is an increasing demand to explore and investigate suitable high-energy electrode materials that can provide greater capacity and output voltage for the next generation of LIBs.This paper aims to provide a comprehensive overview of the latest researches on five typical high-voltage cathode materials.Specifically,this review will focus on the detailed analysis of their crystalline structures,reaction mechanisms during cycling,current research status and strategies aimed at improving or enhancing their overall electrochemical performance.Overall,the insights presented in this review will help researchers design and develop high-energy cathode materials with improved performance for the next generation of LIBs.

Transformation of Supercapacitive Charge Storage Behaviour in a Multi elemental Spinel CuMn_(2)O_(4) Nanofibers with Alkaline and Neutral Electrolytes

Electrode material has been cited as one of the most important determining factors in classifying an energy storage system’s charge storage mechanism,i.e.,as battery-type or supercapacitive-type.In this paper,we show that along with the electrode material,the electrolyte also plays a role in determining the charge storage behaviour of the system.For the purpose of our research,we chose multi-elemental spinal type CuMn_(2)O_(4) metal oxide nanofibers to prove the hypothesis.The material is synthesized as nanofibers of diameter~120 to 150 nm in large scales by a pilot scale electrospinning set up.It was then tested in three different electrolytes(1 M KOH,1 M Na_(2)SO_(4) and 1 M Li_(2)SO_(4)),two of which are neutral and the third is alkaline(KOH).The cyclic voltammograms and the galvanostatic charge-discharge of the electrode material in a three-electrode sys-tem measurement showed that it exhibit different charge storage mechanism in different electrolyte solutions.For the neutral electrolytes,a capacitive behaviour was observed whereas a battery-type behaviour was seen for the alkaline electrolyte.This leads us to conclude that the charge storage mechanism,along with the active material,also depends on the electrolyte used.

Influence of Atmospheric Plasma-Sprayed Composite Cathode on the Performance of Solid Oxide Fuel Cells

Ni-Al2O3 cermet supported tubular solid oxide fuel cells(SOFCs)with different cathodes were fabricated by thermal spraying.The anode,electrolyte and cathode were deposited by atmospheric plasma spraying(APS)aimed at reducing the manufacturing cost of SOFCs.Three porous composite cathodes of lanthanum strontium manganite(LSM)and yttria-stabilized zirconia(YSZ),lanthanum strontium cobalt oxide(LSC)and YSZ,LSC and scandia-stabilized zirconia(ScSZ)were prepared to investigate influence of cathode constitutions on the cell's performance.The electrode polarization can be improved through using a composite cathode.The maximum power density of the cell with APS YSZ electrolyte and LSC/ScSZ composite cathode is increased about 12%than pure LSM cathode.The maximum output power density of the cell with APS ScSZ electrolyte and LSC/ScSZ composite cathode reaches 1.0 W/cm 2 at 1000 o C.The further optimization of the performance of plasma-sprayed composite cathode can be made through improving the interface contact between YSZ electrolyte and composite cathode.

Soft Chemical Synthesis of Novel Oxide Electrode Materials for Lithium-ion Batteries

1 Results Low-temperature synthetic techniques called "chimie douce" have resulted in major developments in the field of solid state chemistry of transition metal oxides. The systematic study of oxide bronzes in the period 1950-1980 paved the way to further advances in the solid state chemistry of oxides, including the alkali metal intercalation(deintercalation chemistry by soft chemical and/or electrochemical methods. These techniques also gave access to new metastable compounds such as several new f...

Large-scale synthesis of isolated Mn2O_(3) nanotube/fiber with ferric nitrate as catalyst

Isolated Mn2O_(3) nanotubes and nanofibers were prepared very easily at a large scale with the liquid-phase catalysis method.The Mn2O_(3) nanotubes had dimensions of 30–50 nm(exterior diameter)and 0.2–1.0 mm(length),approximately.The Mn2O_(3) nanofibers had dimensions of 10–30 nm(diameter)and 0.4–2.0 mm(length),approxim-ately.Nano-Mn2O_(3) with different microstructures including nanotubes,nanofibers and nanoparticles could be selectively synthesized by controlling the contents and proportions of potassium permanganate and ferric nitrate.Ferric nitrate was an ideal catalyst for the preparation of Mn2O_(3) nanotube/fiber.When cobalt nitrate or nickel nitrate was used as catalyst,only amorphous nano-Mn2O_(3) was synthesized.X-ray diffraction(XRD)result shows that the Mn2O_(3) nanotube has a crystalline structure different from o-Mn2O_(3),t-Mn2O_(3),h-Mn2O_(3) and c-Mn2O_(3).