Structure and electrochemical properties of (La, Ce, Pr, Nd)_2MgNi_9 hydrogen storage alloys were investigated through orthogonal design experiments, and the alloys were obtained through induction melting followed by ...Structure and electrochemical properties of (La, Ce, Pr, Nd)_2MgNi_9 hydrogen storage alloys were investigated through orthogonal design experiments, and the alloys were obtained through induction melting followed by annealing treatment. The structure of main phase in alloys belongs to PuNi_3-type with a space group R3m. Rare earth elements, as a substitute of lanthanum, have a significant effect on phase structure of alloys, elements of cerium and neodymium are beneficial to the formation of Gd_2Co_7-type phase with a space group P 6_3/mmc. Rare earth elements can decrease the unit cell volume of main phase of alloys dramatically, and increase the axis ratio. The results of electrochemical experiment showed that the discharge capacity of alloy electrodes ranged from 342.97 to 380.68 mAh·g -1, and elements of cerium and neodymium can reduce the discharge capacity of alloy electrodes significantly. Compared to the electrode of La_2MgNi_9 alloy, the substitution of lanthanum by rare earth elements did not improve the cyclic stability of alloy electrodes due to the anisotropic structure change of unit cell. While rare-earth elements can improve the high rate dischargeability of alloy electrodes, the high rate dischargeability of alloy electrodes could reach the maximum when the unit cell volume of PuNi_3-type structure was about 0532 nm.展开更多
Sodium-ion batteries(SIBs)have recently gained wildly interest due to the abundance of sodium,lower production costs,and better low-temperature performance compared to lithium-ion batteries(LIBs).Among various cathode...Sodium-ion batteries(SIBs)have recently gained wildly interest due to the abundance of sodium,lower production costs,and better low-temperature performance compared to lithium-ion batteries(LIBs).Among various cathode materials of SIBs,O_(3)-type NaNi_(0.4)Fe_(0.2)Mn_(0.4)O_(2)(NFM424)demonstrates high capacity and ease of synthesis,yet suffers from structural degradation and sluggish Na^(+)kinetics caused by large ionic radius and strong electrostatic interactions.To overcome these issues,a configuration strategy combined with TiO_(2) and Co_(3)O_(4) by a simple solid-state reaction method was introduced to improve structural and electrochemical stability.XRD,SEM,TEM,and various electrochemical characterizations as well as TGA/DSC tests were conducted.The resulting NaNi_(0.4)Fe_(0.2)Mn_(0.3)Co_(0.05)Ti_(0.05)O_(2)(NFMCT)cathode mitigated Jahn-Teller distortions and Na^(+)/vacancy ordering while enhancing phase integrity and diffusion pathways.The obtained NFMCT maintained 93.7 mAh·g^(−1) after 550 cycles at 1 C,with superior rate capabilities at 2 C and 5 C.These findings deepen the understanding of configuration strategy by using multi-element oxide and highlight a practical strategy for designing high-performance SIB cathodes.展开更多
03-type layered oxide serves as dominant components in sodium ion batteries;however,the unstable electronic structure between transition metal and oxygen inevitably induces framework instability and severe kinetic hin...03-type layered oxide serves as dominant components in sodium ion batteries;however,the unstable electronic structure between transition metal and oxygen inevitably induces framework instability and severe kinetic hindrance.In this study,a two-in-one approach to synergistically modulate the local electro nic and interfacial structure of NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)by Ce modification is proposed.We present an indepth study to reveal the strong-covalent Ce-O bonds,which make local charge around oxygen more negative,enhance O 2p-Mn 3d hybridization,and preserve the octahedral structural integrity.This modification tailors local electronic structure between the octahedral metal center and oxygen,thus enhancing reversibility of 03-P3-03 phase transition and expanding Na+octahedral-tetrahedral-octahedral transport channel.Additionally,the nanoscale perovskite layer induced by Ce element is in favor of minimizing interfacial side reaction as well as enhancing Na^(+)diffusivity.As a result,the designed 03-NaNi_(0.305)Fe_(0.33)Mn_(0.33)Ce_(0.025)O_(2)material delivers an exceptionally low volume variation,an ultrahigh rate capacity of 76.9 mA h g^(-1)at 10 C,and remarkable cycling life over 250 cycles with capacity retention of 80% at 5 C.展开更多
The development of high-performance cathode materials is critical to the practical application of sodiumion batteries(SIBs).O3-type NaCrO_(2)(NCO)is one of the most competitive cathodes,but it suffers from rapid capac...The development of high-performance cathode materials is critical to the practical application of sodiumion batteries(SIBs).O3-type NaCrO_(2)(NCO)is one of the most competitive cathodes,but it suffers from rapid capacity decay caused by severe irreversible structural evolution.An Mg-Ti co-doped Na_(0.99)Cr_(0.95)Mg_(0.02)Ti_(0.03)O_(2)(NCO-MT)cathode material is designed and synthesized via a facile solid-state reaction to enhance the cyclability of NCO.A capacity retention of 71.6%after 2500 cycles with the capacity fade rate of 0.011%per cycle is achieved for NCO-MT at 5 C,which is attributed to the highly reversible crystal structure during cycling.Our findings offer a novel insight into the high-performance O3-type layered cathode materials for SIBs and are beneficial to promote the development of high-rate SIBs.展开更多
To address the challenges of air stability and slurry processability in layered transition metal oxide O_(3)-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)for sodium-ion batteries(SIBs),we have designed an innovative 500℃...To address the challenges of air stability and slurry processability in layered transition metal oxide O_(3)-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)for sodium-ion batteries(SIBs),we have designed an innovative 500℃reheating strategy.This method improves the surface properties of NFM without the need for additional coating layers,making it more efficient and suitable for large-scale applications.Pristine NFM(NFM-P)was first synthesized through a high-temperature solid-state method and then modified using this reheating approach(NFM-HT).This strategy significantly enhances air stability and electrochemical performance,yielding an initial discharge specific capacity of 151.46 mAh/g at 0.1C,with a remarkable capacity retention of 95.04%after 100 cycles at 0.5C.Additionally,a 1.7 Ah NFM‖HC(hard carbon)pouch cell demonstrates excellent long-term cycling stability(94.64%retention after 500 cycles at 1C),superior rate capability(86.48%retention at 9C),and strong low-temperature performance(77%retention at-25℃,continuing power supply at-40℃).Notably,even when overcharged to 8.29 V,the pouch cell remained safe without combustion or explosion.This reheating strategy,which eliminates the need for a coating layer,offers a simpler,more scalable solution for industrial production while maintaining outstanding electrochemical performance.These results pave the way for broader commercial adoption of NFM materials.展开更多
One prominent cathode material utilized in commercial sodium-ion batteries is the O3-type NaNi_(0.5)Mn_(0.5)O_(2).The application of this material is hindered by multistage phase transitions and insufficient air stabi...One prominent cathode material utilized in commercial sodium-ion batteries is the O3-type NaNi_(0.5)Mn_(0.5)O_(2).The application of this material is hindered by multistage phase transitions and insufficient air stability.In this study,an innovative O3-type NaNi_(0.5)Mn_(0.5)O_(2),derived from Ni-MOFs (referred to as M-NNMO),has been developed as a cathode material for sodium-ion batteries.The M-NNMO cathode exhibits a discharge specific capacity of 124 mAh·g^(-1)at a rate of0.1C within 2.0 to 4.0 V.Furthermore,this material demonstrates an impressive capacity retention of 75%after undergoing 100 cycles.Complex phase transitions can be inhibited and ion diffusion rates can be increased simultaneously by Ni-MOFs through the enhancement of transition metal-oxygen bonding and the rise n Na layer gap,which are in charge of the remarkable performance improvement.Importantly,the enhanced stability of the M-NNMO transition metal layer based on the uniquestructural properties of Ni-MOFs in air stability tests.This work will provide theoretical guidance to design sodiumion battery cathode materials with superior performance.展开更多
Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing exp...Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing experimental phenomena of alloy phase transitions during extremely slow variation in temperature by equilibrium thinking mode and then taking erroneous knowledge of experimental phenomena as selected information for establishing Gibbs energy function and so-called equilibrium phase diagram. Second, the equilibrium holographic network phase diagrams of AuCu3-type sublattice system may be used to describe systematic correlativity of the composition?temperature-dependent alloy gene arranging structures and complete thermodynamic properties, and to be a standard for studying experimental subequilibrium order-disorder transition. Third, the equilibrium transition of each alloy is a homogeneous single-phase rather than a heterogeneous two-phase, and there exists a single-phase boundary curve without two-phase region of the ordered and disordered phases; the composition and temperature of the top point on the phase-boundary curve are far away from the ones of the critical point of the AuCu3 compound.展开更多
O3-type Na NiO_(2)-based cathode materials undergo irreversible phase transition and serious capacity decay at high voltage above 4.0 V in sodium-ion batteries. To address these challenges, effects of Fsubstitution on...O3-type Na NiO_(2)-based cathode materials undergo irreversible phase transition and serious capacity decay at high voltage above 4.0 V in sodium-ion batteries. To address these challenges, effects of Fsubstitution on the structure and electrochemical performance of Na Ni_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(2) are investigated in this article. The F-substitution leads to expanding of interlayer, which can enhance the mobility of Na+. NaNi_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(1.92)F_(0.08)(NMTC-F_(0.08)) with the optimal F-substitution degree exhibits much improved rate capability and cyclic stability. It delivers reversible capacities of 177 and 97 m Ah g^(-1) at 0.05 and 5 C within 2.0–4.4 V, respectively. Galvanostatic intermittent titration technique verifies faster kinetics of Na+diffusion in NMTC-F_(0.08). And in-situ XRD investigation reveals the phase evolution of NMTC-F_(0.08), indicating enhanced structural stability results from F-substitution. This study may shed light on the development of high performance cathode materials for sodium-ion storage at high voltage.展开更多
Recent years have witnessed a continuous discovering of new thermoelectric materials which has experienced a paradigm shift from try-and-error efforts to experience-based discovering and first-principles calculation. ...Recent years have witnessed a continuous discovering of new thermoelectric materials which has experienced a paradigm shift from try-and-error efforts to experience-based discovering and first-principles calculation. However, both the experiment and first-principles calculation deriving routes to determine a new compound are time and resources consuming. Here, we demonstrated a machine learning approach to discover new M_(2)X_(3)-type thermoelectric materials with only the composition information. According to the classic Bi_(2)Te_(3) material, we constructed an M_(2)X_(3)-type thermoelectric material library with 720 compounds by using isoelectronic substitution, in which only 101 compounds have crystalline structure information in the Inorganic Crystal Structure Database(ICSD) and Materials Project(MP) database. A model based on the random forest(RF) algorithm plus Bayesian optimization was used to explore the underlying principles to determine the crystal structures from the known compounds. The physical properties of constituent elements(such as atomic mass, electronegativity, ionic radius) were used to define the feature of the compounds with a general formula ^(1)M^(2)M^(1)X^(2)X^(3)X(^(1)M +^(2)M:^(1)X +^(2)X+^(3)X = 2:3). The primary goal is to find new thermoelectric materials with the same rhombohedral structure as Bi_(2)Te_(3) by machine learning.The final trained RF model showed a high accuracy of 91% on the prediction of rhombohedral compounds. Finally, we selected four important features to proceed with the polynomial fitting with the prediction results from the RF model and used the acquired polynomial function to make further discoveries outside the pre-defined material library.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrolla...O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.展开更多
A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys...A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.展开更多
The Na-deficient P3-type layered oxide cathode material usually experience complex in-plane Na^(+)/vacancy ordering rearrangement and undesirable P3-O3 phase transitions in the high-voltage region,leading to inferior ...The Na-deficient P3-type layered oxide cathode material usually experience complex in-plane Na^(+)/vacancy ordering rearrangement and undesirable P3-O3 phase transitions in the high-voltage region,leading to inferior cycling performance.Additionally,they exhibit unsatisfactory stability when exposed to water for extended periods.To address these challenges,we propose a Cu/Ti co-doped P3-type cathode material(Na_(0.67)Ni_(0.3)Cu_(0.03)Mn_(0.6)Ti_(0.07)O_(2)),which effectively mitigates Na^(+)/vacancy ordering and suppresses P3-O3 phase transitions at high voltages.As a result,the as-prepared sample exhibited outstanding cyclic performance,with 81.9%retention after 500 cycles within 2.5–4.15 V,and 75.7%retention after300 cycles within 2.5–4.25 V.Meanwhile,it demonstrates enhanced Na^(+)transport kinetics during desodiation/sodiation and reduced growth of charge transfer impedance(R_(ct))after various cycles.Furthermore,the sample showed superb stability against water,exhibiting no discernible degradation in structure,morphology,or electrochemical performance.This co-doping strategy provides new insights for innovative and prospective cathode materials.展开更多
In this work,a small amount of Al_(2)O_(3)powders(≤0.3 wt%)were incorporated into the Sm_(2)Co_(17)-type sin-tered magnets,obtaining both high mechanical and magnetic properties.It is found that 0.1%weight percentage...In this work,a small amount of Al_(2)O_(3)powders(≤0.3 wt%)were incorporated into the Sm_(2)Co_(17)-type sin-tered magnets,obtaining both high mechanical and magnetic properties.It is found that 0.1%weight percentage of Al_(2)O_(3)doping is enough to enhance the flexural strength by about 20%(∼180 MPa for the case of the c-axis parallel to height).Meanwhile,the(BH)max remains around 219 kJ/m^(3),and Hcj is 2052 kA/m,which is over 95%of that of the original magnets without doping.The promising improvement in flexural strength is mainly attributed to the grain size effective refinement caused by Sm_(2)O_(3)particles including newly-formed ones from the reaction of the Al_(2)O_(3)powder and Sm in the matrix.Furthermore,the grain size of the magnets decreases significantly with increasing of Al_(2)O_(3)doping up to 0.3 wt%.Espe-cially,the grain size of 0.3 wt%Al_(2)O_(3)doped magnets is refined by 37%.However,the flexural strengths(for the c-axis parallel to height and the c-axis parallel to width cases)of the magnets decrease sequen-tially and are even lower than that of the original magnet.The microstructure investigations indicate that the decrease in flexural strength may closely be correlated to the larger cell size and the incomplete cell boundaries phase.The obtained results infer that the flexural strength is susceptible to not only grain size but also the cellular structure of the magnets.展开更多
The effects of the Cr3C2 content and wheel speed on the amorphization behavior of the melt-spun SmCo7-x（Cr3C2）x （x=0.10-0.25） alloys were studied systematically by X-ray diffraction analysis （XRD）, differential ...The effects of the Cr3C2 content and wheel speed on the amorphization behavior of the melt-spun SmCo7-x（Cr3C2）x （x=0.10-0.25） alloys were studied systematically by X-ray diffraction analysis （XRD）, differential scanning calorimetry （DSC） and magnetic measurements. The ribbon melt-spun at lower wheel speed （20 m/s） has composite structure composed of mostly SmCo7 and a small amount of Sm2Co17R. The grain size of SmCo7 phase decreases with the increase of Cr3C2 content. With the increase of wheel speed, the XRD peaks become lower and accompanied with a broad increase in backgrounds, indicating a considerable decrease in the grain size of the SmCo7 phase. When the wheel speed increases to 40 m/s, SmCo7-x（Cr3C2）x alloys can be obtained in the amorphous state for 0.15≤x≤0.25 with intrinsic coercive Hci of 0.004-0.007 T. The DSC analysis reveals that SmCo7 phase firstly precipitates from the amorphous matrix at 650 °C, followed by the crystallization of Sm2Co17 phase at 770 °C.展开更多
The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X...The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.展开更多
The temperature dependence of the Al2O3 solubility in bridgmanite has been determined in the system MgSiO3–Al_(2)O_(3)at temperatures of 2750–3000 K under a constant pressure of 27 GPa using a multi-anvil apparatus....The temperature dependence of the Al2O3 solubility in bridgmanite has been determined in the system MgSiO3–Al_(2)O_(3)at temperatures of 2750–3000 K under a constant pressure of 27 GPa using a multi-anvil apparatus.Bridgmanite becomes more aluminous with increasing temperatures.A LiNbO3-type phase with a pyrope composition(Mg_(3)Al_(2)Si_(3)O_(12))forms at 2850 K,which is regarded as to be transformed from bridgmanite upon decompression.This phase contains 30 mol%Al_(2)O_(3)at 3000 K.The MgSiO3 solubility in corundum also increases with temperatures,reaching 52 mol%at 3000 K.Molar volumes of the hypothetical Al_(2)O_(3)bridgmanite and MgSiO_(3)corundum are constrained to be 25.950.05 and 26.24±0.06 cm^(3)/mol,respectively,and interaction parameters of non-ideality for these two phases are 5.6±0.5 and 2.2±0.5 KJ/mol,respectively.The increases in Al^(2)O^(3)and MgSiO^(3)contents,respectively,in bridgmanite and corundum are caused by a larger entropy of Al_(2)O_(3)bridgmanite plus MgSiO_(3)corundum than that of MgSiO_(3)bridgmanite plus Al_(2)O_(3)corundum with temperature,in addition to the configuration entropy.Our study may help explain dynamics of the top lower mantle and constrain pressure and temperature conditions of shocked meteorites.展开更多
Expanding the cutoff voltage of layered oxide cathodes for sodium-ion batteries(SIBs)is crucial for overcoming their existing energy density limitations.However,cationic/anodic redox-triggered multiple phase transitio...Expanding the cutoff voltage of layered oxide cathodes for sodium-ion batteries(SIBs)is crucial for overcoming their existing energy density limitations.However,cationic/anodic redox-triggered multiple phase transitions and unfavorable interfacial side reactions accelerate capacity and voltage decay.Herein,we present a straightforward melting plus reactive wetting strategy using H_(3)BO_(3)for surface modification of O_(3)-type Na_(0.9)Cu_(0.12)Ni_(0.33)Mn_(0.4)Ti_(0.15)O_(2)(CNMT).The transformation of H_(3)BO_(3)from solid to liquid under mild heating facilitates the uniform dispersion and complete surface coverage of CNMT particles.By neutralizing the residual alkali and extracting Na^(+)from the CNMT lattice,H_(3)BO_(3)forms a multifunctional Na_(2)B_(2)O_(5)-dominated layer on the CNMT surface.This Na_(x)B_(y)O_(z)(NBO)layer plays a positive role in providing low-barrier Na^(+)transport channels,suppressing phase transitions,and minimizing the generation of O_(2)/CO_(2)gases and resistive byproducts.As a result,at a charge cutoff voltage of 4.5 V,the NBO-coated CNMT delivers a high discharge capacity of 149,1 mAh g^(-1)at 10 mA g^(-1)and exhibits excellent cycling stability at 100 mA g^(-1)over 200 cycles with a higher capacity retention than that of pristine CNMT(86,4%vs,62.1%).This study highlights the effectiveness of surface modification using lowmelting-point solid acids,with potential applications for other layered oxide cathode materials to achieve stable high-voltage cycling.This proposed strategy opens new avenues for the construction of highquality coatings for high-voltage layered oxide cathodes in SIBs.展开更多
The O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)has emerged as a highly promising cathode material for sodiumion batteries due to its facile synthesis and high theoretical capacity.However,it suffers from severe capac...The O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)has emerged as a highly promising cathode material for sodiumion batteries due to its facile synthesis and high theoretical capacity.However,it suffers from severe capacity and rate capability degradation caused by multiple coupled failure mechanisms,including irreversible phase transitions,structural deterioration at high voltages,and electrolyte-induced surface corrosion.This work addresses the challenge of high-voltage stability in NFM cathodes via a synergistic bulk-phase and interface engineering strategy.Firstly,Li,Ti,and Co are codoped into the bulk lattice structure to suppress the Mn^(3+)-induced Jahn-Teller distortion and improve Na^(+)diffusion kinetics.And then,an AlPO_(4) protective coating layer is fabricated to mitigate electrolyte corrosion and interfacial side reactions.Consequently,the as-designed composite cathode(AP@NFMLTC)can effectively suppress the P3 to O3’phase transition within the voltage range of 2.0 to 4.2 V,resulting in a highly reversible sodium storage mechanism.After 100 cycles at a rate of 1 C,the capacity retention rate significantly improves from 45.6%to 83.6%,with a minimal voltage decay of just 0.08 V.The dual bulk-interface synergistic strategy in this work provides valuable insights into achieving high stable operation for sodium-ion batteries(SIBs)cathodes under enhanced voltage.展开更多
Sodium-based O3-type layered oxide materials are attractive for Sodium-ion batteries(SIBs)due to their simple synthesis,affordability,and high capacity.However,challenges remain,including limited reversible capacity a...Sodium-based O3-type layered oxide materials are attractive for Sodium-ion batteries(SIBs)due to their simple synthesis,affordability,and high capacity.However,challenges remain,including limited reversible capacity and poor cycling stability caused by detrimental phase tran-sitions during cycling and the tendency to form sodium carbonate upon air exposure.In this study,based on O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NNFM),a high-entropy strategy was introduced to successfully synthesize O3-type NaNi_(0.25)Fe_(0.21)Mn_(0.18)Co_(0.21)Ti_(0.1)Mg_(0.05)O_(2)(HE-NNFM).The introduction of Co,Ti,and Mg ions increases the system's disorder,highlighting the synergistic interactions among inert atoms.The delayed phase transformation effect in high-entropy materials alleviates the destruction of the O3 structure by the insertion and extraction of sodium ions.Simultaneously,the narrower sodium layer in HE-NNFM acts as a physical barrier,effectively preventing adverse reactions with H2O and CO_(2) in the air,resulting in excellent reversibility and air stability of the HE-NNFM material.Consequently,the HE-NNFM material exhibits a reversible capacity of 110 mAh·g^(-1)with a capacity retention of 97.3%after 200 cycles at 1 C.This work provides insights into the design of high-entropy sodium layered oxides for high-power density storage systems.展开更多
文摘Structure and electrochemical properties of (La, Ce, Pr, Nd)_2MgNi_9 hydrogen storage alloys were investigated through orthogonal design experiments, and the alloys were obtained through induction melting followed by annealing treatment. The structure of main phase in alloys belongs to PuNi_3-type with a space group R3m. Rare earth elements, as a substitute of lanthanum, have a significant effect on phase structure of alloys, elements of cerium and neodymium are beneficial to the formation of Gd_2Co_7-type phase with a space group P 6_3/mmc. Rare earth elements can decrease the unit cell volume of main phase of alloys dramatically, and increase the axis ratio. The results of electrochemical experiment showed that the discharge capacity of alloy electrodes ranged from 342.97 to 380.68 mAh·g -1, and elements of cerium and neodymium can reduce the discharge capacity of alloy electrodes significantly. Compared to the electrode of La_2MgNi_9 alloy, the substitution of lanthanum by rare earth elements did not improve the cyclic stability of alloy electrodes due to the anisotropic structure change of unit cell. While rare-earth elements can improve the high rate dischargeability of alloy electrodes, the high rate dischargeability of alloy electrodes could reach the maximum when the unit cell volume of PuNi_3-type structure was about 0532 nm.
基金funded by the National Natural Science Foundation of China(Grants 21701083 and 22179054)Jiangsu Provincial Key Research and Development Program(BZ2023010)2023 Jiangsu Government Scholarship for Overseas Studies.
文摘Sodium-ion batteries(SIBs)have recently gained wildly interest due to the abundance of sodium,lower production costs,and better low-temperature performance compared to lithium-ion batteries(LIBs).Among various cathode materials of SIBs,O_(3)-type NaNi_(0.4)Fe_(0.2)Mn_(0.4)O_(2)(NFM424)demonstrates high capacity and ease of synthesis,yet suffers from structural degradation and sluggish Na^(+)kinetics caused by large ionic radius and strong electrostatic interactions.To overcome these issues,a configuration strategy combined with TiO_(2) and Co_(3)O_(4) by a simple solid-state reaction method was introduced to improve structural and electrochemical stability.XRD,SEM,TEM,and various electrochemical characterizations as well as TGA/DSC tests were conducted.The resulting NaNi_(0.4)Fe_(0.2)Mn_(0.3)Co_(0.05)Ti_(0.05)O_(2)(NFMCT)cathode mitigated Jahn-Teller distortions and Na^(+)/vacancy ordering while enhancing phase integrity and diffusion pathways.The obtained NFMCT maintained 93.7 mAh·g^(−1) after 550 cycles at 1 C,with superior rate capabilities at 2 C and 5 C.These findings deepen the understanding of configuration strategy by using multi-element oxide and highlight a practical strategy for designing high-performance SIB cathodes.
基金supported by the Science and technology plan project of Yulin(2023-CXY-193)the Project funded by Shaanxi Postdoctoral Science Foundation(2023BSHEDZZ274)+2 种基金the Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0588,Z20210201)the Science and technology plan project of Beilin(GX2319)the Science and technology plan project of Ankang(AK2023-GY-08)。
文摘03-type layered oxide serves as dominant components in sodium ion batteries;however,the unstable electronic structure between transition metal and oxygen inevitably induces framework instability and severe kinetic hindrance.In this study,a two-in-one approach to synergistically modulate the local electro nic and interfacial structure of NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)by Ce modification is proposed.We present an indepth study to reveal the strong-covalent Ce-O bonds,which make local charge around oxygen more negative,enhance O 2p-Mn 3d hybridization,and preserve the octahedral structural integrity.This modification tailors local electronic structure between the octahedral metal center and oxygen,thus enhancing reversibility of 03-P3-03 phase transition and expanding Na+octahedral-tetrahedral-octahedral transport channel.Additionally,the nanoscale perovskite layer induced by Ce element is in favor of minimizing interfacial side reaction as well as enhancing Na^(+)diffusivity.As a result,the designed 03-NaNi_(0.305)Fe_(0.33)Mn_(0.33)Ce_(0.025)O_(2)material delivers an exceptionally low volume variation,an ultrahigh rate capacity of 76.9 mA h g^(-1)at 10 C,and remarkable cycling life over 250 cycles with capacity retention of 80% at 5 C.
基金financially supported by National Key Research and Development Program of China(No.2022YFE0202400)the National Natural Science Foundation of China(No.22379103)+2 种基金Natural Science Foundation of Guangdong Province of China(No.2021A1515010388)the Science and Technology Projects of Suzhou City(No.SYC2022043)the Qing Lan Project of Jiangsu Province(2022)。
文摘The development of high-performance cathode materials is critical to the practical application of sodiumion batteries(SIBs).O3-type NaCrO_(2)(NCO)is one of the most competitive cathodes,but it suffers from rapid capacity decay caused by severe irreversible structural evolution.An Mg-Ti co-doped Na_(0.99)Cr_(0.95)Mg_(0.02)Ti_(0.03)O_(2)(NCO-MT)cathode material is designed and synthesized via a facile solid-state reaction to enhance the cyclability of NCO.A capacity retention of 71.6%after 2500 cycles with the capacity fade rate of 0.011%per cycle is achieved for NCO-MT at 5 C,which is attributed to the highly reversible crystal structure during cycling.Our findings offer a novel insight into the high-performance O3-type layered cathode materials for SIBs and are beneficial to promote the development of high-rate SIBs.
基金the financial support provided by the Longzihu New Energy Laboratory Joint Fund of Henan Province(2023008)the Energy Storage Mater.and Processes Key Laboratory of Henan Province Open Fund(2021003)+1 种基金the Collaborative Innovation Team Project Fund of Industry-University-Research(32214085)the financial support received from Zhejiang Vast Na Technology Co.,Ltd.(24110380)。
文摘To address the challenges of air stability and slurry processability in layered transition metal oxide O_(3)-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)for sodium-ion batteries(SIBs),we have designed an innovative 500℃reheating strategy.This method improves the surface properties of NFM without the need for additional coating layers,making it more efficient and suitable for large-scale applications.Pristine NFM(NFM-P)was first synthesized through a high-temperature solid-state method and then modified using this reheating approach(NFM-HT).This strategy significantly enhances air stability and electrochemical performance,yielding an initial discharge specific capacity of 151.46 mAh/g at 0.1C,with a remarkable capacity retention of 95.04%after 100 cycles at 0.5C.Additionally,a 1.7 Ah NFM‖HC(hard carbon)pouch cell demonstrates excellent long-term cycling stability(94.64%retention after 500 cycles at 1C),superior rate capability(86.48%retention at 9C),and strong low-temperature performance(77%retention at-25℃,continuing power supply at-40℃).Notably,even when overcharged to 8.29 V,the pouch cell remained safe without combustion or explosion.This reheating strategy,which eliminates the need for a coating layer,offers a simpler,more scalable solution for industrial production while maintaining outstanding electrochemical performance.These results pave the way for broader commercial adoption of NFM materials.
基金financially supported by the National Natural Science Foundation of China(Nos.52164029,52074099 and 52464033)Natural Science Foundation of Hainan Province(Nos.221RC585,821MS0782,221MS048 and 221RC 1072)+1 种基金Hainan Province Science and Technology Special Fund(Nos.ZDYF2022GXJS004 and ZDYF2021GXJS028)Scientific Research Foundation of Hainan Tropical Ocean University(No.RHDRC202112)
文摘One prominent cathode material utilized in commercial sodium-ion batteries is the O3-type NaNi_(0.5)Mn_(0.5)O_(2).The application of this material is hindered by multistage phase transitions and insufficient air stability.In this study,an innovative O3-type NaNi_(0.5)Mn_(0.5)O_(2),derived from Ni-MOFs (referred to as M-NNMO),has been developed as a cathode material for sodium-ion batteries.The M-NNMO cathode exhibits a discharge specific capacity of 124 mAh·g^(-1)at a rate of0.1C within 2.0 to 4.0 V.Furthermore,this material demonstrates an impressive capacity retention of 75%after undergoing 100 cycles.Complex phase transitions can be inhibited and ion diffusion rates can be increased simultaneously by Ni-MOFs through the enhancement of transition metal-oxygen bonding and the rise n Na layer gap,which are in charge of the remarkable performance improvement.Importantly,the enhanced stability of the M-NNMO transition metal layer based on the uniquestructural properties of Ni-MOFs in air stability tests.This work will provide theoretical guidance to design sodiumion battery cathode materials with superior performance.
基金Project(51071181)supported by the National Natural Science Foundation of ChinaProject(2013FJ4043)supported by the Natural Science Foundation of Hunan Province,China
文摘Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing experimental phenomena of alloy phase transitions during extremely slow variation in temperature by equilibrium thinking mode and then taking erroneous knowledge of experimental phenomena as selected information for establishing Gibbs energy function and so-called equilibrium phase diagram. Second, the equilibrium holographic network phase diagrams of AuCu3-type sublattice system may be used to describe systematic correlativity of the composition?temperature-dependent alloy gene arranging structures and complete thermodynamic properties, and to be a standard for studying experimental subequilibrium order-disorder transition. Third, the equilibrium transition of each alloy is a homogeneous single-phase rather than a heterogeneous two-phase, and there exists a single-phase boundary curve without two-phase region of the ordered and disordered phases; the composition and temperature of the top point on the phase-boundary curve are far away from the ones of the critical point of the AuCu3 compound.
基金financial support from the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (No. NSFC51621001)the Guangdong Special Support Program (2017TQ04N224)+1 种基金the Guangdong Natural Science Funds for Distinguished Young Scholar (Grant No. 2017B030306004)the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme。
文摘O3-type Na NiO_(2)-based cathode materials undergo irreversible phase transition and serious capacity decay at high voltage above 4.0 V in sodium-ion batteries. To address these challenges, effects of Fsubstitution on the structure and electrochemical performance of Na Ni_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(2) are investigated in this article. The F-substitution leads to expanding of interlayer, which can enhance the mobility of Na+. NaNi_(0.4)Mn_(0.25)Ti_(0.3)Co_(0.05)O_(1.92)F_(0.08)(NMTC-F_(0.08)) with the optimal F-substitution degree exhibits much improved rate capability and cyclic stability. It delivers reversible capacities of 177 and 97 m Ah g^(-1) at 0.05 and 5 C within 2.0–4.4 V, respectively. Galvanostatic intermittent titration technique verifies faster kinetics of Na+diffusion in NMTC-F_(0.08). And in-situ XRD investigation reveals the phase evolution of NMTC-F_(0.08), indicating enhanced structural stability results from F-substitution. This study may shed light on the development of high performance cathode materials for sodium-ion storage at high voltage.
基金the National Key Research and Development Program of China (No. 2018YFB0703600)Shenzhen Key Projects of Long-Term Support Plan (No. 20200925164021002)。
文摘Recent years have witnessed a continuous discovering of new thermoelectric materials which has experienced a paradigm shift from try-and-error efforts to experience-based discovering and first-principles calculation. However, both the experiment and first-principles calculation deriving routes to determine a new compound are time and resources consuming. Here, we demonstrated a machine learning approach to discover new M_(2)X_(3)-type thermoelectric materials with only the composition information. According to the classic Bi_(2)Te_(3) material, we constructed an M_(2)X_(3)-type thermoelectric material library with 720 compounds by using isoelectronic substitution, in which only 101 compounds have crystalline structure information in the Inorganic Crystal Structure Database(ICSD) and Materials Project(MP) database. A model based on the random forest(RF) algorithm plus Bayesian optimization was used to explore the underlying principles to determine the crystal structures from the known compounds. The physical properties of constituent elements(such as atomic mass, electronegativity, ionic radius) were used to define the feature of the compounds with a general formula ^(1)M^(2)M^(1)X^(2)X^(3)X(^(1)M +^(2)M:^(1)X +^(2)X+^(3)X = 2:3). The primary goal is to find new thermoelectric materials with the same rhombohedral structure as Bi_(2)Te_(3) by machine learning.The final trained RF model showed a high accuracy of 91% on the prediction of rhombohedral compounds. Finally, we selected four important features to proceed with the polynomial fitting with the prediction results from the RF model and used the acquired polynomial function to make further discoveries outside the pre-defined material library.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金supported by the Science and Technology Program of Suzhou(ST202304)the National Natural Science Foundation of China(12275189)+1 种基金the Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 project。
文摘O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.
基金Project(2007AA11A104) supported by the High-tech Research and Development Program of ChinaProject(2009CB220100) supported by the National Basic Research Program of China
文摘A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.
基金supported by the National Natural Science Foundation of China(Nos.22179077,51774251,21908142)Shanghai Science and Technology Commission’s“2020 Science and Technology In-novation Action Plan”(No.20511104003)Natural Science Foundation in Shanghai(No.21ZR1424200)。
文摘The Na-deficient P3-type layered oxide cathode material usually experience complex in-plane Na^(+)/vacancy ordering rearrangement and undesirable P3-O3 phase transitions in the high-voltage region,leading to inferior cycling performance.Additionally,they exhibit unsatisfactory stability when exposed to water for extended periods.To address these challenges,we propose a Cu/Ti co-doped P3-type cathode material(Na_(0.67)Ni_(0.3)Cu_(0.03)Mn_(0.6)Ti_(0.07)O_(2)),which effectively mitigates Na^(+)/vacancy ordering and suppresses P3-O3 phase transitions at high voltages.As a result,the as-prepared sample exhibited outstanding cyclic performance,with 81.9%retention after 500 cycles within 2.5–4.15 V,and 75.7%retention after300 cycles within 2.5–4.25 V.Meanwhile,it demonstrates enhanced Na^(+)transport kinetics during desodiation/sodiation and reduced growth of charge transfer impedance(R_(ct))after various cycles.Furthermore,the sample showed superb stability against water,exhibiting no discernible degradation in structure,morphology,or electrochemical performance.This co-doping strategy provides new insights for innovative and prospective cathode materials.
基金supported by the National Key Research and Development Program of China(Nos.2021YFB3503100,2022YFB3505303,2021YFB3501500)the Major Projects in the Inner Mongolia Autonomous Region of China.
文摘In this work,a small amount of Al_(2)O_(3)powders(≤0.3 wt%)were incorporated into the Sm_(2)Co_(17)-type sin-tered magnets,obtaining both high mechanical and magnetic properties.It is found that 0.1%weight percentage of Al_(2)O_(3)doping is enough to enhance the flexural strength by about 20%(∼180 MPa for the case of the c-axis parallel to height).Meanwhile,the(BH)max remains around 219 kJ/m^(3),and Hcj is 2052 kA/m,which is over 95%of that of the original magnets without doping.The promising improvement in flexural strength is mainly attributed to the grain size effective refinement caused by Sm_(2)O_(3)particles including newly-formed ones from the reaction of the Al_(2)O_(3)powder and Sm in the matrix.Furthermore,the grain size of the magnets decreases significantly with increasing of Al_(2)O_(3)doping up to 0.3 wt%.Espe-cially,the grain size of 0.3 wt%Al_(2)O_(3)doped magnets is refined by 37%.However,the flexural strengths(for the c-axis parallel to height and the c-axis parallel to width cases)of the magnets decrease sequen-tially and are even lower than that of the original magnet.The microstructure investigations indicate that the decrease in flexural strength may closely be correlated to the larger cell size and the incomplete cell boundaries phase.The obtained results infer that the flexural strength is susceptible to not only grain size but also the cellular structure of the magnets.
基金Project (51104188) supported by the National Natural Science Foundation for Young Scholars of China
文摘The effects of the Cr3C2 content and wheel speed on the amorphization behavior of the melt-spun SmCo7-x（Cr3C2）x （x=0.10-0.25） alloys were studied systematically by X-ray diffraction analysis （XRD）, differential scanning calorimetry （DSC） and magnetic measurements. The ribbon melt-spun at lower wheel speed （20 m/s） has composite structure composed of mostly SmCo7 and a small amount of Sm2Co17R. The grain size of SmCo7 phase decreases with the increase of Cr3C2 content. With the increase of wheel speed, the XRD peaks become lower and accompanied with a broad increase in backgrounds, indicating a considerable decrease in the grain size of the SmCo7 phase. When the wheel speed increases to 40 m/s, SmCo7-x（Cr3C2）x alloys can be obtained in the amorphous state for 0.15≤x≤0.25 with intrinsic coercive Hci of 0.004-0.007 T. The DSC analysis reveals that SmCo7 phase firstly precipitates from the amorphous matrix at 650 °C, followed by the crystallization of Sm2Co17 phase at 770 °C.
基金financially supported by (i) Suranaree University of Technology,(ii) Thailand Science Research and Innovation,and (iii) National Science,Research and Innovation Fund(project codes 90464 and 160363)。
文摘The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.
基金Z.L.was financially supported by the Bayerisches Geoinstitut Visitor’s Program and the Fundamental Research Funds for the Central Universities of Ministry of Education of China(Grant No.45119031C037)This project has received funding from the European Research Council(ERC)under the European Union’s Horizon 2020 research and innovation programme(Proposal No.787527)+2 种基金It is also supported by research grants to T.K.(BMBF:05K13WC2,05K16 WC2DFG:KA3434/3–1,KA3434/7–1,KA3434/8–1,KA3434/9–1)Z.L.(the National Science Foundation of China Grant No.41902034).
文摘The temperature dependence of the Al2O3 solubility in bridgmanite has been determined in the system MgSiO3–Al_(2)O_(3)at temperatures of 2750–3000 K under a constant pressure of 27 GPa using a multi-anvil apparatus.Bridgmanite becomes more aluminous with increasing temperatures.A LiNbO3-type phase with a pyrope composition(Mg_(3)Al_(2)Si_(3)O_(12))forms at 2850 K,which is regarded as to be transformed from bridgmanite upon decompression.This phase contains 30 mol%Al_(2)O_(3)at 3000 K.The MgSiO3 solubility in corundum also increases with temperatures,reaching 52 mol%at 3000 K.Molar volumes of the hypothetical Al_(2)O_(3)bridgmanite and MgSiO_(3)corundum are constrained to be 25.950.05 and 26.24±0.06 cm^(3)/mol,respectively,and interaction parameters of non-ideality for these two phases are 5.6±0.5 and 2.2±0.5 KJ/mol,respectively.The increases in Al^(2)O^(3)and MgSiO^(3)contents,respectively,in bridgmanite and corundum are caused by a larger entropy of Al_(2)O_(3)bridgmanite plus MgSiO_(3)corundum than that of MgSiO_(3)bridgmanite plus Al_(2)O_(3)corundum with temperature,in addition to the configuration entropy.Our study may help explain dynamics of the top lower mantle and constrain pressure and temperature conditions of shocked meteorites.
基金supported by the National Natural Science Foundation of China(22169002 and 22469003)the Chongzuo Key Research and Development Program of China(20241205 and 20231204)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)。
文摘Expanding the cutoff voltage of layered oxide cathodes for sodium-ion batteries(SIBs)is crucial for overcoming their existing energy density limitations.However,cationic/anodic redox-triggered multiple phase transitions and unfavorable interfacial side reactions accelerate capacity and voltage decay.Herein,we present a straightforward melting plus reactive wetting strategy using H_(3)BO_(3)for surface modification of O_(3)-type Na_(0.9)Cu_(0.12)Ni_(0.33)Mn_(0.4)Ti_(0.15)O_(2)(CNMT).The transformation of H_(3)BO_(3)from solid to liquid under mild heating facilitates the uniform dispersion and complete surface coverage of CNMT particles.By neutralizing the residual alkali and extracting Na^(+)from the CNMT lattice,H_(3)BO_(3)forms a multifunctional Na_(2)B_(2)O_(5)-dominated layer on the CNMT surface.This Na_(x)B_(y)O_(z)(NBO)layer plays a positive role in providing low-barrier Na^(+)transport channels,suppressing phase transitions,and minimizing the generation of O_(2)/CO_(2)gases and resistive byproducts.As a result,at a charge cutoff voltage of 4.5 V,the NBO-coated CNMT delivers a high discharge capacity of 149,1 mAh g^(-1)at 10 mA g^(-1)and exhibits excellent cycling stability at 100 mA g^(-1)over 200 cycles with a higher capacity retention than that of pristine CNMT(86,4%vs,62.1%).This study highlights the effectiveness of surface modification using lowmelting-point solid acids,with potential applications for other layered oxide cathode materials to achieve stable high-voltage cycling.This proposed strategy opens new avenues for the construction of highquality coatings for high-voltage layered oxide cathodes in SIBs.
基金supported by the National Natural Science Foundation of China(No.22209073 to Z.H.L.)the Natural Science Foundation of Jiangsu Province(No.BK20220912 to Z.H.L.)+3 种基金the Science the Technology Innovation Fund for Emission Peak and Carbon Neutrality of Jiangsu province(No.BK20231512 to M.B.Z.)the National Natural Science Foundation of China(No.52072173 to L.F.S.)International Science and Technology Cooperation Program of Jiangsu Province(No.SBZ2022000084 to L.F.S.)the Fundamental Research Funds for the Central Universities(Nos.ILA22061 and ILA22075 to L.F.S.).
文摘The O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM)has emerged as a highly promising cathode material for sodiumion batteries due to its facile synthesis and high theoretical capacity.However,it suffers from severe capacity and rate capability degradation caused by multiple coupled failure mechanisms,including irreversible phase transitions,structural deterioration at high voltages,and electrolyte-induced surface corrosion.This work addresses the challenge of high-voltage stability in NFM cathodes via a synergistic bulk-phase and interface engineering strategy.Firstly,Li,Ti,and Co are codoped into the bulk lattice structure to suppress the Mn^(3+)-induced Jahn-Teller distortion and improve Na^(+)diffusion kinetics.And then,an AlPO_(4) protective coating layer is fabricated to mitigate electrolyte corrosion and interfacial side reactions.Consequently,the as-designed composite cathode(AP@NFMLTC)can effectively suppress the P3 to O3’phase transition within the voltage range of 2.0 to 4.2 V,resulting in a highly reversible sodium storage mechanism.After 100 cycles at a rate of 1 C,the capacity retention rate significantly improves from 45.6%to 83.6%,with a minimal voltage decay of just 0.08 V.The dual bulk-interface synergistic strategy in this work provides valuable insights into achieving high stable operation for sodium-ion batteries(SIBs)cathodes under enhanced voltage.
基金support from Natural Science Foundation of China(Grant Nos.52371187)the Beijing-Tianjin-Hebei Basic Research Cooperation Special Project(B2024209048)+1 种基金the Central Government Guides Local Science and Technology Development Funds of Hebei Province(226Z4403G)the Ph.D.Research Startup Foundation of North China University of Science and Technology(No.BS2019001).
文摘Sodium-based O3-type layered oxide materials are attractive for Sodium-ion batteries(SIBs)due to their simple synthesis,affordability,and high capacity.However,challenges remain,including limited reversible capacity and poor cycling stability caused by detrimental phase tran-sitions during cycling and the tendency to form sodium carbonate upon air exposure.In this study,based on O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NNFM),a high-entropy strategy was introduced to successfully synthesize O3-type NaNi_(0.25)Fe_(0.21)Mn_(0.18)Co_(0.21)Ti_(0.1)Mg_(0.05)O_(2)(HE-NNFM).The introduction of Co,Ti,and Mg ions increases the system's disorder,highlighting the synergistic interactions among inert atoms.The delayed phase transformation effect in high-entropy materials alleviates the destruction of the O3 structure by the insertion and extraction of sodium ions.Simultaneously,the narrower sodium layer in HE-NNFM acts as a physical barrier,effectively preventing adverse reactions with H2O and CO_(2) in the air,resulting in excellent reversibility and air stability of the HE-NNFM material.Consequently,the HE-NNFM material exhibits a reversible capacity of 110 mAh·g^(-1)with a capacity retention of 97.3%after 200 cycles at 1 C.This work provides insights into the design of high-entropy sodium layered oxides for high-power density storage systems.
