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1.
Kim  A.-Young  Kim  Min Kyu  Kim  Ji Young  Wen  Yuren  Gu  Lin  Dao  Van-Duong  Choi  Ho-Suk  Byun  Dongjin  Lee  Joong Kee 《Nano Research》2017,10(6):2083-2095
Lithium-sulfur battery has become one of the most promising candidates for next generation batteries,and it is still restricted due to the low sulfur conductivity,large volume expansion and severe polysulfide shuttling.Herein,we present a novel hybrid electrode with a ternary nanomaterial based on sulfur-impregnated multiwalled carbon nanotubes filled with ordered tin-monoxide nanoparticles (MWCNT-SnO/S).Using a dry plasma reduction method,a mechanically robust material is prepared as a cathode host material for lithium-sulfur batteries.The MWCNT-SnO/S electrode exhibits high conductivity,good ability to capture polysulfides,and small volume change during a repeated charge-discharge process.In situ transmission electron microscopy and ultraviolet-visible absorption results indicate that the MWCNT-SnO host efficiently suppresses volume expansion during lithiation and reduces polysulfide dissolution into the electrolyte.Furthermore,the ordered SnO nanoparticles in the MWCNTs facilitate fast ion/electron transfer during the redox reactions by acting as connective links between the walls of the MWCNTs.The MWCNT-SnO/S cathode with a high sulfur content of 70 wt.% exhibits an initial discharge capacity of 1,682.4 mAh·g-1 at 167.5 mA·g-1 (0.1 C rate) and retains a capacity of 530.1 mAh·g-1 at 0.5 C after 1,000 cycles with nearly 100% Coulombic efficiency.Furthermore,the electrode exhibits the high capacity even at a high current rate of 20 C.  相似文献   

2.
Transition-metal oxides (TMOs) have gradually attracted attention from researchers as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of their high theoretical capacity.However,their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic conductivity limit their applications.To solve the problems of TMOs,carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks (MOFs) have emerged as promising electrode materials for LIBs and SIBs.In this study,we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imidazolate frameworks.This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process.The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation,and the carbon matrix improves the electrical conductivity of the electrode.As an anode for LIBs,the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability (1,100 mAh·g-1 after 120 cycles at 200 mA·g-1).As an anode for SIBs,the composites exhibit an outstanding rate capability (307 mAh·g-1 at 1,000 mA·g-1 and 269 mAh·g-1 at 2,000 mA·g-1).Detailed electrochemical kinetic analysis indicates that the energy storage for Li+ and Na+ in yolk-shell Co3O4/C dodecahedrons shows a dominant capacitive behavior.This work introduces an effective approach for fabricating carbonbased metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.  相似文献   

3.
A Co-based metal-organic framework (Co-MOF) with a unique three-dimensional starfish-like nanostructure was successfully synthesized using a simple ultrasonic method.After subsequent carbonization and oxidation,a nanocomposite of nitrogen-doped carbon with a Co3O4 coating (Co3O4@N-C) with a porous starfish-like nanostructure was obtained.The final hybrid exhibited excellent lithium storage performance when evaluated as an anode material in a lithiumion battery.A remarkable and stable discharge capacity of 795 mAh·g-1 was maintained at 0.5 A·g-1 after 300 cycles.Excellent rate capability was also obtained.In addition,a full Co3O4@N-C/LiFePO4 battery displayed stable capacity retention of 95% after 100 cycles.This excellent lithium storage performance is attributed to the unique porous starfish-like structure,which effectively buffers the volume expansion that occurs during Li+ insertion/deinsertion.Meanwhile,the nitrogendoped carbon coating enhances the electrical conductivity and provides a buffer layer to accommodate the volume change and accelerate the formation of a stable solid electrolyte interface layer.  相似文献   

4.
We report for the first time a Na-ion battery anode material composed of P-doped CoSe2 nanoparticles(P-CoSe2)with the size of 5-20 nm that are uniformly embed in a 3D porous honeycomb-like carbon network.High rate capability and cycling stability are achieved simultaneously.The honeycomb-like carbon network is rationally designed to support high electrical conductivity,rapid Na-ion diffusion as well as the accommodation of the volume expansion from the active P-CoSe2 nanoparticles.In particular,heteroatom P-doping within CoSe2 introduces stronger P-Co bonds and additional P-Se bonds that signif-icantly improve the structure stability of P-CoSe2 for highly stable sodiation/desodiation over long-term cycling.P-doping also improves the electrical conductivity of the CoSe2 nanoparticles,leading to highly elevated electrochemical kinetics to deliver high specific capacities at high current densities.Benefiting from the unique nanostructure and atomic-level P-doping,the P-CoSe2(2∶1)/C anode delivers an excel-lent cycle stability with a specific capacity of 206.9 mA h g-1 achieved at 2000 mA g-1 after 1000 cycles.In addition,this material can be synthesized using a facile pyrolysis and selenization/phosphorization approach.This study provides new opportunities of heteroatom doping as an effective method to improve the cycling stability of Na-ion anode materials.  相似文献   

5.
Low-cost and easily obtainable electrode materials are crucial for the application of supercapacitors.Nickel hydroxides have recently attracted intensive attention owning to their high theoretical specific capacitance,high redox activity,low cost,and eco-friendliness.In this study,novel three-dimensional (3D) interspersed flower-like nickel hydroxide was assembled under mild conditions.When ammonia was used as the precipitant and inhibitor and CTAB was used as an exfoliation agent,the obtained exfoliated ultrathin Ni(OH)2 nanosheets were assembled into 3D interspersed flower-like nickel hydroxide.In this novel 3D structure,the ultrathin Ni(OH)2 nanosheets not only provided a large contact area with the electrolyte,reducing the polarization of the electrochemical reaction and providing more active sites,but also reduced the concentration polarization in the electrode solution interface.Consequently,the utilization efficiency of the active material was improved,yielding a high capacitance.The electrochemical performance was improved via promoting the electrical conductivity by mixing the as-synthesized Ni(OH)2 with carbon tubes (N-4-CNT electrode),yielding excellent specific capacitances of 2,225.1 F·g-1 at 0.5 A·g-1 in a three-electrode system and 722.0 F·g-1 at 0.2 A·g-1 in a two-electrode system.The N-4-CNT//active carbon (AC) device exhibited long-term cycling performance (capacitance-retention ratio of 111.4% after 10,000 cycles at 5 A·g-1) and a high specific capacitance of 180.5 F·g-1 with a high energy density of 33.5 W·h·kg-1 and a power density of 2,251.6 W·kg-1.  相似文献   

6.
Here,an agricultural waste (the stem pith of helianthus annuus,SPHA) is firstly used as the precursor for preparing three-dimensional (3D) porous carbon sponge (PCS).The as-prepared 3D PCS (SPHA-700) pos-sesses unique sponge-like structure,large specific surface area (SSA) and high nitrogen doping level (4.52 at.%),which benefit the enhancement of conductivity (5.8 S cm-1) and wettability.As a binder-free elec-trode for solid-state symmetric supercapacitor,SPHA-700 delivers a relatively high specific capacitance of 137.1 F g-1 at 0.5 A g-1.Moreover,activated SPHA-700 (SPHA-ac-700-2) displays an even higher specific capacitance (403.6 F g-1 at 0.5 A g-1) in 6.0 M KOH electrolyte.The SPHA-ac-700-2-based symmetrical supercapacitor can offer high specific capacitance (271 F g-1 at 1 A g-1) and good rate capability (82.1%of capacitance retention at 1-80 A g-1) in 6.0 M KOH electrolyte,together with high energy density(23.3 Wh kg-1 at 450 W kg-1) in 1.0 M Na2SO4 electrolyte.Such excellent performance of SPHA-ac-700-2 is believed to have originated from the crushed sponge-like structure,O/N-co-doping (10.6 at.% O and 3.3 at.% N),high SSA,large total pore volume,and hierarchical pore structure.  相似文献   

7.
Molybdenum disulfide(MoS2) is a promising electrode material for sodium-ion batteries as it offers a large capacity through a distinct conversion reaction.However,the electrochemical potential of MoS2 is often restrained by the poor conductivity as the dominant 2 H phase is a semiconductor while the metallic1 T phase is thermodynamically unstable.In this work,we report a hybrid design and material preparation of freestanding nanosheets of MoS2 composed of both 1 T and 2 H phases based on mild hydrothermal reaction.The introduction of the metallic 1 T-MoS2 phase into 2 H-MoS2 and their intimate hybridization enable a significant improvement in electronic conductivity,while the freestanding architecture avoids possible electrochemical aggregation.When used as electrodes for sodium storage,such a hybrid MoS2 affords a high capacity of~500 mA h g-1 at 0.5 A g-1 after 300 cycles,and retains capacity of~200 mA h g-1 at a high current rate of 4 A g-1,thus demonstrating their potential in high-performance battery applications.  相似文献   

8.
Searching for advanced anode materials with excellent electrochemical properties in sodium-ion battery is essential and imperative for next-generation energy storage system to solve the energy shortage problem.In this work,two-dimensional(2D)ultrathin FePS3 nanosheets,a typical ternary metal phosphosulfide,are first prepared by ultrasonic exfoliation.The novel 2D/2D heterojunction of FePS3 nanosheets@MXene composite is then successfully synthesized by in situ mixing ultrathin MXene nanosheets with FePS3 nanosheets.The resultant FePS3 nanosheets@MXene hybrids can increase the electronic conductivity and specific surface area,assuring excellent surface and interfacial charge transfer abilities.Furthermore,the unique heterojunction endows FePS3 nanosheets@MXene composite to promote the diffusion of Na^+ and alleviate the drastic change in volume in the cyclic process,enhancing the sodium storage capability.Consequently,the few-layered FePS3 nanosheets uniformly coated by ultrathin MXene provide an exceptional reversible capacity of 676.1 mAh g^−1 at the current of 100 mA g^−1 after 90 cycles,which is equivalent to around 90.6% of the second-cycle capacity(746.4 mAh g^−1).This work provides an original protocol for constructing 2D/2D material and demonstrates the FePS3@MXene composite as a potential anode material with excellent property for sodium-ion batteries.  相似文献   

9.
Transition metal oxides as anode materials for high-performance lithium-ion batteries suffer from severe capacity decay,originating primarily from particle pulverization upon volume expansion/shrinkage and the intrinsically sluggish electron/ion transport.Herein,in-situ encapsulation of α-Fe2O3 nanoparticles into micro-sized ZnFe2O4 capsules is facilely fulfilled through a co-precipitation process and followed by heat-treatment at optimal calcination temperature.The porous ZnFe2C4 scaffold affords a synergistic confinement effect to suppress the grain growth of α-Fe2O3 nanocrystals during the calcination process and to accommodate the stress generated by volume expansion during the charge/discharge process,leading to an enhanced interfacial conductivity and inhibit electrode pulverization and mechanical failure in the active material.With these merits,the prepared α-Fe2O3/ZnFe2O4 composite delivers prolonged cycling stability and improved rate capability with a higher specific capacity than sole α-Fe2O3 and ZnFe2O4.The discharge capacity is retained at 700 mAh g-1 after 500 cycles at 200 mA g-1 and 940 mAh g-1 after 50 cycles at 100 mA g-1.This work provides a new perspective in designing transition metal oxides for advanced lithium-ion batteries with superior electrochemical properties.  相似文献   

10.
硒化锡用于钠离子电池负极时具有较高的理论比容量且其成本低廉,因而备受关注.然而,由于其固有的低导电性,以及在充放电过程中的缓慢动力学和体积膨胀,硒化锡作为钠离子电池负极材料表现出的性能较差.本文首次合成SnSe2纳米晶耦合分层多孔碳微球(SnSe2NCs/C)用于增强钠离子电池的比容量、倍率能力和持久性.SnSe2NCs/C独特的结构可以有效阻止SnSe2纳米晶的团聚,减轻材料体积膨胀,加快电子和离子的扩散,增大电解液与电极材料的接触面积,提高材料结构的稳定性.所制备的SnSe2NCs/C微球具有较高的可逆比容量(在100 mA g^-1的电流密度下循环100圈后仍保持565 mA hg^-1的比容量),出色的倍率能力和长循环寿命稳定性(在1 Ag^-1的电流密度下循环1000圈后仍保持363 mAhg^-1的比容量).  相似文献   

11.
Lithium–sulfur batteries (LSBs) are considered as one of the best candidates for novel rechargeable batteries due to their high energy densities and abundant required materials. However, the poor conductivity and large volume expansion of sulfur and the “shuttle effect” of lithium polysulfides (LPSs) have significantly hindered the development and successful commercialization of LSBs. Bean‐like B,N codoped carbon nanotubes loaded with Co nanoparticles (Co@BNTs), which can act as advanced sulfur hosts for the novel LSB cathode, are fabricated. Uniform graphitic nanotubes improve the conductivity of the electrode and load more electroactive sulfur and buffer volume expansion during the electrochemical reaction. In addition, loaded Co nanoparticles and codoped B,N sites can significantly suppress the “shuttle effect” of LPSs with strong chemical interaction. It is established that the Co nanoparticles and codoped B,N can provide more active sites to catalyze the redox reaction of sulfur cathode. This stable Co@BNTs‐S cathode displays an exceptional electrochemical performance (1160 mA h g?1 after 200 cycles at 0.1 C) and outstanding stable cycle performance (1008 mA h g?1 after 400 cycles at 1.0 C with an extremely low attenuation rate of 0.038% per cycle).  相似文献   

12.
Carbonaceous materials are promising sodium-ion battery anodes. Improving their performance requires a detailed understanding of the ion transport in these materials, some important aspects of which are still under debate. In this work, nitrogen-doped porous hollow carbon spheres (N-PHCSs) are employed as a model system for operando analysis of sodium storage behavior in a commercial liquid electrolyte at the nanoscale. By combining the ex situ characterization at different states of charge with operando transmission electron microscopy experiments, it is found that a solvated ionic layer forms on the surface of N-PHCSs at the beginning of sodiation, followed by the irreversible shell expansion due to the solid-electrolyte interphase (SEI) formation and subsequent storage of Na(0) within the porous carbon shell. This shows that binding between Na(0) and C creates a Schottky junction making Na deposition inside the spheres more energetically favorable at low current densities. During sodiation, the SEI fills the gap between N-PHCSs, binding spheres together and facilitating the sodium ions' transport toward the current collector and subsequent plating underneath the electrode. The N-PHCSs layer acts as a protective layer between the electrolyte and the current collector, suppressing the possible growth of dendrites at the anode.  相似文献   

13.
Sodium-ion batteries(SIBs)are considered one of the most promising energy storage systems for replac-ing lithium-ion batteries because of the high abundance and low cost of sodium.Iron oxyfluoride(FeOF)is a promising conversion-based cathode material for SIBs because of its high theoretical capacity of about 855 mA h g-1,low-cost chemical compositions,and its lower sensitivity to the size of charged carrier ions.However,the poor electrical conductivity and ionic diffusion of FeOF result in a low rate capability and cyclability.In this work,FeOF nanoparticles wrapped by graphitic carbon layers were synthesized using abietic or maleopimaric acid as both the carbon source and organic ligand.In addition,the mor-phology of the FeOF particles was gradually controlled from rod to spherical shapes,simply depending on the rosin acids.The FeOF nanoparticles prepared with maleopimaric acid showed a large reversible discharge capacity of 356.7 mA h g-1 with a fading rate of 0.21%per cycle after 100 cycles at a current density of 100 mA g-1 and an excellent rate capability.  相似文献   

14.
Co-Pt nanoparticles encapsulated in carbon cages have been prepared by sonoelectrodeposition followed by annealing in a CO atmosphere. Sonoelectrodeposition is a useful technique to make metallic nanoparticles, using ultrasound during electrodeposition to remove nanoparticles as they grow on the cathode surface. We used an electrolyte containing chloroplatinic acid and cobalt chloride and found that the atomic ratio of Co:Pt in the as-formed materials varied from 0.2 to 0.8 as the deposition current density was changed from 15 to 35 mA cm(-2). However, the as-deposited materials were inhomogeneous, comprising a mixture of Pt-rich and Co-rich nanoparticles. X-ray diffraction indicated that subsequent heat treatment (700?°C for 1 h) under CO gas created an ordered CoPt alloy phase that exhibited hard magnetic properties. Transmission electron microscopy showed many of the resulting nanoparticles to be encapsulated in carbon cages, which we ascribe to Co-catalyzed decomposition of CO during annealing. The thickness of the carbon cages was about ten layers, which may have helped reduce sintering during annealing. The size of the resultant nanoparticles was about 100 nm diameter, larger than the typical 5-10 nm diameter of as-deposited nanoparticles.  相似文献   

15.
Nickel sulfides with high theoretical capacity are considered as promising anode materials for sodium-ion batteries (SIBs); however, their intrinsic poor electric conductivity, large volume change during charging/discharging, and easy sulfur dissolution result in inferior electrochemical performance for sodium storage. Herein, a hierarchical hollow microsphere is assembled from heterostructured NiS/NiS2 nanoparticles confined by in situ carbon layer (H-NiS/NiS2@C) via regulating the sulfidation temperature of the precursor Ni-MOFs. The morphology of ultrathin hollow spherical shells and confinement of in situ carbon layer to active materials provide rich channels for ion/electron transfer and alleviate the effects of volume change and agglomeration of the material. Consequently, the as-prepared H-NiS/NiS2@C exhibit superb electrochemical properties, satisfactory initial specific capacity of 953.0 mA h g−1 at 0.1 A g−1, excellent rate capability of 509.9 mA h g−1 at 2 A g−1, and superior longtime cycling life with 433.4 mA h g−1 after 4500 cycles at 10 A g−1. Density functional theory calculation shows that heterogenous interfaces with electron redistribution lead to charge transfer from NiS to NiS2, and thus favor interfacial electron transport and reduce ion-diffusion barrier. This work provides an innovative idea for the synthesis of homologous heterostructures for high-efficiency SIB electrode materials.  相似文献   

16.
Silicon (Si) anode suffers from huge volume expansion which causes poor structural stability in terms of electrode material, solid electrolyte interface, and electrode, limiting its practical application in high-energy-density lithium-ion batteries. Rationally designing architectures to optimize the stress distribution of Si/carbon (Si/C) composites has been proven to be effective in enhancing their structural stability and cycling stability, but this remains a big challenge. Here, metal-organic frameworks (ZIF-67)-derived carbon nanotube-reinforced carbon framework is employed as an outer protective layer to encapsulate the inner carbon-coated Si nanoparticles (Si@C@CNTs), which features dual carbon stress-buffering to enhance the structural stability of Si/C composite and prolong their cycling lifetime. Finite element simulation proves the structural advantage of dual carbon stress-buffering through significantly relieving stress concentration when Si lithiation. The outer carbon framework also accelerates the charge transfer efficiency during charging/discharging by the improvement of lithium-ion diffusion and electron transport. As a result, the Si@C@CNTs electrode exhibits excellent long-term lifetime and good rate capability, showing a specific capacity of 680 mAh g−1 even at a high rate of 1 A g−1 after 1000 cycles. This work provides insight into the design of robust architectures for Si/C composites by stress optimization.  相似文献   

17.
Sodium-ion capacitors(SICs)have received increasing interest for grid stationary energy storage application due to their affordability,high power,and energy densities.The major challenge for SICs is to overcome the kinetics imbalance between faradaic anode and nonfaradaic cathode.To boost the Na+reaction kinetics,the present work demonstrated a high-rate MnS-based anode by embedding the MnS nanocrystals into the N,S-co-doped carbon matrix(MnS@NSC).Benefiting from the fast pseudocapacitive Na+storage behavior,the resulting composite exhibits extraordinary rate capability(205.6 mAh g−1 at 10 A g−1)and outstanding cycling stability without notable degradation after 2000 cycles.A prototype SIC was demonstrated using MnS@NSC anode and N-doped porous carbon(NC)cathode;the obtained hybrid SIC device can display a high energy density of 139.8 Wh kg−1 and high power density of 11,500 W kg−1,as well as excellent cyclability with 84.5%capacitance retention after 3000 cycles.The superior electrochemical performance is contributed to downsizing of MnS and encapsulation of conductive N,S-co-doped carbon matrix,which not only promote the Na+and electrons transport,but also buffer the volume variations and maintain the structure integrity during Na+insertion/extraction,enabling its comparable fast reaction kinetics and cyclability with NC cathode.  相似文献   

18.
Hollow nanostructures with intricate interior and catalytic effects hold great promise for the construction of advanced lithium–sulfur batteries. Herein, a double‐shelled hollow polyhedron with inlaid cobalt nanoparticles encapsulated by nitrogen‐doped carbon (Co/NC) nanodots (Co‐NC@Co9S8/NPC) is reported, which is acquired by using imidazolium‐based ionic‐polymer‐encapsulated zeolitic imidazolate framework‐67 as a core‐shelled precursor. The Co/NC nanodots promote redox kinetics and chemical adsorbability toward polysulfides, while the interconnected double shells serve as a nanoscale electrochemical reaction chamber, which effectively suppresses the polysulfide shuttling and accelerates ion/electron transport. Benefiting from structural engineering and reaction kinetics modulation, the Co‐NC@Co9S8/NPC‐S electrode exhibits high cycling stability with a low capacity decay of 0.011% per cycle within 2000 cycles at 2 C. The electrode still shows high rate performance and cyclability over 500 cycles even in the case of high sulfur loading of 4.5 mg cm?2 and 75 wt% sulfur content. This work provides one type of new hollow nanoarchitecture for the development of advanced Li–S batteries and other energy storage systems.  相似文献   

19.
Both silicon and tin are promising anodes for new generation lithium ion batteries due to high lithium storage capacities (theoretically 4200 mA h g-1 and 992 mA h g-1,respectively).However,their large volumetric expansions (both are above 300 %) usually lead to poor cycling stability.In this case,we synthesized closely packed Si@C and Sn@C nano-particles anchored by reduced graphene oxide (denoted as Si@C/Sn@C/rGO) by the way of solution impregnation and subsequent hydrogenation reduction.Sn particles with a diameter of 100 nm are coated by carbon and surrounded by Si@C particles around 40 nm in average diameter through the high-resolution transmission electron microscopy.Expansions of Si and Sn are alleviated by carbon shells,and reduced graphene oxide sheets accommodate their volume changes.The prepared Si@C/Sn@C/rGO electrode delivers an enhanced initial coulombic efficiency (78%),rate capability and greatly improved cycle stability (a high reversible capacity of nearly 1000 mA h g-1 is achieved after 300 cycles at a current density of 1000 mA g-1).It can be believed that packing Sn@C nano-particles with Si@C relieves the volume expansion of both and releases the expansion stresses.Sn@C particles enhance anode process kinetics by reducing charge transfer resistance and increasing lithium ion diffusion coefficient.The present work provides a viable strategy for facilely synthesizing silicon-tin-carbon composite anode with long life.  相似文献   

20.
The oxygen vacancies and micro-nano structure can optimize the electron/Li+migration kinetics in anode materials for lithium batteries(LIBs).Here,porous micro-nano structured VNb9O25 composites with rich oxygen vacancies were reasonably prepared via a facile solvothermal method combined with annealing treatment at 800℃for 30 h(VNb9 O25-30 h).This micro-nano structure can enhance the contact of active material/electrolyte,and shorten the Li+diffusion distance.The introduction of oxygen vacancies can further boosts the intrinsic conductivity of VNb9O25-30 h for achieving excellent LIB performance.The as-prepared VNb9O25-30 h anode showed advanced rate capability with reversible capacity of 122.2 mA h g-1 at 4 A g-1,and delivered excellent capacity retention of~100%after 2000 cycles.Meanwhile,VNb9O25-30 h provides unexpected long-cycle life(i.e.,reversible capacity of 165.7 mA h g-1 at 1 A g-1 with a high capacity retention of 85.6%even after 8000 cycles).Additionally,coupled with the LiFePO4 cathode,the LiFePO4//VNb9O25-30 h full cell delivers superior LIB properties with high reversible capacities of 91.6 mA h g-1 at 5C for 1000 cycles.Thus,such reasonable construction method can assist in other high-performance niobium-based oxides in LIBs.  相似文献   

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