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1.
High‐rate performance flexible lithium‐ion batteries are desirable for the realization of wearable electronics. The flexibility of the electrode in the battery is a key requirement for this technology. In the present work, spinel lithium titanate (Li4Ti5O12, LTO) cuboid arrays are grown on flexible carbon fiber cloth (CFC) to fabricate a binder‐free composite electrode (LTO@CFC) for flexible lithium‐ion batteries. Experimental results show that the LTO@CFC electrode exhibits a remarkably high‐rate performance with a capacity of 105.8 mAh g?1 at 50C and an excellent electrochemical stability against cycling (only 2.2% capacity loss after 1000 cycles at 10C). A flexible full cell fabricated with the LTO@CFC as the anode and LiNi0.5Mn1.5O4 coated on Al foil as the cathode displays a reversible capacity of 109.1 mAh g?1 at 10C, an excellent stability against cycling and a great mechanical stability against bending. The observed high‐rate performance of the LTO@CFC electrode is due to its unique corn‐like architecture with LTO cuboid arrays (corn kernels) grown on CFC (corn cob). This work presents a new approach to preparing LTO‐based composite electrodes with an architecture favorable for ion and electron transport for flexible energy storage devices.  相似文献   

2.
Omnibearing acceleration of charge/ion transfer in Li4Ti5O12 (LTO) electrodes is of great significance to achieve advanced high‐rate anodes in lithium‐ion batteries. Here, a synergistic combination of hydrogenated LTO nanoparticles (H‐LTO) and N‐doped carbon fibers (NCFs) prepared by an electrodeposition‐atomic layer deposition method is reported. Binder‐free conductive NCFs skeletons are used as strong support for H‐LTO, in which Ti3+ is self‐doped along with oxygen vacancies in LTO lattice to realize enhanced intrinsic conductivity. Positive advantages including large surface area, boosted conductivity, and structural stability are obtained in the designed H‐LTO@NCF electrode, which is demonstrated with preeminent high‐rate capability (128 mAh g?1 at 50 C) and long cycling life up to 10 000 cycles. The full battery assembled by H‐LTO@NCFs anode and LiFePO4 cathode also exhibits outstanding electrochemical performance revealing an encouraging application prospect. This work further demonstrates the effectiveness of self‐doping of metal ions on reinforcing the high‐rate charge/discharge capability of batteries.  相似文献   

3.
High‐performance of lithium‐ion batteries (LIBs) rely largely on the scrupulous design of nanoarchitectures and smart hybridization of bespoke active materials. In this work, the pine‐needle‐like Cu–Co skeleton is reported to support highly active Li4Ti5O12 (LTO) forming Cu–Co/LTO core–branch arrays via a united hydrothermal‐atomic layer deposition (ALD) method. ALD‐formed LTO layer is uniformly anchored on the pine‐needle‐like heterostructured Cu–Co backbone, which consists of branched Co nanowires (diameters in 20 nm) and Cu nanowires (250–300 nm) core. The designed Cu–Co/LTO core–branch arrays show combined advantages of large porosity, high electrical conductivity, and good adhesion. Due to the unique positive features, the Cu–Co/LTO electrodes are demonstrated with enhanced electrochemical performance including excellent high‐rate capacity (155 mAh g?1 at 20 C) and noticeable long‐term cycles (144 mAh g?1 at 20 C after 3000 cycles). Additionally, the full cell assembled with activated carbon positive electrode and Cu–Co/LTO negative electrode exhibits high power/energy densities (41.6 Wh kg?1 at 7.5 kW kg?1). The design protocol combining binder‐free characteristics and array configuration opens a new door for construction of advanced electrodes for application in high‐rate electrochemical energy storage.  相似文献   

4.
Metallic lithium (Li), considered as the ultimate anode, is expected to promise high‐energy rechargeable batteries. However, owing to the continuous Li consumption during the repeated Li plating/stripping cycling, excess amount of the Li metal anode is commonly utilized in lithium‐metal batteries (LMBs), leading to reduced energy density and increased cost. Here, an all‐solid‐state lithium‐metal battery (ASSLMB) based on a garnet‐oxide solid electrolyte with an ultralow negative/positive electrode capacity ratio (N/P ratio) is reported. Compared with the counterpart using a liquid electrolyte at the same low N/P ratios, ASSLMBs show longer cycling life, which is attributed to the higher Coulombic efficiency maintained during cycling. The effect of the species of the interface layer on the cycling performance of ASSLMBs with low N/P ratio is also studied. Importantly, it is demonstrated that the ASSLMB using a limited Li metal anode paired with a LiFePO4 cathode (5.9 N/P ratio) delivers a stable long‐term cycling performance at room temperature. Furthermore, it is revealed that enhanced specific energies for ASSLMBs with low N/P ratios can be further achieved by the use of a high‐voltage or high mass‐loading cathode. This study sheds light on the practical high‐energy all‐solid‐state batteries under the constrained condition of a limited Li metal anode.  相似文献   

5.
Supercapacitors have aroused considerable attention due to their high power capability, which enables charge storage/output in minutes or even seconds. However, to achieve a high energy density in a supercapacitor has been a long‐standing challenge. Here, graphite is reported as a high‐energy alternative to the frequently used activated carbon (AC) cathode for supercapacitor application due to its unique Faradaic pseudocapacitive anion intercalation behavior. The graphite cathode manifests both higher gravimetric and volumetric energy density (498 Wh kg?1 and 431.2 Wh l?1) than an AC cathode (234 Wh kg?1 and 83.5 Wh l?1) with peak power densities of 43.6 kW kg?1 and 37.75 kW l?1. A new type of Li‐ion pseudocapacitor (LIpC) is thus proposed and demonstrated with graphite as cathode and prelithiated graphite or Li4Ti5O12 (LTO) as anode. The resultant graphite–graphite LIpCs deliver high energy densities of 167–233 Wh kg?1 at power densities of 0.22–21.0 kW kg?1 (based on active mass in both electrodes), much higher than 20–146 Wh kg?1 of AC‐derived Li‐ion capacitors and 23–67 Wh kg?1 of state‐of‐the‐art metal oxide pseudocapacitors. Excellent rate capability and cycling stability are further demonstrated for LTO‐graphite LIpCs.  相似文献   

6.
Much attention is paid to metal lithium as a hopeful negative material for reversible batteries with a high specific capacity. Although applying 3D hosts can relieve the dendrite growth to some extent, gradient‐distributed lithium ion in 3D uniform hosts still induces uncontrolled lithium dendrites growth, especially at high lithium capacity and high current density. Herein, a 3D conductive carbon nanofiber framework with gradient‐distributed ZnO particles as nucleation seeds (G‐CNF) to regulate lithium deposition is proposed. Based on such a unique structure, the G‐CNF electrode exhibits a high average Coulombic efficiency (CE) of 98.1% for 700 cycles at 0.5 mA cm?2. Even at 5 mA cm?2, the G‐CNF electrode performs a stable cycling process and high CE of 96.0% for over 200 cycles. When the lithium‐deposited G‐CNF (G‐CNF‐Li) anode is applied in a full cell with a commercial LiFePO4 cathode, it exhibits a stable capacity of 115 mAh g?1 and high retention of 95.7% after 300 cycles. Through inducing the gradient‐distributed nucleation seeds to counter the existing Li‐ion concentration polarization, a uniform and stable lithium deposition process in the 3D host is achieved even under the condition of high current density.  相似文献   

7.
Li||NMC811 battery, with lithium-metal (high specific capacity and low redox potential) as anode and LiNi0.8Co0.1Mn0.1O2 (NMC811) as cathode, has been widely accepted to be a good candidate as one of the high-energy-density batteries. However, its cyclability needs improvement to fulfill the requirement for its future commercial use, especially under practical conditions. Electrolyte plays a key role in improving the cycling performance of Li||NMC811 batteries, where a high voltage/electrochemical window and good stability with the electrodes of the electrolyte are required. Herein, a localized high-concentration electrolyte with an additive of lithium difluoro(oxalate)borate (LiDFOB) is reported that improves the cycling performance of Li||NMC811 cells under crucial conditions with Li foil thickness of 50 µm, cathode areal loading of 4 mAh cm−2, the areal capacity ratio between the negative and positive electrodes (N/P ratio) of 2.6 and the electrolyte/cell capacity ratio (E/C ratio) of 3.0 g (Ah)−1. These cells can maintain 80% of the capacity after 195 cycles.  相似文献   

8.
Silicon anode with extremely high theoretical specific capacity (≈4200 mAh g?1), experiences huge volume changes during Li‐ion insertion and extraction, causing mechanical fracture of Si particles and the growth of a solid–electrolyte interface (SEI), which results in a rapid capacity fading of Si electrodes. Herein, a mechanically reinforced localized structure is designed for carbon‐coated Si nanoparticles (C@Si) via elongated TiO2 nanotubes networks toward stabilizing Si electrode via alleviating mechanical strain and stabilizing the SEI layer. Benefited from the rational localized structure design, the carbon‐coated Si nanoparticles/TiO2 nanotubes composited electrode (C@Si/TiNT) exhibits an ideal electrode thickness swelling, which is lower than 1% after the first cycle and increases to about 6.6% even after 1600 cycles. While for traditional C@Si/carbon nanotube composited electrode, the initial swelling ratio is about 16.7% and reaches ≈190% after 1600 cycles. As a result, the C@Si/TiNT electrode exhibits an outstanding capacity of 1510 mAh g?1 at 0.1 A g?1 with high rate capability and long‐time cycling performance with 95% capacity retention after 1600 cycles. The rational design on mechanically reinforced localized structure for silicon electrode will provide a versatile platform to solve the current bottlenecks for other alloyed‐type electrode materials with large volume expansion toward practical applications.  相似文献   

9.
Although the high energy density and environmental benignancy of LiNi0.8Co0.15Al0.05O2 (NCA) holds promise for use as cathode material in Li‐ion batteries, present low rate capabilities, and fast capacity fade limit its broad commercial applications. Here, it is reported that surface modification of NCA cathode (R‐3m) with 5 nm‐thick nanopillar layers and Fm‐3m structures significantly improves electrode structure, morphology, and electrochemical performance. The formation of nanopillar layers increases cycling and working voltage stability of NCA by shielding the host material from hydrofluoric acid and improves structural stability with the electrolyte. The modified NCA cathode exhibits an enhanced 89% capacity retention at a rate of 1 C over that of pristine NCA (75.2%) after 150 cycles and effectively suppresses working voltage fade (a drop of 0.025 V after 300 cycles) during repeated charge–discharge cycles. In addition, the diffusion barrier of Li ions in NCA crystals at 0.80 V is noticeably smaller than that of Li ions in pristine NCA (0.87 eV). These findings demonstrate that this unique surface structure design considerably enhances cycle and rate performance of NCA, which has potential applications in other Ni‐rich layered cathode materials.  相似文献   

10.
Lithium (Li) metal anodes have attracted much interest recently for high‐energy battery applications. However, low coulombic efficiency, infinite volume change, and severe dendrite formation limit their reliable implementation over a wide range. Here, an outstanding stability for a Li metal anode is revealed by designing a highly porous and hollow Li foam. This unique structure is capable of tackling many Li metal problems simultaneously: first, it assures uniform electrolyte distribution over the inner and outer electrode's surface; second, it reduces the local current density by providing a larger electroactive surface area; third, it can accommodate volume expansion and dissipate heat efficiently. Moreover, the structure shows superior stability compared to fully Li covered foam with low porosity, and bulky Li foil electrode counterparts. This Li foam exhibits small overpotential (≈25 mV at 4 mA cm?2) and high cycling stability for 160 cycles at 4 mA cm?2. Furthermore, when assembled, the porous Li metal as the anode with LiFePO4 as the cathode for a full cell, the battery has a high‐rate performance of 138 mAh g?1 at 0.2 C. The beneficial structure of the Li hollow foam is further studied through density functional theory simulations, which confirms that the porous structure has better charge mobility and more uniform Li deposition.  相似文献   

11.
The coupling of thick and dense cathodes with anode-free lithium metal configuration is a promising path to enable the next generation of high energy density solid-state batteries. In this work, LiCoO2 (30 µm)/LiPON/Ti is considered as a model system to study the correlation between fundamental electrode properties and cell electrochemical performance, and a physical model is proposed to understand the governing phenomena. The first cycle loss is demonstrated to be constant and independent of both cathode thickness and anode configuration, and only ascribed to the diffusion coefficient's abrupt fall at high lithium contents. Subsequent cycles achieve close to 100% coulombic efficiency. The examination of the effect of cathode thickness demonstrate a nearly linear correlation with areal specific capacity for sub-100 µm LiCoO2 and 0.1 mA cm−2 current density. These findings bring new insights to better understand the energy density limiting factors and to suggest potential optimization approaches.  相似文献   

12.
Li metal is considered as an ideal anode for Li‐based batteries. Unfortunately, the growth of Li dendrites during cycling leads to an unstable interface, a low coulombic efficiency, and a limited cycling life. Here, a novel approach is proposed to protect the Li‐metal anode by using a uniform agarose film. This natural biopolymer film exhibits a high ionic conductivity, high elasticity, and chemical stability. These properties enable a fast Li‐ion transfer and feasiblity to accomodate the volume change of Li metal, resulting in a dendrite‐free anode and a stable interface. Morphology characterization shows that Li ions migrate through the agarose film and then deposit underneath it. A full cell with the cathode of LiFPO4 and an anode contaning the agarose film exhibits a capacity retention of 87.1% after 500 cycles, much better than that with Li foil anode (70.9%) and Li‐deposited Cu anode (5%). This study provides a promising strategy to eliminate dendrites and enhance the cycling ability of lithium‐metal batteries through coating a robust artificial film of natural biopolymer on lithium‐metal anode.  相似文献   

13.
The performance of pseudocapacitive electrodes at fast charging rates are typically limited by the slow kinetics of Faradaic reactions and sluggish ion diffusion in the bulk structure. This is particularly problematic for thick electrodes and electrodes highly loaded with active materials. Here, a surface-functionalized 3D-printed graphene aerogel (SF-3D GA) is presented that achieves not only a benchmark areal capacitance of 2195 mF cm−2 at a high current density of 100 mA cm−2 but also an ultrahigh intrinsic capacitance of 309.1 µF cm−2 even at a high mass loading of 12.8 mg cm−2. Importantly, the kinetic analysis reveals that the capacitance of SF-3D GA electrode is primarily (93.3%) contributed from fast kinetic processes. This is because the 3D-printed electrode has an open structure that ensures excellent coverage of functional groups on carbon surface and facilitates the ion accessibility of these surface functional groups even at high current densities and large mass loading/electrode thickness. An asymmetric device assembled with SF-3D GA as anode and 3D-printed GA decorated with MnO2 as cathode achieves a remarkable energy density of 0.65 mWh cm−2 at an ultrahigh power density of 164.5 mW cm−2, outperforming carbon-based supercapacitors operated at the same power density.  相似文献   

14.
Aluminum is regarded as a promising alternative for graphite anode in next‐generation lithium‐ion batteries, but its application is hindered by the simultaneous presence of aluminum oxide and the huge volume changes. Herein, hydrogenation‐induced self‐assembly of robust Al nanocrystals with high purity that are uniformly anchored on graphene is demonstrated. The strong molecular interaction between Al and graphene can not only thermodynamically facilitate the homogenous distribution of Al on graphene but also effectively alleviate the volume changes and preserve the structural integrity of the electrode. More importantly, density functional theory calculations reveal that the absence of oxidation can lower the energy barrier for Li diffusion inside the Al matrix to less than 1/6 of that in an Al matrix with only one monolayer coverage of oxygen. These unique structural features enable the aluminum/graphene nanosheets (Al@GNs) electrode to realize a high reversible capacity of 1219 mAh g?1 and an excellent cycling stability with capacity of 766 mAh g?1 after 1000 cycles at the 3 A g?1 rate. Furthermore, a full cell, comprising an Al@GNs anode and LiFePO4 cathode, exhibits remarkable capacity retention of 96.4% after 100 cycles at the 0.5 A g?1 rate.  相似文献   

15.
Aqueous rechargeable batteries show great application prospects in large-scale energy storage because of their reliable safety and low cost. However, a key challenge in developing this battery system lies in its low energy density. Herein, a high-energy manganese–metal hydride (Mn–MH) hybrid battery is reported in which a Mn-based cathode operated by the Mn2+/MnO2 deposition–dissolution reactions, a hydrogen-storage alloy anode that absorbs and desorbs hydrogen in an alkaline solution, and a proton-exchange membrane separator are employed. Given the benefit derived from the high solubility and high specific capacity of the Lewis acidic MnCl2 in the cathode and the low electrode potential of the MH anode, this aqueous Mn–MH hybrid battery exhibits impressive electrochemical properties with admirable discharge voltage plateaus up to 2.2 V, a competitive energy density of about 240 Wh kg−1 (based on the total mass of the 5.5 m MnCl2 solution and the hydrogen storage alloy electrode system), good cycling stability over 130 cycles, and a desirable rate capability. This work demonstrates a new strategy for achieving high-performance and low-cost aqueous rechargeable batteries.  相似文献   

16.
A novel uniform amorphous carbon‐coated SnO2 nanocrystal (NCs) for use in lithium‐ion batteries is formed by utilizing bovine serum albumin (BSA) as both the ligand and carbon source. The SnO2–carbon composite is then coated by a controlled thickness of polydopamine (PD) layer through in situ polymerization of dopamine. The PD‐coated SnO2–carbon composite is finally mixed with polyacrylic acid (PAA) which is used as binder to accomplish a whole anode system. A crosslink reaction is built between PAA and PD through formation of amide bonds to produce a robust network in the anode system. As a result, the designed electrode exhibits improved reversible capacity of 648 mAh/g at a current density of 100 mA/g after 100 cycles, and an enhanced rate performance of 875, 745, 639, and 523 mAh/g at current densities of 50, 100, 250, and 500 mA/g, respectively. FTIR spectra confirm the formation of crosslink reaction and the stability of the robust network during long‐term cycling. The great improvement of capacity and rate performance achieved in this anode system is attributed to two stable interfaces built between the active material (SnO2–carbon composite) and the buffer layer (PD) and between the buffer layer and the binder (PAA), which effectively diminish the volume change of SnO2 during charge/discharge process and provide a stable matrix for active materials.  相似文献   

17.
Nanomaterials with electrochemical activity are always suffering from aggregations, particularly during the high-temperature synthesis processes, which will lead to decreased energy-storage performance. Here, hierarchically structured lithium titanate/nitrogen-doped porous graphene fiber nanocomposites were synthesized by using confined growth of Li4Ti5O12 (LTO) nanoparticles in nitrogen-doped mesoporous graphene fibers (NPGF). NPGFs with uniform pore structure are used as templates for hosting LTO precursors, followed by high-temperature treatment at 800 °C under argon (Ar). LTO nanoparticles with size of several nanometers are successfully synthesized in the mesopores of NPGFs, forming nanostructured LTO/NPGF composite fibers. As an anode material for lithium-ion batteries, such nanocomposite architecture offers effective electron and ion transport, and robust structure. Such nanocomposites in the electrodes delivered a high reversible capacity (164 mAh·g–1 at 0.3 C), excellent rate capability (102 mAh·g–1 at 10 C), and long cycling stability.
  相似文献   

18.
The performance of the lithium-ion cell is heavily dependent on the ability of the host electrodes to accommodate and release Li+ ions from the local structure. While the choice of electrode materials may define parameters such as cell potential and capacity, the process of intercalation may be physically limited by the rate of solid-state Li+ diffusion. Increased diffusion rates in lithium-ion electrodes may be achieved through a reduction in the diffusion path, accomplished by a scaling of the respective electrode dimensions. In addition, some electrodes may undergo large volume changes associated with charging and discharging, the strain of which, may be better accommodated through nanostructuring. Failure of the host to accommodate such volume changes may lead to pulverisation of the local structure and a rapid loss of capacity. In this review article, we seek to highlight a number of significant gains in the development of nanostructured lithium-ion battery architectures (both anode and cathode), as drivers of potential next-generation electrochemical energy storage devices.  相似文献   

19.
Despite the recent attention for Li metal anode (LMA) with high theoretical specific capacity of ≈ 3860 mA h g?1, it suffers from not enough practical energy densities and safety concerns originating from the excessive metal load, which is essential to compensate for the loss of Li sources resulting from their poor coulombic efficiencies (CEs). Therefore, the development of high‐performance LMA is needed to realize anode‐minimized Li metal batteries (LMBs). In this study, high‐performance LMAs are produced by introducing a hierarchically nanoporous assembly (HNA) composed of functionalized onion‐like graphitic carbon building blocks, several nanometers in diameter, as a catalytic scaffold for Li‐metal storage. The HNA‐based electrodes lead to a high Li ion concentration in the nanoporous structure, showing a high CE of ≈ 99.1%, high rate capability of 12 mA cm?2, and a stable cycling behavior of more than 750 cycles. In addition, anode‐minimized LMBs are achieved using a HNA that has limited Li content ( ≈ 0.13 mg cm?2), corresponding to 6.5% of the cathode material (commercial NCM622 ( ≈ 2 mg cm?2)). The LMBs demonstrate a feasible electrochemical performance with high energy and power densities of ≈ 510 Wh kgelectrode?1 and ≈ 2760 W kgelectrode?1, respectively, for more than 100 cycles.  相似文献   

20.
The practical implementation of the lithium metal anode is hindered by obstacles such as Li dendrite growth, large volume changes, and poor lifespan. Here, copper nitride nanowires (Cu3N NWs) printed Li by a facile and low-cost roll-press method is reported, to operate in carbonate electrolytes for high-voltage cathode materials. Through one-step roll pressing, Cu3N NWs can be conformally printed onto the Li metal surface, and form a Li3N@Cu NWs layer on the Li metal. The Li3N@Cu NWs layer can assist homogeneous Li-ion flux with the 3D channel structure, as well as the high Li-ion conductivity of the Li3N. With those beneficial effects, the Li3N@Cu NWs layer can guide Li to deposit into a dense and planar structure without Li-dendrite growth. Li metal with Li3N@Cu NWs protection layer exhibits outstanding cycling performances even at a high current density of 5.0 mA cm−2 with low overpotentials in Li symmetric cells. Furthermore, the stable cyclability and improved rate capability can be realized in a full cell using LiCoO2 over 300 cycles. When decoupling the irreversible reactions of the cathode using Li4Ti5O12, stable cycling performance over 1000 cycles can be achieved at a practical current density of ≈2 mA cm−2.  相似文献   

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