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1.
The lithium metal anode is one of the most promising anodes for next‐generation high‐energy‐density batteries. However, the severe growth of Li dendrites and large volume expansion leads to rapid capacity decay and shortened lifetime, especially in high current density and high capacity. Herein, a soft 3D Au nanoparticles@graphene hybrid aerogel (Au? GA) as a lithiophilic host for lithium metal anode is proposed. The large surface area and interconnected conductive pathways of the Au? GA significantly decrease the local current density of the electrode, enabling uniform Li deposition. Furthermore, the 3D porous structure effectively accommodates the large volume expansion during Li plating/stripping, and the LixAu alloy serves as a solid solution buffer layer to completely eliminate the Li nucleation over‐potential. Symmetric cells can stably cycle at 8 mA cm?2 for 8 mAh cm?2 and exhibit ultra‐long cycling: 1800 h at 2 mA cm?2 for 2 mAh cm?2, and 1200 h at 4 mA cm?2 for 4 mAh cm?2, with low over‐potential. Full cells assemble with a Cu@Au? GA? Li anode and LiFePO4 cathode, can sustain a high rate of 8 C, and retain a high capacity of 59.6 mAh g?1 after 1100 cycles at 2 C.  相似文献   

2.
The practical application of lithium metal anode has been hindered by safety and cyclability issues due to the uncontrollable dendrite growth, especially during fast cycling and deep plating/stripping process. Here, a composite Li metal anode supported by periodic, perpendicular, and lithiophilic TiO2/poly(vinyl pyrrolidone) (PVP) nanofibers via a facial rolling process is reported. TiO2/PVP nanofibers with good Li affinity provide low-tortuosity and directly inward Li+ transport paths to facilitate Li nucleation and deposition under high areal capacities and current densities. The micrometer-scale interspaces between TiO2/PVP walls offer enough space to circumvent the huge volume variation and avoid structure collapsing during the repeated deep Li plating/stripping. The unique structure enables stable cycling under ultrahigh currents (12 mA cm−2), and ultra-deep plating/stripping up to 60 mAh cm−2 with a long cycle life in commercial carbonate electrolytes. The gassing behavior in operating pouch cells is observed using ultrasonic transmission mapping. When paired with LiFePO4 (5 mAh cm−2), sulfur (3 mAh cm−2), and high-voltage LiNi0.8Co0.1Mn0.1O2 cathodes, the composite Li anodes deliver remarkably improved rate performance and cycling stability, demonstrating that it could be a promising strategy for balancing high-energy density and high-power density in Li metal batteries.  相似文献   

3.
Nonuniform local electric field and few nucleation sites on the reactive interface tend to cause detrimental lithium (Li) dendrites, which incur severe safety hazards and hamper the practical application of Li metal anodes in batteries. Herein, a carbon nanofiber (CNF) mat decorated with ultrafine titanium nitride (TiN) nanoparticles (CNF‐TiN) as both current collector and host material is reported for Li metal anodes. Uniform Li deposition is achieved by a synergetic effect of lithiophilic TiN and 3D CNF configuration with a highly conductive network. Theoretical calculations reveal that Li prefers to be adsorbed onto the TiN sheath with a low diffusion energy barrier, leading to controllable nucleation sites and dendrite‐free Li deposits. Moreover, the pseudocapacitive behavior of TiN identified through kinetics analysis is favorable for ultrafast Li+ storage and the charge transfer process, especially under a high plating/stripping rate. The CNF‐TiN‐modified Li anodes deliver lower nucleation overpotential for Li plating and superior electrochemical performance under a large current density (200 cycles at 3 mA cm?2) and high capacity (100 cycles with 6 mAh cm?2), as well as a long‐running lifespan (>600 h). The CNF‐TiN‐based full cells using lithium iron phosphate and sulfur cathodes exhibit excellent cycling stability.  相似文献   

4.
Considerable endeavors are developed to suppress lithium (Li) dendrites and improve the cycling stability of Li metal batteries in order to promote their commercial application. Herein, continuous zinc (Zn) nanoparticles-assembled film with homogenous nanopores is proposed as a modified layer for separator via a scalable method. The in situ formed LiZn alloy film during initial Li plating can serve as a Li+ ion rectification and lithiophilic layer to regulate the nucleation and reverse deposition of Li. When applied in Li|LiFePO4 full cells with traditional carbonate-based electrolyte, the modified separator enables outstanding cycling stability of up to 350 cycles without capacity loss at a large rate of 5 C (3.4 mA cm−2) and a remarkable reversible capacity of 144 mAh g−1 after 120 cycles at a commercial mass loading as high as 19.72 mg cm−2. The excellent electrochemical performances are ascribed to the dendrite-free reverse Li deposition induced by modified layer by means of its lithiophilic property for regulating homogeneous Li nucleation on the separator as well as its well-distributed nanopores for homogenizing Li+ ion flux and enhancing electrolyte wetting.  相似文献   

5.
Lithium metal anodes are widely regarded as the ideal candidate for the next generation of high-energy-density lithium batteries. Here, a 3D host made of lithiophilic Mo2C clusters-embedded carbon nanofibers (Mo2C@CNF) is developed. The uniformly dispersed clusters and large specific surface areas of Mo2C@CNF provide numerous nucleation sites for lithium deposition. Mo2C clusters exhibit ultralow nucleation overpotential compared to MoO2, which is also supported by density functional theory calculations. Furthermore, the transition metal element serves as a catalyst for the formation of a stable and robust solid electrolyte interphase layer containing LiF on Mo2C@CNF, effectively mitigating the occurrence of dead lithium and enhancing the Coulombic efficiency during prolonged operation. As a result, the Mo2C@CNF composite delivers superior electrochemical performance (>1600 h) at 1 mA cm−2 and lower nucleation overpotential (13 mV) for lithium plating. The Li/Mo2C@CNF anode coupled with the commercial LiFePO4 cathode exhibits excellent cycling stability (300 cycles at 1 C) and high rate capability at low N/P ratios.  相似文献   

6.
Li metal is one of the most promising anode materials for high energy density batteries. However, uncontrollable Li dendrite growth and infinite volume change during the charge/discharge process lead to safety issues and capacity decay. Herein, a carbonized metal–organic framework (MOF) nanorod arrays modified carbon cloth (NRA-CC) is developed for uniform Li plating/stripping. The carbonized MOF NRAs effectively convert the CC from lithiophobic to lithiophilic, decreasing the polarization and ensuring homogenous Li nucleation. The 3D interconnected hierarchal CC provides adequate Li nucleation sites for reducing the local current density to avoid Li dendrite growth, and broadens internal space for buffering the volume change during Li plating/stripping. These characteristics afford a stable cycling of the NRA-CC electrode with ultrahigh Coulombic efficiencies of 96.7% after 1000 h cycling at 2 mA cm−2 and a prolonged lifespan of 200 h in the symmetrical cell under ultrahigh areal capacity (12 mAh cm−2) and current (12 mA cm−2). The solid-state batteries assembled with the composite Li anode, high-voltage cathode (LiNi0.5Co0.2Mn0.3O2), and composite solid-state electrolyte also deliver excellent cyclic and rate performance at 25 °C. This work sheds fresh insights on the design principles of a dendrite-free Li metal anode for safe solid-state Li metal batteries.  相似文献   

7.
Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO2 and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO2-Li3N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm−2, which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm−2 can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO2-Li3N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li3N guides Li deposition along the LiTiO2-Li3N-C skeleton to avoid dendrite growth.  相似文献   

8.
Silicon (Si) and lithium metal are the most favorable anodes for high‐energy‐density lithium‐based batteries. However, large volume expansion and low electrical conductivity restrict commercialization of Si anodes, while dendrite formation prohibits the applications of lithium‐metal anodes. Here, uniform nanoporous Si@carbon (NPSi@C) from commercial alloy and CO2 is fabricated and tested as a stable anode for lithium‐ion batteries (LIBs). The porosity of Si as well as graphitization degree and thickness of the carbon layer can be controlled by adjusting reaction conditions. The rationally designed porosity and carbon layer of NPSi@C can improve electronic conductivity and buffer volume change of Si without destroying the carbon layer or disrupting the solid electrolyte interface layer. The optimized NPSi@C anode shows a stable cyclability with 0.00685% capacity decay per cycle at 5 A g?1 over 2000 cycles for LIBs. The energy storage mechanism is explored by quantitative kinetics analysis and proven to be a capacitance‐battery dual model. Moreover, a novel 2D/3D structure is designed by combining MXene and NPSi@C. As lithiophilic nucleation seeds, NPSi@C can induce uniform Li deposition with buffered volume expansion, which is proven by exploring Li‐metal deposition morphology on Cu foil and MXene@NPSi@C. The practical potential application of NPSi@C and MXene@NPSi@C is evaluated by full cell tests with a Li(Ni0.8Co0.1Mn0.1)O2 cathode.  相似文献   

9.
Lithium (Li) metal anodes have been proposed as a promising candidate for high-energy-density electrode materials in secondary batteries. However, the dendrite growth and unstable electrode–electrolyte interfaces during Li plating/stripping are fatal to their practical applications. Herein, the construction of 3D porous Au/Cu nanoscaffold prepared via a convenient template-sacrificed hot fusion construction method and a nanoseed modification process as an effective Li metal hosting material are proposed. The Au/Cu nanoscaffold can spatially guide uniform deposition of Li metal free from the growth of Li dendrites due to the homogenous Li+ ion flux and negligible nucleation overpotential. Moreover, the Cu skeleton can relieve volume change and stabilize local current density during cycling processes. Benefiting from these advantages, the symmetric cells based on self-supported Li-filled Au/Cu (Li-Au/Cu) nanoscaffold electrodes present highly stable Li plating/stripping for more than 1000 h with a low voltage hysteresis less than 90 mV and a long lifespan over 1300 h at 1.0 mA cm–2 in carbonate-based electrolytes. Impressively, the Li-Au/Cu nanoscaffold||LiFePO4 full cells also exhibit exceptional cycling stability and rate performance. This work provides a promising strategy to construct dendrite-free lithium metal anodes toward high-performance lithium metal batteries.  相似文献   

10.
Lithium metal anodes hold great potential for next-generation high-energy batteries. However, the low Coulombic efficiency (CE) and dendritic growth during lithium metal plating/stripping cause short cycle life and deter its practical application. Herein, nitrogen, oxygen-codoped vertical carbon nanosheet arrays are constructed on Cu foil (NOCA@Cu) as the efficient host to improve CE and suppress Li dendrites through polymer interfacial self-assembly and morphology-preserved pyrolysis. Benefitting from numerous vertical porous channels with abundant lithiophilic heteroatom dopants, 3D structured NOCA@Cu host can guide Li nucleation and growth in a controlled manner, leading to dendrite-free Li deposition with high CE and long life cycles in both carbonate electrolyte and ether electrolyte, surpassing horizontal carbon-coated Cu and pure Cu hosts. Finite element simulation further reveals the structural function of vertical carbon arrays as not only directing Li plating in the nanoarray-constructed confined space but also homogenizing the distribution of ion concentration and electrical field throughout the 3D electrode. To demonstrate the practical application of lithiated NOCA@Cu anode, it is coupled with a commercial LiFePO4 cathode, delivering high capacity and long-cycle stability with nearly 100% CE. The cost-effective, scalable, and efficient features render NOCA@Cu a promising Li host toward practical lithium metal batteries.  相似文献   

11.
All-solid-state Li batteries (ASSLBs) with solid-polymer electrolytes are considered promising battery systems to achieve improved safety and high energy density. However, Li dendrite formation at the Li anode under high charging current density/capacity has limited their development. To tackle the issue, Li-metal alloying has been proposed as an alternative strategy to suppress Li dendrite growth in ASSLBs. One drawback of alloying is the relatively lower operating cell voltages, which will inevitably lower energy density compared to cells with pure Li anode. Herein, a Li-rich Li13In3 alloy electrode (LiRLIA) is proposed, where the Li13In3 alloy scaffold guides Li nucleation and hinders Li dendrite formation. Meanwhile, the free Li can recover Li's potential and facilitate fast charge transfer kinetics to realize high-energy-density ASSLBs. Benefitting from the stronger adsorption energy and lower diffusion energy barrier of Li on a Li13In3 substrate, Li prefers to deposit in the 3D Li13In3 scaffold selectively. Therefore, the Li–Li symmetric cell constructed with LiRLIA can operate at a high current density/capacity of 5 mA cm−2/5 mAh cm−2 for almost 1000 h.  相似文献   

12.
Rechargeable Li-ion batteries (LIBs) are ubiquitous in present society and play an important role in consumer electronics and electric vehicles. Increasing LIBs’ energy density is therefore becoming a crucial research challenge with great implications. Li metal is a high-specific-capacity anode, which suffers from uneven Li deposition, “dead” Li formation, dendrite growth, and the resulting severe capacity fading. Here, a strategy to enable a tremendous improvement for LiCoO2-based Li metal batteries (Li||LCO) is described and experimentally demonstrated. By simply adjusting the charge cut-off voltage from 4.1 to 4.6 V, a high-voltage stimulation effect (HvSE) is demonstrated, which offers a uniform, dense, and crack-free Li deposition. As a result, the Li||LCO cell delivers a high energy density (ED) of 891 Wh kg-LCO−1 and a high capacity of 217 mAh g−1 can be maintained for more than 69 cycles. In contrast, the Li||LCO cell with the lower charge cut-off voltage of 4.1 V only delivers a low ED (458 Wh kg-LCO−1), specific capacity (117 mAh g−1), and “capacity diving” occurs after only 35 cycles. This HvSE is also applied to run pouch cells, which generate greater than 20% capacity and cycling performance improvement with the higher charge cut-off voltage.  相似文献   

13.
The urgent demand for high energy and safety batteries has generated the rapid development of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) type solid-state lithium metal batteries. However, severe dendritic lithium growth, which is caused by poor interfacial contact of the Li/LLZTO interface and loss of electrical contact during cycles due to low intrinsic Li+ diffusion coefficient of lithium, greatly hampers its practical application. Here, from the point of view of reducing surface tension and improving ion diffusion of lithium, a composite lithium anode (CLA) with high wettability and ion diffusion coefficient is prepared by adding GaP into molten lithium, thus strengthening the CLA/LLZTO interface even in cycling. As envisioned, compared to pure lithium, CLA presents lower surface tension, larger adhesion work, and higher ion diffusion coefficient, ensuring close contact of the CLA/LLZTO interface. Therefore, the assembled symmetric cells exhibit a low area specific resistance of 4.5 Ω cm2, a large critical current density of 2.5 mA cm−2, and ultra-long lifespan of 5700 h at 0.3 mA cm−2 at 25 °C. Meanwhile, full cells coupled with LiFePO4 cathode show a high-capacity retention of 97.32% after 490 cycles at 1C. This work provides a new solution to the interfacial challenges of solid-state lithium-metal batteries.  相似文献   

14.
Lithium metal (LM) is a promising anode material for next generation lithium ion based electrochemical energy storage devices. Critical issues of unstable solid electrolyte interphases (SEIs) and dendrite growth however still impede its practical applications. Herein, a composite gel polymer electrolyte (GPE), formed through in situ polymerization of pentaerythritol tetraacrylate with fumed silica fillers, is developed to achieve high performance lithium metal batteries (LMBs). As evidenced theoretically and experimentally, the presence of SiO2 not only accelerates Li+ transport but also regulates Li+ solvation sheath structures, thus facilitating fast kinetics and formation of stable LiF-rich interphase and achieving uniform Li depositions to suppress Li dendrite growth. The composite GPE-based Li||Cu half-cells and Li||Li symmetrical cells display high Coulombic efficiency (CE) of 90.3% after 450 cycles and maintain stability over 960 h at 3 mA cm−2 and 3 mAh cm−2, respectively. In addition, Li||LiFePO4 full-cells with a LM anode of limited Li supply of 4 mAh cm−2 achieve capacity retention of 68.5% after 700 cycles at 0.5 C (1 C = 170 mA g−1). Especially, when further applied in anode-free LMBs, the carbon cloth||LiFePO4 full-cell exhibits excellent cycling stability with an average CE of 99.94% and capacity retention of 90.3% at the 160th cycle at 0.5 C.  相似文献   

15.
Lithium (Li) metal battery is considered the most promising next-generation battery due to its low potential and high theoretical capacity. However, Li dendrite growth causes serious safety problems. Herein, the 15-Crown-5 (15-C-5) is reported as an electrolyte additive based on solvation shell regulation. The strong complex effect between Li+ ion and 15-C-5 can reduce the concentration of Li ions on the electrode surface, thus changing the nucleation, and repressing the growth of Li dendrites in the plating process. Significantly, the strong coordination of Li+/15-C-5 would be able to make them aggregate around the Li crystal surface, which could form a protective layer and favor the formation of a smooth and dense solid electrolyte interphase with high toughness and Li+ ion conductivity. Therefore, the electrolyte system with 2.0 wt% 15-C-5 achieves excellent electrochemical performance with 170 cycles at 1.0 mA cm−2 with capacity of 0.5 mA h cm−2 in symmetric Li|Li cells. The obviously enhanced cycle and rate performance are also achieved in Li|LiNi0.6Co0.2Mn0.2O2 (NCM622) full cells. The 15-C-5 demonstrates to be a promising additive for the electrolytes toward safe and efficient Li metal batteries.  相似文献   

16.
Lithium (Li) metal anodes exhibit intriguing advantages for application in high-energy-density batteries. However, the short cycle life and security issues of these anodes induced by the dendrite growth and huge volumetric change of Li severely limit their practical application. Herein, a heuristic method to fabricate a self–supported seaweed-like Li metal anode directly to improve the cycle life of Li metal batteries, is reported. The unique seaweed-like morphology of the Li anode facilitates the dispersion of the local current density, impeding the uneven growth of Li dendrites, and remits the volume expansion of the anode, leading to excellent cycle performance. The as-prepared Li metal anode exhibits excellent plating–stripping stability over 600 cycles at high current density of 2 mA cm−2 and delivers excellent stability even with the Li4Ti5O12 cathode in the full cell. This study provides a facile strategy to prepare stable and dendrite-free Li anodes by controlling the morphology of Li metal. Thus, this study can further inspire new research ideas for preparing stable Li metal anodes.  相似文献   

17.
Constructing artificial solid‐electrolyte interphase (SEI) on the surface of Li metal is an effective approach to improve ionic conductivity of surface SEI and buffer Li dendrite growth of Li metal anode. However, constructing of homogenous ideal artificial SEI is still a great challenge. Here, a mixed lithium‐ion conductive Li2S/Li2Se (denoted as LSSe) protection layer, fabricated by a facile and inexpensive gas–solid reaction, is employed to construct stable surface SEI with high ionic conductivity. The Li2S/Li2Se‐protected Li metal (denoted as LSSe@Li) exhibits a stable dendrite‐free cycling behavior over 900 h with a high lithium stripping/plating capacity of 3 mAh cm?2 at 1.5 mA cm?2 in the symmetrical cell. Compared to bare Li anode, full batteries paired with LiFePO4, sulfur/carbon, and LiNi0.6Co0.2Mn0.2O2 cathodes all present better battery cycling and rate performance when LSSe@Li anode is used. Moreover, Li2Se exhibits a lower lithium‐ion migration energy barrier in comparison with Li2S which is proved by density functional theory calculation.  相似文献   

18.
Lithium metal is an exciting anode candidate with extra high theoretical specific capacity for new high‐energy rechargeable batteries. However, uncontrolled Li deposition and an unsteady solid electrolyte interface seriously obstruct the commercial application of Li anodes in Li metal batteries. Herein, 3D carbon cloth (CC) supporting N‐doped carbon (CN) nanosheet arrays embedded with tiny Co nanoparticles (CC@CN‐Co) are employed as a lithiophilic framework to regulate homogenous Li nucleation/growth behavior in a working Li metal anode. The emergence of Li dendrites is supposed to be inhibited by the conductive 3D scaffold that reduces local current density. The uniform nucleation of Li can be guided by N‐containing functional groups as they have a strong interaction with Li atoms, and the tiny Co nanoparticles can provide active sites to guide Li deposition. As a result, the current CC@CN‐Co host exhibits Li dendrite–free features and stable cycling performance with a low overpotential (20 mV) throughout 800 h cycles. When paired with the typical LiFePO4 (LFP) cathode, the assembled CC@CN‐Co@Li//LFP@C full cell exhibits outstanding rate capability and improved cycling performance.  相似文献   

19.
The applications of lithium metal anode are limited by uncontrollable lithium dendrite growth and infinite volume changes during cycling. These fundamental issues are exacerbated at high cycling current densities and capacities. Herein, a mechanically stable and resilient lithium metal host is fabricated by covalently cross-linking a highly-conductive and lithiophilic MXene/silver nanowire scaffold through a silylation reaction between MXene nanosheets and polysiloxane. Compared with the control sample (an MXene scaffold assembled by weak van der Waals forces), the covalently cross-linked MXene scaffold displays excellent mechanical strength and resilience, which is conducive to buffer the large internal stress fluctuations generated during rapid and deep lithium plating-stripping and guaranteed that the integrated framework structure is maintained during long-term charging-discharging cycles. When used in a symmetric cell, the lithium composite anode based on the covalently cross-linked MXene host affords an unprecedented cyclic lithium plating-stripping stability of a record-high 3000 h lifespan at an ultrahigh current density (20 mA cm−2) and areal capacity (10 mAh cm−2). When this composite anode is coupled with a LiNi0.5Co0.2Mn0.3O2 cathode, the full cell delivers an ultrahigh rate of 10 C for up to 1000 cycles, with an average capacity decay of 0.043% per cycle and a stable Coulombic efficiency of 98.7%.  相似文献   

20.
Germanium is considered as a promising anode material because of its comparable lithium and sodium storage capability, but it usually exhibits poor cycling stability due to the large volume variation during lithium or sodium uptake and release processes. In this paper, germanium@graphene nanofibers are first obtained through electrospinning followed by calcination. Then atomic layer deposition is used to fabricate germanium@graphene@TiO2 core–shell nanofibers (Ge@G@TiO2 NFs) as anode materials for lithium and sodium ion batteries (LIBs and SIBs). Graphene and TiO2 can double protect the germanium nanofibers in charge and discharge processes. The Ge@G@TiO2 NFs composite as an anode material is versatile and exhibits enhanced electrochemical performance for LIBs and SIBs. The capacity of the Ge@G@TiO2 NFs composite can be maintained at 1050 mA h g?1 (100th cycle) and 182 mA h g?1 (250th cycle) for LIBs and SIBs, respectively, at a current density of 100 mA g?1, showing high capacity and good cycling stability (much better than that of Ge nanofibers or Ge@G nanofibers).  相似文献   

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