Aluminum-metal batteries show great potential as next-generation energy storage due to their abundant resources and intrinsic safety.However,the crucial limitations of metallic Al anodes,such as dendrite and corrosion...Aluminum-metal batteries show great potential as next-generation energy storage due to their abundant resources and intrinsic safety.However,the crucial limitations of metallic Al anodes,such as dendrite and corrosion problems in conventional aluminum-metal batteries,remain challenging and elusive.Here,we report a novel electrodeposition strategy to prepare an optimized 3D Al anode on carbon cloth with an uniform deposition morphology,low local current density,and mitigatory volume change.The symmetrical cells with the 3D Al anode show superior stable cycling(>450 h)and low-voltage hysteresis(~170 mV)at 0.5 mA cm^(−2).High reversibility(~99.7%)is achieved for the Al plating/stripping.The graphite||Al‐4/CC full batteries show a long lifespan of 800 cycles with 54 mAh g^(−1) capacity at a high current density of 1000 mA g^(−1),benefiting from the high capacitive-controlled distribution.This study proposes a novel strategy to design 3D Al anodes for metallic-Al-based batteries by eliminating the problems of planar Al anodes and realizing the potential applications of aluminum-graphite batteries.展开更多
Aluminum(Al)exhibits excellent electrical conductivity,mechanical ductility,and good chemical compatibility with high-ionic-conductivity electrolytes.This makes it more suitable as an anode material for all-solid-stat...Aluminum(Al)exhibits excellent electrical conductivity,mechanical ductility,and good chemical compatibility with high-ionic-conductivity electrolytes.This makes it more suitable as an anode material for all-solid-state lithium batteries(ASSLBs)compared to the overly reactive metallic lithium anode and the mechanically weak silicon anode.This study finds that the pre-lithiated Al anode demonstrates outstanding interfacial stability with the Li_6PS_5Cl(LPSCl)electrolyte,maintaining stable cycling for over 1200 h under conditions of deep charge-discharge.This paper combines the pre-lithiated Al anode with a high-nickel cathode,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2),paired with the highly ionic conductive LPSCl electrolyte,to design an ASSLB with high energy density and stability.Using anode pre-lithiation techniques,along with dual-reinforcement technology between the electrolyte and the cathode active material,the ASSLB achieves stable cycling for 1000 cycles at a 0.2C rate,with a capacity retention rate of up to 82.2%.At a critical negative-to-positive ratio of 1.1,the battery's specific energy reaches up to 375 Wh kg^(-1),and it maintains over 85.9%of its capacity after 100 charge-discharge cycles.This work provides a new approach and an excellent solution for developing low-cost,high-stability all-solid-state batteries.展开更多
Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from...Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from several issues,such as the dendrite formation,during Al stripping-deposition cycling,which has been verified to account for the short circuit and limited cyclic performance.Herein,we use a facile and applicable method to in-situ reconstruct the Al anode surface with F-Al-O chemical bonds,which could preferentially induce the planar growth of Al along the interface plane,thus leading to the dendrite-free morphology evolution during the cycling.Benefiting from F-Al-O chemical bonds on the surface of Al anodes,long lifespan of symmetric cells can be realized even under 1 m A cm^(-2)and 1 m Ah cm^(-2).Coupling the F-Al anode with graphite-based cathodes,high-voltage dual-ion Al metal batteries can be achieved with long-term cycle stability up to 1,200 cycles(at 0.5 m A cm^(-2)),surpassing the counterparts using pristine Al metal anode.Furthermore,the effectiveness of this surficial modification strategy is also elucidated with the aid of theoretical calculation.This work provides novel insights on low-cost and facile strategies against the Al dendrite growth in aluminum batteries.展开更多
The effect of rolling processing on the microstructure,electrochemical property and anti-corrosion property of Al-Mg-Sn-Bi-Ga-In alloy anode in alkaline solution(80℃,Na2SnO3+5 mol/L NaOH)was analyzed by the chronopot...The effect of rolling processing on the microstructure,electrochemical property and anti-corrosion property of Al-Mg-Sn-Bi-Ga-In alloy anode in alkaline solution(80℃,Na2SnO3+5 mol/L NaOH)was analyzed by the chronopotentiometry (E-T curves),hydrogen collection tests and modern microstructure analysis.The results show that when the rolling temperature is 370℃,the electrochemical activity of Al anode decreases gradually with the increase of pass deformation in rolling,while the anti-corrosion property is improved in the beginning and then declined rapidly.When the pass deformation of rolling is 40%,the Al anode has good electrochemical activity as good as the anti-corrosion property and with the increase of rolling temperature,both electrochemical activity and anti-corrosion property of Al anode increase first and then decrease.When the rolling temperature is 420 ℃,the aluminum alloy anode has the most negative electrode potential of about-1.521 V(vs Hg/HgO)and the lowest hydrogen evolution rate of 0.171 6 mL/(min·cm2).The optimum comprehensive performance of Al alloy anode is obtained.展开更多
Anodized composite films containing Si C nanoparticles were synthesized on Ti6Al4 V alloy by anodic oxidation procedure in C4O6H4Na2 electrolyte. Scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) ...Anodized composite films containing Si C nanoparticles were synthesized on Ti6Al4 V alloy by anodic oxidation procedure in C4O6H4Na2 electrolyte. Scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and X-ray photoelectron spectroscopy(XPS) were employed to characterize the morphology and composition of the films fabricated in the electrolytes with and without addition of Si C nanoparticles. Results show that Si C particles can be successfully incorporated into the oxide film during the anodizing process and preferentially concentrate within internal cavities and micro-cracks. The ball-on-disk sliding tests indicate that Si C-containing oxide films register much lower wear rate than the oxide films without Si C under dry sliding condition. Si C particles are likely to melt and then are oxidized by frictional heat during sliding tests. Potentiodynamic polarization behavior reveals that the anodized alloy with Si C nanoparticles results in a reduction in passive current density to about 1.54×10-8 A/cm2, which is more than two times lower than that of the Ti O2 film(3.73×10-8 A/cm2). The synthesized composite film has good anti-wear and anti-corrosion properties and the growth mechanism of nanocomposite film is also discussed.展开更多
Ti6Al4V substrates were anodized in a 0.5 mol/L H_2SO_4 solution at applied voltages of 90-140 V.A hydroxyapatite-titanium oxide（HA-TiO2）coating was then deposited on the anodized Ti6Al4 V substrates via a hydrother...Ti6Al4V substrates were anodized in a 0.5 mol/L H_2SO_4 solution at applied voltages of 90-140 V.A hydroxyapatite-titanium oxide（HA-TiO2）coating was then deposited on the anodized Ti6Al4 V substrates via a hydrothermal-electrochemicalmethod at a constant current.The obtained films and coatings were characterized by X-ray diffraction,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and Fourier-transform infrared spectrometry.The microstructures of the porous films on the Ti6Al4 V substrates were studied to investigate the effect of the anodizing voltage on the phase and morphology of the HATiO_2 coating.The results indicated that both the phase composition and the morphology of the coatings were significantly influenced by changes in the anodizing voltage.HA-TiO_2 was directly precipitated onto the surface of the substrate when the applied voltage was between 110 and 140 V.The coatings had a gradient structure and the HA exhibited both needle-like and cotton-like structures.The amount of cotton-like HA structures decreased with an increase in voltage from 90 to 120 V,and then increased slightly when the voltage was higher than 120 V.The orientation index of the（002）plane of the coating was at a minimum when the Ti6Al4 V substrate was pretreated at 120 V.展开更多
Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a f...Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.展开更多
Aqueous rechargeable aluminium metal batteries(ARAMBs)have advantages of high energy density,cost efficiency and reasonable safety.However,parasitic reactions between the Al anode and electrolyte,sluggish dynamics and...Aqueous rechargeable aluminium metal batteries(ARAMBs)have advantages of high energy density,cost efficiency and reasonable safety.However,parasitic reactions between the Al anode and electrolyte,sluggish dynamics and low reversibility of the Al anode,and structural instability caused by the high charge density of Al3+ions lead to a short cycling life and inferior high-rate performance in ARAMBs.Herein,in this review,we summarize the research progress on ARAMBs by emphasizing the reported strategies to address the above-mentioned intractable issues.Initially,we discuss how to regulate the Al anode and interphase to accelerate the kinetics of Al stripping,which mainly includes strategies of ionic liquid analogue-derived solid electrolyte interphases(SEIs),artificial interfacial functional layer and aluminium alloy.Subsequently,the electrolyte modification approaches are highlighted including preparing highly concentrated singlesalt/bi-salt electrolytes and designing electrolyte additives to reduce the parasitic reactions of ARAMBs.Finally,we introduce the progress on fabricating cathodes,such as vanadium-based materials,manganeseoxide materials,molybdenum-based materials,Prussian blue analogues,carbon materials,and organic materials to accommodate Al3+ions.We propose that the further development of ARAMBs requires the cooperation of the above-mentioned strategies to improve their overall electrochemical performance and the development of new methods to illustrate the reaction mechanism of batteries.展开更多
基金This study was funded by the Science and Technology Development Fund,Macao SAR(File no.0191/2017/A3,0041/2019/A1,0046/2019/AFJ,0021/2019/AIR)the University of Macao(File no.MYRG2017-00216-FST and MYRG2018-00192-IAPME)+2 种基金the UEA funding,Science and Technology Program of Guangzhou(2019050001)the National Key Research and Development Program of China(2019YFE0198000)Fuming Chen acknowledges the Pearl River Talent Program(2019QN01L951).
文摘Aluminum-metal batteries show great potential as next-generation energy storage due to their abundant resources and intrinsic safety.However,the crucial limitations of metallic Al anodes,such as dendrite and corrosion problems in conventional aluminum-metal batteries,remain challenging and elusive.Here,we report a novel electrodeposition strategy to prepare an optimized 3D Al anode on carbon cloth with an uniform deposition morphology,low local current density,and mitigatory volume change.The symmetrical cells with the 3D Al anode show superior stable cycling(>450 h)and low-voltage hysteresis(~170 mV)at 0.5 mA cm^(−2).High reversibility(~99.7%)is achieved for the Al plating/stripping.The graphite||Al‐4/CC full batteries show a long lifespan of 800 cycles with 54 mAh g^(−1) capacity at a high current density of 1000 mA g^(−1),benefiting from the high capacitive-controlled distribution.This study proposes a novel strategy to design 3D Al anodes for metallic-Al-based batteries by eliminating the problems of planar Al anodes and realizing the potential applications of aluminum-graphite batteries.
基金the technical support for Nano-X from Suzhou Institute of Nano-Tech and NanoBionics,Chinese Academy of Sciences(SINANO)supported by the National Key R&D Program of China(2021YFB3800300)+2 种基金the National Natural Science Foundation of China(22179059,22239002,92372201)the science and technology innovation fund for emission peak and carbon neutrality of Jiangsu province(BK20231512,BK20220034)the Key R&D project funded by department of science and technology of Jiangsu Province(BE2020003)。
文摘Aluminum(Al)exhibits excellent electrical conductivity,mechanical ductility,and good chemical compatibility with high-ionic-conductivity electrolytes.This makes it more suitable as an anode material for all-solid-state lithium batteries(ASSLBs)compared to the overly reactive metallic lithium anode and the mechanically weak silicon anode.This study finds that the pre-lithiated Al anode demonstrates outstanding interfacial stability with the Li_6PS_5Cl(LPSCl)electrolyte,maintaining stable cycling for over 1200 h under conditions of deep charge-discharge.This paper combines the pre-lithiated Al anode with a high-nickel cathode,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2),paired with the highly ionic conductive LPSCl electrolyte,to design an ASSLB with high energy density and stability.Using anode pre-lithiation techniques,along with dual-reinforcement technology between the electrolyte and the cathode active material,the ASSLB achieves stable cycling for 1000 cycles at a 0.2C rate,with a capacity retention rate of up to 82.2%.At a critical negative-to-positive ratio of 1.1,the battery's specific energy reaches up to 375 Wh kg^(-1),and it maintains over 85.9%of its capacity after 100 charge-discharge cycles.This work provides a new approach and an excellent solution for developing low-cost,high-stability all-solid-state batteries.
基金supported by the National Natural Science Foundation of China(22075028)the Beijing Institute of Technology Research Fund Program for Young Scholars(XSQD202108005)。
文摘Al metal possesses ultrahigh theoretical volumetric capacity of 8,040 m Ah cm^(-3),and gravimetric capacity of 2,980 m Ah g^(-1),and thus is highly attractive for electrochemical energy storage.However,it suffers from several issues,such as the dendrite formation,during Al stripping-deposition cycling,which has been verified to account for the short circuit and limited cyclic performance.Herein,we use a facile and applicable method to in-situ reconstruct the Al anode surface with F-Al-O chemical bonds,which could preferentially induce the planar growth of Al along the interface plane,thus leading to the dendrite-free morphology evolution during the cycling.Benefiting from F-Al-O chemical bonds on the surface of Al anodes,long lifespan of symmetric cells can be realized even under 1 m A cm^(-2)and 1 m Ah cm^(-2).Coupling the F-Al anode with graphite-based cathodes,high-voltage dual-ion Al metal batteries can be achieved with long-term cycle stability up to 1,200 cycles(at 0.5 m A cm^(-2)),surpassing the counterparts using pristine Al metal anode.Furthermore,the effectiveness of this surficial modification strategy is also elucidated with the aid of theoretical calculation.This work provides novel insights on low-cost and facile strategies against the Al dendrite growth in aluminum batteries.
基金Project(50721003) supported by the Creative Research Group of National Natural Science Foundation of China
文摘The effect of rolling processing on the microstructure,electrochemical property and anti-corrosion property of Al-Mg-Sn-Bi-Ga-In alloy anode in alkaline solution(80℃,Na2SnO3+5 mol/L NaOH)was analyzed by the chronopotentiometry (E-T curves),hydrogen collection tests and modern microstructure analysis.The results show that when the rolling temperature is 370℃,the electrochemical activity of Al anode decreases gradually with the increase of pass deformation in rolling,while the anti-corrosion property is improved in the beginning and then declined rapidly.When the pass deformation of rolling is 40%,the Al anode has good electrochemical activity as good as the anti-corrosion property and with the increase of rolling temperature,both electrochemical activity and anti-corrosion property of Al anode increase first and then decrease.When the rolling temperature is 420 ℃,the aluminum alloy anode has the most negative electrode potential of about-1.521 V(vs Hg/HgO)and the lowest hydrogen evolution rate of 0.171 6 mL/(min·cm2).The optimum comprehensive performance of Al alloy anode is obtained.
基金Project(51271012)supported by the National Natural Science Foundation of China
文摘Anodized composite films containing Si C nanoparticles were synthesized on Ti6Al4 V alloy by anodic oxidation procedure in C4O6H4Na2 electrolyte. Scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and X-ray photoelectron spectroscopy(XPS) were employed to characterize the morphology and composition of the films fabricated in the electrolytes with and without addition of Si C nanoparticles. Results show that Si C particles can be successfully incorporated into the oxide film during the anodizing process and preferentially concentrate within internal cavities and micro-cracks. The ball-on-disk sliding tests indicate that Si C-containing oxide films register much lower wear rate than the oxide films without Si C under dry sliding condition. Si C particles are likely to melt and then are oxidized by frictional heat during sliding tests. Potentiodynamic polarization behavior reveals that the anodized alloy with Si C nanoparticles results in a reduction in passive current density to about 1.54×10-8 A/cm2, which is more than two times lower than that of the Ti O2 film(3.73×10-8 A/cm2). The synthesized composite film has good anti-wear and anti-corrosion properties and the growth mechanism of nanocomposite film is also discussed.
基金Funded in part by the Key Laboratory of Inorginic Coating MaterialsChinese Academy of Sciences(No.KLICM-2014-11)the Shanghai Municipal Natural Science Foundation Sponsored by Shanghai Municipal Science and Technology Commissions(No.15ZR1428300)
文摘Ti6Al4V substrates were anodized in a 0.5 mol/L H_2SO_4 solution at applied voltages of 90-140 V.A hydroxyapatite-titanium oxide（HA-TiO2）coating was then deposited on the anodized Ti6Al4 V substrates via a hydrothermal-electrochemicalmethod at a constant current.The obtained films and coatings were characterized by X-ray diffraction,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and Fourier-transform infrared spectrometry.The microstructures of the porous films on the Ti6Al4 V substrates were studied to investigate the effect of the anodizing voltage on the phase and morphology of the HATiO_2 coating.The results indicated that both the phase composition and the morphology of the coatings were significantly influenced by changes in the anodizing voltage.HA-TiO_2 was directly precipitated onto the surface of the substrate when the applied voltage was between 110 and 140 V.The coatings had a gradient structure and the HA exhibited both needle-like and cotton-like structures.The amount of cotton-like HA structures decreased with an increase in voltage from 90 to 120 V,and then increased slightly when the voltage was higher than 120 V.The orientation index of the（002）plane of the coating was at a minimum when the Ti6Al4 V substrate was pretreated at 120 V.
基金National Natural Science Foundation of China!No. 59774031
文摘Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.
基金supported by the National Natural Science Foundation of China(no.52201259 and 22372083)the National Key R&D Program of China(2021YFB2500300)+1 种基金the Natural Science Foundation of Tianjin(no.22JCZDJC00380)the Young Elite Scientist Sponsorship Program by CAST.
文摘Aqueous rechargeable aluminium metal batteries(ARAMBs)have advantages of high energy density,cost efficiency and reasonable safety.However,parasitic reactions between the Al anode and electrolyte,sluggish dynamics and low reversibility of the Al anode,and structural instability caused by the high charge density of Al3+ions lead to a short cycling life and inferior high-rate performance in ARAMBs.Herein,in this review,we summarize the research progress on ARAMBs by emphasizing the reported strategies to address the above-mentioned intractable issues.Initially,we discuss how to regulate the Al anode and interphase to accelerate the kinetics of Al stripping,which mainly includes strategies of ionic liquid analogue-derived solid electrolyte interphases(SEIs),artificial interfacial functional layer and aluminium alloy.Subsequently,the electrolyte modification approaches are highlighted including preparing highly concentrated singlesalt/bi-salt electrolytes and designing electrolyte additives to reduce the parasitic reactions of ARAMBs.Finally,we introduce the progress on fabricating cathodes,such as vanadium-based materials,manganeseoxide materials,molybdenum-based materials,Prussian blue analogues,carbon materials,and organic materials to accommodate Al3+ions.We propose that the further development of ARAMBs requires the cooperation of the above-mentioned strategies to improve their overall electrochemical performance and the development of new methods to illustrate the reaction mechanism of batteries.
