Developing of high-performance and low-cost electrocatalysts is of great significance to reduce the overpotential and accelerated the reaction rate of oxygen evolution in water splitting and related energy conversion ...Developing of high-performance and low-cost electrocatalysts is of great significance to reduce the overpotential and accelerated the reaction rate of oxygen evolution in water splitting and related energy conversion applications.Herein,Fe,O-dual doped Ni2P(Fe,O-Ni2P)nanoarray is successfully synthesized on carbon cloth demonstrating enhanced electrocatalytic activity and stability for oxygen evolution reaction(OER)under alkaline media.The as-synthesized Fe,O-Ni2P nanoarray exhibits obviously improved OER performance with a low overpotential of 210 mV at 10 mA cm^-2 current density and a Tafel slope of48 mV dec^-1,as well as long-term durability.The strong coupling interaction induced changes in electronic structure lead to relatively higher oxidation state and stronger oxidation ability of the Fe,O-Ni2P nanoarray,together with the high electrochemical surface area and good conductivity contribute to the superior OER performance.This work highlights the anion-cation dual doping strategy may be an effective method for fabrication of catalysts relating to energy conversion applications.展开更多
Electrocatalytic nitrogen reduction reaction (e NRR) at the ambient conditions is attractive for ammonia(NH_(3)) synthesis due to its energy-efficient and eco-friendly features. However, the extremely strong N≡N trip...Electrocatalytic nitrogen reduction reaction (e NRR) at the ambient conditions is attractive for ammonia(NH_(3)) synthesis due to its energy-efficient and eco-friendly features. However, the extremely strong N≡N triple-bonds in nitrogen molecules and the competitive hydrogen evolution reaction lead to the unsatisfactory NH_(3) yield and the Faradaic efficiency (FE) of e NRR, making the development of high-performance catalysts with adequate active sites and high selectivity essential for further development of e NRR.Addressing this, we herein report a Bi and K dual-doped titanium oxide (BTO@KTO) material, which is prepared by a cation exchange reaction between K_(2)Ti_(4)O_(5) and molten BiCl_(2), for high-performance e NRR catalysts. Benefiting from the controllable molten-salt cation exchange process, a highly active surface containing Bi/K sites and rich oxygen vacancies has been obtained on titanium oxide. Under the synergy of these two merits, an efficient e NRR catalysis, with the NH_(3) yield rate of 32.02 μg h^(-1)mg_(cat)^(-1) and the FE of 12.71%, has been achieved, much superior to that of pristine K_(2)Ti_(4)O_(9). This work thus offers a highperformance electrocatalyst for e NRR, and more importantly, a versatile cation-exchange strategy for efficiently manipulating materials’ functionalities.展开更多
The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herei...The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.展开更多
Zn-N_(2)batteries,which are comprised of nitrogen reduction reaction(NRR)and oxygen evolution reaction(OER),represent an emerging technology for efficient ammonia production and simultaneous power generation.Neverthel...Zn-N_(2)batteries,which are comprised of nitrogen reduction reaction(NRR)and oxygen evolution reaction(OER),represent an emerging technology for efficient ammonia production and simultaneous power generation.Nevertheless,the intrinsic limitations of NRR and OER currently preclude its advancement.In this paper,Co and B co-doped Lavoisier framework series materials(MIL)are synthesized.Rapid mass transfer is rendered feasible with B_(0.25)-MIL-88-Fe_(4)Co_(1) by the distinctive double cone microrods structure.The addition of soft acid metal node Co^(2+)and B with defective electronic structure modifies the electronic configuration of MIL-88-Fe.At the same time,doping causes defects in the metal-organic frameworks,expands effectively the pore size,and increases the specific surface area,thereby expediting the adsorption of N_(2)and the release of O_(2).The electrocatalysis results show that the dual-doping scheme increases the NH_(3)yield(127.27μg^(-1)h^(-1)mg_(cat)^(-1))and Faraday efficiency(25.81%)while reducing the overpotential of OER(330 mV),achieving a power density of 8.30 mW cm^(-2)for Zn-N_(2)batteries.This discovery implements another avenue for the exploration of Zn-N_(2)battery materials and holds broader significance for advancing the field of energy storage and conversion.展开更多
Hard carbon (HC) is perceived as an anode candidate for sodium-ion batteries and potassium-ion batteries due to its disordered structure and cost-effectiveness,yet its capacity is restricted by limited active sites.He...Hard carbon (HC) is perceived as an anode candidate for sodium-ion batteries and potassium-ion batteries due to its disordered structure and cost-effectiveness,yet its capacity is restricted by limited active sites.Heteroatom-induced defect engineering of HC is commonly applied for enhancing its reversible capacity,but high heteroatom doping (>14 at%) is challenging due to the absence of heteroatoms in most biomasses.Not only that,the heteroatom doping strategy is also bothered with high diffusion barriers toward Na^(+)/K^(+).Herein,based on a rationally selected low-cost precursor (sodium alginateDmelamineDNaCl),a new HC with high-level N,O heteroatom dopants (21.4 at%) and well-regulated porous structure has been constructed via acylating and controllable pore engineering.Experimental proof and theoretical calculations have been conducted to clarify the influence of heteroatom dopants and porous structures on the ion storage behavior of the designed HC.The rich N,O co-doping could enable efficient Na+/K+adsorption and enhanced electron transfer behavior.Besides,benefiting from the hierarchical porous structures (micro to macropores),the interfacial reaction kinetics and electrochemical behavior can be boosted.Particularly,the optimized N,O dualdoped hierarchical porous HC (NO-HPHC-1,0.285 mol L-1NaCl in precursor) with abundant defects from macropores and moderate micropores make it exhibit excellent Na^(+)storage:127 mAh g^(-1)at 0.5 A g^(-1)even after 2000 cycles.Meanwhile,the superiority of NO-HPHC-1 can be well maintained for K^(+)storage with a reversible capacity of 199 mAh g^(-1)at 0.1 A g^(-1).More importantly,the diverse Na^(+)/K^(+)storage behaviors have been elucidated.展开更多
In this work,P and Mo dual-doped CoNiS(PMo-CoNiS)nanosheet arrays were successfully constructed through a common solvothermal treatment.The precise doping of P and Mo species into the CoNiS can regulate the microstruc...In this work,P and Mo dual-doped CoNiS(PMo-CoNiS)nanosheet arrays were successfully constructed through a common solvothermal treatment.The precise doping of P and Mo species into the CoNiS can regulate the microstructures and meanwhile endow with PMo-CoNiS abundant amorphous/crystalline heterointerfaces,which can adjust the electronic structure,thus enhancing the intrinsic activity of hydro-gen evolution reaction(HER)and oxygen evolution reaction(OER).As a result,ultra-low overpotentials of merely 156 and 58 mV are required to deliver a current density of 10 mA cm^(−2) for OER and HER,respec-tively,and the electrocatalysts PMo-CoNiS also exhibit low Tafel slopes and maintain robust stability for 48 h in alkaline media at a high current density of 50 mA cm^(−2).In addition,in an assembled electrolyte cell for overall water splitting,a voltage as low as 1.48 V is sufficient to yield a current density of 10 mA cm^(−2).Density functional theory(DFT)calculations further confirmed that the enhanced OER and HER result from the optimized OH^(∗)and H^(∗)adsorption energy of PMo-CoNiS due to P,Mo dual doping and generated interfacial effect.This work may offer an avenue for designing low-cost bifunctional catalysts with superior catalytic activity and provide a new application strategy for broader applications in various electrocatalytic fields.展开更多
The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device.Realizing this purpose by utilizing sustainable and low-cost resources is still a big challeng...The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device.Realizing this purpose by utilizing sustainable and low-cost resources is still a big challenge.Herein,N,B co-doped carbon nanosheets are obtained through the proposed dual-template assisted approach by using methyl cellulose as the precursor.Due to the synergistic effects form the high surface area with the hierarchical porous structure,N/B dual doping,and a high degree of graphitization,the resultant carbon electrode exhibits a high capacitance of 572 F g^(-1)at 0.5 A g^(-1)and retains 281 F g^(-1)at 50 A g^(-1)in an acidic electrolyte.Furthermore,the symmetric device assembled using bacterial cellulose-based gel polymer electrolyte can deliver high energy density of 43 W h kg^(-1)and excellent cyclability with 97.8%capacity retention after 20000 cycles in“water in salt”electrolyte.This work successfully realizes the fabrication of high-performance allcellulose-based quasi-solid-state supercapacitors,which brings a cost-effective insight into jointly designing electrodes and electrolytes for supporting highly efficient energy storage.展开更多
As a type of candidate for all-solid-state Li batteries,argyrodite solid electrolytes possess high ionic conductivity,but poor compatibility against Li metal.Here,we report novel Li_(6) PS_(5) I-based argyrodite sulfi...As a type of candidate for all-solid-state Li batteries,argyrodite solid electrolytes possess high ionic conductivity,but poor compatibility against Li metal.Here,we report novel Li_(6) PS_(5) I-based argyrodite sulfides with Sn-O dual doping,which is a powerful solution to comprehensively improve the performance of a material.The combination of O and Sn-aliovalent doping not only enables an improved ionic conductivity but more importantly realizes an intensively enhanced interfacial compatibility between argyrodite and Li metal and Li dendrite suppression capability.The assembled battery with Sn-O dual-doped electrolyte and Li anode demonstrates high capacity and decent cycling stability.Dual doping is thus believed to be an effective way to develop high performance sulfide solid electrolytes.展开更多
The(electro)chemical stability and Li dendrite suppression capability of sulfide solid electrolytes(SEs)need further improvement for developing all-solid-state Li batteries(ASSLBs).Here,we report advanced halogen-rich...The(electro)chemical stability and Li dendrite suppression capability of sulfide solid electrolytes(SEs)need further improvement for developing all-solid-state Li batteries(ASSLBs).Here,we report advanced halogen-rich argyrodites via I and Cl co-occupation on the crystal lattice.Notably,a proper I content forms a single phase,whereas an excessive I causes precipitation of two argyrodite phases like a superlattice structure.The resultant synergistic effect of the optimized composition allows to gain high ionic conductivities at room temperature and-20℃,and enhances the(electro)chemical stability against Li and Li dendrite suppression capability.The Li|argyrodite interface is very sensitive to the ratio of I and Cl.A LiCl-and LiI-rich double-layer interface is observed from the cell using the SE with optimized composition,whereas too high I content forms only a single interface layer with a mixture of Lil and LiCl.This double-layer interface is found to effectively mitigate the Li/SE reaction.The proper designed argyrodite enables ASSLBs to achieve good electrochemical properties at a broad temperature range regardless of the electrode materials.This co-occupation strategy provides a novel exploration for advanced halogen-rich argyrodite system.展开更多
Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidel...Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.展开更多
Nanopowders of Znl_x_y_zMnxNiyLizO [（x = 0.04, y = 0, z = 0）, （x = 0.04, y = 0.03, z = 0） and （x = 0.04, y = 0.03, z = 0.03）] have been synthesized by sol-gel precursor route using ethylene diamine tetraacetic a...Nanopowders of Znl_x_y_zMnxNiyLizO [（x = 0.04, y = 0, z = 0）, （x = 0.04, y = 0.03, z = 0） and （x = 0.04, y = 0.03, z = 0.03）] have been synthesized by sol-gel precursor route using ethylene diamine tetraacetic acid （EDTA） as a metal chelating agent. X-ray diffraction analysis confirms the formation of wurtzite hexagonal structure for all the three compositions. Mn2＋ doped ZnO exhibits room temperature ferromagnetism （RTFM）, and it is found that further Ni2＋ doping has decreased Ms because of limit of solid solubility of transition metal in ZnO. But codoping of monovalent Li1＋, further increases the ferromagnetism （FM） value, due to introduction of free carriers compared to the dual doped samples. Photoluminescence （PL） spectra of the system, exhibit near band edge （NBE） emission peak at --464 nm due to the electron transition from interstitials to the valence band. Recombination of conduction electron with hole trapped at oxygen vacancy, leads to prominent defect emission peaks at --482 nm and 532 nm. The evidence of the formation of metaI-EDTA complexes are found from the Fourier transform infrared spectra at 2800-3800 cm-1 with shifting, splitting of the peak and also drastic variations in the intensity.展开更多
The irreversible phase transition and interface side reactions during the cycling process severely limit the large scale application of nickel-rich layered oxides Li[Ni_(x)Co_(y)Mn_(1−x−y)]O_(2)(NCM,x>0.8).Herein,w...The irreversible phase transition and interface side reactions during the cycling process severely limit the large scale application of nickel-rich layered oxides Li[Ni_(x)Co_(y)Mn_(1−x−y)]O_(2)(NCM,x>0.8).Herein,we have designed LiNi_(0.8)Co_(0.1)Mn 0.1 O_(2)cathodes modified by Nb/Al co-doping and LiNbO_(3)/LiAlO_(2)composite coating.Detailed characterization reveals that Nb/Al co-doping can stabilize the crystal structure of the cathodes and expand the layer spacing of the layered lattice,thereby increasing the diffusion rate and reversibility of Li^(+).And the composite coatings can improve the electrochemical kinetic and inhibit the erosion of acidic substances by hindering direct contact between the cathodes and electrolyte.As a result,the Ni-rich cathodes with dual modification can still exhibit a higher capacity of 184.02 mA·h/g after 100 cycles with a capacity retention of up to 98.1%,and can still release a capacity of 161.6 mA·h/g at a high rate of 7 C,meanwhile,it shows excellent thermal stability compared to bare NCM.This work provides a new perspective for enhancing electrochemical properties of cathodes through integrated strategies.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
The Bi0.5Na0.02Sb1.48-xInxTe3alloys（x =0.02-0.20） were synthesized by vacuum melting and hot pressing methods at 753 K,60 MPa for 30 min.Effects of Na and In dual partial substitutions for Sb on the thermoelectric p...The Bi0.5Na0.02Sb1.48-xInxTe3alloys（x =0.02-0.20） were synthesized by vacuum melting and hot pressing methods at 753 K,60 MPa for 30 min.Effects of Na and In dual partial substitutions for Sb on the thermoelectric properties were investigated from 300 to 500 K.Substituting Sb with Na and In can enhance the Seebeck coefficient effectively near room temperature.The electrical resistivity of the Na and In dual-doping samples is higher within the whole test temperature range.The Bi0.5Na0.02Sb1.48-xInxTe3samples（x = 0.02,0.06） play a great role in optimizing the thermal conductivity.As for the Bi0.5Na0.02Sb1.46In0.02Te3alloy,the minimum value of thermal conductivity reaches 0.53 W·m-1·K-1at 320 K.The thermoelectric performance of the Na and In dualdoped samples is greatly improved,and a figure of merit ZT of 1.26 is achieved at 300 K for the Bi0.5Na0.02Sb1.42In0.06Te3,representing 26%enhancement with respect to ZT = 1.0 of the undoped sample.展开更多
Aqueous rechargeable Zn//MnO_(2)batteries show promising prospects for grid-scale energy storage due to their intrinsic safety,abundant resource,and potential high performance.Unfortunately,the real capability of thes...Aqueous rechargeable Zn//MnO_(2)batteries show promising prospects for grid-scale energy storage due to their intrinsic safety,abundant resource,and potential high performance.Unfortunately,the real capability of these devices is far from satisfactory thanks to the low capacity and sluggish kinetics of the MnO_(2)cathode.Herein,we report a dual cation doping strategy by synthesis of MnO_(2)in the presence of Ti_(3)_(2)X MXenes and Ni^(2+)ions to essentially address these drawbacks.Such a process contributes to a Ti,Ni co-dopedα-MnO_(2)anchored on MXenes.The Ti^(3+)ions incorporated in the framework allow a partial multivalent variation for a large capacity while the Ni^(2+)ions promote the H^(+)transfer within the MnO_(2)matrix via the Grotthuss proton transport manner.As a result,the optimal dual cation doped MnO_(2)exhibits a large reversible capacity of 378 mAh·g-1 at 0.1 C and a high rate capability.Moreover,capacity retention as high as 92%is observed after cycling at 4 C for 1000 times,far superior to many of the previously reported results.This facile strategy demonstrated here may shed new insight into the rational design of electrodes based on high-performance Zn//MnO_(2)batteries.展开更多
基金financial support from the National Science Foundation of China(51671094,21606189)China Postdoctoral Science Foundation(2017M612174)+1 种基金Shandong Provincial Natural Science Foundation(ZR2015BQ011)the Science and Technology Project of University of Jinan(XKY1826)。
文摘Developing of high-performance and low-cost electrocatalysts is of great significance to reduce the overpotential and accelerated the reaction rate of oxygen evolution in water splitting and related energy conversion applications.Herein,Fe,O-dual doped Ni2P(Fe,O-Ni2P)nanoarray is successfully synthesized on carbon cloth demonstrating enhanced electrocatalytic activity and stability for oxygen evolution reaction(OER)under alkaline media.The as-synthesized Fe,O-Ni2P nanoarray exhibits obviously improved OER performance with a low overpotential of 210 mV at 10 mA cm^-2 current density and a Tafel slope of48 mV dec^-1,as well as long-term durability.The strong coupling interaction induced changes in electronic structure lead to relatively higher oxidation state and stronger oxidation ability of the Fe,O-Ni2P nanoarray,together with the high electrochemical surface area and good conductivity contribute to the superior OER performance.This work highlights the anion-cation dual doping strategy may be an effective method for fabrication of catalysts relating to energy conversion applications.
基金supported by the National Natural Science Foundation of China (22179093)。
文摘Electrocatalytic nitrogen reduction reaction (e NRR) at the ambient conditions is attractive for ammonia(NH_(3)) synthesis due to its energy-efficient and eco-friendly features. However, the extremely strong N≡N triple-bonds in nitrogen molecules and the competitive hydrogen evolution reaction lead to the unsatisfactory NH_(3) yield and the Faradaic efficiency (FE) of e NRR, making the development of high-performance catalysts with adequate active sites and high selectivity essential for further development of e NRR.Addressing this, we herein report a Bi and K dual-doped titanium oxide (BTO@KTO) material, which is prepared by a cation exchange reaction between K_(2)Ti_(4)O_(5) and molten BiCl_(2), for high-performance e NRR catalysts. Benefiting from the controllable molten-salt cation exchange process, a highly active surface containing Bi/K sites and rich oxygen vacancies has been obtained on titanium oxide. Under the synergy of these two merits, an efficient e NRR catalysis, with the NH_(3) yield rate of 32.02 μg h^(-1)mg_(cat)^(-1) and the FE of 12.71%, has been achieved, much superior to that of pristine K_(2)Ti_(4)O_(9). This work thus offers a highperformance electrocatalyst for e NRR, and more importantly, a versatile cation-exchange strategy for efficiently manipulating materials’ functionalities.
基金supported by the National Natural Science Foundation of China(Nos.21203008,21975025,12274025)the Hainan Province Science and Technology Special Fund(Nos.ZDYF2021SHFZ232,ZDYF2023GXJS022)the Hainan Province Postdoctoral Science Foundation(No.300333)。
文摘The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.
基金supported by the Special Project for Local Science and Technology Development Guided by the Central Government of China(No.236Z1406G)。
文摘Zn-N_(2)batteries,which are comprised of nitrogen reduction reaction(NRR)and oxygen evolution reaction(OER),represent an emerging technology for efficient ammonia production and simultaneous power generation.Nevertheless,the intrinsic limitations of NRR and OER currently preclude its advancement.In this paper,Co and B co-doped Lavoisier framework series materials(MIL)are synthesized.Rapid mass transfer is rendered feasible with B_(0.25)-MIL-88-Fe_(4)Co_(1) by the distinctive double cone microrods structure.The addition of soft acid metal node Co^(2+)and B with defective electronic structure modifies the electronic configuration of MIL-88-Fe.At the same time,doping causes defects in the metal-organic frameworks,expands effectively the pore size,and increases the specific surface area,thereby expediting the adsorption of N_(2)and the release of O_(2).The electrocatalysis results show that the dual-doping scheme increases the NH_(3)yield(127.27μg^(-1)h^(-1)mg_(cat)^(-1))and Faraday efficiency(25.81%)while reducing the overpotential of OER(330 mV),achieving a power density of 8.30 mW cm^(-2)for Zn-N_(2)batteries.This discovery implements another avenue for the exploration of Zn-N_(2)battery materials and holds broader significance for advancing the field of energy storage and conversion.
基金financially supported by the National Natural Science Foundation of China(Nos.52072193,U22A20131,U22A20250,and 52361165657)Shandong Provincial Natural Science Foundation(Nos.ZR2021JQ16 and ZR2023YQ040)the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials(No.KF2217)
文摘Hard carbon (HC) is perceived as an anode candidate for sodium-ion batteries and potassium-ion batteries due to its disordered structure and cost-effectiveness,yet its capacity is restricted by limited active sites.Heteroatom-induced defect engineering of HC is commonly applied for enhancing its reversible capacity,but high heteroatom doping (>14 at%) is challenging due to the absence of heteroatoms in most biomasses.Not only that,the heteroatom doping strategy is also bothered with high diffusion barriers toward Na^(+)/K^(+).Herein,based on a rationally selected low-cost precursor (sodium alginateDmelamineDNaCl),a new HC with high-level N,O heteroatom dopants (21.4 at%) and well-regulated porous structure has been constructed via acylating and controllable pore engineering.Experimental proof and theoretical calculations have been conducted to clarify the influence of heteroatom dopants and porous structures on the ion storage behavior of the designed HC.The rich N,O co-doping could enable efficient Na+/K+adsorption and enhanced electron transfer behavior.Besides,benefiting from the hierarchical porous structures (micro to macropores),the interfacial reaction kinetics and electrochemical behavior can be boosted.Particularly,the optimized N,O dualdoped hierarchical porous HC (NO-HPHC-1,0.285 mol L-1NaCl in precursor) with abundant defects from macropores and moderate micropores make it exhibit excellent Na^(+)storage:127 mAh g^(-1)at 0.5 A g^(-1)even after 2000 cycles.Meanwhile,the superiority of NO-HPHC-1 can be well maintained for K^(+)storage with a reversible capacity of 199 mAh g^(-1)at 0.1 A g^(-1).More importantly,the diverse Na^(+)/K^(+)storage behaviors have been elucidated.
基金financial support of the National Natural Science Foundation of China(22078233)。
文摘In this work,P and Mo dual-doped CoNiS(PMo-CoNiS)nanosheet arrays were successfully constructed through a common solvothermal treatment.The precise doping of P and Mo species into the CoNiS can regulate the microstructures and meanwhile endow with PMo-CoNiS abundant amorphous/crystalline heterointerfaces,which can adjust the electronic structure,thus enhancing the intrinsic activity of hydro-gen evolution reaction(HER)and oxygen evolution reaction(OER).As a result,ultra-low overpotentials of merely 156 and 58 mV are required to deliver a current density of 10 mA cm^(−2) for OER and HER,respec-tively,and the electrocatalysts PMo-CoNiS also exhibit low Tafel slopes and maintain robust stability for 48 h in alkaline media at a high current density of 50 mA cm^(−2).In addition,in an assembled electrolyte cell for overall water splitting,a voltage as low as 1.48 V is sufficient to yield a current density of 10 mA cm^(−2).Density functional theory(DFT)calculations further confirmed that the enhanced OER and HER result from the optimized OH^(∗)and H^(∗)adsorption energy of PMo-CoNiS due to P,Mo dual doping and generated interfacial effect.This work may offer an avenue for designing low-cost bifunctional catalysts with superior catalytic activity and provide a new application strategy for broader applications in various electrocatalytic fields.
基金supported by the National Natural Science Foundation of China(No.22179123 and 21471139)the Shandong Provincial Natural Science Foundation,China(ZR2020ME038)+2 种基金the Fundamental Research Funds for the Central Universities(No.201941010)the Shandong Provincial Key R&D Plan and the Public Welfare Special Program,China(2019GGX102038)the Qingdao City Programs for Science and Technology Plan Projects(19-6-2-77-cg)。
文摘The key to construct high-energy supercapacitors is to maximize the capacitance of electrode and the voltage of the device.Realizing this purpose by utilizing sustainable and low-cost resources is still a big challenge.Herein,N,B co-doped carbon nanosheets are obtained through the proposed dual-template assisted approach by using methyl cellulose as the precursor.Due to the synergistic effects form the high surface area with the hierarchical porous structure,N/B dual doping,and a high degree of graphitization,the resultant carbon electrode exhibits a high capacitance of 572 F g^(-1)at 0.5 A g^(-1)and retains 281 F g^(-1)at 50 A g^(-1)in an acidic electrolyte.Furthermore,the symmetric device assembled using bacterial cellulose-based gel polymer electrolyte can deliver high energy density of 43 W h kg^(-1)and excellent cyclability with 97.8%capacity retention after 20000 cycles in“water in salt”electrolyte.This work successfully realizes the fabrication of high-performance allcellulose-based quasi-solid-state supercapacitors,which brings a cost-effective insight into jointly designing electrodes and electrolytes for supporting highly efficient energy storage.
基金supported by the National Key R&D Program of China(No.2018YFB0104300)the Natural Science Foundation of Hebei Province(No.E2018203301)。
文摘As a type of candidate for all-solid-state Li batteries,argyrodite solid electrolytes possess high ionic conductivity,but poor compatibility against Li metal.Here,we report novel Li_(6) PS_(5) I-based argyrodite sulfides with Sn-O dual doping,which is a powerful solution to comprehensively improve the performance of a material.The combination of O and Sn-aliovalent doping not only enables an improved ionic conductivity but more importantly realizes an intensively enhanced interfacial compatibility between argyrodite and Li metal and Li dendrite suppression capability.The assembled battery with Sn-O dual-doped electrolyte and Li anode demonstrates high capacity and decent cycling stability.Dual doping is thus believed to be an effective way to develop high performance sulfide solid electrolytes.
基金supported by the National Natural Science Foundation of China(52172243)。
文摘The(electro)chemical stability and Li dendrite suppression capability of sulfide solid electrolytes(SEs)need further improvement for developing all-solid-state Li batteries(ASSLBs).Here,we report advanced halogen-rich argyrodites via I and Cl co-occupation on the crystal lattice.Notably,a proper I content forms a single phase,whereas an excessive I causes precipitation of two argyrodite phases like a superlattice structure.The resultant synergistic effect of the optimized composition allows to gain high ionic conductivities at room temperature and-20℃,and enhances the(electro)chemical stability against Li and Li dendrite suppression capability.The Li|argyrodite interface is very sensitive to the ratio of I and Cl.A LiCl-and LiI-rich double-layer interface is observed from the cell using the SE with optimized composition,whereas too high I content forms only a single interface layer with a mixture of Lil and LiCl.This double-layer interface is found to effectively mitigate the Li/SE reaction.The proper designed argyrodite enables ASSLBs to achieve good electrochemical properties at a broad temperature range regardless of the electrode materials.This co-occupation strategy provides a novel exploration for advanced halogen-rich argyrodite system.
文摘Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.
文摘Nanopowders of Znl_x_y_zMnxNiyLizO [（x = 0.04, y = 0, z = 0）, （x = 0.04, y = 0.03, z = 0） and （x = 0.04, y = 0.03, z = 0.03）] have been synthesized by sol-gel precursor route using ethylene diamine tetraacetic acid （EDTA） as a metal chelating agent. X-ray diffraction analysis confirms the formation of wurtzite hexagonal structure for all the three compositions. Mn2＋ doped ZnO exhibits room temperature ferromagnetism （RTFM）, and it is found that further Ni2＋ doping has decreased Ms because of limit of solid solubility of transition metal in ZnO. But codoping of monovalent Li1＋, further increases the ferromagnetism （FM） value, due to introduction of free carriers compared to the dual doped samples. Photoluminescence （PL） spectra of the system, exhibit near band edge （NBE） emission peak at --464 nm due to the electron transition from interstitials to the valence band. Recombination of conduction electron with hole trapped at oxygen vacancy, leads to prominent defect emission peaks at --482 nm and 532 nm. The evidence of the formation of metaI-EDTA complexes are found from the Fourier transform infrared spectra at 2800-3800 cm-1 with shifting, splitting of the peak and also drastic variations in the intensity.
基金Project(2023JJ40759)supported by the Natural Science Foundation of Hunan Province,China。
文摘The irreversible phase transition and interface side reactions during the cycling process severely limit the large scale application of nickel-rich layered oxides Li[Ni_(x)Co_(y)Mn_(1−x−y)]O_(2)(NCM,x>0.8).Herein,we have designed LiNi_(0.8)Co_(0.1)Mn 0.1 O_(2)cathodes modified by Nb/Al co-doping and LiNbO_(3)/LiAlO_(2)composite coating.Detailed characterization reveals that Nb/Al co-doping can stabilize the crystal structure of the cathodes and expand the layer spacing of the layered lattice,thereby increasing the diffusion rate and reversibility of Li^(+).And the composite coatings can improve the electrochemical kinetic and inhibit the erosion of acidic substances by hindering direct contact between the cathodes and electrolyte.As a result,the Ni-rich cathodes with dual modification can still exhibit a higher capacity of 184.02 mA·h/g after 100 cycles with a capacity retention of up to 98.1%,and can still release a capacity of 161.6 mA·h/g at a high rate of 7 C,meanwhile,it shows excellent thermal stability compared to bare NCM.This work provides a new perspective for enhancing electrochemical properties of cathodes through integrated strategies.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金financially supported by the National Natural Science Foundation of China (No. 51161009)the Research Project of Jiangxi Provincial Education Department (No. GJJ13722 and GJJ11615)
文摘The Bi0.5Na0.02Sb1.48-xInxTe3alloys（x =0.02-0.20） were synthesized by vacuum melting and hot pressing methods at 753 K,60 MPa for 30 min.Effects of Na and In dual partial substitutions for Sb on the thermoelectric properties were investigated from 300 to 500 K.Substituting Sb with Na and In can enhance the Seebeck coefficient effectively near room temperature.The electrical resistivity of the Na and In dual-doping samples is higher within the whole test temperature range.The Bi0.5Na0.02Sb1.48-xInxTe3samples（x = 0.02,0.06） play a great role in optimizing the thermal conductivity.As for the Bi0.5Na0.02Sb1.46In0.02Te3alloy,the minimum value of thermal conductivity reaches 0.53 W·m-1·K-1at 320 K.The thermoelectric performance of the Na and In dualdoped samples is greatly improved,and a figure of merit ZT of 1.26 is achieved at 300 K for the Bi0.5Na0.02Sb1.42In0.06Te3,representing 26%enhancement with respect to ZT = 1.0 of the undoped sample.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21975258,22179145,22005341,and 21878336)the startup support grant from China University of Petroleum(East China)Shandong Provincial Natural Science Foundation(Nos.ZR2020ZD08 and ZR2018ZC1458).
文摘Aqueous rechargeable Zn//MnO_(2)batteries show promising prospects for grid-scale energy storage due to their intrinsic safety,abundant resource,and potential high performance.Unfortunately,the real capability of these devices is far from satisfactory thanks to the low capacity and sluggish kinetics of the MnO_(2)cathode.Herein,we report a dual cation doping strategy by synthesis of MnO_(2)in the presence of Ti_(3)_(2)X MXenes and Ni^(2+)ions to essentially address these drawbacks.Such a process contributes to a Ti,Ni co-dopedα-MnO_(2)anchored on MXenes.The Ti^(3+)ions incorporated in the framework allow a partial multivalent variation for a large capacity while the Ni^(2+)ions promote the H^(+)transfer within the MnO_(2)matrix via the Grotthuss proton transport manner.As a result,the optimal dual cation doped MnO_(2)exhibits a large reversible capacity of 378 mAh·g-1 at 0.1 C and a high rate capability.Moreover,capacity retention as high as 92%is observed after cycling at 4 C for 1000 times,far superior to many of the previously reported results.This facile strategy demonstrated here may shed new insight into the rational design of electrodes based on high-performance Zn//MnO_(2)batteries.
