Li_(3)V_(2)(PO_(4))_(3) is a promising high-voltage cathode for zincion batteries,but it suffers from a poor electronic conductivity and vanadium dissolution in aqueous electrolytes.The growth of carboncoated Li_(3)V_...Li_(3)V_(2)(PO_(4))_(3) is a promising high-voltage cathode for zincion batteries,but it suffers from a poor electronic conductivity and vanadium dissolution in aqueous electrolytes.The growth of carboncoated Li_(3)V_(2)(PO_(4))_(3)(LVP@C)nanoparticles on carbon nanofibers(CNFs)has been achieved by an electrospinning technique followed by calcination.The protective carbon coating prevents the aggregation of the LVP nanoparticles and suppresses V dissolution by preventing direct contact with aqueous electrolytes.The CNFs derived from the electrospun nanofibers provide a 3D network to increase the electronic conductivity of the LVP electrode,and the LVP@C-CNF hybrid film can be directly used as a freestanding cathode for zinc-ion batteries without adding conductive additives and binders.A mechanism for the formation of a uniform and continuous carbon coating has been proposed.This nanostructure,combined with the uniform and intact carbon coverage,significantly increases the electronic conductivity.This LVP@C-CNF freestanding electrode has an excellent rate capability(47.3%retention at 2 C)and cycling stability(61.2%retention after 100 cycles)within the voltage range 0.6 V to 1.95 V and is highly suitable for zinc-ion battery applications.展开更多
High dispersed carbon black was applied for LiFePO4 cathodes as conductive agent.Nano-conductive carbon agent was pre-dispersed with poly acrylic acid(PAA) as dispersant in organic N-methyl-pyrrolidone(NMP) solvent sy...High dispersed carbon black was applied for LiFePO4 cathodes as conductive agent.Nano-conductive carbon agent was pre-dispersed with poly acrylic acid(PAA) as dispersant in organic N-methyl-pyrrolidone(NMP) solvent system.The dispersion property of nano-conductive carbon agent was evaluated using particle size distribution measurements,scanning electron microscopy(SEM) and transmission electron microscope(TEM).LiFePO4 cathode with as-received nano-conductive carbon agent(SP) and LiFePO4 cathode with pre-dispersed nano-conductive carbon agent(SP-PAA) were examined by scanning electron microscopy(SEM),cyclic voltammetry(CV),electrochemical impendence spectroscopy(EIS) and charge/discharge cycling performance.Results show that the dispersion property of carbon black is improved by using PAA as the dispersant.The LiFePO4 cathodes with SP-PAA exhibit improved rate behaviors(4C,135.1 mAh/g) and cycle performance(95%,200 cycles) compared to LiFePO4 cathodes with SP(4C,103.9 mAh/g and 83%,200 cycles).Because pre-dispersed carbon black(SP-PAA) is dispersed homogeneously in the dried composite electrode to form a more uniform conductive network between the active material particles,electrochemical performances of the LiFePO4 cathodes are improved.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
Zinc-ion supercapacitors(ZISCs)have received considerable interest for energy storage because of their low cost,high safety,and minimal environmental impact.However,they have a low energy density and poor cycling perf...Zinc-ion supercapacitors(ZISCs)have received considerable interest for energy storage because of their low cost,high safety,and minimal environmental impact.However,they have a low energy density and poor cycling performance.The design of a better cathode material is needed to overcome these limitations.A simple method was used to synthesize binder-free electrochemically exfoliated carbon paper(EECP)which modifies the surface of the paper by introducing oxygen functional groups and thus improves its pseudocapacitance.When used in a Zn-ion supercapacitor(ZISC),an EECPbased cathode provides a large surface area and quick charge transfer.As a result,the ZISC had remarkable charge storage properties and had a dominant capacitive-type charge storage mechanism with 78.8%retention of capacity at 10 mV/s of the total storage.Furthermore,at 1 A/g,the EECP electrode had a maximum capacitance of 252.5 F/g.The EECP electrode retained 81.7%of its capacitance after 10000 cycles,indicating its promise for use in the growing renewable energy sector.A ZISC was also constructed using EECP as the positive electrode and Zn as the negative electrode with a 1 mol L^(−1) ZnSO_(4) electrolyte.It had a capacitance of 186.22 F/g at 1 A/g and a 97.01%retention rate after 10000 cycles.It also had an excellent energy density of 46.6 Wh/kg at a power density of 500.4 W/kg.The material is therefore suitable for use in high-rate next-generation ZISCs.展开更多
Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-p...Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.展开更多
Aqueous Zn-S batteries have shown great potential in advanced en-ergy storage systems due to their low cost,high theoretical capacity,and in-trinsic safety.However,the slow kinet-ics and low electrical conductivity of...Aqueous Zn-S batteries have shown great potential in advanced en-ergy storage systems due to their low cost,high theoretical capacity,and in-trinsic safety.However,the slow kinet-ics and low electrical conductivity of sul-fur prevent the full use of their capacity,leading to poor cycling performance.We used graphite carbon nitride(g-C_(3)N_(4))as the nitrogen source,and nitrogen-doped Ketjenblack(NKB)was synthesized by solid-phase calcination for use as the sulfur host.Results demonstrate that pyrrolic nitrogen serves as the primary catalytic active site in the sulfur reduction process.The high electronegativity of nitrogen significantly alters the charge distribution of the carbon matrix,changing the electron distribution around sulfur and rendering it electron-rich,which increases the interaction between S and Zn^(2+)and accelerates the reduction kinetics.NKB also forms a three-dimensional cross-linked carbon sphere network,providing abundant defect sites and a large specific surface area,which facilitates electron transfer and improves electrolyte wettability.Combined with the contribution of the ZnI2 additive,the Zn-S battery prepared with the precursor of a g-C_(3)N_(4)∶KB ratio of 3∶4 achieved an ultrahigh discharge capacity of 2069 mAh g^(-1) at a current density of 1 A/g.It also had an excellent rate performance(1257 mAh g^(-1) at 10 A/g)and a long cycling stability(705 mAh g^(-1) after 180 cycles at 5 A/g).This study provides a simple and effective strategy for improving the reduction kinetics of the sulfur cathode in Zn-S batteries and design-ing advanced cathode materials.展开更多
Lithium-air batteries(LABs)are regarded as a next-generation energy storage option due to their relatively high energy density.The cyclic stability and lifespan of LABs are mainly influenced by the formation and decom...Lithium-air batteries(LABs)are regarded as a next-generation energy storage option due to their relatively high energy density.The cyclic stability and lifespan of LABs are mainly influenced by the formation and decomposition of lithium-based oxides at the air cathode,which not only lead to a low cathode catalytic efficiency but also restrict the electrochemical reversibility and cause side reaction problems.Carbon materials are considered key to solving these problems due to their conductivity,functional flexibility,and adjustable pore structure.This paper considers the research progress on carbon materials as air cathode catalytic materials for LABs,focusing on their structural characteristics,electrochemical behavior,and reaction mechanisms.Besides being used as air cathodes,carbon materials also show potential for being used as protective layers for metal anodes or as anode materials for LABs.展开更多
Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operati...Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operating voltage window of their activated carbon(AC)cathodes.We report a scalable thermal treatment strategy to develop high-voltage-tolerant AC cathodes.Through controlled thermal treatment of commer-cial activated carbon(Raw-AC)under a H_(2)/Ar atmosphere at 400-800℃,the targeted reduction of degradation-prone functional groups can be achieved while preserving the critical pore structure and increasing graph-itic microcrystalline ordering.The AC treated at 400℃(HAC-400)had a significant increase in specific capacity(96.0 vs.75.1 mAh/g at 0.05 A/g)and better rate capability(61.1 vs.36.1 mAh/g at 5 A/g)in half-cell LICs,along with an 83.5%capacity retention over 7400 cycles within an extended voltage range of 2.0-4.2 V in full-cell LICs.Scalability was demonstrated by a 120 g batch production,enabling fabrication of pouch-type LICs with commercial hard carbon anodes that delivered a higher energy density of 28.3 Wh/kg at 1 C,and a peak power density of 12.1 kW/kg compared to devices using raw AC.This simple,industry-compatible approach may be used for producing ad-vanced cathode materials for practical high-performance LICs.展开更多
As classical cathode materials of solid oxide fuel cell(SOFC),Fe-based perovskite materials are favored for their affordable price,low thermal expansion coefficient and high stability.In this study,B-site high-entropy...As classical cathode materials of solid oxide fuel cell(SOFC),Fe-based perovskite materials are favored for their affordable price,low thermal expansion coefficient and high stability.In this study,B-site high-entropy perovskite oxide La_(0.7)Sr_(0.3)(FeNiCo)_(0.8)Mo_(0.1)Ti_(0.1)O_(3-δ)(LSFNCMT)was prepared by the citric acid-nitrate combustion method.Due to the faster oxygen surface exchange rate of the high-entropy material,the LSFNCMT cathode shows excellent oxygen reduction reaction(ORR)activity with a polarization impedance(Rp)of 0.11Ω·cm^(2) at 800℃,which is much lower than that of the La_(0.7)Sr_(0.3)FeO_(3-δ)(LSF)cathode(0.31Ω·cm^(2)).Furthermore,the high-entropy material exhibits superior stability due to incorporation of highly acidic Ni,Co,and Mo cations as well as Ti cation with more negative average bonding energy(ABE)of metal-oxygen.In the 22 h-stability test of the symmetric cell with LSFNCMT cathode in the Cr-containing atmosphere,Rp only increases from 1.07Ω·cm^(2) to 2.98Ω·cm^(2),while Rp of the LSF cathode increases from 2.62Ω·cm^(2) to 7.90Ω·cm^(2) under the same conditions,indicating better Cr-resistance of LSFNCMT due to the high-entropy strategy.The fact that the maximum power density(MPD)of the single cell with LSFNCMT cathode at 800℃is 1105.26 mW·cm^(-2),significantly higher than that of LSF cathode(830.74 mW·cm^(-2)),and Rp at 800℃is 0.24Ω·cm^(2),lower than that of LSF cathode(0.36Ω·cm^(2)),confirming excellent toxicity resistance of the high-entropy cathode.This study shows that B-position high entropy is an effective way to improve the catalytic activity and chromium resistance of cathode materials.展开更多
Lithium nickel oxide(Li_(2)NiO_(2)),as a sacrificial cathode prelithiation additive,has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries(LIBs).However,high-cost Li_(2)Ni...Lithium nickel oxide(Li_(2)NiO_(2)),as a sacrificial cathode prelithiation additive,has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries(LIBs).However,high-cost Li_(2)NiO_(2)suffers from inferior delithiation kinetics during the first cycle.Herein,we investigated the effects of the cost-effective copper substituted Li_(2)Ni_(1-x)Cu_(x)O_(2)(x=0,0.2,0.3,0.5,0.7)synthesized by a high-temperature solid-phase method on the structure,morphology,electrochemical performance of graphite‖LiFePO_(4)battery.The X-ray diffraction(XRD)refinement result demonstrated that Cu substitution strategy could be favorable for eliminating the NiO_(x)impurity phase and weakening Li-O bond.Analysis on density of states(DOS)indicates that Cu substitution is good for enhancing the electronic conductivity,as well as reducing the delithi-ation voltage polarization confirmed by electrochemical characterizations.Therefore,the optimal Li_(2)Ni_(0.7)Cu_(0.3)O_(2)delivered a high delithiation capacity of 437 mAh·g^(-1),around 8%above that of the pristine Li_(2)NiO_(2).Furthermore,a graphite‖LiFePO_(4)pouch cell with a nominal capacity of 3000 mAh demonstrated a notably improved reversible capacity,energy density and cycle life through introducing 2 wt%Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive,delivering a 6.2 mAh·g^(-1)higher initial discharge capacity and achieving around 5%improvement in capacity retentnion at 0.5P over 1000 cycles.Additionally,the post-mortem analyses testified that the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive could suppress solid electrolyte interphase(SEI)decomposition and homogenize the Li distribution,which benefits to stabilizing interface between graphite and electrolyte,and alleviating dendritic Li plating.In conclusion,the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive may offer advantages such as lower cost,lower delithiation voltage and higher prelithiation capacity compared with Li_(2)NiO_(2),making it a promising candidate of cathode prelithiation additive for next-generation LIBs.展开更多
Rich-nickel layered ternary NCM811 has been widely used in the field of electric vehicles ascribed to its high theoretical specific capacity.However,poor cycling stability and rate-performance hindered its further dev...Rich-nickel layered ternary NCM811 has been widely used in the field of electric vehicles ascribed to its high theoretical specific capacity.However,poor cycling stability and rate-performance hindered its further development.Herein,different amounts of nitrogen-doped carbon were wrapped on the surface of NCM811 via a facile rheological phase method by regulating the amount of dopamine hydrochloride.The effects of the coating amounts on the structure and electrochemical performance are investigated.The DFT calculation,XRD,SEM and XPS reveal that an appropriate amount of nitrogen-doped carbon coating could uniformly form a protective layer on the NCM811 surface and the introduced N could anchor Ni atoms to inhibit the Li^(+)/Ni^(2+)mixing,but excessive amount would reduce Ni^(3+)to Ni^(2+)so as to conversely aggravate Li^(+)/Ni^(2+)mixing.Among the samples,the NCM811-CN0.75 sample exhibits the most excellent electrochemical performance,delivering a high-rate capacity of 151.6 mA·h/g at 10C,and long-term cyclability with 82.2%capacity retention after 300 cycles at 5C,exhibiting remarkable rate-performance and cyclability.展开更多
This study focuses on using a green reagent scheme of methanesulfonic acid (MSA) and citric acid (CA) to extract valuable metals from the cathodes, aiming to minimize environmental impact during the recycling process....This study focuses on using a green reagent scheme of methanesulfonic acid (MSA) and citric acid (CA) to extract valuable metals from the cathodes, aiming to minimize environmental impact during the recycling process. Leaching studies on LiCoO_(2) identified optimal conditions as follows: 2.4 mol/L MSA, 1.6 mol/L CA, S/L ratio of 80 g/L, leaching temperature of 90oC and leaching time of 6 h. The maximum Co and Li extraction achieved was 92% and 85%, respectively. LiCoO_(2) dissolution in MSA-CA leaching solution is highly impacted by temperature;Avrami equation showed a good fitting for the leaching data. The experimental activation energy of Co and Li was 50.98 kJ/mol and 50.55 kJ/mol, respectively, indicating that it is a chemical reaction-controlled process. Furthermore, cobalt was efficiently recovered from the leachate using oxalic acid, achieving a precipitation efficiency of 99.91% and a high-purity cobalt oxalate product (99.85 wt.%). In the MSA-CA leaching solution, MSA served as a lixiviant, while CA played a key role in reducing Co in LiCoO_(2). The overall organic acid leaching methodology presents an attractive option due to its reduced environmental impact.展开更多
As a cathode material for thermal batteries,NiS_(2)has a high theoretical capacity but low thermal stability.Besides,the poor formability of NiS_(2)powders also restricts the cathode performance of thermal batteries.I...As a cathode material for thermal batteries,NiS_(2)has a high theoretical capacity but low thermal stability.Besides,the poor formability of NiS_(2)powders also restricts the cathode performance of thermal batteries.In this paper,the novel NiS_(2)/SiO_(2)composite material was developed by high temperature vulcanization to improve the thermal stability formability of NiS_(2).The good filling and lubrication of spherical SiO_(2)can improve the thermal conductivity of NiS_(2)electrode.The discharge test shows that the NiS_(2)/SiO_(2)cathode has a stable discharge voltage at a current density of 200 mA/cm^(2),and the activation time is shortened by nearly 20%compared with the NiS_(2)cathode.In addition,due to the favorable thermal insulation protection of SiO_(2),the initial decomposition temperature of NiS_(2)is increased by 30℃after the addition of SiO_(2).The incorporation of SiO_(2)not only effectively improves the thermal stability and electrochemical properties of NiS_(2),but also improves the cold pressing forming performance of the NiS_(2)powder.Therefore,the novel NiS_(2)/SiO_(2)composite material is more suitable for thermal batteries with high stability and fast response,which is of great significance for improving the maneuverability and quality reliability of weapons and equipment.展开更多
The effects of NOx(in a ratio of NO∶NO2=9∶1) and SO2in cathode streamonthe performance of a single proton ex-change membrane fuel cell(PEMFC) were investigated.NOxwith concentrations of 1×10-3%(in volume,the sa...The effects of NOx(in a ratio of NO∶NO2=9∶1) and SO2in cathode streamonthe performance of a single proton ex-change membrane fuel cell(PEMFC) were investigated.NOxwith concentrations of 1×10-3%(in volume,the same as fol-lows),1.4×10-2%and 1×10-3%could cause significant detri mental effects on the cell performance.However,nearly com-plete recovery of the cell performance could be observed after NOxwas shut off and purged with clean air.The electrochemicalmeasurements suggested that thei mpacts of NOxresulted mainlyfromthe superposition of the oxygen reduction reaction(ORR),NOand HNO2oxidation reactions,and the increased cathodic i mpedance.Trace SO2with concentrations of 5×10-6%,5×10-3%,2×10-4%and 3.2×10-4%influenced the cell muchseverer,which could be attributed toits strong adsorption onthesurface of Pt atoms.The cell performance could not be completely recovered after purged with clean air and cyclic voltammetry(CV) tests,due to the changes of electrochemical i mpedance spectroscopy(EIS) and electrochemical active surface(EAS) causedby surface state change after SO2exposure.展开更多
In the present investigation, electroless Ni-Cu-P/n-TiN composite coating was prepared using alkaline citrate-based bath. X-ray diffraction （XRD）, scanning electron microscopy（SEM）, energy-dispersive spectroscopy...In the present investigation, electroless Ni-Cu-P/n-TiN composite coating was prepared using alkaline citrate-based bath. X-ray diffraction （XRD）, scanning electron microscopy（SEM）, energy-dispersive spectroscopy（EDS）, electrochemical measurements, weight loss tests and Raman spectrometer were used to character the properties of the coating. As the Cu content increased from 7.3 wt% to 24.8 wt%, the corrosion current density of the Ni-Cu-P/n-TiN coating decreased from 10.80 to 4.34 ~tA. And the inclusion of Cu in NiP alloy resulted in refinement and less porosity in microstructure. The addition of TiN resulted in a slight decline in anti-corrosion property of the coating. As the mass loss test showed, Ni-24.8%Cu-P exhibited perfect corrosion resistance. Studies by Raman spectroscopy on coatings proved that Cu（II）3（PO4）（OH）3, Cu（OH）2 and CuO were examined while no compound of nickel was found, and Cu exhibited preferred corrosion in saline solution, providing cathodic protection to Ni alloy.展开更多
The electrolysis expansion of semigraphitic cathode in [K3AlF6/Na3AlF6]-AlF3-Al2O3 bath system was tested by self-made modified Rapoport apparatus. A mathematical model was introduced to discuss the effects of acR （c...The electrolysis expansion of semigraphitic cathode in [K3AlF6/Na3AlF6]-AlF3-Al2O3 bath system was tested by self-made modified Rapoport apparatus. A mathematical model was introduced to discuss the effects of acR （cryolite ratio） and βKR （elpasolite content divided by the total amount of elpasolite and sodium cryolite） on performance of cathode electrolysis expansion. The results show that K and Na （potassium and sodium） penetrate into the cathode together and have an obvious influence on the performance of cathode electrolysis expansion. The electrolysis expansion and K/Na penetration rate increase with the increase of αCR. When αCR=1.9 and βKR=0.5, the electrolysis expansion is the highest, which is 3.95%; and when αCR=I.4 and βKR=0.1, the electrolysis expansion is the lowest, which is 1.28%. But the effect offlKR is correlative with αCR. When αCR=1.6 and 1.9, with the increase of titan, the electrolysis expansion and K/Na penetration rate increase. However, when αCR=l.4, the electrolysis expansion and K/Na penetration rate firstly increase and then decrease with the increase of βKR.展开更多
The sodium expansion curves of semi-graphitic cathode measured with the improved Rapoport-Samoilenko apparatus. The and TiB2/C composite cathode with different TiB2 contents were mathematic model of the sodium expansi...The sodium expansion curves of semi-graphitic cathode measured with the improved Rapoport-Samoilenko apparatus. The and TiB2/C composite cathode with different TiB2 contents were mathematic model of the sodium expansion was deduced on the basis of the experimental results. The sodium expansion parameter （a） and penetration rate factor （Q）, were introduced into the model The model was validated with the experimental sodium expansion curves self-measured and reported. The results show that the variation tendency of the sodium expansion parameter （a） and penetration rate factor （Q） is consistent with that of the experimental curves. The model is capable of not only conveniently judging the cathode quality, but also favorably establishing a unified standard of the resistance to sodium penetration of cathode.展开更多
A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted un...A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.展开更多
文摘Li_(3)V_(2)(PO_(4))_(3) is a promising high-voltage cathode for zincion batteries,but it suffers from a poor electronic conductivity and vanadium dissolution in aqueous electrolytes.The growth of carboncoated Li_(3)V_(2)(PO_(4))_(3)(LVP@C)nanoparticles on carbon nanofibers(CNFs)has been achieved by an electrospinning technique followed by calcination.The protective carbon coating prevents the aggregation of the LVP nanoparticles and suppresses V dissolution by preventing direct contact with aqueous electrolytes.The CNFs derived from the electrospun nanofibers provide a 3D network to increase the electronic conductivity of the LVP electrode,and the LVP@C-CNF hybrid film can be directly used as a freestanding cathode for zinc-ion batteries without adding conductive additives and binders.A mechanism for the formation of a uniform and continuous carbon coating has been proposed.This nanostructure,combined with the uniform and intact carbon coverage,significantly increases the electronic conductivity.This LVP@C-CNF freestanding electrode has an excellent rate capability(47.3%retention at 2 C)and cycling stability(61.2%retention after 100 cycles)within the voltage range 0.6 V to 1.95 V and is highly suitable for zinc-ion battery applications.
基金Project(51204211) supported by the National Natural Science Foundation of ChinaProject(2012M521543) supported by the China Postdoctoral Science Foundation
文摘High dispersed carbon black was applied for LiFePO4 cathodes as conductive agent.Nano-conductive carbon agent was pre-dispersed with poly acrylic acid(PAA) as dispersant in organic N-methyl-pyrrolidone(NMP) solvent system.The dispersion property of nano-conductive carbon agent was evaluated using particle size distribution measurements,scanning electron microscopy(SEM) and transmission electron microscope(TEM).LiFePO4 cathode with as-received nano-conductive carbon agent(SP) and LiFePO4 cathode with pre-dispersed nano-conductive carbon agent(SP-PAA) were examined by scanning electron microscopy(SEM),cyclic voltammetry(CV),electrochemical impendence spectroscopy(EIS) and charge/discharge cycling performance.Results show that the dispersion property of carbon black is improved by using PAA as the dispersant.The LiFePO4 cathodes with SP-PAA exhibit improved rate behaviors(4C,135.1 mAh/g) and cycle performance(95%,200 cycles) compared to LiFePO4 cathodes with SP(4C,103.9 mAh/g and 83%,200 cycles).Because pre-dispersed carbon black(SP-PAA) is dispersed homogeneously in the dried composite electrode to form a more uniform conductive network between the active material particles,electrochemical performances of the LiFePO4 cathodes are improved.
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supported by National Natural Science Foundation of China(52472194)the Deanship of Research and Graduate Studies at King Khalid University through Large Research Project(RGP-2/687/46).
文摘Zinc-ion supercapacitors(ZISCs)have received considerable interest for energy storage because of their low cost,high safety,and minimal environmental impact.However,they have a low energy density and poor cycling performance.The design of a better cathode material is needed to overcome these limitations.A simple method was used to synthesize binder-free electrochemically exfoliated carbon paper(EECP)which modifies the surface of the paper by introducing oxygen functional groups and thus improves its pseudocapacitance.When used in a Zn-ion supercapacitor(ZISC),an EECPbased cathode provides a large surface area and quick charge transfer.As a result,the ZISC had remarkable charge storage properties and had a dominant capacitive-type charge storage mechanism with 78.8%retention of capacity at 10 mV/s of the total storage.Furthermore,at 1 A/g,the EECP electrode had a maximum capacitance of 252.5 F/g.The EECP electrode retained 81.7%of its capacitance after 10000 cycles,indicating its promise for use in the growing renewable energy sector.A ZISC was also constructed using EECP as the positive electrode and Zn as the negative electrode with a 1 mol L^(−1) ZnSO_(4) electrolyte.It had a capacitance of 186.22 F/g at 1 A/g and a 97.01%retention rate after 10000 cycles.It also had an excellent energy density of 46.6 Wh/kg at a power density of 500.4 W/kg.The material is therefore suitable for use in high-rate next-generation ZISCs.
基金supported by National Key R&D Program of China(2021YFB4001401)National Natural Science Foundation of China(52272190,22178023).
文摘Solid oxide electrolysis cells(SOECs)can effectively convert CO_(2)into high value-added CO fuel.In this paper,Sc-doped Sr_(2)Fe_(1.5)Mo_(0.3)Sc_(0.2)O_(6−δ)(SFMSc)perovskite oxide material is synthesized via solid-phase method as the cathode for CO_(2)electrolysis by SOECs.XRD confirms that SFMSc exhibits a stable cubic phase crystal structure.The experimental results of TPD,TG,EPR,CO_(2)-TPD further demonstrate that Sc-doping increases the concentration of oxygen vacancy in the material and the chemical adsorption capacity of CO_(2)molecules.Electrochemical tests reveal that SFMSc single cell achieves a current density of 2.26 A/cm^(2) and a lower polarization impedance of 0.32Ω·cm^(2) at 800°C under the applied voltage of 1.8 V.And no significant performance attenuation or carbon deposition is observed after 80 h continuous long-term stability test.This study provides a favorable support for the development of SOEC cathode materials with good electro-catalytic performance and stability.
文摘Aqueous Zn-S batteries have shown great potential in advanced en-ergy storage systems due to their low cost,high theoretical capacity,and in-trinsic safety.However,the slow kinet-ics and low electrical conductivity of sul-fur prevent the full use of their capacity,leading to poor cycling performance.We used graphite carbon nitride(g-C_(3)N_(4))as the nitrogen source,and nitrogen-doped Ketjenblack(NKB)was synthesized by solid-phase calcination for use as the sulfur host.Results demonstrate that pyrrolic nitrogen serves as the primary catalytic active site in the sulfur reduction process.The high electronegativity of nitrogen significantly alters the charge distribution of the carbon matrix,changing the electron distribution around sulfur and rendering it electron-rich,which increases the interaction between S and Zn^(2+)and accelerates the reduction kinetics.NKB also forms a three-dimensional cross-linked carbon sphere network,providing abundant defect sites and a large specific surface area,which facilitates electron transfer and improves electrolyte wettability.Combined with the contribution of the ZnI2 additive,the Zn-S battery prepared with the precursor of a g-C_(3)N_(4)∶KB ratio of 3∶4 achieved an ultrahigh discharge capacity of 2069 mAh g^(-1) at a current density of 1 A/g.It also had an excellent rate performance(1257 mAh g^(-1) at 10 A/g)and a long cycling stability(705 mAh g^(-1) after 180 cycles at 5 A/g).This study provides a simple and effective strategy for improving the reduction kinetics of the sulfur cathode in Zn-S batteries and design-ing advanced cathode materials.
文摘Lithium-air batteries(LABs)are regarded as a next-generation energy storage option due to their relatively high energy density.The cyclic stability and lifespan of LABs are mainly influenced by the formation and decomposition of lithium-based oxides at the air cathode,which not only lead to a low cathode catalytic efficiency but also restrict the electrochemical reversibility and cause side reaction problems.Carbon materials are considered key to solving these problems due to their conductivity,functional flexibility,and adjustable pore structure.This paper considers the research progress on carbon materials as air cathode catalytic materials for LABs,focusing on their structural characteristics,electrochemical behavior,and reaction mechanisms.Besides being used as air cathodes,carbon materials also show potential for being used as protective layers for metal anodes or as anode materials for LABs.
文摘Lithium-ion capacitors(LICs)combine the high power dens-ity of electrical double-layer capacitors with the high energy density of lithium-ion batteries.However,they face practical limitations due to the narrow operating voltage window of their activated carbon(AC)cathodes.We report a scalable thermal treatment strategy to develop high-voltage-tolerant AC cathodes.Through controlled thermal treatment of commer-cial activated carbon(Raw-AC)under a H_(2)/Ar atmosphere at 400-800℃,the targeted reduction of degradation-prone functional groups can be achieved while preserving the critical pore structure and increasing graph-itic microcrystalline ordering.The AC treated at 400℃(HAC-400)had a significant increase in specific capacity(96.0 vs.75.1 mAh/g at 0.05 A/g)and better rate capability(61.1 vs.36.1 mAh/g at 5 A/g)in half-cell LICs,along with an 83.5%capacity retention over 7400 cycles within an extended voltage range of 2.0-4.2 V in full-cell LICs.Scalability was demonstrated by a 120 g batch production,enabling fabrication of pouch-type LICs with commercial hard carbon anodes that delivered a higher energy density of 28.3 Wh/kg at 1 C,and a peak power density of 12.1 kW/kg compared to devices using raw AC.This simple,industry-compatible approach may be used for producing ad-vanced cathode materials for practical high-performance LICs.
基金Key-Area Research and Development Program of Guangdong Province(2022B0111130004)National Natural Science Foundation of China(52272257)。
文摘As classical cathode materials of solid oxide fuel cell(SOFC),Fe-based perovskite materials are favored for their affordable price,low thermal expansion coefficient and high stability.In this study,B-site high-entropy perovskite oxide La_(0.7)Sr_(0.3)(FeNiCo)_(0.8)Mo_(0.1)Ti_(0.1)O_(3-δ)(LSFNCMT)was prepared by the citric acid-nitrate combustion method.Due to the faster oxygen surface exchange rate of the high-entropy material,the LSFNCMT cathode shows excellent oxygen reduction reaction(ORR)activity with a polarization impedance(Rp)of 0.11Ω·cm^(2) at 800℃,which is much lower than that of the La_(0.7)Sr_(0.3)FeO_(3-δ)(LSF)cathode(0.31Ω·cm^(2)).Furthermore,the high-entropy material exhibits superior stability due to incorporation of highly acidic Ni,Co,and Mo cations as well as Ti cation with more negative average bonding energy(ABE)of metal-oxygen.In the 22 h-stability test of the symmetric cell with LSFNCMT cathode in the Cr-containing atmosphere,Rp only increases from 1.07Ω·cm^(2) to 2.98Ω·cm^(2),while Rp of the LSF cathode increases from 2.62Ω·cm^(2) to 7.90Ω·cm^(2) under the same conditions,indicating better Cr-resistance of LSFNCMT due to the high-entropy strategy.The fact that the maximum power density(MPD)of the single cell with LSFNCMT cathode at 800℃is 1105.26 mW·cm^(-2),significantly higher than that of LSF cathode(830.74 mW·cm^(-2)),and Rp at 800℃is 0.24Ω·cm^(2),lower than that of LSF cathode(0.36Ω·cm^(2)),confirming excellent toxicity resistance of the high-entropy cathode.This study shows that B-position high entropy is an effective way to improve the catalytic activity and chromium resistance of cathode materials.
基金supported by the Significant Science and Technology Project in Xiamen(Future Industry Field)(Grant No.3502Z20231057).
文摘Lithium nickel oxide(Li_(2)NiO_(2)),as a sacrificial cathode prelithiation additive,has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries(LIBs).However,high-cost Li_(2)NiO_(2)suffers from inferior delithiation kinetics during the first cycle.Herein,we investigated the effects of the cost-effective copper substituted Li_(2)Ni_(1-x)Cu_(x)O_(2)(x=0,0.2,0.3,0.5,0.7)synthesized by a high-temperature solid-phase method on the structure,morphology,electrochemical performance of graphite‖LiFePO_(4)battery.The X-ray diffraction(XRD)refinement result demonstrated that Cu substitution strategy could be favorable for eliminating the NiO_(x)impurity phase and weakening Li-O bond.Analysis on density of states(DOS)indicates that Cu substitution is good for enhancing the electronic conductivity,as well as reducing the delithi-ation voltage polarization confirmed by electrochemical characterizations.Therefore,the optimal Li_(2)Ni_(0.7)Cu_(0.3)O_(2)delivered a high delithiation capacity of 437 mAh·g^(-1),around 8%above that of the pristine Li_(2)NiO_(2).Furthermore,a graphite‖LiFePO_(4)pouch cell with a nominal capacity of 3000 mAh demonstrated a notably improved reversible capacity,energy density and cycle life through introducing 2 wt%Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive,delivering a 6.2 mAh·g^(-1)higher initial discharge capacity and achieving around 5%improvement in capacity retentnion at 0.5P over 1000 cycles.Additionally,the post-mortem analyses testified that the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive could suppress solid electrolyte interphase(SEI)decomposition and homogenize the Li distribution,which benefits to stabilizing interface between graphite and electrolyte,and alleviating dendritic Li plating.In conclusion,the Li_(2)Ni_(0.7)Cu_(0.3)O_(2)additive may offer advantages such as lower cost,lower delithiation voltage and higher prelithiation capacity compared with Li_(2)NiO_(2),making it a promising candidate of cathode prelithiation additive for next-generation LIBs.
基金Project(2021H0028) supported by the Natural Scienceof Fujian Province,ChinaProject(JAT200455) supported by the Fujian Provincial Young and Middle-aged Teacher Education Project,ChinaProject(fma2023003) supported by the Open Fund of Fujian Provincial Key Laboratory of Functional Materials and Applications,China。
文摘Rich-nickel layered ternary NCM811 has been widely used in the field of electric vehicles ascribed to its high theoretical specific capacity.However,poor cycling stability and rate-performance hindered its further development.Herein,different amounts of nitrogen-doped carbon were wrapped on the surface of NCM811 via a facile rheological phase method by regulating the amount of dopamine hydrochloride.The effects of the coating amounts on the structure and electrochemical performance are investigated.The DFT calculation,XRD,SEM and XPS reveal that an appropriate amount of nitrogen-doped carbon coating could uniformly form a protective layer on the NCM811 surface and the introduced N could anchor Ni atoms to inhibit the Li^(+)/Ni^(2+)mixing,but excessive amount would reduce Ni^(3+)to Ni^(2+)so as to conversely aggravate Li^(+)/Ni^(2+)mixing.Among the samples,the NCM811-CN0.75 sample exhibits the most excellent electrochemical performance,delivering a high-rate capacity of 151.6 mA·h/g at 10C,and long-term cyclability with 82.2%capacity retention after 300 cycles at 5C,exhibiting remarkable rate-performance and cyclability.
文摘This study focuses on using a green reagent scheme of methanesulfonic acid (MSA) and citric acid (CA) to extract valuable metals from the cathodes, aiming to minimize environmental impact during the recycling process. Leaching studies on LiCoO_(2) identified optimal conditions as follows: 2.4 mol/L MSA, 1.6 mol/L CA, S/L ratio of 80 g/L, leaching temperature of 90oC and leaching time of 6 h. The maximum Co and Li extraction achieved was 92% and 85%, respectively. LiCoO_(2) dissolution in MSA-CA leaching solution is highly impacted by temperature;Avrami equation showed a good fitting for the leaching data. The experimental activation energy of Co and Li was 50.98 kJ/mol and 50.55 kJ/mol, respectively, indicating that it is a chemical reaction-controlled process. Furthermore, cobalt was efficiently recovered from the leachate using oxalic acid, achieving a precipitation efficiency of 99.91% and a high-purity cobalt oxalate product (99.85 wt.%). In the MSA-CA leaching solution, MSA served as a lixiviant, while CA played a key role in reducing Co in LiCoO_(2). The overall organic acid leaching methodology presents an attractive option due to its reduced environmental impact.
基金Project(23JCYBJC01870)supported by the Natural Science Foundation of Tianjin,ChinaProject(U22A20119)supported by the National Natural Science Foundation of China。
文摘As a cathode material for thermal batteries,NiS_(2)has a high theoretical capacity but low thermal stability.Besides,the poor formability of NiS_(2)powders also restricts the cathode performance of thermal batteries.In this paper,the novel NiS_(2)/SiO_(2)composite material was developed by high temperature vulcanization to improve the thermal stability formability of NiS_(2).The good filling and lubrication of spherical SiO_(2)can improve the thermal conductivity of NiS_(2)electrode.The discharge test shows that the NiS_(2)/SiO_(2)cathode has a stable discharge voltage at a current density of 200 mA/cm^(2),and the activation time is shortened by nearly 20%compared with the NiS_(2)cathode.In addition,due to the favorable thermal insulation protection of SiO_(2),the initial decomposition temperature of NiS_(2)is increased by 30℃after the addition of SiO_(2).The incorporation of SiO_(2)not only effectively improves the thermal stability and electrochemical properties of NiS_(2),but also improves the cold pressing forming performance of the NiS_(2)powder.Therefore,the novel NiS_(2)/SiO_(2)composite material is more suitable for thermal batteries with high stability and fast response,which is of great significance for improving the maneuverability and quality reliability of weapons and equipment.
文摘The effects of NOx(in a ratio of NO∶NO2=9∶1) and SO2in cathode streamonthe performance of a single proton ex-change membrane fuel cell(PEMFC) were investigated.NOxwith concentrations of 1×10-3%(in volume,the same as fol-lows),1.4×10-2%and 1×10-3%could cause significant detri mental effects on the cell performance.However,nearly com-plete recovery of the cell performance could be observed after NOxwas shut off and purged with clean air.The electrochemicalmeasurements suggested that thei mpacts of NOxresulted mainlyfromthe superposition of the oxygen reduction reaction(ORR),NOand HNO2oxidation reactions,and the increased cathodic i mpedance.Trace SO2with concentrations of 5×10-6%,5×10-3%,2×10-4%and 3.2×10-4%influenced the cell muchseverer,which could be attributed toits strong adsorption onthesurface of Pt atoms.The cell performance could not be completely recovered after purged with clean air and cyclic voltammetry(CV) tests,due to the changes of electrochemical i mpedance spectroscopy(EIS) and electrochemical active surface(EAS) causedby surface state change after SO2exposure.
基金Project(K1403375-11)supported by Science and Technology Planning Project of Changsha,ChinaProject(2015D009)supported by the Planned Science and Technology Project of Qingyuan City,ChinaProject(2015B04)supported by the Planned Science and Technology Project of Qingcheng District,Qingyuan City,China
文摘In the present investigation, electroless Ni-Cu-P/n-TiN composite coating was prepared using alkaline citrate-based bath. X-ray diffraction （XRD）, scanning electron microscopy（SEM）, energy-dispersive spectroscopy（EDS）, electrochemical measurements, weight loss tests and Raman spectrometer were used to character the properties of the coating. As the Cu content increased from 7.3 wt% to 24.8 wt%, the corrosion current density of the Ni-Cu-P/n-TiN coating decreased from 10.80 to 4.34 ~tA. And the inclusion of Cu in NiP alloy resulted in refinement and less porosity in microstructure. The addition of TiN resulted in a slight decline in anti-corrosion property of the coating. As the mass loss test showed, Ni-24.8%Cu-P exhibited perfect corrosion resistance. Studies by Raman spectroscopy on coatings proved that Cu（II）3（PO4）（OH）3, Cu（OH）2 and CuO were examined while no compound of nickel was found, and Cu exhibited preferred corrosion in saline solution, providing cathodic protection to Ni alloy.
基金Project (2005CB623703) supported by the Major State Basic Research and Development Program of ChinaProject (2008AA030502) supported by the National High-Tech Research and Development Program of China
文摘The electrolysis expansion of semigraphitic cathode in [K3AlF6/Na3AlF6]-AlF3-Al2O3 bath system was tested by self-made modified Rapoport apparatus. A mathematical model was introduced to discuss the effects of acR （cryolite ratio） and βKR （elpasolite content divided by the total amount of elpasolite and sodium cryolite） on performance of cathode electrolysis expansion. The results show that K and Na （potassium and sodium） penetrate into the cathode together and have an obvious influence on the performance of cathode electrolysis expansion. The electrolysis expansion and K/Na penetration rate increase with the increase of αCR. When αCR=1.9 and βKR=0.5, the electrolysis expansion is the highest, which is 3.95%; and when αCR=I.4 and βKR=0.1, the electrolysis expansion is the lowest, which is 1.28%. But the effect offlKR is correlative with αCR. When αCR=1.6 and 1.9, with the increase of titan, the electrolysis expansion and K/Na penetration rate increase. However, when αCR=l.4, the electrolysis expansion and K/Na penetration rate firstly increase and then decrease with the increase of βKR.
基金Project(2005CB623703) supported by the Major State Basic Research and Development Program of ChinaProject(2008AA030502) supported by the National High-Tech Research and Development Program of ChinaProject(GUIKEJI0639032) supported by the Science Fund Project of Guangxi Province, China
文摘The sodium expansion curves of semi-graphitic cathode measured with the improved Rapoport-Samoilenko apparatus. The and TiB2/C composite cathode with different TiB2 contents were mathematic model of the sodium expansion was deduced on the basis of the experimental results. The sodium expansion parameter （a） and penetration rate factor （Q）, were introduced into the model The model was validated with the experimental sodium expansion curves self-measured and reported. The results show that the variation tendency of the sodium expansion parameter （a） and penetration rate factor （Q） is consistent with that of the experimental curves. The model is capable of not only conveniently judging the cathode quality, but also favorably establishing a unified standard of the resistance to sodium penetration of cathode.
基金Project(50302016) supported by the National Natural Science Foundation of China
文摘A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.
