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
Extending the charging voltage of LiCoO_(2)(LCO)is an ongoing and promising approach to increase its energy density.However,the main challenge of the approach lies in the insuperable cathodic interfacial processes at ...Extending the charging voltage of LiCoO_(2)(LCO)is an ongoing and promising approach to increase its energy density.However,the main challenge of the approach lies in the insuperable cathodic interfacial processes at high voltage,which leads to rapid failure both in the performance and structure of the LCO cathode.Herein,a Li_(2)CO_(3)-based additive was prepared by a simple sand-milling method,enabling a low electrochemical decomposition voltage<4.6 V from commonly>4.8 V,stabilizing the interface of the LCO cathode at 4.6 V.The decomposition of Li_(2)CO_(3)provides extra Li^(+)and CO_(2)to supplement the Li consumption required in the initial irreversible interfacial reactions and rapidly form a uniform and stable cathode electrolyte interphase layer(less organic and more inorganic components)on the LCO cathode by reducing CO_(2).Thus,the phase transformation and the emergence of high-valent Co ions on the surface of LCO at 4.6 V high voltage were inhibited.Thanks to this,with 2%Li_(2)CO_(3)-based additive,the capacity retention of commercial LCO at a high voltage of 4.6 V at 0.5 C for 100 cycles was improved from 59.3%to 79.3%.This work improves the high-voltage stability of LCO and provides a new idea for realizing the high-voltage operation of batteries.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits t...Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries.Herein,a uniform,sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate(NaPVS).The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(3)(NVP)|PEOsodium hexauorophosphate(NaPF6)|Na battery shows a higher initial capacity of 111.2 mAh.g^(-1)and an ultra-high capacity retention of 90.5%after 300 cycles.The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)|PEO-NaPF_(6)|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh.g^(-1)at 0.5C for 100 cycles with a capacity retention of 79%,which is much better than that of the pristine-NVPF(PR-NVPF)|PEO-NaPF_(6)|Na battery(33.2%).The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery,thus bolstering its viability for high-energy applications.In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature.This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.展开更多
Lithium/Sodium-ion batteries(LIB/SIB)have attracted enormous attention as a promising electrochemical energy storage system due to their high energy density and long cycle life.One of the major hurdles is the initial ...Lithium/Sodium-ion batteries(LIB/SIB)have attracted enormous attention as a promising electrochemical energy storage system due to their high energy density and long cycle life.One of the major hurdles is the initial irreversible capacity loss during the first few cycles owing to forming the solid electrolyte interphase layer(SEI).This process consumes a profusion of lithium/sodium,which reduces the overall energy density and cycle life.Thus,a suitable approach to compensate for the irreversible capacity loss must be developed to improve the energy density and cycle life.Pre-lithiation/sodiation is a widely accepted process to compensate for the irreversible capacity loss during the initial cycles.Various strategies such as physical,chemical,and electrochemical pre-lithiation/sodiation have been explored;however,these approaches add an extra step to the current manufacturing process.Alternative to these strategies,pre-lithiation/sodiation additives have attracted enormous attention due to their easy adaptability and compatibility with the current battery manufacturing process.In this review,we consolidate recent developments and emphasize the importance of using pre-lithiation/sodiation additives(anode and cathode)to overcome the irreversible capacity loss during the initial cycles in lithium/sodium-ion batteries.This review also addresses the technical and scientific challenges of using pre-lithiation/sodiation additives and offers the insights to boost the energy density and cycle life with their possible commercial exploration.The most important prerequisites for designing effective pre-lithiation/sodiation additives have been explored and the future directions have been discussed.展开更多
Li_(2)C_(2)O_(4),with a high theoretical capacity of 525 mAh·g^(−1)and good air stability,is regarded as a more attractive cathode prelithiation additive in contrast to the reported typical inorganic pre-lithiati...Li_(2)C_(2)O_(4),with a high theoretical capacity of 525 mAh·g^(−1)and good air stability,is regarded as a more attractive cathode prelithiation additive in contrast to the reported typical inorganic pre-lithiation compounds which are quite air sensitive.However,its obtained capacity is much lower than the theoretical value and its delithiation potential(>4.7 V)is too high to match with the most commercial cathode materials,which greatly impedes its practical application.Herein,we greatly improve the pre-lithiation performance of Li_(2)C_(2)O_(4)as cathode additive with fulfilled capacity at a much-reduced delithiation voltage,enabling its wide applicability for typical commercial cathodes.We increase the capacity of Li_(2)C_(2)O_(4)from 436 to 525 mAh·g^(−1)by reducing its particle size.Through optimizing the types of conductive additives,introducing nano-morphological NiO,MnO2,etc.as catalysts,and innovatively designing a bilayer electrode,the delithiation potential of Li_(2)C_(2)O_(4)is successfully reduced from 4.778 to 4.288 V.We systematically study different particle size,conductive additives,and catalysts on the delithiation behavior of Li_(2)C_(2)O_(4).Finally,it is applied to pre-lithiate the hard carbon anode,and it is found that Li_(2)C_(2)O_(4)could effectively increase the capacity of the full cell from 79.0 to 140.0 mAh·g^(−1)in the first cycle.In conclusion,our study proves that improving the reactivity is an effective strategy to boost the pre-lithiation of Li_(2)C_(2)O_(4).展开更多
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supported by the National Key Research and Development Program of China(2022YFB2502103)the Xiamen Science and Technology Project(No.3502Z20231057)+2 种基金the National Natural Science Foundation of China(No.22288102,No.22279107,No.22309153)the Fujian Provincial Natural Science Foundation of China(No.2024J01040)the Fundamental Research Funds for the Central Universities(No.20720230039)。
文摘Extending the charging voltage of LiCoO_(2)(LCO)is an ongoing and promising approach to increase its energy density.However,the main challenge of the approach lies in the insuperable cathodic interfacial processes at high voltage,which leads to rapid failure both in the performance and structure of the LCO cathode.Herein,a Li_(2)CO_(3)-based additive was prepared by a simple sand-milling method,enabling a low electrochemical decomposition voltage<4.6 V from commonly>4.8 V,stabilizing the interface of the LCO cathode at 4.6 V.The decomposition of Li_(2)CO_(3)provides extra Li^(+)and CO_(2)to supplement the Li consumption required in the initial irreversible interfacial reactions and rapidly form a uniform and stable cathode electrolyte interphase layer(less organic and more inorganic components)on the LCO cathode by reducing CO_(2).Thus,the phase transformation and the emergence of high-valent Co ions on the surface of LCO at 4.6 V high voltage were inhibited.Thanks to this,with 2%Li_(2)CO_(3)-based additive,the capacity retention of commercial LCO at a high voltage of 4.6 V at 0.5 C for 100 cycles was improved from 59.3%to 79.3%.This work improves the high-voltage stability of LCO and provides a new idea for realizing the high-voltage operation of batteries.
基金supported by the Natural Science Foundation of China(No.22109079)the Natural Science Foundation of China(No.21973008)+2 种基金the Natural Science Foundation of China(No.22179010)the National Key R&D Program of China(No.2021YFB2400200)Taishan Scholars of Shandong Province(No.tsqnz20231212)。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries.Herein,a uniform,sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate(NaPVS).The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(3)(NVP)|PEOsodium hexauorophosphate(NaPF6)|Na battery shows a higher initial capacity of 111.2 mAh.g^(-1)and an ultra-high capacity retention of 90.5%after 300 cycles.The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)|PEO-NaPF_(6)|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh.g^(-1)at 0.5C for 100 cycles with a capacity retention of 79%,which is much better than that of the pristine-NVPF(PR-NVPF)|PEO-NaPF_(6)|Na battery(33.2%).The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery,thus bolstering its viability for high-energy applications.In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature.This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.
基金the support of the Deputyship for Research and Innovation-Ministry of Education,Kingdom of Saudi Arabia,for this research through a grant(NU/IFC/INT/01/002)under the Institutional Funding Committee at Najran University,Kingdom of Saudi Arabiathe support from the National Research Foundation of Korea(NRF)funded by the Brain Pool program(2021H1D3A2A02039346)。
文摘Lithium/Sodium-ion batteries(LIB/SIB)have attracted enormous attention as a promising electrochemical energy storage system due to their high energy density and long cycle life.One of the major hurdles is the initial irreversible capacity loss during the first few cycles owing to forming the solid electrolyte interphase layer(SEI).This process consumes a profusion of lithium/sodium,which reduces the overall energy density and cycle life.Thus,a suitable approach to compensate for the irreversible capacity loss must be developed to improve the energy density and cycle life.Pre-lithiation/sodiation is a widely accepted process to compensate for the irreversible capacity loss during the initial cycles.Various strategies such as physical,chemical,and electrochemical pre-lithiation/sodiation have been explored;however,these approaches add an extra step to the current manufacturing process.Alternative to these strategies,pre-lithiation/sodiation additives have attracted enormous attention due to their easy adaptability and compatibility with the current battery manufacturing process.In this review,we consolidate recent developments and emphasize the importance of using pre-lithiation/sodiation additives(anode and cathode)to overcome the irreversible capacity loss during the initial cycles in lithium/sodium-ion batteries.This review also addresses the technical and scientific challenges of using pre-lithiation/sodiation additives and offers the insights to boost the energy density and cycle life with their possible commercial exploration.The most important prerequisites for designing effective pre-lithiation/sodiation additives have been explored and the future directions have been discussed.
基金the financial support provided by the National Natural Science Foundation of China(No.52072138)the National Key Research and Development Program of China(No.2018YFE0206900)+1 种基金the Shenzhen Science and Technology Program(No.JCYJ20220530160816038)the Australian Research Council(ARC)through the Discovery Project(No.DP180102297).
文摘Li_(2)C_(2)O_(4),with a high theoretical capacity of 525 mAh·g^(−1)and good air stability,is regarded as a more attractive cathode prelithiation additive in contrast to the reported typical inorganic pre-lithiation compounds which are quite air sensitive.However,its obtained capacity is much lower than the theoretical value and its delithiation potential(>4.7 V)is too high to match with the most commercial cathode materials,which greatly impedes its practical application.Herein,we greatly improve the pre-lithiation performance of Li_(2)C_(2)O_(4)as cathode additive with fulfilled capacity at a much-reduced delithiation voltage,enabling its wide applicability for typical commercial cathodes.We increase the capacity of Li_(2)C_(2)O_(4)from 436 to 525 mAh·g^(−1)by reducing its particle size.Through optimizing the types of conductive additives,introducing nano-morphological NiO,MnO2,etc.as catalysts,and innovatively designing a bilayer electrode,the delithiation potential of Li_(2)C_(2)O_(4)is successfully reduced from 4.778 to 4.288 V.We systematically study different particle size,conductive additives,and catalysts on the delithiation behavior of Li_(2)C_(2)O_(4).Finally,it is applied to pre-lithiate the hard carbon anode,and it is found that Li_(2)C_(2)O_(4)could effectively increase the capacity of the full cell from 79.0 to 140.0 mAh·g^(−1)in the first cycle.In conclusion,our study proves that improving the reactivity is an effective strategy to boost the pre-lithiation of Li_(2)C_(2)O_(4).
