Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion...Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion O^(2-).In this work,the modified LATP with a series of LiCl(LATPClx,x=0.1,0.2,0.3,0.4)additives is prepared to enhance ionic conductivity.The successful introduction of Cl-makes the length of the c axis decrease from 20.822(2)to 20.792(1)Å,and the bulk conductivity of 2.13×10^(-3) S·cm^(-1) is achieved in LATPCl_(0.3).Moreover,the Al/Ti-O1/Cl1 and Al/Ti-O_(2)/Cl_(2) distance decrease,while the Li1-O_(2)/Cl_(2) distance increases.Lithium ions migrate more easily in the nanochannel of M3-M1-M3.In addition,the LiCl additive increases the relative density and the grain boundary conductivity of LATPClx compounds.Naturally,a higher ionic conductivity of 2.12×10^(–4) S·cm^(-1) and a low activation energy of 0.30 eV are obtained in LATPCl_(0.3).Correspondingly,the symmetric cell exhibits a low overpotential of±50 mV for over 200 h in LATPCl_(0.3).The solid-state Li|LATPCl_(0.3)|NCM811(NCM811=LiNi0.8Co0.1Mn0.1O_(2))battery exhibits high initial capacity 185.1 mAh·g^(-1) with a capacity retention rate of 95.4%after 100 cycles at 0.5 C.This result suggests that LiCl additive is an effective strategy to promote electrochemical properties of LATP solid electrolyte and can be considered for reference to other inorganic solid electrolytes systems.展开更多
The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP...The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP in high-energy density solid-state Li metal batteries.In this work,a multifunctional ferroelectric BaTiO_(3)(BTO)/poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene)(P[VDF-TrFE-CTFE])composite interlayer(B-TERB)is constructed between LATP and Li metal anode,which not only suppresses the Li dendrite growth,but also improves the interfacial stability and maintains the intimate interfacial contact to significantly decrease the interfacial resistance by two orders of magnitude.The B-TERB interlayer generates a uniform electric field to induce a uniform and lateral Li deposition,and therefore avoids the side reactions between Li metal and LATP achieving excellent interface stability.As a result,the Li/LATP@B-TERB/Li symmetrical batteries can stably cycle for 1800 h at 0.2 mA cm^(-2)and 1000 h at 0.5 mA cm^(-2).The solid-state LiFePO_(4)/LATP@B-TERB/Li full batteries also exhibit excellent cycle performance for 250 cycles at 0.5 C and room temperature.This work proposes a novel strategy to design multifunctional ferroelectric interlayer between ceramic electrolytes and Li metal to enable stable room-temperature cycling performance.展开更多
Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),of much interest owing to its high ionic conductivity,superior air stability,and low cost,has been regarded as one of the most promising solid-state electrolytes for next-gen...Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),of much interest owing to its high ionic conductivity,superior air stability,and low cost,has been regarded as one of the most promising solid-state electrolytes for next-generation solid-state lithium batteries(SSLBs).Unfortunately,the commercialization of SSLBs is still impeded by severe interfacial issues,such as high interfacial impedance and poor chemical stability.Herein,we proposed a simple and convenient in-situ approach to constructing a tight and robust interface between the Li anode and LATP electrolyte via a SnO_(2)gradient buffer layer.It is firmly attached to the surface of LATP pellets due to the volume expansion of SnO_(2)when in-situ reacting with Li metal,and thus effectively alleviates the physical contact loosening during cycling,as confirmed by the mitigated impedance rising.Meanwhile,the as-formed SnO_(2)/Sn/LixSn gradient buffer layer with low electronic conductivity successfully protects the LATP electrolyte surface from erosion by the Li metal anode.Additionally,the LixSn alloy formed at the Li surface can effectively regulate uniform lithium deposition and suppress Li dendrite growth.Therefore,this work paves a new way to simultaneously address the chemical instability and poor physical contact of LATP with Li metal in developing low-cost and highly stable SSLBs.展开更多
Poly(vinylidenefluoride-co-hexafluoropropylene)(P(VDF-HFP))/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)/P(VDFHFP) sandwiched hybrid solid electrolytes were precisely tailored and successfully fabricated to assemble int...Poly(vinylidenefluoride-co-hexafluoropropylene)(P(VDF-HFP))/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)/P(VDFHFP) sandwiched hybrid solid electrolytes were precisely tailored and successfully fabricated to assemble into allsolid-state lithium-ion batteries,which were systematically evaluated on microstructure,morphology,thermal stability and electrochemical performance.The sandwiched hybrid solid electrolytes can achieve intimate contact with cathode and anode electrodes to present an excellent interfacial stability.Furthermore,the sandwiched hybrid solid electrolytes possess flexible surface,wide electrochemical working window of 4.7 V,high ionic conductivity of 0.763 mS·cm^(-1) and high thermal stability of 460℃,which may contribute to realizing the practical application in all-solid-state lithium-ion batteries.The assembled cells with the hybrid solid electrolytes can quickly stabilize at a specific discharge capacity of 145.4 mAh·g^(-1) at 0.1 C after only 5 cycles and present admirable rate performance.In addition,morphology characterizations of the sandwiched hybrid solid electrolytes after long-term cycles show a relatively integrated structure coating with a compact LATP layer.The investigations afford a promising strategy that the sandwiched hybrid solid electrolytes can overcome the mechanical limitations of the interface between electrodes and inorganic solid electrolytes to provide favorable properties for all-solid-state lithium-ion batteries.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.51772239,51972262 and 22005186)the 111 Project(No.B14040).
文摘Nowadays,the majority of the studies on the substitution are focused on cations(such as Y^(3+),Ti^(4+),P^(5+),etc.)in Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),while there are few studies on the substitution of anion O^(2-).In this work,the modified LATP with a series of LiCl(LATPClx,x=0.1,0.2,0.3,0.4)additives is prepared to enhance ionic conductivity.The successful introduction of Cl-makes the length of the c axis decrease from 20.822(2)to 20.792(1)Å,and the bulk conductivity of 2.13×10^(-3) S·cm^(-1) is achieved in LATPCl_(0.3).Moreover,the Al/Ti-O1/Cl1 and Al/Ti-O_(2)/Cl_(2) distance decrease,while the Li1-O_(2)/Cl_(2) distance increases.Lithium ions migrate more easily in the nanochannel of M3-M1-M3.In addition,the LiCl additive increases the relative density and the grain boundary conductivity of LATPClx compounds.Naturally,a higher ionic conductivity of 2.12×10^(–4) S·cm^(-1) and a low activation energy of 0.30 eV are obtained in LATPCl_(0.3).Correspondingly,the symmetric cell exhibits a low overpotential of±50 mV for over 200 h in LATPCl_(0.3).The solid-state Li|LATPCl_(0.3)|NCM811(NCM811=LiNi0.8Co0.1Mn0.1O_(2))battery exhibits high initial capacity 185.1 mAh·g^(-1) with a capacity retention rate of 95.4%after 100 cycles at 0.5 C.This result suggests that LiCl additive is an effective strategy to promote electrochemical properties of LATP solid electrolyte and can be considered for reference to other inorganic solid electrolytes systems.
基金supported by National Natural Science Foundation of China(No.U2001220)Local Innovative Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01N111)+1 种基金Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center(XMHT20200203006)Shenzhen Technical Plan Project(Nos.RCJC20200714114436091,JCYJ20180508152210821,and JCYJ20180508152135822).
文摘The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP in high-energy density solid-state Li metal batteries.In this work,a multifunctional ferroelectric BaTiO_(3)(BTO)/poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene)(P[VDF-TrFE-CTFE])composite interlayer(B-TERB)is constructed between LATP and Li metal anode,which not only suppresses the Li dendrite growth,but also improves the interfacial stability and maintains the intimate interfacial contact to significantly decrease the interfacial resistance by two orders of magnitude.The B-TERB interlayer generates a uniform electric field to induce a uniform and lateral Li deposition,and therefore avoids the side reactions between Li metal and LATP achieving excellent interface stability.As a result,the Li/LATP@B-TERB/Li symmetrical batteries can stably cycle for 1800 h at 0.2 mA cm^(-2)and 1000 h at 0.5 mA cm^(-2).The solid-state LiFePO_(4)/LATP@B-TERB/Li full batteries also exhibit excellent cycle performance for 250 cycles at 0.5 C and room temperature.This work proposes a novel strategy to design multifunctional ferroelectric interlayer between ceramic electrolytes and Li metal to enable stable room-temperature cycling performance.
基金financially supported by the China Postdoctoral Science Foundation(2021M700396)the National Natural Science Foundation of China(52102206)the research grants from the National Research Foundation(2022K1A3A1A20014496 and 2022R1F1A1074707)funded by the government of the Republic of Korea。
文摘Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP),of much interest owing to its high ionic conductivity,superior air stability,and low cost,has been regarded as one of the most promising solid-state electrolytes for next-generation solid-state lithium batteries(SSLBs).Unfortunately,the commercialization of SSLBs is still impeded by severe interfacial issues,such as high interfacial impedance and poor chemical stability.Herein,we proposed a simple and convenient in-situ approach to constructing a tight and robust interface between the Li anode and LATP electrolyte via a SnO_(2)gradient buffer layer.It is firmly attached to the surface of LATP pellets due to the volume expansion of SnO_(2)when in-situ reacting with Li metal,and thus effectively alleviates the physical contact loosening during cycling,as confirmed by the mitigated impedance rising.Meanwhile,the as-formed SnO_(2)/Sn/LixSn gradient buffer layer with low electronic conductivity successfully protects the LATP electrolyte surface from erosion by the Li metal anode.Additionally,the LixSn alloy formed at the Li surface can effectively regulate uniform lithium deposition and suppress Li dendrite growth.Therefore,this work paves a new way to simultaneously address the chemical instability and poor physical contact of LATP with Li metal in developing low-cost and highly stable SSLBs.
基金financially supported by the National Natural Science Foundation of China (Nos.51874046 and 51404038)the Outstanding Youth Foundation of Hubei Province (No.2020CFA090)。
文摘Poly(vinylidenefluoride-co-hexafluoropropylene)(P(VDF-HFP))/Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)/P(VDFHFP) sandwiched hybrid solid electrolytes were precisely tailored and successfully fabricated to assemble into allsolid-state lithium-ion batteries,which were systematically evaluated on microstructure,morphology,thermal stability and electrochemical performance.The sandwiched hybrid solid electrolytes can achieve intimate contact with cathode and anode electrodes to present an excellent interfacial stability.Furthermore,the sandwiched hybrid solid electrolytes possess flexible surface,wide electrochemical working window of 4.7 V,high ionic conductivity of 0.763 mS·cm^(-1) and high thermal stability of 460℃,which may contribute to realizing the practical application in all-solid-state lithium-ion batteries.The assembled cells with the hybrid solid electrolytes can quickly stabilize at a specific discharge capacity of 145.4 mAh·g^(-1) at 0.1 C after only 5 cycles and present admirable rate performance.In addition,morphology characterizations of the sandwiched hybrid solid electrolytes after long-term cycles show a relatively integrated structure coating with a compact LATP layer.The investigations afford a promising strategy that the sandwiched hybrid solid electrolytes can overcome the mechanical limitations of the interface between electrodes and inorganic solid electrolytes to provide favorable properties for all-solid-state lithium-ion batteries.
