LiMn_(y)Fe_(1-y)PO_(4) is considered a promising cathode material for next-generation lithium-ion batteries(LIBs) due to its high energy density and low cost. Its energy density degradation is often ascribed to the ca...LiMn_(y)Fe_(1-y)PO_(4) is considered a promising cathode material for next-generation lithium-ion batteries(LIBs) due to its high energy density and low cost. Its energy density degradation is often ascribed to the capacity loss during cycling. However, in this study, we find that the energy density degradation mainly roots in voltage decay. We have synthesized a series of LiMn_(y)Fe_(1-y)PO_(4) /C(0.5 ≤ y ≤ 0.8) and find this voltage decay is correlated with the Mn content. A high amount Mn leads to a heavier voltage decay.In-situ X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM) reveal the nature of this effect, which show a mismatch along the b-axis of-2.68%(charge) and +3.4%(discharge), a volume misfit of-4.41%(charge) and +4.54%(discharge) between Li_(x)Mn_(y)Fe_(1-y)PO_(4) and Mn_(y)Fe_(1-y)PO_(4) during phase transitions. The resultant misfit strains during Li+insertion compared to extraction result in structural degradations, such as amorphization and impurity(Mn F3) accumulation after cycling. The voltage decay can be alleviated by kinetic relaxations and recovered by a wild reannealing. This work demonstrates effective strategies to improve the energy density and cycling performance of LiMn_(y)Fe_(1-y)PO_(4) /C,providing good references for other LIB cathodes, such as the Li-rich cathodes.展开更多
Current methodologies used for the inference of thin film stress through curvature measurements are strictly restricted to stress and curvature states which are assumed to remain uniform over the entire film/substrate...Current methodologies used for the inference of thin film stress through curvature measurements are strictly restricted to stress and curvature states which are assumed to remain uniform over the entire film/substrate system. By considering a circular thin film/substrate system subject to non-uniform, but axisymmetric misfit strain distributions in the thin film, we derived relations between the film stresses and the misfit strain, and between the plate system＇s curvatures and the misfit strain. These relations feature a “local” part which involves a direct dependence of the stress or curvature components on the misfit strain at the same point, and a “non-local” part which reflects the effect of misfit strain of other points on the location of scrutiny. Most notably, we also derived relations between the polar components of the film stress and those of system curvatures which allow for the experimental inference of such stresses from full-field curvature measurements in the presence of arbitrary radial non-uniformities. These relations also feature a “non-local” dependence on curvatures making a full-field measurement a necessity. Finally, it is shown that the interfacial shear tractions between the film and the substrate are proportional to the radial gradients of the first curvature invariant and can also be inferred experimentally.展开更多
High quality strain-relaxed thin SiGe virtual substrates have been achieved by combining the misfit strain technique and the point defect technique. The point defects were first injected into the coherently strained S...High quality strain-relaxed thin SiGe virtual substrates have been achieved by combining the misfit strain technique and the point defect technique. The point defects were first injected into the coherently strained SiGe layer through the ＂inserted Si layer＂ by argon ion implantation. After thermal annealing, an in- termediate SiGe layer was grown with a strained Si cap layer. The inserted Si layer in the SiGe film serves as the source of the misfit strain and prevents the threading dislocations from propagating into the next epitaxial layer. A strained-SilSiGelinserted-SilSiGe heterostructure was achieved with a threading dislocation density of 1×10^4 cm-2 and a root mean square surface roughness of 0.87 nm. This combined method can effectively fabricate device-quality SiGe virtual substrates with a low threading dislocation density and a smooth surface.展开更多
A theoretical model was suggested which describes the generation of the misfit dislocation dipole in the system of the viscoelastic matrix containing a circular stiff nanoscale inhomogeneity.The critical condition of ...A theoretical model was suggested which describes the generation of the misfit dislocation dipole in the system of the viscoelastic matrix containing a circular stiff nanoscale inhomogeneity.The critical condition of misfit dislocation dipole and the solution of equilibrium position were given.The influence of the ratio of shear modulus,the misfit strain and viscosity on the equilibrium of the dislocation and critical parameter of inhomogeneity was investigated.The result shows that the equilibrium position de increases with the increase of the ratio of original shear modulus and the effect decreases with the increase of viscosity of matrix.Along with the increase of viscosity of matrix,de first increases and then decreases and possesses maximum value when t=0.3τ and tends to a stable value when t≥1.0τ.Along with the increase of viscosity of matrix,Rc first decreases and then increases and possesses minimum value when t=0.3τ and tends to a stable value when t≥1.0τ.展开更多
Many distinguished properties of epitaxial ferroelectric thin films can be tunable through the misfit strain.The strain tunability of ferroelectric and dielectric properties in epitaxial lead titanate ultrathin films ...Many distinguished properties of epitaxial ferroelectric thin films can be tunable through the misfit strain.The strain tunability of ferroelectric and dielectric properties in epitaxial lead titanate ultrathin films is numerically investigated by using a phase field model,in which the surface effect of polarization is taken into account.The response of polarization to the applied electric field in the thickness direction is examined with different misfit strains at room temperature.It is found that a compressive misfit strain increases the coercive field and the remanent polarization while a tensile misfit strain decreases both of them.The nonlinear dielectric constants of the thin films with tensile misfit strains are much larger than those of the thin films without misfit strains,which are attributed to the existence of the a/c/a/c multiple domains in the thin films under tensile misfit strains.展开更多
The crystallography and morphology of precipitates in different systems were rationalized based on the optimum matching conditions. The interfaces that obey these conditions were conveniently identified in reciprocal ...The crystallography and morphology of precipitates in different systems were rationalized based on the optimum matching conditions. The interfaces that obey these conditions were conveniently identified in reciprocal space,in terms of three △g's parallelism rules. The theoretic basis of the O-lattice and CSL/DSC theory for these rules was provided briefly. Examples of small lattice misfit system(a Ti alloy),and large lattice misfit systems(Al and Mg alloys) were presented. The effect of lattice parameters on the orientation relationship and morphology was also discussed.展开更多
Assuming that the lithiation reaction occurs randomly in individual small particles in the vicinity of the reaction front, a simple model of diffusion- induced dislocations was developed. The diffusion-induced disloca...Assuming that the lithiation reaction occurs randomly in individual small particles in the vicinity of the reaction front, a simple model of diffusion- induced dislocations was developed. The diffusion-induced dislocations are con- trolled by the misfit strain created by the diffusion of solute atoms or the phase transformation in the vicinity of the reaction front. The dislocation density is proportional to the total surface area of the ＂lithiated particle＂ and inversely pro- portional to the particle volume. The diffusion-induced dislocations relieve the diffusion-induced stresses.展开更多
基金supported by the 21C Innovation Laboratory,Contemporary Amperex Technology Ltd. by project No. 21C-OP-202103the National Natural Science Foundation of China(52072061)。
文摘LiMn_(y)Fe_(1-y)PO_(4) is considered a promising cathode material for next-generation lithium-ion batteries(LIBs) due to its high energy density and low cost. Its energy density degradation is often ascribed to the capacity loss during cycling. However, in this study, we find that the energy density degradation mainly roots in voltage decay. We have synthesized a series of LiMn_(y)Fe_(1-y)PO_(4) /C(0.5 ≤ y ≤ 0.8) and find this voltage decay is correlated with the Mn content. A high amount Mn leads to a heavier voltage decay.In-situ X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM) reveal the nature of this effect, which show a mismatch along the b-axis of-2.68%(charge) and +3.4%(discharge), a volume misfit of-4.41%(charge) and +4.54%(discharge) between Li_(x)Mn_(y)Fe_(1-y)PO_(4) and Mn_(y)Fe_(1-y)PO_(4) during phase transitions. The resultant misfit strains during Li+insertion compared to extraction result in structural degradations, such as amorphization and impurity(Mn F3) accumulation after cycling. The voltage decay can be alleviated by kinetic relaxations and recovered by a wild reannealing. This work demonstrates effective strategies to improve the energy density and cycling performance of LiMn_(y)Fe_(1-y)PO_(4) /C,providing good references for other LIB cathodes, such as the Li-rich cathodes.
文摘Current methodologies used for the inference of thin film stress through curvature measurements are strictly restricted to stress and curvature states which are assumed to remain uniform over the entire film/substrate system. By considering a circular thin film/substrate system subject to non-uniform, but axisymmetric misfit strain distributions in the thin film, we derived relations between the film stresses and the misfit strain, and between the plate system＇s curvatures and the misfit strain. These relations feature a “local” part which involves a direct dependence of the stress or curvature components on the misfit strain at the same point, and a “non-local” part which reflects the effect of misfit strain of other points on the location of scrutiny. Most notably, we also derived relations between the polar components of the film stress and those of system curvatures which allow for the experimental inference of such stresses from full-field curvature measurements in the presence of arbitrary radial non-uniformities. These relations also feature a “non-local” dependence on curvatures making a full-field measurement a necessity. Finally, it is shown that the interfacial shear tractions between the film and the substrate are proportional to the radial gradients of the first curvature invariant and can also be inferred experimentally.
基金Supported by the National Natural Science Foundation of China(Nos. 60476017 and 60636010)the Basic Research Foundation of Tsinghua National Laboratory for Information Science andTechnology (TNList)
文摘High quality strain-relaxed thin SiGe virtual substrates have been achieved by combining the misfit strain technique and the point defect technique. The point defects were first injected into the coherently strained SiGe layer through the ＂inserted Si layer＂ by argon ion implantation. After thermal annealing, an in- termediate SiGe layer was grown with a strained Si cap layer. The inserted Si layer in the SiGe film serves as the source of the misfit strain and prevents the threading dislocations from propagating into the next epitaxial layer. A strained-SilSiGelinserted-SilSiGe heterostructure was achieved with a threading dislocation density of 1×10^4 cm-2 and a root mean square surface roughness of 0.87 nm. This combined method can effectively fabricate device-quality SiGe virtual substrates with a low threading dislocation density and a smooth surface.
基金Project(10472030) supported by the National Natural Science Foundation of China
文摘A theoretical model was suggested which describes the generation of the misfit dislocation dipole in the system of the viscoelastic matrix containing a circular stiff nanoscale inhomogeneity.The critical condition of misfit dislocation dipole and the solution of equilibrium position were given.The influence of the ratio of shear modulus,the misfit strain and viscosity on the equilibrium of the dislocation and critical parameter of inhomogeneity was investigated.The result shows that the equilibrium position de increases with the increase of the ratio of original shear modulus and the effect decreases with the increase of viscosity of matrix.Along with the increase of viscosity of matrix,de first increases and then decreases and possesses maximum value when t=0.3τ and tends to a stable value when t≥1.0τ.Along with the increase of viscosity of matrix,Rc first decreases and then increases and possesses minimum value when t=0.3τ and tends to a stable value when t≥1.0τ.
基金the financial support from the National Nature Science Foundation of China (Grants Nos.11002123 and 10832009)Zhejiang Provincial Qianjiang Talent Fund(E9027)Key Innovation Fund(2009R50025)
文摘Many distinguished properties of epitaxial ferroelectric thin films can be tunable through the misfit strain.The strain tunability of ferroelectric and dielectric properties in epitaxial lead titanate ultrathin films is numerically investigated by using a phase field model,in which the surface effect of polarization is taken into account.The response of polarization to the applied electric field in the thickness direction is examined with different misfit strains at room temperature.It is found that a compressive misfit strain increases the coercive field and the remanent polarization while a tensile misfit strain decreases both of them.The nonlinear dielectric constants of the thin films with tensile misfit strains are much larger than those of the thin films without misfit strains,which are attributed to the existence of the a/c/a/c multiple domains in the thin films under tensile misfit strains.
基金Projects(59871021, 50271035, 50471012) supported by the National Natural Science Foundation of China.
文摘The crystallography and morphology of precipitates in different systems were rationalized based on the optimum matching conditions. The interfaces that obey these conditions were conveniently identified in reciprocal space,in terms of three △g's parallelism rules. The theoretic basis of the O-lattice and CSL/DSC theory for these rules was provided briefly. Examples of small lattice misfit system(a Ti alloy),and large lattice misfit systems(Al and Mg alloys) were presented. The effect of lattice parameters on the orientation relationship and morphology was also discussed.
文摘Assuming that the lithiation reaction occurs randomly in individual small particles in the vicinity of the reaction front, a simple model of diffusion- induced dislocations was developed. The diffusion-induced dislocations are con- trolled by the misfit strain created by the diffusion of solute atoms or the phase transformation in the vicinity of the reaction front. The dislocation density is proportional to the total surface area of the ＂lithiated particle＂ and inversely pro- portional to the particle volume. The diffusion-induced dislocations relieve the diffusion-induced stresses.
