CN108845214B - Method for analyzing performance of resistance valve plate in zinc oxide arrester - Google Patents
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- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
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Abstract
The invention discloses a method for analyzing the performance of a resistance valve plate in a zinc oxide arrester, which adopts a first principle and utilizes a computer to construct a two-phase crystal boundary structure of a ZnO resistance valve plate; adopting a CAStep software package to optimize the structure of the unit cell; carrying out relaxation calculation on the established crystal boundary structure, comparing the crystal boundary structure before and after relaxation, and analyzing atomic displacement; performing secondary differential charge density analysis and atomic electron population analysis on the relaxed crystal boundary structure; and carrying out electron potential energy analysis and interface atom wave-splitting state density analysis on the grain boundary structure. Compared with an experimental measurement method, the invention researches the microstructure existing in the ZnO resistance valve plate, analyzes the built-in electric field of a crystal boundary structure, determines the electric charge quantity of an electron orbit of interface atoms, analyzes the bonding condition of atoms in a layer, and has important significance for improving the nonlinear volt-ampere characteristic of materials and developing high-performance zinc oxide arresters.
Description
Technical Field
The invention belongs to the field of lightning arrester characteristic research, and particularly relates to a method for analyzing the performance of a resistance valve plate in a zinc oxide lightning arrester.
Background
The basic structure of the metal zinc oxide lightning arrester is a valve plate, the valve plate takes zinc oxide as a main material, and a small amount of other metal oxides are added to the zinc oxide lightning arrester to be calcined at high temperature. Under normal working voltage, the valve plate passes through a small resistive current which is generally about 10-15 muA and is close to an insulation state. When the lightning overvoltage is applied to the lightning arrester, the resistance of the lightning arrester is rapidly reduced, the passing current is large, the residual voltage is small, the equipment is protected, and when the overvoltage disappears, the resistance valve plate of the lightning arrester returns to a high-resistance state. Because the metal zinc oxide arrester has excellent nonlinear volt-ampere characteristics, the metal zinc oxide arrester has wide application as the most basic protective equipment in a power system.
At present, the research on the zinc oxide resistance valve plate of the lightning arrester mainly adopts an experimental method of electronic probe measurement, has large limitation, and cannot deeply analyze the performance of the zinc oxide resistance valve plate of the lightning arrester from a micro molecular layer surface.
The first principle is that according to the principle of interaction between atomic nucleus and electron and the basic motion law thereof, the quantum mechanics principle is applied, and from specific requirements, the algorithm of the Schrodinger equation is directly solved after some approximate treatment, so that the physical and chemical properties of the material can be calculated only under the condition of giving atomic coordinates and element types without depending on experimental parameters. The CAStep (Cambridge Serial Total Energy Package) software package is a head-to-head computation quantum mechanics program based on the density functional theory, utilizes the Total Energy plane wave pseudopotential method to replace the ion potential with pseudopotential, the electronic wave function is developed by plane wave basis group, the exchange of the electronic-electronic interaction and the related potential are corrected by local-intensity approximation (LDA) or Generalized Gradient Approximation (GGA), and is a current more accurate electronic structure computation program.
Therefore, by adopting a first principle, the grain boundary structure of the zinc oxide resistance valve plate of the lightning arrester is researched from a micro molecular level.
Disclosure of Invention
The invention aims to solve the problems and provides a method for analyzing the performance of a zinc oxide resistor valve plate in a zinc oxide arrester.
The technical scheme of the invention is a method for analyzing the performance of a resistance valve plate in a zinc oxide arrester, which comprises the following steps,
step 1: constructing a two-phase grain boundary structure of the ZnO resistance valve plate by using a computer;
step 1.1 construction of ZnO/Bi2O3A two-phase grain boundary structure;
step 1.2, carrying out structure optimization on the unit cell;
step 1.3, determining exchange and relevant potential, and solving a Kohn-Sham equation in a self-consistent manner;
step 2: carrying out relaxation calculation on the established crystal boundary structure, comparing the crystal boundary structure before and after relaxation, and analyzing atomic displacement;
and step 3: performing secondary differential charge density analysis on the relaxed crystal boundary structure, and analyzing the charge transfer condition among the layers;
and 4, step 4: performing electronic population analysis of atoms;
step 4.1: analyzing the occupation condition of atomic orbital electrons;
step 4.2: analyzing the atom charge condition;
step 4.3: counting the electric charge of the crystal wafer;
and 5: carrying out electron potential energy analysis on the crystal boundary structure, and comparing the electron potential energy of the two crystal layer sheets;
step 6: carrying out interface atom wave splitting state density analysis and analyzing the bonding condition among atoms;
and 7: and summarizing the characteristics of the grain boundary structure, and analyzing the influence of the grain boundary structure on the performance of the lightning arrester.
Further, the two-phase grain boundary structure is ZnO (002)/beta-Bi2O3(210) Two-phase grain boundary structure in orientation relation.
Further, parameters of the unit cell are that the ZnO unit cell has a rib length of a =0.32815nm, a rib length of b =0.32815nm, and a rib length of c =0.52950 nm; beta-Bi2O3Unit cell edge length a =0.77169nm, edge length b =0.77169nm, edge length c =0.5580 nm.
Further, the convergence condition of the iterative solution of the Kohn-Sham equation is that the tolerance deviation is less than 0.00005nm and the stress deviation is less than 0.02 GPA.
The invention has the beneficial effects that:
1) the invention researches the microstructure existing in the ZnO resistance valve plate by means of computer simulation, and especially analyzes the relaxation displacement of a crystal boundary structure, charge transfer among laminas, an electronic structure of an interface, an electronic potential energy diagram and state density distribution, and deduces an internal electric field of the crystal boundary structure, thereby having important significance for researching the nonlinear volt-ampere characteristic of a material;
2) compared with an observation and measurement method utilizing experimental equipment, the research method provided by the invention greatly reduces the input manpower and material resources, reduces the research and development cost of the novel ZnO resistance valve plate, and provides a theoretical basis for developing a resistance plate with higher performance;
3) compared with an experimental measurement method, the method can determine which atoms play a main role in the interface combination, calculate the charge quantity of the electron orbit of each atom, and analyze the atom bonding condition in the slice, which has important significance for developing the high-performance zinc oxide arrester.
Drawings
The invention is further illustrated by the following figures and examples.
Fig. 1 is a flow chart of a method for analyzing the performance of a resistance valve plate in a zinc oxide arrester.
FIG. 2 shows ZnO/Bi2O3The structure of the interface structure.
FIG. 3 shows ZnO/Bi after relaxation2O3The structure of the interface structure.
FIG. 4 is a graph of the second order differential charge density for a cross section of the ZnO/Bi2O3 interface structure.
Fig. 5 is a graph of the electron potential along the grain boundary axis direction.
FIG. 6 is a graph of the density of interface states and atomic wavelength division states.
FIG. 7 is a chart of interface layer sheet atomic partial wave density.
FIG. 8 is a single beta-Bi2O3Lamellar and interfacial structure beta-Bi2O3Lamellar atomic wave separation density of states contrast diagram.
Detailed Description
As shown in fig. 1, a method for analyzing the performance of a resistance valve plate in a zinc oxide arrester includes the following steps,
step 1: constructing a two-phase grain boundary structure of the ZnO resistance valve plate by using a computer;
step 1.1-construction of ZnO (002)/beta-Bi2O3(210) A two-phase grain boundary structure;
step 1.2, adopting a CASSTEP software package to optimize the structure of the unit cell;
step 1.3, determining exchange and relevant potential, and solving a Kohn-Sham equation in a self-consistent manner;
step 2: carrying out relaxation calculation on the established crystal boundary structure, comparing the crystal boundary structure before and after relaxation, and analyzing atomic displacement;
and step 3: performing secondary differential charge density analysis on the relaxed crystal boundary structure, and analyzing the charge transfer condition among the layers;
and 4, step 4: performing electronic population analysis of atoms;
step 4.1: analyzing the occupation condition of atomic orbital electrons;
step 4.2: analyzing the atom charge condition;
step 4.3: counting the electric charge of the crystal wafer;
and 5: carrying out electron potential energy analysis on the crystal boundary structure, and comparing the electron potential energy of the two crystal layer sheets;
step 6: carrying out interface atom wave splitting state density analysis and analyzing the bonding condition among atoms;
and 7: and summarizing the characteristics of the grain boundary structure, and analyzing the influence of the grain boundary structure on the performance of the lightning arrester.
In step 1, Bi of different phases is generated at grain boundaries2O3And pyrochlore phase and spinel phase structures. The nonlinear coefficient of the resistor chip can be different under different annealing temperatures. Bi in beta phase and delta phase in ZnO resistance valve plate2O3The resistor disc has excellent nonlinear characteristics when the resistor disc is used as a main component. ZnO (002)/beta-Bi exists in ZnO resistance valve plate2O3(210) An interface structure of orientation relation, which is constructed by a computer.
Using CAStep software package, carrying out structure optimization on the unit cell under the GGA framework, and obtaining unit cell parameters as follows: the ZnO unit cell has a ridge length of a =0.32815nm, a ridge length of b =0.32815nm, and a ridge length of c =0.52950 nm; beta-Bi2O3Unit cell edge length a =0.77169nm, edge length b =0.77169nm, edge length c =0.5580 nm. The model is established by adopting a ZnO surface taking Zn atoms as a terminal, the ZnO surface taking Zn as the terminal has small energy, and the formed interface has better stability than the ZnO surface taking O as the terminal, so that the ZnO surface taking Zn as the terminal is selected to be more in line with the actual situation. Degree of lattice mismatch between two crystal planes<2%, the interface model is separated by vacuum, and the thickness of the vacuum layer is 1 nm.
In the step 2, the step of the method is carried out,and relaxing the grain boundary structure, and reaching a new equilibrium position after meeting the convergence condition. The structural comparison shows that the atomic displacement of O1 and O2 layers in the relaxed ZnO structure is changed obviously and moves to the side close to the interface. The distance of movement of the atoms of the O1 layer to the interface was 0.605 a slightly greater than the distance of movement of the atoms of the O2 layer 0.571 a. The atoms of the Zn1 layer were shifted 0.135 a away from the grain boundary and the atoms of the Zn2 layer were shifted 0.091 a towards the grain boundary. The arch-shaped Zn-O bonds present in the ZnO layer disappeared to be nearly flat. beta-Bi2O3The atomic reconstruction is severe and the initial state beta-Bi is completely destroyed2O3The lattice is periodic. The relaxation shifts of atoms in the atomic layers on both sides of the interface become less and less pronounced with increasing distance from the interface.
And 3, making a secondary differential charge density diagram of the relaxed structure, and calculating the charge quantity carried by the two crystal chips.
As shown in FIG. 4, from the second order differential charge density map, the ZnO crystal layer lost electrons and was positively charged, and β -Bi2O3The crystal lamellae gain electrons, which are negatively charged.
In step 4, the atomic electron population distribution analysis was performed, and as shown in table 1, the electron distribution change of atoms near the interface was analyzed, and it was found that the closer to the interface, the more intense the sheet charge exchange at both sides. By calculating the total electric quantity of the two crystal layer sheets, the ZnO layer sheet is found to be positively charged by 23.61e, beta-Bi2O3The laminate was negatively charged 23.64 e. The two crystal layers are neutral, and the charge transfer occurs between the two crystal layers, so that the ZnO (002)/beta-Bi2O3(210) beta-Bi pointed by ZnO layer sheet is formed in the interface structure2O3The electric field of the lamellae.
As shown in FIG. 5, after the electron potential diagram is formed in step 4, it can be seen that there is a potential difference between the two crystal lamellae, and the average electron potential of the ZnO lamellae is lower than that of β -Bi2O3The average electronic potential energy of the lamellar is consistent with the conclusion that the built-in electric field exists in the grain boundary structure obtained in the step 3, and the direction of the electric field points to beta-Bi from the ZnO lamellar2O3A ply.
As shown in fig. 2 and 3, the relaxed ZnO structureIn the middle, the atomic shifts of the O1 and O2 layers change significantly and move closer to the interface. The Zn1 layer atoms moved away from the grain boundaries and the Zn2 layer atoms moved towards the grain boundaries. The atoms at the boundaries of the ZnO lamellae are slightly upwarped due to the lattice mismatch. beta-Bi2O3Each layer of atoms move to the interface, the structure after relaxation is a transition region of two phases, and the mutation of the phase atom structure does not occur, so that the structural rule of the interface structure is met.
As shown in FIG. 4, it is visually shown that the ZnO layer sheet and the beta-Bi layer sheet are caused to be laminated2O3The interaction of the lamellae influences the electron distribution of the atoms in the interface structure. It can be seen that the localized distribution of electrons around the O atom in the same plane is significant, showing stronger ionic bonds. The appearance of a cloud of electrons extending around the Zn atom and around the O atom indicates that beta-Bi is present due to the presence of an interfacial structure2O3There is charge transfer between the O atoms in the lamellae and the Zn atoms in the Zn lamellae.
As shown in table 1, the numbers of electrons lost by Zn atoms with different distances from the grain boundary were different, and the number of s-state electrons having the relatively largest degree of freedom among Zn1 atoms was 0.50, the number of s-state electrons of Zn2 atom was 0.61, and the difference between them was 0.11, and the numbers of p-state electrons and d-state electrons of Zn1 and Zn2 atom were almost the same. In the ZnO layer sheet, the orbital electron changes of O1 and O2 atoms are very small, and the numbers of p-state electrons and d-state electrons of the two atoms are only 0.01. The amount of positive charge carried by the atoms of the first layer, consisting of atoms Zn1 and O1, is greater than the amount of positive charge carried by the atoms of the second layer, consisting of atoms Zn2 and O2. Bi2O3The number of s-state electrons in Bi atom in layer 1 is 1.88, Bi2O3The number of s-state electrons in the Bi atom in the 2 layers was 1.75, and there was a difference of 0.12 between the two. The p-state electron number of the former atom is 2.08, and the p-state electron number of the latter atom is 1.72, and the difference between the two is 0.36. beta-Bi2O3The orbital electrons of the O atoms in the 1 and 2 layers in the layer sheet do not change much. Bi can be obtained by the same method2O3The amount of negative charge of layer 1 is greater than that of Bi2O3The negative charge carried by layer 2. Therefore, the closer to the grain boundary, the more intense the charge exchange of the lamellae on both sides. By calculating ZnO layer sheet and beta-Bi in the crystal boundary structure2O3The total charge of the laminate was found to be a ZnO layerPositive charge of 23.61e, beta-Bi2O3The laminate was negatively charged 23.64 e. In ZnO (002)/beta-Bi2O3(210) beta-Bi pointed by ZnO layer sheet is formed in the interface structure2O3The electric field of the lamellae.
TABLE 1 electronic population of different atoms
| Species | s | p | d | Total/e | Charge/e |
| Zn1 | 0.50 | 0.59 | 9.96 | 11.05 | 0.95 |
| Zn1(a) | 0.49 | 0.61 | 9.97 | 11.07 | 0.93 |
| Zn2 | 0.61 | 0.59 | 9.97 | 11.17 | 0.83 |
| O1 | 1.87 | 4.99 | 0.00 | 6.86 | -0.86 |
| O2 | 1.86 | 5.00 | 0.00 | 6.86 | -0.86 |
| Bi1 | 1.88 | 2.08 | 0.00 | 3.96 | 1.04 |
| Bi2 | 1.75 | 1.72 | 0.00 | 3.47 | 1.53 |
| O in Bi2O3 1 | 1.93 | 5.00 | 0.00 | 6.93 | -0.93 |
| O in Bi2O3 2 | 1.93 | 4.97 | 0.00 | 6.90 | -0.90 |
As shown in FIG. 5, the similar sine function curve at the upper left is the electron potential diagram of the ZnO layer sheet, and the similar sine curve at the lower right is beta-Bi2O3Sheet electron potential energy diagram. It can be seen that the average electronic potential of the ZnO layer sheet is higher than that of beta-Bi2O3Average electronic potential of the lamellar, so that a built-in electric field exists in the grain boundary structure, and the direction of the electric field is from the ZnO lamellar to beta-Bi2O3A ply.
Due to the existence of the interface structure, the electronic wave function near the interface changes to form an electronic state different from that in the crystal, the periodic arrangement of atoms near the interface can be further influenced by the uneven distribution of charges, the irregular arrangement of atoms influences the electronic wave function, the mutual influence causes different self-consistent potentials to be established in the interface region and in the crystal, because the whole material is electrically neutral, electrons at the interface can form a plurality of tiny electric potential fields in the material, and the electric potential fields formed in the material are important reasons for forming the nonlinear volt-ampere characteristics of the zinc oxide resistor disc.
As shown in FIG. 6, the total state Density TDOS (Total Density of states) and atomic wavelength division Density are analyzed, and in the energy region of-5.11 eV to-8.42 eV, the region is mainly contributed by the 2p orbital of O and the 3d orbital of Zn, and the hybridization effect of the p-d orbital exists. In the region of-8.45 eV to-12.36 eV, the molecular structure is mainly contributed by the 2p orbital of O and the 6s orbital of Bi, and the region has s-p orbital hybridization.
As shown in FIG. 7, the interface ZnO side Zn atom3d valence electron of the seed with beta-Bi2O3The partial density of states of the 2p valence electrons of the flanking O atoms yields better coincidence in the low energy region. The combination of the interface mainly depends on Zn atoms and beta-Bi in ZnO layer sheets2O3The O atoms in the lamellae interact.
As shown in FIG. 8, it is known that the Bi atom 6p orbital near the interface is more active and has a non-localized enhancement, and at the same time, one peak of the atomic density of states of O atom and Bi atom in the interface structure moves to a low energy region and approaches to another peak, and β -Bi in the interface2O3The bonding between O atoms and Bi atoms in the laminate is weakened.
In conclusion, the performance of the arrester is better when the electric field intensity built in the arrester resistance valve plate is higher in combination with the performance of the arrester, and the performance of the arrester can be improved by analyzing from a molecular level and increasing the charge transfer quantity between the arrester resistance valve plate layers. Adding other crystal powder into the arrester resistance valve plate to change the crystal structure and increase charge transfer between crystal layers; or the size of ZnO crystal grains is reduced, the number of crystal boundary structures in the material is increased, and the charge transfer between crystal chips is increased; or controlling the sintering temperature and the cooling time of the arrester resistance valve plate, controlling the size of ZnO crystal grains, and changing the charge transfer amount to increase the charge transfer among crystal layer sheets. The performance of the arrester is improved by the measures and the like.
Claims (4)
1. A method for analyzing the performance of a resistance valve plate in a zinc oxide arrester is characterized by comprising the following steps:
step 1: constructing a two-phase grain boundary structure of the ZnO resistance valve plate by using a computer;
step 1.1: structure ZnO/Bi2O3The two-phase grain boundary structure of (1);
step 1.2: carrying out structure optimization on the unit cell;
step 1.3: determining exchange and related potential, and solving Kohn-Sham equation in a self-consistent manner;
step 2: carrying out relaxation calculation on the established crystal boundary structure, comparing the crystal boundary structure before and after relaxation, and analyzing atomic displacement;
and step 3: performing secondary differential charge density analysis on the relaxed crystal boundary structure, and analyzing the charge transfer condition among the layers;
and 4, step 4: performing electronic population analysis of atoms;
step 4.1: analyzing the occupation condition of atomic orbital electrons;
step 4.2: analyzing the atom charge condition;
step 4.3: counting the electric charge of the crystal wafer;
and 5: carrying out electron potential energy analysis on the crystal boundary structure, comparing the electron potential energy of the two crystal layer sheets, and analyzing to obtain a built-in electric field of the crystal boundary structure;
step 6: carrying out interface atom wave splitting state density analysis and analyzing the bonding condition among atoms;
and 7: obtaining measures for improving the interface strength of the resistance valve plate according to the interaction condition of Zn atoms, O atoms and Bi atoms at the crystal boundary; and analyzing the relationship between the built-in electric field in the resistance valve plate and the charge transfer amount among the layers and the volt-ampere characteristic of the lightning arrester to obtain measures for improving the performance of the lightning arrester.
2. The method for analyzing the performance of the resistance valve plate in the zinc oxide arrester as claimed in claim 1, wherein the two-phase grain boundary structure is ZnO (002)/β -Bi2O3(210) Two-phase grain boundary structure in orientation relation.
3. The method for analyzing the performance of the resistance valve plate in the zinc oxide arrester as claimed in claim 1, wherein the parameters of the unit cell are that the ZnO unit cell has a =0.32815nm in edge length, b =0.32815nm in edge length, and c =0.52950nm in edge length; beta-Bi2O3Unit cell edge length a =0.77169nm, edge length b =0.77169nm, edge length c =0.5580 nm.
4. The method for analyzing the performance of the resistance valve plate in the zinc oxide arrester as claimed in claim 1, wherein the convergence conditions of the iterative solution of the Kohn-Sham equation are that the tolerance deviation is less than 0.00005nm and the stress deviation is less than 0.02 GPA.
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