CN111519250B - Preparation method of bismuth-iodine-copper crystal - Google Patents

Preparation method of bismuth-iodine-copper crystal Download PDF

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CN111519250B
CN111519250B CN202010561558.2A CN202010561558A CN111519250B CN 111519250 B CN111519250 B CN 111519250B CN 202010561558 A CN202010561558 A CN 202010561558A CN 111519250 B CN111519250 B CN 111519250B
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bismuth
crystal
copper
quartz crucible
iodide
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CN111519250A (en
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孙瑞
徐家跃
申慧
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/002—Crucibles or containers for supporting the melt
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents

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  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention discloses a preparation method of a bismuth iodide copper crystal, which comprises the preparation of a bismuth iodide copper polycrystal material and the growth of the bismuth iodide copper crystal; weighing raw materials according to a stoichiometric ratio, then loading the raw materials into a quartz crucible, vacuumizing and sealing the quartz crucible, and then placing the quartz crucible into a swinging furnace for sectional heating to obtain a bismuth-copper-iodide polycrystal material; and then placing the quartz crucible filled with the polycrystalline material in a crystal furnace for crystal growth to finally obtain the bismuth iodide copper crystal. The invention successfully grows the bismuth iodide copper crystal by adopting a two-step method of the rocking furnace and the crystal furnace, the size of the obtained bismuth iodide copper crystal is 17 multiplied by 80mm, the technical bottleneck of the existing bismuth iodide copper crystal growth is overcome, the technical problem that the bismuth iodide copper crystal cannot be successfully grown is solved, and a new thought is provided for the growth of the bismuth iodide copper crystal.

Description

Preparation method of bismuth-iodine-copper crystal
Technical Field
The invention relates to the technical field of crystal growth, in particular to a preparation method of a bismuth iodide copper crystal.
Background
The perovskite material is a material of calcium titanate (CaTiO)3) A series of compound materials with the same crystal structure have been popular research materials due to their excellent photoelectric properties and better thermoelectric properties, such as larger light absorption coefficient, high carrier mobility, long diffusion length, low exciton confinement energy, photoluminescence, electroluminescence, etc. And the preparation is simple, the production cost is low, and the like, so that the preparation method is widely applied to various devices. In the present stage, the problem of energy shortage is increasingly emphasized, and perovskite materials become indispensable basic materials for obtaining green renewable energy in modern times because the perovskite materials can be widely applied to solar cell devices. With the increasing demand of industrialization, the requirements on the cost, quality, performance and environmental protection of perovskite materials are higher and higher.
The 2009 japanese scientist Miyasaka first reported perovskite solar cells with a photoelectric conversion efficiency of only 3.8%, which has risen to 25.2% by 2020. Organic-inorganic hybrid perovskite is a superior perovskite solar material, and Julian Burschka et al, 2013, deposit CH on porous metal oxide film3NH3PbI3Perovskite, a 15% photoelectric conversion efficiency is achieved. Nam Joong Jeon et al adopted FAPbI in 20153And MAPbI3As a double-layer solar cell structure, the photoelectric conversion efficiency of 18 percent can be achieved. In 2018, rubidium and cesium are used by Silver-Hamill Turren-Cruz and the like to replace traditional bromine and MA ions, so that the photoelectric conversion efficiency is 20.35%, and the stability is improved. Beta used by Yong WANG et al in 2019-CsPbI3The prepared tandem solar cell realizes 18.4% of photoelectric conversion efficiency at 45 ℃.
From the above documents, it is known that perovskite materials are developed vigorously today, but there is a prominent environmental problem that most of perovskites contain heavy metal Pb as a component, and thus, have problems of contamination and high recovery cost. Therefore, the search for new perovskite materials that do not contain heavy metals has become a focus of research in recent years. In order to solve the problem that perovskite contains heavy metals, researchers have found that the Bi element, which is an element having the same cycle as the Pb element, is an excellent choice for replacing Pb because it is non-toxic and has a rich earth content. In 2018, Shuzi Hayase et al adopt a spin-coating method to prepare a bismuth iodide copper film, and the bismuth iodide copper film is assembled into a solar cell to obtain the photoelectric conversion efficiency of 0.8%. The domestic subject group obtains 1.119% photoelectric conversion efficiency by using the bismuth iodide copper crystal film prepared in situ by room temperature gas-solid reaction. However, the reported bismuth iodide copper perovskite materials are all thin film materials and have the problems of poor stability, more defects and the like. Generally, the performance of the crystal is more stable than that of a film, but the preparation of the bismuth iodide copper crystal has certain technical problems and is difficult to grow successfully, and at present, no relevant report about the growth of the bismuth iodide copper crystal exists, so that the bismuth iodide copper crystal is not used for carrying out relevant performance research.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing bismuth iodide copper crystal, which adopts a two-step method to grow bismuth iodide copper crystal. The method comprises the steps of firstly, synthesizing the bismuth copper iodide polycrystal material by heating a swinging furnace in sections, solving the problems of large heat release and crucible explosion easily caused by too large vapor pressure in the traditional solution preparation process of the polycrystal material, and secondly, successfully growing a high-quality bismuth copper iodide crystal by adopting an in-situ solidification growth technology under the condition of not taking out the crucible, thereby breaking through the technical barriers existing in the bismuth copper iodide crystal growth process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of bismuth iodide copper crystal comprises the following steps:
1) preparing a bismuth iodide copper polycrystal material; the preparation process comprises the following steps:
weighing raw materials in a dark room according to a stoichiometric ratio, wherein the raw materials comprise iodine particles, copper powder and bismuth powder;
uniformly mixing the weighed copper powder and bismuth powder in a dark room, grinding the weighed iodine particles, respectively loading the raw materials into quartz crucibles, and placing the iodine particles on the upper layers of the quartz crucibles; carrying out vacuum pumping and sealing treatment on the quartz crucible filled with the raw materials;
thirdly, fixing the sealed quartz crucible in a swinging furnace for heating in a segmented manner to obtain a bismuth-iodine-copper polycrystal material;
2) growing a bismuth iodide copper crystal; the preparation process comprises the following steps:
putting the quartz crucible filled with the bismuth-copper-iodide polycrystal material into a crystal furnace, so that the bismuth-copper-iodide polycrystal material is positioned in a high-temperature area in the crystal furnace, and preserving heat for 24 hours at 650-700 ℃;
secondly, the quartz crucible is lowered at the speed of 0.5-1.0 mm/h, the temperature gradient of a solid-liquid interface is kept at 20-30 ℃, and crystal growth is carried out;
and thirdly, after the crystal growth is finished, reducing the temperature in the crystal furnace to room temperature at the rate of 30-50 ℃/h, and opening the crucible to obtain the bismuth-iodine-copper crystal.
Aiming at the technical scheme, the iodine particles are placed on the top layer to prevent the raw materials from being sucked away during vacuumizing, so that the stability of the proportion of the raw materials can be ensured, and the serious component segregation of crystals grown in the later period is avoided; the raw materials are sealed in a dark room, so that the iodine particles can be prevented from being decomposed by light, and the stability of the components is further ensured; the vacuum sealing of the quartz crucible ensures that the raw materials do not react with air, and excessive oxide impurities in the crystal are avoided; the adoption of the swinging furnace can promote the uniform mixing of the raw materials; because the melting points and the boiling points of the raw materials are different, the raw materials can be melted more thoroughly through sectional heating, and meanwhile, the raw materials are favorably and fully mixed; the high-quality bismuth-iodine-copper crystal can be successfully grown by adopting the crystal growth conditions.
Preferably, the rocking in step 1)Heating is carried out in 20-40 temperature sections in the furnace, and the heat preservation time of each section is 30-60min until the temperature is 600-700 ℃ and the heat preservation time is 12-24 h. The staged heating is to prevent the insufficient mixing and reaction of the raw materials, i.e. I in the raw materials, when the temperature rises too fast2And BiI generated subsequently3The vaporization to boiling point is achieved without complete reaction, so that a large vapor pressure exists in the crucible, resulting in explosion of the crucible. The method is beneficial to fully dissolving all the raw materials, avoids serious segregation of crystal components and existence of a capsule, and is beneficial to improving the quality of the crystal.
Preferably, the quartz crucible is continuously swung in the process of heating in the swinging furnace, so that the raw materials in the quartz crucible are uniformly mixed.
Preferably, the temperature of the rocking furnace is reduced to room temperature at a speed of 10-30 ℃/h after the heating is finished.
Preferably, the raw materials in the step 1) are cuprous iodide and bismuth iodide.
Preferably, the wall thickness of the quartz crucible is 1-1.5mm, and the bottom of the quartz crucible is provided with a tip with an angle of 30-45 degrees. The spontaneous nucleation of the crystal is facilitated, and the growth of the crystal is promoted; the wall thickness of the quartz crucible can enable the crystal to be in an optimal growth environment, and the excessive thickness of the wall thickness can easily cause that the internal raw materials are heated slowly and melted incompletely, and the excessive thickness of the wall thickness is easy to crack, so that the crystal growth failure is caused.
Preferably, the degree of vacuum of the quartz crucible in the step 1) is 1 × 10 after the quartz crucible is vacuumized-1～1×10-5Pa。
Preferably, a seed well for placing a seed crystal is arranged at the bottom of the quartz crucible.
Preferably, the direction of the seed crystal is <100> or <110 >. The quality of the crystal can be improved by adopting the seed crystal to grow the crystal.
The invention has the beneficial effects that:
the invention adopts the rocking furnace and the crystal furnace to realize the preparation of polycrystal materials and crystals, successfully grows the bismuth-iodide copper crystal, and the size of the obtained bismuth-iodide copper crystal is 17 multiplied by 80mm, thereby overcoming the technical bottleneck of the existing bismuth-iodide copper crystal growth, solving the technical problem that the bismuth-iodide copper crystal cannot be successfully grown, and providing a new idea for the growth of the bismuth-iodide copper crystal. The invention avoids the error of raw material proportioning by adopting darkroom operation and vacuum sealing, and reduces the condition of component segregation in the crystal. The sectional heating is to prevent the raw materials from not being fully mixed and reacted when the temperature is increased too fast, and the raw materials reach boiling point gasification so that the crucible is exploded due to larger vapor pressure in the crucible.
The bismuth-iodide copper crystal grown by the method does not contain Pb and is pollution-free, can be used for researching the photoelectric property, the environmental stability and other characteristics of the bismuth-iodide copper perovskite crystal, can be applied to the research of perovskite solar cells, and provides a new choice for solving the problem of poor photoelectric property stability of the existing bismuth-iodide copper film.
Drawings
FIG. 1 is a powder XRD pattern of a bismuth iodide copper crystal.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of bismuth iodide copper crystal comprises the following steps:
1) preparing a bismuth iodide copper polycrystal material; the preparation process comprises the following steps:
weighing copper powder, bismuth powder and iodine particles with the purity of more than or equal to 99.99% in a dark room according to the molar ratio of Cu to Bi to I =1 to 4.
Uniformly mixing 5.7019g of copper powder and 18.7516g of bismuth powder in a dark room, grinding 45.5465g of iodine particles in a mortar, then loading the copper-bismuth mixture into the bottom of a quartz crucible, and loading the ground iodine particles into the upper layer of the quartz crucible; wrapping tin paper outside the quartz crucible to prevent light, and then carrying out vacuum-pumping sealing treatment on the quartz crucible filled with the raw materials to ensure that the vacuum degree in the quartz crucible is 1 multiplied by 10-1Pa. The wall thickness of the adopted quartz crucible is 1mm, and the bottom of the quartz crucible is provided with a tip with an angle of 30 degrees.
Thirdly, fixing the sealed quartz crucible in a swinging furnace, heating the quartz crucible in 20 temperature sections, keeping the temperature for 60min in each section until the temperature is 600 ℃, keeping the temperature for 12h, and then cooling the quartz crucible to room temperature at the speed of 10 ℃/h to obtain a bismuth copper iodide polycrystal material; and the quartz crucible continuously swings in the process of heating in the swinging furnace, so that the raw materials in the quartz crucible are uniformly mixed.
2) Growing a bismuth iodide copper crystal; the preparation process comprises the following steps:
putting the quartz crucible filled with the bismuth-copper-iodide polycrystal material into a crystal furnace, and keeping the bismuth-copper-iodide polycrystal material in a high-temperature area in the crystal furnace, and preserving heat at 650 ℃ for 24 hours to perform spontaneous nucleation;
secondly, the quartz crucible is lowered at the speed of 0.5mm/h, the temperature gradient of a solid-liquid interface is kept at 200 ℃, and crystal growth is carried out;
and thirdly, after the crystal growth is finished, reducing the temperature in the crystal furnace to room temperature at the rate of 30 ℃/h, and opening the crucible to obtain the bismuth-iodine-copper crystal.
Example 2
A preparation method of bismuth iodide copper crystal comprises the following steps:
1) preparing a bismuth iodide copper polycrystal material; the preparation process comprises the following steps:
weighing copper powder, bismuth powder and iodine particles with the purity of more than or equal to 99.99% in a dark room according to the molar ratio of Cu to Bi to I =1 to 4. The raw materials are cuprous iodide and bismuth iodide. A quartz crucible having a wall thickness of 1.2mm and having a tip with an angle of 40 DEG at the bottom thereof was prepared, and a seed well for placing a seed crystal was further provided at the bottom of the quartz crucible. Polishing the bismuth-iodine-copper crystal growing by spontaneous nucleation into a cylinder with the length of 60mm and the diameter of 2mm and the direction of <100> as a seed crystal, and putting the seed crystal into a seed well of a quartz crucible in advance.
5.7019g of copper powder and 18.7516g of bismuth powder are uniformly mixed in a dark room, 45.5465g of iodine particles are put into a mortar for grinding, then the copper-bismuth mixture is put below a quartz crucible, and the ground iodine particles are put on the upper layer of the quartz crucible; wrapping tin paper outside the quartz crucible to prevent light, and then carrying out vacuum-pumping sealing treatment on the quartz crucible filled with the raw materials to ensure that the vacuum degree in the quartz crucible is 1 multiplied by 10-4Pa。
Thirdly, fixing the sealed quartz crucible in a swinging furnace, heating the quartz crucible in 30 temperature sections, keeping the temperature for 45min in each section until the temperature is 650 ℃, keeping the temperature for 20h, and then cooling the quartz crucible to room temperature at the speed of 25 ℃/h to obtain a bismuth copper iodide polycrystal material; and the quartz crucible continuously swings in the process of heating in the swinging furnace, so that the raw materials in the quartz crucible are uniformly mixed.
2) Growing a bismuth iodide copper crystal; the preparation process comprises the following steps:
putting the quartz crucible filled with the bismuth-copper-iodide polycrystal material into a crystal furnace, so that the bismuth-copper-iodide polycrystal material is positioned in a high-temperature area in the crystal furnace, and preserving heat for 24 hours at 680 ℃;
secondly, the quartz crucible is lowered at the speed of 0.7mm/h, the temperature gradient of a solid-liquid interface is kept at 25 ℃, and crystal growth is carried out;
and thirdly, after the crystal growth is finished, reducing the temperature in the crystal furnace to room temperature at the rate of 40 ℃/h, and opening the crucible to obtain the bismuth-iodine-copper crystal.
Example 3
A preparation method of bismuth iodide copper crystal comprises the following steps:
1) preparing a bismuth iodide copper polycrystal material; the preparation process comprises the following steps:
cuprous iodide and bismuth iodide having a purity of 99.99% or more were weighed in a dark room at a molar ratio of Cu: Bi =1: 1. A quartz crucible having a wall thickness of 1.5mm and having a tip with an angle of 45 DEG at the bottom thereof is prepared, and a seed well for placing a seed crystal is further provided at the bottom of the quartz crucible. Polishing the bismuth-iodine copper crystal growing by spontaneous nucleation into a cylinder with the length of 60mm and the diameter of 2mm and the direction of <110> as a seed crystal, and putting the seed crystal into a seed well of a quartz crucible in advance.
Secondly, filling weighed cuprous iodide below the quartz crucible in a dark room, and filling weighed bismuth iodide on the upper layer of the quartz crucible; wrapping tin paper outside the quartz crucible to prevent light, and then carrying out vacuum-pumping sealing treatment on the quartz crucible filled with the raw materials to ensure that the vacuum degree in the quartz crucible is 1 multiplied by 10-3Pa。
Thirdly, fixing the sealed quartz crucible in a swinging furnace, heating the quartz crucible in 40 temperature sections, keeping the temperature for 30min in each section until the temperature is 700 ℃, keeping the temperature for 24h, and then cooling the quartz crucible to room temperature at the speed of 30 ℃/h to obtain a bismuth copper iodide polycrystal material; and the quartz crucible continuously swings in the process of heating in the swinging furnace, so that the raw materials in the quartz crucible are uniformly mixed.
2) Growing a bismuth iodide copper crystal; the preparation process comprises the following steps:
putting the quartz crucible filled with the bismuth-copper-iodide polycrystalline material into a crystal furnace, and keeping the bismuth-copper-iodide polycrystalline material in a high-temperature area in the crystal furnace at 700 ℃ for 24 hours;
secondly, the quartz crucible is lowered at the rate of 1.0mm/h, the temperature gradient of a solid-liquid interface is kept at 30 ℃, and crystal growth is carried out;
and thirdly, after the crystal growth is finished, reducing the temperature in the crystal furnace to room temperature at the speed of 50 ℃/h, and opening the crucible to obtain the bismuth-iodine-copper crystal.
Example 4
The difference between the present example and example 2 is that the crystal growth conditions are different, and the other steps are the same as example 2.
The difference lies in that: the quartz crucible containing the <100> seed crystal and the polycrystalline material was placed in a high temperature zone in a crystal furnace, the furnace temperature was controlled at 680 ℃ and held for 24 hours, and then the crucible was lowered at a rate of 0.5 mm/h. And after the crystal growth is finished, reducing the temperature in the crystal furnace to room temperature at the speed of 40 ℃/h, and opening the crucible to obtain the bismuth-iodine-copper crystal.
The intermediate part of the bismuth-iodide copper crystal grown in example 1 was ground into powder and subjected to XRD pattern analysis, as shown in FIG. 1, from which it was seen that the crystal grown was a bismuth-iodide copper crystal. The invention realizes the growth of the bismuth iodide copper crystal and opens the barrier that the existing bismuth iodide copper crystal can not successfully grow.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.

Claims (6)

1. A preparation method of bismuth iodide copper crystal is characterized by comprising the following steps:
1) preparing a bismuth iodide copper polycrystal material; the preparation process comprises the following steps:
weighing raw materials in a dark room according to a stoichiometric ratio, wherein the raw materials comprise iodine particles, copper powder and bismuth powder;
uniformly mixing the weighed copper powder and bismuth powder in a dark room, grinding the weighed iodine particles, respectively loading the raw materials into quartz crucibles, and placing the iodine particles on the upper layers of the quartz crucibles; carrying out vacuum pumping and sealing treatment on the quartz crucible filled with the raw materials; the vacuum degree of the quartz crucible is 1 multiplied by 10 after the quartz crucible is vacuumized-1～1×10-5Pa；
Thirdly, fixing the sealed quartz crucible in a swinging furnace for heating in a segmented manner to obtain a bismuth-iodine-copper polycrystal material; heating the swing furnace in 20-40 temperature sections, wherein the heat preservation time of each section is 30-60min until the temperature is 600-700 ℃, and preserving the heat for 12-24 h; after the heating of the swing furnace is finished, cooling to room temperature at a speed of 10-30 ℃/h;
2) growing a bismuth iodide copper crystal; the preparation process comprises the following steps:
putting the quartz crucible filled with the bismuth-copper-iodide polycrystal material into a crystal furnace, so that the bismuth-copper-iodide polycrystal material is positioned in a high-temperature area in the crystal furnace, and preserving heat for 24 hours at 650-700 ℃;
secondly, the quartz crucible is lowered at the speed of 0.5-1.0 mm/h, the temperature gradient of a solid-liquid interface is kept at 20-30 ℃, and crystal growth is carried out;
and thirdly, after the crystal growth is finished, reducing the temperature in the crystal furnace to room temperature at the rate of 30-50 ℃/h, and opening the crucible to obtain the bismuth-iodine-copper crystal.
2. The method for preparing bismuth iodide copper crystal according to claim 1, wherein the quartz crucible is continuously oscillated during the heating in the oscillating furnace to uniformly mix the raw materials in the quartz crucible.
3. The method for producing a bismuth iodide copper crystal according to claim 1, wherein the raw materials in step 1) are cuprous iodide and bismuth iodide.
4. The method for preparing a bismuth-iodine-copper crystal according to claim 1, wherein the quartz crucible has a wall thickness of 1 to 1.5mm and a bottom provided with a tip having an angle of 30 to 45 °.
5. The method for preparing a bismuth-iodine-copper crystal according to claim 1, wherein a seed well for placing a seed crystal is provided at the bottom of the quartz crucible.
6. The method for preparing a bismuth-iodine-copper crystal according to claim 5, wherein the direction of the seed crystal is <100> or <110 >.
CN202010561558.2A 2020-06-18 2020-06-18 Preparation method of bismuth-iodine-copper crystal Active CN111519250B (en)

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