CN111041559A - Synthetic container and synthetic method of quaternary sulfur lithium compound polycrystal - Google Patents

Synthetic container and synthetic method of quaternary sulfur lithium compound polycrystal Download PDF

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CN111041559A
CN111041559A CN201911285498.XA CN201911285498A CN111041559A CN 111041559 A CN111041559 A CN 111041559A CN 201911285498 A CN201911285498 A CN 201911285498A CN 111041559 A CN111041559 A CN 111041559A
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crucible
pbn
quartz crucible
pbn crucible
layer
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CN111041559B (en
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黄巍
何知宇
陈宝军
朱世富
赵北君
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Sichuan University
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Sichuan University
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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
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient

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Abstract

The invention discloses a synthesis container and a synthesis method of quaternary lithium sulfide compound polycrystal. The synthesis container is formed by combining a first PBN crucible, a second PBN crucible, an inner-layer quartz crucible and an outer-layer quartz crucible. The synthesis method uses high purity Li2The method comprises the following steps of taking high-purity simple substances of S, the simple substance S and other two elements of the quaternary sulfur-lithium compound as raw materials: cleaning and drying a synthesis container; (II) charging; (III) synthesizing polycrystal in a tiltable and rotatable two-zone heating tube furnace, wherein the two-zone heating tube furnace is obliquely arranged, a synthesizing container filled with raw materials and sealed is placed in the two-zone heating tube furnace, one end filled with the raw materials is positioned in a high-temperature zone, and the other end not filled with the raw materials is positioned in a low-temperature zone. The synthesis container and the method can obtain single-phase quaternary lithium sulfide compound polycrystal under the condition of ensuring the synthesis safety, and increase the single synthesis of the quaternary lithium sulfide compound polycrystalThe amount of the raw material (c).

Description

Synthetic container and synthetic method of quaternary sulfur lithium compound polycrystal
Technical Field
The invention belongs to the field of preparation of quaternary compound semiconductor materials, and particularly relates to a synthesis method of a sulfur-lithium quaternary compound polycrystal and a synthesis container used in the method.
Background
The sulfur-lithium quaternary compound crystal is a novel infrared nonlinear optical material with excellent performance, and has wide application prospect in the fields of infrared countermeasure, laser radar, laser communication, national defense science and technology and the like.
The compound polycrystal is generally synthesized in a quartz ampoule as a synthesis vessel. The synthesis of the sulfur-lithium quaternary compound crystal is characterized in that the raw material contains Li2S or elemental Li, with Li2S or Li reacts with quartz at high temperature to corrode the quartz ampoule, so that the explosion risk exists and the safety is difficult to guarantee. In order to solve the safety problem, the disclosed synthetic methods of the sulfur-lithium quaternary compound mainly comprise the following steps:
youngsik Kim, university of Iowa State, USA, uses 1g of reactant (raw material) -Li2S、GeS2And Ga2S3(ratio: 1:4:1) to synthesize Li2Ga2GeS6(see charaterification of New Infrared nonlinear Optical Material with High Laser Damage Threshold, Li2Ga2GeS6Chem. mater.2008,20, 6048-. The reaction vessel of the method is a quartz tube plated with a carbon film, and the process comprises the following steps: the temperature is increased from the room temperature to 950 ℃ for 5h after 10h, then is reduced to 750 ℃ after 7h, is reduced to 500 ℃ for 20h after 100h, and finally is rapidly cooled to the room temperature. The problems of the method are that: (1) the method is only suitable for synthesizing a small amount of quaternary lithium sulfide compound, when the reaction raw materials are increased and the reaction time is prolonged, the carbon film is easy to fall off and enters into the reaction product, and due to the falling off of the carbon film, the material and quartz react seriously to cause the explosion of a quartz ampoule; (2) synthesized Compound Li2Ga2GeS6Contains a heterogeneous phase.
SONG Man of Wuhan university in China directly synthesizes 5g of Li in a quartz tube2Ga2GeS6Compound with 30% Li as raw material2S, 30% Ga2S3And the balance GeS2(see Synthesis and Properties of New InfraredNonlinear Optical Li2Ga2GeS6Crystal, Journal of Wuhan University of technology-Mater,2015,03, 509-511). The process comprises the following steps: heating from room temperature to 120 ℃ and preserving heat for 1 hour, then heating to 400 ℃ at the speed of 1.5 ℃/min and preserving heat for 1 hour, then heating to 800 ℃ at the speed of 1.5 ℃/min and preserving heat for 1 hour from 800 ℃ to 950 ℃ at the speed of 51 ℃/min, then cooling to 850 ℃ and preserving heat for 1 hour, and finally rapidly cooling to room temperature. The problems of the method are that: (1) the safety of the synthesis process is still difficult to guarantee; (2) obtained Li2Ga2GeS6Deliquescence indicates that Li still remains after the reaction2S, the reaction is incomplete.
Suseela Devi in CdS (0.039 g; 0.027mmol), SnS (0.041 g; 0.027mmol), Li, India M.Suseela Devi2Li was synthesized from S (0.1 g; 0.218mmol) and S (0.349 g; 1.088mmol) as starting materials in a quartz tube having a length of 13cm and a diameter of 1.3cm as a synthesis vessel2CdSnS4(First examples of sulfides in the quaternary A/Cd/Sn/S(A＝Li,Na)systems:molten flux synthesis and single crystal X-ray structures ofLi2CdSnS4,Na2CdSnS4and Na6CdSn4S12Journal of The Chemical Society-DALTON transactions-J CHEM SOC DALTON TRANS,2002,04, 2092-: the mixture was heated from room temperature to 560 ℃ for 4 days and then slowly cooled to room temperature (cooling time was more than 4 days). The problems of the method are that: the synthesis time is long, and only 53.5 percent of Li is contained in the synthesized product2CdSnS4And the purity is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a synthesis container and a synthesis method of a quaternary lithium sulfide polycrystal, so as to obtain a single-phase quaternary lithium sulfide polycrystal under the condition of ensuring the synthesis safety and increase the raw material amount for synthesizing the quaternary lithium sulfide polycrystal at one time.
The technical idea of the invention is as follows: the synthesis vessel consists of a combined pyrolytic boron nitride crucible (abbreviated as PBN crucible, in the following description "PBN crucible" is a "pyrolytic boron nitride crucibleCrucible ") and a double-layer quartz crucible, the synthesis is carried out in a two-zone heating tube furnace which can be inclined and rotated, the raw materials are loaded in a PBN crucible, the raw materials are firstly reacted in a high-temperature zone, the generated S steam enters the quartz crucible in a low-temperature zone and is condensed to form liquid S, the liquid S flows back to the PBN crucible, the circulating reaction is carried out until all S simple substances are converted into compounds, the vapor pressure is reduced, and the Li is prevented from being converted into compounds2S is contacted with the quartz crucible to prevent explosion; and (3) in the process, the temperature is kept at 950-960 ℃ for at least 24 hours, the quaternary lithium sulfide compound polycrystal is synthesized by combining a temperature oscillation method, and the decomposition of the product is inhibited by adopting a gradient cooling mode after the synthesis is finished, so that the aim of obtaining a single-phase quaternary lithium sulfide compound polycrystal is fulfilled.
The invention relates to a synthesis container of quaternary lithium sulfide compound polycrystal, which is formed by combining a first PBN crucible, a second PBN crucible, an inner-layer quartz crucible and an outer-layer quartz crucible;
initial state: the first PBN crucible is a PBN circular tube with an opening at one end and a closed end, and the length L1 of the first PBN crucible meets the requirement that the distance from the upper surface of the contained raw material powder to the end surface of the opening end of the first PBN crucible is more than 1/2L 1; the second PBN crucible is a PBN truncated cone pipe with openings at two ends, the outer diameter of the large end of the second PBN crucible is less than or equal to the inner diameter of the first PBN crucible, a circular outer edge is arranged around the outer wall of the large end of the second PBN crucible, the outer diameter of the circular outer edge is greater than the outer diameter of the first PBN crucible, and the length L2 of the second PBN crucible is 1/8-2/5 of the length L1 of the first PBN crucible; the inner-layer quartz crucible and the outer-layer quartz crucible are both quartz round tubes with one open end and one closed end, or quartz round tubes with two open ends, the inner diameter of the inner-layer quartz crucible is the same as the nominal size of the outer diameter of the circular outer edge of the second PBN crucible and is in movable fit, the ratio of the length L3 of the inner-layer quartz crucible to the length L1 of the first PBN crucible is 1.3-1.7, the inner diameter of the outer-layer quartz crucible is larger than the outer diameter of the inner-layer quartz crucible, and the length of the outer-layer quartz crucible is larger than that of the inner-layer quartz crucible;
the working state is as follows: the inner-layer quartz crucible and the outer-layer quartz crucible are both quartz round tubes with two closed ends, one end of the outer-layer quartz crucible is provided with a hanging piece, and the inner-layer quartz crucible is positioned in the outer-layer quartz crucible; the first PBN crucible is positioned in the inner-layer quartz crucible, and the closed end of the first PBN crucible is contacted with one end of the inner-layer quartz crucible, which is far away from the outer-layer quartz crucible, where the hanging piece is arranged; the second PBN crucible is arranged at the opening end of the first PBN crucible through the circular outer edge of the second PBN crucible, and the body part behind the circular outer edge is positioned in the first PBN crucible.
In the container for synthesizing the quaternary lithium sulfide compound polycrystal, the ratio of the large-end aperture d2 to the small-end aperture d1 of the second PBN crucible is 3-6, so that the escape of S vapor and the reflux of liquid S meet the reaction requirement.
According to the synthesis container of the quaternary lithium sulfide compound polycrystal, the inner diameter of the outer-layer quartz crucible is equal to the outer diameter of the inner-layer quartz crucible plus (4-6) mm, so that the quaternary lithium sulfide compound polycrystal can be conveniently combined and meets the synthesis requirement.
In the container for synthesizing the quaternary lithium sulfide polycrystal, the inner diameter and the length of the first PBN crucible are adjusted according to the amount of the raw material, and from the viewpoint of ensuring safety and reducing cost, the inner diameter of the first PBN crucible is preferably 20 to 30mm, and the length of the first PBN crucible is preferably 150 to 250 mm.
In the container for synthesizing the quaternary lithium sulfide compound polycrystal, the wall thickness of the first PBN crucible and the second PBN crucible is 0.3-0.5 mm, the wall thickness of the inner-layer quartz crucible and the wall thickness of the outer-layer quartz crucible are 1.5-2 mm, and the outer diameter of the circular outer edge arranged around the outer wall of the large end of the second PBN crucible only needs to be slightly larger than the outer diameter of the first PBN crucible.
The synthesis method of the quaternary lithium sulfide compound polycrystal adopts high-purity Li2S, the simple substance S and high-purity simple substances of other two elements of the compound are used as raw materials;
the process comprises the following steps:
(I) cleaning and drying of the synthesis vessel
The synthesis container is of the structure, the first PBN crucible, the second PBN crucible, the inner-layer quartz crucible and the outer-layer quartz crucible in the initial state are injected with cleaning liquid to be repeatedly cleaned until the PBN crucible, the inner-layer quartz crucible and the outer-layer quartz crucible are cleaned, and then the PBN crucible, the inner-layer quartz crucible and the outer-layer quartz crucible are dried to completely remove water in the PBN crucible;
(II) charging
When the inner quartz crucible and the outer quartz crucible are quartz round tubes with openings at two ends, the first PBN crucible and the second PBN crucible which are combined are placed into the inner quartz crucible, then the opening end of the inner quartz crucible facing the closed end of the first PBN crucible is sealed, then the first exhaust tube is sintered at the other opening end of the inner quartz crucible, all the weighed raw materials are loaded into the first PBN crucible through the first exhaust tube and the second PBN crucible, after the raw materials are loaded, the inner quartz crucible is vacuumized and degassed through the first exhaust tube, and when the pressure is lower than 10-4When Pa is needed, the quartz crucible on the inner layer is sealed and jointed towards the open end of the second PBN crucible, one end of the quartz crucible on the outer layer is sealed and jointed, then the quartz crucible on the inner layer is placed into the quartz crucible on the outer layer, the closed end of the first PBN crucible is made to face the sealed and jointed end of the quartz crucible on the outer layer, then the second exhaust pipe is sintered at the other open end of the quartz crucible on the outer layer, the quartz crucible on the outer layer is vacuumized and degassed through the second exhaust pipe, and when the pressure is 10, the pressure is 10-1The outer quartz crucible is sealed after Pa and faces the opening end of the second PBN crucible (2), and a hanging piece is connected to the sealed position;
when the inner quartz crucible and the outer quartz crucible are quartz round tubes with one open end and one closed end, the combined first PBN crucible and the second PBN crucible are placed into the inner quartz crucible, the closed end of the first PBN crucible is close to or in contact with the closed end of the inner quartz crucible, then the first exhaust tube is sintered at the open end of the inner quartz crucible, all weighed raw materials are loaded into the first PBN crucible through the first exhaust tube and the second PBN crucible, after the raw materials are loaded, the inner quartz crucible is vacuumized and degassed through the first exhaust tube, and when the pressure is lower than 10 DEG, the pressure is lower than 10 DEG-4Sealing the opening end of the inner-layer quartz crucible when Pa is needed; or putting all the weighed raw materials into a first PBN crucible, combining a second PBN crucible with the first PBN crucible, putting the first PBN crucible and the second PBN crucible which are filled with the raw materials and combined into an inner-layer quartz crucible, enabling the closed end of the first PBN crucible to be close to or contact with the closed end of the inner-layer quartz crucible, sintering a first exhaust tube at the open end of the inner-layer quartz crucible, vacuumizing and degassing the inner-layer quartz crucible through the first exhaust tube, and vacuumizing and degassing the inner-layer quartz crucible when the pressure is lower than 10-4Sealing the opening end of the inner quartz crucible when the pressure is Pa(ii) a Then, the inner-layer quartz crucible is placed into the outer-layer quartz crucible, the closed end of the first PBN crucible faces the closed end of the outer-layer quartz crucible, a second exhaust pipe is sintered at the open end of the outer-layer quartz crucible, then the outer-layer quartz crucible is vacuumized and degassed through the second exhaust pipe, and the pressure is 10-1Sealing the opening end of the outer quartz crucible after Pa, and connecting a hanging piece at the sealed position;
the combination of the first PBN crucible and the second PBN crucible is that the second PBN crucible is arranged at the opening end of the first PBN crucible through the circular outer edge of the second PBN crucible, and the body section behind the circular outer edge is inserted into the first PBN crucible;
(III) Synthesis of polycrystal
① the synthesis is carried out in a tiltable and rotatable two-area heating tube furnace, the two-area heating tube furnace is placed in an inclined way, the inclination angle α is 15-25 degrees, the high end of the two-area heating tube furnace is a low-temperature area, and the low end is a high-temperature area;
②, heating the low-temperature area of the two-area heating tube furnace at a speed of 50-60 ℃/h, heating the high-temperature area at a speed of 30-40 ℃/h, preserving heat at the temperature when the low-temperature area is heated to a temperature T of more than or equal to 300 ℃ and less than 445 ℃, preserving heat for at least 16h when the high-temperature area is heated to a temperature of 720-800 ℃, then heating to a temperature of 950-960 ℃ at a speed of 8-12 ℃/h, preserving heat for at least 24h, after the high-temperature area is preserved heat, simultaneously heating the low-temperature area and the high-temperature area at a constant speed, raising the temperature of the low-temperature area to 1060-1100 ℃ within 8-9 h, raising the temperature of the high-temperature area to 1020-1060 ℃, preserving heat for at least 20h, and then keeping the temperature of the low-temperature area at 1060-1100 ℃ so that the high-temperature area;
③, after the temperature oscillation is finished, reducing the inclination angle α of the two-area heating tube furnace to 10-15 degrees, then respectively cooling the low-temperature area and the high-temperature area to 600-680 ℃ and 550-640 ℃ at the speed of 20-25 ℃/h, and then cooling the low-temperature area and the high-temperature area to room temperature within 2-4 h to obtain the quaternary lithium sulfur compound polycrystal.
In the above method, the quaternary lithium sulfide compound polycrystal is Li2Ga2GeS6Polycrystalline with high purity Li2S and simple substances Ga, Ge and S are taken as raw materials, and the molar ratio of the ingredients is Li2S: ga: ge: and (3) adding the Ge in an amount of 20-50% based on the molar ratio, wherein the S is 1:2:1:5, and the adding amount of the S is 2 times of the molar number increased by the Ge based on the molar ratio.
In the above method, the quaternary lithium sulfide compound polycrystal is Li2CdSnS4Polycrystalline with high purity Li2S and simple substances Cd, Sn and S are used as raw materials, and the molar ratio of the ingredients is Li2S: cd: sn: the amount of S added is increased by 0.1 to 0.5% based on the weight calculated by the molar ratio.
Compared with the prior art, the invention has the following beneficial effects:
1. because the synthesis container is formed by combining a first PBN crucible, a second PBN crucible, an inner layer quartz crucible and an outer layer quartz crucible, when the synthesis container is in a working state, the inner layer quartz crucible is positioned in the outer layer quartz crucible, the combined first PBN crucible and the second PBN crucible are positioned in the inner layer quartz crucible, all raw materials are filled in the first PBN crucible, the inner layer quartz crucible and the outer layer quartz crucible are respectively in a high vacuum state and a low vacuum state, and the heating tube furnace in the two areas is obliquely placed during synthesis, so that one end of the synthesis container filled with the raw materials is positioned in the low end high temperature area of the tube furnace, one end of the synthesis container not filled with the raw materials is positioned in the high end low temperature area of the tube furnace, the raw materials are firstly reacted in the high temperature area through process control, the generated S steam enters the quartz crucible in the low temperature area to be condensed to form liquid S, and then flows back to the first PBN crucible through the, the cyclic reaction is carried out until all S simple substances are converted into compounds, thereby effectively reducing the vapor pressure in the synthesis process and avoiding Li2The contact of S and the inner layer quartz crucible achieves the purpose of preventing the explosion of the synthesis container and ensures the safety of the synthesis process.
2. According to the synthesis process, when a high-temperature area is heated to 720-800 ℃, heat preservation is carried out for at least 16h, when the high-temperature area is heated to 950-960 ℃, heat preservation is carried out for at least 24h, after the heat preservation of the high-temperature area is finished, the temperature of the high-temperature area and the temperature of a low-temperature area are reversed and heat preservation is carried out for at least 20h, then the synthesis of the quaternary sulfur lithium compound polycrystal is carried out by combining a temperature oscillation method, and after the synthesis is finished, the decomposition of a product is inhibited by adopting a gradient cooling mode, so that the synthesized product is a single-phase quaternary sulfur lithium compound polycrystal and.
3. The structure and the synthesis process of the synthesis container can increase the raw material amount (the raw material can reach 50g) for synthesizing the quaternary lithium sulfide compound polycrystal in one time
4. Since the length of the first PBN crucible is greatly shortened compared with the length of the inner quartz crucible, and the second PBN crucible can be reused, the synthesis cost can be reduced.
Drawings
FIG. 1 is a schematic view of a first PBN crucible in a synthesis vessel according to the invention;
FIG. 2 is a left side view of FIG. 1;
FIG. 3 is a schematic view of a second PBN crucible in a synthesis vessel according to the invention;
FIG. 4 is a left side view of FIG. 3;
FIG. 5 is a schematic view of the combination of a second PBN crucible and a first PBN crucible;
FIG. 6 is a first schematic view of an inner quartz crucible in a synthesis vessel according to the invention;
FIG. 7 is a first schematic view of an outer quartz crucible in a synthesis vessel according to the invention;
FIG. 8 is a second schematic view of an inner quartz crucible in a synthesis vessel according to the invention;
FIG. 9 is a second schematic view of an outer quartz crucible in a synthesis vessel according to the invention;
FIG. 10 is a schematic view showing the opening end of the inner quartz crucible sintered with the first exhaust tube after the combined second PBN crucible and first PBN crucible are placed in the inner quartz crucible;
FIG. 11 is a schematic view of the feedstock being charged into a first PBN crucible and sealed after vacuum degassing of the inner quartz crucible;
FIG. 12 is a schematic view showing that the open end of the outer quartz crucible is sintered with the second exhaust tube after the sealed inner quartz crucible is placed in the outer quartz crucible;
FIG. 13 is a schematic view showing the inner quartz crucible being positioned in the outer quartz crucible and sealed after the outer quartz crucible is evacuated and degassed;
FIG. 14 is a schematic view of a two-zone heated tube furnace and a synthesis vessel containing feedstock placed within the two-zone heated tube furnace for use in synthesis in the process of the invention;
FIG. 15 shows Li synthesized in example 12Ga2GeS6A photograph of the polycrystal;
FIG. 16 shows Li synthesized in example 12Ga2GeS6X-ray diffraction pattern of the polymorph;
FIG. 17 shows Li synthesized in example 22CdSnS4A photograph of the polycrystal;
FIG. 18 shows Li synthesized in example 22CdSnS4X-ray diffraction pattern of the polymorph.
In the figure, 1-a first PBN crucible, 2-a second PBN crucible, 2-1-a circular outer edge, 3-an inner layer quartz crucible, 4-an outer layer quartz crucible, 5-a first extraction pipe, 6-a first temperature control thermocouple, 7-a second temperature control thermocouple, 8-a heating element, 9-a raw material, 10-condensed S, 11-S steam, 12-reflowed liquid S, 13-a furnace body, 14-a hanger and 15-a second extraction pipe.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example synthesizes Li2Ga2GeS6Polycrystalline with 6N simple substances Ga, Ge. S powder and 5N Li2S powder is taken as a raw material, and the molar ratio of the ingredients is Li2S: ga: ge: and S is 1:2:1:5, the addition amount of Ge is increased by 40% on the basis of the molar ratio, and the addition amount of S is increased by 2 times of the molar number increased by Ge on the basis of the molar ratio. In particular, Li20.10590mol (4.86551g) of S, 0.21180mol (14.67182g) of Ga, 0.14826mol (10.76812g) of Ge and 0.61422mol (19.69496g) of S, and the total weight of the raw materials is about 50 g.
The synthesis container is formed by combining a first PBN crucible 1, a second PBN crucible 2, an inner-layer quartz crucible 3 and an outer-layer quartz crucible 4; the initial state of the first PBN crucible 1 is as shown in figures 1 and 2, and is a PBN circular tube with one open end and one closed end, the length L1 of the first PBN crucible is 250mm, the inner diameter is 25.5mm, the wall thickness is 0.5mm, and after all raw materials are filled, the distance between the upper surface of the raw material powder and the end face of the open end of the first PBN crucible is 130 mm; the initial state of the second PBN crucible 2 is as shown in figures 3 and 4, and is a PBN truncated cone pipe with two open ends, a circular outer edge 2-1 is arranged around the outer wall of the large end of the second PBN crucible 2, the outer diameter of the large end of the second PBN crucible 2 is smaller than the inner diameter of the first PBN crucible 1, the length L2 is 2/5 of the length L1 of the first PBN crucible 1, the wall thickness is 0.5mm, the aperture diameter d1 of the small end is 6mm, the ratio of the aperture d2 of the large end to the aperture d1 of the small end is 4, the outer diameter of the circular outer edge 2-1 is +1mm of the outer diameter of the first PBN crucible 1, and the thickness is 0.5 mm; the initial state of the inner layer quartz crucible 3 is shown in fig. 8, which is a quartz circular tube with one open end and one closed end, the inner diameter of the quartz circular tube is the same as the nominal size of the outer diameter of the circular outer edge 2-1 of the second PBN crucible 2 and is in movable fit, the ratio of the length L3 to the length L1 of the first PBN crucible 1 is 1.4, and the wall thickness is 1.5 mm; as shown in fig. 9, the outer layer quartz crucible 4 is an open-ended and closed-ended quartz circular tube, and has an inner diameter of +5mm, a length of +5mm and a thickness of 1.5mm, respectively, with respect to the outer diameter of the inner layer quartz crucible 3.
The process comprises the following steps:
(I) cleaning and drying of the synthesis vessel
The inner quartz crucible 3 in the initial state is washed with tap water and then injected with HF and HNO3Solution prepared from tap water (solution prepared from HF and HNO)3From tap waterPrepared by 2:1: 5) for 5 minutes, then washed by tap water to be neutral, and then repeatedly cleaned by deionized water; repeatedly cleaning the first PBN crucible 1, the second PBN crucible 2 and the outer-layer quartz crucible 4 in the initial state by using deionized water; putting the cleaned inner-layer quartz crucible 3, the outer-layer quartz crucible 4, the first PBN crucible 1 and the second PBN crucible 2 into a vacuum drying oven, and drying for later use;
(II) charging
Placing the combined first PBN crucible 1 and second PBN crucible 2 into the inner quartz crucible 3, making the closed end of the first PBN crucible 1 close to the closed end of the inner quartz crucible 3, sintering a first exhaust tube 5 at the open end of the inner quartz crucible 3 (see figure 10), and weighing the raw materials Ga and Li2S, Ge and S are loaded into a first PBN crucible 1 through a first exhaust tube 5 and a second PBN crucible 2, after the raw materials are loaded, the inner-layer quartz crucible is vacuumized and degassed through the first exhaust tube 5, and the pressure is lower than 10-4At Pa, the open end of the inner quartz crucible 3 is sealed (see FIG. 11); then the inner quartz crucible 3 is placed into the outer quartz crucible 4, the closed end of the first PBN crucible 1 faces the closed end of the outer quartz crucible 4, a second exhaust tube 15 (shown in figure 12) is sintered at the open end of the outer quartz crucible 4, and then the outer quartz crucible is vacuumized and degassed through the second exhaust tube 15, and the pressure is 10-1Sealing the opening end of the outer quartz crucible 4 after Pa, and connecting a pendant 14 at the sealed position (see figure 13); the combination of the first PBN crucible 1 and the second PBN crucible 2 is such that the second PBN crucible 2 is placed at the open end of the first PBN crucible 1 by its circular outer edge 2-1, the body section following the circular outer edge being inserted into the first PBN crucible (see fig. 5 and 10). After the completion of the charging, the combination of the synthesizing vessels is also completed, and the respective members are brought into operation.
(III) Synthesis of polycrystal
① the synthesis is carried out in a tiltable and rotatable two-zone heating tube furnace, the two-zone heating tube furnace comprises a furnace body 13 and a heating element 8 arranged on the furnace body, the two-zone heating tube furnace is obliquely arranged during the synthesis, the inclination angle α is 25 degrees, the high end of the two-zone heating tube furnace is a low-temperature zone I, and the low end is a high-temperature zone II;
② heating the low temperature zone of the two-zone heating tube furnace at a speed of 50 ℃/h, heating the high temperature zone at a speed of 40 ℃/h, preserving heat at the temperature when the low temperature zone is heated to 300 ℃, preserving heat for 16h when the high temperature zone is heated to 760 ℃, then heating to 960 ℃ at a speed of 10 ℃/h, preserving heat for 24h, after the high temperature zone is preserved, simultaneously heating the low temperature zone and the high temperature zone at a constant speed, raising the temperature of the low temperature zone to 1080 ℃ within 8h, raising the temperature of the high temperature zone to 1040 ℃ and preserving heat at the temperature for 20h, and then keeping the temperature of the low temperature zone at 1080 ℃ and carrying out three-time temperature oscillation between 960 ℃ and 1040 ℃;
③ after the temperature oscillation is finished, the inclination angle α of the two-area heating tube furnace is reduced to 15 degrees, then the low-temperature area and the high-temperature area are respectively cooled to 660 ℃ and 600 ℃ at the speed of 25 ℃/h, and then the low-temperature area and the high-temperature area are cooled to room temperature within 2h to obtain Li2Ga2GeS6A polycrystalline body.
Li synthesized in this example2Ga2GeS6The form of the polycrystal is shown in FIG. 15, the surface particles are removed, the polycrystal ingot is taken and ground into powder, and the X-ray diffraction spectrum of the powder is shown in FIG. 16 after the X-ray diffraction analysis, as can be seen from FIG. 16, the product synthesized by the embodiment has no impurity phase and is single-phase Li2Ga2GeS6A polycrystalline body.
Example 2
This example synthesizes Li2CdSnS4Polycrystalline body, with 6N simple substance Cd, Sn, S powder and 5N Li2S powder is taken as a raw material, and the molar ratio of the ingredients is Li2S: cd: sn: the amount of S added was increased by 0.5% based on the weight calculated in the above molar ratio, and the total weight of the raw materials was weighed to 40g based on the above ratio.
The synthesis container is formed by combining a first PBN crucible 1, a second PBN crucible 2, an inner-layer quartz crucible 3 and an outer-layer quartz crucible 4; the initial state of the first PBN crucible 1 is as shown in figures 1 and 2, and is a PBN circular tube with one open end and one closed end, the length L1 of the first PBN crucible is 220mm, the inner diameter is 25mm, the wall thickness is 0.5mm, and after all raw materials are filled, the distance from the upper surface of the raw material powder to the end face of the open end of the first PBN crucible is 120 mm; the initial state of the second PBN crucible 2 is as shown in fig. 3 and fig. 4, which is a PBN truncated cone-shaped tube with two open ends, a circular outer edge 2-1 is arranged around the outer wall of the large end of the second PBN crucible 2, the outer diameter of the large end of the second PBN crucible 2 is equal to the inner diameter of the first PBN crucible 1, the length L2 is 80mm, the wall thickness is 0.5mm, the aperture d1 of the small end is 4mm, the ratio of the aperture d2 of the large end to the aperture d1 of the small end is 6, the outer diameter of the circular outer edge 2-1 is +1mm of the outer diameter of the first PBN crucible 1, and the thickness is 0.5 mm; the initial state of the inner layer quartz crucible 3 is shown in FIG. 6, which is a quartz circular tube with openings at both ends, the inner diameter of the quartz circular tube is the same as the nominal size of the outer diameter of the circular outer edge 2-1 of the second PBN crucible 2 and is in movable fit, the ratio of the length L3 to the length L1 of the first PBN crucible 1 is 1.6, and the wall thickness is 1.5 mm; the outer quartz crucible 4 is a circular quartz tube having both ends open as shown in fig. 7, and has an inner diameter of +6mm, a length of +6mm and a thickness of 1.5mm, respectively, of the outer diameter of the inner quartz crucible 3 and the length of the inner quartz crucible 3.
The process comprises the following steps:
(I) cleaning and drying of the synthesis vessel
The cleaning and drying operations of the synthesis vessel were the same as in example 1.
(II) charging
Placing the combined first PBN crucible 1 and second PBN crucible 2 into an inner layer quartz crucible 3, then sealing the opening end of the inner layer quartz crucible 3 facing the closed end of the first PBN crucible 1, and sintering a first exhaust tube 5 at the other opening end of the inner layer quartz crucible 3 (as shown in figure 10); weighing Cd and Li as raw materials2S, Sn and S are sequentially put into the first PBN crucible 1 through the first exhaust tube 5 and the second PBN crucible 2, after the raw materials are put, the inner-layer quartz crucible is vacuumized and degassed through the first exhaust tube 5, and the pressure is lower than 10-4Pa, opening of the quartz crucible 3 of the sealed inner layer toward the second PBN crucible 2Sealing one end of the outer quartz crucible 4 at the opening end (as shown in fig. 11), placing the inner quartz crucible 3 into the outer quartz crucible 4, making the closed end of the first PBN crucible 1 face the sealed end of the outer quartz crucible 4, sintering a second air exhaust tube 15 at the other open end of the outer quartz crucible 4 (as shown in fig. 12), degassing the outer quartz crucible by vacuum pumping through the second air exhaust tube 15, and sealing one end of the outer quartz crucible 4 at a pressure of 10-1After Pa, the outer quartz crucible 4 is sealed and connected to the opening end of the second PBN crucible 2, and a hanger 14 is connected to the sealed position (shown in FIG. 13); the combination of the first PBN crucible 1 and the second PBN crucible 2 is such that the second PBN crucible 2 is placed at the open end of the first PBN crucible 1 by its circular outer edge 2-1, the body section following the circular outer edge being inserted into the first PBN crucible (see fig. 5 and 10). After the completion of the charging, the combination of the synthesizing vessels is also completed, and the respective members are brought into operation.
(III) Synthesis of polycrystal
① the synthesis is carried out in a tiltable and rotatable two-zone heating tube furnace, the two-zone heating tube furnace comprises a furnace body 13 and a heating element 8 arranged on the furnace body, the two-zone heating tube furnace is obliquely arranged during the synthesis, the inclination angle α is 20 degrees, the high end of the two-zone heating tube furnace is a low-temperature zone I, and the low end is a high-temperature zone II;
② heating the low temperature zone of the two-zone heating tube furnace at a speed of 50 ℃/h, heating the high temperature zone at a speed of 40 ℃/h, keeping the temperature at the temperature when the low temperature zone is heated to 300 ℃, keeping the temperature for 20h when the high temperature zone is heated to 720 ℃, then heating to 960 ℃ at a speed of 10 ℃/h, keeping the temperature for 30h, after the heat preservation of the high temperature zone is finished, simultaneously heating the low temperature zone and the high temperature zone at a constant speed, increasing the temperature of the low temperature zone to 1060 ℃ in 8h, increasing the temperature of the high temperature zone to 1040 ℃ and keeping the temperature at the temperature for 20h, and then keeping the temperature of the low temperature zone at 1060 ℃ to carry out three-time temperature oscillation between 960 ℃ and 1040 ℃;
③ after the temperature oscillation is finished, the inclination angle α of the two-area heating tube furnace is reduced to 15 degrees, then the low temperature area and the high temperature area are respectively cooled to 600 ℃ and 550 ℃ at the speed of 25 ℃/h, and then the low temperature area and the high temperature area are cooled to room temperature within 2h to obtain Li2CdSnS4A polycrystalline body.
Li synthesized in this example2CdSnS4The form of the polycrystal is shown in FIG. 17, and the X-ray diffraction spectrum thereof is shown in FIG. 18 after the X-ray diffraction analysis, and it can be seen from FIG. 18 that the product synthesized by the present example has no hetero-phase and is a single-phase Li2CdSnS4A polycrystalline body.

Claims (6)

1. A synthesis container of quaternary lithium sulfide compound polycrystal is characterized in that the synthesis container is formed by combining a first PBN crucible (1), a second PBN crucible (2), an inner-layer quartz crucible (3) and an outer-layer quartz crucible (4);
initial state: the first PBN crucible (1) is a PBN circular tube with an opening at one end and a closed end, and the length L1 of the first PBN crucible meets the requirement that the distance from the upper surface of the contained raw material powder to the end surface of the opening end of the first PBN crucible is more than 1/2L 1; the second PBN crucible (2) is a PBN truncated cone pipe with openings at two ends, the outer diameter of the large end of the second PBN crucible (2) is less than or equal to the inner diameter of the first PBN crucible (1), a circular outer edge (2-1) is arranged around the outer wall of the large end of the second PBN crucible (2), the outer diameter of the circular outer edge (2-1) is greater than the outer diameter of the first PBN crucible (1), and the length L2 of the second PBN crucible (2) is 1/8-2/5 of the length L1 of the first PBN crucible (1); the inner-layer quartz crucible (3) and the outer-layer quartz crucible (4) are both quartz round tubes with one open end and one closed end or quartz round tubes with two open ends, the nominal size of the inner diameter of the inner-layer quartz crucible (3) and the outer diameter of the circular outer edge (2-1) of the second PBN crucible (2) is the same, and the inner diameter of the inner-layer quartz crucible is movably matched with the outer diameter of the circular outer edge (2-1), the ratio of the length L3 of the inner-layer quartz crucible (3) to the length L1 of the first PBN crucible (1) is 1.3-1.7, the inner diameter of the outer-layer quartz crucible (4) is larger than the outer diameter of the inner-layer quartz crucible (3), and the length of the outer-layer quartz crucible (4;
the working state is as follows: the inner-layer quartz crucible (3) and the outer-layer quartz crucible (4) are both quartz round tubes with two closed ends, one end of the outer-layer quartz crucible (4) is provided with a hanging piece (14), and the inner-layer quartz crucible (3) is positioned in the outer-layer quartz crucible (4); the first PBN crucible (1) is positioned in the inner-layer quartz crucible (3) and the closed end of the first PBN crucible is contacted with the end, far away from the outer-layer quartz crucible (4), of the inner-layer quartz crucible (3) and provided with the hanging piece (14); the second PBN crucible (2) is arranged at the opening end of the first PBN crucible (1) through the circular outer edge (2-1), and the main body section behind the circular outer edge is positioned in the first PBN crucible.
2. The container for synthesizing quaternary lithium sulfide compound polycrystal according to claim 1, wherein the ratio of the large end aperture d2 to the small end aperture d1 of the second PBN crucible (2) is 3 to 6.
3. The container for synthesizing the quaternary lithium sulfide compound polycrystal according to claim 1 or 2, wherein the inner diameter of the outer layer quartz crucible (4) is equal to the outer diameter of the inner layer quartz crucible (3) + (4 to 6) mm.
4. A method for synthesizing a quaternary sulfur lithium compound polycrystal by using high-purity Li2The S powder, the simple substance S powder and the high-purity simple substance powder of other two elements of the compound are used as raw materials, and the process comprises the following steps:
(I) cleaning and drying of the synthesis vessel
The synthesis container is as claimed in any one of claims 1 to 3, the first PBN crucible (1), the second PBN crucible (2), the inner quartz crucible (3) and the outer quartz crucible (4) in the initial state are injected with cleaning liquid to be repeatedly cleaned until the PBN crucibles are clean, and then the PBN crucibles are dried to completely remove water in the PBN crucibles;
(II) charging
When the inner quartz crucible (3) and the outer quartz crucible (4) are quartz round tubes with openings at two ends, the first PBN crucible (1) and the second PBN crucible (2) which are combined are placed into the inner quartz crucible (3), then the opening end of the inner quartz crucible (3) facing the closed end of the first PBN crucible (1) is sealed, and then the opening end of the inner quartz crucible (3) facing the closed end of the first PBN crucible (1) is sealedSintering a first exhaust pipe (5) at the other opening end of the inner-layer quartz crucible (3), loading all weighed raw materials into a first PBN crucible (1) through the first exhaust pipe (5) and a second PBN crucible (2), vacuumizing and degassing the inner-layer quartz crucible through the first exhaust pipe (5) after the raw materials are loaded, and when the pressure is lower than 10 DEG, degassing-4When Pa is needed, the inner quartz crucible (3) is sealed and jointed towards the open end of the second PBN crucible (2), then one end of the outer quartz crucible (4) is sealed and jointed, then the inner quartz crucible (3) is placed into the outer quartz crucible (4) and the closed end of the first PBN crucible (1) is made to face the sealed and jointed end of the outer quartz crucible (4), then the second exhaust tube (15) is sintered at the other open end of the outer quartz crucible (4), the outer quartz crucible is vacuumized and degassed through the second exhaust tube (15), and when the pressure is 10 degrees, the pressure is 10 degrees-1The outer quartz crucible (4) is sealed after Pa and faces the opening end of the second PBN crucible (2), and a hanging piece (14) is connected at the sealed position;
when the inner quartz crucible (3) and the outer quartz crucible (4) are quartz round tubes with one open end and one closed end, the first PBN crucible (1) and the second PBN crucible (2) which are combined are placed into the inner quartz crucible (3), the closed end of the first PBN crucible (1) is close to or in contact with the closed end of the inner quartz crucible (3), then the first exhaust tube (5) is sintered at the open end of the inner quartz crucible (3), all the weighed raw materials are placed into the first PBN crucible (1) through the first exhaust tube (5) and the second PBN crucible (2), after the raw materials are placed, the inner quartz crucible is vacuumized and degassed through the first exhaust tube (5), and when the pressure is lower than 10-4When Pa is needed, the opening end of the inner layer quartz crucible (3) is sealed; or all the weighed raw materials are put into a first PBN crucible (1), a second PBN crucible (2) is combined with the first PBN crucible (1), then the first PBN crucible (1) and the second PBN crucible (2) which are filled with the raw materials and combined are put into an inner-layer quartz crucible (3), the closed end of the first PBN crucible (1) is close to or contacted with the closed end of the inner-layer quartz crucible (3), then a first exhaust pipe (5) is sintered at the open end of the inner-layer quartz crucible (3), the inner-layer quartz crucible is vacuumized and degassed through the first exhaust pipe (5), and the pressure is lower than 10-4When Pa is needed, the opening end of the inner layer quartz crucible (3) is sealed; then the inner quartz crucible (3) is placed into the outer quartz crucible (4), and the closed end of the first PBN crucible (1) faces to the outer layerThe closed end of the quartz crucible (4) is sintered at the open end of the outer layer quartz crucible (4) by a second exhaust tube (15), and then the outer layer quartz crucible is vacuumized and degassed by the second exhaust tube (15), and the pressure is 10-1Sealing the opening end of the outer quartz crucible (4) after Pa, and connecting a hanging piece (14) at the sealed position;
the combination of the first PBN crucible (1) and the second PBN crucible (2) is that the second PBN crucible (2) is arranged at the opening end of the first PBN crucible (1) through the circular outer edge (2-1), and the body part behind the circular outer edge is inserted into the first PBN crucible;
(III) Synthesis of polycrystal
① the synthesis is carried out in a tiltable and rotatable two-area heating tube furnace, the two-area heating tube furnace is placed in an inclined way, the inclination angle α is 15-25 degrees, the high end of the two-area heating tube furnace is a low-temperature area, and the low end is a high-temperature area;
②, heating the low-temperature area of the two-area heating tube furnace at a speed of 50-60 ℃/h, heating the high-temperature area at a speed of 30-40 ℃/h, preserving heat at the temperature when the low-temperature area is heated to a temperature T of more than or equal to 300 ℃ and less than 445 ℃, preserving heat for at least 16h when the high-temperature area is heated to a temperature of 720-800 ℃, then heating to a temperature of 950-960 ℃ at a speed of 8-12 ℃/h, preserving heat for at least 24h, after the high-temperature area is preserved heat, simultaneously heating the low-temperature area and the high-temperature area at a constant speed, raising the temperature of the low-temperature area to 1060-1100 ℃ within 8-9 h, raising the temperature of the high-temperature area to 1020-1060 ℃, preserving heat for at least 20h, and then keeping the temperature of the low-temperature area at 1060-1100 ℃ so that the high-temperature area;
③, after the temperature oscillation is finished, reducing the inclination angle α of the two-area heating tube furnace to 10-15 degrees, then respectively cooling the low-temperature area and the high-temperature area to 600-680 ℃ and 550-640 ℃ at the speed of 20-25 ℃/h, and then cooling the low-temperature area and the high-temperature area to room temperature within 2-4 h to obtain the quaternary lithium sulfur compound polycrystal.
5. The method according to claim 4, wherein the quaternary lithium sulfide compound polycrystal is Li2Ga2GeS6Polycrystalline with high purity Li2S and simple substances Ga, Ge and S are taken as raw materials, and the molar ratio of the ingredients is Li2S: ga: ge: and (3) adding the Ge in an amount of 20-50% based on the molar ratio, wherein the S is 1:2:1:5, and the adding amount of the S is 2 times of the molar number increased by the Ge based on the molar ratio.
6. The method according to claim 4, wherein the quaternary lithium sulfide compound polycrystal is Li2CdSnS4Polycrystalline with high purity Li2S and simple substances Cd, Sn and S are used as raw materials, and the molar ratio of the ingredients is Li2S: cd: sn: the amount of S added is increased by 0.1 to 0.5% based on the weight calculated by the molar ratio.
CN201911285498.XA 2019-12-13 2019-12-13 Synthetic container and synthetic method of quaternary sulfur lithium compound polycrystal Expired - Fee Related CN111041559B (en)

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