Low-temperature preparation method of silver-containing liquid metal alloy

Abstract

The invention provides a low-temperature preparation method of a silver-containing liquid metal alloy, which comprises the following steps: adding Ag powder into a mother solution, and mechanically grinding and standing in a nitrogen atmosphere at the temperature of 20-40 DEG C to obtain the silver-containing liquid metal alloy, the mass fraction of Ag in the silver-containing liquid metal alloy is 1%-4%; the mother liquor is pure Ga, a GaIn eutectic alloy, a GaInSn eutectic alloy or a GaInSnZn eutectic alloy. According to the method, under the nitrogen protection condition and the low-temperature condition of 20-40 DEG C, the Ag powder is evenly added into the gallium-based liquid metal, mechanical stirring is conducted, the silver-containing liquid metal is prepared, the smelting temperature of the silver-containing liquid metal is remarkably reduced, the preparation technology is simplified, low-temperature preparation of the liquid metal reducing agent with the low oxygen content is achieved, and the method is suitable for large-scale production. The prepared silver-containing liquid metal alloy can be used for reducing tungsten oxide to prepare a hydrogen tungsten bronze material.

Description

Technical Field

[0001] The invention belongs to the technical field of liquid metal material preparation, and in particular relates to a low-temperature preparation method of a silver-containing liquid metal alloy. Background Art

[0002] Liquid metal is liquid at room temperature, has high boiling point, strong electrical conductivity, high thermal conductivity and other properties, and contains many novel properties that have never been known before. It is providing important inspiration and extremely rich research space for a large number of emerging scientific and technological frontiers. The existing liquid metal reducing agent is prepared by high-temperature smelting method. Two or more metal components are mixed together, and the metals are melted to prepare liquid metal. The temperature is usually 200-300℃. Liquid metal is easy to oxidize under high temperature conditions, which increases the content of oxide impurities in the liquid metal. Summary of the invention

[0003] The technical problem to be solved by the present invention is to provide a low-temperature preparation method for a silver-containing liquid metal alloy in view of the deficiencies of the above-mentioned prior art. The method adopts a nitrogen protection condition and a low temperature condition of 20°C to 40°C to uniformly add Ag powder to a gallium-based liquid metal, and mechanically stir to prepare a silver-containing liquid metal, thereby significantly reducing the melting temperature of the silver-containing liquid metal and simplifying the preparation process, thereby realizing the low-temperature preparation of a liquid metal reducing agent with a low oxygen content. The prepared silver-containing liquid metal alloy can be used to reduce tungsten oxide to prepare hydrogen tungsten bronze material.

[0004] In order to solve the above technical problems, the technical solution adopted by the present invention is: a low-temperature preparation method of a silver-containing liquid metal alloy, the method comprising:

[0005] Add Ag powder to the mother liquid, and mechanically grind for 1 min to 10 min in a nitrogen atmosphere at a temperature of 20° C. to 40° C., with a grinding frequency of 10 times / min to 30 times / min, and after standing, obtain a silver-containing liquid metal alloy; the mass fraction of Ag in the silver-containing liquid metal alloy is 1% to 4%; the mother liquid is pure Ga, GaIn eutectic alloy, GaInSn eutectic alloy or GaInSnZn eutectic alloy;

[0006] Preferably, the standing time is 1 h to 12 h.

[0007] Preferably, the average particle size of the Ag powder is 100 nm to 1 μm.

[0008] Compared with the prior art, the present invention has the following advantages:

[0009] The present invention uses gallium-based liquid metal as a mother liquid, and adds a silver additive by mechanical grinding. It is not necessary to heat the metal above the melting point. Under nitrogen protection conditions, at a low temperature of 20°C to 40°C, Ag powder is uniformly added to the liquid metal, and mechanically stirred to prepare a silver-containing liquid metal, which significantly reduces the melting temperature of the silver-containing liquid metal and simplifies the preparation process. The low-temperature preparation of a liquid metal reducing agent with a low oxygen content is achieved, and the prepared liquid metal reducing agent is used to reduce tungsten oxide to prepare a hydrogen tungsten bronze material.

[0010] The present invention is further described in detail below with reference to the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 3 is a SEM image of the silver-containing liquid metal alloy prepared in Example 1 of the present invention.

[0012] Figure 2 It is the energy spectrum diagram of the silver-containing liquid metal alloy prepared in Example 1 of the present invention.

[0013] Figure 3 This is a differential scanning calorimetry analysis diagram of the silver-containing liquid metal alloy prepared in Example 1 of the present invention.

[0014] Figure 4 1 is the X-ray diffraction pattern of the silver-containing liquid metal alloy prepared in Examples 1-3 of the present invention.

[0015] Figure 5 3 is a SEM image of the silver-containing liquid metal alloy prepared in Example 4 of the present invention.

[0016] Figure 6 3 is an energy spectrum diagram of the silver-containing liquid metal alloy prepared in Example 4 of the present invention.

[0017] Figure 7 3 is a differential scanning calorimetry analysis diagram of the silver-containing liquid metal alloy prepared in Example 4 of the present invention.

[0018] Figure 8 4-5 is the X-ray diffraction pattern of the silver-containing liquid metal alloy prepared in Example 4-5 of the present invention.

[0019] Fig. 9 The silver-containing liquid metal alloy prepared in Example 4 of the present invention is used to reduce WO3 to hydrogen tungsten hydrogen copper structure HWO x X-ray diffraction pattern of . DETAILED DESCRIPTION

[0020] Example 1

[0021] The low-temperature preparation method of the silver-containing liquid metal alloy of this embodiment is as follows:

[0022] Ag powder with an average particle size of 100 nm was added to the mother liquid pure Ga, and mechanically ground in an agate mortar for 1 min in a nitrogen atmosphere at a temperature of 20°C, with a grinding frequency of 10 times / min. After standing for 1 hour to achieve sufficient contact between lattices, a silver-containing liquid metal alloy was obtained, which was named GaAg2%; the mass fraction of Ag in the silver-containing liquid metal alloy was 2%.

[0023] like Figure 1 As shown, it is the SEM picture of GaAg2% prepared in this embodiment. It can be seen from the picture that there is no segregation of GaAg liquid metal.

[0024] Depend on Figure 2 It can be seen that the Ag element is evenly distributed in the liquid metal.

[0025] Depend on Figure 3 It can be seen that the melting point of GaAg2% liquid metal is 29.6°C.

[0026] Example 2

[0027] The low-temperature preparation method of the silver-containing liquid metal alloy in this embodiment is the same as that in Embodiment 1, except that the mass fraction of Ag in the silver-containing liquid metal alloy is 1%, and the obtained silver-containing liquid metal alloy is named GaAg1%.

[0028] Example 3

[0029] The low-temperature preparation method of the silver-containing liquid metal alloy in this embodiment is the same as that in Embodiment 1, except that the mass fraction of Ag in the silver-containing liquid metal alloy is 4%, and the obtained silver-containing liquid metal alloy is named GaAg4%.

[0030] The x-ray diffraction patterns of the silver-containing liquid metal alloys (GaAg2%, GaAg1%, GaAg4%) prepared in Examples 1-3 are as follows: Figure 4 As shown by Figure 4 It can be seen that the formed GaAg alloy has a liquid phase structure at room temperature.

[0031] Example 4

[0032] The low-temperature preparation method of the silver-containing liquid metal alloy of this embodiment is as follows:

[0033] S1. Add Ag powder with an average particle size of 1 μm to the mother liquid GaInSn eutectic alloy, grind it mechanically in an agate mortar for 10 minutes in a nitrogen atmosphere at a temperature of 40°C, with a grinding frequency of 30 times / min. After standing for 12 hours to achieve sufficient contact between crystal lattices, a silver-containing liquid metal alloy is obtained, which is named GaInSn Ag2%; the mass fraction of Ag in the silver-containing liquid metal alloy is 2%.

[0034] The GaInSn eutectic alloy is made of the following raw materials in mass fractions: Ga 68.5%, In 21.5%, and Sn 10%.

[0035] like Figure 5 As shown, it is a SEM picture of GaInSn Ag2% prepared in this embodiment. It can be seen from the picture that the prepared liquid metal is uniform without obvious segregation.

[0036] like Figure 6 As shown, it is the energy spectrum diagram of GaInSn Ag2% prepared in this embodiment. It can be seen from the figure that the elements in the liquid metal are evenly distributed.

[0037] Depend on Figure 7 It can be seen that the melting point of GaInSnAg2% is 10.7°C.

[0038] Example 5

[0039] The low-temperature preparation method of the silver-containing liquid metal alloy of this embodiment is the same as that of Embodiment 4, except that the mass fraction of Ag in the silver-containing liquid metal alloy is 4%. The obtained silver-containing liquid metal alloy is named GaInSn Ag4%.

[0040] like Figure 8 As shown, the x-ray diffraction pattern of the silver-containing liquid metal alloy (GaInSn Ag2%, GaInSnAg4%) prepared in Example 4-5 is shown. Figure 8 It can be seen that the formed GaInSnAg alloy presents a liquid phase structure at room temperature.

[0041] Example 6

[0042] The low-temperature preparation method of the silver-containing liquid metal alloy of this embodiment is as follows:

[0043] S1. Add Ag powder with an average particle size of 1 μm to the mother liquid GaIn eutectic alloy, grind it mechanically in an agate mortar for 10 minutes in a nitrogen atmosphere at a temperature of 40°C, with a grinding frequency of 30 times / min. After standing for 1 hour, a silver-containing liquid metal alloy is obtained, which is named GaIn Ag2%; the mass fraction of Ag in the silver-containing liquid metal alloy is 2%.

[0044] The GaIn eutectic alloy is made of the following raw materials in mass fractions: Ga 60% and In 40%.

[0045] Example 7

[0046] The low-temperature preparation method of the silver-containing liquid metal alloy of this embodiment is as follows:

[0047] S1. Add Ag powder with an average particle size of 100 nm to the mother liquid GaInSnZn eutectic alloy, grind it mechanically in an agate mortar for 5 minutes in a nitrogen atmosphere at a temperature of 20°C, with a grinding frequency of 20 times / min. After standing for 10 hours, a silver-containing liquid metal alloy is obtained, which is named GaInSnZn Ag2%; the mass fraction of Ag in the silver-containing liquid metal alloy is 2%.

[0048] The GaInSnZn eutectic alloy is made of the following raw materials in mass fractions: Ga 65%, In 23%, Sn 11%, and Zn 1%.

[0049] The silver-containing liquid metal alloy prepared by the present invention can undergo redox reactions with materials such as CuO, WO3, and MoO3, and can be used as a liquid metal reducing agent. For example, it can be used to reduce WO3 to a hydrogen tungsten hydrogen copper structure (HWO3) in an environment with a pH value of ≤ 1. x )Material.

[0050] like Fig. 9 As shown, the silver-containing liquid metal alloy prepared in Example 4 is used to reduce WO3 to hydrogen tungsten hydrogen copper structure HWO x , hydrogen tungsten hydrogen copper structure HWO x It is a class of non-stoichiometric compounds with a variety of unique electronic properties and has broad application prospects in photocatalysis, solid oxide fuel cells, organic photovoltaic cells, energy storage, electrochromism and photochromism.

[0051] The above is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent change made to the above embodiment according to the technical essence of the invention still falls within the protection scope of the technical solution of the present invention.

Claims

1. A low-temperature preparation method of a silver-containing liquid metal alloy, characterized in that: The method is: Add Ag powder to the mother liquor, and mechanically grind for 1 min to 10 min in a nitrogen atmosphere at a temperature of 20° C. to 40° C., with a grinding frequency of 10 times / min to 30 times / min. After standing, a silver-containing liquid metal alloy is obtained; the mass fraction of Ag in the silver-containing liquid metal alloy is 1% to 4%; the mother liquor is pure Ga, GaIn eutectic alloy, GaInSn eutectic alloy or GaInSnZn eutectic alloy.

2. The low-temperature preparation method of a silver-containing liquid metal alloy according to claim 1, characterized in that: The standing time is 1h to 12h.

3. The low-temperature preparation method of a silver-containing liquid metal alloy according to claim 1, characterized in that: The average particle size of the Ag powder is 100 nm to 1 μm.

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