Preparation method and application of silicon-based inorganic filler for extracting interface structure recombination from mine tailing solid waste

Abstract

The invention discloses a preparation method and application of a silicon-based inorganic filler for extracting interface structure recombination from mine tailing solid waste, and the ore tailing solid waste comes from a non-ferrous metal mine in Hunan province, including but not limited to tin ore, lead zinc ore and copper ore. According to the method, the non-ferrous metal mine tailing solid waste is extracted by adopting a plasma-assisted high-energy ball milling technology, the silicon-based inorganic filler with a recombined interface structure can be effectively prepared and is applied to the lithium metal solid-state battery, and the technical blank of secondary utilization of low-grade solid waste is filled. According to the invention, by utilizing high disorder and interaction among various trace transition metals in solid wastes, the high ionic conductivity and high interface stability of the silicon-based inorganic filler are effectively improved, and the mass transfer process in the sodium metal solid-state battery in a wide temperature range is effectively promoted; the first coulombic efficiency and charge-discharge capacity of the medium-nickel-based solid-state battery at normal temperature are effectively improved, the medium-nickel-based solid-state battery can be used as a new energy electrochemical battery material, and the resource utilization rate is high. In addition, the surface reconstruction technology is relatively low in production cost, simple in preparation process and mild in reaction condition, the used materials are safe and non-toxic, and industrial-grade implementation and application of the sodium-ion battery positive electrode material are facilitated.

Description

Technical Field

[0001] The present invention belongs to the field of solid waste treatment and recycling, and relates to a preparation method and application of a silicon-based inorganic filler material for lithium metal batteries extracted from mine tailings solid waste. Background Art

[0002] Tailings refer to a large amount of solid waste generated after the beneficiation and smelting of non-ferrous metal ores. They usually contain residual heavy metals, chemical reagents and other harmful substances, posing problems of environmental pollution and waste of resources.

[0003] Among them, the main component of mine tailings is SiO2, with a content of more than 70%, and also contains a certain amount of trace metal components. SiO2 materials with stable physicochemical properties and high conductivity have been widely used in many fields such as electrocatalysis and electrochemical energy storage. Therefore, mine tailings rich in SiO2 are expected to be used in the field of solid-state lithium-ion batteries, realize the recycling of resources, and open up a new application environment for the treatment of tailings. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention aims to provide a silicon-based inorganic filler Si for extracting interface structure reorganization from mine tailings solid waste. 1-x TM x Preparation method and application technology of O2. This silicon-based inorganic filler has high conductivity and stable structure, which can effectively promote the ion diffusion process of solid-state lithium-ion batteries at room temperature, solving the limitation that traditional solid-state lithium metal batteries can only work at high temperatures (≥45°C).

[0005] At the same time, the extraction and processing method has mild conditions, simple process, short production cycle and stable material properties, which is conducive to expanding production.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions to achieve it.

[0007] A preparation method and application of a silicon-based inorganic filler for extracting an interface structure reorganization from mine tailings solid waste, characterized in that it comprises a silicon-based inorganic filler and an amorphous carbon-based modification layer modified on the surface of the silicon-based inorganic filler, and a solid-state lithium battery electrolyte modified by the silicon-based inorganic filler; the silicon-based inorganic filler is Si doped with a large amount of trace mining metals. 1- x TM x O2 material; the TM metal is transition metal elements such as Sn, Pb, Zn and Cu derived from mining materials; the thickness of the amorphous carbon-based modification layer is 10~20nm.

[0008] The method for preparing a silicon-based inorganic filler with reorganized interface structure extracted from mine tailings solid waste as described above comprises the following steps: 1) A certain mass of mine tailings solid waste blocks are dispersed in anhydrous ethanol, and the evenly dispersed suspension is placed in an agate ball mill jar and pre-treated in a planetary ball mill; thereafter, the crushed mine tailings solid waste powder is washed with concentrated hydrochloric acid, filtered, and dried to obtain mine tailings solid waste powder; wherein the mass fraction of concentrated hydrochloric acid is 20-30%; the rotation speed of the planetary ball mill is 300-500rpm, and the processing time is 8-16h; 2) The mine tailings solid waste powder obtained in step 1) is mixed evenly with urea in a certain mass ratio, and the evenly mixed powder sample components are placed in a stainless steel ball mill, and the tank is filled with a protective atmosphere and then placed in a plasma-assisted high-energy ball mill for treatment, and the discharge treatment is carried out under high voltage and low current conditions for 16 to 20 hours, and a silicon-based precursor material is obtained after the reaction is completed; 3) The silicon-based precursor material obtained in step 2) is sintered under a protective atmosphere to obtain a silicon-based inorganic filler with a reorganized interface structure.

[0009] Preferably, in the mixed powder of mine tailings solid waste powder and urea in a certain mass ratio in step 2), the mass ratio of the solid waste powder to urea is 1:2-1:6.

[0010] Preferably, in step 2), the protective atmosphere is one or both of argon and nitrogen; the high voltage of the plasma-assisted high-energy ball mill is 10-15 kV, and the low current is 1-1.5 mA.

[0011] Preferably, the calcination atmosphere in step 3) is one or both of nitrogen and argon; the calcination is carried out at 300-500° C. for 3-6 hours.

[0012] The present invention also includes a method for applying a silicon-based inorganic filler with reorganized interface structure in a solid-state lithium metal battery, comprising the following steps: 1) The obtained silicon-based inorganic filler with reorganized interface structure is evenly mixed with a certain amount of organic lithium salt and polymer material, and then dispersed in an anhydrous organic solvent and stirred evenly; 2) Pour the obtained mixed solution into a polytetrafluoroethylene mold and dry it at 60-80°C for 6-12h to obtain a solid electrolyte for a solid lithium battery treated with a silicon-based inorganic filler.

[0013] Preferably, in step 1), the mass ratio of the silicon-based inorganic filler with reorganized interface structure to the organic lithium salt is 1:100 to 1:25.

[0014] Preferably, in step 1), the organic lithium salt is one or more of lithium trifluoromethanesulfonate or lithium bis(trifluoromethanesulfonyl imide); the polymer material is one or more of polyvinylidene fluoride or polyvinylidene fluoride-hexafluoropropylene; and the anhydrous organic solvent is one or more of ethylbenzene, N,N-dimethylformamide, and diethyl carbonate.

[0015] Application of a silicon-based inorganic filler with reorganized interface structure as described in any of the above items in the preparation of solid-state lithium metal batteries.

[0016] The present invention adopts a recycling method with mild reaction conditions and simple process flow to directly extract silicon-based inorganic fillers from mine tailings solid waste, and construct a structurally reorganized carbon-based surface modification layer on its interface. The trace metal elements remaining in the ore raw materials are doped into the silicon-based inorganic fillers to achieve its structural characteristics of high ionic conductivity and high crystallinity, effectively improving the ionic conductivity and high interface stability characteristics of the solid lithium metal electrolyte.

[0017] The silicon-based inorganic filler Si with reorganized interface structure obtained by the present invention 1-x TM x O2 materials are applied to solid-state lithium metal batteries, and the working capacity of all-solid-state lithium metal batteries at room temperature is significantly improved. When the test temperature is 60°C and 25°C, the current density is 25μA / cm 2 When the all-solid-state lithium metal symmetric battery is charged / discharged for 1 h, the overpotential is only 35.8 mV and 179.8 mV (80 mV and 449.1 mV for the original material); 0.8 Co 0.1 Mn 0.1 When O2 is used as the positive electrode, the assembled all-solid-state lithium metal battery has a first discharge capacity and first coulombic efficiency of 147.85 mAh / g and 86.3 respectively when the charge and discharge voltage range is 2.8~4.3 V and the charge and discharge current is 0.1C, while the original sample cannot work normally at room temperature.

[0018] Compared with the prior art, the advantages of the present invention are: 1) The present invention provides a new solution for the high-value utilization of mine tailings solid waste. The recovery process has mild reaction conditions and a simple process flow, and is suitable for industrial large-scale production.

[0019] 2) The silicon-based inorganic filler with reorganized interface structure prepared by the present invention can effectively improve the comprehensive performance of solid-state lithium metal batteries, and has the advantages of high capacity retention rate at room temperature, long cycle life and high first coulombic efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1This is a scanning electron microscope image of the silicon-based inorganic filler with reorganized interface structure prepared in Example 1 of the present invention.

[0021] Figure 2 This is a transmission electron microscopy image of the silicon-based inorganic filler with reorganized interface structure prepared in Example 1 of the present invention.

[0022] Figure 3 This is the XRD curve of the silicon-based inorganic filler with reorganized interface structure prepared in Example 1 of the present invention.

[0023] Figure 4 The solid electrolyte modified with the silicon-based inorganic filler with reorganized interface structure prepared in Example 1 of the present invention and the original solid electrolyte material of Comparative Example 1 were used to prepare an all-solid-state lithium metal symmetric battery at 60°C and 25 μA / cm 2 Comparison of the first charge and discharge curves of 1h of charge / discharge under the condition of .

[0024] Figure 5 The solid electrolyte modified by the silicon-based inorganic filler with reorganized interface structure prepared in Example 1 of the present invention is made into an all-solid-state lithium metal symmetric battery at 60°C and 25μA / cm 2 1h charge / discharge cycle performance diagram under the condition of .

[0025] Figure 6 This is a scanning electron microscope image of a solid electrolyte modified with a silicon-based inorganic filler and having a reorganized interface structure prepared in Example 2 of the present invention.

[0026] Figure 7 The solid electrolyte modified with the silicon-based inorganic filler with reorganized interface structure prepared in Example 2 of the present invention and the original solid electrolyte material of Comparative Example 1 were used to prepare an all-solid-state lithium metal symmetric battery at 25°C and 25 μA / cm 2 Comparison of the first charge and discharge curves of 1h of charge / discharge under the condition of .

[0027] Figure 8 The first charge and discharge curves of an all-solid-state lithium metal battery made of a solid electrolyte modified with a silicon-based inorganic filler with reorganized interface structure prepared in Example 3 of the present invention at 25°C and 0.1.

[0028] Fig. 9 The first charge and discharge curves of an all-solid-state lithium metal battery made from a solid electrolyte modified with a silicon-based inorganic filler with reorganized interface structure prepared in Comparative Example 1 of the present invention at 25°C and 0.1. Fig.10 The present invention is a flow chart of the method. DETAILED DESCRIPTION

[0029] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully below in conjunction with the accompanying drawings and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0030] Unless otherwise defined, all the professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used below are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0031] Unless otherwise specified, all reagents and raw materials used in the present invention are commercially available products or products that can be prepared by known methods.

[0032] Embodiment 1: A preparation method and application of silicon-based inorganic filler extracted from mine tailings solid waste, wherein the chemical formula of the interface structure reorganization is Si 1-x TM x O2 inorganic filler; in this embodiment, Si 1-x TM x The mass ratio of the total mass of the O2 inorganic filler to the solid electrolyte is 1:100.

[0033] The specific steps of the method for preparing the above-mentioned surface structure reorganized polyanion positive electrode material are: First, 10g of mine tailings solid waste block was dispersed in 200mL of anhydrous ethanol, and the evenly dispersed suspension was placed in an agate ball mill, and the ball mill was run at a speed of 300rpm for 16h. The crushed mine tailings solid waste powder was washed with 20% concentrated hydrochloric acid, filtered, and dried to obtain mine tailings solid waste powder. After that, 1g of mine tailings solid waste powder was evenly mixed with 2g of urea, placed in a stainless steel ball mill, and the tank was filled with Ar and placed in a plasma-assisted high-energy ball mill for treatment. The discharge treatment was carried out under 15kV and 1.5mA for 16h, and the silicon-based precursor material was obtained after the reaction was completed. Finally, the obtained silicon-based precursor material was sintered under Ar, and calcined at 300℃ for 6h to obtain a silicon-based inorganic filler with reorganized interface structure.

[0034] The obtained 0.005g of the silicon-based inorganic filler with reorganized interface structure, 0.5g of lithium bis(trifluoromethanesulfonyl imide) and 0.5g of polyvinylidene fluoride-hexafluoropropylene were evenly mixed and dispersed in 10mL of anhydrous N,N-dimethylformamide, stirred evenly and poured into a polytetrafluoroethylene mold, and dried at 60°C for 12h to obtain a solid-state lithium battery solid electrolyte treated with a silicon-based inorganic filler.

[0035] like Figure 1As shown in FIG. 1 , it is a scanning electron microscope image of the silicon-based inorganic filler with reorganized interface structure prepared in this embodiment. It can be seen from the image that the silicon-based material particles obtained by treating the waste ore solid waste are small, and are agglomerated secondary particles with a diameter of only about 100 nm, which is conducive to improving the ion diffusion process. Figure 2 , which is a transmission electron microscope image of the silicon-based inorganic filler with reorganized interface structure prepared in this embodiment. It can be seen from the image that an amorphous coating layer phase is uniformly grown on the surface of the polyanion positive electrode material, and the thickness of the surface modification layer is about 15 nm.

[0036] The silicon-based inorganic filler with reorganized interface structure prepared in this example was subjected to X-ray diffraction test, and its XRD curve is as follows: Figure 3 As shown in the curve in, by analyzing the XRD data, it can be seen that the prepared silicon-based inorganic material has high crystallinity, which is beneficial to improving the electron transmission process.

[0037] The silicon-based inorganic filler with reorganized interface structure of this embodiment was made into a solid lithium metal battery electrolyte, and its electrochemical performance was tested. The lithium metal symmetric battery composed of the solid lithium metal battery had an electrochemical performance of 60°C and 25μA / cm 2 The first cycle charge / discharge curves and cycle performance of 1h charge / discharge are as follows: Figure 4 and Figure 5 As shown in the figure, the polarization overpotential of the lithium metal symmetric battery at 60°C is only 35.8mV, and it has stable cycle stability, indicating that the fast ion migration channel of the silicon-based inorganic filler material with reorganized interface structure can significantly reduce the polarization overpotential of the material and accelerate the kinetic process.

[0038] Embodiment 2: A preparation method and application of silicon-based inorganic filler extracted from mine tailings solid waste, wherein the chemical formula of the interface structure reorganization is Si 1-x TM x O2 inorganic filler; in this embodiment, Si 1-x TM x The mass ratio of the total mass of the O2 inorganic filler to the solid electrolyte is 1:50.

[0039] The specific steps of the method for preparing the above-mentioned surface structure reorganized polyanion positive electrode material are: Disperse 10g of mine tailings solid waste block in 200mL of anhydrous ethanol, put the evenly dispersed suspension into an agate ball mill, and mill it at a speed of 400rpm for 12h. Wash the crushed mine tailings solid waste powder with 25% concentrated hydrochloric acid, filter and dry it to obtain mine tailings solid waste powder. After that, mix 1g of mine tailings solid waste powder with 4g of urea, put it in a stainless steel ball mill, fill the tank with Ar and put it in a plasma-assisted high-energy ball mill for treatment. Discharge treatment is carried out under the conditions of 10kV and 1mA for 20h. After the reaction is completed, a silicon-based precursor material is obtained. Finally, the obtained silicon-based precursor material is sintered under Ar, and calcined at 400℃ for 5h to obtain a silicon-based inorganic filler with reorganized interface structure.

[0040] The obtained 0.010g of the silicon-based inorganic filler with reorganized interface structure, 0.5g of lithium bis(trifluoromethanesulfonyl imide) and 0.5g of polyvinylidene fluoride-hexafluoropropylene were evenly mixed and dispersed in 10mL of anhydrous N,N-dimethylformamide, stirred evenly and poured into a polytetrafluoroethylene mold, and dried at 70°C for 10h to obtain a solid-state lithium battery solid electrolyte treated with a silicon-based inorganic filler.

[0041] like Figure 6 As shown, it is a scanning electron microscope image of the solid electrolyte modified with silicon-based inorganic filler with reorganized interface structure prepared in this embodiment. It can be seen from the figure that the contact of the solid electrolyte after treatment is closer, which is conducive to shortening the ion diffusion path.

[0042] The silicon-based inorganic filler with reorganized interface structure of this embodiment was made into a solid lithium metal battery electrolyte, and its electrochemical performance was tested. The lithium metal symmetric battery composed of the solid lithium metal electrolyte had an electrochemical performance of 25°C and 25μA / cm 2 The first cycle charge and discharge curve of 1h charge / discharge is as follows: Figure 7 As shown in the figure, the polarization overpotential of the lithium metal symmetric battery at 25°C is only 179.8mV, which is much smaller than the original sample (449.1mV), indicating that the silicon-based inorganic filler material with reorganized interface structure effectively improves the electronic conductivity and surface activity of the solid electrolyte at room temperature, significantly improves the ion diffusion rate of the material at room temperature, and improves the charge and discharge capacity.

[0043] Embodiment 3: A preparation method and application of silicon-based inorganic filler extracted from mine tailings solid waste, wherein the chemical formula of the interface structure reorganization is Si 1-x TM x O2 inorganic filler; in this embodiment, Si 1-x TM x The mass ratio of the total mass of the O2 inorganic filler to the solid electrolyte is 1:25.

[0044] The specific steps of the method for preparing the above-mentioned surface structure reorganized polyanion positive electrode material are: Disperse 10g of mine tailings solid waste block in 200mL of anhydrous ethanol, put the evenly dispersed suspension into an agate ball mill, and mill it at a speed of 500rpm for 8h. Wash the crushed mine tailings solid waste powder with 30% concentrated hydrochloric acid, filter and dry it to obtain mine tailings solid waste powder. After that, mix 1g of mine tailings solid waste powder with 6g of urea, put it in a stainless steel ball mill, fill the tank with Ar and put it in a plasma-assisted high-energy ball mill for treatment. Discharge treatment is carried out under 12kV and 1.3mA for 18h, and silicon-based precursor material is obtained after the reaction is completed. Finally, the obtained silicon-based precursor material is sintered under Ar, and calcined at 500℃ for 3h to obtain a silicon-based inorganic filler with reorganized interface structure.

[0045] The obtained 0.020g of the silicon-based inorganic filler with reorganized interface structure, 0.5g of lithium bis(trifluoromethanesulfonyl imide) and 0.5g of polyvinylidene fluoride-hexafluoropropylene were evenly mixed and dispersed in 10mL of anhydrous N,N-dimethylformamide, stirred evenly and poured into a polytetrafluoroethylene mold, and dried at 80°C for 6h to obtain a solid-state lithium battery solid electrolyte treated with a silicon-based inorganic filler.

[0046] The silicon-based inorganic filler with reorganized interface structure of this embodiment was made into a solid lithium metal battery electrolyte, and its electrochemical performance was tested. 0.8 Co 0.1 Mn 0.1 O2 is used as the positive electrode material to assemble an all-solid-state lithium metal full battery. Figure 8 This is its first cycle charge and discharge curve at 25°C and 0.1C. As shown in the figure, the all-solid-state lithium metal battery still has excellent charge and discharge capabilities at 25°C, and its first discharge specific capacity and first coulombic efficiency are as high as 147.85mAh / g and 86.3%, indicating that the silicon-based inorganic filler material with reorganized interface structure effectively improves the discharge capacity of solid-state lithium metal batteries at room temperature, breaking through the limitation that solid-state lithium batteries can only work at high temperatures.

[0047] Comparative Example 1: 0.5 g of lithium bis(trifluoromethanesulfonyl imide) and 0.5 g of polyvinylidene fluoride-hexafluoropropylene were evenly mixed and dispersed in 10 mL of anhydrous N,N-dimethylformamide. After stirring evenly, the mixture was poured into a polytetrafluoroethylene mold and dried at 60°C for 12 h to obtain the original solid-state lithium battery solid electrolyte.

[0048] Furthermore, the solid-state lithium metal battery electrolyte of this comparative example was subjected to electrochemical performance testing. The composed lithium metal symmetric battery was tested at 60°C and 25 μA / cm 2and 25°C, 25μA / cm 2 The first cycle charge and discharge curves of the charge / discharge cycle for 1h are as follows: Figure 4 and Figure 7 As shown in the figure, the polarization overpotential of the original sample is large, which is 80.0mV and 449.1mV respectively, indicating that it has a lower lithium ion diffusion coefficient at high temperature and room temperature.

[0049] Afterwards, commercial LiNi 0.8 Co 0.1 Mn 0.1 O2 is used as the positive electrode material to assemble an all-solid-state lithium metal battery. Fig. 9 This is its first cycle charge and discharge curve at 25°C and 0.1C. As shown in the figure, the assembled all-solid-state lithium metal battery basically has no charge and discharge capabilities at room temperature and cannot work normally.

[0050] The above embodiment is one of the more preferred specific implementation methods of the present invention. Common changes and substitutions made by those skilled in the art within the scope of this technical solution should be included in the protection scope of the present invention.

Claims

1. A preparation method and application of a silicon-based inorganic filler for extracting interface structure reorganization from mine tailings solid waste, characterized in that: The invention comprises a silicon-based inorganic filler and an amorphous carbon-based modified layer modified on the surface of the silicon-based inorganic filler, and a solid-state lithium battery electrolyte modified with the silicon-based inorganic filler; the silicon-based inorganic filler is Si doped with a plurality of trace mineral metals. 1- x TM x O2 material; the TM metal is one or more of transition metals such as Sn, Pb, Zn and Cu derived from mining materials; the thickness of the amorphous carbon-based modification layer is 10~20nm.

2. The method for preparing a silicon-based inorganic filler with reconstructed interface structure extracted from mine tailings solid waste according to claim 1, characterized in that: The following steps are involved: 1) A certain mass of mine tailings solid waste blocks are dispersed in anhydrous ethanol, and the evenly dispersed suspension is placed in an agate ball mill jar and pre-treated in a planetary ball mill; thereafter, the crushed mine tailings solid waste powder is washed with concentrated hydrochloric acid, filtered, and dried to obtain mine tailings solid waste powder; wherein the mass fraction of concentrated hydrochloric acid is 20-30%; the rotation speed of the planetary ball mill is 300-500rpm, and the processing time is 8-16h; 2) The mine tailings solid waste powder obtained in step 1) is mixed evenly with urea in a certain mass ratio, and the evenly mixed powder sample components are placed in a stainless steel ball mill, and the tank is filled with a protective atmosphere and then placed in a plasma-assisted high-energy ball mill for treatment, and the discharge treatment is carried out under high voltage and low current conditions for 16 to 20 hours, and a silicon-based precursor material is obtained after the reaction is completed; 3) The silicon-based precursor material obtained in step 2) is sintered under a protective atmosphere to obtain a silicon-based inorganic filler with a reorganized interface structure and high crystallinity.

3. The preparation method according to claim 2, characterized in that: In the mixed powder of mine tailings solid waste powder and urea in a certain mass ratio, the mass ratio of the solid waste powder to urea is 1:2-1:

6.

4. The preparation method according to claim 2, characterized in that: The protective atmosphere is one or both of argon and nitrogen.

5. The preparation method according to claim 2, characterized in that: The high voltage of the plasma-assisted high-energy ball mill is 10-15 kV, and the low current is 1-1.5 mA.

6. The preparation method according to claim 2, characterized in that: The calcination atmosphere is one or both of nitrogen and argon. The calcination is carried out at 300-500° C. for 3-6 hours.

7. The method for applying the silicon-based inorganic filler with reorganized interface structure extracted from mine tailings solid waste in solid lithium metal batteries as claimed in claim 2, characterized in that: The following steps are involved: 1) The silicon-based inorganic filler with reorganized interface structure obtained in claim 2) is uniformly mixed with a certain amount of organic lithium salt and polymer material, and then dispersed in an anhydrous organic solvent and stirred uniformly; 2) Pour the obtained mixed solution into a polytetrafluoroethylene mold and dry it at 60-80°C for 6-12h to obtain a solid electrolyte for a solid lithium battery treated with a silicon-based inorganic filler.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the silicon-based inorganic filler with reorganized interface structure to the organic lithium salt is 1:100-1:

25.

9. The preparation method according to claim 7, characterized in that: The organic lithium salt is one or more of lithium trifluoromethanesulfonate or lithium bis(trifluoromethanesulfonyl imide); the polymer material is one or more of polyvinylidene fluoride or polyvinylidene fluoride-hexafluoropropylene; the anhydrous organic solvent is one or more of ethylbenzene, N,N-dimethylformamide, and diethyl carbonate.

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