阅读说明：本技术 一种回收lagp固态电解质中锗、铝、锂的方法 (Method for recovering germanium, aluminum and lithium in LAGP solid electrolyte ) 是由 王嘉楠 马千越 孙世翼 延卫 于 2021-07-27 设计创作，主要内容包括：本发明公开了一种回收LAGP固态电解质中锗、铝、锂的方法,将废旧LAGP固态电解质依次进行超声清洗、浸泡和煅烧,得到去杂质的固态电解质废料；将得到的废料球磨,得到固态电解质粉末,粉末依次经过强酸、柠檬酸酸浸进一步浸出锗,得到含锗酸性溶液,溶液过滤后得到滤渣与含锗碱液；将滤渣煅烧后得到氧化铝；向所述含锗碱液中加入单宁酸沉淀锗,再对得到的锗依次进行氯化蒸馏、水解和还原,得到氧化锗或锗金属；蒸馏余液过滤后干燥后得到碳酸锂原料。本发明回收制备的氧化锗、氧化铝、氧化锂可作为制备新能源锂电池、三效催化剂等材料的原料,提高了材料与能源的回收率与利用效率,解决了锗、铝、锂等资源产能薄弱,消耗大的问题。(The invention discloses a method for recovering germanium, aluminum and lithium in a LAGP solid electrolyte, which comprises the steps of sequentially carrying out ultrasonic cleaning, soaking and calcining on a waste LAGP solid electrolyte to obtain impurity-removed solid electrolyte waste; ball-milling the obtained waste to obtain solid electrolyte powder, further leaching germanium from the powder by acid leaching with strong acid and citric acid in sequence to obtain a germanium-containing acidic solution, and filtering the solution to obtain filter residue and a germanium-containing alkali solution; calcining the filter residue to obtain aluminum oxide; adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then performing chlorination distillation, hydrolysis and reduction on the obtained germanium in sequence to obtain germanium oxide or germanium metal; and filtering and drying the distillation residual liquid to obtain the lithium carbonate raw material. The germanium oxide, the aluminum oxide and the lithium oxide which are recycled and prepared by the method can be used as raw materials for preparing new energy lithium batteries, three-way catalysts and other materials, the recycling rate and the utilization efficiency of the materials and energy are improved, and the problems of weak productivity and high consumption of germanium, aluminum, lithium and other resources are solved.)

1. A method for recovering germanium, aluminum and lithium in a LAGP solid electrolyte is characterized by comprising the following steps:

step 1: ultrasonically cleaning waste LAGP solid electrolyte, transferring the waste LAGP solid electrolyte to an N-methyl pyrrolidone solution for soaking and impurity removal, and calcining the waste LAGP solid electrolyte in a calcining furnace to obtain impurity-removed solid electrolyte waste;

step 2: ball-milling the obtained solid electrolyte waste without impurities to obtain solid electrolyte powder, carrying out acid leaching treatment on the powder by strong acid, and adding citric acid into an acid leaching solution to leach germanium to obtain a germanium-containing acid solution;

and step 3: adjusting the pH value of the germanium-containing acidic solution to be alkaline, then precipitating and separating aluminum hydroxide, and filtering the solution to obtain filter residue and germanium-containing alkali liquor;

and 4, step 4: calcining the filter residue to obtain aluminum oxide;

adding tannic acid into the germanium-containing alkali liquor, then precipitating germanium, and then performing chlorination distillation, hydrolysis and reduction on the obtained germanium in sequence to obtain germanium oxide or germanium metal;

and a distillation residual liquid is obtained in the chlorination distillation process, the pH value of the distillation residual liquid is adjusted to 14, sodium carbonate is added, distillation filter residue is obtained after filtration, and the lithium carbonate raw material is obtained after the distillation filter residue is dried.

2. The method of claim 1, wherein flue gas generated during calcination is absorbed by an absorption bed.

3. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to claim 2, wherein the filler of the absorption bed comprises one or more of quicklime, limestone and magnesium oxide.

4. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to claim 1, wherein in the step 1, the content of Ge, the content of Li and the content of Al in the waste LAGP solid electrolyte are respectively 1-70%, 1-40% and 3-50% in percentage by mass.

5. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to any one of claims 1 and 4, wherein the mass concentration of the N-methylpyrrolidone solution in the step 1 is 30-95%; the calcination temperature is 500-800 ℃.

6. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to claim 1, wherein the ball milling medium used in the ball milling process in the step 2 is ethanol, isopropanol, gasoline or hexane.

7. The method for recycling germanium, aluminum and lithium in the LAGP solid electrolyte according to any one of claims 1 or 6, wherein in the step 2, the ratio of waste to medium is (4-8.5): (2-3.5): 1-2.5); the mesh number of the solid electrolyte powder is 100-430 meshes.

8. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to claim 1, wherein the alkaline solution used for adjusting the pH value in the step 3 comprises one or more of sodium hydroxide, potassium hydroxide and ammonia water, and the pH value is 8-11.

9. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to claim 1, wherein the content of Al in the filter residue of the step 4 is 10.0-34.6% by mass; the lithium content in the distillation residual liquid is 5.0% -16.3%; the calcination temperature is 120-1200 ℃.

10. The method for recovering germanium, aluminum and lithium from the LAGP solid electrolyte according to any one of claims 1 and 9, wherein the recovery rate of germanium is not less than 98%, the recovery rate of aluminum is not less than 92% and the recovery rate of lithium is not less than 85% in step 4.

Technical Field

The invention belongs to the field of solid electrolyte recovery, and relates to a method for recovering germanium, aluminum and lithium in a LAGP solid electrolyte.

Background

Germanium and lithium are used as precious earth resources and widely applied to the fields of new energy materials, optical fiber systems, infrared optics, polymerization catalysts, electronics, solar energy application and the like. Especially in the field of power batteries which are developed rapidly at present, germanium and lithium are important raw materials for synthesizing high-safety all-solid-state lithium electrolyte. For example, NASICON-type solid-state electrolyte Lithium Aluminum Germanium Phosphate (LAGP) synthesized from chemicals such as lithium hydroxide and germanium oxide is currently receiving high attention from the industry and academia. It is expected that more germanium and lithium will be used in the preparation and application of solid electrolytes in the future.

However, the reserves of germanium and lithium are relatively small at present. Particularly, germanium element, which is generally present in minerals containing other elements, cannot form independent minerals, and it is statistically estimated that the reserved amount of currently-discovered germanium ore resources is only 8600t (containing about 4400t of industrial reserve), resulting in an expensive raw material for germanium such as germanium oxide, organogermanium, germanium chloride, etc. Taking germanium oxide as an example, the price of the germanium oxide is about 10000-15000 yuan/kg, and the price of the high-purity germanium oxide can reach over 20000 yuan/kg. The lithium resource capacity is weak, but with the development of new energy automobiles, the lithium consumption is larger and larger, and the price of battery-grade lithium carbonate is close to 10 ten thousand yuan/kg at present. Therefore, how to recover valuable metal resources such as germanium, lithium and the like from equipment and materials has extremely high economic value and strategic significance.

At present, the recovery of germanium element is mainly concentrated in the fields of optical fibers, infrared equipment and the like, and the recovery of lithium element is mainly concentrated in the field of lithium battery electrode materials. The recovery of germanium and lithium elements in lithium solid electrolytes has not been widely regarded. Particularly, the NASICON solid electrolyte represented by LAGP has the germanium content of more than 20%, and also contains metals such as lithium, aluminum and the like, so that a great deal of waste of various metal resources is caused after the NASICON solid electrolyte is discarded.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a method for recovering germanium, aluminum and lithium in a LAGP solid electrolyte.

In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:

a method for recovering germanium, aluminum and lithium in a LAGP solid electrolyte comprises the following steps:

step 1: ultrasonically cleaning waste LAGP solid electrolyte, transferring the waste LAGP solid electrolyte to an N-methyl pyrrolidone solution for soaking and impurity removal, and calcining the waste LAGP solid electrolyte in a calcining furnace to obtain impurity-removed solid electrolyte waste;

step 2: ball-milling the obtained solid electrolyte waste without impurities to obtain solid electrolyte powder, carrying out acid leaching treatment on the powder by strong acid, and adding citric acid into an acid leaching solution to leach germanium to obtain a germanium-containing acid solution;

and step 3: adjusting the pH value of the germanium-containing acidic solution to be alkaline, then precipitating and separating aluminum hydroxide, and filtering the solution to obtain filter residue and germanium-containing alkali liquor;

and 4, step 4: calcining the filter residue to obtain aluminum oxide;

adding tannic acid into the germanium-containing alkali liquor, then precipitating germanium, and then performing chlorination distillation, hydrolysis and reduction on the obtained germanium in sequence to obtain germanium oxide or germanium metal;

and a distillation residual liquid is obtained in the chlorination distillation process, the pH value of the distillation residual liquid is adjusted to 14, sodium carbonate is added, distillation filter residue is obtained after filtration, and the lithium carbonate raw material is obtained after the distillation filter residue is dried.

The invention is further improved in that:

and the flue gas generated in the calcining process is absorbed by an absorption bed.

The filler of the absorption bed comprises one or more of quick lime, limestone and magnesium oxide.

In the step 1, the content of Ge, 1-70%, the content of Li and 3-50% in the waste LAGP solid electrolyte are calculated according to mass percentage.

The mass concentration of the N-methyl pyrrolidone solution in the step 1 is 30-95%; the calcination temperature is 500-800 ℃.

And 2, the ball milling medium used in the ball milling process in the step 2 is ethanol, isopropanol, gasoline or hexane.

In the step 2, the ratio of waste materials to medium is (4-8.5) to (2-3.5) to (1-2.5); the mesh number of the solid electrolyte powder is 100-430 meshes.

The alkaline solution used for adjusting the pH value in the step 3 comprises one or more of sodium hydroxide, potassium hydroxide and ammonia water, and the pH value is 8-11.

The Al content in the filter residue obtained in the step 4 is 10.0-34.6% by mass percent; the lithium content in the distillation residual liquid is 5.0% -16.3%; the calcination temperature is 120-1200 ℃.

In the step 4, the recovery rate of germanium is not less than 98%, the recovery rate of aluminum is not less than 92%, and the recovery rate of lithium is not less than 85%.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a method for recovering germanium, aluminum and lithium in a LAGP solid electrolyte, which comprises the steps of firstly carrying out ultrasonic cleaning on germanium wastes, removing various impurities remained on the surface of the electrolyte materials, reducing the influence of the impurities on a subsequent recovery process, then soaking and removing PVDF (polyvinylidene fluoride) binder in the wastes by using an N-methylpyrrolidone solution, then carrying out high-temperature calcination, further volatilizing the components such as residual sulfur, lithium polysulfide and the binder in the wastes, and greatly reducing the influence of various impurities in the subsequent process on the recovery process; the germanium-containing waste material with impurities removed is subjected to high-energy ball milling, so that the effective reaction area of a subsequent leaching process is increased, and the recovery rate is improved; acid leaching the waste containing germanium after ball milling with strong acid and citric acid in sequence, wherein the leaching rate of germanium can reach more than 99%; the pH value of the germanium-containing acidic solution is adjusted, aluminum ions can be better precipitated and separated, the recovery rate of filter residue aluminum obtained by filtering is improved, the distillation residual liquid obtained in the chlorination distillation process is rich in lithium ions, the content of other metal elements is extremely low, the interference is small, and sodium carbonate is added into the distillation residual liquid to precipitate and separate lithium carbonate. The invention provides a method for recovering metal elements such as germanium, aluminum, lithium and the like in waste LAGP solid electrolyte, wherein the recovered and prepared germanium oxide, aluminum oxide and lithium carbonate can be used as raw materials for preparing materials such as a new energy lithium battery and a three-way catalyst, and the application of the germanium oxide or germanium metal comprises the preparation of the LAGP electrolyte, the LGPS electrolyte, optical fiber equipment and the like; the application of the aluminum oxide comprises the preparation of lithium/sodium solid electrolyte, a three-way catalyst and the like, and the application of the lithium carbonate comprises the preparation of lithium ion battery electrodes, electrolyte materials and lithium metal, so that the recovery rate and the utilization efficiency of the materials and energy are greatly improved, and the waste of metal resources is reduced.

The rear end of the calcining furnace is connected with an absorption bed, and the absorption bed mainly has the function of absorbing sulfur dioxide in high-temperature flue gas through fillers such as quick lime, limestone and the like, so that the pollution of sulfur oxides generated in the calcining process to the atmospheric environment is effectively prevented.

Drawings

In order to more clearly explain the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a flow chart of the method of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.

Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. 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.

It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.

In the description of the embodiments of the present invention, it should be noted that if the terms "upper", "lower", "horizontal", "inner", etc. are used for indicating the orientation or positional relationship based on the orientation or positional relationship shown in the drawings or the orientation or positional relationship which is usually arranged when the product of the present invention is used, the description is merely for convenience and simplicity, and the indication or suggestion that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, cannot be understood as limiting the present invention. Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.

Furthermore, the term "horizontal", if present, does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.

In the description of the embodiments of the present invention, it should be further noted that unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" should be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

The invention is described in further detail below with reference to the accompanying drawings:

referring to fig. 1, the embodiment of the invention discloses a method for recovering germanium, aluminum and lithium in a lag solid electrolyte, which specifically comprises the following steps:

step 1: because various impurities such as conductive carbon black, active substances, binders and the like are usually left on the surface of the waste lithium solid electrolyte and have great influence on the subsequent recovery process, the waste LAGP solid electrolyte is firstly cleaned by ultrasound, then transferred to an N-methyl pyrrolidone solution for soaking and impurity removal, the PVDF binders in the waste are removed, then the waste is calcined in a calcining furnace, and the residual components such as sulfur, lithium polysulfide, binders and the like in the waste are further volatilized, so that the solid electrolyte waste with impurities removed is obtained.

Step 2: the waste solid electrolyte is generally a ceramic block material, and the effective reaction area with the leaching solution is small when the leaching process is implemented, so that the germanium-containing waste material with impurities removed is subjected to high-energy ball milling, the obtained solid electrolyte waste material with impurities removed is subjected to ball milling to obtain solid electrolyte powder, a surfactant is added in the ball milling process to improve the ball milling efficiency, reduce the powder particle size, increase the effective reaction area of the subsequent leaching process and improve the recovery rate, and the germanium-containing waste material subjected to ball milling is subjected to strong acid leaching of three metals, namely lithium, aluminum and germanium, because the leaching effect of pure strong acids such as sulfuric acid, hydrochloric acid and nitric acid on aluminum and lithium is better and can reach more than 95%, but the leaching effect on germanium is not ideal and is generally not more than 90%. And the compound containing dicarboxylic acid and tricarboxylic acid can form a stable complex with germanium, so that after the strong acid is leached, the germanium is further selectively leached by using a citric acid solution, the leaching rate of the germanium can reach more than 99 percent, and finally, the germanium-containing acidic solution is obtained.

And step 3: because germanium and lithium are soluble in an alkaline solution, and elements such as iron elements and the like which are easy to precipitate under an alkaline condition do not exist in the germanium-containing waste, the alkaline solution is added into the germanium-containing acidic solution, the pH value is adjusted to be more than 8, aluminum hydroxide can be well precipitated and separated, and the solution is filtered to obtain filter residue and germanium-containing alkali liquor.

And 4, step 4: and calcining the filter residue to obtain the alumina, wherein the recovery rate of the aluminum can reach more than 92%.

Adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then performing chlorination distillation, hydrolysis and reduction on the obtained germanium in sequence to obtain germanium oxide or germanium metal.

And (3) the distillation residual liquid obtained in the chlorination distillation process is rich in lithium ions, the content of other metal elements is extremely low, the interference is small, the pH value of the distillation residual liquid is adjusted to 14, sodium carbonate is added, filter residue is obtained after filtration, a lithium carbonate raw material is obtained after the filter residue is dried, and the lithium recovery rate is not lower than 84%.

Because the calcining process can generate sulfur dioxide and other atmospheric pollutants, an absorption bed is arranged at the rear end of the calcining furnace, and the filler of the absorption bed comprises one or more of quick lime, limestone and magnesium oxide; the absorption bed mainly has the function of absorbing sulfur dioxide in high-temperature flue gas through fillers such as quick lime, limestone and the like, and effectively prevents the pollution of sulfur oxides generated in the calcining process to the atmospheric environment.

The content of Ge in the LAGP solid electrolyte waste material in the step 1 is 1-70%; the Li content is 1-40%; the Al content is 3% -50%; the concentration of the N-methyl pyrrolidone solution is 30 to 95 percent; the calcination temperature is 500-800 ℃. The ball milling in the step 2 comprises ethanol, isopropanol, gasoline or hexane; wherein the ball: waste materials: the dielectric ratio is 4-8.5: 2-3.5: 1-2.5. The mesh number of the solid electrolyte powder is 100-430 meshes. The alkaline solution used for adjusting the pH value in the step 3 comprises one or more of sodium hydroxide, potassium hydroxide and ammonia water, and the pH value is adjusted to 8-11. The Al content in the filter residue in the step 4 is 10.0-34.6%; the lithium content in the distillation residual liquid is 5.0-16.3%; the calcining temperature is 120-1200 ℃. Wherein the recovery rate of germanium is not less than 98 percent, the recovery rate of aluminum is not less than 92 percent, and the recovery rate of lithium is not less than 85 percent.

The specific steps for obtaining the aluminum hydroxide in the step 3 are as follows:

and (3) treating the aluminum hydroxide filter residue: grinding the filter residue into powder, weighing 2g by using balance, adding a proper amount of distilled water, slowly dripping and adding 20mLHCl solution, shaking up, adding 40mL of distilled water, heating for about 5min, cooling and filtering, repeatedly washing the filter residue and the filter paper by using the distilled water, putting the washed washing liquid into a volumetric flask, washing for about 5-6 times, and finally adding the distilled water to the scale.

Determination of aluminum: measuring 10mL of the above solution, placing the solution into a 250mL conical flask, adding about 25mL of distilled water, shaking uniformly, adding about 20mL of about 0.02mol/LEDTA (ethylene diamine tetraacetic acid) standard solution, sequentially adding about 0.5mL of about 0.2% xylenol orange indicator, ammonia water solution and HCl solution, recovering the color of the reagent from yellow to purple red, dripping about 1mL of hydrochloric acid solution, heating and boiling by using an alcohol lamp, continuously heating for about 5min, standing and cooling, adding 10mL of 20% hexamethylenetetramine solution and 0.5mL of 0.2% xylenol orange indicator, finally carrying out back titration by using 0.02mol/L of zinc standard solution until the test solution recovers purple red as a titration end point, counting the volume of the zinc standard solution, and calculating the content of aluminum hydroxide.

See the following examples for specific methods:

example 1:

weighing 1.25kg of germanium-containing waste, wherein the germanium content is 20.1%, the lithium content is 1.6% and the aluminum content is 5.2%, ultrasonically cleaning the germanium-containing waste for 20min, and drying for 12h at the temperature of 60 ℃. And transferring the dried product to an NMP solution for soaking for 30min, wherein the mass concentration of the solution is 50%, transferring the solution to a muffle furnace, calcining for 2 hours at 600 ℃ to obtain the impurity-removed germanium-containing waste, and allowing the calcined flue gas to pass through an absorption bed, wherein the absorption rate of sulfur dioxide reaches 98.4%.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 200r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 150-200 meshes by taking the medium ratio as 4:2:1, and transferring the powder to a hydrochloric acid solution of 5mol/L for acid leaching. After acid leaching, 1.2mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 5.2 g/L.

Adding sodium hydroxide (with the mass concentration of 28%) into the germanium-containing acidic solution, adjusting the pH value to 8.5, and filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 33.1%.

Calcining the filter residue for 3h at 150 ℃ to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 94.5%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 98.4%. And adjusting the pH value of the distillation residual liquid to 14, wherein the lithium content is 7.9%, adding 2mol/L sodium carbonate into the distillation residual liquid, drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, and ensuring the lithium recovery rate to reach 86.5%.

Example 2:

weighing 1.54kg of germanium-containing waste, wherein the germanium content is 25.4%, the lithium content is 1.3% and the aluminum content is 3.7%, ultrasonically cleaning the germanium-containing waste for 30min, and drying for 12h at the temperature of 60 ℃. And transferring the dried solution to an NMP solution, soaking for 30min at the mass concentration of 55%, transferring the solution to a muffle furnace, and calcining for 2h at 700 ℃ to obtain the impurity-removed germanium-containing waste, wherein the calcined flue gas passes through an absorption bed, and the absorption rate of sulfur dioxide reaches 99.5%.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 300r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 200-300 meshes by taking the medium ratio as 6:3:1.5, and transferring the powder to a sulfuric acid solution of 2.5mol/L for acid leaching. After acid leaching, 1.4mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 6.8 g/L.

Adding potassium hydroxide (the mass concentration is 34%) into the germanium-containing acidic solution, adjusting the pH value to 9.5, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 34.2%.

Calcining the filter residue at 1000 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 92.8%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.1%. And adjusting the content of lithium in the distillation residual liquid to be 6.4%, adjusting the pH value to 14, adding 2mol/L sodium carbonate into the distillation residual liquid, and drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, wherein the lithium recovery rate reaches 85.3%.

Example 3:

weighing 2.08kg of germanium-containing waste, wherein the germanium content is 27.7%, the lithium content is 2.7% and the aluminum content is 8.7%, ultrasonically cleaning the germanium-containing waste for 30min, and drying for 12h at the temperature of 60 ℃. And transferring the dried product to an NMP solution, soaking for 30min until the mass concentration of the solution is 60%, transferring the solution to a muffle furnace, calcining for 2h at 750 ℃ to obtain the impurity-removed germanium-containing waste, and allowing the calcined flue gas to pass through an absorption bed until the absorption rate of sulfur dioxide reaches 98.9%.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 400r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 300-400 meshes by using the medium ratio of 8:2.5:1.5, and transferring the powder into 5mol/L hydrochloric acid for acid leaching. After acid leaching, adding germanium-containing powder into 1.7mol/L citric acid solution, and dropwise adding 2.0mol/L hydrogen peroxide to leach germanium to obtain germanium-containing acid solution, wherein the germanium content is 7.1 g/L.

Adding sodium hydroxide (with mass concentration of 40%) into the germanium-containing acidic solution, adjusting pH to 10.5, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 33.2%.

Calcining the filter residue for 3h at 180 ℃ to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 96.4%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.5%. And adjusting the content of lithium in the distillation residual liquid to be 10.2 percent, adjusting the pH value to be 14, adding 2mol/L sodium carbonate into the distillation residual liquid, and drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, wherein the lithium recovery rate reaches 85.8 percent.

Example 4:

weighing 2.25kg of germanium-containing waste, wherein the germanium content is 26.5%, the lithium content is 3.4% and the aluminum content is 6.7%, ultrasonically cleaning the germanium-containing waste for 40min, and drying for 12h at the temperature of 60 ℃. And transferring the dried solution to an NMP solution, soaking for 30min until the mass concentration of the solution is 65%, transferring the solution to a muffle furnace, calcining for 2h at 800 ℃ to obtain the impurity-removed germanium-containing waste, and allowing the calcined flue gas to pass through an absorption bed until the sulfur dioxide absorption rate reaches 98.7%.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 350r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 200-300 meshes by taking the medium ratio as 6:2:1, and transferring the powder to a hydrochloric acid solution of 5mol/L for acid leaching. After acid leaching, adding the germanium-containing powder into 1.4mol/L citric acid solution, and dropwise adding 1.8mol/L hydrogen peroxide to leach germanium to obtain a germanium-containing acidic solution, wherein the germanium content is 6.8 g/L.

Adding sodium hydroxide (mass concentration is 35%) into the germanium-containing acidic solution, adjusting pH to 11, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 32.4%.

Calcining the filter residue for 3h at 180 ℃ to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 95.2%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.2%. And adjusting the content of lithium in the distillation residual liquid to be 12.8 percent, adjusting the pH value to be 14, adding 2mol/L sodium carbonate into the distillation residual liquid, and drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, wherein the lithium recovery rate reaches 86.2 percent.

Example 5:

weighing 2.52kg of germanium-containing waste, wherein the germanium content is 29.3%, the lithium content is 1.4% and the aluminum content is 7.1%, ultrasonically cleaning the germanium-containing waste for 40min, and drying for 12h at the temperature of 60 ℃. And transferring the dried product to an NMP solution, soaking for 30min until the mass concentration of the solution is 70%, transferring the solution to a muffle furnace, calcining for 2h at 800 ℃ to obtain the impurity-removed germanium-containing waste, and allowing the calcined flue gas to pass through an absorption bed until the absorption rate of sulfur dioxide reaches 99.6%.

And (3) ball-milling the impurity-removed germanium-containing waste for 8 hours at a rotating speed of 250r for high energy, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 250-300 meshes by the medium ratio of 6.5:3:1, and transferring the powder to a sulfuric acid solution of 2.5mol/L for acid leaching. After acid leaching, adding germanium-containing powder into 1.5mol/L citric acid solution, and dropwise adding 2.0mol/L hydrogen peroxide to leach germanium to obtain germanium-containing acid solution, wherein the germanium content is 8.5 g/L.

Adding sodium hydroxide (mass concentration of 43%) into the germanium-containing acidic solution, adjusting pH to 10, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content is 30.7%.

Calcining the filter residue at 1100 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 93.5%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.3%. And adjusting the content of lithium in the distillation residual liquid to be 5.7%, adjusting the pH value to be 14, adding 2mol/L sodium carbonate into the distillation residual liquid, and drying filter residues obtained by filtering to obtain a lithium carbonate raw material, wherein the lithium recovery rate reaches 84.3%.

Example 6:

weighing 1.05kg of germanium-containing waste, wherein the germanium content is 18.2%, the lithium content is 1.8% and the aluminum content is 6.2%, ultrasonically cleaning the germanium-containing waste for 30min, and drying for 12h at the temperature of 60 ℃. Transferring the dried product to NMP solution for soaking for 30min, wherein the mass concentration of the solution is 30%, transferring the product to a muffle furnace for calcining for 2 hours at 500 ℃ to obtain the impurity-removed germanium-containing waste, and allowing the calcined flue gas to pass through an absorption bed until the sulfur dioxide absorption rate reaches 98.9 percent.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 200r, wherein the ball milling comprises the following steps: waste materials: and (3) transferring the powder into a hydrochloric acid solution of 3mol/L for acid leaching, wherein the medium ratio is 4.2:2.5:1.5, and the germanium-containing powder is obtained, the mesh number of the powder is 100-150 meshes. After acid leaching, 1.2mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 4.9 g/L.

Adding sodium hydroxide (mass concentration is 26%) into the germanium-containing acidic solution, adjusting pH to 8.5, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 32.3%.

Calcining the filter residue at 200 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 95.6%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 98.5%. And adjusting the pH value of the distillation residual liquid to 14, wherein the lithium content is 5.8%, adding 2mol/L sodium carbonate into the distillation residual liquid, drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, and ensuring the lithium recovery rate to reach 86.3%.

Example 7

Weighing 2.2kg of germanium-containing waste, wherein the germanium content is 26.2%, the lithium content is 2.2% and the aluminum content is 6.2%, ultrasonically cleaning the germanium-containing waste for 30min, and drying for 12h at the temperature of 60 ℃. And transferring the dried material to an NMP solution for soaking for 30min, wherein the mass concentration of the solution is 58%, transferring the solution to a muffle furnace for calcining for 2 hours at 725 ℃ to obtain the impurity-removed germanium-containing waste material, and allowing the calcined flue gas to pass through an absorption bed, wherein the absorption rate of sulfur dioxide reaches 99.2%.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 350r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the powder mesh number of 250-320 meshes by the medium ratio of 7:2.8:1.8, and transferring the powder into 3mol/L hydrochloric acid solution for acid leaching. After acid leaching, 1.5mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 7.3 g/L.

Adding sodium hydroxide (mass concentration of 36%) into the germanium-containing acidic solution, adjusting pH to 10, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 33.1%.

Calcining the filter residue at 800 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 95.8%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.3%. And adjusting the pH value of the distillation residual liquid to 14, wherein the lithium content is 7.8%, adding 2mol/L sodium carbonate into the distillation residual liquid, drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, and ensuring the lithium recovery rate to reach 85.2%.

Example 8:

weighing 2.35kg of germanium-containing waste, wherein the germanium content is 27.8%, the lithium content is 1.8% and the aluminum content is 6.9%, ultrasonically cleaning the germanium-containing waste for 20min, and drying for 12h at the temperature of 60 ℃. And transferring the dried material to an NMP solution for soaking for 30min, wherein the mass concentration of the solution is 68%, transferring the solution to a muffle furnace for calcining for 2 hours at 785 ℃ to obtain the impurity-removed germanium-containing waste material, and passing the calcined flue gas through an absorption bed, wherein the absorption rate of sulfur dioxide reaches 99.5%.

Carrying out high-energy ball milling on the impurity-removed germanium-containing waste for 8 hours at the rotating speed of 380r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 180-235 meshes by taking the medium ratio as 6.2:2.5:1.5, and transferring the powder into 4mol/L hydrochloric acid solution for acid leaching. After acid leaching, 1.45mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 7.2 g/L.

Adding sodium hydroxide (mass concentration of 36%) into the germanium-containing acidic solution, adjusting pH to 10, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 31.8%.

Calcining the filter residue at 650 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 94.7%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.1%. And adjusting the pH value of the distillation residual liquid to 14, wherein the lithium content is 10.5%, adding 2mol/L sodium carbonate into the distillation residual liquid, drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, and ensuring the lithium recovery rate to reach 87.4%.

Example 9:

weighing 2.78kg of germanium-containing waste, wherein the germanium content is 30.5%, the lithium content is 3.2% and the aluminum content is 8.2%, ultrasonically cleaning the germanium-containing waste for 50min, and drying for 12h at the temperature of 60 ℃. And transferring the dried material to an NMP solution for soaking for 30min, wherein the mass concentration of the solution is 72%, transferring the solution to a muffle furnace for calcining for 2 hours at 765 ℃ to obtain the impurity-removed germanium-containing waste material, and passing the calcined flue gas through an absorption bed until the absorption rate of sulfur dioxide reaches 99.3%.

And (3) ball-milling the impurity-removed germanium-containing waste for 8 hours at a rotating speed of 420r, wherein the ball milling comprises the following steps: waste materials: and (3) obtaining germanium-containing powder with the mesh number of 300-375 meshes by using the medium ratio of 7.8:3.1:2, and transferring the powder into 5mol/L hydrochloric acid solution for acid leaching. After acid leaching, 1.8mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 8.5 g/L.

Adding sodium hydroxide (with the mass concentration of 38%) into the germanium-containing acidic solution, adjusting the pH value to 11, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 34.2%.

Calcining the filter residue at 725 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 96.7%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.2%. And adjusting the pH value of the distillation residual liquid to 14, wherein the lithium content is 13.8%, adding 4mol/L sodium carbonate into the distillation residual liquid, drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, and ensuring the lithium recovery rate to reach 89.4%.

Example 10:

weighing 3.2kg of germanium-containing waste, wherein the germanium content is 45.8%, the lithium content is 5.7% and the aluminum content is 10.2%, ultrasonically cleaning the germanium-containing waste for 50min, and drying for 12h at the temperature of 60 ℃. And transferring the dried product to an NMP solution to be soaked for 30min, wherein the mass concentration of the solution is 90%, transferring the solution to a muffle furnace to be calcined for 2h at 780 ℃ to obtain the impurity-removed germanium-containing waste, and allowing the calcined flue gas to pass through an absorption bed, wherein the absorption rate of sulfur dioxide reaches 99.5%.

And (3) ball-milling the impurity-removed germanium-containing waste for 8 hours at a rotating speed of 500r for high energy, wherein the ball milling comprises the following steps: waste materials: and (3) transferring the powder to a hydrochloric acid solution of 5mol/L for acid leaching, wherein the medium ratio is 8.5:3.3:2.5, the germanium-containing powder is obtained, the mesh number of the powder is 380-430 meshes. After acid leaching, 2.5mol/L citric acid solution is added into the leaching solution to obtain acid solution containing germanium, wherein the content of germanium is 9.6 g/L.

Adding sodium hydroxide (with the mass concentration of 38%) into the germanium-containing acidic solution, adjusting the pH value to 11, filtering and precipitating to obtain filter residue and germanium-containing filtrate, wherein the aluminum content in the filter residue is 34.6%.

Calcining the filter residue at 560 ℃ for 3h to obtain high-purity gamma-type aluminum oxide, wherein the recovery rate of aluminum reaches 97.7%, adding tannic acid into the germanium-containing alkali liquor to precipitate germanium, and then obtaining high-purity germanium dioxide according to conventional chlorination distillation and hydrolysis methods, wherein the recovery rate of germanium reaches 99.8%. And adjusting the pH value of the distillation residual liquid to 14, wherein the lithium content is 16.3%, adding 5mol/L sodium carbonate into the distillation residual liquid, drying the filter residue obtained by filtering to obtain a lithium carbonate raw material, and ensuring the lithium recovery rate to reach 85.6%.

Experimental results show that the recovery method provided by the invention can effectively recover three metal elements, namely germanium, aluminum and lithium, in the LAGP solid electrolyte, the recovery rate of germanium is not lower than 98%, and the recovery rate of aluminum and lithium is not lower than 92%. Therefore, the method can well realize the recovery and the reutilization of the waste LAGP solid electrolyte.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.