阅读说明：本技术 一种基于废旧锂离子电池浸出液制备锰基mof材料的方法 (Method for preparing manganese-based MOF material based on waste lithium ion battery leachate ) 是由 李丽 范二莎 陈人杰 林娇 张晓东 吴锋 于 2020-12-01 设计创作，主要内容包括：本发明提供了一种基于废旧锂离子电池浸出液制备锰基MOF材料的方法,所述方法包括以下步骤：(1)将锂离子电池正极废料溶于酸性试剂,得到含Mn～(2+)、Li～+的浸出液；(2)称取定量的有机配体分散到有机溶剂中,将浸出液和有机溶剂混合后进行水热反应,制得Mn-MOF材料。本发明提出的制备方法步骤简单、原料廉价易得、反应条件温和且易控制,制备产物形貌规则且纯度高,有广泛的应用前景,对废旧锂离子电池高值化利用具有重要的意义。(The invention provides a method for preparing a manganese-based MOF material based on a waste lithium ion battery leachate, which comprises the following steps: (1) dissolving the anode waste of the lithium ion battery in an acid reagent to obtain Mn-containing solution 2+ 、Li + The leachate of (2); (2) weighing quantitative organic ligands, dispersing the organic ligands into an organic solvent, mixing the leachate with the organic solvent, and then carrying out hydrothermal reaction to prepare the Mn-MOF material. The preparation method provided by the invention has the advantages of simple steps, cheap and easily-obtained raw materials, mild and easily-controlled reaction conditions, regular shape and high purity of the prepared product, wide application prospect and important significance in high-valued utilization of the waste lithium ion battery.)

1. A method for preparing a manganese-based MOF material based on a waste lithium ion battery leachate is characterized by comprising the following steps:

(1) mixing the anode material of the waste lithium ion battery with an acidic solvent, and stirring to obtain the Li-containing material⁺，Mn²⁺A solution of metal ions;

(2) adjusting the concentration of manganese ions to 0.1-3 mol/L, adding a pH regulator, controlling the pH of the leachate to be within the range of 5-11, and marking as a solution 1; weighing organic ligand, slowly adding the organic ligand into an organic solvent, and marking as a solution 2; wherein the volume ratio of the leaching solution to the organic solvent is 1: 1-1: 15; and mixing the solutions 1 and 2, carrying out hydrothermal reaction, and centrifuging to obtain the Mn-MOF material.

2. The method for preparing manganese-based MOF materials from the leachate of waste lithium ion batteries according to claim 1, wherein the lithium ion battery cathode material in step (1) is any one or more of a lithium manganate battery cathode material, a lithium nickel manganate battery cathode material or a lithium nickel cobalt manganate battery cathode material.

3. The method for preparing the manganese-based MOF material based on the leachate of the waste lithium ion battery according to claim 1 or 2, wherein the acidic solvent in the step (1) is one or more of inorganic acid sulfuric acid, nitric acid, hydrochloric acid and organic acid citric acid, acetic acid, malic acid, lactic acid or carrot acid.

4. The method for preparing the manganese-based MOF material based on the leachate of the waste lithium ion battery according to claim 1 or 2, wherein the concentration of the manganese ions in the step (2) is 0.5-2 mol/L.

5. The method for preparing the manganese-based MOF material based on the leachate of the waste lithium ion battery according to claim 1 or 2, wherein the pH regulator in the step (2) is any one or more of sodium hydroxide, ammonia water and potassium hydroxide.

6. The method for preparing the manganese-based MOF material based on the leachate of the waste lithium ion battery according to claim 1 or 2, wherein the organic solvent in the step (2) is any one or a combination of at least two of methanol, ethanol or Dimethylformamide (DMF), and the volume ratio of the leachate to the organic solvent is 1: 1-1: 5.

7. The method for preparing manganese-based MOF materials based on leachate of waste lithium ion batteries according to claim 1 or 2, wherein the organic ligand in step (2) is benzoic acid, terephthalic acid (PTA), trimesic acid (BTC), 3, 6-dihydroxyphthalic acid (C)₈H₆O₆) Or polyvinylpyrrolidone (PVP) or a combination of at least two thereof.

8. The method for preparing the manganese-based MOF material based on the leachate of the waste lithium ion battery according to claim 1 or 2, wherein the organic ligand is added in the step (2) according to the addition amount of the organic ligand and Mn in the solution²⁺Adding metal ions at a molar ratio of 1: 1-10: 1;

the hydrothermal reaction temperature is 60-180 ℃, and the reaction time is 2-24 h.

Technical Field

The invention belongs to the field of resource recycling technology and chemical material preparation, and particularly relates to the field of a method for preparing a manganese-based MOF material based on a waste lithium ion battery leachate.

Background

The lithium ion battery has the advantages of small self-discharge, light pollution, high energy density, long cycle life and the like, and is widely applied to consumer electronics, new energy automobiles and large energy storage devices, so that the consumption and the retirement of the lithium ion battery are increased in the global range. How to reasonably treat and recycle the waste lithium ion battery is an urgent problem to be solved. The waste lithium ion battery not only wastes resources but also has great threat to the environment and human health when being improperly disposed. In the case of coming to large-scale decommissioned power batteries, the recycling of the decommissioned power batteries has become an urgent task, because it not only minimizes the demand for critical materials of the batteries, but also solves the pollution and the influence on the environment and ecology caused by the decommissioned power batteries.

Due to coexistence of various metal ions, the retired lithium ion battery has the defects that the separation, extraction and recycling of the leaching solution are more difficult, the separation and extraction process of various metal ions is long, the utilization rate of the leaching solution is low, the added value of the product is low, the shape is uncontrollable, and the purity cannot meet the requirement of commercial application. Particularly, for Mn ions with low product value, how to prepare a high value-added recycled product is a key scientific problem to be solved urgently. At present, MOF materials show good application prospects in the aspects of lithium ion batteries, lithium sulfur batteries, lithium air batteries, electrocatalysis, adsorbents and the like, but the large-scale application of the MOF materials is limited due to the fact that raw materials required by the preparation of the MOF materials are expensive.

Disclosure of Invention

The invention aims to provide a method for preparing a manganese-based MOF material based on a waste lithium ion battery leachate, which realizes the value-added utilization of valuable metal manganese in a lithium ion battery anode material; meanwhile, the method is simple and convenient to operate, efficient and environment-friendly, and the prepared product is regular in shape.

The invention discloses a method for preparing a manganese-based MOF material based on a waste lithium ion battery leachate, which comprises the following steps:

(1) manganese leaching experiment

Mixing the anode material of the waste lithium ion battery with an acidic solution, adding a reducing agent, and stirring to obtain the lithium-containing lithium ion battery⁺，Mn²⁺A solution of metal ions.

(2) Preparation of Mn-MOF materials

Adjusting the concentration of manganese ions to 0.1-3 mol/L, adding a pH regulator, controlling the pH of the leachate to be within the range of 5-11, and marking as a solution 1; weighing organic ligand, slowly adding the organic ligand into an organic solvent, and marking as a solution 2; wherein the volume ratio of the leaching solution to the organic solvent is 1: 1-1: 15; and mixing the solutions 1 and 2, carrying out hydrothermal reaction, and centrifuging to obtain the Mn-MOF material.

The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.

As a preferable technical solution of the present invention, the lithium ion battery positive electrode material in the step (1) is any one of or a combination of at least two of a lithium manganate battery positive electrode material, a nickel manganese acid lithium battery positive electrode material, or a nickel cobalt manganese acid lithium battery positive electrode material.

As a preferred technical solution of the present invention, the acidic solvent in step (1) is one or a combination of at least two of inorganic acids, such as sulfuric acid, nitric acid, hydrochloric acid and organic acids, such as citric acid, acetic acid, malic acid, lactic acid or carotic acid, and typical but non-limiting examples of the combination are: sulfuric acid and nitric acid, sulfuric acid and hydrochloric acid, acetic acid and lactic acid, and nitric acid, acetic acid and lactic acid.

As a preferable technical scheme of the invention, the reducing agent in the step (1) is H₂O₂Ammonium chloride, glucose and Na₂S₂O₅Any one or a combination of at least two of them.

In a preferred embodiment of the present invention, the concentration of manganese ions in step (2) is controlled to be 0.1 to 3mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 3mol/L, etc., but the concentration is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and preferably 0.5 to 2 mol/L.

Preferably, the PH regulator in step (2) is any one or a combination of at least two of sodium hydroxide, ammonia water and potassium hydroxide, and is preferably ammonia water.

Preferably, the PH of the leachate in step (2) is adjusted to 5 to 11, for example 6, 7, 8, 9, 10 or 11, but not limited to the values listed, and other values not listed within this range are equally applicable, preferably 6 to 8.

Preferably, the organic solvent in step (2) is any one of methanol, ethanol or Dimethylformamide (DMF) or a combination of at least two of them, and the combination is exemplified by, typically but not limited to: methanol and DMF, a combination of ethanol and DMF, a combination of methanol and ethanol, a combination of methanol, ethanol and DMF.

Preferably, the organic ligand in step (2) is any one of benzoic acid, terephthalic acid, trimesic acid, 3, 6-dihydroxyphthalic acid or PVP.

Preferably, the organic ligand is added in the step (2) according to the addition amount of the organic ligand and Mn in the solution²⁺Metal ion molar ratio, organic ligand and Mn in solution²⁺The molar ratio of the metal ions is 1:1 to 10:1, for example, 1:1, 2:1, 6:1, 8:1 or 10:1, but the ratio is not limited to the recited values, and other values not recited in the above range are also applicable, and preferably 2:1 to 8: 1.

Preferably, the hydrothermal reaction temperature in step (2) is 60 to 180 ℃, for example, 60 ℃, 90 ℃, 120 ℃, 150 ℃, 180 ℃, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 120 to 180 ℃.

Preferably, the solvothermal reaction time in step (2) is 2 to 24 hours, such as 2 hours, 5 hours, 8 hours, 10 hours, 12 hours and the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 5 to 10 hours.

Compared with the prior art, the method for preparing the manganese-based MOF material based on the waste lithium ion battery leachate has the following beneficial effects:

(1) according to the preparation method provided by the invention, the technical problem that other metal ions interfere with a target metal product in the conventional technology is solved by accurately regulating and controlling the concentration of the metal ions and the pH value of the leaching solution, and the MOF material with complete crystal form, good crystallinity, high purity and uniform size is prepared.

(2) The preparation method provided by the invention has the advantages that the required raw materials are low in price and easy to obtain, the synthesis cost is saved, the prepared product has higher added value, and the excellent performance is expected to be applied to the fields of electrochemical energy storage and catalysis.

Detailed Description

In order to better explain the present invention and to facilitate understanding of the technical solutions, the technical solutions of the present invention are described in detail below with reference to examples. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

Example 1:

the embodiment provides a method for preparing a manganese-based MOF material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium manganate battery, and the method comprises the following steps:

(1) mixing the anode material of the waste lithium ion battery with 1mol/L citric acid solution, and adding H with the volume of 2 percent of the acid solution₂O₂Stirring at 60 deg.C for 60min to obtain Li-containing material⁺，Mn²⁺A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 25g/L, and the stirring speed is 400 rpm.

(2) Controlling the concentration of manganese ions to be 0.5mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 6; weighing benzoic acid according to the molar ratio of the benzoic acid to the manganese ion concentration of 1:1, slowly adding the benzoic acid into the leaching solution, and marking as solution 1; according to the molar ratio of the concentration of benzoic acid to manganese ions of 1:1, BTC is weighed and added into DMF, and the mixture is marked as a solution 2, wherein the volume ratio of the DMF to a leaching solution is 0.5: 1; and mixing the two solutions at room temperature, stirring for 30min, standing in an oven at 180 ℃ for 10h, and centrifuging to obtain the Mn-MOF material.

Example 2:

the embodiment provides a method for preparing a manganese-based MOF material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium manganate battery, and the method comprises the following steps:

(1) mixing the anode material of the waste lithium ion battery with 1mol/L nitric acid solution, and adding H with the volume of 0.5 percent of the volume of the acid solution₂O₂Stirring at 50 deg.C for 30min to obtain Li-containing solution⁺，Co²⁺A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 50g/L, and the stirring speed is 300 rpm.

(2) Controlling the concentration of manganese ions to be 0.5mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 7; weighing benzoic acid according to the molar ratio of the benzoic acid to the manganese ion concentration of 2:1, adding the benzoic acid into the leaching solution, and marking as solution 1; according to the molar ratio of BTC to manganese ion concentration of 2:1, BTC is weighed and added into DMF, and the mixture is marked as a solution 2, wherein the volume ratio of DMF to leachate is 3: 1; and mixing the two solutions at room temperature, stirring for 1h, standing in an oven at 130 ℃ for 8h, and centrifuging to obtain the Mn-MOF material.

Example 3:

the embodiment provides a method for preparing a manganese-based MOF material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste lithium manganate battery, and the method comprises the following steps:

(1) mixing the anode material of the waste lithium ion battery with 1.5mol/L lactic acid solution, and adding H with the volume of 0.5 percent of the volume of the acid solution₂O₂Stirring at 60 deg.C for 30min to obtain Li-containing solution⁺，Co²⁺A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 20g/L, and the stirring speed is 400 rpm.

(2) Controlling the concentration of manganese ions to be 1mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, and adjusting the pH value of the leaching solution to 10; weighing benzoic acid according to the molar ratio of polyvinylpyrrolidone (PVP) to manganese ion concentration of 3:1, adding the benzoic acid into the leaching solution, and marking as solution 1; weighing PTA according to the molar ratio of PTA to manganese ion concentration of 3:1, adding the PTA into ethanol, and marking the solution as solution 2, wherein the volume ratio of ethanol to leaching solution is 1: 1; and mixing the two solutions, stirring at room temperature for 20min, standing in an oven at 120 ℃ for 2h, and centrifuging to obtain the Mn-MOF material.

Example 4:

the embodiment provides a method for preparing a manganese-based MOF material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste nickel cobalt lithium manganate battery, and the method comprises the following steps:

(1) mixing the anode material of the waste lithium ion battery with 1.5mol/L carrot acid solution, and adding H with the volume of 0.5 percent of the acid solution₂O₂Stirring at 80 deg.C for 60min to obtain Li-containing material⁺，Co²⁺A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 25g/L, and the stirring speed is 400 rpm.

(2) Controlling the concentration of cobalt ions to be 1mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, adjusting the pH value of the leaching solution to 7, and marking as a solution 1; according to C₈H₆O₆The molar ratio of the manganese ion to the manganese ion is 6:1, and C is weighed₈H₆O₆Slowly adding the mixture into a mixed solvent of DMF and ethanol, and marking as a solution 2, wherein the volume ratio of the leaching solution to the ethanol to the DMF is 1:1: 10; and mixing the solutions 1 and 2 at room temperature, stirring for 20min, standing in an oven at 120 ℃ for 5h, and centrifuging to obtain the Mn-MOF material.

Example 5:

the embodiment provides a method for preparing a manganese-based MOF material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste nickel cobalt lithium manganate battery, and the method comprises the following steps:

(1) mixing the anode material of the waste lithium ion battery with 1mol/L maleic acid solution, and adding H with the volume of 1 percent of the acid solution₂O₂Stirring at 60 deg.C for 90min to obtain Li-containing material⁺，Co²⁺A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 30g/L, and the stirring speed is 400 rpm.

(2) Controlling the concentration of cobalt ions to be 2mol/L by evaporating the leaching solution; adding a proper amount of ammonia water, adjusting the pH value of the leaching solution to 8, and marking as a solution 1; according to the molar ratio of the BTC to the manganese ion concentration of 10:1, weighing BTC, slowly adding the BTC into a methanol solvent, and marking as a solution 2, wherein the volume ratio of a leaching solution to methanol is 1: 1; and mixing the solutions 1 and 2 at room temperature, stirring for 20min, standing in an oven at 90 ℃ for 12h, and centrifuging to obtain the Mn-MOF material.

Example 6:

the embodiment provides a method for preparing a manganese-based MOF material based on a leachate of a waste lithium ion battery, wherein the lithium ion battery is a waste nickel lithium manganate battery, and the method comprises the following steps:

(1) mixing the anode material of the waste lithium ion battery with 1mol/L acetic acid solution, and adding H with the volume of 2 percent of the acid solution₂O₂Stirring at 70 deg.C for 90min to obtain Li-containing material⁺，Mn²⁺A solution of metal ions; wherein the solid-to-liquid ratio of the anode material of the waste lithium ion battery to the acidic solution is 30g/L, and the stirring speed is 500 rpm.

(2) Controlling the concentration of manganese ions to be 1.5mol/L by evaporating the leaching solution; adding a proper amount of sodium hydroxide, adjusting the pH of the leaching solution to 9, and marking as a solution 1; according to C₈H₆O₆The molar ratio of the manganese ion to the manganese ion is 2:1, and C is weighed₈H₆O₆Slowly adding into ethanol solvent, marked as solution 2, wherein the volume ratio of the leaching solution to the ethanol is 5: 1, in a mixed solution; and stirring the solutions 1 and 2 at room temperature for 20min, standing in an oven at 60 ℃ for 12h, and centrifuging to obtain the Mn-MOF material.

The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modification, equivalent substitution of materials for the invention, addition of additional materials, selection of specific means, etc., which are apparent to those skilled in the art are intended to be within the scope and disclosure of the invention.