阅读说明：本技术 一种从废旧锂离子电池中定向回收环保光学材料的方法 (Method for directionally recycling environment-friendly optical material from waste lithium ion battery ) 是由 阮菊俊 邱锐军 汤叶涛 仇荣亮 于 2021-07-28 设计创作，主要内容包括：本发明属于固体废弃物资源化回收技术领域,具体涉及一种从废旧锂离子电池中定向回收环保光学材料的方法。该方法采用真空热解还原,将废旧锂离子电池电极材料热解生成氧化锰、氧化锂等多种氧化物,进一步采用高温固相反应将镧原子掺杂进晶体产物中进行原子级别的调控,以定向实现产物的制备和高值化回收,将废旧锂离子电极材料回收为高性能环保光学材料镧掺杂LiAl-(5)O-(8),具有非常高的光学强度,经济价值显著提高。并且本发明方法操作简单,整个过程没有添加其他酸性或氧化物质,不会产生二次污染,绿色高效,在废旧锂离子电池资源化领域方面具有重要的应用价值。(The invention belongs to the technical field of solid waste resource recovery, and particularly relates to a method for directionally recovering an environment-friendly optical material from a waste lithium ion battery. The method adopts vacuum pyrolysis reduction to pyrolyze the waste lithium ion battery electrode material to generate various oxides such as manganese oxide, lithium oxide and the like, further adopts high-temperature solid-phase reaction to dope lanthanum atoms into crystal products to regulate and control the atomic level so as to directionally realize the preparation and high-valued recovery of the products, and recovers the waste lithium ion battery electrode material into a high-performance environment-friendly optical material lanthanum-doped LiAl 5 O 8 Has very high optical strength and obviously improved economic value. The method is simple to operate, does not add other acidic or oxidizing substances in the whole process, does not generate secondary pollution, is green and efficient, and can be used for removing the waste lithium ionsHas important application value in the field of the resource utilization of the sub-battery.)

1. A method for directionally recovering environment-friendly optical materials from waste lithium ion batteries is characterized in that positive and negative electrode materials obtained by disassembling the waste lithium ion batteries are uniformly mixed with a lanthanum salt compound, subjected to pyrolysis and redox reaction and then subjected to high-temperature solid-phase synthesis reaction, and recovered to obtain lanthanum-doped LiAl₅O₈An optical material.

2. The method of claim 1, wherein the waste lithium ion battery uses lithium manganate as a negative electrode material and graphite as a positive electrode material.

3. The method according to claim 1, wherein the mass ratio of the positive electrode material to the negative electrode material in the positive electrode material and the negative electrode material is 1 (1-2).

4. The method as claimed in claim 1, wherein the lanthanum salt compound is selected from one or both of lanthanum nitrate and lanthanum chloride.

5. The method according to claim 1, wherein the mass ratio of the lanthanum salt compound to the total mass of the positive and negative electrode materials is 1 (5-6).

6. The method according to any one of claims 1 to 5, comprising the steps of:

s1, disassembling the waste lithium ion battery, crushing and screening the positive electrode material and the negative electrode material, and then stirring and grinding the crushed and screened positive electrode material and the negative electrode material together with a lanthanum salt compound uniformly to obtain mixed solid powder;

s2, fully reacting the mixed solid powder obtained in the step S1 at 300-400 ℃ under a vacuum condition to obtain a thermal decomposition product and a redox product;

s3, raising the reaction temperature to 1400-1600 ℃, and carrying out a solid phase synthesis reaction completely to obtain lanthanum-doped LiAl₅O₈An optical material.

7. The method of claim 6, wherein in step S2, the sufficient reaction time is 5-20 min.

8. The method according to claim 6, wherein in step S3, the reaction is completed for 10-60 min.

9. The lanthanum-doped LiAl prepared by the method for directionally recycling the environment-friendly optical material from the waste lithium ion battery according to any one of claims 1 to 8₅O₈An optical material.

10. The lanthanum-doped LiAl of claim 9₅O₈The application of the optical material in preparing environment-friendly optical materials.

Technical Field

The invention belongs to the technical field of solid waste resource recovery. And more particularly, to a method for directionally recovering an environment-friendly optical material from a waste lithium ion battery.

Background

With the rapid development of lithium ion batteries, the recycling problem of waste lithium ion batteries is receiving wide attention. The latest report estimates that the amount of electronic waste will reach 7470 ten thousand tons by 2030, which is a problem to be urgently solved. On the one hand, improper disposal of the waste lithium ion battery has caused potential environmental pollution risks, such as heavy metal pollution, fluorinated gas pollution and the like, in the past period of time, and finally becomes potential harm to human health along with the enrichment of food chains in the environment; on the other hand, the resources such as metal in the waste lithium ion battery are rich, and are a precious secondary resource. Therefore, the research on resource recovery of the waste lithium ion battery is urgent and accords with the social development trend.

At present, the treatment technology of the waste lithium ion battery mainly focuses on the stabilization treatment aspect. For example, chinese patent application CN104611566A discloses a method for recovering valuable metals from waste lithium ion batteries, in which a waste lithium ion battery and carbon powder are mixed and pyrolyzed at high temperature, and then mixed with a slag-forming agent to obtain valuable metal alloy and oxide slag, but the recovered product needs to be further separated and purified, and has low recovery value. Chinese patent application CN103045870A discloses a method for comprehensively recovering valuable metals from waste lithium ion batteries as resources, which utilizes hydrometallurgy to recover metal resources, but the method consumes a large amount of acidic and oxidizing substances, has high cost and increases the risk of environmental pollution.

Therefore, the technology of recycling the waste lithium ion battery electrode materials in a reduction, harmless and high-value manner is extremely lacking. In the existing methods for recycling a plurality of solid wastes, the research of trial and error exploration accounts for a large proportion, so that large resource waste is caused, and the efficiency is low. Therefore, a method for systematically, directionally, greenly and efficiently recycling the waste lithium ion battery electrode material to prepare a new material is needed.

Disclosure of Invention

The invention aims to solve the technical problems that the recovered product in the prior art has low economic value and needs to be further separated and purified; the method needs to add a large amount of acidic and zinc oxide substances, has the defects of high cost and easy environmental pollution, and provides a method for systematically, directionally, greenly and efficiently recycling the waste lithium ion battery electrode material to prepare a high-value new material.

The invention aims to provide a method for directionally recovering an environment-friendly optical material from a waste lithium ion battery.

The invention also aims to provide lanthanum-doped LiAl prepared by the method for directionally recovering the environment-friendly optical material from the waste lithium ion battery₅O₈An optical material.

Another object of the present invention is to provide the lanthanum-doped LiAl₅O₈The optical material or the method for directionally recycling the environment-friendly optical material from the waste lithium ion battery is applied to the preparation of the environment-friendly optical material.

The above purpose of the invention is realized by the following technical scheme:

a method for directionally recovering environment-friendly optical materials from waste lithium ion batteries comprises the steps of uniformly mixing positive and negative electrode materials obtained by disassembling waste lithium ion batteries with a lanthanum salt compound, carrying out pyrolysis and redox reaction, then carrying out high-temperature solid-phase synthesis reaction, and recovering to obtain lanthanum-doped LiAl₅O₈An optical material.

The method adopts vacuum pyrolysis reduction to pyrolyze the waste lithium ion battery electrode material to generate various oxides such as manganese oxide, lithium oxide and the like, further adopts high-temperature solid-phase reaction to dope lanthanum atoms into crystal products for atomic-level regulation and control so as to directionally realize the preparation and high-valued recovery of the products, and recovers the waste lithium ion battery electrode material into a high-performance environment-friendly optical material lanthanum-doped LiAl₅O₈Has very high optical strength and obviously improved economic value. The method is simple to operate, does not add other acidic or oxidizing substances in the whole process, does not produce secondary pollution, is green and efficient, and has important application value in the field of waste lithium ion battery recycling.

Furthermore, the waste lithium ion battery takes lithium manganate as a negative electrode material and graphite as a positive electrode material.

Furthermore, in the positive electrode material and the negative electrode material, the mass ratio of the positive electrode material to the negative electrode material is 1 (1-2). Preferably, the mass ratio of the cathode material to the anode material is 1: 1.

Further, the lanthanum salt compound is selected from one or two of lanthanum nitrate and lanthanum chloride.

Furthermore, the mass ratio of the lanthanum salt compound to the total mass of the positive electrode material and the negative electrode material is 1 (5-6). Preferably, the mass ratio of the lanthanum salt compound to the total mass of the positive electrode material and the negative electrode material is 1: 5.

Preferably, the pyrolysis reaction, the oxidation-reduction reaction and the high-temperature solid-phase synthesis reaction are carried out under vacuum conditions, wherein the pressure of the vacuum conditions is below 0.05 Pa; more preferably, the vacuum condition is a pressure of 0.01Pa or less.

Further, the method for directionally recovering the environment-friendly optical material from the waste lithium ion battery specifically comprises the following steps:

s1, disassembling the waste lithium ion battery, crushing and screening the positive electrode material and the negative electrode material, and then stirring and grinding the crushed and screened positive electrode material and the negative electrode material together with a lanthanum salt compound uniformly to obtain mixed solid powder;

s2, fully reacting the mixed solid powder obtained in the step S1 at 300-400 ℃ under a vacuum condition to obtain a thermal decomposition product and a redox product;

s3, raising the reaction temperature to 1400-1600 ℃, and carrying out a solid phase synthesis reaction completely to obtain lanthanum-doped LiAl₅O₈An optical material.

Further, in step S2, the time for the sufficient reaction is 5 to 20 min.

Furthermore, in step S3, the time for the reaction to complete is 10-60 min.

Further, in the steps S2 and S3, the temperature rise rate is 10-15 ℃/min; preferably, the rate of temperature rise is 10 deg.C/min.

In addition, the invention providesThe lanthanum-doped LiAl prepared by the method for directionally recovering the environment-friendly optical material from the waste lithium ion battery₅O₈An optical material.

Further, the lanthanum-doped LiAl₅O₈The optical material achieves the highest optical intensity at 530 nm.

In addition, the invention also provides the lanthanum-doped LiAl₅O₈The optical material or the method is applied to the preparation of the environment-friendly optical material.

Further, the environment-friendly optical material can be a light-emitting diode, a noctilucent material or a weak luminescent material.

The invention has the following beneficial effects:

the invention relates to a method for directionally recycling an environment-friendly optical material from a waste lithium ion battery, which takes a waste lithium ion battery electrode material as a main raw material, converts the waste electrode material rich in strategic metal resources such as lithium and aluminum into the environment-friendly optical material with high-efficiency optical performance, thereby realizing the resource and high-value utilization of the waste lithium ion battery electrode material, effectively solving the problem of potential pollution to the environment caused by improper disposal of the waste lithium ion battery electrode material, and simultaneously achieving the recycling of the high-value material. The method is simple to operate, green and efficient, the economic value of the product is high, and the recovery target of 'reduction, harmlessness and recycling' of the solid waste is fully reflected.

Drawings

Fig. 1 is a flowchart of a method for directionally recovering an environmentally friendly optical material from a waste lithium ion battery in embodiment 1 of the present invention.

Detailed Description

The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.

Embodiment 1 method for directionally recycling environment-friendly optical material from waste lithium ion battery

The method specifically comprises the following steps:

s1, after fully discharging the waste lithium ion battery taking lithium manganate as an electrode material, manually disassembling, separating out a plastic shell and a diaphragm, crushing and screening 3.3095g of positive electrode material and negative electrode material respectively, putting into a mortar, adding 0.6828g of lanthanum nitrate powder, stirring together, and grinding uniformly to obtain mixed solid powder;

s2, transferring the mixed solid powder obtained in the step S1 into a crucible, placing the crucible into a high-temperature area of a heating tube furnace, pumping the pressure to be below 0.01Pa by using a vacuum pump, setting the temperature to be 300 ℃, the heating rate to be 10 ℃/min, and carrying out heat preservation reaction for 10min to fully carry out decomposition reaction and redox reaction to obtain a thermal decomposition product LiO₂And MnO₂Redox products Mn and Al₂O₃；

And S3, raising the temperature to 1500 ℃, raising the temperature rate to 10 ℃/min, keeping the temperature for reaction for 30min, and fully performing the high-temperature solid-phase synthesis reaction to obtain the recovered product.

The product obtained in the step S3 is lanthanum-doped LiAl through XRD verification₅O₈An optical material; the maximum optical intensity of the optical material at 530nm is 4.57X 10 measured by photoluminescence spectroscopy⁵(a.u.), and conventional LiAl₅O₈Compared with the matrix optical material, the luminous intensity of the matrix optical material is improved by about 40 times under the same condition, and the matrix optical material can be further applied to the preparation of light-emitting diodes.

Embodiment 2 method for directionally recycling environment-friendly optical material from waste lithium ion battery

The method specifically comprises the following steps:

s1, after fully discharging the waste lithium ion battery taking lithium manganate as an electrode material, manually disassembling, separating out a plastic shell and a diaphragm, crushing and screening 3.2923g of positive electrode material and negative electrode material respectively, putting into a mortar, adding 0.5427g of lanthanum chloride powder, stirring together, and grinding uniformly to obtain mixed solid powder;

s2, transferring the mixed solid powder obtained in the step S1 into a crucible, placing the crucible into a high-temperature area of a heating tube furnace, pumping the pressure to be below 0.01Pa by using a vacuum pump, setting the temperature to be 300 ℃, the heating rate to be 10 ℃/min, and carrying out heat preservation reaction for 10min to fully carry out decomposition reaction and redox reaction to obtain a thermal decomposition product LiO₂And MnO₂Redox products Mn and Al₂O₃；

And S3, raising the temperature to 1500 ℃, raising the temperature rate to 10 ℃/min, keeping the temperature for reaction for 30min, and fully performing the high-temperature solid-phase synthesis reaction to obtain the recovered product.

The product obtained in the step S3 is lanthanum-doped LiAl through XRD verification₅O₈An optical material; the maximum optical intensity of the optical material at 530nm is 4.08X 10 measured by photoluminescence spectrum⁵(a.u.), and conventional LiAl₅O₈Compared with the matrix optical material, the luminous intensity of the matrix optical material is improved by about 40 times under the same condition, and the matrix optical material can be further applied to the preparation of light-emitting diodes.

Embodiment 3 method for directionally recycling environment-friendly optical material from waste lithium ion battery

The method specifically comprises the following steps:

s1, after fully discharging the waste lithium ion battery taking lithium manganate as an electrode material, manually disassembling, separating out a plastic shell and a diaphragm, crushing and screening 3.3102g of positive electrode material and negative electrode material respectively, putting into a mortar, adding 0.6429g of lanthanum chloride powder, stirring together, and grinding uniformly to obtain mixed solid powder;

s2, transferring the mixed solid powder obtained in the step S1 into a crucible, placing the crucible into a high-temperature area of a heating tube furnace, pumping the pressure to be below 0.01Pa by using a vacuum pump, setting the temperature to be 400 ℃, increasing the temperature rate to be 15 ℃/min, carrying out heat preservation reaction for 20min, and fully carrying out decomposition reaction and redox reaction to obtain a thermal decomposition product LiO₂And MnO₂Redox products Mn and Al₂O₃；

And S3, raising the temperature to 1600 ℃, keeping the temperature at the same speed of 15 ℃/min, and reacting for 60min to fully perform the high-temperature solid-phase synthesis reaction, thereby finally obtaining the recovered product.

The product obtained in the step S3 is lanthanum-doped LiAl through XRD verification₅O₈An optical material; the maximum optical intensity of the optical material at 530nm is 4.36 × 10 measured by photoluminescence spectroscopy⁵(a.u.), and conventional LiAl₅O₈Compared with the matrix optical material, the luminous intensity of the matrix optical material is improved by about 40 times under the same condition, and the matrix optical material can be further applied to the preparation of light-emitting diodes.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.