阅读说明：本技术 废旧锂离子电池和稀土超富集生物制备光学材料的方法 (Method for preparing optical material by waste lithium ion battery and rare earth hyper-enrichment organism ) 是由 阮菊俊 邱锐军 汤叶涛 仇荣亮 于 2021-07-31 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,具体涉及废旧锂离子电池和稀土超富集生物制备光学材料的方法。该方法采用真空热解分段冷凝方法对稀土超富集植物进行处理,可以得到热解油和热解气等作为能源物质；进一步采用真空梯度热解技术将热解残渣中的稀土元素与废旧锂离子电池电极材料一起处理,可以制备得到稀土掺杂LiAl-(5)O-(8)光学材料,光学强度高,实现固体废弃物的高值化利用。并且,本发明整个废旧锂离子电池和稀土超富集生物制备光学材料的方法操作简单,不会产生二次污染,绿色高效,在废旧锂离子电池、稀土超富集植物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 preparing an optical material by waste lithium ion batteries and rare earth hyperaccumulation organisms. The method adopts vacuum pyrolysis sectional condensation method to super-enrich rare earth plantsThe pyrolysis oil, the pyrolysis gas and the like can be obtained as energy substances after treatment; further adopting a vacuum gradient pyrolysis technology to treat the rare earth elements in the pyrolysis residue and the waste lithium ion battery electrode material together to prepare rare earth doped LiAl 5 O 8 The optical material has high optical strength, and realizes high-value utilization of solid waste. In addition, the whole method for preparing the optical material by the waste lithium ion battery and the rare earth super-enrichment organisms is simple to operate, does not produce secondary pollution, is green and efficient, and has important application value in the field of recycling of the waste lithium ion battery and the rare earth super-enrichment plants.)

1. A method for preparing an optical material from waste lithium ion batteries and rare earth hyper-enrichment organisms is characterized in that rare earth hyper-enrichment plants are subjected to vacuum pyrolysis and sectional condensation treatment, the obtained pyrolysis residues are mixed with waste lithium ion battery materials, vacuum gradient pyrolysis reaction is carried out, and the optical material is obtained through recovery.

2. The method of claim 1, wherein the rare earth hyperaccumulator comprises dicranopteris pedata, pokeberry, cress monophyllum.

3. The method of claim 1, wherein the spent lithium ion battery is a lithium manganate battery.

4. The method according to any one of claims 1 to 3, comprising the steps of:

s1, collecting plants of the rare earth hyper-enrichment plants, drying, crushing, performing vacuum pyrolysis and sectional condensation treatment, and collecting pyrolysis oil, pyrolysis gas and pyrolysis residues;

and S2, mixing the pyrolysis residue obtained in the step S1 and the waste lithium ion battery electrode powder, uniformly grinding, performing vacuum gradient pyrolysis reaction on the obtained mixed solid powder, and recovering to obtain the optical material.

5. The method according to claim 4, wherein in step S1, the vacuum pyrolysis staged condensation comprises a first stage pyrolysis zone, a second stage condensation zone and a third stage condensation zone; wherein the final temperature of the first-stage pyrolysis zone is set to be 650-700 ℃, and the reaction time is kept for 30-45 min; the condensation temperature of the second section of condensation zone is set to be 160-180 ℃; the condensing temperature of the third section of condensing zone is set to be 60-80 ℃.

6. The method according to claim 4, wherein in step S2, the first gradient temperature of the vacuum gradient pyrolysis reaction is set to 300-400 ℃, and the residence time is 5-20 min; setting the second gradient temperature to be 1400-1600 ℃, and keeping the reaction time to be 10-60 min to obtain a white solid powder product.

7. The method according to claim 4, wherein in the step S2, the mass ratio of the pyrolysis residue to the waste lithium ion battery electrode powder is 1 (5-6).

8. The method for preparing the optical material by the waste lithium ion battery and the rare earth super-enrichment organism according to any one of claims 1 to 7, wherein the method is used for preparing the rare earth-doped LiAl₅O₈An optical material.

9. The rare earth doped LiAl of claim 8₅O₈Optical material, characterized in that it achieves the strongest optical intensity at 550 nm.

10. The rare earth doped LiAl of claim 8 or 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. More particularly, relates to a method for preparing optical materials by waste lithium ion batteries and rare earth super-enrichment organisms.

Background

With the rapid development of mobile devices and new energy automobiles, the demand of lithium ion batteries has increased dramatically, and the number of waste lithium ion batteries has also increased continuously. On one hand, the improper disposal of the waste lithium ion battery can cause the loss and waste of a large amount of valuable metal resources; on the other hand, heavy metals and toxic and harmful substances in the electrode materials of the waste lithium ion batteries are potential pollution factors in the environment. At present, the treatment technology of the electrode material of the waste lithium ion battery is more various. For example, 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 former to obtain valuable metal alloy and oxide slag, but the recovered product cannot be directly applied, needs to be further separated and purified, and has a low recovery value.

The plant repairing technology is a method for planting rare earth hyperaccumulator plants on the rare earth contaminated soil to enrich the rare earth elements in the soil so as to repair the soil. However, in practical application, the treatment of the super-enriched plants after the enrichment of the rare earth elements still has difficulty, and on one hand, the plants are enriched with a large amount of rare earth elements, which greatly influences the application of the plants such as medicinal use, eating use and the like; on the other hand, the prior art has no mature method for extracting and separating the rare earth elements from the hyper-enriched plants. Therefore, research on the recovery processing of the super-enriched plants is still in a blank stage and faces a large challenge. For example, chinese patent application CN110591723A discloses a method for stabilizing heavy metals in super-enriched plants, in which plant powder is subjected to hydrothermal reaction, so that metal elements in hydrothermal carbon are stabilized, and used as soil conditioner, fuel and the like, thereby effectively avoiding heavy metal pollution.

It can be seen that a method for better recovering and treating waste lithium ion batteries and hyper-enriched plants enriched with rare earth elements is still lacking at present, and a method which is green, safe, efficient, free from secondary pollution and capable of simultaneously performing high-value resource recovery on rare earth hyper-enriched plants and waste lithium ion battery materials is urgently needed.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects and shortcomings of resource waste caused by the fact that resources in the waste lithium ion battery and the super-enriched plant after the enrichment of the rare earth elements are not fully utilized or the value of a recovered product is low in the prior art, and provides a method which is green, safe, efficient, free of secondary pollution, capable of simultaneously carrying out high-value resource recovery on the rare earth super-enriched plant and the waste lithium ion battery material and preparing an optical material.

The invention aims to provide a method for preparing an optical material by using waste lithium ion batteries and rare earth hyper-enrichment organisms.

The invention also aims to provide the rare earth doped LiAl prepared by the method for preparing the optical material by the waste lithium ion battery and the rare earth hyperaccumulation organism₅O₈An optical material.

Another object of the present invention is to provide the rare earth doped LiAl₅O₈The optical material or the method 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 preparing an optical material from waste lithium ion batteries and rare earth hyper-enrichment organisms comprises the steps of carrying out vacuum pyrolysis and sectional condensation treatment on rare earth hyper-enrichment plants, mixing obtained pyrolysis residues with waste lithium ion battery materials, carrying out vacuum gradient pyrolysis reaction, and recycling to obtain the optical material.

According to the invention, the rare earth hyper-enriched plant is treated by adopting a vacuum pyrolysis sectional condensation method, the pyrolysis degree is complete, and pyrolysis oil, pyrolysis gas and the like can be obtained as energy substances; further adopting a vacuum gradient pyrolysis technology to treat the rare earth elements in the pyrolysis residue and the waste lithium ion battery electrode material together to prepare rare earth doped LiAl₅O₈The optical material has high optical strength, can be used for preparing optical materials such as light-emitting diodes and the like without complex impurity removal and purification, realizes high-value utilization of solid wastes, and obviously improves the economic value. In addition, the whole method for preparing the optical material by the waste lithium ion battery and the rare earth super-enrichment organisms is simple to operate, does not produce secondary pollution, is green and efficient, and has important application value in the field of recycling of the waste lithium ion battery and the rare earth super-enrichment plants.

Further, the rare earth super-enriched organisms include, but are not limited to, dicranopteris pedata, pokeberry, and crested cress.

Furthermore, the waste lithium ion battery is a lithium manganate lithium ion battery. Preferably, the waste lithium ion battery material is a waste lithium ion battery electrode material, wherein the mass ratio of the positive electrode material to the negative electrode material is 1 (1-1.5); more preferably, the mass ratio of the positive electrode material to the negative electrode material is 1: 1.

Further, the method for preparing the optical material by the waste lithium ion battery and the rare earth hyper-enrichment organism specifically comprises the following steps:

s1, collecting plants of the rare earth hyper-enrichment plants, drying, crushing, performing vacuum pyrolysis and sectional condensation treatment, and collecting pyrolysis oil, pyrolysis gas and pyrolysis residues;

and S2, mixing the pyrolysis residue obtained in the step S1 and the waste lithium ion battery electrode powder, uniformly grinding, performing vacuum gradient pyrolysis reaction on the obtained mixed solid powder, and recovering to obtain the optical material.

Further, in step S1, the vacuum pyrolysis staged condensation includes a first stage pyrolysis zone, a second stage condensation zone, and a third stage condensation zone; wherein the final temperature of the first-stage pyrolysis zone is set to be 650-700 ℃, and the reaction time is kept for 30-45 min; the condensation temperature of the second section of condensation zone is set to be 160-180 ℃; the condensing temperature of the third section of condensing zone is set to be 60-80 ℃.

Further, in step S1, during the vacuum pyrolysis and staged condensation, the vacuum degree is set to 10-100 Pa.

Furthermore, in step S1, in the vacuum pyrolysis sectional condensation process, the temperature rise rate is set to be 20 to 30 ℃/min.

Further, in step S2, the first gradient temperature of the vacuum gradient pyrolysis reaction is set to 300 to 400 ℃, and the residence time is 5 to 20 min; setting the second gradient temperature to be 1400-1600 ℃, and keeping the reaction time to be 10-60 min to obtain a white solid powder product.

Further, in step S2, the vacuum degree is set to 0 to 0.01Pa during the vacuum gradient pyrolysis reaction.

Further, in step S2, in the vacuum gradient pyrolysis reaction process, the temperature increase rate is set to be 5-10 ℃/min.

Furthermore, in the step S2, the mass ratio of the pyrolysis residue to the waste lithium ion battery electrode powder is 1 (5-6).

Further, in step S2, the time for the co-stirring and the grinding to be uniform is 10 to 30 min.

In addition, the invention also provides rare earth doped LiAl prepared by the method for preparing the optical material by the waste lithium ion battery and the rare earth hyperaccumulation organism₅O₈An optical material.

Further, the optical material achieves the highest optical intensity at 550 nm.

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

Furthermore, the environment-friendly optical material can be a light-emitting diode, a weak illumination light source, a noctilucent material and the like.

The invention has the following beneficial effects:

the invention relates to a method for preparing an optical material by using a waste lithium ion battery and a rare earth hyperaccumulator, which takes a rare earth hyperaccumulator and a waste lithium ion battery material as main raw materials, and converts a rare earth-rich hyperaccumulator harvest and a waste lithium ion battery material into an environment-friendly optical material with high-efficiency optical performance, thereby realizing the resource and high-value utilization of the rare earth hyperaccumulator and the waste lithium ion battery, effectively solving the potential pollution problem of the rare earth hyperaccumulator and the waste lithium ion battery to the environment due to improper disposal, and simultaneously achieving the recovery of high-value materials. 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 flow chart of a method for preparing an optical material by using waste lithium ion batteries and rare earth hyperaccumulation organisms.

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.

Example 1 method for preparing optical material by waste lithium ion battery and rare earth hyper-enrichment organism

The method specifically comprises the following steps:

s1, collecting and drying an annual rare earth hyper-enriched plant dicranopteris pedata collected in basalt area of Zhanjiang, Guangdong, crushing the dried plant in a shear type crusher, weighing 40g of the obtained dicranopteris pedata powder, placing the obtained dicranopteris pedata powder in a vacuum pyrolysis sectional condensation device for vacuum pyrolysis sectional condensation treatment, wherein the vacuum degree of a first section pyrolysis area is set to be 10Pa, the final temperature of the first section pyrolysis area is set to be 700 ℃, the heating rate is set to be 30 ℃/min, and the reaction time is kept to be 30 min; the condensation temperature of the second section of condensation zone is set to be 180 ℃; the condensation temperature of the third section of condensation zone is set to be 80 ℃; after pyrolysis is completed, collecting pyrolysis oil and pyrolysis gas to obtain 27.458g of pyrolysis oil and pyrolysis gas in total, and analyzing the pyrolysis oil and pyrolysis gas by adopting GC-MS (gas chromatography-mass spectrometry), wherein the pyrolysis oil and pyrolysis gas mainly comprise ethylene oxide and acetaldehyde and can be recycled as energy substances; collecting pyrolysis residues;

s2, adopting ICP-MS (inductively coupled plasma mass spectrometry) to measure the total content of the rare earth in the pyrolysis residue obtained in the step S1, and obtaining the total content of the rare earth as 6160mg kg^-1(ii) a Weighing 12.356g of residual pyrolysis residue, putting the residual pyrolysis residue into a mortar, adding 67.87g of crushed and ground waste lithium ion battery electrode powder, uniformly stirring for 10min, transferring the obtained mixed solid powder into a crucible, and putting the crucible into a high-temperature area of a heating tube furnace for vacuum gradient pyrolysis reaction, wherein the vacuum degree is set to be 0.01Pa, the first gradient temperature is set to be 300 ℃, and the residence reaction time is 10 min; the second gradient temperature is set to 1500 ℃, the residence time is 30min, and a white solid powder product is obtained.

XRD verifies that the product obtained in the step S2 is rare earth doped LiAl₅O₈An optical material; the optical material has the highest optical intensity of 8.57 multiplied by 10 at 550nm when measured by photoluminescence spectrum⁵(a.u.), and conventional LiAl₅O₈Compared with the single rare earth doped LiAl, the matrix optical material has the luminous intensity improved by about 80 times under the same conditions₅O₈Compared with the material, the material also has better optical performance and can be further applied to the preparation of light-emitting diodes.

Embodiment 2 method for preparing optical material by waste lithium ion battery and rare earth hyper-enrichment organism

The method specifically comprises the following steps:

s1, collecting and drying an annual rare earth hyper-enriched plant Phytolacca americana collected in the basalt area of Zhanjiang, Guangdong, crushing the dried plant in a shear type crusher, weighing 40g of the obtained Phytolacca americana powder, placing the obtained Phytolacca americana powder in a vacuum pyrolysis sectional condensation device for vacuum pyrolysis sectional condensation treatment, wherein the vacuum degree of a first section pyrolysis area is set to be 50Pa, the final temperature of the first section pyrolysis area is set to be 650 ℃, the heating rate is set to be 25 ℃/min, and the remaining reaction time is 30 min; the condensation temperature of the second section of condensation zone is set to be 160 ℃; the condensation temperature of the third section of condensation zone is set to be 70 ℃; after pyrolysis is completed, collecting pyrolysis oil and pyrolysis gas to obtain 35.680g of pyrolysis oil and pyrolysis gas in total, and analyzing the pyrolysis oil and pyrolysis gas by adopting GC-MS (gas chromatography-mass spectrometry), wherein the pyrolysis oil and pyrolysis gas mainly comprise ethylene oxide and acetaldehyde and can be recycled as energy substances; collecting pyrolysis residues;

s2, adopting ICP-MS (inductively coupled plasma mass spectrometry) to measure the total content of rare earth in the pyrolysis residue obtained in the step S1, and obtaining the total content of the rare earth of 5971mg kg^-1(ii) a Weighing 4.53g of residual pyrolysis residue, putting the residual pyrolysis residue into a mortar, adding 24.55g of crushed and ground waste lithium ion battery electrode powder, uniformly stirring for 30min, transferring the obtained mixed solid powder into a crucible, and putting the crucible into a high-temperature area of a heating tube furnace for vacuum gradient pyrolysis reaction, wherein the vacuum degree is set to be 0.01Pa, the first gradient temperature is set to be 300 ℃, and the retention reaction time is 10 min; the second gradient temperature is set to 1400 ℃, and the residence time is 30min, so as to obtain a white solid powder product.

XRD verifies that the product obtained in the step S2 is rare earth doped LiAl₅O₈An optical material; the optical material has the highest optical intensity of 8.33 multiplied by 10 at 550nm when measured by photoluminescence spectrum⁵(a.u.), and conventional LiAl₅O₈Compared with the single rare earth doped LiAl, the matrix optical material has the luminous intensity improved by about 80 times under the same conditions₅O₈Compared with the material, the material also has better optical performance and can be further applied to the preparation of light-emitting diodes.

Embodiment 3 method for preparing optical material by waste lithium ion battery and rare earth hyper-enrichment organism

The method specifically comprises the following steps:

s1, collecting plants of annual rare earth hyper-enriched plant crescent anogeissus chinensis collected in basalt area of Zhanjiang province in Guangdong, drying, crushing the dried plants in a shear type crusher, weighing 40g of the obtained crescent anogeissus chinensis powder, placing the crescent anogeissus chinensis powder in a vacuum pyrolysis sectional condensation device for vacuum pyrolysis sectional condensation treatment, wherein the vacuum degree of a first section pyrolysis area is set to be 100Pa, the final temperature of the first section pyrolysis area is set to be 700 ℃, the heating rate is set to be 30 ℃/min, and the reserved reaction time is 45 min; the condensation temperature of the second section of condensation zone is set to be 180 ℃; the condensation temperature of the third section of condensation zone is set to be 80 ℃; after pyrolysis is completed, collecting pyrolysis oil and pyrolysis gas to obtain 30.257g of pyrolysis oil and pyrolysis gas in total, and analyzing the pyrolysis oil and pyrolysis gas by adopting GC-MS (gas chromatography-mass spectrometry), wherein the pyrolysis oil and pyrolysis gas mainly comprise ethylene oxide and acetaldehyde and can be recycled as energy substances; collecting pyrolysis residues;

s2, adopting ICP-MS (inductively coupled plasma mass spectrometry) to measure the total content of rare earth in the pyrolysis residue obtained in the step S1, and obtaining the total content of rare earth 6034mg kg^-1(ii) a Weighing 7.16g of residual pyrolysis residue, putting the residual pyrolysis residue into a mortar, adding 39.08g of crushed and ground waste lithium ion battery electrode powder, uniformly stirring for 30min, transferring the obtained mixed solid powder into a crucible, and putting the crucible into a high-temperature area of a heating tube furnace for vacuum gradient pyrolysis reaction, wherein the vacuum degree is set to be 0.01Pa, the first gradient temperature is set to be 400 ℃, and the retention reaction time is 10 min; the second gradient temperature was set at 1600 ℃ and the residence time was 60min to obtain a white solid powder product.

XRD verifies that the product obtained in the step S2 is rare earth doped LiAl₅O₈An optical material; the optical material has the highest optical intensity of 8.41 multiplied by 10 at 550nm when measured by photoluminescence spectrum⁵(a.u.), and conventional LiAl₅O₈Compared with the matrix optical material, under the same condition, the luminous intensity is improved by about 80 times, and compared with the single matrix optical materialRare earth doped LiAl₅O₈Compared with the material, the material also has better optical performance and 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.