CN106252771B - Batch pre-processes the cleaner discharge method of waste and old lithium ion battery - Google Patents
Batch pre-processes the cleaner discharge method of waste and old lithium ion battery Download PDFInfo
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- CN106252771B CN106252771B CN201610659045.9A CN201610659045A CN106252771B CN 106252771 B CN106252771 B CN 106252771B CN 201610659045 A CN201610659045 A CN 201610659045A CN 106252771 B CN106252771 B CN 106252771B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention provides it is a kind of can batch processing waste and old lithium ion battery high-efficiency cleaning charging method, including electric discharge liquid prepares, and launches battery, gas purification, battery separation and elution, dry, fluid infusion.It is discharged into air after being handled for gas issuable in discharge process using device for absorbing tail gas and avoids atmosphere pollution；To the waste and old lithium ion battery after electric discharge using the dry method of elution so as to subsequent processing；Effective reflow treatment is carried out to the solution after elution simultaneously, improves the utilization rate of electric discharge mixed solution.The advantages of compared with other charging methods, the present invention has equipment simple, and discharging efficiency is high, does not generate secondary pollution, allows continuous production, is easy to industrial application.
Description
Technical field
It is remaining for waste and old lithium ion battery the present invention relates to the application discharged on a large scale waste and old lithium ion battery
The charging method for effective environmental protection that energy carries out belongs in field of environment protection convenient for the recovery processing such as subsequent Mechanical Crushing
Electron wastes processing, recycling field.
Background technique
Science and technology is constantly progressive and develops so that the figure of lithium ion battery is seen everywhere, small to mobile, computer, camera
Equal portable electronic devices, arrive greatly the energy storage fields such as new-energy automobile, military aerospace, lithium ion battery is answered as accumulation power supply
It is further extensive with space.Studies have shown that the cycle period of lithium ion is 500 times or so, and during repeated charge, lithium from
The electrode expansion of sub- battery easily blocks active material, causes to inactivate.The surge of lithium ion battery usage amount will also result in it, and it is huge
Big learies.However waste and old lithium ion battery is different from other electron wastes.Lithium ion battery after scrapping is still remaining
Variable amount of electricity, if directly carrying out the recovery processing of next step, such as Mechanical Crushing, remaining energy is under sharp impacts
Spark, which may be generated, and existed sets off an explosion, threatens the risks such as safety.
Currently at home and abroad there is no the cases that high-volume is recycled waste and old lithium ion battery, to waste and old lithium ion battery
A small amount of recovery processing during, it is most of to use NaCl solution charging methods.As Chinese invention patent " a kind of waste and old lithium from
Sub- battery-efficient crushes new process " (Wu Caibin etc., patent No. CN201010510406.6), propose it is a kind of for waste and old lithium from
Sub- battery Wet-type high-efficient crushes the process of new process, wherein the process of the remaining electricity of release is to use waste and old lithium ion battery to be processed
5%NaCl solution carries out impregnating 2h processing, makes remaining electric Spontaneous release by salt water immersion.The electric discharge system carries out NaCl solution
Series reaction occurs for electrolysis, and reaction equation is as follows:
2H2O+2Na→2NaOH+H2
H2O+Cl2→HCl+HClO
NaOH+HCl→NaCl+H2O
2Al+2NaOH+2H2O→2NaAlO2+3H2
NaAlO2+HCl+H2O→Al(OH)3+NaCl
Can be seen that NaCl electric discharge system by above-mentioned reaction equation will generate bulk gas, and discharge process also causes
The solution that discharges is in stronger alkalinity.Serious corrosion is caused to waste and old lithium ion battery, leaks electrolyte, a large amount of alkane can be generated
The organic gas such as hydrocarbon, alkene and dimethyl carbonate and flocculation sedimentation.This method is opening system, the meeting in industrial practice
The health of safety and operator to working environment causes grave danger.
Through retrieving, and Chinese invention patent " a kind of highly effective and safe charging method of waste and old lithium ion battery " (Song Jishun etc., specially
Benefit CN201510293356.3), provide a kind of electrochemical discharge method for being placed in mixed solution by waste and old lithium ion battery.
This mixed solution is NaSO4,K2SO4,NaNO3And KNO3Deng one or more kinds of saturated salt solution arbitrary proportions and Na2CO3,
K2CO3, the mixture of one or more of NaOH and KOH arbitrary proportion, modulation pH value to 10-12.The electric discharge of this method
Solution is in strong basicity, is easily corroded to the shell of lithium ion battery, the electrolyte of inside battery leaks, polluting property
The generation of organic gas can also jeopardize the health of staff in industrial practice.The discharge process is total simultaneously
Duration is 70h or so, and discharge process is very long, and discharging efficiency is very low, is unfavorable for industrial application.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides it is a kind of can batch processing waste and old lithium ion battery high-efficiency cleaning
Charging method, including electric discharge liquid are prepared, and battery, gas purification, battery separation and elution are launched, dry, fluid infusion and etc..For
Issuable gas is discharged into air after being handled using device for absorbing tail gas and avoids atmosphere pollution in discharge process；To electric discharge
Waste and old lithium ion battery afterwards is using the dry method of elution so as to subsequent processing；The solution after elution is effectively returned simultaneously
Stream process improves the utilization rate of electric discharge mixed solution.Compared with other charging methods, the present invention has equipment simple, electric discharge effect
The advantages of rate is high, does not generate secondary pollution, allows continuous production, is easy to industrial application.
Technical scheme is as follows:
Step 1: ferrous sulfate heptahydrate and manganese sulfate are mixed according to amount 2:1~5:1 of substance, it is configured to 1.0~
1.2mol/L FeSO4And MnSO4Mixed solution, wherein ferrous sulfate solution be 20 DEG C near saturated solution, by the mixing
Electric discharge solution, which stirs evenly, to be placed in tight discharge vessel, and solution bottom is equipped with the strainer that can be promoted, and there are certain spaces on upper layer.
Step 2: waste and old ion battery is put among the electric discharge solution in step 1, keep waste and old lithium ion battery complete
It is immersed in above-mentioned mixed liquor entirely.
Step 3: the negative pressure ventilation device connected above operation closed container opens the device while electric discharge starts,
The gas generated in discharge process is detached, and imports subsequent exhaust treatment system.
Step 4: by 14h, the voltage of lithium ion battery is down to 0.5V hereinafter, lithium-ion electric tank discharge is complete at this time, leads to
Filter screen separates waste and old lithium ion battery from electric discharge solution, and the battery after separation is then put into eluting column and is drenched
It washes.
Step 5: the battery after eluting in step 4 is dried, the battery after drying process can be entered
The recovery process such as next step Mechanical Crushing.
Further, to the mixed solution in step 1, after every a collection of waste and old lithium ion battery puts elution reflux, to guarantee
Its concentration, will carry out quantitative supplement to the mixed solution, and by ferrous sulfate heptahydrate and manganese sulfate according to amount 2:1~5 of substance:
1 ratio fills into the 1% of initial input.
The negative pressure ventilation device is located above tight discharge vessel, and is connected to tight discharge vessel, which takes out
The outlet of device of air is connected with exhaust treatment system.
Present invention solution compared with traditional NaCl discharges solution is in neutrality, and battery case is corrosion-free, and noxious gas emission is bright
Aobvious to reduce, tail gas collection system ensures discharge without secondary pollution.Discharging efficiency greatly improves compared with other discharge solution.
Detailed description of the invention
Fig. 1 is waste and old lithium ion battery clean and effective discharge processes flow diagram of the present invention；
Fig. 2 is that gas flow flow graph is generated in figure discharge process of the present invention；
Fig. 3 is the mass spectrogram that gas is generated in the discharge process that traditional NaCl discharges solution；
Fig. 4 is the mass spectrogram that the mixing electric discharge solution that the present invention uses generates gas；
Fig. 5 is that the certain proportion mixed solution of ferrous sulfate and manganese sulfate that the present invention uses puts waste and old lithium ion battery
The voltage change figure of electricity.
Specific embodiment
Below with reference to concrete operations example, the present invention will be described in detail.Following case study on implementation will be helpful to this field
Technical staff further understand the present invention, but in any form limitation the present invention.It should be pointed out that this field
For those of ordinary skill, under the premise of not departing from inventive concept, various modifications and improvements can be made.It is wanted based on right
It asks, the size of adjustment container in each step, the type of battery, the modification and improvement of the parameters such as quantity of battery belong to this hair
Bright protection scope.
Embodiment 1
Step 1: at normal temperature, weighing the ferrous sulfate heptahydrate of 2224g and manganese sulfate mixing (i.e. seven water of 604g respectively
Ferrous sulfate and manganese sulfate are matched according to the amount of substance to be dissolved in the water of 10L after 2:1), are configured to 0.8mol/L FeSO4With
0.4mol/L MnSO4Mixed solution, wherein ferrous sulfate solution be 20 DEG C near saturated solution, by the mixing discharge it is molten
Liquid, which stirs evenly, to be placed in tight discharge vessel, and there are certain spaces on upper layer.
Step 2: it is molten that the different waste and old ion battery of 200 remaining capacity differences, specifications is put into the electric discharge in step 1
Among liquid, be totally submerged waste and old lithium ion battery in above-mentioned mixed liquor, lithium ion battery can in the electric discharge solution into
The efficient electric discharge of row.
Step 3: the negative pressure ventilation device connected above operation closed container opens the device while electric discharge starts,
The gas generated in discharge process is detached, and imports subsequent exhaust treatment system, Fig. 3, figure are shown in the mass spectral analysis of gas
4。
Step 4: the voltage of all lithium ion batteries is down to 0.5V hereinafter, seeing Fig. 5 by 14h.At this time this batch of lithium from
Sub- battery discharges completely substantially, and battery can be separated to waste and old lithium ion battery by promoting strainer.To the electricity after separation
Pond is eluted, and is flowed back to the solution after elution.
Step 5: the battery after eluting in step 4 is dried, the battery after drying process can be entered
The recovery process such as next step Mechanical Crushing.
Step 6: to the mixed solution in step 1, after every a collection of waste and old lithium ion battery puts elution reflux, to guarantee
Its concentration, will carry out quantitative supplement to the mixed solution, and by ferrous sulfate heptahydrate and manganese sulfate according to the ratio of the amount 2:1 of substance
Example fills into the 1% of initial input.
Embodiment 2
Step 1: at normal temperature, weighing the ferrous sulfate heptahydrate of 2780g and manganese sulfate mixing (i.e. seven water of 302g respectively
Ferrous sulfate and manganese sulfate are matched according to the amount of substance to be dissolved in the water of 10L after 5:1), are configured to 1.0mol/L FeSO4With
0.2mol/L MnSO4Mixed solution, wherein ferrous sulfate solution be 20 DEG C near saturated solution, by the mixing discharge it is molten
Liquid, which stirs evenly, to be placed in tight discharge vessel, and there are certain spaces on upper layer.
Step 2: it is molten that the different waste and old ion battery of 200 remaining capacity differences, specifications is put into the electric discharge in step 1
Among liquid, be totally submerged waste and old lithium ion battery in above-mentioned mixed liquor, lithium ion battery can in the electric discharge solution into
The efficient electric discharge of row.
Step 3: the negative pressure ventilation device connected above operation closed container opens the device while electric discharge starts,
The gas generated in discharge process is detached, and imports subsequent exhaust treatment system, Fig. 3, figure are shown in the mass spectral analysis of gas
4。
Step 4: the voltage of all lithium ion batteries is down to 0.5V hereinafter, seeing Fig. 5 by 14h.At this time this batch of lithium from
Sub- battery discharges completely substantially, and battery can be separated to waste and old lithium ion battery by promoting strainer.To the electricity after separation
Pond is eluted, and is flowed back to the solution after elution.
Step 5: the battery after eluting in step 4 is dried, the battery after drying process can be entered
The recovery process such as next step Mechanical Crushing.
Step 6: to the mixed solution in step 1, after every a collection of waste and old lithium ion battery puts elution reflux, to guarantee
Its concentration, will carry out quantitative supplement to the mixed solution, and by ferrous sulfate heptahydrate and manganese sulfate according to the ratio of the amount 5:1 of substance
Example fills into the 1% of initial input.
Claims (3)
1. a kind of cleaner discharge method of batch pretreatment waste and old lithium ion battery, which is characterized in that mixed with the electric discharge of preparation
Electric discharge of the liquid to waste and old lithium ion battery efficient stable handles the gas generated in discharge process using device for absorbing tail gas
After be discharged into air and avoid atmosphere pollution；To the waste and old lithium ion battery after electric discharge using the dry method of elution so as to subsequent
Processing；Effective reflow treatment is carried out to the solution after elution simultaneously, improves the utilization rate of electric discharge mixed liquor, the specific steps are as follows:
Step 1: ferrous sulfate heptahydrate and manganese sulfate are mixed according to amount 2:1~5:1 of substance, it is configured to 1.0~
1.2mol/L FeSO4And MnSO4Electric discharge mixed liquor, which is stirred evenly and is placed in tight discharge vessel；
Step 2: the waste and old lithium ion battery of batch is put into the electric discharge mixed liquor of step 1, and waste and old lithium ion battery is complete
It is immersed in the electric discharge mixed liquor entirely；
Step 3: opening negative pressure ventilation device, the gas generated in discharge process is detached, and import vent gas treatment system
System；
Step 4: waste and old lithium ion battery electric discharge completely after, by strainer by waste and old lithium ion battery from electric discharge mixed liquor in
It separates, the waste and old lithium ion battery after separation is then put into eluting column and is eluted；
Step 5: the waste and old lithium ion battery after eluting in step 4 is dried, it is broken subsequently into conventional mechanical
It is recycled process.
2. the cleaner discharge method of batch pretreatment waste and old lithium ion battery according to claim 1, which is characterized in that leaching
The outlet for washing tower is connected with tight discharge vessel, so that solution after elution is carried out reflow treatment, that is, is back to tight discharge vessel；?
After every a batch waste and old lithium ion battery elution reflux, quantitative supplement is carried out to electric discharge mixed liquor, by ferrous sulfate heptahydrate and sulfuric acid
Manganese fills into the 1% of initial input according to the ratio of amount 2:1~5:1 of substance.
3. the cleaner discharge method of batch pretreatment waste and old lithium ion battery according to claim 1, which is characterized in that institute
The negative pressure ventilation device stated is located above tight discharge vessel, and is connected to tight discharge vessel, which goes out
Mouth is connected with exhaust treatment system.
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| CN107706476A (en) * | 2017-07-10 | 2018-02-16 | 长沙佳纳锂业科技有限公司 | A kind of solvent sorting preprocess method of waste and old lithium ion battery |
| CN108879010A (en) * | 2018-06-27 | 2018-11-23 | 深圳市恒创睿能环保科技有限公司 | A kind of technique of discarded soft-package battery electric discharge and component dissociation |
| CN109133117A (en) * | 2018-08-17 | 2019-01-04 | 湖南金凯循环科技有限公司 | A method of battery-level lithium carbonate is prepared by waste metal lithium battery |
| CN111525208B (en) * | 2020-04-28 | 2022-05-27 | 蜂巢能源科技有限公司 | Discharge solution for treating a lithium ion battery, discharge device and use, method for discharging a lithium ion battery |
| CN111900503A (en) * | 2020-08-04 | 2020-11-06 | 威立雅新能源科技(江门)有限公司 | Mixed solution for discharging lithium ion battery and discharging method thereof |
| SE2051553A1 (en) * | 2020-12-23 | 2022-06-24 | Northvolt Ab | Solution discharge of cells and modules for battery recycling |
| CN114050339B (en) * | 2021-10-11 | 2022-12-27 | 生态环境部南京环境科学研究所 | Dry recovery device for waste power lithium battery |
| CN114006068B (en) * | 2021-10-11 | 2022-12-27 | 生态环境部南京环境科学研究所 | Pretreatment method for resource recovery of waste power lithium battery |
| CN114583303B (en) * | 2022-01-12 | 2024-04-19 | 顺尔茨环保(北京)有限公司 | Crushing method and system for waste lithium ion batteries |
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