CN108011146A - Waste lithium cell renewable resources recovery method - Google Patents
Waste lithium cell renewable resources recovery method Download PDFInfo
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- CN108011146A CN108011146A CN201711146734.0A CN201711146734A CN108011146A CN 108011146 A CN108011146 A CN 108011146A CN 201711146734 A CN201711146734 A CN 201711146734A CN 108011146 A CN108011146 A CN 108011146A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Mechanical Engineering (AREA)
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Secondary Cells (AREA)
Abstract
The invention belongs to battery recycling field, specifically discloses a kind of high and environmentally protective waste lithium cell renewable resources recovery method of resource recovery.The waste lithium cell renewable resources recovery method, including lithium battery pretreatment step, broken and drying steps, battery chip separation step and isolate processing step.By carrying out that electrolyte is recovered by filtration to the lithium battery after break process, and the exhaust to drying equipment carries out condensation and collects electrolyte, improves the rate of recovery of electrolyte, reduces the treating capacity of sewage and exhaust gas；Meanwhile it is beneficial to be sufficiently separated away the electrolyte on battery fragment by drying equipment drying；And stirring and screening process are passed sequentially through to dried battery fragment, beneficial to resources such as the battery pole piece collectors and valuable and scarcity metals being separately recovered in lithium battery, and the rate of recovery is higher, less pollution caused by whole removal process.
Description
Technical field
The invention belongs to battery recycling field, and in particular to a kind of waste lithium cell renewable resources recovery method.
Background technology
With the development of science and technology, electronic product has penetrated into the every nook and cranny of people's life.Due to lithium ion battery with
Ickel-cadmium cell, Ni-H cell are compared, high, memoryless with small, light weight, operating voltage height, volume and specific energy
Effect, the advantages that self discharge is small, operating temperature range is wide, long lifespan, have dominated small-sized portable electronic product market, example
Such as：Applied to portable phone, video camera, portable notebook etc..As society continues to develop, weather, the energy and environment are asked
The appearance of topic, lithium ion battery are also widely used to electric automobile field.
2010, the yield of China's lithium ion battery was about 26.87 hundred million；2013, China's lithium ion battery yield reached
To 47.68 hundred million；2016, China's lithium battery yield reached 78.42 hundred million.China's lithium battery production, which disappears, is presented becoming for rapid growth
Gesture, it is contemplated that following lithium ion battery yield can continue quick increase with the development of electric automobile, and lithium ion battery uses the longevity
Life generally 3~5 years, thus possessed in market it is a large amount of scrap lithium battery in the case of, future have more waste and old lithiums from
Sub- battery occurs.
The LiPF contained in lithium ion battery6、LiBF4、LiClO4It is right Deng organic solvents such as electrolyte and EC, EMC, DMC
Environment and human body have larger harm, are set to hazardous waste by country.On the other hand, since anode material for lithium-ion batteries was mostly
Cross metal oxide, such as LiFePO4、LiCoO2, Li [NixCo1-2xMnx] O2Deng wherein containing valuable and scarcity metals such as
Cobalt, nickel, lithium etc.；Also electrodes of lithium-ion batteries collector such as copper, aluminum foil material resource etc..Therefore, to waste and old lithium ion battery
Carry out harmless treatment and to metal therein carry out recycling recycling it is significant.
With the fast development of lithium ion battery technology, the yield and learies of lithium ion battery all present quick increased
Trend, studies the patent of waste and old lithium ion battery renewable resources and reports for work also more, mainly there is hydrometallurgic recovery and Dry recovery.Than
Patent application such as Application No. 201610314509.2 discloses a kind of waste lithium cell full constituent feed separation collection device
And method, it mainly uses the simple dry method means such as Mechanical Crushing, vacuum separation, shaking-sieving, proportion separation, air-flow separation,
Realize that electrode material in waste lithium cell, collector metal, plastic diaphragms, battery case separate and collect；Its electrolyte uses
The method of vacuum recycling, organic efficiency is low, and equipment investment is big.And for example the patent of application number 201010262198.2 discloses one kind
From the method for waste lithium cell recycling valuable metal, using by the waste lithium cell mechanical crushing after electric discharge, 350 DEG C -400 of high temperature
DEG C calcining, obtain the material containing cobalt, copper and aluminium, then carry out wet-treating；Its advantage is that processing early period is simple, after shortcoming is sintering
Exhaust-gas treatment is difficult, of high cost.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of resource recovery, high and environmentally protective waste lithium cell is again
Resource recycle method.
The technical solution adopted by the present invention to solve the technical problems is：Waste lithium cell renewable resources recovery method, bag
Include lithium battery pretreatment step, broken and drying steps, battery chip separation step and isolate processing step；
Lithium battery pretreatment step：Lithium battery is put into more than when electric discharge 2 is small in pond of discharging, the lithium battery after electric discharge is through water
It is filtered dry after washing and completes pretreatment；
Broken and drying steps：Break process is carried out to the lithium battery after being filtered dry using crushing plant, is then obtained by filtration
Battery fragment and electrolyte；Battery fragment is sent into drying 10~50 minutes in drying equipment, the exhaust of drying equipment is condensed
After collect electrolyte；
Battery chip separation step：Dried battery fragment is stirred, makes cobalt acid lithium and carbon dust from electrode
Depart from paper tinsel；Screening process is carried out to the battery fragment after stirring, isolates cobalt acid lithium and toner mixture；
Isolate processing step：Oversize is obtained into metallic monolith thing, plastics block, metal foil and membrane through selection by winnowing
Paper, cobalt acid lithium and toner mixture carry out refining Call Provision, lithium and nickel after sintering.
It is further that in lithium battery pretreatment step, the aqueous sodium chloride that concentration is 5%~20% is contained in pond of discharging
Liquid is as conduction liquid.
It is further that in broken and drying steps, for blade crusher, the drying of use is set the crushing plant used
Standby be the tunnel type drying oven with delivery tray, control the drying temperature of tunnel type drying oven 90 in drying process~
200℃；In tunnel type drying oven, drying temperature gradually increases along the direction of transfer of delivery tray.
It is further in battery chip separation step, to be stirred using mixing drum, sieved using vibrating screen
Point.
It is further that in battery chip separation step, dedusting is exhausted to mixing drum and vibrating screen respectively.
It is further in broken and drying steps, crushing plant and drying equipment is in outer casing device, and makes outer
Negative pressure state is in closure assembly.
It is further that inert gas is passed through in outer casing device.
It is further that the inert gas is nitrogen.
The beneficial effects of the invention are as follows：By carrying out that electrolyte is recovered by filtration to the lithium battery after break process, and to dry
The exhaust of dry equipment carries out condensation and collects electrolyte, improves the rate of recovery of electrolyte, reduces the treating capacity of sewage and exhaust gas；
Meanwhile it is beneficial to be sufficiently separated away the electrolyte on battery fragment by drying equipment drying；It is and broken to dried battery
Piece passes sequentially through stirring and screening process, beneficial to the battery pole piece collector and valuable and scarcity metals being separately recovered in lithium battery
Etc. resource, and the rate of recovery is higher, less pollution caused by whole removal process.
Brief description of the drawings
Fig. 1 is the process flow chart of the method for the present invention；
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.
With reference to shown in Fig. 1, waste lithium cell renewable resources recovery method, including it is lithium battery pretreatment step, broken and dry
Dry step, battery chip separation step and isolate processing step；
Lithium battery pretreatment step：Lithium battery is put into more than when electric discharge 2 is small in pond of discharging, the lithium battery after electric discharge is through water
It is filtered dry after washing and completes pretreatment；In this step, the conduction liquid for making lithium battery discharge is loaded with electric discharge pond；Conduction liquid can
Think it is a variety of, be preferably concentration be 5%~20% sodium-chloride water solution；Electric discharge is put into after generally waste and old lithium battery is framed up
Chi Zhong；
Broken and drying steps：Break process is carried out to the lithium battery after being filtered dry using crushing plant, is then obtained by filtration
Battery fragment and electrolyte；Battery fragment is sent into drying 10~50 minutes in drying equipment, the exhaust of drying equipment is condensed
After collect electrolyte, remaining tail gas outer row after processing after condensation；In this step, the crushing plant of use is usually blade
Formula crusher, the drying equipment of use is usually the tunnel type drying oven with delivery tray, does tunnel type in drying process
The drying temperature of dry stove is controlled at 90~200 DEG C；Purpose to the drying of battery fragment by heating primarily to make to be attached to
Electrolyte and water evaporation on battery fragment remove；In order to improve security, in tunnel type drying oven, drying temperature is along biography
The direction of transfer of pallet is sent gradually to increase；In this way, under the transmission effect of delivery tray, the electrolyte on battery fragment can basis
Volatilization point volatilizees successively from low to high, can avoid the relatively low electrolyte heated combustion of burning point；
Battery chip separation step：Dried battery fragment is stirred, makes cobalt acid lithium and carbon dust from electrode
Depart from paper tinsel；Screening process is carried out to the battery fragment after stirring, isolates cobalt acid lithium and toner mixture；In this step,
Generally use mixing drum is stirred, and generally use vibrating screen is sieved；In order to reduce pollution, it usually needs respectively to stirring
Mix roller and dedusting is exhausted in vibrating screen；
Isolate processing step：Oversize is obtained into metallic monolith thing, plastics block, metal foil and membrane through selection by winnowing
Paper, cobalt acid lithium and toner mixture carry out refining Call Provision, lithium and nickel after sintering.
As a preferred embodiment of the present invention, in broken and drying steps, it is in crushing plant and drying equipment
In outer casing device, and make to be in negative pressure state in outer casing device.Exhaust and solvent condensation recycling are typically arranged with outer casing device
Device.Inert gas can be passed through in outer casing device as needed, is burnt to avoid the heated electrolyte of volatilization；Inert gas is excellent
Elect nitrogen as.
The method of the present invention is adapted to scale quickly to handle waste lithium cell, high to waste lithium cell renewable resources degree, keeps away
The problem of sewage disposal is exempted from, exhaust-gas treatment amount is small.
Claims (8)
1. waste lithium cell renewable resources recovery method, it is characterised in that including lithium battery pretreatment step, broken and drying step
Suddenly, battery chip separation step and isolate processing step；
Lithium battery pretreatment step：Lithium battery is put into more than when electric discharge 2 is small in pond of discharging, the lithium battery after electric discharge is after washing
It is filtered dry and completes pretreatment；
Broken and drying steps：Break process is carried out to the lithium battery after being filtered dry using crushing plant, battery is then obtained by filtration
Fragment and electrolyte；Battery fragment is sent into 10~50 minutes dry in drying equipment, the condensed rear receipts of exhaust of drying equipment
Collect electrolyte；
Battery chip separation step：Dried battery fragment is stirred, makes cobalt acid lithium and carbon dust from electrode foil
Depart from；Screening process is carried out to the battery fragment after stirring, isolates cobalt acid lithium and toner mixture；
Isolate processing step：Oversize is obtained into metallic monolith thing, plastics block, metal foil and diaphragm paper through selection by winnowing,
Cobalt acid lithium and toner mixture carry out refining Call Provision, lithium and nickel after sintering.
2. waste lithium cell renewable resources recovery method as claimed in claim 1, it is characterised in that：Lithium battery pretreatment step
In, the sodium-chloride water solution that splendid attire concentration is 5%~20% in pond of discharging is as conduction liquid.
3. waste lithium cell renewable resources recovery method as claimed in claim 2, it is characterised in that：Broken and drying steps
In, the crushing plant used for blade crusher, for the tunnel type drying oven with delivery tray do by the drying equipment used
The drying temperature of tunnel type drying oven is controlled at 90~200 DEG C during dry；In tunnel type drying oven, drying temperature along
The direction of transfer of delivery tray gradually increases.
4. waste lithium cell renewable resources recovery method as claimed in claim 3, it is characterised in that：Battery chip separation step
In, it is stirred using mixing drum, is sieved using vibrating screen.
5. waste lithium cell renewable resources recovery method as claimed in claim 4, it is characterised in that：Battery chip separation step
In, dedusting is exhausted to mixing drum and vibrating screen respectively.
6. the waste lithium cell renewable resources recovery method as described in claim 1,2,3,4 or 5, it is characterised in that：It is broken and
In drying steps, crushing plant and drying equipment is in outer casing device, and make to be in negative pressure state in outer casing device.
7. waste lithium cell renewable resources recovery method as claimed in claim 6, it is characterised in that：It is passed through in outer casing device
Inert gas.
8. waste lithium cell renewable resources recovery method as claimed in claim 7, it is characterised in that：The inert gas is nitrogen
Gas.
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| CN201711146734.0A CN108011146B (en) | 2017-11-17 | 2017-11-17 | Recycling method of waste lithium battery |
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| CN201711146734.0A CN108011146B (en) | 2017-11-17 | 2017-11-17 | Recycling method of waste lithium battery |
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| CN108011146B CN108011146B (en) | 2021-04-23 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108550947A (en) * | 2018-06-30 | 2018-09-18 | 贵州中伟资源循环产业发展有限公司 | Waste lithium cell electrolyte lithium hexafluoro phosphate recycle device and application method |
| CN108808156A (en) * | 2018-08-24 | 2018-11-13 | 广西师范大学 | The recovery method of electrolyte in a kind 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 |
| CN109244578A (en) * | 2018-09-10 | 2019-01-18 | 李的根 | A kind of recovery method of waste lithium cell valuable metal |
| CN109360996A (en) * | 2018-11-07 | 2019-02-19 | 合肥国轩高科动力能源有限公司 | A kind of method of waste and old lithium ionic cell electrolyte resource utilization |
| CN109772557A (en) * | 2019-02-02 | 2019-05-21 | 贵州中伟资源循环产业发展有限公司 | A kind of lithium battery recycling complete set of equipments |
| CN109786882A (en) * | 2019-02-25 | 2019-05-21 | 上海毅信环保科技有限公司 | A kind of dry-type pulverizing recovery method of waste and old lithium ion battery |
| CN109852819A (en) * | 2019-02-25 | 2019-06-07 | 上海毅信环保科技有限公司 | A kind of broken recovery method of the wet type of waste and old lithium ion battery |
| CN110336090A (en) * | 2019-05-20 | 2019-10-15 | 昌鑫生态科技(陕西)有限公司 | Old and useless battery environmental protection is recycled technology |
| CN111430832A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Full resource recovery method for waste ternary lithium ion battery without discharge pretreatment |
| CN114050339A (en) * | 2021-10-11 | 2022-02-15 | 生态环境部南京环境科学研究所 | Dry recovery device for waste power lithium battery |
| CN114583303A (en) * | 2022-01-12 | 2022-06-03 | 顺尔茨环保(北京)有限公司 | Crushing method and system for waste lithium ion batteries |
| WO2023223144A1 (en) * | 2022-05-19 | 2023-11-23 | Altero S.A.S. | Dry process for recycling lithium-ion rechargeable batteries, lithium-polymer rechargeable batteries and nickel-metal hydride rechargeable batteries and directly recovering cobalt, nickel, lithium, manganese, base metals and electrolyte |
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