CN106654433A - Method for recovering lithium by adopting waste lithium iron phosphate batteries - Google Patents

Method for recovering lithium by adopting waste lithium iron phosphate batteries Download PDF

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Publication number
CN106654433A
CN106654433A CN201611018662.7A CN201611018662A CN106654433A CN 106654433 A CN106654433 A CN 106654433A CN 201611018662 A CN201611018662 A CN 201611018662A CN 106654433 A CN106654433 A CN 106654433A
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CN
China
Prior art keywords
lithium
iron phosphate
lithium iron
waste lithium
positive
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611018662.7A
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Chinese (zh)
Inventor
杨毅红
何怀文
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University of Electronic Science and Technology of China Zhongshan Institute
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University of Electronic Science and Technology of China Zhongshan Institute
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Priority to CN201611018662.7A priority Critical patent/CN106654433A/en
Publication of CN106654433A publication Critical patent/CN106654433A/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

The invention discloses a method for recovering lithium by using waste lithium iron phosphate batteries, which comprises the steps of firstly, carrying out safe discharge treatment on the waste lithium iron phosphate batteries, cutting the batteries along the top by using a cold cutting method, disassembling and removing shells to obtain battery roll cores, calcining the battery roll cores at 600-900 ℃ in the atmosphere of protective gas, crushing and sieving to obtain mixed materials of positive and negative electrodes; adding sodium hydroxide solution into the mixed material of the positive electrode and the negative electrode, alternately carrying out ultrasonic stirring and mechanical stirring for 4-8 minutes, and filtering to obtain filter mud; adding chloric acid into the filter mud, wherein the reaction temperature is 70-85 ℃, and the solid-liquid ratio is 1/4-1/8; leaching lithium solution, filtering to obtain leachate, adjusting the pH value of the leachate by adopting potassium hydroxide, filtering, and adding sodium carbonate into the filtrate to obtain lithium carbonate precipitate. The method has the advantages of simple process, high recovery efficiency and high recovery purity, can quickly and efficiently recover lithium in the waste lithium iron phosphate batteries, and is suitable for large-scale industrial production.

Description

A kind of method that employing waste lithium iron phosphate battery reclaims lithium
Technical field
The invention belongs to battery recycling technical field, and in particular to a kind of employing waste lithium iron phosphate battery reclaims the side of lithium Method.
Background technology
As over the years necessarily becoming for replacement orthodox car is gradually paid attention to, promoted and become to new-energy automobile Gesture, also has been enter into increasing the phase rapidly as the yield of the dynamic lithium battery of new-energy automobile " heart ".Expect 2012, newly The annual production of energy automobile is up to 1,000,000, will drive the demand of 5.2 ten thousand tons of anode material of lithium battery.In view of lithium electricity The restricted lifetime in pond, these new-energy automobile lithium batteries will progress into the superseded date of retirement after several years, the lithium in its positive electrode If the great wasting of resources will be caused by arbitrarily discarding.
LiFePO4 (the LiFePO of olivine shape structure4) battery because with good heat endurance and cycle performance into For the main force of dynamic lithium battery.Lithium iron phosphate positive material composition is complicated, containing substantial amounts of copper and aluminium simple substance and a small amount of iron The impurity such as simple substance.The presence of impurity iron, copper and aluminium gives back to receipts lithium and brings difficulty.In traditional direct alkaline leaching, impurity iron, copper Leached jointly in a large number with the leaching that aluminium is usually associated with lithium, therefore remain a need for being separated these impurity with lithium.And use The method high cost of extract and separate these impurity, and environmental pollution is big, is unfavorable for industrial operation.
The content of the invention
It is an object of the invention to provide a kind of method that employing waste lithium iron phosphate battery reclaims lithium, process is simple, reclaim Efficiency high, reclaims the lithium that purity is high, in recovery waste lithium iron phosphate battery that can be rapidly and efficiently, it is adaptable to which large-scale industry is given birth to Produce.
The invention discloses a kind of method that employing waste lithium iron phosphate battery reclaims lithium, first by waste lithium iron phosphate electricity Pond is carried out after safe-discharge process, along top open is cut battery using cold cut segmentation method, is disassembled to shell and is obtained battery roll core, will Battery roll core 600-900 DEG C of calcining in a nitrogen atmosphere, grinding and sieving obtains both positive and negative polarity batch mixing;Add in both positive and negative polarity batch mixing Enter for sodium hydroxide solution, after ultrasound and mechanical agitation alternately 4-8 minutes, filter to obtain filter mud;Chloric acid will be added in filter mud, Reaction temperature is 70-85 DEG C, and solid-to-liquid ratio is 1/4-1/8;Lithium solution is leached, is filtered, obtain leachate, adjusted using potassium hydroxide Leachate pH, filters, and to filtrate sodium carbonate is added, and obtains lithium carbonate precipitation.
Preferably, under nitrogen atmosphere calcination time is 3-5h.
Any of the above-described scheme is preferably, and the battery roll core crosses 80-120 mesh sieves after crushing, and obtains both positive and negative polarity batch mixing.
Any of the above-described scheme is preferably, and the concentration of the chloric acid is 3-5mol/L.
Any of the above-described scheme is preferably, and leachate is adjusted to pH 6.5-7.5 using potassium hydroxide, precipitates a small amount of iron, mistake Filter to obtain filtrate.
Beneficial effects of the present invention are as follows:
Present invention process is simple, and organic efficiency is high, purity height is reclaimed, in recovery waste lithium iron phosphate battery that can be rapidly and efficiently Lithium, it is adaptable to large-scale industrial production.
Specific embodiment
Following embodiments are further illustrating using as the explaination to the technology of the present invention content for present invention, but The present invention flesh and blood be not limited in described in following embodiments, one of ordinary skill in the art can with and should know appoint What simple change or replacement based on true spirit all should belong to protection domain of the presently claimed invention.
Embodiment 1:
The present invention provides a kind of method that employing waste lithium iron phosphate battery reclaims lithium, first carries out waste lithium iron phosphate battery After safe-discharge process, battery is cut open along top using cold cut segmentation method, disassemble to shell and obtain battery roll core, by battery winding Core 600 DEG C of calcinings under the atmosphere of protective gas nitrogen, the mesh sieve of grinding and sieving 80 obtains both positive and negative polarity batch mixing;To both positive and negative polarity Sodium hydroxide solution is incorporated as in batch mixing, ultrasound and mechanical agitation filter to obtain filter mud after alternately 5 minutes;To add in filter mud Enter chloric acid, reaction temperature is 70 DEG C, and solid-to-liquid ratio is 1/4;Lithium solution is leached, is filtered, obtain leachate, adjusted using potassium hydroxide and soaked Go out liquid to pH 6.5, precipitate a small amount of iron, filter to get filtrate.
Embodiment 2:
The present invention provides a kind of method that employing waste lithium iron phosphate battery reclaims lithium, first carries out waste lithium iron phosphate battery After safe-discharge process, battery is cut open along top using cold cut segmentation method, disassemble to shell and obtain battery roll core, by battery winding Core 700 DEG C of calcinings under the atmosphere of protective gas nitrogen, the mesh sieve of grinding and sieving 90 obtains both positive and negative polarity batch mixing;To both positive and negative polarity Sodium hydroxide solution is incorporated as in batch mixing, ultrasound and mechanical agitation filter to obtain filter mud after alternately 5 minutes;To add in filter mud Enter chloric acid, reaction temperature is 75 DEG C, and solid-to-liquid ratio is 1/5;Lithium solution is leached, is filtered, obtain leachate, adjusted using potassium hydroxide and soaked Go out liquid to pH 7, precipitate a small amount of iron, filter to get filtrate.
Embodiment 3:
The present invention provides a kind of method that employing waste lithium iron phosphate battery reclaims lithium, first carries out waste lithium iron phosphate battery After safe-discharge process, battery is cut open along top using cold cut segmentation method, disassemble to shell and obtain battery roll core, by battery winding Core is calcined 2 hours for 700 DEG C under the atmosphere of protective gas nitrogen, and the mesh sieve of grinding and sieving 100 obtains both positive and negative polarity batch mixing;To Sodium hydroxide solution is incorporated as in both positive and negative polarity batch mixing, the mass fraction of NaOH is 25-35%, ultrasound replaces with mechanical agitation After carrying out 5 minutes, filter mud is filtered to obtain;Chloric acid will be added in filter mud, reaction temperature is 80 DEG C, and solid-to-liquid ratio is 1/8;Leach lithium molten Liquid, filters, and obtains leachate, and leachate is adjusted to pH 7.5 using potassium hydroxide, precipitates a small amount of iron, filters to get filtrate.
The preferred embodiment of the present invention described in detail above.It should be appreciated that one of ordinary skill in the art without Need creative work just can make many modifications and variations with design of the invention.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical scheme, all should be in the protection domain being defined in the patent claims.

Claims (5)

1. a kind of method that employing waste lithium iron phosphate battery reclaims lithium, it is characterised in that first by waste lithium iron phosphate battery After carrying out safe-discharge process, battery is cut open along top using cold cut segmentation method, disassemble to shell and obtain battery roll core, by electricity Pond core 600-900 DEG C of calcining in a nitrogen atmosphere, grinding and sieving obtains both positive and negative polarity batch mixing;Add in both positive and negative polarity batch mixing For sodium hydroxide solution, after ultrasound and mechanical agitation alternately 4-8 minutes, filter mud is filtered to obtain;Chloric acid will be added in filter mud, instead Temperature is answered for 70-85 DEG C, solid-to-liquid ratio is 1/4-1/8;Lithium solution is leached, is filtered, obtain leachate, adjusted using potassium hydroxide and soaked Go out liquid pH, filter, to filtrate sodium carbonate is added, obtain lithium carbonate precipitation.
2. the method that a kind of employing waste lithium iron phosphate battery according to claim 1 reclaims lithium, it is characterised in that in nitrogen Atmosphere encloses lower calcination time for 3-5h.
3. the method that a kind of employing waste lithium iron phosphate battery according to claim 1 reclaims lithium, it is characterised in that described Battery roll core crosses 80-120 mesh sieves after crushing, and obtains both positive and negative polarity batch mixing.
4. the method that a kind of employing waste lithium iron phosphate battery according to claim 1 reclaims lithium, it is characterised in that described The concentration of chloric acid is 3-5mol/L.
5. the method that a kind of employing waste lithium iron phosphate battery according to claim 1 reclaims lithium, it is characterised in that adopt Potassium hydroxide adjusts leachate to pH 6.5-7.5, precipitates a small amount of iron, filters to get filtrate.
CN201611018662.7A 2016-11-21 2016-11-21 Method for recovering lithium by adopting waste lithium iron phosphate batteries Pending CN106654433A (en)

Priority Applications (1)

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CN201611018662.7A CN106654433A (en) 2016-11-21 2016-11-21 Method for recovering lithium by adopting waste lithium iron phosphate batteries

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Application Number Priority Date Filing Date Title
CN201611018662.7A CN106654433A (en) 2016-11-21 2016-11-21 Method for recovering lithium by adopting waste lithium iron phosphate batteries

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981699A (en) * 2017-05-13 2017-07-25 合肥国轩高科动力能源有限公司 A kind of method that lithium is reclaimed from waste lithium iron phosphate battery
CN109244586A (en) * 2018-10-24 2019-01-18 北京工业大学 A kind of waste and old power battery environmental protection recycling and reusing method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103280610A (en) * 2013-03-29 2013-09-04 江西省电力科学研究院 Method for recovering waste lithium iron phosphate battery positive pieces
CN105024106A (en) * 2015-07-31 2015-11-04 合肥国轩高科动力能源股份公司 Method for recovering ferric phosphate from waste lithium ion battery and scrapped anode piece
CN105186058A (en) * 2014-06-16 2015-12-23 上海奇谋能源技术开发有限公司 Method for environmentally-friendly resource recycling of lithium ion battery electrodes
WO2015192743A1 (en) * 2014-06-16 2015-12-23 王武生 Resource reclamation and environmental protection method for recycling lithium ion battery wastes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103280610A (en) * 2013-03-29 2013-09-04 江西省电力科学研究院 Method for recovering waste lithium iron phosphate battery positive pieces
CN105186058A (en) * 2014-06-16 2015-12-23 上海奇谋能源技术开发有限公司 Method for environmentally-friendly resource recycling of lithium ion battery electrodes
WO2015192743A1 (en) * 2014-06-16 2015-12-23 王武生 Resource reclamation and environmental protection method for recycling lithium ion battery wastes
CN105024106A (en) * 2015-07-31 2015-11-04 合肥国轩高科动力能源股份公司 Method for recovering ferric phosphate from waste lithium ion battery and scrapped anode piece

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981699A (en) * 2017-05-13 2017-07-25 合肥国轩高科动力能源有限公司 A kind of method that lithium is reclaimed from waste lithium iron phosphate battery
CN109244586A (en) * 2018-10-24 2019-01-18 北京工业大学 A kind of waste and old power battery environmental protection recycling and reusing method
CN109244586B (en) * 2018-10-24 2021-03-30 北京工业大学 Environment-friendly recycling method for waste power batteries

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