CN103757418A - Leaching method of lithium iron phosphate waste battery positive electrode material - Google Patents

Leaching method of lithium iron phosphate waste battery positive electrode material Download PDF

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Publication number
CN103757418A
CN103757418A CN201310736638.7A CN201310736638A CN103757418A CN 103757418 A CN103757418 A CN 103757418A CN 201310736638 A CN201310736638 A CN 201310736638A CN 103757418 A CN103757418 A CN 103757418A
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China
Prior art keywords
leaching
positive electrode
pyrolusite
sulfuric acid
acid
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CN201310736638.7A
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Chinese (zh)
Inventor
龙炳清
曹攀
秦丹
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四川师范大学
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Priority to CN201310736638.7A priority Critical patent/CN103757418A/en
Publication of CN103757418A publication Critical patent/CN103757418A/en

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    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention provides a leaching method of a lithium iron phosphate waste battery positive electrode material, which comprises the following steps: putting a positive electrode material separated from lithium iron phosphate waste batteries and ground pyrolusite into a pressure-resistant sulfuric-acid/nitric-acid-corrosion-resistant container, pumping sulfuric acid and nitric acid into the container, sealing the container, and leaching the lithium iron phosphate waste battery positive electrode material.

Description

The leaching method of iron lithium phosphate refuse battery positive electrode material

Technical field

The present invention relates to a kind of leaching method of iron lithium phosphate refuse battery positive electrode material.

Background technology

Ferric phosphate lithium cell (the major metal element that positive electrode material contains is the battery of lithium, aluminium and iron) is a class novel battery, and this battery will produce a large amount of refuse batteries after using and scrapping.If this class battery is abandoned into environment, will environment be produced to very large direct and potential hazard.Lithium iron phosphate battery positive material is mainly containing lithium, aluminium and iron, and wherein the total content of lithium is up to more than 4%, has very much a recovery value.The technique that reclaims at present lithium from iron lithium phosphate refuse battery positive electrode material is mainly wet processing.Leaching is a requisite process in wet processing.The leaching method of iron lithium phosphate refuse battery positive electrode material mainly contains hydrochloric acid leaching process, sulfuric acid leaching, nitric acid lixiviation process and nitration mixture (sulfuric acid adds nitric acid) lixiviation process at present.Hydrochloric acid leaching process, equipment corrosion is large, the large and contaminate environment of acid mist generation.The reductive agent (as hydrogen peroxide etc.) that sulfuric acid leaching consumption is more expensive.The nitric acid consumption of nitric acid lixiviation process is large, and can produce a large amount of oxynitride, contaminate environment.All there is the problem that improves how economically leaching velocity, raising metal leaching rate, reduces acid consumption and other supplementary product onsumption in all wet processings.Although nitric acid processing industry pure oxygen lixiviation process and nitration mixture processing industry pure oxygen lixiviation process have solved the problems referred to above preferably, but leaching plant is more complicated, and the required industrial pure oxygen amount of refuse battery leaching is little, refuse battery is processed enterprise, and manufacture pure oxygen is personal uneconomical on the spot, and the storage of industrial pure oxygen, transportation and use are cumbersome.Development equipment corrosion is little, leaching velocity is fast, leaching yield is high, acid consumes and other supplementary product onsumption is low, easy to use, the leaching method of the iron lithium phosphate refuse battery positive electrode material of basic non-environmental-pollution has larger practical value.

Summary of the invention

The problem leaching for current iron lithium phosphate refuse battery positive electrode material, the object of the invention is to find a kind of metal leaching rate high, leaching velocity is fast, acid consumption and other supplementary product onsumption are low, easy to use, need not expensive reductive agent, the leaching method of the iron lithium phosphate refuse battery positive electrode material of basic non-environmental-pollution, it is characterized in that from iron lithium phosphate refuse battery, (comprising by elementary positive electrode material artificial or that mechanical separation goes out by isolated positive electrode material, the positive pole powder material that elementary positive electrode material obtains through broken and ball milling or rod milling, the purer positive electrode material that elementary positive electrode material or positive pole powder material obtain through pre-treatment such as alkali cleanings) and levigate pyrolusite put into the container of withstand voltage and resistance to sulfuric acid and nitric acid corrosion, and sulfuric acid and nitric acid are pumped into this container, then sealed vessel, carry out the leaching of iron lithium phosphate refuse battery positive electrode material, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution.Extraction temperature is 40 ℃~80 ℃, and the sulfuric acid starting point concentration of leaching is 1 mol/L~5 mol/L, and nitric acid starting point concentration is 5 g/L~20g/L, and extraction time is 1h~3h, and leaching process stirs, stirring velocity 30 r/min~120r/min.Sulphuric acid is to add 101%~200% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel and pyrolusite, all metals leach.The MnO of pyrolusite used 2content>=40%, particle diameter≤180 order.The add-on of pyrolusite is with MnO 2count in oxidation positive electrode material all 100%~110% of the required theoretical amount of metallic aluminum.

The object of the present invention is achieved like this: under the condition existing at airtight, pyrolusite and nitric acid, sulfuric acid leaching iron lithium phosphate refuse battery positive electrode material is when (aluminium in material is metal form, other metallic element is oxide form), and in leaching process, following main chemical reactions occurs aluminium:

2Al?+?2HNO 3?+?3H 2SO 4?=?Al 2(SO 4) 3?+?2NO?+?4H 2O

2NO?+?3MnO 2?+?3H 2SO 4?=?3MnSO 4?+?2H 2O?+?2HNO 3

Total reaction is:

2Al?+?6H 2SO 4?+?3MnO 2?=?Al 2(SO 4) 3?+?3MnSO 4?+?6H 2O

Meanwhile, the NO that aluminium leaching process produces and the FePO in positive electrode material 4there is following chemical reaction:

6FePO 4?+?2NO?+?6H 2SO 4?+?4H 2O??=?6FeSO 4?+?6H 3PO 4?+?2HNO 3

LiFePO in positive electrode material 4there is following chemical reaction:

2LiFePO 4?+?3H 2SO 4?=?Li 2SO 4?+?2H 3PO 4?+?2FeSO 4

The Al that leaching process produces 3+with PO 4 3-generate AlPO 4precipitation.

Through above-mentioned series reaction, finally make iron lithium phosphate refuse battery positive electrode material and pyrolusite leach simultaneously, saved pyrolusite and leached and need reducing roasting (reduction ratio is about 85%, unreduced MnO 2in nitric acid, can not leach) etc. preprocessing process, improved the generation that metal leaching rate has been avoided nitrogen oxides pollution thing substantially, realized cleaning of technique.The NO that leaching process produces is regeneration nitric acid in slurry substantially, the NO overflowing on a small quantity and return to regeneration nitric acid in slurry by stirrings, and whole leaching process carries out under pressure-fired, is easy to engineering and applies.

Owing to leaching the reducing power of aluminium generation NO than in existing leaching method, generally the reducing power of the hydrogen peroxide of use is much better than.Whole leaching process does not need another additional reducing agent.NO can thoroughly destroy positive electrode material FePO 4laminate structure, improve speed of response, improve the leaching yield of valuable metal lithium.

With respect to existing method, outstanding advantages of the present invention is that iron lithium phosphate refuse battery positive electrode material and pyrolusite leach simultaneously; Leach aluminium generation NO and thoroughly destroy positive electrode material FePO 4laminate structure; Can improve metal leaching rate, not need to use in addition reductive agent; Equipment is simple, is easy to engineering application; Substantially avoid the generation of pollutent oxynitride, thereby do not needed the Pollution abatement of oxynitride, saved pollution abatement costs, there is obvious economic benefit and environmental benefit.

specific implementation method

embodiment 1: by 100g iron lithium phosphate refuse battery positive electrode material (containing lithium 4.3%, aluminium 5.2%, iron 34.8%) and levigate pyrolusite (particle diameter 200 orders, MnO 2content 55%, add-on is theoretical amount 100%) to add volume be in the stainless steel cauldron of 1L, adds the sulfuric acid 530ml of 3.0mol/L, adds nitric acid 3.2g (with HNO 3meter), at 50 ℃~60 ℃, stir (stirring velocity 80r/min) and leach 2.5 hours, after leaching finishes, carry out liquid-solid separation, obtain 490ml infusion solution (containing leached mud washing water).The about 0.47L of reaction end gas, nitrous oxides concentration is 2.3mg/m 3.The leaching yield of lithium, aluminium, iron and manganese be respectively 99.2%, 0.005%, 97.3% and 97.5%(by entering lithium in infusion solution and leached mud washings, aluminium, iron and manganese, calculate).

Embodiment 2: by 500g iron lithium phosphate refuse battery positive electrode material (containing lithium 4.3%, aluminium 5.2%, iron 34.8%) and levigate pyrolusite (particle diameter 200 orders, MnO 2content 55%, add-on is theoretical amount 103%) to add volume be in the stainless steel cauldron of 10L, adds the sulfuric acid 6000ml of 2.0mol/L, adds nitric acid 35g (with HNO 3meter), at 50 ℃~60 ℃, stir (stirring velocity 70r/min) and leach 3 hours, after leaching finishes, carry out liquid-solid separation, obtain 5500ml infusion solution (containing leached mud washing water).The about 4000ml of reaction end gas, nitrous oxides concentration is 2.6mg/m 3.The leaching yield of lithium, aluminium, iron and manganese be respectively 99.7%, 0.01%, 98.0% and 97.3%(by entering lithium in infusion solution and leached mud washings, aluminium, iron and manganese, calculate).

Claims (1)

1. the leaching method of an iron lithium phosphate refuse battery positive electrode material, be characterised in that isolated positive electrode material from iron lithium phosphate refuse battery and levigate pyrolusite are put into the container of withstand voltage and resistance to sulfuric acid and nitric acid corrosion, and sulfuric acid and nitric acid are pumped into this container, then sealed vessel, carry out the leaching of iron lithium phosphate refuse battery positive electrode material, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution, extraction temperature is 40 ℃~80 ℃, the sulfuric acid starting point concentration leaching is 1 mol/L~5 mol/L, nitric acid starting point concentration is 5 g/L~20g/L, extraction time is 1h~3h, leaching process stirs, stirring velocity 30 r/min~120r/min, sulphuric acid is to add 101%~200% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel and pyrolusite, all metals leach, the MnO of pyrolusite used 2content>=40%, particle diameter≤180 order, the add-on of pyrolusite is with MnO 2count in oxidation positive electrode material all 100%~110% of the required theoretical amount of metallic aluminum.
CN201310736638.7A 2013-12-29 2013-12-29 Leaching method of lithium iron phosphate waste battery positive electrode material CN103757418A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928831A (en) * 2009-06-23 2010-12-29 四川师范大学 Leaching method of anode material of lithium cobalt oxide waste battery
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
CN103305698A (en) * 2013-06-09 2013-09-18 南康市恒源循环科技有限公司 Method for recovering gold, silver, tin and copper from industrial wastes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928831A (en) * 2009-06-23 2010-12-29 四川师范大学 Leaching method of anode material of lithium cobalt oxide waste battery
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
CN103305698A (en) * 2013-06-09 2013-09-18 南康市恒源循环科技有限公司 Method for recovering gold, silver, tin and copper from industrial wastes

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Application publication date: 20140430