CN103757408A - Leaching method of lithium cobaltate waste battery positive electrode material - Google Patents

Leaching method of lithium cobaltate waste battery positive electrode material Download PDF

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Publication number
CN103757408A
CN103757408A CN201310736619.4A CN201310736619A CN103757408A CN 103757408 A CN103757408 A CN 103757408A CN 201310736619 A CN201310736619 A CN 201310736619A CN 103757408 A CN103757408 A CN 103757408A
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China
Prior art keywords
leaching
positive electrode
pyrolusite
sulfuric acid
acid
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CN201310736619.4A
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Chinese (zh)
Inventor
龙炳清
陈建文
邓国海
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四川师范大学
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Priority to CN201310736619.4A priority Critical patent/CN103757408A/en
Publication of CN103757408A publication Critical patent/CN103757408A/en

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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

Abstract

The invention provides a leaching method of a lithium cobaltate waste battery positive electrode material, which comprises the following steps: putting a positive electrode material separated from lithium cobaltate 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 cobaltate waste battery positive electrode material.

Description

The leaching method of anode material of waste LiCoO battery

Technical field

The present invention relates to a kind of leaching method of anode material of waste LiCoO battery.

Background technology

Cobalt acid lithium battery is the widely used battery of a class, and this battery will produce a large amount of refuse batteries after using and scrapping.Because this class battery contains plurality of heavy metal, if abandon into environment, will environment be produced to very large direct and potential hazard.Anode material of waste LiCoO battery is mainly containing cobalt, lithium, copper and aluminium, and wherein cobalt, lithium and copper three's total content is greater than 60%, has very much a recovery value.The technique that reclaims at present cobalt, lithium and copper from anode material of waste LiCoO battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, cobalt, lithium and copper that very difficult acquisition is purer.Wet processing becomes more readily available purer cobalt, lithium and copper.Leaching is a requisite process in wet processing.The leaching method of anode material of waste LiCoO battery 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 oxygenant (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 wet processings all exist and eliminate how cost-effectively the package action of organic polymer to metal and metal oxide in this type of raw material, improve the problem of metal leaching rate.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 storage, transportation and the use of industrial pure oxygen are cumbersome.Development equipment corrosion is little, leaching yield is high, cost is low, the leaching method of the anode material of waste LiCoO battery of easy to use, basic non-environmental-pollution has larger practical value.

Summary of the invention

The problem leaching for current anode material of waste LiCoO battery, the object of the invention is to find one need not expensive oxygenant, the leaching method of the anode material of waste LiCoO battery that basic nitrogenfree oxide pollutes, it is characterized in that from waste LiCoO 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 roastings) 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 anode material of waste LiCoO battery, 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 1mol/L～5mol/L, and nitric acid starting point concentration is 5g/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>=50%, 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 state metal.

The object of the present invention is achieved like this: under the condition existing at airtight, pyrolusite and nitric acid, (cobalt in material and lithium exist with cobalt acid lithium form sulfuric acid leaching anode material of waste LiCoO battery, copper and aluminium are mainly metal form) time, there is following chemical reaction in the process that metallic copper generates copper sulfate:

Cu?+?2HNO 3?+?H 2SO 4?=?CuSO 4?+?2NO 2?+?2H 2O

3Cu?+?2HNO 3?+?3H 2SO 4?=?3CuSO 4?+?2NO?+?4H 2O

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

3NO 2?+?H 2O?=?2HNO 3?+?NO

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

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

Total reaction is:

Cu?+?2H 2SO 4?+?MnO 2?=?CuSO 4?+?MnSO 4?+?2H 2O

Under the condition existing at airtight, pyrolusite and nitric acid, during sulfuric acid leaching anode material of waste LiCoO battery, there is following chemical reaction in the process that metallic aluminium generates Tai-Ace S 150:

2Al?+?6HNO 3?+?3H 2SO 4?=?Al 2(SO 4) 3?+?6NO 2?+?6H 2O

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

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

3NO 2?+?H 2O?=?2HNO 3?+?NO

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

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

Total reaction is:

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

During sulfuric acid leaching anode material of waste LiCoO battery, there is following chemical reaction in cobalt acid lithium:

4LiCoO 2?+?6H 2SO 4?=?4CoSO 4?+?2Li 2SO 4?+?6H 2O?+?O 2

The O producing 2the NO producing with previous reaction reacts and generates NO 2, finally generate nitric acid.

Utilize NO 2to the strong corrosion effect of organic polymer, eliminate the package action of organic polymer to metal and metal oxide in anode material of waste LiCoO battery, can fully react with sulfuric acid, improved metal leaching rate.

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

With respect to existing method, outstanding advantages of the present invention is that anode material of waste LiCoO battery and pyrolusite leach simultaneously, can improve the utilization ratio of metal leaching rate and nitric acid and sulfuric acid, does not need to use in addition oxygenant; 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 anode material of waste LiCoO battery (containing cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) and levigate pyrolusite (particle diameter 200 orders, MnO 2content 55%, add-on is theoretical amount 105%) to add volume be in the lining titanium pressure reaction still of 1L, adds the sulfuric acid 900ml of 5.0mol/L, adds nitric acid 15g (with HNO 3meter), at 50 ℃～60 ℃, stir (stirring velocity 80r/min) and leach 2 hours, after finishing, leaching carries out liquid-solid separation, obtain 860ml infusion solution (containing leached mud washing water).The about 0.1L of reaction end gas, nitrous oxides concentration is 1.5mg/m 3.The leaching yield of cobalt, lithium, copper, aluminium and manganese is respectively 98.4%, 98.8%, 97.7%, 98,2% and 98.4%(by the cobalt, lithium, copper, aluminium and the manganese that enter in infusion solution and leached mud washings, calculate).

Embodiment 2: by 400g anode material of waste LiCoO battery (containing cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) and levigate pyrolusite (particle diameter 180 orders, MnO 2content 45%, add-on is theoretical amount 103%) to add volume be in the lining titanium pressure reaction still of 5L, adds the sulfuric acid 4.5L of 4.5mol/L, adds nitric acid 40g (with HNO 3meter), at 60 ℃～70 ℃, stir (stirring velocity 60r/min) and leach 3 hours, after finishing, reaction carries out liquid-solid separation, obtain 4.3L infusion solution (not comprising leached mud washing water), the about 0.7L of reaction end gas, nitrous oxides concentration is 1.7 mg/m 3.The leaching yield of cobalt, lithium, copper, aluminium and manganese be respectively 98.6%, 98.8%, 98.1%, 99.0% and 99.2%(by entering cobalt in infusion solution and leached mud washings, lithium, copper, aluminium and manganese, calculate).

       

Claims (1)

1. the leaching method of an anode material of waste LiCoO battery, it is characterized in that isolated positive electrode material from waste LiCoO battery and levigate pyrolusite to 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 anode material of waste LiCoO battery, 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 1mol/L～5mol/L, nitric acid starting point concentration is 5g/L～20g/L, extraction time is 1h～3h, leaching process stirs, stirring velocity 30r/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>=50%, 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 state metal.
CN201310736619.4A 2013-12-29 2013-12-29 Leaching method of lithium cobaltate waste battery positive electrode material CN103757408A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101586189A (en) * 2009-06-23 2009-11-25 四川师范大学 Leaching method for anode material of waste LiCoO battery
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
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
CN101586189A (en) * 2009-06-23 2009-11-25 四川师范大学 Leaching method for anode material of waste LiCoO battery
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
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