CN103757390B - The leaching method of anode material of waste LiCoO battery - Google Patents

The leaching method of anode material of waste LiCoO battery Download PDF

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Publication number
CN103757390B
CN103757390B CN201310736590.XA CN201310736590A CN103757390B CN 103757390 B CN103757390 B CN 103757390B CN 201310736590 A CN201310736590 A CN 201310736590A CN 103757390 B CN103757390 B CN 103757390B
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China
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leaching
sulfuric acid
acid
battery
nitric acid
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CN201310736590.XA
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Chinese (zh)
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CN103757390A (en
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龙炳清
聂付江
邓其军
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四川师范大学
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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 leaching method of the anode material of waste LiCoO battery of introduction of the present invention is by isolated from waste LiCoO battery and the positive electrode material obtained through roasting pretreatment and reed powder add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions.

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 battery after using and scrapping.Because this kind of battery contains plurality of heavy metal, if abandon into environment, very large direct and potential hazard will be produced to environment.Anode material of waste LiCoO battery is mainly containing cobalt, lithium, copper and aluminium, and wherein the total content of cobalt, lithium and copper three is greater than 60%, has very much a recovery value.From anode material of waste LiCoO battery, the technique of Call Provision, lithium and copper mainly contains thermal process and wet processing at present.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 current 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.Hydrochloric acid leaching process, equipment corrosion is large, and acid mist generation is contaminate environment greatly.Sulfuric acid leaching consumption reductive agent costly (as hydrogen peroxide etc.).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 improving leaching velocity how economically, improve metal leaching rate, reduce 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 solve the problems referred to above preferably, but leaching plant is more complicated, and the required technical pure oxygen amount of refuse battery leaching is little, refuse battery process enterprise on the spot manufacture pure oxygen uses by oneself uneconomical, and the storage of industrial pure oxygen, transport and use are cumbersome.Development equipment corrosion is little, leaching velocity is fast, leaching yield is high, acid consumes and the leaching method of the anode material of waste LiCoO battery of low, easy to use, the basic non-environmental-pollution of other supplementary product onsumption has larger practical value.

Summary of the invention

For the problem that current anode material of waste LiCoO battery leaches, the object of the invention is to find a kind of metal leaching rate high, leaching velocity is fast, leaching yield is high, acid consumption is low with other supplementary product onsumption, easy to use, need not expensive reductive agent, the leaching method of the anode material of waste LiCoO battery of basic non-environmental-pollution, isolated from waste LiCoO battery and the positive electrode material obtained through roasting pretreatment and≤1.5mm reed powder is it is characterized in that to add withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions.Carry out solid-liquor separation after leaching terminates, obtain required infusion solution.Temperature of reaction is 60 DEG C ~ 80 DEG C, and the sulfuric acid starting point concentration of leaching is 1mol/L ~ 4mol/L, and the starting point concentration of nitric acid is 5g/L ~ 10g/L extraction time is 2h ~ 4h, and leaching process stirs, and stirring velocity is 30r/min ~ 120r/min.Sulphuric acid be in the positive electrode material adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption.The add-on of reed powder counts LiCoO in positive electrode material with butt 290% ~ 120% of quality.

The object of the present invention is achieved like this: airtight and under having reed powder and nitric acid existent condition, (cobalt in material and lithium exist with cobalt acid lithium form the anode material of waste LiCoO battery of sulfuric acid leaching after roasting pretreatment, copper and aluminium are mainly in metal oxide form) time, there is following main chemical reactions in leaching process:

CuO+H 2SO 4=CuSO 4+H 2O

Al 2O 3+3H 2SO 4=3Al 2(SO 4) 3+3H 2O

nC 6H 10O 5+nH 2SO 4=n(C 5H 11O 5)HSO 4

n(C 5H 11O 5)HSO 4+nH 2O=nC 6H 12O 6+nH 2SO 4

C 6H 12O 6+8HNO 3=8NO+6CO 2+10H 2O

nC 6H 10O 5+8nHNO 3=8nNO+6nCO 2+9nH 2O

6LiCoO 2+9H 2SO 4+2NO=6CoSO 4+3Li 2SO 4+2HNO 3+8H 2O

The total reaction of cobalt acid lithium is:

24nLiCoO 2+nC 6H 10O 5+36nH 2SO 4=24nCoSO 4+12nLi 2SO 4+6nCO 2+41nH 2O

Other organism in reed powder also generates NO, CO with nitric acid reaction 2and H 2o, NO and the LiCoO of generation 2and H 2sO 4coSO is generated by previous reaction 4, Li 2sO 4, HNO 3and H 2o.

Because the speed of response of nitric acid and reed powder is very fast, NO and the LiCoO of generation 2reaction also very fast, accelerate whole leaching process thus, and realize LiCoO 2leach more completely.NO thoroughly can destroy the laminate structure of high oxide in positive electrode material, improves the leaching yield of valuable metal.

Relative to existing method, outstanding advantages of the present invention adopts reed powder to make reductive agent, and nitric acid is done to leach accelerator and leached anode material of waste LiCoO battery, and speed of response is fast, and such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and reed powder is cheap; In positive electrode material, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; Do not need in leach liquor subsequent disposal to neutralize a large amount of acid, cost is lower; The waste amount produced in leach liquor subsequent disposal is few, reduces pollution abatement costs, has obvious economic benefit and environmental benefit; Process is carried out in confined conditions, avoids the environmental pollution that NO effusion produces.

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≤1.5mm reed powder 30g to add volume be in the lining titanium pressure reaction still of 2L, add the mixed acid solution 1180ml that sulfuric acid concentration is 1.5mol/L, concentration of nitric acid is 5g/L, at 60 DEG C ~ 70 DEG C, 4.0h is leached in airtight stirring (stirring velocity 80r/min), carry out solid-liquor separation after leaching terminates, obtain 1160ml infusion solution (not containing leached mud washing water).The leaching yield of cobalt, lithium, copper and aluminium be respectively 99.0%, 99.2%, 98.9% and 98.8%(calculate by the cobalt, lithium, copper and the aluminium that enter in infusion solution and leached mud washings).

Embodiment 2: by 500g anode material of waste LiCoO battery (containing cobalt 53.6%, lithium 5.3%, copper 8.2%, aluminium 3.4%) to add volume be in the lining titanium pressure reaction still of 5L to≤1.5mm reed powder 190g, adding sulfuric acid concentration is 3.0mol/L, concentration of nitric acid is the mixed acid solution 3500ml of 10g/L, at 70 DEG C ~ 80 DEG C, 2h is leached in airtight stirring (stirring velocity 70r/min), solid-liquor separation is carried out after leaching terminates, obtain 3300ml infusion solution (not containing leached mud washing water), cobalt, lithium, the leaching yield of copper and aluminium is respectively 99.1%, 99.3%, 99.0% and 98.9%(by the cobalt entered in infusion solution and leached mud washings, lithium, copper and aluminium calculate).

Claims (1)

1. the leaching method of an anode material of waste LiCoO battery, isolated from waste LiCoO battery and the positive electrode material obtained through roasting pretreatment and≤1.5mm reed powder is it is characterized in that to add withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions, solid-liquor separation is carried out after leaching terminates, obtain required infusion solution, temperature of reaction is 60 DEG C ~ 80 DEG C, the sulfuric acid starting point concentration leached is 1mol/L ~ 4mol/L, the starting point concentration of nitric acid is 5g/L ~ 10g/L, extraction time is 2h ~ 4h, leaching process stirs, stirring velocity is 30r/min ~ 120r/min, sulphuric acid be in the positive electrode material adding reaction vessel all metal leach 110% ~ 140% of sulfuric acid theoretical consumption, the add-on of reed powder counts LiCoO in positive electrode material with butt 290% ~ 120% of quality.
CN201310736590.XA 2013-12-29 2013-12-29 The leaching method of anode material of waste LiCoO battery CN103757390B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006024482A (en) * 2004-07-09 2006-01-26 Sumitomo Metal Mining Co Ltd Method of dissolving lithium-containing cathode activator
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
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using invalid lithium ion battery
CN102101701A (en) * 2010-12-31 2011-06-22 湖南邦普循环科技有限公司 Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite
CN102163760A (en) * 2011-03-17 2011-08-24 江西格林美资源循环有限公司 Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006024482A (en) * 2004-07-09 2006-01-26 Sumitomo Metal Mining Co Ltd Method of dissolving lithium-containing cathode activator
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
CN102030375A (en) * 2010-10-29 2011-04-27 北京矿冶研究总院 Method for preparing lithium cobaltate by directly using invalid lithium ion battery
CN102101701A (en) * 2010-12-31 2011-06-22 湖南邦普循环科技有限公司 Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite
CN102163760A (en) * 2011-03-17 2011-08-24 江西格林美资源循环有限公司 Method for separating and recovering lithium and cobalt from positive electrode material of lithium battery

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