CN103757370B

CN103757370B - The leaching method of anode material of waste LiCoO battery

Info

Publication number: CN103757370B
Application number: CN201310736568.5A
Authority: CN
Inventors: 龙炳清; 舒曼; 曾伟
Original assignee: Sichuan Normal University
Current assignee: Sichuan Normal University
Priority date: 2013-12-29
Filing date: 2013-12-29
Publication date: 2016-01-20
Anticipated expiration: 2033-12-29
Also published as: CN103757370A

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 bamboo bits 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, it is characterized in that isolated from waste LiCoO battery and the bamboo bits of the positive electrode material obtained through roasting pretreatment and≤1.5mm 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 bamboo bits counts LiCoO in positive electrode material with butt ₂90% ~ 120% of quality.

The object of the present invention is achieved like this: airtight and have bamboo consider to be worth doing and nitric acid existent condition under, (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 bamboo bits 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.

The speed of response of considering to be worth doing due to nitric acid and bamboo 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 bamboo bits 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 bamboo bits are 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 bamboo bits 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 98.9%, 99.2%, 99.0% and 98.9%(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 bamboo bits 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 99.2%, 99.2%, 99.1% and 98.7%(by the cobalt entered in infusion solution and leached mud washings, lithium, copper and aluminium calculate).

Claims

1. the leaching method of an anode material of waste LiCoO battery, it is characterized in that isolated from waste LiCoO battery and the bamboo bits of the positive electrode material obtained through roasting pretreatment and≤1.5mm 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 bamboo bits counts LiCoO in positive electrode material with butt ₂90% ~ 120% of quality.