CN103757345A

CN103757345A - Leaching method of nickel cobalt lithium manganate waste battery positive-negative electrode mixed material

Info

Publication number: CN103757345A
Application number: CN201310736539.9A
Authority: CN
Inventors: 龙炳清; 崔伟; 张章
Original assignee: Sichuan Normal University
Current assignee: Sichuan Normal University
Priority date: 2013-12-29
Filing date: 2013-12-29
Publication date: 2014-04-30

Abstract

The invention provides a leaching method of a nickel cobalt lithium manganate waste battery positive-negative electrode mixed material, which comprises the following steps: adding a positive-negative electrode mixed material subjected to roasting pretreatment and separated from nickel cobalt lithium manganate waste batteries and corn straw powder into a pressure-resistant sulfuric-acid/nitric-acid-corrosion-resistant reaction kettle, adding a sulfuric acid-nitric acid mixed solution, and carrying out agitation leaching under sealed conditions.

Description

The leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery

Technical field

The present invention relates to a kind of leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery.

Background technology

Nickle cobalt lithium manganate battery (the major metal element that anode and cathode mixed materials contains is the battery of nickel, cobalt, manganese, lithium) is a class novel battery, 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.Nickle cobalt lithium manganate battery plus-negative plate mixing material is nickeliferous, cobalt, lithium, copper, aluminium and manganese mainly, and wherein the total content of nickel, cobalt and lithium is up to more than 50%, has very much a recovery value.The technique that reclaims at present cobalt, lithium and copper from anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery mainly contains thermal process and wet processing.The product that thermal process obtains is alloy material, nickel, cobalt and lithium that very difficult acquisition is purer.Wet processing becomes more readily available purer nickel, cobalt and lithium.Leaching is a requisite process in wet processing.The leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 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 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 anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of basic non-environmental-pollution has larger practical value.

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Summary of the invention

The problem leaching for current anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, 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 and other supplementary product onsumption are low, easy to use, need not expensive reductive agent, the leaching method of the anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of basic non-environmental-pollution, it is characterized in that by anode and cathode mixed materials isolated from waste LiCoxNiyMnzO 2 battery and that obtain through roasting pretreatment and≤corn stalk powder of 1.5mm adds withstand voltage, in the reactor of resistance to sulfuric acid and nitric acid corrosion, the mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach.After leaching finishes, carry out liquid-solid separation, obtain required infusion solution.Temperature of reaction is 50 ℃～80 ℃, and the sulfuric acid starting point concentration of leaching is 1mol/L～4mol/L, and the starting point concentration of nitric acid is that 5g/L～10g/L extraction time is 2h～4h, and leaching process stirs, and stirring velocity is 30r/min～120r/min.Sulphuric acid is to add 110%～140% of sulfuric acid theoretical consumption that in the anode and cathode mixed materials of reaction vessel, all metals leach.The add-on of corn stalk powder is counted 60%～75% of nickel in anode and cathode mixed materials, cobalt and manganese total mass with butt.

The object of the present invention is achieved like this: airtight and have under the condition that corn stalk powder and nitric acid exists, the anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery of sulfuric acid leaching after roasting pretreatment is when (metallic element in material is oxide form), and following main chemical reactions occurs leaching process:

NiO?+?H ₂SO ₄?=?NiSO ₄?+?H ₂O

CuO?+?H ₂SO ₄?=?CuSO ₄?+?H ₂O

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

Li ₂O?+?H ₂SO ₄?=?Li ₂SO _4?+?H 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

3Ni ₂O ₃?+?6H ₂SO ₄?+?2NO?=?6NiSO ₄?+?2HNO ₃?+?5H ₂O

3Co ₂O ₃?+?6H ₂SO ₄?+?2NO?=?6CoSO ₄?+?2HNO ₃?+?5H ₂O

3Mn ₂O ₃?+?6H ₂SO ₄?+?2NO?=?6MnSO ₄?+?2HNO ₃?+?5H ₂O

Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃total reaction be:

12nNi ₂O ₃?+?nC ₆H ₁₀O ₅?+?24nH ₂SO ₄?=?24nNiSO ₄?+?6nCO ₂?+?29nH ₂O

12nCo ₂O ₃?+?nC ₆H ₁₀O ₅?+?24nH ₂SO ₄?=?24nCoSO ₄?+?6nCO ₂?+?29nH ₂O

12nMn ₂O ₃?+?nC ₆H ₁₀O ₅?+?24nH ₂SO ₄?=?24nMnSO ₄?+?6nCO ₂?+?29nH ₂O

Other organism in corn stalk powder also generates NO, CO with nitric acid reaction ₂and H ₂o, the NO of generation and Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃by previous reaction, generate NiSO ₄, CoSO ₄, MnSO ₄, HNO ₃and H ₂o.

Because the speed of response of nitric acid and corn stalk powder is very fast, the NO of generation and Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃reaction also very fast, accelerate thus whole leaching process, and realize Ni ₂o ₃, Co ₂o ₃and Mn ₂o ₃leach more completely.NO can thoroughly destroy the laminate structure of high oxide in anode and cathode mixed materials, improves the leaching yield of valuable metal.

With respect to existing method, outstanding advantages of the present invention is to adopt corn stalk powder to make reductive agent, and nitric acid is made to leach accelerator and leached anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, speed of response is fast, such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little, and corn stalk powder is cheap; In anode and cathode mixed materials, the laminate structure of high oxide is destroyed thoroughly, can improve metal leaching rate; In leach liquor subsequent disposal, do not need to neutralize a large amount of acid, cost is lower; The waste amount producing in leach liquor subsequent disposal is few, has reduced pollution abatement costs, has obvious economic benefit and environmental benefit; Process is carried out in confined conditions, the environmental pollution of having avoided NO to overflow and produce.

specific implementation method

embodiment 1: by 100g anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery (nickeliferous 14.5%, cobalt 20.3%, lithium 17.5%, aluminium 2.2%, copper 2.5%, manganese 12.9%) and≤to add volume be in the lining titanium pressure reaction still of 2L to 1.5mm corn stalk powder 29g, adding sulfuric acid concentration is the mixed acid solution 1650ml that 1.5mol/L, concentration of nitric acid are 5g/L, at 50 ℃～60 ℃, 4h is leached in airtight stirring (stirring velocity 80r/min), after leaching finishes, carry out liquid-solid separation, obtain 1600ml infusion solution (not containing leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, aluminium and manganese be respectively 99.0%, 98.8%, 99.1%, 99.0%, 98.9% and 99.1%(by entering nickel in infusion solution and leached mud washings, cobalt, lithium, copper, aluminium and manganese, calculate).

Embodiment 2: by 300g anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery (nickeliferous 14.5%, cobalt 20.3%, lithium 17.5%, aluminium 2.2%, copper 2.5%, manganese 12.9%) and≤to add volume be in the lining titanium pressure reaction still of 5L to 1.5mm corn stalk powder 105g, adding sulfuric acid concentration is the mixed acid solution 3000ml that 3mol/L, concentration of nitric acid are 10g/L, at 70 ℃～80 ℃, 2h is leached in airtight stirring (stirring velocity 70r/min), after leaching finishes, carry out liquid-solid separation, obtain 2800ml infusion solution (not comprising leached mud washing water).The leaching yield of nickel, cobalt, lithium, copper, aluminium and manganese be respectively 99.3%, 99.2%, 99.4%, 99.5%, 98.9% and 99.2%(by entering nickel in infusion solution and leached mud washings, cobalt, lithium, copper, aluminium and manganese, calculate).

Claims

1. the leaching method of an anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, it is characterized in that by anode and cathode mixed materials isolated from waste LiCoxNiyMnzO 2 battery and that obtain through roasting pretreatment and≤corn stalk powder of 1.5mm adds in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion, the mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach, after leaching finishes, carry out liquid-solid separation, obtain required infusion solution.

2. temperature of reaction is 50 ℃～80 ℃, the sulfuric acid starting point concentration leaching is 1mol/L～4mol/L, the starting point concentration of nitric acid is that 5g/L～10g/L extraction time is 2h～4h, leaching process stirs, stirring velocity is 30r/min～120r/min, sulphuric acid is to add 110%～140% of sulfuric acid theoretical consumption that in the anode and cathode mixed materials of reaction vessel, all metals leach, and the add-on of corn stalk powder is counted 60%～75% of nickel in anode and cathode mixed materials, cobalt and manganese total mass with butt.