CN103757388A - 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 PDFInfo
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- CN103757388A CN103757388A CN201310736588.2A CN201310736588A CN103757388A CN 103757388 A CN103757388 A CN 103757388A CN 201310736588 A CN201310736588 A CN 201310736588A CN 103757388 A CN103757388 A CN 103757388A
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- China
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- leaching
- positive electrode
- electrode material
- sulfuric acid
- battery positive
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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 iron phosphate waste battery positive electrode material, which comprises the following steps: putting a positive-negative electrode mixed material subjected to roasting pretreatment separated from lithium iron phosphate waste batteries into a pressure-resistant sulfuric-acid-corrosion-resistant container, pumping sulfuric acid into the container, sealing the container, and introducing SO2 to perform leaching.
Description
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, 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 iron lithium phosphate refuse battery positive electrode material of basic non-environmental-pollution, it is characterized in that will be isolated from iron lithium phosphate refuse battery, and the positive electrode material obtaining through roasting pretreatment puts into withstand voltage and container sulfuric acid corrosion resistant, and sulfuric acid is pumped into this container, then sealed vessel, and pass into SO
2leach, after leaching finishes, carry out liquid-solid separation, obtain required infusion solution.Temperature of reaction is 40 ℃～80 ℃, and the sulfuric acid starting point concentration of leaching is 1mol/L～4mol/L, and extraction time is 1h～3h, and leaching process stirs, and stirring velocity is 30r/min～120r/min.Sulphuric acid is to add the sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel, all metal leaches (not deduct and generate AlPO
4the sulfuric acid theoretical consumption that precipitation reduces) 101%～140%.The pressure of leaching process is 0.05MPa～0.2MPa.
The object of the present invention is achieved like this: at airtight and SO
2under the condition existing, the iron lithium phosphate refuse battery positive electrode material of sulfuric acid leaching after roasting pretreatment is when (metallic element in material is oxide form), and following main chemical reactions occurs leaching process:
Al
2O
3 + 3H
2SO
4 = Al
2(SO
4)
3 + 3H
2O
2LiFePO
4 + 3H
2SO
4 = Li
2SO
4 + 2H
3PO
4 + 2FeSO
4
2FePO
4 + H
2SO
4 + SO
2 + 2H
2O = 2FeSO
4 + 2H
3PO
4
Al
2(SO
4)
3 + H
3PO
4 = AlPO
4
Due to SO
2reducing power more much better than than the reducing power of the hydrogen peroxide generally using in existing leaching method, and need under strong acidic environment, could reduce, can reduce like this acidity of leaching process, the consumption of minimizing sulfuric acid and reductive agent, raising speed of response.SO
2can thoroughly destroy positive electrode material FePO
4laminate structure, improve the leaching yield there is valency lithium.
With respect to existing method, outstanding advantages of the present invention is to adopt SO
2make reductive agent and leach iron lithium phosphate refuse battery positive electrode material, speed of response is fast, and such as reaction acidity is lower, and the consumption of sulfuric acid and reductive agent is little; FePO in positive electrode material
4laminate structure destroy thoroughly, can improve the leaching yield of lithium; 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.
specific implementation method
embodiment 1: it is in the stainless steel cauldron of 1L that 100g iron lithium phosphate refuse battery positive electrode material (containing lithium 4.3%, aluminium 5.2%, iron 34.8%) is added to volume, the sulfuric acid 820ml that adds 1.5mol/L stirs (stirring velocity 80r/min) and passes into SO at 40 ℃～50 ℃
2leach 3.0h, leaching pressure is 0.05MPa, after leaching finishes, carries out liquid-solid separation, obtains 780ml infusion solution (containing leached mud washing water).The leaching yield of lithium, aluminium and iron be respectively 99.7%, 0.01% and 99.5%(by entering lithium in infusion solution and leached mud washings, aluminium and iron, calculate).
Embodiment 2: it is in the stainless steel cauldron of 2L that 300g iron lithium phosphate refuse battery positive electrode material (containing lithium 4.3%, aluminium 5.2%, iron 34.8%) is added to volume, the sulfuric acid 1500ml that adds 3.0mol/L, at 70 ℃～80 ℃, stir (stirring velocity 70r/min) and leach 1h, leaching pressure is 0.15MPa, after leaching finishes, carry out liquid-solid separation, obtain 1300ml infusion solution (not comprising leached mud washing water).The leaching yield of lithium, aluminium and iron be respectively 99.8%, 0.01% and 99.7%(by entering lithium in infusion solution and leached mud washings, aluminium and iron, calculate).
Claims (2)
1. the leaching method of an iron lithium phosphate refuse battery positive electrode material, being characterised in that will be isolated from iron lithium phosphate refuse battery, and the positive electrode material obtaining through roasting pretreatment puts into withstand voltage and container sulfuric acid corrosion resistant, and sulfuric acid is pumped into this container, then sealed vessel, and pass into SO
2leach, after finishing, leaching carries out liquid-solid separation, obtain required infusion solution, temperature of reaction is 40 ℃～80 ℃, the sulfuric acid starting point concentration leaching is 1mol/L～4mol/L, and extraction time is 1h～3h, and leaching process stirs, stirring velocity is 30r/min～120r/min, and sulphuric acid is to add 101%～140% of sulfuric acid theoretical consumption that in the positive electrode material of reaction vessel, all metals leach.
2. the pressure of leaching process is 0.05MPa～0.2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736588.2A CN103757388A (en) | 2013-12-29 | 2013-12-29 | Leaching method of lithium iron phosphate waste battery positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736588.2A CN103757388A (en) | 2013-12-29 | 2013-12-29 | Leaching method of lithium iron phosphate waste battery positive electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103757388A true CN103757388A (en) | 2014-04-30 |
Family
ID=50524702
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|---|---|---|---|
| CN201310736588.2A Pending CN103757388A (en) | 2013-12-29 | 2013-12-29 | Leaching method of lithium iron phosphate waste battery positive electrode material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109075407A (en) * | 2016-05-20 | 2018-12-21 | 魁北克电力公司 | The method for recycling electrode material of lithium battery |
| CN110484726A (en) * | 2016-08-26 | 2019-11-22 | 湖南金源新材料股份有限公司 | The method of ferric phosphate lithium cell waste material selectively leaching lithium |
| CN115537566A (en) * | 2022-10-28 | 2022-12-30 | 中南大学 | Comprehensive recovery method of lithium iron phosphate anode material |
Citations (2)
| 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 |
| CN102030375A (en) * | 2010-10-29 | 2011-04-27 | 北京矿冶研究总院 | Method for preparing lithium cobaltate by directly using failed lithium ion battery |
-
2013
- 2013-12-29 CN CN201310736588.2A patent/CN103757388A/en active Pending
Patent Citations (2)
| 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 |
| CN102030375A (en) * | 2010-10-29 | 2011-04-27 | 北京矿冶研究总院 | Method for preparing lithium cobaltate by directly using failed lithium ion battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109075407A (en) * | 2016-05-20 | 2018-12-21 | 魁北克电力公司 | The method for recycling electrode material of lithium battery |
| CN109075407B (en) * | 2016-05-20 | 2021-12-28 | 魁北克电力公司 | Method for recycling electrode material of lithium battery |
| CN110484726A (en) * | 2016-08-26 | 2019-11-22 | 湖南金源新材料股份有限公司 | The method of ferric phosphate lithium cell waste material selectively leaching lithium |
| CN115537566A (en) * | 2022-10-28 | 2022-12-30 | 中南大学 | Comprehensive recovery method of lithium iron phosphate anode material |
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Application publication date: 20140430 |