CN108298514A - A kind of method of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode - Google Patents
A kind of method of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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Abstract
The present invention provides a kind of methods of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode.It the described method comprises the following steps：(1) waste lithium iron phosphate positive electrode is calcined, obtains clinker；(2) it by after step (1) described clinker cooling, is leached with acid solution, obtains slurry；(3) slurries filtration for obtaining step (2), and rich lithium solution and phosphoric acid scum after residue washing, will be obtained.Lithium in this method selective extraction waste lithium iron phosphate positive electrode, and asynchronous extraction phosphorus therein and iron, flow are simple, process cleans, no waste water and exhaust gas discharge, the rate of recovery of lithium does not add auxiliary agent up to 95% or more, has saved cost.
Description
Technical field
The invention belongs to technical field of resource recovery, are related to a kind of method more particularly to one recycling lithium in positive electrode
The method of lithium in kind high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode.
Background technology
Lithium iron phosphate positive material (abbreviation LFP) is because its raw material sources is abundant, inexpensive, nontoxic, theoretical capacity is high, thermostabilization
Property good and good cycle the advantages that be concerned, be the developing direction of power battery.As lithium iron phosphate dynamic battery makes
The disposition of the increase of dosage, waste lithium iron phosphate battery will be as the key link of new energy field.Old and useless battery positive electrode
If cannot get safe handling, huge harm will be generated to environment and public safety.Normal practice is mainly by battery through putting at present
The metal simple-substance in crust and positive and negative anodes collector is recycled after electricity, dismantling, for the maximum positive electrode of recovery value without reasonable
Recovering means.The elemental lithium contained in positive material of waste lithium iron phosphate is national strategy metal, while being also in short supply
Resource, external dependence degree is big, realizes that the cleaning recycling of lithium in positive electrode is of great significance.
It is dissolved in acid medium currently, the basic process that selectivity carries lithium route is the useless positive electrode of LiFePO4, it is molten
It solves liquid to be neutralized with precipitated impurities with sodium hydroxide, using sodium carbonate precipitation prepared by lithium carbonate to scavenging solution.The route can be achieved
The high level of lithium recycles, but non-flow is complicated, and auxiliary material usage amount is big, and residue and waste liquid yield are big, seriously pollute environment.
103280610 A of CN disclose aluminium, iron in a kind of soda acid lixiviation process recycling LiFePO4 old and useless battery anode waste paper
With the method for lithium.This method first removes lithium iron phosphate battery anode, and first with alkali soluble solution, after filtering, filter residue is dissolved with mix acid liquor,
So that iron exists with ferric phosphate precipitation form and is detached with lithium-containing solution with impurity such as carbon blacks.95 DEG C of saturations can be added in lithium-containing solution
Sodium carbonate liquor, precipitation obtain lithium carbonate.Ore Leaching iron ion is added in iron content precipitation, adds lye adjusting pH value and obtains Fe
(OH)3.But the method first decomposes lithium iron phosphate positive material with after alkali with acid, flow is complicated, and processing cost is high；Meanwhile
Iron mixes after being precipitated in the form of ferric phosphate with impurity such as carbon blacks to be discharged as waste residue, not by its commercialization, causes iron, phosphor resource
Waste.
Invention content
It is useless in view of the deficiencies of the prior art, the present invention intends to provide a kind of high temperature solid-state method selective recovery
The method of lithium in old lithium iron phosphate positive material, the method aoxidize two in LiFePO4 using gaseous oxidant at high temperature
Valence iron converts iron to ferric iron, and ferric iron is combined into ferric phosphate not soluble in water with phosphate radical, is leached by acid solution
Afterwards, the anion binding in the lithium and acid solution of dissociation generates water-soluble lithium salts, is leached to liquid phase.The method selectively carries
The lithium in waste lithium iron phosphate positive electrode is taken, and asynchronous extraction phosphorus therein and iron, the leaching rate of lithium are high, process cleans.
In order to achieve the above object, the present invention uses following technical scheme：
The method that the present invention provides lithium in a kind of solid phase method recycling waste lithium iron phosphate positive electrode, the method includes with
Lower step：
(1) waste lithium iron phosphate positive electrode is calcined, obtains clinker；
(2) it by after step (1) described clinker cooling, is leached with acid solution, obtains slurry；
(3) slurries filtration for obtaining step (2), and rich lithium solution and phosphoric acid scum after residue washing, will be obtained.
In high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode provided by the invention in the method for lithium, step
(1) calcining is high-temperature calcination；Step (2) described acid solution is acidic aqueous solution；The slurry that step (2) obtains after leaching
In, lithium salts is leached to liquid phase, and iron is present in the form of ferric phosphate precipitates in solid phase with phosphorus；In step (3), generated after filtering
Filter residue be phosphoric acid scum.
The basic principle of method provided by the invention is under oxidative conditions that the ferrous ion in LiFePO4 is by high temperature oxygen
Trivalent is turned to, stable phosphoric acid iron construction is formed, lithium ion is released, and can be prepared by rich lithium after the leaching of simple acid solution
Solution, and then lithium carbonate product is prepared, it is added without the auxiliary agent for helping lithium to dissolve in an acidic solution, cost has been saved, has realized
The high level of lithium recycles.
In method provided by the invention, the effect of step (1) described calcining is in addition to high by the ferrous ion in LiFePO4
Temperature is oxidized to except ferric iron, further includes that binder subsidiary on waste lithium ion cell anode material is decomposed volatilization.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, the temperature of step (1) described calcining is 600 DEG C -1300 DEG C, such as 600
DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C or 1300 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range, preferably 800 DEG C -1200 DEG C.In the present invention, when calcination temperature is low
LiFePO4 binder has just decomposed complete when 600 DEG C, and LiFePO4 structure fails to decompose；When calcination temperature is higher than 1300
DEG C when, oxidation material sintering is serious, and volatilization loss occurs for a small amount of lithium.
As currently preferred technical solution, the atmosphere of step (1) described calcining is oxidizing atmosphere.
Preferably, the oxidizing atmosphere is any one in air atmosphere, oxygen atmosphere or ozone atmosphere or at least two
Kind combination, it is typical but be non-limiting combination and have：The combination of air atmosphere and oxygen atmosphere, oxygen atmosphere and ozone atmosphere
Combination, the combination etc. of air atmosphere and ozone atmosphere.In pyroreaction, above-mentioned three kinds of gas and combinations thereof is feasible oxygen
Agent.
As currently preferred technical solution, the time of step (1) described calcining is 30min-360min, such as
30min, 60min, 120min, 180min, 240min, 300min or 360min etc., it is not limited to cited numerical value, it should
Other unrequited numerical value are equally applicable in numberical range, preferably 120min-240min.Here, calcined oxide most in short-term
Between be 30min, and 360min in the reaction was complete.
As currently preferred technical solution, step (2) described acid solution be dioxide solution, hydrochloric acid solution,
In sulfuric acid solution or salpeter solution any one or at least two combination, it is typical but be non-limiting combination and have：Dioxy
Change the combination of carbon solution and hydrochloric acid solution, the combination of hydrochloric acid solution and sulfuric acid solution, the combination etc. of sulfuric acid solution and salpeter solution.
As currently preferred technical solution, the pH of step (2) described acid solution is 2-6, such as 2,3,4,5 or 6
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.In the present invention, institute
It is weakly acidic solution to state acid solution.
As currently preferred technical solution, the temperature of step (2) described leaching is 25 DEG C -110 DEG C, such as 25 DEG C,
50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C or 110 DEG C etc., it is not limited to cited numerical value, in the numberical range
Other unrequited numerical value are equally applicable, preferably 60 DEG C -90 DEG C.In the present invention, leaches, can make below in room temperature (25 DEG C)
It is too big to leach fluid viscosity, is unfavorable for being separated by filtration；At 110 DEG C or more, leachate moisture evaporation is too fast, and it is difficult also to increase leaching
Degree.
As currently preferred technical solution, the time of step (2) described leaching is 30min-240min, such as
30min, 60min, 90min, 120min, 150min, 180min, 210min or 240min etc., it is not limited to cited
Numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
As currently preferred technical solution, time that step (2) leaches is 60min-120min, such as 60min,
70min, 80min, 90min, 100min, 110min or 120min etc., it is not limited to cited numerical value, the numberical range
Other interior unrequited numerical value are equally applicable.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) 120min-240min is calcined at a temperature of 800 DEG C -1200 DEG C to waste lithium iron phosphate positive electrode, obtained
Clinker；
(2) by after step (1) described clinker cooling, 60min-120min is leached at 60 DEG C -90 DEG C with acid solution, is obtained
To slurry；The pH of the acid solution is 2-6；
(3) by step (2) slurries filtration, and after being washed to filter residue, rich lithium solution and phosphoric acid scum are obtained.
Compared with the prior art, the present invention has the advantages that：
(1) group of waste lithium iron phosphate positive powder most worthy is divided into lithium, and method choice provided by the invention extracts it
In lithium, and asynchronous extraction phosphorus therein and iron, process are more simple, of low cost；
(2) method lithium leaching rate provided by the invention is high (being more than 95%), and oxidation process is selectively strong, impurity content
Low, removing difficulty is small, can realize that the purity of lithium carbonate product is more than 98.5wt% easily；
(3) procedure of lithium cleans in selective recovery waste lithium iron phosphate positive electrode provided by the invention, without useless
Water and exhaust gas discharge.
(4) method provided by the invention does not use any auxiliary agent, has saved cost.
Description of the drawings
Fig. 1 is a kind of high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode that the embodiment of the present invention 1 provides
The process flow chart of middle lithium.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
The method that the present invention provides lithium in a kind of solid phase method recycling waste lithium iron phosphate positive electrode, the method includes with
Lower step：
(1) waste lithium iron phosphate positive electrode is calcined, obtains clinker；
(2) it by after step (1) described clinker cooling, is leached with acid solution, obtains slurry；
(3) slurries filtration for obtaining step (2), and rich lithium solution and phosphoric acid scum after residue washing, will be obtained.
It is present invention typical case but non-limiting embodiment below：
Embodiment 1
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 1300 DEG C, oxygen under conditions of being passed through large quantity of air (oxidant)
Change calcining, binder in waste lithium iron phosphate positive electrode is made to decompose volatilization, when calcining does not add auxiliary agent, and calcination time is
120min obtains clinker, and the ferrous ion in LiFePO4 is trivalent by high-temperature oxydation；
(2) clinker after calcining leaches 120min in the sulfuric acid solution that pH value is 2 at 90 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
The technological process of lithium in high temperature solid-state method selective recovery waste lithium iron phosphate positive electrode provided in this embodiment
Figure is as shown in Figure 1.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.5% with lithium carbonate purity made from rich lithium solution.
Embodiment 2
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 1300 DEG C, oxidizing roasting under conditions of being passed through large quantity of air makes
Binder in waste lithium iron phosphate positive electrode decomposes volatilization, and when calcining does not add auxiliary agent, and calcination time 120min is obtained
Clinker；
(2) clinker after calcining leaches 240min in the sulfuric acid solution that pH value is 6 at 90 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 99.2% with lithium carbonate purity made from rich lithium solution.
Embodiment 3
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 1200 DEG C, oxidizing roasting under conditions of being passed through a large amount of oxygen makes
Binder in waste lithium iron phosphate positive electrode decomposes volatilization, and when calcining does not add auxiliary agent, and calcination time 120min is obtained
Clinker；
(2) clinker after calcining leaches 120min in the hydrochloric acid solution that pH value is 2 at 90 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.9% with lithium carbonate purity made from rich lithium solution.
Embodiment 4
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 1200 DEG C, oxidizing roasting under conditions of being passed through a large amount of oxygen makes
Binder in waste lithium iron phosphate positive electrode decomposes volatilization, and when calcining does not add auxiliary agent, and calcination time 240min is obtained
Clinker；
(2) clinker after calcining leaches 240min in the hydrochloric acid solution that pH value is 6 at 90 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.6% with lithium carbonate purity made from rich lithium solution.
Embodiment 5
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 1200 DEG C, oxidizing roasting under conditions of being passed through large quantity of air makes
Binder in waste lithium iron phosphate positive electrode decomposes volatilization, and when calcining does not add auxiliary agent, and calcination time 120min is obtained
Clinker；
(2) clinker after calcining leaches 240min in the salpeter solution that pH value is 6 at 90 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.5% with lithium carbonate purity made from rich lithium solution.
Embodiment 6
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 600 DEG C, oxidizing roasting under conditions of being passed through large quantity of air makes
Binder in waste lithium iron phosphate positive electrode decomposes volatilization, and when calcining does not add auxiliary agent, and calcination time 360min is obtained
Clinker；
(2) clinker after calcining leaches 60min in the sulfuric acid solution that pH value is 4 at 60 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.5% with lithium carbonate purity made from rich lithium solution.
Embodiment 7
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific methods
For：
(1) by waste lithium iron phosphate positive electrode at 1300 DEG C, oxidizing roasting under conditions of being passed through a large amount of oxygen makes
Binder in waste lithium iron phosphate positive electrode decomposes volatilization, and when calcining does not add auxiliary agent, and calcination time 30min is obtained
Clinker；
(2) clinker after calcining leaches 30min in the hydrochloric acid solution that pH value is 6 at 110 DEG C, and lithium salts is leached to liquid
Phase, and iron is present in solid phase with phosphorus in the form of ferric phosphate precipitates, and obtains slurry；
(3) it is filtered separation to leaching slurry, and after being washed to filter residue, obtains rich lithium solution and phosphoric acid scum.
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.7% with lithium carbonate purity made from rich lithium solution.
Embodiment 8
The present embodiment provides a kind of method that solid phase method recycles lithium in waste lithium iron phosphate positive electrode, specific method ginsengs
According to embodiment 5, difference lies in step (1), calcination temperature is 800 DEG C, and in step (2), it is pH to leach the acid solution used
Value is 2 salpeter solution, and the temperature of leaching is room temperature (25 DEG C).
Iron, phosphorus concentration are less than 0.2g/L in rich lithium solution, are more than 98.9% with lithium carbonate purity made from rich lithium solution.
Comparative example 1
For the specific method of this comparative example with reference to embodiment 1, difference lies in step (2), be added without the sulfuric acid that pH value is 2
Solution, and neutral water is added.
As a result lithium does not leach substantially.
Based on the above embodiments with comparative example it is found that solid phase method provided by the invention recycles waste lithium iron phosphate positive electrode
Lithium in the method choice extraction waste lithium iron phosphate positive electrode of middle lithium, and asynchronous extraction phosphorus therein and iron, process
Simply, of low cost, the leaching rate of lithium is high, process cleans, no waste water and exhaust gas discharge.Comparative example is not provided using the present invention
Scheme, thus can not obtain the present invention effect.
Applicant states, the foregoing is merely the specific implementation mode of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can be readily occurred in are all fallen within protection scope of the present invention and the open scope.
Claims (10)
1. the method for lithium in a kind of solid phase method recycling waste lithium iron phosphate positive electrode, which is characterized in that the method includes with
Lower step：
(1) waste lithium iron phosphate positive electrode is calcined, obtains clinker；
(2) it by after step (1) described clinker cooling, is leached with acid solution, obtains slurry；
(3) slurries filtration for obtaining step (2), and rich lithium solution and phosphoric acid scum after residue washing, will be obtained.
2. according to the method described in claim 1, it is characterized in that, the temperature of step (1) described calcining be 600 DEG C -1300 DEG C,
Preferably 800 DEG C -1200 DEG C.
3. method according to claim 1 or 2, which is characterized in that the atmosphere of step (1) described calcining is oxidizing atmosphere；
Preferably, the oxidizing atmosphere is any one in air atmosphere, oxygen atmosphere or ozone atmosphere or at least two
Combination.
4. according to claim 1-3 any one of them methods, which is characterized in that the time of step (1) described calcining is
30min-360min, preferably 120min-240min.
5. according to claim 1-4 any one of them methods, which is characterized in that step (2) described acid solution is titanium dioxide
In carbon solution, hydrochloric acid solution, sulfuric acid solution or salpeter solution any one or at least two combination.
6. according to claim 1-5 any one of them methods, which is characterized in that the pH of step (2) described acid solution is 2-
6。
7. according to claim 1-6 any one of them methods, which is characterized in that the temperature of step (2) described leaching be 25 DEG C-
110 DEG C, preferably 60 DEG C -90 DEG C.
8. according to claim 1-7 any one of them methods, which is characterized in that the time of step (2) described leaching is
30min-240min。
9. according to the method described in claim 8, it is characterized in that, the time that step (2) leaches is 60min-120min.
10. according to claim 1-9 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) 120min-240min is calcined at a temperature of 800 DEG C -1200 DEG C to waste lithium iron phosphate positive electrode, obtained ripe
Material；
(2) by after step (1) described clinker cooling, 60min-120min is leached at 60 DEG C -90 DEG C with acid solution, is starched
Material；The pH of the acid solution is 2-6；
(3) by step (2) slurries filtration, and after being washed to filter residue, rich lithium solution and phosphoric acid scum are obtained.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179359A (en) * | 2018-11-27 | 2019-01-11 | 成都绿锂环保科技有限公司 | A method of extracting lithium and ferric phosphate from LiFePO4 waste material |
| CN111960396A (en) * | 2020-08-26 | 2020-11-20 | 界首市南都华宇电源有限公司 | Method for preparing soluble phosphate from iron phosphate slag |
| CN112310499A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院过程工程研究所 | Recovery method of waste lithium iron phosphate material and obtained recovery liquid |
| CN112626357A (en) * | 2020-12-14 | 2021-04-09 | 赣州有色冶金研究所 | Method for extracting lithium from waste lithium iron phosphate powder |
| CN112687973A (en) * | 2019-09-02 | 2021-04-20 | 江西迈特循环科技有限公司 | Method and equipment for treating material containing lithium iron phosphate |
| CN115627346A (en) * | 2022-10-28 | 2023-01-20 | 中南大学 | Method for recovering anode material of waste lithium battery |
| CN118291779A (en) * | 2024-03-20 | 2024-07-05 | 赣州力赛科新技术有限公司 | Method for recovering lithium from lithium iron phosphate black powder |
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