CN106684485A - Method for recovering waste/used lithium iron phosphate positive-pole material by acid leaching method - Google Patents
Method for recovering waste/used lithium iron phosphate positive-pole material by acid leaching method Download PDFInfo
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Abstract
The invention belongs to the technical field of recovery of lithium-ion batteries and particularly relates to a method for recovering a waste/used lithium iron phosphate positive-pole material by an acid leaching method. The method provided by the invention comprises the following steps: (a) carrying out acid leaching: adding acid into the lithium iron phosphate positive-pole material for acid leaching so as to obtain a suspension, and carrying out filtration, so as to obtain filtrate; (b) carrying out oxidation: adjusting the pH value of the filtrate obtained in the step (a) to be smaller than 1, and adding an oxidant into the filtrate to oxidate ferrous ions in the filtrate into ferric ions, so as to obtain a mixed solution; (c) carrying out separation: adjusting the pH value of the mixed solution obtained in the step (b) to be 1.5 to 4, carrying out a reaction for 1 to 3 hours at the temperature of 60 DEG C to 95 DEG C so as to produce ferric phosphate precipitates, and carrying out filtrating and washing, thereby obtaining lithium-containing filtrate and ferric phosphate. The method provided by the invention is simple in process, continuous in cycle, low in cost and easy to industrialize and is environmentally friendly; the recovery rate of Li, Fe and P reaches 95% or more, subsequent prepared FePO4 is low in impurity content, the particle size is 1 to 6 microns, is uniform and is narrow in distribution, and the morphology is controllable, so that the FePO4 is battery-grade ferric phosphate.
Description
Technical field
The invention belongs to lithium ion battery recovery technology field, and in particular to a kind of acid-hatching of young eggs recycles waste and old ferric phosphate
The method of lithium anode material.
Background technology
At present, energy and environment problem is increasingly becoming one of topmost problem of puzzlement people.From wind energy, waterpower to core
Can, the step that people explore new energy does not stop all the time.But due to by condition systems such as season, geographical position, technical merits
About, the appearance of these new energy does not have thoroughly solution energy problem.With the fast development of electronic technology, various electronic products
As mobile phone, digital camera, notebook computer are increasingly miniaturized, wider demand, therefore various lithiums are produced to compact power supply
Ion battery arises at the historic moment.2012, China turned into lithium battery production and consumption state maximum in addition to Japan in the world.It is huge
Output cause the waste lithium cell of substantial amounts to produce.The waste lithium cell of enormous amount how is processed, is closed as people
The problem of the heart.
Although there is substantial amounts of lithium battery returned enterprise in China, significant portion is in " not haveing enough to eat " state.Old and useless battery
Recovery problem, is the maximum obstruction for hindering waste lithium cell resource.Country should increase the throwing of old and useless battery utilization of resources research
Enter the old and useless battery recovery system of simultaneously Erecting and improving, to tackle increasingly severe resource and energy problem, realize sustainable development
Exhibition.Not yet there is situation about scrapping on a large scale in China's Vehicular dynamic battery.For existing recovery system, there is also delayed existing
As organic efficiency is low.The reason for mainly having the following aspects：Battery recycling amount is few；Reclaim network unsound；Environmentally friendly risk
Greatly.
With the promotion of domestic industries policy, ferric phosphate lithium cell is inevitable to turn into domestic electrokinetic cell in the coming years
The main flow of development.LiFePO 4 material is mainly used in power battery anode or energy-storage battery positive pole, due to power and energy storage
Battery is greater than conventional compact battery to the demand of battery material, and it is carried out to reclaim has social value very high, but returns
Harvest is originally very high.Therefore, the key for solving ferric phosphate lithium cell recovery problem is to reduce cost recovery, in ferric phosphate lithium cell
Before reclaiming upsurge arrival, more efficient and environmentally friendly recovery process is worked out.At present, existing LiFePO4 recovery technology is deposited
In larger problem.First, there is pollution in complex process, and the rate of recovery of lithium is relatively low.Secondly, prior art does not have
Follow-up continuous recovery is carried out specifically designed for iron, phosphorus.
For example：Publication No. " CN104953200A ", it is entitled " battery-grade iron phosphate to be reclaimed in ferric phosphate lithium cell
And the method that lithium iron phosphate positive material is prepared using waste lithium iron phosphate battery ", disclose a kind of using following methods recovery
The method of lithium iron phosphate positive material：First, positive plate is crushed, is heat-treated；2nd, acid solution dissolving；3rd, surfactant is added；4th,
Plus alkali lye, obtain battery-grade iron phosphate.5th, add sodium carbonate, obtain lithium carbonate；6th, ferric phosphate, lithium carbonate and carbon source reducing agent mixing；
7th, calcine.The patent needs to first pass through high-temperature heat treatment, that is, need first to be calcined raw material, then carries out acidleach, so in roasting
During burning, there is the oxidation of ferrous ion while organic matter is burnt, the ferric phosphate generated after oxidation is readily retained in solid
Phase, is unfavorable for leaching, and causes the rate of recovery low.
Accordingly, it would be desirable to a kind of continuous recyclable waste and old LiFePO of recovery of environmental protection of exploratory development4Positive electrode prepares lithium salts
And FePO4Method, to reach process is simple, continuous circulation, low cost, easily industrialization, environmental protection, the rate of recovery of Li, Fe, P is high,
The purpose of the pattern size tunable of the follow-up FP for preparing.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of using acid-hatching of young eggs recycling waste lithium iron phosphate positive pole
The method of material.
The method that the acid-hatching of young eggs of the present invention recycles waste lithium iron phosphate positive electrode, comprises the following steps：
A, acidleach：Waste lithium iron phosphate positive electrode is taken, acid adding acidleach obtains suspension, filtered, obtain filtrate；
B, oxidation：Take the filtrate that a steps are obtained, regulation filtrate pH value ＜ 1, oxidizer, by the ferrous ion in filtrate
Iron ion is oxidized to, mixed solution is obtained；
C, separation：Take b step mixed solution, regulation mixed solution pH value is 1.5~4, react 1 at 60~95 DEG C~
3h, generation ferric phosphate precipitation, filtering, washing obtains filtrate containing lithium and ferric phosphate.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, uses sulfuric acid, salt wherein in a steps
At least one in acid, nitric acid carries out acidleach.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein in a steps after acid adding, excessive acid
0~300%；It is preferred that excessive acid 100~300%.
Further, the method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein acid adding in a steps
Liquid-solid ratio afterwards is 1.5~5:1.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein acidleach temperature are 25~95 DEG C,
Leaching time is 30~180min.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, oxidant is peroxide wherein in b step
Change at least one in hydrogen, sodium peroxide, potassium permanganate；Preferably hydrogen peroxide.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, the oxidant added wherein in b step
Excessive 50~200%.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, oxidizing temperature is 45 wherein in b step
~60 DEG C, oxidization time is 1~5h.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, it is molten in regulation mixing wherein in step c
Surfactant is added in the forward direction mixed solution of liquid pH value.
Further, the method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein the surface is lived
Property agent is preferably at least one in hexadecyltrimethylammonium chloride, lauryl sodium sulfate, polyvinylpyrrolidone.
The present invention provides a kind of environmental protection the continuous recyclable waste and old LiFePO of recovery4Positive electrode prepares lithium salts and FePO4's
Method, process is simple, continuous circulation, low cost, easily industrialization, environmental protection, the rate of recovery of Li, Fe, P is up to more than 95%, subsequently
The FePO of preparation4Impurity content is low, and particle diameter is 1~6 μm, and narrowly distributing uniform in size, morphology controllable, is battery-grade iron phosphate.
Specific embodiment
The method that the acid-hatching of young eggs of the present invention recycles waste lithium iron phosphate positive electrode, comprises the following steps：
A, acidleach：Waste lithium iron phosphate positive electrode is taken, acid adding acidleach obtains suspension, filtered, obtain filtrate；
Waste and old lithium ion battery after the treatment such as lithium iron phosphate positive material of the present invention can be selected by crushing, purification is just
Pole material；
B, oxidation：Take the filtrate that a steps are obtained, regulation filtrate pH value ＜ 1, oxidizer, by the ferrous ion in filtrate
Iron ion is oxidized to, mixed solution is obtained；
C, separation：B step mixed solution is taken, alkali lye is added, regulation mixed solution pH value is 1.5~4, at 60~95 DEG C
1~3h of reaction, generation ferric phosphate precipitation, filtering, washing obtains filtrate containing lithium and ferric phosphate；The alkali lye can be conventional alkali
Liquid, such as NaOH, potassium hydroxide, but in order to reduce impurity content, it is to avoid the addition of foreign matter, alkali lye is preferably hydrogen
Lithia；
Step c regulation pH value is that regulation temperature is because phosphoric acid in order to control the granularity and impurity content of generation ferric phosphate
The solubility and temperature of iron are the relations being inversely proportional, and inventor has found by lot of experiments, is reacted at 60~95 DEG C,
The solubility of ferric phosphate can be reduced so that phosphoric acid iron recovery is improved, and can effectively be economized on resources again, control production efficiency.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, uses sulfuric acid, salt wherein in a steps
At least one in acid, nitric acid carries out acidleach.Excessive 0~300%, excess coefficient is according to equation is leached, with real every time
Test the Mass Calculation of the old and useless battery raw material of use.The method that the above-mentioned acid-hatching of young eggs reclaims lithium iron phosphate positive material, wherein a steps
In rapid after acid adding, preferably by excessive acid 0~300%；More elect 100~300% as.
Further, the method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein acid adding in a steps
Liquid-solid ratio afterwards is 1.5~5:1.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein acidleach temperature are 25~95 DEG C,
Leaching time is 30~180min.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, oxidant is peroxide wherein in b step
Change at least one in hydrogen, sodium peroxide, potassium permanganate；Preferably hydrogen peroxide.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, in order that ferrous ion is all oxidized
Into iron ion, the oxidant added wherein in b step excessive 50~200%.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, oxidizing temperature is 45 wherein in b step
~60 DEG C, oxidization time is 1~5h.
The method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, it is molten in regulation mixing wherein in step c
Surfactant is added in the forward direction mixed solution of liquid pH value.Make by the 1wt% addition surfactants of theory generation ferric phosphate
Obtain reaction system and tend to homogeneous, so that the particle diameter distribution of the powder of generation is more uniform.
Further, the method that the above-mentioned acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, wherein the surface is lived
Property agent is preferably at least one in hexadecyltrimethylammonium chloride, lauryl sodium sulfate, polyvinylpyrrolidone.
Specific embodiment of the invention is further described with reference to embodiment, is not therefore limited the present invention
System is among described scope of embodiments.
Embodiment 1
(1) waste lithium iron phosphate battery positive electrode active materials 50g is weighed, is added in sulfuric acid solution.By lithium in raw material
Stoichiometry is calculated, excess sulfuric acid 0%.It is 1.5 to control liquid-solid ratio:1, extraction temperature is 25 DEG C, and extraction time 30min is hanged
Supernatant liquid.By the filtering of above-mentioned suspension.
The waste and old lithium ion battery material processed in this step can be by the applying waste lithium ionic after smashing, purified treatment
Cell positive material.
(2) oxidation of ferrous ion：The pH for adjusting filtrate is less than 1, adds hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 50%, oxidizing temperature is 45 DEG C, reacts 1h.
(3) lithium and iron phosphorus separation prepares ferric phosphate：It is 1.5 that LiOH, regulation pH are added in the reaction solution of step (2), control
Temperature processed is 60 DEG C, and reaction 2h generation ferric phosphate precipitations, filtration washing obtains ferric phosphate.Filtrate is containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table 1.
Embodiment 2
(1) waste lithium iron phosphate battery positive electrode active materials 50 are weighed, is added in sulfuric acid solution.By the change of lithium in raw material
Learn metering to calculate, excess sulfuric acid 0%.It is 1.5 to control liquid-solid ratio:1, extraction temperature is 60 DEG C, and extraction time 100min is suspended
Liquid.By the filtering of above-mentioned suspension.
The waste and old lithium ion battery material processed in this step can be by the applying waste lithium ionic after smashing, purified treatment
Cell positive material.
(2) oxidation of ferrous ion：The pH for adjusting filtrate is less than 1, adds hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 100%, oxidizing temperature is 45 DEG C, reacts 5h.
(3) lithium and iron phosphorus separation prepares ferric phosphate：LiOH is added in the reaction solution of step (2), pH 2, control temperature is adjusted
It is 60 DEG C to spend, and reaction 1h generation ferric phosphate precipitations, filtration washing obtains ferric phosphate.Filtrate is containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table shown in 1.
Embodiment 3
(1) waste lithium iron phosphate battery positive electrode active materials 50g is weighed, is added in sulfuric acid solution.By lithium in raw material
Stoichiometry is calculated, excess sulfuric acid 100%.It is 2.5 to control liquid-solid ratio:1, extraction temperature is 60 DEG C, and extraction time 100min is obtained
Suspension.By the filtering of above-mentioned suspension.
The waste and old lithium ion battery material processed in this step can be by the applying waste lithium ionic after smashing, purified treatment
Cell positive material.
(2) oxidation of ferrous ion：The pH for adjusting filtrate is less than 1, adds hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 100%, oxidizing temperature is 45 DEG C, reacts 2h.
(3) lithium and iron phosphorus separation prepares ferric phosphate：LiOH is added in the reaction solution of step (2), pH 2, control temperature is adjusted
It is 60 DEG C to spend, and reaction 1.5h generation ferric phosphate precipitations, filtration washing obtains ferric phosphate.Filtrate is containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table shown in 1.
Embodiment 4
(1) waste lithium iron phosphate battery positive electrode active materials 50g is weighed, is added in sulfuric acid solution.By lithium in raw material
Stoichiometry is calculated, excess sulfuric acid 100%.It is 4 to control liquid-solid ratio:1, extraction temperature is 60 DEG C, and extraction time 100min is hanged
Supernatant liquid.By the filtering of above-mentioned suspension.
The waste and old lithium ion battery material processed in this step can be by the applying waste lithium ionic after smashing, purified treatment
Cell positive material.
(2) oxidation of ferrous ion：The pH for adjusting filtrate is less than 1, adds hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 100%, oxidizing temperature is 60 DEG C, reacts 2h.
(3) lithium and iron phosphorus separation prepares ferric phosphate：LiOH, regulation pH is added to be about 4, control in the reaction solution of step (2)
Temperature processed is 95 DEG C, and reaction 3h generation ferric phosphate precipitations, filtration washing obtains ferric phosphate.Filtrate is containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table shown in 1.
Embodiment 5
(1) waste lithium iron phosphate battery positive electrode active materials 50g is weighed, is added in sulfuric acid solution.By lithium in raw material
Stoichiometry is calculated, excess sulfuric acid 300%.It is 5 to control liquid-solid ratio:1, extraction temperature is 95 DEG C, and extraction time 180min is hanged
Supernatant liquid.By the filtering of above-mentioned suspension.
The waste and old lithium ion battery material processed in this step can be by the applying waste lithium ionic after smashing, purified treatment
Cell positive material.
(2) oxidation of ferrous ion：The pH for adjusting filtrate is less than 1, adds hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 200%, oxidizing temperature is 50 DEG C, reacts 5h.
(3) lithium and iron phosphorus separation prepares ferric phosphate：LiOH, regulation pH is added to be about 4, control in the reaction solution of step (2)
Temperature processed is 95 DEG C, and reaction 3h generation ferric phosphate precipitations, filtration washing obtains ferric phosphate.Filtrate is containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table shown in 1.
Embodiment 6
(1) waste lithium iron phosphate battery positive electrode active materials 50g is weighed, is added in sulfuric acid solution.By lithium in raw material
Stoichiometry is calculated, excess sulfuric acid 0%.It is 1.5 to control liquid-solid ratio:1, extraction temperature is 95 DEG C, and extraction time 180min is hanged
Supernatant liquid.By the filtering of above-mentioned suspension.
The waste and old lithium ion battery material processed in this step can be by the applying waste lithium ionic after smashing, purified treatment
Cell positive material.
(2) oxidation of ferrous ion：The pH for adjusting filtrate is less than 1, adds hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 200%, oxidizing temperature is 50 DEG C, reacts 5h.
(3) lithium and iron phosphorus separation prepares ferric phosphate：First by the 1% of theoretical generation ferric phosphate in the reaction solution of step (2)
Wt, adds hexadecyltrimethylammonium chloride, adds LiOH, and regulation pH is about 4, controls temperature for 95 DEG C, reaction 3h generations
Ferric phosphate is precipitated, and filtration washing obtains ferric phosphate.Filtrate is containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table shown in 1, because adding
Surfactant so that the particle diameter of the ferric phosphate for ultimately generating is smaller, is distributed narrower.
Comparative example 1
(1) waste lithium iron phosphate battery positive electrode active materials 50g is weighed, by splitting, crushing, is heat-treated at 400 DEG C
2h, then screening is vibrated, take the mixed powder under sieve；
(2) to adding sulfuric acid, excess coefficient to be leached for 100% in mixed powder；
(3) filter, by the 1wt% of theory generation ferric phosphate to addition surfactant cetyl trimethyl chlorine in filtrate
Change ammonium；
(4) add LiOH to adjust pH value to 2 in the solution that surfactant is added to step (3), control temperature for 60 DEG C,
Reaction 1.5h generation ferric phosphate precipitations, then will precipitate filtering, washing, dry, and obtain battery-grade iron phosphate and containing Li+Solution.
The rate of recovery of Li, Fe, P for finally giving, and the particle diameter etc. of ferric phosphate the results are shown in Table 1；Can from table 1
Go out, by first high-temperature oxydation, then the step of acidleach so that lithium in battery, iron, phosphorus the rate of recovery it is relatively low, first raw material is roasted
Burn, then carry out acidleach, so first there is the oxidation of ferrous ion while organic matter is burnt in roasting process, aoxidize
The ferric phosphate for generating afterwards is readily retained in solid phase, is unfavorable for leaching, and causes the rate of recovery low.
The rate of recovery and ferric phosphate particle diameter of Li, P, Fe that the embodiment of table 1 and comparative example are obtained
In summary, technical solution of the present invention controls pH and reaction temperature in separating step, strictly, in course of reaction
PH and temperature are basically unchanged, and the growth rate of particle is slower, and the ferric phosphate prepared is substantially spherical or spherical particle,
Pattern rule.
Claims (10)
1. the method that the acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode, it is characterised in that comprise the following steps：
A, acidleach：Waste lithium iron phosphate positive electrode is taken, acid adding acidleach obtains suspension, filtered, obtain filtrate；
B, oxidation：Take the filtrate that a steps are obtained, regulation filtrate pH value ＜ 1, oxidizer, by the ferrous ions in filtrate
Into iron ion, mixed solution is obtained；
C, separation：B step mixed solution is taken, regulation mixed solution pH value is 1.5~4,1~3h is reacted at 60~95 DEG C, it is raw
Into ferric phosphate precipitation, filtering, washing obtains filtrate containing lithium and ferric phosphate.
2. the method that the acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode according to claim 1, it is characterised in that：a
Acidleach is carried out using at least one in sulfuric acid, hydrochloric acid, nitric acid in step.
3. the method that the acid-hatching of young eggs according to claim 1 or claim 2 recycles waste lithium iron phosphate positive electrode, its feature exists
In：In a steps after acid adding, excessive acid 0~300%；It is preferred that excessive acid 100~300%.
4. the method that the acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode according to claim 3, it is characterised in that：a
Liquid-solid ratio in step after acid adding is 1.5~5:1.
5. the method that the acid-hatching of young eggs according to any one of Claims 1 to 4 recycles waste lithium iron phosphate positive electrode, it is special
Levy and be：Acidleach temperature is 25~95 DEG C, and leaching time is 30~180min.
6. the method that the acid-hatching of young eggs according to any one of Claims 1 to 5 recycles waste lithium iron phosphate positive electrode, it is special
Levy and be：Oxidant is at least one in hydrogen peroxide, sodium peroxide, potassium permanganate in b step；Preferably hydrogen peroxide.
7. the method that the acid-hatching of young eggs according to any one of claim 1~6 recycles waste lithium iron phosphate positive electrode, it is special
Levy and be：The oxidant excessive 50~200% added in b step.
8. the method that the acid-hatching of young eggs according to any one of claim 1~7 recycles waste lithium iron phosphate positive electrode, it is special
Levy and be：Oxidizing temperature is 45~60 DEG C in b step, and oxidization time is 1~5h.
9. the method that the acid-hatching of young eggs according to any one of claim 1~8 recycles waste lithium iron phosphate positive electrode, it is special
Levy and be：In step c surfactant is added in the forward direction mixed solution of regulation mixed solution pH value.
10. the method that the acid-hatching of young eggs recycles waste lithium iron phosphate positive electrode according to claim 9, it is characterised in that：
The surfactant is at least in hexadecyltrimethylammonium chloride, lauryl sodium sulfate, polyvinylpyrrolidone
Kind.
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