CN109095481A - A kind of comprehensive recovering process of the useless powder of LiFePO4 - Google Patents

A kind of comprehensive recovering process of the useless powder of LiFePO4 Download PDF

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CN109095481A
CN109095481A CN201810887736.3A CN201810887736A CN109095481A CN 109095481 A CN109095481 A CN 109095481A CN 201810887736 A CN201810887736 A CN 201810887736A CN 109095481 A CN109095481 A CN 109095481A
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lifepo4
powder
liquid
gives
added
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CN109095481B (en
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廖贻鹏
周玉琳
张桂海
林文军
戴慧敏
易鹏飞
王勇
刘敏
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Zhuzhou Smelter Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

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  • Engineering & Computer Science (AREA)
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Abstract

A kind of LiFePO4 gives up the comprehensive recovering process of powder, comprising the following steps: A, LiFePO4 is made to give up powder oxidizing roasting, the calcining after being activated；B, sour regurgitation leaches, and the Li in calcining after making activation is leached as far as possible, and valuable element phosphorus and iron is made to form ferric phosphate；C, a certain amount of precipitating reagent is added, removes impurity phosphate anion；D, by the adjusting of neutralizer and soda ash, the impurity calcium and magnesium etc. in solution is removed；E, sodium carbonate is added under the high temperature conditions, obtains battery-level lithium carbonate；F, sodium sulphate synthesizes.The present invention has recycled valuable element phosphorus, iron and the lithium in the useless powder of LiFePO4 to the maximum extent, and has many advantages, such as rational technology, low manufacture cost, pollution-free, nonhazardous.

Description

A kind of comprehensive recovering process of the useless powder of LiFePO4
Technical field
The present invention relates to a kind of LiFePO4 give up powder synthetical recovery method, in particular to a kind of LiFePO4 give up powder it is wet Method comprehensive recovering process.
Background technique
China in Recent Years has become the first big producer of lithium battery, quick-fried with new-energy automobile field since 2012 Hair, has driven the explosive growth of power battery demand.In especially on January 14th, 2017, Ministry of Industry and Information, which takes the lead, has worked out " automobile industry Long-and Medium-term Development planning ", it specifies to China's new-energy automobile annual output in 2020 and is up to 2,000,000, and to 2025 The ratio that year China new-energy automobile sales volume accounts for total sales volume reaches 20% or more developing goal；Meanwhile in September, 2017, Ministry of Industry and Information Responsible person indicates that the release timetable of conventional fuel oil car is studied in China's starting.
With skyrocketing for power battery preparation process middle and upper reaches material price, industry by sight turn to waste and old power battery this On seat " invisible mine ".It was predicted that 2,500,000,000 will be generated to the year two thousand twenty China, about 520,000 tons of waste and old new energy resource power batteries, Waste and old power battery by can at least provide 50% raw material supply.Meanwhile new energy resource power battery as waste electric products Dangerous waste is set to by each country, battery various pieces have potential hazard, if dealt with improperly, it can be to environment and the mankind Health causes serial injury.Therefore, either economically or for environmental protection above, it is necessary to carry out new energy resource power battery money Source comprehensively utilizes work.
Currently, lithium ion secondary battery recovery process is divided into: soda acid dissolve lixiviation process, chemical precipitation method and salting out method, from Sub- exchange process, extraction and electrodeposition process.Domestic and international waste lithium cell recycling research is most of about bodies such as cobalt acid lithium and ternarys System etc. more valuable lithium ion secondary battery, and ferric phosphate lithium cell because recycle economic value less due to study it is less.
Patent CN200710076890.4 (a kind of comprehensive recovering process of positive pole waste tablet from ferric phosphate lithium cell), patent A kind of regeneration method of iron phosphate lithium positive pole waste material of CN200710077245.4(), a kind of LiFePO4 of patent CN10138441A( The comprehensive recovering process of anode waste paper) a kind of regeneration method of iron phosphate lithium positive pole waste material of patent CN10394015A(), specially A kind of sharp recovery method of lithium iron phosphate anode material from lithium ionic cell waste of 200710129898.2(), patent CN A kind of recovery method of lithium iron phosphate anode material from lithium ionic cell waste of 101359756A() will produce in be collected into Positive waste paper or useless powder etc. are crushed, subsequently heat-treated to remove the simple process such as most conductive agent and binder, are obtained The ground obtained iron phosphate lithium positive pole reclaimed materials of positive electrode.Above-mentioned 6 patents are recovered as full pyrogenic process recycling.
A kind of method of waste lithium iron phosphate battery synthetical recovery of other patents such as CN101847763A(), patent The method of CN101916889A(preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery), CN102208707A(it is a kind of The method of positive material of waste lithium iron phosphate reparative regeneration), a kind of patent 201010148325.6(waste lithium iron phosphate electricity The method of pond synthetical recovery) etc. or Whote-wet method or wet process+pyrogenic attack obtain LiFePO4 product or prepare the electricity of LiFePO4 Pond material, this method long flow path, processing cost is relatively high, there are different degrees of " three wastes ".Therefore, recycling at present LiFePO4The method of lithium ion cell positive is using low with economic value, it is difficult to practical to promote.
The patent of invention that number of patent application is 201310105716.3 discloses a kind of mix acid liquor infusion method recycling phosphoric acid The method of iron lithium old and useless battery cathode waste paper copper foil.This method first removes lithium iron phosphate battery negative electrode, and adds at a certain temperature It after hot a period of time, is dissolved and is impregnated with mix acid liquor, cathode waste paper is separated with copper foil, and copper foil is isolated in cleaning, which is one The convenient and simple effective method of kind, and realize that soda acid recycles and reuses, and avoids the recycling method that usual manner is cumbersome well, But there is no the effective recycling for realizing lithium for the invention.
Therefore, how to find a kind of effectively LiFePO4 is given up and powder synthetical recovery and prepare the side of battery-level lithium carbonate Method realizes that valuable element phosphorus, iron and lithium recycle entirely in LiFePO4, by the separation of effective impurity, reduces raw and auxiliary material consumption, The rate of recovery of LiFePO4 is improved, guarantees lithium carbonate, ferric phosphate and the quality of sodium sulphate product and the rate of recovery of P, Fe and Li is Need the problem further explored.
Summary of the invention
It is an object of the invention to for the deficiencies of the prior art, provide a kind of synthetical recovery side of useless powder of LiFePO4 Method.
The technical scheme is that
A kind of comprehensive recovering process of the useless powder of LiFePO4, which comprises the following steps:
Step A, oxidizing roasting: the LiFePO4 powder that gives up is put into roaster, is roasted under the atmospheric condition of air or oxygen It burns, 150-250 DEG C of temperature, time 90-150 minute, calcining after being activated.
Step B, sour regurgitation leach: after the resulting activation of step A calcining carry out sour regurgitation leaching, liquid-solid ratio by quality ratio, Its accounting be 2.5:1-4:1,75-90 DEG C of extraction temperature, extraction time 3-5 hours, terminal pH 2.5-4.0, the addition side of sulfuric acid Formula keeps process pH between 3-4 using being slowly added dropwise, and leaches terminal and is separated by filtration to obtain leached mud and leachate；Leachate Middle Li+When content is less than 16g/L, calcining leaching, Li in leachate are returned+Content enters subsequent processing when being 16-21g/L.
Step C, purification removes phosphate radical: the 1.1- of the theoretical amount of ferric phosphate precipitating being added in the resulting leachate of step B 1.2 times of Fe2+, and it is slowly added to oxidant, purification is 55-70 DEG C except the temperature of phosphate radical, and the clarification time is 3-5 hours, only Neutralizer is added in change process, and terminal pH is 3.5-5.0, filters to obtain scavenging solution.
Step D, removing calcium and magnesium: the resulting scavenging solution of step C is subjected to removing calcium and magnesium, temperature is 50-60 DEG C, clarification time 1- 2 hours, neutralizer tune pH to 7-9 is first used, 3-5g/L soda ash is added, is separated by filtration to obtain deliming magnesium liquid.
Step E, it synthesizes: by step D resulting deliming magnesium liquid sodium hydroxide tune pH to 12-13, being warming up to 98-105 DEG C, Sodium carbonate is added by 1.05-1.15 times of theoretical amount, in reaction time 3-5 hour, battery-level lithium carbonate and conjunction is obtained by filtration in terminal At rear liquid.
Step F, sodium sulphate synthesizes: by liquid sulfuric acid tune pH to 2-3 after the resulting synthesis of step E, then it is anti-with sodium hydroxide PH to 6.5-7.5 is adjusted, condensing crystallizing obtains liquid after sodium sulphate and crystallization, and liquid returns removing calcium and magnesium process after crystallization.
As a further refinement of the present invention, the LiFePO4 in the step A gives up, powder carries out in roasting process It stirs, 5-10 revs/min, is sufficiently mixed it with oxygen.
As a further refinement of the present invention, being added dropwise at the extraction time residue in the step B 30-40 minutes 20-30mL oxidant hydrogen peroxide, leached mud are recycled with phosphoric acid iron product.
As a further refinement of the present invention, the oxidant in the step C is the dioxygen for not bringing new impurity into Water, neutralizer refer to sodium hydroxide.
As a further refinement of the present invention, the neutralizer in the step D is sodium hydroxide.
Key reaction principle of the invention and its chemical equation are as follows:
Oxidizing roasting is to play activation Li immersion Zn while making oxidant using oxygen, to the ferrous iron in LiFePO4 into Row oxidation, reaction equation are as follows:
12LiFePO4+3O2= 4Li3Fe2(PO4)3+2Fe2O3………………………………(1)
Other reaction equation has:
2Li3Fe2(PO4)3+Fe2O3+3H2SO4=3Li2SO4+6FePO4↓+3H2O………………(2)
2H++2PO4 3-+2Fe2++H2O2=2FePO4↓+2H2O………………………………(3)
Ca2++CO3 2-=CaCO3↓……………………………………………...………(4)
Mg2++2OH-=2Mg(OH)2↓…………………………………………………(5)
2Li++CO3 2-=Li2CO3↓……………………………………………...………(6)
CO3 2-+2H-=H2O+CO2↑……………………………………………………(7)
2Na++SO4 2-=Na2SO4↓……………………………………………………(8)
The present invention at different temperatures to LiFePO4 give up powder carry out direct oxidation roasting, change LiFePO4 chemistry knot Structure gives up shown in powder calcining SEM and XRD testing result Fig. 1 and Fig. 2 to LiFePO4 under different maturing temperatures.
As shown in Figure 1, from the SEM of calcining detection in it follows that with maturing temperature rising, calcining The trend risen is presented in granularity.When 200 DEG C of roastings, the partial size of LiFePO4 calcining is in 30nm or so；And it is roasted to 750 DEG C When, the partial size of LiFePO4 calcining has increased to 60~80nm, and there are also certain sintering phenomenons.
As shown in Figure 2, the peak type of sample xrd diffraction curve and iron oxide and LiFePO4 standard card (PDF#73-2234, PDF#80-1517) completely the same, illustrate sample for the two mixture, in addition, in the calcining such as figure that roast out under the high temperature conditions Contain weaker unknown peak at the triangle mark of 7-4-4,7-4-5 and 7-4-6, illustrates to generate a small amount of ferroso-ferric oxide miscellaneous Matter.As maturing temperature increases, the sample that the sample roasted out from 150-250 DEG C roasts out to 750 DEG C, xrd diffraction curve Peak intensity gradually increases, and illustrates that the crystallinity of iron oxide and LiFePO4 is higher and higher in material, namely have opposite sintering phenomenon；Together When also illustrate that the 150-250 DEG C of sample roasted out is completely un-sintered.
Ferric phosphate (III) lithium after 150-250 DEG C of calcination activation, under conditions of sour regurgitation leaches, Li sulfuric acid easily generated Lithium, the leaching rate of Li are more than 98%, and phosphate radical and iron generate phosphoric acid iron product；Meanwhile as maturing temperature increases, the leaching of Li Extracting rate also reduces, and when arriving sample 7-4-4, the leaching rate of Li is 62.5%, also demonstrates the SEM figure and XRD of calcining in turn in fact Diffraction pattern.
According to the solubility of lithium carbonate and temperature curve figure it is found that the synthesis of lithium carbonate selects 98-105 DEG C, optimization It is 101-105 DEG C, ensure that the direct yield of Li 90% or more；Simultaneously with this condition, other impurity Ca, Mg etc. are improved The solubility of carbonate optimizes product lithium carbonate quality, battery-level lithium carbonate product can be obtained.Liquid is dense by evaporating after synthesis Contracting, obtains sodium sulphate product, solution containing Li returns removing calcium and magnesium process, and the rate of recovery of Li is up to 97%, while phosphoric acid and iron are with ferric phosphate Form is recycled, and the rate of recovery is up to 98%.
Make sodium carbonate as precipitating reagent imurity-removal calcium in the present invention in deliming, in synthesis using sodium carbonate as conjunction At agent, lithium carbonate product is generated, this is also the dissolution properties for taking full advantage of calcium carbonate and lithium carbonate: calcium carbonate is with temperature It increases, solubility rises, and lithium carbonate is then the solubility decline as temperature increases.
The beneficial effects of the present invention are:
1, recycle object of the invention is that LiFePO4 gives up powder, in useless powder impurity content and granularity etc. without particular/special requirement, because , to the recycling of LiFePO4 without dead angle, yield is big, has saved resource for this, has prevented pollution of the LiFePO4 to environment.
2, the present invention simply directly aoxidizes iron, reduces hydrogen peroxide in sour regurgitation leaching process by oxidizing roasting Consumption；Lithium is activated, and be ensure that the high leaching rate of Li and the purity of product ferric phosphate, has been recycled ferric phosphate to the maximum extent Valuable element phosphorus, iron and lithium in the useless powder of lithium；It is leached by the sour regurgitation of calcining, it is molten to ensure that Li is leached into greatest extent Liquid.
3, the synthetical recovery of lithium iron phosphate positive material has rational technology, low manufacture cost, pollution-free, nonhazardous etc. excellent Point, product battery-level lithium carbonate can be used for preparing lithium battery raw material, and product ferric phosphate can meet preparation lithium iron phosphate cell material It is required that and by-product sodium sulphate can do chemical products take-away, therefore application prospect is boundless.
Detailed description of the invention
Fig. 1 is the useless powder calcining SEM figure of LiFePO4 under different maturing temperatures.
Fig. 2 is the useless powder calcining XRD diffraction pattern of LiFePO4 under different maturing temperatures.
Fig. 3 is process flow chart of the invention.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with Embodiment, invention is further described in detail.It should be appreciated that specific embodiment described herein is used only for explaining this Invention, is not intended to limit the present invention, and the present invention includes other embodiment and and its deformation within the scope of its technical idea.
In the present invention, the separating step of useless pole piece or iron phosphate lithium positive pole piece is increased sometimes according to material difference, or is subtracted Screening and magnetic deironing are lacked, or have increased the destruction step of LiFePO4, but as long as typical process flow is constant, then The present invention can also apply.
The embodiment of the invention provides a kind of comprehensive recovering process of the useless powder of LiFePO4, process flow chart please refers to figure 3。
Below by specific embodiment, invention is further explained.
Embodiment 1
Step A, oxidizing roasting: the useless powder of 15 kg of phosphoric acid iron lithiums is put into roaster, is roasted in air, temperature 150 DEG C, the time 150 minutes, calcining after being activated.
Step B, sour regurgitation leaches: liquid-solid ratio 2.5:1, and 90 DEG C of temperature, the time 5 hours, sulfuric acid was added dropwise in terminal pH=4.0, Process pH=3 obtain leached mud, Li in leachate+Content is 21g/L.
Step C, purification removes phosphate radical: 1.1 times of Fe of the theoretical amount of ferric phosphate precipitating being added in leachate2+, and delay Slow that oxidant is added, temperature 70 C, the time 3 hours, neutralizer was added in process, and scavenging solution is filtered to obtain in terminal pH=5.0.Wherein, For oxidant preferentially using the hydrogen peroxide for not bringing new impurity into, neutralizer preferentially uses sodium hydroxide.
Step D, removing calcium and magnesium: temperature 50 C, time 2 h first use neutralizer tune pH=9, add 3g/L soda ash, mistake Filter separates to obtain deliming magnesium liquid；Wherein, neutralizer preferentially uses sodium hydroxide.
Step E, it synthesizes: by deliming magnesium liquid sodium hydroxide tune pH=13,98 DEG C of temperature, by the 1.15 of removing calcium and magnesium theoretical amount Sodium carbonate is added again, the time 5 hours, liquid after battery-level lithium carbonate and synthesis is obtained by filtration.
Step F, sodium sulphate synthesizes: demodulating pH=6.5, concentration knot by sulfuric acid tune pH=3 of liquid after synthesis, then with sodium hydroxide Crystalline substance obtains liquid after sodium sulphate and crystallization, and liquid returns removing calcium and magnesium process after crystallization.
It is given up the synthetical recovery of powder by LiFePO4, obtains battery-level lithium carbonate, ferric phosphate and sodium sulphate product, Li's is straight Yield is 93.6%, the rate of recovery 98.5%；The rate of recovery of phosphate radical and iron is 99.1%, while sulfate radical and sodium are also with sodium sulphate Mode recycles.
Embodiment 2
Step A, oxidizing roasting: being put into 15 kg of phosphoric acid iron lithiums useless powder in roaster, roasted under Oxygen Condition, and T= 250 DEG C, t=90 minute, calcining after being activated.
Step B, sour regurgitation leaches: the liquid-solid ratio (counting in mass ratio) of sour regurgitation leachate and calcining is 4:1, T=75 DEG C, and t=3 are small When, terminal pH=2.5 between process pH=4, leach terminal and are separated by filtration to obtain leached mud and leachate；Leached mud is obtained, is soaked Li content is 16g/L in liquid out.
Step C, purification removes phosphate radical: 1.2 times of Fe of the theoretical amount of ferric phosphate precipitating being added in leachate2+, and delay Slow to be added oxidant, neutralizer is added in purification process in T=55 DEG C, t=5 hour, and scavenging solution is filtered to obtain in terminal pH=3.5.
Step D, removing calcium and magnesium: T=60 DEG C, t=1 hour first use neutralizer tune pH to 7, add 5g/L soda ash, filtering point From deliming magnesium liquid.
Step E, it synthesizes: by deliming magnesium liquid sodium hydroxide tune pH to 12, T=105 DEG C, by the theoretical amount of removing calcium and magnesium 1.05 times of addition sodium carbonate, the reaction time 3 hours, liquid after battery-level lithium carbonate and synthesis was obtained by filtration in terminal.
Step F, sodium sulphate synthesize: by liquid after synthesis with sulfuric acid tune pH to 2, then with sodium hydroxide demodulate pH to 7.5, concentration Crystallization obtains liquid after sodium sulphate and crystallization, and liquid returns removing calcium and magnesium process after crystallization.
It is given up the synthetical recovery of powder by LiFePO4, obtains battery-level lithium carbonate, ferric phosphate and sodium sulphate product, Li's is straight Yield is 94.2%, the rate of recovery 98.9%；The rate of recovery of phosphate radical and iron is 99.3%, while sulfate radical and sodium are also with sodium sulphate Mode recycles.
Embodiment 3
Step A, oxidizing roasting: being put into 15 kg of phosphoric acid iron lithiums useless powder in roaster, roasted under air conditions, and T= 180 DEG C, t=120 minute, calcining after being activated.
Step B, sour regurgitation leaches: sulfuric acid, mistake is slowly added dropwise in liquid-solid ratio 3:1, T=80 DEG C, t=4 hour, terminal pH=3.0 Journey pH=3.5 leach terminal and are separated by filtration to obtain leached mud and leachate；Leached mud is obtained, Li content is 19g/L in leachate.
Step C, purification removes phosphate radical: 1.15 times of Fe of the theoretical amount of ferric phosphate precipitating being added in leachate2+, and delay Slow that oxidant is added, T=60 DEG C, t=4 hour, process addition neutralizer, scavenging solution is filtered to obtain in terminal pH=4.0.
Step D, removing calcium and magnesium: T=55 DEG C, t=1.5 hour first use neutralizer tune pH=8, add 4g/L soda ash, filter Separate to obtain deliming magnesium liquid.
Step E, it synthesizes: by deliming magnesium liquid sodium hydroxide tune pH to 12.5, T=104 DEG C, by 1.1 times of additions of theoretical amount Liquid after battery-level lithium carbonate and synthesis is obtained by filtration in sodium carbonate, t=4 hour, terminal.
Step F, sodium sulphate synthesize: by liquid after synthesis with sulfuric acid tune pH to 2.5, then with sodium hydroxide demodulate pH to 7.0, it is dense Sheepshank crystalline substance obtains liquid after sodium sulphate and crystallization, and liquid returns removing calcium and magnesium process after crystallization.
It is given up the synthetical recovery of powder by LiFePO4, obtains battery-level lithium carbonate, ferric phosphate and sodium sulphate product, Li's is straight Yield is 94.3%, the rate of recovery 99.1%；The rate of recovery of phosphate radical and iron is 99.4%, while sulfate radical and sodium are also with sodium sulphate Mode recycles.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (7)

  1. The comprehensive recovering process of powder 1. a kind of LiFePO4 gives up, which comprises the following steps:
    A, oxidizing roasting: being put into the LiFePO4 powder that gives up in roaster, roasted under the atmospheric condition of air or oxygen, temperature 150-250 DEG C of degree, time 90-150 minute, calcining after being activated；
    B, sour regurgitation leaches: calcining after the resulting activation of step A being carried out sour regurgitation leaching, liquid-solid ratio is calculated as 2.5:1- in mass ratio 4:1,75-90 DEG C of extraction temperature, extraction time 3-5 hours, terminal pH 2.5-4.0, the adding manner of sulfuric acid, which uses, slowly dripped Add, keep process pH between 3-4, leaches terminal and be separated by filtration to obtain leached mud and leachate；Li in leachate+Content is less than When 16g/L, calcining leaching, Li in leachate are returned+Content enters subsequent processing when being 16-21g/L；
    C, purification removes phosphate radical: Fe is added in the resulting leachate of step B2+, and it is slowly added to oxidant, purification removes phosphate radical Temperature be 55-70 DEG C, the clarification time is 3-5 hour, and process addition neutralizer, terminal pH 3.5-5.0 filters to obtain scavenging solution；
    D, removing calcium and magnesium: the resulting scavenging solution of step C is subjected to removing calcium and magnesium, temperature is 50-60 DEG C, and the clarification time is 1-2 hours, first Using neutralizer tune pH to 7-9,3-5g/L soda ash is added, is separated by filtration to obtain deliming magnesium liquid；
    E, it synthesizes: by step D resulting deliming magnesium liquid sodium hydroxide tune pH to 12-13, being warming up to 98-105 DEG C, carbonic acid is added Liquid after battery-level lithium carbonate and synthesis is obtained by filtration in sodium, reaction time 3-5 hour, terminal；
    F, sodium sulphate synthesizes: by liquid sulfuric acid tune pH to 2-3 after the resulting synthesis of step E, then demodulating pH with sodium hydroxide and arrives 6.5-7.5, condensing crystallizing obtain liquid after sodium sulphate and crystallization, and liquid returns removing calcium and magnesium process after crystallization.
  2. The comprehensive recovering process of powder 2. a kind of LiFePO4 according to claim 1 gives up, it is characterised in that: the step The useless powder of LiFePO4 in A is stirred in roasting process, 5-10 revs/min, is sufficiently mixed it with oxygen.
  3. The comprehensive recovering process of powder 3. a kind of LiFePO4 according to claim 1 gives up, it is characterised in that: the step At the extraction time residue in B 30-40 minutes, 20-30mL oxidant hydrogen peroxide is added dropwise, leached mud is returned with phosphoric acid iron product It receives.
  4. The comprehensive recovering process of powder 4. a kind of LiFePO4 according to claim 1 gives up, it is characterised in that: the step Oxidant in C is hydrogen peroxide, and neutralizer is sodium hydroxide.
  5. The comprehensive recovering process of powder 5. a kind of LiFePO4 according to claim 1 gives up, it is characterised in that: the step Neutralizer in D is sodium hydroxide.
  6. The comprehensive recovering process of powder 6. a kind of LiFePO4 according to claim 1 gives up, it is characterised in that: in step B institute Fe is added in the leachate obtained2+Quality be 1.1-1.2 times of Theoretical Mass of ferric phosphate precipitating.
  7. The comprehensive recovering process of powder 7. a kind of LiFePO4 according to claim 1 gives up, it is characterised in that: will be in step D The quality that sodium carbonate is added is 1.05-1.15 times of removing calcium and magnesium Theoretical Mass.
CN201810887736.3A 2018-08-06 2018-08-06 Comprehensive recovery method of waste lithium iron phosphate powder Active CN109095481B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626350A (en) * 2019-02-25 2019-04-16 中钢集团南京新材料研究院有限公司 A kind of method that waste lithium iron phosphate battery positive plate prepares battery-grade iron phosphate
CN110040751A (en) * 2019-05-13 2019-07-23 中国科学院过程工程研究所 A kind of recycling processing method of the shraff containing lithium
CN110294466A (en) * 2019-08-19 2019-10-01 四川轻化工大学 A kind of preparation method of nano-sheet ferric phosphate
CN110980776A (en) * 2019-12-03 2020-04-10 四川致远锂业有限公司 High-efficiency aluminum removal method for lithium salt production
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
CN115611252A (en) * 2021-07-16 2023-01-17 中国科学院过程工程研究所 Method for recycling iron phosphate and lithium carbonate from waste lithium iron phosphate positive electrode material
CN115716653A (en) * 2022-11-23 2023-02-28 郴州金铖环保科技有限公司 Method for rapidly and directionally leaching lithium from lithium iron phosphate waste
WO2023123621A1 (en) * 2021-12-29 2023-07-06 荆门市格林美新材料有限公司 Method for preparing battery material by using nickel-iron alloy

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848469A (en) * 2017-02-24 2017-06-13 中南大学 A kind of method that valuable metal is reclaimed in the material from waste lithium ion cell anode
CN107017443A (en) * 2017-03-28 2017-08-04 北京科技大学 A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery
CN107381604A (en) * 2017-07-12 2017-11-24 深圳佳彬科技有限公司 A kind of method that lithium carbonate is reclaimed from ferric phosphate lithium cell
CN108178170A (en) * 2017-12-27 2018-06-19 江西赣锋循环科技有限公司 It is a kind of that the method that lithium prepares battery-level lithium carbonate is recycled from lithium iron phosphate waste
CN108264068A (en) * 2018-03-14 2018-07-10 中国科学院过程工程研究所 A kind of method for recycling lithium in waste material containing lithium battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106848469A (en) * 2017-02-24 2017-06-13 中南大学 A kind of method that valuable metal is reclaimed in the material from waste lithium ion cell anode
CN107017443A (en) * 2017-03-28 2017-08-04 北京科技大学 A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery
CN107381604A (en) * 2017-07-12 2017-11-24 深圳佳彬科技有限公司 A kind of method that lithium carbonate is reclaimed from ferric phosphate lithium cell
CN108178170A (en) * 2017-12-27 2018-06-19 江西赣锋循环科技有限公司 It is a kind of that the method that lithium prepares battery-level lithium carbonate is recycled from lithium iron phosphate waste
CN108264068A (en) * 2018-03-14 2018-07-10 中国科学院过程工程研究所 A kind of method for recycling lithium in waste material containing lithium battery

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626350A (en) * 2019-02-25 2019-04-16 中钢集团南京新材料研究院有限公司 A kind of method that waste lithium iron phosphate battery positive plate prepares battery-grade iron phosphate
CN110040751A (en) * 2019-05-13 2019-07-23 中国科学院过程工程研究所 A kind of recycling processing method of the shraff containing lithium
CN110294466A (en) * 2019-08-19 2019-10-01 四川轻化工大学 A kind of preparation method of nano-sheet ferric phosphate
CN110294466B (en) * 2019-08-19 2020-11-17 四川轻化工大学 Preparation method of nano flaky iron phosphate
CN110980776A (en) * 2019-12-03 2020-04-10 四川致远锂业有限公司 High-efficiency aluminum removal method for lithium salt production
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
CN112626357B (en) * 2020-12-14 2022-09-27 赣州有色冶金研究所有限公司 Method for extracting lithium from waste lithium iron phosphate powder
CN115611252A (en) * 2021-07-16 2023-01-17 中国科学院过程工程研究所 Method for recycling iron phosphate and lithium carbonate from waste lithium iron phosphate positive electrode material
CN115611252B (en) * 2021-07-16 2024-03-01 中国科学院过程工程研究所 Method for recycling ferric phosphate and lithium carbonate from waste lithium iron phosphate anode material
WO2023123621A1 (en) * 2021-12-29 2023-07-06 荆门市格林美新材料有限公司 Method for preparing battery material by using nickel-iron alloy
CN115716653A (en) * 2022-11-23 2023-02-28 郴州金铖环保科技有限公司 Method for rapidly and directionally leaching lithium from lithium iron phosphate waste

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