CN107857244A - A kind of recycling treatment process of LiFePO4 waste material - Google Patents
A kind of recycling treatment process of LiFePO4 waste material Download PDFInfo
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- CN107857244A CN107857244A CN201711292205.1A CN201711292205A CN107857244A CN 107857244 A CN107857244 A CN 107857244A CN 201711292205 A CN201711292205 A CN 201711292205A CN 107857244 A CN107857244 A CN 107857244A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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Abstract
The invention discloses a kind of recycling treatment process of LiFePO4 waste material.LiFePO4 waste material alkali soluble is obtained to contain aluminum solutions and the first filter residue；Hydrogen peroxide oxidation is added after first filter residue acid is molten to precipitate to obtain ferric phosphate, urea precipitation is added after iron removaling again and obtains rough lithium carbonate, rough lithium carbonate is added into water slurry, water is heated under vacuo to seethe with excitement completely, then reacted 23 hours under the conditions of boiling, then filter, obtain the mixed solution of magnesium carbonate filter residue and lithium hydroxide and lithia, CO is passed through at being 90 95 DEG C in temperature by the mixed solution of lithium hydroxide and lithia2, pH is 9 9.5 to terminal for reaction, obtains battery-level lithium carbonate.Present invention process is simple, and cost is low, and technological process is short, and can obtain the ferric phosphate of LITHIUM BATTERY and the lithium carbonate of LITHIUM BATTERY, realizes the recovery of full constituent, and the added value of product that recovery obtains is high, is the raw material of LiFePO4, and the rate of recovery of each component is high.
Description
Technical field
The present invention relates to a kind of recycling treatment process of LiFePO4 waste material, belong to recycling economy technical field.
Background technology
LiFePO4 (molecular formula：LiFePO4；English：Lithiumironphosphate；Also known as iron lithium phosphate, lithium iron
Phosphorus；Abbreviation LFP), it is a kind of positive electrode of lithium ion battery.The NTT Japanese from 1996 discloses AyMPO4 first, and (A is alkali
Metal, M are both CoFe combination：LiFeCOPO4 after the anode material of lithium battery of olivine structural), the U.S. in 1997
It is de- that the research group such as state university John.B.Goodenough in Texas has also then reported reversibly moving into for LiFePO4
Go out the characteristic of lithium, the U.S. coincidentally delivers olivine structural (LiMPO4) with Japan so that the material receives greatly
Pay attention to, and cause extensive research and rapidly development.With traditional lithium ion secondary battery anode material, spinel structure
LiMn2O4 compares with the LiCoO2 of layer structure, LiMPO4 raw material source more extensively, price it is less expensive and dirty without environment
Dye.
The application field of LiFePO4 mainly has：
(1) energy storage device
The energy storage device of solar energy, wind generator system, UPS UPS, solar cell is coordinated to use as storage
Can equipment (BYD is producing such battery)；
(2) electric tool class
High power electric tool (wireless), electric drill, weeder etc.；
(3) lightweight electric powered vehicles
Electric motor car, electric bicycle, recreation vehicle, golf cart, electric lift truck, clean car, hybrid vehicle
(HEV), recent 2-3 target；
(4) mini-plant
Medical Devices：Electric wheel-chair vehicle, electric bicycle), toy (Romoto-control electric aeroplane, car, ship)；
(5) other compact electric apparatus
Mine lamp, the medicine equipment (LiFePO4 is non-toxic, and lithium battery only iron lithium can meet to require) of implantable, substitutes lead
Acid, ni-mh, NI-G, lithium cobalt, application of the lithium manganese class battery on compact electric apparatus.
(6) portable power source
German New Energy Corporation Deboch has successfully researched and developed with volume production the ferric phosphate of composite nano materials by studying for a long period of time
Lithium battery, unit capacity ratio is improved, overcome that LiFePO4 unit volume is excessive, be not suitable for the difficulty in digital product field
Topic.Present single-unit 32650 (diameter 32mm, length 65mm) size battery cell, capacity break through 6000mAh, are arranged in pairs or groups by two sections, with regard to energy
Reach 12000mAh.Portable power source energy is up to 38.4Wh, it is sufficient to and the iPhone4S to 5.3Wh (1432mAh) charges nearly 6 times,
It is adapted to the user of long-distance outdoor travel.
But with the development of electric automobile, the LiFePO4 in old and useless battery and production process that LiFePO4 is scrapped
The recycling of waste material turns into everybody focus of attention, and the recovery of waste lithium iron phosphate at present mainly has following several：
(1) LiFePO4 for directly arranging in pairs or groups new after screening by waste lithium iron phosphate uses, although the method is simple,
Be arrange in pairs or groups the LiFePO4 obtained afterwards performance reduce, be only used for low side industry；
(2) after LiFePO4 is dissolved, iron precipitates to obtain iron oxide red, lithium recovery, phosphate recovery, but this technique
Long flow path, and value-added content of product is low.
The content of the invention
In view of this, the invention provides a kind of recycling treatment process of LiFePO4 waste material, technique is simple, cost
Low, technological process is short, and can obtain the ferric phosphate of LITHIUM BATTERY and the lithium carbonate of LITHIUM BATTERY, realizes the recovery of full constituent, and
It is high to reclaim obtained added value of product, is the raw material of LiFePO4, and the rate of recovery of each component is high.
The present invention solves above-mentioned technical problem by following technological means：
A kind of recycling treatment process of LiFePO4 waste material of the present invention, it is following steps：
(1) LiFePO4 waste material is added into aqueous slkali stirring and dissolving 2-3 hours at 70-85 DEG C, then filters, contained
Aluminum solutions and the first filter residue；
(2) the first filter residue is added in sulfuric acid solution, connected in 85-90 DEG C of stirring reaction 3-4 hour, while in course of reaction
Continuous at the uniform velocity to add iron powder, it is 2.0-2.5 to react to the pH of solution, then adds hydroxylamine hydrochloride and causes hydroxylamine hydrochloride in reaction system
Concentration be 0.01-0.02mol/L, then filter, obtain the first filtrate and the second filter residue；
(3) it is 50-55 DEG C, mixing speed 300-350r/min in temperature by the first filtrate, adds hydrogen peroxide, add double
The time of oxygen water is 1-1.5 hours, then heats to 90-95 DEG C and continues to stir 1-2 hours, then filters, obtain the second filtrate
With the 3rd filter residue, by the 3rd filter residue according to solid-to-liquid ratio 1:2 add pure water pulp to obtain pulp material, then prepare 4-5mol/L phosphoric acid
Solution, then the 1/4 of pulp material volume is added in phosphoric acid solution, it is 95-100 DEG C to be warming up to temperature, 500-800r/min
High-speed stirred 1-3 hours are changed into clarifying to solution, are then added thereto again by the 3/4 of remaining pulp material volume, then in temperature
For 95-100 DEG C, continue to react 1-3 hours under 500-800r/min high-speed stirreds, to material color be changed into white slightly powder after stop
Only react, then filter, obtained phosphoric acid mother liquor is collected separately, untill then the pH of pure water to washings is 6-6.5, so
Afterwards battery-grade iron phosphate is obtained by drying, iron removaling, screening；
(4) it is 80-85 DEG C in temperature by the second filtrate, the pH for adding magnesia regulation solution is 5-6, then stirring reaction
1-2 is filtered after hour, obtains filter residue and the 3rd filtrate of iron content, and the 3rd filtrate is added into urea, anti-at being 85-95 DEG C in temperature
Should, the pH for maintaining terminal is 9-9.5, filtering, obtains rough carbonic acid crystalline lithium and the 4th filtrate；
(5) the rough lithium carbonate that step (4) obtains is added into water slurry, is vacuumized in sealing reactor and maintain the pressure to be
5000-8000Pa is then heated to water and seethed with excitement completely, and 2-3 hours are then reacted under the conditions of boiling, then filters, obtains carbonic acid
The mixed solution of magnesium filter residue and lithium hydroxide and lithia, in temperature it is 90-95 by the mixed solution of lithium hydroxide and lithia
CO is passed through at DEG C2, pH is 9-9.5 to terminal for reaction, obtains battery-level lithium carbonate.
What the step (1) obtained adds neopelex and polyethylene glycol containing aluminum solutions so that in solution
The concentration of neopelex is 0.01-0.015mol/L, and the concentration of polyethylene glycol is 0.01-0.015mol/L, then
Added with aluminium chloride ammonium salt solution, acid-base modifier cocurrent in the liquid of bottom, reaction temperature is 30-35 DEG C, and bottom liquid is that pH is 9.5-10's
The mixed solution of ammonium carbonate and ammoniacal liquor, it is 9.5-10 to maintain dropwise addition process pH, and the addition time is 1-2 hours, and continuation is added dropwise
0.5-1 hours are reacted, are then filtered, filter residue is dried after washing at 80-85 DEG C, after air-flow is broken, at 950-1050 DEG C
Calcining obtains nano aluminium oxide.
Mol ratio hydroxy is 1 in aluminium and aqueous slkali in the step (1) in LiFePO4 waste material:1.05-1.1
The concentration of aqueous slkali is 0.5-1mol/L.
The mol ratio of phosphate radical is 0.05-0.1 in the iron powder and the first filter residue that are added in the step (2):1, sulfuric acid is molten
The concentration of liquid is 2.5-4mol/L, and the second filter residue for reacting to obtain returns to be continued to dissolve in the first filter residue.
The mol ratio of step (3) hydrogen peroxide and the first filtrate ferrous ions is 1.1-1.15:2, the matter of hydrogen peroxide
Amount fraction is 25-30%, and the mol ratio of iron ion is 0.3-0.35 in the phosphoric acid and the 3rd filter residue in the phosphoric acid solution of addition:1.
The phosphoric acid mother liquor obtained in the step (3) is continuing with by being concentrated into concentration to be returned after 4-5mol/L.
The mol ratio of lithium ion is 4-5 in urea and the 3rd filtrate in the step (4):1, the 4th filtrate and the 3rd
Continue to react after filtrate mixing, the lithium ion content into the 4th filtrate is less than outer row after 100ppm.
Magnesium carbonate filter residue in the step (5), which returns to mix with the first filter residue, to be continued to dissolve, the lithium in magnesium carbonate filter residue
Content is arranged less than outside 100ppm.
The present invention first dissolves aluminium by the way of alkali soluble solution, then aluminium is prepared into nano aluminium oxide, then is dissolved using acid,
Iron powder is added simultaneously, whole process is maintained and carries out under reducing atmosphere, avoid the oxidation of ferrous ion, while ferrous ion
It is somewhat excessive, the utilization rate of phosphate radical can also be improved.
The obtained dissolving coexisted for ferrous ion, phosphate radical and lithium ion is dissolved, oxidant is added and causes ferrous ion
Ferric ion is oxidized to, then is combined with phosphate radical to obtain ferric phosphate, so, you can to realize the recovery of phosphate radical, iron ion,
The separation of phosphate radical, iron ion and lithium ion is also achieved simultaneously, turn avoid lithium ion caused by producing ferric hydroxide colloid
Loss the problem of, obtained battery-grade iron phosphate compares iron oxide red etc., and added value improves, current battery level ferric phosphate
Price about per ton 2.7 ten thousand or so, and the price of iron oxide red it is per ton be only 5000 yuan or so.
Remaining iron ion, pH is adjusted using magnesia, the generation of ferric hydroxide colloid can be avoided, so as to avoid
The loss of lithium ion, then using urea come precipitation from homogeneous solution lithium ion, compare carbonate deposition, of obtained rough lithium carbonate
Grain is bigger, and crystallinity is more preferable, convenient washing, avoids the entrainment of other ions, purity is higher.
Lithium carbonate is boiled using boiling under vacuum again again, while under vacuum condition so that lithium carbonate decomposes generation oxygen faster
Change lithium and carbon dioxide, carbon dioxide are pumped immediately, so as to accelerate the decomposition of lithium carbonate, obtained lithia can dissolve
Into water, simultaneous oxidation lithium and water, which react to obtain lithium hydroxide, can also be dissolved into water, and magnesium carbonate can not then be decomposed, then will
Carbon dioxide is passed through under pure lithium hydroxide and the mixed solution of lithia, then high temperature, lithium carbonate can be obtained with a step, obtained
Lithium carbonate narrow particle size distribution, purity is high.
The nano-aluminium oxide product index finally given is as follows：
| Index | Alundum (Al2O3) | Primary particle size | Aggregate particle size | Reunion index |
| Numerical value | 99.9% | 15-30nm | 100-150nm | ＜ 10 |
| Index | BET | Pine dress | Tap density | Angle of repose |
| Numerical value | 200-250m2/g | 0.4-0.5g/mL | 0.9-1g/mL | 15-20° |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.3-0.6ppm | 1-2ppm | 0.8-1.2ppm | 0.9-2ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5-6ppm | 0.1-0.3ppm | 0.5-0.9ppm | 1-3ppm |
| Index | Pattern | pH | Sulfate radical | Chlorion |
| Numerical value | Ball-type | 6-8 | 1.2-1.5ppm | 1.1-1.5ppm |
The index of obtained battery-grade iron phosphate is as follows：
The index of obtained battery-level lithium carbonate is as follows：
| Index | Main content | D10 | D50 | D90 |
| Numerical value | ＞ 99.75% | 0.2-0.3μm | 0.5-0.6μm | 0.8-0.9μm |
| Index | Pb | Co | Cu | Fe |
| Numerical value | 1-1.5ppm | 0.5-1.5ppm | 0.5-1.5ppm | 2-3ppm |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.2-0.6ppm | 1-2ppm | 0.8-1.2ppm | 1.5-2ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5-6ppm | 0.1-0.3ppm | 0.5-0.9ppm | 1-3ppm |
| Index | K | P | Sulfate radical | Chlorion |
| Numerical value | 0.5-1.5ppm | 5-10ppm | 1.2-1.5ppm | 1.1-1.5ppm |
Beneficial effects of the present invention：Technique is simple, and cost is low, and technological process is short, and can obtain the ferric phosphate of LITHIUM BATTERY
With the lithium carbonate of LITHIUM BATTERY, the recovery of full constituent is realized, and the added value of product that recovery obtains is high, is the original of LiFePO4
Material, and the rate of recovery of each component is high.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the process chart of the present invention.
Embodiment
Below with reference to accompanying drawing, the present invention is described in detail, as shown in Figure 1：A kind of LiFePO4 of the present embodiment gives up
The recycling treatment process of material, it is following steps：
(1) LiFePO4 waste material is added into aqueous slkali stirring and dissolving 2-3 hours at 70-85 DEG C, then filters, contained
Aluminum solutions and the first filter residue；
(2) the first filter residue is added in sulfuric acid solution, connected in 85-90 DEG C of stirring reaction 3-4 hour, while in course of reaction
Continuous at the uniform velocity to add iron powder, it is 2.0-2.5 to react to the pH of solution, then adds hydroxylamine hydrochloride and causes hydroxylamine hydrochloride in reaction system
Concentration be 0.01-0.02mol/L, then filter, obtain the first filtrate and the second filter residue；
(3) it is 50-55 DEG C, mixing speed 300-350r/min in temperature by the first filtrate, adds hydrogen peroxide, add double
The time of oxygen water is 1-1.5 hours, then heats to 90-95 DEG C and continues to stir 1-2 hours, then filters, obtain the second filtrate
With the 3rd filter residue, by the 3rd filter residue according to solid-to-liquid ratio 1:2 add pure water pulp to obtain pulp material, then prepare 4-5mol/L phosphoric acid
Solution, then the 1/4 of pulp material volume is added in phosphoric acid solution, it is 95-100 DEG C to be warming up to temperature, 500-800r/min
High-speed stirred 1-3 hours are changed into clarifying to solution, are then added thereto again by the 3/4 of remaining pulp material volume, then in temperature
For 95-100 DEG C, continue to react 1-3 hours under 500-800r/min high-speed stirreds, to material color be changed into white slightly powder after stop
Only react, then filter, obtained phosphoric acid mother liquor is collected separately, untill then the pH of pure water to washings is 6-6.5, so
Afterwards battery-grade iron phosphate is obtained by drying, iron removaling, screening；
(4) it is 80-85 DEG C in temperature by the second filtrate, the pH for adding magnesia regulation solution is 5-6, then stirring reaction
1-2 is filtered after hour, obtains filter residue and the 3rd filtrate of iron content, and the 3rd filtrate is added into urea, anti-at being 85-95 DEG C in temperature
Should, the pH for maintaining terminal is 9-9.5, filtering, obtains rough carbonic acid crystalline lithium and the 4th filtrate；
(5) the rough lithium carbonate that step (4) obtains is added into water slurry, is vacuumized in sealing reactor and maintain the pressure to be
5000-8000Pa is then heated to water and seethed with excitement completely, and 2-3 hours are then reacted under the conditions of boiling, then filters, obtains carbonic acid
The mixed solution of magnesium filter residue and lithium hydroxide and lithia, in temperature it is 90-95 by the mixed solution of lithium hydroxide and lithia
CO is passed through at DEG C2, pH is 9-9.5 to terminal for reaction, obtains battery-level lithium carbonate.
What the step (1) obtained adds neopelex and polyethylene glycol containing aluminum solutions so that in solution
The concentration of neopelex is 0.01-0.015mol/L, and the concentration of polyethylene glycol is 0.01-0.015mol/L, then
Added with aluminium chloride ammonium salt solution, acid-base modifier cocurrent in the liquid of bottom, reaction temperature is 30-35 DEG C, and bottom liquid is that pH is 9.5-10's
The mixed solution of ammonium carbonate and ammoniacal liquor, it is 9.5-10 to maintain dropwise addition process pH, and the addition time is 1-2 hours, and continuation is added dropwise
0.5-1 hours are reacted, are then filtered, filter residue is dried after washing at 80-85 DEG C, after air-flow is broken, at 950-1050 DEG C
Calcining obtains nano aluminium oxide.
Mol ratio hydroxy is 1 in aluminium and aqueous slkali in the step (1) in LiFePO4 waste material:1.05-1.1
The concentration of aqueous slkali is 0.5-1mol/L.
The mol ratio of phosphate radical is 0.05-0.1 in the iron powder and the first filter residue that are added in the step (2):1, sulfuric acid is molten
The concentration of liquid is 2.5-4mol/L, and the second filter residue for reacting to obtain returns to be continued to dissolve in the first filter residue.
The mol ratio of step (3) hydrogen peroxide and the first filtrate ferrous ions is 1.1-1.15:2, the matter of hydrogen peroxide
Amount fraction is 25-30%, and the mol ratio of iron ion is 0.3-0.35 in the phosphoric acid and the 3rd filter residue in the phosphoric acid solution of addition:1.
The phosphoric acid mother liquor obtained in the step (3) is continuing with by being concentrated into concentration to be returned after 4-5mol/L.
The mol ratio of lithium ion is 4-5 in urea and the 3rd filtrate in the step (4):1, the 4th filtrate and the 3rd
Continue to react after filtrate mixing, the lithium ion content into the 4th filtrate is less than outer row after 100ppm.
Magnesium carbonate filter residue in the step (5), which returns to mix with the first filter residue, to be continued to dissolve, the lithium in magnesium carbonate filter residue
Content is arranged less than outside 100ppm.
Embodiment 1
A kind of recycling treatment process of LiFePO4 waste material, it is following steps：
(1) LiFePO4 waste material is added into aqueous slkali stirring and dissolving 2.5 hours at 79 DEG C, then filters, obtain containing aluminium
Solution and the first filter residue；
(2) the first filter residue is added in sulfuric acid solution, in 88 DEG C of stirring reactions 3.5 hours, and meanwhile it is continuous in course of reaction
Iron powder is at the uniform velocity added, it is 2.3 to react to the pH of solution, then adds the concentration that hydroxylamine hydrochloride causes hydroxylamine hydrochloride in reaction system
For 0.015mol/L, then filter, obtain the first filtrate and the second filter residue；
(3) it is 53 DEG C, mixing speed 330r/min in temperature by the first filtrate, adds hydrogen peroxide, add hydrogen peroxide
Time is 1.2 hours, then heats to 93 DEG C and continues stirring 1.6 hours, then filters, obtain the second filtrate and the 3rd filter residue,
By the 3rd filter residue according to solid-to-liquid ratio 1:2 add pure water pulp to obtain pulp material, then prepare 4.5mol/L phosphoric acid solution, then will
The 1/4 of pulp material volume is added in phosphoric acid solution, is warming up to temperature as 98 DEG C, and 700r/min high-speed stirreds 1.5 hours are to molten
Liquid is changed into clarifying, and is then added thereto again by the 3/4 of remaining pulp material volume, then temperature be 98 DEG C, 700r/min at a high speed
Continue reaction 1.8 hours under stirring, the color to material is changed into stopping reaction after white omits powder, then filters, obtained phosphoric acid
Mother liquor is collected separately, and untill then the pH of pure water to washings is 6.3, then obtains battery by drying, iron removaling, screening
Level ferric phosphate；
(4) it is 81 DEG C in temperature by the second filtrate, the pH for adding magnesia regulation solution is 5.5, then stirring reaction 1.7
Filtered after hour, obtain filter residue and the 3rd filtrate of iron content, the 3rd filtrate is added into urea, reacted, tie up at being 89 DEG C in temperature
The pH for holding terminal is 9.3, filtering, obtains rough carbonic acid crystalline lithium and the 4th filtrate；
(5) the rough lithium carbonate that step (4) obtains is added into water slurry, is vacuumized in sealing reactor and maintain the pressure to be
7000Pa is then heated to water and seethed with excitement completely, then reacts 2.6 hours under the conditions of boiling, then filters, and obtains magnesium carbonate filter
The mixed solution of slag and lithium hydroxide and lithia, it is passed through at being 93 DEG C in temperature by the mixed solution of lithium hydroxide and lithia
CO2, pH is 9.25 to terminal for reaction, obtains battery-level lithium carbonate.
What the step (1) obtained adds neopelex and polyethylene glycol containing aluminum solutions so that in solution
The concentration of neopelex is 0.013mol/L, and the concentration of polyethylene glycol is 0.012mol/L, then with aluminium chloride ammonium
Solution, acid-base modifier cocurrent are added in the liquid of bottom, and reaction temperature is 33 DEG C, and bottom liquid is the mixed of the ammonium carbonate that pH is 9.8 and ammoniacal liquor
Solution is closed, it is 9.8 to maintain dropwise addition process pH, and it is 1.5 hours to add the time, is added dropwise and continues reaction 0.6 hour, then mistake
Filter, filter residue, in 83 DEG C of drying, after air-flow is broken, is calcined at 995 DEG C after washing and obtain nano aluminium oxide.
Mol ratio hydroxy is 1 in aluminium and aqueous slkali in the step (1) in LiFePO4 waste material:1.07 alkali soluble
The concentration of liquid is 0.7mol/L.
The mol ratio of phosphate radical is 0.07 in the iron powder and the first filter residue that are added in the step (2):1, sulfuric acid solution
Concentration is 2.98mol/L, and the second filter residue for reacting to obtain returns to be continued to dissolve in the first filter residue.
The mol ratio of step (3) hydrogen peroxide and the first filtrate ferrous ions is 1.13:2, the quality point of hydrogen peroxide
Number is 27.5%, and the mol ratio of iron ion is 0.33 in the phosphoric acid and the 3rd filter residue in the phosphoric acid solution of addition:1.
The phosphoric acid mother liquor obtained in the step (3) is continuing with by being concentrated into concentration to be returned after 4.7mol/L.
The mol ratio of lithium ion is 4.6 in urea and the 3rd filtrate in the step (4):1, the 4th filtrate and the 3rd
Continue to react after filtrate mixing, the lithium ion content into the 4th filtrate is less than outer row after 100ppm.
Magnesium carbonate filter residue in the step (5), which returns to mix with the first filter residue, to be continued to dissolve, the lithium in magnesium carbonate filter residue
Content is arranged less than outside 100ppm.
The nano-aluminium oxide product index finally given is as follows：
| Index | Alundum (Al2O3) | Primary particle size | Aggregate particle size | Reunion index |
| Numerical value | 99.9% | 19nm | 135nm | 7.1 |
| Index | BET | Pine dress | Tap density | Angle of repose |
| Numerical value | 230m2/g | 0.44g/mL | 0.93g/mL | 18° |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.55ppm | 1.5ppm | 0.95ppm | 1.2ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5.6ppm | 0.18ppm | 0.72ppm | 1.9ppm |
| Index | Pattern | pH | Sulfate radical | Chlorion |
| Numerical value | Ball-type | 7.1 | 1.45ppm | 1.35ppm |
The index of obtained battery-grade iron phosphate is as follows：
The index of obtained battery-level lithium carbonate is as follows：
| Index | Main content | D10 | D50 | D90 |
| Numerical value | 99.79% | 0.23μm | 0.55μm | 0.86μm |
| Index | Pb | Co | Cu | Fe |
| Numerical value | 1.3ppm | 0.8ppm | 0.9ppm | 2.1ppm |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.4ppm | 1.2ppm | 0.95ppm | 1.8ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5.5ppm | 0.3ppm | 0.8ppm | 1.8ppm |
| Index | K | P | Sulfate radical | Chlorion |
| Numerical value | 0.9ppm | 5.8ppm | 1.4ppm | 1.4ppm |
The rate of recovery of final products is as follows：
The rate of recovery 98.9% of ferric phosphate, the rate of recovery 98.2% of lithium, the rate of recovery 99.1% of aluminium.
Waste and old LiFePO4 waste material per ton, calculated with LiFePO4 content 70%, aluminium content 20%, can caused profit
Moisten for 7.5 ten thousand yuan, higher than other handling process.
Embodiment 2
A kind of recycling treatment process of LiFePO4 waste material, it is following steps：
(1) LiFePO4 waste material is added into aqueous slkali stirring and dissolving 2.5 hours at 79 DEG C, then filters, obtain containing aluminium
Solution and the first filter residue；
(2) the first filter residue is added in sulfuric acid solution, in 88 DEG C of stirring reactions 3.5 hours, and meanwhile it is continuous in course of reaction
Iron powder is at the uniform velocity added, it is 2.3 to react to the pH of solution, then adds the concentration that hydroxylamine hydrochloride causes hydroxylamine hydrochloride in reaction system
For 0.015mol/L, then filter, obtain the first filtrate and the second filter residue；
(3) it is 51 DEG C, mixing speed 330r/min in temperature by the first filtrate, adds hydrogen peroxide, add hydrogen peroxide
Time is 1.3 hours, then heats to 92 DEG C and continues stirring 1.3 hours, then filters, obtain the second filtrate and the 3rd filter residue,
By the 3rd filter residue according to solid-to-liquid ratio 1:2 add pure water pulp to obtain pulp material, then prepare 4.3mol/L phosphoric acid solution, then will
The 1/4 of pulp material volume is added in phosphoric acid solution, is warming up to temperature as 96 DEG C, and 600r/min high-speed stirred 1-3 hours are to molten
Liquid is changed into clarifying, and is then added thereto again by the 3/4 of remaining pulp material volume, then temperature be 96 DEG C, 700r/min at a high speed
Continue reaction 2.3 hours under stirring, the color to material is changed into stopping reaction after white omits powder, then filters, obtained phosphoric acid
Mother liquor is collected separately, and untill then the pH of pure water to washings is 6.3, then obtains battery by drying, iron removaling, screening
Level ferric phosphate；
(4) it is 80-85 DEG C in temperature by the second filtrate, the pH for adding magnesia regulation solution is 5.7, then stirring reaction
Filtered after 1.6 hours, obtain filter residue and the 3rd filtrate of iron content, the 3rd filtrate is added into urea, reacted at being 87 DEG C in temperature,
The pH for maintaining terminal is 9.2, filtering, obtains rough carbonic acid crystalline lithium and the 4th filtrate；
(5) the rough lithium carbonate that step (4) obtains is added into water slurry, is vacuumized in sealing reactor and maintain the pressure to be
6000Pa is then heated to water and seethed with excitement completely, then reacts 2.1 hours under the conditions of boiling, then filters, and obtains magnesium carbonate filter
The mixed solution of slag and lithium hydroxide and lithia, it is passed through at being 92 DEG C in temperature by the mixed solution of lithium hydroxide and lithia
CO2, pH is 9.3 to terminal for reaction, obtains battery-level lithium carbonate.
What the step (1) obtained adds neopelex and polyethylene glycol containing aluminum solutions so that in solution
The concentration of neopelex is 0.013mol/L, and the concentration of polyethylene glycol is 0.012mol/L, then with aluminium chloride ammonium
Solution, acid-base modifier cocurrent are added in the liquid of bottom, and reaction temperature is 33 DEG C, and bottom liquid is the mixed of the ammonium carbonate that pH is 9.8 and ammoniacal liquor
Solution is closed, it is 9.8 to maintain dropwise addition process pH, and it is 1.5 hours to add the time, is added dropwise and continues reaction 0.6 hour, then mistake
Filter, filter residue, in 83 DEG C of drying, after air-flow is broken, is calcined at 995 DEG C after washing and obtain nano aluminium oxide.
Mol ratio hydroxy is 1 in aluminium and aqueous slkali in the step (1) in LiFePO4 waste material:1.07 alkali soluble
The concentration of liquid is 0.7mol/L.
The mol ratio of phosphate radical is 0.07 in the iron powder and the first filter residue that are added in the step (2):1, sulfuric acid solution
Concentration is 2.98mol/L, and the second filter residue for reacting to obtain returns to be continued to dissolve in the first filter residue.
The mol ratio of step (3) hydrogen peroxide and the first filtrate ferrous ions is 1.13:2, the quality point of hydrogen peroxide
Number is 27.5%, and the mol ratio of iron ion is 0.33 in the phosphoric acid and the 3rd filter residue in the phosphoric acid solution of addition:1.
The phosphoric acid mother liquor obtained in the step (3) is continuing with by being concentrated into concentration to be returned after 4.7mol/L.
The mol ratio of lithium ion is 4.6 in urea and the 3rd filtrate in the step (4):1, the 4th filtrate and the 3rd
Continue to react after filtrate mixing, the lithium ion content into the 4th filtrate is less than outer row after 100ppm.
Magnesium carbonate filter residue in the step (5), which returns to mix with the first filter residue, to be continued to dissolve, the lithium in magnesium carbonate filter residue
Content is arranged less than outside 100ppm.
The nano-aluminium oxide product index finally given is as follows：
| Index | Alundum (Al2O3) | Primary particle size | Aggregate particle size | Reunion index |
| Numerical value | 99.9% | 17nm | 125nm | 7.4 |
| Index | BET | Pine dress | Tap density | Angle of repose |
| Numerical value | 230m2/g | 0.44g/mL | 0.93g/mL | 18° |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.53ppm | 1.5ppm | 0.95ppm | 1.2ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5.6ppm | 0.18ppm | 0.72ppm | 1.8ppm |
| Index | Pattern | pH | Sulfate radical | Chlorion |
| Numerical value | Ball-type | 7.1 | 1.45ppm | 1.35ppm |
The index of obtained battery-grade iron phosphate is as follows：
The index of obtained battery-level lithium carbonate is as follows：
| Index | Main content | D10 | D50 | D90 |
| Numerical value | 99.85% | 0.23μm | 0.51μm | 0.87μm |
| Index | Pb | Co | Cu | Fe |
| Numerical value | 1.3ppm | 0.8ppm | 0.9ppm | 2.1ppm |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.3ppm | 1.2ppm | 0.95ppm | 1.8ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5.5ppm | 0.3ppm | 0.8ppm | 1.8ppm |
| Index | K | P | Sulfate radical | Chlorion |
| Numerical value | 0.9ppm | 5.9ppm | 1.4ppm | 1.4ppm |
The rate of recovery of final products is as follows：
The rate of recovery 98.8% of ferric phosphate, the rate of recovery 98.1% of lithium, the rate of recovery 99.2% of aluminium.
Waste and old LiFePO4 waste material per ton, calculated with LiFePO4 content 70%, aluminium content 20%, can caused profit
Moisten for 7.5 ten thousand yuan, higher than other handling process.
Embodiment 3
A kind of recycling treatment process of LiFePO4 waste material, it is following steps：
(1) LiFePO4 waste material is added into aqueous slkali stirring and dissolving 2.5 hours at 79 DEG C, then filters, obtain containing aluminium
Solution and the first filter residue；
(2) the first filter residue is added in sulfuric acid solution, in 88 DEG C of stirring reactions 3.5 hours, and meanwhile it is continuous in course of reaction
Iron powder is at the uniform velocity added, it is 2.3 to react to the pH of solution, then adds the concentration that hydroxylamine hydrochloride causes hydroxylamine hydrochloride in reaction system
For 0.015mol/L, then filter, obtain the first filtrate and the second filter residue；
(3) it is 51 DEG C, mixing speed 330r/min in temperature by the first filtrate, adds hydrogen peroxide, add hydrogen peroxide
Time is 1.3 hours, then heats to 92 DEG C and continues stirring 1.3 hours, then filters, obtain the second filtrate and the 3rd filter residue,
By the 3rd filter residue according to solid-to-liquid ratio 1:2 add pure water pulp to obtain pulp material, then prepare 4.3mol/L phosphoric acid solution, then will
The 1/4 of pulp material volume is added in phosphoric acid solution, is warming up to temperature as 96 DEG C, and 600r/min high-speed stirred 1-3 hours are to molten
Liquid is changed into clarifying, and is then added thereto again by the 3/4 of remaining pulp material volume, then temperature be 96 DEG C, 700r/min at a high speed
Continue reaction 2.3 hours under stirring, the color to material is changed into stopping reaction after white omits powder, then filters, obtained phosphoric acid
Mother liquor is collected separately, and untill then the pH of pure water to washings is 6.3, then obtains battery by drying, iron removaling, screening
Level ferric phosphate；
(4) it is 80-85 DEG C in temperature by the second filtrate, the pH for adding magnesia regulation solution is 5.7, then stirring reaction
Filtered after 1.6 hours, obtain filter residue and the 3rd filtrate of iron content, the 3rd filtrate is added into urea, reacted at being 87 DEG C in temperature,
The pH for maintaining terminal is 9.2, filtering, obtains rough carbonic acid crystalline lithium and the 4th filtrate；
(5) the rough lithium carbonate that step (4) obtains is added into water slurry, is vacuumized in sealing reactor and maintain the pressure to be
6000Pa is then heated to water and seethed with excitement completely, then reacts 2.1 hours under the conditions of boiling, then filters, and obtains magnesium carbonate filter
The mixed solution of slag and lithium hydroxide and lithia, it is passed through at being 92 DEG C in temperature by the mixed solution of lithium hydroxide and lithia
CO2, pH is 9.3 to terminal for reaction, obtains battery-level lithium carbonate.
What the step (1) obtained adds neopelex and polyethylene glycol containing aluminum solutions so that in solution
The concentration of neopelex is 0.011mol/L, and the concentration of polyethylene glycol is 0.014mol/L, then with aluminium chloride ammonium
Solution, acid-base modifier cocurrent are added in the liquid of bottom, and reaction temperature is 31 DEG C, and bottom liquid is the mixed of the ammonium carbonate that pH is 9.6 and ammoniacal liquor
Solution is closed, it is 9.8 to maintain dropwise addition process pH, and it is 1.1 hours to add the time, is added dropwise and continues reaction 0.6 hour, then mistake
Filter, filter residue, in 83 DEG C of drying, after air-flow is broken, is calcined at 1020 DEG C after washing and obtain nano aluminium oxide.
Mol ratio hydroxy is 1 in aluminium and aqueous slkali in the step (1) in LiFePO4 waste material:1.08 alkali soluble
The concentration of liquid is 0.7mol/L.
The mol ratio of phosphate radical is 0.078 in the iron powder and the first filter residue that are added in the step (2):1, sulfuric acid solution
Concentration is 2.6mol/L, and the second filter residue for reacting to obtain returns to be continued to dissolve in the first filter residue.
The mol ratio of step (3) hydrogen peroxide and the first filtrate ferrous ions is 1.13:2, the quality point of hydrogen peroxide
Number is 28%, and the mol ratio of iron ion is 0.32 in the phosphoric acid and the 3rd filter residue in the phosphoric acid solution of addition:1.
The phosphoric acid mother liquor obtained in the step (3) is continuing with by being concentrated into concentration to be returned after 4.5mol/L.
The mol ratio of lithium ion is 4.3 in urea and the 3rd filtrate in the step (4):1, the 4th filtrate and the 3rd
Continue to react after filtrate mixing, the lithium ion content into the 4th filtrate is less than outer row after 100ppm.
The nano-aluminium oxide product index finally given is as follows：
The index of obtained battery-grade iron phosphate is as follows：
| Index | Fe | P | Quick moisture | High temperature moisture |
| Numerical value | 29.7% | 16.5% | ＜ 0.5% | 19.98% |
| Index | BET | Pine dress | Tap density | Co |
| Numerical value | 27m2/g | 0.51g/mL | 0.93g/mL | 1.1ppm |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.7ppm | 1.8ppm | 0.91ppm | 1.2ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5.2ppm | 0.15ppm | 0.58ppm | 1.8ppm |
| Index | K | pH | Sulfate radical | Chlorion |
| Numerical value | 0.9ppm | 3.5 | 1.3ppm | 1.2ppm |
| Index | Primary particle size | D10 | D50 | D90 |
| Numerical value | 23nm | 0.53μm | 1.9μm | 5.4μm |
The index of obtained battery-level lithium carbonate is as follows：
| Index | Main content | D10 | D50 | D90 |
| Numerical value | 99.85% | 0.21μm | 0.53μm | 0.82μm |
| Index | Pb | Co | Cu | Fe |
| Numerical value | 1.2ppm | 0.95ppm | 1.21ppm | 2.3ppm |
| Index | Ni | Ca | Mn | Zn |
| Numerical value | 0.47ppm | 1.6ppm | 0.9ppm | 1.75ppm |
| Index | Na | Cd | Mg | Li |
| Numerical value | 5.5ppm | 0.3ppm | 0.8ppm | 1.8ppm |
| Index | K | P | Sulfate radical | Chlorion |
| Numerical value | 0.9ppm | 5.9ppm | 1.4ppm | 1.4ppm |
The rate of recovery of final products is as follows：
The rate of recovery 98.7% of ferric phosphate, the rate of recovery 98.2% of lithium, the rate of recovery 99.0% of aluminium.
Waste and old LiFePO4 waste material per ton, calculated with LiFePO4 content 70%, aluminium content 20%, can caused profit
Moisten for 7.5 ten thousand yuan, higher than other handling process.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (8)
1. a kind of recycling treatment process of LiFePO4 waste material, it is characterised in that be following steps：
(1) LiFePO4 waste material is added into aqueous slkali stirring and dissolving 2-3 hours at 70-85 DEG C, then filtered, obtained molten containing aluminium
Liquid and the first filter residue；
(2) the first filter residue is added in sulfuric acid solution, in 85-90 DEG C of stirring reaction 3-4 hour, and meanwhile it is continuously even in course of reaction
Speed adds iron powder, and it be 2.0-2.5 to react to the pH of solution, and then addition hydroxylamine hydrochloride causes the dense of hydroxylamine hydrochloride in reaction system
Spend for 0.01-0.02mol/L, then filter, obtain the first filtrate and the second filter residue；
(3) it is 50-55 DEG C, mixing speed 300-350r/min in temperature by the first filtrate, adds hydrogen peroxide, add hydrogen peroxide
Time be 1-1.5 hours, then heat to 90-95 DEG C and continue to stir 1-2 hours, then filter, obtain the second filtrate and the
Three filter residues, by the 3rd filter residue according to solid-to-liquid ratio 1:2 add pure water pulp to obtain pulp material, and the phosphoric acid for then preparing 4-5mol/L is molten
Liquid, then the 1/4 of pulp material volume is added in phosphoric acid solution, is warming up to temperature as 95-100 DEG C, 500-800r/min is high
Speed stirring 1-3 hours are changed into clarifying to solution, are then added thereto again by the 3/4 of remaining pulp material volume, then be in temperature
95-100 DEG C, continue under 500-800r/min high-speed stirreds to react 1-3 hours, to material color be changed into white slightly powder after stop
Reaction, is then filtered, and obtained phosphoric acid mother liquor is collected separately, untill then the pH of pure water to washings is 6-6.5, then
Battery-grade iron phosphate is obtained by drying, iron removaling, screening；
(4) it is 80-85 DEG C in temperature by the second filtrate, the pH for adding magnesia regulation solution is 5-6, then stirring reaction 1-2
Filtered after hour, obtain filter residue and the 3rd filtrate of iron content, the 3rd filtrate is added into urea, reacted at being 85-95 DEG C in temperature,
The pH for maintaining terminal is 9-9.5, filtering, obtains rough carbonic acid crystalline lithium and the 4th filtrate；
(5) the rough lithium carbonate that step (4) obtains is added into water slurry, is vacuumized in sealing reactor and maintain the pressure to be
5000-8000Pa is then heated to water and seethed with excitement completely, and 2-3 hours are then reacted under the conditions of boiling, then filters, obtains carbonic acid
The mixed solution of magnesium filter residue and lithium hydroxide and lithia, in temperature it is 90-95 by the mixed solution of lithium hydroxide and lithia
CO is passed through at DEG C2, pH is 9-9.5 to terminal for reaction, obtains battery-level lithium carbonate.
A kind of 2. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(1) what is obtained adds neopelex and polyethylene glycol containing aluminum solutions so that the neopelex in solution
Concentration be 0.01-0.015mol/L, the concentration of polyethylene glycol is 0.01-0.015mol/L, then with aluminium chloride ammonium salt solution, acid
Alkali conditioning agent cocurrent is added in the liquid of bottom, and reaction temperature is 30-35 DEG C, and bottom liquid is the mixing of ammonium carbonate and ammoniacal liquor that pH is 9.5-10
Solution, it is 9.5-10 to maintain dropwise addition process pH, and the addition time is 1-2 hours, is added dropwise and continues to react 0.5-1 hours, then
Filtering, filter residue, in 80-85 DEG C of drying, after air-flow is broken, is calcined at 950-1050 DEG C after washing and obtain nano aluminium oxide.
A kind of 3. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(1) mol ratio hydroxy is 1 in the aluminium and aqueous slkali in LiFePO4 waste material:1.05-1.1, the concentration of aqueous slkali are
0.5-1mol/L。
A kind of 4. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(2) mol ratio of phosphate radical is 0.05-0.1 in the iron powder and the first filter residue that are added in:1, the concentration of sulfuric acid solution is 2.5-
4mol/L, the second filter residue for reacting to obtain returns to be continued to dissolve in the first filter residue.
A kind of 5. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(3) mol ratio of hydrogen peroxide and the first filtrate ferrous ions is 1.1-1.15:2, the mass fraction of hydrogen peroxide is 25-30%,
The mol ratio of iron ion is 0.3-0.35 in phosphoric acid and the 3rd filter residue in the phosphoric acid solution of addition:1.
A kind of 6. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(3) the phosphoric acid mother liquor obtained in is continuing with by being concentrated into concentration to be returned after 4-5mol/L.
A kind of 7. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(4) mol ratio of lithium ion is 4-5 in urea and the 3rd filtrate in:1, the 4th filtrate is continued anti-after being mixed with the 3rd filtrate
Should, the lithium ion content into the 4th filtrate is less than outer row after 100ppm.
A kind of 8. recycling treatment process of LiFePO4 waste material according to claim 1, it is characterised in that：The step
(5) the magnesium carbonate filter residue in, which returns to mix with the first filter residue, to be continued to dissolve, and the lithium content in magnesium carbonate filter residue is less than outside 100ppm
Row.
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| CN108929956A (en) * | 2018-07-11 | 2018-12-04 | 方嘉城 | A kind of processing method of discarded LiFePO4 middle material |
| CN113104866A (en) * | 2021-03-30 | 2021-07-13 | 中国石油大学(北京) | Method for preparing battery-grade lithium carbonate from lithium iron phosphate waste |
| CN115072689A (en) * | 2022-08-19 | 2022-09-20 | 矿冶科技集团有限公司 | Energy-saving and efficient lithium iron phosphate battery treatment method for recovering lithium iron |
| CN115872422A (en) * | 2022-10-28 | 2023-03-31 | 中国科学院过程工程研究所 | Method for preparing battery-grade lithium carbonate by using microbubbles to strengthen carbon dioxide reaction crystallization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108929956A (en) * | 2018-07-11 | 2018-12-04 | 方嘉城 | A kind of processing method of discarded LiFePO4 middle material |
| CN108929956B (en) * | 2018-07-11 | 2019-11-22 | 方嘉城 | A kind of processing method of discarded LiFePO4 middle material |
| CN113104866A (en) * | 2021-03-30 | 2021-07-13 | 中国石油大学(北京) | Method for preparing battery-grade lithium carbonate from lithium iron phosphate waste |
| CN113104866B (en) * | 2021-03-30 | 2021-11-09 | 中国石油大学(北京) | Method for preparing battery-grade lithium carbonate from lithium iron phosphate waste |
| CN115072689A (en) * | 2022-08-19 | 2022-09-20 | 矿冶科技集团有限公司 | Energy-saving and efficient lithium iron phosphate battery treatment method for recovering lithium iron |
| CN115072689B (en) * | 2022-08-19 | 2022-11-11 | 矿冶科技集团有限公司 | Energy-saving and efficient lithium iron phosphate battery treatment method for recovering lithium iron |
| CN115872422A (en) * | 2022-10-28 | 2023-03-31 | 中国科学院过程工程研究所 | Method for preparing battery-grade lithium carbonate by using microbubbles to strengthen carbon dioxide reaction crystallization |
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