CN108183276A - The preparation method of ferric phosphate - Google Patents
The preparation method of ferric phosphate Download PDFInfo
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- CN108183276A CN108183276A CN201711373496.7A CN201711373496A CN108183276A CN 108183276 A CN108183276 A CN 108183276A CN 201711373496 A CN201711373496 A CN 201711373496A CN 108183276 A CN108183276 A CN 108183276A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The present invention relates to the preparation methods of ferric phosphate, belong to ferric phosphate lithium cell recovery technology field.The technical problem to be solved by the present invention is to provide the preparation methods of ferric phosphate, and the ferric phosphate precipitation of high-purity is prepared.This method adds in LiFePO4 solution, oxidant and precipitating reagent in reactor simultaneously respectively, the charging rate for controlling LiFePO4 solution is 113~400mL/h, temperature is 40~70 DEG C in reaction process, pH value of reaction system is 2~3, after the completion of charging, then ageing is filtered to the reaction was complete, solid is washed, obtains ferric phosphate；Wherein, the excessive 25~150wt% of the oxidant of addition.The conversion ratio of the method for the present invention iron is more than 98%, and the phosphoric acid iron tramp prepared is less, and purity is higher, and tap density is larger, even particle size, superior product quality.Method is simple, and continuous controllable, raw material sources enrich, at low cost, and environmental protection is easy to industrialize.
Description
Technical field
The present invention relates to the preparation methods of ferric phosphate, belong to ferric phosphate lithium cell recovery technology field.
Background technology
New-energy automobile explosive growth in recent years is scrapped on a large scale accompanying problem is that power battery will enter
Phase.Ferric phosphate lithium cell is always the mainstream of domestic power battery development.Waste lithium iron phosphate battery currently on the market is carried out
Analysis calculates, and has a large amount of valuable elements in waste lithium iron phosphate battery, such as lithium, iron, phosphorus.Waste lithium iron phosphate battery is carried out
Recycling has very high social value, but its cost recovery is very high.Therefore, it is arrived in ferric phosphate lithium cell recycling upsurge
Before, the key for solving the problems, such as ferric phosphate lithium cell recycling is on the basis of low cost recovery is ensured, is worked out efficient and environmentally friendly
Recovery process.
For waste lithium iron phosphate battery, since elemental lithium has larger market, each large enterprises and research institution
Research hotspot be the recycling of lithium, it is and less about the research that iron, phosphorus recycle.According to the literature, time about iron and phosphorus
Receipts form is generally individually recovered as the compound of iron and the compound of phosphorus.
Presoma ferric phosphate is used due to more in the industrial manufacturing process of LiFePO 4 material.Consider battery material
The deposit and its relatively low cost of a large amount of iron, P elements in prepared by material in ferric phosphate dosage, waste lithium iron phosphate battery, needle
To phosphorus source and source of iron needed for the synthesis of battery ferric phosphate, can largely be mended from waste lithium iron phosphate battery
It gives.The method of the utilization of resources on the one hand larger cost for reducing ferric phosphate synthesis, another aspect environmental protection and saving.Therefore,
It needs to work out the iron and phosphorus in a kind of simple and environmentally-friendly method recycling waste lithium iron phosphate battery, it is higher to prepare purity
Ferric phosphate.
The preparation process of ferric phosphate is mainly two aspects at present：A. ferric phosphate is directly prepared using ferric iron source；B. by two
Precipitation prepares ferric phosphate after valency source of iron initial oxidation.In the precipitation process of ferric phosphate, it is primarily present two kinds of reaction process：It is main anti-
Should be that ferric iron is converted to ferric phosphate, while is generated with a small amount of iron hydroxide, the two reaction has competition.Due to iron hydroxide
On the one hand there is the ability of adsorpting anion, another aspect iron hydroxide particle is thinner, causes system viscosity larger, sad filter,
Moisture content is larger in product, and more than reason causes product purity relatively low.Therefore, it if the higher ferric phosphate of purity need to be prepared, needs
Stringent control reaction condition, reduces the generation of iron hydroxide.
The patent of invention that number of patent application is 201611176572.0 discloses a kind of acid-hatching of young eggs and is recycled waste and old phosphoric acid
The method of iron lithium anode material obtains LiFePO4 solution by acidleach, then add in it is oxidizing after, then adjust pH value of solution
It is 1.5~4 to be worth, and 1~3h is reacted at 60~95 DEG C, obtains ferric phosphate precipitation.This method be first will be ferrous oxidising after, into
Row precipitation, using this method, preparation condition must be controlled strictly, more demanding to the control of reaction system stability, and be prepared
The purity of the ferric phosphate gone out needs further to be improved.In addition, the product primary particle and second particle of this method generation are thinner,
The tap density of product is 0.68~0.7g/cm3, it is relatively low.Purity and tap density are relatively low, are unfavorable for follow-up LiFePO4
Preparation, the large effect performance of LiFePO 4 material.
Invention content
For disadvantages described above, the technical problem to be solved by the present invention is to provide the preparation methods of ferric phosphate, are prepared high-purity
The ferric phosphate precipitation of degree.
LiFePO4 solution, oxidant and precipitating reagent are added in reaction by the preparation method of ferric phosphate of the present invention simultaneously respectively
In device, the charging rate of control LiFePO4 solution is 113~400mL/h, and temperature is 40~70 DEG C in reaction process, reactant
Be pH value it is 2~3, after the completion of charging, then ageing is filtered to the reaction was complete, is washed solid, is obtained ferric phosphate；Wherein, it adds in
The excessive 25~150wt% of oxidant.
Preferably, the LiFePO4 solution is prepared with the following method：By lithium iron phosphate positive material powder into
Row acidleach obtains LiFePO4 solution.
It is further preferred that the lithium iron phosphate positive material powder comes from waste and old ferric phosphate lithium cell, lithium battery
The positive plate production of anode leftover pieces, lithium battery generated in the anode waste that is generated in production process, Production Process of Lithium Battery
The waste material generated in the process.
Preferably, the oxidant is at least one of hydrogen peroxide, sodium peroxide, potassium permanganate.
Preferably, the precipitating reagent is at least one of carbonate, hydroxide, ammonia.Preferably, the hydroxide
For lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, digestion time is 0.5~2.5h.
Preferably, LiFePO4 solution, oxidant, precipitating reagent and surfactant are added in reactor simultaneously respectively.
Preferably, the addition of surfactant is 1~the 5 ‰ of the content of LiFePO4 solution ferrous ions.
Compared with prior art, the present invention has the advantages that：
1) present invention uses the method precipitated in oxidation, and the conversion ratio of iron is more than 98%, and the ferric phosphate prepared
Impurity is less, and purity is higher, and tap density is larger, even particle size, superior product quality.
2) the raw material ferrous phosphate used in the method for the present invention can derive from various LiFePO4 old and useless batterys, waste material or side
Corner material, raw material sources enrich, and significantly reduce the manufacturing cost of ferric phosphate.
3) the method for the present invention, method is simple, continuous controllable, at low cost, and environmental protection is easy to industrialize.
Description of the drawings
Fig. 1 is the SEM figures for the ferric phosphate being prepared in the embodiment of the present invention 1.
Specific embodiment
The preparation method of ferric phosphate of the present invention, includes the following steps：
LiFePO4 solution, oxidant and precipitating reagent are added in reactor simultaneously respectively, control LiFePO4 solution
Charging rate is 113~400mL/h, and temperature is 40~70 DEG C in reaction process, and pH value of reaction system is 2~3, and charging is completed
Afterwards, then ageing is filtered to the reaction was complete, is washed solid, is obtained ferric phosphate；Wherein, the oxidant of addition excessive 25~
150wt%.
The method of the present invention is ferrous during the reaction to be once oxidized to trivalent by the way of simultaneous oxidation and precipitation
Iron converts ferric phosphate, ferric concentration is relatively low in reaction process, and the amount for being converted to iron hydroxide is less, the phosphorus prepared
The purity of sour iron is higher.Inventor has found, each reaction condition such as pH, feed way and speed, material rate in the reaction,
Reaction temperature etc. generates large effect to product property.By many experiments, the reaction condition of the present invention, control are explored
Conversion ratio, the nucleation of product grain and growth, the reaction process of oxidation/precipitation that could preferably control in this way, are prepared pure
The higher ferric phosphate of degree.
The oxidant of addition of the present invention excessive 25~150% refers to according to the ferrous ion in LiFePO4 solution
Content, can be calculated completely by ferrous ions into the required oxidant theoretical amount of iron ion, and it is practical plus
The oxidant entered is 1.25~2.5 times of theoretical amount, that is, the 25~150wt% of oxidant excess added in.
The method of the present invention is fed simultaneously using three additions.Described distinguishes LiFePO4 solution, oxidant and precipitating reagent
It adds in reactor and refers in certain feed time simultaneously, LiFePO4 solution is slowly added in reactor, feed
Speed can be at the uniform velocity or it is non-at the uniform velocity, preferably at the uniform velocity.Meanwhile oxidant is slowly added in reactor, according to phosphorus
The addition speed of ferrous ion content and LiFePO4 solution in sour iron lithium solution, can be aoxidized by conventionally calculation
The addition of agent and addition speed.Meanwhile also add in precipitating reagent in reactor, to adjust the pH value of reaction system as 2~3
Subject to.LiFePO4 solution, oxidant with precipitating reagent this three charging beginning and end time it is identical.
Preferably, the LiFePO4 solution is prepared with the following method：By lithium iron phosphate positive material powder into
Row acidleach obtains LiFePO4 solution.In acid condition, lithium, iron and the phosphorus in lithium iron phosphate positive material powder will dissolve
Into solution.Common acid may be used in the acidleach, such as sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the lithium iron phosphate positive material powder comes from waste and old ferric phosphate lithium cell, lithium battery produced
In the anode leftover pieces that are generated in the anode waste that is generated in journey, Production Process of Lithium Battery, the positive plate production process of lithium battery
The waste material of generation.By the method for the present invention, it can be recycled from above-mentioned old and useless battery, waste material or leftover pieces and obtain the phosphorus of high-purity
Sour iron, raw material sources enrich, and the manufacturing cost of ferric phosphate greatly reduces.
The effect of oxidant is into iron ion by the ferrous ions in LiFePO4 solution, and common oxidant is fitted
For the present invention.Preferably, the oxidant is at least one of hydrogen peroxide, sodium peroxide, potassium permanganate.
The precipitating reagent of the present invention is preferably at least one of carbonate, hydroxide, ammonia.Precipitating reagent can not only be adjusted
PH value, moreover it is possible to play the role of buffering and coordination.Wherein, hydroxide is preferably lithium hydroxide, sodium hydroxide or potassium hydroxide.
Ageing can generally meet the requirement of the present invention to the time that the reaction was complete in more than 0.5h, in order to save time into
This, it is preferred that digestion time is 0.5~2.5h.
In precipitation process, surfactant can also be added in, by surfactant, controls ferric phosphate crystalline deposit
Process so that precipitation process more uniformly carries out.Preferably, by LiFePO4 solution, oxidant, precipitating reagent and surface-active
Agent is added in reactor simultaneously respectively.
The addition of surfactant can be obtained by the content calculation of LiFePO4 solution ferrous ions, it is preferred that
The addition of surfactant is 1~the 5 ‰ of the content of LiFePO4 solution ferrous ions, and percentage herein is quality hundred
Score.
The specific embodiment of the present invention is further described with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
1. it disassembles, remove：Waste lithium iron phosphate battery is disassembled, separates lithium iron phosphate positive material.
2. it leaches：In acid condition, lithium, iron, the phosphorus in lithium iron phosphate positive material are dissolved in sulfuric acid solution, obtained
To the solution of LiFePO4.
3. synthesis：LiFePO4 solution 200ml, hydrogen peroxide and concentrated ammonia liquor in step 2 is added in into reaction simultaneously respectively
In device.Wherein, it is calculated according to stoichiometry ferrous in LiFePO4 solution, hydrogen peroxide excess 25%wt.Reaction temperature is protected
It holds in 40 DEG C, feed time 1h, reaction process by controlling the flow of ammonium hydroxide using control system pH as 2；It is aged 0.5h.
4. it is filtered, washed：Reaction product in step 3 is filtered, washing obtains ferric phosphate；Filtrate is lithium-containing solution.
The SEM figures of gained ferric phosphate are shown in Fig. 1.The conversion ratio that iron is calculated is 98.1%.Detect the vibration density of ferric phosphate
The content of degree, grain size and impurity sulfate radical, the result is shown in tables 1.
Embodiment 2
1. it disassembles, remove：Waste lithium iron phosphate battery is disassembled, separates lithium iron phosphate positive material.
2. it leaches：In acid condition, lithium, iron, the phosphorus in lithium iron phosphate positive material are dissolved in sulfuric acid solution, obtained
To the solution of LiFePO4.
3. synthesis：LiFePO4 solution 100ml, hydrogen peroxide and concentrated ammonia liquor in step 2 is added in into reaction simultaneously respectively
In device.Wherein, it is calculated according to stoichiometry ferrous in LiFePO4 solution, hydrogen peroxide excess 90%wt.Reaction temperature is protected
It holds in 65 DEG C, feed time 0.88h, reaction process by controlling the flow of ammonium hydroxide using control system pH as 2.3；Ageing
1h。
4. it is filtered, washed：Reaction product in step 3 is filtered, washing obtains ferric phosphate；Filtrate is lithium-containing solution.
The SEM figures of gained ferric phosphate are similar with Fig. 1.The conversion ratio that iron is calculated is 98.6%.Detection ferric phosphate shakes
The content of real density, grain size and impurity sulfate radical, the result is shown in tables 1.
Embodiment 3
1. it disassembles, remove：Waste lithium iron phosphate battery is disassembled, separates lithium iron phosphate positive material.
2. it leaches：In acid condition, lithium, iron, the phosphorus in lithium iron phosphate positive material are dissolved in sulfuric acid solution, obtained
To the solution of LiFePO4.
3. synthesis：LiFePO4 solution 300ml, hydrogen peroxide and concentrated ammonia liquor in step 2 is added in into reaction simultaneously respectively
In device.Wherein, it is calculated according to stoichiometry ferrous in LiFePO4 solution, hydrogen peroxide excess 100%wt.Reaction temperature is protected
It holds in 50 DEG C, feed time 0.75h, reaction process by controlling the flow of ammonium hydroxide using control system pH as 2.4；Ageing
1.5h。
4. it is filtered, washed：Reaction product in step 3 is filtered, washing obtains ferric phosphate；Filtrate is lithium-containing solution.
The SEM figures of gained ferric phosphate are similar with Fig. 1.The conversion ratio that iron is calculated is 98.9%.Detection ferric phosphate shakes
The content of real density, grain size and impurity sulfate radical, the result is shown in tables 1.
Embodiment 4
1. it disassembles, remove：Waste lithium iron phosphate battery is disassembled, separates lithium iron phosphate positive material.
2. it leaches：In acid condition, lithium, iron, the phosphorus in lithium iron phosphate positive material are dissolved in sulfuric acid solution, obtained
To the solution of LiFePO4.
3. synthesis：LiFePO4 solution 350ml, hydrogen peroxide and concentrated ammonia liquor in step 2 is added in into reaction simultaneously respectively
In device.Wherein, it is calculated according to stoichiometry ferrous in LiFePO4 solution, hydrogen peroxide excess 150%wt.Reaction temperature is protected
It holds in 70 DEG C, feed time 2.5h, reaction process by controlling the flow of ammonium hydroxide using control system pH as 2.7；It is aged 2h.
4. it is filtered, washed：Reaction product in step 3 is filtered, washing obtains ferric phosphate；Filtrate is lithium-containing solution.
The SEM figures of gained ferric phosphate are similar with Fig. 1.The conversion ratio that iron is calculated is 99.5%.Detection ferric phosphate shakes
The content of real density, grain size and impurity sulfate radical, the result is shown in tables 1.
Embodiment 5
1. it disassembles, remove：Waste lithium iron phosphate battery is disassembled, separates lithium iron phosphate positive material.
2. it leaches：In acid condition, lithium, iron, the phosphorus in lithium iron phosphate positive material are dissolved in sulfuric acid solution, obtained
To the solution of LiFePO4.
3. synthesis：LiFePO4 solution 500ml, hydrogen peroxide and concentrated ammonia liquor in step 2 is added in into reaction simultaneously respectively
In device.Wherein, it is calculated according to stoichiometry ferrous in LiFePO4 solution, hydrogen peroxide excess 120%wt.Reaction temperature is protected
It holds in 60 DEG C, feed time 1.5h, reaction process by controlling the flow of ammonium hydroxide using control system pH as 3；It is aged 2.5h.
4. it is filtered, washed：Reaction product in step 3 is filtered, washing obtains ferric phosphate；Filtrate is lithium-containing solution.
The SEM figures of gained ferric phosphate are similar with Fig. 1.The conversion ratio that iron is calculated is 99.6%.Detection ferric phosphate shakes
The content of real density, grain size and impurity sulfate radical, the result is shown in tables 1.
Comparative example 1
1. it disassembles, remove：Waste lithium iron phosphate battery is disassembled, separates lithium iron phosphate positive material.
2. it leaches：In acid condition, lithium, iron, the phosphorus in lithium iron phosphate positive material are dissolved in sulfuric acid solution, obtained
To the solution of LiFePO4.
3rd, it aoxidizes：The solution ph for adjusting LiFePO4 is less than 1, adds in hydrogen peroxide by ferrous ions, peroxidating
Excess hydrogen 120%, oxidizing temperature are 45 DEG C, react 2h.
4th, it precipitates：Lithium hydroxide is added in liquid after above-mentioned reaction, it is 2 to adjust pH, controls temperature 60 C, reaction
1.5h production ferric phosphate precipitations, filtration washing obtain ferric phosphate, and filtrate is lithium-containing solution.
The conversion ratio that iron is calculated is 93%.Detect containing for the tap density of ferric phosphate, grain size and impurity sulfate radical
Amount, the result is shown in tables 1.
1 each embodiment of table corresponds to the tap density and grain size of product ferric phosphate
As it can be seen from table 1 the method for the present invention, the ferric phosphate being prepared, the content of impurity sulfate radical is relatively low,
0.008% hereinafter, tap density is higher, more than 0.7g/cm3；Relative to the method precipitated after initial oxidation, the pure of product is improved
Degree and tap density.
Claims (9)
1. the preparation method of ferric phosphate, it is characterised in that：LiFePO4 solution, oxidant and precipitating reagent are added in simultaneously respectively anti-
It answers in device, the charging rate of control LiFePO4 solution is 113~400mL/h, and temperature is 40~70 DEG C in reaction process, reaction
System pH is 2~3, and after the completion of charging, then ageing is filtered to the reaction was complete, is washed solid, is obtained ferric phosphate；Wherein, add
Excessive 25~the 150wt% of oxidant entered.
2. the preparation method of ferric phosphate according to claim 1, it is characterised in that：The LiFePO4 solution is using as follows
Method is prepared：Lithium iron phosphate positive material powder is subjected to acidleach, obtains LiFePO4 solution.
3. the preparation method of ferric phosphate according to claim 2, it is characterised in that：The lithium iron phosphate positive material powder
Come from the anode waste generated in waste and old ferric phosphate lithium cell, Production Process of Lithium Battery, Production Process of Lithium Battery and generate
Anode leftover pieces, lithium battery positive plate production process in the waste material that generates.
4. according to the preparation method of claims 1 to 3 any one of them ferric phosphate, it is characterised in that：The oxidant was
At least one of hydrogen oxide, sodium peroxide, potassium permanganate.
5. according to the preparation method of Claims 1 to 4 any one of them ferric phosphate, it is characterised in that：The precipitating reagent is carbon
At least one of hydrochlorate, hydroxide, ammonia.
6. the preparation method of ferric phosphate according to claim 5, it is characterised in that：The hydroxide for lithium hydroxide,
Sodium hydroxide or potassium hydroxide.
7. according to the preparation method of claim 1~6 any one of them ferric phosphate, it is characterised in that：Digestion time for 0.5~
2.5h。
8. according to the preparation method of claim 1~7 any one of them ferric phosphate, it is characterised in that：By LiFePO4 solution,
Oxidant, precipitating reagent and surfactant are added in reactor simultaneously respectively.
9. the preparation method of ferric phosphate according to claim 8, it is characterised in that：The addition of surfactant is phosphoric acid
1~the 5 ‰ of the content of iron lithium solution ferrous ions.
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| CN110371943A (en) * | 2019-06-28 | 2019-10-25 | 湖南邦普循环科技有限公司 | A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste |
| CN110474123A (en) * | 2019-08-23 | 2019-11-19 | 贵州红星电子材料有限公司 | Positive material of waste lithium iron phosphate comprehensive recovering process |
| CN110474123B (en) * | 2019-08-23 | 2022-08-09 | 贵州红星电子材料有限公司 | Comprehensive recovery method of waste lithium iron phosphate battery positive electrode material |
| CN111129636A (en) * | 2019-12-31 | 2020-05-08 | 深圳清华大学研究院 | Regeneration method of waste lithium iron phosphate battery positive electrode material |
| CN114105116A (en) * | 2021-12-15 | 2022-03-01 | 格林美股份有限公司 | Method for preparing battery-grade iron phosphate from nickel-iron alloy |
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Application publication date: 20180619 |