CN110422831A - A method of recycling ferric phosphate from ferric phosphate lithium cell - Google Patents
A method of recycling ferric phosphate from ferric phosphate lithium cell Download PDFInfo
- Publication number
- CN110422831A CN110422831A CN201910711370.9A CN201910711370A CN110422831A CN 110422831 A CN110422831 A CN 110422831A CN 201910711370 A CN201910711370 A CN 201910711370A CN 110422831 A CN110422831 A CN 110422831A
- Authority
- CN
- China
- Prior art keywords
- ferric phosphate
- lithium cell
- recycling
- mixed liquor
- phosphate lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Primary Cells (AREA)
Abstract
The present invention relates to battery material recovery technology field, especially a kind of method that ferric phosphate is recycled from ferric phosphate lithium cell, comprising the following steps: ferric phosphate lithium cell S1, is discharged into 2.0V hereinafter, being put into crusher broken dismantling；S2, LiFePO4 powder in S1 is put into vacuum tube furnace, is passed through inert gas, high-temperature process 5-10h；S3, by the S2 LiFePO4 powder that obtains that treated, be added in dilute hydrochloric acid solution while stirring；S4, the mixed liquor that oxidant and S3 obtain is added drop-wise in three-necked flask simultaneously, stirring, ultrasound；S5, into mixed liquor obtained by S4, addition adsorbent adsorbs undesired impurities；S6, filtrate is heated up, carries out phosphorating treatment, after mixing evenly Fe, P content in sample presentation detection solution, add phosphorus source adjustment system terminal pH between 2.5-3.The present invention has the characteristics that improve the rate of recovery of the leaching rate of LiFePO4 and ferric phosphate.
Description
Technical field
The present invention relates to battery material recovery technology fields, more particularly to one kind, and ferric phosphate is recycled from ferric phosphate lithium cell
Method.
Background technique
Battery recycling is collected used battery, prevents it from entering the ecosystem, causes damages to environment
A kind of behavior.Contain the electrolyte solutions such as a large amount of heavy metal and spent acid, salkali waste in old and useless battery.It is rotten if arbitrarily abandoned
The battery lost can destroy our water source, corrode crops and soil that we depend on for existence, our living environment will be faced with
Huge threat.So we it is necessary to which the old and useless battery after use is carried out recycling and reusing, one can prevent pollution ring
Border, two can recycle wherein useful ingredient, economize on resources, existing ferric phosphate lithium cell, carry out phosphoric acid
Iron recovery is not high, while not uniform form, so it is proposed that a kind of recycle ferric phosphate from ferric phosphate lithium cell
Method, to solve the problems, such as this.
Summary of the invention
The purpose of the present invention is to solve disadvantages existing in the prior art, and propose a kind of from ferric phosphate lithium cell
The method of middle recycling ferric phosphate.
To achieve the goals above, present invention employs following technical solutions:
Design a kind of method that ferric phosphate is recycled from ferric phosphate lithium cell, comprising the following steps:
S1, ferric phosphate lithium cell is discharged into 2.0V hereinafter, being put into crusher broken dismantling, then carry out screening and air-flow
The separation of LiFePO4 powder, aluminium powder and copper powder in battery is realized in separation；
S2, LiFePO4 powder in S1 is put into vacuum tube furnace, is passed through inert gas, high-temperature process 5-10h；
S3, by the S2 LiFePO4 powder that obtains that treated, be added in dilute hydrochloric acid solution while stirring；
S4, the mixed liquor for obtaining oxidant and S3 are added drop-wise in three-necked flask simultaneously, stirring, ultrasound, make oxidant and
Above-mentioned solution obtains mixed liquor by certain reaction ratio simultaneous implantation three-necked flask reactor and reaction is exactly completed；
S5, into mixed liquor obtained by S4, addition adsorbent adsorbs undesired impurities, continues to add PAC stirring, filtering, be soaked
Liquid out；
S6, filtrate is heated up, carries out phosphorating treatment, Fe, P content in sample presentation detection solution, add phosphorus source after mixing evenly
Adjustment system terminal pH controls reaction temperature, is aged to the above mixed liquor between 2.5-3, until white ferric phosphate is generated,
Above-mentioned suspension is separated by solid-liquid separation, dry, sintering obtains the ferric phosphate of cuboid crystal form；
The liquid reservation of S7, solid-liquid separation, test P% content, recycle.
Preferably, in S2 step, the inert gas is nitrogen or argon gas, the temperature of the high-temperature process is 400 DEG C-
550℃。
Preferably, dilute hydrochloric acid solution concentration is 1mol/L-5mol/L.
Preferably, in S4 step, oxidant is hydrogen peroxide or sodium chlorite, and mass fraction 20%-30% is stirred
Mix speed 20r/min-50r/min, ultrasonic power 50kHz-100kHz.
Preferably, in step s 5, it is sodium dihydrogen phosphate or active carbon, the quality of adsorbent that adsorbent is added in mixed liquor
Score is 3 ‰ -1%.
Preferably, in step s 6, solid-liquid separating reacts addition to leachate again.
Preferably, in step s 6, sintering temperature is 500 DEG C -600 DEG C.
Preferably, the ferric phosphate obtained in step s 6 is the second particle being made of primary particle, the grain of primary particle
Diameter is 100nm-300nm.
A kind of method recycling ferric phosphate from ferric phosphate lithium cell proposed by the present invention, beneficial effect are: improving phosphorus
The leaching rate of sour iron lithium and the rate of recovery of ferric phosphate reach valuable resource and maximize recycling, and can control the ferric phosphate of preparation
Pattern, obtain the ferric phosphate of the cuboid pattern of stable homogeneous.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.
A method of recycling ferric phosphate from ferric phosphate lithium cell, comprising the following steps:
S1, ferric phosphate lithium cell is discharged into 2.0V hereinafter, being put into crusher broken dismantling, then carry out screening and air-flow
The separation of LiFePO4 powder, aluminium powder and copper powder in battery is realized in separation, is separated by sieving with air-flow, is prevented ferric phosphate
Lithium powder adulterates other impurities, increases the effect of separation；
S2, LiFePO4 powder in S1 is put into vacuum tube furnace, is passed through inert gas, high-temperature process 5-10h is described
Inert gas is nitrogen or argon gas, and the temperature of the high-temperature process is 400 DEG C -550 DEG C, by inert gas to vacuum tube furnace
It is filled, LiFePO4 powder is prevented to be oxidized when heated, introduce other impurity；
S3, by the S2 LiFePO4 powder that obtains that treated, be added in dilute hydrochloric acid solution while stirring, dilute hydrochloric acid solution
Concentration is 1mol/L-5mol/L, carries out reaction dissolution to LiFePO4 powder by the way that dilute hydrochloric acid is added；
S4, the mixed liquor for obtaining oxidant and S3 are added drop-wise in three-necked flask simultaneously, stirring, ultrasound, make oxidant and
Above-mentioned solution obtains mixed liquor by certain reaction ratio simultaneous implantation three-necked flask reactor and reaction is exactly completed.Oxidation
Agent is hydrogen peroxide or sodium chlorite, mass fraction 20%-30%, mixing speed 20r/min-50r/min, ultrasonic power
The touch opportunity of mixed liquor and oxidant is enhanced, reaction is increased by stirring and ultrasonic treatment for 50kHz-100kHz
Effect；
S5, into mixed liquor obtained by S4, addition adsorbent adsorbs undesired impurities, continues to add PAC stirring, filtering, be soaked
Liquid out, addition adsorbent is sodium dihydrogen phosphate or active carbon in mixed liquor, and the mass fraction of adsorbent is 3 ‰ -1%, passes through suction
Attached dose of absorption undesired impurities, improve the leaching rate of LiFePO4 and the rate of recovery of ferric phosphate, reach valuable resource and maximize back
It receives；
S6, filtrate is heated up, carries out phosphorating treatment, Fe, P content in sample presentation detection solution, add phosphorus source after mixing evenly
Adjustment system terminal pH controls reaction temperature, is aged to the above mixed liquor between 2.5-3, until white ferric phosphate is generated,
Above-mentioned suspension is separated by solid-liquid separation, dry, sintering obtains the ferric phosphate of cuboid crystal form, and solid-liquid separating reacts addition extremely again
Leachate, sintering temperature are 500 DEG C -600 DEG C, and ferric phosphate is the second particle being made of primary particle, the partial size of primary particle
For 100nm-300nm, the ferric phosphate of the cuboid pattern of stable homogeneous is obtained by sintering, ensure that the pattern of ferric phosphate；
The liquid reservation of S7, solid-liquid separation, test P% content, recycle, and carry out circulation benefit by liquid reservation
With avoiding the waste of P in liquid, save resource.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell, which comprises the following steps:
S1, ferric phosphate lithium cell is discharged into 2.0V hereinafter, being put into crusher broken dismantling, then carry out sieving gentle flow point
From the separation of LiFePO4 powder, aluminium powder and copper powder in realization battery；
S2, LiFePO4 powder in S1 is put into vacuum tube furnace, is passed through inert gas, high-temperature process 5-10h；
S3, by the S2 LiFePO4 powder that obtains that treated, be added in dilute hydrochloric acid solution while stirring；
S4, the mixed liquor for obtaining oxidant and S3 are added drop-wise in three-necked flask simultaneously, stirring, ultrasound, make oxidant and above-mentioned
Solution obtains mixed liquor by certain reaction ratio simultaneous implantation three-necked flask reactor and reaction is exactly completed；
S5, into mixed liquor obtained by S4, addition adsorbent adsorbs undesired impurities, continues to add PAC stirring, filtering, be leached
Liquid；
S6, filtrate is heated up, carries out phosphorating treatment, Fe, P content in sample presentation detection solution, add phosphorus source adjustment after mixing evenly
System terminal pH controls reaction temperature, is aged to the above mixed liquor between 2.5-3, until white ferric phosphate is generated, it will be upper
Suspension separation of solid and liquid is stated, dry, sintering obtains the ferric phosphate of cuboid crystal form；
The liquid reservation of S7, solid-liquid separation, test P% content, recycle.
2. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in S2
In step, the inert gas is nitrogen or argon gas, and the temperature of the high-temperature process is 400 DEG C -550 DEG C.
3. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in S3
In step, dilute hydrochloric acid solution concentration is 1mol/L-5mol/L.
4. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in S4
In step, oxidant is hydrogen peroxide or sodium chlorite, mass fraction 20%-30%, mixing speed 20r/min-50r/
Min, ultrasonic power 50kHz-100kHz.
5. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in step
It is sodium dihydrogen phosphate or active carbon that adsorbent is added in rapid S5, in mixed liquor, and the mass fraction of adsorbent is 3 ‰ -1%.
6. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in step
In rapid S6, solid-liquid separating reacts addition to leachate again.
7. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in step
In rapid S6, sintering temperature is 500 DEG C -600 DEG C.
8. a kind of method for recycling ferric phosphate from ferric phosphate lithium cell according to claim 1, which is characterized in that in step
Ferric phosphate obtained in rapid S6 is the second particle being made of primary particle, and the partial size of primary particle is 100nm-300nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910711370.9A CN110422831A (en) | 2019-08-02 | 2019-08-02 | A method of recycling ferric phosphate from ferric phosphate lithium cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910711370.9A CN110422831A (en) | 2019-08-02 | 2019-08-02 | A method of recycling ferric phosphate from ferric phosphate lithium cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110422831A true CN110422831A (en) | 2019-11-08 |
Family
ID=68413844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910711370.9A Pending CN110422831A (en) | 2019-08-02 | 2019-08-02 | A method of recycling ferric phosphate from ferric phosphate lithium cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110422831A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285341A (en) * | 2020-02-21 | 2020-06-16 | 北京蒙京石墨新材料科技研究院有限公司 | Method for extracting battery-grade iron phosphate from waste lithium iron phosphate batteries |
| CN111653846A (en) * | 2020-07-27 | 2020-09-11 | 中南大学 | Treatment method of waste lithium iron phosphate battery |
| CN111977628A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Method for recovering and preparing lithium iron phosphate from lithium ion battery |
| CN113880064A (en) * | 2021-11-09 | 2022-01-04 | 株洲冶炼集团股份有限公司 | Method for treating high-impurity lithium iron phosphate waste powder by using low-consumption phosphoric acid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101439427B1 (en) * | 2013-03-14 | 2014-09-11 | 한국과학기술연구원 | Recycling method of olivine-based cathode material for lithium secondary battery, cathode material fabricated therefrom, and cathode and lithium secondary battery having the same |
| US20170084965A1 (en) * | 2015-09-22 | 2017-03-23 | Kangwon National University University-Industry Cooperation Foundation | Manufacturing method of high purity lithium phosphate from the waste liquid of the exhausted litium-ion battery |
| CN107720715A (en) * | 2017-09-28 | 2018-02-23 | 湖南华菱节能环保科技有限公司 | A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material |
| CN107915239A (en) * | 2017-12-08 | 2018-04-17 | 天齐锂业股份有限公司 | A kind of method for recycling hydro-thermal method production LiFePO4 waste liquid and preparing high-purity sulphuric acid lithium |
| 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 |
| CN109179358A (en) * | 2018-11-08 | 2019-01-11 | 广东省稀有金属研究所 | A method of preparing battery-grade iron phosphate from waste lithium iron phosphate battery |
| CN109250696A (en) * | 2017-07-12 | 2019-01-22 | 深圳佳彬科技有限公司 | A method of recycling nano ferric phosphate from ferric phosphate lithium cell |
-
2019
- 2019-08-02 CN CN201910711370.9A patent/CN110422831A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101439427B1 (en) * | 2013-03-14 | 2014-09-11 | 한국과학기술연구원 | Recycling method of olivine-based cathode material for lithium secondary battery, cathode material fabricated therefrom, and cathode and lithium secondary battery having the same |
| US20170084965A1 (en) * | 2015-09-22 | 2017-03-23 | Kangwon National University University-Industry Cooperation Foundation | Manufacturing method of high purity lithium phosphate from the waste liquid of the exhausted litium-ion battery |
| CN109250696A (en) * | 2017-07-12 | 2019-01-22 | 深圳佳彬科技有限公司 | A method of recycling nano ferric phosphate from ferric phosphate lithium cell |
| CN107720715A (en) * | 2017-09-28 | 2018-02-23 | 湖南华菱节能环保科技有限公司 | A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material |
| CN107915239A (en) * | 2017-12-08 | 2018-04-17 | 天齐锂业股份有限公司 | A kind of method for recycling hydro-thermal method production LiFePO4 waste liquid and preparing high-purity sulphuric acid lithium |
| 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 |
| CN109179358A (en) * | 2018-11-08 | 2019-01-11 | 广东省稀有金属研究所 | A method of preparing battery-grade iron phosphate from waste lithium iron phosphate battery |
Non-Patent Citations (1)
| Title |
|---|
| 牛福生等: "《铁矿石选矿技术》", 31 May 2012, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285341A (en) * | 2020-02-21 | 2020-06-16 | 北京蒙京石墨新材料科技研究院有限公司 | Method for extracting battery-grade iron phosphate from waste lithium iron phosphate batteries |
| CN111653846A (en) * | 2020-07-27 | 2020-09-11 | 中南大学 | Treatment method of waste lithium iron phosphate battery |
| CN111653846B (en) * | 2020-07-27 | 2021-10-29 | 中南大学 | Treatment method of waste lithium iron phosphate battery |
| CN111977628A (en) * | 2020-09-04 | 2020-11-24 | 中南大学 | Method for recovering and preparing lithium iron phosphate from lithium ion battery |
| CN113880064A (en) * | 2021-11-09 | 2022-01-04 | 株洲冶炼集团股份有限公司 | Method for treating high-impurity lithium iron phosphate waste powder by using low-consumption phosphoric acid |
| CN113880064B (en) * | 2021-11-09 | 2023-08-01 | 株洲冶炼集团股份有限公司 | Method for treating high-impurity lithium iron phosphate waste powder by low-consumption phosphoric acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110422831A (en) | A method of recycling ferric phosphate from ferric phosphate lithium cell | |
| Li et al. | Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries | |
| CN113443640B (en) | Method for preparing battery-grade lithium carbonate and battery-grade iron phosphate by using waste positive and negative electrode powder of lithium iron phosphate battery | |
| CN105355996B (en) | A kind of method of the separating Li from useless lithium cell cathode material and graphite and recycling | |
| WO2022213678A1 (en) | Method for recycling aluminum in waste positive electrode sheet by using selective leaching and application thereof | |
| CN110371943A (en) | A kind of selective recovery technique of nickle cobalt lithium manganate and LiFePO4 mixing waste | |
| CN106807325A (en) | Fe/C composites and its application | |
| Yang et al. | A closed-circuit cycle process for recovery of carbon and valuable components from spent carbon cathode by hydrothermal acid-leaching method | |
| CN113174486A (en) | Method for recovering valuable metals of waste lithium ion batteries | |
| CN113809424B (en) | Recovery method of nickel cobalt lithium manganate and lithium iron phosphate mixed waste | |
| CN106350670A (en) | Treatment process of pyrrhotite | |
| CN108546822A (en) | The method for recycling noble metal from discarded lithium battery using microorganism | |
| CN107129349A (en) | One kind load carbon-based magnetic biological fertilizer of ferroso-ferric oxide biomass and preparation method thereof | |
| CN107915239A (en) | A kind of method for recycling hydro-thermal method production LiFePO4 waste liquid and preparing high-purity sulphuric acid lithium | |
| CN108751234A (en) | A kind of method of purification of lithium fluoride | |
| CN107350482B (en) | A kind of liquid phase reactor preparation method of V-Ti-Fe hydrogen storing alloy powder | |
| CN112850679A (en) | Method for preparing iron phosphate by using waste acid | |
| US20240113326A1 (en) | Vanadium electrolyte, preparation process and use thereof | |
| CN108502852A (en) | A kind of method that selenium in copper anode mud is recycled in microwave sulfating roasting | |
| CN115491527B (en) | Pretreatment method of uranium-containing waste residues and recycling method of uranium | |
| CN108579659A (en) | The ferromagnetism adsorbent and its preparation method and application of cyanide is removed in a kind of cyanating solution | |
| CN107285292A (en) | The method that reaction of high order prepares battery-grade iron phosphate | |
| CN109592878A (en) | A method of reducing cyanide content in gold smelting cyanidation tailings | |
| CN102329954A (en) | Method for pretreating vanadium slag of converter by alkaline leaching and desiliconizing under action of electric field | |
| CN108854966A (en) | A kind of preparation method of silica gel supported composite adsorbing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191108 |