CN103276406A - Electrochemical lithium recovery method - Google Patents
Electrochemical lithium recovery method Download PDFInfo
- Publication number
- CN103276406A CN103276406A CN201310105752XA CN201310105752A CN103276406A CN 103276406 A CN103276406 A CN 103276406A CN 201310105752X A CN201310105752X A CN 201310105752XA CN 201310105752 A CN201310105752 A CN 201310105752A CN 103276406 A CN103276406 A CN 103276406A
- Authority
- CN
- China
- Prior art keywords
- lithium
- iron phosphate
- electrode
- tertiary iron
- carbon
- 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.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
Abstract
The invention discloses an electrochemical lithium recovery method. Lithium in a solution is enriched through an electrochemical process by iron phosphate (FePO4), and the obtained lithiated iron phosphate material undergoes heat treatment to prepare a lithium iron phosphate positive electrode material. The electrochemical method which is used to extract lithium has a high lithium extraction selectivity, and is not influenced by other ions in the solution, and the electrochemical product lithiated iron phosphate can be directly converted to the lithium iron phosphate material after processing. So the method is very suitable for the direct extraction of lithium from the ionic solution having low values, and has the advantages of simple process, easy control and low cost, substantial practical values and good application prospect.
Description
Technical field
The present invention relates to method and iron lithium phosphate (LiFePO4) Reuse of materials that a kind of electrochemistry reclaims lithium, belong to energy and material and technical field.
Background technology
Lithium ion battery has extended cycle life because it has the specific storage height, and operating temperature range is wide, and self-discharge is little, characteristics such as memory-less effect, and at notebook computer, mobile telephone has obtained widespread use in the portable type electronic products such as digital camera.According to statistics, global lithium ion battery turnout surpassed 5.8 hundred million in 2000, about 100,000,000 of output in domestic, and global output reached 12.55 hundred million in 2003, and 2008 annual production have reached 27.1 hundred million, and global output had surpassed 3,000,000,000 in 2010.And along with the development and use of economic development of science and technology and global resources, lithium ion battery will become the major impetus source of electromobile, and this will further promote the development of lithium cell.
Therefore the use of lithium ion battery is the mutual conversion of its inner chemical energy and electric energy, environment is polluted less, can be described as new and effective green secondary cell.But because work-ing life of lithium ion battery is limited, in case after discharging and recharging through hundreds of, active material will be because of structural changes, problems such as dissolving losss lose activity, and cause the capacity decline of battery and battery is scrapped.And the inside battery of scrapping contains inflammable and explosive and poisonous material, can decompose in malaria as electrolytic salt LiPF6 etc. and to generate objectionable impurities, and organic solvent EC, DMC, meetings such as EMC cause serious pollution and the ecosystem are produced harm ambient water, atmosphere and soil.Moreover, because anode material for lithium-ion batteries mostly is transition metal oxide, as LiCoO2, LiFePO4, LiMnO4 etc., wherein contain valuable and rare metal such as cobalt, nickel, lithium etc., therefore, the focus that waste and old lithium ion battery is carried out harmless treatment and the resource utilization recycling of valuable metal wherein become current domestic and international research.
At present, to the recovery of waste and old lithium ion battery, mainly concentrate on the recovery to valuable metal cobalt, nickel and lithium both at home and abroad, because these metals belong to rare metal, have higher recovery value with respect to other metals.Its removal process comprises that mainly the fractionation of old and useless battery pulverizes, the separation of each several part and the enrichment of valuable metal, and eliminate or reduce objectionable impurities to the pollution of environment.Recovery method mainly is divided into two kinds: pyrometallurgical method and hydrometallurgical.Pyrometallurgical method namely directly adopts the method for pyroprocessing to abolish plastic casing and metal shell, then uses methods such as flotation, precipitation to obtain metallic compound.This method technology is simple relatively, but also exists the thermal treatment energy consumption higher, and other compositions change gases such as carbonic acid gas and other objectionable constituent (as Vanadium Pentoxide in FLAKES etc.) in electrolytic solution and the electrode by burning, can cause secondary pollution.Hydrometallurgical, namely use mechanical means to abolish plastics, metal shell earlier, then take methods such as leaching, precipitation, ion-exchange, absorption to obtain metallic compound, this method is higher to recovery rate of valuable metals, the operational condition gentleness, and environmental pollution is less, becomes at present the extensive method that adopts of investigator both at home and abroad.
Though to the existing many reports of the recovery of transition metal, but the recovery method at lithium is then less, mainly adopts chemical precipitation method that the form of lithium with Li2CO3 is fixed up, and this is for behind transition metal such as hydrometallurgic recovery cobalt, nickel, reclaiming lithium with precipitation forms again, is comparatively easily.But still have problems such as organic efficiency is low, purity is not high, and needing purification process again, cost recovery increases sharply.On the other hand, for the LiFePO4 batteries that are used for electromobile or accumulation power supply now in a large number, if still by after wet separation was worth not high Fe and Al factor in the past, the redeposition lithium will cause higher lithium cost recovery.Therefore, need that development is novel, cleaning, lithium recovery method efficiently.
Summary of the invention
The invention discloses a kind of electrochemical process and reclaim lithium, and can be used as the approach that the LiFePO4 material recycles.It is characterized in that adopting the FePO4 material directly from solution, to reclaim lithium by electrochemical method, and the Li1-xFePO4 material that forms is prepared the new LiFePO4 material of generation again.That this scheme has namely reached is directed, efficient, technology reclaims lithium simply, and can convert the LiFePO4 material to after product is directly handled with reclaiming, and be used further to make lithium ion battery.
The key point of technical solution of the present invention is: adopt the FePO4 material directly to reclaim lithium by electrochemical method from solution, it is characterized in that:
1. method and utilization that electrochemistry reclaims lithium, it is characterized in that adopting tertiary iron phosphate (FePO4) material by the lithium in the electrochemical process enrichment solution, and the tertiary iron phosphate material after the lithiumation can be prepared into lithium iron phosphate positive material again by thermal treatment.
2. described electrochemical method adopts two electrodes and a kind of aqueous electrolyte liquid that contains lithium.One of them electrode is the electrode of phosphoric acid iron material, and another is noble electrode, as platinum, nickel, carbon, ruthenium, titanium, carbon dioxide process carbon electrode.Containing the lithium electrolyte aqueous solution is to scrap the lithium ion battery lithium iron phosphate positive material through the acid dissolving and the nearly neutral solution after handling.
3. described tertiary iron phosphate material is nano ferric phosphate, and chemical formula is FePO4, also can be the tertiary iron phosphate/carbon composite of carbon coated.
4. the electrode of described tertiary iron phosphate material is that the mixture of tertiary iron phosphate material and carbon is compressed on the electrode on the conductive current collector.
The electrochemical method implementation process be the ferroelectric utmost point of phosphoric acid as negative pole, noble electrode is anodal, logical continuous current charges, and makes tertiary iron phosphate material embedding lithium form lithiumation tertiary iron phosphate material.
Another characteristics of the present invention are can be directly with the lithiumation tertiary iron phosphate material that produces, the lithium source that the metering of pressing LiFePO 4 material is more suitable than adding, after dispersing and mixing, thermal treatment under inert atmosphere, can form the ferric phosphate lithium cell material, and be applied to the preparation of ferric phosphate lithium cell again.
Based on the foregoing invention principle, the present invention compared with prior art, have the following advantages and beneficial effect: the electrochemical method of this employing extracts the selected material-tertiary iron phosphate of lithium, under certain current potential, can only embed lithium, all insensitive to iron ion, aluminum ion, ammonium ion etc., have high selectivity, be implemented in and directly extract lithium in the mixing solutions.This method is very suitable for directly extracting lithium in being worth not high solion.In addition, the lithiumation iron lithium phosphate through electrochemical reaction obtains by after metering coupling and the thermal treatment, can change into commercial lithium iron phosphate positive material again, has realized the resource circulation utilization.Therefore, technology of the present invention is simple, and is easy to control, and cost is low, has significant practical value and good prospects for application.
Description of drawings
Fig. 1 is the SEM picture of the tertiary iron phosphate material for preparing in the embodiment of the invention.
Fig. 2 is the discharge curve of tertiary iron phosphate electrode in hybrid ionic solution in the embodiment of the invention.
Concrete embodiment
Embodiment
The preparation of tertiary iron phosphate material:
With 11.3g Fe (NO
3)
36H
2O, 2.74gH
3PO
4Mix, be made into the 70ml aqueous solution, pouring 100ml into has in the stainless steel cauldron of Teflon liner, at 150 ℃ of following hydro-thermal reaction 24h, naturally cool to room temperature after, remove all solvents and get presoma.Precursor is placed 60 ℃ of dryings in the loft drier, namely obtain the target product tertiary iron phosphate.
Fig. 1 is the SEM figure of gained tertiary iron phosphate material, the as can be seen from the figure globosity of the synthetic material of this method with even rule, and particle diameter is 2～3 μ m, each microballoon is to be assembled mutually by the nanoparticle about 100nm to form.
The preparation of tertiary iron phosphate electrode:
Be that tertiary iron phosphate material and acetylene black are even according to the mixed of quality 9:1 with Fig. 2, at the ptfe emulsion that adds 1%, the uniform pasty state of furnishing, it is online to be coated in conductive nickel, is pressed into the tertiary iron phosphate electrode.
Contain the preparation of lithium electrolytic solution:
After waste lithium iron phosphate battery disassembled, take out anodally, put into hydrochloric acid soln and dissolve, regulate the nearly neutrality of pH value with ammoniacal liquor again, remove by filter precipitation, namely get and contain lithium electrolytic solution.
Electrochemistry is extracted lithium:
Tertiary iron phosphate electrode and a graphite cake electrode put into fill the above-mentioned groove that contains lithium electrolytic solution, the tertiary iron phosphate electrode connects the working electrode of potentiostat, and Graphite Electrodes connects counter electrode, adopts silver/silver chloride electrode as reference electrode.Calculate by the amount of tertiary iron phosphate with 50mA/g() continuous current the tertiary iron phosphate electrode is discharged, the discharge stopping potential is-0.5V, discharge curve such as Fig. 2. as can be seen from Figure 2, the tertiary iron phosphate material can obtain the capacity of nearly 120mAh/g, is equivalent to every mole of phosphoric acid iron and embeds 0.7 lithium ion.Extract repeatedly if upgrade electrode, the extraction efficiency of lithium can reach more than 98%.
Claims (5)
1. the method for an electrochemistry recovery lithium it is characterized in that adopting tertiary iron phosphate (FePO4) material by the lithium in the electrochemical process enrichment solution, and the tertiary iron phosphate material after the lithiumation can be prepared into lithium iron phosphate positive material again by thermal treatment.
2. electrochemistry as claimed in claim 1 reclaims the method for lithium, it is characterized in that described electrochemical method adopts two electrodes and a kind of aqueous electrolyte liquid that contains lithium, one of them electrode is the electrode of phosphoric acid iron material, another is noble electrode, as platinum, nickel, carbon, ruthenium, titanium, carbon dioxide process carbon electrode, containing the lithium electrolyte aqueous solution is to scrap the lithium ion battery lithium iron phosphate positive material through the acid dissolving and the nearly neutral solution after handling.
3. as the method for claim 1 and 2 described electrochemistry recovery lithiums, it is characterized in that the tertiary iron phosphate material is nano ferric phosphate, chemical formula is FePO4, also can be the tertiary iron phosphate/carbon composite of carbon coated.
4. electrochemistry as claimed in claim 2 reclaims the method for lithium, and the electrode that it is characterized in that the tertiary iron phosphate material is that the mixture of tertiary iron phosphate material and carbon is compressed on the electrode on the conductive current collector.
5. as the method for claim 1 and 2 described electrochemistry recovery lithiums, it is characterized in that the ferroelectric utmost point of phosphoric acid as negative pole, noble electrode is anodal, and logical continuous current charges, and makes tertiary iron phosphate material embedding lithium form lithiumation tertiary iron phosphate material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310105752.XA CN103276406B (en) | 2013-03-29 | 2013-03-29 | Electrochemical lithium recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310105752.XA CN103276406B (en) | 2013-03-29 | 2013-03-29 | Electrochemical lithium recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103276406A true CN103276406A (en) | 2013-09-04 |
| CN103276406B CN103276406B (en) | 2017-04-12 |
Family
ID=49059015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310105752.XA Active CN103276406B (en) | 2013-03-29 | 2013-03-29 | Electrochemical lithium recovery method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103276406B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015121684A1 (en) * | 2014-02-14 | 2015-08-20 | University Of Southampton | Sequestration of lithium |
| CN105937038A (en) * | 2016-06-17 | 2016-09-14 | 天齐锂业股份有限公司 | Method for recycling lithium in lithium iron phosphate through electrochemical method |
| WO2017136328A1 (en) * | 2016-02-01 | 2017-08-10 | Northwestern University | Compounds for lithium extraction via ion exchange |
| CN108172922A (en) * | 2016-12-07 | 2018-06-15 | 北京好风光储能技术有限公司 | A kind of recycling method of semisolid lithium battery anode slurry |
| CN115818612A (en) * | 2022-12-27 | 2023-03-21 | 蜂巢能源科技股份有限公司 | Recovery method of lithium iron phosphate anode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916889A (en) * | 2010-08-16 | 2010-12-15 | 长春劲能锂电池科技有限公司 | Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery |
| CN102049237A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Iron phosphate ion sieve for selectively extracting Li and application thereof |
| US20120177842A1 (en) * | 2011-01-07 | 2012-07-12 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing power storage device |
| CN102881865A (en) * | 2012-09-14 | 2013-01-16 | 北京鼎能开源电池科技股份有限公司 | Method for manufacturing positive plate of battery |
| CN104112882A (en) * | 2014-07-24 | 2014-10-22 | 国家电网公司 | Method for electrochemically extracting lithium from positive electrode material of lithium ion battery |
-
2013
- 2013-03-29 CN CN201310105752.XA patent/CN103276406B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916889A (en) * | 2010-08-16 | 2010-12-15 | 长春劲能锂电池科技有限公司 | Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery |
| CN102049237A (en) * | 2010-11-19 | 2011-05-11 | 中南大学 | Iron phosphate ion sieve for selectively extracting Li and application thereof |
| US20120177842A1 (en) * | 2011-01-07 | 2012-07-12 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing power storage device |
| CN102881865A (en) * | 2012-09-14 | 2013-01-16 | 北京鼎能开源电池科技股份有限公司 | Method for manufacturing positive plate of battery |
| CN104112882A (en) * | 2014-07-24 | 2014-10-22 | 国家电网公司 | Method for electrochemically extracting lithium from positive electrode material of lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 石晓茜等，: ""磷酸铁锂材料在水溶液中嵌锂行为研究"", 《广州化工》 * |
| 邓凌峰等，: ""电化学合成磷酸铁锂正极材料的前驱体"", 《材料导报B：研究篇》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015121684A1 (en) * | 2014-02-14 | 2015-08-20 | University Of Southampton | Sequestration of lithium |
| WO2017136328A1 (en) * | 2016-02-01 | 2017-08-10 | Northwestern University | Compounds for lithium extraction via ion exchange |
| CN105937038A (en) * | 2016-06-17 | 2016-09-14 | 天齐锂业股份有限公司 | Method for recycling lithium in lithium iron phosphate through electrochemical method |
| WO2017215283A1 (en) * | 2016-06-17 | 2017-12-21 | 天齐锂业股份有限公司 | Method for recycling lithium in lithium iron phosphate by means of electrochemical process |
| CN108172922A (en) * | 2016-12-07 | 2018-06-15 | 北京好风光储能技术有限公司 | A kind of recycling method of semisolid lithium battery anode slurry |
| CN115818612A (en) * | 2022-12-27 | 2023-03-21 | 蜂巢能源科技股份有限公司 | Recovery method of lithium iron phosphate anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103276406B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Sustainable and facile method for the selective recovery of lithium from cathode scrap of spent LiFePO4 batteries | |
| Ma et al. | High-performance graphite recovered from spent lithium-ion batteries | |
| Fujita et al. | Reduction, reuse and recycle of spent Li-ion batteries for automobiles: A review | |
| CN102751549B (en) | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries | |
| CN102676827B (en) | Method for recovering valuable metal from nickel cobalt lithium manganate batteries and positive pole materials | |
| CN102751548B (en) | Method for recovering and preparing lithium iron phosphate from waste lithium iron phosphate battery | |
| CN102517448B (en) | Method for recycling metal ion from waste lithium-ion battery | |
| CN103474718B (en) | A kind of method of Call Provision from anode material of lithium battery | |
| CN102382987B (en) | Method for recovering and regenerating positive electrode material of lithium ion battery | |
| CN105428745A (en) | Method for comprehensive harmless recovery and utilization of waste lithium ion power battery | |
| CN104112882A (en) | Method for electrochemically extracting lithium from positive electrode material of lithium ion battery | |
| CN103184340B (en) | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster | |
| CN101847763A (en) | Comprehensive recovering method of waste lithium iron phosphate battery | |
| CN101710632A (en) | Method for recovering and restoring anode material graphite of waste lithium ion battery | |
| CN102738539A (en) | Method and apparatus for recovering lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries | |
| Zhao et al. | Recycling technology and principle of spent lithium-ion battery | |
| CN106992328B (en) | The waste lithium iron phosphate positive electrode method that recycling recycles in Hawkins cell | |
| CN109536713A (en) | A method of utilizing ionic liquid separating waste, worn active substance of lithium ion battery anode and aluminium foil | |
| CN110311186A (en) | A method of recycling valuable element from waste and old lithium ion battery | |
| CN103276406B (en) | Electrochemical lithium recovery method | |
| Fei et al. | Dual-function regeneration of waste lithium cobalt oxide for stable high voltage cycle performance | |
| CN103956533A (en) | Method for preparing cathode material of lithium ion battery | |
| CN107069133B (en) | A kind of method of lithium in recycling lithium cell cathode material | |
| CN105098280A (en) | Method for recycling current collector from waste lithium-ion battery | |
| CN112038722A (en) | Method for efficiently treating waste lithium iron phosphate positive plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180709 Address after: 330096 No. 88, min Qiang Road, private science and Technology Park, Nanchang, Jiangxi Co-patentee after: State Grid Corporation of China Patentee after: Power Science Research Institute of Jiangxi Electric Power Co., Ltd. Address before: No. 88 City Road, Nanchang, Jiangxi, Jiangxi Co-patentee before: State Grid Corporation of China Patentee before: Jiangxi Electric Power Science Academy |
|
| TR01 | Transfer of patent right |