CN106654436A - Regeneration processing method of lithium iron phosphate material - Google Patents
Regeneration processing method of lithium iron phosphate material Download PDFInfo
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- CN106654436A CN106654436A CN201611062223.6A CN201611062223A CN106654436A CN 106654436 A CN106654436 A CN 106654436A CN 201611062223 A CN201611062223 A CN 201611062223A CN 106654436 A CN106654436 A CN 106654436A
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- Prior art keywords
- lithium
- nitrogen
- iron phosphate
- alkali lye
- lifepo
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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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- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a regeneration processing method of a lithium iron phosphate material. The method comprises the steps of heating lithium iron phosphate electrode material powder in a closed furnace under the condition of flowing nitrogen protection to 250-280 DEG C, keeping for 1-2 hours, introducing effluent nitrogen into an alkali liquid for absorption, cooling the alkali liquid to a room temperature and taking out a product; and measuring the content of lithium and iron, calculating the molar ratio of Li and Fe, carrying out calculation at the final ratio of Li:Fe being 1:1, supplementing the lithium by using lithium carbonate, carrying out thermal treatment under a protective atmosphere of 600-700 DEG C for 3-5 hours, cooling the product to below 80 DEG C, taking out the product, obtaining regenerated lithium iron phosphate and introducing the effluent nitrogen into the alkali liquid for absorption. The specific discharge capacity of the material is more than 150mAh/g, the self-discharge rate is low and the shelf property is good.
Description
Technical field
The present invention relates to a kind of regeneration treating method of LiFePO 4 material, belongs to chemical field.
Background technology
The sharpest edges of electric automobile are to lead low-carbon (LC), informationization, the developing direction of intelligent future automobile industry,
Life cycle internal ratio orthodox car has the more preferable energy and environmental benefit.Just because of this, from reply Energy restructuring, guarantor
Retaining ring border, cultivation future technology competitive advantage are set out, and it is high that new-energy automobile is all risen to national strategy by Main Developed Countries
Degree, in technology, the market level many strength measures have been put into effect.
Under this situation, China in recent years Development of Electric Vehicles is swift and violent.According to estimates, to the year two thousand twenty, China's pure electric automobile
Recoverable amount reach 16,980,000, to the year two thousand thirty, the recoverable amount of China's pure electric automobile reaches 68,590,000.Wherein, using phosphorus
Sour iron lithium accounts for more than 60% for the electrokinetic cell of positive pole.The extensive application of lithium iron phosphate dynamic battery, future is bound to produce greatly
The ferric phosphate lithium cell that amount is scrapped.And in the refuse battery for reclaiming, the recycling of LiFePO 4 material is that a resource is sharp again
Problem.
The elemental lithium in iron phosphate lithium positive pole piece in old and useless battery necessarily has different degrees of disappearance：On the one hand,
Because LiFePO 4 material battery forming process, lithium ion therein can be moved in negative pole, positive pole is then again returned to, and arrived
The elemental lithium of a rare part can be consumed in this process, and the SEI films for graphite cathode are formed.Because different batteries are adopted
Graphite cathode performance is different, and this consumption ratio for causing elemental lithium is differed；On the other hand, the lithium unit in LiFePO 4 material
Cellulose content is inversely proportional to the state-of-charge of battery, and when disassembling, battery can not possibly be completely in complete discharge condition, causes lithium unit
Element can be lacked a lot.So LiFePO 4 material is recycled the problem that must consider that elemental lithium is not enough.
CN 101359756A (a kind of recovery method of lithium iron phosphate anode material from lithium ionic cell waste), will be waste and old
LiFePO4 powder is dried 2～5 hours at 450～600 DEG C, is subsequently adding the ethanol solution of soluble ferric iron salt, and with lithium salts, phosphorus
The ammonium salt mixing of acid, calcines under protective atmosphere, obtains LiFePO4.This method make use of solid phase method to prepare the work of LiFePO4
Skill, can with it is relatively effective control granule integrity and second particle reunion, but the lithium to lacking originally in LiFePO4
Element is not supplemented, therefore, this method can not effectively reclaim the LiFePO4 in battery.
CN 102751548A (a kind of method that recovery prepares LiFePO4 in old and useless battery from LiFePO4) though in patent
So the comprehensive utilization to lithium considers very comprehensive, but does not remove the compositions such as graphite in positive pole, carbon black, even if the phosphorus after processing
The perfect crystalline of sour iron lithium, the gram volume of simulated battery are also higher, but occur that the processability of LiFePO4 is asked aborning
Topic, such as the specific surface area of material is very high, adhesion is very poor, compacted density is very low etc., causes material to come into operation.
CN 102208707A (a kind of method of positive material of waste lithium iron phosphate reparative regeneration) in patent although examine
Consider and supplement the loss of lithium in positive plate with the mode of addition lithium salts, but alkali soluble has been used when LiFePO4 to be repaired is obtained
Liquid so that generate ferric ion in the solution, even if being also difficult to ensure that without Fe using reducing agent in subsequent steps3+
Residual, this can cause the self discharge of material to aggravate.And it is very high to its equipment requirement using hydro-thermal method synthesizing iron lithium phosphate, produce
The cost of product is difficult to decline, so as to lose the competitiveness of material.
This method makes the LiFePO 4 material after process meet the use requirement of battery by supplementing the elemental lithium for lacking.
The invention provides a kind of method, again regeneration is processed the iron phosphate powder that recovery is obtained, and continuation can be made
For battery material application.
The content of the invention
A kind of regeneration treating method of LiFePO 4 material, it is characterised in that process step is：
1) lithium iron phosphate electrode material powder is heated to 250～280 DEG C in sealed furnace under flowing nitrogen protective condition,
Kept for 1～2 hour, the nitrogen of outflow is passed through in alkali lye and absorbs, be then cooled to room temperature taking-up.During this, LiFePO4
Adsorb a small amount of electrolyte component in electrode material, such as EC, PC, EMC, DMC is evaporated, as nitrogen condenses to alkali lye
In, and LiPF6Gaseous material is decomposed into, as nitrogen enters alkali lye, LiF and Li is generated3PO4Material.
2) the LiFePO 4 material powder after processing, measures the content of Li elements and ferro element, calculate Li, Fe mole
Than, calculate with final Li: Fe=1: 1, the amount of lithium is supplemented with lithium carbonate, then under 600～700 DEG C of protective atmospheres, heat treatment 3
～5 hours, cool to less than 80 DEG C, take out, obtain the LiFePO4 for regenerating, the nitrogen of outflow is passed through in alkali lye and absorbs.
Described alkali lye is LiOH solution, wherein containing 20%～50% urea, temperature is at 30～50 DEG C.When alkali lye goes out
During existing crystalline deposit, a collection of new alkali lye is changed.Moisture content is evaporated from the alkali lye changed, crystal LiF and Li is obtained3PO4It is mixed
Compound.
Contain a certain proportion of material with carbon element in the LiFePO 4 material for according to said method processing, without the need for adding carbon again when using
Conductive agent.The specific discharge capacity of material is in more than 150mAh/g, and self discharge is little, and shelving performance is good.
The alkali lye of absorption is supplied to chemical plant to carry out separating-purifying, further extracts organic solvent, inorganic lithium salt.
Specific embodiment
With reference to embodiment, the present invention is further described, and following embodiments are illustrative, be not it is determinate,
Protection scope of the present invention can not be limited with following embodiments.
Embodiment 1
Positive pole iron phosphate powder 100g disassembled in battery is taken, in being placed in tube furnace, under nitrogen protection, is heated to
250 DEG C, kept for 2 hours, be then cooled to room temperature taking-up, the nitrogen of outflow is passed through 30 DEG C of LiOH (purity containing 20% urea
96%, Shanghai China Lithium Industrial Co., Ltd.) absorb in solution.Measurement, mol ratio Li for calculating material after heat treatment: Fe=0.85
: 1,3.14g lithium carbonates (purity 99.99%, Shanghai China Lithium Industrial Co., Ltd.) are added, it is well mixed, then in 700 DEG C of protections
Under atmosphere, it is heat-treated 3 hours, cools to 50 DEG C, take out, obtain the LiFePO4 for regenerating, the nitrogen of outflow is passed through 30 DEG C
Absorb in LiOH solution containing 20% urea.
The LiFePO 4 material of test regeneration, with lithium metal as negative pole, under 0.2C discharge-rates, gram volume is the material
152mAh/g.Coordinated with this material and FSN-1 graphite cathodes and make 18650 size batteries, according to standard testing, normal temperature one month
Self-discharge rate be 2%/moon, capacity restoration rate more than 99%.
Embodiment 2
The positive pole LiFePO4 100g disassembled in battery is taken, in being placed in tube furnace, under nitrogen protection, 280 DEG C is heated to,
Kept for 1 hour, be then cooled to room temperature taking-up, the nitrogen of outflow is passed through in 50 DEG C of LiOH solution containing 50% urea and absorbs.
Measurement, mol ratio Li for calculating material after heat treatment: Fe=0.65: 1,7.50g lithium carbonates are added, it is well mixed, then 600
Under DEG C protective atmosphere, it is heat-treated 5 hours, cools to 40 DEG C, take out, obtain the LiFePO4 for regenerating, the nitrogen of outflow leads to
Enter in 50 DEG C of LiOH solution containing 50% urea and absorb.
The LiFePO 4 material of test regeneration, with lithium metal as negative pole, under 0.2C discharge-rates, gram volume is the material
151mAh/g.Coordinated with this material and FSN-1 graphite cathodes and make 18650 size batteries, according to standard testing, normal temperature one month
Self-discharge rate be 2%/moon, capacity restoration rate more than 99%.
Claims (2)
1. a kind of regeneration treating method of LiFePO 4 material, it is characterised in that process step is：1) iron phosphate lithium electrode material
Feed powder end is heated to 250～280 DEG C in sealed furnace under flowing nitrogen protective condition, kept for 1～2 hour, and the nitrogen of outflow leads to
Enter in alkali lye and absorb, be then cooled to room temperature taking-up, during this, a small amount of electrolyte is adsorbed in lithium iron phosphate electrode material
Composition, such as EC, PC, EMC, DMC are evaporated, and as nitrogen is condensed in alkali lye, and LiPF6 is decomposed into gaseous state thing
Matter, as nitrogen enters alkali lye, forms LiF and Li3PO4Material；2) the LiFePO 4 material powder after processing, measures Li elements
With the content of ferro element, the mol ratio of Li, Fe is calculated, calculated with final Li: Fe=1: 1, supplement the amount of lithium with lithium carbonate, so
Afterwards under 600～700 DEG C of protective atmospheres, it is heat-treated 3～5 hours, cools to less than 80 DEG C, take out, obtains the phosphorus for regenerating
Sour iron lithium, the nitrogen of outflow is passed through in alkali lye and absorbs.
2. according to claim 1, a kind of regeneration treating method of LiFePO 4 material, it is characterised in that described alkali lye is
LiOH solution, wherein containing 20%～50% urea, temperature is at 30～50 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611062223.6A CN106654436A (en) | 2016-11-19 | 2016-11-19 | Regeneration processing method of lithium iron phosphate material |
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| CN201611062223.6A CN106654436A (en) | 2016-11-19 | 2016-11-19 | Regeneration processing method of lithium iron phosphate material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111392718A (en) * | 2019-12-23 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Recycling method of retired lithium battery negative electrode material |
| CN111755768A (en) * | 2020-07-28 | 2020-10-09 | 韶山润泽新能源科技有限公司 | Waste battery negative electrode powder regeneration treatment system and process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0854530A1 (en) * | 1996-12-24 | 1998-07-22 | Canon Kabushiki Kaisha | Process and apparatus for recovering constituent components of battery |
| CN1973399A (en) * | 2004-06-21 | 2007-05-30 | 丰田自动车株式会社 | Method of disposing of lithium battery |
-
2016
- 2016-11-19 CN CN201611062223.6A patent/CN106654436A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0854530A1 (en) * | 1996-12-24 | 1998-07-22 | Canon Kabushiki Kaisha | Process and apparatus for recovering constituent components of battery |
| CN1973399A (en) * | 2004-06-21 | 2007-05-30 | 丰田自动车株式会社 | Method of disposing of lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| 谢英豪等: "从废旧动力电池中回收制备磷酸铁锂", 《电源技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111392718A (en) * | 2019-12-23 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Recycling method of retired lithium battery negative electrode material |
| CN111755768A (en) * | 2020-07-28 | 2020-10-09 | 韶山润泽新能源科技有限公司 | Waste battery negative electrode powder regeneration treatment system and process |
| CN111755768B (en) * | 2020-07-28 | 2021-02-19 | 韶山润泽新能源科技有限公司 | Waste battery negative electrode powder regeneration treatment system and process |
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Application publication date: 20170510 |