CN110085937A - A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material - Google Patents

A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material Download PDF

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Publication number
CN110085937A
CN110085937A CN201810099365.2A CN201810099365A CN110085937A CN 110085937 A CN110085937 A CN 110085937A CN 201810099365 A CN201810099365 A CN 201810099365A CN 110085937 A CN110085937 A CN 110085937A
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China
Prior art keywords
lifepo
lithium
regeneration
waste
waste material
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CN201810099365.2A
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李青文
张联齐
宋大卫
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Tianjin University of Technology
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Tianjin University of Technology
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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
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material, steps are as follows；It 1) will be from waste and old LiFePO4The LiFePO recycled in battery4Waste material drying, ball milling, screening removal of impurities, obtain LiFePO4Powdery waste；2) by above-mentioned LiFePO4Powdery waste is calcined under reducing atmosphere after mending lithium (1.01-1.05), the CO-N that the volume percent content that the reducing atmosphere is CO is 5%2Gaseous mixture or CO-Ar gaseous mixture, H2Volume percent content be 5% H2- Ar gaseous mixture or H2‑N2Gaseous mixture, calcination temperature are 600-700 DEG C, calcination time 1-3h, and mixing material positive after calcining is washed, extra lithium source is washed off, the positive mixing material for mending lithium Regeneration and Repair is obtained after dry.The invention has the advantages that this method is easy to operate, at low cost, without secondary pollution, it can effective regeneration reparation LiFePO4Waste material, the positive mixing material for obtaining mending lithium Regeneration and Repair are able to reuse that.

Description

A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material
Technical field
The invention belongs to waste and old lithium ion batteries to be recycled technical field, specially a kind of LiFePO4The benefit lithium of waste material Regeneration and Repair method.
Background technique
It is more and more extensive to the research of lithium ion battery with the high speed development of modernization science and technology and the support of national policy And it quickly grows.Since 1991, lithium ion battery began to increase rapidly in terms of portable electronic device, to being at present Only, it since lithium ion battery specific capacity is high, is widely used the advantages that small in size, memory-less effect.Recycling LiFePO at present4 The method of waste material, which has, recycles metal therein by chemical method, repairs anode by the method that solution mends lithium, these methods are deposited The shortcomings that be cost recovery height, technique is more complex, also there is heat-treating methods.But this method is for lacking the serious anode of lithium Material repairing effect is unobvious, for example, part of the square lithium ion power battery after charge and discharge cycles many times, in anode LiFePO4FePO is decomposed into since lithium volatilizees4And P2O5.Therefore from waste and old LiFePO4The LiFePO recycled in battery4It is useless Material will be unable to reuse such as without overfill lithium Regeneration and Repair.
Summary of the invention
The purpose of the present invention is there are problems for above-mentioned, a kind of LiFePO is provided4The benefit lithium Regeneration and Repair method of waste material, This method is easy to operate, at low cost, without secondary pollution, the positive mixing material (LiFePO obtained after overfill lithium Regeneration and Repair4 Positive electrode and acetylene black) it is able to reuse that.Technical solution of the present invention:
A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material, steps are as follows:
It 1) will be from waste and old LiFePO4The LiFePO recycled in battery4Waste material drying, ball milling, screening removal of impurities, obtain LiFePO4Powdery waste；
2) by above-mentioned LiFePO4Powdery waste is forged under reducing atmosphere after mending excessive lithium (1.01-1.05) It burns, the CO-N that the volume percent content that the reducing atmosphere is CO is 5%2Gaseous mixture, CO volume percent content be 5% CO-Ar gaseous mixture, H2Volume percent content be 5% H2- Ar gaseous mixture or H2Volume percent content be 5% H2-N2Gaseous mixture, calcination temperature are 600 DEG C -700 DEG C, calcination time 1h-3h,
3) mixing material positive after calcining is washed, washes off extra lithium source, obtain mending lithium Regeneration and Repair after dry Positive mixing material.
4) above-mentioned mended lithium is Li2CO3Or LiOH.
The invention has the advantages that this method is easy to operate, at low cost, without secondary pollution, lithium Regeneration and Repair can be effectively mended LiFePO4Waste material, the positive mixing material after obtaining benefit lithium Regeneration and Repair are able to reuse that.
Detailed description of the invention
Fig. 1 is LiFePO of the present invention4Waste material mends the XRD comparison diagram of sample before and after lithium Regeneration and Repair.
Fig. 2 is LiFePO of the present invention4600 DEG C of the waste material cycle performance comparison diagrams mended before and after lithium Regeneration and Repair.
Fig. 3 is LiFePO of the present invention4650 DEG C of the waste material cycle performance comparison diagrams mended before and after lithium Regeneration and Repair.
Fig. 4 is LiFePO of the present invention4700 DEG C of the waste material cycle performance comparison diagrams mended before and after lithium Regeneration and Repair.
Specific embodiment
Embodiment 1:
It 1) will be from waste and old LiFePO4The LiFePO recycled in battery4Waste material at 40 DEG C drying, ball milling, with 300 mesh Sieve screening removal of impurities, obtains LiFePO4Powdery waste；
2) by above-mentioned LiFePO4Powdery waste is calcined under reducing atmosphere after mending lithium (1.03), reproducibility gas Atmosphere is H2Volume percent content be 5% H2-N2Gaseous mixture, calcination temperature are 600 DEG C, calcination time 1h, after calcining Positive mixing material is washed, and extra lithium source is washed off, and the positive mixing material for mending lithium Regeneration and Repair is obtained after dry.
Fig. 1 is LiFePO of the present invention4Waste material mends the XRD comparison diagram of sample before and after lithium (1.03) Regeneration and Repair, wherein not mending The LiFePO of lithium Regeneration and Repair4Waste material contains FePO4And P2O5Impurity.Show in figure: obtaining mending lithium reparative regeneration under this condition Positive mixing material surveys XRD and does not find above-mentioned impurity, this is because when above-mentioned impurity is calcined in a reducing atmosphere and institute Mend Li2CO3Or LiOH reacts, and has recombined LiFePO4.Fig. 2 is LiFePO of the present invention4600 DEG C of benefit lithiums (1.03) of waste material Cycle performance figure after reparative regeneration.Show in figure: not mending the regenerated LiFePO of lithium4Positive mixing material loop attenuation is very fast, And discharge capacity is 132.4mAh/g after circulation 50 weeks, and the LiFePO after 600 DEG C are mended lithium (1.03) regeneration4Anode is mixed Condensation material circulation is relatively stable, is 142mAh/g or more in 50 weeks discharge capacities of circulation, remains as after circulation 100 weeks 134.9mAh/g。
Embodiment 2:
It 1) will be from waste and old LiFePO4The LiFePO recycled in battery4Waste material at 50 DEG C drying, ball milling, with 350 mesh Sieve screening removal of impurities, obtains LiFePO4Powdery waste；
2) by above-mentioned LiFePO4Powdery waste is calcined under reducing atmosphere after mending lithium (1.03), the reduction The CO-N that the volume percent content that property atmosphere is CO is 5%2Gaseous mixture, calcination temperature are 650 DEG C, calcination time 2h, will Positive mixing material is washed after calcining, washes off extra lithium source, and the anode for mending lithium (1.03) Regeneration and Repair is obtained after dry Mixing material.
Fig. 1 is LiFePO of the present invention4Waste material mends the XRD comparison diagram of sample before and after lithium (1.03) Regeneration and Repair, wherein not mending The LiFePO of lithium Regeneration and Repair4Waste material contains FePO4And P2O5Impurity.Show in figure: obtaining mending lithium reparative regeneration under this condition Positive mixing material surveys XRD and does not find above-mentioned impurity, this is because when above-mentioned impurity is calcined in a reducing atmosphere and institute Mend Li2CO3Or LiOH reacts, and has recombined LiFePO4.Fig. 3 is LiFePO of the present invention4650 DEG C of benefit lithiums (1.03) of waste material Cycle performance figure after reparative regeneration.Show in figure: not mending the regenerated LiFePO of lithium4Positive mixing material loop attenuation is very fast, And discharge capacity is 132.4mAh/g after circulation 50 weeks, and the LiFePO after 650 DEG C are mended lithium (1.03) regeneration4Anode is mixed Condensation material circulation is relatively stable, and discharge capacity is 145.9mAh/g or more after circulation 50 weeks, remains as after circulation 100 weeks 140.4mAh/g。
Embodiment 3:
It 1) will be from waste and old LiFePO4The LiFePO recycled in battery4Waste material at 70 DEG C drying, ball milling, with 400 mesh Sieve screening removal of impurities, obtains LiFePO4Powdery waste；
2) by above-mentioned LiFePO4Powdery waste is calcined under reducing atmosphere after mending lithium (1.03), the reduction Property atmosphere be H2Volume percent content be 5% H2- Ar gaseous mixture, calcination temperature are 700 DEG C, and calcination time 3h will be forged Positive mixing material is washed after burning, washes off extra lithium source, and the positive mixing material for mending lithium Regeneration and Repair is obtained after dry.
Fig. 1 is LiFePO of the present invention4Waste material mends the XRD comparison diagram of sample before and after lithium (1.03) Regeneration and Repair, wherein not mending The LiFePO of lithium Regeneration and Repair4Waste material contains FePO4And P2O5Impurity.Show in figure: obtaining mending lithium reparative regeneration under this condition Positive mixing material surveys XRD and does not find above-mentioned impurity, this is because when above-mentioned impurity is calcined in a reducing atmosphere and institute Mend Li2CO3Or LiOH reacts, and has recombined LiFePO4.Fig. 4 is LiFePO of the present invention4700 DEG C of benefit lithiums (1.03) of waste material Cycle performance figure after reparative regeneration.Show in figure: not mending the regenerated LiFePO of lithium4Positive mixing material loop attenuation is very fast, And discharge capacity is 132.4mAh/g after circulation 50 weeks, and the LiFePO after 700 DEG C are mended lithium (1.03) regeneration4Anode is mixed Condensation material circulation is relatively stable, and discharge capacity is 143.1mAh/g after circulation 50 weeks, remains as after circulation 100 weeks 138.6mAh/g。
Above said content is only the preferred embodiment of the invention, should not be considered as limiting the invention creation Practical range.Any changes and improvements made in the scope of the application of the invention should still belong to the invention Patent covering scope within.

Claims (1)

1. a kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material, it is characterised in that steps are as follows:
It 1) will be from waste and old LiFePO4The LiFePO recycled in battery4Waste material drying, ball milling, screening are miscellaneous, obtain LiFePO4Powder Last shape waste material；
2) by above-mentioned LiFePO4Powdery waste is calcined under reducing atmosphere after mending lithium (1.01-1.05), the reduction The CO-N that the volume percent content that property atmosphere is CO is 5%2Gaseous mixture, the CO-Ar that the volume percent content of CO is 5% are mixed Close gas, H2Volume percent content be 5% H2- Ar gaseous mixture or H2Volume percent content be 5% H2-N2Mixing Gas；
3) calcination temperature is 600-700 DEG C；
4) calcination time is 1-3h；
5) lithium mended is Li2CO3Or LiOH.
CN201810099365.2A 2018-01-26 2018-01-26 A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material Pending CN110085937A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111180660A (en) * 2019-12-31 2020-05-19 兰溪致德新能源材料有限公司 Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery
WO2021114747A1 (en) * 2019-12-09 2021-06-17 贝特瑞（天津）纳米材料制造有限公司 Method for selective oxidation-reduction regeneration from waste lithium iron phosphate, regenerated lithium iron phosphate, and lithium ion battery
CN116119638A (en) * 2021-11-12 2023-05-16 中南大学 Method for preparing lithium iron manganese phosphate by recycling waste lithium iron phosphate powder
CN117117165A (en) * 2022-12-13 2023-11-24 山东华劲电池材料科技有限公司 Method for repairing ternary positive electrode material by wet method
CN117117166A (en) * 2022-12-13 2023-11-24 山东华劲电池材料科技有限公司 Method for repairing ternary positive electrode material by dry method
CN116119638B (en) * 2021-11-12 2024-05-10 中南大学 Method for preparing lithium iron manganese phosphate by recycling waste lithium iron phosphate powder

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021114747A1 (en) * 2019-12-09 2021-06-17 贝特瑞（天津）纳米材料制造有限公司 Method for selective oxidation-reduction regeneration from waste lithium iron phosphate, regenerated lithium iron phosphate, and lithium ion battery
CN111180660A (en) * 2019-12-31 2020-05-19 兰溪致德新能源材料有限公司 Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery
CN111180660B (en) * 2019-12-31 2023-02-03 兰溪致德新能源材料有限公司 Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery
CN116119638A (en) * 2021-11-12 2023-05-16 中南大学 Method for preparing lithium iron manganese phosphate by recycling waste lithium iron phosphate powder
CN116119638B (en) * 2021-11-12 2024-05-10 中南大学 Method for preparing lithium iron manganese phosphate by recycling waste lithium iron phosphate powder
CN117117165A (en) * 2022-12-13 2023-11-24 山东华劲电池材料科技有限公司 Method for repairing ternary positive electrode material by wet method
CN117117166A (en) * 2022-12-13 2023-11-24 山东华劲电池材料科技有限公司 Method for repairing ternary positive electrode material by dry method

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