CN106785161B - A kind of regeneration treating method of the graphite cathode of environmental protection - Google Patents

A kind of regeneration treating method of the graphite cathode of environmental protection Download PDF

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Publication number
CN106785161B
CN106785161B CN201611062077.7A CN201611062077A CN106785161B CN 106785161 B CN106785161 B CN 106785161B CN 201611062077 A CN201611062077 A CN 201611062077A CN 106785161 B CN106785161 B CN 106785161B
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graphite cathode
graphite
environmental protection
treating method
material powder
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CN106785161A (en
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郝德利
叶丽光
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TIANJIN HEWEI TECHNOLOGY CO LTD
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TIANJIN HEWEI TECHNOLOGY CO LTD
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A kind of regeneration treating method of the graphite cathode of environmental protection, graphite cathode material powder is heated to 250~280 DEG C in sealed furnace under the conditions of moving air, it is kept for 1~2 hour, it is then cooled to room temperature and removes, the air of outflow, which is passed through in lye, to be absorbed, treated graphite cathode material powder, measure the content of Cu element and P element, the molar ratio of Cu, P are calculated, is calculated with 2: 1, is higher than this value complement and P is added2O5, then under 1000~1700 DEG C of protective atmospheres, it is heat-treated 3~5 hours, cools to 80 DEG C or less and take out, obtain regenerated negative electrode material.For the negative electrode material specific capacity of the method regeneration treatment up to 360mAh/g, self discharge is small, meets the requirement of battery.

Description

A kind of regeneration treating method of the graphite cathode of environmental protection
Technical field
The present invention relates to a kind of regeneration treating methods of the graphite cathode of environmental protection, belong to chemical field.
Background technique
The negative electrode material for the lithium ion battery being commercialized at present is all graphite.As power battery is widely applied, future one Surely the lithium ion battery largely scrapped can be generated.And recycle battery in graphite cathode material recycling be a resource again The problem of utilization.
A kind of graphite negative electrode of lithium ion battery regeneration method of CN 104638316A, step are to disassemble battery at cathode, just Pole, diaphragm etc., then to cathode carry out N- first class pyrrolidones immersion make cathode coating shedding, then with centrifuge separation, pickling, It is dried to obtain recycled graphite.The determination of this method is to impregnate coating for the graphite cathode N- first class pyrrolidones of aqueous coating Not easily to fall off, effect is poor.Also, electrolyte is largely adsorbed in cathode coating, is easy when being impregnated with N- first class pyrrolidones It reacts, generates LiF or HF or POF5Equal substances, these substances do not remove, and can deteriorate the performance of recycling graphite.
A kind of recycling of anode material graphite of waste lithium ion battery of CN 101710632A and restorative procedure, it is basic to use Wet processing largely uses inorganic acid, hydrogen peroxide, sodium chlorate in the process, these can all destroy graphite knot to a certain extent Structure deteriorates the state of graphite surface.Simultaneously as the pollution of use process complex conditions is big, no using a large amount of organic-inorganic solvents Environmental protection.
It in negative electrode tab, is mainly made of graphite, copper foil, carbon dust, bonding agent, in addition, being also adsorbed with a small amount of electrolyte With the lithium from anode.The P element wherein contained is doped to and forms the mechanism that P stores up lithium with graphite jointly in graphite, and the storage lithium of P Amount can achieve 1000mAh/g or more, therefore P doping can be such that the gram volume of graphite significantly improves.The present invention is using in cathode Remaining P element, and suitably adulterate P2O5, the self discharge that compound solves the problems, such as graphite is on the one hand formed with Cu, on the other hand again Improve the gram volume of graphite.
The present invention provides a kind of method, the graphite cathode powder regeneration treatment again that recycling is obtained, obtained graphite Material specific capacity improves, and meets the requirement of battery.
Summary of the invention
A kind of regeneration treating method of the graphite cathode of environmental protection, which is characterized in that processing step is:
1) graphite cathode material powder is heated to 250~280 DEG C in sealed furnace under the conditions of moving air, keeps 1~2 Hour, it is then cooled to room temperature and removes, the air of outflow, which is passed through in lye, to be absorbed.
2) treated graphite cathode material powder measures the content of Cu element and P element, calculates mole of Cu, P Than calculating with 2: 1, adding if being higher than this value into P2O5, then under 1000~1700 DEG C of protective atmospheres, heat treatment 3~ It 5 hours, cools to 80 DEG C hereinafter, take out, obtains regenerated negative electrode material.
The lye is LiOH solution, wherein temperature is at 30~50 DEG C containing 20%~50% urea.When lye goes out When existing crystalline deposit, the new lye of replacement a batch.Moisture content is evaporated from the lye changed, obtains crystal LiF and Li3PO4Mixing Object.
For negative electrode material specific capacity through regeneration treatment up to 360mAh/g, self discharge is small, meets the requirement of battery.
Specific embodiment
Below with reference to embodiment, the present invention is further described, following embodiments be it is illustrative, be not restrictive, It cannot be limited the scope of protection of the present invention with following embodiments.
Embodiment 1
It takes graphite cathode material powder 100g to be placed in tube furnace, 250 DEG C is heated under the conditions of moving air, keep 2 Hour, it is then cooled to room temperature taking-up, the air of outflow, which is passed through in 30 DEG C of LiOH solution containing 20% urea, to be absorbed.Processing Graphite cathode material powder afterwards, measurement Cu constituent content is 0.1% and the content of P element is 0.2%, and the molar ratio of Cu, P are 0.24: 1, then under logical high pure nitrogen, 1000 DEG C are heat-treated 5 hours, are cooled to 40 DEG C and are taken out, obtain regenerated cathode Material.
Regenerated graphite cathode material is tested, is anode with lithium metal, under 0.1C discharge-rate, gram volume is the material 360mAh/g.18650 models electricity is made with this material and the cooperation of LiFePO4 (Tianjin You Lianglineng Science and Technology Ltd.) anode Pond, according to standard testing, one month self-discharge rate of room temperature is 2%/moon, 99% or more capacity restoration rate.
Embodiment 2
It takes graphite cathode material powder 100g to be placed in tube furnace, 280 DEG C is heated under the conditions of moving air, keep 1 Hour, it is then cooled to room temperature taking-up, the air of outflow, which is passed through in 50 DEG C of LiOH solution containing 50% urea, to be absorbed.Processing Graphite cathode material powder afterwards, measurement Cu constituent content is 0.8% and the content of P element is 0.1%, and the molar ratio of Cu, P are 3.87: 1,0.59g P is added2O5, then under logical high pure nitrogen, 1700 DEG C are heat-treated 3 hours, and it cools to 40 DEG C and takes out, Obtain regenerated negative electrode material.
Regenerated graphite cathode material is tested, is anode with lithium metal, under 0.1C discharge-rate, gram volume is the material 362mAh/g.18650 models electricity is made with this material and the cooperation of LiFePO4 (Tianjin You Lianglineng Science and Technology Ltd.) anode Pond, according to standard testing, one month self-discharge rate of room temperature is 2%/moon, 99% or more capacity restoration rate.

Claims (2)

1. a kind of regeneration treating method of the graphite cathode of environmental protection, which is characterized in that processing step is: 1) graphite cathode material Powder is heated to 250~280 DEG C in sealed furnace under the conditions of moving air, kept for 1~2 hour, be then cooled to room temperature and remove, The air of outflow, which is passed through in lye, to be absorbed；2) treated graphite cathode material powder measures the content of Cu element and P element, The molar ratio of Cu, P are calculated, calculates with 2: 1, then adds higher than this value into P2O5, then in 1000~1700 DEG C of protective atmospheres Under, it is heat-treated 3~5 hours, cools to 80 DEG C hereinafter, take out, obtain regenerated negative electrode material.
2. a kind of according to claim 1, regeneration treating method of the graphite cathode of environmental protection, which is characterized in that the lye is LiOH solution, wherein temperature is at 30~50 DEG C containing 20%~50% urea.
CN201611062077.7A 2016-11-19 2016-11-19 A kind of regeneration treating method of the graphite cathode of environmental protection Active CN106785161B (en)

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CN111644189B (en) * 2020-05-07 2022-10-18 广东邦普循环科技有限公司 Oxygen reduction catalyst using waste battery negative electrode graphite and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101604752A (en) * 2009-07-22 2009-12-16 北京化工大学 A kind of lithium ion battery phosphorus/carbon compound cathode materials and preparation method thereof
CN103618120A (en) * 2013-12-06 2014-03-05 广东邦普循环科技股份有限公司 Method for separating and recycling graphite and copper sheets in negative pole materials of waste lithium ion batteries
CN105355996A (en) * 2015-10-09 2016-02-24 同济大学 Method for separating lithium and graphite from negative electrode material of waste lithium battery and resource utilization
CN106129522A (en) * 2016-08-31 2016-11-16 合肥国轩高科动力能源有限公司 Preparation method for recycling graphite by using lithium ion battery cathode

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101841019A (en) * 2010-04-30 2010-09-22 湖南大学 Carbon cladding layer expansion graphite composite material used for lithium ion batteries and preparation method thereof
CN105720255B (en) * 2016-03-04 2018-08-07 深圳市翔丰华科技股份有限公司 A kind of preparation method of nitrogen-phosphor codoping carbon coating graphite cathode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101604752A (en) * 2009-07-22 2009-12-16 北京化工大学 A kind of lithium ion battery phosphorus/carbon compound cathode materials and preparation method thereof
CN103618120A (en) * 2013-12-06 2014-03-05 广东邦普循环科技股份有限公司 Method for separating and recycling graphite and copper sheets in negative pole materials of waste lithium ion batteries
CN105355996A (en) * 2015-10-09 2016-02-24 同济大学 Method for separating lithium and graphite from negative electrode material of waste lithium battery and resource utilization
CN106129522A (en) * 2016-08-31 2016-11-16 合肥国轩高科动力能源有限公司 Preparation method for recycling graphite by using lithium ion battery cathode

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