CN113528832A - Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits - Google Patents

Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits Download PDF

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Publication number
CN113528832A
CN113528832A CN202110788207.XA CN202110788207A CN113528832A CN 113528832 A CN113528832 A CN 113528832A CN 202110788207 A CN202110788207 A CN 202110788207A CN 113528832 A CN113528832 A CN 113528832A
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China
Prior art keywords
ion battery
lithium ion
green
waste lithium
anode material
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CN202110788207.XA
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Chinese (zh)
Inventor
陈钰
赵娣
孙炫超
段耀廷
刘聪
白月
马博航
王福纬
赵瞳
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Langfang Normal University
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Langfang Normal University
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Priority to CN202110788207.XA priority Critical patent/CN113528832A/en
Publication of CN113528832A publication Critical patent/CN113528832A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B15/00—Other processes for the manufacture of iron from iron compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a method for green and efficient recovery of a waste lithium ion battery anode material by using citrus fruits. The method comprises the steps of preparing a green solvent by using pomelos or oranges as raw materials, and recycling lithium cobaltate or lithium iron phosphate in the anode material of the waste lithium ion battery by using the green solvent under the conditions of temperature of 25-140 ℃ and time of 0.17-72 hours. The method for green and efficient recovery of the waste lithium ion battery anode material by using the citrus fruits is green and environment-friendly, low in cost, simple to operate, and high in application value, and accords with the concept of sustainable development.

Description

Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits
Technical Field
The invention relates to a method for green and efficient recovery of a waste lithium ion battery anode material by using citrus fruits, and belongs to the application of the lithium battery recovery field and the kitchen garbage recovery application field.
Background
The lithium ion battery is a recyclable battery, and the working principle of the lithium ion battery is that lithium ions move between a positive electrode and a negative electrode in the charging and discharging process. At present, lithium ion batteries are widely used, and are widely applied in the fields of electronic communication and transportation, and meanwhile, more and more waste lithium ion batteries are generated. The waste lithium ion battery contains various harmful substances and is corrosive, and certain harm can be caused to the environment due to improper treatment.
The kitchen waste is waste generated by residents in activities such as daily life, food processing, food service, unit meal supply and the like, and the waste is mainly from the household catering part of the residents. The kitchen garbage contains a large amount of water and organic matters, is easy to rot, and can breed mosquitoes, flies and germs to spread diseases. The rotten fruits and the fruit peels belong to a part of kitchen waste, and the rotten fruits and the fruit peels have important significance in recycling and utilizing the kitchen waste.
The traditional method for recycling the anode material of the waste lithium ion battery has the problems of environmental unfriendliness, high cost, complex operation and the like. The invention provides a method for green and efficient recovery of a waste lithium ion battery anode material by using citrus fruits, which can fully recycle kitchen waste generated by the citrus fruits and can also carry out green and efficient recovery on the waste lithium ion battery anode material.
Disclosure of Invention
The method for green and efficient recovery of the anode material of the waste lithium ion battery by using the citrus fruits is green and environment-friendly, low in cost and simple in operation, can be used for fully recycling kitchen garbage generated by the citrus fruits and also can be used for green and efficient recovery of the anode material of the waste lithium ion battery, and has extremely high application value.
The technical scheme adopted by the invention is that,
a method for green and efficient recovery of waste lithium ion battery anode materials by using citrus fruits comprises the following steps:
1) the green solvent for recycling the anode material of the waste lithium ion battery is prepared by taking citrus fruits as raw materials.
2) Dissolving and recycling the anode material of the waste lithium ion battery by using the green solvent prepared in the step 1).
3) Analyzing the metal ion concentration in the solution in the step 2) and calculating the leaching efficiency.
Preferably, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and in the step 1), the citrus fruits are any one of grapefruit and tangerine.
Preferably, in the step 1), the solvent is grapefruit juice, orange pulp juice, grapefruit peel juice and orange peel juice prepared from citrus fruits such as grapefruit and tangerine.
Optimally, the green and efficient recovery of the waste lithium ion battery anode material by using the citrus fruits is carried out in the step 1), wherein the mass ratio of the pomelo peel (orange peel) to water in the raw materials for preparing the pomelo peel juice and the orange peel juice is 1: 2, the temperature is 100 ℃, and the time is 20 minutes.
Optimally, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and in the step 2), the waste lithium ion battery anode material is any one of lithium cobaltate or lithium iron phosphate.
Optimally, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and in the step 2), the mass of the anode material such as lithium cobaltate or lithium iron phosphate is 0.1 g.
Optimally, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and in the step 2), the mass of the green solvent is 5 g.
Optimally, the citrus fruits are used for green and high-efficiency recovery of the waste lithium ion battery anode material, and in the step 2), the dissolving temperature is 25-140 DEG C
Optimally, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and the dissolution time is 0.17-24 hours in the step 2).
Optimally, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and in the step 3), the centrifugal rate is 12000 r/min.
Optimally, the citrus fruits are used for green and efficient recovery of the waste lithium ion battery anode material, and in the step 3), the concentration of metal ions is measured by using an inductively coupled plasma emission spectrometer, and the leaching efficiency is calculated.
Detailed Description
Example 1
Juicing the shaddock pulp by using a juicer, pouring the squeezed shaddock pulp into a centrifugal tube, centrifuging at the rotating speed of 8000 rpm for 20 minutes, taking out the centrifugal tube, and collecting the upper layer shaddock pulp into a wide-mouth bottle by using a dropper. Weighing 0.1 g of lithium iron phosphate and 5 g of shaddock juice into a reaction bottle, putting the reaction bottle into an oil bath pot, dissolving and recovering for 24 hours at 140 ℃, and then stopping heating and stirring. Taking out the reagent bottle, sucking out the magnetons by using a magnet, pouring the solid-liquid mixture after reaction into a 10 ml centrifugal tube, centrifuging for 20 minutes at the rotating speed of 12000 r/min, taking out the centrifugal tube after the centrifugation is finished, sucking out the upper solution in the centrifugal tube by using a dropper, measuring the concentration of metal ions by using an inductively coupled plasma emission spectrometer, and calculating the leaching efficiency. The leaching efficiency of the pomelo juice to lithium ions in the lithium iron phosphate is 98.0% and the leaching efficiency of iron ions is 66.1% under the conditions of 140 ℃ and 24 hours through analysis.
Example 2
The specific implementation process is the same as that of example 1, the temperature is changed to 25 ℃, other conditions are not changed, the leaching efficiency of the pomelo juice on lithium ion in the lithium iron phosphate is 41.9% at 25 ℃ for 24 hours, and the leaching efficiency of iron ions is 10.5%.
Example 3
The specific implementation process is the same as that of example 1, the lithium iron phosphate in the anode material of the waste lithium ion battery is changed into lithium cobaltate, other conditions are not changed, the leaching efficiency of the pomelo juice on cobalt ions in the lithium cobaltate at 140 ℃ for 24 hours is 73.8%, and the leaching efficiency of the lithium ions is 43.1%.
Example 4
The specific implementation process is the same as that of example 1, the lithium iron phosphate in the anode material of the waste lithium ion battery is changed into lithium cobaltate, the temperature is changed into 25 ℃, other conditions are not changed, the leaching efficiency of the pomelo pulp juice on cobalt ions in the lithium cobaltate is 7.1% under the conditions of 25 ℃ and 24 hours, and the leaching efficiency of the lithium ions is 11.1%.
Example 5
The specific implementation process is the same as that of example 1, the temperature is changed to 80 ℃, the time is changed to 72 hours, other conditions are not changed, the leaching efficiency of the pomelo juice on lithium ions in the lithium iron phosphate is 91.3% under the conditions of 80 ℃ and 72 hours, and the leaching efficiency of iron ions is 73.4%.
Example 6
The specific implementation process is the same as that of example 1, the temperature is changed to 80 ℃, the time is changed to 0.17 hour, other conditions are not changed, the leaching efficiency of the pomelo juice on lithium ions in the lithium iron phosphate is 37.4% under the conditions of 80 ℃ and 0.17 hour, and the leaching efficiency of iron ions is 24.8%.
Example 7
The specific implementation process is the same as that of example 1, the pomelo pulp juice is changed into the pomelo peel juice, the temperature is changed into 80 ℃, other conditions are not changed, the leaching efficiency of the pomelo peel juice on lithium ions in the lithium iron phosphate is 20.7% under the conditions of 80 ℃ and 24 hours, and the leaching efficiency of iron ions is 3.0%.
Example 8
The specific implementation process is the same as that of example 1, the pomelo juice is changed into the rotten pomelo juice, the temperature is changed into 80 ℃, other conditions are not changed, the leaching efficiency of the rotten pomelo juice on lithium ions in the lithium iron phosphate is 85.2% under the conditions of 80 ℃ and 24 hours, and the leaching efficiency of iron ions is 63.2%.
Example 9
The specific implementation process is the same as that of example 1, the pomelo juice is changed into the tangerine pulp juice, the temperature is changed into 25 ℃, other conditions are not changed, the leaching efficiency of the tangerine pulp juice on lithium ions in the lithium iron phosphate is 43.3 percent under the conditions of 25 ℃ and 24 hours, and the leaching efficiency of iron ions is 25.6 percent.
Example 10
The specific implementation process is the same as that of example 1, the pomelo juice is changed into the orange peel juice, the temperature is changed into 100 ℃, other conditions are not changed, the leaching efficiency of the orange peel juice on lithium ions in the lithium iron phosphate is 41.0% under the conditions of 100 ℃ and 24 hours, and the leaching efficiency of iron ions is 14.1%.
Example 11
The specific implementation process is the same as that of example 1, the pomelo juice is changed into the rotten orange juice, the temperature is changed into 100 ℃, other conditions are not changed, the leaching efficiency of the rotten orange juice on lithium iron phosphate is 8.8% under the conditions of 100 ℃ and 24 hours, and the leaching efficiency of iron ions is 2.1%.
Example 12
The specific implementation process is the same as that of example 1, the pomelo juice is changed into the orange peel juice, the temperature is changed to 100 ℃, the lithium iron phosphate is changed into the lithium cobaltate, other conditions are not changed, the leaching efficiency of the orange peel juice on cobalt ions in the lithium cobaltate is 25.8% under the conditions of 100 ℃ and 24 hours, and the leaching efficiency of the lithium ions is 46.6%.
Example 13
The specific implementation process is the same as that of example 1, the pomelo flesh juice is changed into the rotten orange flesh juice, the temperature is changed into 100 ℃, the lithium iron phosphate is changed into lithium cobaltate, other conditions are not changed, the leaching efficiency of the rotten orange peel juice on cobalt ions in the lithium cobaltate is 13.6% under the conditions of 100 ℃ and 24 hours, and the leaching efficiency of the lithium ions is 24.9%.
Example 14
The specific implementation process is the same as that of the embodiment 1, the pomelo pulp juice is changed into the rotten orange peel juice, the temperature is changed into 100 ℃, the lithium iron phosphate is changed into lithium cobaltate, other conditions are not changed, the leaching efficiency of the rotten orange peel juice on cobalt ions in the lithium cobaltate is 14.1% under the conditions of 100 ℃ and 24 hours, and the leaching efficiency of the lithium ions is 20.9%.
Example 15
The specific implementation process is the same as that of example 1, the pomelo juice is changed into rotten pomelo juice, the temperature is changed into 140 ℃, lithium iron phosphate is changed into lithium cobaltate in the anode material of the waste lithium ion battery, the time is changed into 72 hours, other conditions are not changed, the leaching efficiency of the rotten pomelo juice on cobalt ions in the anode material lithium cobaltate of the waste lithium ion battery at 140 ℃ for 72 hours is 22.9%, and the leaching efficiency of the lithium ions is 32.2%.

Claims (8)

1. A method for green and efficient recovery of waste lithium ion battery anode materials by using citrus fruits is characterized in that green and efficient recovery is carried out on the waste lithium ion battery anode materials by using a green solvent prepared by taking the citrus fruits as a raw material.
2. The method for green and efficient recovery of the waste lithium ion battery positive electrode material by using the citrus fruits as claimed in claim 1, wherein the citrus fruits are any one of grapefruit and tangerine.
3. The method for efficiently recovering the anode material of the waste lithium ion battery in a green manner by using the citrus fruits as claimed in claim 1, wherein the green solvent is any one of grapefruit juice, tangerine pulp juice, shaddock peel juice and tangerine peel juice.
4. The method for green and efficient recovery of the waste lithium ion battery cathode material by using citrus fruits according to claim 1 is characterized in that the mass ratio of the pomelo peel (orange peel) to water in the raw materials for preparing the pomelo peel juice and the orange peel juice is 1: 2, the temperature is 100 ℃, and the time is 20 minutes.
5. The method for green and efficient recovery of the anode material of the waste lithium ion battery by using the citrus fruits as claimed in claim 1, wherein the anode material of the waste lithium ion battery is any one of lithium cobaltate and lithium iron phosphate.
6. The method for green and efficient recovery of the anode material of the waste lithium ion battery by using the citrus fruits as claimed in claim 1, wherein the mass of the anode material of the waste lithium ion battery is 0.1 g, and the mass of the green solvent is 5 g.
7. The method for green and efficient recovery of the anode material of the waste lithium ion battery by using the citrus fruits as claimed in claim 1, wherein the temperature for dissolving and recovering the anode material of the waste lithium ion battery is 25-140 ℃.
8. The method for green and efficient recovery of the anode material of the waste lithium ion battery by using the citrus fruits as claimed in claim 1, wherein the time for dissolving and recovering the anode material of the waste lithium ion battery is 0.17-72 hours.
CN202110788207.XA 2021-07-12 2021-07-12 Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits Pending CN113528832A (en)

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CN202110788207.XA CN113528832A (en) 2021-07-12 2021-07-12 Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits

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CN202110788207.XA CN113528832A (en) 2021-07-12 2021-07-12 Method for green and efficient recovery of waste lithium ion battery anode material by using citrus fruits

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3288103A1 (en) * 2015-04-21 2018-02-28 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Method for preparing negative electrode material of lithium-ion battery by using biomass gasification furnace filter residue
CN108281730A (en) * 2018-01-10 2018-07-13 浙江衡远新能源科技有限公司 The recovery method of metallic element in a kind of waste and old ternary lithium-ion-power cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3288103A1 (en) * 2015-04-21 2018-02-28 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Method for preparing negative electrode material of lithium-ion battery by using biomass gasification furnace filter residue
CN108281730A (en) * 2018-01-10 2018-07-13 浙江衡远新能源科技有限公司 The recovery method of metallic element in a kind of waste and old ternary lithium-ion-power cell

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