CN111647747A - Method for recovering valuable metals in lithium battery of new energy automobile - Google Patents

Method for recovering valuable metals in lithium battery of new energy automobile Download PDF

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Publication number
CN111647747A
CN111647747A CN202010183247.7A CN202010183247A CN111647747A CN 111647747 A CN111647747 A CN 111647747A CN 202010183247 A CN202010183247 A CN 202010183247A CN 111647747 A CN111647747 A CN 111647747A
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lithium battery
solid
new energy
energy automobile
recovering valuable
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CN202010183247.7A
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Chinese (zh)
Inventor
宋伟明
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Liuzhou Yonganhang Automobile Technology Co ltd
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Liuzhou Yonganhang Automobile Technology Co ltd
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Priority to CN202010183247.7A priority Critical patent/CN111647747A/en
Publication of CN111647747A publication Critical patent/CN111647747A/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
    • C22B7/001—Dry 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting 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
    • 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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a method for recovering valuable metals in a lithium battery of a new energy automobile, which comprises the following steps: disassembling the lithium battery, namely disassembling the lithium battery after discharge treatment, separating a positive plate and a negative plate, and then separating a positive material in the positive plate and a negative material in the negative plate from an aluminum foil; mixing the separated positive electrode material, negative electrode material and a roasting agent, and roasting at low temperature to obtain a roasted material, wherein the roasting agent is ammonium bisulfate, and the quantity of the roasting agent and the positive electrode material meets the requirement that the ratio of (n ((NH4)2SO4) + n ((NH4) HSO4) }ton (Ni + Co + Mn +2Li) is 0.9-1.5 according to the molar ratio; and (3) carrying out solid-liquid separation, placing the obtained roasted material into a container, adding a proper amount of chemical reagent, stirring, and standing for 15 minutes. The method can be used for recycling the lithium battery, the time required by the process flow is short, a large amount of acid and alkali are not required to be consumed, a large amount of solid waste and wastewater are not generated, the waste battery can be secondarily utilized, the energy is saved, and the method has the advantages of popularization, no pollution, high enrichment degree, high product purity and the like.

Description

Method for recovering valuable metals in lithium battery of new energy automobile
Technical Field
The invention relates to the field of new energy batteries, in particular to a method for recovering valuable metals in a lithium battery of a new energy automobile.
Background
The new energy battery develops a novel battery by utilizing the characteristic that lithium ions rapidly shuttle in large quantities between the surface of graphene and an electrode, wherein a large amount of valuable metals exist in the lithium battery and can be recovered;
however, the battery is scrapped along with the loss of the battery, valuable metals in the waste lithium battery need to be recycled, and a large amount of acid and alkali is needed when the waste battery is recycled in the traditional technology, so that the cost is high, and meanwhile, certain adverse effects are easily brought to the environment, so that a method for recycling the valuable metals in the lithium battery of the new energy automobile is provided.
Disclosure of Invention
The invention aims to provide a method for recovering valuable metals in a lithium battery of a new energy automobile, which aims to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: the method for recovering valuable metals in the lithium battery of the new energy automobile comprises the following steps:
s1: disassembling the lithium battery, namely disassembling the lithium battery after discharge treatment, separating a positive plate and a negative plate, and then separating a positive material in the positive plate and a negative material in the negative plate from an aluminum foil;
s2: mixing the separated positive electrode material, negative electrode material and a roasting agent, and roasting at low temperature to obtain a roasted material, wherein the roasting agent is ammonium bisulfate, and the quantity of the roasting agent and the positive electrode material meets the requirement that the ratio of (n ((NH4)2SO4) + n ((NH4) HSO4) }ton (Ni + Co + Mn +2Li) is 0.9-1.5 according to the molar ratio;
s3: solid-liquid separation, namely placing the obtained roasted material into a container, adding a proper amount of chemical reagent, stirring, standing for 15 minutes, and carrying out solid-liquid separation when solid is precipitated at the bottom of the container;
s4: pH value measurement and pH meter measures the pH value of the filtrate obtained by solid-liquid separation, ammonium carbonate or ammonium bicarbonate is added into the filtrate or CO2 is blown into the filtrate to precipitate lithium, and after the reaction is finished, solid-liquid separation is carried out to obtain lithium carbonate;
s5: and (4) valuable metal recovery, namely heating and melting the lithium carbonate in S4, removing impurities, adding an additive, melting, and recovering valuable metal lithium from the upper layer liquid when the upper layer liquid is silvery white.
Preferably, the precipitating agent is ammonium oxalate or ammonium hydrogen oxalate.
Preferably, the anode material of the positive plate is titanium-based lead dioxide or titanium coated with noble metal, and the cathode material of the negative plate is stainless steel or Ti.
Preferably, in S4, an alkali solution may be added instead of ammonium carbonate or ammonium bicarbonate, the alkali solution being a sodium carbonate solution or a liquid alkali of 10 to 20% by mass concentration.
Preferably, the temperature for the low-temperature calcination in S2 is 80-120 ℃.
Preferably, in S3, a solid-liquid separator is used to separate the solid matter and the solution of the lithium battery, and the solid-liquid separator has a cylindrical structure with a diameter of 380mm and a height of 4.45m, and has an inclined tube inside, and the inclined tube forms an angle of 60 ° with the separator body.
Preferably, the additive is alpha-tocopherol.
Compared with the prior art, the invention has the beneficial effects that: the method can be used for recycling the lithium battery, the time required by the process flow is short, a large amount of acid and alkali are not required to be consumed, a large amount of solid waste and wastewater are not generated, the waste battery can be secondarily utilized, the energy is saved, and the method has the advantages of popularization, no pollution, high enrichment degree, high product purity and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides the technical scheme that: the method for recovering valuable metals in the lithium battery of the new energy automobile comprises the following steps:
s1: disassembling the lithium battery, namely disassembling the lithium battery after discharge treatment, separating a positive plate and a negative plate, and then separating a positive material in the positive plate and a negative material in the negative plate from an aluminum foil;
s2: mixing the separated positive electrode material, negative electrode material and a roasting agent, and roasting at low temperature to obtain a roasted material, wherein the roasting agent is ammonium bisulfate, and the quantity of the roasting agent and the positive electrode material meets the requirement that the ratio of (n ((NH4)2SO4) + n ((NH4) HSO4) }ton (Ni + Co + Mn +2Li) is 0.9-1.5 according to the molar ratio;
s3: solid-liquid separation, namely placing the obtained roasted material into a container, adding a proper amount of chemical reagent, stirring, standing for 15 minutes, and carrying out solid-liquid separation when solid is precipitated at the bottom of the container;
s4: pH value measurement and pH meter measures the pH value of the filtrate obtained by solid-liquid separation, ammonium carbonate or ammonium bicarbonate is added into the filtrate or CO2 is blown into the filtrate to precipitate lithium, and after the reaction is finished, solid-liquid separation is carried out to obtain lithium carbonate;
s5: and (4) valuable metal recovery, namely heating and melting the lithium carbonate in S4, removing impurities, adding an additive, melting, and recovering valuable metal lithium from the upper layer liquid when the upper layer liquid is silvery white.
The precipitator is ammonium oxalate or ammonium hydrogen oxalate; the anode material of the anode plate is titanium-based lead dioxide or titanium coated with noble metal, and the cathode material of the cathode plate is stainless steel or Ti; adding an alkali solution to replace ammonium carbonate or ammonium bicarbonate in S4, wherein the alkali solution is a sodium carbonate solution or a liquid alkali with the mass concentration of 10-20%; the low-temperature roasting temperature in S2 is 80-120 ℃; in S3, a solid-liquid separator is adopted to separate solid matters and solution of the lithium battery, the solid-liquid separator is of a cylindrical structure, the diameter is 380mm, the height is 4.45m, an inclined pipe is arranged in the solid-liquid separator, and the included angle between the inclined pipe and the separator body is 60 degrees; the additive is alpha-tocopherol.
It should be noted that: the method comprises the following steps: discharging lithium cobalt oxide lithium ion waste batteries by using 100g/L of salt solution, disassembling and removing a metal shell, separating out a positive plate, a negative plate, a diaphragm and electrolyte, crushing the obtained positive plate, screening out an aluminum foil and a positive electrode material, mixing the obtained positive electrode material with ammonium bisulfate according to the condition that n ((NH4)2SO4)/n (Co +2Li) ═ 1.3, roasting in a tubular furnace, wherein the roasting temperature is 650 ℃, the roasting time is 2 hours, crushing the obtained roasted material, mixing with pure water (or tap water) according to the liquid-solid ratio of 3: 1ml/g, and stirring and leaching for 30min in a water bath environment at 60 ℃. After leaching, completely reacting the slurry, performing liquid-solid separation to obtain carbon slag and a leaching solution containing Co and Li, recovering the carbon slag, wherein the leaching rate of Co is 98.6%, the leaching rate of Li is 99.2%, adding an ammonium oxalate solution into the obtained leaching solution to precipitate lithium, stirring and reacting for 2 hours at 60 ℃, after the reaction is completed, performing liquid-solid separation to obtain a cobalt oxalate product and a filtrate, the recovery rates are 99.5%, introducing NH3 collected in a roasting section into the obtained filtrate, adjusting the pH value to 11.5, adding an ammonium carbonate solution, reacting for 2 hours at 70 ℃, after the reaction is completed, performing liquid-solid separation to obtain a lithium carbonate product, the recovery rate is 95.7%, adjusting the pH value of the obtained liquid after liquid-solid separation by using ammonia-containing flue gas to be 5-8, heating and crystallizing to obtain an ammonium sulfate product, crushing the ammonium sulfate product for later use, and using as a roasting agent.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. The method for recovering valuable metals in the lithium battery of the new energy automobile is characterized by comprising the following steps of:
s1: disassembling the lithium battery, namely disassembling the lithium battery after discharge treatment, separating a positive plate and a negative plate, and then separating a positive material in the positive plate and a negative material in the negative plate from an aluminum foil;
s2: mixing the separated positive electrode material, negative electrode material and a roasting agent, and roasting at low temperature to obtain a roasted material, wherein the roasting agent is ammonium bisulfate, and the quantity of the roasting agent and the positive electrode material meets the requirement that the ratio of (n ((NH4)2SO4) + n ((NH4) HSO4) }ton (Ni + Co + Mn +2Li) is 0.9-1.5 according to the molar ratio;
s3: solid-liquid separation, namely placing the obtained roasted material into a container, adding a proper amount of chemical reagent, stirring, standing for 15 minutes, and carrying out solid-liquid separation when solid is precipitated at the bottom of the container;
s4: pH value measurement and pH meter measures the pH value of the filtrate obtained by solid-liquid separation, ammonium carbonate or ammonium bicarbonate is added into the filtrate or CO2 is blown into the filtrate to precipitate lithium, and after the reaction is finished, solid-liquid separation is carried out to obtain lithium carbonate;
s5: and (4) valuable metal recovery, namely heating and melting the lithium carbonate in S4, removing impurities, adding an additive, melting, and recovering valuable metal lithium from the upper layer liquid when the upper layer liquid is silvery white.
2. The method for recovering valuable metals from the lithium battery of the new energy automobile as claimed in claim 1, wherein the method comprises the following steps: the precipitator is ammonium oxalate or ammonium hydrogen oxalate.
3. The method for recovering valuable metals from the lithium battery of the new energy automobile as claimed in claim 1, wherein the method comprises the following steps: the anode material of the anode plate is titanium-based lead dioxide or titanium coated with noble metal, and the cathode material of the cathode plate is stainless steel or Ti.
4. The method for recovering valuable metals from the lithium battery of the new energy automobile as claimed in claim 1, wherein the method comprises the following steps: in S4, an alkali solution can be added to replace ammonium carbonate or ammonium bicarbonate, wherein the alkali solution is a sodium carbonate solution or liquid alkali with the mass concentration of 10-20%.
5. The method for recovering valuable metals from the lithium battery of the new energy automobile as claimed in claim 1, wherein the method comprises the following steps: the temperature of the low-temperature roasting in S2 is 80-120 ℃.
6. The method for recovering valuable metals from the lithium battery of the new energy automobile as claimed in claim 1, wherein the method comprises the following steps: in S3, a solid-liquid separator is adopted to separate solid matters and solution of the lithium battery, the solid-liquid separator is of a cylindrical structure, the diameter is 380mm, the height is 4.45m, an inclined pipe is arranged in the solid-liquid separator, and the included angle between the inclined pipe and the separator body is 60 degrees.
7. The method for recovering valuable metals from the lithium battery of the new energy automobile as claimed in claim 1, wherein the method comprises the following steps: the additive is alpha-tocopherol.
CN202010183247.7A 2020-03-16 2020-03-16 Method for recovering valuable metals in lithium battery of new energy automobile Withdrawn CN111647747A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010183247.7A CN111647747A (en) 2020-03-16 2020-03-16 Method for recovering valuable metals in lithium battery of new energy automobile

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Application Number Priority Date Filing Date Title
CN202010183247.7A CN111647747A (en) 2020-03-16 2020-03-16 Method for recovering valuable metals in lithium battery of new energy automobile

Publications (1)

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