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WO2015192743A1 - Procédé de récupération de ressources et et de protection de l'environnement permettant de recycler des déchets de batteries aux ions de lithium - Google Patents

Procédé de récupération de ressources et et de protection de l'environnement permettant de recycler des déchets de batteries aux ions de lithium Download PDF

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Publication number
WO2015192743A1
WO2015192743A1 PCT/CN2015/081421 CN2015081421W WO2015192743A1 WO 2015192743 A1 WO2015192743 A1 WO 2015192743A1 CN 2015081421 W CN2015081421 W CN 2015081421W WO 2015192743 A1 WO2015192743 A1 WO 2015192743A1
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Prior art keywords
positive electrode
negative electrode
current collector
temperature liquid
electrode material
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PCT/CN2015/081421
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English (en)
Chinese (zh)
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王武生
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Individual
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Individual
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Priority claimed from CN201410267512.4A external-priority patent/CN105244560B/zh
Priority claimed from CN201410267159.XA external-priority patent/CN105186058B/zh
Priority claimed from CN201410267043.6A external-priority patent/CN105304966B/zh
Priority claimed from CN201410522975.0A external-priority patent/CN105576312B/zh
Application filed by Individual filed Critical Individual
Publication of WO2015192743A1 publication Critical patent/WO2015192743A1/fr
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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
    • 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

Definitions

  • the invention relates to a method for recycling environmentally-friendly lithium-ion battery waste, and belongs to the technical field of lithium ion battery recycling.
  • the object of the present invention is to provide a method for recycling lithium-ion battery waste by recycling resources, realizing the recycling of lithium ion battery waste, and achieving energy saving and emission reduction purposes.
  • the present invention adopts the following technical solutions:
  • the invention relates to a method for recycling lithium-ion battery waste in an environmentally-friendly manner, wherein the lithium ion battery waste is derived from waste products generated in a waste lithium ion battery or a lithium ion battery, including a battery core, and the battery core includes a positive electrode And a negative electrode comprising a positive electrode material, a positive electrode current collector and a positive electrode tab, the negative electrode comprising a negative electrode material, a negative electrode current collector and a negative electrode tab.
  • the method includes the following steps:
  • the positive electrode material is separated from the positive electrode current collector, the negative electrode material and the negative electrode current collector by heating of the high temperature liquid to obtain a positive electrode material, a negative electrode material, a positive electrode current collector with a positive electrode tab, and a negative electrode with a negative electrode tab.
  • the separator adheres to the positive electrode material and the negative electrode material during use of the lithium ion battery, the positive electrode material and the negative electrode material enter the high temperature liquid when the separator is decomposed by the heating of the high temperature liquid.
  • a gas and/or oil recovery device is disposed above the container for holding the high-temperature liquid to recover the gas generated by the decomposition of the separator. / or oil, to avoid secondary pollution to the environment, to achieve the use of this resource.
  • the separated mixture of the positive electrode material, the negative electrode material, the positive electrode current collector with the positive electrode tab, the negative electrode current collector with the negative electrode tab, and the high temperature liquid is subjected to water-soluble filtration to obtain a positive electrode material, a negative electrode material, and a A mixture of a positive electrode current collector of a positive electrode tab and a negative electrode current collector with a negative electrode tab, and a filtrate containing a high temperature liquid. Since the positive electrode material and the negative electrode material are in a powder form, and the positive electrode current collector having the positive electrode tab and the negative electrode current collector having the negative electrode tab are in the form of a sheet, the positive electrode material and the negative electrode can be obtained by sieving the filter cake. The material is separated from a positive current collector with a positive electrode tab and a negative current collector with a negative electrode tab.
  • the mixture of the separated positive electrode material and the positive electrode current collector with the positive electrode tab and the high temperature liquid or the mixture of the negative electrode material and the negative electrode current collector with the negative electrode tab and the high temperature liquid is subjected to water-soluble filtration.
  • a filter cake comprising a mixture of a positive electrode material and a positive electrode current collector having a positive electrode tab or a mixture cake containing a negative electrode material and a negative electrode current collector having a negative electrode tab, and a filtrate containing a high temperature liquid, or filtered to obtain a positive electrode
  • a mixture of a positive electrode current collector having a positive electrode tab and a negative electrode current collector having a negative electrode tab separated by sieving is separated by a difference in melting point or specific gravity, and a positive electrode current collector having a positive electrode tab can be obtained. Separated from the negative current collector with the negative electrode tab.
  • the positive electrode current collector with the positive electrode tab or the negative electrode current collector with the negative electrode tab separated by sieving is crushed, and then the magnetic fluid is sorted or magnetically selected to make the tab and the current collector phase Separation.
  • the mixture of the positive electrode material and the negative electrode material obtained by the sieving treatment is subjected to a calcination treatment to separate the positive electrode material from the negative electrode material. Because graphite will volatilize when calcined, and lithium salts will be preserved.
  • the positive electrode material and the negative electrode material can pass through the filter hole to obtain a mixture filter cake of the positive electrode current collector with the positive electrode tab and the negative electrode current collector with the negative electrode tab, and the positive electrode material and the negative electrode material. And the filtrate of the high temperature liquid.
  • the separated filtrate containing the positive electrode material, the negative electrode material, and the high-temperature liquid is subjected to secondary filtration to obtain a mixture cake containing a positive electrode material and a negative electrode material, and a filtrate containing a high-temperature liquid.
  • the obtained filter cake containing the mixture of the positive electrode material and the negative electrode material is subjected to a calcination treatment to separate the positive electrode material from the negative electrode material.
  • the filtrate containing the high temperature liquid is subjected to evaporation and concentration, and the high temperature liquid can be recovered for recycling.
  • the positive current collector is aluminum foil and the negative current collector is copper foil
  • the negative current collector is copper foil
  • a separator mesh is disposed in the container for holding the high temperature liquid, so that the aluminum foil is melted.
  • the copper foil is stopped by the isolation net and the copper foil is directly removed from the isolation net, thereby facilitating the separation between the positive current collector and the negative current collector.
  • the fracture separation means that the battery core is torn into a sheet under a protective gas, and the electrolyte is pumped.
  • the tearing method is to tear the cell into a sheet rather than a powder.
  • a protective gas such as argon, prevents the positive and negative phases from coming into contact during the crushing process to produce combustion.
  • the pumping electrolyte can prevent contamination of the atmosphere, on the other hand, it can reduce the burning probability in the crushing process, and at the same time, the electrolyte can be recycled.
  • the invention relates to a method for recycling lithium-ion battery waste in an environmentally-friendly manner, wherein the lithium ion battery waste is derived from waste products generated in a waste lithium ion battery or a lithium ion battery, including a positive electrode and a negative electrode constituting a lithium ion battery core; Any one of the separators or a mixture formed arbitrarily between them, the positive electrode including a positive electrode material, a positive electrode current collector, and a positive electrode tab, the negative electrode including a negative electrode material, a negative electrode current collector, and a negative electrode tab. Due to the wide variety of lithium-ion batteries and complex specifications, a large number of battery and accessory waste products are also produced in the production process.
  • the method comprises the following steps:
  • the waste product When the waste product is a diaphragm, it is added to the high temperature liquid, and the temperature of the high temperature liquid reaches a decomposition temperature of the membrane to between 450 degrees, and the diaphragm is decomposed into gas and/or oil by heating of the high temperature liquid;
  • a gas and/or oil recovery device is disposed above the vessel to recover the gas and/or oil produced by the decomposition of the membrane to avoid secondary pollution to the environment and to utilize the resource.
  • the high temperature liquid is then filtered to obtain a filter cake comprising a positive electrode material and/or a negative electrode material.
  • the waste product is a positive electrode or a negative electrode
  • the temperature of the high temperature liquid is not lower than the decomposition or separation temperature of the binder for bonding the positive electrode material and the negative electrode material.
  • the high temperature liquid and the positive electrode material or the negative electrode material are filtered to obtain a filter cake of the positive electrode material or the negative electrode material and a filtrate containing the high temperature liquid; the filtrate is subjected to evaporation and concentration, and the high temperature liquid can be recovered for recycling.
  • the adhesive remaining therein can be decomposed and removed by heat oxidation.
  • the positive electrode material obtained by the separation may leave some binder or a decomposition residue of the binder such as carbon, etc., and the carbon dioxide may be volatilized by high-temperature oxidation treatment, thereby improving the purity of the obtained positive electrode material such as lithium salt.
  • oxygen can be added during the high temperature oxidation treatment to enhance the effect of the oxidation treatment.
  • the waste product When the waste product is a mixture of a positive electrode and a negative electrode, it is added to a high temperature liquid, and the temperature of the high temperature liquid is not lower than the decomposition or separation temperature of the binder for bonding the positive electrode material and the negative electrode material.
  • the positive electrode material is separated from the positive electrode current collector, the negative electrode material and the negative electrode current collector by heating of the high temperature liquid to obtain a positive electrode current collector, a negative electrode material, a positive electrode current collector with a positive electrode tab, and a negative electrode current collector with a negative electrode tab. And a mixture of high temperature liquids.
  • the separated mixture of the positive electrode material, the negative electrode material, the positive electrode current collector with the positive electrode tab, the negative electrode current collector with the negative electrode tab, and the high temperature liquid is subjected to water-soluble filtration to obtain a positive electrode material, a negative electrode material, and a A mixture of a positive electrode current collector of a positive electrode tab and a negative electrode current collector with a negative electrode tab, and a filtrate containing a high temperature liquid. Since the positive electrode material and the negative electrode material are in a powder form, the positive electrode material and the negative electrode material can be separated from the positive electrode current collector of the positive electrode tab and the negative electrode current collector having the negative electrode tab by sieving the filter cake.
  • a mixture of a positive electrode current collector having a positive electrode tab and a negative electrode current collector having a negative electrode tab separated by sieving is separated by a difference in melting point or specific gravity, and a positive electrode current collector having a positive electrode tab can be obtained. Separated from the negative current collector with the negative electrode tab.
  • a positive current collector with a positive electrode tab or a negative current collector with a negative electrode tab obtained by separating the difference in melting point or specific gravity is used for crushing, and then magnetic fluid separation or magnetic separation is used to make the pole The ear is separated from the current collector.
  • the mixture of the positive electrode material and the negative electrode material obtained by the sieving treatment is subjected to a calcination treatment to separate the positive electrode material from the negative electrode material. Because graphite will volatilize when calcined, and lithium salts will be preserved.
  • the positive electrode material and the negative electrode material can pass through the filter hole to obtain a mixture filter cake of the positive electrode current collector with the positive electrode tab and the negative electrode current collector with the negative electrode tab, and the positive electrode material and the negative electrode material. And the filtrate of the high temperature liquid.
  • the separated filtrate containing the positive electrode material, the negative electrode material, and the high-temperature liquid is subjected to secondary filtration to obtain a mixture cake containing a positive electrode material and a negative electrode material, and a filtrate containing a high-temperature liquid.
  • the obtained filter cake containing the mixture of the positive electrode material and the negative electrode material is subjected to a calcination treatment to separate the positive electrode material from the negative electrode material.
  • the filtrate containing the high temperature liquid is subjected to evaporation and concentration, and the high temperature liquid can be recovered for recycling.
  • the positive current collector is aluminum foil and the negative current collector is copper foil
  • the negative current collector is copper foil
  • a separator mesh is disposed in the container for holding the high temperature liquid, so that the aluminum foil is melted.
  • the copper foil is stopped by the isolation net and the copper foil is directly removed from the isolation net, thereby facilitating the separation between the positive current collector and the negative current collector. Since the thickness of the aluminum foil is very thin, it is recovered in the air by a conventional method, such as heat recovery, easy oxidation, low recovery rate, and waste of resources.
  • the temperature of the high-temperature liquid is higher than the melting point of aluminum
  • the aluminum foil is melted into aluminum particles, and when the aluminum particles are melted and recovered, the aluminum particles have the advantages of low loss and high yield, thereby improving the recovery value.
  • the high temperature liquid is a molten salt, and the molten salt is in a stable state at a high temperature and is not decomposed by heat.
  • a mixed salt of chloride or chloride Because the price of chlorinated salt is cheap, such as sodium chloride, magnesium chloride, etc., the raw materials are widely available. Chloride, such as salt, does not decompose at high temperatures, and the aluminum foil therein can be melted.
  • the high temperature liquid does not chemically react with the waste product added thereto to ensure the purity and reuse value of the recovered product.
  • the high temperature liquid used for recycling the positive electrode does not chemically react with the positive electrode and the positive electrode material
  • the high temperature liquid for recycling the negative electrode does not chemically react with the negative electrode and the negative electrode material
  • the high temperature liquid for recovering the mixture of the positive electrode and the negative electrode does not react with the positive electrode and the positive electrode.
  • the material reacts with the negative electrode and the negative electrode material.
  • the present invention has the following beneficial effects:
  • the method for recycling and recycling lithium ion battery waste by the invention can not only realize the resource recycling of the lithium ion battery waste, but also complete the recycling and separation, and can realize the separation and resource utilization of various constituent resources; There is no waste water, waste gas and waste residue in the recycling process, which can avoid secondary pollution and achieve real energy saving and emission reduction.
  • the method of the invention can be applied to any form of lithium ion battery waste, has wide application range, and recycling operation Simple, low cost, and easy to achieve scale.
  • FIG. 1 is a flow chart of a process for recycling a positive electrode of a lithium ion battery according to the first embodiment.
  • Embodiment 2 is a flow chart of a process for recycling and recycling an anode of a lithium ion battery according to Embodiment 2.
  • FIG. 3 is a flow chart showing another process for recycling and recycling a positive electrode of a lithium ion battery according to Embodiment 3.
  • FIG. 4 is a flow chart showing another process for recycling a lithium ion battery negative electrode according to the fourth embodiment.
  • FIG. 5 is a flow chart showing a process for recycling and recycling a separator of a lithium ion battery according to Embodiment 5.
  • FIG. 6 is a flow chart showing a process for recycling resources of a positive and negative electrode mixture of a lithium ion battery according to Embodiment 6.
  • FIG. 7 is a flow chart showing another process for recycling resources of the positive and negative electrodes of the lithium ion battery according to the seventh embodiment.
  • FIG. 8 is a process flow diagram of a negative electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided in the eighth embodiment.
  • FIG. 9 is a process flow diagram of a positive electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided by the embodiment.
  • FIG. 10 is a process flow diagram of another negative electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided by the embodiment 10.
  • FIG. 11 is a process flow diagram of another positive electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery, which is provided by the embodiment 11.
  • FIG. 12 is a process flow diagram of resource recycling and environmental protection recycling of a lithium ion battery cell according to Embodiment 12.
  • FIG. 13 is a flow chart showing another process for recycling and recycling a lithium ion battery cell according to Embodiment 13.
  • a process for recycling and recycling a positive electrode of a lithium ion battery is as follows: a positive electrode of a lithium ion battery is placed in a high temperature liquid, and the positive electrode may be a waste lithium ion battery. Separated, it can also be the positive waste produced in the production process.
  • the temperature of the high temperature liquid is greater than the melting point of aluminum; the high temperature liquid described herein may be a molten salt such as sodium chloride, which is heated by a high temperature liquid, wherein the positive current collector-aluminum foil is melted and adhered to the positive electrode set.
  • the positive electrode material on the fluid (such as lithium cobalt oxide) will be separated into the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution for one filtration.
  • the so-called primary filtration is through the mesh of the control filter.
  • the size of the pores enables the positive electrode material to be filtered and the aluminum particles cannot be filtered, thereby obtaining an aluminum filter cake and a mixed filtrate containing the positive electrode material and the high temperature liquid; the aluminum filter cake is washed and dried to obtain an aluminum block; Enter By secondary filtration, a filter cake containing a positive electrode material (such as a lithium salt) and a filtrate containing a high temperature liquid are obtained; the filter cake is washed and dried, and then heated and oxidized to obtain a high content of a positive electrode material (eg, cobalt). Lithium acid powder). The filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.
  • a positive electrode material such as a lithium salt
  • a process for recycling and recycling an anode of a lithium ion battery is as follows: a negative electrode of a lithium ion battery is added to a high temperature liquid, and the negative electrode may be separated from a waste lithium ion battery. The obtained waste can also be produced in the production process.
  • the temperature of the high temperature liquid is generally controlled between 400 ° C and 500 ° C. At this temperature, the adhesive bonding the negative electrode material can be decomposed, so that the negative electrode material adhered to the negative electrode current collector is separated and enters the high temperature liquid.
  • Water is added to the high-temperature liquid, and an aqueous solution is formed by the dissolution of water, and filtration is performed once to obtain a mixed cake containing the negative electrode current collector and a mixed filtrate containing the negative electrode material and the high-temperature liquid.
  • the so-called primary filtration is to control the size of the filter mesh to filter the negative electrode material and the negative electrode current collector can not be filtered; after the filter cake containing the negative electrode current collector is cleaned and dried, the negative electrode current collector, such as copper foil;
  • the mixed filtrate is subjected to secondary filtration to obtain a filter cake containing a negative electrode material and a filtrate containing a high temperature liquid; the filter cake is washed and dried to obtain a negative electrode material, such as graphite powder; the graphite powder can be washed and dried again. use.
  • the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.
  • another process for recycling and recycling the positive electrode of the lithium ion battery is as follows: the positive electrode of the lithium ion battery is put into the high temperature liquid, and the temperature of the high temperature liquid is higher than the melting point of the aluminum; The heating of the high-temperature liquid causes the positive current collector-aluminum foil to melt, so that the positive electrode material-lithium salt (such as lithium cobalt oxide) adhered to the positive current collector is separated into the high-temperature liquid; Water is added, an aqueous solution is formed by dissolution of water, and filtration is carried out to obtain a mixture cake containing a positive electrode material and a positive electrode current collector and a filtrate containing a high-temperature liquid; the obtained mixture cake is washed and dried, and then subjected to a sieving treatment.
  • the positive electrode of the lithium ion battery is put into the high temperature liquid, and the temperature of the high temperature liquid is higher than the melting point of the aluminum;
  • the heating of the high-temperature liquid causes the positive current collector-alum
  • the positive electrode material is powdery, the size and specific gravity of the aluminum particles of the positive electrode current collector are different, so the two can be separated by sieving to obtain aluminum powder and fine powder of the positive electrode material; the fine powder of the positive electrode material is subjected to heat oxidation treatment, The residual adhesive is oxidized to carbon dioxide to volatilize, thereby obtaining a high content of a positive electrode material such as lithium cobalt oxide powder.
  • the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.
  • another process for recycling and recycling the lithium ion battery negative electrode is as follows: the negative electrode of the lithium ion battery is added to the high temperature liquid, and the temperature of the high temperature liquid is generally controlled at 400 ° C. Between 500 ° C, at this temperature, the adhesive bonding the negative electrode material can be decomposed, so that the negative electrode material adhered to the negative electrode is negative.
  • the polar current collector is detached and enters into the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution, which is filtered to obtain a mixture cake containing the negative electrode material and the negative electrode current collector and a filtrate containing the high temperature liquid;
  • the obtained mixture cake is washed and dried, and then subjected to sieving treatment; since the anode material is powdery, the size and specific gravity of the anode current collector-copper foil are different, so the two can be separated by sieving. Separate copper foil and anode material.
  • the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.
  • the process for resource recycling and environmental protection of the separator of the lithium ion battery is as follows: the waste lithium ion battery is split to obtain a diaphragm, and the positive and negative materials are adhered to the two sides of the diaphragm respectively.
  • the separator is added to a high temperature liquid, and the temperature of the high temperature liquid is generally controlled between 400 ° C and 500 ° C. At this temperature, the oil obtained after decomposition of the separator has the highest recovery rate. By the heating of the high temperature liquid, the separator can be decomposed into gas and/or oil for recovery.
  • a process for recycling a positive and negative mixture of a lithium ion battery is as follows: the positive and negative mixture obtained by separating the used lithium ion battery into the mixture is put into In a high temperature liquid, the temperature of the high temperature liquid is greater than the melting point of aluminum lower than the melting point of copper. By the heating action of the high temperature liquid, the positive electrode current collector-aluminum foil is melted, and the positive electrode material (such as lithium cobalt oxide) adhered to the positive electrode current collector is separated from the positive electrode current collector aluminum foil into the high temperature liquid.
  • the anode current collector—the graphite powder on the copper foil will detach from the high temperature liquid under the action of high temperature.
  • the mixture of the positive and negative materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization to obtain lithium cobalt oxide powder.
  • the mixture of the positive and negative current collectors is physically separated, for example, by utilizing the difference in specific gravity between the two or the difference in melting point between the two, for example, by magnetic fluid separation, the metal aluminum block and the metal copper foil can be separated.
  • FIG. 7 another embodiment of the present invention provides a resource ring for the positive and negative electrodes of a lithium ion battery.
  • the recycling process is as follows: the positive and negative electrode mixture obtained by disassembling the waste lithium ion battery is put into a high temperature liquid, and the temperature of the high temperature liquid is higher than the melting point of aluminum lower than the melting point of copper. By the heating action of the high temperature liquid, the positive electrode current collector-aluminum foil is melted, and the positive electrode material (such as lithium cobaltate) adhered to the positive electrode current collector is separated from the positive electrode current collector-aluminum foil into the high temperature liquid.
  • the anode current collector—the graphite powder on the copper foil will detach from the high temperature liquid under the action of high temperature.
  • the resulting filter cake was a mixture of particulate and flake positive and negative current collectors. Since the positive and negative materials are fine powder and the positive and negative current collectors are granular and flake-shaped, the size of the filter pores can be adjusted to allow the fine powdered positive and negative materials to pass through the filter screen. Fluid cannot pass.
  • the filtrate is subjected to secondary filtration, and the positive and negative materials in the filtrate are filtered to obtain a filter cake containing a mixture of positive and negative materials and a filtrate containing a high temperature liquid, and the filtrate is subjected to evaporation treatment to recover a high temperature liquid for recycling.
  • the filter cake containing the mixture of positive and negative materials is washed and dried to obtain a mixture of positive and negative materials, and the mixture of the positive and negative materials is heated and oxidized to oxidize the graphite powder to carbon dioxide to be separated. A lithium cobaltate powder is obtained.
  • the filter cake containing the mixture of the positive and negative current collectors is washed and dried to obtain a mixture of positive and negative current collectors, and the mixture of the positive and negative current collectors is physically separated, for example, by utilizing the difference in specific gravity between the two or The difference in melting point between the two can be separated into a metal aluminum block and a metal copper foil.
  • a process for recycling a negative electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery is as follows: a mixture of a positive electrode and a negative electrode obtained by crushing and separating a lithium ion battery The positive electrode and the negative electrode are separated by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method.
  • the separated negative electrode is placed in a high temperature liquid having a temperature greater than a decomposition or separation temperature of the binder; and a negative electrode material (for example, graphite powder) adhered to the negative electrode current collector by heating of the high temperature liquid It will separate into the high temperature liquid; add water to the high temperature liquid, form an aqueous solution by dissolving the water, and filter to obtain a filter cake and a filtrate.
  • the filter cake is washed and dried, and then sieved to obtain a negative electrode material (such as graphite powder) and a negative electrode current collector (such as copper foil).
  • the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.
  • a process for recycling a positive electrode in a mixture of a positive electrode and a negative electrode of a waste lithium ion battery provided by the present embodiment is as follows: a mixture of a positive electrode and a negative electrode obtained by crushing and separating a lithium ion battery The positive electrode and the negative electrode are separated by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method. The separated positive electrode is placed in a high temperature liquid, and the temperature of the high temperature liquid is generally controlled between 450 ° C and 700 ° C at this temperature.
  • the adhesive for bonding the positive electrode material is decomposed, so that the positive electrode material adhered to the positive electrode current collector is detached and enters the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution. Filtration can obtain a filter cake containing a positive electrode current collector and a mixed filtrate containing a positive electrode material and a high temperature liquid.
  • the so-called primary filtration is to control the size of the filter mesh to filter the positive electrode material and the positive electrode current collector cannot be filtered;
  • a positive current collector is obtained, such as an aluminum block;
  • the mixed filtrate is subjected to secondary filtration to obtain a filter cake containing a positive electrode material and a filtrate containing a high temperature liquid;
  • the filter cake is cleaned and baked.
  • Dry that is, to obtain a positive electrode material, such as: lithium cobalt oxide powder, the heating and oxidation treatment of the filter cake after washing and drying can increase the content thereof;
  • the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and the high temperature liquid can be recovered to recycle use.
  • another process for recycling the negative electrode in the mixture of the positive electrode and the negative electrode of the waste lithium ion battery provided by the present embodiment is as follows: the positive electrode and the negative electrode obtained by crushing and separating the lithium ion battery are obtained.
  • the mixture is separated from the negative electrode by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method.
  • the separated negative electrode is placed in a high temperature liquid, and the negative electrode material (such as graphite powder) adhered to the negative electrode current collector is separated into the high temperature liquid by the heating action of the high temperature liquid; water is added to the high temperature liquid, The aqueous solution is formed by dissolution of water, and once filtered, a filter cake containing a negative electrode current collector and a mixed filtrate containing a negative electrode material and a high temperature liquid can be obtained.
  • the so-called primary filtration is to filter the negative electrode material by controlling the size of the filter mesh hole and the negative electrode.
  • the current collector cannot be filtered; after the filter cake containing the negative current collector is cleaned and dried, a negative current collector, such as a copper foil, is obtained; and the mixed filtrate is subjected to secondary filtration to obtain a filter cake containing the negative electrode material and a high temperature.
  • the liquid filtrate; the filtrate containing the high temperature liquid is subjected to evaporation concentration treatment, and the high temperature liquid can be recovered for recycling.
  • another process for recycling the positive electrode in the mixture of the positive electrode and the negative electrode of the waste lithium ion battery provided by the present embodiment is as follows: the positive electrode and the negative electrode obtained by crushing and separating the lithium ion battery are obtained.
  • the mixture is separated from the negative electrode by a jigging beneficiation method or a magnetic fluid separation method or a specific gravity separation method or an artificial separation method.
  • the separated positive electrode is placed in a high temperature liquid, and the temperature of the high temperature liquid is generally controlled between 450 ° C and 700 ° C. At this temperature, the adhesive bonding the positive electrode material can be decomposed to adhere to the positive electrode.
  • the positive electrode material is separated from the positive electrode current collector into the high temperature liquid; water is added to the high temperature liquid, and the water solution is dissolved to form an aqueous solution, which is filtered to obtain a mixture filter cake containing the positive electrode material and the positive electrode current collector and a high temperature liquid containing liquid. Filtrate; the obtained mixture cake is washed and dried before being subjected to sieving treatment; since the positive electrode material is powdery, the size and specific gravity of the positive electrode current collector aluminum particles are different, so the two can be separated by sieving. The separated aluminum particles and the fine powder of the positive electrode material are obtained; the content of the positive electrode material powder is heated and oxidized to increase the content thereof, and a positive electrode material such as lithium cobaltate powder is obtained.
  • the filtrate is subjected to evaporation concentration treatment, and a high temperature liquid can be recovered for recycling.
  • a process for recycling and recycling a lithium ion battery core is as follows: a lithium ion battery core obtained by disassembling a waste lithium ion battery is put into a high temperature liquid, and a high temperature liquid The temperature is generally controlled between 400 ° C ⁇ 500 ° C; because the two sides of the diaphragm are adhered to the positive and negative materials, when the diaphragm is added to the high temperature liquid, the diaphragm is decomposed into gas and / or by the heating of the high temperature liquid The oil is recovered.
  • the positive electrode current collector aluminum foil is melted by the further heating of the high temperature liquid, and the positive electrode material adhered to the positive electrode current collector is lithium.
  • the salt (such as lithium cobalt oxide) will leave the positive current collector - the aluminum foil enters the high temperature liquid, and the graphite powder adhered to the negative current collector - copper foil also escapes into the high temperature liquid under the action of high temperature. Water is added to the high-temperature liquid, and the aqueous solution is dissolved by water to perform primary filtration.
  • the positive and negative electrode materials are fine powder
  • the positive and negative current collectors are granular and flake-shaped, and the size of the filter pores is adjusted by adjusting the size of the filter.
  • the fine powdery positive and negative materials pass through the sieve, and the positive and negative current collectors cannot pass, and the filter cake and the filtrate are obtained.
  • the obtained filter cake is a granular and flake-shaped positive and negative current collector.
  • the filtrate is subjected to secondary filtration to obtain a filter cake and a filtrate containing the positive and negative materials, and the obtained filtrate is subjected to evaporation to recover a high-temperature liquid for recycling; the filter cake containing the positive and negative materials is washed and dried to obtain positive and a mixture of negative electrode materials; the obtained mixture of positive and negative materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization, that is, lithium cobaltate powder is separated.
  • the filter cake containing the positive and negative current collectors is washed and dried to obtain a positive and negative current collector mixture, and the obtained positive and negative current collector mixtures are physically separated, for example, by utilizing the difference in specific gravity between the two or the melting point of the two.
  • the difference is that a separated metal aluminum block and a metal copper foil can be obtained.
  • another process for recycling and recycling the lithium ion battery core is as follows: the lithium ion battery core obtained by disassembling the waste lithium ion battery is put into the high temperature liquid, The two sides of the diaphragm are respectively adhered to the positive and negative materials.
  • the temperature of the high temperature liquid is generally controlled between 400 ° C and 500 ° C. At this temperature, the oil obtained after the decomposition of the separator is recovered. The highest rate, by the heating of the high temperature liquid, the membrane is decomposed into gas and / or oil to be recovered.
  • the temperature of the high temperature liquid is continuously increased so that the temperature of the high temperature liquid is higher than the melting point of aluminum lower than the melting point of copper.
  • the positive electrode current collector-aluminum foil is melted, and the positive electrode material (such as lithium cobalt oxide) adhered to the positive electrode current collector is separated from the positive electrode current collector - the aluminum foil enters the high temperature liquid.
  • the graphite powder adhered to the negative current collector-copper foil also escapes into the high temperature liquid under the action of high temperature.
  • the mixture of the positive and negative electrode materials is subjected to heat oxidation treatment, and the graphite powder therein is oxidized to carbon dioxide volatilization, and lithium cobaltate powder is separated.
  • the positive and negative current collector mixtures are physically separated, for example, by using the difference in specific gravity between the two or the difference in melting point between the two, the two are separated to obtain a separated metal aluminum block and a metal copper foil.

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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)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de récupération de ressources et de protection de l'environnement permettant de recycler des déchets de batteries aux ions de lithium. Le procédé comprend les étapes suivantes : mise en place d'un élément de batterie auparavant broyé et séparé dans un liquide haute température, de sorte que le chauffage du liquide haute température décompose un diaphragme dans l'élément de batterie en gaz et/ou en huile à évacuer ; et séparation d'un matériau à pôle positif d'un collecteur de courant à pôle positif, et séparation d'un matériau à pôle négatif d'un collecteur de courant à pôle négatif par chauffage du liquide haute température, pour obtenir un mélange contenant le matériau à pôle positif, le matériau à pôle négatif, le collecteur de courant à pôle positif portant une languette de pôle positif, le collecteur de courant à pôle négatif portant une languette de pôle négatif, et le liquide haute température, la température du liquide haute température n'étant pas inférieure à la température de décomposition et/ou de séparation d'un adhésif. La présente invention permet non seulement d'effectuer une ré-utilisation des ressources des déchets de batteries aux ions de lithium, mais également d'effectuer la séparation et le recyclage de diverses ressources qui les composent ; le processus de recyclage est respectueux de l'environnement ; le procédé peut être utilisé pour le recyclage de déchets de batteries aux ions de lithium de toute forme et peut être largement utilisé ; l'opération de recyclage est simple, d'un coût peu élevé, et permet facilement une production de masse.
PCT/CN2015/081421 2014-06-16 2015-06-15 Procédé de récupération de ressources et et de protection de l'environnement permettant de recycler des déchets de batteries aux ions de lithium Ceased WO2015192743A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
CN201410267512.4A CN105244560B (zh) 2014-06-16 2014-06-16 一种锂离子电池的资源化回收方法
CN201410267159.XA CN105186058B (zh) 2014-06-16 2014-06-16 一种对锂离子电池电极进行资源化环保回收的方法
CN201410267043.6A CN105304966B (zh) 2014-06-16 2014-06-16 一种锂离子电池的环保回收方法
CN201410267512.4 2014-06-16
CN201410267043.6 2014-06-16
CN201410267159.X 2014-06-16
CN201410522975.0A CN105576312B (zh) 2014-10-06 2014-10-06 回收废旧锂离子电池的正负极混合物的方法
CN201410522975.0 2014-10-06

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654433A (zh) * 2016-11-21 2017-05-10 电子科技大学中山学院 一种采用废旧磷酸铁锂电池回收锂的方法
CN106654435A (zh) * 2016-11-19 2017-05-10 天津赫维科技有限公司 一种报废铝塑膜磷酸铁锂电池的干式回收方法
WO2020229477A1 (fr) * 2019-05-15 2020-11-19 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de broyage d'un generateur electrochimique
CN112207118A (zh) * 2020-10-04 2021-01-12 湖南金源新材料股份有限公司 一种废旧锂电池拆解物料的湿法脱胶方法
CN112246834A (zh) * 2020-10-04 2021-01-22 湖南金源新材料股份有限公司 废旧锂电池拆解后各组分的跳汰分离方法
CN113560308A (zh) * 2020-04-29 2021-10-29 南通江海储能技术有限公司 电容器集流体与活性物质及正、负极活性物质分离方法
CN113659225A (zh) * 2021-07-20 2021-11-16 河南巨峰环保科技有限公司 锂电池隔膜废料的回收利用方法
CN113826249A (zh) * 2019-05-15 2021-12-21 法国原子能源和替代能源委员会 电化学发生器中的中和方法
CN114006071A (zh) * 2021-10-31 2022-02-01 湖南江冶机电科技股份有限公司 一种废旧锂电池的正极片极粉剥离回收的方法
CN114079095A (zh) * 2021-11-24 2022-02-22 广东邦普循环科技有限公司 一种利用废旧电池制备铜基负极材料的方法
CN114243140A (zh) * 2021-11-19 2022-03-25 广东邦普循环科技有限公司 一种退役电池极片回收处理的方法
CN114649598A (zh) * 2022-02-17 2022-06-21 广东邦普循环科技有限公司 一种废旧电池回收活性材料脱附的方法
CN117357963A (zh) * 2023-12-07 2024-01-09 山西亿通源制造设备有限公司 一种带式固液分离装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4058396A (en) * 1976-11-26 1977-11-15 Electric Power Research Institute, Inc. Recovery of lead from batteries
CN201441833U (zh) * 2008-07-12 2010-04-28 包良玉 一种处理废电池回收有害气态物质的装置
CN102251118A (zh) * 2011-06-25 2011-11-23 鞍山鑫普新材料有限公司 一种从废旧镍氢电池中回收金属的方法
WO2012169073A1 (fr) * 2011-06-10 2012-12-13 日本磁力選鉱株式会社 Procédé de récupération de métaux de valeur dans les accumulateurs au lithium-ion mis aux rebuts
WO2013023640A1 (fr) * 2011-08-12 2013-02-21 Technische Universität Braunschweig Carolo-Wilhelmina Procédé de récupération de matière active à partir d'une cellule galvanique et installation de séparation de matière active, en particulier installation de séparation de métal actif
CN103311600A (zh) * 2013-05-16 2013-09-18 清华大学 用水溶性离子液体回收废锂离子电池中金属的方法及装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4058396A (en) * 1976-11-26 1977-11-15 Electric Power Research Institute, Inc. Recovery of lead from batteries
CN201441833U (zh) * 2008-07-12 2010-04-28 包良玉 一种处理废电池回收有害气态物质的装置
WO2012169073A1 (fr) * 2011-06-10 2012-12-13 日本磁力選鉱株式会社 Procédé de récupération de métaux de valeur dans les accumulateurs au lithium-ion mis aux rebuts
CN102251118A (zh) * 2011-06-25 2011-11-23 鞍山鑫普新材料有限公司 一种从废旧镍氢电池中回收金属的方法
WO2013023640A1 (fr) * 2011-08-12 2013-02-21 Technische Universität Braunschweig Carolo-Wilhelmina Procédé de récupération de matière active à partir d'une cellule galvanique et installation de séparation de matière active, en particulier installation de séparation de métal actif
CN103311600A (zh) * 2013-05-16 2013-09-18 清华大学 用水溶性离子液体回收废锂离子电池中金属的方法及装置

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654435A (zh) * 2016-11-19 2017-05-10 天津赫维科技有限公司 一种报废铝塑膜磷酸铁锂电池的干式回收方法
CN106654433A (zh) * 2016-11-21 2017-05-10 电子科技大学中山学院 一种采用废旧磷酸铁锂电池回收锂的方法
CN113826249A (zh) * 2019-05-15 2021-12-21 法国原子能源和替代能源委员会 电化学发生器中的中和方法
WO2020229477A1 (fr) * 2019-05-15 2020-11-19 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de broyage d'un generateur electrochimique
FR3096179A1 (fr) * 2019-05-15 2020-11-20 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de broyage d’un generateur electrochimique
JP7581242B2 (ja) 2019-05-15 2024-11-12 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 電気化学的発電機を破砕する方法
JP2022533598A (ja) * 2019-05-15 2022-07-25 コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ 電気化学的発電機を破砕する方法
CN113826265A (zh) * 2019-05-15 2021-12-21 法国原子能源和替代能源委员会 用于破碎电化学发生器的方法
CN113560308A (zh) * 2020-04-29 2021-10-29 南通江海储能技术有限公司 电容器集流体与活性物质及正、负极活性物质分离方法
CN112246834A (zh) * 2020-10-04 2021-01-22 湖南金源新材料股份有限公司 废旧锂电池拆解后各组分的跳汰分离方法
CN112246834B (zh) * 2020-10-04 2022-04-15 湖南金源新材料股份有限公司 废旧锂电池拆解后各组分的跳汰分离方法
CN112207118A (zh) * 2020-10-04 2021-01-12 湖南金源新材料股份有限公司 一种废旧锂电池拆解物料的湿法脱胶方法
CN113659225A (zh) * 2021-07-20 2021-11-16 河南巨峰环保科技有限公司 锂电池隔膜废料的回收利用方法
CN114006071A (zh) * 2021-10-31 2022-02-01 湖南江冶机电科技股份有限公司 一种废旧锂电池的正极片极粉剥离回收的方法
CN114243140A (zh) * 2021-11-19 2022-03-25 广东邦普循环科技有限公司 一种退役电池极片回收处理的方法
CN114243140B (zh) * 2021-11-19 2024-07-09 广东邦普循环科技有限公司 一种退役电池极片回收处理的方法
CN114079095A (zh) * 2021-11-24 2022-02-22 广东邦普循环科技有限公司 一种利用废旧电池制备铜基负极材料的方法
CN114079095B (zh) * 2021-11-24 2024-04-09 广东邦普循环科技有限公司 一种利用废旧电池制备铜基负极材料的方法
US12095058B2 (en) 2021-11-24 2024-09-17 Guangdong Brunp Recycling Technology Co., Ltd. Method for preparing copper-based negative electrode material by using waste battery
CN114649598A (zh) * 2022-02-17 2022-06-21 广东邦普循环科技有限公司 一种废旧电池回收活性材料脱附的方法
CN117357963A (zh) * 2023-12-07 2024-01-09 山西亿通源制造设备有限公司 一种带式固液分离装置
CN117357963B (zh) * 2023-12-07 2024-02-20 山西亿通源制造设备有限公司 一种带式固液分离装置

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