CN115172923A - Method for recovering battery powder through low-temperature pyrolysis desorption - Google Patents
Method for recovering battery powder through low-temperature pyrolysis desorption Download PDFInfo
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- CN115172923A CN115172923A CN202210716640.7A CN202210716640A CN115172923A CN 115172923 A CN115172923 A CN 115172923A CN 202210716640 A CN202210716640 A CN 202210716640A CN 115172923 A CN115172923 A CN 115172923A
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000003795 desorption Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 14
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010926 waste battery Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 239000002699 waste material Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002932 luster Substances 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003832 thermite Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 206010024769 Local reaction Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007133 aluminothermic reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0006—Preliminary treatment without modification of the copper constituent by 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
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- 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
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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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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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
- H01M10/05—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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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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Abstract
The invention discloses a method for recovering battery powder by low-temperature pyrolysis desorption, which comprises the step of reacting crushed waste battery materials under the mixed atmosphere of CO and CO at the pressure of 3-8MPa and the temperature of 120-150 DEG C 2 、NO、O 2 The obtained reaction materials are reacted under negative pressure at 310-360 ℃, and then the copper-aluminum foil and the battery powder are obtained by sorting. The invention adopts a combined process of low-temperature high-pressure pyrolysis and medium-temperature negative-pressure pyrolysis, the temperature of the whole process is controlled below 400 ℃, and the purpose of separating the polymer from the current collector can be achieved, thereby not only realizing the chain breaking of the polymer, but also avoiding the oxidation of copper and aluminum。
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for recovering battery powder through low-temperature pyrolysis desorption.
Background
The lithium ion battery has a complex structure and consists of a plurality of components such as a shell, a diaphragm, a positive electrode, a negative electrode and the like, and different components are required to be separated by a series of methods in the process of recycling the waste battery. The negative electrode is composed of graphite, a binder, a conductive agent and a current collector copper foil, the positive electrode is prepared by coating active substance powder, the binder and the conductive agent on a current collector aluminum foil, and the positive electrode active substance powder mainly contains LiCoO 2 ，LiNiO 2 ，LiMnO 2 ，LiFePO 4 And LiNi x Co y Mn 1-x-y O 2 And the like.
The pretreatment process of waste lithium ion battery recovery usually requires a certain technical means to desorb and separate active material powder from a current collector.
Currently, separating active materials from current collectors is primarily done from three aspects: (1) according to the characteristic that metal aluminum can be dissolved in alkaline solution, the purpose of separating the anode powder from the current collector can be achieved by soaking the anode roll core in the alkaline solution. In addition, a large amount of alkali solution is needed in the process, neutralization treatment is needed to prevent the alkali solution from generating secondary pollution, so that extra cost is needed, and desorption active substances are fully washed or neutralized by acid in the filtering process to avoid pollution of the introduced alkali solution to powder; (2) the PVDF binder is dissolved by an organic solvent, so that the metal foil of the current collector can be recovered in a solid form, but the organic solvent is usually expensive and is not suitable for large-scale industrial application; (3) the direct heating in the air to a specific temperature can deactivate the adhesive to achieve the purpose of separating the current collector aluminum foil, which is also the most reported pretreatment process for lithium battery recovery pyrolysis.
Pyrolysis pretreatment processes are widely used in existing industrial production, but have some major problems, such as: (1) the conventional pyrolysis temperature is above 500 ℃, due to the complex material types, the electrolyte and the diaphragm are burnt at the temperature, so that local reaction in the pyrolysis furnace is severe easily, the temperature is out of control, the aluminothermic reaction of aluminum metal in the battery is carried out at the temperature of above 600 ℃, the instantaneous temperature is increased rapidly, and the pyrolysis furnace is burnt through, so that a large safety risk is brought; (2) at the temperature, metal copper and aluminum in the battery are greatly oxidized, so that the impurity content in battery powder is high, and when the battery powder is leached by subsequent acid liquor, the oxide is dissolved to generate a large amount of copper-aluminum slag, so that great pressure is brought to subsequent purification.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for recovering battery powder through low-temperature pyrolysis desorption, which can enable active materials of waste batteries to be separated from a current collector at a lower temperature.
According to one aspect of the invention, a method for recovering battery powder through low-temperature pyrolysis desorption is provided, which comprises the following steps:
s1: discharging, disassembling and crushing the waste battery to obtain a crushed material;
s2: reacting the crushed materials in a mixed atmosphere at a temperature of 120-150 ℃ and a pressure of 3-8MPa, wherein the mixed atmosphere is a mixed gas of CO2, NO and O2, and the volume ratio of the mixed gas to the mixed gas is 100: (10-15): (0-2);
s3: and (3) reacting the reaction material obtained in the step (S2) at the negative pressure and the temperature of 310-360 ℃, and then sorting to obtain the copper-aluminum foil and the battery powder.
In some embodiments of the invention, in step S1, the particle size of the crushed material is 5cm or less.
In some embodiments of the invention, in step S1, the waste battery is at least one of a ternary lithium ion battery, a lithium iron phosphate battery, a lithium cobaltate battery, a lithium manganate battery or a lithium nickelate battery.
In some embodiments of the invention, in step S2, the reaction time is 3 to 5 hours.
In some embodiments of the present invention, the reaction is performed in a pyrolysis furnace in step S2, and the filling rate of the crushed material in the pyrolysis furnace is controlled to be 5 to 15%.
In some embodiments of the invention, in step S3, the negative pressure has a pressure of-0.01 to-0.08 MPa.
In some embodiments of the invention, in step S3, the reaction time is 1 to 3 hours.
In some embodiments of the present invention, after the reaction in step S2 is completed, the pressure in the pyrolysis furnace is released to the normal pressure at a rate of 0.1-0.5MPa/min, and then the vacuum pump is started to pump to the negative pressure.
In some embodiments of the invention, in step S3, heating is carried out to the reaction temperature at a ramp rate of 5-10 deg.C/min.
In some embodiments of the present invention, the copper-aluminum foil obtained in step S3 has a copper content of not less than 45wt% and an aluminum content of not less than 35wt%.
In some embodiments of the present invention, the battery powder obtained in step S3 has an aluminum content of not higher than 0.5wt%.
In some embodiments of the present invention, in step S3, the sorting process is: and (4) screening by using a double-layer screen, wherein the obtained upper layer is the copper-aluminum foil, and the obtained bottom layer is the battery powder.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. in the scheme of the invention, aiming at the problems that the waste battery is easy to have potential safety hazard and the copper and aluminum are oxidized in a large area at a higher pyrolysis temperature, a combined process of low-temperature high-pressure pyrolysis and medium-temperature negative-pressure pyrolysis is adopted, the temperature in the whole process is controlled below 400 ℃, the medium-temperature negative-pressure pyrolysis is carried out under an anaerobic condition, the phenomenon of temperature runaway caused by the combustion of electrolyte and a diaphragm in a crushed material is avoided, a pyrolysis furnace is protected, and the degree of copper and aluminum oxidation is reduced.
2. Under the condition that high-pressure mixed gas is introduced, NO is used as a single-electron free radical, the high-activity organic polymer composite material has higher activity at the temperature of over 100 ℃, and carbon-carbon bonds in an organic polymer can be randomly attacked under the catalysis of trace oxygen, so that the polymer is broken to form a small-molecular compound, the thermal decomposition temperature of the polymer is reduced, and the following reaction formula is referred to:
·NO+[-CH 2 -CF 2 -]→R1-CH 2 -N＝O+R 2 -CF 2 -N＝O。
by utilizing the specific absorption characteristic of PVDF to carbon dioxide, larger volume expansion can occur, certain mechanical damage can be caused to PVDF, and NO can be facilitated to break a carbon-carbon bond more deeply.
At a lower temperature, the invention realizes the chain breaking of the polymer, avoids the oxidation of copper and aluminum and further avoids the thermite reaction.
3. When negative pressure pyrolysis is carried out, the organic polymer after chain scission can be decomposed and carbonized at a slightly high temperature without being heated to more than 500 ℃, electrolyte and the like in the organic polymer can easily reach a boiling point under negative pressure and enter an exhaust gas treatment system in a gaseous state, and meanwhile, copper and aluminum can not be oxidized, thermite reaction can not occur, and the purpose of separating and desorbing battery powder and copper and aluminum foils is achieved.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
A method for recovering battery powder through low-temperature pyrolysis desorption refers to FIG. 1, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 5%, introducing high-pressure mixed gas, sealing, controlling the air pressure in the pyrolysis furnace to be 3MPa and the temperature to be 120 ℃, keeping the temperature for 5 hours, and using CO as the high-pressure mixed gas 2 、NO、O 2 The volume ratio of the mixed gas of (1) is 100;
step 3, after the reaction is finished, releasing the pressure in the pyrolysis furnace to the normal pressure at 0.1MPa/min, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.01 MPa, heating to 310 ℃ at the heating rate of 5 ℃/min, and continuing for 3 hours;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain the battery powder with the upper layer being the pyrolyzed copper-aluminum foil and the bottom layer being the battery powder taken off in the pyrolysis process.
Monitoring the conditions in the pyrolysis furnace: during high-pressure pyrolysis, only the surface layer of the crushed material is observed to be dissolved like liquid drops, the volume is slightly expanded, and other obvious changes are not observed; during negative pressure pyrolysis, the temperature in the furnace is kept constant, the powder falls off obviously, and metallic luster appears.
Example 2
A method for recovering battery powder by low-temperature pyrolysis desorption comprises the following specific processes:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 10%, introducing high-pressure mixed gas, sealing, controlling the air pressure in the pyrolysis furnace to be 5MPa and the temperature to be 130 ℃, and keeping for 4 hours; a mixed gas of high-pressure mixed gases CO2, NO and O2, wherein the volume ratio is 100;
step 3, after the reaction is finished, releasing the pressure in the pyrolysis furnace to normal pressure at 0.3MPa/min, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.04 MPa, heating to 340 ℃ at the heating rate of 8 ℃/min, and continuing for 2 hours;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain battery materials with the upper layer subjected to pyrolysis and battery powder with the bottom layer subjected to the pyrolysis.
Monitoring the conditions in the pyrolysis furnace: during high-pressure pyrolysis, only the surface layer of the crushed material is observed to be dissolved like liquid drops, the volume is slightly expanded, and other obvious changes are not observed; during negative pressure pyrolysis, the temperature in the furnace is kept constant, the powder falls off obviously, and metallic luster appears.
Example 3
A method for recovering battery powder by low-temperature pyrolysis desorption comprises the following specific processes:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to be 15%, introducing high-pressure mixed gas, sealing, controlling the air pressure in the pyrolysis furnace to be 8MPa and the temperature to be 150 ℃, and continuing for 3 hours; the volume ratio of the high-pressure mixed gas of CO2, NO and O2 is (100);
step 3, after the reaction is finished, releasing the pressure in the pyrolysis furnace to the normal pressure at 0.5MPa/min, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.08 MPa, heating to 360 ℃ at the heating rate of 10 ℃/min, and continuing for 1h;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain battery materials with the upper layer subjected to pyrolysis and battery powder with the bottom layer subjected to the pyrolysis.
Monitoring the conditions in the pyrolysis furnace: during high-pressure pyrolysis, only the surface layer of the crushed material is observed to be dissolved out like liquid drops, the volume is slightly expanded, and other obvious changes are not observed; during negative pressure pyrolysis, the temperature in the furnace is kept constant, the powder falls off obviously, and metallic luster appears.
Comparative example 1
The method for recovering the battery powder through pyrolysis desorption is different from the method in example 1 in that low-temperature high-pressure pyrolysis is not carried out, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, and controlling the filling rate of the pyrolysis furnace to be 5%;
step 3, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.01 MPa, heating to 310 ℃ at the heating rate of 5 ℃/min, and continuing for 3 hours;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain battery materials with the upper layer subjected to pyrolysis and battery powder with the bottom layer subjected to the pyrolysis.
Monitoring the conditions in the pyrolysis furnace: and during negative pressure pyrolysis, the temperature in the furnace is kept constant, molten liquid drops appear on the surface layer of the crushed aggregates, and the crushed aggregates are cooled and do not have obvious metallic luster.
Comparative example 2
The method for recovering the battery powder through pyrolysis desorption is different from the method in example 2 in that low-temperature high-pressure pyrolysis is not carried out, and the specific process comprises the following steps:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, and controlling the filling rate of the pyrolysis furnace to be 10%;
step 3, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.04 MPa, heating to 340 ℃ at the heating rate of 8 ℃/min, and continuing for 2 hours;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain battery materials with the upper layer subjected to pyrolysis and battery powder with the bottom layer subjected to the pyrolysis.
Monitoring the conditions in the pyrolysis furnace: and during negative pressure pyrolysis, the temperature in the furnace is kept constant, molten liquid drops appear on the surface layer of the crushed aggregates, and the crushed aggregates are cooled and do not have obvious metallic luster.
Comparative example 3
The method for recovering the battery powder through pyrolysis desorption is different from the method in example 3 in that low-temperature high-pressure pyrolysis is not carried out, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, and controlling the filling rate of the pyrolysis furnace to be 15%;
step 3, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.08 MPa, heating to 360 ℃ at a heating rate of 10 ℃/min, and keeping for 1h;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain battery materials with the upper layer subjected to pyrolysis and battery powder with the bottom layer subjected to the pyrolysis.
Monitoring the conditions in the pyrolysis furnace: and during negative pressure pyrolysis, the temperature in the furnace is kept constant, molten liquid drops appear on the surface layer of the crushed aggregates, and the crushed aggregates are cooled and do not have obvious metallic luster.
Comparative example 4
The method for recovering the battery powder through pyrolysis desorption is different from the method in embodiment 2 in that low-temperature high-pressure pyrolysis is not carried out, and the pyrolysis temperature in the step 3 is increased, and the specific process is as follows:
step 1, discharging and disassembling a waste ternary lithium ion battery, and crushing the battery into a crushed material with the granularity of less than 5 cm;
step 2, adding the crushed materials into a pyrolysis furnace, and controlling the filling rate of the pyrolysis furnace to be 10%;
step 3, starting a vacuum pump to pump negative pressure, controlling the pressure in the pyrolysis furnace to be-0.04 MPa, heating to 450 ℃ at the heating rate of 8 ℃/min, and continuing for 1h;
and 4, after the pyrolysis reaction is finished, screening the materials in the pyrolysis furnace by using a double-layer screen to obtain battery materials with the upper layer subjected to pyrolysis and battery powder with the bottom layer subjected to the pyrolysis.
Monitoring the conditions in the pyrolysis furnace: during negative pressure pyrolysis, after the temperature in the furnace reaches 450 ℃, flame appears, the temperature is not controlled, the flame rises automatically, the phenomenon of spark splashing occurs rapidly, the material is in a red molten state, and after cooling, obvious metal luster does not appear.
The battery powders and metal foils obtained in examples 1 to 3 and comparative examples 1 to 4 were examined, and the results are shown in Table 1.
TABLE 1
In comparative examples 1 to 3, a large amount of transition metal remained in the metal foil, indicating that the pyrolysis temperature was insufficient and the pyrolysis reaction was difficult to completely occur; comparative example 4 clearly shows thermite reaction, and substantially all of the aluminum was oxidized into black powder, resulting in no formed aluminum foil.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The method for recovering the battery powder through low-temperature pyrolysis desorption is characterized by comprising the following steps of:
s1: discharging, disassembling and crushing the waste battery to obtain a crushed material;
s2: reacting the crushed materials in a mixed atmosphere at a temperature of 120-150 ℃ and a pressure of 3-8MPa, wherein the mixed atmosphere is CO 2 、NO、O 2 The volume ratio of the mixed gas of (2) is 100: (10-15): (0-2);
s3: and (3) reacting the reaction material obtained in the step (S2) at the negative pressure and the temperature of 310-360 ℃, and then sorting to obtain the copper-aluminum foil and the battery powder.
2. The method according to claim 1, wherein in step S1, the particle size of the crushed material is 5cm or less.
3. The method according to claim 1, wherein in step S1, the waste battery is at least one of a ternary lithium ion battery, a lithium iron phosphate battery, a lithium cobalt oxide battery, a lithium manganate battery or a lithium nickel oxide battery.
4. The method of claim 1, wherein in step S2, the reaction time is 3-5h.
5. The method according to claim 1, wherein the reaction is performed in a pyrolysis furnace in step S2, and a filling rate of the crushed material in the pyrolysis furnace is controlled to be 5-15%.
6. The method according to claim 1, wherein in step S3, the negative pressure has a pressure of-0.01 to-0.08 MPa.
7. The method of claim 1, wherein in step S3, the reaction time is 1-3h.
8. The method of claim 5, wherein after the reaction of step S2 is completed, the pressure in the pyrolysis furnace is released to the normal pressure at a rate of 0.1-0.5MPa/min, and then the vacuum pump is started to the negative pressure.
9. The method according to claim 1, wherein in step S3, the reaction temperature is increased at a temperature increase rate of 5-10 ℃/min.
10. The method according to claim 1, wherein in step S3, the sorting process is: and (4) screening by using a double-layer screen, wherein the upper layer is the copper aluminum foil, and the bottom layer is the battery powder.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210716640.7A CN115172923B (en) | 2022-06-23 | 2022-06-23 | Method for recycling battery powder through low-temperature pyrolysis |
| DE112022002405.4T DE112022002405T5 (en) | 2022-06-23 | 2022-09-20 | METHOD FOR RECOVERY OF BATTERY POWDER BY LOW TEMPERATURE PYROLYSIS DESORPTION |
| GB2318191.0A GB2624545A (en) | 2022-06-23 | 2022-09-20 | Method for recovering battery powder by low-temperature pyrolysis desorption |
| HU2400037A HUP2400037A1 (en) | 2022-06-23 | 2022-09-20 | Method for recovering battery powder by low-temperature pyrolysis desorption |
| MX2023014862A MX2023014862A (en) | 2022-06-23 | 2022-09-20 | Method for recovering battery powder by low-temperature pyrolysis desorption. |
| PCT/CN2022/119978 WO2023245889A1 (en) | 2022-06-23 | 2022-09-20 | Method for recovering battery powder by low-temperature pyrolysis desorption |
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| CN202210716640.7A CN115172923B (en) | 2022-06-23 | 2022-06-23 | Method for recycling battery powder through low-temperature pyrolysis |
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| CN (1) | CN115172923B (en) |
| DE (1) | DE112022002405T5 (en) |
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| CN115608755A (en) * | 2022-10-13 | 2023-01-17 | 合肥国轩循环科技有限公司 | Method for separating positive electrode material and current collector in waste lithium iron phosphate battery |
| WO2024130855A1 (en) * | 2022-12-22 | 2024-06-27 | 广东邦普循环科技有限公司 | Low-copper-aluminum fluorine-free black powder and preparation method therefor |
| WO2024207144A1 (en) * | 2023-04-03 | 2024-10-10 | 广东邦普循环科技有限公司 | Method for removing pvdf in waste lithium battery in whole industry chain of lithium batteries |
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Also Published As
| Publication number | Publication date |
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| MX2023014862A (en) | 2024-01-16 |
| GB2624545A (en) | 2024-05-22 |
| DE112022002405T5 (en) | 2024-02-22 |
| CN115172923B (en) | 2024-11-08 |
| GB202318191D0 (en) | 2024-01-10 |
| WO2023245889A1 (en) | 2023-12-28 |
| HUP2400037A1 (en) | 2024-06-28 |
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