CN113300019A - Recovered product and recovery method of waste lithium cobalt oxide battery - Google Patents
Recovered product and recovery method of waste lithium cobalt oxide battery Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 238000011084 recovery Methods 0.000 title claims abstract description 24
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims abstract description 12
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 78
- 239000000047 product Substances 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 239000012065 filter cake Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 26
- 239000010941 cobalt Substances 0.000 abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 26
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000010926 waste battery Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000001055 blue pigment Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 235000016709 nutrition Nutrition 0.000 description 1
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Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
Abstract
The invention discloses a recovered product of waste lithium cobaltate batteries, which mainly comprises 98.1-99.0 wt% of Co3O4 and 1.0-1.8 wt% of LiXCoyO2, wherein x is more than or equal to 0.8 and less than or equal to 1.0, and y is more than or equal to 0.7 and less than or equal to 1.0. The invention also discloses a recovery method of the waste lithium cobalt oxide battery, which comprises the following steps: pretreating the waste lithium cobaltate battery to obtain anode powder; dissolving and leaching the positive electrode powder by using an acid leaching agent, stopping leaching when the leaching rate of Co reaches 10-40% and the leaching rate of Li reaches 88-99%, and filtering to obtain a filter cake and a filtrate; and drying and calcining the filter cake to obtain a recovered product. According to the recovery method, the leaching rates of Co and Li are monitored, when the leaching rate of cobalt and lithium reaches a target range, the leaching step is immediately finished, and the ceramic-grade cobaltosic oxide recovery product is obtained through one-step sintering.
Description
Technical Field
The invention belongs to the technical field of waste lithium battery recovery, and particularly relates to a method for recovering ceramic-grade cobaltosic oxide from waste lithium cobaltate batteries and a recovered product obtained by the method.
Background
Since the successful commercialization of lithium cobaltate batteries since the end of the 20 th century, lithium cobaltate batteries have the advantages of high energy density, high working voltage, no memory effect, high charging and discharging efficiency, long working life and the like, and have gradually replaced the traditional secondary batteries, and are widely used as 3C consumer-grade batteries in mobile electronic products. After the lithium ion battery is subjected to multiple charge-discharge cycles, the active material is inactivated and scrapped due to the change of the structure, so that the number of the waste lithium cobalt oxide batteries is increased year by year and the scrapped amount is huge, the decommissioning amount of the lithium ion battery in 2019 is 12.34GWH, and the decommissioning amount of 125.6GWH is expected to be realized in 2025.
The waste lithium cobaltate battery can pollute the environment and harm the ecological system, and meanwhile, the electrode material contains a large amount of valuable metals such as cobalt, lithium and the like, so that the waste lithium cobaltate battery can be scientifically and economically recycled to realize the reutilization of mineral resources. The existing method for recovering lithium cobaltate generally comprises the steps of pretreating a lithium cobaltate battery, leaching cobalt and lithium by using acid, controlling the leaching rate of the cobalt and the lithium to be more than 97%, separating cobalt ions by using a cobalt ion extracting agent or sodium hydroxide, and sintering the cobalt ions into cobaltosic oxide, so that the cobaltosic oxide is reused as a raw material for producing a lithium cobaltate anode material. However, the recovery method has low efficiency and no advantage in cost in large-scale production, and in order to pursue high metal leaching rate, not only hydrogen peroxide needs to be added for reduction, but also long leaching time is needed, and meanwhile, in order to separate cobalt from a leaching solution, the recovery cost is greatly increased by adopting extraction or alkali addition reaction. Therefore, if the recovery cost can be greatly reduced and the recovered product has a value for direct application, it becomes a problem to be solved in the field of lithium cobalt oxide waste battery recovery.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art, and provide a recovery product and a recovery method of waste lithium cobaltate batteries, which can efficiently recover the waste lithium cobaltate batteries in a large scale and remarkably improve the economic benefit of recovering the waste lithium cobaltate batteries.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a recovered product of a waste lithium cobalt oxide battery is mainly prepared from 98.1-99.0 wt% of Co3O4And 1.0 wt% to 1.8wt% of LiXCoyO2Wherein x is more than or equal to 0.8 and less than or equal to 1.0, and y is more than or equal to 0.7 and less than or equal to 1.0.
The above recovered product preferably has a median particle diameter D50 of 2 to 18 μm and a specific surface area of 9 to 18m2/g。
As a general inventive concept, the present invention also provides a method for recovering waste lithium cobalt oxide batteries, comprising the following steps:
(1) pretreating the waste lithium cobaltate battery to obtain anode powder;
(2) dissolving and leaching the positive electrode powder obtained in the step (1) by using an acid leaching agent, stopping leaching when the leaching rate of Co reaches 10-40% and the leaching rate of Li reaches 88-99%, and filtering to obtain a filter cake and a filtrate;
(3) and (3) drying and calcining the filter cake obtained in the step (2) to obtain a ceramic-grade cobaltosic oxide recovery product.
The applicant of the invention finds that the leaching rates of Co and Li are improved along with the increase of the leaching time, and the leaching speed of Li at the early stage is obviously higher than that of Co through intensive research. Therefore, the invention monitors the change of the leaching rates of Li and Co in the leaching process, detects the concentrations of Li and Co in the leaching solution by adopting an interval sampling mode and calculates the leaching rates of the Li and Co, preferably samples every 5-10 min and carries out ICP test, and can also carry out adaptive adjustment on the interval time of sampling detection according to the actual requirement of the production scale. When the leaching rates of cobalt and lithium reach the target range, the leaching is immediately stopped and the next step is carried out.
According to the invention, the leaching rate of cobalt is controlled to be 10-40%, if the leaching rate of cobalt is lower than 10%, the leaching rate of lithium is relatively low, the obtained filter cake contains more Li impurities, and the content of Co in the recovered product can not reach the standard of ceramic-grade cobaltosic oxide; if the leaching rate of the cobalt is higher than 40%, the leaching rate of the cobalt indicates that the Co is dissolved more in the leaching process, the amount of the obtained solid after filtering is small, the economic benefit is poor, and along with the gradual increase of the leaching rate of the cobalt, the leaching rate of the lithium is high, the leaching speed is very slow, the lithium content in the filter cake is basically not changed, the cobalt content is gradually reduced, and the Co content in the recovered product cannot meet the requirement. Only when the leaching rate of the cobalt is controlled to be 10-40% and the leaching rate of the Li reaches 88-99%, the cobalt content of the recovered product can meet the requirement of ceramic-grade cobaltosic oxide, and better economic benefit can be obtained.
In the above recovery method, preferably, in the step (2), the acid leaching agent is one or a mixture of hydrochloric acid, sulfuric acid and nitric acid, and the total concentration of acid in the acid leaching agent is 1.5-2.5 mol/L.
In the above recovery method, preferably, in the step (2), the leaching temperature is 60-90 ℃.
In the above recovery method, preferably, in the step (1), the pretreatment specifically comprises: discharging the waste lithium cobalt oxide battery in a salt solution, then disassembling to obtain a positive plate, soaking the positive plate in an alkali solution to remove aluminum foil, washing for multiple times, drying, calcining at 400-600 ℃ for 6-8 hours, grinding, and sieving to obtain positive powder.
In the above recovery method, preferably, the salt solution is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, sodium chloride, potassium chloride and magnesium chloride, and the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 2 to 4 mol/L.
In the above recovery method, preferably, in the step (3), the calcining temperature is 700 to 950 ℃, and the calcining time is 2 to 4 hours.
In the above recovery method, preferably, the calcination is carried out in an air atmosphere, and the air flow rate is 2 to 6m3/h。
Compared with the prior art, the invention has the advantages that:
(1) the method for recycling the waste lithium cobaltate battery breaks through the conventional thought of recycling the waste lithium cobaltate battery in the prior art, namely, the higher leaching rate is not pursued in the acid leaching process, the leaching rate of Co and Li is controlled by controlling the concentration and the leaching temperature of acid and paying attention to the change of the leaching rate of Co and Li, when the leaching rate of Co reaches 10-40% and the leaching rate of Li reaches 88-99%, the leaching is immediately finished, and a recycled product is obtained by one-step sintering, and can be applied to the fields of coloring pigments, electronic element materials, bonding agents of hard alloy materials, catalysts, livestock nutritional agents and the like.
(2) The recovery method can prepare the ceramic-grade cobaltosic oxide material only by simple acid leaching and calcination, is simple and easy to operate, has low production cost, and can obtain excellent economic benefit after popularization and application.
(3) The content of cobaltosic oxide in the recovered product is more than 98.1 percent, the cobalt content can reach more than 72 percent, and the product meets the standard of ceramic-grade cobaltosic oxide.
(4) The median particle diameter D50 of the recovered product of the invention is 2-18 μm, and the specific surface area is 9-18m2The recovery product not only completely meets the ceramic grade requirement, but also is not easy to generate an incomplete crystal structure in the pigment in the reaction process, has better crystal integrity and excellent ultraviolet reflection performance, and the color of the produced cobalt blue pigment is more bright.
Drawings
FIG. 1 is an XRD pattern of the recovered product obtained in example 1 of the present invention.
FIG. 2 is an SEM photograph of a recovered product obtained in example 2 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention discloses a method for recovering waste lithium cobaltate batteries, which comprises the following steps:
(1) fully discharging a waste lithium cobalt oxide battery from a certain recycling enterprise of Dongguan city, Guangdong province in 1mol/L sodium chloride solution, disassembling to obtain a positive plate, placing the positive plate in 2mol/L sodium hydroxide solution to remove aluminum foil, washing for multiple times, drying, calcining for 6 hours at the calcining temperature of 400 ℃ through a muffle furnace, removing impurities such as carbon, PVDF and the like in the positive material, grinding, and sieving to obtain positive powder, wherein the element content is shown in Table 1;
TABLE 1 elemental composition content of cathode powder
(2) Weighing 200g of the positive electrode powder obtained in the step (1), placing the positive electrode powder into a beaker, and adding 1.5mol/L H with 30% excess according to the stoichiometric ratio of the positive electrode material to sulfuric acid reaction2SO4Heating to 60 ℃, monitoring the change of the leaching rate of cobalt and lithium, stopping leaching when the leaching rate of Co reaches 11.5% and the leaching rate of Li reaches 89%, leaching for 55min, and filtering to obtain a filter cake and a filtrate;
(3) drying the filter cake obtained by filtering in the step (2) in a vacuum drying oven at 70 ℃ for 24 hours, then placing the filter cake in a muffle furnace, and introducing the filter cake with the flow of 2m3And h, keeping the atmosphere in the furnace with air, heating to 700 ℃, calcining for 2h, and naturally cooling to room temperature to obtain a recovered product.
The XRD of the recovered product prepared in this example is shown in FIG. 1, and its cobalt content was 72.5 wt% by ICP test. XRD test results show that lithium cobaltate is subjected to acid leaching process of incomplete acid dissolution, cobalt and lithium leaching rates are strictly controlled, and then high-temperature calcination can convert lithium cobaltate with a layered structure into spinel-type Co3O4And the purity of the obtained product meets the standard of ceramic-grade cobaltosic oxide.
The recovered product prepared in this example was tested for composition, including 98.1 wt% Co3O4And 1.0 wt% Li0.8Co0.7O2. The recovered product had a particle diameter D50 of 9 μm and a specific surface area of 18m2The recovered product can be used as a raw material for producing the cobalt blue pigment, the specific surface area is large, and the color of the produced cobalt blue pigment is bright.
Example 2:
the invention discloses a method for recovering waste lithium cobaltate batteries, which comprises the following steps:
(1) taking the waste battery same as the waste battery in the embodiment 1, fully discharging in 2mol/L potassium chloride solution, disassembling to obtain a positive plate, then placing the positive plate in 2mol/L potassium hydroxide solution to remove aluminum foil, washing for multiple times, drying, calcining in a muffle furnace to 500 ℃, preserving heat for 6 hours, removing impurities such as carbon, PVDF and the like in a positive material, grinding, and sieving to obtain positive powder, wherein the element content is shown in Table 2;
TABLE 2 elemental composition content of positive electrode powder
(2) Weighing 200g of the positive electrode powder obtained in the step (1), placing the positive electrode powder into a beaker, and adding 2mol/L H with 30% excess according to the stoichiometric ratio of the positive electrode material to sulfuric acid reaction2SO4Heating to 80 ℃, monitoring the change of the leaching rate of cobalt and lithium, stopping leaching when the leaching rate of Co is 38% and the leaching rate of Li is 98%, taking 70min for leaching, and filtering to obtain a filter cake and filtrate;
(3) putting the filter cake obtained by filtering in the step (2) into a vacuum drying oven, drying for 24 hours at 70 ℃, and then introducing the filter cake into a muffle furnace at the flow rate of 3m3And h, heating to 800 ℃ in air, calcining for 3h at the temperature, and naturally cooling to room temperature to obtain a recovered product.
The SEM of the recovered product obtained in this example is shown in FIG. 2, and it was found that the cobalt content was 73.0 wt% by ICP.
The recovered product prepared in this example was tested for its composition,comprising 98.5 wt% Co3O4And 1.1 wt% Li0.9CoO2The recovered product had a particle size D50 of 9 μm and a specific surface area of 18m2/g。
Example 3:
the invention discloses a method for recovering waste lithium cobaltate batteries, which comprises the following steps:
(1) taking the same waste battery sample as in example 1, fully discharging in 2mol/L potassium chloride solution, then disassembling to obtain a positive plate, then placing the positive plate in 2mol/L potassium hydroxide solution to remove aluminum foil, washing for multiple times, drying, then placing in a muffle furnace, calcining for 8 hours at 500 ℃, removing impurities such as carbon, PVDF and the like in the positive material, grinding, and sieving to obtain positive powder, wherein the element content is shown in Table 3;
TABLE 3 elemental composition content of cathode powder
(2) Weighing 200g of the positive electrode powder obtained in the step (1), placing the positive electrode powder in a beaker, and adding 1.75mol/L HNO with 30% excess according to the stoichiometric ratio of the positive electrode material to the acid reaction3Heating to 70 ℃, monitoring the change of the leaching rate of cobalt and lithium, stopping leaching when the leaching rate of Co is 24% and the leaching rate of Li is 95%, taking 65min for leaching, and filtering to obtain a filter cake and a filtrate;
(3) putting the filter cake obtained in the step (2) into a vacuum drying oven, drying for 24 hours at 70 ℃, then putting into a muffle furnace, and introducing the filter cake with the flow of 3m3And h, heating to 800 ℃ in air, calcining for 3h at the temperature, and naturally cooling to room temperature to obtain a recovered product.
The recovered product obtained in this example was found to have a cobalt content of 72.9% by weight by ICP analysis and a purity in accordance with the standard for ceramic grade tricobalt tetroxide.
The recovered product obtained in this example comprised 98.4 wt% Co3O4And 1.2 wt% LiCo0.8O2The recovered product had a particle diameter D50 of 10 μm and a specific surface area of 15m2/g。
Example 4:
the invention discloses a method for recovering waste lithium cobaltate batteries, which comprises the following steps:
(1) taking the waste battery same as the waste battery in the embodiment 1, fully discharging in 2mol/L potassium chloride solution, then disassembling to obtain a positive plate, then placing the positive plate in 2mol/L potassium hydroxide solution to remove aluminum foil, washing for multiple times, drying, then placing in a muffle furnace, calcining at 500 ℃, removing impurities such as carbon, PVDF and the like in a positive material, grinding, and sieving to obtain positive powder, wherein the element content is shown in Table 4;
TABLE 4 elemental composition content of cathode powder
(2) Weighing 200g of the positive electrode powder obtained in the step (1), placing the positive electrode powder in a beaker, and adding 2mol/L HNO with 30% excess according to the stoichiometric ratio3Heating to 90 ℃, stopping leaching when the Co leaching rate is 15% and the Li leaching rate is 93%, wherein the leaching time is 50min, and filtering to obtain a filter cake and a filtrate;
(3) putting the filter cake obtained in the step (2) into a vacuum drying oven, drying for 24 hours at 70 ℃, then putting into a muffle furnace, and introducing the filter cake with the flow of 3m3And h, heating to 800 ℃ in air, calcining for 3h at the temperature, and naturally cooling to room temperature to obtain a recovered product.
The recovered product obtained in this example had a cobalt content of 72.8% by weight as measured by ICP, and the purity of the obtained product was in accordance with the standard for ceramic grade tricobalt tetroxide.
The recovered product obtained in this example comprised 98.5 wt% Co3O4And 1.0 wt% LiCo0.7O2The recovered product had a particle size D50 of 11 μm and a specific surface area of 17m2/g。
Claims (9)
1. The recovered product of the waste lithium cobalt oxide battery is characterized by mainly comprising 98.1-99.0 wt% of Co3O4And 1.0 wt%. E to E1.8 wt% LiXCoyO2Wherein x is more than or equal to 0.8 and less than or equal to 1.0, and y is more than or equal to 0.7 and less than or equal to 1.0.
2. The recovered product of claim 1, wherein the recovered product has a median particle diameter D50 of 2 to 18 μm and a specific surface area of 9 to 18m2/g。
3. A method for recovering waste lithium cobalt oxide batteries is characterized by comprising the following steps:
(1) pretreating the waste lithium cobaltate battery to obtain anode powder;
(2) dissolving and leaching the positive electrode powder obtained in the step (1) by using an acid leaching agent, stopping leaching when the leaching rate of Co reaches 10-40% and the leaching rate of Li reaches 88-99%, and filtering to obtain a filter cake and a filtrate;
(3) and (3) drying and calcining the filter cake obtained in the step (2) to obtain a ceramic-grade cobaltosic oxide recovery product.
4. The recycling method according to claim 3, wherein in the step (2), the acid leaching agent is one or more of hydrochloric acid, sulfuric acid and nitric acid, and the total concentration of acid in the acid leaching agent is 1.5-2.5 mol/L.
5. A recovery method as claimed in claim 3, characterised in that in step (2), the temperature of the leach is 60-90 ℃.
6. The recycling method according to any one of claims 3 to 5, wherein in the step (1), the pretreatment comprises the following specific steps: discharging the waste lithium cobalt oxide battery in a salt solution, then disassembling to obtain a positive plate, soaking the positive plate in an alkali solution to remove aluminum foil, washing for multiple times, drying, calcining at 400-600 ℃ for 6-8 hours, grinding, and sieving to obtain positive powder.
7. The recycling method according to claim 6, wherein the salt solution is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, sodium chloride, potassium chloride and magnesium chloride, and the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution with a concentration of 2-4 mol/L.
8. The recycling method according to any one of claims 3 to 5, wherein in the step (3), the calcination temperature is 700 to 950 ℃ and the calcination time is 2 to 4 hours.
9. The recovery method according to claim 8, wherein the calcination is carried out in an air atmosphere with an air flow of 2 to 6m3/h。
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