CN114854989B - Method for leaching anode active material of photocatalytic reinforced waste lithium ion battery - Google Patents
Method for leaching anode active material of photocatalytic reinforced waste lithium ion battery Download PDFInfo
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- CN114854989B CN114854989B CN202210457557.2A CN202210457557A CN114854989B CN 114854989 B CN114854989 B CN 114854989B CN 202210457557 A CN202210457557 A CN 202210457557A CN 114854989 B CN114854989 B CN 114854989B
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- 238000002386 leaching Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 239000006183 anode active material Substances 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000005286 illumination Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 4
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 4
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 claims description 4
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 4
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 235000003704 aspartic acid Nutrition 0.000 claims description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 239000010926 waste battery Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- -1 photoelectrons Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for leaching out an anode active material of a photocatalytic reinforced waste lithium ion battery and application thereof. The method solves the problems of high cost, high subsequent treatment difficulty and the like caused by the addition of the traditional reducing agent, has high leaching rate of valuable metals, low energy consumption, can recycle the photocatalyst, does not produce secondary pollution, and is an efficient and safe environment-friendly leaching method.
Description
Technical Field
The invention relates to the field of waste battery recovery treatment, in particular to a method for leaching out anode active substances of a photocatalytic reinforced waste lithium ion battery and application of the method in reinforcing the recovery of the anode active substances of the waste lithium ion battery.
Background
Lithium ion batteries, one of the most popular types of rechargeable batteries in portable electronic devices that have emerged since the 90 s of the 20 th century, have been widely used in mobile electronic devices such as cellular phones and computers, and have been increasingly popular in the fields of military, aerospace navigation, electric vehicles, medical devices, and the like. Although the large-scale use of lithium ion batteries brings great convenience to the life of people, the influence of a large number of abandoned lithium ion batteries on the environment and resource waste is immeasurable. The waste lithium battery contains a plurality of valuable resources such as cobalt, lithium, nickel, manganese and the like, and particularly the metal cobalt and lithium contained in the positive electrode active material are internationally accepted strategic substances. If the effective recovery treatment cannot be obtained, the environment is polluted, and the waste of resources is also caused. Therefore, developing a method for efficiently recovering rare noble metals in the anode material of the waste lithium ion battery becomes one of the current research hot spot fields.
At present, after pretreatment such as discharging and disassembling, the waste lithium ion batteries are divided into three main categories according to main key extraction process technologies: physical recovery techniques, chemical recovery techniques, biological recovery techniques. The chemical recovery technology, mainly wet method, is widely used for separating and recovering metals, which is to leach the metal ions in the positive electrode of the waste battery by using proper acid, alkali, reducing agent and the like, and then separate the metal elements in the leaching solution by methods of precipitation, ion exchange, extraction, salting-out, electrochemistry and the like. Among them, acid leaching is the most commonly used method for recovering metal elements in the positive electrode waste, and acids generally used are inorganic acids (e.g., HCl, HNO 3, and H 2SO4), organic acids (e.g., citric acid, oxalic acid, and ascorbic acid), and the like. However, since cobalt in the positive electrode lithium cobaltate active material exists in the form of Co (III), only Co (II) is easily extracted by leaching acid.
In the present stage, more research is still needed to add hydrogen peroxide, iron powder, sodium thiosulfate, sodium bisulfate and the like as reducing agents to reduce the active substances of the positive electrode so as to promote the dissolution of valuable metals such as cobalt, lithium, nickel, manganese and the like. For example, patent CN101381817a is leached by a hydrochloric acid and hydrogen peroxide system, however, hydrogen peroxide is easy to self-decompose, has low utilization rate and severe reaction under acidic conditions, has potential safety hazards, and the addition of a reducing agent also causes cost rise and subsequent treatment difficulty increase; CN108504865A discloses that adding a reducing agent with chloride salt or chlorine-containing solution still causes cost increase and secondary pollution, and the subsequent treatment difficulty increases, although the steps are complex, the cost recovery cost is high, and the application of the acid leaching method in industry is greatly limited. Therefore, it is very necessary to seek an economical and environment-friendly method to improve the leaching efficiency of the anode material of the waste lithium ion battery.
Disclosure of Invention
Aiming at the technical defects, the invention aims to provide a leaching method for leaching the anode active material of the waste lithium ion battery by utilizing the reducing functions of the photocatalyst, such as photoelectrons, hydrogen peroxide and the like under the illumination condition, which solves the problems of high cost, increased subsequent treatment difficulty and the like caused by the addition of the traditional reducing agent, has high leaching rate of valuable metals, low energy consumption, can be recycled, does not produce secondary pollution, and is an efficient and safe environment-friendly leaching method.
In order to achieve the purpose, the method for leaching the anode active material of the photocatalytic reinforced waste lithium ion battery comprises the step of leaching the anode active material of the waste lithium ion battery through a leaching agent and a photocatalyst, wherein the leaching agent is an aqueous solution of organic acid or inorganic acid.
Further, the method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1 is characterized by comprising the following steps:
s1: uniformly mixing the leaching agent and the photocatalyst;
S2: and adding the positive electrode active material of the waste lithium ion battery into the mixed solution obtained in the step S1, leaching under the illumination condition, and collecting the leaching solution.
Further, the method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1 or 2, wherein the organic acid is any one or a combination of more than two of citric acid, acetic acid, oxalic acid, ascorbic acid and aspartic acid; the inorganic acid is any one or the combination of more than two of hydrochloric acid, sulfuric acid or nitric acid.
Further, the method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to any one of claims 1 or 2, wherein the photocatalyst is selected from at least one of TiO 2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4 and/or at least one modified photocatalyst of TiO 2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4.
Further, the method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1 is characterized in that the active material in the anode sheet is any one or more than two mixtures of LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2.
Further, the method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1 is characterized in that the molar ratio of H + to the anode active material in the leaching agent in the leaching process is (3-5): 1, and the mass ratio of the photocatalyst to the anode active material is (0.2-0.7): 1.
Further, the method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1 is characterized in that the leaching process temperature is 20-80 ℃; the leaching time is more than or equal to 30min.
The invention also aims to provide application of the method in reinforcing recovery of the positive electrode active material of the waste lithium ion battery.
The invention has the beneficial effects that:
1. According to the invention, the photocatalyst is used for replacing the reducing agent to leach the positive electrode active material of the waste lithium ion battery, the leaching rate of valuable metals is more than 97%, and the problems of cost increase, subsequent treatment difficulty increase and the like caused by the addition of the traditional reducing agent are solved;
2. The invention can generate photoelectron, hydrogen peroxide and other reducing functions by utilizing the photocatalyst under the illumination condition, has low energy consumption, can be recycled, does not generate secondary pollution in the whole process, and is an efficient and safe environment-friendly leaching method.
Detailed Description
The inventive method of the present invention is described and illustrated in detail below in conjunction with specific examples. The content of which is to be interpreted as an explanation of the invention and not to limit the scope of the invention.
The method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery is characterized by comprising the following steps of:
s1: uniformly mixing the leaching agent and the photocatalyst;
S2: and adding the positive electrode active material of the waste lithium ion battery into the mixed solution obtained in the step S1, leaching under the illumination condition, and collecting the leaching solution.
The organic acid is any one or the combination of more than two of citric acid, acetic acid, oxalic acid, ascorbic acid or aspartic acid; the inorganic acid is any one or the combination of more than two of hydrochloric acid, sulfuric acid or nitric acid.
The photocatalyst is selected from any one or more than two of TiO 2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4 and modified TiO 2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4.
The active material in the positive plate is any one or more than two mixtures of LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2.
The molar ratio of H + to the positive electrode active material in the leaching agent in the leaching process is (3-5) 1, and the mass ratio of the photocatalyst to the positive electrode active material is (0.2-0.7) 1.
The temperature of the leaching process is 20-80 ℃; the leaching time is more than or equal to 30min.
Example 1
Diluting 13mL of concentrated sulfuric acid, magnetically stirring for assistance, fully dissolving, finally fixing the volume to 100mL, adding 2.5g g-C 3N4, and performing ultrasonic dispersion. And (3) adding the LiNi xCoyMn1-x-yO2 anode powder material obtained by disassembling the scrapped lithium ion battery on the new energy automobile into the solution, controlling the solid-to-liquid ratio to be 120 (g/L), and leaching at 40 ℃ for 60min under the illumination condition, wherein leaching rates of Ni, co and Mn are 98.62%,99.29% and 99.91% respectively.
Example 2
Diluting 20mL of concentrated hydrochloric acid, magnetically stirring for assistance, fully dissolving, finally fixing the volume to 100mL, adding 2g of TiO 2, and performing ultrasonic dispersion. And (3) adding the LiNi xCoyMn1-x-yO2 anode powder material obtained by disassembling the waste batteries of the mobile phone into the solution, controlling the solid-liquid ratio to be 100 (g/L), and leaching at 60 ℃ for 60min under the illumination condition, wherein leaching rates of Ni, co and Mn are 98.62%,99.29% and 99.91%, respectively.
Example 3
Taking 10g of citric acid, fully dissolving, finally fixing the volume to 100mL, adding 2g of CdS, and performing ultrasonic dispersion. LiCoO 2 positive electrode powder material obtained by disassembling waste batteries of mobile phones is added into the solution, the solid-to-liquid ratio is controlled to be 110 (g/L), leaching is carried out for 60min at 50 ℃ under the illumination condition, and the leaching rate of Co is 98.29%.
Example 4
Diluting 13mL of concentrated sulfuric acid, magnetically stirring for assistance, fully dissolving, finally fixing the volume to 100mL, adding 2.5g g-C 3N4, and performing ultrasonic dispersion. The composition of the waste battery positive electrode material provided by the waste battery disassembly workshop comprises LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2 powder materials, the solid-to-liquid ratio is controlled to be 120 (g/L), leaching is carried out for 120min at 40 ℃ under the illumination condition, and leaching rates of Ni, co and Mn are 98.53%,98.92% and 99.85% respectively.
Example 5
Diluting 20mL of concentrated nitric acid, magnetically stirring for assistance, fully dissolving, finally fixing the volume to 100mL, adding 2g of WO 3, and performing ultrasonic dispersion. The LiMn 2O4 positive electrode plate powder material of a certain battery factory is added into the solution, the solid-liquid ratio is controlled to be 120 (g/L), leaching is carried out for 120min at 40 ℃ under the illumination condition, and leaching rates of Li and Mn are 97.36% and 98.47% respectively.
Example 6
Taking 12g of oxalic acid, fully dissolving, finally fixing the volume to 100mL, adding 2g of Ag 3PO4, and performing ultrasonic dispersion. And (3) adding the LiNi xCoyMn1-x-yO2 anode powder material obtained by disassembling the waste batteries of the mobile phone into the solution, controlling the solid-to-liquid ratio to be 120 (g/L), and leaching for 120min at 70 ℃ under the illumination condition, wherein leaching rates of Ni, co and Mn are 98.39%,99.56% and 98.98% respectively.
Example 7
10G of ascorbic acid is taken and fully dissolved, the volume is finally fixed to 100mL, 4g of Fe 2O3 is added, and ultrasonic dispersion is carried out. And (3) adding the LiNi xCoyMn1-x-yO2 anode powder material obtained by disassembling the waste batteries of the mobile phone into the solution, controlling the solid-to-liquid ratio to be 120 (g/L), and leaching for 120min at 70 ℃ under the illumination condition, wherein leaching rates of Ni, co and Mn are 97.46%,99.35% and 99.12% respectively.
Example 8
Taking 12g of aspartic acid, fully dissolving, finally fixing the volume to 100mL, adding 4g g-C 3N4, and performing ultrasonic dispersion. The LiMn 2O4 positive electrode plate powder material of a certain battery factory is added into the solution, the solid-liquid ratio is controlled to be 110 (g/L), leaching is carried out for 120min at 60 ℃ under the illumination condition, and leaching rates of Li and Mn are 98.24% and 98.36% respectively.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (7)
1. A method for leaching a photo-catalytic reinforced anode active material of a waste lithium ion battery is characterized in that the anode active material of the waste lithium ion battery is leached by a leaching agent and a photo-catalyst, wherein the leaching agent is an aqueous solution of organic acid or inorganic acid;
the method comprises the following steps:
s1: uniformly mixing the leaching agent and the photocatalyst;
S2: and adding the positive electrode active material of the waste lithium ion battery into the mixed solution obtained in the step S1, leaching under the illumination condition, and collecting the leaching solution.
2. The method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1, wherein the organic acid is any one or more of citric acid, acetic acid, oxalic acid, ascorbic acid and aspartic acid; the inorganic acid is any one or the combination of more than two of hydrochloric acid, sulfuric acid or nitric acid.
3. The method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to any one of claims 1 or 2, wherein the photocatalyst is selected from any one or a combination of more than two of TiO 2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4 and modified TiO 2、WO3、Fe2O3、CdS、Ag3PO4、g-C3N4.
4. The method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1, wherein the active material in the anode plate is any one or more than two mixtures of LiCoO2、LiNiO2、LiMn2O4、LiNixCoyMn1-x-yO2、LiNixCoyAl1-x-yO2.
5. The method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1, wherein the molar ratio of H + to the anode active material in the leaching agent in the leaching process is (3-5): 1, and the mass ratio of the photocatalyst to the anode active material is (0.2-0.7): 1.
6. The method for leaching the anode active material of the photocatalytic enhanced waste lithium ion battery according to claim 1, wherein the leaching process temperature is 20-80 ℃; the leaching time is more than or equal to 30 min.
7. The method of claim 1, wherein the method is used for enhancing recovery of positive electrode active materials of waste lithium ion batteries.
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