CN114854989A - Method for enhancing leaching of active substances of positive electrode of waste lithium ion battery through photocatalysis - Google Patents
Method for enhancing leaching of active substances of positive electrode of waste lithium ion battery through photocatalysis Download PDFInfo
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- CN114854989A CN114854989A CN202210457557.2A CN202210457557A CN114854989A CN 114854989 A CN114854989 A CN 114854989A CN 202210457557 A CN202210457557 A CN 202210457557A CN 114854989 A CN114854989 A CN 114854989A
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- lithium ion
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- ion batteries
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- 238000002386 leaching Methods 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 239000013543 active substance Substances 0.000 title claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 9
- 230000002708 enhancing effect Effects 0.000 title description 5
- 239000011941 photocatalyst Substances 0.000 claims abstract description 21
- 238000005728 strengthening Methods 0.000 claims abstract description 6
- 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
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- 238000005286 illumination Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000011084 recovery Methods 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
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 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
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 4
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 4
- 229910013290 LiNiO 2 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
- 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 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
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000694 effects 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
- 239000011572 manganese Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- 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
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011149 active material Substances 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
- 239000010405 anode material Substances 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- -1 photoelectrons Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001804 chlorine 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 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
Landscapes
- 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 strengthening leaching of anode active substances of waste lithium ion batteries through photocatalysis and application thereof. The method solves the problems of cost rise, increased difficulty in subsequent treatment and the like caused by adding of the traditional reducing agent, has high leaching rate of valuable metals, low energy consumption and no secondary pollution, and can recycle the photocatalyst, thereby being 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 strengthening leaching of positive active substances of a waste lithium ion battery through photocatalysis and application of the method in the aspect of strengthening recovery of the positive active substances of the waste lithium ion battery.
Background
Lithium ion batteries, which are one of the most popular rechargeable battery types in portable electronic devices appearing in the 90 s of the 20 th century, have been widely used in mobile electronic devices such as mobile phones and computers, and have been increasingly popularized in the fields of military, aerospace, 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 amount of discarded lithium ion batteries on the environment and the waste of resources 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 active material are the strategic substances which are internationally recognized. If the waste water cannot be effectively recycled, the waste water not only pollutes the environment, but also wastes resources. Therefore, the development of a method for efficiently recovering rare and precious metals in the anode material of the waste lithium ion battery becomes one of the research hotspots at present.
At present, after the waste lithium ion battery is pretreated by discharging, disassembling and the like, according to main key extraction process technologies, resource treatment process methods can be divided into three main categories: physical recovery technology, chemical recovery technology, and biological recovery technology. The chemical recovery technology, mainly a wet method, is widely used for separating and recovering metals, and is to leach metal ions in the anode of the waste battery by using proper acid, alkali, reducing agent and the like, and then separate metal elements in the leachate by using methods of precipitation, ion exchange, extraction, salting out, electrochemistry and the like. Among them, the acid leaching method is the most commonly used method for recovering metal elements from the cathode scrap, and the acid used is usually an inorganic acid (e.g., HCl, HNO) 3 And H 2 SO 4 ) 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 the leaching acid.
At present, many researches still need to add hydrogen peroxide, iron powder, sodium thiosulfate, sodium bisulfite and the like as reducing agents to reduce positive active substances and promote the dissolution of valuable metals such as cobalt, lithium, nickel, manganese and the like. For example, patent CN101381817A uses hydrochloric acid and hydrogen peroxide system for leaching, however, under acidic conditions, hydrogen peroxide is easy to self-decompose, the utilization rate is low, the reaction is severe, and there is a safety hazard, and the addition of a reducing agent also causes the cost to increase, the difficulty of subsequent treatment increases, and the like; CN108504865A discloses that the addition of a reducing agent with a chlorine salt or a chlorine-containing solution still causes cost increase and secondary pollution, increases the difficulty of subsequent treatment, and although the method can be recycled, the steps are complex, the cost recovery cost is high, and the application of the acid leaching method in the industry is greatly limited. Therefore, it is necessary to find an economic and environmental-friendly method for improving 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 method for leaching the anode active substance of the waste lithium ion battery by using the reducibility function of the photocatalyst, such as photoelectrons, hydrogen peroxide and the like, under the illumination condition, the method solves the problems of cost rise, subsequent treatment difficulty increase and the like caused by the addition of the traditional reducing agent, has high leaching rate of valuable metals, low energy consumption and recyclable photocatalyst, does not generate secondary pollution, and is an efficient and safe environment-friendly leaching method.
In order to achieve the purpose, the method for strengthening the leaching of the anode active substance of the waste lithium ion battery through photocatalysis comprises the step of leaching the anode active substance 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 photocatalytic enhancement of leaching of positive active materials of waste lithium ion batteries according to claim 1 is characterized by comprising the following steps:
s1: uniformly mixing a leaching agent and a photocatalyst;
s2: and adding the positive active substance of the waste lithium ion battery into the mixed solution obtained in the step S1, leaching under the illumination condition, and collecting the leachate.
Further, the method for photocatalytic enhancement of leaching of positive active materials of waste lithium ion batteries according to claim 1 or 2 is characterized in that the organic acid is any one or a combination of two or more 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.
Further, the method for enhancing leaching of active materials of the positive electrode of the waste lithium ion battery through photocatalysis according to any one of claims 1 or 2, wherein the photocatalyst is selected from TiO 2 、WO 3 、Fe 2 O 3 、CdS、Ag 3 PO 4 、g-C 3 N 4 And/or TiO 2 、WO 3 、Fe 2 O 3 、CdS、Ag 3 PO 4 、g-C 3 N 4 At least one modified photocatalyst as described in (1).
Further, the method for enhancing leaching of the active material of the positive electrode of the waste lithium ion battery through photocatalysis according to claim 1, wherein the active material in the positive electrode plate is LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 Any one or a mixture of two or more of them.
Further, the method for photocatalytic enhancement of leaching of positive active materials of waste lithium ion batteries according to claim 1 is characterized in that H in a leaching agent in the leaching process + The molar ratio of the photocatalyst to the positive electrode active material is (3-5):1, and the mass ratio of the photocatalyst to the positive electrode active material is (0.2-0.7): 1.
Further, the method for photocatalytic enhancement of leaching of active substances of the positive electrode of the waste lithium ion battery is characterized in that the temperature of the leaching process is 20-80 ℃; the leaching time is more than or equal to 30 min.
The invention also aims to provide application of the method in enhancing recovery of positive active materials of waste lithium ion batteries.
The invention has the beneficial effects that:
1. according to the invention, the photocatalyst is used for replacing a reducing agent to leach the active substances of the anode of the waste lithium ion battery, the leaching rate of valuable metals is more than 97%, and the problems of increased cost, increased difficulty in subsequent treatment and the like caused by the addition of the traditional reducing agent are solved;
2. the invention utilizes the reductive functions of the photocatalyst such as photoelectrons, hydrogen peroxide and the like under the illumination condition, has low energy consumption, can recycle the photocatalyst, does not generate secondary pollution in the whole process, and is an efficient and safe environment-friendly leaching method.
Detailed Description
The process of the present invention is described and illustrated in detail below with reference to specific examples. The content is to explain the invention and not to limit the scope of protection of the invention.
A method for strengthening leaching of active substances of a positive electrode of a waste lithium ion battery through photocatalysis is characterized by comprising the following steps:
s1: uniformly mixing a leaching agent and a photocatalyst;
s2: and adding the positive active substance of the waste lithium ion battery into the mixed solution obtained in the step S1, leaching under the illumination condition, and collecting the leachate.
The organic acid is any one or combination of more than two of citric acid, acetic acid, oxalic acid, ascorbic acid or aspartic acid; the inorganic acid is any one or combination of more than two of hydrochloric acid, sulfuric acid or nitric acid.
The photocatalyst is selected from TiO 2 、WO 3 、Fe 2 O 3 、CdS、Ag 3 PO 4 、g-C 3 N 4 And modified TiO 2 、WO 3 、Fe 2 O 3 、CdS、Ag 3 PO 4 、g-C 3 N 4 Any one or a combination of two or more of them.
The active substance in the positive pole piece is LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 Or a mixture of two or more thereof.
H in the leaching agent in the leaching process + The molar ratio of the photocatalyst to the positive electrode active material 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 in the leaching process is 20-80 ℃; the leaching time is more than or equal to 30 min.
Example 1
Diluting 13mL of concentrated sulfuric acid, and magnetically stirringAuxiliary, fully dissolving, finally fixing the volume to 100mL, adding 2.5g g-C 3 N 4 And (4) ultrasonic dispersion. Obtaining LiNi by disassembling scrapped lithium ion batteries on new energy automobiles x Co y Mn 1-x-y O 2 Adding the anode powder material into the solution, controlling the solid-to-liquid ratio to be 120(g/L), leaching for 60min at 40 ℃ under the light condition, wherein the leaching rates of Ni, Co and Mn are respectively 98.62%, 99.29% and 99.91%.
Example 2
Diluting 20mL of concentrated hydrochloric acid, magnetically stirring for assisting, fully dissolving, finally fixing the volume to 100mL, adding 2g of TiO 2 And (4) ultrasonic dispersion. LiNi obtained by disassembling waste battery of mobile phone x Co y Mn 1-x-y O 2 Adding the anode powder material into the solution, controlling the solid-to-liquid ratio to be 100(g/L), leaching for 60min at 60 ℃ under the illumination condition, wherein the leaching rates of Ni, Co and Mn are respectively 98.62%, 99.29% and 99.91%.
Example 3
And taking 10g of citric acid, fully dissolving, finally fixing the volume to 100mL, adding 2g of CdS, and performing ultrasonic dispersion. LiCoO obtained by disassembling waste battery of mobile phone 2 Adding the anode powder material into the solution, controlling the solid-to-liquid ratio to be 110(g/L), leaching for 60min at 50 ℃ under the illumination condition, and controlling the leaching rate of Co to be 98.29%.
Example 4
Diluting 13mL of concentrated sulfuric acid, magnetically stirring for assisting, dissolving completely, diluting to 100mL, adding 2.5g g-C 3 N 4 And (4) ultrasonic dispersion. The anode material of the waste battery provided by the waste battery dismantling workshop comprises LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 Adding the powder material into the above solution, controlling the solid-to-liquid ratio at 120(g/L), leaching at 40 deg.C for 120min under illumination condition, wherein the leaching rates of Ni, Co and Mn are respectively 98.53%, 98.92% and 99.85%.
Example 5
Diluting with 20mL of concentrated nitric acid, and performing magnetic forceStirring for assisting, fully dissolving, finally fixing the volume to 100mL, adding 2g of WO 3 And (4) ultrasonic dispersion. LiMn in certain Battery factory 2 O 4 Adding the positive pole piece powder material into the solution, controlling the solid-to-liquid ratio to be 120(g/L), leaching for 120min at 40 ℃ under the illumination condition, wherein the 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 3 PO 4 And (4) ultrasonic dispersion. Obtaining LiNi by disassembling waste battery of mobile phone x Co y Mn 1-x-y O 2 Adding the anode powder material into the solution, controlling the solid-to-liquid ratio to be 120(g/L), leaching for 120min at 70 ℃ under the illumination condition, wherein the leaching rates of Ni, Co and Mn are 98.39%, 99.56% and 98.98% respectively.
Example 7
10g of ascorbic acid is fully dissolved and finally the volume is determined to be 100mL, 4g of Fe is added 2 O 3 And (4) ultrasonic dispersion. Obtaining LiNi by disassembling waste battery of mobile phone x Co y Mn 1-x-y O 2 Adding the anode powder material into the solution, controlling the solid-to-liquid ratio to be 120(g/L), leaching for 120min at 70 ℃ under the illumination condition, wherein the leaching rates of Ni, Co and Mn are 97.46%, 99.35% and 99.12% respectively.
Example 8
Dissolving 12g aspartic acid completely, adding 4g g-C to the solution to a final volume of 100mL 3 N 4 And (4) ultrasonic dispersion. LiMn in certain Battery factory 2 O 4 Adding the powder material of the positive pole piece into the solution, controlling the solid-to-liquid ratio to be 110(g/L), leaching for 120min at 60 ℃ under the illumination condition, wherein the leaching rates of Li and Mn are 98.24% and 98.36% respectively.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for strengthening leaching of positive active substances of waste lithium ion batteries through photocatalysis is characterized in that the positive active substances of the waste lithium ion batteries are leached through a leaching agent and a photocatalyst, wherein the leaching agent is an aqueous solution of organic acid or inorganic acid.
2. The method for photocatalytic enhancement of leaching of positive active substances of waste lithium ion batteries according to claim 1 is characterized by comprising the following steps:
s1: uniformly mixing a leaching agent and a photocatalyst;
s2: and adding the positive active substance of the waste lithium ion battery into the mixed solution obtained in the step S1, leaching under the illumination condition, and collecting the leachate.
3. The method for photocatalytic enhancement of leaching of positive active materials of waste lithium ion batteries according to claim 1 or 2, wherein the organic acid is any one or a combination of two or more 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.
4. The method for photocatalytic enhanced leaching of positive active materials of waste lithium ion batteries according to any one of claims 1 or 2, wherein the photocatalyst is selected from TiO 2 、WO 3 、Fe 2 O 3 、CdS、Ag 3 PO 4 、g-C 3 N 4 And modified TiO 2 、WO 3 、Fe 2 O 3 、CdS、Ag 3 PO 4 、g-C 3 N 4 Any one or a combination of two or more of them.
5. The method for photocatalytic enhancement of leaching of positive active substances of waste lithium ion batteries according to claim 1, wherein the activity in the positive pole pieceThe substance is LiCoO 2 、LiNiO 2 、LiMn 2 O 4 、LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 Any one or a mixture of two or more of them.
6. The method for photocatalytic enhancement of leaching of positive active materials of waste lithium ion batteries according to claim 1, wherein H in a leaching agent in the leaching process is H + The molar ratio of the photocatalyst to the positive electrode active material is (3-5):1, and the mass ratio of the photocatalyst to the positive electrode active material is (0.2-0.7): 1.
7. The method for photocatalytic enhancement of leaching of positive active substances of waste lithium ion batteries according to claim 1, wherein the temperature of the leaching process is 20-80 ℃; the leaching time is more than or equal to 30 min.
8. The use of the method of claim 1 to enhance the recovery of positive active materials from spent lithium ion batteries.
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