A lithium battery recovery solution and a method for recovering positive electrode materials of waste ternary batteries

Abstract

The present disclosure relates to a lithium battery recycling solution and a method for recycling positive electrode materials of waste ternary batteries. The lithium battery recycling solution comprises: a nitrogen-containing heterocyclic compound and an organic solvent; the nitrogen-containing heterocyclic compound has a structure as shown in Formula I:.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium battery materials, and in particular to a lithium battery recovery solution and a method for recovering positive electrode materials of waste ternary batteries. Background Art

[0002] Lithium-ion batteries have become the most ideal energy storage device in the 21st century due to their light weight, small size, high energy, low self-discharge, and long cycle life. Driven by consumer electronics, the market demand for lithium-ion batteries has grown significantly in the past decade. Since 2006, the average annual growth rate of global lithium battery sales has remained above 25%. There are currently 7.19 billion active mobile phones and nearly 1 billion laptops in the world; in addition, the inventory of electric vehicles is expected to increase from about 8 million in 2019 to about 50 million in 2025, and close to 140 million by 2030.

[0003] The existing process is mainly aimed at the recovery of lithium cobalt oxide. For example, the publication number is "CN105304971A" and the invention name is "Mechanical Chemical Recycling Method for Waste Lithium Battery Positive Electrode Materials". It discloses a method for treating waste lithium batteries by mechanochemical method, selectively recovering metallic lithium and simultaneously preparing cobalt-based magnetic functional materials in a directional manner. The method specifically includes five steps: discharging, splitting, ball milling, lithium recovery and calcination. Specifically, dry ball milling is adopted to make the material and the auxiliary agent undergo solid-phase reaction without generating waste liquid; the metallic lithium is selectively recovered by controlling the reaction process, and the metallic cobalt is directional to synthesize magnetic materials.

[0004] For the recovery of nickel-cobalt-manganese ternary materials, strong acids and alkalis are mostly used for leaching, and then valuable metals are precipitated step by step, or certain raw materials are added to synthesize nickel-cobalt-manganese ternary material precursors. Summary of the invention

[0005] The present invention provides a lithium battery recovery solution and a method for recovering the positive electrode material of waste ternary batteries to solve the deficiencies in the related art.

[0006] According to a first aspect of an embodiment of the present disclosure, a lithium battery recovery solution is provided, comprising: a nitrogen-containing heterocyclic compound and an organic solvent; the nitrogen-containing heterocyclic compound has a structure as shown in Formula I:

[0007] ;

[0008] wherein A1 and A2 are selected from C and N, and at least one of A1 and A2 is N; A3 and A4 are selected from C and N, and at least one of A3 and A4 is N; R1 and R2 are each independently selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, a carboxyl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclyl group, a substituted or unsubstituted 5-30 membered heteroaryl group, or a substituted or unsubstituted 3-30 membered ring formed by bonding with an adjacent substituent.

[0009] In one aspect of the embodiments of the present disclosure, based on the total volume of the lithium battery recovery solution, the volume percentage of the nitrogen-containing heterocyclic compound is selected from 3%-10%.

[0010] In one aspect of the embodiments of the present disclosure, based on the total volume of the lithium battery recovery solution, the volume percentage of the nitrogen-containing heterocyclic compound is selected from 4%-5%.

[0011] In one aspect of the embodiments of the present disclosure, the nitrogen-containing heterocyclic compound has a structure as shown in Formula I-1 to Formula I-6:

[0012] ;

[0013] R1 and R2 are each independently selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, a carboxyl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclic group, a substituted or unsubstituted 5-30 membered heteroaryl group, or a substituted or unsubstituted 3-30 membered ring formed by bonding with an adjacent substituent.

[0014] In one aspect of the embodiments of the present disclosure, the nitrogen-containing heterocyclic compound is selected from at least one of the following compounds:

[0015] ;

[0016] ;

[0017] In one aspect of the embodiments of the present disclosure, the organic solvent is selected from kerosene, sulfonated kerosene or aliphatic hydrocarbon solvent oil.

[0018] In one aspect of the embodiments of the present disclosure, the organic solvent further includes an organic phosphate solvent.

[0019] According to a second aspect of an embodiment of the present disclosure, a method for recycling positive electrode materials of waste ternary batteries is provided, the recycling method comprising the following steps:

[0020] Step 1: disassembling the lithium battery to obtain a positive electrode sheet; subjecting the positive electrode sheet to a high temperature treatment under a first inert gas atmosphere to obtain a positive electrode current collector and a positive electrode coating by separation, and crushing the positive electrode coating;

[0021] Step 2: placing the obtained crushed positive electrode coating in a first acidic solution to obtain a mixed solution;

[0022] Step 3: using the aforementioned lithium battery recovery solution to extract the mixed solution obtained in step 2 to obtain a loaded organic phase and a raffinate water phase;

[0023] Step 4: stripping the loaded organic phase with water to obtain manganese and cobalt respectively.

[0024] In one aspect of the embodiments of the present disclosure, the first acidic solution is selected from at least one of malic acid, tartaric acid, succinic acid, bitter acid, citric acid and maleic acid.

[0025] In one aspect of the disclosed embodiments, the first acidic solution is selected from a mixture of tartaric acid and succinic acid.

[0026] In one aspect of the embodiments of the present disclosure, the volume ratio of the loaded organic phase to water is (1-50):1.

[0027] In one aspect of the embodiments of the present disclosure, before stripping, a step of washing the loaded organic phase is also included.

[0028] In one aspect of the embodiments of the present disclosure, before extraction, a step of stepwise impurity removal using extractants P204 and / or M5640 is also included, wherein P204 removes trace zinc, calcium and magnesium impurities in the mixed solution, and M5640 removes trace copper impurities in the mixed solution.

[0029] The technical solution provided by the embodiments of the present disclosure may have the following beneficial effects:

[0030] It can be seen from the above embodiments that the present disclosure provides a recovery solution and a recovery method that can effectively recover manganese and cobalt in the positive electrode materials of waste ternary lithium batteries.

[0031] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. DETAILED DESCRIPTION

[0032] The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Instead, they are merely examples of devices and methods consistent with some aspects of the present disclosure as detailed in the appended claims.

[0033] The terms used in this disclosure are for the purpose of describing specific embodiments only and are not intended to limit the disclosure. The singular forms of "a", "said" and "the" used in this disclosure and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise. It should also be understood that the term "and / or" used herein refers to and includes any or all possible combinations of one or more associated listed items.

[0034] In the description herein, unless otherwise specified, “above” and “below” include the number.

[0035] In the present disclosure, unless otherwise specified, the terms used in the present disclosure have the well-known meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of the various parameters mentioned in the present disclosure can be measured by various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of the present disclosure).

[0036] In the present disclosure, the term "about" is used to describe and illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. In addition, amounts, ratios, and other numerical values ​​are sometimes presented in this article in a range format. It should be understood that such a range format is for convenience and simplicity, and should be flexibly understood to include not only numerical values ​​explicitly designated as range limits, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0037] In the present disclosure, a list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0038] In the present disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight or branched, containing about 1 to about 20 carbon atoms in the chain. Preferred alkyl groups contain about 1 to about 12 carbon atoms in the chain, and more preferred alkyl groups contain about 1 to about 6 carbon atoms in the chain. Branched refers to one or more lower alkyl groups connected to a linear alkyl chain, such as methyl, ethyl or propyl. "Lower alkyl" refers to a group containing about 1 to about 6 carbon atoms in the chain, which can be straight or branched. The term "substituted alkyl" refers to an alkyl group that can be substituted by one or more substituents, which can be the same or different. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, heptyl, nonyl, decyl, fluoromethyl, trifluoromethyl and cyclopropylmethyl.

[0039] In the present disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group, which contains at least one carbon-carbon double bond, which can be straight or branched, containing about 2 to about 15 carbon atoms in the chain, preferably alkenyl containing about 2 to about 12 carbon atoms in the chain, more preferably containing about 2 to about 6 carbon atoms in the chain. Branched refers to one or more lower alkyl groups connected to a linear alkenyl chain, such as methyl, ethyl or propyl. "Lower alkenyl" refers to a group containing about 2 to about 6 carbon atoms in the chain, which can be straight or branched. The term "substituted alkenyl" means that the alkenyl can be substituted by one or more substituents, which can be the same or different, and each substituent is independently selected from halo, alkyl, aryl, cycloalkyl, cyano and alkoxy. Non-limiting examples of suitable alkenyls include vinyl, propenyl, n-butenyl, 3-methylbut-2-enyl, n-pentenyl, octenyl and decenyl.

[0040] In the present disclosure, the term "halo" refers to fluoro, chloro, bromo or iodo, preferably fluoro, chloro or bromo, more preferably fluoro and chloro. "Halogen" refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine and chlorine.

[0041] In this disclosure, "ring system substituent" refers to a substituent attached to an aromatic or non-aromatic ring system which, for example, replaces an available hydrogen on the ring system. The ring system substituents may be the same or different and each is independently selected from aryl, heteroaryl, aralkyl, alkaryl, aralkenyl, heteroaralkyl, alkylheteroaryl, heteroaralkenyl, hydroxy, hydroxyalkyl, alkoxy, aryloxy, aralkoxy, acyl, aroyl, halo, nitro, cyano, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, alkylsulfonyl, arylsulfonyl, heteroarylsulfonyl, alkylsulfinyl, arylsulfinyl, heteroarylsulfinyl, alkylthio, arylthio, heteroarylthio, aralkylthio, heteroarylalkylthio, cycloalkyl, cycloalkenyl, heterocyclyl, heterocyclalkenyl, Y1Y2N-, Y1Y2N-alkyl-, Y1Y2NC(O)- and Y1Y2NSO2-, wherein Y1 and Y2 may be the same or different and are independently selected from hydrogen, alkyl, aryl and aralkyl.

[0042] In the present disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond, which can be straight or branched, containing about 2 to about 15 carbon atoms in the chain, preferably the alkynyl contains about 2 to about 12 carbon atoms in the chain, and more preferably contains about 2 to about 4 carbon atoms in the chain. Branched refers to one or more lower alkyl groups, such as methyl, ethyl or propyl, attached to a linear alkynyl chain. "Lower alkynyl" refers to containing about 2 to about 6 carbon atoms in the chain, which can be straight or branched. Non-limiting examples of suitable alkynyls include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl and decynyl. The term "substituted alkynyl" refers to an alkynyl group that can be substituted by one or more substituents, which can be the same or different, each of which is independently selected from alkyl, aryl and cycloalkyl.

[0043] In the present disclosure, the term "alkoxy" refers to an alkyl-O-group, wherein the alkyl group is as described above, and non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and heptoxy, and the bond to the parent is an ether oxygen. "Aryloxy" refers to an aryl-O-group, wherein the aryl group is as described above, and non-limiting examples of suitable aryloxy groups include phenoxy and naphthoxy. The bond to the parent is an ether oxygen.

[0044] In the present disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system containing about 3 to about 10 carbon atoms, preferably about 5 to about 10 carbon atoms, with preferred cycloalkyl rings containing about 5 to about 7 ring atoms. The cycloalkyl may optionally be substituted with one or more "ring system substituents", which may be the same or different and are as defined above. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Non-limiting examples of suitable polycyclic cycloalkyls include 1-decalinyl, norbornyl, adamantyl, etc.

[0045] In the present disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system containing about 6 to about 14 carbon atoms, preferably about 6 to about 10 carbon atoms. The aryl group may be optionally substituted with one or more "ring system substituents", which may be the same or different, and are as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0046] In the present disclosure, the term "heterocyclyl" refers to a non-aromatic saturated monocyclic or polycyclic ring system containing about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, wherein one or more of the ring atoms in the ring system is an element other than carbon, such as nitrogen, oxygen or sulfur, either alone or in combination. There are no adjacent oxygen and / or sulfur atoms in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxa or thia before the heterocyclyl root name indicates that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The heterocyclyl group may be optionally substituted by one or more "ring system substituents", which may be the same or different, as defined herein. The nitrogen or sulfur atom of the heterocyclyl group may be optionally oxidized to the corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings include piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, and the like.

[0047] In the present disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system containing about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, wherein one or more of the ring atoms is an element other than carbon, such as nitrogen, oxygen or sulfur, either alone or in combination, with preferred heteroaryls containing about 5 to about 6 ring atoms. The "heteroaryl" may be optionally substituted with one or more "ring system substituents", which may be the same or different, and are as defined herein. The prefix aza, oxa or thia before the heteroaryl root name means that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The nitrogen atom of the heteroaryl may be optionally oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl groups include pyridinyl, pyrazinyl, furanyl, thiophenyl, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-naphthyridinyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothiophenyl, quinolinyl, imidazolyl, thienopyridinyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridinyl, imidazopyridinyl, isoquinolinyl, benzazaindolyl, 1,2,4-triazinyl, benzothiazolyl, and the like.

[0048] In the present disclosure, the lithium battery involved in the present disclosure includes a negative electrode, the negative electrode includes a negative electrode plate, the negative electrode plate includes a current collector and a negative electrode active material layer disposed on the current collector. The specific types of negative electrode active materials are not subject to specific restrictions and can be selected according to needs. Specifically, the negative electrode active material is selected from natural graphite, artificial graphite, mesophase microcarbon beads (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composites, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO2, spinel structured lithiated TiO2-Li4Ti5O 12 , Li-Al alloy. Non-limiting examples of carbon materials include crystalline carbon, amorphous carbon and mixtures thereof. Crystalline carbon can be amorphous or flake-shaped, platelet-shaped, spherical or fibrous natural graphite or artificial graphite. Amorphous carbon can be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, etc.

[0049] In some embodiments of the present disclosure, the negative electrode active material layer may include a binder and optionally a conductive material. The binder improves the bonding between the negative electrode active material particles and the bonding between the negative electrode active material and the current collector.

[0050] In some embodiments of the present disclosure, non-limiting examples of binders include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.

[0051] In some embodiments of the present disclosure, the negative electrode active material layer includes a conductive material so that the electrode has conductivity. The conductive material may include any conductive material as long as it does not cause chemical changes. Non-limiting examples of conductive materials include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., such as copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives) and mixtures thereof.

[0052] In some embodiments of the present disclosure, the negative electrode active material of the present disclosure may also be selected from other materials that can electrochemically absorb and release metal ions such as lithium ions. Specifically, it can be selected from carbonaceous materials, silicon materials, alloy materials, lithium-containing metal oxide materials, etc. They can be used alone or in any combination of two or more.

[0053] In some embodiments of the present disclosure, the negative electrode current collector may be selected from copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.

[0054] In the present disclosure, the lithium battery involved in the present disclosure includes a positive electrode, and the positive electrode includes a positive electrode collector and a positive electrode active material disposed on the positive electrode collector.

[0055] In some embodiments of the present disclosure, the positive electrode current collector may be selected from one of stainless steel, nickel, aluminum, titanium, carbon, a conductive resin, an aluminum sheet coated with nickel or titanium, and a stainless steel sheet coated with nickel or titanium.

[0056] In some preferred embodiments of the present disclosure, the positive electrode current collector may be made of metal foil or porous metal plate, for example, foil or porous plate of metal such as aluminum, copper, nickel, titanium or silver or alloys thereof, such as aluminum foil.

[0057] In some embodiments of the present disclosure, the positive electrode active material is a lithium nickel cobalt manganese oxide material, which may have the following chemical formula: LiNi a Co b Mn c M 1 d O2, where a+b+c+d=1, 0.80≤a≤1, 0≤b≤0.20, 0≤c≤0.20, 0≤d≤0.10, M 1 At least one selected from the group consisting of not present, Al, B, Sr, Y, Ba, W, Ca, Cu, Fe, V, Cr, Ti, Zr, Zn, In, La, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg and Mo. Preferably, it may have the following chemical formula: LiNi x Co y Mn (1-x-y) O2; specifically, it can be NCM111 (the molar ratio of nickel, cobalt and manganese is 1:1:1), NCM523 (the molar ratio of nickel, cobalt and manganese is approximately 5:2:3), NCM622 (the molar ratio of nickel, cobalt and manganese is approximately 6:2:2), NCM811 (the molar ratio of nickel, cobalt and manganese is approximately 8:1:1).

[0058] In some embodiments of the present disclosure, the positive electrode further includes a conductive agent, non-limiting examples of which include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives), and mixtures thereof.

[0059] In some embodiments of the present disclosure, the positive electrode further comprises a binder. Non-limiting examples of the binder include polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc.

[0060] In some embodiments of the present disclosure, a separator is provided between the positive electrode and the negative electrode of the lithium battery of the present disclosure to prevent short circuit. The material and shape of the separator used in the lithium battery of the present disclosure are not particularly limited, and it can be any technology disclosed in the prior art.

[0061] In some embodiments of the present disclosure, the separator includes a polymer or an inorganic substance formed of a material that is stable to the electrolyte of the present disclosure.

[0062] In some embodiments of the present disclosure, the separator may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate and polyimide.

[0063] Specifically, a polypropylene porous film, a polyethylene porous film, a polypropylene non-woven fabric, a polyethylene non-woven fabric or a polypropylene-polyethylene-polypropylene porous composite film may be used.

[0064] A surface treatment layer is disposed on at least one surface of the substrate layer. The surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic layer.

[0065] The inorganic layer comprises inorganic particles and a binder, wherein the inorganic particles are selected from one or a combination of aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium dioxide, tin oxide, cerium dioxide, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate. The binder is selected from one or a combination of polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinyl pyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.

[0066] The polymer layer contains polymers, and the material of the polymer is selected from at least one of polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylic acid salt, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride, and poly(vinylidene fluoride-hexafluoropropylene).

[0067] In the present disclosure, the lithium ion battery involved in the present disclosure further comprises an electrolyte. In some embodiments, the electrolyte comprises a lithium salt and a solvent.

[0068] In some embodiments of the present disclosure, the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt. In some embodiments, the lithium salt includes, but is not limited to: lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium difluorophosphate (LiPO2F2), lithium trifluoromethanesulfonyl imide LiN(CF3SO2)2 (LiTFSI), lithium bis(fluorosulfonyl)imide Li(N(SO2F)2) (LiFSI), lithium bis(oxalate borate) LiB(C2O4)2 (LiBOB) or lithium difluorooxalate borate LiBF2(C2O4) (LiDFOB). In some embodiments, the concentration of the lithium salt in the electrolyte is: about 0.5 mol / L to 3 mol / L, about 0.5 mol / L to 2 mol / L, or about 0.8 mol / L to 1.5 mol / L.

[0069] In some embodiments of the present disclosure, the solvent may be selected from one or more of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS) and diethyl sulfone (ESE).

[0070] In some embodiments of the present disclosure, the electrolyte may optionally include additives. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high temperature performance, additives that improve battery low temperature performance, etc.

[0071] The present application is further described below in conjunction with the examples. It should be understood that these examples are only used to illustrate the present application and are not used to limit the scope of the present application.

[0072] Examples and Comparative Examples

[0073] Example 1

[0074] Embodiment 1 includes the following:

[0075] (1) The recycled waste ternary lithium battery positive electrode material (NCM111) was immersed in a 5% sodium chloride solution for 24 hours, the fully discharged waste ternary lithium battery was taken out and washed once with distilled water, and then dried under 40°C with air blowing;

[0076] (2) Mechanically crushing the dried waste ternary lithium battery positive electrode material under the condition of spraying liquid nitrogen to obtain ternary lithium battery crushed material, transferring the ternary lithium battery positive electrode material crushed material to a vacuum rake drying equipment while it is still cold, drying it at 0 MPa and 160° C. for 15 min, and then condensing the volatile gas to recover the electrolyte after removing the volatile gas;

[0077] (3) The dried ternary lithium battery positive electrode material fragments were placed in an electric furnace, nitrogen protection was introduced, the gas flow rate was 100 mL / min, the temperature was increased to 300°C at a heating rate of 5°C / min and maintained for 60 min, and then the temperature was increased to 600°C at a heating rate of 10°C / min and maintained for 60 min, and then naturally cooled to room temperature. The obtained material was separated by cyclone and the positive electrode current collector fragments were recovered from the top;

[0078] (4) preparing a first acidic solution, wherein the first acidic solution includes succinic acid (10 g / L) and malic acid (10 g / L); soaking the high-temperature treated cathode material fragments in the first acidic solution for 5 hours to obtain a mixed solution;

[0079] (5) Preparing a lithium battery recovery solution, wherein in Example 1, kerosene is used as a solvent for the recovery solution, and the solution comprises compound 1 and PC-88A (2-ethylhexyl phosphate mono-2-ethylhexyl ester), and the chemical formula of compound 1 is as follows:

[0080] ;

[0081] Among them, the volume percentage of PC-88A is 5%, and the volume percentage of compound 1 is 5%;

[0082] (6) extracting the mixed solution prepared in (4) using the mixed solution prepared in (5) to obtain a loaded organic phase and a raffinate aqueous phase through three-stage countercurrent extraction;

[0083] (7) After the extraction is completed, the layers are allowed to stand for 5-7 minutes, and then the aqueous phase is discharged through the aqueous phase port, and the organic phase enters the washing section, where a multi-stage washing reaction is performed on the organic phase;

[0084] (8) Taking the organic phase after the multi-stage washing reaction, performing a stripping operation on the organic phase, discharging the aqueous phase, and mixing the aqueous phases after extraction, washing and stripping to separate a solution containing manganese ions and cobalt ions.

[0085] Example 2

[0086] The steps of Example 2 are the same as those of Example 1, except that Example 2 uses Compound 3 instead of Compound 1; wherein the chemical formula of Compound 3 is as follows:

[0087] ;

[0088] Example 3

[0089] The steps of Example 3 are the same as those of Example 1, except that Example 3 uses Compound 4 instead of Compound 1; wherein the chemical formula of Compound 4 is as follows:

[0090] ;

[0091] Example 4

[0092] The steps of Example 4 are the same as those of Example 1, except that Example 4 uses Compound 9 instead of Compound 1; wherein the chemical formula of Compound 9 is as follows:

[0093] ;

[0094] Example 5

[0095] The steps of Example 5 are the same as those of Example 1, except that Example 5 uses Compound 10 instead of Compound 1; wherein the chemical formula of Compound 10 is as follows:

[0096] ;

[0097] Example 6

[0098] The steps of Example 6 are the same as those of Example 1, except that Example 6 uses Compound 12 instead of Compound 1; wherein the chemical formula of Compound 12 is as follows:

[0099] ;

[0100] Comparative Example 1:

[0101] The steps of Comparative Example 1 are the same as those of Example 1, except that Compound 1 is not used in Comparative Example 1.

[0102] Comparative Example 2:

[0103] The steps of Comparative Example 2 are the same as those of Example 1, except that Cyanex 301 is used instead of Compound 1 in Comparative Example 2.

[0104] The chemical contents of manganese and cobalt in the solutions containing manganese ions and cobalt ions obtained in this embodiment and the comparative example were analyzed, and the calculation results are shown in Table 1:

[0105]

[0106] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. The present disclosure is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art that are not disclosed in the present disclosure. The description and examples are to be considered exemplary only, and the true scope and spirit of the present disclosure are indicated by the following claims.

[0107] It should be understood that various modifications and changes can be made to the present disclosure without departing from its scope. The scope of the present disclosure is limited only by the appended claims.

Claims

1. A lithium battery recovery solution, characterized in that: The lithium battery recovery solution comprises a nitrogen-containing heterocyclic compound and an organic solvent; wherein the nitrogen-containing heterocyclic compound has a structure as shown in Formula I: ； wherein A1 and A2 are selected from C and N, and at least one of A1 and A2 is N; A3 and A4 are selected from C and N, and at least one of A3 and A4 is N; R1 and R2 are each independently selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, a carboxyl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heterocyclyl group, a substituted or unsubstituted 5-30 membered heteroaryl group, or a substituted or unsubstituted 3-30 membered ring formed by bonding with an adjacent substituent.

2. The lithium battery recovery solution according to claim 1, characterized in that: Based on the total volume of the lithium battery recovery solution, the volume percentage of the nitrogen-containing heterocyclic compound is selected from 3%-10%.

3. The lithium battery recovery solution according to claim 1, characterized in that: Based on the total volume of the lithium battery recovery solution, the volume percentage of the nitrogen-containing heterocyclic compound is selected from 4%-5%.

4. The lithium battery recovery solution according to claim 1, characterized in that: The nitrogen-containing heterocyclic compound has a structure as shown in Formula I-1 to Formula I-6: ； Wherein, R1 and R2 are defined as in claim 1.

5. The lithium battery recovery solution according to claim 1, characterized in that: The nitrogen-containing heterocyclic compound is selected from at least one of the following compounds: ； 。 6. The lithium battery recovery solution according to claim 1, characterized in that: The organic solvent is selected from kerosene, sulfonated kerosene or aliphatic hydrocarbon solvent oil.

7. The lithium battery recovery solution according to claim 6, characterized in that: The organic solvent also includes an organic phosphate solvent.

8. A method for recycling the positive electrode material of waste ternary batteries, characterized in that: The recovery method comprises the following steps: Step 1: disassembling the lithium battery to obtain a positive electrode sheet; subjecting the positive electrode sheet to a high temperature treatment under a first inert gas atmosphere to obtain a positive electrode current collector and a positive electrode coating by separation, and crushing the positive electrode coating; Step 2: placing the obtained crushed positive electrode coating in a first acidic solution to obtain a mixed solution; Step 3: extracting the mixed solution obtained in step 2 using the lithium battery recovery solution described in any one of claims 1 to 7 to obtain a loaded organic phase and a raffinate aqueous phase; Step 4: stripping the loaded organic phase with water to obtain manganese and cobalt respectively.

9. The recycling method according to claim 8, characterized in that: The first acidic solution is selected from at least one of malic acid, tartaric acid, succinic acid, bitter acid, citric acid and maleic acid.

10. The recycling method according to claim 8 or 9, characterized in that: The recovery method satisfies at least one of the following conditions: The first acidic solution is selected from a mixture of tartaric acid and succinic acid; The volume ratio of the loaded organic phase to water is (1-50):1; Before stripping, the method further includes a step of washing the loaded organic phase; Before extraction, the method also includes a step of using extractant P204 and / or M5640 to perform step-by-step impurity removal, wherein P204 removes trace zinc, calcium and magnesium impurities in the mixed solution, and M5640 removes trace copper impurities in the mixed solution.

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