CN113314777B - Recovery method of solid-state battery material - Google Patents
Recovery method of solid-state battery material Download PDFInfo
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- CN113314777B CN113314777B CN202110588774.0A CN202110588774A CN113314777B CN 113314777 B CN113314777 B CN 113314777B CN 202110588774 A CN202110588774 A CN 202110588774A CN 113314777 B CN113314777 B CN 113314777B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention provides a method for recovering a solid battery material, in particular to a method for recovering metal elements in an oxide solid electrolyte and an electrode material step by step, which comprises the following steps: and putting the waste solid battery material into a first leaching solution, recovering metal elements in the oxide solid electrolyte material according to different solubilities, putting the material selected from the filter residue into a second leaching solution, recovering the metal elements in the anode material, and finally realizing the selective recovery of the solid battery material. The method uses the cheap green solvent to react with lithium and transition metal in the solid battery material, so that the oxide solid electrolyte and the anode material are dissolved in the leaching solution step by step, and the battery material is separated and recovered by utilizing the difference of solubility.
Description
Technical Field
The invention relates to the field of solid-state battery recovery, in particular to a metal recovery processing method of waste solid-state battery materials.
Background
The nonrenewability of chemical energy sources and the pollution to the environment make high-efficiency and clean electrochemical energy storage devices increasingly favored. Lithium ion batteries have the advantages of high energy density, long service life, low self-discharge, and the like, and have been widely used in wearable electronic devices. However, with the development of electric vehicles and other electronic devices, the demand for lithium secondary batteries is increasing. The conventional lithium ion battery mainly adopts liquid electrolyte, contains a large amount of combustible organic solvent, has serious potential safety hazard, has a narrow electrochemical window, and is difficult to adapt to a battery system with high energy density. Therefore, the development of solid-state batteries is a key to the next generation of lithium batteries. At present, solid electrolytes mainly include polymer solid electrolytes, inorganic solid electrolytes, and composite solid electrolytes. Among the inorganic solid electrolytes, the oxide solid electrolyte has the advantages of high ionic conductivity, wide electrochemical window, high mechanical strength, easy manufacture and the like, and has wide application prospect.
Solid-state batteries have better safety than liquid-state batteries, but still have many problems resulting in the failure of the batteries. Generally, the failure behaviors of the lithium battery include cycle capacity loss, internal resistance increase, overcharge, gas generation, internal short circuit, thermal runaway, calendar failure and the like, and the cycle capacity failure, safety failure and calendar failure are common problems in the solid-state battery, and the main reasons include dendritic growth of a lithium metal negative electrode, positive electrode structure evolution and mechanical failure, interface microstructure evolution and interface reaction and the like. In addition, the solid electrolyte contains rare elements such as lanthanum (La) and the like, has rare earth reserves, is high in price and has high recovery value. Therefore, under the background that the development of the solid-state battery is widely concerned, the recovery processing of the oxide solid electrolyte is of great significance for reducing the cost of the battery and saving resources.
CN110661051A discloses a method for recovering sulfide electrolyte and electrode material. Compared with sulfide electrolytes, the oxide electrolytes have good chemical stability, easy manufacture and wide application prospect. At present, the recovery of the oxide solid electrolyte is rarely reported, and the method reported by the invention is helpful for promoting the development of the solid-state battery industry.
Disclosure of Invention
In view of the wide application prospect of the solid-state battery, the invention aims to provide a method for recovering a solid-state battery material. Specifically, the solid-state battery material recovery in the invention includes recovery of metal elements in the positive electrode material and the oxide solid electrolyte.
A method for recovering solid-state battery materials comprises the steps of putting waste solid-state battery materials into a first leaching solution, recovering metal elements in oxide solid electrolyte materials according to different solubilities, putting materials selected from filter residues into a second leaching solution, recovering the metal elements in anode materials, and finally achieving selective recovery of the solid-state battery materials. The first leach solution is an acid and alcohol eutectic solvent and the second leach solution is an acidic eutectic solvent including an acidic hydrogen bond donor and a hydrogen bond acceptor.
The eutectic solvent (Deep eutectic solvent) is a two-component or three-component eutectic mixture formed by combining a hydrogen bond acceptor and a hydrogen bond donor in a certain stoichiometric ratio, the freezing point of the eutectic solvent is obviously lower than the melting point of pure substances of each component, and the eutectic solvent is a green solvent with low price and good performance.
Concretely, the recycling method of the solid-state battery material comprises the following steps:
1) Discharging waste solid batteries, disassembling and crushing;
2) Preparing a first leaching solution, putting a battery material into the first leaching solution for reaction to obtain a first filtrate and a first filter residue, and recovering one or more metal elements in an oxide solid electrolyte from the first filtrate and the first filter residue;
3) Preparing a second leaching solution, and putting the positive electrode material sorted from the filter residue into the second leaching solution for reaction to obtain a filtrate II and a filter residue II;
4) And recovering one or more metal elements in the cathode material from the filtrate II and the filter residue II.
In the invention, the first leaching solution in the step 2) is a eutectic solvent based on acid and alcohol, the acid is organic acid and is selected from one or more of benzoic acid, acetic acid, adipic acid, malonic acid, oxalic acid, maleic acid, fumaric acid, succinic acid, citric acid, p-toluenesulfonic acid, p-hydroxybenzoic acid, succinic acid, levulinic acid and caffeic acid.
The alcohol is selected from one or more of ethanol, ethylene glycol, glycerol, butanediol, xylitol, sorbitol, isosorbide, glucose and fructose.
Because eutectic is that monomers interact through hydrogen bonds, physical properties and monomer differences are large, in the first leaching solution, while the hydrogen bonding effect is fully considered, factors such as induction effect, dissolving performance, viscosity, electrostatic effect, space exclusion and the like of functional groups are comprehensively considered, and acid in the first leaching solution is preferably dicarboxylic acid or aromatic carboxylic acid, and is specifically selected from one or more of benzoic acid, adipic acid, malonic acid, oxalic acid, maleic acid, fumaric acid, succinic acid, p-toluenesulfonic acid, p-hydroxybenzoic acid and succinic acid, and is more preferably benzoic acid, maleic acid and malonic acid.
The alcohol in the first leaching solution is preferably a polyhydric alcohol having two or more hydroxyl groups, such as ethylene glycol, glycerol, butylene glycol.
In the invention, a proper eutectic solvent leaching solution is prepared, and the metal is effectively recovered through the mutual dissociation of hydrogen bonds and the like between the eutectic solvent leaching solution and the oxide solid electrolyte.
In the invention, the molar ratio of the alcohol to the organic acid in the first leaching solution in the step 2) is 1-6:1, preferably 2 to 4:1, the preparation temperature is 30-100 ℃, and the viscosity of the first leaching solution is 10-5000 cp, preferably 400-1000cp.
In the invention, the waste battery in the step 1) is crushed, and the particle size of the battery material is less than or equal to 10mm.
In the invention, the anode material of the waste battery in the step 1) comprises a layered anode material, a spinel type anode material, an olivine type anode material and a corresponding doped and modified anode material, and specifically includes but is not limited to LiCoO 2 、LiFePO 4 、LiMn 2 O 4 、LiNi x Co y Mn z O 2 (x+y+z＝1)、LiNi x Co y AlzO 2 (x+y+z＝1)、LiNiO 2 、LiVO 2 、LiCrO 2 、LiCoMnO 4 、Li 2 NiMn 3 O 8 、LiNi 0.5 Mn 1.5 O 4 And the like.
In the invention, the negative electrode material of the waste battery in the step 1) includes, but is not limited to, one or more of metallic lithium, carbon-based materials, silicon-based materials, tin-based materials, lithium titanate and the like.
In the invention, the oxide solid electrolyte of the waste battery in the step 1) comprises Perovskite type (Perovskite), sodium fast ion conductor (NASICON), lithium fast ion conductor (LISICON), garnet type (Garnet) and amorphous solid electrolyte, and the like, and specifically includes but is not limited to Li 3 xLa 2/3-x TiO 3 、Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP)、Li 1+x Al x Ge 2-x (PO 4 ) 3 (LAGP)、LiI 4 Zn(GeO 4 ) 4 、Li 5 La 3 M 2 O 12 (M＝Ta、Nb)、Li 7 La 3 Zr 2 O 12 One or more of LiPON (lithium phosphorus oxygen nitrogen), and the likeAnd (4) combining. In addition, for the above-mentioned oxide solid electrolyte, doping of one or more of the following elements is included, but not limited to: mg, al, ca, ti, ga, nb, hf, ta, etc., in a doping ratio of 0.1<x<1. Garnet type (Garnet) and Perovskite type (Perovskite) are preferred, such as in the embodiment of the present invention, the oxide solid electrolyte is Li 7 La3Zr 2 O 12 、Li 6.28 Al 0.24 La 3 Zr 2 O 12 、Li 0.33 La 0.56 TiO 3 。
In the invention, the reaction temperature of the battery material in the first leaching solution in the step 2) is 20-100 ℃, the reaction time is 2-10 h, the stirring speed is 200-500rpm, and the mass ratio of the solid electrolyte in the battery to the first leaching solution is 1:5 to 20, preferably 1:10-20.
In the invention, the second leaching solution in the step 3) is an acidic eutectic solvent and comprises an acidic hydrogen bond donor and a hydrogen bond acceptor.
The hydrogen bond donor (hydrogen bond donor) is a compound containing a proton (hydrogen atom) to be supplied, and the hydrogen bond acceptor (hydrogen bond acceptor) is a compound containing a lone pair of electrons involved in the formation of a hydrogen bond.
The acidic hydrogen bond donor is organic acid, and is selected from one or more of benzoic acid, acetic acid, adipic acid, malonic acid, oxalic acid, maleic acid, fumaric acid, succinic acid, citric acid, phenylacetic acid, p-toluenesulfonic acid, p-hydroxybenzoic acid, succinic acid, levulinic acid and caffeic acid, and oxalic acid and malonic acid are preferred.
The hydrogen bond acceptor is selected from one or more of choline chloride, choline bromide, choline fluoride, ethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, methyltriphenylphosphine bromide, N, N-diethyl-2-hydroxyethane-1-ammonium chloride, and preferably choline chloride, choline bromide or choline fluoride of a quaternary ammonium salt type.
In the invention, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor in the second leaching solution in the step 3) is 1-6:1, preferably 1 to 4:1, the preparation temperature is 60-150 ℃, and the viscosity of the second leaching solution is 10-5000 cp, preferably 200-1000cp.
In the invention, the sorting method in the step 3) comprises the following steps: sorting is carried out by utilizing the difference of physicochemical properties of components in the battery material, such as material density, ferromagnetism of metal, particle size of materials, difference of physical properties of material surfaces and the like.
In the invention, the reaction temperature of the cathode material in the second leaching solution in the step 3) is 80-200 ℃, preferably 100-150 ℃, the reaction time is 6-24 h, preferably 6-12h, and the stirring speed is 200-500rpm, wherein the mass ratio of active components in the cathode material to the second leaching solution is 1:5 to 30, preferably 1:5-20.
Monomers of the eutectic solvent interact with each other through hydrogen bonds, and the physical properties and the monomers are greatly different. The higher the temperature, the better the leaching effect, and the reflux can be condensed. In the present invention, the reaction temperature in at least one embodiment is 120 ℃.
In the invention, step 2) recovers one or more metal elements in the oxide solid electrolyte material from the first filtrate, and step 4) recovers one or more metal elements in the cathode material from the second filtrate, wherein the steps include adding a precipitator into the first filtrate or the second filtrate after dilution for precipitation and purification. The precipitant comprises saturated carbonate, oxalate or lithium hydroxide; the purification comprises recrystallization and high-temperature calcination.
In the invention, step 2) recovers one or more metal elements in the oxide solid electrolyte material from the first filter residue, and step 4) recovers one or more metal elements in the cathode material from the second filter residue, including the purification process of the product. The purification process comprises recrystallization and high-temperature calcination.
The metals recovered by the leaching solution of the present invention include metal compounds such as simple metals, metal oxides or metal salts, and the recovery efficiency of the metal elements is calculated.
By adopting the recovery method provided by the invention, the first leaching solution and the second leaching solution are prepared, the recovery rate of metal elements in the electrode material in the waste battery is more than or equal to 97.6%, and the recovery rate of metal elements in the oxide solid electrolyte is more than or equal to 97%.
The invention has the advantages that:
1. the method adopts the eutectic solvent to leach the metal elements, has higher leaching rate of the metal elements, shortens the process flow, is easy to realize industrialization, and the prepared material has excellent electrochemical performance.
2. The method for recovering the solid-state battery material provided by the invention selectively separates the oxide solid electrolyte by utilizing the different solubility of the novel solvent to the metal in the oxide solid electrolyte, the used solvent is prepared from common chemical reagents, the cost is low, the raw materials are easy to obtain, the separation method and the reaction conditions are mild, the purity of the metal compound obtained by selective separation is high, and the metal compound can be further processed and used as the battery material.
3. According to the invention, by utilizing the matching of the first leaching solution and the second leaching solution, the metal in the oxide solid electrolyte and the metal in the battery anode material can be effectively separated and recovered by a one-step method, the metal recovery rate is more than 97%, the recycling of valuable metal materials is realized, the battery recovery and recycling closed-loop industrial chain is further realized, and the residual value of the waste battery is fully exerted.
4. The method can be used for treating various anode materials of waste lithium ion batteries such as lithium cobaltate, lithium chromate, lithium manganate, nickel cobalt lithium manganate or metal-doped lithium ion batteries, has strong applicability, green and environment-friendly leaching solvent, good operating environment and reduced equipment cost.
5. The method effectively recovers the metal elements in the oxide solid electrolyte for the first time, expands the recovery field of the lithium ion battery solid electrolyte, has wider solid electrolyte range and realizes the recovery and reutilization of resources.
6. The method uses the cheap green solvent to react with lithium and transition metal in the solid battery material, so that the oxide solid electrolyte and the anode material are dissolved in the leaching solution step by step, and the metal elements in the oxide solid electrolyte and the electrode material are recovered step by utilizing the difference of solubility, thereby realizing the separation and recovery of the battery material.
Drawings
FIG. 1 is a flow chart of a method for recycling solid-state battery materials according to the present invention.
Fig. 2 is a structural view of a battery according to example 17 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The present invention will be further described with reference to specific examples, but the present invention is not limited to the specific examples. All proportions in the examples of the present invention are mass ratios unless otherwise specified.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The recovery efficiency is calculated by the following method in the following embodiment
m L Is the total mass of the diluted solution, x is the mass fraction of the metal element in the test sample, m S To test the mass of the sample, m R For the total mass of the sample recovered after leaching, m P Is the mass of the metal element in the selected battery material. Where x the metal content in the filtrates obtained under different conditions was quantitatively tested using a PerkinElmer Optima 8300ICP-OES system. The samples were diluted with 2% aqueous nitric acid and calibration curves were generated using at least 5 ICP standard solutions, resulting only from correlation coefficients greater than 0.999. Unless otherwise stated, the flow rate range of the gas atomizer was set to 0.45 to 0.75L min -1 And each element uses 2 wavelengths in the axial mode: cobalt (228.616 and 230.786 nm), lithium (670.784 nm (radial mode) and 610.362 nickel (231.604 and 341.476 nm) and manganese (257.610 and 259.372 nm).
Example 1
The positive electrode of the solid-state battery is lithium cobaltate (LiCoO) 2 ) The negative electrode is graphite, and the oxide solid electrolyte is lithium lanthanum zirconium oxygen (Li) 7 La 3 Zr 2 O 12 ). Wherein LiCoO is an active material on the positive electrode side 2 And the mass ratio of the oxide electrolyte is 9.5:0.5 (total mass of positive electrode 10 g), oxide solid electrolyte layer was Li 7 La 3 Zr 2 O 12 Ceramic chip (total solid electrolyte mass 0.8 g), the mass ratio of negative electrode side graphite to oxide solid electrolyte was 4.3:0.5 (negative electrode Total Mass: 4.8 g).
(1) And crushing the solid-state battery with complete discharge in a drying room by using a hydraulic press, and further performing ball milling until the particle size of solid particles is less than 5 mm.
(2) A first leaching solution is prepared, 12.4g of glycol (0.2 mol) and 5.8g of maleic acid (0.05 mol) are added into a flask, heated to 60 ℃, and stirred until the solution is colorless and transparent to serve as the first leaching solution.
(3) 15.6g of crushed battery materials are added into the prepared first leaching solution, stirring and reacting are carried out for 6 hours at the temperature of 60 ℃, lithium (Li) and lanthanum (La) in the battery materials react with the solution, and the lithium (Li) and the lanthanum (La) are dissolved in the first leaching solution.
(4) Filtering under reduced pressure to obtain filtrate I and residue I, diluting the filtrate I with deionized water, adding oxalic acid to precipitate La 2 (C 2 O 4 ) 3 And then carbon dioxide is introduced to obtain Li 2 CO 3 . Separating unreacted ZrO in oxide solid electrolyte from filter residue I 2 。
(5) A second leaching solution was prepared by adding 61.2g (0.48 mol) of oxalic acid dihydrate and 33.8g (0.24 mol) of choline chloride to a flask, heating to 80 ℃ and stirring until the solution became colorless and transparent as the second leaching solution.
(6) And (4) separating the filter residue I to obtain a positive electrode material, adding the positive electrode material into the prepared second leaching solution, and stirring and reacting at 120 ℃ for 12 hours to completely dissolve the positive electrode material lithium cobaltate into the solution.
(7) Vacuum filtering to obtain filtrate II, diluting filtrate II with deionized water, and filteringAdding oxalic acid to obtain CoC 2 O 4 。
(8) Calcination of the resulting CoC at 500 deg.C 2 O 4 The oxide thereof is precipitated to obtain high-purity Co 3 O 4 Calcining La at 700 deg.C 2 (C 2 O 4 ) 3 Obtaining high-purity La 2 O 3 To Li 2 CO 3 And (4) recrystallizing.
(9) The recovery rate of the metal element in the oxide solid electrolyte and the recovery rate of the metal element in the positive electrode material were measured.
Example 2
Fig. 1 shows a method for recycling a solid-state battery.
The positive electrode of the solid-state battery is nickel cobalt lithium manganate (LiNi) 0.6 Co 0.2 Mn 0.2 O 2 ) The negative electrode is graphite, and the oxide solid electrolyte is lithium lanthanum zirconium oxide (Li) 7 La 3 Zr 2 O 12 ). Wherein the positive electrode side active material LiNi 0.6 Co 0.2 Mn 0.2 O 2 And the mass ratio of the oxide solid electrolyte is 9.5:0.5 (total mass of positive electrode 10 g), oxide solid electrolyte layer was Li 7 La 3 Zr 2 O 12 Ceramic sheet (total solid electrolyte mass 0.8 g), mass ratio of negative electrode side graphite to oxide solid electrolyte was 4.6:0.5 (negative electrode Total Mass 5.1 g).
(1) And crushing the solid-state battery with complete discharge in a drying room by a hydraulic press, and further performing ball milling until the particle size of solid particles is less than 5 mm.
(2) Preparing a first leaching solution, adding 12.4g of ethylene glycol and 5.8g of maleic acid into a flask, heating to 60 ℃, and stirring until the solution is colorless and transparent to serve as the first leaching solution.
(3) 15.9g of crushed battery materials are added into the prepared first leaching solution, stirring and reacting are carried out for 6 hours at the temperature of 60 ℃, lithium (Li) and lanthanum (La) in the battery materials react with the solution, and the lithium (Li) and the lanthanum (La) are dissolved in the first leaching solution.
(4) Filtering under reduced pressure to obtain filtrate I and residue I, diluting the filtrate I with deionized water, adding oxalic acid to precipitate La 2 (C 2 O 4 ) 3 And then carbon dioxide is introduced to obtain Li 2 CO 3 . Separating unreacted ZrO in oxide solid electrolyte from filter residue I 2 。
(5) A second leaching solution was prepared by adding 61.2g (0.48 mol) of oxalic acid dihydrate and 33.8g (0.24 mol) of choline chloride to a flask, heating to 80 ℃ and stirring until the solution became colorless and transparent as the second leaching solution.
(6) And (3) separating the filter residue I to obtain a positive electrode material, adding the positive electrode material into the prepared second leaching solution, and reacting under stirring at 120 ℃ for 12 hours, wherein the nickel cobalt lithium manganate serving as the positive electrode material is partially dissolved in the solution.
(7) Filtering under reduced pressure to obtain a second filtrate and a second filter residue, and diluting the second filtrate with deionized water to obtain CoC 2 O 4 And then adjusting ph to 10 to obtain Mn (OH) 2 And oxide precipitation thereof, washing the filter residue II by deionized water to obtain NiC 2 O 4 。
(8) The CoC obtained is calcined at 500 ℃ respectively 2 O 4 ，NiC 2 O 4 And Mn (OH) 2 And the precipitation of oxides thereof to obtain high-purity Co 3 O 4 NiO and MnO 2 Calcination of La at 700 deg.C 2 (C 2 O 4 ) 3 Obtaining high-purity La 2 O 3 To Li 2 CO 3 And (4) recrystallizing.
(9) The recovery rate of the metal element in the oxide solid electrolyte and the recovery rate of the metal element in the positive electrode material were measured.
Example 3
The same as example 1 except that the solid electrolyte was lithium lanthanum titanium oxide (Li) 0.33 La 0.56 TiO 3 )。
Example 4
The same as example 1 except that the solid electrolyte was Li-La-Zr-Ta-O (Li) 6.28 Al 0.24 La 3 Zr 2 O 12 )。
Example 5
The rest was the same as in example 1, except that 14g of glycerol (0.15 mol) and 4.4g (0.038 mol) of maleic acid were used to prepare the first leaching solution.
Example 6
The rest was the same as in example 1, except that 12.4g of ethylene glycol and 5.2g of malonic acid were used to prepare a first leaching solution.
Example 7
The same as in example 1 was repeated except that 6.2g (0.1 mol) of ethylene glycol and 12.2g (0.1 mol) of benzoic acid were used to prepare a first leaching solution.
Example 8
The same as in example 1 was followed, except that 9.25g (0.15 mol) of ethylene glycol and 8.9g (0.076 mol) of maleic acid were used to prepare the first leaching solution.
Example 9
The same as in example 1 was followed, except that 6.2g (0.1 mol) of ethylene glycol and 11.6g (0.1 mol) of maleic acid were used to prepare a first leaching solution.
Example 10
The rest was the same as in example 1, except that 13.8g (0.22 mol) of ethylene glycol and 4.3g of maleic acid (0.037 mol) were used to prepare the first leaching solution.
Example 11
The same as in example 1 was repeated except that a first leaching solution was prepared using 12.4g of ethylene glycol and 5.8g of maleic acid, a second leaching solution was prepared using 30.6g (0.24 mol) of oxalic acid dihydrate and 16.9g (0.12 mol) of choline chloride, and the charged crushed battery material was 7.8g (solid electrolyte mass 0.9g, positive electrode active component 4.75 g).
Example 12
The first leaching solution was prepared using 12.4g of ethylene glycol and 5.8g of maleic acid, except that a second leaching solution prepared using 122.4g of oxalic acid dihydrate and 67.6g of choline chloride was charged to the crushed battery material at 31.2g (mass of solid electrolyte 3.6g, positive electrode active component 19 g), which was the same as in example 1.
Example 13
The same as in example 2 except that 54.9g of oxalic acid dihydrate (0.44 mol) and 40.1g (0.22 mol) of choline bromide were used to prepare a second leaching solution.
Example 14
The procedure of example 2 was repeated except that 57.0g of malonic acid (0.55 mol) and 38.0g (0.27 mol) of choline chloride were used to prepare a second leaching solution.
Example 15
The rest is the same as example 2, except that the positive electrode material of the solid-state battery is LiNi 0.8 Co 0.1 Mn 0.1 O 2 。
Example 16
The rest is the same as example 2, except that the positive electrode material of the solid-state battery is LiNi 0.8 Co 0.15 Al 0.05 O 2 。
Example 17
The procedure was as in example 2 except that the negative electrode material for solid-state batteries was lithium metal.
Example 18
The procedure was as in example 2 except that 45g of oxalic acid dihydrate, 50g of choline chloride, oxalic acid: the mol ratio of choline chloride is 1:1.
example 19
The same as in example 2 except that 74g of oxalic acid dihydrate, 21g of choline chloride, oxalic acid: the mol ratio of choline chloride is 4:1.
example 20
The procedure was as in example 2 except that 80g of oxalic acid dihydrate, 15g of choline chloride, oxalic acid: the mol ratio of choline chloride is 6:1.
example 21
The same as in example 2 was followed except that a first leaching solution was prepared using 6.2g of ethylene glycol and 2.9g of maleic acid, a second leaching solution was prepared using 61.2g of oxalic acid dihydrate and 33.8g of choline chloride, and 8.0g of the crushed battery material was charged.
Example 22
The same as in example 2 except that a first leaching solution was prepared using 24.8g of ethylene glycol and 11.6g of maleic acid, a second leaching solution was prepared using 61.2g of oxalic acid dihydrate and 33.8g of choline chloride, and the charge of the crushed battery material was 31.8g.
The recovery efficiency of the examples contained in the present invention for the solid electrolyte and the metal recovery efficiency for the positive electrode material are shown in table 1.
Table 1 examples recovery of metals from solid electrolytes and positive electrode materials
m S : the mass of solid electrolyte (solid electrolyte); m is L1 : the mass of the first leach solution; m is L2 : the mass of the second leach solution; m is a unit of C : mass of positive electrode material (cathode) active component. In the examples, the recovery amount of some doping elements such as Al is relatively small, so that no calculation is made.
As can be seen from examples 1,3 and 4, the first leach solution has better metal recovery for different systems of oxide solid electrolytes.
From examples 1,7-10, it can be seen that the molar ratio of alcohol/acid in the first leach solution is 1-6:1, the metal recovery rate of the solid electrolyte is more than 97%, particularly the metal recovery rate of the solid electrolyte is calculated according to the molar ratio of 2-4: within the range of 1, the recovery rate of each metal of the solid electrolyte can reach more than 98 percent, and the recovery effect is better.
As can be seen from examples 1, 11 to 12, the mass ratio of the first leaching solution to the solid electrolyte was in the range of 1:5-20, preferably 1:10-20, and has higher solid electrolyte metal recovery efficiency.
As can be seen from examples 2, 18-20, the molar ratio of oxalic acid/choline chloride in the second leach solution is in the range of 1-6:1, the metal recovery efficiency in the anode material can reach more than 97.6%, and particularly, the molar ratio of the metal recovery efficiency to the anode material is 1-4: within 1 range, the metal recovery efficiency of the cathode material is high.
As can be seen from examples 2, 21-22, the mass ratio of the second leaching solution to the active component of the positive electrode material was in the range of 1:5-20, and has higher solid electrolyte metal recovery efficiency.
According to the method for recovering the solid-state battery material, the oxide solid electrolyte and the electrode material are respectively obtained from the liquid phase and the solid phase of the waste battery through the leachate according to different solubilities, and high-value metal in the anode material is leached step by step through the proper leachate. The method effectively separates and recovers the metal in the oxide solid electrolyte and the metal in the battery anode material at the same time by a simple one-step method, the metal recovery rate is more than 97 percent, the solid electrolyte recovery method is expanded, the recycling of valuable metal materials is realized, further the closed-loop industrial chain of battery recovery and recycling is realized, and the residual value of the waste battery is fully exerted.
It will be understood by those skilled in the art that the foregoing embodiments are provided merely for clarity of disclosure and are not intended to limit the scope of the invention. Other variations or modifications will be apparent to persons skilled in the art in light of the above disclosure and which are within the scope of the invention.
Claims (6)
1. A method for recycling a solid-state battery material, the method comprising the steps of:
1) Discharging waste solid batteries, disassembling and crushing;
2) Preparing a first leaching solution, putting a battery material into the first leaching solution for reaction to obtain a first filtrate and a first filter residue, and recovering one or more metal elements in the oxide solid electrolyte from the first filtrate and the first filter residue according to different solubilities; the first leach solution is a eutectic solvent of an organic acid and an alcohol; the molar ratio of alcohol to organic acid in the first leach solution is 2-4:1; the mass ratio of the solid electrolyte to the first leaching solution in the battery is 1:5 to 20; the organic acid is maleic acid, and the alcohol is one or more of ethylene glycol, glycerol and butanediol; the reaction temperature of the battery material in the first leaching solution is 30-100 ℃, and the viscosity of the first leaching solution is 10-5000cp;
3) Preparing a second leaching solution, and putting the positive electrode material sorted from the filter residue into the second leaching solution for reaction to obtain a filtrate II and a filter residue II; the second leach solution is an acidic eutectic solvent comprising an acidic hydrogen bond donor and a hydrogen bond acceptor; the molar ratio of the acidic hydrogen bond donor to the hydrogen bond acceptor is 1-6:1; the mass ratio of the active component in the positive electrode material to the second leaching solution is 1:5 to 30 percent; the acidic hydrogen bond donor is selected from one or more of benzoic acid, acetic acid, adipic acid, malonic acid, oxalic acid, maleic acid, fumaric acid, succinic acid, citric acid, phenylacetic acid, p-toluenesulfonic acid, p-hydroxybenzoic acid, succinic acid, levulinic acid and caffeic acid; the hydrogen bond acceptor is selected from one or more of choline chloride, choline bromide, choline fluoride, ethyl ammonium chloride, tetramethyl ammonium chloride, tetrabutyl ammonium chloride, methyl triphenyl phosphonium bromide and N, N-diethyl-2-hydroxy ethane-1-ammonium chloride;
4) Recovering one or more metal elements in the anode material from the filtrate II and the filter residue II;
step 2) recovering one or more metal elements in the oxide solid electrolyte material from the first filtrate, and step 4) recovering one or more metal elements in the positive electrode material from the second filtrate, wherein the recovery comprises the steps of adding a precipitator into the diluted first filtrate or the diluted second filtrate for precipitation and purification; the precipitant comprises saturated carbonate, oxalate or lithium hydroxide; the purification comprises recrystallization and high-temperature calcination;
the oxide solid electrolyte in the waste solid-state battery is selected from Li 5 La 3 M 2 O 12 Where M = Ta, nb, li 7 La 3 Zr 2 O 12 One or more of (a); the positive electrode material in the waste solid-state battery is selected from LiNi x Co y Mn z O 2 、LiNi x Co y Al z O 2 、LiCoMnO 4 、Li 2 NiMn 3 O 8 、LiNi 0.5 Mn 1.5 O 4 X + y + z =1.
2. A method as claimed in claim 1, wherein the first leach solution has a viscosity in the range of 400 to 1000cp.
3. The method of claim 1, wherein the cell material of step 2) is reacted in the first leaching solution for a period of time of 2h to 10h, at a stirring rate of 200 to 500rpm, and the mass ratio of the solid electrolyte to the first leaching solution in the cell is 1:10-20.
4. The method as claimed in claim 1, wherein the reaction temperature of the cathode material in the second leaching solution in the step 3) is 80-200 ℃ and the reaction time is 6-24 h, wherein the mass ratio of the active component in the cathode material to the second leaching solution is 1:5-20.
5. The method as claimed in claim 4, wherein the reaction temperature of the cathode material in the second leaching solution in the step 3) is 100-150 ℃ and the reaction time is 6-12 h.
6. The method according to claim 1, wherein the pulverization of the used solid-state batteries in the step 1) means that the particle size of the battery material is 10mm or less.
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