CN115472948A - Method for regenerating sodium-electricity positive electrode material by using waste lithium manganate - Google Patents
Method for regenerating sodium-electricity positive electrode material by using waste lithium manganate Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 39
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000003980 solgel method Methods 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 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 12
- 239000011734 sodium Chemical class 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 229910052708 sodium Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a method for separating lithium and regenerating a positive electrode material of a sodium-ion battery by using a waste lithium manganate battery positive electrode. Taking a waste lithium manganate positive electrode material as a raw material, sequentially carrying out carbothermic reduction of the positive electrode material, leaching sodium carbonate of a reduction product, acid leaching of leaching residue and sol-gel method preparation of a precursor, and finally calcining to obtain a sodium ion battery positive electrode material; the method makes full use of valuable metal components in the waste lithium manganate anode material, quantitatively separates lithium, and prepares the high-performance anode material by doping modification of the lithium on the sodium-ion battery anode material, thereby improving the value of recycling the regenerated product.
Description
Technical Field
The invention relates to the field of waste lithium battery recovery, in particular to a method for separating lithium from a waste lithium manganate positive electrode material and regenerating a P2 layered structure sodium ion battery positive electrode material.
Background
As lithium ion batteries produced in early stages are gradually scrapped, the number of waste lithium ion batteries is also increasing year by year. How to efficiently treat and recycle the electrode materials of the waste lithium ion batteries has become a worldwide research hotspot. The research on the recovery and regeneration direction of the lithium manganate as the positive electrode material mostly focuses on the separation and purification of lithium manganese metal. Most of the traditional methods for recovering the lithium manganate battery positive electrode material are wet leaching methods, namely, waste lithium manganate is placed in an acid reduction system for leaching, then an alkaline method is used for precipitating manganese, finally lithium is selectively precipitated by utilizing the difference of solubility, and the lithium manganese metal salt is recovered and used in other fields. There are also some studies on improvement of the separation and recovery of the conventional method. For example, CN109207725B discloses a method and system for recovering lithium and manganese from waste lithium manganate batteries. According to the method, waste lithium manganate is disassembled to obtain a positive electrode material, acid dissolution is carried out to obtain valuable elements in a positive electrode plate, then, lithium ions are separated from other cations by ultrafiltration, and finally, lithium and manganese are precipitated by a chemical precipitation method to realize recovery. The method has the advantages of advanced separation technology, good separation effect, reduction of the introduction of impurity ions due to physical separation, reduction of the recovery cost, relatively low income of recovered products, relatively long recovery flow and relatively high investment cost of equipment, and further improvement of the overall recovery benefit.
In order to solve the problem, a new research idea is formed by directly carrying out structural repair or material regeneration on the waste lithium manganate battery to prepare a new battery anode material, and the mode can reduce the battery recovery process, save the cost and improve the recovery value. The sodium ion battery has better research prospect due to the advantages of excellent quick charge performance, good low-temperature performance, good safety performance and low cost and the electrochemical property similar to that of the lithium ion battery, becomes a research hotspot in recent years and is a reasonable reproduction target.
The invention starts from the aspects of material value increment and resource utilization. The control of the leaching rate of lithium is realized by utilizing a sodium carbonate solution, so that the quantitative doping of lithium in the regeneration process of the material is realized, the transition of a crystal from a P2 structure to an O2 structure is inhibited by partial replacement of transition metal in the sodium ion anode material by the lithium, the stability of the structure is maintained, and the specific capacity of the material is improved to a certain extent.
Disclosure of Invention
Aiming at the problems of low recovery value and poor benefit of waste lithium manganate electrode materials, the invention provides a method for separating lithium from the waste lithium manganate anode materials and regenerating the sodium ion battery anode materials, and the quantitative doping of the lithium in the material regeneration process is realized. The method can effectively regenerate the sodium-ion battery cathode material with P2 layered structure with excellent performance on the basis of simplicity and reasonability.
The invention adopts the following technical scheme for realizing the purpose:
a method for separating lithium from a waste lithium manganate positive electrode material and regenerating a sodium ion battery positive electrode material comprises the following steps:
(1) Pretreating waste lithium manganate batteries to obtain a positive electrode material, and then carrying out carbothermic reduction on the positive electrode material to obtain mixed powder containing elements of lithium and manganese;
(2) Putting the mixed powder obtained in the step (1) into a sodium carbonate solution for leaching so as to quantitatively control the leaching amount of lithium, filtering to obtain a leaching solution containing lithium and leaching residues, further acid leaching the leaching residues by using an acid solution to obtain a leaching solution containing Mn 2+ And Li + The leachate of (2);
(3) Detecting the Mn content obtained in the step (2) 2+ And Li + Fitting the target P2 layered structure sodium ion battery anode material according to the concentrations of the lithium and manganese elements in the leachate, calculating and adding the Mn-containing positive electrode material obtained in the step (2) 2+ And Li + Obtaining a mixed solution by using the leachate and metal salts of nickel, magnesium and sodium, and then preparing a precursor of the positive electrode material of the sodium-ion battery with a P2 layered structure by using a sol-gel method;
(4) Calcining the precursor of the positive electrode material of the sodium-ion battery with the P2 layered structure obtained in the step (3) to obtain the positive electrode material Na of the sodium-ion battery with the target P2 layered structure 0.67 Li x Ni y Mn 1-x-y-z Mg z O 2 (0<x≤0.1,0<y<0.2,0<z<0.1)。
Preferably, in the step (1), the mass ratio of the positive electrode material to the graphite in the carbothermic reduction process is 1-10: 1, the carbothermic reduction reaction temperature is 600-800 ℃, and the carbothermic reduction reaction time is 2-6 h.
Preferably, in the step (2), the mass ratio of the mixed powder to water is 1:10 to 60, the leaching time is 1 to 4 hours, and the added amount of sodium carbonate is 100 to 120 percent of the theoretical added amount.
Preferably, in the step (2), the mass ratio of the mixed powder to water is 1:20 to 40.
Preferably, in the step (2), the type of the acid solution is nitric acid, the amount of substances added in the nitric acid is 5-10 times of the amount of manganese substances in the leaching residue, the leaching time is 0.5-2 h, and the leaching temperature is 40-80 ℃.
Preferably, in the step (3), the sol-gel method is to adjust the pH of the mixed solution to 7-8, then add a chelating agent, react at 70-90 ℃ for 6-8 h, dry, and grind to obtain the precursor of the positive electrode material of the sodium-ion battery with the P2 layered structure.
Preferably, in step (3), the chelating agent is one or more selected from citric acid, EDTA and sucrose.
Preferably, in the step (4), the calcination is divided into two-stage sintering, wherein the first-stage sintering temperature is 450-500 ℃, and the sintering time is 4-6 h; the sintering temperature of the second section is 700-900 ℃, the calcining time is 10-12 h, and the temperature rising rate of the two-section calcining is 5-10 ℃ min -1 。
The invention has the beneficial effects that:
(1) According to the method, the traditional extraction process and the chemical precipitation separation process are not needed, after the spinel structure of lithium manganate is damaged through carbothermic reduction, the separation of lithium and manganese and the quantitative precipitation of lithium are realized by utilizing the water solubility of lithium oxide and the slightly solubility of lithium carbonate, and the effect of doping the regenerated material lithium is finally achieved;
(2) According to the method, the recovery process is further simplified, meanwhile, quantitative lithium precipitation is realized by controlling the leaching parameters of the sodium carbonate solution, the prepared sodium ion battery anode material is subjected to doping modification, transition from a P2 phase to an O2 phase is inhibited through partial substitution of lithium for transition metal, the stability of the sodium ion battery anode material is improved, and the sodium ion battery anode material has good electrochemical performance. The recycling cost is reduced, the value of the recycled product is further improved, valuable metals are fully utilized, and the recycling benefit is good.
Drawings
FIG. 1 shows a positive electrode material Na for a sodium-ion battery prepared in example 1 of the present invention 0.67 Li x Ni y Mn 1-x-y-z Mg z O 2 (0<x≤0.1,0<y<0.2,0<z<0.1 An XRD pattern of the sample;
FIG. 2 shows a positive electrode material Na for a sodium-ion battery prepared in example 1 of the present invention 0.67 Li x Ni y Mn 1-x-y-z Mg z O 2 (0<x≤0.1,0<y<0.2,0<z<0.1 A map of electrochemical performance of the assembled cell.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
(1) Decomposing and splitting the waste lithium manganate battery to obtain a positive electrode, stripping the positive electrode material from the positive electrode, and crushing and calcining to obtain the positive electrode material. 5g of the positive electrode material and 1g of graphite were thoroughly mixed by a ball mill for 1 hour at 450 RPM. Sintering the powder uniformly mixed with the graphite in an argon atmosphere at the sintering temperature of 750 ℃ for 2h to obtain mixed powder containing lithium manganese oxide;
(2) The reduced powder was added to 150mL deionized water, followed by Na 2 CO 3 And filtering 110 percent of the theoretical calculated amount, namely 24.64g to obtain the lithium-rich leaching solution. And mixing the leaching residue with 60mL of 2mol/L nitric acid, leaching for 2h at 60 ℃, and filtering to obtain a solution containing manganese and lithium.
(3) By ICP analysis of Li and Mn in the leach solutionThe mass concentration is respectively 16.31mg/L and 2996.95mg/L, the leaching rate of manganese is calculated to be about 99 percent, and Na is synthesized according to the content of lithium and manganese in the leaching solution 0.67 Li 0.1 Ni 0.17 Mn 0.66 Mg 0.07 O 2 And calculating the amount of each element to be supplemented, and adding corresponding metal salt to obtain a mixed solution. Subsequently, 15.86g of citric acid was added, the pH was adjusted to 7 to 8 using ammonia, heated to 80 ℃ and stirred until the solution became a gel. And (3) drying the gel in an oven at 80 ℃ for 12h, and grinding to obtain the precursor of the P2 layered structure sodium-ion battery positive electrode material.
(4) And (4) performing muffle furnace solid phase sintering on the P2 layered structure sodium ion battery anode material precursor obtained in the step (3), wherein the sintering process is divided into two sections, one section is sintered at 450 ℃ for 6 hours, and the other section is sintered at 900 ℃ for 12 hours, so as to obtain the P2 layered structure sodium ion battery anode material.
Mixing the prepared sodium ion battery positive electrode material powder with the P2 laminated structure, the super-conductive carbon and the polyvinylidene fluoride according to a mass ratio of 8. And assembling in an argon glove box, and assembling into a CR2032 type button cell by using a metal sodium sheet as a counter electrode and Celgard 2300 as a diaphragm. The charge and discharge test was carried out at 25 ℃ and 1C rate in a voltage range of 2-4V, and the result is shown in FIG. 2, and the initial capacity was 117.6mAh g -1 After circulating for 150 circles, the specific discharge capacity of the lithium ion battery still remains 95.4mAh g -1 。
Example 2
(1) Decomposing and splitting the waste lithium manganate battery to obtain a positive electrode, stripping the positive electrode material from the positive electrode, and crushing and calcining to obtain the positive electrode material. 4g of the positive electrode material and 1g of graphite were thoroughly mixed by a ball mill for 1 hour at 450 RPM. Sintering the powder uniformly mixed with the graphite in an argon atmosphere at 700 ℃ for 3h to obtain mixed powder containing lithium manganese oxide;
(2) The reduced powder was added to 120mL of deionized water, followed by addition of Na 2 CO 3 110% of the theoretical amount, i.e. 19.71g, was filtered to obtain a lithium-rich leachate.And mixing the leaching residue with 50mL of 2mol/L nitric acid, leaching for 2h at 60 ℃, and filtering to obtain a solution containing manganese and a small amount of lithium.
(3) By adopting ICP analysis, the mass concentration of Li and Mn in the leaching solution is respectively 13.30mg/L and 2401.53mg/L, the leaching rate of manganese is calculated to be about 99 percent, and Na is synthesized according to the content of lithium and manganese in the leaching solution 0.67 Li 0.1 Ni 0.17 Mn 0.66 Mg 0.07 O 2 And calculating the amount of each element to be supplemented, and adding corresponding metal salt to obtain a mixed solution. Then, 12.71g of citric acid was added, the pH was adjusted to 7 to 8 using ammonia, heated to 80 ℃ and stirred until the solution became a gel. And (3) drying the gel in an oven at 80 ℃ for 12h, and grinding to obtain the precursor of the P2 layered structure sodium-ion battery positive electrode material.
(4) And (4) performing muffle furnace solid phase sintering on the P2 layered structure sodium ion battery anode material precursor obtained in the step (3), wherein the sintering process is divided into two sections, one section is sintered at 450 ℃ for 6 hours, and the other section is sintered at 800 ℃ for 12 hours, so as to obtain the P2 layered structure sodium ion battery anode material.
Mixing the prepared sodium ion battery positive electrode material powder with the P2 laminated structure, the super-conductive carbon and the polyvinylidene fluoride according to a mass ratio of 8. And assembling in an argon glove box, and assembling into a CR2032 type button cell by using a metal sodium sheet as a counter electrode and Celgard 2300 as a diaphragm. The charge and discharge test was carried out at 25 ℃ and 1C rate in a voltage range of 2-4V, and the results are shown in FIG. 2, and the initial capacity was 124.7mAh g -1 After circulating for 150 circles, the specific discharge capacity of the lithium ion battery still remains 96.2mAh g -1 。
Claims (8)
1. The method for separating lithium and regenerating the positive electrode material of the sodium ion battery by using the positive electrode of the waste lithium manganate battery is characterized by comprising the following steps of:
(1) Pretreating waste lithium manganate batteries to obtain a positive electrode material, and then carrying out carbothermic reduction on the positive electrode material to obtain mixed powder containing elements of lithium and manganese;
(2) Putting the mixed powder obtained in the step (1) into a sodium carbonate solution for leaching so as to quantitatively control the leaching amount of lithium, filtering to obtain a leaching solution containing lithium and leaching residues, further acid leaching the leaching residues by using an acid solution to obtain a leaching solution containing Mn 2+ And Li + The leachate of (2);
(3) Detecting the Mn content obtained in the step (2) 2+ And Li + Fitting the target P2 layered structure sodium ion battery anode material according to the concentrations of the lithium and manganese elements in the leachate, calculating and adding the Mn-containing positive electrode material obtained in the step (2) 2+ And Li + Obtaining a mixed solution by the leachate and metal salts of nickel, magnesium and sodium, and then preparing a precursor of the positive electrode material of the sodium-ion battery with a P2 layered structure by a sol-gel method;
(4) Calcining the precursor of the positive electrode material of the sodium-ion battery with the P2 layered structure obtained in the step (3) to obtain the positive electrode material Na of the sodium-ion battery with the target P2 layered structure 0.67 Li x Ni y Mn 1-x-y-z Mg z O 2 (0<x≤0.1,0<y<0.2,0<z<0.1)。
2. The method for separating lithium and regenerating the positive electrode material of the sodium-ion battery with the P2 layered structure by using the positive electrodes of the waste lithium manganate batteries as claimed in claim 1, wherein in the step (1), the mass ratio of graphite to the positive electrode material is 1-10: 1, the carbothermic reduction reaction temperature is 600-800 ℃, and the carbothermic reduction reaction time is 2-6 h.
3. The method for separating lithium and regenerating the positive electrode material of the sodium-ion battery with the P2 layered structure by using the positive electrode of the waste lithium manganate battery as in claim 2, wherein in the step (2), the lithium is quantitatively leached by controlling the addition of sodium carbonate by using the slightly solubility of lithium carbonate, and the mass ratio of the mixed powder to water is 1:10 to 60, the leaching time is 1 to 4 hours, and the added amount of sodium carbonate is 100 to 120 percent of the theoretical added amount.
4. The method for separating lithium and regenerating the positive electrode material of the sodium-ion battery with the P2 layered structure by using the positive electrode of the waste lithium manganate battery as in claim 2 or 3, wherein in the step (2), the mass ratio of the mixed powder to water is 1:20 to 40.
5. The method for separating lithium and regenerating the positive electrode material of the sodium-ion battery with the P2 layered structure by using the positive electrode of the waste lithium manganate battery as in claim 1 or 3, wherein in the step (2), the type of the acid solution is nitric acid, the amount of substances added in the nitric acid is 5-10 times of the amount of manganese substances in the leaching residue, the leaching time is 0.5-2 h, and the leaching temperature is 40-80 ℃.
6. The method for separating lithium and regenerating the positive electrode material of the sodium-ion battery with the P2 layered structure by utilizing the positive electrodes of the waste lithium manganate batteries as claimed in claim 1, wherein in the step (3), the pH value of the mixed solution is adjusted to 7-8, then a chelating agent is added, the mixture is reacted for 6-8 hours at 70-90 ℃, and the precursor of the positive electrode material of the sodium-ion battery with the P2 layered structure is obtained after drying and grinding.
7. The method for separating lithium and regenerating a positive electrode material of a sodium-ion battery with a P2 laminated structure by using the positive electrodes of waste lithium manganate batteries as claimed in claim 1 or 6, wherein in the step (3), the chelating agent is one or more selected from citric acid, EDTA and sucrose.
8. The method for separating lithium and regenerating the positive electrode material of the sodium ion battery with the P2 layered structure by utilizing the positive electrodes of the waste lithium manganate batteries as claimed in claim 1, wherein in the step (4), the calcination is divided into two-stage sintering, the first-stage sintering temperature is 450-500 ℃, and the sintering time is 4-6 hours; the sintering temperature of the second section is 700-900 ℃, the calcining time is 10-12 h, and the temperature rising rate of the two-section calcining is 5-10 ℃ min -1 。
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| CN116102080A (en) * | 2022-12-20 | 2023-05-12 | 广州大学 | Method for preparing positive electrode material by regenerating waste sodium ion battery |
| CN116354402A (en) * | 2023-03-02 | 2023-06-30 | 福州大学 | Treatment method of waste lithium manganate ion battery anode material |
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| CN116102080A (en) * | 2022-12-20 | 2023-05-12 | 广州大学 | Method for preparing positive electrode material by regenerating waste sodium ion battery |
| CN116354402A (en) * | 2023-03-02 | 2023-06-30 | 福州大学 | Treatment method of waste lithium manganate ion battery anode material |
| CN116354402B (en) * | 2023-03-02 | 2024-08-09 | 福州大学 | Treatment method of waste lithium manganate ion battery anode material |
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