CN116031525A - Method for recycling lithium iron from waste lithium iron phosphate battery positive plate - Google Patents
Method for recycling lithium iron from waste lithium iron phosphate battery positive plate Download PDFInfo
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- CN116031525A CN116031525A CN202310167511.1A CN202310167511A CN116031525A CN 116031525 A CN116031525 A CN 116031525A CN 202310167511 A CN202310167511 A CN 202310167511A CN 116031525 A CN116031525 A CN 116031525A
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- Prior art keywords
- filtrate
- lithium iron
- positive electrode
- electrode material
- iron
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Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 22
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 title claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 23
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 23
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 12
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 12
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 239000000706 filtrate Substances 0.000 claims description 32
- 229910052742 iron Inorganic materials 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229910001385 heavy metal Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- -1 fluorine ions Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 229920001817 Agar Polymers 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 239000008272 agar Substances 0.000 claims description 5
- 235000010419 agar Nutrition 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000008262 pumice Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011888 foil Substances 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000002386 leaching Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000005185 salting out Methods 0.000 abstract description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000011554 ferrofluid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Secondary Cells (AREA)
Abstract
The invention provides a method for recycling lithium iron from a waste lithium iron phosphate battery positive plate. The invention directly separates out aluminum foil and positive electrode material by using organic solvent, and then separates out lithium carbonate and ferric phosphate by wet leaching, air oxidation, precipitation crystallization and other methods of the positive electrode material. The invention has short recovery flow, low cost and good recycling of waste.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a method for recycling lithium iron from a waste lithium iron phosphate battery positive plate.
Background
The traditional energy source is exhausted and the environmental problems are increasingly serious, and the lithium battery is widely applied to the fields of new energy automobiles, aerospace, communication and the like by virtue of the characteristics of high energy density, long service life, green environmental protection and the like. The lithium iron phosphate serving as a battery anode material has the advantages of good cycle performance, high safety, wide sources and the like, and is widely applied to the field of manufacturing of new energy batteries; and the problem of how to treat the scrapped batteries is solved at the same time of wide application, so that a recycling method with simple recycling process and low cost is urgently needed to realize recycling of resources.
At present, wet leaching of elements such as iron, lithium and the like is commonly used for recycling the waste lithium iron phosphate anode material, the recycling process is long, a large amount of strong oxidizing acid alkali liquid is used for multiple times in the process, the cost is high, and a large amount of salt-containing wastewater is produced.
Disclosure of Invention
The invention provides a method for recycling lithium iron from a waste lithium iron phosphate battery positive plate, which aims to solve the defects. At present, the waste lithium iron phosphate anode material is recovered by commonly using a wet method to leach elements such as iron, lithium and the like, and a large amount of strong oxidizing acid-alkali liquor is used repeatedly in the process, so that an aluminum foil is dissolved in the acid-alkali liquor, which is a treatment procedure for wastewater treatment; the battery manufacturers add various additives to the battery, wherein various heavy metals are present, which makes the recycling process very difficult. The invention directly separates out aluminum foil and positive electrode material by using organic solvent, and then separates out lithium carbonate and ferric phosphate by wet leaching, air oxidation, precipitation crystallization and other methods of the positive electrode material.
The invention is realized by the following scheme:
the invention aims to provide a method for recycling lithium iron from a waste lithium iron phosphate battery positive plate, which comprises the following steps:
(1) Pouring the positive plate of the lithium iron phosphate battery into a separating agent, and heating, stirring and separating a positive electrode material from a positive electrode current collector;
(2) Crushing the positive electrode material obtained by separation in the step (1), pouring the crushed positive electrode material into water, adding hydrochloric acid solution, stirring, introducing oxygen to dissolve lithium iron phosphate in the positive electrode material, and carrying out solid-liquid separation to obtain filtrate;
(3) Removing fluorine ions in the filtrate obtained in the step (2) by using a fluorine ion precipitator, an adsorbent or an ion exchange membrane to obtain filtrate without fluorine ions;
(4) Adding a heavy metal chelating agent into the filtrate which does not contain fluoride ions in the step (3);
(5) Adjusting the pH value of the filtrate in the step (4) to 2-3, heating, and thermally filtering to obtain ferric phosphate and filtrate;
(6) And (3) regulating the pH value of the filtrate obtained in the step (5) to 9-10, filtering to obtain lithium carbonate and filtrate, and recycling the obtained filtrate into the step (4).
In one embodiment of the invention, in step (1), the separating agent is selected from one or more of DMF, NMP, DMI, THF and ionic liquid. The invention uses the adhesive to adhere to the aluminum foil positive current collector in the positive electrode material, so that the adhesive is dissolved by the organic solvent separating agent, so that the positive electrode material and the aluminum foil are easy to separate after being stirred, and the aluminum foil does not react with the organic solvent separating agent or dissolve in the organic solvent separating agent at the moment, thereby realizing good separation.
In one embodiment of the present invention, in the step (1), the positive electrode current collector is not limited, and may be copper foil, aluminum foil, nickel mesh, stainless steel, etc., preferably aluminum foil.
In one embodiment of the invention, in step (1), at least one of the following conditions is satisfied:
1) The heating temperature is 35-60 ℃;
2) The mass ratio of the positive plate to the separating agent of the lithium iron phosphate battery is 3-6:10.
in one embodiment of the invention, in step (2), at least one of the following conditions is satisfied:
a) The concentration of the hydrochloric acid solution is 0.1mol/L-0.3mol/L;
b) The mass ratio of the positive electrode material to the hydrochloric acid solution is 1-3:2;
c) The flow rate of the oxygen is 20L/h-30L/h.
In one embodiment of the present invention, in step (3), the fluoride ion precipitating agent is selected from one or more of calcium chloride, calcium nitrate, calcium carbonate, calcium bicarbonate, and calcium phosphate.
In one embodiment of the present invention, in step (3), the adsorbent is selected from one or more of activated carbon, modified or non-modified quartz stone, modified or non-modified glass pumice, zeolite, and activated montmorillonite.
Further, the quartz stone is modified by one or more of amination modification, quaternary ammonium salt modification, ferric salt modification, aluminum salt modification, magnesium salt modification, magnetic modification and starch modification.
Further, the glass pumice stone is modified by boric acid.
In one embodiment of the present invention, in step (4)The heavy metal chelating agent is one or more selected from iron-based magnetic chitosan, iron-based magnetic sodium alginate, iron-based magnetic gelatin, iron-based magnetic agar, EDTA, chitosan, sodium alginate, gelatin and agar. The state of the iron-based heavy metal chelating agent is not limited, and magnetic beads, microspheres and the like can be adopted. The heavy metal chelating agent is used for removing other heavy metal ions such as nickel, cobalt, manganese and the like doped in the positive electrode material of the battery. Wherein the iron-based magnetic chitosan, the iron-based magnetic sodium alginate, the iron-based magnetic gelatin and the iron-based magnetic agar are derived from Fe with magnetism in the preparation raw materials 3 O 4 Iron, gamma-Fe 2 O 3 Iron sources such as magnetite, iron ore, ferrite, ferrofluid, and the like, such materials being conventional iron-based magnetic materials in the art.
In one embodiment of the present invention, the mass ratio of the heavy metal chelating agent to the positive electrode material in step (2) is 1-2:100.
in one embodiment of the invention, in the step (5) and the step (6), the regulator for regulating the pH value of the filtrate is one or more selected from sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate. Sodium carbonate is preferred. Furthermore, the adjustment agents in the step (5) and the step (6) are required to be consistently selected. The pH regulator is not only used for regulating pH, but also provides carbonate for subsequent precipitation of lithium ions.
In one embodiment of the invention, the concentration of the modifier is 0.05mol/L to 0.2mol/L.
Preferably, in the step (5), the concentration of the regulator is 0.05mol/L to 0.1mol/L; the heating temperature is 40-60 ℃.
Preferably, in step (6), the concentration of the regulator is 0.1mol/L to 0.2mol/L.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention utilizes the hydrochloric acid solution and oxygen to carry out dissolution oxidation on the lithium iron phosphate anode material, thereby avoiding the phenomenon of corrosion to equipment caused by using a strong oxidant; in the third step, the adsorbent is used for adsorbing fluoride ions and organic matters in advance, so that the purity of the ferric phosphate and the lithium carbonate can be improved; the chelating agent is used for chelating the heavy metal ions in the fourth step, so that the influence of the heavy metal ions on the precipitation of the ferric phosphate and the lithium carbonate can be reduced.
In order to avoid the aluminum foil from being dissolved by acid liquor and increasing the treatment steps, the invention uses an organic solvent to directly separate aluminum foil and powder of positive electrode materials, uses a small amount of acid liquor to dissolve lithium iron oxide, adds a heavy metal chelating agent to stabilize other heavy metal ions to avoid affecting the precipitation of lithium carbonate and ferric phosphate, uses sodium carbonate and other regulators to adjust pH to gradually separate precipitated ferric phosphate and lithium carbonate, and the treated filtrate contains the chelating agent for recycling.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a schematic flow chart of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
The embodiment provides a method for recycling lithium iron from a waste lithium iron phosphate battery positive plate, which comprises the following steps (the flow chart is shown in figure 1):
(1) And pouring the collected 30g of lithium iron phosphate battery positive plate into 100g of DMF, heating to 40 ℃, and stirring to separate the positive electrode material and the aluminum foil.
(2) And (3) crushing the positive electrode material obtained in the step (1), pouring the crushed positive electrode material into water, adding 20mL of 0.1mol/L hydrochloric acid, rapidly stirring, introducing oxygen to oxidize and dissolve lithium iron phosphate, and filtering insoluble substances to obtain filtrate, wherein the flow rate of the oxygen is 20L/h.
(3) And (3) adding calcium chloride into the filtrate obtained in the step (2), and filtering to obtain filtrate with fluorine and organic matters removed.
(4) And (3) adding 0.5g of iron-based chitosan magnetic pellets into the filtrate obtained in the step (3), and filtering to obtain filtrate with heavy metal ions removed.
(5) And (3) adding 0.1mol/L sodium carbonate solution into the filtrate from which the heavy metal ions are removed in the step (4), adjusting the pH to 2, heating to 60 ℃, and filtering while the filtrate is hot to obtain ferric phosphate and filtrate.
(6) And (3) adding sodium carbonate solution into the filtrate obtained in the step (5) at room temperature to adjust the pH to 9, and filtering to obtain lithium carbonate and filtrate. And recycling the obtained filtrate to the step (4). The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Example 2:
the method for recovering lithium iron in this example differs from that in example 1 in that: the mass of lithium iron phosphate in the step (1) is 40g, and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Example 3:
the method for recovering lithium iron in this example differs from that in example 1 in that: the mass of the lithium iron phosphate in the step (2) is 50g, and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Example 4:
the method for recovering lithium iron in this example differs from that in example 1 in that: the oxygen flow in the step (2) is 25L/h, and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Example 5:
the method for recovering lithium iron in this example differs from that in example 1 in that: the oxygen flow in the step (2) is 30L/h, and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Example 6:
the method for recovering lithium iron in this example differs from that in example 1 in that: in the step (3), the activated carbon adsorbent is used instead of the calcium chloride, and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Example 7:
the method for recovering lithium iron in this example differs from that in example 1 in that: the adsorbent active montmorillonite is used in the step (3), and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Comparative example 1
The method for recovering lithium iron in this example differs from that in example 1 in that: and (2) introducing no oxygen, and the rest steps are the same. The recovery and purity of the resulting product lithium carbonate and iron phosphate are shown in tables 1 and 2.
Comparative example 2
The method for recovering lithium iron in this example differs from that in example 1 in that: the step (3) does not use a fluoride ion precipitator, an adsorbent or an ion exchange membrane, and the rest steps are the same. The recovery yields and purities of the resulting products lithium carbonate and iron phosphate are shown in tables 1 and 2.
Wherein recovery yield (%) =actual recovery mass/theoretical recovery mass×100%, specifically: taking the positive electrode material powder in the step 1, measuring and calculating the actual content of lithium iron element, and calculating theoretical lithium iron recovery quality; and taking the recovered lithium carbonate and ferric phosphate, measuring the actual mass of lithium iron elements, and calculating the actual lithium iron recovery mass.
Purity (%) = actual lithium or iron ion concentration/theoretical lithium or iron ion concentration x 100%, specifically: taking the positive electrode material powder in the step 1, and measuring and calculating the theoretical concentration of lithium or iron element; and (3) adding acid to dissolve the finally recovered lithium carbonate/ferric phosphate with a certain quality, and diluting and measuring the actual lithium ion concentration.
TABLE 1 recovery yield of lithium carbonate
| Sample of | Recovery yield (%) | Purity (%) |
| Example 1 | 97.6 | 99.3 |
| Example 2 | 97.9 | 99 |
| Example 3 | 97.6 | 99.4 |
| Example 4 | 98 | 99.2 |
| Example 5 | 97.9 | 99.3 |
| Example 6 | 98.9 | 99.3 |
| Example 7 | 98.4 | 99.4 |
| Comparative example 1 | 62.1 | 99.4 |
| Comparative example 2 | 98.3 | 98.4 |
TABLE 2 recovery yield of iron phosphate
| Sample of | Recovery yield (%) | Purity (%) |
| Example 1 | 98.1 | 99.2 |
| Example 2 | 98.3 | 99.1 |
| Example 3 | 95.2 | 99.3 |
| Example 4 | 98.4 | 99.3 |
| Example 5 | 98.4 | 99.2 |
| Example 6 | 98.6 | 99.3 |
| Example 7 | 98 | 99.2 |
| Comparative example 1 | 57.2 | 99.1 |
| Comparative example 2 | 98.6 | 98.2 |
As is clear from tables 1 and 2, comparative examples 1 and 1, in which the oxygen is not introduced, only relies on the oxygen in the air and hydrochloric acid for dissolution, and the oxygen concentration in the air is low, and the oxidizing property is weak, so that the iron element cannot be completely oxidized and leached, resulting in low recovery yields of lithium carbonate and iron phosphate. Comparative examples 1 and 2, due to the absence of the fluoride ion precipitating agent in comparative example 2, resulted in more impurities after precipitation of lithium carbonate and ferric phosphate, affecting the purity of the product and less on recovery yield. Therefore, the invention realizes the purposes of high recovery yield and high purity of the product by introducing oxygen and adding the defluorinating agent.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The method for recycling the lithium iron from the waste lithium iron phosphate battery positive plate is characterized by comprising the following steps of:
(1) Pouring the positive plate of the lithium iron phosphate battery into a separating agent, and heating, stirring and separating a positive electrode material from a positive electrode current collector;
(2) Crushing the positive electrode material obtained by separation in the step (1), pouring the crushed positive electrode material into water, adding hydrochloric acid solution, stirring, introducing oxygen to dissolve lithium iron phosphate in the positive electrode material, and carrying out solid-liquid separation to obtain filtrate;
(3) Removing fluorine ions in the filtrate obtained in the step (2) by using a fluorine ion precipitator, an adsorbent or an ion exchange membrane to obtain filtrate without fluorine ions;
(4) Adding a heavy metal chelating agent into the filtrate which does not contain fluoride ions in the step (3);
(5) Adjusting the pH value of the filtrate in the step (4) to 2-3, heating, and thermally filtering to obtain ferric phosphate and filtrate;
(6) And (3) regulating the pH value of the filtrate obtained in the step (5) to 9-10, filtering to obtain lithium carbonate and filtrate, and recycling the obtained filtrate into the step (4).
2. The method of claim 1, wherein in step (1), the separating agent is selected from one or more of DMF, NMP, DMI, THF and ionic liquid.
3. The method of claim 1, wherein in step (1), at least one of the following conditions is satisfied:
1) The heating temperature is 35-60 ℃;
2) The mass ratio of the positive plate to the separating agent of the lithium iron phosphate battery is 3-6:10.
4. The method of claim 1, wherein in step (2), at least one of the following conditions is satisfied:
a) The concentration of the hydrochloric acid solution is 0.1mol/L-0.3mol/L;
b) The mass ratio of the positive electrode material to the hydrochloric acid solution is 1-3:2;
c) The flow rate of the oxygen is 20L/h-30L/h.
5. The method of claim 1, wherein in step (3), the fluoride ion precipitating agent is selected from one or more of calcium chloride, calcium nitrate, calcium carbonate, calcium bicarbonate, and calcium phosphate.
6. The method of claim 1, wherein in step (3), the adsorbent is selected from one or more of activated carbon, modified or non-modified quartz, modified or non-modified glass pumice, zeolite, and activated montmorillonite.
7. The method of claim 1, wherein in step (4), the heavy metal chelator is selected from one or more of iron-based magnetic chitosan, iron-based magnetic sodium alginate, iron-based magnetic gelatin, iron-based magnetic agar, EDTA, chitosan, sodium alginate, gelatin, and agar.
8. The method of claim 1, wherein in step (4), the mass ratio of the heavy metal chelating agent to the positive electrode material in step (2) is 1-2:100.
9. the method according to claim 1, wherein in the step (5) and the step (6), the regulator for regulating the pH value of the filtrate is one or more selected from sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
10. The method of claim 9, wherein the concentration of the modifier is 0.05mol/L to 0.2mol/L.
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| CN110649342A (en) * | 2018-06-26 | 2020-01-03 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
| CN113772693A (en) * | 2021-10-27 | 2021-12-10 | 江西金辉锂业有限公司 | Method for selectively leaching and extracting lithium from lithium iron phosphate waste |
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| CN110649342A (en) * | 2018-06-26 | 2020-01-03 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
| CN113772693A (en) * | 2021-10-27 | 2021-12-10 | 江西金辉锂业有限公司 | Method for selectively leaching and extracting lithium from lithium iron phosphate waste |
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