CN117712544A - Resource utilization method of waste lithium iron phosphate battery - Google Patents
Resource utilization method of waste lithium iron phosphate battery Download PDFInfo
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- CN117712544A CN117712544A CN202410166481.7A CN202410166481A CN117712544A CN 117712544 A CN117712544 A CN 117712544A CN 202410166481 A CN202410166481 A CN 202410166481A CN 117712544 A CN117712544 A CN 117712544A
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- iron phosphate
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- aluminum
- battery
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- 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 127
- 239000002699 waste material Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000004064 recycling Methods 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 239000013067 intermediate product Substances 0.000 claims description 16
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 8
- -1 aluminum ion Chemical class 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to the technical field of battery recycling, and particularly discloses a resource utilization method of a waste lithium iron phosphate battery. According to the recycling method of the waste lithium iron phosphate battery, firstly, aluminum-containing lithium iron phosphate waste powder is subjected to hydrothermal reaction at a specific temperature under an alkaline condition, and impurities F contained in the waste lithium iron phosphate powder are sufficiently removed; adding phosphate solution into the leached slag after F removal to adjust the iron-phosphorus ratio, realizing aluminum ion doping through hydrothermal reaction, and finally calcining to obtain the aluminum doped lithium iron phosphate anode material. The method for processing the waste lithium iron phosphate battery can obtain the high-performance aluminum-doped lithium iron phosphate positive electrode material, thereby realizing the resource utilization of the waste lithium iron phosphate material, being suitable for industrialized batch processing of the waste lithium iron phosphate battery, having higher practical value and having important significance for sustainable development in the field of the lithium iron phosphate battery.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery treatment, in particular to a resource utilization method of waste lithium iron phosphate batteries.
Background
The lithium iron phosphate (LFP) material has the unique advantages of large specific capacity, high safety, low cost, long cycle life and the like, and is widely applied to the fields of energy storage systems, electric vehicles (such as buses, low-speed electric vehicles and other special vehicles), power grids and the like. In 2022, the output of the lithium ion battery anode material in China is about 190 ten thousand tons, and the same ratio is increased by 68.1%, wherein the output of the lithium iron phosphate anode material is up to 58.5%, and the output of the lithium iron phosphate anode material reaches 111.15 ten thousand tons, so that the lithium iron phosphate anode material becomes the new generation lithium ion battery anode material with the most development potential. In view of the fact that the average service life of the power battery of the new energy automobile is about 6-8 years, the power battery will be retired in large scale in the future, and therefore how to realize efficient recovery of the waste lithium iron phosphate battery becomes a hot spot of current research.
At present, the recovery methods of the positive electrode materials of the waste lithium iron phosphate batteries mainly comprise two methods: pyrometallurgy and hydrometallurgy. The pyrometallurgy has higher energy consumption, high process cost and poor process sustainability; hydrometallurgy is carried out by taking crude ferric phosphate and lithium-containing leaching solution as raw materials to synthesize lithium carbonate as product. The great challenge faced in the current recovery process is the removal of impurity elements (e.g., al, F) therein. Under mechanical treatment, since iron ions and aluminum ions have the same valence state, have similar ionic radii, and aluminum phosphate and iron phosphate have similar ksps, it is inevitable that aluminum is contained in the positive electrode powder. The difficulty of the current research is how to reduce the impurity content in the waste lithium iron phosphate anode powder on the basis of economy and environmental protection, and how to improve the discharge specific capacity and other electrochemical performances by regenerating and modifying the material. Therefore, it is very necessary to develop an efficient, low-cost and environment-friendly method for recycling the waste lithium iron phosphate batteries.
Disclosure of Invention
Aiming at the problems of the existing recovery method of the waste lithium iron phosphate battery, the invention provides a recycling method of the waste lithium iron phosphate battery, the method realizes the recycling of the anode material in the waste lithium iron phosphate battery, and the recovered aluminum-doped lithium iron phosphate material has good electrochemical performance and has important significance for promoting the sustainable development of the lithium iron phosphate battery.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a resource utilization method of waste lithium iron phosphate batteries comprises the following steps:
step a, discharging, disassembling, pyrolyzing, crushing and screening the waste lithium iron phosphate batteries to obtain aluminum-containing lithium iron phosphate waste powder;
step b, adding the aluminum-containing lithium iron phosphate waste powder into an alkaline solution, uniformly dispersing, performing hydrothermal reaction at 150-250 ℃, and performing solid-liquid separation to obtain leaching liquid and leaching residues;
step c, adding an acidic phosphate solution and a reducing agent into the leaching slag, uniformly mixing, performing hydrothermal reaction at 100-200 ℃, performing solid-liquid separation, and drying to obtain an intermediate product;
and d, calcining the intermediate product in an inert atmosphere to obtain the aluminum-doped lithium iron phosphate anode material.
Compared with the prior art, the recycling method of the waste lithium iron phosphate battery provided by the invention comprises the steps of firstly carrying out hydrothermal reaction on aluminum-containing lithium iron phosphate waste powder at a specific temperature under an alkaline condition, and fully removing impurities F contained in the aluminum-containing lithium iron phosphate waste powder; adding phosphate solution into the leached slag after F removal to adjust the iron-phosphorus ratio, realizing aluminum ion doping through hydrothermal reaction, and finally calcining to obtain the aluminum doped lithium iron phosphate anode material. The method for processing the waste lithium iron phosphate battery can obtain the high-performance aluminum-doped lithium iron phosphate positive electrode material, thereby realizing the resource utilization of the waste lithium iron phosphate material, being suitable for industrialized batch processing of the waste lithium iron phosphate battery, having higher practical value and having important significance for sustainable development in the field of the lithium iron phosphate battery.
In the invention, discharging, disassembling, pyrolyzing and sorting in the step a to obtain a positive plate; and crushing and screening the positive plate to obtain aluminum-containing lithium iron phosphate waste powder.
The discharge, disassembly, pyrolysis, separation, crushing and screening in the process can be carried out by adopting a conventional operation method in the field, the invention is not particularly limited, and specific process conditions can be adjusted by a person skilled in the art through routine experiments.
Further, the step a specifically comprises the following steps: discharging and disassembling the waste lithium iron phosphate battery to obtain a battery core; pyrolyzing the battery cell under vacuum condition, and then separating to obtain a battery positive plate; and crushing, screening and air flow sorting the battery positive plate to obtain aluminum-containing lithium iron phosphate waste powder.
In step a, the pyrolysis temperature is 50 ℃ to 200 ℃. Most of organic components and electrolyte in the battery can be removed through vacuum pyrolysis, and doping of organic components such as binders in the positive electrode material is reduced.
Further, in the step a, the aluminum content of the aluminum-containing lithium iron phosphate waste powder is 0.2-3 wt% and the fluorine content is 0.15-2 wt%.
The aluminum content in the lithium iron phosphate waste powder can be controlled by the pore diameter of a screen used for screening, and the larger the pore diameter of the screen is, the higher the aluminum content in the separated lithium iron phosphate waste powder is.
Further, in the step b, the concentration of the alkaline solution is 0.5 mol/L-6 mol/L.
Further, in the step b, the alkaline solution is at least one of sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution.
In the step b, the mass volume ratio of the aluminum-containing lithium iron phosphate waste powder to the alkaline solution is 1g (1-10) mL.
In the step b, the hydrothermal reaction time is 3-6 h.
Specifically, the main chemical reactions occurring in step b are:
LiF+OH - →LiOH+F -
LiFePO 4 +3OH - →LiOH+Fe(OH) 2 ↓+PO 4 3-
2Al+2OH - +2H 2 O→2(AlO 2 - )+3H 2 ∈ (partial dissolution of aluminium)
The fluorine element contained in the lithium iron phosphate waste powder is hardly removed therefrom by a conventional method. Through creative thinking, the invention carries out hydrothermal reaction on the aluminum-containing lithium iron phosphate waste powder in a hydrothermal kettle at a specific temperature under an alkaline condition, so that the impurity F element is replaced and enters a liquid phase, and the full removal of the impurity F in the lithium iron phosphate can be realized through solid-liquid separation.
Further, in step c, the acidic phosphate solution is a lithium dihydrogen phosphate solution.
The lithium dihydrogen phosphate solution is acidic and can react with Al in the lithium iron phosphate waste powder under the hydrothermal condition to generate Al 3+ At the same time, al in the hydrothermal process 3+ Can enter into crystal lattice of lithium iron phosphate to realize doping of aluminum ions.
In the step c, the solid-liquid ratio of the hydrothermal reaction system is 1g (3-10) mL.
In step c, the hydrothermal reaction time is 2-5 h.
Further, in the step c, the reducing agent is at least one of glucose, sucrose, citric acid, ascorbic acid or hydrazine hydrate.
The addition of the reducing agent can prevent Fe in the hydrothermal reaction process 2+ Oxidized.
In the step c, the molar ratio of P in the acidic phosphate solution to Fe in the leaching residue is (0.2-0.9): 1.
In the step c, the molar ratio of the reducing agent to Fe in the leaching slag is (0.01-0.03): 1.
In the preferential reaction condition, the Al in the waste lithium iron phosphate powder can react with the acidic lithium dihydrogen phosphate solution to generate Al 3+ Al and Fe have similar covalent radiuses, and can enter lithium iron phosphate lattices in a hydrothermal reaction to realize aluminum doping, and the main chemical reaction of the hydrothermal process is as follows. The conductivity and the multiplying power performance of the lithium iron phosphate anode material can be effectively improved through aluminum doping, and the method is very beneficial to the practical application of recycling the lithium iron phosphate anode material.
LiFePO 4 +XAl 3+ →Li 1-X Fe 1-X Al X PO 4 +XFe 2+ +XLi +
In the step d, the calcination temperature is 500-800 ℃ and the calcination time is 1-2 h.
Further, in the step d, the calcining adopts a segmented calcining mode, and the specific steps are as follows: calcining the intermediate product at 300-500 ℃ for 2-6 hours, and then calcining at 600-800 ℃ for 8-12 hours to obtain the aluminum-doped lithium iron phosphate anode material.
By adopting the preferred calcination mode, the crystallinity and purity of the lithium iron phosphate crystal grains can be improved, thereby being beneficial to improving the electrochemical performance of the lithium iron phosphate.
The aluminum-doped lithium iron phosphate positive electrode material prepared in the invention is Li 1-X Fe 1-X Al X PO 4 C, wherein 0<X<0.05。
Illustratively, in step d, the inert atmosphere may be provided by inert gases conventional in the art, which may be argon, nitrogen, etc.
Compared with the prior art, the invention has the following advantages:
(1) The invention provides a novel method for recycling aluminum-doped lithium iron phosphate from waste lithium iron phosphate, which realizes 99% fluorine removal and aluminum doping by a novel process of hot dipping alkali water to remove impurities and then hot dipping aluminum on the premise of not damaging the structure of the waste lithium iron phosphate and not changing components, and effectively improves the electrochemical performance of the recycled lithium iron phosphate material;
(2) According to the invention, a two-step hydrothermal reaction method is adopted, the purpose of doping aluminum element while directly regenerating the lithium iron phosphate material is realized, the problems of short cycle life and poor rate capability of the material caused by aluminum element impurities are solved, the conductivity of the material is improved by doping aluminum into lithium iron phosphate crystal lattices, and the rate capability and the cycle performance of the material are improved;
(3) The method is suitable for recycling the anode material in the waste lithium iron phosphate battery, the reagent raw materials used in the recycling process are cheap and easy to obtain, the environmental protection and the economic benefit are taken into account, the engineering amplification can be realized, and the method is suitable for continuously treating the waste lithium iron phosphate battery in industrialized batch.
Drawings
FIG. 1 is a process flow block diagram of a method for treating a waste lithium iron phosphate battery in an embodiment of the invention;
FIG. 2 is an XRD pattern of aluminum-containing lithium iron phosphate waste powder prepared in step a of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A resource utilization method of waste lithium iron phosphate batteries comprises the following steps:
step a, after carrying out discharge treatment on waste retired lithium iron phosphate batteries, disassembling the waste retired lithium iron phosphate batteries to obtain battery cores, then carrying out constant temperature on the battery cores in a vacuum tank for 3 hours at 200 ℃, pyrolyzing residual electrolyte and binder in the battery cores, then carrying out disassembly and separation to obtain battery positive plates, crushing the positive plates by a crusher, screening by a screen mesh with 0.5mm, carrying out airflow separation, and collecting to obtain aluminum-containing lithium iron phosphate waste powder, wherein the structural components are shown in figure 2;
step B, mixing 100g of the aluminum-containing lithium iron phosphate waste powder (with F content of 0.75% and Al content of 0.2%) with 800mL of 0.75mol/L sodium hydroxide solution, adding the mixture into a hydrothermal kettle, reacting for 6 hours at 150 ℃, filtering after the reaction is finished to obtain a leaching solution A and a leaching residue B, and analyzing a small amount of leaching solution A by using a fluoride ion electrode to obtain a leaching rate of fluorine of 99.64%;
step c, mixing leaching residue B and lithium dihydrogen phosphate solution, adding the mixture into a hydrothermal kettle, wherein the molar ratio of P in lithium dihydrogen phosphate to Fe in leaching residue is 0.3:1, adding a reducing agent hydrazine hydrate with the molar amount of Fe in leaching residue being 2%, finally adjusting the liquid-solid ratio of the solution to be 4mL/g, and reacting at 150 ℃ for 5 hours to obtain an intermediate product;
step d, calcining the intermediate product in a gradient way under nitrogen atmosphere, wherein the first gradient calcining temperature is 350 ℃, the calcining time is 4 hours, the second gradient calcining temperature is 750 ℃, and the calcining time is 10 hours, so as to obtain the aluminum doped lithium iron phosphate positive electrode material, analyzing the element content of the final product through ICP test, and preparing the final product of Li 1-X Fe 1-X Al X PO 4 /C, where x=0.004.
Mixing the prepared aluminum-doped lithium iron phosphate positive electrode material, carbon black and polyvinylidene fluoride in the mass ratio of 94:4:2 in NMP to form slurry, uniformly coating the slurry on aluminum foil, vacuum drying at 120 ℃ for 6 hours, and cutting into wafers with the diameter of 15mm to serve as positive electrodes, wherein the surface density of the pole pieces is ensured to be 2-3 mg/cm 2 . Lithium ion battery (CR 2032) was assembled in an argon-filled glove box using lithium metal foil as the negative electrode and electrolyte LiPF at 1.0mol/L 6 A button cell is assembled by using a mixture of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) (1:1, v/v) as a solvent and Polyethylene (PE) as a diaphragm, and a charge and discharge test is carried out.
And (3) performing rate cycle performance tests at current densities of 0.1C, 0.2C, 0.5C and 1C in a voltage interval of 2.5-3.6V respectively, wherein the measured specific discharge capacities are 143mAh/g, 138mAh/g, 133mAh/g and 122mAh/g respectively.
Example 2
A resource utilization method of waste lithium iron phosphate batteries comprises the following steps:
step a, after carrying out discharge treatment on waste retired lithium iron phosphate batteries, disassembling the waste retired lithium iron phosphate batteries to obtain battery cores, then carrying out constant temperature on the battery cores in a vacuum tank for 4 hours at 150 ℃, pyrolyzing residual electrolyte and binder in the battery cores, then carrying out disassembly and separation to obtain battery positive plates, crushing the positive plates by a crusher, screening by a screen mesh with 1mm, carrying out airflow separation, and collecting to obtain aluminum-containing lithium iron phosphate waste powder;
step B, mixing 100g of the aluminum-containing lithium iron phosphate waste powder (with F content of 1.1% and Al content of 0.5%) with 600mL of 1mol/L sodium hydroxide solution, adding the mixture into a hydrothermal kettle, reacting for 4 hours at 200 ℃, filtering after the reaction is finished to obtain a leaching solution A and a leaching residue B, and analyzing a small amount of leaching solution A by a fluoride ion electrode to obtain a leaching rate of 99.89% of fluorine;
step c, mixing leaching residue B and lithium dihydrogen phosphate solution, adding the mixture into a hydrothermal kettle, wherein the molar ratio of P in lithium dihydrogen phosphate to Fe in leaching residue is 0.5:1, adding a reducing agent hydrazine hydrate with the molar amount of Fe in leaching residue of 1%, finally adjusting the liquid-solid ratio of the solution to be 6mL/g, and reacting at 180 ℃ for 4 hours to obtain an intermediate product;
step d, calcining the intermediate product in a gradient way under nitrogen atmosphere, wherein the first gradient calcining temperature is 300 ℃, the calcining time is 6h, the second gradient calcining temperature is 600 ℃, the calcining time is 12h, and the aluminum doped lithium iron phosphate positive electrode material is obtained, and the element content of the final product is analyzed through ICP test, wherein the prepared final product is Li 1-X Fe 1-X Al X PO 4 /C, where x=0.011.
A lithium ion battery (CR 2032) was prepared in the same manner as in example 1, and a charge and discharge test was performed. And (3) performing rate cycle performance tests at current densities of 0.1C, 0.2C, 0.5C and 1C in a voltage interval of 2.5-3.6V respectively, wherein the measured specific discharge capacities are 155mAh/g, 145mAh/g, 140mAh/g and 138mAh/g respectively.
Example 3
A resource utilization method of waste lithium iron phosphate batteries comprises the following steps:
step a, after carrying out discharge treatment on waste retired lithium iron phosphate batteries, disassembling the waste retired lithium iron phosphate batteries to obtain battery cores, then carrying out constant temperature on the battery cores in a vacuum tank for 6 hours at 100 ℃, pyrolyzing residual electrolyte and binder in the battery cores, then carrying out disassembly and separation to obtain battery positive plates, crushing the positive plates by a crusher, screening by a screen mesh with 1.5mm, carrying out airflow separation, and collecting to obtain aluminum-containing lithium iron phosphate waste powder, wherein the structural components are shown in figure 2;
step B, mixing 100g of the aluminum-containing lithium iron phosphate waste powder (with F content of 1.3 percent and Al content of 1 percent) with 400mL of 1.5mol/L sodium hydroxide solution, adding the mixture into a hydrothermal kettle, reacting for 5 hours at 200 ℃, filtering after the reaction is finished to obtain a leaching solution A and a leaching residue B, and analyzing a small amount of leaching solution A by a fluoride ion electrode to obtain a leaching rate of 99.24 percent of fluorine;
step c, mixing leaching residue B and lithium dihydrogen phosphate solution, adding the mixture into a hydrothermal kettle, wherein the molar ratio of P in lithium dihydrogen phosphate to Fe in leaching residue is 0.6:1, adding reducing agent hydrazine hydrate with the molar amount of Fe in leaching residue of 3%, finally adjusting the liquid-solid ratio of the solution to 8mL/g, and reacting at 200 ℃ for 3.5h to obtain an intermediate product;
step d, calcining the intermediate product in a gradient way under nitrogen atmosphere, wherein the first gradient calcining temperature is 500 ℃, the calcining time is 2 hours, the second gradient calcining temperature is 800 ℃, the calcining time is 8 hours, and the aluminum doped lithium iron phosphate positive electrode material is obtained, and the element content of the final product is analyzed through ICP test, wherein the prepared final product is Li 1-X Fe 1-X Al X PO 4 and/C, wherein x=0.019.
A lithium ion battery (CR 2032) was prepared in the same manner as in example 1, and a charge and discharge test was performed. And (3) performing rate cycle performance tests at current densities of 0.1C, 0.2C, 0.5C and 1C in a voltage interval of 2.5-3.6V respectively, wherein the measured specific discharge capacities are 138mAh/g, 130mAh/g, 125mAh/g and 120mAh/g respectively.
Example 4
A resource utilization method of waste lithium iron phosphate batteries comprises the following steps:
step a, after carrying out discharge treatment on waste retired lithium iron phosphate batteries, disassembling the waste retired lithium iron phosphate batteries to obtain battery cores, then carrying out constant temperature on the battery cores in a vacuum tank for 8 hours at 80 ℃, pyrolyzing residual electrolyte and binder in the battery cores, then carrying out disassembly and separation to obtain battery positive plates, crushing the positive plates by a crusher, screening by a screen mesh with 2mm, carrying out airflow separation, and collecting to obtain aluminum-containing lithium iron phosphate waste powder, wherein the structural components are shown in figure 2;
step B, mixing 100g of the aluminum-containing lithium iron phosphate waste powder (with F content of 1.5% and Al content of 1.5%) with 200mL of 5mol/L sodium hydroxide solution, adding the mixture into a hydrothermal kettle, reacting for 4 hours at 150 ℃, filtering after the reaction is finished to obtain a leaching solution A and a leaching residue B, and analyzing a small amount of leaching solution A by a fluoride ion electrode to obtain a leaching rate of 98.06% of fluorine;
step c, mixing leaching residue B and lithium dihydrogen phosphate solution, adding the mixture into a hydrothermal kettle, wherein the molar ratio of P in lithium dihydrogen phosphate to Fe in leaching residue is 0.8:1, adding a reducing agent hydrazine hydrate with the molar amount of Fe in leaching residue being 2%, finally adjusting the liquid-solid ratio of the solution to 10mL/g, and reacting at 200 ℃ for 2 hours to obtain an intermediate product;
step d, calcining the intermediate product in a gradient way under nitrogen atmosphere, wherein the first gradient calcining temperature is 400 ℃, the calcining time is 3h, the second gradient calcining temperature is 700 ℃, the calcining time is 11h, and the aluminum doped lithium iron phosphate positive electrode material is obtained, and the element content of the final product is analyzed through ICP test, wherein the prepared final product is Li 1-X Fe 1-X Al X PO 4 C, wherein x=0.0275.
A lithium ion battery (CR 2032) was prepared in the same manner as in example 1, and a charge and discharge test was performed. And (3) performing rate cycle performance tests at current densities of 0.1C, 0.2C, 0.5C and 1C in a voltage interval of 2.5-3.6V respectively, wherein the measured specific discharge capacities are 130mAh/g, 122mAh/g, 113mAh/g and 105mAh/g respectively.
Comparative example 1
The comparative example provides a resource utilization method of waste lithium iron phosphate batteries, which is different from the method in the embodiment 1 only in that the raw material is aluminum-free lithium iron phosphate waste powder, and specifically comprises the following steps:
step a, after carrying out discharge treatment on a waste retired lithium iron phosphate battery, disassembling to obtain a battery core, then carrying out constant temperature on the battery core in a vacuum tank at 200 ℃ for 3 hours, pyrolyzing residual electrolyte and binder in the battery core, then carrying out disassembly and separation to obtain a battery positive plate, and physically scraping and collecting aluminum-free positive powder to obtain aluminum-free lithium iron phosphate waste powder;
step B, mixing 100g of the lithium iron phosphate waste powder with 800mL of 0.75mol/L sodium hydroxide solution, adding the mixture into a hydrothermal kettle, reacting for 6 hours at 150 ℃, filtering after the reaction is finished to obtain a leaching solution A and a leaching residue B, and analyzing a small amount of leaching solution A by a fluoride ion electrode to obtain a leaching rate of 99.89% of fluorine;
step c, mixing leaching residue B and lithium dihydrogen phosphate solution, adding the mixture into a hydrothermal kettle, wherein the molar ratio of P in lithium dihydrogen phosphate to Fe in leaching residue is 0.3:1, adding a reducing agent hydrazine hydrate with the molar amount of Fe in leaching residue being 2%, finally adjusting the liquid-solid ratio of the solution to be 4mL/g, and reacting at 150 ℃ for 5 hours to obtain an intermediate product;
and d, carrying out gradient calcination on the intermediate product in nitrogen atmosphere, wherein the first gradient calcination temperature is 350 ℃, the calcination time is 4 hours, the second gradient calcination temperature is 750 ℃, and the calcination time is 10 hours, so as to obtain the regenerated lithium iron phosphate positive electrode material.
A lithium ion battery (CR 2032) was prepared in the same manner as in example 1, and a charge and discharge test was performed. And (3) performing rate cycle performance tests at current densities of 0.1C, 0.2C, 0.5C and 1C in a voltage interval of 2.5-3.6V respectively, wherein the measured specific discharge capacities are 125mAh/g, 120mAh/g, 116mAh/g and 110mAh/g respectively.
Comparative example 2
The comparative example provides a method for recycling waste lithium iron phosphate batteries, which is different from the method in the embodiment 1 only in that the reaction in the step b is a non-hydrothermal kettle reaction, and the steps a and b specifically comprise the following steps:
step a, after carrying out discharge treatment on waste retired lithium iron phosphate batteries, disassembling the waste retired lithium iron phosphate batteries to obtain battery cores, then carrying out constant temperature on the battery cores in a vacuum tank for 3 hours at 200 ℃, pyrolyzing residual electrolyte and binder in the battery cores, then carrying out disassembly and separation to obtain battery positive plates, crushing the positive plates by a crusher, screening by a screen mesh with 0.5mm, carrying out airflow separation, and collecting to obtain aluminum-containing lithium iron phosphate waste powder, wherein the structural components are shown in figure 2;
and B, mixing 100g of the aluminum-containing lithium iron phosphate waste powder (with the F content of 0.75% and the Al content of 0.2%) with 800mL of 0.75mol/L sodium hydroxide solution, reacting for 4 hours at 90 ℃ in a three-neck flask, filtering after the reaction is finished to obtain a leaching solution A and a leaching residue B, and analyzing a small amount of leaching solution A by using a fluoride ion electrode to obtain the leaching rate of fluorine of 24.6%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The method for recycling the waste lithium iron phosphate battery is characterized by comprising the following steps of:
step a, discharging, disassembling, pyrolyzing and sorting the waste lithium iron phosphate battery to obtain a positive plate; crushing and screening the positive plate to obtain aluminum-containing lithium iron phosphate waste powder;
step b, adding the aluminum-containing lithium iron phosphate waste powder into an alkaline solution, uniformly dispersing, performing hydrothermal reaction at 150-250 ℃, and performing solid-liquid separation to obtain leaching liquid and leaching residues;
step c, adding an acidic phosphate solution and a reducing agent into the leaching slag, uniformly mixing, performing hydrothermal reaction at 100-200 ℃, performing solid-liquid separation, and drying to obtain an intermediate product;
and d, calcining the intermediate product in an inert atmosphere to obtain the aluminum-doped lithium iron phosphate anode material.
2. The method for recycling the waste lithium iron phosphate battery according to claim 1, wherein the step a is specifically as follows: discharging and disassembling the waste lithium iron phosphate battery to obtain a battery core; pyrolyzing the battery cell under vacuum condition, and then separating to obtain a battery positive plate; and crushing, screening and air flow sorting the battery positive plate to obtain aluminum-containing lithium iron phosphate waste powder.
3. The method for recycling waste lithium iron phosphate batteries according to claim 1 or 2, wherein in the step a, the pyrolysis temperature is 50-200 ℃.
4. The recycling method of the waste lithium iron phosphate battery according to claim 1 or 2, wherein in the step a, the aluminum content in the aluminum-containing lithium iron phosphate waste powder is 0.2-3 wt% and the fluorine content is 0.15-2 wt%.
5. The method for recycling the waste lithium iron phosphate battery according to claim 1, wherein in the step b, the concentration of the alkaline solution is 0.5 mol/L-6 mol/L; and/or
In the step b, the alkaline solution is at least one of sodium hydroxide solution, potassium hydroxide solution or lithium hydroxide solution.
6. The recycling method of the waste lithium iron phosphate battery according to claim 1 or 5, wherein in the step b, the mass volume ratio of the aluminum-containing lithium iron phosphate waste powder to the alkaline solution is 1g (1-10) mL; and/or
In the step b, the time of the hydrothermal reaction is 3-6 hours.
7. The method for recycling the waste lithium iron phosphate battery according to claim 1, wherein in the step c, the acidic phosphate solution is a lithium dihydrogen phosphate solution; and/or
In the step c, the solid-to-liquid ratio of the hydrothermal reaction system is 1g (3-10) mL; and/or
In the step c, the time of the hydrothermal reaction is 2-5 hours; and/or
In the step c, the reducing agent is at least one of glucose, sucrose, citric acid, ascorbic acid or hydrazine hydrate.
8. The method for recycling the waste lithium iron phosphate battery according to claim 1 or 7, wherein in the step c, the molar ratio of P in the acidic phosphate solution to Fe in the leaching residue is (0.2-0.9): 1; and/or
In the step c, the mol ratio of the reducing agent to Fe in the leaching slag is (0.01-0.03): 1.
9. The method for recycling the waste lithium iron phosphate battery according to claim 1, wherein in the step d, the calcination temperature is 500-800 ℃ and the calcination time is 1-2 h; and/or
In the step d, the aluminum-doped lithium iron phosphate positive electrode material is Li 1-X Fe 1-X Al X PO 4 C, wherein 0<X<0.05。
10. The method for recycling waste lithium iron phosphate batteries according to claim 1 or 9, wherein in the step d, the calcining adopts a segmented calcining mode, and the specific steps are as follows: calcining the intermediate product at 300-500 ℃ for 2-6 hours, and then calcining at 600-800 ℃ for 8-12 hours to obtain the aluminum-doped lithium iron phosphate anode material.
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