CN115148483A - Preparation of LiFe by using waste lithium iron phosphate battery 5 O 8 Method for producing magnetic material - Google Patents
Preparation of LiFe by using waste lithium iron phosphate battery 5 O 8 Method for producing magnetic material Download PDFInfo
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- CN115148483A CN115148483A CN202210900251.XA CN202210900251A CN115148483A CN 115148483 A CN115148483 A CN 115148483A CN 202210900251 A CN202210900251 A CN 202210900251A CN 115148483 A CN115148483 A CN 115148483A
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- lithium iron
- magnetic material
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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 86
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 239000000696 magnetic material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 238000000498 ball milling Methods 0.000 claims description 25
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 16
- 229940032296 ferric chloride Drugs 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910010710 LiFePO Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000004137 mechanical activation Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a method for preparing LiFe by using waste lithium iron phosphate batteries 5 O 8 A method for magnetic materials belongs to a new solid waste recycling technology in the fields of environmental protection and comprehensive utilization of resources. The core comprises the mechanochemical activation and calcination of the lithium iron phosphate anode material to generate LiFe 5 O 8 And the like. The method is characterized in that: disassembling a waste lithium iron phosphate battery to obtain positive electrode powder, mixing the positive electrode powder with a grinding aid of a certain mass, performing mechanical activation, leaching, adjusting the proportion of lithium and iron in a lithium-containing filtrate, adding an additive, performing evaporation concentration in a water bath, and calcining a sample in a muffle furnace to obtain LiFe 5 O 8 A magnetic material. The invention has simple operation, mild reaction condition and strong economic and practical applicability, and the prepared LiFe 5 O 8 Has good magnetism.
Description
Technical Field
The invention relates to a method for preparing LiFe by utilizing waste lithium iron phosphate batteries through mechanical activation 5 O 8 A process for preparing a magnetic material belongs to a novel solid waste treatment technology in the field of environmental protection and comprehensive resource utilization, and is suitable for resource recycling of a waste lithium iron phosphate battery positive electrode material.
Background
With the popularization of 3C products and new energy automobiles, the demand of lithium ion batteries is increasing day by day.In recent years, lithium iron phosphate batteries stand out from their advantages in terms of cost, cycle performance, safety performance and the like, and have a market share that is equal to that of ternary batteries. However, the life of the lithium ion power battery is generally about 5 years, and a large number of lithium ion batteries are already out of service at present. Therefore, the resource utilization of the waste lithium ion battery can not only recover corresponding resources and reduce the exploitation of natural resources, but also reduce the environmental burden, and has great significance. The existing recovery method of the waste lithium iron phosphate battery mainly comprises element recovery, high-temperature regeneration and other methods. The most studied element recovery is the hydrometallurgical process, which is mainly used for recovering Fe in lithium iron phosphate under the action of a strong acid and strong oxidant system 2+ Is oxidized to Fe 3+ Lithium ions are extracted from the crystal lattice of the iron phosphate and then from the solution as Li 2 CO 3 And Li 3 PO 4 Recovering lithium in the form of (1). The high-temperature regeneration is mainly to directly treat the recycled lithium iron phosphate anode material at high temperature in an inert atmosphere, or to calcine the recycled lithium iron phosphate anode material at high temperature in an inert atmosphere after supplementing a proper lithium source, iron source or phosphorus source. The high-temperature treatment process is simple, the operation is easy, a large amount of acid and alkali is not needed, but copper and aluminum impurities have certain influence on the performance of the repaired lithium iron phosphate anode material, the high-temperature treatment cost and the material purification cost are high, and tail gas treatment is needed.
The mechanochemical method is to excite the material reaction activity by mechanical force such as friction, extrusion, shearing, impact and the like, thereby inducing the chemical reaction to proceed. The mechanochemical method is widely applied to the fields of metal smelting, material synthesis, waste treatment and the like. Therefore, the mechanochemical method is expected to become an economic and green process for recycling waste lithium iron phosphate.
LiFe 5 O 8 The magnetic material has wide application in the fields of microwave radar and the like, but currently LiFe 5 O 8 The magnetic material is mostly prepared by synthesizing chemical reagents, lithium and iron are finally calcined in a nitrate form by a gel sol method, the process is complicated, and the production cost is increased.
The economic and green recovery problem of the waste lithium ion batteryThe invention develops a method for selectively extracting lithium from waste lithium iron phosphate batteries by using mechanical activation without using strong acid and strong oxidant and directly preparing LiFe 5 O 8 A method of making a magnetic material. The method is simple to operate, mild in reaction condition, green, environment-friendly, economical and strong in practicability.
Disclosure of Invention
Aiming at the problem of economic and green recovery of waste lithium iron phosphate batteries, the invention provides a method for preparing LiFe by using waste lithium iron phosphate batteries 5 O 8 The method for preparing the magnetic material avoids the use of strong acid and strong oxidant in the recovery process, has high extraction rate of lithium, and can prepare the LiFe with high added value by utilizing the waste lithium iron phosphate battery 5 O 8 A magnetic material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
preparation of LiFe by using waste lithium iron phosphate battery 5 O 8 A method of magnetic material, comprising:
step S1, separating lithium iron phosphate anode powder: discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
step S2, ball-milling and activating lithium iron phosphate anode powder: ball-milling the lithium iron phosphate anode powder obtained in the step S1 and a grinding aid with a certain mass together, leaching the ball-milled sample by using distilled water after ball-milling for a certain time, and filtering to obtain iron phosphate residues and lithium-containing filtrate;
step S3, liFe 5 O 8 Preparing precursor gel: adjusting the proportion of lithium and iron in the lithium-containing solution obtained in the step S2; adding an organic acid solution, and evaporating excessive water in a water bath to obtain a gel sample;
step S4, liFe 5 O 8 Synthesizing: placing the gel sample obtained in the step S3 in a muffle furnace for calcining to obtain LiFe 5 O 8 A magnetic material.
Preferably, in step S2, the grinding aid is at least one of ferric chloride and ferric chloride hexahydrate.
Preferably, in step S2, the grinding aid is added in an amount of massageMole ratio, iron chloride in grinding aid: lithium iron phosphate powder LiFePO4= 1-5 (such as 1. Too low grinding aid affects the leaching rate of lithium, too high grinding aid wastes raw materials and affects subsequent LiFe 5 O 8 Purity of the magnetic material.
Preferably, in step S2, the ball milling time is 5-120min (e.g., 5min, 10min, 20min, 30min, 60min, 100min, etc.).
The ball milling speed is 200-1000r/min (such as 300r/min, 500r/min, 600r/min, 700r/min, 800r/min, 1000r/min and the like).
Preferably, in step S3, the molar ratio of lithium to iron in the adjusted lithium-containing solution is 1; the organic acid is one or a mixture of more than two of citric acid, oxalic acid and tartaric acid.
Preferably, in step S4, the calcination temperature is 500-1000 ℃ (such as 500 ℃,600 ℃,700 ℃,800 ℃,1000 ℃) and the calcination time is 1-5h (such as 1h, 2h, 3h, 4h, 5 h).
The technical principle of the application comprises the following steps:
ferric chloride or ferric chloride hexahydrate is used as a grinding aid, and waste lithium iron phosphate anode powder and the grinding aid are activated under the action of mechanical forces such as collision, friction, shearing and the like, so that electrons are transferred, and Fe 2+ Is oxidized to Fe 3+ The ferric phosphate still keeps an olivine structure, and lithium ions can be smoothly removed from the crystal lattice of the ferric phosphate, so that the selective extraction of lithium is realized. Because the positive ions in the ball milling leachate only comprise lithium ions and iron ions, the lithium ions and the iron ions are directly added into the organic acid solution and then evaporated to obtain a gel substance, and the lithium ferrite magnetic material with uniform particles can be obtained after calcination.
Compared with the prior art, the scheme of the application has the following beneficial effects:
1. the process is simple and easy to operate;
2. the reaction condition is mild, economic and environment-friendly;
3. the selective recovery of lithium can be realized without using strong acid, strong base and strong oxidant;
4. can utilize the waste lithium iron phosphate batteries to prepare the magnetic functional material LiFe with higher added value 5 O 8 。
Drawings
FIG. 1 shows a process for preparing LiFe by using waste lithium iron phosphate batteries provided by the application 5 O 8 Process flow diagram for magnetic materials
Fig. 2 is an XRD pattern of the waste lithium iron phosphate positive electrode material used in the preferred embodiment of the present application
FIG. 3 is a LiFe prepared in the preferred embodiment of the present application 5 O 8 XRD pattern of
FIG. 4 is a LiFe prepared in the preferred embodiment of the present application 5 O 8 SEM image of
FIG. 5 is a LiFe prepared in the preferred embodiment of the present application 5 O 8 Magnetic hysteresis loop
FIG. 6 is an XRD pattern of a sample prepared in a comparative example of the present application
Detailed Description
FIG. 1 shows that lithium carbonate is recovered and LiFe is prepared by using waste lithium iron phosphate batteries provided by the application 5 O 8 A process flow diagram for a magnetic material, comprising essentially the steps of:
step S1, discharging, disassembling and stripping a waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
step S2, ball-milling the lithium iron phosphate anode powder obtained in the step S1 and a grinding aid with a certain mass together, leaching a ball-milled sample by using distilled water after ball-milling for a certain time, and filtering to obtain residues of iron phosphate and lithium-containing filtrate;
s3, adjusting the proportion of lithium and iron in the lithium-containing solution obtained in the step S2; adding an organic acid solution, and evaporating excessive water in a water bath to obtain a gel sample;
and S4, placing the gel sample obtained in the step S3 into a muffle furnace for calcining to obtain LiFe 5 O 8 A magnetic material.
Preferably, in step S2, the grinding aid is at least one of ferric chloride and ferric chloride hexahydrate.
Preferably, in step S2, the first step,the weight of the grinding aid is that the ratio of the grinding aid to lithium iron phosphate powder = 1-5. Too low grinding aid affects the leaching rate of lithium, too high grinding aid wastes raw materials and affects the subsequent LiFe 5 O 8 Purity of the magnetic material.
Preferably, in the step S2, the ball milling time is 5-120min; the ball milling speed is 200-1000r/min.
Preferably, in step S3, the molar ratio of lithium iron is 1; the organic acid is one or a mixture of more than two of citric acid, oxalic acid and tartaric acid.
Preferably, in step S4, the calcination temperature is 500-1000 ℃ and the calcination time is 1-5h.
The present application will be described in further detail by way of examples with reference to the accompanying drawings, and the scope of the present application includes, but is not limited to, the following examples. The invention is not limited to the above embodiments, but may be modified in various ways.
The various reagents and starting materials used in the examples are all commercially available products.
The XRD pattern of the lithium iron phosphate cathode material used in the examples is shown in fig. 2.
Example 1:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride at a rotating speed of 500r/min for 60min according to a mass ratio of 1; the leaching rate of lithium is 95.18 percent;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) Then placing the gel-like sample in the step (3) in a muffle furnace, and calcining for 3h at 700 ℃ to obtain LiFe 5 O 8 A magnetic material.
Example 2:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride at a rotating speed of 600r/min for 30min according to a mass ratio of 1.2, leaching the ball-milled sample with distilled water, and filtering to obtain residues of ferric phosphate and lithium-containing filtrate; the leaching rate of lithium is 97.44%;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) Then placing the gel-like sample obtained in the step (3) in a muffle furnace, and calcining for 2h at 800 ℃ to obtain LiFe 5 O 8 A magnetic material.
FIG. 3 shows LiFe obtained in this example 5 O 8 XRD pattern of magnetic material, FIG. 4 is LiFe obtained in this example 5 O 8 SEM image of magnetic material, FIG. 5 is LiFe obtained in this example 5 O 8 The magnetic material had a hysteresis loop with a saturation magnetization of 49.23emu/g.
Example 3:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 30min at the rotating speed of 700r/min according to the mass ratio of 1.5; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 95.54 percent;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) And (4) putting the gel sample obtained in the step (3) into a muffle furnace, and calcining for 2h at 900 ℃ to obtain LiFe 5 O 8 A magnetic material.
Example 4:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 60min at the rotating speed of 800r/min according to the mass ratio of 1.2; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 97.66%;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) And (4) putting the gel sample obtained in the step (3) into a muffle furnace, and calcining for 2h at 800 ℃ to obtain LiFe 5 O 8 A magnetic material.
Example 5:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 60min at the rotating speed of 600r/min according to the mass ratio of 1; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 95.77%;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding oxalic acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) And (4) putting the gel sample obtained in the step (3) into a muffle furnace, and calcining for 4 hours at 600 ℃ to obtain LiFe 5 O 8 A magnetic material.
Example 6:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 120min at the rotating speed of 600r/min according to the mass ratio of 1.2; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 97.64%;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) And (4) putting the gel sample obtained in the step (3) into a muffle furnace, and calcining for 1h at 1000 ℃ to obtain LiFe 5 O 8 A magnetic material.
Example 7:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride hexahydrate for 60min at the rotating speed of 600r/min according to the mass ratio of 1.5; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 96.88%;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding oxalic acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) And (4) putting the gel sample obtained in the step (3) into a muffle furnace, and calcining for 2h at 900 ℃ to obtain LiFe 5 O 8 A magnetic material.
Example 8:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride hexahydrate for 120min at the rotating speed of 800r/min according to the mass ratio of 1; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 98.53 percent;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) And (4) putting the gel sample obtained in the step (3) into a muffle furnace, and calcining for 2h at 850 ℃ to obtain LiFe 5 O 8 A magnetic material.
Comparative example 1:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride hexahydrate for 120min at the rotating speed of 600r/min according to the mass ratio of 3; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 30.22%; the LiFe is not prepared continuously because the leaching rate of lithium is too low due to too low addition amount of the grinding aid 5 O 8 A magnetic material.
Comparative example 2:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Putting lithium iron phosphate anode powder and ferric chloride into 100ml of water according to the mass ratio of 1; filtering the solution to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium was 86.63%; because the direct leaching is carried out, the mechanical activation is not carried out, and the leaching rate of the lithium is lower;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample; then placing the sample in a muffle furnace, and calcining for 2h at 800 ℃ to obtain LiFe 5 O 8 A magnetic material.
Comparative example 3:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 120min at the rotating speed of 600r/min according to the mass ratio of 1.2; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 97.64%;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) Then placing the sample in a muffle furnace, calcining for 3h at 800 ℃ to obtain the product containing a large amount of alpha-Fe 2 O 3 A mixture of impurities. This is because the lithium content is too low, and oxygen reacts with iron to form α -Fe during calcination 2 O 3 Impurities.
Comparative example 4:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 120min at the rotating speed of 600r/min according to the mass ratio of 1.2; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 97.64 percent;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) Then placing the sample in a muffle furnace, calcining for 3h at 1200 ℃ to obtain the product containing a large amount of Fe 3 O 4 And alpha-Fe 2 O 3 A mixture of impurities. This is because the calcination temperature is too high and lithium is volatilized in the form of steam, which results in too little lithium content in the sample and large amounts of impurities generated by calcination.
Comparative example 5:
(1) Discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
(2) Ball-milling lithium iron phosphate anode powder and ferric chloride for 120min at the rotating speed of 600r/min according to the mass ratio of 1.2; leaching the ball-milled sample with distilled water, and filtering to obtain iron phosphate residue and lithium-containing filtrate; the leaching rate of lithium is 97.64 percent;
(3) Adjusting the molar ratio of lithium to iron of the lithium-containing solution in the step (2) to be 1; adding citric acid solution, and evaporating excessive water in water bath to obtain a gel sample;
(4) Then placing the sample in a muffle furnace, calcining for 2h at 350 ℃ to obtain the product containing a large amount of alpha-Fe 2 O 3 A mixture of impurities. This is because the calcination temperature is too low, the energy is not sufficient, and the lithium and iron lattices cannot be recombined to form new substances.
Fig. 6 is an XRD pattern of the sample prepared in this comparative example.
The process parameters, leaching rate and LiFe of examples 1 to 8 and comparative examples 1 to 5 were measured 5 O 8 The quality of the magnetic material was measured and the results are shown in Table 1.
TABLE 1
The method is suitable for recycling various lithium iron phosphate batteries, and the invention is not limited to the above examples, can be implemented and has good effect. The foregoing embodiments and description have been provided merely to illustrate the principles of the invention and various changes and modifications may be made therein without departing from the scope of the invention.
Claims (5)
1. Preparation of LiFe by using waste lithium iron phosphate battery 5 O 8 A method of magnetic material, comprising:
step S1, separating lithium iron phosphate anode powder: discharging, disassembling and stripping the waste lithium iron phosphate battery to obtain lithium iron phosphate anode powder;
step S2, ball milling and activating lithium iron phosphate anode powder: ball-milling the lithium iron phosphate anode powder obtained in the step S1 and a grinding aid together to obtain a ball-milled activated sample, leaching the ball-milled activated sample with distilled water, and filtering to obtain iron phosphate residues and lithium-containing filtrate;
step S3, liFe 5 O 8 Preparing precursor gel: adjusting the proportion of lithium and iron in the lithium-containing solution obtained in the step S2, then adding an organic acid solution, and evaporating excessive water to obtain a gel-like sample;
step S4, liFe 5 O 8 Synthesizing: putting the gel sample obtained in the step S3 into a muffle furnace for calcining to obtain LiFe 5 O 8 A magnetic material.
2. The method for preparing LiFe by using waste lithium iron phosphate batteries according to claim 1 5 O 8 The method for preparing the magnetic material is characterized in that in the step S2, the grinding aid is ferric chloride, ferric chloride hexahydrate or a mixture of the ferric chloride and the ferric chloride hexahydrate, wherein ferric chloride in the grinding aid and LiFePO in lithium iron phosphate powder 4 1 to 5.
3. The method for preparing LiFe by using waste lithium iron phosphate batteries according to claim 1 5 O 8 Of magnetic materialsThe method is characterized in that in the step S2, the ball milling time is 5-120min, and the rotating speed is 200-1000r/min.
4. The method for preparing LiFe by using the waste lithium iron phosphate batteries according to claim 1 5 O 8 The method for preparing the magnetic material is characterized in that in the step S3, the molar ratio of lithium to iron in the adjusted lithium-containing solution is 1; the organic acid is one or a mixture of more than two of citric acid, oxalic acid and tartaric acid.
5. The method for preparing LiFe by using waste lithium iron phosphate batteries according to claim 1 5 O 8 The method for preparing the magnetic material is characterized in that in the step S4, the calcining temperature is 500-1000 ℃, and the calcining time is 1-5h.
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