CN117550571A - Method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder - Google Patents
Method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder Download PDFInfo
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- CN117550571A CN117550571A CN202311693847.8A CN202311693847A CN117550571A CN 117550571 A CN117550571 A CN 117550571A CN 202311693847 A CN202311693847 A CN 202311693847A CN 117550571 A CN117550571 A CN 117550571A
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- lithium
- dihydrogen phosphate
- lithium dihydrogen
- phosphate
- battery powder
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- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 title claims abstract description 103
- 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 46
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000843 powder Substances 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 239000000706 filtrate Substances 0.000 claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000005955 Ferric phosphate Substances 0.000 claims description 8
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 8
- 229940032958 ferric phosphate Drugs 0.000 claims description 8
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- -1 CN113321194B Chemical compound 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
- C01B25/303—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates with elimination of impurities
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
Abstract
The invention belongs to the technical field of recycling of lithium batteries, and discloses a method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder, which comprises the following steps: (1) Fully contacting lithium iron phosphate battery powder with phosphoric acid in an aqueous solution, stirring at constant temperature to dissolve lithium iron phosphate, and carrying out solid-liquid separation to obtain a lithium-containing filtrate; (2) Adding hydrogen peroxide solution into the lithium-containing filtrate, oxidizing ferrous ions into ferric ions, adding lithium hydroxide to adjust the pH value, and filtering to remove precipitate to obtain filtrate containing lithium dihydrogen phosphate; (3) Evaporating and concentrating the filtrate containing lithium dihydrogen phosphate, slowly cooling and crystallizing, and filtering to obtain a crude product of lithium dihydrogen phosphate; (4) Dissolving the lithium dihydrogen phosphate crude product, adding phosphoric acid to adjust the pH value of the aqueous solution, evaporating, concentrating and crystallizing, filtering to obtain a lithium dihydrogen phosphate wet material, and finally drying to obtain a battery grade lithium dihydrogen phosphate product. The method has the advantages of short process flow, low production cost, high product yield, easy industrial production and better economic benefit.
Description
Technical Field
The invention belongs to the technical field of recycling of lithium batteries, and particularly relates to a method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder.
Background
With the development of new energy technology, new energy automobiles and energy storage devices are rapidly rising, and the demand for lithium ion batteries is also increased. Lithium iron phosphate batteries are widely used because of their low cost, high specific energy, excellent safety performance, and the like. Due to the large-scale use of the lithium iron phosphate battery, the estimated 2025 years, the scrapped lithium iron phosphate battery in the world can reach 136 ten thousand tons, and if the waste lithium iron phosphate battery cannot be effectively solved, a large amount of metal resources are lost, and the environment is polluted. Therefore, the efficient and economical waste LiFePO is developed 4 Battery recycling processes are one of the global hot spots.
At present, the lithium dihydrogen phosphate is used as a lithium source for preparing lithium iron phosphate, so that a large amount of ammonia gas generated by using ammonium dihydrogen phosphate can be avoided, the environment is polluted, and a lithium source and a phosphorus source can be simultaneously provided, so that the lithium iron phosphate has good process stability and uniformity. However, the conventional preparation process of battery grade lithium dihydrogen phosphate is mainly prepared by neutralization and evaporative crystallization of phosphoric acid and lithium hydroxide. The process route is longer, the preparation process is complex, and the quality and the yield of the obtained lithium dihydrogen phosphate are difficult to control. CN101638225B discloses a method for preparing battery grade lithium dihydrogen phosphate by using lithium carbonate and phosphoric acid as raw materials, CN102351160B discloses a method for preparing battery grade lithium dihydrogen phosphate by using high-purity lithium carbonate precipitation mother liquor, CN103553016B discloses a method for preparing lithium dihydrogen phosphate by using lithium hydroxide, monoammonium phosphate and polyphosphoric acid as raw materials, and taking the lithium dihydrogen phosphate as an intermediate product of a lithium iron phosphate positive electrode material. In addition, in the prior art, waste lithium iron phosphate battery powder obtained from waste lithium iron phosphate batteries is used as a raw material, and lithium carbonate and/or iron phosphate, such as CN113321194B, CN114988382B, are obtained through various processes; the method for preparing battery grade lithium dihydrogen phosphate by recycling all elements of waste lithium iron phosphate disclosed in CN116462169A has the advantages of excessive process steps, complex preparation process, high requirements on operators and difficult control of the production process.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder, which has the advantages of high efficiency, short process, low cost and environmental protection.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
adding waste lithium iron phosphate battery powder (60 meshes) into deionized water according to a solid-liquid mass ratio of 1 (1-5), and fully stirring; then according to mole ratio of Li + :H 3 PO 4 Adding phosphoric acid solution into (1-6), stirring for 2-6 h at 25-60 ℃, and filtering to obtain lithium-containing filtrate and filter residues containing insoluble impurities such as carbon;
step (2), according to the mole ratio of Fe 2+ :H 2 O 2 Adding 30wt% hydrogen peroxide into the lithium-containing filtrate obtained in the step (1) to completely oxidize ferrous ions into ferric ions, then adding a lithium hydroxide solution to adjust the pH value to 2-3, aging at 70-100 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain a lithium dihydrogen phosphate-containing filtrate;
step (3), heating the lithium dihydrogen phosphate-containing filtrate obtained in the step (2) to 120-135 ℃, evaporating and concentrating until crystallization is separated out, then slowly cooling to 40 ℃, and cooling and crystallizing to obtain a lithium dihydrogen phosphate crude product;
step (4), dissolving the lithium dihydrogen phosphate crude product into water, supplementing phosphoric acid to adjust the pH value to 2-3, filtering, heating the filtrate to 120-130 ℃, evaporating and concentrating until crystallization is separated out, then slowly cooling to 35-40 ℃, and filtering to obtain a lithium dihydrogen phosphate wet material; and drying to obtain a battery grade lithium dihydrogen phosphate product.
Preferably, in the step (1), the solid-liquid mass ratio of the waste lithium iron phosphate battery powder to the deionized water is 1 (2-4), and more preferably 1:3; li (Li) + :H 3 PO 4 =1, (2 to 5), more preferably 1:3; the concentration of the phosphoric acid solution is 85% (mass percent); the stirring temperature was 25℃and the time was 4 hours.
Preferably, the ageing temperature in step (2) is from 90 to 100 ℃, preferably 100 ℃.
Preferably, the lithium dihydrogen phosphate-containing filtrate in step (3) is heated to 125-135 ℃, preferably 135 ℃.
Preferably, the cooling temperature in the step (4) is 40 ℃; the drying temperature is 105-120 ℃, preferably 105 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention prepares the battery grade lithium dihydrogen phosphate by using the waste lithium iron phosphate battery powder, is used for producing the lithium iron phosphate product with stable quality, and realizes the resource utilization of the waste lithium iron phosphate.
(2) Compared with the prior art, the method directly prepares the battery grade lithium dihydrogen phosphate through acid leaching, iron removal, concentration and crystallization, has simple and efficient process route, and avoids quality and yield loss caused by complex preparation process. After the steps 1 and 2, the obtained lithium dihydrogen phosphate-containing filtrate has extremely high content of lithium dihydrogen phosphate and extremely low content of impurities, and metal elements such as iron and the like in the waste battery powder are basically removed in a precipitation form after being treated by hydrogen peroxide solution and lithium hydroxide solution.
(3) According to the invention, the lithium dihydrogen phosphate is prepared by utilizing the solubility of the lithium dihydrogen phosphate and the concentration and solubility difference of the lithium dihydrogen phosphate and other metal salts, and the lithium dihydrogen phosphate is evaporated and crystallized, and raw materials containing other metal elements (such as sodium and potassium) or non-metal elements (such as sulfur, chlorine and nitrogen) are not used in the process, so that the introduction of impurities can be prevented, and the lithium dihydrogen phosphate with high purity can be conveniently obtained.
(4) In the invention, the addition amount of deionized water is different and the solid-liquid ratio of the reaction is different, so that the reaction and the reaction products are obviously affected. When the liquid-solid ratio is small, the solid product can cover part of reactants, so that the reactants cannot contact with the liquid phase, the reaction is insufficient, and the lithium leaching rate is reduced; when the liquid-solid ratio is increased to a certain value, the reaction is fully carried out, and the lithium leaching rate gradually becomes stable. If the solid-liquid ratio is continuously improved, the amount of wastewater is increased, and the economic cost is increased.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples.
In each example, the waste lithium iron phosphate battery powder raw material is derived from Tianjin Baud Rui technology Co., ltd, wherein the content of each metal element is shown in Table 1.
TABLE 1 content of metallic elements (mass%) in raw materials (60 mesh) of waste lithium iron phosphate battery powder
| Li | Fe | Cu | Al | Na | Ca | Ni | Co | Mn |
| 2.693 | 23.472 | 2.076 | 1.379 | 0.365 | 0.075 | 0.130 | 0.065 | 0.391 |
Example 1
A method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
(1) 300g of lithium iron phosphate battery powder (60 meshes) is weighed, added into 900g of deionized water, fully stirred, then 402.7g of 85wt% phosphoric acid is added, stirred for 4 hours at 25 ℃, and filtered to obtain filtrate and filter residue (containing carbon powder) containing lithium;
(2) Adding 127g of 30wt% hydrogen peroxide solution into the lithium-containing filtrate, regulating the pH to 2 by using 1mol/L lithium hydroxide solution, aging at 90 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain lithium dihydrogen phosphate-containing filtrate;
(3) Heating the lithium dihydrogen phosphate-containing filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and cooling for crystallization to obtain a lithium dihydrogen phosphate crude product;
(4) Dissolving the crude product of lithium dihydrogen phosphate into water, adding 85wt% phosphoric acid to adjust the pH to 2, filtering, heating the filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and filtering to obtain wet product of lithium dihydrogen phosphate (impurities such as copper, sodium, calcium, nickel, cobalt, manganese and the like are removed in the process); drying at 105 ℃ to obtain a battery grade lithium dihydrogen phosphate product. The composition analysis table of the battery grade lithium dihydrogen phosphate is shown in table 2, the product quality meets YS/T967-2014, the leaching rate of lithium is 98%, and the total recovery rate can reach 95%.
Example 2
A method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
(1) 300g of lithium iron phosphate battery powder (60 meshes) is weighed, added into 900g of deionized water, fully stirred, then 671.2g of 85wt% phosphoric acid is added, stirred for 4 hours at 25 ℃, and filtered to obtain filtrate and filter residue (carbon-containing powder) containing lithium;
(2) Adding 127g of 30wt% hydrogen peroxide solution into the lithium-containing filtrate, regulating the pH to 2 by using 1mol/L lithium hydroxide solution, aging at 90 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain lithium dihydrogen phosphate-containing filtrate;
(3) Heating the filtrate containing lithium dihydrogen phosphate to 135 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and cooling for crystallization to obtain a crude product of lithium dihydrogen phosphate;
(4) Dissolving the crude product of lithium dihydrogen phosphate into water, adding 85wt% phosphoric acid to adjust the pH to 2, filtering, heating the filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and filtering to obtain wet product of lithium dihydrogen phosphate (impurities such as copper, sodium, calcium, nickel, cobalt, manganese and the like are removed in the process); drying at 105 ℃ to obtain a battery grade lithium dihydrogen phosphate product. The composition analysis table of the battery grade lithium dihydrogen phosphate is shown in table 2, the product quality meets YS/T967-2014, the leaching rate of lithium is 97%, and the lithium recovery rate can reach 96%.
Example 3
A method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
(1) 300g of lithium iron phosphate battery powder (60 meshes) is weighed, added into 900g of deionized water, fully stirred, then 402.7g of 85wt% phosphoric acid is added, stirred for 4 hours at 60 ℃, and filtered to obtain filtrate containing lithium and filter residues (carbon powder);
(2) Adding 127g of 30wt% hydrogen peroxide solution into the lithium-containing filtrate, regulating the pH to 2 by using 1mol/L lithium hydroxide solution, aging at 90 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain lithium dihydrogen phosphate-containing filtrate;
(3) Heating the lithium dihydrogen phosphate-containing filtrate to 130 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and cooling for crystallization to obtain a lithium dihydrogen phosphate crude product;
(4) Dissolving the crude lithium dihydrogen phosphate into water, adding 85wt% phosphoric acid to adjust the pH to 2, filtering, heating the filtrate to 120 ℃, evaporating and concentrating until crystals are separated out, slowly cooling to 40 ℃, filtering to obtain a wet lithium dihydrogen phosphate product (impurities such as copper, sodium, calcium, nickel, cobalt, manganese and the like are removed in the process), and drying at 105 ℃ to obtain a battery grade lithium dihydrogen phosphate product. The composition analysis table of the battery grade lithium dihydrogen phosphate of the product is shown in Table 2, the product quality meets YS/T967-2014, the leaching rate of lithium is 97%, and the lithium recovery rate can reach 96%.
Comparative example 1
A method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
(1) 300g of lithium iron phosphate battery powder (60 meshes) is weighed, added into 600g of deionized water, fully stirred, then 402.7g of 85wt% phosphoric acid is added, stirred for 4 hours at 60 ℃, and filtered to obtain filtrate and filter residue (containing carbon powder) containing lithium;
(2) Adding 127g of 30wt% hydrogen peroxide solution into the lithium-containing filtrate, regulating the pH to 2 by using 1mol/L lithium hydroxide solution, aging at 90 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain lithium dihydrogen phosphate-containing filtrate;
(3) Heating the lithium dihydrogen phosphate-containing filtrate to 130 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and cooling for crystallization to obtain a lithium dihydrogen phosphate crude product;
(4) Dissolving the lithium dihydrogen phosphate crude product into water, adding 85wt% phosphoric acid to adjust the pH to 2, filtering, heating the filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and filtering to obtain a lithium dihydrogen phosphate wet product; drying at 105 ℃ to obtain a battery grade lithium dihydrogen phosphate product. The composition analysis table of the battery grade lithium dihydrogen phosphate is shown in Table 2, the product quality meets YS/T967-2014, the leaching rate of lithium is only 75%, and the total yield is 62%.
Comparative example 2
A method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
(1) 300g of lithium iron phosphate battery powder (60 meshes) is weighed, added into 900g of deionized water, fully stirred, then 402.7g of 85wt% phosphoric acid is added, stirred for 4 hours at 25 ℃, and filtered to obtain filtrate and filter residue (containing carbon powder) containing lithium;
(2) Adding 127g of 30wt% hydrogen peroxide solution into the lithium-containing filtrate, regulating the pH to 2 by using 1mol/L lithium hydroxide solution, aging at 90 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain lithium dihydrogen phosphate-containing filtrate;
(3) Heating the lithium dihydrogen phosphate-containing filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and cooling for crystallization to obtain a lithium dihydrogen phosphate crude product;
(4) Dissolving the lithium dihydrogen phosphate crude product into water, adding 85wt% phosphoric acid to adjust the pH to 2, filtering, heating the filtrate to 80 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and filtering to obtain a lithium dihydrogen phosphate wet product; drying at 105 ℃ to obtain a battery grade lithium dihydrogen phosphate product. The composition analysis table of the battery grade lithium dihydrogen phosphate is shown in Table 2, the product quality does not meet YS/T967-2014, the leaching rate of lithium is 97%, and the total recovery rate is 95%.
Comparative example 3
A method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder comprises the following steps:
(1) 300g of lithium iron phosphate battery powder (60 meshes) is weighed, added into 900g of deionized water, fully stirred, then 402.7g of 85wt% phosphoric acid is added, stirred for 4 hours at 25 ℃, and filtered to obtain filtrate and filter residue (containing carbon powder) containing lithium;
(2) Adding 127g of 30wt% hydrogen peroxide solution into the lithium-containing filtrate, regulating the pH to 2 by using 1mol/L lithium hydroxide solution, aging at 90 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain lithium dihydrogen phosphate-containing filtrate;
(3) Heating the lithium dihydrogen phosphate-containing filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 40 ℃, and cooling for crystallization to obtain a lithium dihydrogen phosphate crude product;
(4) Dissolving the lithium dihydrogen phosphate crude product into water, adding 85wt% phosphoric acid to adjust the pH to 2, filtering, heating the filtrate to 120 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 50 ℃, and filtering to obtain a lithium dihydrogen phosphate wet product; drying at 105 ℃ to obtain a battery grade lithium dihydrogen phosphate product. The composition analysis table of the battery grade lithium dihydrogen phosphate is shown in table 2, the product quality basically meets YS/T967-2014, the leaching rate of lithium is 69%, and the total recovery rate is 54%.
The battery grade lithium dihydrogen phosphate samples prepared in examples 1 to 3 and comparative examples 1 to 3 were analyzed and compared with national standards, and the results are shown in table 2.
TABLE 2 analysis of battery grade lithium dihydrogen phosphate samples prepared in examples 1 to 3 and comparative examples 1 to 3 and national standard
Note that: a certain amount of the battery grade lithium dihydrogen phosphate products obtained in examples 1 to 3 and comparative examples 1 to 3 was weighed as samples, and each sample was dried for a sufficiently long period of time and then measured to obtain each content in the table.
As can be seen from Table 2, the preparation method of the battery grade lithium dihydrogen phosphate is simple, the reaction condition is mild, and the production cost is low. The battery grade lithium dihydrogen phosphate prepared in the examples 1-3 has high content and low impurity content, and meets the raw material index requirements of the lithium ion battery anode material.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications without departing from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.
Claims (7)
1. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder is characterized by comprising the following steps:
step (1), screening the waste lithium iron phosphate battery powder obtained by screening a 60-mesh sieve according to the quality of solid and liquid1:1-5, adding into deionized water, and fully stirring; then according to mole ratio of Li + : H 3 PO 4 1, (1) adding phosphoric acid solution, stirring and filtering to obtain lithium-containing filtrate and filter residue containing carbon;
step (2), according to the mole ratio of Fe 2+ : H 2 O 2 1-2:1, adding 30wt% hydrogen peroxide into the lithium-containing filtrate obtained in the step (1), completely oxidizing ferrous ions into ferric ions, then adding a lithium hydroxide solution to adjust the pH value to 2-3, aging at 70-100 ℃, and filtering to remove impurities such as ferric phosphate, aluminum phosphate and the like to obtain a lithium dihydrogen phosphate-containing filtrate;
step (3), heating the lithium dihydrogen phosphate-containing filtrate obtained in the step (2) to 120-135 ℃, evaporating and concentrating until crystallization is separated out, then slowly cooling to 40 ℃, and cooling and crystallizing to obtain a lithium dihydrogen phosphate crude product;
step (4), dissolving the lithium dihydrogen phosphate crude product into water, supplementing phosphoric acid to adjust the pH value to 2-3, filtering, heating the filtrate to 120-130 ℃, evaporating and concentrating until crystallization is separated out, slowly cooling to 35-40 ℃, and filtering to obtain a lithium dihydrogen phosphate wet material; and drying to obtain a battery grade lithium dihydrogen phosphate product.
2. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder as defined in claim 1, wherein the method comprises the following steps: in the step (1), the solid-liquid mass ratio of the waste lithium iron phosphate battery powder to the deionized water is 1 (2-4), and more preferably 1:3.
3. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder as defined in claim 1, wherein the method comprises the following steps: in step (1), li + : H 3 PO 4 1 (2-5), more preferably 1:3; the concentration of the phosphoric acid solution was 85wt%.
4. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder as defined in claim 1, wherein the method comprises the following steps: in the step (1), the stirring temperature is 25-60 ℃, the stirring time is 2-6 h, preferably the stirring temperature is 25 ℃, and the stirring time is 4h.
5. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder as defined in claim 1, wherein the method comprises the following steps: in step (2), the aging temperature is 90-100deg.C, preferably 100deg.C.
6. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder as defined in claim 1, wherein the method comprises the following steps: in step (3), the lithium dihydrogen phosphate-containing filtrate is heated to 125-135 ℃, preferably 135 ℃.
7. The method for preparing lithium dihydrogen phosphate from waste lithium iron phosphate battery powder as defined in claim 1, wherein the method comprises the following steps: in the step (4), the filtrate is heated to 120 ℃; the target temperature for cooling was 40 ℃; the drying temperature is 105-120 ℃, preferably 105 ℃.
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