CN117303330A - Method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste - Google Patents
Method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste Download PDFInfo
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- CN117303330A CN117303330A CN202311215436.8A CN202311215436A CN117303330A CN 117303330 A CN117303330 A CN 117303330A CN 202311215436 A CN202311215436 A CN 202311215436A CN 117303330 A CN117303330 A CN 117303330A
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- Prior art keywords
- lithium
- phosphate
- dihydrogen phosphate
- iron phosphate
- lithium iron
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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 60
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 80
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000706 filtrate Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 38
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 34
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000000536 complexating effect Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 59
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 35
- 238000011084 recovery Methods 0.000 claims description 31
- 239000012452 mother liquor Substances 0.000 claims description 27
- 239000012535 impurity Substances 0.000 claims description 21
- 239000010413 mother solution Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011574 phosphorus Substances 0.000 abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 25
- 229910052744 lithium Inorganic materials 0.000 description 25
- 235000011007 phosphoric acid Nutrition 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 16
- 239000011575 calcium Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 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
- 159000000007 calcium salts Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 229940062993 ferrous oxalate Drugs 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 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
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- 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
Abstract
The invention discloses a method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste, which comprises the steps of firstly adding lithium iron phosphate powder into oxalic acid solution, and stirring to fully dissolve the lithium iron phosphate powder to obtain slurry; regulating the pH value of the slurry, stirring and filtering to obtain filtrate 1; EDTA is added into the filtrate 1 for complexing, the pH value is regulated, then the mixture is heated, and lithium phosphate wet material is obtained through filtration; washing by boiling deionized water; dissolving the washed lithium phosphate wet material in a high-purity phosphoric acid solution, and filtering to obtain a lithium dihydrogen phosphate clean solution; evaporating the lithium dihydrogen phosphate clean solution when the solution temperature reachesCooling to 40-50 ℃ at 125-130 ℃, centrifuging and drying to obtain battery grade lithium dihydrogen phosphate. The method selectively removes Fe element in the lithium iron phosphate, not only recovers the lithium element in the lithium iron phosphate, but also recovers the phosphorus element, and the byproduct FeC 2 O 4 Can be used as raw material for producing lithium iron phosphate.
Description
Technical Field
The invention relates to the technical field of waste battery recovery, in particular to a method for preparing battery grade lithium dihydrogen phosphate by utilizing lithium iron phosphate waste material recovery.
Background
With the wide application of lithium ion batteries, the waste lithium ion batteries enter a failure and recovery stage in a large amount. How to recycle waste lithium ion batteries and recycle resources has become a common concern for society. The battery in the power battery scrapping tide at the near stage in China mainly comprises a lithium iron phosphate battery. Compared with a ternary waste battery, the waste lithium iron phosphate battery has low metal value, is mainly aimed at recycling metal lithium, and has relatively few documents for comprehensive recycling research of lithium, iron and phosphorus. Lithium in the lithium iron phosphate material is an important resource, iron and phosphorus also have certain recovery values, and the recycling of the lithium iron phosphate positive electrode material has economic benefit and can reduce environmental pollution.
At present, the recovery method of the waste lithium iron phosphate battery mainly comprises high-temperature solid-phase pyrogenic recovery, high-temperature solid-phase repair, liquid-phase wet recovery, bioactive leaching recovery, high-energy mechanochemical activation recovery and the like. The high-temperature solid-phase fire recovery and high-temperature solid-phase repair have the advantages of simple process and easy industrialization, but have strict pretreatment requirements on waste materials, high process energy consumption, easy release of toxic gas under the high-temperature condition in the regeneration repair process, and the regeneration product has the defects of more impurities, imperfect structural repair and the like, so that the recovery economic benefit is low; however, the technology of biological leaching and mechanochemical activation recovery is not mature enough, and meanwhile, the technology has the defects of long period, harsh leaching conditions and the like, so that the industrial application cannot be realized temporarily. Although the liquid phase wet recovery has the defects of higher process cost, more complex flow and the like, the method has obvious advantages in the aspects of mature technology, high metal recovery rate, high purity of the obtained material and the like, and is the most widely applied method at present. However, wet recovery is usually only a recovery of a part of components, for example, the recovery technology of scrapped lithium iron phosphate mainly focuses on selectively extracting and recovering lithium from waste pole pieces or active substances, then adding a precipitant for recovery to obtain a lithium salt product, and the rest of solid waste contains higher content of iron and phosphorus, but is not usually recovered, thereby wasting resources and endangering the environment. Although the wet recovery process is mature, the problems of incomplete recovery of materials, poor selectivity and the like exist.
The Chinese patent publication No. CN106629646A discloses a resource recovery method of lithium iron phosphate waste, the lithium iron phosphate waste is changed into ferric iron by roasting, ball milling and oxidation, lithium phosphate slag and lithium dihydrogen phosphate are generated by adding phosphoric acid for dissolution, and the filtered lithium dihydrogen phosphate is concentrated and crystallized to obtain the product. In the patent, only lithium is recovered as a main product, iron and phosphorus are precipitated in the form of byproduct ferric phosphate, and an oxidant is needed to be provided to convert ferrous iron into ferric iron, so that the solid iron source is directly oxidized by oxygen, and the process is slowly carried out, so that the industrial application is not facilitated.
The Chinese patent publication No. CN108147384A discloses a resource recovery method of lithium iron phosphate waste. Although lithium and phosphorus are recovered in the main product of the patent, the intermediate product ferric phosphate filter residues are used for adding alkali to generate sodium phosphate and ferric hydroxide, the process is not easy to carry out, the conversion rate is low, a large amount of phosphorus and iron cannot be recycled, the patent process is too complex, a large amount of oxidant is needed to convert ferrous iron into ferric iron, and a large amount of other chemical reagents are needed to generate a large amount of waste liquid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste, which not only recycles lithium, but also recycles phosphorus, does not need to use an oxidant to convert ferrous iron into ferric iron, and can use byproduct ferrous oxalate as a raw material for producing lithium iron phosphate, wherein the main content of a product (battery grade lithium dihydrogen phosphate) reaches the standard of 99.5 percent, and the process flow is simplified greatly, so that the method is more suitable for industrialization.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste, which comprises the following steps:
1) Adding lithium iron phosphate powder into oxalic acid solution, and stirring to fully dissolve the lithium iron phosphate powder to obtain slurry;
2) Regulating the pH value of the slurry to 5.6-5.8, continuously stirring, and filtering to obtain filtrate 1;
3) Adding EDTA into the filtrate 1 for complexing, then adjusting the pH value to 13-14, heating to 95-100 ℃, stirring for 10-15min, and filtering to obtain a lithium phosphate wet material and mother liquor; the mother liquor is recycled to the step 2) for adjusting the pH value of the slurry;
4) Washing the wet lithium phosphate material by boiling deionized water (soluble salts are removed, and the soluble salts comprise sodium and potassium salts);
5) Dissolving the washed lithium phosphate wet material in a high-purity phosphoric acid solution (namely 85% of industrial high-purity phosphoric acid), and filtering (insoluble salts are removed, and the insoluble salts are small amounts of calcium salt and magnesium salt) to obtain a lithium dihydrogen phosphate clean solution;
6) Evaporating lithium dihydrogen phosphate clean solution, cooling to 40-50deg.C (too high temperature) when the solution temperature reaches 125-130deg.C, and centrifuging once to obtain too much mother solution, wherein the lithium yield can be reduced; and 2) after the temperature is too low and the materials are too thick to be centrifuged, centrifuging and drying to obtain battery-grade lithium dihydrogen phosphate, centrifuging to obtain lithium dihydrogen phosphate mother liquor, and adding the lithium dihydrogen phosphate mother liquor into the step 1) for preparing oxalic acid solution.
Further, in the step 1), the molar ratio of the lithium iron phosphate powder to oxalic acid in the oxalic acid solution is 1:1.1-1.2.
Still further, in the step 1), the stirring time is 10-15min.
Still further, in the step 2), lithium hydroxide is added to the slurry to adjust the pH value to 5.6-5.8.
Still further, in the step 3), the molar ratio of the metal impurity element to EDTA in the filtrate 1 is 1:1.1-1.5.
Still further, in the step 3), the complexing time is 30-60min. The preferred time is 30min.
Still further, in the step 4), the mass ratio of the lithium phosphate wet material to the boiling deionized water is 1:3-4.
Still further, in the step 5), li in the wet lithium phosphate material 3 PO 4 With H in phosphoric acid solution 3 PO 4 The molar ratio of (2) is 1:2-2.1; and the mass fraction of the high-purity phosphoric acid solution is 85%.
Still further, in the step 6), the temperature of the solution reaches 125 ℃.
The principle of the invention is as follows:
1. according to the invention, the oxalic acid solution is used for acidifying and dissolving the lithium iron phosphate powder, so that subsequent lithium extraction is facilitated, and in addition, the oxalate is beneficial to removing Ca, mg and other impurities in the lithium iron phosphate powder, which cannot be achieved by other acids;
2. the present invention uses lithium hydroxide to adjust ph=5.6-5.8 in order to form FeC 2 O 4 ·2H 2 O precipitates, to ensure that oxalic acid is reacted with C 2 O 4 2- In the form of a pH of at least 5.5 and when the pH is greater than 6, fe is formed 3 (PO 4 ) 2 Precipitation, causing P element loss, so that the pH value is 5.6-5.8 for removing Fe element only; at the same time remove FeC by filtration 2 O4·2H 2 O (ferrous oxalate) and very small amounts of other oxalates precipitate (the lithium iron phosphate raw material may contain other impurities such as Ca, mg, etc., ca C is formed 2 O 4 And Mg C 2 O 4 And the like.
3. The EDTA of the invention mainly removes Fe, and the rest can remove Mg and Ca. EDTA is added first and pH value is adjusted first to form lithium phosphate precipitate, and calcium phosphate, magnesium phosphate, calcium hydroxide, magnesium hydroxide and other impurity precipitate, so that the subsequent EDTA can not complex calcium and magnesium. EDTA is added to complex Mg and Ca and then exist in the solution, and then the pH is adjusted to 13-14, so that only lithium phosphate precipitate can be formed, and other impurity precipitates can not be introduced.
The reaction formula is as follows:
LiH 2 PO 4 +2LiOH＝Li 3 PO 4 +2H 2 O、
Li 2 HPO 4 +LiOH＝Li 3 PO 4 +H 2 O。
4. the invention uses lithium hydroxide to adjust the pH to 13-14, and in order to ensure that the p element exists in the form of orthophosphate, the p element must be under the condition of strong alkali, otherwise HPO is adopted 4 2- 、H 2 PO 4 - In the form of Li only 3 PO 4 The solubility is the lowest, so that the lithium loss in the mother liquor after filtration is the smallest. Heating may promote HPO 4 2- 、H 2 PO 4 - Ionizing H ions to form orthophosphoric acid radical; when the pH was adjusted to 12 using LiOH, 48.5% of the lithium was lost in the mother liquor (since part of the Li in the mother liquor was in LiH) 2 PO 4 And Li (lithium) 2 HPO 4 In the form of (a) to cause low single lithium and phosphorus yields, requires increased cycle times, and is liable to cause impurity enrichment.
5. Reaction formula of lithium phosphate wet material and high-purity phosphoric acid solution:
Li 3 PO 4 +2H 3 PO 4 ＝3LiH 2 PO 4 。
the invention has the beneficial effects that:
1. the method selectively removes Fe element in the lithium iron phosphate, not only recovers the lithium element in the lithium iron phosphate, but also recovers the phosphorus element, and the byproduct FeC 2 O 4 Can be used as raw material for producing lithium iron phosphate.
2. The invention realizes waste utilization, has low production cost, large economic benefit, high lithium yield and less waste liquid discharge.
3. The invention greatly shortens the process flow and has simple operation.
Drawings
FIG. 1 is a graph showing the pH profile of oxalic acid forms;
in the figure, curve 1 represents H 2 C 2 O 4 Curve 2 represents HC 2 O 4 - Curve 3 represents C 2 O 4 2- 。
Detailed Description
The present invention is described in further detail below in conjunction with specific embodiments for understanding by those skilled in the art.
The method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste material comprises the following steps:
1) Adding lithium iron phosphate powder into oxalic acid solution, and stirring to fully dissolve the lithium iron phosphate powder to obtain slurry;
2) Regulating the pH value of the slurry to 5.6-5.8, continuously stirring, and filtering to obtain filtrate 1;
3) Adding EDTA into the filtrate 1 for complexing, then adjusting the pH value to 13-14, heating to 95-100 ℃, stirring for 10-15min, and filtering to obtain a lithium phosphate wet material and mother liquor; the mother liquor is recycled to the step 2) for adjusting the pH value of the slurry;
4) Washing the lithium phosphate wet material by boiling deionized water;
5) Dissolving the washed lithium phosphate wet material in a high-purity phosphoric acid solution, and filtering to obtain a lithium dihydrogen phosphate clean solution;
6) Evaporating the lithium dihydrogen phosphate clean solution, cooling to 40-50 ℃ when the temperature of the solution reaches 125-130 ℃, centrifuging, drying to obtain battery grade lithium dihydrogen phosphate, centrifuging to obtain lithium dihydrogen phosphate mother solution, and adding the lithium dihydrogen phosphate mother solution into the step 1) for preparing oxalic acid solution.
The theoretical basis of the parameter selection of the method is as follows:
1. selection of pH of slurry
a. Method of
The slurry is obtained according to the method, the slurry is divided into three parts, the pH value of the filtrate 1 is adjusted to 5.6, 5.7 and 5.8 by using LiOH respectively, stirring is continued, the filtrate 1 is obtained by filtering, and the concentration of various impurities in the filtrate 1 is detected;
b. conclusion(s)
When the pH of the slurry is 5.6, fe in filtrate 1 2+ 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ Impurity concentration of 2.2×10 -2 g/L、8.2*10 -3 g/L、4.6*10 -3 g/L、3.1*10 -2 g/L、9.7*10 -2 g/L、4.1*10 -2 g/L。PO 4 3- The concentration is 61.23g/L;
when the pH of the slurry is 5.7, fe in filtrate 1 2+ 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ Impurity concentration of 1.8×10 -2 g/L、8.0*10 -3 g/L、4.7*10 -3 g/L、2.9*10 -2 g/L、9.7*10 -2 g/L、4.0*10 -2 g/L。PO 4 3- The concentration is 60.99g/L;
when the pH of the slurry is 5.8, fe in filtrate 1 2+ 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ Impurity concentration of 1.3×10 -2 g/L、8.1*10 -3 g/L、4.6*10 -3 g/L、2.8*10 -2 g/L、9.5*10 -2 g/L、3.7*10 -2 g/L。PO 4 3- The concentration is 60.66g/L.
From the above, it can be seen that: as the pH rises, the impurity removal effect is better, but PO in filtrate 1 4 3- Concentration decreases; the pH of the filtrate 1 is adjusted to 5.6-5.8 with best results.
2. Selection of pH value to be adjusted after complexing filtrate 1
a. Method of
Obtaining filtrate 1 according to the method, and detecting the concentration of Fe to be 2.2 x 10 -2 g/L, dividing the filtrate 1 into three parts, respectively using LiOH to adjust the pH value of the filtrate 1 to 12, 13 and 14, heating and filtering, and detecting the lithium loss condition in the mother liquor;
b. conclusion(s)
When the pH of the filtrate 1 was 13, the lithium loss in the mother liquor was 13.3% (because part of Li in the mother liquor was in LiH 2 PO 4 And Li (lithium) 2 HPO 4 In the form of (c) or (d)),
when the pH of filtrate 1 was brought to 14, the lithium loss in the mother liquor was 7.4% (since the mother liquor still had a small amount of Li 2 HPO 4 Presence);
when the pH of filtrate 1 was brought to 12, the lithium loss in the mother liquor was 48.5% (because part of Li in the mother liquor was in LiH 2 PO 4 And Li (lithium) 2 HPO 4 The single lithium and phosphorus yields are low, the cycle times are required to be increased, and impurity enrichment is easy to cause;
from the above, it can be seen that: the pH value of the filtrate 1 is adjusted to be 13-14 after complexing.
Example 1
A method for preparing battery grade lithium dihydrogen phosphate 1 by recycling lithium iron phosphate waste, comprising the following steps:
1) Adding 1mol of lithium iron phosphate powder into 1.2L of oxalic acid solution according to the molar ratio of the lithium iron phosphate powder to oxalic acid in the oxalic acid solution of 1:1.1, and stirring for 10-15min to fully dissolve the lithium iron phosphate powder to obtain slurry;
2) Adding lithium hydroxide into the slurry to adjust the pH value to 5.6, continuously stirring for 10-15min, and filtering to remove FeC 2 O 4 ·2H 2 Precipitating O and a very small amount of other oxalate to obtain filtrate 1;
3) Sampling and detecting Fe in filtrate 1 2+ 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ Impurity content of 2.2 x 10 -2 g/L、8.2*10 - 3 g/L、4.6*10 -3 g/L、3.1*10 -2 g/L、9.7*10 -2 g/L、4.1*10 -2 g/L；
4) Adding EDTA into the filtrate 1 according to the mol ratio of metal elements to EDTA in the filtrate 1 of 1:1.1 for complexing for 30min, then adding LiOH to adjust the pH value to 13, heating to 95-100 ℃, stirring for 10-15min, and filtering to obtain lithium phosphate wet material and mother liquor; the mother liquor is recycled to the step 2) for adjusting the pH value of the slurry;
5) Washing the lithium phosphate wet material with boiling deionized water according to the mass ratio of 1:3 (soluble salts are removed, wherein the soluble salts comprise sodium and potassium salts), stirring and washing for 20-30min, and detecting the impurity content Na in the washed lithium phosphate wet material + 、Fe 2+ 、K + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、C 2 O 4 2- 3.4ppm, 4.5ppm, 1.2ppm, 8.4ppm, 1.3ppm, 1.4ppm, 21ppm, respectively.
6) According to Li in lithium phosphate wet material 3 PO 4 With H in phosphoric acid solution 3 PO 4 The molar ratio of (1:2.1) is that the washed lithium phosphate wet material is dissolved in a high-purity phosphoric acid solution (namely 85% of industrial high-purity phosphoric acid, namely 85% of the mass fraction of the high-purity phosphoric acid solution), and the solution is filtered (insoluble salt is removed, and the insoluble salt is a small amount of calcium salt and magnesium salt), so that a lithium dihydrogen phosphate clean solution is obtained;
7) Evaporating lithium dihydrogen phosphate clean solution, cooling to 40-50deg.C (too high temperature) when the solution temperature reaches 125deg.C, and centrifuging to obtain mother solution with too much mother solution, wherein lithium yield can be reduced; the temperature is too low, the materials are too thick to be centrifuged), and then the battery grade lithium dihydrogen phosphate 1 (meeting YS/T967-2014 LiH) is obtained after centrifugation and drying 2 PO 4 -2 standard, the detection results are shown in table 1), and the lithium dihydrogen phosphate mother liquor obtained by centrifugation is added into the step 1) for preparing oxalic acid solution.
Example 2
A method for preparing battery grade lithium dihydrogen phosphate 2 by recycling lithium iron phosphate waste, comprising the following steps:
1) Adding 1mol of lithium iron phosphate powder into 1.2L of oxalic acid solution according to the molar ratio of the lithium iron phosphate powder to oxalic acid in the oxalic acid solution of 1:1.2, and stirring for 10-15min to fully dissolve the lithium iron phosphate powder to obtain slurry;
2) Adding lithium hydroxide into the slurry to adjust the pH value to 5.6, continuously stirring for 10-15min, and filtering to remove FeC 2 O 4 ·2H 2 Precipitating O and a very small amount of other oxalate to obtain filtrate 1;
3) Sampling and detecting Fe in filtrate 1 2+ 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ Impurity content of 1.9×10 -2 g/L、7.6*10 - 3 g/L、3.9*10 -3 g/L、2.7*10 -2 g/L、4.3*10 -2 g/L、5.4*10 -2 g/L；
4) Adding EDTA into the filtrate 1 according to the molar ratio of metal elements to EDTA in the filtrate 1 of 1:1.2 for complexing for 30min, then adding LiOH to adjust the pH value to 14, heating to 95-100 ℃, stirring for 10-15min, and filtering to obtain lithium phosphate wet material and mother liquor; the mother liquor is recycled to the step 2) for adjusting the pH value of the slurry;
5) Washing the lithium phosphate wet material with boiling deionized water according to the mass ratio of 1:3 (soluble salts are removed, wherein the soluble salts comprise sodium and potassium salts), stirring and washing for 20-30min, and detecting the impurity content Na in the washed lithium phosphate wet material + 、Fe 2+ 、K + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、C 2 O 4 2- 3.1ppm, 3.4ppm, 2.3ppm, 7.4ppm, 1.1ppm, 2.1ppm, 34ppm, respectively.
6) According to Li in lithium phosphate wet material 3 PO 4 With H in phosphoric acid solution 3 PO 4 The molar ratio of (1:2.1) is that the washed lithium phosphate wet material is dissolved in a high-purity phosphoric acid solution (namely 85% of industrial high-purity phosphoric acid, namely 85% of the mass fraction of the high-purity phosphoric acid solution), and the solution is filtered (insoluble salt is removed, and the insoluble salt is a small amount of calcium salt and magnesium salt), so that a lithium dihydrogen phosphate clean solution is obtained;
7) Evaporating lithium dihydrogen phosphate clean solution, cooling to 40-50deg.C (too high temperature) when the solution temperature reaches 125deg.C, and centrifuging to obtain mother solution with too much mother solution, wherein lithium yield can be reduced; the temperature is too low, the materials are too thick to be centrifuged), and then the battery grade lithium dihydrogen phosphate 2 (meeting YS/T967-2014 LiH) is obtained after centrifugation and drying 2 PO 4 -2 standard, the detection results are shown in table 1), and the lithium dihydrogen phosphate mother liquor obtained by centrifugation is added into the step 1) for preparing oxalic acid solution.
Example 3
A method for preparing battery grade lithium dihydrogen phosphate 3 by recycling lithium iron phosphate waste, comprising the following steps:
1) Adding 1mol of lithium iron phosphate powder into 1.2L of oxalic acid solution according to the molar ratio of the lithium iron phosphate powder to oxalic acid in the oxalic acid solution of 1:1.2, and stirring for 10-15min to fully dissolve the lithium iron phosphate powder to obtain slurry;
2) Adding lithium hydroxide into the slurry to adjust the pH value to 5.8, continuously stirring for 10-15min, and filtering to remove FeC 2 O 4 ·2H 2 Precipitating O and a very small amount of other oxalate to obtain filtrate 1;
3) Sampling and detecting Fe in filtrate 1 2+ 、Na + 、K + 、Ca 2+ 、Mg 2+ 、Cu 2+ Impurity content of 1.7×10 -2 g/L、7.4*10 - 3 g/L、4.1*10 -3 g/L、2.6*10 -2 g/L、4.1*10 -2 g/L、4.9*10 -2 g/L；
4) Adding EDTA into the filtrate 1 according to the mol ratio of metal elements to EDTA in the filtrate 1 of 1:1.2 for complexing for 30min, then adding LiOH to adjust the pH value to 14, heating to 95-100 ℃, stirring for 10-15min, and filtering to obtain lithium phosphate wet material and mother liquor; the mother liquor is recycled to the step 2) for adjusting the pH value of the slurry;
4) Washing the lithium phosphate wet material with boiling deionized water according to the mass ratio of 1:3 (soluble salts are removed, wherein the soluble salts comprise sodium and potassium salts), stirring and washing for 20-30min, and detecting the impurity content Na in the washed lithium phosphate wet material + 、Fe 2+ 、K + 、Mg 2+ 、Ca 2+ 、Cu 2+ 、C 2 O 4 2- 3.1ppm, 3.4ppm, 2.3ppm, 7.4ppm, 1.1ppm, 2.1ppm, 34ppm, respectively.
5) According to Li in lithium phosphate wet material 3 PO 4 With H in phosphoric acid solution 3 PO 4 The molar ratio of (1:2.1) is that the washed lithium phosphate wet material is dissolved in a high-purity phosphoric acid solution (namely 85% of industrial high-purity phosphoric acid, namely 85% of the mass fraction of the high-purity phosphoric acid solution), and the solution is filtered (insoluble salt is removed, and the insoluble salt is a small amount of calcium salt and magnesium salt), so that a lithium dihydrogen phosphate clean solution is obtained;
6) Evaporating lithium dihydrogen phosphate clean solution, cooling to 40-50deg.C (too high temperature) when the solution temperature reaches 125deg.C, and centrifuging to obtain mother solution with too much mother solution, wherein lithium yield can be reduced; the temperature is too low, the materials are too thick to be centrifuged), and then the battery grade lithium dihydrogen phosphate 3 (meeting YS/T967-2014 LiH) is obtained after centrifugation and drying 2 PO 4 -2 standard, the detection results are shown in table 1), and the lithium dihydrogen phosphate mother liquor obtained by centrifugation is added into the step 1) for preparing oxalic acid solution.
TABLE 1 content of substances in battery grade lithium dihydrogen phosphate
From the above, it can be seen that: the battery grade lithium dihydrogen phosphate prepared by the three embodiments can meet the indexes of the existing battery grade lithium dihydrogen phosphate products, and the invention selectively removes Fe element in the lithium iron phosphate, not only recovers the lithium element in the lithium iron phosphate, but also recovers the phosphorus element, and byproducts FeC 2 O 4 Can act as lithium iron phosphateA production raw material; the method realizes waste utilization, has low production cost, large economic benefit, high lithium yield and less waste liquid discharge; greatly shortens the process flow and is simple to operate.
Other parts not described in detail are prior art. Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste is characterized in that: the method comprises the following steps:
1) Adding lithium iron phosphate powder into oxalic acid solution, and stirring to fully dissolve the lithium iron phosphate powder to obtain slurry;
2) Regulating the pH value of the slurry to 5.6-5.8, continuously stirring, and filtering to obtain filtrate 1;
3) Adding EDTA into the filtrate 1 for complexing, then adjusting the pH value to 13-14, heating to 95-100 ℃, stirring for 10-15min, and filtering to obtain a lithium phosphate wet material and mother liquor; the mother liquor is recycled to the step 2) for adjusting the pH value of the slurry;
4) Washing the lithium phosphate wet material by boiling deionized water;
5) Dissolving the washed lithium phosphate wet material in a high-purity phosphoric acid solution, and filtering to obtain a lithium dihydrogen phosphate clean solution;
6) Evaporating the lithium dihydrogen phosphate clean solution, cooling to 40-50 ℃ when the temperature of the solution reaches 125-130 ℃, centrifuging, drying to obtain battery grade lithium dihydrogen phosphate, centrifuging to obtain lithium dihydrogen phosphate mother solution, and adding the lithium dihydrogen phosphate mother solution into the step 1) for preparing oxalic acid solution.
2. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 1), the molar ratio of the lithium iron phosphate powder to oxalic acid in the oxalic acid solution is 1:1.1-1.2.
3. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 1), the stirring time is 10-15min.
4. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 2), lithium hydroxide is added into the slurry to adjust the pH value to 5.6-5.8.
5. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 3), the molar ratio of the metal impurity element to EDTA in the filtrate 1 is 1:1.1-1.5.
6. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1 or 5, wherein the method comprises the steps of: the molar ratio of the metal impurity element to EDTA in the filtrate 1 is 1:1.1-1.2.
7. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 3), the complexing time is 30-60min.
8. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 4), the mass ratio of the lithium phosphate wet material to the boiling deionized water is 1:3-4.
9. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in the step 5), li in the lithium phosphate wet material 3 PO 4 With H in phosphoric acid solution 3 PO 4 The molar ratio of (2) is 1:2-2.1; and the mass fraction of the high-purity phosphoric acid solution is 85%.
10. The method for preparing battery grade lithium dihydrogen phosphate by utilizing the recovery of lithium iron phosphate waste material as defined in claim 1, wherein the method comprises the following steps: in said step 6), the solution temperature reached 125 ℃.
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| CN101767782A (en) * | 2010-03-05 | 2010-07-07 | 四川国理锂材料有限公司 | Production method of lithium dihydrogen phosphate |
| CN108147384A (en) * | 2017-12-28 | 2018-06-12 | 江西赣锋循环科技有限公司 | A kind of method that battery-grade lithium dihydrogen phosphate is prepared using lithium iron phosphate waste |
| WO2020134773A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Method for recovering and preparing lithium iron phosphate cathode material |
| CN116216674A (en) * | 2022-12-31 | 2023-06-06 | 湖北百杰瑞新材料股份有限公司 | Method for obtaining battery-grade lithium phosphate from waste lithium iron phosphate battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101767782A (en) * | 2010-03-05 | 2010-07-07 | 四川国理锂材料有限公司 | Production method of lithium dihydrogen phosphate |
| CN108147384A (en) * | 2017-12-28 | 2018-06-12 | 江西赣锋循环科技有限公司 | A kind of method that battery-grade lithium dihydrogen phosphate is prepared using lithium iron phosphate waste |
| WO2020134773A1 (en) * | 2018-12-29 | 2020-07-02 | 宁德时代新能源科技股份有限公司 | Method for recovering and preparing lithium iron phosphate cathode material |
| CN116216674A (en) * | 2022-12-31 | 2023-06-06 | 湖北百杰瑞新材料股份有限公司 | Method for obtaining battery-grade lithium phosphate from waste lithium iron phosphate battery anode material |
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