CN116143146A - Leaching method of waste lithium iron phosphate anode powder - Google Patents
Leaching method of waste lithium iron phosphate anode powder Download PDFInfo
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- CN116143146A CN116143146A CN202111401074.2A CN202111401074A CN116143146A CN 116143146 A CN116143146 A CN 116143146A CN 202111401074 A CN202111401074 A CN 202111401074A CN 116143146 A CN116143146 A CN 116143146A
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- leaching
- iron phosphate
- lithium iron
- ferric sulfate
- waste lithium
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- 238000002386 leaching Methods 0.000 title claims abstract description 79
- 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 56
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 53
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 50
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002893 slag Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 8
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 5
- 230000001502 supplementing effect Effects 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 229960004887 ferric hydroxide Drugs 0.000 description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- -1 Ni and Co Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the field of battery treatment, in particular to a leaching method of waste lithium iron phosphate anode powder. The leaching method comprises the following steps: mixing waste lithium iron phosphate anode powder with water or ferric sulfate solution, and stirring and heating the mixture; adding ferric sulfate solid into the mixture in a supplementing way; after the ferric sulfate solid is completely dissolved and reacts for 20-30 minutes, adding hydrogen peroxide for continuous reaction, and filtering after the reaction is finished to obtain leaching liquid and leaching slag containing lithium sulfate; removing impurities from the leaching solution to prepare lithium carbonate; adding sulfuric acid into the leaching residue to obtain an insoluble ferric sulfate solution, filtering to remove filter residues, and returning the ferric sulfate solution to the step one for mixing with the waste lithium iron phosphate positive electrode powder. The invention realizes Fe in a process system 2 (SO 4 ) 3 Zero consumption of (2) and greatly reduce doubleConsumption of oxygen water and sulfuric acid.
Description
Technical Field
The invention relates to the field of battery treatment, in particular to a leaching method of waste lithium iron phosphate anode powder.
Background
In China, electric automobiles are popularized and applied from 2009, the number of new energy automobiles in China is rapidly increased in recent years, a power battery is continuously started to enter a large-scale scrapping period, valuable elements in the lithium battery are recovered, and considerable economic benefits and investment opportunities are generated while resource waste and environmental pollution are avoided.
According to statistics, the production of new energy automobiles in China in 2017 reaches 7.4 ten thousand, the production and marketing of the new energy automobiles in 2018 reaches 127.05 ten thousand, the production and marketing of the new energy automobiles in 2019 respectively reach 124.2 ten thousand and 120.6 ten thousand, and the production and marketing of the new energy automobiles in 2020 respectively reach 136.6 ten thousand and 136.7 ten thousand. The estimated sales of the new energy vehicles in 2021 is 200 ten thousand, and the estimated sales of the new energy vehicles in 2030 is 40% of the total sales of the automobile industry, which is 1200 ten thousand to 1600 ten thousand.
In 2018, 15 ten thousand tons (12 GWh) of waste lithium batteries are produced in China, 20 ten thousand tons (20 GWh) of waste lithium batteries are produced in 2020, 100 ten thousand tons (100 GWh) of waste lithium batteries are expected to be produced in 2025, and 300 ten thousand tons (300 GWh) of waste lithium batteries are expected to be produced in 2035. The recovery yield of waste power batteries in 2020 is over 100 hundred million yuan, and the predicted 2022 is 200 hundred million, and the predicted 2025 is over 300 hundred million yuan.
The lithium iron phosphate battery has the advantages of most stable structure, abundant resources, good safety performance, no toxicity, wider raw material sources, lower price and relatively lower environmental pollution, and is one of widely used automobile power batteries. The invention provides a novel leaching method aiming at waste lithium iron phosphate batteries.
The treatment process of the waste power lithium battery is divided into a fire process and a wet process, an industrial test plant with 4000 tons of treatment capacity per year is built by a Umic company through the fire process, the total recovery rate of total metal in the whole process is more than 80%, after the waste battery is smelted at high temperature, slag containing Si, al, mn, ca and Fe and alloy containing Co, cu, ni and a small amount of Fe are formed, the obtained alloy is used for refining metals such as Ni and Co, and the slag can be used as a building material. Because of the longer recovery route, the overall recovery rate of valuable elements is lower, the recovery rate of Co in the process is relatively lower, and Li cannot be recovered.
Because the recovery rate of valuable metal elements is low and Li is not recovered in the pyrogenic process, a wet recovery process is basically adopted in China.
The wet treatment of the waste lithium iron phosphate anode powder usually adopts an acid leaching or alkaline leaching process, the oxidation means mainly comprise oxidation roasting and hydrogen peroxide oxidation, the leaching means mainly comprise acid leaching, and a few of the waste lithium iron phosphate anode powder adopt alkaline leaching, and the leached acid mainly comprises sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.
In the above methods for leaching the lithium iron phosphate positive electrode powder, a large amount of sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid is used. The acid belongs to dangerous chemicals and easily-made chemicals, the transaction and transportation of the acid are monitored strictly, and if the recovery treatment process of the waste lithium iron phosphate battery can avoid the use of sulfuric acid and hydrochloric acid, the treatment cost is reduced, and great convenience is brought to a treatment plant.
Disclosure of Invention
The invention aims to solve the technical problems that: provides a leaching method of waste lithium iron phosphate anode powder, and realizes Fe in a process system 2 (SO 4 ) 3 Zero consumption of hydrogen peroxide and sulfuric acid, and greatly reduces the consumption of hydrogen peroxide and sulfuric acid.
The invention provides a leaching method of waste lithium iron phosphate anode powder, which comprises the following steps:
step one: mixing waste lithium iron phosphate anode powder with water or ferric sulfate solution, and stirring and heating the mixture; adding ferric sulfate solid into the mixture in a supplementing way;
step two: after the ferric sulfate solid is completely dissolved and reacts for 20-30 minutes, adding hydrogen peroxide for continuous reaction, and filtering after the reaction is finished to obtain leaching liquid and leaching slag containing lithium sulfate;
step three: removing impurities from the leaching solution to prepare lithium carbonate; adding sulfuric acid into the leaching residue to obtain an insoluble ferric sulfate solution, filtering to remove filter residues, and returning the ferric sulfate solution to the step one for mixing with the waste lithium iron phosphate positive electrode powder.
Preferably, in the first step, the liquid-solid ratio of the waste lithium iron phosphate positive electrode powder to water or ferric sulfate solution is 2:1-4:1.
Preferably, in the first step, the heating is performed to a temperature of 30 ℃ to 60 ℃.
Preferably, the total molar amount of ferric sulfate in the ferric sulfate solution and ferric sulfate solids is 1/6 of the molar amount of lithium iron phosphate and is in excess of 20%.
Preferably, in the second step, the molar amount of the hydrogen peroxide is 1/2 of the molar amount of the lithium iron phosphate, and the molar amount is excessive by 20%.
Preferably, in the second step, hydrogen peroxide is added to continue the reaction for 20-100 minutes, and stirring is performed during the reaction.
Preferably, in the second step, hydrogen peroxide is added to continue the reaction for 40-60 minutes.
Preferably, in the third step, sulfuric acid is added to the leaching residue, and the pH value of the solution is controlled to be 1.45-1.55.
Preferably, in the third step, sulfuric acid is added to the leaching residue, and the pH value of the solution is controlled to be 1.5.
Compared with the prior art, the leaching method of the waste lithium iron phosphate positive electrode powder adopts ferric sulfate as a leaching agent, utilizes the acidity of the ferric sulfate and the oxidizing property of ferric iron to leach lithium and iron in the waste lithium iron phosphate battery positive electrode powder, oxidizes the generated ferrous iron with hydrogen peroxide to form ferric hydroxide precipitate, realizes the separation from a lithium sulfate solution, then dissolves the ferric hydroxide with a theoretical amount of sulfuric acid, converts the ferric hydroxide into the ferric sulfate solution, and returns the ferric sulfate solution as the leaching agent to realize Fe in a process system 2 (SO 4 ) 3 Zero consumption of hydrogen peroxide and sulfuric acid, and greatly reduces the consumption of hydrogen peroxide and sulfuric acid.
Drawings
FIG. 1 shows a flow chart of a leaching method of waste lithium iron phosphate anode powder.
Detailed Description
For a further understanding of the present invention, embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the invention.
The embodiment of the invention discloses a leaching method of waste lithium iron phosphate anode powder, which is shown in figure 1 and comprises the following steps:
step one: mixing waste lithium iron phosphate anode powder with water or ferric sulfate solution, and stirring and heating the mixture; adding ferric sulfate solid into the mixture in a supplementing way;
step two: after the ferric sulfate solid is completely dissolved and reacts for 20-30 minutes, adding hydrogen peroxide for continuous reaction, and filtering after the reaction is finished to obtain leaching liquid and leaching slag containing lithium sulfate;
step three: removing impurities from the leaching solution to prepare lithium carbonate; adding sulfuric acid into the leaching residue to obtain an insoluble ferric sulfate solution, filtering to remove filter residues, and returning the ferric sulfate solution to the step one for mixing with the waste lithium iron phosphate positive electrode powder.
The invention utilizes ferric sulfate leaching, ferric sulfate is added to react with lithium iron phosphate firstly in the leaching process to generate soluble lithium sulfate, ferrous sulfate and insoluble ferric phosphate, then ferrous ions are oxidized by hydrogen peroxide to change into ferric ions, ferric hydroxide precipitate is formed, and the related reaction equation in the process is as follows:
6LiFePO 4 +3Fe 2 (SO 4 ) 3 →6FeSO 4 +3Li 2 SO 4 +6FePO 4
3H 2 O 2 +6FeSO 4 →2Fe(OH) 3 ↓+2Fe 2 (SO4) 3
combining the two reaction equations gives the following reaction equation: 3H (3H) 2 O 2 +Fe 2 (SO 4 ) 3 +6LiFePO 4 →2Fe(OH) 3 ↓+3Li 2 SO 4 +6FePO 4 ———①
The invention is realized by the following steps:
step one: mixing waste lithium iron phosphate anode powder with water or ferric sulfate solution, and stirring and heating the mixture; adding ferric sulfate solid into the mixture in a supplementing way;
the liquid-solid ratio of the waste lithium iron phosphate anode powder to water or ferric sulfate solution is 2:1-4:1.
The solid-liquid ratio is the volume-weight ratio.
The water quantity of the added phase or the recycled water of the waste lithium iron phosphate anode powder is ferric sulfate solution, stirring is started, the waste lithium iron phosphate anode powder is heated to the required temperature, and the heating temperature is 30-60 ℃.
As in reaction equation (1), the total molar amount of ferric sulfate in the ferric sulfate solution and ferric sulfate solids is 1/6 of the molar amount of lithium iron phosphate and is in excess of 20%.
Step two: after the ferric sulfate solid is completely dissolved and reacts for 20-30 minutes, adding hydrogen peroxide for continuous reaction, and filtering after the reaction is finished to obtain leaching liquid and leaching slag containing lithium sulfate;
as in the reaction equation (1), the molar amount of the hydrogen peroxide is 1/2 of the molar amount of the lithium iron phosphate, and the excess is 20%.
Adding hydrogen peroxide to continue the reaction for 20-100 minutes, preferably 40-60 minutes, and stirring during the reaction.
And obtaining leaching liquid containing lithium sulfate after the national rate, and leaching slag containing ferric oxide and ferric phosphate.
Step three: removing impurities from the leaching solution to prepare lithium carbonate; adding sulfuric acid into the leaching residue to obtain an insoluble ferric sulfate solution, filtering to remove filter residues, and returning the ferric sulfate solution to the step one for mixing with the waste lithium iron phosphate positive electrode powder.
Adding sulfuric acid into leaching slag containing ferric oxide and ferric phosphate to dissolve the ferric oxide, obtaining ferric sulfate solution, and controlling the pH value of the solution to be 1.45-1.55, preferably 1.5. Filtering to obtain Fe 2 (SO 4 ) 3 Solution and FePO-containing solution 4 Is insoluble in Fe 2 (SO 4 ) 3 And returning the solution to the first step, and leaching the lithium iron phosphate positive electrode powder.
The invention has the following effects:
1. adopts Fe as 2 (SO 4 ) 3 The leaching agent replaces the traditional leaching process which takes strong acid such as hydrochloric acid, sulfuric acid and the like as the leaching agent, and is the core and innovation point of the invention.
2. Leaching agent Fe 2 (SO 4 ) 3 Zero consumption and greatly reduced consumption of hydrogen peroxide and sulfuric acid. The ferrous iron generated by oxydol oxidation forms ferric hydroxide sediment, is dissolved by sulfuric acid after liquid-solid separation, is converted into ferric sulfate solution, and is returned to be used as a leaching agent to realize Fe in a process system 2 (SO 4 ) 3 Zero consumption of hydrogen peroxide and sulfuric acid is greatly reduced.
3. Sulfur used in the conventional leaching method of lithium iron phosphate positive electrode powderAcid or hydrochloric acid and other strong acids, and the dosage of the acid is large, the acid belongs to dangerous and easily-made chemicals, the transaction and transportation monitoring is very strict, and Fe is adopted 2 (SO 4 ) 3 As a leaching agent, the cost of the treated reagent is reduced, and great convenience is brought.
In order to further understand the present invention, the leaching method of the waste lithium iron phosphate positive electrode powder provided by the present invention is described in detail below with reference to examples, and the scope of the present invention is not limited by the following examples.
Example 1
A certain waste lithium iron phosphate positive electrode powder comprises the following components:
TABLE 1 composition of lithium iron phosphate cathode powder (%)
| Composition of the components | Li | Fe | P | Al |
| Content% | 3.8 | 33.4 | 18.6 | 2.3 |
500g of the lithium iron phosphate positive electrode powder is weighed, 1500mL of tap water is firstly added into a 3000mL three-neck flask, then heating is started, the temperature is set to 50 ℃, stirring is started, the lithium iron phosphate positive electrode powder is added, and weighing is carried out257g (1.2 times of theoretical value) of ferric sulfate reagent is crushed and then added into a three-neck flask, after ferric sulfate is dissolved, stirring is continued for 20min, and then hydrogen peroxide H with the concentration of 50% is added into a reaction vessel 2 O 2 130mL, after the hydrogen peroxide is added, stirring and reacting for 40min, filtering and washing to obtain 1800mL of leaching solution, wherein the Li concentration of the leaching solution is 10.4g/L, and the leaching rate of the lithium solution is 98.5 percent.
The main component of the leaching slag is Fe (OH) 3 And FePO 4 Adding 1200mL of water into the leaching residue, stirring and pulping, slowly adding sulfuric acid, continuously stirring, and dissolving Fe (OH) in the leaching residue 3 The addition amount of sulfuric acid is controlled to control the pH value of the dissolution liquid to be about 1.5 and stable, and the final addition amount of 98% concentrated sulfuric acid is 116mL. Filtering and washing to obtain Fe-containing material 2 (SO 4 ) 3 147g/L solution 1500mL and FePO containing 4 492g of insoluble slag, the insoluble slag contains Li0.15%, and the slag leaching rate of lithium is 96.1%.
Example 2
500g of the lithium iron phosphate positive electrode powder in Table 1 was weighed, and the Fe-containing powder produced in example 1 was first added into a 3000mL three-necked flask 2 (SO 4 ) 3 147g/L of solution 1500mL, stirring, heating to 60 ℃, adding lithium iron phosphate positive electrode powder, weighing 30g of ferric sulfate reagent, crushing, adding into a three-neck flask, continuously stirring for 30min after the ferric sulfate is dissolved, and adding hydrogen peroxide H with the concentration of 50% into a reaction container 2 O 2 140mL, after the hydrogen peroxide is added, stirring and reacting for 30min, filtering and washing to obtain 1820mL of leaching solution, wherein the Li concentration of the leaching solution is 10.3g/L, and the liquid metering leaching rate of lithium is 98.6%.
Adding 1000mL of water into leaching residue, stirring, slowly adding concentrated sulfuric acid, continuously stirring, stopping adding sulfuric acid after the pH value is about 1.5 and is stable, adding 113mL of sulfuric acid, filtering and washing to obtain Fe-containing material 2 (SO 4 ) 3 152g/L solution 1450mL containing FePO 4 495g of insoluble slag, wherein the insoluble slag contains Li0.14 percent, and the slag leaching rate of lithium is 96.4 percent. Fe (Fe) 2 (SO 4 ) 3 1450mL of the solution is returned to be used as the next leaching agent.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The leaching method of the waste lithium iron phosphate anode powder is characterized by comprising the following steps of:
step one: mixing waste lithium iron phosphate anode powder with water or ferric sulfate solution, and stirring and heating the mixture; adding ferric sulfate solid into the mixture in a supplementing way;
step two: after the ferric sulfate solid is completely dissolved and reacts for 20-30 minutes, adding hydrogen peroxide for continuous reaction, and filtering after the reaction is finished to obtain leaching liquid and leaching slag containing lithium sulfate;
step three: removing impurities from the leaching solution to prepare lithium carbonate; adding sulfuric acid into the leaching residue to obtain an insoluble ferric sulfate solution, filtering to remove filter residues, and returning the ferric sulfate solution to the step one for mixing with the waste lithium iron phosphate positive electrode powder.
2. The method for leaching the waste lithium iron phosphate positive electrode powder according to claim 1, wherein in the first step, the liquid-solid ratio of the waste lithium iron phosphate positive electrode powder to water or ferric sulfate solution is 2:1-4:1.
3. The method for leaching the waste lithium iron phosphate anode powder according to claim 2, wherein in the first step, the temperature is 30-60 ℃.
4. The method for leaching the waste lithium iron phosphate positive electrode powder according to claim 1, wherein the total molar amount of ferric sulfate in the ferric sulfate solution and the ferric sulfate solid is 1/6 of the molar amount of lithium iron phosphate, and the excess is 20%.
5. The method for leaching the waste lithium iron phosphate anode powder according to claim 1, wherein in the second step, the molar amount of the hydrogen peroxide is 1/2 of the molar amount of the lithium iron phosphate, and the excess is 20%.
6. The method for leaching the waste lithium iron phosphate anode powder according to claim 1, wherein in the second step, hydrogen peroxide is added for continuous reaction for 20-100 minutes, and stirring is performed during the reaction.
7. The method for leaching the waste lithium iron phosphate anode powder according to claim 6, wherein hydrogen peroxide is added in the second step for continuous reaction for 40-60 minutes.
8. The method for leaching the waste lithium iron phosphate positive electrode powder according to claim 1, wherein in the third step, the leaching slag is added with sulfuric acid, and the pH value of the solution is controlled to be 1.45-1.55.
9. The method for leaching the waste lithium iron phosphate positive electrode powder according to claim 1, wherein in the third step, the leaching slag is added with sulfuric acid, and the pH value of the solution is controlled to be 1.5.
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| CN202111401074.2A CN116143146A (en) | 2021-11-19 | 2021-11-19 | Leaching method of waste lithium iron phosphate anode powder |
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| CN108899601A (en) * | 2018-06-11 | 2018-11-27 | 衢州华友钴新材料有限公司 | A method of recycling lithium from LiFePO4 |
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| CN110474123A (en) * | 2019-08-23 | 2019-11-19 | 贵州红星电子材料有限公司 | Positive material of waste lithium iron phosphate comprehensive recovering process |
| KR20200046295A (en) * | 2018-10-24 | 2020-05-07 | 코스모에코켐(주) | Selective leaching method of trivalent cathode active material |
| CN111926191A (en) * | 2020-09-21 | 2020-11-13 | 天齐锂业（江苏）有限公司 | Method for recycling lithium iron phosphate battery |
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| CN108899601A (en) * | 2018-06-11 | 2018-11-27 | 衢州华友钴新材料有限公司 | A method of recycling lithium from LiFePO4 |
| KR20200046295A (en) * | 2018-10-24 | 2020-05-07 | 코스모에코켐(주) | Selective leaching method of trivalent cathode active material |
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