CN102285673B - Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile - Google Patents
Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 15
- 239000005955 Ferric phosphate Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229940032958 ferric phosphate Drugs 0.000 claims description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 14
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims 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 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 27
- 239000003513 alkali Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 235000014413 iron hydroxide Nutrition 0.000 abstract 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 2
- 230000001376 precipitating effect Effects 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000010304 firing Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
- Compounds Of Iron (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering lithium and iron from a lithium iron phosphate power battery for an electromobile. The method comprises the following steps: 1) disassembling the lithium iron phosphate power battery so as to obtain a positive electrode material, smashing and screening so as to obtain a powder material; 2) adding an alkali solution in the powder material to dissolve aluminum and oxide of aluminum, and filtering so as to obtain filter mud; 3) lixiviating the filter mud with a mixed solution of an acid and a reducing agent so as to obtain lixivium; 4) adding an alkali to regulate the pH value of the lixivium to 1.5-3, precipitating to separate out iron hydroxide, and filtering so as to obtain filtrate; 5) firing iron hydroxide obtained in the step 4) so as to obtain iron oxide; 6) regulating the pH value of the lixivium to 5.0-8.0 with an alkali, precipitating impurities in the lixivium, and filtering so as to obtain filtrate; and 7) adding a solid sodium carbonate in the filtrate, and concentrating and crystallizing the obtained solution so as to obtain lithium carbonate. The recovering method disclosed by the invention has simple process, can be used for simultaneously recovering iron and lithium and can be directly used for production, and the purity of prepared lithium carbonate can reach above 98.5%.
Description
Technical field
The present invention relates to a kind of method that reclaims lithium and iron, particularly a kind of method that reclaims lithium and iron from electric automobile lithium ferric phosphate power cell.
Background technology
The automobile electric gasification is a main direction of Chinese automobile future development, estimates according to " electromobile development in science and technology " 12 " ad hoc planning ", and Electric Cars in China recoverable amount in 2015 plan reaches 1,000,000, and the power cell production capacity approximately reaches 10,000,000,000 watt-hours.The research and development that a plurality of domestic and international Automobile Enterprises drop into the new forms of energy power vehicle with all strength, the launch of some mass production.Along with popularizing of new forms of energy power vehicle, we will face Tough questions how to process discarded power cell.Power cell includes various metals and compound, if do not deal carefully with recovery, not only can cause the wasting of resources, also can do great damage to physical environment.
Lithium iron phosphate dynamic battery is a kind of Novel power battery, compare with cobalt acid lithium battery with traditional lead-acid cell, lithium iron phosphate dynamic battery has good chemical property, safe, the characteristics such as good cycle, and starting material are relatively cheap, will become the main flow of automobile power cell.The technology that the research lithium iron phosphate dynamic battery is recycled can avoid first polluting rear improvement, and is all very meaningful to the reasonable recycling of protection of the environment and resource.
Also more immature about the technical study of lithium iron phosphate dynamic battery recovery at present.CN102017276 discloses a kind of recovery method of lithium iron phosphate dynamic battery, and the method directly coordinates with negative material after cleaning and screening and again makes battery by disassembling positive plate.But because the positive plate of original lithium iron phosphate dynamic battery lost efficacy, only in fact can't recover its performance by simple cleaning and screening, can there be defective in the battery performance that this method is made.
CN 101916889 discloses a kind of lithium-ion-power cell and has reclaimed the method for preparing iron lithium phosphate, and the method leaches Li with mineral acid after separating lithium iron phosphate positive material
+, Fe
2+And PO
4 3-, then add lithium salts or molysite and xitix, control the pH value and precipitated, ball milling, drying and calcining obtain iron lithium phosphate in aqueous sucrose solution at last.Lack the step of removing metallic impurity in the method technological process, can make product contain a large amount of other metals, affect quality.
Summary of the invention
The object of the present invention is to provide a kind of method that reclaims lithium and iron from electric automobile lithium ferric phosphate power cell.
The technical solution used in the present invention is:
A kind of method that reclaims lithium and iron from electric automobile lithium ferric phosphate power cell comprises the following steps:
1) disassemble lithium iron phosphate dynamic battery and obtain positive electrode material and pulverize, sieve, obtain powder;
2) add alkaline solution in powder, the oxide compound of dissolved aluminum and aluminium filters to get filter mud;
3) mixing solutions of filter mud with acid and reductive agent leached, filter and obtain leach liquor;
4) adding alkali, to regulate the pH value of leach liquor be 1.5～3, the Precipitation ironic hydroxide, and filtration obtains filtrate;
5) with the ironic hydroxide calcination that obtains in step 4), obtain ferric oxide;
6) continue regulating step 4 with alkali) in the pH to 5.0～8.0 of filtrate, precipitated impurities filters to get filtrate;
7) add solid sodium carbonate in the filtrate that obtains to step 6), gained solution condensing crystal obtains Quilonum Retard.
Step 2) in, alkaline solution is at least a in sodium hydroxide, potassium hydroxide.
Step 2) in, the mass concentration of alkaline solution is 10-30%.
In step 3), described acid is the sulfuric acid of 3.0-5.0mol/L.
In step 3), described reductive agent is the hydrogen peroxide solution of 30-50%.
In step 3), the volume of mixing solutions and the mass ratio of filter mud are 4-6L:1Kg.
In step 3), the temperature of leaching is 60～90 ℃.
In step 4) and step 6), described alkali is at least a in sodium hydroxide, potassium hydroxide, sodium carbonate, ammoniacal liquor.
The step 5) calcination temperature is 300～500 ℃.
The invention has the beneficial effects as follows: recovery method technique of the present invention is simple, can reclaim simultaneously elemental lithium and ferro element, and the Quilonum Retard purity of making reaches more than 98.5%, can directly apply to production.
Embodiment
A kind of method that reclaims lithium from electric automobile lithium ferric phosphate power cell comprises the following steps:
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice, pulverize, sieve, obtain powder;
2) the lower powder of sieve is put into container, is placed in the water bath with thermostatic control of 50～80 ℃, and adding mass percent in powder is that sodium hydroxide solution or the potassium hydroxide solution of 10-30% flooded 1～3 hour, and the oxide compound of dissolved aluminum and aluminium filters to get filter mud;
3) be that the mixing solutions of 30～50% hydrogen peroxide solution leaches with the sulphuric acid soln of 3～5mol/L and mass concentration with filter mud, the ratio that institute adds liquid volume and filter mud solid masses is 4～6L:1kg, extraction temperature is 60～90 ℃, and extraction time is 1～2 hour, filters at last and obtains leach liquor;
4) adding alkali, to regulate the pH value of leach liquor be 1.5～3, the Precipitation ironic hydroxide, and filtration obtains filtrate;
5) with the ironic hydroxide calcination that obtains in step 4), obtain ferric oxide;
6) with alkali lye regulating step 4) in the pH of filtrate be 5.0～8.0, stirring reaction 1～2 hour, precipitated impurities filters to get filtrate;
7) add solid sodium carbonate in the filtrate that obtains to step 6), gained solution condensing crystal obtains Quilonum Retard.
The Quilonum Retard that obtains according to the method described above is more than the purity to 98.5% of gained Quilonum Retard.
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice.Then be put in the vertical and high-speed rotary mill and pulverize, grinding time is 10 minutes.Material after pulverizing sieves with 80 purpose standard sieves, and the powder of getting under the 50g sieve is put into beaker;
The beaker that 2) will be placed with powder is put into the water bath with thermostatic control the inside of 60 ° of C, and adding mass concentration is 25% sodium hydroxide solution 250ml, under agitation reacts 1 hour, filters, and with the distilled water flushing filter mud for several times, is placed on the beaker the inside;
3) add the sulfuric acid 200ml of 4.0mol/L and 40% hydrogen peroxide 30ml, be heated to 60 ° of C and leached 1 hour, refilter and obtain leach liquor;
4) prepare 25% sodium hydroxide solution, slowly drip sodium hydroxide solution under the state that stirs in leach liquor and monitor simultaneously pH value, pH stopped stirring and dripping sodium hydroxide solution at 1.5 o'clock, the Precipitation bulky ferric hydroxide precipitate, and filtration obtains filtrate;
5) with the ironic hydroxide that obtains in step 4) 300-350 ℃ of lower calcination, obtain ferric oxide;
6) with mass concentration be 25% sodium hydroxide solution regulating step 4) in the pH value of the filtrate that obtains, until pH is 6, the contamination precipitation with in leach liquor filters to get filtrate;
7) add 20g sodium carbonate in the filtrate that obtains to step 6), stirring and dissolving with the solution condensing crystal, obtains the Quilonum Retard solid.
The purity of gained Quilonum Retard reaches 98.6%.
Embodiment 2:
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice.Then be put in the vertical and high-speed rotary mill and pulverize, grinding time is 15 minutes.Material after pulverizing sieves with 80 purpose standard sieves, and the powder of getting under the 100g sieve is put into beaker;
The beaker that 2) will be placed with powder is put into the water bath with thermostatic control the inside of 50 ° of C, and adding mass concentration is 10% sodium hydroxide solution 300ml, under agitation reacts 3 hours, filters, and with the distilled water flushing filter mud for several times, puts into beaker;
3) add the sulfuric acid 450ml of 3.0mol/L and 30% hydrogen peroxide 50ml, be heated to 90 ° of C and leached 2 hours, filter to get leach liquor;
4) the pH value of hydro-oxidation sodium solution adjusting leach liquor is 2, and the Precipitation ironic hydroxide filters and obtains filtrate;
5) with the ironic hydroxide that obtains in step 4) 350～400 ℃ of lower calcinations, obtain ferric oxide;
6) drip mass concentration in the filtrate that obtains in the step 4) under stirring and be 25% sodium hydroxide solution, stop stirring and dripping when pH is 8.0, the throw out that filters out generation gets filtrate;
7) add 40g sodium carbonate in the filtrate that obtains to step 6), stirring and dissolving with the solution condensing crystal, obtains the Quilonum Retard solid.
The purity of gained Quilonum Retard reaches 98.9%.
Embodiment 3:
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice.Then be put in the vertical and high-speed rotary mill and pulverize, grinding time is 15 minutes.Material after pulverizing sieves with 80 purpose standard sieves, and the powder of getting under the 200g sieve is put into beaker;
The beaker that 2) will be placed with powder is put into the water bath with thermostatic control the inside of 80 ° of C, and adding mass concentration is 30% sodium hydroxide solution 500ml, under agitation reacts 3 hours, filters, and with the distilled water flushing filter mud for several times, puts into beaker;
3) add the sulfuric acid 600ml of 5.0mol/L and 50% hydrogen peroxide 200ml in filter mud, be heated to 80 ° of C and leached 1.5 hours, filter to get leach liquor;
4) the pH value of hydro-oxidation sodium solution adjusting leach liquor is 3, and the Precipitation ironic hydroxide filters and obtains filtrate;
5) with the ironic hydroxide that obtains in step 4) 450～500 ℃ of lower calcinations, obtain ferric oxide;
6) drip mass concentration in the filtrate that obtains in the step 4) under stirring and be 20% potassium hydroxide solution, stop stirring and dripping when pH is 7.0, the throw out that filters out generation gets filtrate;
7) add 80g sodium carbonate in the filtrate that obtains to step 6), stirring and dissolving with the solution condensing crystal, obtains the Quilonum Retard solid.
The purity of gained Quilonum Retard reaches 99.2%.
Embodiment 4:
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice.Then be put in the vertical and high-speed rotary mill and pulverize, grinding time is 15 minutes.Material after pulverizing sieves with 80 purpose standard sieves, and the powder of getting under the 500g sieve is put into beaker;
The beaker that 2) will be placed with powder is put into the water bath with thermostatic control the inside of 70 ° of C, and adding mass concentration is 20% sodium hydroxide solution 1.5L, under agitation reacts 2 hours, filters, and with the distilled water flushing filter mud for several times, puts into beaker;
3) add the sulfuric acid 1400ml of 5.0mol/L and 50% hydrogen peroxide 600ml in filter mud, be heated to 80 ° of C and leached 1.5 hours, filter to get leach liquor;
4) the pH value of hydro-oxidation potassium solution adjusting leach liquor is 3, and the Precipitation ironic hydroxide filters and obtains filtrate;
5) with the ironic hydroxide that obtains in step 4) 400-450 ℃ of lower calcination, obtain ferric oxide;
6) drip mass concentration in the filtrate that obtains in the step 4) under stirring and be 28% sodium hydroxide solution, stop stirring and dripping when pH is 5.0, the throw out that filters out generation gets filtrate;
7) add 200g sodium carbonate in the filtrate that obtains to step 6), stirring and dissolving with the solution condensing crystal, obtains the Quilonum Retard solid.
The purity of gained Quilonum Retard reaches 99.0%.
Claims (1)
1. method that reclaims lithium and iron from electric automobile lithium ferric phosphate power cell comprises the following steps:
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice, then be put in the vertical and high-speed rotary mill and pulverize, grinding time is 15 minutes, material after pulverizing sieves with 80 purpose standard sieves, and the powder of getting under the 200g sieve is put into beaker;
The beaker that 2) will be placed with powder is put into the water bath with thermostatic control the inside of 80 ° of C, and adding mass concentration is 30% sodium hydroxide solution 500ml, under agitation reacts 3 hours, filters, and with the distilled water flushing filter mud for several times, puts into beaker;
3) add the sulfuric acid 600ml of 5.0mol/L and 50% hydrogen peroxide 200ml in filter mud, be heated to 80 ° of C and leached 1.5 hours, filter to get leach liquor;
4) the pH value of hydro-oxidation sodium solution adjusting leach liquor is 3, and the Precipitation ironic hydroxide filters and obtains filtrate;
5) with the ironic hydroxide that obtains in step 4) 450～500 ℃ of lower calcinations, obtain ferric oxide;
6) drip mass concentration in the filtrate that obtains in the step 4) under stirring and be 20% potassium hydroxide solution, stop stirring and dripping when pH is 7.0, the throw out that filters out generation gets filtrate;
7) add 80g sodium carbonate in the filtrate that obtains to step 6), stirring and dissolving with the solution condensing crystal, obtains the Quilonum Retard solid;
The purity of gained Quilonum Retard reaches 99.2%;
Perhaps, a kind of method that reclaims lithium and iron from electric automobile lithium ferric phosphate power cell comprises the following steps:
1) disassemble after waste and old electric automobile lithium ferric phosphate power cell discharge, obtain battery anode slice, then be put in the vertical and high-speed rotary mill and pulverize, grinding time is 15 minutes, material after pulverizing sieves with 80 purpose standard sieves, and the powder of getting under the 500g sieve is put into beaker;
The beaker that 2) will be placed with powder is put into the water bath with thermostatic control the inside of 70 ° of C, and adding mass concentration is 20% sodium hydroxide solution 1.5L, under agitation reacts 2 hours, filters, and with the distilled water flushing filter mud for several times, puts into beaker;
3) add the sulfuric acid 1400ml of 5.0mol/L and 50% hydrogen peroxide 600ml in filter mud, be heated to 80 ° of C and leached 1.5 hours, filter to get leach liquor;
4) the pH value of hydro-oxidation potassium solution adjusting leach liquor is 3, and the Precipitation ironic hydroxide filters and obtains filtrate;
5) with the ironic hydroxide that obtains in step 4) 400-450 ℃ of lower calcination, obtain ferric oxide;
6) drip mass concentration in the filtrate that obtains in the step 4) under stirring and be 28% sodium hydroxide solution, stop stirring and dripping when pH is 5.0, the throw out that filters out generation gets filtrate;
7) add 200g sodium carbonate in the filtrate that obtains to step 6), stirring and dissolving with the solution condensing crystal, obtains the Quilonum Retard solid;
The purity of gained Quilonum Retard reaches 99.0%.
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| CN 201110147698 CN102285673B (en) | 2011-06-03 | 2011-06-03 | Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile |
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| CN 201110147698 CN102285673B (en) | 2011-06-03 | 2011-06-03 | Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile |
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Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102956936B (en) * | 2011-08-25 | 2015-04-15 | 深圳市格林美高新技术股份有限公司 | Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile |
| CN102916236B (en) * | 2012-10-22 | 2014-07-16 | 四川天齐锂业股份有限公司 | Comprehensive recycling method for lithium iron phosphate positive plates |
| CN103035977B (en) * | 2013-01-05 | 2015-09-09 | 深圳市泰力废旧电池回收技术有限公司 | A kind of method of separation and recovery lithium from waste and old lithium ion battery |
| CN103280610B (en) * | 2013-03-29 | 2015-11-11 | 江西省电力科学研究院 | A kind of positive pole waste tablet from ferric phosphate lithium cell recovery method |
| CN105355998A (en) * | 2015-11-03 | 2016-02-24 | 百顺松涛（天津）动力电池科技发展有限公司 | Recovery method of LiFePO4 positive electrode material |
| AU2017220394B2 (en) * | 2016-02-18 | 2021-12-23 | Li-Technology Pty Ltd | Lithium recovery from phosphate minerals |
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| CN108677014B (en) * | 2018-04-28 | 2019-08-30 | 长沙理工大学 | A kind of recovery method of waste and old power battery |
| CN109167059A (en) * | 2018-08-07 | 2019-01-08 | 陈子清 | A method of lithium carbonate is prepared using waste lithium iron phosphate battery |
| CN109573974A (en) * | 2018-10-22 | 2019-04-05 | 天齐锂业（江苏）有限公司 | Aluminum removing method based on acid leaching solution in waste lithium iron phosphate battery recycling |
| CN111960396A (en) * | 2020-08-26 | 2020-11-20 | 界首市南都华宇电源有限公司 | Method for preparing soluble phosphate from iron phosphate slag |
| CN115498299A (en) * | 2022-09-22 | 2022-12-20 | 广东邦普循环科技有限公司 | Method for recovering Prussian positive electrode material and manganese-based Prussian white positive electrode material prepared by same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6514311B1 (en) * | 2001-08-20 | 2003-02-04 | Industrial Technology Research Institute | Clean process of recovering metals from waste lithium ion batteries |
| CN1617380A (en) * | 2003-11-11 | 2005-05-18 | 财团法人工业技术研究院 | Method for recovering valuable metal from waste secondary cell |
| CN101519726A (en) * | 2009-04-16 | 2009-09-02 | 北京矿冶研究总院 | Method for directly roasting and treating waste lithium ion battery and recycling valuable metal |
| CN101555030A (en) * | 2009-05-04 | 2009-10-14 | 佛山市邦普镍钴技术有限公司 | Method for recovering and recycling waste lithium ion battery cathode material |
| CN101942569A (en) * | 2010-10-28 | 2011-01-12 | 湖南邦普循环科技有限公司 | Method for recovering lithium from waste lithium ion battery and waste pole piece |
-
2011
- 2011-06-03 CN CN 201110147698 patent/CN102285673B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6514311B1 (en) * | 2001-08-20 | 2003-02-04 | Industrial Technology Research Institute | Clean process of recovering metals from waste lithium ion batteries |
| CN1617380A (en) * | 2003-11-11 | 2005-05-18 | 财团法人工业技术研究院 | Method for recovering valuable metal from waste secondary cell |
| CN101519726A (en) * | 2009-04-16 | 2009-09-02 | 北京矿冶研究总院 | Method for directly roasting and treating waste lithium ion battery and recycling valuable metal |
| CN101555030A (en) * | 2009-05-04 | 2009-10-14 | 佛山市邦普镍钴技术有限公司 | Method for recovering and recycling waste lithium ion battery cathode material |
| CN101942569A (en) * | 2010-10-28 | 2011-01-12 | 湖南邦普循环科技有限公司 | Method for recovering lithium from waste lithium ion battery and waste pole piece |
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