CN106299526A - Recycling method of strong alkali solution in waste lithium battery recycling industry - Google Patents
Recycling method of strong alkali solution in waste lithium battery recycling industry Download PDFInfo
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- CN106299526A CN106299526A CN201610832665.8A CN201610832665A CN106299526A CN 106299526 A CN106299526 A CN 106299526A CN 201610832665 A CN201610832665 A CN 201610832665A CN 106299526 A CN106299526 A CN 106299526A
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- aluminum
- strong base
- base solution
- waste lithium
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- 239000003513 alkali Substances 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 91
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 62
- 239000002585 base Substances 0.000 claims abstract description 59
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- -1 aluminum ions Chemical class 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 16
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 230000001939 inductive effect Effects 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 2
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 claims description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000012266 salt solution Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 229910017238 Ni0.8Co0.15Al0.05(OH)2 Inorganic materials 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The invention relates to a method for recycling a strong alkali solution in waste lithium battery recycling industry. The invention belongs to the technical field of waste lithium ion battery recovery. The method for recycling the strong alkali solution in the waste lithium battery recycling industry comprises the following steps: (1) separating aluminum-containing materials: mechanically crushing waste lithium batteries, adding water, stirring, and sieving to obtain an aluminum-containing material as oversize; (2) dissolving of aluminum: adding an aluminum-containing material into 3-25mol/L sodium hydroxide solution, stirring to react, and screening to obtain filtrate which is aluminum-containing strong base solution; (3) adjusting the ion proportion of the aluminum strong alkali solution: adding sodium hydroxide or water to adjust the concentration of sodium ions to be 6-25mol/L and the concentration of aluminum ions to be 0.001-1mol/L in the solution; (4) utilization of aluminum-containing strong alkali solution: and the obtained strong alkaline solution is used as a precipitator and reacts with the target salt solution to prepare a precursor of the lithium iron phosphate and the ternary material cathode material, so that the lithium iron phosphate and the ternary material target cathode material are prepared. The method has the advantages of simple process, convenient operation, environmental protection, low cost, high added value and the like.
Description
Technical field
The invention belongs to waste and old lithium ion battery recovery technology field, particularly relate to a kind of waste lithium cell and reclaim industry
The recoverying and utilizing method of strong base solution.
Background technology
At present, along with ev industry quickly increases, to the year two thousand twenty, only China's electric automobile power battery is accumulative scraps
Amount is up to the scale of 120,000-17 ten thousand tons.If appropriate recycling can not be carried out, it will environment to be caused huge breaking
Bad.
Patent CN101921917B discloses a kind of method reclaiming valuable metal from waste lithium cell.The method will electric discharge
After waste lithium cell mechanical activation comminution, 350 DEG C～400 DEG C calcinings of high temperature, obtain containing cobalt, aluminum, the material of copper, adding content is
The sodium hydroxide solution of 5%～10%, reacts 2-3h, filters alkali liquor, and washing is dried to obtain containing cobalt, the material of copper.Therein
Containing substantial amounts of aluminum in alkali liquor, obtain aluminum hydroxide crystals through technology such as further acid treatment and filtration washings.In this patent
Aluminium foil recovery method is the main recovery method of aluminium foil in current lithium ion battery recovery industry, patent CN101217206A,
CN104157926A etc. use same method to reach the purpose of aluminium foil recycling.This method need to add when acid treatment greatly
Amount sulphuric acid, neutralizes the alkali in alkali liquor, reaches regulate pH value and then realize the purpose of aluminum hydroxide precipitation.Now, filtrate contains
Having a large amount of sodium sulfate to recycle, the waste liquid of generation need to carry out processing to avoid the secondary pollution to environment, at waste water
Reason amount is big, and consumes a large amount of sulphuric acid during acid treatment, relatively costly.
Patent CN102285738B discloses the processing method of a kind of high-salinity waste water in waste lithium battery recovering industry.This method is led to
Crossing reverse osmosis process and be purified water and dense water, dense water, by natural evaporation or low temperature crystallization or the method for multistage flash evaporation, obtains
Product salt.Reverse osmosis membrane used is relatively costly, and treatment effeciency is limited, and deposits or place relatively big with later stage salinity crystallization process energy consumption
The technical problem such as compole length during reason.
Summary of the invention
The present invention solves that technical problem present in known technology provides a kind of waste lithium cell to reclaim industry highly basic
The recoverying and utilizing method of solution.
It is an object of the invention to provide one and there is technique simply, easy to operate, only need to finely tune ion ratio and can be not only used for
The production process of the precursor such as lithium ion battery anode material lithium iron phosphate, ternary material, green, environmental protection, low cost, high additional
The waste lithium cell of the features such as value reclaims the recoverying and utilizing method of industry strong base solution.
Waste lithium cell of the present invention reclaims the recoverying and utilizing method of industry strong base solution, including technical process:
(1) the separation of aluminiferous material: the waste lithium cell discharged completely carries out Mechanical Crushing, adds water and is stirred adding
Speed pole piece material separates with collector；By the sieve by 60 mesh of the slurry after stirring, oversize is aluminiferous material；
(2) the dissolving of aluminum: in gained aluminiferous material joins the sodium hydroxide solution of 3-25mol/L in (1), stirring is anti-
Answering 1-2h disposed slurry by sieve, joined by filtering residue in the sodium hydroxide solution of same concentration, same technique carries out secondary alkali
Filtering after leaching, filtering residue carries out subsequent treatment, and filtrate is incorporated in first time filtrate, and filtrate is containing aluminum strong after multiple times of filtration removes the gred
Aqueous slkali；
(3) the adjustment containing aluminum strong base solution ion ratio: with inductive coupling plasma emission spectrograph (ICP) in (2)
Sodium ion, aluminium ion concentration are tested, and according to target product composition, add sodium hydroxide or water adjustment sodium ion in liquor is dense
Degree is 6-25mol/L, and aluminium ion concentration is 0.001-1mol/L；
(4) recycling containing aluminum strong base solution: with (3) gained strong base solution as precipitant, carry out with target saline solution
Liquid-phase precipitation reacts, and prepares the precursor of the positive electrode such as LiFePO4, ternary material, and then prepared LiFePO4, ternary material
The target positive electrode finished products such as material.
Waste lithium cell of the present invention reclaims the recoverying and utilizing method of industry strong base solution and is adopted the technical scheme that:
A kind of waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, is characterized in: waste lithium cell reclaims
The recoverying and utilizing method of industry strong base solution includes following technical process:
(1) separation of aluminiferous material
The waste lithium cell discharged completely is carried out Mechanical Crushing, adds water and be stirred accelerating pole piece material and collector
Separation；Being sifted out by slurry after stirring, oversize is aluminiferous material；
(2) dissolving of aluminum
In in (1), gained aluminiferous material joins the sodium hydroxide solution of 3-25mol/L, stirring reaction 1-2h disposed slurry
By 60 mesh sieve, filtrate is containing aluminum strong base solution；
(3) adjustment of aluminum strong base solution ion ratio
According to target product composition, add sodium hydroxide or water to adjust sodium ion in liquor concentration be 6-25mol/L, aluminum from
Sub-concentration is 0.001-1mol/L；
(4) utilization containing aluminum strong base solution
With (3) gained strong base solution as precipitant, carry out liquid-phase precipitation reaction with target saline solution, prepared LiFePO4,
The precursor of ternary material positive electrode, and then prepared LiFePO4, ternary material target positive electrode finished product.
Waste lithium cell of the present invention reclaims the recoverying and utilizing method of industry strong base solution and can also adopt the following technical scheme that
Described waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, is characterized in: the course of dissolution of aluminum
In, gained aluminiferous material in (1) is joined stirring reaction 1-2h disposed slurry in the sodium hydroxide solution of 3-25mol/L and passes through sieve
After son, being joined by filtering residue in the sodium hydroxide solution of same concentration, same technique filters after carrying out secondary alkali leaching, and filtering residue is carried out
Subsequent treatment, filtrate is incorporated in first time filtrate, and filtrate is containing aluminum strong base solution after 2-6 filter cleaner.
Described waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, is characterized in: aluminum strong base solution from
During the adjustment of sub-ratio, with inductive coupling plasma emission spectrograph (ICP) to sodium ion, aluminium ion concentration in (2)
Test, then add sodium hydroxide according to target product composition or water adjusts sodium ion in liquor concentration.
Described waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, is characterized in: containing aluminum strong base solution
Utilization during, ternary material includes cobalt nickel oxide manganses lithium, cobalt nickel oxide aluminum lithium and corresponding doping vario-property material.
Described waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, is characterized in: before LiFePO4
Body includes iron phosphate and corresponding doping component, and the precursor of ternary material includes hydroxide nickel cobalt manganese or nickel cobalt aluminum hydroxide
And corresponding doping component.
Described waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, is characterized in: time prepared by iron phosphate
Saline solution includes iron-containing liquor, solution containing phosphate or the mixed solution of the two；Time prepared by ternary material saline solution include solution containing nickel,
Cobalt-carrying solution, manganese containing solution or the most several mixed solutions.
The present invention has the advantage that with good effect:
Waste lithium cell reclaims the recoverying and utilizing method technical side brand-new owing to have employed the present invention of industry strong base solution
Case, compared with prior art, the present invention has a characteristic that
(1) technique is simple: i.e. can be used as new raw materials for production, nothing after being dissolved by the aluminium foil aqueous slkali in waste lithium cell
Need precipitation follow-up in prior art, wash, separate and the operation such as reproduction, make whole recovery process simplify；
(2) environmental protection: carry out acid treatment without adding a large amount of sulphuric acid, it is to avoid a large amount of by-products and the generation of waste water, both
The cost reducing strong base solution recycling turn avoid the secondary pollution that by-product brings；
(3) high added value: the strong base solution of recovery is used for the preparation process of anode material for lithium-ion batteries precursor, both
Save existing recovery technology input in recycle of alkali liquor, eliminate again required sodium hydroxide and aluminium salt time prepared by precursor
Cost, improves the added value of whole recycling technique.
Accompanying drawing explanation
Fig. 1 is that strong base solution of the present invention recycles artwork；
Fig. 2 is that embodiment 1 gained ternary material precursor SEM schemes (Ni1/3Co1/3Mn1/3(OH)2, containing Al 1200ppm)；
Fig. 3 is that embodiment 2 gained ternary material precursor SEM schemes (Ni0.5Co0.2Mn0.3(OH)2, containing Al 1500ppm)；
Fig. 4 is that embodiment 3 ternary material precursor SEM schemes (Ni0.6Co0.2Mn0.2(OH)2, containing Al 2000ppm)；
Fig. 5 is that embodiment 4 ternary material precursor SEM schemes (Ni0.8Co0.15Al0.05(OH)2)。
Detailed description of the invention
For the summary of the invention of the present invention, feature and effect can be further appreciated that, hereby enumerate following example, and coordinate accompanying drawing
Describe in detail as follows:
Refering to accompanying drawing 1 to Fig. 5.
Embodiment 1
A kind of waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, including following technical process:
1. the separation of aluminiferous material: the waste lithium cell discharged completely carries out Mechanical Crushing, adds water and is stirred adding
Speed pole piece material separates with collector；By the sieve by 60 mesh of the slurry after stirring, oversize is aluminiferous material；
2. the dissolving of aluminum: in gained aluminiferous material joins the sodium hydroxide solution of 12mol/L in (1), stirring reaction
2h disposed slurry passes through 60 mesh sieve, is joined by filtering residue in the sodium hydroxide solution of same concentration, and same technique carries out secondary alkali
Filtering after leaching, filtering residue carries out subsequent treatment, and filtrate is incorporated in first time filtrate, and filtrate is containing aluminum strong after multiple times of filtration removes the gred
Aqueous slkali；
3. the adjustment containing aluminum strong base solution ion ratio: with inductive coupling plasma emission spectrograph (ICP) to (2) institute
Obtaining alkali liquor to test, Na ion concentration is 11.5mol/L, and aluminium ion concentration is 0.1mol/L, according to target product composition, adds
It is 6mol/L that hydro-oxidation sodium and water adjust sodium ion in liquor concentration, and aluminium ion concentration is 0.01mol/L；
4. the recycling containing aluminum strong base solution: with (3) gained strong base solution as precipitant, with nickel ion concentration be
0.8mol/L, concentration of cobalt ions is 0.8mol/L, and it is anti-that manganese ion concentration is that the mixing salt solution of 0.8mol/L carries out liquid-phase precipitation
Should, prepare 111 type ternary material precursors.
Embodiment 2
A kind of waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, including following technical process:
1. the separation of aluminiferous material: the waste lithium cell discharged completely carries out Mechanical Crushing, adds water and is stirred adding
Speed pole piece material separates with collector；By the sieve by 60 mesh of the slurry after stirring, oversize is aluminiferous material；
2. the dissolving of aluminum: in gained aluminiferous material joins the sodium hydroxide solution of 16mol/L in (1), stirring reaction
1.5h disposed slurry passes through 60 mesh sieve, is joined by filtering residue in the sodium hydroxide solution of same concentration, and same technique carries out secondary
Filtering after alkali leaching, filtering residue carries out subsequent treatment, and filtrate is incorporated in first time filtrate, and filtrate is containing aluminum after multiple times of filtration removes the gred
Strong base solution；
3. the adjustment containing aluminum strong base solution ion ratio: with inductive coupling plasma emission spectrograph (ICP) to (2) institute
Obtaining alkali liquor to test, Na ion concentration is 15mol/L, and aluminium ion concentration is 0.2mol/L, according to target product composition, adds
It is 8mol/L that sodium hydroxide and water adjust sodium ion in liquor concentration, and aluminium ion concentration is 0.02mol/L；
4. the recycling containing aluminum strong base solution: with (3) gained strong base solution as precipitant, with nickel ion concentration be
1.2mol/L, concentration of cobalt ions is 0.48mol/L, and manganese ion concentration is that the mixing salt solution of 0.72mol/L carries out liquid-phase precipitation
Reaction, prepares 523 type ternary material precursors.
Embodiment 3
A kind of waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, including following technical process:
1. the separation of aluminiferous material: the waste lithium cell discharged completely carries out Mechanical Crushing, adds water and is stirred adding
Speed pole piece material separates with collector；By the sieve by 60 mesh of the slurry after stirring, oversize is aluminiferous material；
2. the dissolving of aluminum: in gained aluminiferous material joins the sodium hydroxide solution of 20mol/L in (1), stirring reaction
1h disposed slurry passes through 60 mesh sieve, is joined by filtering residue in the sodium hydroxide solution of same concentration, and same technique carries out secondary alkali
Filtering after leaching, filtering residue carries out subsequent treatment, and filtrate is incorporated in first time filtrate, and filtrate is containing aluminum strong after multiple times of filtration removes the gred
Aqueous slkali；
3. the adjustment containing aluminum strong base solution ion ratio: with inductive coupling plasma emission spectrograph (ICP) to (2) institute
Obtaining alkali liquor to test, Na ion concentration is 19mol/L, and aluminium ion concentration is 0.4mol/L, according to target product composition, adds
It is 10mol/L that sodium hydroxide and water adjust sodium ion in liquor concentration, and aluminium ion concentration is 0.04mol/L；
4. the recycling containing aluminum strong base solution: with (3) gained strong base solution as precipitant, with nickel ion concentration be
1.44mol/L, concentration of cobalt ions is 0.48mol/L, and manganese ion concentration is that the mixing salt solution of 0.48mol/L carries out liquid-phase precipitation
Reaction, prepares 622 type ternary material precursors.
Embodiment 4
A kind of waste lithium cell reclaims the recoverying and utilizing method of industry strong base solution, including following technical process:
1. the separation of aluminiferous material: the waste lithium cell discharged completely carries out Mechanical Crushing, adds water and is stirred adding
Speed pole piece material separates with collector；By the sieve by 60 mesh of the slurry after stirring, oversize is aluminiferous material；
2. the dissolving of aluminum: in gained aluminiferous material joins the sodium hydroxide solution of 24mol/L in (1), stirring reaction
0.5h disposed slurry passes through 60 mesh sieve, is joined by filtering residue in the sodium hydroxide solution of same concentration, and same technique carries out secondary
Filtering after alkali leaching, filtering residue carries out subsequent treatment, and filtrate is incorporated in first time filtrate, and filtrate is containing aluminum after multiple times of filtration removes the gred
Strong base solution；
3. the adjustment containing aluminum strong base solution ion ratio: with inductive coupling plasma emission spectrograph (ICP) to (2) institute
Obtaining alkali liquor to test, Na ion concentration is 22mol/L, and aluminium ion concentration is 3mol/L, according to target product composition, adds hydrogen
It is 12mol/L that sodium oxide and water adjust sodium ion in liquor concentration, and aluminium ion concentration is 0.3mol/L；
4. the recycling containing aluminum strong base solution: with (3) gained strong base solution as precipitant, with nickel ion concentration be
1.92mol/L, concentration of cobalt ions is 0.36mol/L, and manganese ion concentration is that the mixing salt solution of 0.12mol/L carries out liquid-phase precipitation
Reaction, prepares NCA type ternary material precursor.
Constituent content in table 1 each embodiment gained precursor
| Content (%) | Na | Al | Fe | Cu | Ca | Zn | Mg |
| Embodiment 1 | 0.0224 | 0.12 | 0.0037 | 0.0006 | 0.0008 | 0.0009 | 0.0031 |
| Embodiment 2 | 0.0213 | 0.15 | 0.0046 | 0.0006 | 0.0010 | 0.0005 | 0.0025 |
| Embodiment 3 | 0.0221 | 0.2 | 0.0036 | 0.0007 | 0.0005 | 0.0006 | 0.0028 |
| Embodiment 4 | 0.0245 | 1.48 | 0.0048 | 0.0010 | 0.0006 | 0.0014 | 0.0054 |
It is simple that the present embodiment has described technique, easy to operate, and only need to finely tune ion ratio can be not only used for lithium-ion electric
The production process of the precursors such as pond LiFePO 4 of anode material, ternary material, green, environmental protection, low cost, high added value etc. is actively
Effect.
Claims (6)
1. waste lithium cell reclaims a recoverying and utilizing method for industry strong base solution, it is characterized in that: waste lithium cell reclaims row
The recoverying and utilizing method of industry strong base solution includes following technical process:
(1) separation of aluminiferous material
The waste lithium cell discharged completely is carried out Mechanical Crushing, add water be stirred accelerating pole piece material and collector point
From；Being sifted out by slurry after stirring, oversize is aluminiferous material；
(2) dissolving of aluminum
In in (1), gained aluminiferous material joins the sodium hydroxide solution of 3-25mol/L, stirring reaction 1-2h disposed slurry sieves
Son, filtrate is containing aluminum strong base solution；
(3) adjustment of aluminum strong base solution ion ratio
According to target product composition, adding sodium hydroxide or water adjustment sodium ion in liquor concentration is 6-25mol/L, aluminium ion is dense
Degree is 0.001-1mol/L；
(4) utilization containing aluminum strong base solution
With (3) gained strong base solution as precipitant, carry out liquid-phase precipitation reaction with target saline solution, prepare LiFePO4, ternary
The precursor of material positive electrode, and then prepared LiFePO4, ternary material target positive electrode finished product.
Waste lithium cell the most according to claim 1 reclaims the recoverying and utilizing method of industry strong base solution, it is characterized in that: aluminum
Course of dissolution in, after gained aluminiferous material in (1) is joined in the sodium hydroxide solution of 3-25mol/L stirring reaction 1-2h
Slurry by, after sieve, joining in the sodium hydroxide solution of same concentration by filtering residue, and same technique carries out mistake after secondary alkali leaching
Filter, filtering residue carries out subsequent treatment, and filtrate is incorporated in first time filtrate, and it is molten that filtrate is the highly basic containing aluminum after 2-6 filter cleaner
Liquid.
Waste lithium cell the most according to claim 1 reclaims the recoverying and utilizing method of industry strong base solution, it is characterized in that: aluminum
During the adjustment of strong base solution ion ratio, with inductive coupling plasma emission spectrograph (ICP) to sodium ion in (2),
Aluminium ion concentration is tested, and then adds sodium hydroxide according to target product composition or water adjusts sodium ion in liquor concentration.
4. the recoverying and utilizing method of industry strong base solution, its feature is reclaimed according to the waste lithium cell described in claim 1,2 or 3
It is: during the utilization containing aluminum strong base solution that ternary material includes cobalt nickel oxide manganses lithium, cobalt nickel oxide aluminum lithium and mixes accordingly
Miscellaneous material modified.
5. the recoverying and utilizing method of industry strong base solution, its feature is reclaimed according to the waste lithium cell described in claim 1,2 or 3
It is: the precursor of LiFePO4 includes iron phosphate and corresponding doping component, and the precursor of ternary material includes hydroxide nickel cobalt
Manganese or nickel cobalt aluminum hydroxide and corresponding doping component.
6. the recoverying and utilizing method of industry strong base solution, its feature is reclaimed according to the waste lithium cell described in claim 1,2 or 3
It is: time prepared by iron phosphate, saline solution includes iron-containing liquor, solution containing phosphate or the mixed solution of the two；Time prepared by ternary material, salt is molten
Liquid includes solution containing nickel, cobalt-carrying solution, manganese containing solution or the most several mixed solutions.
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