CN106299526B - 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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- CN106299526B CN106299526B CN201610832665.8A CN201610832665A CN106299526B CN 106299526 B CN106299526 B CN 106299526B CN 201610832665 A CN201610832665 A CN 201610832665A CN 106299526 B CN106299526 B CN 106299526B
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- strong base
- base solution
- aluminium
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- waste lithium
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- 238000000034 method Methods 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 39
- 239000003513 alkali Substances 0.000 title claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 98
- 239000000243 solution Substances 0.000 claims abstract description 92
- 239000000463 material Substances 0.000 claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002585 base Substances 0.000 claims description 58
- 239000004411 aluminium Substances 0.000 claims description 40
- 238000000926 separation method Methods 0.000 claims description 14
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 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
- 230000001376 precipitating effect Effects 0.000 claims description 7
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 3
- 239000005955 Ferric phosphate Substances 0.000 claims description 3
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- 229940032958 ferric phosphate Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000399 iron(III) phosphate Inorganic materials 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
- 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
- 239000002893 slag Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 abstract description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 3
- -1 aluminum ions Chemical class 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005406 washing Methods 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 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
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 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
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 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
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material 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
-
- 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 a method for recycling strong base solution in waste lithium battery recycling industry, belonging to the technical field of waste lithium battery recycling, wherein (1) aluminum-containing material is separated, waste lithium batteries are mechanically crushed, water is added for stirring, slurry is sieved, and the oversize product is aluminum-containing material, (2) aluminum is dissolved, the aluminum-containing material is added into 3-25 mol/L sodium hydroxide solution and is stirred and reacted through a sieve, and the filtrate is aluminum-containing strong base solution, (3) the ion proportion of the aluminum strong base solution is adjusted, namely sodium hydroxide or water is added to adjust the concentration of sodium ions in the solution to be 6-25 mol/L and the concentration of aluminum ions to be 0.001-1 mol/L, and (4) the aluminum-containing strong base solution is utilized, the obtained strong base solution is used as a precipitator and is reacted with a target salt solution to prepare lithium iron phosphate and a precursor of a ternary material positive material, so as to prepare the lithium iron phosphate and the ternary material target positive material.
Description
Technical field
The invention belongs to waste and old lithium ion battery recovery technology fields, and industry is recycled more particularly to a kind of waste lithium cell
The recoverying and utilizing method of strong base solution.
Background technology
Currently, with ev industry rapid growth, the year two thousand twenty is arrived, only China's electric automobile power battery is accumulative scraps
Amount is up to 120,000-17 ten thousand tons of scale.If appropriate recovery processing cannot be carried out, it will caused to environment huge broken
It is bad.
Patent CN101921917B discloses a kind of method recycling valuable metal from waste lithium cell.This method will discharge
Waste lithium cell mechanical crushing afterwards, 350 DEG C~400 DEG C calcinings of high temperature, obtains the material containing cobalt, aluminium, copper, adding content is
5%~10% sodium hydroxide solution reacts 2-3h, is filtered to lye, and washing is dried to obtain the material containing cobalt, copper.It is therein
Contain a large amount of aluminium in lye, aluminum hydroxide crystals are obtained through the technologies such as further acid processing and filtration washing.In the patent
Aluminium foil recovery method is the main recovery method of aluminium foil in current lithium ion battery recycling industry, patent CN101217206A,
CN104157926A etc. is achieved the purpose that using same method by aluminium foil recycling.The method need to be added big when acid is handled
Sulfuric acid is measured, to neutralize the alkali in lye, achievees the purpose that adjust pH value and then realizes aluminum hydroxide precipitation.At this point, containing in filtrate
There are a large amount of sodium sulphate and can not recycle, the waste liquid of generation need to be handled to avoid the secondary pollution to environment, at waste water
Reason amount is big, and consumes a large amount of sulfuric acid when acid processing, and cost is higher.
Patent CN102285738B discloses a kind of processing method of high-salinity waste water in waste lithium battery recovering industry.The method is logical
It crosses reverse osmosis process and is purified water and concentrated water, concentrated water is obtained by natural evaporation or low temperature crystallization or the method for multistage flash distillation
Product salt.Reverse osmosis membrane cost used is higher, and treatment effeciency is limited, and deposit with later stage salinity crystallization process energy consumption it is larger or place
Manage time extremely long etc. technical problems.
Invention content
The present invention provides a kind of waste lithium cell recycling industry highly basic to solve technical problem present in known technology
The recoverying and utilizing method of solution.
The object of the present invention is to provide one kind have it is simple for process, it is easy to operate, only need to finely tune ion ratio and can be not only used for
The production process of the precursors such as lithium ion battery anode material lithium iron phosphate, ternary material, green, environmental protection, low cost, height are additional
The recoverying and utilizing method of the waste lithium cell recycling industry strong base solution of the features such as value.
The recoverying and utilizing method of waste lithium cell recycling industry strong base solution of the present invention, including technical process：
(1) the separation of aluminiferous material：The waste lithium cell to discharge completely is subjected to Mechanical Crushing, addition water, which is stirred, to be added
The separation of fast pole piece material and collector；By the slurry after stirring by the sieve of 60 mesh, oversize is aluminiferous material；
(2) the dissolving of aluminium：Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 3-25mol/L, stirring is anti-
Filter residue is added to by sieve in the sodium hydroxide solution of same concentration by slurry after answering 1-2h, and same technique carries out secondary alkali
It is filtered after leaching, filter residue carries out subsequent processing, and filtrate is incorporated in first time filtrate, and filtrate is strong containing aluminium after slagging-off is filtered for multiple times
Aqueous slkali；
(3) the adjustment of the ion ratio of strong base solution containing aluminium：With inductive coupling plasma emission spectrograph (ICP) in (2)
Sodium ion, aluminium ion concentration are tested, and according to target product ingredient, add sodium hydroxide or water adjustment sodium ion in liquor is dense
Degree is 6-25mol/L, aluminium ion concentration 0.001-1mol/L；
(4) recycling of the strong base solution containing aluminium：Using strong base solution obtained by (3) as precipitating reagent, carried out with target salting liquid
Liquid-phase precipitation reacts, and the precursor of the positive electrodes such as LiFePO4, ternary material is made, and then LiFePO4, ternary material is made
The targets positive electrode finished products such as material.
The recoverying and utilizing method of waste lithium cell recycling industry strong base solution of the present invention is adopted the technical scheme that：
A kind of recoverying and utilizing method of waste lithium cell recycling industry strong base solution, its main feature is that：Waste lithium cell recycles
The recoverying and utilizing method of industry strong base solution includes following technical process：
(1) separation of aluminiferous material
The waste lithium cell to discharge completely is subjected to Mechanical Crushing, water is added and is stirred acceleration pole piece material and collector
Separation；Slurry after stirring is sifted out, oversize is aluminiferous material；
(2) dissolving of aluminium
Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 3-25mol/L, slurry after 1-2h is stirred to react
By 60 mesh sieve, filtrate is strong base solution containing aluminium；
(3) adjustment of aluminium strong base solution ion ratio
According to target product ingredient, add sodium hydroxide or water adjust a concentration of 6-25mol/L of sodium ion in liquor, aluminium from
A concentration of 0.001-1mol/L of son；
(4) utilization of the strong base solution containing aluminium
Using strong base solution obtained by (3) as precipitating reagent, carries out liquid-phase precipitation with target salting liquid and react, obtained LiFePO4,
The precursor of ternary material positive electrode, and then LiFePO4, ternary material target positive electrode finished product is made.
The recoverying and utilizing method of waste lithium cell recycling industry strong base solution of the present invention can also adopt the following technical scheme that：
The recoverying and utilizing method of the waste lithium cell recycling industry strong base solution, its main feature is that：The course of dissolution of aluminium
In, gained aluminiferous material in (1) is added in the sodium hydroxide solution of 3-25mol/L to slurry after being stirred to react 1-2h and passes through sieve
After son, filter residue is added in the sodium hydroxide solution of same concentration, same technique filters after carrying out secondary alkali leaching, and filter residue carries out
Subsequent processing, filtrate are incorporated in first time filtrate, and filtrate is strong base solution containing aluminium after 2-6 filtering and removing slag.
The recoverying and utilizing method of the waste lithium cell recycling industry strong base solution, its main feature is that：Aluminium 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)
It is tested, sodium hydroxide is then added according to target product ingredient or water adjusts sodium ion in liquor concentration.
The recoverying and utilizing method of the waste lithium cell recycling industry strong base solution, its main feature is that：Strong base solution containing aluminium
Utilization during, ternary material includes cobalt nickel oxide manganses lithium, cobalt nickel oxide aluminium lithium and corresponding doping vario-property material.
The recoverying and utilizing method of the waste lithium cell recycling industry strong base solution, its main feature is that：Before LiFePO4
Body includes ferric 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.
The recoverying and utilizing method of the waste lithium cell recycling industry strong base solution, its main feature is that：When prepared by ferric phosphate
Salting liquid includes the mixed solution of iron-containing liquor, solution containing phosphate or the two；Ternary material prepare when salting liquid include solution containing nickel,
Cobalt-carrying solution, manganese containing solution or arbitrary several mixed solution.
The invention has the advantages and positive effects that：
Waste lithium cell recycles the recoverying and utilizing method of industry strong base solution as a result of the completely new technical side of the present invention
Case, compared with prior art, the present invention have following features：
(1) simple for process：It can be used as new raw materials for production, nothing after aluminium foil in waste lithium cell is dissolved with aqueous slkali
The processes such as subsequent precipitation, washing, separation and reproduction in the prior art are needed, entire recovery process is made to simplify；
(2) environmentally protective：Sour processing is carried out it is not necessary that a large amount of sulfuric acid are added, avoids the generation of a large amount of by-products and waste water, both
The cost for reducing strong base solution recycling in turn avoids the secondary pollution that by-product is brought；
(3) high added value：The strong base solution of recycling is used for the preparation process of anode material for lithium-ion batteries precursor, both
Input of the existing recovery technology in recycle of alkali liquor has been saved, and has eliminated required sodium hydroxide and aluminium salt when prepared by precursor
Cost improves the entire added value for recycling technique.
Description of the drawings
Fig. 1 is that strong base solution of the present invention recycles artwork；
Fig. 2 is that 1 gained ternary material precursor SEM of embodiment schemes (Ni1/3Co1/3Mn1/3(OH)2, 1200ppm containing Al)；
Fig. 3 is that 2 gained ternary material precursor SEM of embodiment schemes (Ni0.5Co0.2Mn0.3(OH)2, 1500ppm containing Al)；
Fig. 4 is that 3 ternary material precursor SEM of embodiment schemes (Ni0.6Co0.2Mn0.2(OH)2, 2000ppm containing Al)；
Fig. 5 is that 4 ternary material precursor SEM of embodiment schemes (Ni0.8Co0.15Al0.05(OH)2)。
Specific implementation mode
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and coordinate attached drawing
Detailed description are as follows：
Refering to attached drawing 1 to Fig. 5.
Embodiment 1
A kind of recoverying and utilizing method of waste lithium cell recycling industry strong base solution, including following technical process：
1. the separation of aluminiferous material：The waste lithium cell to discharge completely is subjected to Mechanical Crushing, addition water, which is stirred, to be added
The separation of fast pole piece material and collector；By the slurry after stirring by the sieve of 60 mesh, oversize is aluminiferous material；
2. the dissolving of aluminium：Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 12mol/L, is stirred to react
Filter residue is added to by 60 mesh sieve in the sodium hydroxide solution of same concentration by slurry after 2h, and same technique carries out secondary alkali
It is filtered after leaching, filter residue carries out subsequent processing, and filtrate is incorporated in first time filtrate, and filtrate is strong containing aluminium after slagging-off is filtered for multiple times
Aqueous slkali；
3. the adjustment of the ion ratio of strong base solution containing aluminium：With inductive coupling plasma emission spectrograph (ICP) to (2) institute
It obtains lye to be tested, Na ion concentration 11.5mol/L, aluminium ion concentration 0.1mol/L adds according to target product ingredient
Sodium hydroxide is added to adjust sodium ion in liquor a concentration of 6mol/L, aluminium ion concentration 0.01mol/L with water；
4. the recycling of the strong base solution containing aluminium：It is with nickel ion concentration as precipitating reagent using strong base solution obtained by (3)
0.8mol/L, concentration of cobalt ions 0.8mol/L, it is anti-that the mixing salt solution that manganese ion concentration is 0.8mol/L carries out liquid-phase precipitation
It answers, 111 type ternary material precursors is made.
Embodiment 2
A kind of recoverying and utilizing method of waste lithium cell recycling industry strong base solution, including following technical process：
1. the separation of aluminiferous material：The waste lithium cell to discharge completely is subjected to Mechanical Crushing, addition water, which is stirred, to be added
The separation of fast pole piece material and collector；By the slurry after stirring by the sieve of 60 mesh, oversize is aluminiferous material；
2. the dissolving of aluminium：Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 16mol/L, is stirred to react
Filter residue is added to by 60 mesh sieve in the sodium hydroxide solution of same concentration by slurry after 1.5h, and same technique carries out secondary
It is filtered after alkali leaching, filter residue carries out subsequent processing, and filtrate is incorporated in first time filtrate, and filtrate is to contain aluminium after slagging-off is filtered for multiple times
Strong base solution；
3. the adjustment of the ion ratio of strong base solution containing aluminium：With inductive coupling plasma emission spectrograph (ICP) to (2) institute
It obtains lye to be tested, Na ion concentration 15mol/L, aluminium ion concentration 0.2mol/L, according to target product ingredient, addition
Sodium hydroxide and water adjustment sodium ion in liquor a concentration of 8mol/L, aluminium ion concentration 0.02mol/L；
4. the recycling of the strong base solution containing aluminium：It is with nickel ion concentration as precipitating reagent using strong base solution obtained by (3)
1.2mol/L, concentration of cobalt ions 0.48mol/L, the mixing salt solution that manganese ion concentration is 0.72mol/L carry out liquid-phase precipitation
523 type ternary material precursors are made in reaction.
Embodiment 3
A kind of recoverying and utilizing method of waste lithium cell recycling industry strong base solution, including following technical process：
1. the separation of aluminiferous material：The waste lithium cell to discharge completely is subjected to Mechanical Crushing, addition water, which is stirred, to be added
The separation of fast pole piece material and collector；By the slurry after stirring by the sieve of 60 mesh, oversize is aluminiferous material；
2. the dissolving of aluminium：Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 20mol/L, is stirred to react
Filter residue is added to by 60 mesh sieve in the sodium hydroxide solution of same concentration by slurry after 1h, and same technique carries out secondary alkali
It is filtered after leaching, filter residue carries out subsequent processing, and filtrate is incorporated in first time filtrate, and filtrate is strong containing aluminium after slagging-off is filtered for multiple times
Aqueous slkali；
3. the adjustment of the ion ratio of strong base solution containing aluminium：With inductive coupling plasma emission spectrograph (ICP) to (2) institute
It obtains lye to be tested, Na ion concentration 19mol/L, aluminium ion concentration 0.4mol/L, according to target product ingredient, addition
Sodium hydroxide and water adjustment sodium ion in liquor a concentration of 10mol/L, aluminium ion concentration 0.04mol/L；
4. the recycling of the strong base solution containing aluminium：It is with nickel ion concentration as precipitating reagent using strong base solution obtained by (3)
1.44mol/L, concentration of cobalt ions 0.48mol/L, the mixing salt solution that manganese ion concentration is 0.48mol/L carry out liquid-phase precipitation
622 type ternary material precursors are made in reaction.
Embodiment 4
A kind of recoverying and utilizing method of waste lithium cell recycling industry strong base solution, including following technical process：
1. the separation of aluminiferous material：The waste lithium cell to discharge completely is subjected to Mechanical Crushing, addition water, which is stirred, to be added
The separation of fast pole piece material and collector；By the slurry after stirring by the sieve of 60 mesh, oversize is aluminiferous material；
2. the dissolving of aluminium：Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 24mol/L, is stirred to react
Filter residue is added to by 60 mesh sieve in the sodium hydroxide solution of same concentration by slurry after 0.5h, and same technique carries out secondary
It is filtered after alkali leaching, filter residue carries out subsequent processing, and filtrate is incorporated in first time filtrate, and filtrate is to contain aluminium after slagging-off is filtered for multiple times
Strong base solution；
3. the adjustment of the ion ratio of strong base solution containing aluminium：With inductive coupling plasma emission spectrograph (ICP) to (2) institute
It obtains lye to be tested, Na ion concentration 22mol/L, aluminium ion concentration 3mol/L, according to target product ingredient, adds hydrogen
Sodium oxide molybdena and water adjustment sodium ion in liquor a concentration of 12mol/L, aluminium ion concentration 0.3mol/L；
4. the recycling of the strong base solution containing aluminium：It is with nickel ion concentration as precipitating reagent using strong base solution obtained by (3)
1.92mol/L, concentration of cobalt ions 0.36mol/L, the mixing salt solution that manganese ion concentration is 0.12mol/L carry out liquid-phase precipitation
NCA type ternary material precursors are made in reaction.
Constituent content in precursor obtained by 1 each embodiment of table
| 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 |
The present embodiment has described simple for process, and easy to operate, 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. are positive
Effect.
Claims (6)
1. a kind of recoverying and utilizing method of waste lithium cell recycling industry strong base solution, it is characterized in that：Waste lithium cell recycling row
The recoverying and utilizing method of industry strong base solution includes following technical process：
(1) separation of aluminiferous material
The waste lithium cell to discharge completely is subjected to Mechanical Crushing, water is added and is stirred point for accelerating pole piece material and collector
From；Slurry after stirring is sifted out, oversize is aluminiferous material；
(2) dissolving of aluminium
Gained aluminiferous material in (1) is added in the sodium hydroxide solution of 3-25mol/L, slurry is sieved after being stirred to react 1-2h
Son, filtrate are strong base solution containing aluminium；
(3) adjustment of aluminium strong base solution ion ratio
According to target product ingredient, adds sodium hydroxide or water adjusts a concentration of 6-25mol/L of sodium ion in liquor, aluminium ion is dense
Degree is 0.001-1mol/L；
(4) utilization of the strong base solution containing aluminium
Using aluminium strong base solution obtained by (3) as precipitating reagent, carries out liquid-phase precipitation with target salting liquid and react, LiFePO4, three are made
The precursor of first material positive electrode, and then LiFePO4, ternary material target positive electrode finished product is made.
2. the recoverying and utilizing method of waste lithium cell recycling industry strong base solution according to claim 1, it is characterized in that：Aluminium
Course of dissolution in, gained aluminiferous material in (1) is added to after being stirred to react 1-2h in the sodium hydroxide solution of 3-25mol/L
After slurry is by sieve, filter residue is added in the sodium hydroxide solution of same concentration, same technique carries out mistake after secondary alkali leaching
Filter, filter residue carry out subsequent processing, and filtrate is incorporated in first time filtrate, and filtrate is that highly basic containing aluminium is molten after 2-6 filtering and removing slag
Liquid.
3. the recoverying and utilizing method of waste lithium cell recycling industry strong base solution according to claim 1, it is characterized in that：Aluminium
During the adjustment of strong base solution ion ratio, with inductive coupling plasma emission spectrograph to sodium ion, aluminium ion in (2)
Concentration is tested, and then adds sodium hydroxide according to target product ingredient or water adjusts sodium ion in liquor concentration.
4. the recoverying and utilizing method of waste lithium cell recycling industry strong base solution according to claim 1,2 or 3, feature
It is：During the utilization of the strong base solution containing aluminium, ternary material include cobalt nickel oxide manganses lithium, doping vario-property cobalt nickel oxide manganses lithium,
The cobalt nickel oxide aluminium lithium of cobalt nickel oxide aluminium lithium, doping vario-property.
5. the recoverying and utilizing method of waste lithium cell recycling industry strong base solution according to claim 1,2 or 3, feature
It is：The precursor of LiFePO4 includes ferric phosphate and corresponding doping component, and the precursor of ternary material includes hydroxide nickel cobalt
Manganese, the hydroxide nickel cobalt manganese of doping, nickel cobalt aluminum hydroxide, the nickel cobalt aluminum hydroxide of doping.
6. the recoverying and utilizing method of waste lithium cell recycling industry strong base solution according to claim 1,2 or 3, feature
It is：Salting liquid includes the mixed solution of iron-containing liquor, solution containing phosphate or the two when prepared by LiFePO4；Salt when prepared by ternary material
Solution includes solution containing nickel, cobalt-carrying solution, manganese containing solution or arbitrary several mixed solution.
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| CN110277552B (en) * | 2018-03-16 | 2022-07-15 | 荆门市格林美新材料有限公司 | Method for repairing and regenerating nickel-cobalt-manganese ternary cathode material in waste battery |
| CN108899604B (en) * | 2018-06-28 | 2020-10-27 | 郑州中科新兴产业技术研究院 | Method for preparing ternary positive electrode material precursor by utilizing waste lithium battery positive electrode piece |
| CN109193059B (en) * | 2018-09-26 | 2020-08-14 | 嘉兴晟源工业设计有限公司 | Regeneration treatment method of lithium iron phosphate waste |
| CN109786753A (en) * | 2018-12-11 | 2019-05-21 | 广东工业大学 | A kind of bipolarity sodium-ion battery assembly and its assembling, recovery method |
| CN109742472A (en) * | 2018-12-12 | 2019-05-10 | 江西赣锋循环科技有限公司 | A method of aluminium foil and ternary powder in recycling ternary pole piece |
| CN110010990B (en) * | 2019-03-27 | 2020-12-01 | 欣旺达电子股份有限公司 | Method for preparing nickel-cobalt-manganese ternary material with aluminum oxide coating layer by taking retired lithium ion battery as raw material |
| CN110862110A (en) * | 2019-11-26 | 2020-03-06 | 宁夏百川新材料有限公司 | Method for preparing ternary positive electrode material precursor by using waste lithium ion battery |
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