CN106395784B - The method that cobalt lithium prepares cobalt phosphate is detached in a kind of cobalt acid lithium from waste lithium cell - Google Patents
The method that cobalt lithium prepares cobalt phosphate is detached in a kind of cobalt acid lithium from waste lithium cell Download PDFInfo
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- CN106395784B CN106395784B CN201610852236.7A CN201610852236A CN106395784B CN 106395784 B CN106395784 B CN 106395784B CN 201610852236 A CN201610852236 A CN 201610852236A CN 106395784 B CN106395784 B CN 106395784B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000010941 cobalt Substances 0.000 title claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 229910000152 cobalt phosphate Inorganic materials 0.000 title claims abstract description 24
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 title claims abstract description 16
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000011149 active material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910032387 LiCoO2 Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229910012820 LiCoO Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- REERVHLUKHFRQT-UHFFFAOYSA-N cobalt phosphoric acid Chemical compound [Co].P(O)(O)(O)=O REERVHLUKHFRQT-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- VCSZKSHWUBFOOE-UHFFFAOYSA-N dioxidanium;sulfate Chemical class O.O.OS(O)(=O)=O VCSZKSHWUBFOOE-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of method that separation cobalt lithium prepares cobalt phosphate in cobalt acid lithium from waste lithium cell, this method includes the following steps：1) waste lithium cell disassembled, removed, obtain positive and negative anodes active material；2) the positive and negative anodes active material is calcined and is ground, obtained containing LiCoO2Powder material；3) it is described to contain LiCoO2Powder material use H3PO4And H2O2Mixing leaching liquid leached, gained leachate by neutralize, separation of solid and liquid, obtain cobalt phosphate precipitation and lithium-containing solution.This method efficiently separates Co and Li using typical waste lithium cell cobalt acid lithium as raw material, using roasting with reference to leaching method, and recycles its high added value cobalt and prepare cobalt phosphate (cobalt violet), realizes resource utilization and the utilization of waste lithium cell cobalt acid lithium.
Description
Technical field
The present invention relates to a kind of method that valuable metal is recycled from waste lithium cell more particularly to a kind of use wet method smeltings
The method that golden method is detached and recycled to Co in positive active material and Li belongs to old and useless battery valuable metal recovery neck
Domain.
Background technology
Lithium ion battery has many excellent chemical properties, is set in the portable mobiles instrument such as mobile phone, laptop
It is widely used in standby and electric/hybrid automobile.According to statistics, global lithium ion battery output in 2010 is close to 2,000,000,000；In advance
Counting the year two thousand twenty yield will be more than 5,000,000,000；The general common lithium ion battery service life is about 2~3 years, to its composition analysis result
Show：Every battery averagely contains：Cobalt about 15%, lithium about 1.5%, copper about 18%, aluminium about 5%.With these service life of lithium battery
Termination, certainly will generate discarded battery, and considerable part is then directly mixed in rubbish, this may cause environment potentially to pollute,
It is also a kind of waste to resource simultaneously.How to handle and (especially contain from these batteries and recycling wherein metal values
Measuring cobalt larger, that added value is higher) oneself becomes social hotspots.
Contain in waste and old lithium ion battery there are many non-ferrous metal (such as cobalt, lithium) with very high recovery value, but at present
Recovery method and technique for typical waste lithium cell mainly have pyrometallurgy, hydrometallurgy and bioleaching process, these
Method and technique there are recovery process flow it is complicated, easily generate secondary pollution, the more low apparent defect of organic efficiency.How
It solves the problems, such as to high-efficiency environment friendly to become urgently to be resolved hurrily there are these shortcomings in removal process.
Invention content
For it is existing from waste and old lithium ion battery recycle valuable metal method there are the defects of, the purpose of the present invention
To be to provide one kind using cobalt acid lithium in typical waste lithium cell as raw material, using roasting combine leaching method effectively realize Co with
Li is separated and recovered from the new method that its high added value cobalt prepares cobalt phosphate (cobalt violet), and this method realizes the recycling of cobalt acid lithium waste material
Recycling and utilization.
In order to realize above-mentioned technical purpose, the preparation of cobalt lithium is detached from waste lithium cell cobalt acid lithium the present invention provides one kind
The method of cobalt phosphate, this method include the following steps：
1) waste lithium cell disassembled, removed, obtain positive and negative anodes active material；
2) the positive and negative anodes active material is calcined and is ground, obtained containing LiCoO2Powder material；
3) it is described to contain LiCoO2Powder material use H3PO4And H2O2Mixing leaching liquid leached, gained leachate
By neutralizing, separation of solid and liquid obtains cobalt phosphate precipitation and lithium-containing solution.
Preferred scheme, the temperature of the calcining is 500~1000 DEG C.More preferably calcination temperature is 600~800 DEG C.
Most preferred calcination temperature is 700 DEG C.
More preferably scheme, the time of the calcining is 1~4h.More preferably calcination time is 1.5~2.5h.Most preferably
For 2h.
Preferred scheme, the condition of the leaching are：40~80 DEG C, 30~150min of extraction time of extraction temperature, solid-liquid
Compare 1g:15~30mL, mixing speed are 200~600rpm.More preferably scheme, the condition of the leaching are：Extraction temperature 50
~70 DEG C, 50~120min of extraction time, solid-to-liquid ratio 1g:18~22mL, mixing speed are 350~450rpm.Preferred side
Case, the condition of the leaching are：60 DEG C, extraction time 60min, solid-to-liquid ratio 1g of extraction temperature:20mL, mixing speed are
400rpm。
More preferably scheme, it is described mixing leaching liquid in phosphoric acid a concentration of 0.4~0.8mol/L, hydrogen peroxide it is a concentration of
≤ 4vol.%.Further preferred scheme, a concentration of 0.6mol/L for mixing phosphoric acid in leaching liquid, the concentration of hydrogen peroxide
For 4vol.%.
More preferably scheme, the positive and negative anodes active material are crushed to granularity below 200 mesh after calcining.
In technical scheme of the present invention, old and useless battery is discharged, is manually disassembled, is existed using N-Methyl pyrrolidone (NMP)
Collector is removed under ultrasonic oscillation instrument heating condition, and will remove gained positive and negative anodes active material carry out recycling and
It is dry.
In technical scheme of the present invention, process of lapping meets its granularity and is less than 200 mesh using ball mill grinding 2h or so
.
Compared with existing technology and technique, the present invention has following obvious characteristic and advantage：
(1) technical scheme of the present invention, can by roasting technique combination phosphoric acid/hydrogen peroxide mixing leachate extract technology
It realizes cobalt, the lithium Selectively leaching in positive and negative anodes active material, and the height that lithium and cobalt can be realized can be operated by simple filtration
Effect separation and recycling directly obtain the cobalt violet product of high added value；Effectively solve the problems, such as that existing recovery process flow is complicated.
(2) technical scheme of the present invention is leached using phosphoric acid/hydrogen peroxide mixing leachate, can realize the choosing of cobalt, lithium
Selecting property leaches, and phosphoric acid and generates water directly as the raw material for preparing cobalt violet product after hydrogen peroxide oxidation, environmentally protective, can be effective
Mitigate and avoid the secondary pollution problem in the big strong acid of traditional three (sulfuric acid, nitric acid and hydrochloric acid) leaching process (mainly harmful
Gas, unreacted spent acid etc.).In addition, phosphoric acid chemical property is stable, price is cheap compared with organic acid, compared with organic acid in cost
Leach the advantage having in apparent price.
(3) technical scheme of the present invention process conditions are mild, extraction time is short, liquid-solid ratio is small, the separation of cobalt and lithium and return
The advantages that rate of producing effects is high, and can corresponding cobalt phosphate product directly be obtained by Leach reaction, without to valuable in leachate
The separation and reclaimer operation that metal is repeated.
Description of the drawings：
【Fig. 1】For the present invention under different leaching conditions gained precipitated products and LiCoO2XRD diagram；
【Fig. 2】The infrared spectrum analysis comparison diagram of precipitated products and pure phosphoric acid cobalt obtained by the present invention.
Specific embodiment
Specific examples below is intended to further illustrate the content of present invention rather than limitation scope of the claims.
Characterization and analysis means：
X-ray powder diffraction instrument (XRD) and Fourier infrared spectrograph (FT-IR) are characterized and are divided to precipitated products
Analysis；
The metal ion content in filtrate is detected using inductive coupling plasma emission spectrograph (ICP-OES)
And analysis.
Embodiment 1
(1) by the typical waste lithium cell of about 5kg or so, (its positive active material is LiCoO2) disassemble and locate in advance
Reason, can respectively obtain metal shell, diaphragm, collector pole piece (Al foils and Cu foils), positive and negative anodes active material powder mixture with
And other components.2.17kg positive and negative anodes active material powder (the main component LiCoO that will be obtained again2And C) in Muffle furnace
700 DEG C of calcining 2h are fully ground and cross 200 mesh sieve, obtain the fine grain waste and old LiCoO of 1.38kg in the ball mill2Powder.
(2) and then every time fine grain LiCoO obtained above is accurately weighed2About 5 grams of powder, is positioned over tri- mouthfuls of 250mL
In flask；Design corresponding orthogonal experiment (L16 (45), totally 16 groups of experiments：No.1~No.16), controlling reaction temperature for 40~
80 DEG C, under the experiment condition that stir speed (S.S.) is 400rpm and liquid-solid ratio is 15~30mL/g, add in suitable phosphoric acid and dioxygen
Water mixed liquid 100mL (wherein phosphoric acid concentration is 0.5~0.8mol/L, and hydrogen peroxide volume content is 0~4vol.%) is to LiCoO2
It is leached, you can obtain the suspension containing cobalt phosphate precipitated products and lithium ion leachate.
(3) suspension of above-mentioned gained is filtered using vacuum filtration machine, and with distilled water repeatedly clean precipitation 3 to
It 5 times, respectively obtains precipitated products and leaches filtrate；Obtained precipitation is positioned in baking oven and maintains the temperature at 105 DEG C of drying 12
Hour；Then obtained precipitated products are adequately ground using mortar, you can obtain the precipitated products of cobalt phosphate.
(4) No.2 (reaction time 30min, reaction temperature in the step of choosing (2) orthogonal experiment under different experimental conditions
50 DEG C, dioxygen water consumption 2vol.%, liquid-solid ratio 20mL/g, phosphoric acid concentration 0.5mol/L), No.8 (reaction time 40min, reaction
Temperature 70 C, dioxygen water consumption 3vol.%, liquid-solid ratio 20mL/g, phosphoric acid concentration 0.5mol/L), the No.10 (reaction time
50min, 50 DEG C, dioxygen water consumption 4vol.% of reaction temperature, liquid-solid ratio 25mL/g, phosphoric acid concentration 0.5mol/L) and No.13
(reaction time 60min, 40 DEG C, dioxygen water consumption 4vol.% of reaction temperature, liquid-solid ratio 20mL/g, phosphoric acid concentration 0.7mol/L)
It for object, is handled using the operation of step (3), obtained different precipitated products and cobalt acid lithium waste material are carried out using XRD
Characterization and analysis primarily determine the chemical constituent and purity of precipitated products.
In the present invention, using the orthogonal design table of design gained, (5 factor, 4 horizontal quadrature is tested, L16(5^4), altogether 16
Group leaching experiment, No.1~No.16), study different extraction temperatures (40,50,60,70 and 80 DEG C), the reaction time (30,
60th, 90,120 and 150min), phosphoric acid concentration (0.4,0.5,0.6,0.7 and 0.8mol/L), reducing agent dioxygen water consumption (0,1,
2nd, 3 and 4vol.%) and cobalt and lithium are detached liquid-solid ratio and the influence of organic efficiency, by Orthogonal experiment results and to leaching
Go out result and analyze and can obtain, best extract technology condition is：40 DEG C of extraction temperature, reaction time 60min, hydrogen peroxide are used
Amount 4vol.%, liquid-solid ratio is 20mL/g and phosphoric acid concentration is 0.7mol/L.It is compared with previous research technique, this recycling work
Skill reaction condition is milder, and phosphoric acid and dioxygen water consumption are less in leaching agent, and organic efficiency is higher, and cobalt and lithium can then pass through one
Step leaches and separation and recycling is obtained by filtration, and can directly obtain corresponding cobalt precipitated products, and obtained precipitated products are passed through
XRD and FT-IR is characterized and is analyzed it is found that this is precipitated as pure Co3(PO4)2(i.e. cobalt violet).All orthogonal experiment conditions
Under carry out 3 parallel laboratory tests, the average value of 3 groups of parallel laboratory test results under gained specific condition of experiment is as final experiment
As a result.
To the above-mentioned precipitated products and LiCoO obtained under different condition2Waste material carries out its chemical composition using XRD
Discriminating and comparative analysis primarily determine the chemical composition of precipitated products；Then, using analytically pure ten sulfate dihydrates cobalt
(CoSO4·12H2) and sodium phosphate (Na O3PO4) in molar ratio 3:2 are dissolved in solution, and synthesis obtains pure cobalt phosphate (Co3
(PO4)2) precipitation (precipitated products obtained under No.13 experiment conditions being chosen, as Fig. 2 is infrared), it is filtered and dry；Finally will
Obtained precipitated products and pure cobalt phosphate carry out contrast table using FT-IR (the infrared wide spectrum of Fourier) and seek peace analysis, determine institute
The chemical composition of obtained precipitated products.
It is precipitated products (it is precipitated products to choose No.2,8,10,13) and the cobalt acid lithium under different leaching conditions in Fig. 1
(wherein A is Co to the XRD diagram of waste material3(PO4)2Ingredient, B LiCoO2Ingredient).
Fig. 2 is the pictorial diagram and infared spectrum of precipitated products (A, No.13) and pure phosphoric acid cobalt (B).
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the invention as claimed with
Modification should all belong to the covering scope of the claims in the present invention.
Claims (4)
1. the method that cobalt lithium prepares cobalt phosphate is detached in a kind of cobalt acid lithium from waste lithium cell, it is characterised in that：Including following step
Suddenly：
1) waste lithium cell disassembled, removed, obtain positive and negative anodes active material；
2) the positive and negative anodes active material is calcined and is ground, obtained containing LiCoO2Powder material；
3) it is described to contain LiCoO2Powder material use H3PO4And H2O2Mixing leaching liquid leached, gained leachate passes through
It neutralizes, separation of solid and liquid, obtains cobalt phosphate precipitation and lithium-containing solution；The condition of the leaching is：Extraction temperature is 40~80 DEG C, leaching
Go out the time for 30~150min, solid-to-liquid ratio 1g:15~30mL, mixing speed are 200~600rpm；In the mixing leaching liquid
A concentration of 0.4~0.8mol/L of phosphoric acid, a concentration of≤4vol.% of hydrogen peroxide.
2. the method that cobalt lithium prepares cobalt phosphate is detached in the slave waste lithium cell cobalt acid lithium according to right 1, it is characterised in that：
The temperature of the calcining is 500~1000 DEG C.
3. detaching the method that cobalt lithium prepares cobalt phosphate in the slave waste lithium cell cobalt acid lithium according to right 1 or 2, feature exists
In：The time of the calcining is 1~4h.
4. the method that cobalt lithium prepares cobalt phosphate is detached in the slave waste lithium cell cobalt acid lithium according to right 1, it is characterised in that：
The positive and negative anodes active material is crushed to granularity below 200 mesh after calcining.
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| CN107083483A (en) * | 2017-04-18 | 2017-08-22 | 中科过程（北京）科技有限公司 | A kind of method for strengthening waste and old lithium ion battery metal recovery |
| CN111533108A (en) * | 2020-05-11 | 2020-08-14 | 蒋达金 | Method for preparing lithium cobalt phosphate by using waste lithium cobalt oxide |
| CN112157107A (en) * | 2020-08-28 | 2021-01-01 | 威立雅新能源科技(江门)有限公司 | Method for separating positive and negative electrode materials from waste lithium batteries |
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|---|---|---|---|---|
| CN1688065A (en) * | 2005-04-25 | 2005-10-26 | 武汉理工大学 | Method for separating and recovering cobalt from waste lithium ion cell |
| CN103474718A (en) * | 2013-08-27 | 2013-12-25 | 华中科技大学武昌分校 | Method for recovering cobalt from lithium battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688065A (en) * | 2005-04-25 | 2005-10-26 | 武汉理工大学 | Method for separating and recovering cobalt from waste lithium ion cell |
| CN103474718A (en) * | 2013-08-27 | 2013-12-25 | 华中科技大学武昌分校 | Method for recovering cobalt from lithium battery anode material |
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