CN106395784A - Method for separating Co (cobalt) and Li (lithium) from LiCoO2 (lithium cobalt oxide) of waste lithium batteries to prepare cobaltous phosphate - Google Patents
Method for separating Co (cobalt) and Li (lithium) from LiCoO2 (lithium cobalt oxide) of waste lithium batteries to prepare cobaltous phosphate Download PDFInfo
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- CN106395784A CN106395784A CN201610852236.7A CN201610852236A CN106395784A CN 106395784 A CN106395784 A CN 106395784A CN 201610852236 A CN201610852236 A CN 201610852236A CN 106395784 A CN106395784 A CN 106395784A
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- cobalt
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- 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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- 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
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- 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
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- 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
Abstract
The invention discloses a method for separating Co (cobalt) and Li (lithium) from LiCoO2 (lithium cobalt oxide) of waste lithium batteries to prepare cobaltous phosphate. The method comprises the following steps: (1) disassembling and peeling the waste lithium batteries to obtain anode and cathode active substances; (2) calcining and grinding the anode and cathode active substances to obtain LiCoO2-containing powder materials; (3) performing leaching on the LiCoO2-containing powder materials by mixed leaching liquid of H3PO4 and H2O2; neutralizing the obtained leaching liquid; performing solid-liquid separation to obtain cobaltous phosphate sediment and a lithium-containing solution. The method has the advantages that the LiCoO2 of typical waste lithium batteries is used as a raw material; the Co and the Li are effectively separated by a roasting and leaching method; the cobalt with high additional values is recovered for preparing the cobaltous phosphate (cobalt violet); the resource recycling and utilization of the LiCoO2 of the waste lithium batteries are realized.
Description
Technical field
The present invention relates to a kind of method reclaiming valuable metal from waste lithium cell, more particularly, to one kind adopt wet method smelting
Golden method is separated the method with being reclaimed to Co and Li in positive active material, belongs to old and useless battery valuable metal recovery neck
Domain.
Background technology
Lithium ion battery has many excellent chemical properties, sets in the portable mobile instrument such as mobile phone, notebook computer
Widely use 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
Meter the year two thousand twenty yield will exceed 5,000,000,000；The typically common lithium ion battery life-span 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 produce discarded battery, considerable part is then directly mixed with rubbish, this may cause to environment potentially to pollute,
It is also one kind waste to resource simultaneously.How to process and from these batteries and reclaim wherein metal values and (especially contain
The cobalt that amount is larger, added value is higher) oneself becomes social hotspots.
Multiple non-ferrous metals (such as cobalt, lithium) with very high recovery value are contained in waste and old lithium ion battery, but at present
Recovery method for typical waste lithium cell and technique mainly have pyrometallurgy, hydrometallurgy and bioleaching process, these
There is recovery process flow process complexity, easily produce secondary pollution, the more low obvious defect of organic efficiency in method and technique.How
High-efficiency environment friendly ground solves there is, in removal process, the difficult problem that these shortcomings become urgently to be resolved hurrily.
Content of the invention
The defect existing for the existing method reclaiming valuable metal from waste and old lithium ion battery, the purpose of the present invention
Be be to provide a kind of with cobalt acid lithium in typical waste lithium cell as raw material, using roasting with reference to leaching method effectively realize Co and
Li is separated and recovered from the new method that its high added value cobalt prepares cobalt phosphate (cobalt violet), and the method realizes the resource of cobalt acid lithium waste material
Reclaim and utilize.
In order to realize above-mentioned technical purpose, the invention provides one kind separates the preparation of cobalt lithium from waste lithium cell cobalt acid lithium
The method of cobalt phosphate, the method comprises the following steps：
1) waste lithium cell carried out disassembling, peel off, obtain both positive and negative polarity active material；
2) described both positive and negative polarity active material is calcined and ground, obtained containing LiCoO2Powder material；
3) contain LiCoO described in2Powder material adopt H3PO4And H2O2Mixing leaching liquid leached, gained leachate
By neutralization, separation of solid and liquid, obtain cobalt phosphate precipitation and lithium-containing solution.
Preferably scheme, the temperature of described calcining is 500～1000 DEG C.More preferably calcining heat is 600～800 DEG C.
Most preferably calcining heat is 700 DEG C.
More preferably scheme, the time of described calcining is 1～4h.More preferably calcination time is 1.5～2.5h.Most preferably
For 2h.
Preferably scheme, the condition of described leaching is：40～80 DEG C of extraction temperature, extraction time 30～150min, solid-liquid
Compare 1g:15～30mL, mixing speed is 200～600rpm.More preferably scheme, the condition of described leaching is：Extraction temperature 50
～70 DEG C, extraction time 50～120min, solid-to-liquid ratio 1g:18～22mL, mixing speed is 350～450rpm.More preferably square
Case, the condition of described leaching is：60 DEG C of extraction temperature, extraction time 60min, solid-to-liquid ratio 1g:20mL, mixing speed is
400rpm.
More preferably scheme, in described mixing leaching liquid, the concentration of phosphoric acid is 0.4～0.8mol/L, and the concentration of hydrogen peroxide is
≤ 4vol.%.Further preferred scheme, in described mixing leaching liquid, the concentration of phosphoric acid is 0.6mol/L, the concentration of hydrogen peroxide
For 4vol.%.
More preferably scheme, described both positive and negative polarity active material is crushed to granularity below 200 mesh after calcining.
In technical scheme, old and useless battery discharged, manually disassemble, being existed using 1-METHYLPYRROLIDONE (NMP)
Under ultrasonic oscillation instrument heating condition, collector is peeled off, and by peel off gained both positive and negative polarity active material carry out reclaim and
It is dried.
In technical scheme, process of lapping adopt ball mill grinding 2h about so as to granularity meet be less than 200 mesh
?.
Compared with existing technology and technique, the present invention has following obvious characteristic and advantage：
(1). technical scheme, phosphoric acid/hydrogen peroxide mixing leachate extract technology is combined by roasting technique, can
Realize cobalt in both positive and negative polarity active material, lithium Selectively leaching, and the height that can achieve lithium and cobalt can be operated by simple filtration
Effect separates and reclaims, and directly obtains the cobalt violet product of high added value；The complicated difficult problem of effectively solving existing recovery process flow process.
(2). technical scheme, is leached using phosphoric acid/hydrogen peroxide mixing leachate, it is possible to achieve cobalt, the choosing of lithium
Selecting property leaches, and phosphoric acid is directly as the raw material of preparation cobalt violet product, and generates water after hydrogen peroxide oxidation, and environmental protection 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.).Additionally, phosphoric acid stable chemical nature, price are cheap compared with organic acid, compared with organic acid on cost
Leach the advantage having in obvious price.
(3). technical scheme process conditions are gentle, extraction time is short, liquid-solid ratio is little, the separation of cobalt and lithium and returning
The advantages of rate of producing effects is high, and directly can obtain corresponding cobalt phosphate product by Leach reaction, need not be to having valency in leachate
Separation and reclaimer operation that metal is repeated.
Brief description：
【Fig. 1】For the present invention under different leaching conditions gained precipitated products and LiCoO2XRD；
【Fig. 2】Infrared spectrum analysis comparison diagram for gained precipitated products of the present invention and pure phosphoric acid cobalt.
Specific embodiment
Specific examples below is intended to further illustrate present invention, rather than limits scope of the claims.
Characterize and analysis means：
X-ray powder diffraction instrument (XRD) and Fourier infrared spectrograph (FT-IR) are characterized to precipitated products and are divided
Analysis；
Using inductive coupling plasma emission spectrograph (ICP-OES), the metal ion content in filtrate is detected
And analysis.
Embodiment 1
(1) by about 5kg about typical waste lithium cell (its positive active material be LiCoO2) carry out disassembling and locate in advance
Reason, can respectively obtain metal shell, barrier film, collector pole piece (Al paper tinsel and Cu paper tinsel), both positive and negative polarity active material powder mixture with
And other components.By the 2.17kg obtaining both positive and negative polarity active material powder, (main component is LiCoO again2And C) in Muffle furnace
700 DEG C of calcining 2h, are fully ground in ball mill and cross 200 mesh sieves, obtain the fine grain waste and old LiCoO of 1.38kg2Powder.
(2) accurately weigh and then every time fine grain LiCoO obtained above2About 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 be 40～
80 DEG C, stir speed (S.S.) be under 400rpm and experiment condition that liquid-solid ratio is 15～30mL/g, add appropriate 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
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
5 times, respectively obtain precipitated products and leach filtrate；The precipitation obtaining is positioned in baking oven and maintains the temperature at 105 DEG C of drying 12
Hour；Then using mortar, the precipitated products obtaining sufficiently are ground, you can obtain the precipitated products of cobalt phosphate.
(4) No.2 (reaction time 30min, the reaction temperature under different experimental conditions in step (2) orthogonal experiment chosen
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 of reaction temperature, dioxygen water consumption 4vol.%, liquid-solid ratio 25mL/g, phosphoric acid concentration 0.5mol/L) and No.13
(reaction time 60min, 40 DEG C of reaction temperature, dioxygen water consumption 4vol.%, liquid-solid ratio 20mL/g, phosphoric acid concentration 0.7mol/L)
For object, the operation using step (3) is processed, and the different precipitated products obtaining and cobalt acid lithium waste material are carried out using XRD
Characterize and analyze, primarily determine that chemical constituent and the purity of precipitated products.
In the present invention, using orthogonal design table (experiment of 5 factor 4 horizontal quadrature, the L of design gained16(5^4), altogether 16
Group leaching experiment, No.1～No.16), research 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), reduction agent hydrogen peroxide consumption (0,1,
2nd, 3 with 4vol.%) and liquid-solid ratio cobalt is separated with lithium and organic efficiency impact, by Orthogonal experiment results and to leaching
Go out result to be analyzed obtaining, its optimal extract technology condition is：40 DEG C of extraction temperature, reaction time 60min, hydrogen peroxide are used
Amount 4vol.%, liquid-solid ratio are 20mL/g and phosphoric acid concentration is 0.7mol/L.Compare with conventional research technique, this recovery work
Skill reaction condition is gentleer, and in leaching agent, phosphoric acid and dioxygen water consumption are less, and organic efficiency is higher, and cobalt and lithium then can pass through one
Step leaches and is filtrated to get and separates and reclaim, and can directly obtain corresponding cobalt precipitated products, and the precipitated products obtaining are passed through
XRD and FT-IR is characterized and is analyzed and understood, this is precipitated as pure Co3(PO4)2(i.e. cobalt violet).All of orthogonal experiment condition
Under all carry out 3 parallel laboratory tests, the mean value of 3 under gained specific condition of experiment group parallel laboratory test result is as final experiment
Result.
To the above-mentioned precipitated products obtaining under different condition and LiCoO2Waste material is carried out to its chemical composition using XRD
Differentiate and comparative analysis, primarily determine that the chemical composition of precipitated products；Then, using analytically pure ten sulfate dihydrate cobalts
(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 (choosing the precipitated products obtaining under No.13 experiment condition, as infrared in Fig. 2), filtered and be dried；Finally will
The precipitated products obtaining 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 the precipitated products obtaining.
It is precipitated products (choosing No.2,8,10,13 is precipitated products) and the cobalt acid lithium under different leaching conditions in Fig. 1
(wherein A is Co to the XRD of waste material3(PO4)2Composition, B is LiCoO2Composition).
Fig. 2 is pictorial diagram and the infared spectrum of precipitated products (A, No.13) and pure phosphoric acid cobalt (B).
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the invention as claimed with
Modify, all should belong to the covering scope of the claims in the present invention.
Claims (6)
1. a kind of cobalt acid lithium from waste lithium cell separate cobalt lithium prepare cobalt phosphate method it is characterised in that：Walk including following
Suddenly：
1) waste lithium cell carried out disassembling, peel off, obtain both positive and negative polarity active material；
2) described both positive and negative polarity active material is calcined and ground, obtained containing LiCoO2Powder material；
3) contain LiCoO described in2Powder material adopt H3PO4And H2O2Mixing leaching liquid leached, gained leachate passes through
Neutralization, separation of solid and liquid, obtain cobalt phosphate precipitation and lithium-containing solution.
2. according to right 1 from waste lithium cell cobalt acid lithium separate cobalt lithium prepare cobalt phosphate method it is characterised in that：
The temperature of described calcining is 500～1000 DEG C.
3. the method that separation cobalt lithium prepares cobalt phosphate from waste lithium cell cobalt acid lithium according to right 1 or 2, its feature exists
In：The time of described calcining is 1～4h.
4. according to right 1 from waste lithium cell cobalt acid lithium separate cobalt lithium prepare cobalt phosphate method it is characterised in that：
The condition of described leaching is：Extraction temperature is 40～80 DEG C, and extraction time is 30～150min, and solid-to-liquid ratio is 1g:15～30mL,
Mixing speed is 200～600rpm.
5. the method that separation cobalt lithium prepares cobalt phosphate from waste lithium cell cobalt acid lithium according to right 1 or 4, its feature exists
In：In described mixing leaching liquid, the concentration of phosphoric acid is 0.4～0.8mol/L, and the concentration of hydrogen peroxide is≤4vol.%.
6. according to right 1 from waste lithium cell cobalt acid lithium separate cobalt lithium prepare cobalt phosphate method it is characterised in that：
Described both positive and negative polarity active material is crushed to granularity below 200 mesh after calcining.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| 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 |
-
2016
- 2016-09-26 CN CN201610852236.7A patent/CN106395784B/en active Active
Patent Citations (2)
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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