CN107394298A - Lithium resource recovery method on waste and old lithium ion battery negative plate - Google Patents
Lithium resource recovery method on waste and old lithium ion battery negative plate Download PDFInfo
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- CN107394298A CN107394298A CN201710476135.9A CN201710476135A CN107394298A CN 107394298 A CN107394298 A CN 107394298A CN 201710476135 A CN201710476135 A CN 201710476135A CN 107394298 A CN107394298 A CN 107394298A
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- lithium
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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
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Abstract
The present invention provides lithium resource recovery method on a kind of waste and old lithium ion battery negative plate, the block powder on negative plate surface is made into fine powder first, and with being aided with ultrasonic agitation in watery hydrochloric acid course of reaction, realize the efficient leaching of lithium resource.The present invention has that technological process is simple, cost is cheap, it is easy to batch recovery anode plate for lithium ionic cell and realizes the advantage of commercial application, and the pure Lithium Carbonate powder obtained by the recovery method can be directly used for industrial production, improve the economic value of recovery.
Description
【Technical field】
The invention belongs to lithium resource recovery side on cell art, more particularly to a kind of waste and old lithium ion battery negative plate
Method.
【Background technology】
Lithium ion battery due to voltage it is high, it is bigger than energy, have extended cycle life, have a safety feature the advantages that and be widely used in
In electric automobile, mobile phone and notebook, however, with the extensive application of lithium ion battery, the recovery of old and useless battery becomes important
It is and urgent.
The phenomenon that lithium is not deviate from and deposited on negative plate in time easily occurs in use for lithium ion battery, especially
It is to utilize waste and old lithium ion battery of the rear capacity residue below 50% for echelon.In addition, high/low temperature, super-charge super-discharge or
After being abused under other special operation conditions, deposition of the lithium on negative plate is also extremely serious.By disassembling lithium ion battery it can be found that
There is substantial amounts of yellow metal lithium simple substance on negative plate surface, and aoxidizes rapidly in atmosphere.If it can not use rational
The lithium resource deposited on method recovery negative plate, is not only the waste to lithium resource, it is also possible to cause the pollution to environment.In view of
This, is necessary to provide in fact on a kind of waste and old lithium ion battery negative plate lithium resource recovery method to overcome disadvantages described above.
【The content of the invention】
The present invention proposes lithium resource recovery method on a kind of waste and old lithium ion battery negative plate, can high efficiente callback be deposited on
Lithium resource on negative plate.
Lithium resource recovery method on a kind of waste and old lithium ion battery negative plate provided by the invention, comprises the following steps：
1) the block powder on the negative plate surface obtained after waste and old lithium ion battery being disassembled strips down, then by ball
Mill, sieving obtain fine powder；
2) the fine powder is added in watery hydrochloric acid, suspension is obtained after a period of time is stirred by ultrasonic；
3) the first filtrate is obtained after suspension filtering, the pH value of first filtrate is adjusted to 5.0-8.0, again
It is filtrated to get the second filtrate；
4) second filtrate is concentrated by evaporation and addition saturated sodium carbonate is molten when 80-100 DEG C of temperature range at which
Liquid is precipitated with obtaining lithium carbonate；
5) pure Lithium Carbonate powder is obtained after the lithium carbonate washing of precipitate is dried.
In a preferred embodiment, in step 1), the fine powder can pass through the screen cloth of 200 mesh.
In a preferred embodiment, in step 2), the concentration of the watery hydrochloric acid is 1-5mol/L；Ultrasonic power is
200-600W, stir speed (S.S.) 30-50r/min, ultrasonic agitation time are 10-30min.
In a preferred embodiment, in step 3), concentrated ammonia liquor adjustment described the of the mass fraction for 22-25% is used
The pH value of one filtrate.
In a preferred embodiment, in step 5), lithium carbonate precipitation is with after hot wash 2-3 times, in 80-
10-15h is dried within the temperature range of 100 DEG C to obtain pure Lithium Carbonate powder.
In a preferred embodiment, the purity of the pure Lithium Carbonate powder is more than 99%.
On waste and old lithium ion battery negative plate provided by the invention in lithium resource recovery method, first by negative plate surface
Fine powder is made in block powder, and with being aided with ultrasonic agitation in watery hydrochloric acid course of reaction, realizes the efficient leaching of lithium resource
Go out.The recovery method has that technological process is simple, cost is cheap, is easy to batch recovery anode plate for lithium ionic cell and realizes industry
Change the advantage of application, and the pure Lithium Carbonate powder obtained by the recovery method can be directly used for industrial production, improve
The economic value of recovery.
【Brief description of the drawings】
Fig. 1 is the flow chart of lithium resource recovery method on waste and old lithium ion battery negative plate provided by the invention.
Fig. 2 is the used ultrasonic agitation dress of lithium resource recovery method on the waste and old lithium ion battery negative plate shown in Fig. 1
Put schematic diagram.
Fig. 3 is obtained in one embodiment for lithium resource recovery method on the waste and old lithium ion battery negative plate shown in Fig. 1
Pure Lithium Carbonate powder XRD spectrum.
Fig. 4 is the SEM figures of the pure Lithium Carbonate powder shown in Fig. 2.
【Embodiment】
Referring to Fig. 1, the present invention provides lithium resource recovery method on a kind of waste and old lithium ion battery negative plate, including it is following
Step：
1) the block powder on the negative plate surface obtained after waste and old lithium ion battery being disassembled strips down, then by ball
Mill, sieving obtain fine powder；
2) the fine powder is added in watery hydrochloric acid, suspension is obtained after a period of time is stirred by ultrasonic；
3) the first filtrate is obtained after suspension filtering, the pH value of first filtrate is adjusted to 5.0-8.0, again
It is filtrated to get the second filtrate；
4) second filtrate is concentrated by evaporation and addition saturated sodium carbonate is molten when 80-100 DEG C of temperature range at which
Liquid is precipitated with obtaining lithium carbonate；
5) pure Lithium Carbonate powder is obtained after the lithium carbonate washing of precipitate is dried.
Specifically, in step 1), the fine powder is that block powder is obtained after ball milling by the screen cloth of 200 mesh
's.In step 2), the concentration of the watery hydrochloric acid is 1-5mol/L；Ultrasonic power is 200-600W, stir speed (S.S.) 30-50r/
Min, ultrasonic agitation time are 10-30min.When the concentration of the watery hydrochloric acid used is larger, substantially reduce ultrasonic agitation when
Between, when the concentration of watery hydrochloric acid is relatively low, required ultrasonic time can extend.In step 3), mass fraction is used as 22-
25% concentrated ammonia liquor adjusts the pH value of first filtrate.In step 5), lithium carbonate precipitation with after hot wash 2-3 times,
10-15h is dried within the temperature range of 80-100 DEG C to obtain pure Lithium Carbonate powder, and the pure Lithium Carbonate powder is pure
Degree is more than 99%.
Embodiment
The block powder on the negative plate surface obtained after waste and old lithium ion battery is disassembled strips down, after ball milling by
The screen cloth of 200 mesh obtains fine powder；Then the fine powder is added in the enough watery hydrochloric acid that concentration is 3mol/L
Row ultrasonic agitation.Referring to Fig. 2, carrying out required device is stirred by ultrasonic includes glass container 1, supersonic cleaning machine 2 and agitator
3, specifically, watery hydrochloric acid is contained in glass container 1 with fine powder, the glass container 1 is positioned over the water of supersonic cleaning machine 2
In groove and clip is used to fix the glass container 1 to avoid it from significantly rocking, the agitating paddle of the agitator 3 can extend into
The inside of the glass container 1.In present embodiment, the ultrasonic power of the supersonic cleaning machine 2 is 400W, the agitator 3
Stir speed (S.S.) be 50r/min, the ultrasonic agitation time is 20min.Next the suspension obtained after ultrasonic agitation was used
Filter filters, and filter residue is washed with a small amount and obtains the first filtrate afterwards twice；Then by be added dropwise mass fraction be 25% it is dense
Ammoniacal liquor adjusts the pH value of first filtrate to 6.0 or so, reuses filter and is filtrated to get the second filtrate；To described
The heating of two filtrates makes its evaporation reach the purpose of concentration, and saturated carbon is added dropwise when 80-100 DEG C of temperature range at which
Acid sodium solution is precipitated with obtaining lithium carbonate；Finally the lithium carbonate washing of precipitate is dried afterwards three times with hot water, you can obtain high
Pure lithium carbonate powder.
Further, using XRD (X-ray diffraction) and SEM (Scanning electron
Microscopy) technology carries out material phase analysis and displaing microstructure observing to the pure Lithium Carbonate powder obtained in embodiment, as a result
As shown in Figures 3 and 4.XRD analysis result shows, any miscellaneous peak beyond lithium carbonate is not present in XRD spectrum, illustrates the height
The purity of pure lithium carbonate powder is really very high.It can be seen that the micron order rod to interlock layer by layer in the micro-structure diagram obtained from SEM
Shape carbonic acid crystalline lithium, therefore it is used directly for industrial production.
On waste and old lithium ion battery negative plate provided by the invention in lithium resource recovery method, first by negative plate surface
Fine powder is made in block powder, and with being aided with ultrasonic agitation in watery hydrochloric acid course of reaction, realizes the efficient leaching of lithium resource
Go out.The recovery method has that technological process is simple, cost is cheap, is easy to batch recovery anode plate for lithium ionic cell and realizes industry
Change the advantage of application, and the pure Lithium Carbonate powder obtained by the recovery method can be directly used for industrial production, improve
The economic value of recovery.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is to combine specific preferred embodiment to institute of the present invention
The further description of work, it is impossible to assert that the specific implementation of the present invention is confined to these explanations.It is all the present invention spirit and
All any modification, equivalent and improvement made within principle etc., should be included within the scope of the present invention.
Claims (6)
- A kind of 1. lithium resource recovery method on waste and old lithium ion battery negative plate, it is characterised in that：Comprise the following steps：1) the block powder on the negative plate surface obtained after waste and old lithium ion battery being disassembled strips down, then by ball milling, Sieving obtains fine powder；2) the fine powder is added in watery hydrochloric acid, suspension is obtained after a period of time is stirred by ultrasonic；3) the first filtrate is obtained after the suspension filtering, the pH value of first filtrate is adjusted to 5.0-8.0, filtered again Obtain the second filtrate；4) by second filtrate be concentrated by evaporation and at which when 80-100 DEG C of temperature range addition saturated sodium carbonate solution with Obtain lithium carbonate precipitation；5) pure Lithium Carbonate powder is obtained after the lithium carbonate washing of precipitate is dried.
- 2. lithium resource recovery method on waste and old lithium ion battery negative plate as claimed in claim 1, it is characterised in that：Step 1) In, the fine powder can pass through the screen cloth of 200 mesh.
- 3. lithium resource recovery method on waste and old lithium ion battery negative plate as claimed in claim 1, it is characterised in that：Step 2) In, the concentration of the watery hydrochloric acid is 1-5mol/L；Ultrasonic power is 200-600W, stir speed (S.S.) 30-50r/min, and ultrasound is stirred It is 10-30min to mix the time.
- 4. lithium resource recovery method on waste and old lithium ion battery negative plate as claimed in claim 1, it is characterised in that：Step 3) In, use mass fraction to adjust the pH value of first filtrate for 22-25% concentrated ammonia liquor.
- 5. lithium resource recovery method on waste and old lithium ion battery negative plate as claimed in claim 1, it is characterised in that：Step 5) In, it is high-purity to obtain to dry 10-15h with after hot wash 2-3 times within the temperature range of 80-100 DEG C for the lithium carbonate precipitation Lithium carbonate powder.
- 6. lithium resource recovery method on the waste and old lithium ion battery negative plate as described in claim 1 or 5, it is characterised in that：Institute The purity for stating pure Lithium Carbonate powder is more than 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710476135.9A CN107394298A (en) | 2017-06-21 | 2017-06-21 | Lithium resource recovery method on waste and old lithium ion battery negative plate |
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| CN201710476135.9A CN107394298A (en) | 2017-06-21 | 2017-06-21 | Lithium resource recovery method on waste and old lithium ion battery negative plate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107959079A (en) * | 2017-12-28 | 2018-04-24 | 中南大学 | A kind of method of negative electrode material of waste lithium ion battery recycling |
| CN108075203A (en) * | 2017-12-28 | 2018-05-25 | 中南大学 | A kind of method that valuable metal component recycles in waste and old lithium ion battery material |
| CN108923096A (en) * | 2018-09-10 | 2018-11-30 | 厦门理工学院 | A kind of recycling of waste and old lithium ion battery cathode full constituent and regeneration method |
| CN108987839A (en) * | 2018-07-27 | 2018-12-11 | 同济大学 | A kind of method of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation |
| CN109037722A (en) * | 2018-08-17 | 2018-12-18 | 湖南金凯循环科技有限公司 | A method of recycling lithium in waste and old lithium titanate series lithium ion battery negative electrode tab |
| CN109088119A (en) * | 2018-08-17 | 2018-12-25 | 湖南金凯循环科技有限公司 | A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab |
| CN110668473A (en) * | 2019-08-13 | 2020-01-10 | 中国科学院过程工程研究所 | Method for recovering lithium from waste lithium ion battery negative electrode material |
-
2017
- 2017-06-21 CN CN201710476135.9A patent/CN107394298A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107959079A (en) * | 2017-12-28 | 2018-04-24 | 中南大学 | A kind of method of negative electrode material of waste lithium ion battery recycling |
| CN108075203A (en) * | 2017-12-28 | 2018-05-25 | 中南大学 | A kind of method that valuable metal component recycles in waste and old lithium ion battery material |
| CN108987839A (en) * | 2018-07-27 | 2018-12-11 | 同济大学 | A kind of method of pair of lithium battery anode failure cobalt acid lithium reconstruction reparation |
| CN108987839B (en) * | 2018-07-27 | 2019-12-27 | 同济大学 | Method for reforming and repairing failed lithium cobalt oxide structure of positive electrode of lithium battery |
| CN109037722A (en) * | 2018-08-17 | 2018-12-18 | 湖南金凯循环科技有限公司 | A method of recycling lithium in waste and old lithium titanate series lithium ion battery negative electrode tab |
| CN109088119A (en) * | 2018-08-17 | 2018-12-25 | 湖南金凯循环科技有限公司 | A method of recycling lithium in waste and old graphite series lithium ion battery negative electrode tab |
| CN108923096A (en) * | 2018-09-10 | 2018-11-30 | 厦门理工学院 | A kind of recycling of waste and old lithium ion battery cathode full constituent and regeneration method |
| CN108923096B (en) * | 2018-09-10 | 2020-05-19 | 厦门理工学院 | Method for recycling and regenerating all components of negative electrode of waste lithium ion battery |
| CN110668473A (en) * | 2019-08-13 | 2020-01-10 | 中国科学院过程工程研究所 | Method for recovering lithium from waste lithium ion battery negative electrode material |
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Application publication date: 20171124 |
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