CN107528100A - By the method for lithium rechargeable battery manufacture aluminium copper - Google Patents
By the method for lithium rechargeable battery manufacture aluminium copper Download PDFInfo
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- CN107528100A CN107528100A CN201610439834.1A CN201610439834A CN107528100A CN 107528100 A CN107528100 A CN 107528100A CN 201610439834 A CN201610439834 A CN 201610439834A CN 107528100 A CN107528100 A CN 107528100A
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- Prior art keywords
- rechargeable battery
- aluminium
- copper
- alloy
- lithium rechargeable
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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
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
-
- 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides the method that aluminium copper is manufactured by lithium rechargeable battery.[problem] is not melted using dry process and by the collector of positive electrode side（Aluminium foil）With the collector of negative material side（Copper foil）During separation, the metal of aluminium and copper contains than high material（Aluminum bronze shot-like particle）Occur with admixture.They allow to added material sufficiently as steel etc., but due to containing micro lithium, therefore it is not used as the added material of aluminium alloy.When aluminum bronze shot-like particle is put into stove and makes its melting by [solution], lithium composition is removed from metal side.As specific method, melting salt deposit is set on molten substrate metal, puts into aluminum bronze shot-like particle thereto.Aluminium and copper are heated and melted, and are gradually transferred in molten substrate metal and mix from melting salt deposit, but lithium composition is separated and is adsorbed in melting salt deposit and remains.
Description
Technical field
The present invention relates to the recovery method of the valuable metal included in lithium rechargeable battery, especially, pays close attention to current collection material
Material is related to the recovery method of aluminium and copper.
Background technology
The lithium rechargeable battery used now is that negative material, positive pole material are enclosed in the external packing body of bag or shelly
Obtained from material, barrier film and electrolyte, positive active material turns into lithium-metal composite oxides.
The light weight and electric capacity height etc. of lithium rechargeable battery, therefore it is used as various portable machines all the time with secondary
Battery, still, recently in the purposes towards automobile, demand significantly expands.
Therefore, can largely occur used product from now on, landfill place also gradually welcomes the limit, and therefore, present situation is
Through not allowing the random waste treatment as in the past, for recycling, it is strongly required that returning for valuable metal can be improved
Yield and with the widely used renewable resources of low cost.
Therefore, in patent document 1, proposed as the method for recovery valuable metal：Battery is disassembled, and it is clear with alcohol or water
Disintegration thing is washed to remove electrolyte, thereafter, the composition metal of collector is separated and recovered using wet type, by solvent extraction and
Instead extract to the lithium in the aqueous solution of residual（Li）After being concentrated, reclaimed in the form of lithium carbonate solid.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-122885 publications
Patent document 2：Japanese Unexamined Patent Publication 2012-193424 publications.
The content of the invention
The invention problem to be solved
Above-mentioned conventional method is that cost is higher always using the method for wet type operation, it is necessary to carry out drainage sunk well.Exploitation recently
LiMn2O4 with the characteristic that can be equal to cobalt acid lithium is used for the lithium rechargeable battery of positive active material, with cobalt phase
Than, the feed metal price of manganese is low, predicts that the use of manganese can turn into main flow from now on, but in wet type recovery method as described above
It can not use.
Therefore, it have studied the method using dry type operation, in patent document 2, be used as one of them, it is proposed that utilize dry type
The method that process reclaims Mn series alloy, it can be reclaimed as Mn-Ni alloys in the form of being adapted to use.
In addition, the collector of positive electrode side is made up of aluminium foil, the collector of negative material side is made up of copper foil, is not utilized
When dry process is melted and them is separated from battery, it may appear that the metal of aluminium and copper contains than high material.Especially, divide
When stripping machine is placed in from after, it may appear that metal contains than higher material.
Contemplate they can directly or carry out briquet processing or press process and after being molded, now sufficiently as steel etc.
The added material of copper, although the component ratio that can effectively apply flexibly is high, but recycling is not realized energetically.
In addition, it is contemplated that by the blending constituent of aluminium and copper sufficiently as the added material of casting aluminum alloy, even if
Lithium for it is micro containing, for example only contain 100ppm when, MOLTEN STEEL FLOW can also be deteriorated, therefore be not used as the addition material of aluminium alloy
Material.
Therefore, it is an object of the present invention to provide can manufacture essence by lithium rechargeable battery with good yield rate
The parent metal of the upper Al-zn-mg-cu alloy without lithium（Ground gold）, can also be sufficiently as the added material, new and useful of aluminium alloy
By lithium rechargeable battery manufacture aluminium copper method.
The means used to solve the problem
The present invention is carried out to solve above-mentioned problem, the invention of claim 1 be by lithium rechargeable battery manufacture aluminium-
The method of copper alloy, it is characterised in that using the positive electrode collector from aluminium system as silicon source, with the negative electrode collector from copper system
As copper source, when putting into respectively into stove and making its melting, closed with the melting method that lithium composition is substantially free of in alloy
Aurification.
The invention of claim 2 is the side according to claim 1 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery
Method, it is characterised in that when making its melting, air is blocked with melting salt deposit.
The invention of claim 3 is the side according to claim 2 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery
Method, it is characterised in that form melting salt deposit with chloride.
The invention of claim 4 is the side according to claim 3 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery
Method, it is characterised in that the mixture comprising salt is used as chloride.
The invention of claim 5 is being manufactured by lithium rechargeable battery according to any one of claim 1 ~ 4
The method of aluminium copper, it is characterised in that the molten substrate metal of manufacture aluminium system in advance（Lower Soup）Or the mixing of aluminium and copper
The molten substrate metal of system, and silicon source and Tong Yuan are put into thereon.
The invention of claim 6 is the side according to claim 5 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery
Method, it is characterised in that while making molten substrate metal be in stirring, side input silicon source and Tong Yuan.
Invention effect
The method according to the invention, can with good yield rate by lithium rechargeable battery manufacture be substantially free of the aluminium of lithium-
Copper alloy.
Description of reference numerals
Fig. 1 is the lithium rechargeable battery used in embodiments of the present invention（Laminated cell unit）Stereogram.
Fig. 2 is the overall flow figure for the valuable metal recovery method for including embodiment methods described.
Fig. 3 is the schematic diagram of the embodiment methods described of the part as Fig. 2.
Fig. 4 is the ideograph of the fusing boiler and agitating device used in embodiment methods described.
Fig. 5 is to represent to produce by the punching plate and high-speed rotary stripping machine of the A3004P materials used in embodiment
The photo of the high material of AlCu metal ratios.
Embodiment
（Object to be processed）
Process object is lithium rechargeable battery.
In lithium rechargeable battery, mainly in the state being laminated via electrolyte in the external packing body of bag or shelly
Under be sealed with positive electrode, negative material and barrier film.
External packing body is made up of metal, and the main flow of raw material metal is aluminium.
Positive electrode is mainly formed by the positive electrode collector of sheet with the positive active material for being fixed on the collector.Now
As main flow, positive electrode collector is made up of aluminium foil, and positive active material is the metal composite oxide containing lithium.Negative material
Mainly formed by the negative electrode collector of sheet with the negative electrode active material for being fixed on the collector.Turn into main flow now, bear
Electrode current collector is made up of copper or copper alloy foil, and negative electrode active material is made up of carbon materials such as the graphite for the lithium that can attract deposit-discharge.
Fig. 1 is the lithium rechargeable battery 1 of the laminated cell element form as one（About 30cm × about 30cm）Show
It is intended to, external packing body 3 is formed with aluminum bag.Layered product 5 is accommodated in external packing body 3, it is such as positive electrode-barrier film-negative pole
Obtained from material-barrier film-positive electrode is alternately laminated like that.Lithium rechargeable battery 1 just extremely aluminium sheet, negative pole are table
The copper coin of face nickel plating, typically exhibit tied structure.
Using above-mentioned substance again as resource.Fig. 2 is the outline recycling flow chart of lithium rechargeable battery.
Heat disintegration process
Lithium rechargeable battery is directly loadable into rotary-type heating furnace, rotated, also, brush the flame of burner first and
Make its heating burning, when reaching more than 500 DEG C in stove, electrolyte gasifies rapidly, using combustion flame as ignition source, even if stopping
Only burner, with also beginning to linksystem self-burning.Thus, heating disintegration process starts, and positive electrode and negative material occur
Separate and gradually disintegrated.
Now, positive active material and negative pole graphite for being peeled off etc. fall through the punching inwall of stove.
Sieve process
The metal for being sieved into the aluminium discharged from stove and copper contains than high thick thing and is mixed with the composition metal oxidation containing lithium
The thin thing of thing and graphite.
The metal of aluminium and copper is contained than high oversize for subsequent handling.
In addition, screenings is used as resource again by smelting reduction process in the form of Mn-Ni alloy substrate metallic articles.
Broken apart process
The metal of aluminium and copper is contained than high oversize and is carried out with high-speed rotary impact peel machine broken apart, that is, makes it
Sieved again on the basis of stripping, further remove positive active material and carbon dust, metal is contained than further improving
More than 0.25mm oversize occurs as the shot-like particle of aluminium and copper under admixture.As the processing in the present invention
Object, so as to be used as resource.
In addition, the screenings in the stage also by above-mentioned smelting reduction process in the form of Mn-Ni alloy substrate metallic articles
Resource is used as again.
Then, the alloy manufacturing methods of the invention for having used process object shot-like particle are described in detail according to Fig. 3.
Fig. 3 is figure obtained from the process content of the alloy manufacturing methods is made into figure sequentially in time.
In Fig. 4, symbol 7 represents fusing boiler, is open above the fusing boiler 7, accommodates pot（Crucible）9.Thermal source into
For gas burner.Symbol 11 represents agitating device, and the bottom of the support shaft 13 of the agitating device 11 is provided with flat blade
15.Support shaft 13 is pivoted, and when being rotated, blade 15 is pivoted in pot 9 and molten metal is stirred.
First, aluminium is put into the pot 9 of the fusing boiler 7, it is melted and is made molten substrate metal.The aluminium is
The punching plate of A3004P materials.It should be noted that the compounding ratio of Solder for Al-Cu Joint Welding shot-like particle and molten substrate metal is closed according to aluminum bronze
The ingredient standard of golden product sets input amount.
On the molten substrate metal, melting agent is covered as molten metal（=solder flux）, put into chloride.Chloride is excellent
NaCl and KCl is elected as with 1:The material that 1 mass ratio is obtained by mixing.Because：Because fusing point is low, thus easily melting and
Stable salt bath layer is formed on molten substrate metal（=melting salt deposit）.The chloride now used is that fusing point is low and will not produce
It is also effective when the salt or its mixture of raw pernicious gas.When forming salt bath layer, molten substrate metal is covered, so as to present
Air is blocked with salt bath layer（Oxygen）State.When the thickness of salt bath layer is blocked up, produces heat loss or hinder aftermentioned melting
Metal ingredient shifts to molten substrate metal side, and on the other hand, when thickness is excessively thin, the covering of shot-like particle is insufficient and is formed and exposed
Position, therefore, when shot-like particle is below 30mm, preferably 5 ~ 40mm or so, more preferably 20~40mm or so.
Thus pretreatment is completed.
In pot 9, molten metal temperature can be kept as uniformly if stirring.By the stirring, importing effect described later
It can have an effect.
In this condition, the metal isolated that object to be processed disintegrated from lithium rechargeable battery contains than high
Material is put into pot 9.If starting to stir, it is not only molten substrate metal and flow regime, the salt bath layer of upper layer side is presented
Flow regime is presented, therefore, input shot-like particle is promptly fed in salt bath layer from outermost top layer with the flowing, from
And it is capped.Therefore, also the aluminium easily aoxidized can be prevented to aoxidize.
Also, in salt bath layer, metal object, i.e. aluminium and copper are heated and melted, and are gradually transferred to melting base from salt bath layer
In down payment category and mix.Now, even being attached to the lithium of positive active material side and the lithium melting salt deposit from electrolyte
It is easily adsorbed, especially in the case of salt bath layer, due to carry out chemical combination with chloride and from lithium-metal composite oxides and
Lithium organic compound side successfully departs from, and remains in salt bath layer side.
So operate, the molten metal of aluminium and copper is formed in pot 9, and gradually increase, but lithium turns into slag and is trapped in
In salt bath layer.
When molten metal occurs and is cooled in pot 9, turn into the parent metal of Al-zn-mg-cu alloy.Gained parent metal
Yield rate is good, and is substantially free of lithium, can be sufficiently as the added material of aluminium alloy.
It should be noted that Al-zn-mg-cu alloy is from the viewpoint of the added material purpose of copper, preferably it is total to comprising 33%
Fisheye is the material of copper, sets copper match ratio as needed.
More than, had been described in detail for embodiments of the present invention, but specific form is not limited to these embodiments, i.e.,
Make that there is design alteration etc. without departing from the scope of the subject in the invention, be also included in the present invention.
If for example, Ajax-Wyatt furnace is used as into calciner, it plays the automatic stirring effect of molten metal, therefore is not required to
Want other agitating device.
Embodiment
Pot 9 is the pot of 500Kg aluminium, is highly 865mm, upper end bore is 876mm, bottom footpath is 350mm, capacity is
326L。
Each material put into thereto including material shown in Fig. 5 under the following conditions, carry out alloying.
It is to disintegrate by the punching plate of A3004P materials and from lithium rechargeable battery to separate and with rotation at a high speed shown in Fig. 5
The metal of transition stripping machine production contains the photo than high shot-like particle.
（Embodiment 1）
[table 1]
In table, oxidation reaction sedative is potassium chloride, when putting into bulk material in order to suppress oxidation reaction and combining makes
With.In addition, granular feedstock is little by little put into respectively.
By so operating, the growing amount of slag is suppressed to a certain extent.
In addition, it can be confirmed according to fluorescent X-ray diffraction patterns：The LiClLiCO of significant quantity in slag be present2·
LiClO4, demonstrate the lithium of the lithium-metal composite oxides included from positive active material and the lithium compound from electrolyte
In be separated.
（Embodiment 2）
[table 2]
Granular feedstock is all once put into, and is successfully melted, and oxidation reaction does not occur.
It can be confirmed according to fluorescent X-ray diffraction patterns：The LiClLiCO of significant quantity in slag be present2·LiClO4, checking
It is separated in the lithiums of lithium-metal composite oxides and the lithium compound from electrolyte that are included from positive active material.
Yield rate also significantly improves.
It can be confirmed by the result：When salt bath layer has thickness to a certain degree, significant effect improves.
In addition, parent metal is close to substantially eutectic composition.
（Comparative example 1）
In order to be contrasted with embodiment 2, no solder flux, the experiment i.e. without salt bath layer are carried out, it is as follows when being compared.
[table 3]
[table 4]
It can verify that according to the above results：Melting salt deposit is formed by using the alloyage process of the present invention, not only yield rate
Well, lithium can also separate from metal side.
Industry applications
If using the present invention method, can by used lithium rechargeable battery, the material occurred in the fabrication stage with
Component ratio and the cost performance height that can effectively apply flexibly, the mode that can be applied flexibly extensively are used as resource again, and not as discarded
Thing.
Description of reference numerals
1 ‥ ‥ lithium rechargeable batteries（Battery unit）
The ‥ ‥ layered products of 3 ‥ ‥ external packing bodies 5
7 ‥ ‥ melt the ‥ ‥ pots of boiler 9
The ‥ ‥ support shafts of 11 ‥ ‥ agitating devices 13
15 ‥ ‥ blades.
Claims (6)
1. the method for Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery, it is characterised in that to make from the positive electrode collector of aluminium system
For silicon source, using the negative electrode collector from copper system as copper source, when putting into respectively into stove and making its melting, with essence in alloy
On not lithium-containing melting method carry out alloying.
2. the method according to claim 1 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery, it is characterised in that make it
During melting, air is blocked with melting salt deposit.
3. the method according to claim 2 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery, it is characterised in that use chlorine
Compound forms melting salt deposit.
4. the method according to claim 3 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery, it is characterised in that as
Chloride uses the mixture comprising salt.
5. the method that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery according to any one of claim 1 ~ 4, its feature
It is, manufactures the molten substrate metal of aluminium system or the molten substrate metal of the mixed system of aluminium and copper in advance, and in its upslide
Enter silicon source and Tong Yuan.
6. the method according to claim 5 that Al-zn-mg-cu alloy is manufactured by lithium rechargeable battery, it is characterised in that while making
Molten substrate metal is in stirring, side input silicon source and Tong Yuan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610439834.1A CN107528100A (en) | 2016-06-20 | 2016-06-20 | By the method for lithium rechargeable battery manufacture aluminium copper |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610439834.1A CN107528100A (en) | 2016-06-20 | 2016-06-20 | By the method for lithium rechargeable battery manufacture aluminium copper |
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| Publication Number | Publication Date |
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| CN107528100A true CN107528100A (en) | 2017-12-29 |
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| CN201610439834.1A Pending CN107528100A (en) | 2016-06-20 | 2016-06-20 | By the method for lithium rechargeable battery manufacture aluminium copper |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016564A (en) * | 2019-04-26 | 2019-07-16 | 先进储能材料国家工程研究中心有限责任公司 | The method for preparing aluminium White brass alloy using waste lithium cell recycling |
-
2016
- 2016-06-20 CN CN201610439834.1A patent/CN107528100A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016564A (en) * | 2019-04-26 | 2019-07-16 | 先进储能材料国家工程研究中心有限责任公司 | The method for preparing aluminium White brass alloy using waste lithium cell recycling |
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