CN106252770A - A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector - Google Patents
A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector Download PDFInfo
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- CN106252770A CN106252770A CN201610658042.3A CN201610658042A CN106252770A CN 106252770 A CN106252770 A CN 106252770A CN 201610658042 A CN201610658042 A CN 201610658042A CN 106252770 A CN106252770 A CN 106252770A
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- collector
- lithium
- positive electrode
- positive
- anode material
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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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- 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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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention discloses a kind of method of separating waste, worn anode material for lithium-ion batteries and collector, comprises the following steps: disassembling after waste and old lithium ion battery electric discharge completely, take out positive plate, deionized water cleans up, and dries stand-by；Positive plate is placed in electrolyte immersion makes it fully infiltrate, and with positive plate as positive pole, graphite flake is negative pole, and oxalic acid solution is electrolyte, and energising carries out electrochemical anodization reaction, and aluminum foil current collector separates with positive electrode；Aluminum foil current collector directly recycles；The positive electrode split away off reclaims.The present invention proposes a kind of method of contact interface destroying aluminum collector and positive electrode innovatively, thus can be directly realized by the separation of aluminum collector and positive electrode；The inventive method is gentle, will not relate to thermal extremes or produces a large amount of gases etc., and method is simply effective, and environmental friendliness and energy consumption are low.
Description
Technical field
The present invention relates to waste and old lithium ion battery recovery technology field, particularly to positive plate active substance and anode collection
The separation method of body.
Background technology
In recent years, along with the fast development of whole world lithium ion battery industry, its production capacity also increases rapidly, right in industry
The demand of associated materials is equally in steady increase.The environment brought to tackle fuel-engined vehicle the most in recent years is asked
Topic, electric automobile becomes the important development direction in future, and power lithium-ion battery has the most also welcome big good opportunity to develop.
It is foreseeable, however, that the consumption of power lithium-ion battery material will be probably thousands of times of conventional batteries, even
The metals such as lithium therein and cobalt there will be the phenomenon that supply falls short of demand.Meanwhile, the life-span of lithium ion battery is limited, a large amount of lithiums electricity
The use in pond will imply that the appearance of a large amount of waste lithium cell.If the valuable metal of old and useless battery can be reclaimed, it is possible not only to
Alleviate resource nervous, create huge economic worth, it is also possible to solve the old and useless battery pollution problem to environment.Therefore, lithium from
The recovery of sub-battery and recycling become a problem demanding prompt solution.
At present, the interior recovery technology to old and useless battery of industry is still in the recovery that primary level, not yet neither one are perfect
Scheme.Recovery method is mostly that the indiscriminate battery by empty electricity state is pulverized, and then uses floatation, magnetic method and wet chemistry method
Etc. the valuable metal isolating target.Owing to early stage does not carry out category filter to battery material, the later stage is caused to recycle
Time complex steps, energy consumption is higher, and organic efficiency is the highest.And the method separated with collector by electrode material in advance is the most relatively
Few.Positive active material is coated on aluminum collector after being typically to be homogenized with the organic binder bond (such as PVDF) being dissolved in NMP, combines
Closing document, the method separated with collector by positive electrode at present mainly has removal binding agent and dissolves collector two kinds.Remove
The method of binding agent generally requires high-temperature process, and the control to temperature is critically important, too high or too low the most not all right, and processes
In journey, organic burning can cause atmospheric pollution；And alkali dissolution collector can produce substantial amounts of gas, gas can take one out of
Point alkali liquor, can bring certain injury to environment and people, and this processing method does not reach the effect that separates in advance, molten
After solution, positive active material is also mixed in alkali liquor, needs extra separating step.Therefore, there is presently no one simple the most also
That takes into account energy consumption, environmental protection etc. separates positive electrode and the method for collector.
Summary of the invention
It is an object of the invention to overcome prior art, it is provided that a kind of separating waste, worn anode material for lithium-ion batteries and afflux
The method of body, is destroyed the contact interface of aluminum collector and positive electrode, thus reaches the purpose separated by anodic oxidation.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector, it is characterised in that comprise the following steps:
(1) disassembling after waste and old lithium ion battery electric discharge completely, take out positive plate, deionized water cleans up, and dries stand-by；
(2) positive plate is placed in electrolyte immersion a period of time make it fully infiltrate, with positive plate as positive pole, graphite flake is negative
Pole, oxalic acid solution is electrolyte, and energising carries out electrochemical anodization reaction, and aluminum foil current collector separates with positive electrode；
(3), after step (2) electrochemical anodization reaction, aluminum foil current collector directly recycles；The positive electrode split away off
It is recovered by filtration.
Scheme further, the solubility of described step (2) oxalic acid solution is 0.2-0.6mol/L, and oxidizing reaction temperature is 5-25
DEG C, oxidation reaction voltage is 40-80V, and oxidation time is at 20-60min.
Scheme further, described step (2) soak time is 5-20min.
Scheme further, described step (2) anodic oxidation generates one layer of Woelm Alumina at collection liquid surface；Pellumina
Formed and will destroy aluminum collector and the contact interface of positive electrode, and aoxidize the process being to expand, expand the stress produced
Would be further forced the separation of positive electrode and aluminium foil.
Beneficial effects of the present invention: the present invention proposes a kind of contact destroying aluminum collector and positive electrode innovatively
The method at interface, thus the separation of aluminum collector and positive electrode can be directly realized by；Its two, this method directly from internal sabotage its
Contact interface, aluminium flake and positive electrode are sufficiently separated, the leading portion sorting being truly realized in removal process；Its three, with existing point
From Technical comparing, the method that the present invention uses is gentle, will not relate to thermal extremes or produces a large amount of gases etc., and method simply has
Effect, environmental friendliness and energy consumption are low.
Accompanying drawing explanation
Fig. 1 is Anodic Oxidation apparatus structure schematic diagram of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector, including step: by applying waste lithium ionic electricity
Disassembling after tank discharge is complete, take out positive plate, deionized water cleans up, and dries stand-by；Positive plate is placed in electrolyte leaching
Bubble a period of time makes it fully infiltrate, and with positive plate as positive pole, graphite flake is negative pole, and oxalic acid solution is electrolyte, and energising is carried out
Electrochemical anodization reaction, positive plate edge fit sealing device is fixed, and front surface region is directly exposed to electrolysis
In liquid, contact conductor is drawn at side aluminium foil, and aluminum foil current collector separates with positive electrode；After electrochemical anodization reaction,
Aluminum foil current collector directly recycles；The positive electrode split away off is recovered by filtration.
Electrochemical anodization reaction is carried out in anodic oxidation device, as shown in Figure 1.
Embodiment 1
The widest 89 mm, high 144 mm, the Soft Roll laminated batteries of thick 12.5mm are disassembled after overdischarge, takes out therein
Positive plate, once purged acquisition 69 mm*139 mm(height * width) positive plate.Positive plate is fixed on positive pole position, positive plate
Tow sides all expose in the electrolytic solution, and surrounding seals.Stood 10min to reach the purpose of infiltration.From aluminium foil afflux
Draw the positive pole of wire connecting power at body, using graphite as negative pole, with the oxalic acid of 0.2mol/L as electrolyte, at voltage be
60V, temperature be 20 DEG C under conditions of be energized 60min.At the end of, the positive electrode after coming off directly proceeds to follow-up recovery work
Step, reclaims positive electrode by modes such as filtrations, and remaining bulk aluminium flake can directly take off recovery.
Embodiment 2
The widest 89 mm, high 144 mm, the Soft Roll laminated batteries of thick 12.5mm are disassembled after overdischarge, takes out therein
Positive plate, once purged acquisition 69 mm*139 mm(height * width) positive plate.Positive plate is fixed on positive pole position, positive plate
Tow sides all expose in the electrolytic solution, and surrounding seals.Stood 5min to reach the purpose of infiltration.From aluminum foil current collector
The positive pole of wire connecting power is drawn at place, using graphite as negative pole, with the oxalic acid of 0.5mol/L as electrolyte, is 80V at voltage,
Temperature be 10 DEG C under conditions of be energized 40min.At the end of, the positive electrode after coming off directly proceeds to follow-up recovery work step, logical
The modes such as filtration reclaim positive electrode, and remaining bulk aluminium flake can directly take off recovery.
Embodiment 3
The widest 89mm, high 144mm, the Soft Roll laminated batteries of thick 12.5mm are disassembled after overdischarge, take out therein just
Pole piece, once purged acquisition 69 mm*139 mm(height * width) positive plate.Positive plate is fixed on positive pole position, and positive plate is just
Anti-two sides all exposes in the electrolytic solution, and surrounding seals.Stood 20min to reach the purpose of infiltration.From aluminum foil current collector
The positive pole of wire connecting power is drawn at place, using graphite as negative pole, with the oxalic acid of 0.6mol/L as electrolyte, is 40V at voltage,
Temperature be 25 DEG C under conditions of be energized 20min.At the end of, the positive electrode after coming off directly proceeds to follow-up recovery work step, logical
The modes such as filtration reclaim positive electrode, and remaining bulk aluminium flake can directly take off recovery.
Claims (4)
1. a separating waste, worn anode material for lithium-ion batteries and the method for collector, it is characterised in that comprise the following steps:
(1) disassembling after waste and old lithium ion battery electric discharge completely, take out positive plate, deionized water cleans up, and dries stand-by；
(2) positive plate is placed in electrolyte immersion a period of time make it fully infiltrate, with positive plate as positive pole, graphite flake is negative
Pole, oxalic acid solution is electrolyte, and energising carries out electrochemical anodization reaction, and aluminum foil current collector separates with positive electrode；
(3), after step (2) electrochemical anodization reaction, aluminum foil current collector directly recycles；The positive electrode split away off
It is recovered by filtration.
Separating waste, worn anode material for lithium-ion batteries the most according to claim 1 and the method for collector, it is characterised in that
The solubility of described step (2) oxalic acid solution is 0.2-0.6mol/L, and oxidizing reaction temperature is 5-25 DEG C, and oxidation reaction voltage is
40-80V, oxidation time is at 20-60min.
Separating waste, worn anode material for lithium-ion batteries the most according to claim 1 and the method for collector, it is characterised in that
Described step (2) soak time is 5-20min.
Separating waste, worn anode material for lithium-ion batteries the most according to claim 1 and the method for collector, it is characterised in that
Described step (2) anodic oxidation generates one layer of Woelm Alumina at collection liquid surface；The formation of pellumina will destroy aluminum afflux
Body and the contact interface of positive electrode, and aoxidize the process being to expand, expand the stress produced and would be further forced positive pole material
Material and the separation of aluminium foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610658042.3A CN106252770A (en) | 2016-08-11 | 2016-08-11 | A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610658042.3A CN106252770A (en) | 2016-08-11 | 2016-08-11 | A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector |
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| CN106252770A true CN106252770A (en) | 2016-12-21 |
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| CN201610658042.3A Pending CN106252770A (en) | 2016-08-11 | 2016-08-11 | A kind of separating waste, worn anode material for lithium-ion batteries and the method for collector |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659642A (en) * | 2018-12-14 | 2019-04-19 | 广西师范大学 | The method of aluminium foil and positive active material in separating waste, worn based lithium-ion battery positive plate |
| CN110238165A (en) * | 2019-06-26 | 2019-09-17 | 天津赛德美新能源科技有限公司 | A kind of separation equipment of lithium battery cathode plate dismantling |
| CN112151902A (en) * | 2020-08-20 | 2020-12-29 | 昆明理工大学 | Method for quickly separating electrode material from current collector and utilizing electrode material and current collector in high-value mode |
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|---|---|---|---|---|
| WO2004082060A1 (en) * | 2003-03-13 | 2004-09-23 | Apex Energy Inc. | High current capacity battery |
| JP2010062073A (en) * | 2008-09-05 | 2010-03-18 | Kankyo Kagaku Kenkyusho:Kk | Battery using acid electrolyte |
| CN102965508A (en) * | 2012-11-02 | 2013-03-13 | 中南大学 | Electrolytic treatment method for positive pole materials of waste lithium batteries |
| CN104485492A (en) * | 2014-12-03 | 2015-04-01 | 浙江工业大学 | Method for separating electrode material and current collector of waste lithium ion battery |
-
2016
- 2016-08-11 CN CN201610658042.3A patent/CN106252770A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004082060A1 (en) * | 2003-03-13 | 2004-09-23 | Apex Energy Inc. | High current capacity battery |
| JP2010062073A (en) * | 2008-09-05 | 2010-03-18 | Kankyo Kagaku Kenkyusho:Kk | Battery using acid electrolyte |
| CN102965508A (en) * | 2012-11-02 | 2013-03-13 | 中南大学 | Electrolytic treatment method for positive pole materials of waste lithium batteries |
| CN104485492A (en) * | 2014-12-03 | 2015-04-01 | 浙江工业大学 | Method for separating electrode material and current collector of waste lithium ion battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109659642A (en) * | 2018-12-14 | 2019-04-19 | 广西师范大学 | The method of aluminium foil and positive active material in separating waste, worn based lithium-ion battery positive plate |
| CN110238165A (en) * | 2019-06-26 | 2019-09-17 | 天津赛德美新能源科技有限公司 | A kind of separation equipment of lithium battery cathode plate dismantling |
| CN112151902A (en) * | 2020-08-20 | 2020-12-29 | 昆明理工大学 | Method for quickly separating electrode material from current collector and utilizing electrode material and current collector in high-value mode |
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Application publication date: 20161221 |