CN102709622A - Method for ultrasonic-assisted hydrothermal restoration of lithium cobalt oxide material in spent lithium ion battery - Google Patents
Method for ultrasonic-assisted hydrothermal restoration of lithium cobalt oxide material in spent lithium ion battery Download PDFInfo
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- CN102709622A CN102709622A CN2012101872412A CN201210187241A CN102709622A CN 102709622 A CN102709622 A CN 102709622A CN 2012101872412 A CN2012101872412 A CN 2012101872412A CN 201210187241 A CN201210187241 A CN 201210187241A CN 102709622 A CN102709622 A CN 102709622A
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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 invention relates to a method for the ultrasonic-assisted hydrothermal restoration of a lithium cobalt oxide material in a spent lithium ion battery. The method specifically comprises the following steps of: separating the spent lithium ion battery in a mechanical stripping way to obtain powdery lithium cobalt oxide waste; impregnating the powdery lithium cobalt oxide waste into a 1 to 2 mol/L solution of lithium hydroxide, placing the mixed solution in an ultrasonic hydrothermal reactor, heating the reactor to 150 to 200 DEG C, and applying ultrasonic irradiation for 6 to 12 hours; cleaning and filtering the ultrasonically cooled mixed solution by using de-ionized water for three to five times to obtain black lithium cobalt oxide paste; and drying the black lithium cobalt oxide paste for 6 to 10 hours in an environment of 50 to 80 DEG C to obtain the restored lithium cobalt oxide material. By the ultrasonic-assisted hydrothermal restoration method, the lithium content of the lithium cobalt oxide material in the spent lithium ion battery is increased, the electrochemical performance of lithium cobalt oxide is regained, and the lithium cobalt oxide material can be reused as a cathode material to produce a new lithium ion battery. The lithium cobalt oxide material in the spent lithium ion battery can be effectively treated; and the method has the characteristics of simplicity, high operability, no secondary pollution and good social benefits, economic benefits and environmental benefits.
Description
Technical field
The invention belongs to environmental protection technical field, be specifically related to the method that cobalt acid lithium material hydro-thermal is repaired in a kind of disabled lithium ion cell of supersonic synergic.
Background technology
Lithium ion battery has, and voltage is high, specific energy big, have extended cycle life, security performance is good, but the little fast charging and discharging of self discharge, operating temperature range are wide, remarkable advantages such as environmental protection relatively; Be widely used in electronic product fields such as mobile phone, notebook computer, video camera, digital camera, and be expected to be used widely at aspects such as electric automobile, space flight and energy storage.Under a large amount of situation about using of lithium ion battery, certainly will cause scrapping in a large number of lithium ion battery.In the lithium ion battery that portable type electronic product uses, cobalt acid lithium is the positive electrode active materials that unique large-scale commercial applications is used at present.Cobalt, lithium metal in the cobalt acid lithium material all are valuable resource, the especially internationally recognized especially strategic materials of metallic cobalt.Owing to use discarded mobile phone lithium ion battery to contain the cobalt heavy metal, like any stacking, landfill, or the mishandling serious environmental that must cause is polluted harm humans health.
The recycling of cobalt acid lithium waste material is at present by the environment protection method of extensive employing, and it is also ripe relatively to reclaim cobalt acid lithium waste material reutilization technology.From the recycle of cobalt acid lithium the lithium battery industry, after it lost efficacy, cobalt acid lithium waste material is separated with refining; And then be back to the preparation of lithium battery anode; Whole process link is many, and relates to the repeatedly conversion of cobalt and lithium product form, and overall craft is complicated and consume energy higher.
At present, directly reclaiming cobalt acid lithium technology has high-temperature calcination and two kinds of methods of hydrothermal treatment consists.Exist the energy consumption height in the high-temperature process cobalt acid lithium waste material, form auxiliary air easily and pollute and generate problems such as cobalt oxygen inert substance.Hydro-thermal regeneration research experiment temperature requirement is 200 ℃, and the experiment reaction time is 20 hours; Problems such as hot environment and the reaction time of growing and the corrosivity to consersion unit that is caused thus are strong are restricting the application of inefficacy cobalt acid lithium hydro-thermal recovery technique.
Summary of the invention
The object of the present invention is to provide the method that cobalt acid lithium material hydro-thermal is repaired in the disabled lithium ion cell of the gentle supersonic synergic of a kind of device simple and reaction condition; The reparation energy consumption of reaction is low; Environmental impact is little; The cobalt acid lithium material chemical property of handling after repairing through using supersonic, water-heating is good, and can be as the positive electrode active materials reuse again of lithium ion battery.
The method that cobalt acid lithium material hydro-thermal is repaired in the disabled lithium ion cell of a kind of supersonic synergic that the present invention proposes; At first adopt the method for mechanical separation to carry out preliminary treatment to using the lithium ion battery that lost efficacy; Separate obtaining cobalt acid lithium waste material, place 1 ~ 2 mol/L lithium hydroxide solution to cobalt acid lithium waste material, adopt ultrasonic acceleration hydro-thermal reaction then; Make cobalt acid lithium in lithium hydroxide solution, realize repairing, concrete steps are following:
(1) will use the lithium ion battery machinery that lost efficacy to split, obtain the cobalt acid lithium waste material in the positive electrode;
(2) cobalt acid lithium waste material is positioned in ultrasonic-hydrothermal reactor that lithium hydroxide solution is housed; Said ultrasonic-hydrothermal reactor is made up of water cooling system 1, temperature sensor 2, electric mixer 4, electric heater unit 5, closed reactor 6 and ultrasonic amplitude transformer 7; Electric heater unit 5 is fixed in outside the closed reactor 6; Be provided with electric mixer 4 in the closed reactor 6; Temperature sensor 2 inserts closed reactor 6 with water cooling system 1 by closed reactor 6 tops, and closed reactor 6 bottoms are provided with ultrasonic amplitude transformer 6; Control ultrasonic amplitude transformer 6 power are 650 ± 2W, and supersonic frequency is 20-30 kHz, and closed reactor 6 is heated at constant temperature under 150 ~ 200 ℃ of temperature, after the ultrasonic radiation time is 4 ~ 12h, and natural cooling;
(4) treat ultrasonic-during the hydrothermal reactor cool to room temperature, cobalt acid lithium material and uses deionized water wash 3 ~ 5 times through filtering in the lithium hydroxide solution;
(5) will filter the cobalt acid lithium material that obtains, drying is 6 ~ 10 hours in 50-80 ℃ of environment, reclaims the cobalt acid lithium material that obtains to be back to lithium battery anode.
Among the present invention, said electric mixer rotating speed is 100 ~ 250rpm.
Inductively coupled plasma atomic emission (ICP-AES) elementary analysis through material; The Li/Co value of original inefficacy cobalt acid lithium material is 0.76 (mean value); The Li/Co value of the cobalt acid lithium material of repairing increases to more than 1.0; Improve situation preferably, thereby recovered to have the cobalt acid lithium structure of good electrochemical activity because of lithium content chemical property decline on the low side in the cobalt acid lithium material.
Description of drawings
Fig. 1 for the present invention ultrasonic-structural diagrams of hydrothermal reactor.
Label among the figure: 1 is water cooling system, and 2 is temperature sensor, and 3 is set bolt, and 4 is electric mixer, and 5 is electric heater unit, and 6 is closed reactor, and 7 is ultrasonic amplitude transformer.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described:
Embodiment 1
(1) will use disabled lithium ion battery of mobile phone machinery to split, obtain the cobalt acid lithium waste material in the positive electrode;
(2) cobalt acid lithium waste material is positioned in ultrasonic-hydrothermal reactor that the 2M lithium hydroxide solution is housed; Ultrasonic-hydrothermal reactor is equipped with electric mixer, electric heater unit, temperature sensor, water cooling system, closed reactor; And at closed reactor bottom installation ultrasonic amplitude transformer, the ultrasonic amplitude transformer head is immersed under the liquid level;
(3) ultrasonic device power is 650 W, and supersonic frequency is 25 kHz, is heated to 150 ℃, behind the ultrasonic 12h, and natural cooling;
When (4) treating the ultrasonic reactor cool to room temperature, cobalt acid lithium material and uses deionized water wash 3 ~ 5 times through filtering in the lithium hydroxide solution;
(5) will filter and obtain cobalt acid lithium material,, reclaim the cobalt acid lithium material that obtains to be back to lithium battery anode in 80 ℃ of environment dry 6 hours.
Inductively coupled plasma atomic emission (ICP-AES) elementary analysis through material; The Li/Co value of original inefficacy cobalt acid lithium material is 0.76 (mean value); The Li/Co value of the cobalt acid lithium material of repairing increases to 0.980 (mean value), thereby using supersonic, water-heating has been repaired the chemical property of cobalt acid lithium material.
Embodiment 2
(1) will use disabled lithium ion battery of mobile phone machinery to split, obtain the cobalt acid lithium waste material in the positive electrode;
(2) cobalt acid lithium waste material is positioned in the using supersonic, water-heating reactor that the 1M lithium hydroxide solution is housed; Reactor is equipped with electric heater unit, agitating device, temperature control equipment, current cooling device; And at reactor bottom installation ultrasonic amplitude transformer, the horn head is immersed under the liquid level;
(3) ultrasonic device power is 650 W, and supersonic frequency is 25 kHz, is heated to 200 ℃, behind the ultrasonic 4h, and natural cooling;
When (4) treating the ultrasonic reactor cool to room temperature, cobalt acid lithium material and uses deionized water wash 3 ~ 5 times through filtering in the lithium hydroxide solution;
(5) will filter and obtain cobalt acid lithium material,, reclaim the cobalt acid lithium material that obtains to be back to lithium battery anode in 80 ℃ of environment dry 6 hours.
Inductively coupled plasma atomic emission (ICP-AES) elementary analysis through material; The Li/Co value of original inefficacy cobalt acid lithium material is 0.76 (mean value); The Li/Co value of the cobalt acid lithium material of repairing increases to 1.013 (mean values), thereby using supersonic, water-heating has been repaired the chemical property of cobalt acid lithium material.
Claims (2)
1. the method that cobalt acid lithium material hydro-thermal is repaired in the disabled lithium ion cell of a supersonic synergic; It is characterized in that at first adopting the method for mechanical separation to carry out preliminary treatment to using the lithium ion battery that lost efficacy; Separate obtaining cobalt acid lithium waste material, place 1 ~ 2 mol/L lithium hydroxide solution to cobalt acid lithium waste material, adopt ultrasonic acceleration hydro-thermal reaction then; Make cobalt acid lithium in lithium hydroxide solution, realize repairing, concrete steps are following:
(1), will use the lithium ion battery machinery fractionation of losing efficacy, the cobalt acid lithium waste material in the acquisition positive electrode;
(2), cobalt acid lithium waste material is positioned in ultrasonic-hydrothermal reactor that lithium hydroxide solution is housed; Said ultrasonic-hydrothermal reactor is made up of water cooling system (1), temperature sensor (2), electric mixer (4), electric heater unit (5), closed reactor (6) and ultrasonic amplitude transformer (7); Electric heater unit (5) is fixed in outside the closed reactor (6); Be provided with electric mixer (4) in the closed reactor (6); Temperature sensor (2) and water cooling system (1) insert closed reactor (6) by closed reactor (6) top, and closed reactor (6) bottom is provided with ultrasonic amplitude transformer (6), and ultrasonic amplitude transformer (6) head is immersed under the liquid level; Control ultrasonic amplitude transformer (6) power is 650 ± 2W, and supersonic frequency is 20-30 kHz, and closed reactor (6) is heated at constant temperature under 150 ~ 200 ℃ of temperature, after the ultrasonic radiation time is 4 ~ 12h, and natural cooling;
(3), treat ultrasonic-during the hydrothermal reactor cool to room temperature, cobalt acid lithium material and uses deionized water wash 3 ~ 5 times through filtering in the lithium hydroxide solution;
(4), will filter the cobalt acid lithium material that obtains, in 50-80 ℃ of environment dry 6 ~ 10 hours, reclaim the cobalt acid lithium material that obtains to be back to lithium battery anode.
2. the method that cobalt acid lithium material hydro-thermal is repaired in the disabled lithium ion cell of supersonic synergic according to claim 1 is characterized in that said electric mixer rotating speed is 100 ~ 250rpm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101872412A CN102709622A (en) | 2012-06-08 | 2012-06-08 | Method for ultrasonic-assisted hydrothermal restoration of lithium cobalt oxide material in spent lithium ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073071A (en) * | 2013-01-23 | 2013-05-01 | 同济大学 | Method for hydrothermally repairing invalid lithium cobalt oxide material in lithium ion battery by ultrasonic field enhancement |
| CN103151519A (en) * | 2013-02-22 | 2013-06-12 | 同济大学 | Method for oxidizing agent-aided restoration of failed lithium cobalt oxide under reinforcement of ultrasonic field |
| CN105428747A (en) * | 2015-12-30 | 2016-03-23 | 深圳先进技术研究院 | Restoration and recycling method of lithium cobaltate materials of lithium batteries |
| CN108199105A (en) * | 2017-12-27 | 2018-06-22 | 同济大学 | The supersonic, water-heating separating technology of electrode component materials of used lithium batteries |
| CN109502648A (en) * | 2018-12-10 | 2019-03-22 | 中南大学 | A kind of the molybdenum disulfide nano sheet physical separation methods and its device of ultrasonic wave added |
| CN111370799A (en) * | 2019-12-30 | 2020-07-03 | 武汉瑞杰特材料有限责任公司 | Pretreatment method for failure lithium ion battery anode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102367171A (en) * | 2011-11-23 | 2012-03-07 | 陕西科技大学 | Preparation method of LiFePO4 lithium ion battery powder |
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2012
- 2012-06-08 CN CN2012101872412A patent/CN102709622A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367171A (en) * | 2011-11-23 | 2012-03-07 | 陕西科技大学 | Preparation method of LiFePO4 lithium ion battery powder |
Non-Patent Citations (1)
| Title |
|---|
| DO-SU KIM 等: "Simultaneous separation and renovation of lithium cobalt oxide from the cathode of spent lithium ion rechargeable batteries", 《JOURNAL OF POWER SOURCES》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073071A (en) * | 2013-01-23 | 2013-05-01 | 同济大学 | Method for hydrothermally repairing invalid lithium cobalt oxide material in lithium ion battery by ultrasonic field enhancement |
| CN103151519A (en) * | 2013-02-22 | 2013-06-12 | 同济大学 | Method for oxidizing agent-aided restoration of failed lithium cobalt oxide under reinforcement of ultrasonic field |
| CN105428747A (en) * | 2015-12-30 | 2016-03-23 | 深圳先进技术研究院 | Restoration and recycling method of lithium cobaltate materials of lithium batteries |
| CN108199105A (en) * | 2017-12-27 | 2018-06-22 | 同济大学 | The supersonic, water-heating separating technology of electrode component materials of used lithium batteries |
| CN108199105B (en) * | 2017-12-27 | 2020-06-12 | 同济大学 | Ultrasonic hydrothermal separation process for waste lithium battery electrode composition material |
| CN109502648A (en) * | 2018-12-10 | 2019-03-22 | 中南大学 | A kind of the molybdenum disulfide nano sheet physical separation methods and its device of ultrasonic wave added |
| CN109502648B (en) * | 2018-12-10 | 2020-11-03 | 中南大学 | Ultrasonic-assisted molybdenum disulfide nanosheet physical stripping method and device |
| CN111370799A (en) * | 2019-12-30 | 2020-07-03 | 武汉瑞杰特材料有限责任公司 | Pretreatment method for failure lithium ion battery anode material |
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Application publication date: 20121003 |