CN109713393A - A kind of isolated method of lithium battery active material - Google Patents
A kind of isolated method of lithium battery active material Download PDFInfo
- Publication number
- CN109713393A CN109713393A CN201811648644.6A CN201811648644A CN109713393A CN 109713393 A CN109713393 A CN 109713393A CN 201811648644 A CN201811648644 A CN 201811648644A CN 109713393 A CN109713393 A CN 109713393A
- Authority
- CN
- China
- Prior art keywords
- active material
- solvent
- battery active
- lithium battery
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The present invention relates to the recyclings of waste and old lithium ion battery, and in particular to a kind of isolated method of lithium battery active material.Excessive 0.5~5h of stirring solvent is added into battery after broken, and then realizes falling off and separating for battery active material, then lithium battery active material is collected in screening.The positive and negative anodes active material in waste power lithium battery is recycled using mixed solvent in separation process of the present invention, the rate of recovery about 97%, the solvent slop for having removed material carries out recovery, and solvent applies loss about 2%~5%；And the method for the present invention is simple, mild condition, and the solvent lift-off process of battery active material saves the energy consumption of high-temperature roasting and water logging process, obvious environment benefit compared with traditional high-temperature roasting water logging stripping technology.Meanwhile the present invention in electrolyte in lithium battery part lithium salts and PVDF etc. recycle, improve regenerant value, reduce the cost recovery of lithium electricity.
Description
Technical field
The present invention relates to the recyclings of waste and old lithium ion battery, and in particular to a kind of separation of lithium battery active material
Method.
Background technique
Metal resource largely with higher economic value is typically contained in battery, such as the positive electrode of lithium ion battery
Cobalt acid lithium, LiMn2O4, nickel ion doped, LiFePO4 etc. are mostly used greatly, and aluminium foil and copper foil is respectively adopted in anode and negative current collector；
Anode of nickel-metal hydride battery active material is using surface cladding Co (OH)2Spherical Ni (OH)2, negative electrode active material is using LaNi5Deng storage
Nickel foam and stainless (steel) wire is respectively adopted in alloy material for hydrogen, anode and negative current collector；Nickel-cadmium cell anode uses the Ni containing cadmium
(OH)2, cathode is using CdO and Cd (OH)2, nickel foam and stainless (steel) wire is respectively adopted in anode and negative current collector.If cannot incite somebody to action
Defective products in discarded battery or production carries out effective recycling, it will causes the huge wasting of resources, and Cd, Mn etc.
Toxic heavy metal once leaks, it will contaminated soil and underground water generate the ecological environment of the mankind and greatly threatens.Cause
This, which carries out recycling and reusing to old and useless battery, has important strategic importance and economic value.China is that a resource is more rare
Country, especially strategic resources cobalt need to spend a large amount of foreign exchange from overseas import every year, and have ever-increasing trend,
Though and the storage level horn of plenty of metallic nickel and manganese China recycles significant as non-renewable resources.
In the prior art, having decomposes the organic bonds such as PVDF using calcination method, thus isolating active material, but the party
Method reaction condition is violent, and energy consumption is high and be easy to cause atmosphere pollution.Especially as the graphite of negative electrode active material, at high temperature
It is easily denaturalized, is lost.Numerous studies work has been done on solvent method removing battery anode active material by numerous research institutions in recent years
Make, but how economically solvent method processing waste lithium cell positive and negative anodes mix broken material and treated solvent recycled
It is only the key point of solvent method route.
Summary of the invention
It is an object of that present invention to provide a kind of isolated methods of lithium battery active material.
To achieve the above object, the invention adopts a technical scheme as:
Excessive stirring solvent 0.5 is added into broken rear battery in a kind of isolated method of lithium battery active material
~5h, and then realize falling off and separating for battery active material, then the lithium battery active material (active group of battery is collected in screening
Divide nickel cobalt manganese)；Wherein, solvent be n,N-Dimethylformamide (DMF), N-Methyl pyrrolidone (NMP), ethyl alcohol, one in water
Kind is several.
Mass ratio is 1:20-20:1 to the solvent between any two kinds of substances when being mixture.
Further
(1) the waste power lithium battery battery core after electric discharge is put into shear crusher Mechanical Crushing, by broken electricity
Pond material is placed in stirred tank；
(2) excessive solvent is added into stirred tank, 0.5-5h is stirred at 70-100 DEG C, and then realize battery-active material
Material falls off and separates；
(3) by mixture screening, heat filtering, flushing after above-mentioned stirring, copper aluminium foil diaphragm, battery active material is obtained and is given up
Solvent.
Excessive solvent is added into stirred tank in the step (2), make solid-liquid mass ratio in kettle (battery material quality:
Mixed solvent quality) it is 1:5-1:50.
Excessive solvent is added into stirred tank for the step (2), again by ultrasonic vibration 0-30 minutes after stirring, in turn
Realize falling off and separating for battery active material.
Mixture screening, 70-100 DEG C of filtering, flushing screening filter cake after above-mentioned stirring are obtained copper aluminium by the step (3)
Foil diaphragm, battery active material and solvent slop.
The solvent slop that the step (3) generates is passed through distillation in distillation still and handles, and collects solvent set and is used for step (2).
Distillation still residue filters after the distillation processing, and filter residue is lithium phosphate and lithium fluoride mixed salt, filtrate decoloration, removing low boiling
Point volatile component, recycling obtain Kynoar (PVDF).
Advantage for present invention:
The positive and negative anodes active material in waste power lithium battery is returned using mixed solvent in separation process of the present invention
It receives, the rate of recovery about 97%, the solvent slop for having removed material carries out recovery, and solvent applies loss about 2%~5%；And this
Inventive method is simple, mild condition, the solvent lift-off process of battery active material and traditional high-temperature roasting water logging stripping technology
It compares, saves the energy consumption of high-temperature roasting and water logging process, obvious environment benefit.Meanwhile the present invention is to electrolyte in lithium battery
In part lithium salts and PVDF etc. recycled, improve regenerant value, reduce the cost recovery of lithium electricity.
Detailed description of the invention
Fig. 1 is the separation process figure of lithium battery active material provided in an embodiment of the present invention.
Specific embodiment:
With reference to the accompanying drawing and embodiment the present invention will be further explained explanation.
Embodiment 1
By the waste and old 18650 type dynamic lithium battery decladding after the electric discharge of 20 sections, battery core puts into mechanical broken in shear crusher
It is broken, obtain battery mixing pole piece fragment about 650g.Fragment is put into stirred tank, 10kg mixed solvent is added, stirring is warming up to 90
DEG C, 3 hours are kept the temperature, screening filtering, miscible bonding solvent rinses, and obtains the mixing fragment of copper aluminium foil and diaphragm, positive and negative anodes activity material
Expect 421g after (nickel cobalt manganese) is dry (by the active material of single battery for 21.5g based on, active material removing rate is about 97.9%).It will
Flushing liquor and filtrate, which merge, carries out rectification process, and the fraction collection about 9.7kg (mixed solvent) after 110 DEG C continues to apply removing electricity
Pole material, kettle afterheat is filtered after rectifying, and filter cake flushing is dried to obtain lithium phosphate and lithium fluoride mixed salt 19.5g；Filtrate about 0.5kg adds work
Property carbon decoloring, removing volatile component, obtain about 15gPVDF solid.Wherein, mixed solvent is the DMF and H of mass ratio 85:152O
Mixed liquor.
Embodiment 2
The waste and old 18650 type dynamic lithium battery after the electric discharge of 20 sections is handled by the processing method in embodiment 1, obtains battery
Mix pole piece fragment about 650g.Fragment is put into stirred tank, 10kg is added to apply the mixed solvent of the acquisition of above-described embodiment 1
(DMF:H2O mass ratio=82:18), stirring is warming up to 90 DEG C, keeps the temperature 3 hours, and material ultrasonic vibration 5 minutes, screening filtering was molten
Mixed solvent rinses, and obtains the mixing fragment of copper aluminium foil and diaphragm, 416g is (by single battery after positive and negative anodes active material is dry
Active material is 21.5g meter, and active material removing rate is about 96.7%).Flushing liquor and filtrate are merged and carry out rectification process, 112
Fraction collection about 9.5kg (mixed solvent) after DEG C continues to apply stripping electrode material, and kettle afterheat is filtered after rectifying, and filter cake rinses dry
It is dry to obtain lithium phosphate and lithium fluoride mixed salt 19.2g；Filtrate about 0.5kg adds active carbon decoloring, removing volatile component, obtains about
17gPVDF solid.
Embodiment 3
The waste and old 18650 type dynamic lithium battery after the electric discharge of 20 sections is handled by the processing method in embodiment 1, obtains battery
Mix pole piece fragment about 650g.Fragment is put into stirred tank, 10kg mixed solvent (NMP:H is added2O mass ratio=90:10), it stirs
It mixes and is warming up to 90 DEG C, keep the temperature 3 hours, screening filtering, miscible bonding solvent rinses, and obtains the mixing fragment of copper aluminium foil and diaphragm, just
417g after negative electrode active material is dry (by the active material of single battery for 21.5g based on, active material removing rate is about 97%).It will
Flushing liquor and filtrate, which merge, goes rectifying, and the fraction collection about 9.7kg (mixed solvent) after 0.5,115 DEG C of reflux ratio continues to apply stripping
From electrode material, kettle afterheat is filtered after rectifying, and filter cake flushing is dried to obtain lithium phosphate and lithium fluoride mixed salt 20.3g；Filtrate about 0.5kg
Add active carbon decoloring, removing volatile component, obtains about 15gPVDF solid.
Embodiment 4
The waste and old 18650 type dynamic lithium battery after the electric discharge of 20 sections is handled by the processing method in embodiment 1, obtains battery
Mix pole piece fragment about 650g.Fragment is put into stirred tank, 10kg is added to apply the mixed solvent that rear above-described embodiment 3 obtains
(NMP:H2O mass ratio=85:15), stirring is warming up to 90 DEG C, 3 hours are kept the temperature, material ultrasonic vibration 10 minutes, screening filtering,
Miscible bonding solvent rinses, and obtains the mixing fragment of copper aluminium foil and diaphragm, 415g (presses single battery after positive and negative anodes active material is dry
Active material be 21.5g meter, active material removing rate is about 96.5%).Flushing liquor and filtrate are merged and go rectifying, reflux ratio
Fraction collection about 9.6kg (mixed solvent) after 0.5,116 DEG C continues to apply stripping electrode material, and kettle afterheat is filtered after rectifying, filter
Cake flushing is dried to obtain lithium phosphate and lithium fluoride mixed salt 20.6g；Filtrate about 0.5kg adds active carbon decoloring, removing volatile component, obtains
To about 18gPVDF solid.
Claims (7)
1. a kind of isolated method of lithium battery active material, it is characterised in that: be added into broken rear battery excessive molten
0.5~5h is stirred in agent, and then realizes falling off and separating for battery active material, and then lithium battery active material is collected in screening；Its
In, solvent is one or more of n,N-Dimethylformamide (DMF), N-Methyl pyrrolidone (NMP), ethyl alcohol, water.
2. the isolated method of lithium battery active material according to claim 1, it is characterised in that:
(1) the waste power lithium battery battery core after electric discharge is put into shear crusher Mechanical Crushing, by broken battery material
Material is placed in stirred tank；
(2) excessive solvent is added into stirred tank, 0.5-5h is stirred at 70-100 DEG C, and then realize battery active material
It falls off and separates；
(3) by mixture screening, heat filtering, flushing after above-mentioned stirring, copper aluminium foil diaphragm, battery active material is obtained and is given up molten
Agent.
3. the isolated method of lithium battery active material as described in claim 2, it is characterised in that: in the step (2) to
Excessive solvent is added in stirred tank, making solid-liquid mass ratio in kettle (battery material quality: mixed solvent quality) is 1:5-1:50.
4. the isolated method of lithium battery active material as described in claim 2, it is characterised in that: the step (2) is to stirring
It mixes and excessive solvent is added in kettle, again by ultrasonic vibration 0-30 minutes after stirring, and then realize falling off for battery active material
With separate.
5. the isolated method of lithium battery active material as described in claim 2, it is characterised in that: the step (3) will be upper
It states mixture screening after stirring, 70-100 DEG C of filtering, rinse screening filter cake, obtain copper aluminium foil diaphragm, battery active material and give up
Solvent.
6. by the isolated method of lithium battery active material described in claim 2 or 5, it is characterised in that: the step (3) produces
Raw solvent slop is passed through distillation in distillation still and handles, and collects solvent set and is used for step (2).
7. the isolated method of lithium battery active material according to claim 6, it is characterised in that: steamed after the distillation processing
The residual filtering of kettle is evaporated, filter residue is lithium phosphate and lithium fluoride mixed salt, and filtrate decoloration, removing low boiling point volatile component, recycling obtains poly- inclined
Vinyl fluoride (PVDF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811648644.6A CN109713393A (en) | 2018-12-30 | 2018-12-30 | A kind of isolated method of lithium battery active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811648644.6A CN109713393A (en) | 2018-12-30 | 2018-12-30 | A kind of isolated method of lithium battery active material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109713393A true CN109713393A (en) | 2019-05-03 |
Family
ID=66260473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811648644.6A Pending CN109713393A (en) | 2018-12-30 | 2018-12-30 | A kind of isolated method of lithium battery active material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109713393A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364683A (en) * | 2019-05-31 | 2019-10-22 | 天津力神电池股份有限公司 | A kind of stripping means of electrodes of lithium-ion batteries |
| CN110416652A (en) * | 2019-07-03 | 2019-11-05 | 宁波富锂锂电池有限公司 | A method of separating and recovering PVDF from waste lithium iron phosphate positive powder acidleach tailings |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
| CN114180636A (en) * | 2021-11-05 | 2022-03-15 | 新疆师范大学 | Lithium manganese material in lithium ion battery anode waste material and stripping and recycling method thereof |
| CN114512738A (en) * | 2022-03-14 | 2022-05-17 | 中南大学 | Solvothermal pretreatment method and application of waste lithium battery cathode material |
| CN114597531A (en) * | 2022-03-14 | 2022-06-07 | 新疆师范大学 | Method for separating and recycling lithium iron phosphate anode waste material for lithium ion battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819326A (en) * | 2006-01-10 | 2006-08-16 | 东南大学 | Resource separation of waste lithium ion battery |
| CN102703706A (en) * | 2012-06-01 | 2012-10-03 | 奇瑞汽车股份有限公司 | Method for recovering valued metals from waste lithium cobaltate batteries |
| CN104577246A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Recycling method and recycling device for cathode material and anode material of spent lithium-ion battery |
| WO2016012943A1 (en) * | 2014-07-22 | 2016-01-28 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for recycling the electrolyte of a li-ion battery and method for recycling li-ion batteries |
| JP2016058280A (en) * | 2014-09-10 | 2016-04-21 | トヨタ自動車株式会社 | Method for recovering positive electrode active material |
| CN106129513A (en) * | 2016-08-22 | 2016-11-16 | 北京小飞融创新能源科技有限公司 | A kind of recovery method of waste lithium cell |
| CN107275700A (en) * | 2016-04-07 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of waste and old lithium ion battery recovery and treatment method crushed based on wet type |
| CN107591582A (en) * | 2016-07-07 | 2018-01-16 | 皓智环球有限公司 | The method for reclaiming lithium ion battery |
| CN108232352A (en) * | 2018-01-30 | 2018-06-29 | 南京红太阳新能源有限公司 | A kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode |
| CN108288737A (en) * | 2017-12-25 | 2018-07-17 | 衢州北斗星化学新材料有限公司 | A method of recycling lithium hexafluoro phosphate from waste lithium cell positive electrode |
| CN108400402A (en) * | 2018-02-27 | 2018-08-14 | 四川省有色冶金研究院有限公司 | A kind of separation method of waste and old lithium dynamical battery active material and collector |
-
2018
- 2018-12-30 CN CN201811648644.6A patent/CN109713393A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1819326A (en) * | 2006-01-10 | 2006-08-16 | 东南大学 | Resource separation of waste lithium ion battery |
| CN102703706A (en) * | 2012-06-01 | 2012-10-03 | 奇瑞汽车股份有限公司 | Method for recovering valued metals from waste lithium cobaltate batteries |
| WO2016012943A1 (en) * | 2014-07-22 | 2016-01-28 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for recycling the electrolyte of a li-ion battery and method for recycling li-ion batteries |
| JP2016058280A (en) * | 2014-09-10 | 2016-04-21 | トヨタ自動車株式会社 | Method for recovering positive electrode active material |
| CN104577246A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Recycling method and recycling device for cathode material and anode material of spent lithium-ion battery |
| CN107275700A (en) * | 2016-04-07 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of waste and old lithium ion battery recovery and treatment method crushed based on wet type |
| CN107591582A (en) * | 2016-07-07 | 2018-01-16 | 皓智环球有限公司 | The method for reclaiming lithium ion battery |
| CN106129513A (en) * | 2016-08-22 | 2016-11-16 | 北京小飞融创新能源科技有限公司 | A kind of recovery method of waste lithium cell |
| CN108288737A (en) * | 2017-12-25 | 2018-07-17 | 衢州北斗星化学新材料有限公司 | A method of recycling lithium hexafluoro phosphate from waste lithium cell positive electrode |
| CN108232352A (en) * | 2018-01-30 | 2018-06-29 | 南京红太阳新能源有限公司 | A kind of reclaimer and method of lithium-ion battery lithium iron phosphate positive electrode |
| CN108400402A (en) * | 2018-02-27 | 2018-08-14 | 四川省有色冶金研究院有限公司 | A kind of separation method of waste and old lithium dynamical battery active material and collector |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110364683A (en) * | 2019-05-31 | 2019-10-22 | 天津力神电池股份有限公司 | A kind of stripping means of electrodes of lithium-ion batteries |
| CN110416652A (en) * | 2019-07-03 | 2019-11-05 | 宁波富锂锂电池有限公司 | A method of separating and recovering PVDF from waste lithium iron phosphate positive powder acidleach tailings |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
| CN114180636A (en) * | 2021-11-05 | 2022-03-15 | 新疆师范大学 | Lithium manganese material in lithium ion battery anode waste material and stripping and recycling method thereof |
| CN114512738A (en) * | 2022-03-14 | 2022-05-17 | 中南大学 | Solvothermal pretreatment method and application of waste lithium battery cathode material |
| CN114597531A (en) * | 2022-03-14 | 2022-06-07 | 新疆师范大学 | Method for separating and recycling lithium iron phosphate anode waste material for lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109713393A (en) | A kind of isolated method of lithium battery active material | |
| CN102208707B (en) | Method for repair and regeneration of waste lithium iron phosphate battery cathode material | |
| CN100440615C (en) | A recovery method for waste lithium ion cell | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN105990617A (en) | Method for recycling and regenerating waste lithium ion battery electrode materials | |
| CN108285977A (en) | A kind of method of waste lithium ion cell anode material recovery | |
| CN101388479B (en) | Renovating method for lead-acid accumulator | |
| CN101710632A (en) | Method for recovering and restoring anode material graphite of waste lithium ion battery | |
| CN107749503A (en) | A kind of waste and old nickle cobalt lithium manganate ternary electrokinetic cell green reclaim method | |
| CN104810566A (en) | Environmentally friendly recovery and treatment method of waste and old lithium iron phosphate power cells | |
| CN109704300A (en) | A kind of method of lithium iron phosphate battery positive material recycling and reusing | |
| CN108258355A (en) | A kind of method recycled suitable for LiFePO4/nickle cobalt lithium manganate power battery | |
| CN105098281A (en) | Method for recycling multi-element anode material from waste multi-element power lithium ion battery | |
| CN107919507A (en) | The method that LiFePO4 is recycled from waste lithium cell | |
| CN109768344A (en) | A kind of separation method of the anode pole piece of waste lithium iron phosphate battery | |
| CN108172926A (en) | A kind of waste lithium ion cell anode material repair methods | |
| CN109659642B (en) | Method for separating aluminum foil and positive active material in waste lithium ion battery positive plate | |
| CN110468281A (en) | Valuable metal separation and recovery method in a kind of waste and old cobalt acid lithium battery | |
| CN107546435A (en) | A kind of physical purification method of lithium ion battery recovery positive mix | |
| CN109825846A (en) | A kind of method of molten caustic soda electrolytic regeneration waste lithium ion cell anode material | |
| CN110743528B (en) | Method for preparing water decomposition catalyst by using waste battery | |
| CN110176647B (en) | Gradient utilization method for waste lithium ion battery negative electrode material | |
| CN105355997B (en) | A kind of separation method and its application of lithium battery collector and active material | |
| CN113200541A (en) | Method for recycling graphite negative electrode of waste battery | |
| CN111180820B (en) | Method for recovering lithium ion battery original material and regenerating battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190503 |