CN110071341A - A kind of restorative procedure of retired lithium ion battery - Google Patents
A kind of restorative procedure of retired lithium ion battery Download PDFInfo
- Publication number
- CN110071341A CN110071341A CN201910282009.9A CN201910282009A CN110071341A CN 110071341 A CN110071341 A CN 110071341A CN 201910282009 A CN201910282009 A CN 201910282009A CN 110071341 A CN110071341 A CN 110071341A
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- Prior art keywords
- battery
- electrolyte
- retired
- lithium ion
- ion battery
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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
Abstract
The present invention relates to a kind of restorative procedures of retired lithium ion battery, method includes the following steps: step 1, carries out discharge treatment for retired lithium ion battery, minimally invasive punching is then carried out on battery case；Step 2 injects the electrolyte into retired battery；Step 3, sealing and polishing；Step 4, Battery formation.The present invention by way of adding electrolyte, solve the problems, such as lithium ion battery due to caused by the factors such as normal charge and discharge or high temperature electrolyte consume it is too fast.This method is not only economical and practical, strong operability, and is very suitable to the needs of automatic industrial production, can effectively extend the service life of battery, reduce the use cost of battery.
Description
Technical field
The present invention relates to chemical energy storage battery technical field, in particular to a kind of restorative procedure of retired lithium ion battery.
Background technique
Lithium ion battery due to energy density height, good cycle, self discharge is low, high temperature performance is good the advantages that, make it
It is widely used in the consumer battery of 3C, power battery and energy-storage battery.
In use, the consumption of electrolyte will will lead to active lithium-ion loss, battery impedance to lithium ion battery
Increase and the acceleration of capacity decays, and then leads to the failure of battery.On the one hand the random discarding of waste and old lithium ion battery causes big
The environmental problem (such as fluoride pollution, water pollution) of amount, on the other hand also results in a large amount of wasting of resources.Retired lithium-ion electric
Although pond capacity is lower than its rated capacity, the structure of its positive and negative pole material still keeps the crystal structure shape of fresh cells
State, main difference is that the content of active lithium.Retired lithium ion battery is reasonably repaired, can not only effectively be extended
The service life of battery reduces use cost, and can be effectively reduced environmental pressure, increases the utilization rate of resource.
The state of rapid growth is presented in the country of support energetically with to(for) electric car, the volume of production and marketing of China's electric car
Gesture, the service life of the power battery of general electric car are about 3-8, it is anticipated that in future soon, electric car
Power battery will enter the large-scale date of retirement.If retired battery not can be carried out reasonable echelon and utilize and recycle, this will
Increase huge economic pressures and environmental pressure using enterprise and battery recycling enterprise to lithium battery echelon.
Summary of the invention
It is an object of the present invention to solve lithium ion battery due to being electrolysed caused by the factors such as normal charge and discharge or high temperature
Liquid consumes too fast problem.
To achieve the above object, the present invention provides a kind of restorative procedure of retired lithium ion battery, this method include with
Lower step:
Retired lithium ion battery is carried out discharge treatment, minimally invasive punching is then carried out on battery case by step 1；
Step 2 injects the electrolyte into retired battery；
Step 3, sealing and polishing；
Step 4, Battery formation.
Preferably, described that retired lithium ion battery is subjected to discharge treatment step, comprising: by retired battery in room temperature environment
Under discharge, discharge cut-off voltage 0.1V-3.0V.
Preferably, described that minimally invasive punch out step is carried out on battery case, comprising: in inertia and the environment of drying, to adopt
It is punched at the top of battery or side close to the position at top with mechanical or laser method.
Preferably, the electrolyte is mainly made of solvent, electrolyte and additive.
Preferably, the solvent of the electrolyte be ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid two ester,
One or more of methyl ethyl carbonate, dimethyl ether, tetrahydrofuran, methyl acetic acid ester, methylpropionate.
Preferably, the electrolyte of the electrolyte is LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiN
(C2F5SO2)2、LiC(CF3SO2)3、LiN(CF3SO2)2、LiPF3(C2F5)3、 Li(C4F9SO2)(CF3SO2)N、LiBOB
One or more of, and the concentration of electrolyte in the electrolytic solution is 0.1mol/L-1.5mol/L.
Preferably, the additive of the electrolyte be CO2, SO2, Li2CO3, vinylene carbonate, ethylene sulfite,
Methylchloroformate, o-dimethoxybenzene, paradimethoxybenzene, biphenyl, cyclohexyl benzene, trimethyl phosphate, phosphorus nitrence, CH2F-EC,
One of CHF2-EC/CF3-EC and halogenated alkyl phosphate or a variety of, and the content of additive is 0.01%- in electrolyte
10%.
Preferably, the sealing and polishing step seal liquid injection port including the method using laser or machinery.
Preferably, the Battery formation step, including with electric current constant-current charge 10-600 minutes of 0.01C-1.0C；So
Afterwards with the electric current constant-current constant-voltage charging of 0.05C-0.5C, blanking voltage is subject to the specifications of battery, the cut-off electricity of constant-voltage charge
Stream is 0.01C-0.1C, and wherein the environment temperature of Battery formation is 10 DEG C -50 DEG C.
Preferably, the electrolyte is liquid or gel state electrolyte, including liquid organic electrolyte, liquid inorganic electrolyte
Matter, gel-type polymer electrolyte.
The present invention effectively extends the service life of battery and increases the use of battery by the reasonable reparation to retired battery
Performance effectively increases the value that lithium battery echelon utilizes, and can not only alleviate the pressure of battery recycling enterprise, and can increase
Echelon can also share electricity for the user terminal of electric car using the economic benefit of enterprise to a certain extent
Electrical automobile changes battery cost and use cost.Therefore this method is for national new-energy automobile industry, accumulation power supply industry, lithium electricity
The development of pond industry will play positive facilitation.
Detailed description of the invention
Fig. 1 is a kind of restorative procedure flow diagram of retired lithium ion battery provided in an embodiment of the present invention.
Fig. 2 is the capacitance-voltage schematic diagram data that battery repairs front and back in embodiment one；
Fig. 3 is battery and the cycle performance contrast test schematic diagram data for not repairing battery after repairing in embodiment one；
Fig. 4 is the capacitance-voltage schematic diagram data that battery repairs front and back in embodiment two；
Fig. 5 is battery and the cycle performance contrast test schematic diagram data for not repairing battery after repairing in embodiment two；
Fig. 6 is the capacitance-voltage schematic diagram data that battery repairs front and back in embodiment three；
Fig. 7 is battery and the cycle performance contrast test schematic diagram data for not repairing battery after repairing in embodiment three.
Specific embodiment
After embodiments of the present invention are described in detail by way of example below in conjunction with attached drawing, of the invention its
His features, characteristics, and advantages will be more obvious.
Fig. 1 is a kind of restorative procedure flow diagram of retired lithium ion battery provided in an embodiment of the present invention.Such as Fig. 1 institute
Show, method includes the following steps:
Retired lithium ion battery is carried out discharge treatment, minimally invasive punching is then carried out on battery case by step 1；
Specifically, by retired lithium ion battery carry out discharge treatment step, comprising: by retired battery under room temperature environment into
Row electric discharge, discharge cut-off voltage 0.1V-3.0V.
The positive electrode of lithium ion battery can be LiFePO4 and its modified material, LiNixMyCozO2 and its modified material
Material (wherein 0≤x≤1,0≤y≤1,0≤z≤1, M are Mn or Al), one of LiMn2O4 and its modified material；Lithium from
The negative electrode material of sub- battery can be graphite and its modified material, lithium titanate and its modified material, silicon based anode material and its change
Property material, soft carbon and its modified material, one of hard carbon and its modified material or a variety of.
Minimally invasive punch out step is carried out on battery case, comprising: in inertia and the environment of drying, using mechanical or laser
Method battery top or side close to top position punch.
Step 2 injects the electrolyte into retired battery；
Specifically, electrolyte can be liquid or gel state electrolyte, including liquid organic electrolyte, liquid inorganic electrolyte
Matter, gel-type polymer electrolyte.
Electrolyte is mainly made of solvent, electrolyte and additive.The solvent of electrolyte is ethylene carbonate, propylene carbonate
Ester, dimethyl carbonate, carbonic acid two ester, methyl ethyl carbonate, dimethyl ether, tetrahydrofuran, methyl acetic acid ester, in methylpropionate
It is one or more of.
The electrolyte of electrolyte is LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiN (C2F5SO2) 2, LiC
(CF3SO2) 3, one or more of LiN (CF3SO2) 2, LiPF3 (C2F5) 3, Li (C4F9SO2) (CF3SO2) N, LiBOB,
And the concentration of electrolyte in the electrolytic solution is 0.1mol/L-1.5mol/L.
The additive of electrolyte be CO2, SO2, Li2CO3, vinylene carbonate, ethylene sulfite, methylchloroformate,
O-dimethoxybenzene, paradimethoxybenzene, biphenyl, cyclohexyl benzene, trimethyl phosphate, phosphorus nitrence, CH2F-EC, CHF2-EC/
One of CF3-EC and halogenated alkyl phosphate or a variety of, and the content of additive is 0.01%-10% in electrolyte.
Step 3, sealing and polishing；
Specifically, step of sealing and polish seals liquid injection port including the method using laser or machinery.
Step 4, Battery formation.
Specifically, Battery formation step, including with electric current constant-current charge 10-600 minutes of 0.01C-1.0C；Then with
The electric current constant-current constant-voltage charging of 0.05C-0.5C, blanking voltage are subject to the specifications of battery, and the cut-off current of constant-voltage charge is
0.01C-0.1C, wherein the environment temperature of Battery formation is 10 DEG C -50 DEG C.
The embodiment of the present invention can solve lithium ion battery due to normal charge and discharge or height by way of adding electrolyte
Electrolyte consumes too fast problem caused by the factors such as temperature.
It is illustrated below by way of several specific embodiments:
Embodiment one:
Restorative procedure of the embodiment for retired rectangular aluminum hull ferric phosphate lithium cell, the model 2770180 of battery,
Nominal capacity 25Ah, retired battery capacity 18.5Ah or so, wherein positive electrode is LiFePO4, and negative electrode material is artificial stone
Ink.
Battery discharge: battery is discharged under room temperature environment, discharge cut-off voltage 2.0V.
Perforating batteries: it under the atmosphere of inert gas shielding, is punched in the place of cell top end, aperture 4mm；
It injects electrolyte: under inert ambient environment, injecting 65g electrolyte, solute is 1mol L-1's in electrolyte
LiPF6, solvent are EC:PC:DEC (3:3:4), and the VC of the FEC and 1wt% of 1.5wt% is contained in electrolyte as additive；
Sealing and polishing: with the mode of laser welding, the aluminum plate of 8mm*8mm*2mm is welded on to the ground of liquid injection port
Side, is then mechanical grinding to the smooth of the edge, which is also to complete under inert ambient environment；
Battery formation:
Testing environment is 35 DEG C, is stood first for 24 hours；
0.1C constant-current charge 300min, is then allowed to stand 30min；
For 0.2C constant-current constant-voltage charging to 3.6V, constant-voltage charge cut-off current is 0.02C, stands 30min；
0.2C constant-current discharge stands 30min to 2.0V；
Circulation 3 times.
Battery and the cycle performance pair for not repairing battery after battery is repaired the capacitance-voltage data (Fig. 2) of front and back and repaired
Than test data (Fig. 3).
Embodiment two:
The embodiment is directed to the restorative procedure of retired Soft Roll type ternary lithium ion battery, the model of battery
13175275, nominal capacity 38Ah, retired battery capacity 28Ah or so, wherein positive electrode is
LiNi0.33Co0.33Mn0.33O2, negative electrode material are natural graphite.
Battery discharge: battery is discharged under room temperature environment, discharge cut-off voltage 2.5V.
Perforating batteries: it under the atmosphere of inert gas shielding, is carried out in battery right end close to the place of battery 3mm
Punching, aperture 3mm；
It injects electrolyte: under inert ambient environment, injecting 60g electrolyte, solute is 1mol L-1's in electrolyte
LiPF6, solvent are EC:PC:DMC (3:3:4), contain the VC of 1.5wt% as additive in electrolyte；
Sealing: the aluminum plastic film of 5mm*5mm*0.1mm is sealed into liquid injection port with sealing machine, which is also in inert atmosphere ring
It is completed under border；
Battery formation:
Testing environment is 35 DEG C, is stood first for 24 hours；
0.1C constant-current charge 300min, is then allowed to stand 30min；
For 0.2C constant-current constant-voltage charging to 4.1V, constant-voltage charge cut-off current is 0.02C, stands 30min；
0.2C constant-current discharge stands 30min to 2.5V；
Circulation 3 times.
Battery and the cycle performance pair for not repairing battery after battery is repaired the capacitance-voltage data (Fig. 4) of front and back and repaired
Than test data (Fig. 5).
Embodiment three:
Restorative procedure of the embodiment for retired cylindrical lithium titanate battery, the model 40900 of battery, nominally
Capacity 5.5Ah, retired battery capacity 4.0Ah or so, wherein positive electrode is LiNi0.33Co0.33Mn0.33O2, cathode material
Material is Li4Ti5O12.
Battery discharge: battery is discharged under room temperature environment, discharge cut-off voltage 1.2V.
Perforating batteries: it under the atmosphere of inert gas shielding, is punched in cell top end close to the place of slot rolling, aperture
3mm；
It injects electrolyte: under inert ambient environment, injecting 9.5g electrolyte, solute is 1mol L-1's in electrolyte
LiPF6, solvent are PC:EMC (5:5), contain the LiBOB of 1.7wt% as additive in electrolyte；
Sealing and polishing: liquid injection port is sealed with seccotine, is then mechanical grinding to the smooth of the edge, which is also lazy
It is completed under property atmosphere；
Battery formation:
Testing environment is 35 DEG C, is stood first for 24 hours；
0.1C constant-current charge 300min, is then allowed to stand 30min；
For 0.2C constant-current constant-voltage charging to 2.65V, constant-voltage charge cut-off current is 0.02C, stands 30min；
0.2C constant-current discharge stands 30min to 1.2V；
Circulation 3 times.
Battery and the cycle performance pair for not repairing battery after battery is repaired the capacitance-voltage data (Fig. 6) of front and back and repaired
Than test data (Fig. 7).
It should be noted that above-described embodiment is only used to illustrate structure and its working effect of the invention, and it is not used as
It limits the scope of the invention.One of ordinary skilled in the art is right without prejudice to thinking of the present invention and structure
The adjustment or optimization that above-described embodiment carries out, should regard as the claims in the present invention and be covered.
Claims (10)
1. a kind of restorative procedure of retired lithium ion battery, which comprises the following steps:
Retired lithium ion battery is carried out discharge treatment, minimally invasive punching is then carried out on battery case by step 1；
Step 2 injects the electrolyte into retired battery；
Step 3, sealing and polishing；
Step 4, Battery formation.
2. the method according to claim 1, wherein described carry out discharge treatment step for retired lithium ion battery
Suddenly, comprising: retired battery is discharged under room temperature environment, discharge cut-off voltage 0.1V-3.0V.
3. the method according to claim 1, wherein described carry out minimally invasive punch out step, packet on battery case
Include: in inertia and the environment of drying, using mechanical or laser method battery top or side close to top position
Punching.
4. the method according to claim 1, wherein the electrolyte is mainly by solvent, electrolyte and additive
Composition.
5. according to the method described in claim 4, it is characterized by: the solvent of the electrolyte is ethylene carbonate, carbonic acid third
Enester, dimethyl carbonate, carbonic acid two ester, methyl ethyl carbonate, dimethyl ether, tetrahydrofuran, methyl acetic acid ester, in methylpropionate
One or more.
6. according to the method described in claim 4, it is characterized by: the electrolyte of the electrolyte be LiPF6, LiBF4,
LiClO4、LiAsF6、LiCF3SO3、LiN(C2F5SO2)2、LiC(CF3SO2)3、LiN(CF3SO2)2、LiPF3(C2F5)3、
One or more of Li (C4F9SO2) (CF3SO2) N, LiBOB, and the concentration of electrolyte in the electrolytic solution is 0.1mol/L-
1.5mol/L。
7. according to the method described in claim 4, it is characterized by: the additive of the electrolyte be CO2, SO2, Li2CO3,
Vinylene carbonate, ethylene sulfite, methylchloroformate, o-dimethoxybenzene, paradimethoxybenzene, biphenyl, cyclohexyl benzene,
Trimethyl phosphate, one of phosphorus nitrence, CH2F-EC, CHF2-EC/CF3-EC and halogenated alkyl phosphate or a variety of, and be electrolysed
The content of additive is 0.01%-10% in liquid.
8. according to the method described in claim 1, it is characterized by: it is described sealing and polishing step, including use laser or machine
The method of tool, liquid injection port is sealed.
9. according to the method described in claim 1, it is characterized by: the Battery formation step, including with 0.01C-1.0C's
Electric current constant-current charge 10-600 minutes；Then with the electric current constant-current constant-voltage charging of 0.05C-0.5C, blanking voltage is with the rule of battery
Subject to lattice book, the cut-off current of constant-voltage charge is 0.01C-0.1C, and wherein the environment temperature of Battery formation is 10 DEG C -50 DEG C.
10. according to the method described in claim 1, it is characterized by: the electrolyte be liquid or gel state electrolyte, including
Liquid organic electrolyte, liquid inorganic electrolyte, gel-type polymer electrolyte.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910282009.9A CN110071341A (en) | 2019-04-09 | 2019-04-09 | A kind of restorative procedure of retired lithium ion battery |
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| CN201910282009.9A CN110071341A (en) | 2019-04-09 | 2019-04-09 | A kind of restorative procedure of retired lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021093128A1 (en) * | 2019-11-14 | 2021-05-20 | 深圳市普兰德储能技术有限公司 | Liquid injection device and liquid injection method |
| CN113097581A (en) * | 2021-03-26 | 2021-07-09 | 中国人民解放军陆军装甲兵学院 | Laser remanufacturing method for power lithium battery of heavy-load equipment |
| CN115084679A (en) * | 2022-06-16 | 2022-09-20 | 合肥学院 | Method for recovering capacity of retired lithium ion battery |
| WO2022262351A1 (en) * | 2021-06-15 | 2022-12-22 | 宁德时代新能源科技股份有限公司 | Cleaning apparatus, battery cell, electrical device and battery cell processing method |
| CN115084679B (en) * | 2022-06-16 | 2024-05-03 | 合肥学院 | Method for recovering capacity of retired lithium ion battery |
-
2019
- 2019-04-09 CN CN201910282009.9A patent/CN110071341A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021093128A1 (en) * | 2019-11-14 | 2021-05-20 | 深圳市普兰德储能技术有限公司 | Liquid injection device and liquid injection method |
| CN113097581A (en) * | 2021-03-26 | 2021-07-09 | 中国人民解放军陆军装甲兵学院 | Laser remanufacturing method for power lithium battery of heavy-load equipment |
| WO2022262351A1 (en) * | 2021-06-15 | 2022-12-22 | 宁德时代新能源科技股份有限公司 | Cleaning apparatus, battery cell, electrical device and battery cell processing method |
| CN115084679A (en) * | 2022-06-16 | 2022-09-20 | 合肥学院 | Method for recovering capacity of retired lithium ion battery |
| CN115084679B (en) * | 2022-06-16 | 2024-05-03 | 合肥学院 | Method for recovering capacity of retired lithium ion battery |
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