WO2021082341A1 - Procédé de regroupement et de réparation rapide de batteries recyclées - Google Patents
Procédé de regroupement et de réparation rapide de batteries recyclées Download PDFInfo
- Publication number
- WO2021082341A1 WO2021082341A1 PCT/CN2020/080177 CN2020080177W WO2021082341A1 WO 2021082341 A1 WO2021082341 A1 WO 2021082341A1 CN 2020080177 W CN2020080177 W CN 2020080177W WO 2021082341 A1 WO2021082341 A1 WO 2021082341A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery
- voltage
- decommissioned
- batteries
- retired
- Prior art date
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Classifications
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4207—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells for several batteries or cells simultaneously or sequentially
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
- B07C5/00—Sorting according to a characteristic or feature of the articles or material being sorted, e.g. by control effected by devices which detect or measure such characteristic or feature; Sorting by manually actuated devices, e.g. switches
- B07C5/34—Sorting according to other particular properties
- B07C5/344—Sorting according to other particular properties according to electric or electromagnetic properties
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/441—Methods for charging or discharging for several batteries or cells simultaneously or sequentially
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
Definitions
- This application relates to the technical field of lithium ion battery repair, and in particular to a method for rapid grouping and repair of retired batteries.
- Electric vehicles have been popularized for several years, and a large number of lithium-ion batteries with insufficient capacity and performance degradation caused by long-term use have been produced.
- the loss of battery capacity is mainly caused by the increase in impedance caused by the loss of lithium ions and the side reaction caused by the consumption of electrolyte.
- the lost lithium ions mainly include lithium consumed by the formation of SEI film in the battery formation process, lithium consumed by side reactions in the electrolyte, lithium dendrites generated by lithium in the negative electrode, and lithium ion reception caused by changes in the structure of the active material. Loss of lithium caused by missing vacancies. The irreversible capacity loss caused by these lithium losses is irreparable.
- the electrolyte is the medium through which lithium ions are conducted between the positive and negative electrodes. During the charging and discharging process, the electrolyte will react with the pole pieces, and the electrolyte will be lost, and the resulting concentration polarization resistance and charge transfer resistance are paired The capacity decay of the battery has an impact, and the capacity of the lithium battery can be repaired by replenishing the electrolyte.
- the actual capacity parameters of the decommissioned batteries are first fully charged to obtain the actual capacity parameters of the decommissioned batteries. According to the actual capacity, the repairable decommissioned batteries are selected, and then the repairable decommissioned batteries are classified into different files, and the decommissioned batteries of each file are charged. Into the corresponding weight of electrolyte. This method needs to fully charge all retired batteries, and charging and discharging all retired batteries consumes a lot of power.
- the object of the present invention is to provide a fast grouping and repairing method for retired batteries, which can save power consumption and reduce production costs.
- a fast grouping method for retired batteries includes the following steps:
- the decommissioned battery discharged to the cut-off voltage is allowed to stand for a first set period of time at room temperature, and the voltage of the decommissioned battery at this time is measured and recorded as the first voltage;
- a first judgment condition is set according to the first voltage
- a second judgment condition is set according to the second voltage
- a third judgment condition is set according to the third voltage
- a third judgment condition is set according to the first judgment condition, the second judgment condition, and the first judgment condition.
- the retired batteries that are simultaneously selected into the first preselected group, the second preselected group, and the third preselected group are divided into one group.
- a method for repairing decommissioned batteries includes the following steps:
- the decommissioned battery discharged to the cut-off voltage is allowed to stand for a first set period of time at room temperature, and the voltage of the decommissioned battery at this time is measured and recorded as the first voltage;
- a first judgment condition is set according to the first voltage
- a second judgment condition is set according to the second voltage
- a third judgment condition is set according to the third voltage
- a third judgment condition is set according to the first judgment condition, the second judgment condition, and the first judgment condition.
- each decommissioned battery in the repairable decommissioned battery pack is injected with the same weight of the electrolyte; as well as
- the decommissioned battery injected with the electrolyte is charged and discharged for activation.
- the three key voltage values that can characterize the battery performance are first obtained by not charging the battery to full charge. By setting the judgment condition, the rapid grouping of all retired batteries is realized. The electrical performance of the same group of retired batteries is similar, shortening Test time, save energy consumption.
- one or more batteries in each group of retired batteries are selected to be fully charged and fully discharged, and their actual capacity is measured.
- the actual capacity can represent the capacity level of the same group of retired batteries.
- the measured actual capacity selects repairable decommissioned battery packs, and then according to the measured actual capacity, the corresponding weight of electrolyte is injected into each group of repairable decommissioned batteries to restore the decommissioned batteries to the level of in-service power batteries. Since only one or more batteries in each group are fully charged and discharged, the number of fully charged batteries is greatly reduced. Therefore, energy consumption is greatly reduced and production costs are saved.
- the present invention re-sorts and allocates the retired batteries after repair from the aspects of battery capacity and battery charge transfer impedance.
- the consistency ratio is sorted by capacity and internal resistance. Better, it improves the recycling performance of the battery pack.
- the fast grouping and repairing method of the present invention is more suitable for batch repairs and automated operations to improve production efficiency.
- Figure 1 shows the relationship between the voltage and the capacity of a lithium battery during normal charging and discharging.
- Fig. 2 is a comparison diagram of discharge curves of a LiFePO4/graphite decommissioned battery with a nominal capacity of 150Ah before and after refilling electrolyte and activation in an embodiment of the present invention.
- FIG. 3 is a comparison diagram of normal temperature cycling performance of two battery packs obtained by using different grouping methods in an embodiment of the present invention.
- the invention aims at repairing the battery whose capacity is attenuated due to electrolyte loss, so that it can reach the level of in-service power battery, and is re-sorted and paired to continue to be used on power battery vehicles and recycled.
- the battery is usually fully charged and left at room temperature for 5 days or more before testing the voltage to obtain the voltage drop and actual capacity data, and then discharge to a constant current.
- the cut-off voltage is used to obtain the actual capacity of the battery.
- This sorting method takes a long time, and at the same time, full charge also consumes a lot of power resources.
- the four parameters reflecting battery consistency, internal resistance, voltage, capacity, and self-discharge rate, are the key control points for battery sorting. As shown in Figure 1, it is a charge-discharge curve diagram of a lithium battery, where the ordinate is the voltage, and the abscissa is the cumulative capacity of the charge and discharge.
- the cumulative value of the charged or discharged capacity over time during charging or discharging If the abscissa is changed to time, it can be understood as the change in cell voltage over time during charging or discharging. It can be seen that in a single charging process or discharging process, the voltage and the capacity value have a one-to-one correspondence, which is also the fundamental basis for this patent to use voltage to characterize the capacity.
- the method for rapid sorting of lithium batteries in this embodiment is aimed at retired batteries of the same model and batch produced by the same manufacturer.
- the specific voltage conditions are associated with other performance parameters of the battery.
- the correlation of performance parameters is not the same.
- different types of batteries have different shapes, so different types and batchs of retired batteries are not reorganized.
- the present invention provides a fast grouping method for retired batteries, which does not fully discharge the batteries, shortens the sorting time, improves the sorting efficiency, and saves power at the same time, including the following steps:
- the first voltage can reflect the polarization internal resistance of the battery.
- the first set time period is the time for the battery voltage to be fully balanced, and batteries of different materials have different time for fully balancing.
- the rated capacity can be in the range of 20% to 35% of the nominal capacity.
- the third voltage can reflect the self-discharge and AC internal resistance of the battery.
- the second set time period is the time for the battery voltage to be fully balanced, and batteries of different materials have different time for fully balancing.
- the first voltage difference, the second voltage difference, and the third voltage difference of each retired battery relative to the first retired battery are counted.
- the first threshold is the voltage difference threshold of the first voltage
- the second threshold is the voltage difference threshold of the second voltage
- the third threshold is the voltage difference threshold of the third voltage. Assume that the first threshold ⁇ 50 mV, the second threshold ⁇ 50 mV, and the third threshold ⁇ 30 mV.
- the retired batteries are sorted and counted to form a first preselected group, and batteries 1 to 6 are the first preselected group.
- the retired batteries are sorted and counted to form a second preselected group, and batteries 1 to 6 are the second preselected group.
- the retired batteries are sorted and counted to form a third preselected group, and batteries 1 to 8 are the third preselected group.
- the 7 ⁇ 11 batteries are the second group, and so on, all batteries can be divided into several battery packs , The electrical performance of the batteries in each battery pack is similar.
- Retired batteries are sorted according to the first threshold, second threshold, and third threshold, which realizes the purpose of screening and reorganizing retired batteries according to the four key control points of internal resistance, voltage, capacity, and self-discharge.
- the actual capacity of the selected decommissioned battery may represent the actual capacity of the group of decommissioned batteries.
- 2 to 5 decommissioned batteries are selected from each decommissioned battery group.
- a retired battery whose actual capacity is 60%-80% of the nominal capacity is selected for repair, and the actual capacity of the selected retired battery is 60%. % ⁇ 80% of the nominal capacity, the decommissioned battery pack where the selected decommissioned battery is located is a repairable decommissioned battery pack.
- the nominal capacity is 150Ah
- the selected decommissioned battery whose actual capacity is in the range of 90Ah-120Ah is a repairable decommissioned battery.
- the above-mentioned actual capacity detection method is: according to a certain constant current value of the decommissioned battery, specifically, the constant current value can be 0.2C of the nominal capacity, charge and discharge cycle 1 time, record its discharge capacity , Is the actual capacity.
- each decommissioned battery in each repairable decommissioned battery pack to its cut-off voltage to fully discharge.
- the internal environment of the battery including electrolyte, positive and negative plates, separators, etc., is isolated from the external environment.
- the negative lithium material is very active and easily reacts with water and oxygen in the air to release heat , The heat can make the electrolyte at high temperature, and the high temperature will cause other negative chain reactions, or even thermal runaway. Therefore, the battery needs to be fully discharged to ensure the safety of the battery.
- the cut-off voltage refers to a very low voltage range. Different batteries have different cut-off voltage values in the standard.
- the electrolyte is injected under a vacuum condition to prevent air from reacting with the electrolyte and prevent air from affecting the electrolyte.
- the specific method of injecting electrolyte into the decommissioned battery is as follows: remove the upper cover of the decommissioned battery, cut off part of the protective rubber on the battery cover to form a rubber hole in an environment where the dew point temperature is less than or equal to -35°C, and use a drill Align the rubber hole and drill through the battery cover, and then use the liquid injection nozzle to align the rubber hole to start vacuuming. After the vacuum is completed, start to inject the electrolyte.
- the electrolyte is injected in multiple times, each time the electrolyte is injected Before vacuuming.
- the vacuum degree of the vacuum condition is less than or equal to -0.085 MPa.
- 75 g of electrolyte is injected into each decommissioned battery in a group of decommissioned battery packs.
- the electrolyte is injected in 3 times, first vacuumize to -0.085MPa, inject 1/3 of the electrolyte to be injected, or 25g; then vacuum to -0.085MPa, inject 1/3 of the electrolyte to be injected, or 25g; and finally Then vacuumize to -0.085MPa, and inject 1/3 of the electrolyte to be injected, that is, 25g.
- the method of charging and discharging activation is as follows: let the retired battery injected with electrolyte stand still, make the electrolyte fully infiltrate the inside of the battery, charge to the upper limit of battery voltage with a first constant current, and then discharge to the battery cut-off voltage with a second constant current. Since the battery has been fully discharged before the electrolyte is injected, the charging current should be as small as possible in order to better repair the SEI film during charging.
- the first constant current is 0.01 C ⁇ 0.1 C of the nominal capacity of the decommissioned battery .
- the second constant current is 0.5 C ⁇ 1 C of the nominal capacity of the decommissioned battery. Since the electrolyte inside the battery flows faster at high temperatures, it is easy to place the battery in a high temperature environment to allow the injected electrolyte to quickly infiltrate the inside of the battery. However, if the temperature is too high, the internal reaction of the battery will increase. , For example, the SEI film is easy to decompose at high temperature. Therefore, to balance the above two aspects, preferably, the decommissioned battery injected with electrolyte is allowed to stand for 1 to 5 days at 35°C to 50°C. In this embodiment, after each decommissioned battery is injected with electrolyte and placed at 45 degrees for 3 days, the nominal capacity of 0.05C is charged to 3.45V, and the nominal capacity of 0.5C is discharged to 2V for activation.
- Fig. 2 the discharge curve comparison chart before and after refilling electrolyte repair and activation is shown in Fig. 2.
- Curve B in Fig. 2 is the discharge curve of the retired battery after the repair of the present invention
- Curve A is the discharge curve of the decommissioned battery before repair. It can be seen from Fig. 2 that the capacity of the decommissioned LiFePO4/graphite single cell after being repaired by the method of the present invention is significantly improved compared to before being repaired.
- step (6) Group the decommissioned batteries after activation in step (6) to form a battery pack to further optimize the performance of the battery pack, which specifically includes the following steps:
- the nominal capacity of 1C constant current charging and constant current discharge to the upper and lower limit voltages are used to record the discharge capacity and DC internal resistance of each decommissioned battery; the electrochemical workstation tests the AC internal resistance and frequency of each decommissioned battery
- the range is 1000HZ-0.01HZ, and the charge transfer impedance is calculated using ZView2 simulation software.
- the discharge capacity is divided into different bins with the set capacity difference as an interval, and the activated decommissioned battery is binned according to the bins where the discharge capacity is located.
- the capacity difference is 0 ⁇ 5% of the nominal capacity of the decommissioned battery.
- the above-mentioned 20 batteries are classified according to a capacity difference of 10 Ah, and No. 1-4, No. 5-15, and No. 16-20 are respectively of the same grade.
- Retired batteries in the same file are grouped according to charge transfer impedance.
- the charge transfer impedance of the decommissioned battery is divided into different grouping intervals with the set charge transfer impedance difference as an interval, and the activated decommissioned batteries are grouped according to the grouping interval in which the charge transfer impedance of the decommissioned battery is located.
- the charge transfer impedance difference is 10%-15% of the average value of the charge transfer impedance of the decommissioned batteries after activation in the same gear.
- the charge transfer resistance of No. 12, 14, and No. 15 batteries is between 0.35 and 0.4, divided into a group, and the charge transfer resistance of No. 5 and No. 11 batteries is between 0.35 and 0.4, which are left.
- the No. 1 battery is left, and in the bins of No. 16 to 20, the No. 16 battery is left.
- the grouping method of other batteries is the same as the above method.
- the retired batteries divided into the same group form a battery pack.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
Abstract
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2020203011A AU2020203011B2 (en) | 2019-10-29 | 2020-03-19 | Method for quickly grouping and repairing decommissioned batteries |
GB2019104.5A GB2599453A (en) | 2019-10-29 | 2020-03-19 | Rapid grouping and repairing method for recycled batteries |
SG11202003909PA SG11202003909PA (en) | 2019-10-29 | 2020-03-19 | Method for Quickly Grouping and Repairing Decommissioned Batteries |
DE112020005205.2T DE112020005205T5 (de) | 2019-10-29 | 2020-03-19 | Verfahren zur schnellen Gruppierung und Reparatur von ausgedienten Batterien |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911038002.9A CN110797591B (zh) | 2019-10-29 | 2019-10-29 | 一种锂动力梯次电芯重组的快速分选方法以及锂动力梯次重组电池 |
CN201911038002.9 | 2019-10-29 |
Publications (1)
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WO2021082341A1 true WO2021082341A1 (fr) | 2021-05-06 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/CN2020/080177 WO2021082341A1 (fr) | 2019-10-29 | 2020-03-19 | Procédé de regroupement et de réparation rapide de batteries recyclées |
Country Status (7)
Country | Link |
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JP (1) | JP7076495B2 (fr) |
CN (1) | CN110797591B (fr) |
AU (1) | AU2020203011B2 (fr) |
DE (1) | DE112020005205T5 (fr) |
GB (1) | GB2599453A (fr) |
SG (1) | SG11202003909PA (fr) |
WO (1) | WO2021082341A1 (fr) |
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CN110797591B (zh) * | 2019-10-29 | 2021-07-16 | 深圳市普兰德储能技术有限公司 | 一种锂动力梯次电芯重组的快速分选方法以及锂动力梯次重组电池 |
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JP2021072275A (ja) | 2021-05-06 |
DE112020005205T5 (de) | 2022-07-28 |
CN110797591A (zh) | 2020-02-14 |
GB2599453A (en) | 2022-04-06 |
AU2020203011A1 (en) | 2021-05-13 |
JP7076495B2 (ja) | 2022-05-27 |
CN110797591B (zh) | 2021-07-16 |
GB202019104D0 (en) | 2021-01-20 |
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