CN110568363A - Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change - Google Patents

Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change Download PDF

Info

Publication number
CN110568363A
CN110568363A CN201910688305.9A CN201910688305A CN110568363A CN 110568363 A CN110568363 A CN 110568363A CN 201910688305 A CN201910688305 A CN 201910688305A CN 110568363 A CN110568363 A CN 110568363A
Authority
CN
China
Prior art keywords
battery
sei
impedance
lithium
sei film
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
Application number
CN201910688305.9A
Other languages
Chinese (zh)
Inventor
赵光金
王放放
董锐锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
Original Assignee
State Grid Corp of China SGCC
Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by State Grid Corp of China SGCC, Electric Power Research Institute of State Grid Henan Electric Power Co Ltd filed Critical State Grid Corp of China SGCC
Priority to CN201910688305.9A priority Critical patent/CN110568363A/en
Publication of CN110568363A publication Critical patent/CN110568363A/en
Pending legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/378—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC] specially adapted for the type of battery or accumulator
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/385—Arrangements for measuring battery or accumulator variables
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/389—Measuring internal impedance, internal conductance or related variables
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/392—Determining battery ageing or deterioration, e.g. state of health

Abstract

The application relates to a method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change, which mainly comprises the following steps: establishing an electrochemical impedance equivalent circuit and an impedance spectrum model of the lithium battery, respectively testing and analyzing the relationship between the SEI film impedance and the cycle number of the battery under different conditions, and predicting the generation of lithium dendrites in the retired battery through the abnormal change of the SEI impedance. The invention relates to a method for prejudging lithium dendrite generation of an retired battery based on SEI (solid electrolyte interphase) membrane impedance change, which is characterized in that the electrochemical impedance equivalent circuit of the lithium ion battery comprising SEI membrane impedance RSEI is established, and a relation curve between the electrochemical impedance equivalent circuit and the battery cycle performance is established, so that the inflection point characteristic that the SEI membrane impedance is reduced firstly and then increased is adopted, the rapid prejudging of the lithium dendrite generation of the retired battery is realized, and the method has the characteristics of simplicity, high efficiency, accurate judgment result and the like.

Description

Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to a method for prejudging lithium dendrite generation of an out-of-service battery based on SEI (solid electrolyte interphase) film impedance change.
Background
The charge and discharge process of the battery is a complicated electrochemical process, the factors causing the capacity fade of the battery are not unique, and deterioration in one aspect may cause other factors to affect the capacity, cycle performance, energy density, etc. of the battery together.
Starting from the materials, the positive and negative electrode materials have volume effect in the process of releasing and inserting lithium, and the charge and discharge processes of some positive electrode materials are accompanied with phase transfer changes, which can cause material structure rupture and lithium ion releasing and inserting obstruction in long-term circulation. Most of the currently widely used anode materials are transition metal oxides, and the long-time soaking of the materials in electrolyte can cause the dissolution of metal ions, and the dissolution is also aggravated in the electrochemical process. Dissolution not only reduces the amount of active positive electrode material, but also causes changes in the positive electrode structure.
More seriously, metal ions dissolved in the electrolyte can be deposited on the surface of the negative electrode in the form of salt or reduced into metal on the surface of the negative electrode after being transferred to the surface of the negative electrode, and the stability of the SEI film is influenced. The damage of the membrane, the contact point of the electrode and the electrolyte can continuously react to form a membrane, and the repeated actions not only consume the limited lithium ions in the system and decompose the electrolyte, but also cause the increase of the impedance of the negative electrode and the increase of the internal resistance of the battery, thereby seriously affecting the performance of the battery.
The internal resistance of the lithium battery mainly comprises the three parts, and in a broad sense, like ohmic resistance (IR), the activation polarization and the concentration polarization can be understood as the composition factors of the internal resistance of the battery, or the activation impedance and the concentration impedance. The magnitude of the activation polarization and concentration polarization needs to be calculated by establishing a complex mathematical model.
Generally, the electrochemical impedance of the cell can be plotted as an equivalent circuit diagram, having primarily an ohmic impedance RbDouble electric layer capacitance CdResistance to electrochemical reaction RctAnd diffusion resistance RwAnd (4) forming. Generally, R is the amount of lithium ions that are absorbed during the intercalation and deintercalation cycle of the lithium ionbThe value change is generally not large, while CdAnd RctThe change in (c) is more pronounced.
The internal resistance of the lithium ion battery is increased due to the thickening of an SEI film, the change of an electrode structure and the like when the lithium ion battery works for a long time or works under an abuse condition. If lithium precipitation occurs in the negative electrode, when the dendritic growth of lithium is more, the SEI film can be damaged, and the resistance of the SEI film is suddenly reduced. Therefore, through detecting the internal resistance of the battery, parameters with guiding significance can be provided for accelerating the attenuation performance of the power battery and evaluating sudden change.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for predicting the lithium dendrite generation of the retired battery based on the SEI film impedance change is provided for solving the defect that the lithium dendrite generation of the retired battery cannot be rapidly predicted in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
A method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change comprises the following steps:
S1: taking a retired battery, and respectively testing and analyzing the cycle number of the battery and the SEI film impedance R of the retired battery under different conditionsSEIThe relationship of (1);
S2: using the cycle number of the battery as an X axis and the SEI film resistance RSEIThe Y axis represents the cycle number of the battery and the SEI film resistance R under different conditionsSEIEstablishing a relation curve, wherein the resistance R of the SEI filmSEIThe increasing trend is interrupted and a curve segment occurs which decreases and then increases, the corresponding minimum value of said curve segment being the R for the production of lithium dendritesSEIAnd the battery cycle number corresponding to the minimum value corresponding to the curve segment is the battery cycle life of the lithium dendrite.
Preferably, in the method for predicting lithium dendrite generation of the retired battery based on SEI film impedance change of the present invention, the analysis conditions in step S1 include different overcharge conditions, different lithium-rich conditions, and different high-rate charge and discharge.
preferably, according to the method for predicting lithium dendrite generation of the retired battery based on SEI film impedance change, the overcharge condition means that the charging voltage value is not lower than 110% of the charging cut-off voltage of the retired battery.
Preferably, according to the method for predicting lithium dendrite generation of the retired battery based on SEI film impedance change, the lithium-rich condition means that the ratio of the equivalent mass ratio of the positive and negative electrode materials is not lower than 1.2.
Preferably, according to the method for prejudging lithium dendrite generation of the retired battery based on SEI film impedance change, the high-rate charge and discharge refers to charge and discharge under the rate of not less than 1C.
Preferably, the method for prejudging lithium dendrite generation of the retired battery based on SEI film impedance change, provided by the invention, is used for judging the SEI film impedance R of the retired batterySEIThe impedance is calculated by an alternating current impedance method and an equivalent circuit.
Preferably, the method for predicting lithium dendrite generation of the retired battery based on SEI film impedance change of the invention is that an equivalent circuit is shown in FIG. 1, ReRepresents the resistance of the electrolyte, CSEIIs a capacitance equivalent to a solid electrolyte membrane, RSEIFor the SEI film impedance of an ex-service battery, Rct represents the charge transfer step impedance of the electrode, ZwThen the Warburg impedance.
The invention has the beneficial effects that:
the invention relates to a method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change, which mainly comprises the following steps: establishing an electrochemical impedance equivalent circuit and an impedance spectrum model of the lithium battery, respectively testing and analyzing the relationship between the SEI film impedance and the cycle number of the battery under different conditions, and predicting the generation of lithium dendrites in the retired battery through the abnormal change of the SEI impedance. The invention relates to a method for prejudging lithium dendrite generation of an retired battery based on SEI (solid electrolyte interface) membrane impedance change, which is characterized in that an electrochemical impedance equivalent circuit of the lithium ion battery comprising SEI membrane impedance RSEI is established, a relation curve between the electrochemical impedance equivalent circuit and the battery cycle performance is established, the inflection point characteristic that the SEI membrane impedance is reduced firstly and then increased is adopted, and lithium dendrite generation of the retired battery is carried out at the inflection point, so that the lithium dendrite generation of the retired battery is quickly prejudged, and the method has the characteristics of simplicity, high efficiency, accurate judgment result and the like.
Drawings
the technical solution of the present application is further explained below with reference to the drawings and the embodiments.
Fig. 1 shows an equivalent circuit of a lithium battery including an SEI film resistance.
FIG. 2 is a typical electrochemical impedance spectrum.
FIG. 3(a) EIS spectra at 3.6V normal voltage after different cycles; (b) diffusion resistance R of 3.6V normally rechargeable batterySEIRelating to the cycle number; (c) EIS spectra after different cycle cycles at overcharge pressure of 4.0V; (d) diffusion resistance R of 4.0V overcharged cellSEIIn relation to the number of cycles.
FIG. 4 is a scanning electron microscope image of lithium ion battery cathode lithium deposition under different cycle number conditions.
FIG. 5 EIS spectra of ex-service cells after different cycles at overcharge voltages of (a)4.4V and (b)4.6V, respectively, (c) RSEIAs a function of the number of cycles, (d) battery capacity as a function of the number of cycles.
FIG. 6 is a scanning electron microscope image of lithium ion battery cathode lithium deposition under different charging voltage conditions.
FIG. 7 shows EIS spectra of positive and negative electrode active materials of the battery after circulation for different times, wherein the equivalent mass ratio of the positive and negative electrode active materials of the battery is (a)1.1:1, (b)1.2:1, (c)1.3:1, and (d)1.4: 1. (e) The diffusion impedance RSEI and the cycle number under different mass ratios, and (f) the battery capacity and the cycle number.
FIG. 8 shows the battery cycle performance curve, AC impedance spectrum and R at different multiplying powers (1C, 2C, 5C) when the equivalent mass ratio of positive electrode to negative electrode is 1.2:1SEINumerical values.
FIG. 9 is a scanning electron microscope image of lithium ion battery cathode lithium deposition under different charging and discharging current conditions.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
the technical solutions of the present application will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
Example 1
The embodiment provides a method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change, which comprises the following steps:
S1: taking a retired lithium iron phosphate battery as a sample, establishing SEI film impedance RSEIThe lithium ion battery electrochemical impedance equivalent circuit respectively tests the battery cycle number and R under the normal charging state and the 4.0V overcharging stateSEIThe relationship of (1);
S2: using the cycle number of the battery as an X axis and the SEI film resistance RSEIThe Y axis represents the cycle number of the battery and the SEI film resistance R under different conditionsSEIEstablishing a relation curve, wherein the resistance R of the SEI filmSEIThe increasing trend is interrupted and a curve segment occurs which decreases and then increases, the corresponding minimum value of said curve segment being the R for the production of lithium dendritesSEIAnd the battery cycle number corresponding to the minimum value corresponding to the curve segment is the battery cycle life of the lithium dendrite.
At 4.0V overcharge, RSEIthe values increase faster as the number of cycles increases. Surface layer diffusion resistance R during the first 30 weeks of a charge-discharge cycleSEIThe gradual increase from 44.56 omega to 224.2 omega after 10 weeks shows that the SEI film on the surface of the electrode is obviously thickened along with the increase of the cycle number, and the film resistance is increased. And when the cycle is up to 40 weeks, RSEIThe value became 157.3 Ω, and suddenly decreased more than 30 weeks, after which RSEIAnd continued to increase to 585.4 omega at 50 weeks.
Fig. 4 shows the topography of the disassembled negative electrode after cycling 100, 200, 300 times under overcharge conditions. As can be seen from fig. 4, the degree of lithium deposition from the battery negative electrode gradually increases as the number of cycles increases. In fig. 4(a), almost no white lithium is seen, while in fig. 4(b), white lithium is significantly increased, and as for fig. 4(c), it is apparent that the amount and density of lithium are greater than those of the first two. If the surface of the graphite negative electrode is still smooth in fig. 4(a), the surface of fig. 4(b) is relatively fluctuated, while the surface of fig. 4(c) is extremely uneven, cracks occur, and lithium dendrites are generated.
After the battery with the inflection point is disassembled, SEM observation is carried out on the negative pole piece, lithium dendrite is easy to find, and R is shownSEIThe abrupt decrease of (b) may be caused by lithium dendrite, and the growth of the lithium dendrite causes local damage to the SEI film, thereby lowering the diffusion resistance value of lithium ions in the surface layer. At the moment, the lithium dendrite only occurs in a local area, short circuit in the battery is not directly caused, the SEI film is repaired again in the subsequent cycle, the film resistance continues to increase, but the battery is failed soon afterwards. Thus, RSEIThe appearance of the inflection point suggests that lithium crystals in the battery damage the SEI film, and the battery is about to generate short circuit in dendrites.
Example 2
the embodiment provides a method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change, which comprises the following steps:
S1: taking a retired lithium iron phosphate battery as a sample, establishing SEI film impedance RSEIThe electrochemical impedance equivalent circuit of the lithium ion battery respectively tests the cycle number and R of the battery under different normal charging states and over-charging statesSEIThe different overcharge voltages include 4.4V, 4.6V;
S2: using the cycle number of the battery as an X axis and the SEI film resistance RSEIThe Y axis represents the cycle number of the battery and the SEI film resistance R under different conditionsSEIEstablishing a relation curve, wherein the resistance R of the SEI filmSEIThe increasing trend is interrupted and a curve segment occurs which decreases and then increases, the corresponding minimum value of said curve segment being the R for the production of lithium dendritesSEIAnd the battery cycle number corresponding to the minimum value corresponding to the curve segment is the battery cycle life of the lithium dendrite. As a result, as shown in fig. 5, when the battery charge cut-off voltage was set to 4.4V, the surface layer diffusion resistance gradually increased from 25.67 Ω to 74.04 Ω after 10 cycles in the first 30 cycles of the charge-discharge cycle, indicating that the SEI film gradually thickened during the cycle, the RSEI value decreased to 60.55 Ω during the cycle of week 40, and the inflection point appeared at weeks 30 to 40.
When the charge cut-off voltage of the battery is 4.6V, the SEI film impedance on the electrochemical impedance spectrogram is greatly improved and is obviously reduced when the battery is cycled to 20 circles, which indicates that the turning point appears at the 10 th to 20 th weeks. Indicating that the lithium ion battery impedance increases with increasing cutoff voltage under overcharge conditions, but the RSEI inflection point occurs earlier, indicating that lithium dendrites occur earlier, see fig. 5c for details). And fig. 5d) shows that at higher overcharge voltages, more severe capacity fade results due to more rapid lithium dendrite growth during cycling, while some structural failure of the positive electrode material occurs and the cell fails more rapidly.
Fig. 6 shows the morphology of the negative electrode after 100 cycles when the charge-discharge current is 2C under different charge cut-off voltage conditions. It can be seen visually that the graphite negative electrode of the picture (a) under normal charge and discharge conditions has a flat surface and almost no white lithium, while the pictures (b) and (c) under overcharge conditions have uneven surfaces and white impurities on the graphite surface, and meanwhile, the picture (c) has cracks, which shows that the pole piece structure is damaged and lithium dendrites are generated.
Example 3
The embodiment provides a method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change, which comprises the following steps:
S1: still taking an retired lithium iron phosphate battery as a research sample, and establishing an electrochemical impedance equivalent circuit of the lithium ion battery comprising SEI (solid electrolyte interphase) membrane impedance RSEI; respectively testing the cycle times of the battery and the SEI film impedance R of the retired battery under four different anode-cathode ratio analysis conditionsSEIThe relationship of (1);
S2: using the cycle number of the battery as an X axis and the SEI film resistance RSEIThe Y axis represents the cycle number of the battery and the SEI film resistance R under different conditionsSEIEstablishing a relation curve, wherein the resistance R of the SEI filmSEIThe increasing trend is interrupted and a curve segment occurs which decreases and then increases, the corresponding minimum value of said curve segment being the R for the production of lithium dendritesSEIand the battery cycle number corresponding to the minimum value corresponding to the curve segment is the battery cycle life of the lithium dendrite.
fig. 7 shows the variation of the RSEI with cycle number for four lithium ion batteries with different anode and cathode ratios. When the charge cut-off voltage of the battery is set to be 4.4V, and the equivalent mass ratio of the anode material to the cathode material is 1.1:1, 1.2:1, 1.3:1 and 1.4:1 respectively, the RSEI of the battery is gradually increased in the charge-discharge cycle process. The lithium-rich phenomenon is more obvious when the positive electrode of the battery with the same charging voltage and different positive electrode and negative electrode proportions is more excessive, the RSEI inflection point appears earlier, and the lithium dendrite phenomenon is aggravated along with the excessive increase of the lithium-rich.
When the equivalent mass ratio is 1.1:1, the diffusion impedance is increased all the time without an inflection point; at mass ratios of 1.2:1 to 1.3:1, the RSEI inflection point occurs at 40 weeks; at a mass ratio of 1.4:1, the RSEI inflection point occurred at 30 weeks. It shows that the internal short circuit problem caused by lithium dendrite is intensified and the internal short circuit time is advanced along with the increase of the excessive proportion of the anode material.
This means that the occurrence of an inflection point, i.e., suppression of internal short circuit by lithium dendrite, can be avoided when the negative electrode ratio is high. Similarly, the higher the positive electrode ratio, the more the capacity of the battery is degraded, as can be seen from the change in the capacity of the battery with the cycle number. The low proportion of the positive and negative active materials is proved to be capable of delaying the generation of lithium dendrites and internal short circuit, thereby improving the safety of the battery.
Comparative examples
This example uses a retired lithium iron phosphate battery as a research sample.
(1) and establishing an electrochemical impedance equivalent circuit of the lithium ion battery, which comprises an SEI film impedance RSEI. Under the cutoff voltage of 4.4V, when the equivalent mass ratio of the positive electrode to the negative electrode is 1.2:1, the cycle performance curve of the battery under the multiplying power charge and discharge (1C, 2C and 5C) and the EIS after 25 weeks of cycle. It can be seen from fig. 8 that the larger the charge-discharge rate of the battery, the lower the capacity of the battery, and the more significant the capacity fading, and simultaneously, the R of the ac impedance test isSEIthe larger the impedance, but no inflection point occurred. Under the condition of large current, certain damage is caused to battery materials and interface structures, the cycle performance of the battery is reduced, an SEI film is thickened to some extent, and lithium dendrite is not generated.
Fig. 9 shows scanning electron micrographs of the negative electrode of the battery with charge and discharge currents of 2C, 3C, and 4C, respectively, and a cycle number of 100 cycles, and it can be seen that when the charge and discharge currents are increased, the rougher the electrode surface is, lithium impurities can be seen on the graphite negative electrode surface under the current of 4C, but lithium dendrites are not formed.
The SEI film means that in the first charge and discharge process of the lithium ion battery, an electrode material and an electrolyte react on a solid-liquid phase interface to form a passivation layer covering the surface of the electrode material. The passivation layer is an interfacial layer, characterized by a solid electrolyte, which is an electronic insulator but Li+Of good electrical conductivity, Li+Can be freely inserted and extracted through the passivation layer, so the passivation film is called a solid electrolyte interface film (SEI film) for short.
An alternating current impedance method, also called Electrochemical Impedance Spectroscopy (EIS) technology, is an Electrochemical measurement method using small-amplitude sine wave potential (or current) as a disturbance signal, wherein alternating voltage (or alternating current) of an electrode is controlled to change according to a small-amplitude (generally less than 10mV) sine wave rule, then alternating impedance of the electrode is measured, and further Electrochemical parameters of a research system are calculated.
In light of the foregoing description of the preferred embodiments according to the present application, it is to be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of the claims.

Claims (7)

1. A method for prejudging lithium dendrite generation of an ex-service battery based on SEI film impedance change is characterized by comprising the following steps:
S1: taking a retired battery, and respectively testing and analyzing the cycle number of the battery and the SEI film impedance R of the retired battery under different conditionsSEIThe relationship of (1);
S2: using the cycle number of the battery as an X axis and the SEI film resistance RSEIThe Y axis represents the cycle number of the battery and the SEI film resistance R under different conditionsSEIEstablishing a relation curve, wherein the resistance R of the SEI filmSEIThe increasing trend is interrupted and a curve segment occurs which decreases and then increases, the corresponding minimum value of said curve segment being the R for the production of lithium dendritesSEIImpedance value, minimum corresponding to said curve segmentThe corresponding number of battery cycles is the battery cycle life that produces lithium dendrites.
2. The method of claim 1, wherein the analysis conditions in step S1 include different overcharge conditions, different lithium-rich conditions, and different high-rate charge and discharge.
3. The method of predicting lithium dendrite generation of ex-service battery based on SEI film impedance change according to claim 2, wherein the overcharge condition means a charged voltage value not less than 110% of a charged cut-off voltage of the ex-service battery.
4. The method for predicting lithium dendrite generation of the retired battery based on SEI film impedance change of claim 2, wherein the lithium-rich condition means that the ratio of the equivalent mass ratio of the positive and negative electrode materials is not lower than 1.2.
5. The method for predicting lithium dendrite generation of an ex-service battery based on SEI film impedance change according to claim 2, wherein the high-rate charge-discharge refers to charge-discharge at a rate of not less than 1C.
6. The method for predicting lithium dendrite generation of ex-service battery based on SEI film resistance variation according to any one of claims 1-5, wherein the SEI film resistance R of the ex-service batterySEIThe impedance is calculated by an alternating current impedance method and an equivalent circuit.
7. The method of claim 6, wherein the equivalent circuit is shown in FIG. 1, R is ReRepresents the resistance of the electrolyte, CSEIis a capacitance equivalent to a solid electrolyte membrane, RSEIFor the SEI film impedance of an ex-service battery, Rct represents the charge transfer step impedance of the electrode, ZwThen the Warburg impedance.
CN201910688305.9A 2019-07-29 2019-07-29 Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change Pending CN110568363A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910688305.9A CN110568363A (en) 2019-07-29 2019-07-29 Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910688305.9A CN110568363A (en) 2019-07-29 2019-07-29 Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change

Publications (1)

Publication Number Publication Date
CN110568363A true CN110568363A (en) 2019-12-13

Family

ID=68773574

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910688305.9A Pending CN110568363A (en) 2019-07-29 2019-07-29 Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change

Country Status (1)

Country Link
CN (1) CN110568363A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111458642A (en) * 2020-04-22 2020-07-28 上海空间电源研究所 Nondestructive testing method for lithium separation of lithium ion storage battery
CN111856285A (en) * 2020-07-06 2020-10-30 大连理工大学 Electric automobile retired battery pack equivalent model modeling method applied to power system
CN112098877A (en) * 2020-09-15 2020-12-18 湖北亿纬动力有限公司 Battery detection method and device and battery system
CN112397789A (en) * 2020-11-17 2021-02-23 深圳市新威尔电子有限公司 Three-electrode battery capable of detecting growth of lithium dendrite and method
CN114200322A (en) * 2021-12-07 2022-03-18 欣旺达电动汽车电池有限公司 Lithium ion battery lithium separation detection method
CN114720526A (en) * 2022-03-25 2022-07-08 江苏海基新能源股份有限公司 Rapid evaluation method for cycle performance of lithium iron phosphate material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108508375A (en) * 2018-05-09 2018-09-07 国联汽车动力电池研究院有限责任公司 A kind of systematic analytic method of lithium ion battery failure
CN108535659A (en) * 2018-04-25 2018-09-14 上海力信能源科技有限责任公司 A kind of lithium ion battery recycles the detection method of microcosmic analysis lithium
CN109358290A (en) * 2018-09-06 2019-02-19 深圳市比克动力电池有限公司 A kind of lossless detection method of lithium ion battery analysis lithium
CN109581240A (en) * 2018-11-29 2019-04-05 北京航空航天大学 Lithium ion battery failure analysis method based on AC impedence method
CN109655760A (en) * 2018-12-27 2019-04-19 深圳市比克动力电池有限公司 A kind of lossless detection method and its application method of lithium ion battery analysis lithium
CN109932658A (en) * 2019-03-06 2019-06-25 肇庆遨优动力电池有限公司 A kind of detection method of lithium ion battery analysis lithium

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108535659A (en) * 2018-04-25 2018-09-14 上海力信能源科技有限责任公司 A kind of lithium ion battery recycles the detection method of microcosmic analysis lithium
CN108508375A (en) * 2018-05-09 2018-09-07 国联汽车动力电池研究院有限责任公司 A kind of systematic analytic method of lithium ion battery failure
CN109358290A (en) * 2018-09-06 2019-02-19 深圳市比克动力电池有限公司 A kind of lossless detection method of lithium ion battery analysis lithium
CN109581240A (en) * 2018-11-29 2019-04-05 北京航空航天大学 Lithium ion battery failure analysis method based on AC impedence method
CN109655760A (en) * 2018-12-27 2019-04-19 深圳市比克动力电池有限公司 A kind of lossless detection method and its application method of lithium ion battery analysis lithium
CN109932658A (en) * 2019-03-06 2019-06-25 肇庆遨优动力电池有限公司 A kind of detection method of lithium ion battery analysis lithium

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111458642A (en) * 2020-04-22 2020-07-28 上海空间电源研究所 Nondestructive testing method for lithium separation of lithium ion storage battery
CN111856285A (en) * 2020-07-06 2020-10-30 大连理工大学 Electric automobile retired battery pack equivalent model modeling method applied to power system
CN111856285B (en) * 2020-07-06 2021-06-08 大连理工大学 Electric automobile retired battery pack equivalent model modeling method
CN112098877A (en) * 2020-09-15 2020-12-18 湖北亿纬动力有限公司 Battery detection method and device and battery system
CN112098877B (en) * 2020-09-15 2023-06-30 湖北亿纬动力有限公司 Battery detection method, device and battery system
CN112397789A (en) * 2020-11-17 2021-02-23 深圳市新威尔电子有限公司 Three-electrode battery capable of detecting growth of lithium dendrite and method
CN112397789B (en) * 2020-11-17 2022-09-27 深圳市新威尔电子有限公司 Three-electrode battery capable of detecting growth of lithium dendrite and method
CN114200322A (en) * 2021-12-07 2022-03-18 欣旺达电动汽车电池有限公司 Lithium ion battery lithium separation detection method
CN114200322B (en) * 2021-12-07 2024-04-30 欣旺达动力科技股份有限公司 Lithium ion battery lithium precipitation detection method
CN114720526A (en) * 2022-03-25 2022-07-08 江苏海基新能源股份有限公司 Rapid evaluation method for cycle performance of lithium iron phosphate material
CN114720526B (en) * 2022-03-25 2023-08-04 江苏海基新能源股份有限公司 Rapid evaluation method for cycle performance of lithium iron phosphate material

Similar Documents

Publication Publication Date Title
Zhang et al. Capacity fading mechanism during long-term cycling of over-discharged LiCoO2/mesocarbon microbeads battery
CN110568363A (en) Method for prejudging lithium dendrite generation of retired battery based on SEI film impedance change
Kim et al. Effects of capacity ratios between anode and cathode on electrochemical properties for lithium polymer batteries
KR101873329B1 (en) Charging method for lithium ion batteries
CN109037811B (en) Charging method of graphite negative electrode system lithium ion battery
Xiao et al. Electrochemical behavior of biphenyl as polymerizable additive for overcharge protection of lithium ion batteries
CN108427077A (en) A kind of experimental method for analysing lithium using reference electrode monitoring cathode
CN109581240B (en) Lithium ion battery failure analysis method based on alternating current impedance method
Guan et al. The effect of elevated temperature on the accelerated aging of LiCoO2/mesocarbon microbeads batteries
WO2011065009A1 (en) Method for charging lithium-ion secondary battery and battery pack
CN112433159B (en) Detection method for lithium ion battery graphite negative electrode lithium separation
KR20110053252A (en) Nonaqueous electrolyte secondary battery charging method and charging device
CN111458642A (en) Nondestructive testing method for lithium separation of lithium ion storage battery
Tobishima et al. Influence of electrolyte additives on safety and cycle life of rechargeable lithium cells
An et al. Multi-stage constant-current charging protocol for a high-energy-density pouch cell based on a 622NCM/graphite system
Bohinsky et al. Preventing lithium plating under extremes: an untold tale of two electrodes
CN111366863B (en) Lithium ion battery service life acceleration pre-judging method based on low-temperature circulation
CN111430801A (en) Electrolyte of lithium ion secondary battery and application thereof
US10559862B2 (en) Method of forming a negative electrode for a lithium-ion cell
CN114221049B (en) Judgment method for lithium precipitation of battery cell
CN112946490A (en) FA analysis method for lithium ion battery cell capacity attenuation
CN111948554A (en) Method for reducing mechanical degradation of lithium ion battery
Nakamura et al. Influence of Li-salts on cycle durability of Sn-Ni alloy anode for lithium-ion capacitor
CN115084679B (en) Method for recovering capacity of retired lithium ion battery
CN218632196U (en) Rechargeable 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

Application publication date: 20191213

RJ01 Rejection of invention patent application after publication