CN108931736B - Method for judging lithium ion battery lithium separation critical condition - Google Patents

Method for judging lithium ion battery lithium separation critical condition Download PDF

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CN108931736B
CN108931736B CN201810769863.3A CN201810769863A CN108931736B CN 108931736 B CN108931736 B CN 108931736B CN 201810769863 A CN201810769863 A CN 201810769863A CN 108931736 B CN108931736 B CN 108931736B
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lithium
ion battery
charging
lithium ion
critical
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CN108931736A (en
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李恺
闫艳红
黎钢
姚万浩
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Jiangsu Zenergy Battery Technologies Co Ltd
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Dongguan Tafel New Energy Technology Co Ltd
Jiangsu Tafel New Energy Technology Co Ltd
Shenzhen Tafel New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention provides a method for judging lithium ion battery lithium separation critical conditions, which comprises the following steps: s1) charging the lithium ion battery at the same temperature by adopting different charging rates, and recording the anode potential; s2) obtaining the critical lithium-separating current or the critical lithium-separating multiplying power of the lithium ion battery according to the relation between the anode potential and the charging current or the charging multiplying power. Compared with the prior art, the judging method provided by the invention can quantitatively and pre-judge the critical multiplying power or current of lithium analysis of the lithium ion battery, does not need to disassemble the battery, saves time and labor, saves resources and has high accuracy.

Description

Method for judging lithium ion battery lithium separation critical condition
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for judging lithium ion battery lithium separation critical conditions.
Background
Lithium ion batteries have received general attention in recent years as a novel green energy source, but as the application space thereof is continuously expanded, the market is more demanding on the lithium ion batteries, and particularly, the lithium ion batteries currently applied to electric vehicles face two difficulties, namely high-rate charging performance and low-temperature charging performance.
When the battery is charged at low temperature or high multiplying power, the internal polarization of the battery is increased, the overpotential of the anode is high, and lithium ions in the battery cell are separated out on the surface of the anode, so that the safety performance of the battery cannot be ensured, and therefore, the critical condition for judging the lithium separation of the battery cell in advance is particularly important.
At present, the most common method is to charge the battery at different multiplying powers and temperatures, disassemble the battery, and judge whether the lithium ion battery separates lithium and the lithium separation degree by naked eyes. However, the method can only perform qualitative judgment, consumes a large amount of manpower and material resources, and has certain potential safety hazard in the battery disassembling process.
Disclosure of Invention
In view of the above, the present invention provides a method for quantitatively determining a lithium deposition critical condition of a lithium ion battery.
The invention provides a method for judging lithium ion battery lithium separation critical conditions, which comprises the following steps:
s1) charging the lithium ion battery at the same temperature by adopting different charging rates, and recording the anode potential;
s2) obtaining the critical lithium-separating current or the critical lithium-separating multiplying power of the lithium ion battery according to the relation between the anode potential and the charging current or the charging multiplying power.
Preferably, the step S2) is specifically: and according to the recorded anode potential, establishing a fitting equation of the anode potential and the charging current or the charging multiplying power to obtain a fitting equation of a lithium analysis region and a fitting equation of a non-lithium analysis region, wherein the intersection point of the two equations is the critical lithium analysis current or the critical lithium analysis multiplying power of the lithium ion battery.
Preferably, the temperature is 5 ℃ to 30 ℃.
Preferably, the charging rate is 0.1-3C.
Preferably, the lithium ion battery uses a lithium-plated electrode as a reference electrode.
Preferably, in S1), when the temperature condition of the lithium ion battery is changed, the lithium ion battery is left standing for 30-240 min, and then is charged with different charging rates.
Preferably, when the lithium ion battery is charged at different charging rates in step S1), standing for 1-10 min after each charging is finished, recording the anode potential, then discharging, standing for 1-10 min, and then performing the next charging.
Preferably, the discharge uses a 1C current.
The invention provides a method for judging lithium ion battery lithium separation critical conditions, which comprises the following steps: s1) charging the lithium ion battery at the same temperature by adopting different charging rates, and recording the anode potential; s2) obtaining the critical lithium-separating current or the critical lithium-separating multiplying power of the lithium ion battery according to the relation between the anode potential and the charging current or the charging multiplying power. Compared with the prior art, the judging method provided by the invention can quantitatively and pre-judge the critical multiplying power or current of lithium analysis of the lithium ion battery, does not need to disassemble the battery, saves time and labor, saves resources and has high accuracy.
Drawings
Fig. 1 is a photograph of a cell interface at a charge current of 4A according to comparative example 1 of the present invention;
fig. 2 is a photograph of a cell interface at a charge current of 4.5A according to comparative example 1 of the present invention;
fig. 3 is a photograph of a cell interface at a charge current of 1.67A according to comparative example 2 of the present invention;
fig. 4 is a photograph of a cell interface at a charge current of 2A according to comparative example 2 of the present invention;
fig. 5 is a photograph of a cell interface at a charge current of 3.89A according to comparative example 3 of the present invention;
fig. 6 is a photograph of the cell interface at a charge current of 4.5A in comparative example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for judging lithium ion battery lithium separation critical conditions, which comprises the following steps: s1) charging the lithium ion battery at the same temperature by adopting different charging rates, and recording the anode potential; s2) according to the recorded anode potential, establishing a fitting equation of the anode potential and the charging current or the charging multiplying power to obtain the critical lithium-separating current or the critical lithium-separating multiplying power of the lithium ion battery.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
Charging the lithium ion battery at the same temperature by adopting different charging multiplying powers, and recording the anode potential; wherein the temperature is preferably 5-30 ℃, and more preferably 10-25 ℃; the lithium ion battery is not particularly limited, but a lithium ion battery well known to those skilled in the art, and a lithium-plated electrode is preferably used as a reference electrode in the present invention; when the temperature condition of the lithium ion battery is changed, preferably standing for 30-240 min, more preferably 60-200 min, further preferably 100-180 min, and most preferably 120-140 min, and then charging by adopting different charging rates; in order to ensure that the charging conditions are the same each time, discharging is preferably carried out first, and then charging is carried out by adopting different charging multiplying powers; the discharge is preferably carried out with a current of 1C; the discharge is preferably discharged to a lower cut-off voltage; the charging multiplying power is preferably 0.1-3C; the charging is preferably to an upper cut-off voltage; after each charging, preferably standing for 1-10 min, more preferably standing for 4-8 min, still more preferably standing for 5-6 min, recording the anode potential, then discharging, and then charging for the next time; the discharge is preferably carried out with a current of 1C.
And obtaining the critical lithium precipitation current or the critical lithium precipitation multiplying power of the lithium ion battery according to the relation between the anode potential and the charging current or the charging multiplying power. The method specifically comprises the following steps: establishing a fitting equation of the anode potential and the charging current or the charging rate according to the recorded anode potential, obtaining different fitting equations due to different surface states of the anode with lithium separated and without lithium separated and different mechanisms of voltage and the charging rate or the charging current, taking the current as an example, a fitting equation U of a non-lithium separated area1=k1*I+b1(k1Is a slope, b1Intercept), lithium precipitation zone: u shape2=k2*I+b2(k2Is a slope, b2Intercept), the intersection point of the two equations is the critical lithium-precipitating current or critical lithium-precipitating multiplying power of the lithium ion battery, namely the critical lithium-precipitating current or multiplying power at the experimental temperature is obtained by solving the equation set according to the equations.
The judging method provided by the invention can quantitatively and pre-judge the critical multiplying power or current of lithium ion battery lithium analysis, and the battery is not required to be disassembled, so that the time and the labor are saved, the resources are saved, and the accuracy is high.
In order to further explain the present invention, the following describes in detail a method for quantitatively determining lithium deposition critical conditions of a lithium ion battery, which is provided by the present invention, with reference to examples.
The reagents used in the following examples are all commercially available.
Example 1
The battery adopts ternary materials: NCM 523; anode material: graphite AK01 (g capacity of 340mAh/g, graphitization degree 94%); the electrolyte is prepared by taking lithium hexafluorophosphate (LiPF6) with the concentration of 1.0M as a lithium salt, ethylene carbonate as an additive and a mixture of Propylene Carbonate (PC), Ethylene Carbonate (EC) and dimethyl carbonate (DMC) as a solvent; the anode-to-lithium potential U of the lithium ion battery under the specified conditions during charging at different multiplying powers is measuredx
The examples are specifically presented below:
embedding a copper wire in the battery cell in the preparation stage, and carrying out lithium plating treatment on the copper wire after the battery cell is activated to prepare a reference electrode; and then, placing the battery cell into a high-low temperature box and connecting the battery cell into a charging and discharging cabinet, completing testing according to the flow, and collecting data.
The specific test flow is as follows:
1) adjusting the ambient temperature to be T (T is set by experimental requirements);
2) standing for 120 min;
3) discharging the nominal 1C current to a lower cutoff voltage;
4) standing for 5 min;
5) nominal XC current charges to the upper cutoff voltage (X is 0.1, 0.5, 1, 1.5, 2, 3);
6) standing for 5 min.
Recording the corresponding potential U of the anode at the same temperature and different multiplying powersx
Establishing an equation of anode potential Ux and charging current I in the charging process of the lithium ion battery through test data, wherein the potential Ux and the charging current I show different mechanisms due to different surface states of the anode without lithium separation and the lithium separation of the battery, and obtaining different fitting equations;
non-lithium-separation region: u shape1=k1*I+b1(k1Is a slope, b1Is a intercept distance)
A lithium separation zone: u shape2=k2*I+b2(k2Is a slope, b2Is a intercept distance)
And solving an equation system through an equation obtained by fitting to obtain the critical lithium precipitation current under the experimental temperature condition, wherein the critical lithium precipitation charging current at 25 ℃ is 4.03A, and the critical lithium precipitation charging current at 10 ℃ is 1.67A.
Ux at different currents at 125 deg.C
I/A 0.229 1.145 2.290 3.435 4.580 5.725 6.870
Ux potential/V 0.0464 0.0224 -0.0033 -0.0281 -0.0479 -0.0637 -0.0724
Fitting equation U1 ═ -0.0231 × I + 0.0504;
fitting equation U2 ═ -0.0107 × I-0.0001;
TABLE Ux at different currents at 210 deg.C
I/A 0.229 0.570 0.921 1.141 2.290 3.440 3.580
Ux potential/V 0.0280 0.0121 -0.0027 -0.0118 -0.0541 -0.0717 -0.0907
Fitting equation U1 ═ -0.0516 × I + 0.0378;
fitting equation U2 ═ -0.0143 × I + 0.0294;
example 2
The battery adopts ternary materials: NCM 523; anode material: artificial graphite SF01 (g capacity of 350mAh/g, graphitization degree 96.5%); the electrolyte was prepared using lithium hexafluorophosphate (LiPF6) of concentration 1.0M as a lithium salt, ethylene carbonate as an additive, and a mixture of Propylene Carbonate (PC), Ethylene Carbonate (EC) and dimethyl carbonate (DMC) as a solvent.
The method of example 1 was used to determine the anode-to-lithium potential U of a lithium ion battery when charged at different rates at 25 deg.CxThe critical lithium deposition current was determined to be 3.89A.
TABLE 325 ℃ Ux under different currents
I/A 0.229 1.145 2.290 3.435 4.580 5.725 6.870
Ux potential/V 0.0352 0.0102 -0.0150 -0.0394 -0.0557 -0.0664 -0.0727
Fitting equation U1 ═ -0.0231 × I + 0.0387;
fitting equation U2 ═ 0.0074 × I-0.0224;
comparative example 1
The lithium ion battery in the embodiment 1 is adopted, the temperature is controlled to be 25 ℃ (normal temperature), charging is carried out under different multiplying powers, then a fully-charged battery core is manually disassembled in a safety house, the interface lithium separation condition is observed, and the critical lithium separation multiplying power is judged; wherein fig. 1 is a photograph of a cell interface with no lithium deposition at a charging current of 4A, and fig. 2 is a photograph of a cell interface with slight lithium deposition at a charging current of 4.5A; from fig. 1 and fig. 2, it can be concluded that the normal temperature critical lithium deposition current of the lithium ion battery is between 4 and 4.5A.
Comparative example 2
The lithium ion battery in the embodiment 1 is adopted, the temperature is controlled to be 10 ℃, charging is carried out under different multiplying powers, then a fully-charged battery core is manually disassembled in a safety house, the condition of interface lithium separation is observed, and the critical lithium separation multiplying power is judged; wherein fig. 3 is a photograph of the cell interface with no lithium deposition at a charging current of 1.67A, and fig. 4 is a photograph of the cell interface with slight lithium deposition at a charging current of 2A; from fig. 3 and fig. 4, it can be concluded that the 10 ℃ critical lithium deposition current of the lithium ion battery is between 1.67 and 2A.
Comparative example 3
The lithium ion battery in the embodiment 2 is adopted, the temperature is controlled to be 25 ℃ (normal temperature), charging is carried out under different multiplying powers, then the fully-charged cell is disassembled manually in a safety house, the interface lithium separation condition is observed, and the critical lithium separation multiplying power is judged; wherein fig. 5 is a photograph of the cell interface with no lithium deposition at a charging current of 3.89A, and fig. 6 is a photograph of the cell interface with slight lithium deposition at a charging current of 4.5A; from fig. 5 and 6, it can be inferred that the lithium ion battery has a room temperature critical lithium deposition current of about 4A.

Claims (4)

1. A method for judging lithium evolution critical conditions of a lithium ion battery is characterized by comprising the following steps:
s1) charging the lithium ion battery at the same temperature by adopting different charging rates, and recording the anode potential;
s2) according to the recorded anode potential, establishing a fitting equation of the anode potential and the charging current or the charging multiplying power to obtain a fitting equation of a lithium analysis region and a fitting equation of a non-lithium analysis region, wherein the intersection point of the two equations is the critical lithium analysis current or the critical lithium analysis multiplying power of the lithium ion battery;
the lithium ion battery takes a lithium-plated electrode as a reference electrode;
when the lithium ion battery is charged by adopting different charging multiplying powers in the step S1), standing for 1-10 min after each charging is finished, recording the anode potential, then discharging, standing for 1-10 min, and then carrying out next charging;
the discharge uses a 1C current.
2. The method according to claim 1, wherein the temperature is 5 ℃ to 30 ℃.
3. The determination method according to claim 1, wherein the charging rate is 0.1 to 3C.
4. The method according to claim 1, wherein in step S1), when the temperature condition of the lithium ion battery is changed, the lithium ion battery is left standing for 30-240 min and then charged with different charging rates.
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CN109596992B (en) * 2018-12-28 2021-08-20 中国标准化研究院 Early verification method for lithium ion battery accelerated lithium precipitation failure
CN110940920B (en) * 2019-11-22 2021-10-01 上海理工大学 Method for acquiring maximum charging current of lithium battery without lithium precipitation under preset SOC (state of charge)
CN111443296A (en) * 2020-03-17 2020-07-24 合肥国轩高科动力能源有限公司 Method for verifying feedback charging capability of lithium ion battery
CN113125974B (en) * 2021-04-22 2023-06-16 远景动力技术(江苏)有限公司 Method and device for detecting lithium precipitation of battery

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