CN112946500A - Method for rapidly testing cycle life of lithium ion battery - Google Patents
Method for rapidly testing cycle life of lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000012360 testing method Methods 0.000 title claims abstract description 47
- 238000007600 charging Methods 0.000 claims abstract description 64
- 238000010277 constant-current charging Methods 0.000 claims abstract description 30
- 238000013461 design Methods 0.000 claims abstract description 8
- 208000028659 discharge Diseases 0.000 claims description 57
- 238000010280 constant potential charging Methods 0.000 claims description 21
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 238000007599 discharging Methods 0.000 abstract description 20
- 238000010998 test method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000007246 mechanism Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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
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- 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
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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
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Abstract
The invention provides a method for rapidly testing the cycle life of a lithium ion battery, which comprises the steps of carrying out constant current charging on the lithium ion battery after discharging and standing under the condition of low multiplying power, and carrying out constant current charging under the low multiplying power until the constant current charging is less than or equal to 80% of the design capacity of the lithium ion battery; the method is characterized in that the charging current when the battery is in a low SOC (state of charge) state is reduced, so that the newly formed SEI in each charging process is more compact, and the reaction consumption of available lithium ions in the battery is accelerated; meanwhile, by improving the charge cut-off voltage of the charging step in the conventional high-temperature intermittent circulation process, the consumption of lithium ion reaction, the decline of electrode materials and the decomposition of electrolyte are accelerated; the rapid test method can realize the test rate of high-temperature intermittent circulation on the premise of ensuring the consistency of the battery capacity attenuation mechanism, greatly shortens the time required by the test, and is beneficial to the rapid development of battery products.
Description
Technical Field
The invention belongs to the technical field of battery testing methods, and particularly relates to a method for rapidly testing the cycle life of a lithium ion battery.
Background
Lithium ion batteries have been widely used in consumer electronics and electric vehicle products due to their high energy density, long cycle life, no memory effect, and the like. Consumer electronics, particularly notebook computers, require batteries that still have good cycling and storage properties at higher temperatures. The end manufacturer requires that the battery pass some specific high temperature tests to simulate some of the actual operating conditions of the battery.
The current battery high-temperature performance test scheme is high-temperature intermittent circulation, and comprises the following specific steps: fully discharging the fully charged battery at high temperature, standing for a short time (short standing time between known normal discharge and charge specified by a terminal manufacturer, the standing process is not particularly emphasized below), fully charging at constant current and constant voltage, and standing for a long time, wherein the steps are sequentially recorded as a cycle, the long standing time is longer than the short standing time, and the test standard requires that the capacity retention rate of the battery after the battery is circulated for a certain number of times according to the steps is not lower than a specific value. The high temperature intermittent cycle test takes a long time and is carried out according to the general standard, and the total cycle time is generally more than 100 days. The long test period is very disadvantageous to the rapid development and optimization of the battery product, and therefore, it is necessary to develop a corresponding accelerated test scheme.
The working life of the lithium ion battery needs to be evaluated through various circulation systems, and the problem of long test period exists in any circulation test. Aiming at the problem that the cycle test of the lithium ion battery takes too long, the prior art discloses a method for testing the service life of the battery in an accelerated manner, the battery is subjected to floating charging with time increment after constant-current charging under the high-temperature condition until the room-temperature discharge capacity is lower than the nominal capacity by 75 percent, a conversion table of the normal-temperature service life and the high-temperature service life which is tested and manufactured in advance is inquired, and the cycle life of the battery under the normal-temperature condition is estimated. Although the above scheme can achieve the effect of accelerated test of the battery life, the following disadvantages exist: firstly, the high-temperature cycle life and the normal-temperature cycle life correspond to each other only through the normal-temperature discharge capacity, which is not enough to ensure that the attenuation mechanisms of the battery capacity are consistent, but the accelerated test scheme with inconsistent attenuation mechanisms cannot be considered as an effective scheme. Second, although the normal temperature cycle life and the normal high temperature cycle life can be tested in advance and made into a life data conversion table, since the consistency of the capacity fading mechanism cannot be guaranteed, for each battery made of a new material and a new scheme, a large amount of time is required to make the life data conversion table, and it is actually difficult to really achieve the effect of accelerating the test.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for rapidly testing the cycle life of a lithium ion battery, which can well solve the problem that the cycle life test of the lithium ion battery takes too long. The method mainly reduces the charging current when the battery is in a low SOC state, so that the newly formed SEI in each charging process is more compact, and the reaction consumption of the available lithium ions in the battery is accelerated; meanwhile, by improving the charge cut-off voltage of the battery, the lithium ion reaction consumption, the electrode material recession and the electrolyte decomposition are accelerated, the high-temperature intermittent cycle rapid test is realized on the premise of ensuring the consistency of the battery capacity attenuation mechanism, the time required by the test is greatly shortened, and the rapid development of battery products is facilitated.
The purpose of the invention is realized by the following technical scheme:
a method of rapidly testing the cycle life of a lithium ion battery, the method comprising:
(1) the method comprises the following steps of carrying out discharge treatment on the lithium ion battery, and also comprising a discharge standing step after the discharge is finished;
(2) carrying out constant current charging on the lithium ion battery after the lithium ion battery is discharged and kept still under a low-rate condition, and carrying out constant current charging under the low-rate condition until the design capacity of the lithium ion battery is less than or equal to 80%;
(3) performing constant current charging on the lithium ion battery in the step (2) under the known multiplying power condition, and performing constant current charging to the charging upper limit voltage U under the known multiplying powerOn the upper partSaid upper limit charging voltage UOn the upper partGreater than the known upper charge limitVoltage UgOn the upper part；
(4) Performing constant voltage charging on the lithium ion battery in the step (3) to a known cut-off current, wherein the voltage of the constant voltage charging is the charging upper limit voltage UOn the upper part；
(5) The lithium ion battery is in one cycle from the step (1) to the step (4); when the charge-discharge cycle time of the lithium ion battery reaches a threshold value, recording the high-temperature capacity retention rate of the lithium ion battery;
or when the high-temperature capacity retention rate of the lithium ion battery reaches a threshold value, recording the charge-discharge cycle time used by the lithium ion battery, namely realizing the rapid test of the cycle life of the lithium ion battery.
According to the invention, the method is carried out by placing the lithium ion battery in an environment above 40 ℃.
According to the present invention, in the step (1), the discharge treatment may be, for example, a discharge treatment of discharging the lithium ion battery at a discharge rate of 0.2 to 6C (e.g., 0.5 to 1.5C) to a discharge lower limit voltage ULower part’。
In the step (1), the discharge lower limit voltage U of the discharge treatmentLower partEqual to the known lower limit voltage of discharge UgLower part’。
In step (1), the known discharge lower limit voltage UgLower part' is 2.0-3.6V.
According to the invention, in the step (1), the discharge standing time is 1-60 min.
According to the invention, in the step (2), the low rate is a rate smaller than that of the known constant current charging; for example, less than 0.1C or more, which is the rate of conventional constant current charging.
According to the present invention, in step (2), the design capacity of the lithium ion battery is 2000-8000mAh, such as 4000 mAh.
According to the invention, in the step (2), in each cycle process, the low-magnification conditions can be the same or different; the low-magnification conditions may be the same or different during different cycles.
According to the invention, in the step (3), the lithium ion battery is subjected to constant operation under the condition of known rateCharging by current, and charging by constant current to charging upper limit voltage U under known multiplying powerOn the upper part。
In the step (3), the charging upper limit voltage UOn the upper partAnd a known upper limit charging voltage UgOn the upper partSatisfies the following relation: 1V is more than or equal to UOn the upper part-UgOn the upper part>0V。
In the step (3), the known charging upper limit voltage UgOn the upper partFor example, it may be 3.6-4.5V.
According to the invention, in step (4), the known off-current is 0.025C or 0.05C.
According to the invention, in the step (4), the time of the constant voltage charging process is the same or different during each cycle; in the step (5), the time of each cycle process may be the same or different.
The invention has the beneficial effects that:
the invention provides a method for rapidly testing the cycle life of a lithium ion battery, which is characterized in that the charging current when the battery is in a low SOC (state of charge) state is reduced, so that the newly formed SEI in each charging process is more compact, and the reaction consumption of available lithium ions in the battery is accelerated; meanwhile, by improving the charge cut-off voltage of the charging step in the conventional high-temperature intermittent circulation process, the consumption of lithium ion reaction, the decline of electrode materials and the decomposition of electrolyte are accelerated; the rapid test method can realize the test rate of high-temperature intermittent circulation on the premise of ensuring the consistency of the battery capacity attenuation mechanism, greatly shortens the time required by the test, and is beneficial to the rapid development of battery products.
Drawings
Fig. 1 is a schematic flow chart of a method for rapidly testing cycle life of a lithium ion battery according to the present invention.
Detailed Description
As described above, the present invention provides a method for rapidly testing cycle life of a lithium ion battery, the method comprising:
(1) the method comprises the following steps of carrying out discharge treatment on the lithium ion battery, and also comprising a discharge standing step after the discharge is finished;
(2) carrying out constant current charging on the lithium ion battery after the lithium ion battery is discharged and kept still under a low-rate condition, and carrying out constant current charging under the low-rate condition until the design capacity of the lithium ion battery is less than or equal to 80%;
(3) performing constant current charging on the lithium ion battery in the step (2) under the known multiplying power condition, and performing constant current charging to the charging upper limit voltage U under the known multiplying powerOn the upper partSaid upper limit charging voltage UOn the upper partGreater than the known upper limit charging voltage UgOn the upper part；
(4) Performing constant voltage charging on the lithium ion battery in the step (3) to a known cut-off current, wherein the voltage of the constant voltage charging is the charging upper limit voltage UOn the upper part；
(5) The lithium ion battery is in one cycle from the step (1) to the step (4); when the charge-discharge cycle time of the lithium ion battery reaches a threshold value, recording the high-temperature capacity retention rate of the lithium ion battery;
or when the high-temperature capacity retention rate of the lithium ion battery reaches a threshold value, recording the charge-discharge cycle time used by the lithium ion battery, namely realizing the rapid test of the cycle life of the lithium ion battery.
In one embodiment of the present invention, the method is performed by subjecting the lithium ion battery to an environment having a high temperature (e.g., a temperature of 40 ℃ or higher, such as 40-55 ℃, such as 45 ℃).
In one aspect of the present invention, in step (1), the electric discharge treatment may be, for example, an electric discharge step treatment in a high-temperature intermittent cycle process known in the art.
Illustratively, the discharge treatment may be, for example, a discharge treatment of the lithium ion battery at a discharge rate of 0.2 to 6C (e.g., 0.2C, 0.5C, 0.8C, 1C, 1.5C, 2C, 2.5C, 3C, 4C, 5C, or 6C) and discharging to a discharge lower limit voltage ULower part’。
In one embodiment of the present invention, in the step (1), the discharge lower limit voltage U of the discharge treatmentLower partEqual to the known lower limit voltage of discharge UgLower part’。
In one embodiment of the present invention, in step (1), the known discharge lower limit voltage UgLower part' is a discharge lower limit voltage used in a discharge step of a high-temperature intermittent cycle of the battery specified by the terminal manufacturer.
In one embodiment of the present invention, in step (1), the known discharge lower limit voltage UgLower part' is 2.0-3.6V.
In one embodiment of the present invention, in the step (1), the discharge is allowed to stand for 1 to 60 min.
In one aspect of the present invention, in step (2), the low rate is a rate smaller than that of a known constant current charging, and the rate of the known constant current charging refers to a rate adopted in a constant current charging process in a charging step of a battery specified by a terminal manufacturer in a conventional high-temperature intermittent cycle. Illustratively, the known constant current charging rate is, for example, 0.65-0.8C, for example, 0.7C.
In one embodiment of the present invention, in step (2), the low rate is, for example, less than the rate of the known constant current charging by 0.1C or more, for example, less than the rate of the known constant current charging by 0.1C, 0.2C, 0.3C, 0.4C, 0.5C, or 0.6C.
In one embodiment of the present invention, in the step (2), the low magnification is, for example, 0.1 to 0.6C, for example, 0.1C, 0.2C, 0.3C, 0.4C, 0.5C, or 0.6C.
In one aspect of the present invention, in step (2), the design capacity of the lithium ion battery is not particularly limited, and may be, for example, 2000-.
In one embodiment of the present invention, in step (2), when the capacity of the lithium ion battery is less than or equal to 80% of the designed capacity of the lithium ion battery, the battery is charged with a current less than the rate of the known constant current charging, i.e., a low rate, which is mainly set for the purpose of reducing the charging current when the battery is at a low SOC, so that the newly formed SEI film in each charging process can be denser, and the reactive consumption of the available lithium ions in the battery can be accelerated.
In one embodiment of the present invention, in step (2), in each cycle, the low-magnification conditions may be the same or different;
for example, the lithium ion battery is first charged to 80% of its designed capacity with 0.1C, then charged to 4.4V with 0.7C, and then charged to a known cutoff current at a constant voltage of 4.4V.
Also for example, first, charge to 40% of the designed capacity of the lithium ion battery with 0.1C, then charge to 70% of the designed capacity of the lithium ion battery with 0.3C, then charge to 4.4V with 0.7C, and then start constant voltage charge at 4.4V to a known off current.
In one embodiment of the present invention, in step (2), in different recycling processes, the low-magnification conditions may be the same or different;
for example, the operation is repeated several times by first charging to 80% of the designed capacity of the lithium ion battery with 0.1C, then charging to 4.4V with 0.7C, and then charging to a known off-current at a constant voltage of 4.4V.
For example, the first 10 times of the cycle charging process of the lithium ion battery is firstly charged to 50% of the designed capacity of the lithium ion battery by using 0.1C, then charged to 4.38V by using 0.7C, and then the cycle is changed to be charged to 30% of the designed capacity of the lithium ion battery by using 0.2C, then charged to 4.36V by using 0.7C, and then charged to the known cut-off current at the constant voltage of 4.36V.
In one scheme of the invention, in the step (3), the lithium ion battery is subjected to constant current charging under the condition of a known multiplying power, and the lithium ion battery is subjected to constant current charging to the charging upper limit voltage U under the condition of the known multiplying powerOn the upper part。
In one embodiment of the present invention, in the step (3), the charging upper limit voltage U is adjustedOn the upper partGreater than the known upper limit charging voltage UgOn the upper partThe purpose of the method is that the consumption of lithium ion reaction, the decline of electrode materials and the decomposition of electrolyte can be accelerated in the adjusted charging process, and a guarantee is provided for realizing the rapid test of the cycle life of the lithium ion battery.
In one embodiment of the present invention, in the step (3), the charging upper limit voltage UOn the upper partAnd a known upper limit charging voltage UgOn the upper partSatisfies the following relation: 1V is more than or equal to UOn the upper part-UgOn the upper part>0V。
In one aspect of the present invention, in the step (3), the known upper limit charging voltage UgOn the upper partIs the upper limit voltage of charge used in the charging step of the battery high-temperature intermittent cycle specified by the terminal manufacturer.
In one aspect of the present invention, in the step (3), the known upper limit charging voltage UgOn the upper partFor example, it may be 3.6-4.5V.
In one aspect of the present invention, in the step (4), the constant voltage charging is the charging upper limit voltage U in the step (3)On the upper partIs charged at a voltage of (1); various side reactions in the battery can be accelerated in the constant-voltage charging process, and the rapid test of the cycle life of the lithium ion battery is realized.
In one embodiment of the present invention, in the step (4), the known off-current is 0.025C or 0.05C.
In one aspect of the present invention, in the step (4), the time of the constant voltage charging process is the same or different during each cycle, and for example, the time of the constant voltage charging process may be adjusted according to the difference between the time of the discharging process of the step (1), the time of the discharging standing process, and the time of the constant current charging process of the step (2) during each cycle, and thus, the time of the constant voltage charging process may be different during each cycle.
In one embodiment of the present invention, in step (5), the time of each cycle may be the same or different; for example, in step (5), the operations of step (1), step (2), step (3) and step (4) are the same or different in each cycle; for example, the discharging process of step (1), the discharging standing step of step (1), the charging rate of step (2), and the charging upper limit voltage U of step (3) in each cycle processOn the upper partThe constant voltage charging time in step (4) may be the same or different.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The lithium ion battery is manufactured according to the conventional manufacturing process, the positive active material is lithium cobaltate, the negative active material is graphite, and the design capacity of the battery is 4000 mAh. The known upper limit voltage of the lithium ion battery is 4.35V, the known lower limit voltage of the lithium ion battery is 3.0V, the known multiplying power in the constant current charging process is 0.7C, and the known cutoff current is 0.05C.
The lithium ion battery is placed in an environment of 45 ℃, and the test process is as follows:
discharging the fully charged lithium ion battery to 3.0V at a discharge rate of 0.5C, and then discharging and standing for 10 min;
and (3) carrying out charging treatment on the discharged lithium ion battery, firstly charging to 80% of the designed capacity by adopting 0.1C, then charging to 4.4V at the multiplying power of 0.7C, and then carrying out constant voltage charging to the cutoff current of 0.05C at the constant voltage of 4.4V.
The above-mentioned charge and discharge processes were repeated several times, and the results are shown in Table 1, in which the cycle time corresponding to the case where the capacity retention rate reached 90% was recorded.
Example 2
The lithium ion battery was the same as in example 1, and the test method was different from that in example 1.
The test method of this example is as follows:
the lithium ion battery is placed in an environment at 50 ℃, and the test process is as follows:
discharging the fully charged lithium ion battery to 3.0V at a discharge rate of 0.5C, and then discharging and standing for 30 min;
and (3) performing charging treatment on the discharged lithium ion battery, firstly charging to 40% of the designed capacity by using 0.1C, then charging to 70% of the designed capacity by using 0.3C, then charging to 4.4V by using 0.7C, and then starting constant voltage charging to the cutoff current of 0.05C at 4.4V.
The above-mentioned charge and discharge processes were repeated several times, and the results are shown in Table 1, in which the cycle time corresponding to the case where the capacity retention rate reached 90% was recorded.
Example 3
The lithium ion battery was the same as in example 1, and the test method was different from that in example 1.
The test method of this example is as follows:
the lithium ion battery is placed in an environment at 50 ℃, and the test process is as follows:
discharging the fully charged lithium ion battery to 3.0V at a discharge rate of 0.5C, and then discharging and standing for 60 min;
and (3) carrying out charging treatment on the discharged lithium ion battery, wherein the charging process of the first 50 cycles of the battery is firstly to be charged to 50% of the designed capacity by using 0.1C, then to be charged to 4.38V by using 0.7C, then to be charged to the cutoff current of 0.05C at the constant voltage of 4.38V, and then to be charged to 30% of the designed capacity by using 0.2C, then to be charged to 4.36V by using 0.7C, and then to be charged to the cutoff current of 0.05C at the constant voltage of 4.36V.
The above-mentioned charge and discharge processes were repeated several times, and the results are shown in Table 1, in which the cycle time corresponding to the case where the capacity retention rate reached 90% was recorded.
Example 4
The lithium ion battery was the same as in example 1, and the test method was different from that in example 1.
The test method of this example is as follows:
the lithium ion battery is placed in an environment with the temperature of 55 ℃, and the test process is as follows:
discharging the fully charged lithium ion battery to 3.0V at a discharge rate of 0.5C, and then discharging and standing for 30 min;
and (3) charging the discharged lithium ion battery, wherein the charging process of the lithium ion battery in the previous 20 cycles is as follows: charging to 30% of the designed capacity at 0.1C, charging to 4.43V at 0.7C, and then charging to 0.05C at constant voltage of 4.43V; the subsequent cycle was changed to 0.1C to 40% of the designed capacity, and then 0.7C to 4.38V, and then constant voltage charging was performed at 4.38V to 0.05C of the cutoff current, and the corresponding cycle number was recorded when the capacity retention rate reached 90%, and the results are shown in table 1.
Example 5
The lithium ion battery was the same as in example 1, and the test method was different from that in example 1.
The test method of this example is as follows:
the lithium ion battery is placed in an environment of 45 ℃, and the test process is as follows:
discharging the fully charged lithium ion battery to 3.0V at a discharge rate of 0.5C, and then discharging and standing for 30 min;
and (3) charging the discharged lithium ion battery, wherein the charging process of the previous 40 cycles of the battery is firstly to 60% of the designed capacity by using 0.3C, then to 4.4V by using 0.7C, then to start constant voltage charging at 4.4V to the known cut-off current of 0.05C, and then the cycle is changed to 0.2C to 30% of the designed capacity by using 0.7C to 4.38V, and then to start constant voltage charging at 4.38V to the known cut-off current of 0.05C.
The above-mentioned charge and discharge processes were repeated several times, and the results are shown in Table 1, in which the cycle time corresponding to the case where the capacity retention rate reached 90% was recorded.
Comparative example 1
The lithium ion battery was the same as in example 1, and the test method was different from that in example 1.
The test method of this comparative example is as follows:
the lithium ion battery is placed in an environment of 45 ℃, and the test process is as follows:
discharging the fully charged lithium ion battery to 3.0V at a discharge rate of 0.5C, and then discharging and standing for 10 min;
the discharged lithium ion battery was charged to 4.35V at 0.7C rate, and then was subjected to constant voltage charging at 4.35V constant voltage, and the time of constant voltage charging was adjusted so that the total time of each cycle was 24 hours, and the cycle was repeated a plurality of times in the above-described charge and discharge process, and the cycle time corresponding to the capacity retention rate of 90% was recorded, and the results are shown in table 1.
TABLE 1
Table 1 shows the cycle time and the room-temperature capacity recovery rate used when the high-temperature capacity retention rates of the batteries of the examples of the present invention and the comparative examples were the same. The accelerated test scheme greatly shortens the time required by high-temperature intermittent cycle life evaluation, and when the high-temperature capacity retention rate of the accelerated test battery is close to that of the conventional test battery, the normal-temperature capacity recovery rate is also close to that of the conventional test battery, so that the capacity fading mechanism of the accelerated test battery is proved to be not obviously different from that of the conventional test battery.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of rapidly testing the cycle life of a lithium ion battery, the method comprising:
(1) the method comprises the following steps of carrying out discharge treatment on the lithium ion battery, and also comprising a discharge standing step after the discharge is finished;
(2) carrying out constant current charging on the lithium ion battery after the lithium ion battery is discharged and kept still under a low-rate condition, and carrying out constant current charging under the low-rate condition until the design capacity of the lithium ion battery is less than or equal to 80%;
(3) performing constant current charging on the lithium ion battery in the step (2) under the known multiplying power condition, and performing constant current charging to the charging upper limit voltage U under the known multiplying powerOn the upper partSaid upper limit charging voltage UOn the upper partGreater than the known upper limit charging voltage UgOn the upper part；
(4) Performing constant voltage charging on the lithium ion battery in the step (3) to a known cut-off current, wherein the voltage of the constant voltage charging is the charging upper limit voltage UOn the upper part；
(5) The lithium ion battery is in one cycle from the step (1) to the step (4); when the charge-discharge cycle time of the lithium ion battery reaches a threshold value, recording the high-temperature capacity retention rate of the lithium ion battery;
or when the high-temperature capacity retention rate of the lithium ion battery reaches a threshold value, recording the charge-discharge cycle time used by the lithium ion battery, namely realizing the rapid test of the cycle life of the lithium ion battery.
2. The method of claim 1, wherein the method is performed by subjecting the lithium ion battery to an environment above 40 ℃.
3. The method according to claim 1 or 2, wherein in step (1), the discharge lower limit voltage U of the discharge treatmentLower partEqual to the known lower limit voltage of discharge UgLower part'; said known lower limit voltage of discharge UgLower part' is 2.0-3.6V.
4. The method according to any one of claims 1 to 3, wherein in the step (1), the discharge is allowed to stand for 1 to 60 min.
5. The method according to any of claims 1-4, wherein in step (2), the low rate is a rate less than known constant current charging, such as less than 0.1C or more.
6. The method according to any of claims 1-5, wherein in step (2), the lithium ion battery has a design capacity of 2000 and 8000mAh, such as 4000 mAh.
7. The method according to any one of claims 1 to 6, wherein in step (2), the low-rate conditions may be the same or different during each cycle; the low-magnification conditions may be the same or different during different cycles.
8. The method according to any one of claims 1 to 7Wherein, in the step (3), the charging upper limit voltage UOn the upper partAnd a known upper limit charging voltage UgOn the upper partSatisfies the following relation: 1V is more than or equal to UOn the upper part-UgOn the upper part>0V；
In the step (3), the known charging upper limit voltage UgOn the upper partFor example, it may be 3.6-4.5V.
9. The method of any one of claims 1-8, wherein in step (4), the known cutoff current is 0.025C or 0.05C.
10. The method according to any one of claims 1 to 9, wherein in step (4), the time of the constant voltage charging process is the same or different during each cycle; in the step (5), the time of each cycle process may be the same or different.
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