CN112240983A - Method and device for detecting lithium separation of battery - Google Patents
Method and device for detecting lithium separation of battery Download PDFInfo
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- CN112240983A CN112240983A CN202011000928.1A CN202011000928A CN112240983A CN 112240983 A CN112240983 A CN 112240983A CN 202011000928 A CN202011000928 A CN 202011000928A CN 112240983 A CN112240983 A CN 112240983A
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- G01R31/385—Arrangements for measuring battery or accumulator variables
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- 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
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Abstract
The invention provides a battery lithium analysis detection method and a detection device thereof, wherein the method comprises the following steps: acquiring a capacity value and an internal resistance value of the battery to be tested at 15-35 ℃; heating the battery to be tested at high temperature, and calculating the capacity change rate and the internal resistance change rate of the battery to be tested; selecting a plurality of unused lithium ion batteries as test batteries, carrying out cyclic charge and discharge on the test batteries at the temperature lower than 0 ℃, and then obtaining the capacity values C of the test batteries at the temperature of 15-35 DEG C0' and internal resistance value R0'; heating the test batteries at high temperature, and calculating the capacity change rate and the internal resistance change rate of the test batteries, wherein the minimum value of the capacity change rates is used as a preset capacity change rate, and the minimum value of the internal resistance change rates is used as a preset internal resistance change rate; if it is as describedAnd if the capacity and the internal resistance change rate of the battery to be tested are both larger than or equal to the preset capacity and internal resistance change rate, judging that lithium separation occurs inside the battery to be tested.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a battery lithium analysis detection method and a detection device thereof.
Background
Under extreme conditions such as low-temperature charging, high-rate charging, overcharge, and the like, lithium ions in the lithium ion battery are easily precipitated as metal on the surface of the negative electrode to form metal lithium, and the phenomenon is called lithium precipitation. The lithium precipitation leads to a reduction of the available lithium ions inside the battery, causing a rapid decay of the battery capacity. Because the precipitated metal lithium has poor thermal stability, the metal lithium is easy to generate heat reaction with electrolyte in the normal working temperature range (less than 50 ℃) of the lithium ion battery, and the abnormal self-heat generation of the battery is caused. On the other hand, the precipitated lithium metal may grow into lithium dendrites to further pierce the separator, which causes internal short circuit of the battery and seriously affects the safety performance of the battery system. Therefore, in order to ensure the normal use of the battery system and reduce the safety risk, the lithium analysis of the battery needs to be detected in time, and the fault battery which generates the lithium analysis is screened out.
The existing battery detection method detects whether the battery separates lithium or not depending on voltage signals generated in the lithium separation process of the battery or in two cycles after the lithium separation. Or the change rule of the battery capacity and internal resistance data at different service life stages of the battery is used for judging whether the battery separates lithium, the change rule is difficult to obtain in the actual process, the rules of the batteries of different manufacturers and different systems are inconsistent, a large number of preliminary calibration experiments are needed, and the lithium separation condition of the battery is difficult to detect quickly and accurately.
Disclosure of Invention
Therefore, it is necessary to provide a method and an apparatus for detecting lithium deposition in a battery, which can detect whether the battery deposits lithium rapidly and accurately, and have a wide application range.
In one aspect of the invention, a method for detecting lithium separation of a battery is provided, which comprises the following steps:
obtaining the capacity value C of the battery to be tested at 15-35 DEG C0And internal resistance value R0；
Heating the battery to be tested at high temperature to obtain the capacity value C of the battery to be tested after high-temperature heating1And internal resistance value R1The high-temperature heating temperature is more than or equal to 50 ℃;
according to the formula
Calculating the capacity change rate deltaC and the internal resistance change rate deltaR of the battery to be tested;
selecting a plurality of unused lithium ion batteries with the same type as the battery to be tested as test batteries, carrying out cyclic charge and discharge on the test batteries at the temperature lower than 0 ℃, and then obtaining the capacity values C of the test batteries at the temperature of 15-35 DEG C0' and internal resistance value R0’；
Heating a plurality of test batteries at high temperature to obtain a plurality of capacity values C of the test batteries after high-temperature heating1' and internal resistance value R1', the temperature of high-temperature heating is more than or equal to 50 ℃;
according to the formula
Calculating capacity change rates deltaC 'and internal resistance change rates deltaR' of the plurality of test batteries, wherein the minimum value of the capacity change rates is used as a preset capacity change rate, and the minimum value of the internal resistance change rates is used as a preset internal resistance change rate;
and comparing the capacity change rate and the internal resistance change rate of the battery to be detected with the preset capacity change rate and the preset internal resistance change rate respectively, and if the capacity change rate of the battery to be detected is greater than or equal to the preset capacity change rate and the internal resistance change rate of the battery to be detected is greater than or equal to the preset internal resistance change rate, judging that lithium separation occurs inside the battery to be detected.
In one embodiment, the capacity value C0、C0’、C1、C1The acquisition method of the' comprises the steps of fully charging the battery in a constant-current and constant-voltage mode, standing, and discharging the battery in a constant-current mode to the discharge cut-off voltage of the lithium ion battery.
In one embodiment, the internal resistance value R0、R0’、R1、R1The acquisition method comprises the steps of measuring the direct current internal resistance value of the battery by adopting a hybrid power pulse capability characteristic test method or a current step test method when the battery is fully charged or discharged to a cut-off voltage, or measuring the alternating current impedance of the battery under 0.01 Hz-1000 Hz when the battery is fully charged or discharged to the cut-off voltage.
In one embodiment, the step of heating at a high temperature comprises:
heating the battery to a temperature T1At a temperature T1Keeping the temperature for T hours, and cooling to T2Wherein, T1At 50 ℃ or higher, T2T is less than or equal to 35 ℃ and is more than or equal to 0.5 and less than or equal to 8.
In one embodiment, T1At 50-80 ℃ and T2Is 15-35 ℃.
In one embodiment, the heating includes heating external to the battery and/or internal to the battery.
In one embodiment, the temperature of the cyclic charge and discharge of the plurality of test batteries is-30 ℃ to 0 ℃, and the cycle frequency is 1 to 200.
In one embodiment, the test cell is at least 10 unused lithium ion cells.
On the other hand, the invention also provides a detection device based on the battery lithium separation detection method, which comprises a battery tester, a controllable temperature box and a computer, wherein the battery tester comprises a capacity test module and an internal resistance test module, the controllable temperature box is used for heating or cooling the battery, and the computer controls the battery tester to perform capacity and internal resistance tests and control the temperature in the controllable temperature box.
The present invention further provides a computer-readable storage medium for storing a computer instruction, a program, a set of codes, or a set of instructions that, when executed on a computer, causes the computer to perform the method for detecting lithium evolution from a battery.
The present invention still further provides an electronic device, comprising:
one or more processors; and
a storage device storing one or more programs,
when executed by the one or more processors, cause the one or more processors to implement the battery lithium analysis detection method.
According to the method for detecting the lithium separation of the battery, the capacity and the internal resistance of the battery to be detected before and after high-temperature heating are obtained by heating the battery to be detected at high temperature, the capacity change rate and the internal resistance change rate of the battery to be detected are calculated, and whether the lithium separation occurs in the battery to be detected is judged by comparing the capacity change rate and the internal resistance change rate of the battery to be detected with the preset capacity change rate and the internal resistance change rate. The lithium ion battery is charged and discharged circularly at a low temperature lower than 0 ℃, and lithium can be separated out from the lithium ion battery. The metal lithium precipitated in the lithium ion battery has the characteristics of poor thermal stability and low self-heat-generation temperature, and the metal lithium is dissociated in the electrolyte and can react with the electrolyte to cause capacity attenuation and internal resistance increase of the battery. The reaction of the precipitated lithium metal and the electrolyte can be accelerated by heating at a high temperature of more than or equal to 50 ℃, and the capacity change and the internal resistance change of the battery are obvious. The inventor discovers for the first time that a plurality of unused lithium ion batteries are subjected to cyclic charge and discharge at the temperature of lower than 0 ℃ so that lithium precipitation occurs in the unused lithium ion batteries, capacity values and internal resistance values of the unused lithium ion batteries at the temperature of 15-30 ℃ are obtained, and then high-temperature heating is carried out to obtain capacity change rates and internal resistance change rates, wherein the minimum capacity change rate and internal resistance change rate are critical values of lithium precipitation of the batteries, and the minimum capacity change rate and internal resistance change rate can be selected as preset capacity change rates and preset internal resistance change rates. By obtaining the capacity value and the internal resistance value of the lithium ion battery to be tested at 15-35 ℃, then carrying out high-temperature heating, and comparing the capacity change rate and the internal resistance change rate of the battery before and after the high-temperature heating with the preset capacity change rate and internal resistance change rate, whether lithium separation occurs in the lithium ion battery can be judged. The battery lithium analysis detection method provided by the invention can be used for rapidly preparing and judging whether lithium is analyzed in the battery, and is wide in application range.
Drawings
FIG. 1 is a flow chart of a method for detecting lithium deposition in a battery according to the present invention;
FIG. 2 is a schematic structural diagram of the lithium analysis detection device for a battery according to the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The capacity value of the invention is 1C multiplying power discharge capacity when the battery is in a full-charge state to cut-off voltage.
Referring to fig. 1, an embodiment of the invention provides a method for detecting lithium deposition in a battery, including the following steps:
s10, obtaining the initial capacity value C of the battery to be measured at 15-35 DEG C0And an initial internal resistance value R0；
S20, heating the battery to be tested at high temperature to obtain the capacity value C of the battery to be tested after being heated at high temperature1And internal resistance value R1The high-temperature heating temperature is more than or equal to 50 ℃;
s30 according to the formula
Calculating the capacity change rate deltaC and the internal resistance change rate deltaR of the battery to be tested;
s40, selecting a plurality of unused lithium ion batteries with the same type as the batteries to be tested as test batteries, carrying out cyclic charge and discharge on the test batteries at the temperature lower than 0 ℃, and then obtaining the capacity values C of the test batteries at the temperature of 15-35 DEG C0' and internal resistance value R0’；
S50, heating the plurality of test batteries at high temperature to obtain the capacity value C of the plurality of test batteries after being heated at high temperature1' and internal resistance value R1', the temperature of high-temperature heating is more than or equal to 50 ℃;
s60 according to the formula
Calculating the capacity change rate deltaC 'and the internal resistance change rate deltaR' of the plurality of test batteries, wherein the minimum value of the capacity change rates is used as a preset capacity change rate, and the minimum value of the internal resistance change rates is used as a preset capacity change ratePresetting the internal resistance change rate;
and S70, comparing the capacity change rate and the internal resistance change rate of the battery to be tested with the preset capacity change rate and the preset internal resistance change rate respectively, and if the capacity change rate of the battery to be tested is larger than or equal to the preset capacity change rate and the internal resistance change rate of the battery to be tested is larger than or equal to the preset internal resistance change rate, judging that lithium analysis occurs inside the battery to be tested.
According to the method for detecting the lithium separation of the battery, provided by the embodiment of the invention, the capacity and the internal resistance of the battery to be detected before and after high-temperature heating are obtained by heating the battery to be detected at high temperature, the capacity change rate and the internal resistance change rate of the battery to be detected are calculated, and whether the lithium separation occurs in the battery to be detected is judged by comparing the capacity change rate and the internal resistance change rate of the battery to be detected with the preset capacity change rate and the internal resistance change rate. The lithium ion battery is charged and discharged circularly at a low temperature lower than 0 ℃, and lithium can be separated out from the lithium ion battery. The metal lithium precipitated in the lithium ion battery has the characteristics of poor thermal stability and low self-heat-generation temperature, and the metal lithium is dissociated in the electrolyte and can react with the electrolyte to cause capacity attenuation and internal resistance increase of the battery. The reaction of the precipitated lithium metal and the electrolyte can be accelerated by heating at a high temperature of more than or equal to 50 ℃, and the capacity change and the internal resistance change of the battery are obvious. The inventor discovers for the first time that a plurality of unused lithium ion batteries are subjected to cyclic charge and discharge at the temperature of lower than 0 ℃ so that lithium precipitation occurs in the unused lithium ion batteries, capacity values and internal resistance values of the unused lithium ion batteries at the temperature of 15-30 ℃ are obtained, and then high-temperature heating is carried out to obtain capacity change rates and internal resistance change rates, wherein the minimum capacity change rate and internal resistance change rate are critical values of lithium precipitation of the batteries, and the minimum capacity change rate and internal resistance change rate can be selected as preset capacity change rates and preset internal resistance change rates. By obtaining the capacity value and the internal resistance value of the lithium ion battery to be tested at 15-35 ℃, then carrying out high-temperature heating, and comparing the capacity change rate and the internal resistance change rate of the battery before and after the high-temperature heating with the preset capacity change rate and internal resistance change rate, whether lithium separation occurs in the lithium ion battery can be judged. The battery lithium analysis detection method provided by the invention can be used for rapidly preparing and judging whether lithium is analyzed in the battery, and is wide in application range.
The high-temperature heating step involved in the above method for detecting lithium evolution from a battery may comprise:
heating the battery to a temperature T1At a temperature T1Keeping the temperature for T hours, and cooling to T2. Wherein, T1At 50 ℃ or higher, T2T is less than or equal to 35 ℃ and is more than or equal to 0.5 and less than or equal to 8.
Preferably, T1Is any value between 50 ℃ and 80 ℃, and can include, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, T2The temperature can be any value between 15 ℃ and 35 ℃, and can include, for example, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃.
t may be any value between 0.5 and 8, and may further include 1, 2, 3, 4, 5, 6, and 7, for example. Preferably, the holding time t is 0.5 to 3 hours.
The battery heating method may be heating the outside of the battery or heating the inside of the battery.
The method of heating the outside of the battery may be heating the battery by an external heat source. Methods for heating the outside of the battery include, but are not limited to, heating the battery with air, liquid, phase-change material, etc. working medium capable of generating heat source, heating the battery with electric heater, such as controlled temperature box, electric heating sheet, electric heating sleeve, electric heating film, etc. When the liquid is used as a working medium capable of generating a heat source to heat the battery, the non-contact heating or the immersion heating can be adopted.
The method of heating the inside of the battery may be to heat the battery by joule heat generated by passing current through a conductor having a certain resistance value, the conductor being the battery itself. The method for heating the inside of the battery includes, but is not limited to, a direct current discharge heating method, an alternating current discharge heating method, a pulse charge heating method, a pulse discharge heating method, and an internal short circuit heating method.
The direct current discharging heating method is to directly apply a direct current discharging or charging current to the battery, and heat the battery through the heat generated by the battery in the discharging process.
The ac discharge heating method is to apply an ac current across the battery and to heat the battery by using the internal impedance of the battery. The heating speed is faster by the alternating current discharge heating method.
The pulse discharge heating method is a method of discontinuous large current discharge, and realizes heating of the lithium ion battery through heat generated by ohmic impedance in the battery.
The internal short circuit heating method is a method of forming a short circuit inside a battery and heating the battery by heat generated by the short circuit.
In a preferred embodiment, the battery heating method is a pulse discharge heating method, and the method can realize more uniform temperature distribution in the battery, effectively avoid the problem of capacity degradation caused by the temperature gradient in the battery, thereby obtaining more accurate capacity value and internal resistance value and enabling the battery lithium analysis detection method to be more accurate.
In another preferred embodiment, the battery is heated by using a controllable temperature box to heat the outside of the battery. The controllable temperature box can control the heating temperature or the cooling temperature of the battery, and is more convenient, faster and more controllable to operate.
The capacity value C of the battery to be tested in the step S100And step S20, the capacity value C of the battery to be tested after being heated at high temperature1Initial capacity values C of a plurality of the test batteries in step S400', step S50 for a plurality of said test cells after high temperature heating capacity value C1The acquisition method of' can be carried out by the following method:
fully charging the battery in a constant current and constant voltage mode, standing, and discharging the battery to the discharge cut-off voltage of the lithium ion battery in a constant current mode. The capacity value is the discharge capacity of the battery from a full-charge state to a cut-off voltage.
The current during charging is rated current, and the voltage is rated voltage. The current at the time of the discharge is also a rated current.
The standing time may be 5min to 180 min.
The data obtained by adopting the capacity value test is more accurate.
Step S10, the internal resistance value R of the battery to be tested0Step S20, the internal resistance value R of the battery to be tested after being heated at high temperature1Initial internal resistance values R of a plurality of the test cells in step S400', step S50 shows internal resistance R of a plurality of said test cells after being heated at high temperature1The acquisition method of' may be any one of the following methods:
when the battery is fully charged or discharged to a cut-off voltage, a Hybrid Pulse Power Characteristics (HPPC) test method or a current step test method is adopted to measure the direct current internal resistance value of the battery. Alternatively, the first and second electrodes may be,
when the battery is fully charged or discharged to cut-off voltage, the alternating current impedance of the battery under 0.01 Hz-1000 Hz is measured.
In step S40, the number of cycles of the cyclic charge and discharge of the plurality of test batteries is 1 to 200.
Further, the temperature for the cyclic charge and discharge of the plurality of test cells is preferably-30 ℃ to 0 ℃, more preferably-5 ℃.
A plurality of capacity values C of the test cell0' and internal resistance value R0' measurement at 15 ℃ to 35 ℃ can be carried out by any of the above-mentioned capacity measuring methods or internal resistance measuring methods.
In order to make the preset capacity change rate and internal resistance change rate more accurate, the number of samples of the test battery is at least 10, preferably more than 20, and more preferably more than 40.
In an embodiment, the predetermined capacity change rate is 1%, and the predetermined internal resistance change rate is 10%.
In step S70, the condition that no lithium deposition occurs inside the battery to be tested includes:
and if the capacity change rate of the battery to be tested is greater than or equal to the preset capacity change rate and the internal resistance change rate of the battery to be tested is smaller than the preset internal resistance change rate, judging that no lithium precipitation occurs in the battery to be tested.
And if the capacity change rate of the battery to be tested is smaller than the preset capacity change rate and the internal resistance change rate of the battery to be tested is larger than or equal to the preset internal resistance change rate, judging that no lithium precipitation occurs in the battery to be tested.
And if the capacity change rate of the battery to be tested is smaller than the preset capacity change rate and the internal resistance change rate of the battery to be tested is also smaller than the preset internal resistance change rate, judging that no lithium precipitation occurs in the battery to be tested.
The detection method for battery lithium separation provided by the embodiment of the invention is suitable for all kinds of lithium ion batteries, including polymer lithium ion batteries, liquid lithium ion batteries or solid lithium ion batteries. The positive electrode material of the battery is preferably a lithium manganate-based or ternary-system active material. The battery to be tested and the test battery are the same in type and have the same components.
In some embodiments, the positive active material of the lithium ion battery may be LiFePO4、LiMn2O2、LiNixCoyMnzO2(0 < x, y, z < 1, and x + y + z ═ 1). The negative active material of the lithium ion battery can be one or more of graphite, mesocarbon microbeads, hard carbon and soft carbon.
The electrolyte may include an electrolyte and a non-aqueous organic solvent. The electrolyte is preferably LiPF6、LiBF4、LiSbF6、LiAsF6. The non-aqueous organic solvent can be carbonate, ester and ether. Among them, carbonates such as Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) can be preferably used. In some embodiments, the electrolyte is LiPF6The non-aqueous electrolyte of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) with the concentration of 1mol/L, wherein the volume ratio of EC to DMC is 1: 1.
The conductive additive may be carbon black (e.g., acetylene black or Ketjen black) or carbon nanotubes.
The binder may be one or more of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), Styrene Butadiene Rubber (SBR).
The diaphragm can be a microporous membrane made of polyethylene and polypropylene; a multi-layer film of a porous polyethylene film and polypropylene; nonwoven fabrics formed of polyester fibers, aramid fibers, glass fibers, and the like; and a base film formed by adhering ceramic fine particles such as silica, alumina, and titania to the surfaces thereof.
Referring to fig. 2, the present invention further provides a battery lithium analysis detection apparatus, which includes a battery tester 11, a controllable temperature box 12 and a computer 13.
The battery tester 11 includes a capacity testing module 100 and an internal resistance testing module 200. The capacity testing module 100 is internally provided with a capacity tester, and the internal resistance testing module 200 is internally provided with an internal resistance tester.
The temperature-controllable box 12 is used for heating or cooling the battery.
The computer 13 controls the battery tester 11 to perform capacity and internal resistance tests and controls the temperature within the controllable temperature box 12.
The test data of the capacity test module 100 and the internal resistance test module 200 may be stored to the computer in real time.
The present invention also provides a computer-readable storage medium for storing a computer instruction, a program, a set of codes, or a set of instructions which, when run on a computer, causes the computer to perform the battery lithium analysis detection method as described above.
Any combination of one or more computer-readable media may be employed. The computer readable medium may be a computer readable signal medium or a computer readable storage medium. A computer readable storage medium may be, for example, but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, or device, or any combination of the foregoing. More specific examples (a non-exhaustive list) of the computer readable storage medium would include the following: an electrical connection having one or more wires, a portable computer diskette, a hard disk, a Random Access Memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or flash memory), an optical fiber, a portable compact disc read-only memory, an optical storage device, a magnetic storage device, or any suitable combination of the foregoing. In the context of this document, a computer readable storage medium may be any tangible medium that can contain, or store a program for use by or in connection with an instruction execution system, apparatus, or device.
A computer readable signal medium may include a propagated data signal with computer readable program code embodied therein, for example, in baseband or as part of a carrier wave. Such a propagated data signal may take any of a variety of forms, including, but not limited to, electro-magnetic, optical, or any suitable combination thereof. A computer readable signal medium may also be any computer readable medium that is not a computer readable storage medium and that can communicate, propagate, or transport a program for use by or in connection with an instruction execution system, apparatus, or device.
Program code embodied on a computer readable medium may be transmitted using any appropriate medium, including but not limited to wireless, wireline, optical fiber cable, RF, etc., or any suitable combination of the foregoing.
Computer program code for carrying out operations for aspects of the present disclosure may be written in any combination of one or more programming languages, including an object oriented programming language such as Java, Smalltalk, C + +, and conventional procedural programming languages, such as the "C" programming language or similar programming languages. The program code may execute entirely on the user's computer, partly on the user's computer, as a stand-alone software package, partly on the user's computer and partly on a remote computer or entirely on the remote computer or server. In the case of a remote computer, the remote computer may be connected to the user's computer through any type of network, including a Local Area Network (LAN) or a Wide Area Network (WAN), or the connection may be made to an external computer (for example, through the Internet using an Internet service provider).
The present invention further provides an electronic device comprising:
one or more processors; and
a storage device storing one or more programs,
when executed by the one or more processors, cause the one or more processors to implement the battery lithium analysis detection method as described above.
Optionally, the electronic device may further comprise a transceiver. The processor is coupled to the transceiver, such as via a bus. It should be noted that the transceiver in practical application is not limited to one, and the structure of the electronic device does not constitute a limitation to the embodiment of the present invention.
The processor may be a CPU, general purpose processor, DSP, ASIC, FPGA or other programmable logic device, transistor logic device, hardware component, or any combination thereof. Which may implement or perform the various illustrative logical blocks, modules, and circuits described in connection with the disclosure. A processor may also be a combination of computing functions, e.g., comprising one or more microprocessors, a DSP and a microprocessor, or the like.
A bus may include a path that transfers information between the above components. The bus may be a PCI bus or an EISA bus, etc. The bus may be divided into an address bus, a data bus, a control bus, etc. The memory 802 may be, but is not limited to, a ROM or other type of static storage device that can store static information and instructions, a RAM or other type of dynamic storage device that can store information and instructions, an EEPROM, a CD-ROM or other optical disk storage, optical disk storage (including compact disk, laser disk, optical disk, digital versatile disk, blu-ray disk, etc.), a magnetic disk storage medium or other magnetic storage device, or any other medium that can be used to carry or store desired program code in the form of instructions or data structures and that can be accessed by a computer.
The following are specific examples, which are intended to provide further detailed description of the present invention and to assist those skilled in the art and researchers in understanding the present invention, and the technical conditions and the like are not intended to limit the present invention. Any modification made within the scope of the claims of the present invention is within the scope of the claims of the present invention.
Example 1
1. And taking 40 unused batteries, testing the capacity change rate deltaC 'and the internal resistance change rate deltaR' of each battery, and obtaining the preset capacity change rate and the preset internal resistance change rate.
(1) The 40 batteries are respectively placed in a controllable temperature box 12 in the battery lithium precipitation detection device and are electrically connected with a battery tester 11. The temperature in the temperature-controllable box 12 is adjusted to-5 ℃, the charging is carried out in a constant-current and constant-voltage mode at-5 ℃ (the current is the rated current, and the voltage is the rated voltage), after the charging is fully carried out, the discharging is carried out to the cut-off voltage in a constant-current (rated current) mode, and the charging and discharging are repeated for 10 times. Then, the temperature in the temperature-controllable oven 12 is adjusted to 15 ℃, the temperature is charged at 15 ℃ in a constant-current and constant-voltage manner (the current is the rated current, and the voltage is the rated voltage), after the temperature is fully charged, the temperature is discharged to the cut-off voltage in a constant-current (rated current) manner, and a capacity value C is read by a capacity tester built in the battery tester 110' switching to the internal resistance test module 200, and measuring the internal resistance value R of the battery by adopting a hybrid power pulse capability characteristic test method0’。
(2) The temperature in the temperature-controllable chamber 12 was adjusted to 80 ℃, the temperature was maintained at 80 ℃ for 3 hours, and then the temperature was adjusted to 30 ℃ to cool the battery to 30 ℃. Adopting the same capacity and internal resistance test method in the step (1) to test the capacity value C of the battery at the moment1' and internal resistance value R1’。
(3) Calling the capacity value and internal resistance value test data of 40 batteries on a computer, counting the data, and calculating according to a formula
The capacity change rate Δ C 'and the internal resistance change rate Δ R' of 40 batteries were calculated, respectively. Wherein the minimum capacity change rate is 1%, and the minimum internal resistance change rate is 10%.
The preset capacity change rate is 1%, and the preset internal resistance change rate is 10%.
2. And taking 17 batteries, numbering 1-17, wherein No. 1-5 are unused new batteries, and No. 6-17 are known batteries for internally separating lithium. The 17 batteries are operated according to the following steps:
(1) the 17 batteries are respectively placed in a controllable temperature box 12 in the battery lithium separation detection device and are electrically connected with a battery tester 11. Adjusting the temperature in the temperature-controllable box 12 to 15 ℃, charging in a constant-current and constant-voltage manner (current is rated current and voltage is rated voltage) at 15 ℃, discharging in a constant-current (rated current) manner to cut-off voltage after full charging, and reading a capacity value C by a capacity tester built in the battery tester 110Then, the internal resistance value is switched to the internal resistance test module 200, and the internal resistance value R of the battery is measured by adopting a hybrid power pulse capability characteristic test method0。
(2) The temperature in the temperature-controllable chamber 12 was adjusted to 80 ℃, the temperature was maintained at 80 ℃ for 3 hours, and then the temperature was adjusted to 30 ℃ to cool the battery to 30 ℃. Adopting the same capacity and internal resistance test method in the step (1) to test the capacity value C of the battery at the moment1And internal resistance value R1。
(3) The capacity value and internal resistance value test data of 17 batteries are called on a computer, the data are counted, and the formula is used for calculating the capacity value and the internal resistance value test data
The capacity change rate Δ C and the internal resistance change rate Δ R of 17 batteries were calculated, respectively.
The results are shown in table 1 below:
TABLE 1
As can be seen from table 1, the lithium analysis of the battery determined by the method for detecting lithium analysis of a battery according to the present invention is consistent with the actual situation. The battery lithium analysis detection method provided by the invention can quickly and accurately realize battery lithium analysis detection.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A battery lithium separation detection method is characterized by comprising the following steps:
obtaining the capacity value C of the battery to be tested at 15-35 DEG C0And internal resistance value R0；
Heating the battery to be tested at high temperature to obtain the capacity value C of the battery to be tested after high-temperature heating1And internal resistance value R1The high-temperature heating temperature is more than or equal to 50 ℃;
according to the formula
Calculating the capacity change rate deltaC and the internal resistance change rate deltaR of the battery to be tested;
selecting a plurality of unused lithium ion batteries with the same type as the battery to be tested as test batteries, carrying out cyclic charge and discharge on the test batteries at the temperature lower than 0 ℃, and then obtaining the capacity values C of the test batteries at the temperature of 15-35 DEG C0' and internal resistance value R0’；
Heating a plurality of test batteries at high temperature to obtain a plurality of capacity values C of the test batteries after high-temperature heating1' and internal resistance value R1', temperature of said high-temperature heatingThe degree is more than or equal to 50 ℃;
according to the formula
Calculating capacity change rates deltaC 'and internal resistance change rates deltaR' of the plurality of test batteries, wherein the minimum value of the capacity change rates is used as a preset capacity change rate, and the minimum value of the internal resistance change rates is used as a preset internal resistance change rate;
and comparing the capacity change rate and the internal resistance change rate of the battery to be detected with the preset capacity change rate and the preset internal resistance change rate respectively, and if the capacity change rate of the battery to be detected is greater than or equal to the preset capacity change rate and the internal resistance change rate of the battery to be detected is greater than or equal to the preset internal resistance change rate, judging that lithium separation occurs inside the battery to be detected.
2. The method for detecting lithium deposition in a battery according to claim 1, wherein the capacity value C is0、C0’、C1、C1The acquisition method of the' comprises the steps of fully charging the battery in a constant-current and constant-voltage mode, standing, and discharging the battery in a constant-current mode to the discharge cut-off voltage of the lithium ion battery.
3. The method for detecting lithium deposition in a battery according to claim 1, wherein the internal resistance value R is0、R0’、R1、R1The acquisition method comprises the steps of measuring the direct current internal resistance value of the battery by adopting a hybrid power pulse capability characteristic test method or a current step test method when the battery is fully charged or discharged to a cut-off voltage, or measuring the alternating current impedance of the battery under 0.01 Hz-1000 Hz when the battery is fully charged or discharged to the cut-off voltage.
4. The method for detecting lithium deposition in a battery according to claim 1, wherein the step of heating at a high temperature comprises:
heating the battery to a temperature T1At temperature ofT1Keeping the temperature for T hours, and cooling to T2Wherein, T1At 50 ℃ or higher, T2T is less than or equal to 35 ℃ and is more than or equal to 0.5 and less than or equal to 8.
5. The method for detecting lithium deposition from a battery according to claim 4, wherein T is1At 50-80 ℃ and T2Is 15-35 ℃.
6. The battery lithium analysis detection method according to claim 4, wherein the heating comprises heating outside the battery and/or heating inside the battery.
7. The method for detecting lithium deposition from a battery according to claim 1, wherein the temperature of the cyclic charge and discharge of the plurality of test batteries is-30 ℃ to 0 ℃, and the number of cycles is 1 to 200.
8. The method of claim 1, wherein the test cell is at least 10 unused lithium ion cells.
9. A battery lithium analysis detection device based on any one of claims 1 to 8, characterized by comprising a battery tester, a controllable temperature box and a computer, wherein the battery tester comprises a capacity test module and an internal resistance test module, the controllable temperature box is used for heating or cooling a battery, and the computer controls the battery tester to perform capacity and internal resistance tests and control the temperature in the controllable temperature box.
10. A computer readable storage medium storing a computer instruction, program, code set or instruction set which when run on a computer causes the computer to perform a method of battery lithium analysis detection as claimed in any one of claims 1 to 8.
11. An electronic device, comprising:
one or more processors; and
a storage device storing one or more programs,
when executed by the one or more processors, cause the one or more processors to implement a battery lithium analysis detection method as claimed in any one of claims 1 to 8.
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