CN112713323B - Lithium ion battery rapid charging method and lithium ion battery - Google Patents

Lithium ion battery rapid charging method and lithium ion battery Download PDF

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CN112713323B
CN112713323B CN202011438403.6A CN202011438403A CN112713323B CN 112713323 B CN112713323 B CN 112713323B CN 202011438403 A CN202011438403 A CN 202011438403A CN 112713323 B CN112713323 B CN 112713323B
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lithium ion
charging
charge
ion battery
state
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CN112713323A (en
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黎盛才
李书国
艾邓均
李起
张耀
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Xinwangda Power Technology Co ltd
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Sunwoda Electric Vehicle Battery 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
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • 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

Abstract

The application discloses a lithium ion battery and a quick charging method thereof. A lithium ion battery rapid charging method comprises the following steps: detecting a limit charge state corresponding to the first current under a preset condition of the lithium ion battery, wherein the limit charge state is a charge state in which the lithium ion battery is charged under the first current and lithium precipitation of the lithium ion battery is started; obtaining a corresponding relation according to the first current and the limit charge state; formulating a charging flow according to the corresponding relation; and charging the lithium ion battery according to the charging process. By detecting the limit state of charge corresponding to the first current under the preset condition, the corresponding relation between different charging currents and the corresponding limit state of charge can be obtained only by carrying out one experiment, and lithium separation caused by overlarge charging current can be prevented by charging according to the corresponding relation.

Description

Lithium ion battery rapid charging method and lithium ion battery
Technical Field
The present disclosure relates to the field of lithium ion batteries, and in particular, to a method for rapidly charging a lithium ion battery and a lithium ion battery.
Background
Lithium ion batteries have the advantage of no alternatives as the most widely used secondary batteries at present. The charging process of the lithium ion battery is mainly the extraction of lithium ions from the positive electrode and the insertion of lithium ions into the negative electrode, and the rate of the process is influenced by the rates of a plurality of electrochemical processes. With the graphite negative electrode system that generally uses, when the temperature is lower or charging current is too big, the negative pole polarization is great, takes place to analyse lithium phenomenon at the negative pole surface this moment, and this charging efficiency that not only influences the battery just has very big safety risk. In the related technology, although the multi-step multi-stage quick charging method is convenient to apply, the charging current of each stage needs to be determined by a large number of experiments in the method formulation stage, and for a large-scale lithium ion battery with high capacity, the experiment consumes long time and is high in cost, and the practicability is poor.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides a quick charging method for a lithium ion battery, which can be used for carrying out an experiment only once to obtain a charging current change relation during quick charging, and can carry out quick charging without lithium separation.
According to the embodiment of the first aspect of the application, the method for rapidly charging the lithium ion battery comprises the following steps: detecting a limit charge state corresponding to a first current of a lithium ion battery under a preset condition, wherein the limit charge state is a charge state in which the lithium ion battery is charged under the first current and lithium precipitation of the lithium ion battery is started; obtaining a corresponding relation according to the first current and the limit charge state; formulating a charging process according to the corresponding relation; and charging the lithium ion battery according to the charging process.
According to the embodiment of the application, the method for rapidly charging the lithium ion battery at least has the following beneficial effects: by detecting the limit state of charge corresponding to the first current under the preset condition, the corresponding relation between different charging currents and the corresponding limit state of charge can be obtained only by carrying out one experiment, and lithium separation caused by overlarge charging current can be prevented by charging according to the corresponding relation.
According to some embodiments of the present application, the step of detecting the limit state of charge of the lithium ion battery corresponding to the first current under the preset condition specifically includes: and detecting a limit charge state corresponding to the first current of the lithium ion battery under the conditions of the first temperature and the first health state.
According to some embodiments of the present application, the step of detecting the limit state of charge of the lithium ion battery corresponding to the first current under the preset condition specifically includes: and determining the limit charge state according to the charge state when the negative electrode potential of the lithium ion battery is zero under the first current condition.
According to some embodiments of the present application, the step of obtaining the corresponding relationship according to the first current and the limit state of charge specifically includes: and calculating initial charging current according to the first current and the limit state of charge, and obtaining the corresponding relation according to the initial charging current.
According to some embodiments of the present application, the lithium ion battery is a three electrode battery.
According to some embodiments of the present application, the step of formulating the charging flow according to the correspondence specifically includes: and judging the charging condition of the lithium ion battery, determining the corresponding relation according to the charging condition, and formulating a charging process according to the corresponding relation.
According to some embodiments of the present application, the charging conditions include temperature, state of health and state of charge of the battery.
According to some embodiments of the present application, the step of charging the lithium ion battery according to the charging process specifically includes: and if the charging current is smaller than a preset threshold value, stopping charging the lithium ion battery.
According to a second aspect of the present application, a method for rapidly charging a lithium ion battery includes the above-mentioned method for rapidly charging a lithium ion battery of the first aspect.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
The present application is further described with reference to the following figures and examples, in which:
fig. 1 is a flowchart of a method for rapidly charging a lithium ion battery according to an embodiment of the present disclosure;
FIG. 2 is a graph of state of charge versus negative electrode potential according to an embodiment of the present disclosure;
FIG. 3 is a graph of charging current versus time for an ideal state according to an embodiment of the present disclosure;
FIG. 4 is a graph of charge current versus limit state of charge according to an embodiment of the present application;
fig. 5 is a specific flowchart of charging according to an embodiment of the present application.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and larger, smaller, larger, etc. are understood as excluding the present numbers, and larger, smaller, inner, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, unless otherwise expressly limited, terms such as set, mounted, connected and the like should be construed broadly, and those skilled in the art can reasonably determine the specific meaning of the terms in the present application by combining the detailed contents of the technical solutions.
Interpretation of terms:
state Of Charge (SOC): the ratio of the current electric quantity of the battery to the full charge quantity of the battery ranges from 0% to 100%.
State Of Health (State Of Health, SOH): the ratio of the current maximum discharge capacity of the battery to the maximum discharge capacity of the new battery ranges from 0% to 100%.
Battery Management System (BMS): the device is used for detecting the current state of the battery and adjusting the charging and discharging current according to the detection result to prevent the battery from being over-discharged or over-charged.
Some embodiments, referring to fig. 1, the present application provides a method for rapidly charging a lithium ion battery, including:
110, detecting a limit charge state corresponding to the first current of the lithium ion battery under a preset condition;
120, obtaining a corresponding relation according to the first current and the limit charge state;
130, establishing a charging process according to the corresponding relation;
and 140, charging the lithium ion battery according to the charging process.
In the process of constant-current charging of a lithium ion battery, when the state of charge of the battery is increased continuously, the quantity of lithium ions embedded into a negative electrode is increased continuously, the rate of the negative electrode receiving the embedding of the lithium ions is reduced correspondingly, and if the charging current is kept unchanged, the negative electrode cannot complete lithium embedding quickly and timely, so that lithium is separated, and the use of the battery is influenced. The limit state of charge of the present application is the state of charge of the battery when the lithium ion battery just begins to extract lithium under the condition of charging with a constant current charging current of a specific magnitude. The limit charge states of the constant-current charging currents with different sizes are also different, the limit charge states corresponding to the first current under the preset condition are detected, the corresponding relation between the different charging current sizes and the corresponding limit charge states can be obtained through calculation, so that a charging process that lithium cannot be separated from a battery during charging is formulated, the corresponding charging process is executed through a battery management system, the lithium ion battery is charged, and safe and rapid charging is completed. According to the method and the device, only the detection is needed under the preset condition, and the relation curves of different charging currents and corresponding different limit charge states can be obtained by one group of charging currents and the corresponding limit charge states, so that the test times of early detection are reduced, and the corresponding charging process is conveniently formulated.
In some embodiments, the step of detecting the limit state of charge of the lithium ion battery corresponding to the first current under the preset condition includes: and detecting a limit charge state corresponding to the first current of the lithium ion battery under the conditions of the first temperature and the first health state.
The health state of the lithium ion battery is changed after the lithium ion battery is delivered from a factory and used for a period of time, so that the maximum discharge capacity of the lithium ion battery is influenced, and the capacity of the lithium ion battery is different under different temperature conditions, so that the lithium ion battery is different from the corresponding limit charge state. The charging process formulated according to the corresponding relation is more accurate by detecting the temperature and the health state of the lithium ion battery under the specific preset condition and obtaining the corresponding relation, and the charging protection effect of the lithium ion battery is better by detecting the temperature and the health state of the battery during charging and then charging the lithium ion battery. In some other embodiments, the corresponding relationship may be obtained only according to the current battery temperature or the state of health, and the corresponding charging process may also be changed.
In some embodiments, the step of detecting the limit state of charge of the lithium ion battery corresponding to the first current under the preset condition includes: and determining the limit charge state according to the charge state when the negative electrode potential of the lithium ion battery is zero under the first current condition. For example, the mode of detecting the limit state of charge is that when the lithium ion battery begins to separate lithium, the potential of the negative electrode can reach or even be lower than the lithium separation potential, and at this time, a lithium separation phenomenon occurs on the surface of the negative electrode, so that the state of charge when the negative electrode potential is zero is the limit state of charge of the lithium ion battery to be separated. Referring to fig. 2, in order to obtain a relation curve between the SOC of the lithium ion battery and the negative electrode potential in the case of constant current charging, when the negative electrode potential Va is 0, the corresponding SOC is the SOC Extreme limit
In some embodiments, the step of obtaining the corresponding relationship according to the first current and the limit state of charge specifically includes: and calculating initial charging current according to the first current and the limit charge state, and obtaining a corresponding relation according to the initial charging current. In a specific example, according to the existing research, there is an optimal charging curve in the charging process of the lithium ion battery, and referring to fig. 3, for the lithium ion battery with temperature T and state of health SOH, the optimal charging current I and time T satisfy:
I=I 0 e -at (a>0) (1)
in formula (1), I is the optimum charging current at time t, I 0 Is the initial charging current, a is the charge acceptance coefficient, I 0 A is only related to the temperature T during charging, the state of health SOH, the type of the battery and the structural parameters, wherein the charging acceptable region is a range of allowable charging current in a specific time, the battery is charged in the charging acceptable region, and the battery does not generate lithium precipitation due to excessive current in the charging acceptable regionWhen charging in the charging unacceptable region, the battery can be overcharged, which affects the service life of the battery.
According to the optimal charging curve of the formula (1), obtaining the relation between the optimal charging electric quantity Q of the battery and the time t when the battery is charged:
Figure GDA0002974194800000041
when t approaches infinity, the battery charging capacity at this time is the full charge capacity Q of the battery cell 0
Figure GDA0002974194800000042
At time t, when the charging current is I, the state of charge of the battery is a limit state of charge SOC (state of charge) at which lithium deposition does not occur at the current I Extreme limit At this time, SOC Extreme limit Satisfies the following conditions:
Figure GDA0002974194800000043
therefore, only I needs to be measured 0 And obtaining the corresponding relation between the charging current and the limit charge state.
The following describes the steps of obtaining the corresponding relationship in detail with a specific embodiment. Under the condition of 25 ℃ and 100% of SOH, the limit state of charge measured by the charging current of 2C is 40%, namely under the condition, the charging current of 2C can charge the battery to 40% of the full charge state at maximum, and if the charging current of 2C is continuously used for charging, the battery generates lithium precipitation. Let I equal 2C, SOC Extreme limit Equal to 40% into formula (4), calculated to give I 0 Is 10/3C.
Figure GDA0002974194800000051
Thereby obtaining the charging current I and the limit state of charge SOC Extreme limit When BMS detectsAnd when the current charging current reaches the limit charge state of the battery, reducing the charging current, continuing to charge, and continuously reducing the charging current according to the method until the battery is fully charged.
By changing the SOH of the battery, the SOC under different health states is measured Extreme limit With respect to the charging current I. Referring to fig. 4, the relationship between the charging current and the limit state of charge under different state of health SOH, wherein BOL represents the relationship curve under the state of SOH of 100%, MOL represents the relationship curve under the state of SOH of 0-100%, and the relationship between them can be obtained through a plurality of experiments.
In some embodiments, the lithium ion battery is a three electrode battery. When the limit charge state under the specific temperature and specific SOH condition is detected, a three-electrode battery with the same parameters and structure as the lithium ion battery is manufactured, and by introducing a reference electrode, the polarization current and the polarization potential can be measured simultaneously by using a three-electrode system, and the measurement precision is higher. The preparation process of the three-electrode battery is as follows: and in the assembling procedure, the rolled bare cell is opened, the reference electrode is separated from the positive electrode and the negative electrode by a diaphragm and then placed in the bare cell, and the preparation of the battery is continuously completed according to the subsequent procedures to obtain the three-electrode lithium ion battery with the same type of the reference electrode. Preferably, since metallic lithium and lithium-plated copper need to be packaged in a glove box, for the convenience of manufacturing the three-electrode battery, a copper wire is used as a reference electrode, and the packaged three-electrode battery cell is subjected to lithium plating for 4 hours at a current of 10 to 50 microamperes before testing to form a stable lithium-plated copper wire electrode. In some other embodiments, other battery detection methods may be used to detect the limit state of charge of the battery.
In some embodiments, the step of formulating the charging process according to the corresponding relationship specifically includes: and judging the charging condition of the lithium ion battery, determining the corresponding relation according to the charging condition, and formulating a charging process according to the corresponding relation. When the lithium ion battery needs to be charged, the BMS stores the corresponding relation between the charging current and the limit charge state of the lithium ion battery in different temperatures and different health states, which are obtained through the pre-detection, the BMS selects the charging current with the corresponding magnitude by detecting the current charging condition of the battery, when the charge state of the battery obtained through the detection under the charging current magnitude reaches the limit charge state, the magnitude of the charging current is reduced, the charging is continued, and the charging current is continuously reduced according to the method until the battery is fully charged. The degree of current reduction in each time can be set randomly according to actual requirements, and the smaller the amplitude is, the closer the optimal charging curve is.
In some embodiments, the charging conditions include temperature, state of health, and state of charge of the battery. And selecting the corresponding relation between the corresponding charging current and the limit charge state according to the charging conditions, so that the formulated charging process is closer to an ideal charging curve. In some other embodiments, the correspondence may be selected based only on temperature or state of health and the current state of charge.
In some embodiments, the step of charging the lithium ion battery according to the charging process specifically includes: and if the charging current is smaller than the preset threshold value, stopping charging the lithium ion battery.
For example, the relationship between the state of charge and the charging current calculated by the above formula is a theoretical calculation relationship and is denoted as SOC Theory of the invention In actual use, the charging amount Q 'is generally obtained when the charging is performed by a constant current to a certain cutoff current' 0 To calculate the actual limit state of charge, i.e.:
Figure GDA0002974194800000061
wherein, the delta Q is the difference value between the theoretical charging capacity and the actual charging capacity of the battery, and can be obtained by the formula (6) when Q is 0 >Q' 0 When > Δ Q, e.g. Δ Q<1%Q' 0 When it is, it can be considered as SOC Practice of ≈SOC Theory of the invention Therefore, calculation of SOC is required in this process Practice of When the threshold value is reached, it is determined that the smaller the charge cut-off current is, the better, and preferably, the SOC is taken Extreme limit -SOC Practice of 1% as the correspondence between the actual charging current and the limit state of charge. With reference to the following table, measured at 25 ℃ and SOH of 100% and at a charging current of 2CTable of actual state of charge versus limit state of charge and charging current for a limit state of charge of 40%:
charging current I 10/3C 3C 8/3C 7/3C 2C 5/3C 4/3C 1C 2/3C 1/3C 0.05C
SOC
Extreme limit 0 10% 20% 30% 40% 50% 60% 70% 80% 90% 98.5
SOC
Practice of 0 9% 19% 29% 39% 49% 59% 69% 79% 89% 97.5%
And when the charging current is detected to be smaller than the preset threshold value, which is 0.05C in the implementation, the charging is stopped, a charging redundant space is reserved, and the overcharge of the battery is prevented.
A detailed description of a specific charging process of the BMS system for a battery is described below in a specific embodiment. Referring to fig. 5, when the battery starts to be charged, the BMS determines the temperature, SOH, and SOC of the battery, charges the battery according to a preset charging process, selects a corresponding charging current, and then charges the battery, and detects whether a limit state of charge under the current is reached, if not, continues to charge the battery and detects the current in real time, if the limit state of charge is reached, then detects whether the current is less than 0.05C, and if so, determines that the battery is fully charged, and ends charging. If not, selecting the corresponding charging current according to the reached SOC to continue charging, and circulating the steps until the battery is fully charged.
In some embodiments, the present application further provides a lithium ion battery, and the lithium ion battery adopts the lithium ion battery fast charging method in the above embodiments when charging, so that lithium separation of the lithium ion battery is prevented while fast charging, and the service life of the lithium ion battery is prolonged.
In the description of the present application, reference to the description of the terms "some embodiments," "illustrative examples," "specific examples," or the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments of the present application have been described in detail with reference to the drawings, but the present application is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Claims (4)

1. A method for rapidly charging a lithium ion battery is characterized by comprising the following steps:
detecting a first limit state of charge corresponding to a first current of the lithium ion battery at a first temperature and a first health state; the first limit state of charge is a state of charge in which the lithium ion battery is charged under the first current and the lithium ion battery begins to separate lithium;
the charging current I is equal to the first current, the limit state of charge SOC Extreme limit Equal to the first limit state of charge, is substituted into the following formula, and the initial charging current I is calculated 0
Figure FDA0003686973030000011
According to the initial charging current I 0 Obtaining the charging current I and the limit state of charge SOC Extreme limit The corresponding relationship of (a);
when the lithium ion battery needs to be charged, the BMS stores the corresponding relationship between the charging current and the limit state of charge of the lithium ion battery at different temperatures and different health states, which are obtained through the pre-detection;
the BMS selects charging current with corresponding magnitude by detecting the current charging condition of the battery; wherein the charging conditions include temperature, state of health, and state of charge of the battery;
and when the state of charge of the battery reaches the limit state of charge detected under the charging current, reducing the charging current, continuing to charge, and continuously reducing the charging current according to the mode until the battery is fully charged.
2. The method according to claim 1, wherein the step of detecting the first limit state of charge of the lithium ion battery corresponding to the first current at the first temperature and the first state of health comprises:
and determining the first limit charge state according to the charge state when the negative electrode potential of the lithium ion battery is zero under the first current condition.
3. The method according to claim 1 or 2, wherein the lithium ion battery is a three-electrode battery.
4. A lithium ion battery comprising a method for rapidly charging a lithium ion battery according to any one of claims 1 to 3.
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