WO2017030309A1 - 전지 충전 한계 예측 방법과 이를 이용한 전지 급속 충전 방법 및 장치 - Google Patents
전지 충전 한계 예측 방법과 이를 이용한 전지 급속 충전 방법 및 장치 Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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]
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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]
- G01R31/385—Arrangements for measuring battery or accumulator variables
- G01R31/387—Determining ampere-hour charge capacity or SoC
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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]
- G01R31/385—Arrangements for measuring battery or accumulator variables
- G01R31/387—Determining ampere-hour charge capacity or SoC
- G01R31/388—Determining ampere-hour charge capacity or SoC involving voltage measurements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
- H02J7/00714—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery charging or discharging current
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
- H01M2010/4271—Battery management systems including electronic circuits, e.g. control of current or voltage to keep battery in healthy state, cell balancing
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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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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method and apparatus for charging a battery, and more particularly, to a method and apparatus for rapid charging a battery, which uses a stepwise reduction of charging current to rapidly charge a battery while increasing the battery life.
- This application is a priority application for Korean Patent Application No. 10-2015-0116247 filed on August 18, 2015, and all contents disclosed in the specification and drawings of the application are incorporated herein by reference.
- the process of charging a cell involves introducing current into the cell and accumulating charge and energy, which process must be carefully controlled.
- excessive C-rate or charging voltage can permanently degrade the performance of a battery and ultimately cause complete failure or unexpected failures such as leakage or explosion of highly corrosive chemicals.
- the conventional battery charging method is a constant current (CC) method for charging with a constant current from the beginning of the charge to completion, a constant voltage (CV) method for charging at a constant voltage from the beginning of the charge to completion and charging with a constant current at the beginning of the charge, In the last stage, a constant current-constant voltage (CC-CV) method of charging to a constant voltage is used.
- CC constant current
- CV constant voltage
- CC-CV constant current-constant voltage
- the CC method In the CC method, a large current flows due to a large voltage difference at the beginning of charging. The higher the charging current is, the better the charge is done, but charging continuously with a large current decreases the charging efficiency and affects the life of the battery. In addition, since the CC method continues to flow to the battery even when the charging is completed, the Li-plating problem of forming a metal plating film occurs due to the characteristics of lithium (Li) ions, resulting in loss of overcharge adjustment. There is a safety problem. Because of this There is an inconvenience in that the charger and battery must be quickly disconnected when the charging is completed. In addition, the CV method has a disadvantage in that the terminal voltage is greatly changed by the temperature change and the heat generation of the battery itself when the battery is fully charged, and thus it is difficult to set the constant voltage value in advance. There is an inconvenience that the charging time is long.
- the most common method is the CC-CV method.
- C is the battery capacity of the charging unit (often indicated by Q) A ⁇ h
- the current in amperes is selected as the fraction (or multiplier) of C.
- a lithium battery with a capacity of 700mAh can be charged in about 1 hour and 30 minutes.
- this charging method should be charged in a condition suitable for the charging capacity of the charger, it should be charged in a well ventilated room temperature of about 25 °C.
- the CC method is most advantageous for rapid charging.
- Li-plating phenomenon becomes a problem when Li is not intercalated on the cathode during rapid charging at high charge current density, and thus, Li precipitated side reaction with electrolyte and the kinematic balance of the battery. (kinetic balance) changes, etc. may cause battery deterioration in the future.
- a technique for achieving rapid charging without generating Li-plating there is a need for a technique for achieving rapid charging without generating Li-plating.
- the problem to be solved by the present invention is to provide a method for estimating battery charge limit so as not to generate Li-plating.
- Another object of the present invention is to provide a battery charging method and apparatus that can quickly charge the battery through this.
- the battery charge limit prediction method comprises the steps of (a) manufacturing a three-electrode cell having a unit cell and a reference electrode; (b) measuring a cathode potential (CCV) according to SOC while charging the trielectrode cell; And (c) determining a point at which the cathode potential does not fall and starts to become constant and sets the charge limit by determining the point of occurrence of Li-plating.
- the filling limit at the filling rate can be obtained and the filling protocol can be obtained by combining them.
- the battery charging method according to the present invention starts from the initial charging rate higher than 1C and the point where the negative potential of the battery starts to be constant without dropping is determined as the point of occurrence of Li-plating to the charge limit.
- the battery is charged while the charging rate is gradually decreased by setting and charging at the next charging rate when the charging limit is reached.
- the initial charge rate may be 1.5C to 5C.
- the charging rate is decreased to proceed to the next step of charging, and this step may be performed until the SOC of the battery reaches 80%.
- Another battery charging method comprises a data acquisition step of measuring the negative electrode potential according to the SOC through a three-electrode cell experiment having a unit cell and a reference electrode for each different charging rate; Determining a point at which the cathode potential starts to be constant without falling from the acquired data as a point of occurrence of Li-plating and setting a charge limit to obtain a protocol for changing the charge rate step by step; And charging the battery with the protocol.
- the filling rate of the data acquisition step may range from 0.25C to 5C.
- the protocol may be the initial charge rate is higher than 1C.
- the protocol may have an initial charge rate of 1.5C to 5C.
- the protocol may include charging rate gradually decreasing and charging voltage information after the end of charging at each charging rate.
- Battery charging apparatus for solving the other problem is a power supply for outputting a charging voltage input from commercial power; And outputs a charging voltage input from the power supply unit as a charging current to a battery so that the battery is charged.
- the charging current is changed by changing the charging current.
- a battery charger for controlling the change wherein the battery charger determines a point where the negative potential of the battery starts to be constant without falling as a point of occurrence of Li-plating to change the charge rate step by step.
- the charging current is adjusted step by step according to the protocol to allow the battery to be charged.
- the Li-plating occurrence point is determined as the point where the negative potential does not drop any more and the rate at which the negative potential decreases during the CC charging is changed, and the negative potential decreases.
- the present invention it is possible to prevent the Li-plating generation of the battery negative electrode by determining the point where the negative potential does not drop and starts to be constant as the Li-plating occurrence point and setting the charge limit. Accordingly, there is an effect that the battery is quickly charged while the battery life is increased.
- the point at which the cathode potential does not drop and starts to be constant may be different for each cell.
- the present invention does not propose a uniform charging limit that ignores the characteristics of each cell, but experiments with a three-electrode cell to propose an optimized charging method for each cell by clearly understanding the conditions under which Li-plating is formed during charging. .
- FIG. 1 is a flowchart of a method for predicting battery charge limit according to the present invention.
- Figure 2 shows the structure of the pouch type trielectrode cell used in the present invention experiment.
- Figure 3 is a graph of the negative electrode potential according to the SOC obtained according to the experiment of the present invention, and also shows the results of the in-situ visualization (in-situ visualization) analysis.
- FIG. 6 is a flowchart of a battery charging method according to the present invention.
- FIG. 8 is a graph showing the charging rate (charging current) with time when the battery is charged by the method of the present invention.
- FIG. 9 is a graph comparing battery life according to a charging method using a stepwise charging current reduction according to the present invention and a conventional CC-CV charging method.
- the present invention can provide a technique for shortening the charging time without generating the Li-plating of the battery.
- FIG. 1 is a flowchart of a method for predicting battery charge limit according to the present invention.
- a three-electrode cell is manufactured (step s1).
- the three-electrode cell is used to confirm the behavior of each of the negative electrode and the positive electrode when the secondary battery is studied, and includes a unit cell and a reference electrode.
- a well-known structure may be adopted with respect to such a three-electrode cell.
- Figure 2 shows the structure of the pouch-type three-electrode cell used in the experiment of the present invention.
- the three-electrode cell 10 has a separator 40 between the cathode 20 and the anode 30 to insert the reference electrode 60.
- the reference electrode 60 may have a plate-like structure like the cathode 20 or the anode 30, or may be configured as a wire type as shown in order to read a more accurate current flow.
- 2 illustrates a wire-type reference electrode 60 such as a copper wire 55 coated with an insulating layer 50 as an example.
- the three-electrode cell 10 is provided with a stable third reference electrode 60 in the cell without the influence of polarization, and measures the potential difference with the other electrodes 20, 30, and in-situ each. It is a useful analysis tool because it can analyze the polarization of electrodes.
- the negative electrode 20, the positive electrode 30, and an electrolyte constitute a unit cell.
- the negative electrode 20 may include a graphite-based negative active material such as graphite; 1 to 5 parts by weight of the conductive material based on 100 parts by weight of the negative electrode active material; And 1 to 5 parts by weight of the polymeric binder.
- the positive electrode 30 includes a positive electrode active material such as LiCoO 2 ; 1 to 5 parts by weight of the conductive material based on 100 parts by weight of the positive electrode active material; And 1 to 5 parts by weight of the polymeric binder.
- Electrolyte solution is electrolyte solution of general composition.
- the unit cell and the reference electrode 60 are embedded in the pouch.
- step s2 the charging characteristic according to the cathode potential (CCV) is observed (step s2).
- CCV cathode potential
- the stage becomes low and the negative electrode potential decreases. At this time, if the charging current density is increased, the stage is hardly observed, but the cathode potential decreases continuously due to the intercalation of Li and the increase of resistance. In the results of FIG. 3, as the charging proceeds, the cathode potential gradually decreases from about 0.75V, falls below 0V, and falls about -0.45V.
- In-situ visualization was also performed while charging the three-electrode cell 10 shown in FIG. 2 to confirm the change in the negative electrode potential during charging and the electrode state during charging.
- In-situ spheroidization analysis is to observe the intercalation process between the charge and discharge profile and the cathode during charge and discharge by placing the three-electrode cell 10 in the surface observation block cell of the electrochemical reaction visualization confocal system.
- ECCS B310 equipment was used.
- the negative potential-SOC graph of FIG. 3 also shows the results of such an in-situ spheronization analysis.
- the graphite-based negative electrode reaches 100% of SOC in which lithium ions are finally intercalated in all layers through several stages as mentioned above.
- In-situ spheroidization analysis changes the color of the electrode active material to gold.
- the response distribution can be interpreted as the color change during charging from gray to blue red gold before charging.
- the dV / dQ graph as shown in FIG. 4 and the point where the negative potential slope changes, that is, the point at which the rate at which the negative potential drops, are changed (inflection point) are shown. Set it to the limit of charge generated.
- step s2 i.e., the point at which the cathode potential starts to become constant without falling in the cathode potential graph according to the SOC, and at which the rate at which the cathode potential falls is changed (the point where the voltage slope of the cathode changes in the dV / dQ graph).
- (Inflection point) is set as the generation point of the Li-plating, that is, the charging limit (step s3).
- the charge limit at that charge rate can be obtained.
- the charging rate is different and steps s2 and s3 are repeatedly performed to obtain a charging limit until the charging end point, for example, SOC 80%, is satisfied, the information can be combined to obtain a charging protocol for the cell. Charging with this charging protocol is a quick charging method according to the present invention.
- a three-electrode cell is fabricated to observe the charging characteristics according to the negative electrode potential, and the charging limit at which the Li-plating does not occur when charging with each charging current is quantified. .
- This also sets the point at which the cathode potential does not drop and starts to be constant as the charge limit, and when the charge limit is reached, the charge current is gradually reduced by charging to the next charge rate, so that Li-plating does not occur.
- This method is, for example, "keeping the cathode potential above 0V (Li + / Li vs. 0V)" to hold the charge until the cathode potential falls further below 0V compared to the reference.
- Li + / Li vs. In the case of 0V reference, since the cathode potential becomes 0V at about 15% of SOC, it is possible to charge as little SOC at the same charging current density, but according to the present invention, it can be charged up to 30% of SOC at the same charging current density. Therefore, the charging limit prediction of the present invention having such a criterion is more effective in view of the fast charging, which requires charging a large amount in a short time.
- a three-electrode cell (10 in FIG. 2) was fabricated as a pouch type, and the cycle was turned to the point (B point in FIG. 3), before (point A) and after (point C) where Li-plating was formed. Is shown in FIG. 5.
- the life of a battery is a measure of how long the battery can be used, and the unit is expressed as the number of cycles (cycles). In other words, it indicates how many times the battery can be charged and used. In terms of electrical energy, the battery is charged once and used until the battery is fully discharged.
- FIG. 6 is a flowchart of a battery charging method according to the present invention.
- a data acquisition step of measuring a negative electrode potential of a battery according to SOC for each different charging rate is performed (step s10).
- This step may be performed through a three-electrode cell experiment having a unit cell and a reference electrode according to the battery charge limit prediction method according to the present invention described above.
- C is the battery capacity of the charging unit (often indicated by Q) A ⁇ h
- the current in amperes is selected as the fraction (or multiplier) of C.
- 1C charge rate refers to the charge / discharge rate at which the capacity of a fully charged battery is drawn out or filled within an hour, and also the current density at that time.
- the charge rate and discharge rate of most of the C / 2 was required in the past, but in the future, these functions may be further enhanced to require performance corresponding to the charge rate and discharge rate of 1C.
- notebook, EV and PHEV batteries require similar charge rates and much higher discharge rates.
- the filling rate is higher than 1C.
- continuous charging with a high current may cause high heat generation inside the battery, and each electrode may form an overvoltage state due to the resistance of the battery. Therefore, the charging rate should be determined in consideration of the type and characteristics of the battery.
- the range of the charging rate in the data acquisition step may vary depending on the type and characteristics of such a battery.
- an EV battery can acquire data in the range of 0.25C-1.5C of charging rates by setting the initial charging rate to 1.5C.
- a battery for a plug-in hybrid electric vehicle (PHEV) may acquire data in a range of 0.25C to 3C by setting an initial charge rate of 3C. This initial charge rate and the charge rate range may be limited not only by the type of battery, but also by the maximum current of the motor used in the actual vehicle.
- the EV battery may be set to an initial charge rate of 1.5C, and the PHEV battery may be set to an initial charge rate of 3C.
- the initial charge rate can be further increased, for example, up to 5C. Therefore, the initial filling rate may be 1.5C to 5C, and the filling rate of the data acquisition step in the present invention may range from 0.25C to 5C.
- FIG. 7 shows the negative electrode potential according to the filling rate. As shown in FIG. 7, a graph may be obtained by measuring a cathode potential according to SOC state while varying the charging rate from 3C to 0.5C.
- a point at which the negative electrode potential of the battery starts to become constant without dropping is set as a Li-plating occurrence point to obtain a protocol for changing the charging rate step by step (step s20). Setting the point where the cathode potential does not fall and starts to be constant as a Li-plating occurrence point does not cause Li-plating on the cathode.
- a protocol such as "step charge” can be obtained to set the point where the cathode potential does not drop and starts to be constant as the Li-plating occurrence point.
- Charging at an initial charge rate of 3C results in Li-plating at a point of 30% SOC.
- the charge rate is then changed to the next charge rate, 2.5C.
- Li-plating occurs at 37% SOC.
- the charge rate is then changed to the next charge rate, 2.0C.
- the beam is filled is a Li- plating occurs at the point where SOC 61%.
- the charge rate is then changed to the next charge rate, 1.6C.
- Li-plating occurs at the point of 67% SOC.
- the filling rate is then changed to the next filling rate, 1.0C. Accordingly, the charging is completed when charging reaches the point of 80% SOC determined as the charging completion condition.
- the protocol can be obtained, and the negative electrode potential graph according to the SOC varies depending on the type of battery, but this method of obtaining the protocol can be similarly applied.
- the present embodiment has been described in the case of reducing the filling rate from 3C to 1.0C as an example, as mentioned above, the range of the initial charging rate and the range of the charging rate of the data acquisition step may vary as much, and the charging rate is reduced
- the amount may be any value other than 0.5C, 0.6C, 0.4C, etc. as in this embodiment.
- FIG. 8 is a graph showing the charging rate (charging current) with time when the battery is charged by the method of the present invention, and the protocol shown in FIG. 7 is expressed as the charging rate with time.
- the charging current of the charger for charging the battery decreases gradually over time from the initial charging rate of 3C to the final charging rate of 1.0C.
- the holding time t1 to t5 of each charge rate may be changed because the point where the cathode potential does not fall and starts to be constant is set as the Li-plating generation point.
- the present invention measures the negative electrode potential according to the charging rate, and quantifies the charging limit in which Li-plating does not occur when charging with each current.
- the protocol may include a charging rate that gradually decreases and charging voltage information after termination of charging at each charging rate.
- charging may be performed by applying an optimized charging current according to a protocol.
- the charging protocol can be realized using the battery charging device according to the present invention.
- the battery charging device includes a power supply unit for outputting a charging voltage input from a commercial power source;
- the charging voltage input from the power supply unit is output to the battery as a charging current so that the battery is charged.
- the charging current is changed by changing the charging current.
- It includes a battery charging unit to control to.
- the battery charging unit sets the point where the negative potential of the battery starts to be constant without dropping as a Li-plating generation point so that the charging of the battery is performed by adjusting the charging current step by step according to a protocol for changing the charging rate step by step. .
- the logic of the protocol of the charging method according to the invention can be integrated into the battery charging device and used to charge the battery.
- the battery charging unit employs a processor for implementing rapid charging.
- the processor stores the logic of the charging protocol in a memory, and voltage, current, etc. can each be measured with high accuracy to achieve accurate control and preserve device performance.
- the negative electrode since the negative electrode has a charging process for controlling the potential of passing the Li-plating generation point, there is no fear of Li-plating on the negative electrode as compared with the general CC-CV charging method, and thus the life is long. It works.
- FIG. 9 is a graph comparing battery life according to a charging method using a stepwise charging current reduction according to the present invention and a conventional CC-CV charging method.
- the life time in each case was compared with the same charging time and discharge under the same conditions (1C CC).
- the capacity retention rate decreases after 75 cycles, and the capacity retention rate decreases to about 95% after 100 cycles. This amount reaches 100%.
- the life of such a battery is set by various factors, and the structural stability of the electrode, in particular, the stability of the negative electrode is important.
- the ideal negative electrode should have high reaction reversibility with lithium ions. When the ideal reversible reaction is achieved, there is no change in capacity retention with the cycle. It can be seen that the charging method using the stepwise charging current reduction according to the present invention has a higher reaction reversibility than the conventional method, which is a result of preventing Li-plating at the cathode. As such, according to the charging method using the stepwise charging current reduction of the present invention, it can be seen that the battery life is longer than the conventional life by preventing the degradation.
- the charging rate is gradually set by setting the point where Li-plating occurs as a point where the cathode potential does not drop while being rapidly charged using the initial charging rate greater than 1C.
- the charge limit prediction method and the charging method according to the present invention for example, "make the cathode potential to be 0V or more (Li + / Li vs. 0V)" until the cathode potential further falls below 0V compared to the reference.
- Li + / Li vs. Compared to the 0V reference, it can charge even larger SOCs at the same charge current density, which is very effective in terms of fast charging, which requires a large amount of charge in a short time.
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Abstract
Description
Claims (14)
- (a) 단위전지와 기준전극을 구비하는 삼전극셀을 제작하는 단계;(b) 상기 삼전극셀을 충전하면서 SOC에 따른 음극 전위(CCV)를 측정하는 단계; 및(c) 상기 음극 전위가 떨어지지 않고 일정하게 되기 시작하는 지점을 Li-플레이팅의 발생 지점으로 판단하여 충전 한계로 설정하는 단계를 포함하는 전지 충전 한계 예측 방법.
- 제1항에 있어서, 상기 SOC에 따른 음극 전위(CCV)의 그래프에서 음극 전위 기울기가 변하는 지점을 상기 충전 한계로 설정하는 것을 특징으로 하는 전지 충전 한계 예측 방법.
- 제1항에 있어서, 충전율을 달리 하여 상기 (b) 단계 및 (c) 단계를 수행하는 과정을 반복하여, 해당 충전율에서의 충전 한계를 얻고 이것을 종합하여 충전 프로토콜을 얻는 것을 특징으로 하는 전지 충전 한계 예측 방법.
- 1C보다 높은 초기 충전율부터 시작해서 전지의 음극 전위가 떨어지지 않고 일정하게 되기 시작하는 지점을 Li-플레이팅의 발생 지점으로 판단하여 충전 한계로 설정하고 상기 충전 한계 도달시 다음 충전율로 충전하는 식으로 상기 충전율이 단계적으로 감소되면서 전지를 충전하는 전지 충전 방법.
- 제4항에 있어서, 상기 음극 전위가 떨어지지 않고 일정하게 되기 시작하는 지점이면서 음극 전위 기울기가 변하는 지점을 상기 충전 한계로 설정하는 것을 특징으로 하는 전지 충전 방법.
- 제4항에 있어서, 상기 초기 충전율이 1.5C 내지 5C인 것을 특징으로 하는 전지 충전 방법.
- 제4항에 있어서, 충전 도중 상기 충전 한계 도달시 상기 충전율을 감소시켜 다음 단계 충전을 진행하고, 이러한 단계는 상기 전지의 SOC가 80%가 될 때까지 수행하는 것을 특징으로 하는 전지 충전 방법.
- 단위전지와 기준전극을 구비하는 삼전극셀 실험을 통해 SOC에 따른 음극 전위를 서로 다른 충전율별로 측정하는 데이터 취득 단계;상기 취득된 데이터로부터 상기 음극 전위가 떨어지지 않고 일정하게 되기 시작하는 지점을 Li-플레이팅의 발생 지점으로 판단하여 충전 한계로 설정하여 충전율을 단계적으로 변경하는 프로토콜을 얻는 단계; 및상기 프로토콜로 전지를 충전하는 단계를 포함하는 전지 충전 방법.
- 제8항에 있어서, 상기 음극 전위가 떨어지지 않고 일정하게 되기 시작하는 지점이면서 음극 전위 기울기가 변하는 지점을 상기 충전 한계로 설정하는 것을 특징으로 하는 전지 충전 방법.
- 제8항에 있어서, 상기 데이터 취득 단계의 충전율은 0.25C ~ 5C 범위인 것을 특징으로 하는 전지 충전 방법.
- 제8항에 있어서, 상기 프로토콜은 초기 충전율이 1C보다 높은 것을 특징으로 하는 전지 충전 방법.
- 제8항에 있어서, 상기 프로토콜은 초기 충전율이 1.5C 내지 5C인 것을 특징으로 하는 전지 충전 방법.
- 제8항에 있어서, 상기 프로토콜은 단계적으로 감소하는 충전율과 각 충전율에서의 충전 종료 후의 충전전압 정보를 포함하는 것을 특징으로 하는 전지 충전 방법.
- 상용전원으로부터 입력되는 충전 전압을 출력하는 전원부; 및상기 전원부로부터 입력되는 충전전압을 전지에 충전전류로 출력하여 상기 전지가 충전되도록 하고, 상기 전지의 충전전압이 미리 설정된 단계에 도달하면 충전전류를 변경하여 상기 전지로 출력되는 충전전류가 단계적으로 변화되도록 제어하는 전지 충전부를 포함하고,상기 전지 충전부는 상기 전지의 음극 전위가 떨어지지 않고 일정하게 되기 시작하는 지점을 Li-플레이팅의 발생 지점으로 판단하여 충전 한계로 설정하여 충전율을 단계적으로 변경하는 프로토콜에 따라 충전전류가 단계적으로 조절되면서 전지 충전이 이루어지도록 하는 것을 특징으로 하는 전지 충전 장치.
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JP6498792B2 (ja) | 2019-04-10 |
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