CN108235791A - Correct the method for charging lithium-ion battery for making up voltage - Google Patents

Correct the method for charging lithium-ion battery for making up voltage Download PDF

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Publication number
CN108235791A
CN108235791A CN201780002550.9A CN201780002550A CN108235791A CN 108235791 A CN108235791 A CN 108235791A CN 201780002550 A CN201780002550 A CN 201780002550A CN 108235791 A CN108235791 A CN 108235791A
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voltage
battery
charging
constant
current
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唐胜成
曾石华
李利
易世明
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GUANGZHOU FULLRIVER BATTERY NEW TECHNOLOGY Co Ltd
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GUANGZHOU FULLRIVER BATTERY NEW TECHNOLOGY Co Ltd
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    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02JCIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/007Regulation of charging or discharging current or voltage
    • H02J7/0071Regulation of charging or discharging current or voltage with a programmable schedule
    • 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
    • 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
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • HELECTRICITY
    • H02GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02JCIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/007Regulation of charging or discharging current or voltage
    • H02J7/00712Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
    • H02J7/007182Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Charge And Discharge Circuits For Batteries Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention corrects the method for charging lithium-ion battery for making up voltage, during charging when charge to voltage reach charging limitation voltage U then turn constant-voltage charge, until charging current is decreased to 5% to 99.99% cut-off of charging current before constant pressure, preferably charging current is decreased to 50% to 99.99% cut-off of charging current before constant pressure, the charging limitation voltage U=3Uo Us Uso between battery the two poles of the earth;Uso is the standard stabiliser voltage of cell voltage falling after constant-current constant-voltage charging to Uo, and Us is the burning voltage of cell voltage falling after constant-current charge to Uo, and Uo is standard charging blanking voltage.The charging of the present invention has the following advantages:Charging is fast and can be charged into electricity close to saturation;It discharges in standard or user method, there is longer cycle life or identical cycle-index;The capacity higher that electric discharge is released;Constant voltage charging method may be used, more meet the charging custom of lithium ion battery user and the selection of charging IC;A certain current value cut-off can be charged to constant voltage mode, it is easier to realize.

Description

Correct the method for charging lithium-ion battery for making up voltage
Technical field
The invention belongs to method for charging batteries technical field, more particularly to lithium ion battery and polymer Li-ion battery Charging method.
Background technology
Chinese patent CN101388477B discloses a kind of fast charge method, is to increase charging limitation voltage to make up battery The method of charging lithium-ion battery of internal pressure drops, lithium ion battery or polymer Li-ion battery are in charging, when charging to electricity Pressure reaches charging limitation voltage and then stops charging, and the battery charging limitation voltage between battery the two poles of the earth is set as U=2Uo-Us, Us It is the burning voltage that cell voltage is fallen after rise after constant-current charge to Uo, Uo is standard charging blanking voltage, and Uo generally connects for industry The small multiplying power constant current-standard charging blanking voltage used in constant voltage charging method received, the selection of burning voltage Us is from battery Stop constant-current charge and carry out timing when starting to shelve, battery since some period, open a way electricity within some period by battery Pressure drop is pressed to be less than a certain numerical value, the voltage of battery has reached stable, taken the voltage corresponding to first time point of time period Burning voltage Us for battery.
When this method is applied to ferric phosphate lithium cell, Uo small multiplying power constant current-constant-voltage charge sides generally accepted for industry Standard charging blanking voltage 3.60V used in formula is charged to battery charging limitation voltage U=2Uo-Us, fails battery is complete It fills entirely full, fills full degree and only reach 88% or so, fail to give full play to the efficiency of battery.Ferric phosphate lithium cell industry generally connects The small multiplying power constant current received-standard charging blanking voltage Uo used in constant voltage charging method also has 3.50V, 3.65V, 3.7V, fills Electricity fails completely to fill battery full, fails to give full play to the efficiency of battery to battery charging limitation voltage U=2Uo-Us.
When this method is applied to cobalt acid lithium battery, Uo small multiplying power constant current-constant voltage charging methods generally accepted for industry Used standard charging blanking voltage 4.20V is charged to battery charging limitation voltage U=2Uo-Us, fails battery is complete It fills full, fills full degree and only reach 97% or so, fail to play the efficiency of battery completely.
In order to give full play to the efficiency of battery, the appropriate amendment of limitation voltage progress of charging to battery is needed.
Invention content
It is an object of the invention in order to give full play to the efficiency of battery, provide a kind of lithium-ion electric corrected and make up voltage Pond charging method.
Definition
Ideal charging:It is charged using constant-current constant-voltage charging method to lithium ion battery, after disconnecting charging circuit, lithium-ion electric The open circuit burning voltage in pond reaches constant-voltage charge voltage.Theoretically charged using constant-current constant-voltage charging method to lithium ion battery, During constant-voltage charge to infinitesimal electric current, after disconnecting charging circuit, the open circuit burning voltage of lithium ion battery can reach constant pressure Charging voltage.In practice using constant-current constant-voltage charging method to lithium ion battery charge, constant-voltage charge to lithium ion battery from During power consumption stream, lithium ion battery charging current is in dynamic equalization state with consumable electric current, after disconnecting charging circuit, lithium-ion electric The open circuit burning voltage in pond can very close constant-voltage charge voltage.Standard stabiliser voltage:Using as defined in standard or supplier To Uo, constant-voltage charge to as defined in standard or the cut-off current of supplier's agreement, stops charging to the electric current constant-current charge of agreement again; Timing is carried out when being shelved since battery stops constant-current constant-voltage charging, battery is since some period, and battery is in some time Open-circuit voltage pressure drop is less than a certain numerical value in section, and the voltage of battery has reached stable, taken first time point institute of time period Corresponding voltage is the standard stabiliser voltage Uso of battery.
Lithium ion degree of freedom:It is lithium ion degree freely movable in anode.Lithium ion battery is in charging process, lithium Ion, by electrolyte, is embedded into cathode from anode deintercalation.Lithium ion is freely distributed in anode lattice, is respectively suffered from one's own actions To the suitable position of oneself, during deintercalation, lithium ion elder generation deintercalation that road is near, that degree of freedom is big, road it is remote, degree of freedom Deintercalation after small lithium ion, the lithium ion degree of freedom fought by the stringent beam of anode are very low, it is difficult to which deintercalation needs filling for bigger Electric flux can just make the very low lithium ion deintercalation of degree of freedom.
Principle
The charging method of CN101388477B is charged to U=2Uo-Us=Uo+ (Uo-Us) and stops, and compensates for inside battery Pressure drop (Uo-Us), the pressure drop (Uo-Us) are that open circuit shelves generation after constant current I is charged to Uo;Only compensate for corresponding current I's Ohm voltage drop, concentration polarization pressure drop, activation polarization pressure drop and other impedance voltage drops do not have and consider that constant current I is charged to Uo not There is the deintercalation for filling full, not have consideration lithium ion degree of freedom very low part lithium ion, the pressure drop made up is not enough to fill on battery To 100% saturation, it is impossible to reach ideal charging state;The charging method of CN101388477B does not account for equipment error with measuring The influence of error.100% saturation is using as defined in standard or the electric current constant-current charge of supplier's agreement is to Uo constant-voltage charges again To as defined in standard or supplier agreement cut-off current, stop charging, using as defined in standard or supplier agreement electric current As defined in constant-current discharge to standard or the discharge cut-off voltage of supplier's agreement, the capacity released are 100%, institute before electric discharge The charged state at place is exactly 100% saturation.Increase (Uo-Uso) on the basis of U=2Uo-Us=Uo+ (Uo-Us), with electric current I It is charged to U=Uo+ (Uo-Us)+(Uo-Uso)=3Uo-Us-Uso, it is contemplated that the very low part lithium ion of lithium ion degree of freedom Battery could be charged to closer to 100% saturation, reduce the influence of equipment error and measurement error by deintercalation, closer to ideal Charged state.
The scheme that the present invention solves the above problems is as follows:
Using the constant-current constant-voltage charging method of standard, battery is filled full, open circuit is shelved, and finds the standard of ferric phosphate lithium cell Burning voltage differs larger with standard charging blanking voltage, and the standard stabiliser voltage of cobalt acid lithium battery is with standard charging blanking voltage Difference is smaller, and it is directly related that this with ferric phosphate lithium cell fills that full degree is low, cobalt acid lithium battery fills full degree height.
In order to give full play to the efficiency of battery, battery is made to fill every time full, needed on the basis of original U=Uo+ (Uo-Us) Increase (Uo-Uso) correction value, amendment makes up voltage and is:
U=Uo+ (Uo-Us)+(Uo-Uso)=3Uo-Us-Uso
It charges accordingly to ferric phosphate lithium cell and cobalt acid lithium battery, makes up voltage by correcting, battery can be filled more Close to 100% saturation.
After the same method, having is verified to ternary lithium ion battery, lithium manganate battery, lithium titanate battery Identical effect.
It corrects and makes up the method for charging lithium-ion battery of voltage, battery is filled in charging when charging to voltage and reaching battery Electricity limitation voltage U then turns constant-voltage charge, until charging current is decreased to end during 5% to 99.99% of charging current before constant pressure, Battery charging limitation voltage U=3Uo-Us-Uso.
It corrects and makes up the method for charging lithium-ion battery of voltage, battery is filled in charging when charging to voltage and reaching battery Electricity limitation voltage U then turns constant-voltage charge, until charging current is decreased to 50% to 99.99% cut-off of charging current before constant pressure, Battery charging limitation voltage U=3Uo-Us-Uso between battery the two poles of the earth.
Uso is the standard stabiliser voltage of cell voltage falling after constant-current constant-voltage charging to Uo;
Us is the burning voltage of cell voltage falling after constant-current charge to Uo;
Uo is standard charging blanking voltage.
Uso is the standard stabiliser voltage of cell voltage falling after constant-current constant-voltage charging to Uo, and the selection of value is using as follows Mode:Timing is carried out when being shelved since battery stops constant-current constant-voltage charging, and battery is from some period TUsoStart, battery exists Some period TUsoInterior open-circuit voltage pressure drop is less than a certain numerical value, and the voltage of battery has reached stable, taken time period TUso's Voltage corresponding to first time point is the standard stabiliser voltage Uso of battery.
Specifically, using as defined in standard or the electric current constant-current charge of supplier's agreement to Uo again constant-voltage charge to standard gauge The cut-off current of fixed or supplier agreement, stops charging;Timing is carried out when being shelved since battery stops constant-current constant-voltage charging, Battery is from some period TUsoStart, battery is in some period TUsoInterior open-circuit voltage pressure drop is less than a certain numerical value, battery Voltage has reached stable, takes time period TUsoFirst time point corresponding to voltage be battery standard stabiliser voltage Uso。
Us is the burning voltage of cell voltage falling after constant-current charge to Uo, and the selection of value is in the following way:From electricity Pond stops constant-current charge and carries out timing when starting to shelve, and battery is from some period TUsStart, battery is in some period TUsIt is interior Open-circuit voltage pressure drop is less than a certain numerical value, and the voltage of battery has reached stable, taken time period TUsFirst time point institute it is right The voltage answered is the burning voltage Us of battery.
Uo is standard charging blanking voltage, and Uo is made by the generally accepted small multiplying power constant current-constant voltage charging method of industry Charge cutoff voltage.
As an improvement scheme, amendment of the invention makes up the method for charging lithium-ion battery of voltage, and battery can electricity Stream current constant mode is charged to U=3Uo-Us-Uso, that is, stops charging.
As another improvement project, amendment of the invention makes up the non-constant voltage charging method of lithium ion battery of voltage, electricity Pond can be charged to U=3Uo-Us-Uso with current segmenting current constant mode and turn constant-voltage charge, until charging current is filled before being decreased to constant pressure 50% to 99.99% cut-off of electric current, Us are determined with the latter end current measurement stopped before charging.
As another improvement project, amendment of the invention makes up the non-constant voltage charging method of lithium ion battery of voltage, electricity Pond can be charged to U=3Uo-Us-Uso with the non-current constant mode of electric current and turn constant-voltage charge, until charging current charges before being decreased to constant pressure 50% to 99.99% cut-off of electric current, Us are to measure what is determined with the end current stopped before charging.
As a kind of measurement method of Uso, the method for charging lithium-ion battery for making up voltage is corrected, it is permanent that battery stops constant current Pressure charging carries out timing when starting to shelve, and is used as a period within every 5 minutes, when battery is since some period T5, battery In the period T of 5 minutes5Interior open-circuit voltage pressure drop can be considered that the voltage of battery has reached stable after being less than 2mV, take this time Section T5First time point corresponding to voltage be battery standard stabiliser voltage Uso.
As the measurement method of another Uso, the method for charging lithium-ion battery for making up voltage is corrected, battery stops constant current It carries out timing when constant-voltage charge starts to shelve, is used as a period within every 10 minutes, when battery is from some period T10Start, electricity Period T of the pond at 10 minutes10Interior open-circuit voltage pressure drop can be considered that the voltage of battery has reached stable after being less than 1mV, take this Period T10First time point corresponding to voltage be battery standard stabiliser voltage Uso.
As the measurement method of another Us, the selection of Us values is in the following way:Since battery stops constant-current charge Carry out timing when shelving, battery is from some period TUs’Start, battery is in some period TUs’Interior open-circuit voltage pressure drop is less than A certain numerical value, the voltage of battery have reached stable, have taken time period TUs’First time point corresponding to voltage for battery Burning voltage Us.
Uo small multiplying power constant current-charge cutoff voltages used in constant voltage charging method generally accepted for industry.
When battery is cobalt acid lithium battery and when taking Uo=4.2V, Uo ≈ Uso are charged to U ≈ Uo+ (Uo-Us) and then stop filling Electricity.
It should be clear that standard stabiliser voltage Uso has with standard charging blanking voltage Uo and standard charging cut-off current It closes, it is little or almost without relationship with rate of charge relationship.
Well known, for ferric phosphate lithium cell, standard charging blanking voltage Uo can be 3.5V, 3.6V, 3.65V, 3.7V, Corresponding different Uo, can obtain different normal capacity C0.The definition of normal capacity:Using as defined in standard or supplier agreement Electric current constant-current charge to Uo, constant-voltage charge to as defined in standard or the cut-off current of supplier's agreement, is then provided by standard again Or the discharge current of supplier's agreement discharge into as defined in standard or the discharge cut-off voltage of supplier's agreement, the appearance discharged Amount is normal capacity C0.The standard charging blanking voltage Uo of ferric phosphate lithium cell can choose any known value, and when fast charge is thought It to be quickly filled with close to corresponding normal capacity C0Capacity, be all applicable in correct and make up voltage as U=Uo+ (Uo-Us)+(Uo- Uso the charging method of)=3Uo-Us-Uso.
Well known, for cobalt acid lithium battery, classical conventional cobalt acid lithium battery standard charging blanking voltage Uo is 4.2V, The cobalt acid lithium battery of 4.3V and 4.35V high voltages is had developed now, is developing the cobalt acid lithium electricity of 4.4V and 4.5V high voltages Pond, corresponding standard charging blanking voltage Uo are exactly 4.3V, 4.35V, 4.4V, 4.5V, and corresponding different Uo can obtain difference Normal capacity C0.The standard charging blanking voltage Uo of the cobalt acid lithium battery of different voltages can choose it and correspond to known value, soon Want quickly to be filled with close to corresponding normal capacity C when filling0Capacity, all be applicable in correct make up voltage for U=Uo+ (Uo-Us)+ (Uo-Uso) charging method of=3Uo-Us-Uso.
It is well known, for ternary lithium battery (nickel manganese cobalt acid lithium battery), classical conventional ternary lithium battery standard charging Blanking voltage Uo is 4.2V, is developing the ternary lithium battery of 4.3V and 4.35V high voltages now, and corresponding standard charging is cut Only voltage Uo is exactly 4.3V, 4.35V, and corresponding different Uo can obtain different normal capacity C0.The ternary lithium electricity of different voltages The standard charging blanking voltage Uo in pond can choose it and correspond to known value, and when fast charge is wanted quickly to be filled with close to correspondence normal capacity C0Capacity, all be applicable in correct make up voltage for U=Uo+ (Uo-Us)+(Uo-Uso)=3Uo-Us-Uso charging method.
Special case situation, when cobalt acid lithium battery takes Uo=4.2V (as shown in Figure 2), Uo ≈ Uso are charged to U ≈ Uo+ (Uo- Us) then stop charging, with regard to that can obtain with constant-current constant-voltage charging to effect almost the same 4.2V, i.e., for cobalt acid lithium battery Uo= 4.2V when, (Uo-Uso) correction value can be ignored.But in other standard charging blanking voltage Uo, Uo as shown in Figure 3 The deviation of the situation of=4.35V, Uo and Uso are larger, need to consider that (Uo-Uso) correction value could allow battery charging close 100%.
Relatively existing charging method, beneficial effects of the present invention are as follows:
1st, lithium ion battery charging is fast and can be charged into electricity close to saturation;
2nd, charging method of the invention is suitable for the charging of various lithium ion batteries, can fill battery closer 100% saturation can give full play to the efficiency of battery;
3. charging with the inventive method to lithium ion battery, discharge, followed with identical times in standard or user method The electric current constant-current constant-voltage charging of rate is compared, and is had longer cycle life or identical cycle-index, is filled with the inventive method Electricity, the capacity higher for releasing of discharging;
4. charging circuit can be designed using the method for the present invention, charger is made;
5. electronic component can be made using the method for the present invention, use is assembled together with battery core;
6. constant voltage charging method may be used in the method for the present invention, more meet charging custom and the charging of lithium ion battery user The selection of integrated circuit;
7. the method for the present invention can charge to a certain current value cut-off with constant voltage mode, it is easier to realize.
Description of the drawings
Attached drawing 1 is that standard stabiliser voltage Uso curves are arrived with constant-current charge after ferric phosphate lithium cell constant-current constant-voltage charging to Uo Burning voltage Us curves after Uo.
Attached drawing 2 is standard stabiliser voltage Uso curves and constant-current charge to Uo after cobalt acid lithium battery constant-current constant-voltage charging to Uo Burning voltage Us curves afterwards.
Attached drawing 3 be after 4.35V high voltage type cobalt acid lithium battery constant-current constant-voltage chargings to Uo standard stabiliser voltage Uso curves with Burning voltage Us curves after constant-current charge to Uo.
Specific embodiment
With reference to comparative example, the present invention will be further described with embodiment, so as to embody the specific embodiment party of the present invention Formula and advantage.
Comparative example 1.1:Ferric phosphate lithium cell, standard recharging methods
402045Fe15C is high-rate type 3.2V190mAh ferric phosphate lithium cells, and battery system is LiFePO4/C systems monomer Battery (Uo=3.6V), rated capacity Cr=190mAh, reference GB/T18287-2013 standard recharging methods,
1. with 38mA (0.2C) constant-current charges to 3.6V, turn constant pressure 3.6V and charge to electric current to be reduced to 3.8mA (0.02C), Stop charging, record charging time Tc and charging capacity Cc;
2. with 38mA (0.2C) constant-current discharges to 2.0V, record discharge capacity Cd.(this releasable appearance of step assessment charging Amount is not that charging method institute is necessary.)
3. cycle:
3.1 with 1140mA constant-current charges to 3.6V, turn constant pressure 3.6V and charge to electric current to be reduced to 3.8mA
3.2 shelve 5min
3.3 use 1140mA constant-current discharges to 2.0V
3.4 shelve 5min
3.5 cycle 3.1 steps to 3.4 step 1000 times
3.6 terminate
Comparative example 1.2:Ferric phosphate lithium cell, CN101388477B charging methods
With the battery of comparative example 1.1, it is expected battery is fully charged within the time of t=10min, according to CN101388477B A kind of disclosed fast charge method, (6C times required of constant-current charge electric current I=Cr/t*60=190/10*60=1140mA Rate).
1. survey burning voltage:With 1140mA constant-current charges to 3.6V, stop, testing open-circuit voltage, measure burning voltage Us, Burning voltage Us curves are shown in attached drawing 1;Timing is carried out when being shelved since battery stops constant-current charge, when being used as one within every 10 minutes Between section, when battery is since some period, battery open-circuit voltage pressure drop within the period of 10 minutes is less than i.e. visual after 1mV Voltage for battery has reached stable, takes the burning voltage that the voltage corresponding to first time point of time period is battery Us;
2. with 38mA (0.2C) constant-current discharges to 2.0V, (this step is to release the capacity that upper step is filled with, and is in battery and treats State is filled, is not that charging method institute is necessary);
3. with 1140mA constant-current charges to 2Uo-Us, stop charging, record charging time Tc and charging capacity Cc;
4. with 38mA (0.2C) constant-current discharges to 2.0V, record discharge capacity Cd (this releasable capacity of step assessment charging, It is not that charging method institute is necessary);
5. cycle:
5.1 use 1140mA constant-current charges to 2Uo-Us
5.2 shelve 5min
5.3 use 1140mA constant-current discharges to 2.0V
5.4 shelve 5min
5.5 cycle 5.1 steps to 5.4 step 1000 times
5.6 terminate
Embodiment 1:Ferric phosphate lithium cell, the method for the present invention
With the battery of comparative example 1.1, the burning voltage Us measured using comparative example 1.2;
1. mark quasi-steady voltage:With 38mA (0.2C) constant-current charges to 3.6V, turn constant pressure 3.6V and charge to electric current reduction To 3.8mA (0.02C), stop, testing open-circuit voltage, measure standard stabiliser voltage Uso, standard stabiliser voltage Uso curves are shown in attached Fig. 1;Battery stops constant-current constant-voltage charging and timing is carried out when starting to shelve, and is used as a period within every 10 minutes, when battery from certain A period, battery open-circuit voltage pressure drop within the period of 10 minutes can be considered the voltage of battery after being less than 1mV Reach stable, take the standard stabiliser voltage Uso that the voltage corresponding to first time point of time period is battery;
2. with 38mA (0.2C) constant-current discharges to 2.0V;(this step is to release the capacity that step is filled with, and is in battery and treats State is filled, is not that charging method institute is necessary);
3. expectation is fully charged within the time of 10min by battery, according to the present invention to correct the lithium-ion electric for making up voltage Pond charging method, required constant-current charge electric current are 1140mA (6C multiplying powers), are charged to U=3Uo-Us-Uso and turn constant-voltage charge, Until charging current is decreased to 95% cut-off record charging time Tc of charging current and charging capacity Cc before constant pressure;
4. with 38mA (0.2C) constant-current discharges to 2.0V, record discharge capacity Cd (this releasable capacity of step assessment charging, It is not that charging method institute is necessary);
5. cycle:
5.1 turn constant-voltage charge with 1140mA constant-current charges to 3Uo-Us-Uso, until charging current is decreased to 1083mA (perseverances The 95% of charging current before pressure) cut-off
5.2 shelve 5min
5.3 use 1140mA constant-current discharges to 2.0V
5.4 shelve 5min
5.5 cycle 5.1 steps to 5.4 step 1000 times
5.6 terminate
Comparative example 1.1, comparative example 1.2,1 result of the test of embodiment are listed in table 1.
1 comparative example 1.1 of table, comparative example 1.2,1 result of the test of embodiment
Charge saturation degree:It is charged with standard recharging methods, standard charging method electric discharge, the capacity released is 100%;It is non- Standard recharging methods charge, the electric discharge of standard charging method, and the capacity released is full for charging with the percentage of standard discharge capacity And degree.
Comparative example 2.1:Cobalt acid lithium battery, standard recharging methods
703048H10C is high-rate type 3.7V800mAh polymer Li-ion batteries, battery system LiCoO2/ C systems are single Body battery (Uo=4.2V), rated capacity Cr=800mAh, reference GB/T18287-2013 standard recharging methods,
1. with 160mA (0.2C) constant-current charges to 4.2V, turn constant pressure 4.2V and charge to electric current to be reduced to 16mA (0.02C), Record charging time Tc and charging capacity Cc;
2. with 160mA (0.2C) constant-current discharges to 3.0V, record discharge capacity Cd (this releasable appearance of step assessment charging Amount is not that charging method institute is necessary);
3. cycle:
3.1 with 4800mA constant-current charges to 4.2V, turn constant pressure 4.2V and charge to electric current to be reduced to 16mA
3.2 shelve 5min
3.3 use 4800mA constant-current discharges to 3.0V
3.4 shelve 5min
3.5 cycle 3.1 steps to 3.4 step 500 times
3.6 terminate
Comparative example 2.2:Cobalt acid lithium battery, CN101388477B charging methods
With the battery of comparative example 2.1, it is expected battery is fully charged within the time of t=10min, according to CN101388477B A kind of disclosed fast charge method, (6C times required of constant-current charge electric current I=Cr/t*60=800/10*60=4800mA Rate),
1. survey burning voltage:With 4800mA constant-current charges to 4.2V, stop, testing open-circuit voltage, measure burning voltage Us, Burning voltage Us curves are shown in attached drawing 2;Timing is carried out when being shelved since battery stops constant-current charge, when being used as one within every 10 minutes Between section, when battery is since some period, battery open-circuit voltage pressure drop within the period of 10 minutes is less than i.e. visual after 1mV Voltage for battery has reached stable, takes the burning voltage that the voltage corresponding to first time point of time period is battery Us;
2. with 160mA (0.2C) constant-current discharges to 3.0V;(this step is to release the capacity that step is filled with, and is in battery State to be filled is not that charging method institute is necessary)
3. with 4800mA constant-current charges to 2Uo-Us, stop charging, record charging time Tc and charging capacity Cc;
4. with 160mA (0.2C) constant-current discharges to 3.0V, record discharge capacity Cd (this releasable appearance of step assessment charging Amount is not that charging method institute is necessary);
5. cycle
5.1 use 4800mA constant-current charges to 2Uo-Us
5.2 shelve 5min
5.3 use 4800mA constant-current discharges to 3.0V
5.4 shelve 5min
5.5 cycle 5.1 steps to 5.4 step 500 times
5.6 terminate
Embodiment 2:Cobalt acid lithium battery, the method for the present invention
With the battery of comparative example 2.1, the burning voltage Us measured using comparative example 2.2;
1. mark quasi-steady voltage:With 160mA (0.2C) constant-current charges to 4.2V, turn constant pressure 4.2V and charge to electric current reduction To 16mA (0.02C), stop, testing open-circuit voltage, measure standard stabiliser voltage Uso, standard stabiliser voltage Uso curves are shown in attached drawing 2;Battery stops constant-current constant-voltage charging and timing is carried out when starting to shelve, and is used as a period within every 10 minutes, when battery from some Period, battery open-circuit voltage pressure drop within the period of 10 minutes can be considered that the voltage of battery has reached after being less than 1mV To stabilization, the standard stabiliser voltage Uso that the voltage corresponding to first time point of time period is battery is taken;
2. with 160mA (0.2C) constant-current discharges to 3.0V;(this step is to release the capacity that step is filled with, and is in battery State to be filled is not that charging method institute is necessary)
3. expectation is fully charged within the time of 10min by battery, according to the present invention to correct the lithium-ion electric for making up voltage Pond charging method, required constant-current charge electric current are 4800mA (6C multiplying powers), are charged to U=3Uo-Us-Uso and turn constant-voltage charge, The 95% of charging current before charging current is decreased to constant pressure) end record charging time Tc and charging capacity Cc;
4. with 160mA (0.2C) constant-current discharges to 3.0V, record discharge capacity Cd (this releasable appearance of step assessment charging Amount is not that charging method institute is necessary);
5. cycle
5.1 turn constant-voltage charge with 4800mA constant-current charges to 3Uo-Us-Uso, until charging current is decreased to 4560mA (perseverances The 95% of charging current before pressure) cut-off
5.2 shelve 5min
5.3 use 4800mA constant-current discharges to 3.0V
5.4 shelve 5min
5.5 cycle 5.1 steps to 5.4 step 500 times
5.6 terminate
Comparative example 2.1, comparative example 2.2,2 result of the test of embodiment are listed in table 2.
2 comparative example 2.1 of table, comparative example 2.2,2 result of the test of embodiment
Comparative example 3.1:4.35V high voltage cobalt acid lithium batteries, standard recharging methods
601250HV10C is 4.35V high voltage type 235mAh polymer Li-ion batteries, and battery system is 4.35V high electricity Press LiCoO2/ C systems, single battery (Uo=4.35V), rated capacity Cr=235mAh are filled with reference to GB/T18287-2013 standards Method for electrically,
1. with 47mA (0.2C) constant-current charges to 4.35V, turn constant pressure 4.2V and charge to electric current to be reduced to 4.7mA (0.02C), Record charging time Tc and charging capacity Cc;
2. with 47mA (0.2C) constant-current discharges to 3.0V, record discharge capacity Cd (this releasable capacity of step assessment charging, It is not that charging method institute is necessary);
3. cycle:
3.1 with 470mA constant-current charges to 4.35V, turn constant pressure 4.35V and charge to electric current to be reduced to 4.7mA
3.2 shelve 5min
3.3 use 470mA constant-current discharges to 3.0V
3.4 shelve 5min
3.5 cycle 3.1 steps to 3.4 step 500 times
3.6 terminate
Comparative example 3.2:4.35V high voltage cobalt acid lithium batteries, CN101388477B charging methods
With the battery of comparative example 3.1, it is expected battery is fully charged within the time of t=30min, according to CN101388477B A kind of disclosed fast charge method, (2C times required of constant-current charge electric current I=Cr/t*60=235/30*60=470mA Rate),
1. survey burning voltage:With 470mA constant-current charges to 4.35V, stop, testing open-circuit voltage, measure burning voltage Us, Burning voltage Us curves are shown in attached drawing 3;Timing is carried out when being shelved since battery stops constant-current charge, when being used as one within every 5 minutes Between section, when battery is since some period, battery open-circuit voltage pressure drop within the period of 5 minutes is less than i.e. visual after 2mV Voltage for battery has reached stable, takes the burning voltage that the voltage corresponding to first time point of time period is battery Us;
2. with 47mA (0.2C) constant-current discharges to 3.0V;(this step is to release the capacity that step is filled with, and is in battery and treats State is filled, is not that charging method institute is necessary)
3. with 470mA constant-current charges to 2Uo-Us, stop charging, record charging time Tc and charging capacity Cc;
4. with 47mA (0.2C) constant-current discharges to 3.0V, record discharge capacity Cd (this releasable capacity of step assessment charging, It is not that charging method institute is necessary);
5. cycle
5.1 use 470mA constant-current charges to 2Uo-Us
5.2 shelve 5min
5.3 use 470mA constant-current discharges to 3.0V
5.4 shelve 5min
5.5 cycle 5.1 steps to 5.4 step 500 times
5.6 terminate
Embodiment 3:4.35V high voltage cobalt acid lithium batteries, the method for the present invention
With the battery of comparative example 3.1, the burning voltage Us measured using comparative example 3.2;
1. mark quasi-steady voltage:With 47mA (0.2C) constant-current charges to 4.35V, turn constant pressure 4.35V and charge to electric current to subtract It is small to arrive 4.7mA (0.02C), stop, testing open-circuit voltage, measure standard stabiliser voltage Uso, standard stabiliser voltage Uso curves are shown in Attached drawing 3;Battery stops constant-current constant-voltage charging and timing is carried out when starting to shelve, and is used as a period within every 5 minutes, when battery from certain A period, battery open-circuit voltage pressure drop within the period of 5 minutes can be considered that the voltage of battery has reached after being less than 2mV To stabilization, the standard stabiliser voltage Uso that the voltage corresponding to first time point of time period is battery is taken;
2. with 47mA (0.2C) constant-current discharges to 3.0V;(this step is to release the capacity that step is filled with, and is in battery and treats State is filled, is not that charging method institute is necessary)
3. expectation is fully charged within the time of 30min by battery, according to the present invention to correct the lithium-ion electric for making up voltage Pond charging method, required constant-current charge electric current are 470mA (2C multiplying powers), are charged to U=3Uo-Us-Uso and turn constant-voltage charge, directly 95% cut-off of charging current, record charging time Tc and charging capacity Cc before being decreased to constant pressure to charging current;
4. with 47mA (0.2C) constant-current discharges to 3.0V, record discharge capacity Cd;(this releasable appearance of step assessment charging Amount is not that charging method institute is necessary)
5. cycle
5.1 turn constant-voltage charge with 470mA constant-current charges to 3Uo-Us-Uso, until charging current is decreased to 446.5mA (perseverances The 95% of charging current before pressure) cut-off
5.2 shelve 5min
5.3 use 470mA constant-current discharges to 3.0V
5.4 shelve 5min
5.5 cycle 5.1 steps to 5.4 step 500 times
5.6 terminate
Comparative example 3.1, comparative example 3.2,3 result of the test of embodiment are listed in table 3.
3 comparative example 3.1 of table, comparative example 3.2,3 result of the test of embodiment
In specific implementation process, selectively, 1. can be to measure Us, Uso, then by this hair before every battery every time charging The method charging of bright (or CN101388477B), it is clear that pretty troublesome in this way;It 2. can be to measure Us, Uso before every battery charging, so Charging is charged by the method for (or CN101388477B) of the invention every time afterwards, still pretty troublesome in this way;It 3. can be with each size battery Us, Uso are measured before charging, the side that then every battery of this kind of size battery charges by (or CN101388477B) of the invention every time Method charges, thus very convenient.Although there are fine difference or every battery not homogeneous between model Different Individual battery of the same race There are fine differences before number charging, do not influence the implementation of patent;The implementation of this patent can make the nearly saturation of charging, not ensure every Battery 100% saturation of charging every time.
In specific implementation process, it is not necessarily required to that lithium ion batteries is waited to be discharged again to charge completely, at lithium ion battery In the case of empty electric, half electric or more than half electricity, the method for the present invention can be used to charge;It need not then be filled in the case of full electricity Electricity.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party Formula is changed and is changed, such as applied to various lithium ion batteries, battery pack, charging circuit, charger, charge controlling element It waits in products.Therefore, the invention is not limited in specific embodiment disclosed and described above, some modifications to the present invention It should also be as falling into the scope of the claims of the present invention with change.

Claims (12)

1. correcting the method for charging lithium-ion battery for making up voltage, battery is in charging, it is characterised in that:It is reached when charging to voltage Then turn constant-voltage charge to the battery limitation voltage U that charges, until charging current be decreased to 5% of charging current before constant pressure to End when 99.99%, battery charging limitation voltage U=3Uo-Us-Uso.
2. according to claim 1 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:When charging to Voltage reaches battery charging limitation voltage U and then turns constant-voltage charge, the 50% of charging current before charging current is decreased to constant pressure End during to 99.99%, battery charging limitation voltage U=3Uo-Us-Uso;
3. according to claim 1 or 2 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Us values Selection in the following way:Timing is carried out when being shelved since battery stops constant-current charge, and battery is from some period TUsIt opens Begin, battery is in some period TUsInterior open-circuit voltage pressure drop is less than a certain numerical value, and the voltage of battery has reached stable, taken this time Section TUsFirst time point corresponding to voltage be battery burning voltage Us.
4. according to claim 1 or 2 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Battery Battery limitation voltage U is charged to electric current current constant mode.
5. according to claim 1 or 2 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Battery Being charged to battery limitation voltage U, Us with current segmenting current constant mode is determined with the latter end current measurement stopped before charging.
6. according to claim 1 or 2 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Battery It is to measure what is determined with the end current stopped before charging to be charged to battery limitation voltage U, Us with the non-current constant mode of electric current.
7. according to claim 1 or 2 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Uso is When the standard stabiliser voltage that cell voltage is fallen after rise after constant-current constant-voltage charging to Uo is shelved since battery stops constant-current constant-voltage charging Timing is carried out, battery is from some period TUsoStart, battery is in some period TUsoInterior open-circuit voltage pressure drop is less than a certain number Value, the voltage of battery have reached stable, have taken time period TUsoFirst time point corresponding to voltage for battery standard it is steady Constant voltage Uso.
8. according to claim 7 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Battery stops It carries out timing when constant-current constant-voltage charging starts to shelve, is used as a period within every 5 minutes, when battery is from some 5 minutes section T5Start, period T of the battery at 5 minutes5Interior open-circuit voltage pressure drop can be considered that the voltage of battery has reached steady after being less than 2mV It is fixed, take time period T5First time point corresponding to voltage be battery standard stabiliser voltage Uso.
9. according to claim 7 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Battery stops It carries out timing when constant-current constant-voltage charging starts to shelve, is used as a period within every 10 minutes, when battery is from some 10 minutes Section T10Start, period T of the battery at 10 minutes10Interior open-circuit voltage pressure drop can be considered that the voltage of battery has reached after being less than 1mV To stabilization, time period T is taken10First time point corresponding to voltage be battery standard stabiliser voltage Uso.
10. according to claim 7 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Us values It chooses in the following way:Timing is carried out when being shelved since battery stops constant-current charge, and battery is from some period TUs’It opens Begin, battery is in some period TUs’Interior open-circuit voltage pressure drop is less than a certain numerical value, and the voltage of battery has reached stable, taken at this time Between section TUs’First time point corresponding to voltage be battery burning voltage Us.
11. according to claim 1 or 2 correct the method for charging lithium-ion battery for making up voltage, it is characterised in that:Uo is The generally accepted small multiplying power constant current-charge cutoff voltage used in constant voltage charging method of industry institute.
12. according to claim 1 or 2 correct the lithium ion battery method for electrically for making up voltage, it is characterised in that:Work as battery It is cobalt acid lithium battery and when taking Uo=4.2V, Uo ≈ Uso are charged to U ≈ Uo+ (Uo-Us) and then stop charging.
CN201780002550.9A 2017-12-07 2017-12-07 Correct the method for charging lithium-ion battery for making up voltage Pending CN108235791A (en)

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