CN102861726B - Lithium secondary battery consistency screening method - Google Patents

Lithium secondary battery consistency screening method Download PDF

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CN102861726B
CN102861726B CN201110186716.1A CN201110186716A CN102861726B CN 102861726 B CN102861726 B CN 102861726B CN 201110186716 A CN201110186716 A CN 201110186716A CN 102861726 B CN102861726 B CN 102861726B
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voltage
cell
battery
charge
charging
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CN102861726A (en
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唐胜成
成定波
曾石华
张常勇
邱德铭
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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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    • 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
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a lithium secondary battery consistency screening method, belonging to the field of secondary batteries, characterized in that: a unit battery grades the capacity, platform, and internal resistance when conducting capacity grading and detection, and then the unit battery is charged by multi-step constant current and constant voltage, wherein a constant current of 0.3-5C5 is used for charging to a voltage V0, when the charging current is 0.1-0.3 C5, the charge is stopped and the battery is shelved; after the battery is shelved for 5-30 min, the charging is continued with a constant current of 0.1-0.3 C5 to the voltage V0, when the charging current is 0.05-0.1 C5, the charge is stopped and the battery is shelved; after the battery is shelved for 5-30 min, the charging is continued with a constant current of 0.05-0.1 C5 to the voltage V0, when the charging current is 0.03-0.05 C5, the charge is stopped and the battery is shelved; after the battery is shelved for 5-30 min, the charging is continued with a constant current of 0.03-0.05 C5 to the voltage V0, when the charging current is 0.01-0.03 C5, the charge is stopped; after the charging is complete, the unit battery is shelved at a normal temperature, the shelving time is no less than 24h, when the shelving ends, measurement is carried out on the open-circuit voltage Vt of the unit battery, if the open-circuit voltage Vt is no less than the result of V0 minus delta V0 and minus n*delta V, the unit battery is qualified. According to the invention, the qualified unit battery screened by the invention has low self-consuming hazards, the combined battery pack has good self-discharge consistency, high reliability, and rapidness, simpleness and easy operation in practical application, and has a good market application prospect.

Description

A kind of lithium secondary battery consistency screening technique
Technical field
A kind of lithium secondary battery consistency of the present invention screening technique belongs to secondary cell field, particularly relates to a kind of cell consistency screening technique of lithium ion battery group.
Background technology
Along with the fast development of lithium ion battery, lithium ion battery also starts to be widely applied as power, accumulation power supply.Compare with small-sized movable power consumption equipments such as mobile phones, power, the required accumulation power supply power output of energy-storage battery are high, long service life, this just requires how also battery carries out, the combination of many strings, and the price of battery pack is high, is worth large, therefore, battery reliability and consistency are had higher requirement.In battery pack, the arbitrarily functional inefficacy of cell, all can cause the functional inefficacy of whole battery pack, even can cause the problems such as the fail safe of battery pack is out of control.For guaranteeing the consistency of each cell in battery pack, need to screen cell, divide into groups, to guarantee the consistency of each cell in battery pack.The coincident indicator of battery has capacity, voltage, discharge platform, internal resistance, from power consumption rate etc.Wherein, particularly important from power consumption rate with battery, and be difficult to screen.In there is no the system of balance charge/discharge, because of different from power consumption, through storing for a long time and using, the consistency of cell can change a lot.Consumable electric test method is to weigh with retention of charge in CNS GB/T18287 " cell phone lithium ion battery general specification ", is at room temperature full of to establish road by cable and shelve 28 days, with 0.2C 5a electric current is discharged to final voltage, and its discharge capacity should be greater than 85% of rated capacity; In IEC61960-1 standard " Secondary lithium cells and batteries for portable applications-Part 1:Secondary lithium cells ", consumable electric test method is also with retention of charge, to weigh, at room temperature be full of and establish road by cable and shelve 28 days, with 0.2C 5a electric current is discharged to final voltage, and its discharge capacity should be greater than 70% of rated capacity.According to standard, from power consumption, at the cell below 15% or 30%, be all qualified, available, still, if by from power consumption, be 1% and the cell that is 10% from power consumption be made into the battery pack of two strings, even if initial capacity, voltage, internal resistance are consistent, full charging, shelves 28 days, a cell keeps 99% capacity, another cell keeps 90% capacity, and in battery pack, the capacity of cell, voltage become inconsistent, and extends in time difference and widen.
The consumable electric test method of industry universal is to shelve a certain fixedly duration after cell is filled with to certain electric weight at present, and before and after shelving by test, the voltage difference of cell is picked out from power consumption cell bigger than normal.As Chinese patent application CN101764259A discloses, " battery is charged to 50~90% rated capacities; t3 and t4 time point are measured respectively its voltage after charging finishes; obtain V3 and V4; with V3, deduct the voltage drop that V4 obtains secondary cell; determine after voltage drop criterion of acceptability, sub-elect the qualified secondary cell of voltage drop." one of the defect of these class methods is all monomer battery voltage to be measured before and after requirement is shelved; and before and after need to shelving each cell, voltage carries out clear dataization management one to one; and need to carry out bar code management to cell, strengthen the difficulty of production operation.Two of the defect of these class methods be can only provide fixedly shelve battery under time conditions from power consumption criterion, be difficult to the reliability of stock's stock battery in production process to manage and meet the requirement of different production friendship phases.
Summary of the invention
The object of the invention is to avoid weak point of the prior art, and a kind of large-scale production and application that are beneficial to are provided, select the conforming method of cell, especially select cell from the conforming method of power consumption.
For fixing battery system, the relation of battery open circuit voltage capacity charged with it is relatively stable.As cell adopted to constant-potential charge before shelving, guarantee the consistency of the initial state-of-charge of cell, then only need to measure the open circuit voltage of cell, the levels of leakage that can reflect this cell, open circuit voltage is relatively higher, illustrate that cell is less from power consumption, open circuit voltage is lower, shows that cell is larger from power consumption.According to acceptable levels of leakage requirement, set up the qualified cell open circuit voltage standard corresponding with the time of shelving, by measuring the open circuit voltage of cell, to pick out from power consumption cell bigger than normal.Meanwhile, according to the height of the open circuit voltage of cell, to cell from power consumption level, carry out stepping, during cell combo, from the approaching cell of power consumption, be made into one group, to guarantee in battery pack that each cell is from the consistency of power consumption level.
The object of the invention is to realize by following measures:
Cell first to capacity, platform, internal resistance stepping, is then used multi-stage constant current constant voltage charge to battery when partial volume detects,
First paragraph, is used 0.3C 5~5C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.1C 5~0.3C 5stopping charges with turning shelves;
Second segment, shelves after 5~30 minutes and continues with 0.1C 5~0.3C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.05C 5~0.1C 5stopping charges with turning shelves;
The 3rd section, shelve after 5~30 minutes and continue with 0.05C 5~0.1C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.03C 5~0.05C 5stopping charges with turning shelves;
The 4th section, shelve after 5~30 minutes and continue with 0.03C 5~0.05C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.01C 5~0.03C 5stop charging;
Charged and rear cell carried out to normal temperature shelf, shelved duration and be not less than 24h, while shelving cut-off to cell open circuit voltage V tmeasure open circuit voltage V t>=V 0-Δ V 0-n * Δ V cell is judged to be qualified cell.Meanwhile, for qualified cell according to V tsize is carried out voltage stepping with the class of 1~20mV, with class cell, carries out combo.
C 5it is rated capacity.
Charging voltage V 0according to battery system, determine, as cobalt acid lithium-graphite system, LiMn2O4-graphite system, nickle cobalt lithium manganate-graphite system etc. are 3.0~4.2V, preferred, cobalt acid lithium-graphite system, LiMn2O4-graphite system, nickle cobalt lithium manganate-graphite system etc. are 3.3~3.65V.LiFePO4-graphite body is 2.0~3.65V, preferred, and LiFePO4-graphite body is 2.8~3.2V.
Δ V 0battery polarization pressure drop and charging cabinet voltage accuracy error during for charging, its span is 5~20mV, preferred its span is 5~10mV.While wherein charging, battery polarization pressure drop is the product of charging cut-off current and battery DC impedance.
Δ V is for often shelving 12h open circuit voltage decrease speed, and its span is 1~5mV.Can adopt charging method of the present invention, cell is charged to V 0after carry out normal temperature shelf, then every 12h, measure cell open circuit voltage and fall, comprehensive cell reliability and cell utilance, obtain cell by statistics and often shelve 12h monomer battery voltage decrease speed.Preferred its span is 1~3mV.
N is for shelving half number of days, and shelving initial time n value is 0, then shelves every increase of time 12h, and n value increases by 1.
The object of the invention is to realize by following measures:
Cell first to capacity, platform, internal resistance stepping, is then used 0.1C to cell when partial volume detects 5~5C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.01 C 5~0.1C 5charging stops, and then cell is carried out to normal temperature shelf, shelves duration and is not less than 24h, shelves while ending cell open circuit voltage V tmeasure open circuit voltage V t>=V 0-Δ V 0-n * Δ V cell is judged to be qualified cell.Meanwhile, for qualified cell according to V tsize is carried out voltage stepping with the class of 1~20mV, with class cell, carries out combo.
C 5it is rated capacity.
Charging voltage V 0according to battery system, determine, as cobalt acid lithium-graphite system, LiMn2O4-graphite system, nickle cobalt lithium manganate-graphite system etc. are 3.0~4.2V, preferred, cobalt acid lithium-graphite system, LiMn2O4-graphite system, nickle cobalt lithium manganate-graphite system etc. are 3.3~3.65V.LiFePO4-graphite body is 2.0~3.65V, preferred, and LiFePO4-graphite body is 2.8~3.2V.
Δ V 0battery polarization pressure drop and charging cabinet voltage accuracy error sum during for charging, its span is 5~20mV, preferred its span is 5~10mV.While wherein charging, battery polarization pressure drop is the product of charging cut-off current and battery DC impedance.
Δ V is for often shelving 12h open circuit voltage decrease speed, and its span is 1~5mV.Can adopt charging method of the present invention, cell is charged to V 0after carry out normal temperature shelf, then every 12h, measure cell open circuit voltage and fall, comprehensive cell reliability and cell utilance, obtain cell by statistics and often shelve 12h monomer battery voltage decrease speed.Its span is 1~5mV, and preferred its span is 1~3mV.
N is for shelving half number of days, and shelving initial time n value is 0, then shelves every increase of time 12h, and n value increases by 1.
In the reliability effect factor of battery pack, each cell particularly important from power consumption level.The cell of therefore, how to reject consumable TV university in battery becomes the key factor that affects battery pack reliability.
In the inventive method, adopt the method for constant-potential charge, can guarantee that cell has consistent initial state-of-charge, in during shelving, the open circuit voltage of cell can reflect the levels of leakage of this cell, by open circuit voltage and the relation of shelving the time, can reject in production process from power consumption cell bigger than normal.Due to use open circuit voltage management battery from power consumption, can to the levels of leakage of cell, carry out stepping according to open circuit voltage size, to guarantee the consistency of each cell in battery pack, making is not having under the prerequisite of equalization function, and battery pack can be not inconsistent and cause losing efficacy from power consumption because of each cell.Meanwhile, because use is shelved time and open circuit voltage relation management battery from power consumption, be convenient to produce for the difference production management of friendship phase, produce workable.
It is little from power consumption hidden danger that the present invention screens qualified cell, and the battery pack self discharge high conformity, the reliability that combine are high, quick during practical application, simple, easy to operate, have good market application foreground.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1: our company produces 9585175Fe type ferric phosphate lithium ion battery, nominal voltage 3.2V, and rated capacity 12Ah, according to production friendship phase requirement, it is 7 days that cell charging is accomplished to the time that enters packing.
According to the inventive method, after cell forming and capacity dividing completes, select capacity class at 12.6~12.8Ah, 0.5 C 5the cell of electric discharge 3.0V platform>=100 minute, internal resistance≤6m Ω, selected V 0for 3.15V, use 0.3 C 5constant current charge is to 3.15V, and then constant voltage is that 3.15V carries out constant voltage charge, when charging current is 0.1 C 5charging stops turning shelves; Shelve after 10 minutes and continue with 0.1 C 5constant current charge is to 3.15V, and then constant voltage is that 3.15V carries out constant voltage charge, when charging current is 0.05 C 5charging stops turning shelves; Shelve after 10 minutes and continue with 0.05 C 5constant current charge is to 3.15V, and then constant voltage is that 3.15V carries out constant voltage charge, when charging current is 0.03 C 5charging stops turning shelves; Shelve after 10 minutes and continue with 0.03 C 5constant current charge is to 3.15V, and then constant voltage is that 3.15V carries out constant voltage charge, when charging current is 0.01 C 5charging stops.Then cell is carried out to normal temperature shelf and after 7 days, measure cell open circuit voltage, reject from power consumption cell bigger than normal.
According to the inventive method, selected Δ V 0for 10mV, Δ V is 2mV, and n value is 14.Therefore,, when cell is shelved 7 days, the cell open circuit voltage criterion qualified from power consumption is V t>=V 0-Δ V 0-n * Δ V=3.112V.Concrete data are as shown in table 1:
Table 1.
According to data in table, show, F20, two cells of F38 are bigger than normal from power consumption, should give rejecting.Other cell meets manufacturing technique requirent from power consumption level, can carry out combo.
According to the inventive method, cell is shelved to open circuit voltage V after 7 days tthe 10mV of take carries out stepping, i.e. 3.112V≤V as a class t<3.122V is a class, 3.122V≤V t<3.132V is a class, 3.132V≤V t<3.142V is a class, 3.142V≤V t<3.152V is a class.With voltage class cell, be combined into battery pack.
Checking: as stated above, can select F1, F2, F3, F5, F6, F7, F8, F9 combo becomes 1P-8S battery pack, 6A constant current charge is to 29.2V, then turns 29.2V constant voltage charge and ends to 600mA; The rear 6A constant-current discharge that charged ends to 16V.With this, discharge and recharge system and circulate 5 weeks, record battery power discharge capacity and electric discharge cut-off average mark voltage.After final step has been discharged, use above-mentioned charging system to be full of electricity battery pack, normal temperature shelf one month, then discharges and recharges battery pack with above-mentioned charge and discharge system degree again, record battery power discharge capacity and discharge cut-off voltage, and with shelve front battery set charge/discharge performance and compare.Concrete data are as shown in table 2:
Table 2
By table 2 data, can be found out, battery pack discharge capacity, component voltage before and after shelving have good consistency.
Embodiment 2: our company produces 11585135Fe type ferric phosphate lithium ion battery, nominal voltage 3.2V, and rated capacity 10Ah, according to production friendship phase requirement, it is 10 days that cell charging is accomplished to the time that enters packing.
According to the inventive method, after cell forming and capacity dividing completes, select capacity class at 10.6~10.7Ah, 0.5 C 5the cell of electric discharge 3.0V platform>=100 minute, internal resistance≤7m Ω, is used 0.1C 5constant current charge is to voltage V 0for 3.15V, then constant voltage is that 3.15V carries out constant voltage charge, when charging current is 0.01 C 5time charging stops, and then cell is carried out to normal temperature shelf and measures battery open circuit voltage after 10 days, rejects from power consumption cell bigger than normal.
According to the inventive method, selected Δ V 0for 10mV, Δ V is 2mV, and n value is 20.Therefore, when cell is shelved 10 days, from the criterion of the qualified cell open circuit voltage of power consumption, be, V t>=V 0-Δ V 0-n * Δ V=3.10V.Concrete data are as shown in table 3:
Table 3.
According to data in table, show, E10, two cells of E31 are bigger than normal from power consumption, should give rejecting.Other cell meets manufacturing technique requirent from power consumption level, can carry out combo.According to the inventive method, cell is shelved to open circuit voltage V after 10 days tthe 10mV< of take carries out stepping, i.e. 3.100V≤V as a class t<3.110V is a class, 3.110V≤V t<3.120V is a class, 3.120V≤V t<3.130V is a class, 3.130V≤V t<3.140V is a class.With voltage class cell, be combined into battery pack.
Checking: as stated above, can select E2, E3, E4, E5, E6, E9, E11, E12 combo becomes 1P-8S battery pack, 5A constant current charge is to 29.2V, then turns 29.2V constant voltage charge and ends to 500mA; The rear 5A constant-current discharge that charged ends to 16V.With this, discharge and recharge system and circulate 5 weeks, record battery power discharge capacity and electric discharge cut-off average mark voltage.After final step has been discharged, use above-mentioned charging system to be full of electricity battery pack, normal temperature shelf one month, then discharges and recharges battery pack with above-mentioned charge and discharge system degree again, record battery power discharge capacity and discharge cut-off voltage, and with shelve front battery set charge/discharge performance and compare.Concrete data are as shown in table 4:
Table 4
By table 4 data, can be found out, battery pack discharge capacity, component voltage before and after shelving have good consistency.

Claims (1)

1. a lithium secondary battery consistency screening technique, cell when partial volume detects to capacity, platform, internal resistance, from power consumption stepping, it is characterized in that: cell is used to multi-stage constant current constant voltage charge,
First paragraph, is used 0.3C 5~5C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.1C 5~0.3C 5stopping charges with turning shelves;
Charging voltage V 0according to battery system, determine, cobalt acid lithium-graphite system, LiMn2O4-graphite system, nickle cobalt lithium manganate-graphite system are 3.0~4.2V, and LiFePO4-graphite body is 2.0~3.65V;
Second segment, shelves after 5~30 minutes and continues with 0.1C 5~0.3C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.05C 5~0.1C 5stopping charges with turning shelves;
The 3rd section, shelve after 5~30 minutes and continue with 0.05C 5~0.1C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.03C 5~0.05C 5stopping charges with turning shelves;
The 4th section, shelve after 5~30 minutes and continue with 0.03C 5~0.05C 5constant current charge is to voltage V 0, then constant voltage is V 0carry out constant voltage charge, when charging current is 0.01C 5~0.03C 5stop charging;
Charged and rear cell carried out to normal temperature shelf, shelved duration and be not less than 24h, while shelving cut-off to cell open circuit voltage V tmeasure open circuit voltage V t>=V 0-Δ V 0-n * Δ V cell is judged to be qualified cell, meanwhile, for qualified cell according to V tsize is carried out voltage stepping with the class of 1~20mV, carries out combo, Δ V with class cell 0span is 5~20mV, and Δ V span is 1~5mV, C 5be rated capacity, n is for shelving half number of days.
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