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CN107808986A - Secondary battery charging method - Google Patents

Secondary battery charging method Download PDF

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Publication number
CN107808986A
CN107808986A CN201610809699.5A CN201610809699A CN107808986A CN 107808986 A CN107808986 A CN 107808986A CN 201610809699 A CN201610809699 A CN 201610809699A CN 107808986 A CN107808986 A CN 107808986A
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China
Prior art keywords
charging
battery
discharge
current
secondary battery
Prior art date
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Pending
Application number
CN201610809699.5A
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Chinese (zh)
Inventor
高潮
骆福平
方占召
袁庆丰
余红明
龚美丽
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to CN201610809699.5A priority Critical patent/CN107808986A/en
Priority to PCT/CN2017/100235 priority patent/WO2018045920A1/en
Publication of CN107808986A publication Critical patent/CN107808986A/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • HELECTRICITY
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Secondary Cells (AREA)
  • Charge And Discharge Circuits For Batteries Or The Like (AREA)

Abstract

The invention discloses a kind of secondary battery charging method, and it includes:One group of charging current value being sequentially reduced, one group of discharge current value, one group of charging interval value, and one group of discharge time values are set, set charge cutoff voltage V0 and charge cutoff electric current Im;Use set charging current value, charging interval value, discharge current value, discharge time values to carry out pulse charge to battery successively by setting rule, after cell voltage reaches V0, stop charging or to stop charging after V0 constant-voltage charges to cut-off current Im.Compared with prior art, small negative pulse current or the charging modes of standing by the present invention in that the big positive pulse electric current being gradually reduced with substep is arranged in pairs or groups, significantly reducing polarization caused by big pulse current charge influences, reduce cell cathode polarization potential, significantly improve the cycle performance of battery high voltage system, especially high temperature cyclic performance, effectively extend the service life of battery.

Description

Secondary battery charging method
Technical field
The invention belongs to cell art, it is more particularly related to a kind of secondary battery charging method.
Background technology
Existing secondary cell charging modes are:A certain current potential is charged to battery last using constant current, then herein Current potential carries out constant-voltage charge to battery.This charging modes can be such that cathode potential constantly raises, especially in constant voltage charging phase, Negative electrode is continuously maintained in high potential so that the stability of cathode construction is affected, and battery cycle life deteriorates, and works as charging process When carrying out in high temperature environments, it can more aggravate the deterioration of battery cycle life.
In view of this, it is necessary to which a kind of secondary battery charging method that can solve the problem that above mentioned problem is provided.
The content of the invention
It is an object of the invention to:Overcome the deficiencies in the prior art, there is provided one kind can effectively extend battery Secondary battery charging method.
In order to realize foregoing invention purpose, the present invention provides a kind of secondary battery charging method, and it comprises the following steps:
Step 1:Set one group of charging current value being sequentially reduced { Ic1, Ic2, Ic3 ..., Icn }, one group of electric discharge electricity Flow valuve { Id1, Id2, Id3 ... ..., Idn }, one group of charging interval value { tc1, tc2, tc3 ... ..., tcn }, and one group of electric discharge Time value { td1, td2, td3 ... ..., tdn }, setting charge cutoff voltage V0;
Step 2:Battery is charged, charging current Ic1, charging interval tc1, then to battery discharge or by battery Stand, discharge current Id1, discharge time or time of repose are td1, so circulation, until cell voltage reaches V0;
Battery is charged, charging current Ic2, charging interval tc2, then to battery discharge or by battery standing, put Electric current is Id2, and discharge time or time of repose are td2, so circulation, until cell voltage reaches V0;
……
Battery is charged, charging current Icn, charging interval tcn, then to battery discharge or by battery standing, put Electric current is Idn, and discharge time or time of repose are tdn, so circulation, until cell voltage reaches V0.
One kind as secondary battery charging method of the present invention is improved, and the step 1 also includes setting charge cutoff electric current The step of Im, the step 2 are also included to battery with V0 constant-voltage charges, until the step of battery current reaches Im afterwards.
One kind as secondary battery charging method of the present invention is improved, the charging current value Ic1, Ic2, Ic3 ... ..., Icn } in the range of 0.1C~5C.
One kind as secondary battery charging method of the present invention is improved, charging interval value tc1, tc2, tc3 ... ..., Tcn } in the range of 0.1s~30s.
One kind as secondary battery charging method of the present invention is improved, the discharge current value Id1, Id2, Id3 ... ..., Idn } in the range of 0C~0.2C.
One kind as secondary battery charging method of the present invention is improved, the discharge time values td1, td2, td3 ... ..., Tdn } in the range of 0.01s~5s.
One kind as secondary battery charging method of the present invention is improved, and the charge cutoff voltage V0 is 3.6V~4.5V.
One kind as secondary battery charging method of the present invention is improved, and the charge cutoff electric current Im is 0.01C~0.2C.
One kind as secondary battery charging method of the present invention is improved, and methods described also includes battery being placed in 20~50 DEG C Step in environment, this step are completed before step 2.
One kind as secondary battery charging method of the present invention is improved, and the charge cutoff electric current Im is not more than the minimum Charging current value Icn.
Compared with prior art, secondary battery charging method of the present invention at least has technique effect beneficial below:Pass through Using the small negative pulse current of the big positive pulse electric current collocation being gradually reduced step by step or the charging modes of standing, significantly reduce Polarization caused by big pulse current charge influences, and so as to reduce cell cathode polarization potential, greatly improves battery high voltage The cycle performance of system, especially high temperature cyclic performance, effectively extend the service life of battery.
Brief description of the drawings
With reference to the accompanying drawings and detailed description, secondary battery charging method of the present invention and its advantageous effects are entered Row describes in detail.
Fig. 1 is the curve map of the charging current of secondary battery charging method of the present invention.
Fig. 2 is the curve map of the embodiment of the present invention 1 and the charging voltage of comparative example.
Fig. 3 is the curve map of the embodiment of the present invention 1 and the charging current of comparative example.
Fig. 4 is the embodiment of the present invention 1 and the curve map of the capability retention of comparative example.
Embodiment
In order that goal of the invention, technical scheme and the technique effect of the present invention become apparent from understanding, below in conjunction with accompanying drawing and Embodiment, the present invention will be described in further detail.It should be appreciated that the specific implementation described in this specification Mode is not intended to limit the present invention just for the sake of explaining the present invention.
Refer to shown in Fig. 1, secondary battery charging method of the present invention comprises the following steps.
Step 1:Set one group of charging current value being sequentially reduced { Ic1, Ic2, Ic3 ..., Icn }, one group of electric discharge electricity Flow valuve { Id1, Id2, Id3 ... ..., Idn }, one group of charging interval value { tc1, tc2, tc3 ... ..., tcn }, and one group of electric discharge Time value { td1, td2, td3 ... ..., tdn }, setting charge cutoff voltage V0;
Step 2:Battery is charged, charging current Ic1, charging interval tc1, then to battery discharge or by battery Stand, discharge current Id1, discharge time or time of repose are td1, so circulation, until cell voltage reaches V0;
Battery is charged, charging current Ic2, charging interval tc2, then to battery discharge or by battery standing, put Electric current is Id2, and discharge time or time of repose are td2, so circulation, until cell voltage reaches V0;
……
Battery is charged, charging current Icn, charging interval tcn, then to battery discharge or by battery standing, put Electric current is Idn, and discharge time or time of repose are tdn, so circulation, until cell voltage reaches V0.
It is the embodiment and comparative example of secondary battery charging method of the present invention below.
Battery system used by embodiment and comparative example, be using LiCoO2 as negative electrode main material, using graphite as Anode main material, along with barrier film, electrolyte and pack case, by the battery made by technique such as assembling, being melted into and be aged. Wherein, negative electrode is made up of 97.5%LiCoO2,1.3%PVDF (as binding agent) and 1.2%SP (as conductive agent) mixing, sun Pole is made up of 98% Delanium, 1.0%SBR (as binding agent) and 1.0%CMC (as thickener) mixing, barrier film PP, PE or PP composite membranes, electrolyte by (30%EC+30%PC+40%DEC) (as organic solvent), 1mol/L LiPF6 and (0.5%VC, 5%FEC, 4%VEC) (as additive) forms.At 25 DEG C, it is 3750mAh that the expiring of this battery, which fills charging capacity,.
Embodiment 1
Embodiment 1 comprises the following steps that:
1) set one group of charging current value { 1.5C, 1.3C, 1C, 0.8C, 0.5C, 0.2C, 0.1C } being sequentially reduced, one group Discharge current value { 0.02C, 0.015C, 0.01C, 0.01C, 0.01C, 0.01C, 0C }, one group of charging interval value 9.5s, 9.5s, 9.5s 9.5s, 9s, 9s, 8s }, and one group of discharge time values { 0.5s, 0.5s, 0.5s, 0.5s, 0.2s, 0.2s, 0.1s };If It is 4.45V to put charge cutoff voltage;Battery is placed in 45 DEG C of environment, to battery charging and discharging;
2) with electric current 1.5C charge 9.5s, then with electric current 0.02C discharge 0.5s,
3) repeat step 2), until cell voltage reaches 4.45V;
4) with electric current 1.3C charge 9.5s, then with electric current 0.015C discharge 0.5s,
5) repeat step 4), until cell voltage reaches 4.45V;
6) with electric current 1C charge 9.5s, then with electric current 0.01C discharge 0.5s,
7) repeat step 6), until cell voltage reaches 4.45V;
8) with electric current 0.8C charge 9.5s, then with electric current 0.01C discharge 0.5s,
9) repeat step 8), until cell voltage reaches 4.45V;
10) with electric current 1C charge 9.5s, then with electric current 0.01C discharge 0.5s,
11) repeat step 10), until cell voltage reaches 4.45V;
12) with electric current 0.5C charge 9s, then with electric current 0.01C discharge 0.2s,
13) repeat step 12), until cell voltage reaches 4.45V;
14) with electric current 0.2C charge 9s, then with electric current 0.01C discharge 0.2s,
15) repeat step 14), until cell voltage reaches 4.45V;
16) with electric current 0.1C charging 8s, 0.1s is then stood,
17) repeat step 16), until cell voltage reaches 4.45V, stop charging.
Embodiment 2
Embodiment 2 comprises the following steps that:
1) one group of charging current value { 5C, 1.5C, 1C, 0.5C, 0.2C } being sequentially reduced, one group of discharge current value are set { 0.2C, 0.03C, 0.02C, 0.01C, 0.01C }, one group of charging interval value { 1s, 30s, 5s, 5s, 2s }, and during one group of electric discharge Between be worth { 0.01s, 5s, 0.5s, 0.5s, 0.1s };Setting charge cutoff voltage is 4.45V, and charge cutoff electric current is 0.05C;Will Battery is placed in 45 DEG C of environment, to battery charging and discharging;
2) with electric current 5C charge 1s, then with electric current 0.2C discharge 0.01s,
3) repeat step 2), until cell voltage reaches 4.45V;
4) with electric current 1.5C charge 30s, then with electric current 0.03C discharge 5s,
5) repeat step 4), until cell voltage reaches 4.45V;
6) with electric current 1C charge 5s, then with electric current 0.02C discharge 0.5s,
7) repeat step 6), until cell voltage reaches 4.45V;
8) with electric current 0.5C charge 5s, then with electric current 0.01C discharge 0.5s,
9) repeat step 8), until cell voltage reaches 4.45V;
10) with electric current 0.2C charge 2s, then with electric current 0.01C discharge 0.1s,
11) repeat step 10), until cell voltage reaches 4.45V;
12) 0.05C is reached with 4.45V constant-voltage charges to battery current, stops charging.
Embodiment 3
Embodiment 3 comprises the following steps that:
1) set one group be sequentially reduced charging current value 1.5C, 1.4C, 1.3C, 1.2C, 1.1C, 1.0C, 0.9C, 0.8C, 0.7C, 0.6C, 0.5C, 0.4C, 0.3C, 0.2C, 0.1C }, one group of discharge current value 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.05C, 0.02C, 0.02C, 0C, 0.01C }, one group fill Electric time value { 10s, 10s, 10s, 10s, 10s, 10s, 10s, 10s, 10s, 10s, 10s, 5s, 5s, 5s, 0.1s }, and one group Discharge time values { 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 1s, 0.01s }.Charge cutoff voltage is set For 4.45V;Battery is placed in 45 DEG C of environment, to battery charging and discharging;
2) with electric current 1.5C charge 10s, then with electric current 0.05C discharge 1s,
3) repeat step 2), until cell voltage reaches 4.45V;
4) with electric current 1.4C charge 10s, then with electric current 0.05C discharge 1s,
5) repeat step 4), until cell voltage reaches 4.45V;
6) with electric current 1.3C charge 10s, then with electric current 0.05C discharge 1s,
7) repeat step 6), until cell voltage reaches 4.45V;
8) with electric current 1.2C charge 10s, then with electric current 0.05C discharge 1s,
9) repeat step 8), until cell voltage reaches 4.45V;
10) with electric current 1.1C charge 10s, then with electric current 0.05C discharge 1s,
11) repeat step 10), until cell voltage reaches 4.45V;
12) with electric current 1.0C charge 10s, then with electric current 0.05C discharge 1s,
13) repeat step 12), until cell voltage reaches 4.45V;
14) with electric current 0.9C charge 10s, then with electric current 0.05C discharge 1s,
15) repeat step 14), until cell voltage reaches 4.45V;
16) with electric current 0.8C charge 10s, then with electric current 0.05C discharge 1s,
17) repeat step 16), until cell voltage reaches 4.45V;
18) with electric current 0.7C charge 10s, then with electric current 0.05C discharge 1s,
19) repeat step 18), until cell voltage reaches 4.45V;
20) with electric current 0.6C charge 10s, then with electric current 0.05C discharge 1s,
21) repeat step 20), until cell voltage reaches 4.45V;
22) with electric current 0.5C charge 10s, then with electric current 0.05C discharge 1s,
23) repeat step 22), until cell voltage reaches 4.45V;
24) with electric current 0.4C charge 5s, then with electric current 0.02C discharge 1s,
25) repeat step 24), until cell voltage reaches 4.45V;
26) with electric current 0.3C charge 5s, then with electric current 0.02C discharge 1s,
27) repeat step 26), until cell voltage reaches 4.45V;
28) with electric current 0.2C charge 5s, then with electric current 0C electric discharge 1s (standing 1s),
29) repeat step 28), until cell voltage reaches 4.45V;
30) with electric current 0.1C charge 0.1s, then with electric current 0.01C discharge 0.01s,
31) repeat step 30), until cell voltage reaches 4.45V, stop charging.
Comparative example
Comparative example comprises the following steps that:
1) it is 4.45V to set charge cutoff voltage, and charge cutoff electric current is 0.05C;Battery is placed in 45 DEG C of environment, it is right Battery charging and discharging;
2) cell voltage is charged to constant current 1.5C and reaches 4.45V;
3) battery current is charged to constant voltage 4.45V and reaches 0.05C.
Fig. 2 and Fig. 3 is respectively the charging voltage and charging current time history plot of embodiment 1 and comparative example. As seen from the figure, during whole charging, the voltage of embodiment 1 is below the voltage of comparative example mutually in the same time.Therefore, phase For comparative example, the charging method of embodiment effectively reduces the polarizing voltage in charging process.
In order to examine the technique effect that secondary battery charging method of the present invention is reached, with embodiment 1, embodiment 2, implement Secondary cell after example 3 and comparative example charging is as test object, under 45 DEG C of constant temperature, respectively to test object with 0.2C multiplying power does the cycle charge discharge electrical testing of 800 times, and test result is as shown in table 1.It is real relative to comparative example from table Apply its capability retention after 800 charge and discharge cycles of example 1 and increase to 87% by 81%, embodiment 2 is in 800 charge and discharge cycles Its capability retention increases to 86% by 81% afterwards, and its capability retention after 800 charge and discharge cycles of embodiment 3 is increased by 81% Add to 89%.
Table 1, the charge parameter of embodiment and comparative example and capability retention contrast
The curve map that Fig. 4 changes for capability retention in the test result of embodiment 1 and comparative example with cycle-index.By scheming It can be seen that after cycle charge-discharge 500 times, embodiment 1 has higher capability retention relative to comparative example, embodiment 1 Cycle life has obtained obvious improvement.
It should be noted that charging current value { Ic1, Ic2, Ic3 ... ..., Ici ... ..., Icn } preferred model of the present invention Enclose for 0.1C~5C;Charging interval value tc1, tc2, tc3 ..., tci ..., tcn } preferred scope is 0.1s~30s;Put Electric current value Id1, Id2, Id3 ..., Idi ..., Idn } preferred scope is 0C~0.2C;Discharge time values td1, td2, Td3 ..., tdi ..., tdn } preferred scope is 0.01s~5s;Preferred 3.6V~the 4.5V of charge cutoff voltage V0;Charging is cut Only electric current Im is preferably no greater than minimum charge current value Icn, more preferably 0.01C~0.2C;Charging ambient temperature is preferred 20~50 DEG C.Under the conditions of preferred parameter, charging method of the invention is by with more excellent technique effect.
The detailed description of secondary battery charging method of the present invention can be seen that relative to prior art with reference to more than, this Invention secondary battery charging method is carried out by the way of pulse charge after certain time of being charged using high current to battery Low discharging current, accumulated with slowing down lasting charging process to the polarization that battery is brought, reduce the current potential of cell cathode, reduced high Impact of the voltage to battery cathode material, so as to improve the cycle life of battery.Especially using large current charge to cut-off During voltage, cathode potential is continuously in high-voltage state, is now charged by substep using the positive pulse electric current being gradually reduced, and Carry out low discharging current or by battery standing, can further reduce cathode potential, greatly improve the circulation of battery high voltage system, Cycle performance particularly under high temperature, so as to effectively extend the service life of battery.
According to above-mentioned principle, the present invention can also carry out appropriate change and modification to above-mentioned embodiment.Therefore, this hair It is bright to be not limited to embodiment disclosed and described above, some modifications and changes of the present invention should also be as falling into this In the scope of the claims of invention.In addition, although used some specific terms in this specification, but these terms Merely for convenience of description, any restrictions are not formed to the present invention.

Claims (10)

1. a kind of secondary battery charging method, it is characterised in that the described method comprises the following steps:
Step 1:Set one group of charging current value being sequentially reduced { Ic1, Ic2, Ic3 ..., Icn }, one group of discharge current value { Id1, Id2, Id3 ... ..., Idn }, one group of charging interval value { tc1, tc2, tc3 ... ..., tcn }, and one group of discharge time It is worth { td1, td2, td3 ... ..., tdn }, setting charge cutoff voltage V0;
Step 2:Battery is charged, charging current Ic1, charging interval tc1, then to battery discharge or by battery standing, Discharge current is Id1, and discharge time or time of repose are td1, so circulation, until cell voltage reaches V0;
Battery is charged, charging current Ic2, charging interval tc2 are then electric to battery discharge or by battery standing, electric discharge Flow for Id2, discharge time or time of repose are td2, so circulation, until cell voltage reaches V0;
……
Battery is charged, charging current Icn, charging interval tcn are then electric to battery discharge or by battery standing, electric discharge Flow for Idn, discharge time or time of repose are tdn, so circulation, until cell voltage reaches V0.
2. secondary battery charging method according to claim 1, it is characterised in that:The step 1 also includes setting charging The step of cut-off current Im, the step 2 are also included to battery with V0 constant-voltage charges, until battery current reaches Im's afterwards Step.
3. secondary battery charging method according to claim 1, it is characterised in that:The charging current value Ic1, Ic2, Ic3 ..., Icn } in the range of 0.1C~5C.
4. secondary battery charging method according to claim 1, it is characterised in that:Charging interval value tc1, tc2, Tc3 ..., tcn } in the range of 0.1s~30s.
5. secondary battery charging method according to claim 1, it is characterised in that:The discharge current value Id1, Id2, Id3 ..., Idn } in the range of 0C~0.2C.
6. secondary battery charging method according to claim 1, it is characterised in that:The discharge time values td1, td2, Td3 ..., tdn } in the range of 0.01s~5s.
7. secondary battery charging method according to claim 1, it is characterised in that:The charge cutoff voltage V0 is 3.6V ~4.5V.
8. secondary battery charging method according to claim 2, it is characterised in that:The charge cutoff electric current Im is 0.01C~0.2C.
9. secondary battery charging method according to claim 1, it is characterised in that:Methods described also includes battery being placed in Step in 20~50 DEG C of environment, this step are completed before step 2.
10. secondary battery charging method according to claim 2, it is characterised in that:The charge cutoff electric current Im is little In the minimum charge current value Icn.
CN201610809699.5A 2016-09-08 2016-09-08 Secondary battery charging method Pending CN107808986A (en)

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CN201610809699.5A CN107808986A (en) 2016-09-08 2016-09-08 Secondary battery charging method
PCT/CN2017/100235 WO2018045920A1 (en) 2016-09-08 2017-09-01 Method and apparatus for charging secondary batteries

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