CN106876813A - A kind of method for pre-charging lithium ion batteries - Google Patents
A kind of method for pre-charging lithium ion batteries Download PDFInfo
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- CN106876813A CN106876813A CN201510925587.1A CN201510925587A CN106876813A CN 106876813 A CN106876813 A CN 106876813A CN 201510925587 A CN201510925587 A CN 201510925587A CN 106876813 A CN106876813 A CN 106876813A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/463—Aluminium based
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Power Engineering (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of method for pre-charging lithium ion batteries, the positive active material of the lithium ion battery is nickel cobalt aluminum, successively including stage charge step and constant-voltage charge step；Wherein, the stage charge step includes the first charge step and the second charge step successively, the electric current of first charge step less than the second charge step electric current, and first charge step preliminary filling electricity be the lithium ion battery total electricity 20%-40%.The present invention can make battery core reach even more excellent electric property suitable with the battery core using traditional low current long-time preliminary filling technique, while shortening pre-charging time, improve production efficiency.
Description
【Technical field】
The present invention relates to a kind of method for pre-charging lithium ion batteries.
【Background technology】
Current lithium ion battery applications are increasingly extensive, and battery requirements amount is continuously increased, for battery manufacturers, a side
Face wants improve production efficiency to meet market needs, on the other hand requires to improve and replenishment of process, in improve product quality
While improve production efficiency.With the production mechanization of lithium electricity industry, preliminary filling operation has become restriction production at present
The important step of speed and product quality.
It is inevitably negative in graphite due to electrochemical reaction when preliminary filling is initial charge for lithium ion battery
Pole is covered in the passivation thin layer of graphite surface with formation on the boundary of electrolyte, and this thin layer is solid electrolyte interface
(solid electrolyte interface) or SEI films.During to pre-charging lithium ion batteries, in negative terminal surface life
While into SEI films, it may occur that side reaction produces gaseous product, and if gas is produced not exclusively during preliminary filling,
Can continue to release in the electric cyclic process in battery core later stage, have a strong impact on the electrical property and security performance of battery core.Therefore lithium
The priming procedure of ion battery is the important stage for manufacturing battery core, be related to the capacity of battery core, multiplying power, cycle life,
Many performances such as safety.
Preliminary filling operation at this stage, is typically with the charging that low current be up to more than ten hour, to obtain ideal
SEI films, keep battery performance stabilization.But prolonged priming procedure causes production efficiency low.
Nickel cobalt aluminum is a kind of specific capacity positive electrode very high, and its specific capacity exceedes cobalt acid lithium and nickel-cobalt-manganese ternary material
Material, is the preferred positive electrode of high energy density cells product.Nickel cobalt aluminum activity is higher, to improve it in battery
Stability during use, people generally use the electrolyte for matching, while being also required to be formed the SEI films of stabilization.
The electrochemical reaction speed of the material is slow at room temperature, causes the high rate during charging-discharging of the material not good, most of
About the material research all use low range charge and discharge, the relatively low application that will have a strong impact on the system material forthright again,
Therefore preliminary filling is to be charged for a long time using low current still using traditional cobalt acid lithium method for pre-charging, as restricting the material at present
The important step of material system production efficiency and properties of product.
【The content of the invention】
In order to overcome the deficiencies in the prior art, the invention provides it is a kind of for positive active material for nickel cobalt aluminum
The method for pre-charging of lithium ion battery, can be greatly enhanced production efficiency on the premise of battery core performance gets a promotion.
A kind of method for pre-charging lithium ion batteries, the positive active material of the lithium ion battery is nickel cobalt aluminum, successively
Including stage charge step and constant-voltage charge step；
Wherein, the stage charge step includes the first charge step and the second charge step successively, and described first fills
The electric current of electric step less than the second charge step electric current, and first charge step preliminary filling electricity for the lithium from
The 20%-40% of sub- battery total electricity.
In one embodiment,
The preliminary filling electricity of first charge step is the 20%-30% of the lithium ion battery total electricity.
In one embodiment,
The charging current of first charge step is less than 0.2C, and the charging interval is 1-3h.
In one embodiment,
The charging current of first charge step is 0.1C-0.2C, and the charging interval is 1.5h-3h.
In one embodiment,
The charging interval is 1.3h-1.5h.
In one embodiment,
The charging current of second charge step is 0.2C-0.33C.
In one embodiment,
The charging current of the second charge step is 0.3C.
In one embodiment,
The negative pole of the lithium ion battery is graphite cathode.
In one embodiment,
In the nickel cobalt aluminum, Ni：Co：Al=0.8：0.15：0.05.
In one embodiment,
The charging current of first charge step is 0.1C, and the charging interval is 2h.
The beneficial effects of the invention are as follows：
Method for pre-charging of the invention is used to enter line precharge, energy to the lithium ion battery with nickel cobalt aluminium as positive active material
Battery core is enough set to reach even more excellent electric property suitable with the battery core using traditional low current long-time preliminary filling technique, together
When shorten pre-charging time, improve production efficiency；Meanwhile, method for pre-charging of the present invention is embodied as nickel cobalt aluminum more
Extensive utilization provides solid foundation.
【Brief description of the drawings】
Fig. 1 is that to use electric current be the charge graph of 0.1C for the method for pre-charging lithium ion batteries of kind of embodiment, and abscissa is the time,
Ordinate is magnitude of voltage.
【Specific embodiment】
The preferred embodiment invented is described in further detail below.
As shown in figure 1, a kind of method for pre-charging lithium ion batteries of embodiment, wherein, the positive pole of the lithium ion battery
Active material is nickel cobalt aluminum, and the negative pole of the lithium ion battery is graphite cathode, method for pre-charging lithium ion batteries according to
It is secondary including stage charge step and constant-voltage charge step, i.e., stage charge step is before constant-voltage charge step；
Wherein, the stage charge step includes the first charge step and the second charge step successively, and described first fills
The electric current of electric step less than the second charge step electric current, and first charge step preliminary filling electricity for the lithium from
The 20%-40% of sub- battery total electricity.
There is positive role using formation of the low current to SEI films in first charge step, be conducive to improving battery core performance, but
The SEI membrane impedances increase that prolonged low current charge can be resulted in, so as to influence the multiplying power discharging of finished product battery core
Can (being exactly the discharge capacity performance under different electric currents), the time is more long also to influence production efficiency.According to early-stage Study, the
Charge capacity SEI films in 20%-30% can be formed completely in one charge step.High current is introduced in second charge step,
The charging modes of high current can improve efficiency, but be easily destroyed SEI films or cause to analyse lithium, influence the performance of battery core, together
When Precharged cabinet it is larger using high current stability and error, therefore suitable charging current and charging interval should be selected.
Electric current in second charge step of the present embodiment is selected between 0.2C-0.33C, is charged to battery core voltage and is reached constant pressure
The voltage of charging, such as 4.2V.
For same batch battery core, using above-mentioned method for pre-charging lithium ion batteries, according to charging current, time and precharge
The difference of amount, has respectively obtained embodiment 1 to 9, as shown in table 1, wherein, embodiment 1 to 9, and comparative example
1st, battery core used in 2 is the 18650-2.6Ah battery cores of same batch production, and positive active material is nickel cobalt aluminium,
There is consistent both positive and negative polarity dressing amount, electrode density with a batch of battery core, using identical injecting electrolytic solution, fluid injection
The experiment conditions such as amount, the fluid injection, sealing, cleaning, the ageing that maintain like.
A kind of method for pre-charging lithium ion batteries detailed process of embodiment can be as follows using step：It is pre- in battery core after being aged
Fill cabinet and fill 3h by 0.1C, 0.2C is charged to 4.2V, then 4.2V constant-voltage charges to electric current is reduced to 26mA stoppings.Battery core is old
Partial volume is carried out after changing 3 days, partial volume system is carried out by parameter shown in table 2.Investigate its capacity, internal resistance, multiplying power, often
Temperature circulation and 45 DEG C of cycle performances, the results are shown in Table shown in 3.
Wherein battery core internal resistance and high rate performance are investigated because internal resistance is small and good rate capability explanation interface performance is good, SEI films
The performance of formation is good.The influence factor of battery core internal resistance and high rate performance is relatively more, because the battery core selected by us is same
The battery core of a collection of production carries out different method for pre-charging experiments, therefore, it is possible to exclude remaining work beyond method for pre-charging as far as possible
The interference that sequence is brought.If method for pre-charging is unreasonable, causes SEI films unstable or pole piece there are the situations such as local analysis lithium,
Just mutually deserved comparing is high for now interface internal resistance, and internal resistance is understood than larger, and high rate performance can be poor, therefore reality of the invention
Applying internal resistance and high rate performance in example can reflect the index of charging effect as side.
Normal temperature circulation and 45 DEG C of circulations are investigated because in battery core cyclic process, SEI films can for a long time experience lithium ion and pass through
Process therein, if SEI films are unstable, lithium ion is hindered by meeting, charge/discharge capacity can be reduced, and be reflected in
It is exactly that cycle performance declines in circulation；Test of 45 DEG C of the temperature to SEI membrane stabilities is more severe.Therefore normal temperature is followed
Ring and 45 DEG C of circulations can be used as the key indexs of reflection charging effect.
Equally, other embodiment and comparative example 1,2 use identical step, time and electricity that simply method for pre-charging is used
Stream is different.
The method for pre-charging of all embodiments and comparative example is shown in Table 1, and its technique effect data is shown in Table 3.
The method for pre-charging of each embodiment of table 1. and comparative example
The partial volume system of table 2.
| Work step | Mode of operation | Electric current mA | Voltage mV | Ending current mA | End voltage mV | End time min |
| 1 | Constant-current charge | 520 | 4200 | 120 | ||
| 2 | Constant-voltage charge | 520 | 4200 | 26 | 4200 | 120 |
| 3 | Shelve | 5 | ||||
| 4 | Constant-current discharge | 520 | 2500 | 2500 | 360 |
Battery core obtains capacity, referred to as partial volume in the test of this operation.
Each embodiment of table 3. and comparative example technique effect
In table 3,3C discharge capacities/0.2C discharge capacities then illustrate the multiplying power discharging property of battery core.
The as shown by data of embodiment 1-9 and comparative example 1-2, by selecting method for pre-charging of the invention, can reach battery core
Even more excellent chemical property suitable with the battery core of traditional preliminary filling technique, while pre-charging time can greatly be shortened, carries
High efficiency.And embodiment 1-9 understands the necessity of the first low current charge with the tables of data of comparative example 2, if not
Its performance of battery core capacity, internal resistance, high rate performance and cycle performance will be worse if carrying out first step low current preliminary filling.
The present invention can shorten the pre-charging time of battery core, in one embodiment, lithium ion by introducing stage preliminary filling
Battery method for pre-charging is：1.5h is filled with 0.2C, 4.2V is then charged to 0.3C, then 4.2V constant pressures are charged to electric current drop
It is 0.01C.
In one embodiment, the lithium ion battery that this method for pre-charging is applicable, the nickel cobalt aluminium in its positive active material is excellent
Element ratio is selected to meet Ni：Co：Al=0.8：0.15：0.05 nickel cobalt aluminium.Method for pre-charging of the present invention is embodied as nickel cobalt
Aluminum is widely used and accomplishes fluently solid foundation.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For general technical staff of the technical field of the invention,
Without departing from the inventive concept of the premise, some simple deduction or replace can also be made, this should be all considered as belonging to
The scope of patent protection that invention is determined by the claims submitted to.
Claims (10)
1. a kind of method for pre-charging lithium ion batteries, the positive active material of the lithium ion battery is nickel cobalt aluminum, its
It is characterized in, successively including stage charge step and constant-voltage charge step；
Wherein, the stage charge step includes the first charge step and the second charge step successively, and described first fills
The electric current of electric step less than the second charge step electric current, and first charge step preliminary filling electricity for the lithium from
The 20%-40% of sub- battery total electricity.
2. method for pre-charging lithium ion batteries as claimed in claim 1, it is characterized in that, first charge step it is pre-
Charge volume is the 20%-30% of the lithium ion battery total electricity.
3. method for pre-charging lithium ion batteries as claimed in claim 1, it is characterized in that, first charge step is filled
Electric current is less than 0.2C, and the charging interval is 1-3h.
4. method for pre-charging lithium ion batteries as claimed in claim 3, it is characterized in that, first charge step is filled
Electric current is 0.1C-0.2C, and the charging interval is 1.5h-3h.
5. method for pre-charging lithium ion batteries as claimed in claim 3, it is characterized in that, the charging interval is
1.3h-1.5h。
6. method for pre-charging lithium ion batteries as claimed in claim 1, it is characterized in that, second charge step is filled
Electric current is 0.2C-0.33C.
7. method for pre-charging lithium ion batteries as claimed in claim 6, it is characterized in that, the charging electricity of the second charge step
It is 0.3C to flow.
8. method for pre-charging lithium ion batteries as claimed in claim 1, it is characterized in that, the negative pole of the lithium ion battery
It is graphite cathode.
9. method for pre-charging lithium ion batteries as claimed in claim 1, it is characterized in that, in the nickel cobalt aluminum, Ni：
Co：Al=0.8：0.15：0.05.
10. method for pre-charging lithium ion batteries as claimed in claim 1, it is characterized in that, first charge step
Charging current is 0.1C, and the charging interval is 2h.
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| CN201510925587.1A CN106876813A (en) | 2015-12-11 | 2015-12-11 | A kind of method for pre-charging lithium ion batteries |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108254695A (en) * | 2017-12-28 | 2018-07-06 | 上海捷新动力电池系统有限公司 | Battery core monomer Capacity uniformity detection method in a kind of ferric phosphate lithium cell module |
| CN110165318A (en) * | 2019-06-06 | 2019-08-23 | 合肥众禾动力新能源科技有限公司 | A kind of method for pre-charging improving analysis lithium |
| CN114188596A (en) * | 2021-11-23 | 2022-03-15 | 郑州比克电子有限责任公司 | Pre-activation method of lithium ion battery |
| CN114497781A (en) * | 2020-08-04 | 2022-05-13 | 宁德新能源科技有限公司 | Electronic device, charging method for electrochemical device, terminal, and storage medium |
| CN114638416A (en) * | 2022-03-18 | 2022-06-17 | 天津力神电池股份有限公司 | Management and control optimization method for pre-charging time of assembled battery |
| CN114801876A (en) * | 2022-05-23 | 2022-07-29 | 中国第一汽车股份有限公司 | Precharge control method, precharge control device, storage medium, processor and electronic device |
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| CN103715424A (en) * | 2014-01-06 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Core-shell structured cathode material and preparation method thereof |
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| CN102324570A (en) * | 2011-09-07 | 2012-01-18 | 惠州Tcl金能电池有限公司 | Lithium ion battery, its formation method and preparation method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108254695A (en) * | 2017-12-28 | 2018-07-06 | 上海捷新动力电池系统有限公司 | Battery core monomer Capacity uniformity detection method in a kind of ferric phosphate lithium cell module |
| CN110165318A (en) * | 2019-06-06 | 2019-08-23 | 合肥众禾动力新能源科技有限公司 | A kind of method for pre-charging improving analysis lithium |
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| CN114497781A (en) * | 2020-08-04 | 2022-05-13 | 宁德新能源科技有限公司 | Electronic device, charging method for electrochemical device, terminal, and storage medium |
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| CN114188596A (en) * | 2021-11-23 | 2022-03-15 | 郑州比克电子有限责任公司 | Pre-activation method of lithium ion battery |
| CN114188596B (en) * | 2021-11-23 | 2023-09-01 | 郑州比克电子有限责任公司 | Pre-activation method of lithium ion battery |
| CN114638416A (en) * | 2022-03-18 | 2022-06-17 | 天津力神电池股份有限公司 | Management and control optimization method for pre-charging time of assembled battery |
| CN114801876A (en) * | 2022-05-23 | 2022-07-29 | 中国第一汽车股份有限公司 | Precharge control method, precharge control device, storage medium, processor and electronic device |
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