CN105977443B - A kind of electrolyte filling method of lithium ion battery - Google Patents

A kind of electrolyte filling method of lithium ion battery Download PDF

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Publication number
CN105977443B
CN105977443B CN201610382487.3A CN201610382487A CN105977443B CN 105977443 B CN105977443 B CN 105977443B CN 201610382487 A CN201610382487 A CN 201610382487A CN 105977443 B CN105977443 B CN 105977443B
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pressure release
lithium ion
battery
electrolyte
cycle
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CN105977443A (en
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漆振涛
张伟
赵晶晶
郑喜军
曲斌
赵博
张运高
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China Lithium Battery Technology Co Ltd
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China Aviation Lithium Battery Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of electrolyte filling methods of lithium ion battery, include the following steps:1) battery case inside is vacuumized;2) pressurize;3) electrolyte is injected;4) pressure release;5) with what follows pressurization, pressure release, vacuumize, pressure release be one cycle, carry out cycle standing:The nitrogen that charged pressure is 0.020~0.035MPa carries out 60~80s of pressurization, and pressure release, it is -65KPa~-90KPa, pressure release to be evacuated to vacuum degree;6) it is filled with nitrogen and keeps 30~80s;7) fluid injection is completed in pressure release.This method selects effective liquid injection process and adjustment fluid injection parameter, positive/negative-pressure alternately recycles standing, reduces the frequency for spilling liquid at battery liquid-filling hole, and dramatically improves injection and the wetting efficiency of electrolyte by the optimization to injection process parameter;Electrolyte is good to the effect of impregnation of battery core, ensure that chemical property and the safety of lithium ion battery.

Description

A kind of electrolyte filling method of lithium ion battery
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of electrolyte filling method of lithium ion battery.
Background technology
Lithium ion battery generally comprises battery case Anode, cathode and the diaphragm between anode and cathode;Electrolyte plays conduction electricity between lithium ion cell positive, cathode The effect of son is used as lithium-ion electric streaming medium in battery charge and discharge process, is that lithium ion battery obtains high voltage, high ratio The guarantee of the advantages that energy.Therefore, in lithium ion battery production process, fluid injection standing is very important technological operation.Battery After the completion of assembly, plating battery injects electrolyte, and is stood to the battery after fluid injection, so that electrolyte is fully infiltrated positive, negative Pole and diaphragm;Electrolyte is formed fine and close, equal in lithium ion cell positive, negative terminal surface in battery initial charge activation SEI films (Sold Electrolyte Interface, solid electrolyte interface film) that are even, stablizing.And the quality that SEI films are formed The performance of direct relation lithium ion battery, anode after lithium ion battery liquid injection, cathode, the effect of impregnation of diaphragm and electrolyte are direct The formational situation for influencing SEI films, to influence the chemical property of lithium ion battery.
The master operation flow of existing lithium ion battery liquid injection is as follows:→ fluid injection → is vacuumized to pressurize → vacuumize pressurization → standing → secondary fluid injection → battery discharge.It is a critically important process wherein to stand, the time length relationship electrolysis of standing The Infiltrating of liquid, electrolyte infiltration is inadequate if time of repose is short, though as the long electrolysis liquid energy of time of repose well infiltrates, It is that exposure in air, absorbs a large amount of moisture and impurity, influence safety and the chemical property of battery battery for a long time.
In the prior art, CN101944585B discloses a kind of electrolyte filling method of lithium battery, includes the following steps:By lithium from In the good fluid injection area of sub- battery merging leakproofness;It weighs to battery;Installation priming device is carried out to battery port;To battery It is vacuumized, and maintains certain time;To injecting nonaqueous electrolytic solution after battery vacuum-pumping;Battery is carried out to be filled with nitrogen recovery Atmospheric pressure;It is repeated to be filled with nitrogen to battery vacuum-pumping in same station;Battery is discharged;It is weighed for the second time to battery, Supplement electrolyte is carried out to battery;Battery is sealed.It is 3~5 times to be wherein filled with nitrogen to restore atmospheric pressure, and the nitrogen Gas must be dry nitrogen;The air pressure vacuumized is 30mPa~60mPa, and the time is maintained 40~60s, and inflated with nitrogen restores big Air pressure is 1 standard atmospheric pressure.
Although the above method promotes the absorption of electrolyte to a certain extent, inside battery many places during it stands In negative pressure state, permeating speed of the electrolyte to battery core is influenced, causes wetting velocity slow, will appear sepage not as time of repose is short Equal phenomenon, to affect the chemical property of battery.
Invention content
The object of the present invention is to provide a kind of electrolyte filling method of lithium ion battery, fluid injection effect is good, does not spill liquid and efficient.
In order to achieve the goal above, the technical solution adopted in the present invention is:
A kind of electrolyte filling method of lithium ion battery, includes the following steps:
1) it is -90KPa~-95KPa to be evacuated to vacuum degree to battery case inside;
2) it is -90KPa~1~2s of -95KPa pressurizes to maintain battery case internal vacuum;
3) electrolyte is injected into battery case;
4) by battery case pressure release;
5) with what follows pressurization, pressure release, vacuumize, pressure release be one cycle, carry out cycle standing:
60~80s of pressurization is carried out to the nitrogen that charged pressure inside battery case is 0.020~0.035MPa, pressure release, then It is -65KPa~-90KPa, pressure release to be evacuated to vacuum degree to battery case inside;
6) to the nitrogen and 30~80s of holding that charged pressure inside battery case is 0.020~0.035MPa;
7) by battery case pressure release, that is, fluid injection is completed.
The battery case is metal-back.
In step 1), the time vacuumized is 35~75s.The step 1) is evacuated to high vacuum values, and setting vacuumizes value With the time vacuumized, and pressurize is carried out under the high vacuum values state in step 2).The pressurize of high vacuum values in step 2) Time is unsuitable long, prevents that battery case is caused to deform.
In step 3), the injection process time is no longer than the time vacuumized in step 1).
In step 3), the injection process time is 30~70s.Preferably, the injection process time of electrolyte is slightly shorter than step 1) time vacuumized in.
In step 4), the time of the pressure release is 1~2s.The pressure release is to be passed through dry air to battery case to be let out Pressure.The pressure release is quick pressure releasing;Pressure release is to atmospheric pressure.
In step 5), the time of the pressure release is 1~2s.Step 5) be cycle standing process, inflated with nitrogen formed it is low just It presses and vacuumizes the low vacuum cycle alternation to be formed to carry out, electrolyte is made fully to infiltrate battery core.Cycle-index is completed according to fluid injection Liquid injection port judges with the presence or absence of liquid situation is spilt afterwards.The pressure release is quick pressure releasing;Pressure release is to atmospheric pressure.
In step 5), the time vacuumized is 60~80s.
In step 7), the time of the pressure release is 1~2s.The pressure release is to be passed through dry air to battery case to be let out Pressure.
The present invention lithium ion battery liquid injection method, by being vacuumized to battery case, pressurize, fluid injection, cycle stand it is (low Positive pressure, low vacuum cycle), pressurization after complete fluid injection;By the optimization to injection process parameter, select effective liquid injection process and Fluid injection parameter is adjusted, positive/negative-pressure alternately recycles standing, reduces the frequency for spilling liquid at battery liquid-filling hole, and dramatically Improve injection and the wetting efficiency of electrolyte;Electrolyte is good to the effect of impregnation of battery core, ensure that the electrification of lithium ion battery Learn performance and safety.
In the step 5) of above-mentioned electrolyte filling method, cycle-index whether there is according to liquid injection port after step 7) completion fluid injection spills liquid Situation is set;Liquid injection port then increases cycle-index in the presence of liquid situation is spilt after such as completing fluid injection;Liquid injection port is such as completed after fluid injection without spilling Liquid situation, then reduce cycle-index.It is described spill liquid situation refer to vacuumize by electrolyte take out of caused by spill liquid.
Fluid injection experiment is carried out to lithium ion battery using the electrolyte filling method, experimentation ensures that external condition is basically unchanged, To related fluid injection parameter, including the cycle-index in injection process is changed, show that best cycle time of repose (meets battery not Spill the most short fluid injection time under the premise of liquid), then the lithium ion battery by the electrolyte filling method applied to model of the same race or different model Batch fluid injection produces (different model can continue adjusting parameter according to the method described above and cycle-index).This method passes through several pieces a small amount of The experimentation of battery, you can obtain best cycle-index, liquid is not spilt with injection process to take into account the most short fluid injection time Situation, the waste of caused time and resource when reducing by Experience liquid injection process are suitble to large-scale industrial production.
The lithium ion battery liquid injection method of the present invention, under the premise of not spilling liquid in ensureing injection process, by cycle Pressurization during standing pressure release, vacuumizes, the adjustment of the cycle-index of pressure release, realize battery liquid-filling in the shortest time with Recycle the process stood;Parameter, cycle-index that the optimization of entire injection process concentrates on recycling during standing are set, So as to avoid procedure parameter setting complicated in injection process;The electrolyte filling method is suitable for metal casing lithium ion battery, especially Suitable for the batch production of large capacity metal casing lithium ion battery, the production efficiency for improving battery liquid-filling of high degree, drop The low wasting of resources caused by battery spills liquid reduces shell corrosion and leakage caused by subsequent handling is remained due to electrolyte Possibility situation, at low cost, applicability is wide, is suitble to promote the use of.
Description of the drawings
Fig. 1 is the process flow diagram of the electrolyte filling method of the lithium ion battery of the present invention;
Fig. 2 is the elapsed time statistical chart of the electrolyte filling method of the lithium ion battery of embodiment 1.
Specific implementation mode
The present invention is further illustrated With reference to embodiment.
In specific implementation mode, the lithium ion battery for carrying out fluid injection is metal housing battery (laminated cell), and reservoir quantity is 360g。
The lithium ion battery that fluid injection is carried out in the same embodiment is same model battery.
Embodiment 1
The electrolyte filling method of the lithium ion battery of the present embodiment, as shown in Figure 1, including the following steps:
1) it is -95KPa, the time T vacuumized to be evacuated to vacuum degree to battery case inside1=40s;
2) it is -95KPa, dwell time T to maintain condition of high vacuum degree inside battery case2=1s;
3) electrolyte, injection process time T are injected into battery case3=55s, injection process time are slightly shorter than step 1) In time for vacuumizing;
4) dry air pressure release is passed through to atmospheric pressure, venting duration T to battery case4=2s;
5) with what follows pressurization, pressure release, vacuumize, pressure release be one cycle, carry out cycle standing:
Charged pressure is that the nitrogen of 0.020MPa carries out pressurization 80s inside to battery case, leads to air 2s and carries out pressure release, then It is -65KPaKPa to vacuumize 80s to vacuum degree to battery case inside, leads to air 2s and carries out pressure release;The time T of one cycle5 =164s;
Cycle-index is n, and the time for recycling standing is n × T5
6) it pressurizes to the nitrogen that charged pressure inside battery case is 0.020MPa, pressing time T6=40s;
7) battery case is led into dry air 2s and carries out pressure release (i.e. venting duration T7=2s), that is, complete fluid injection.
In above-mentioned electrolyte filling method, time T=T that entire injection process is consumed1+T2+T3+T4+n×T5+T6+T7, wherein n For cycle-index.
Battery liquid-filling hole after battery A completes fluid injection according to above-mentioned electrolyte filling method, is observed in initial setting cycle frequency n=10 Place remains (i.e. without spill liquid phenomenon) without flowable electrolyte, and judgement can reduce cycle-index (as shown in Figure 1);
Cycle-index n=7 (relative to n=10, cycle-index is reduced 3 times) is set, battery B is complete according to above-mentioned electrolyte filling method There are electrolyte spillovers (to exist and spill liquid phenomenon) after fluid injection, at observation battery liquid-filling hole, and judgement should increase cycle time Number (as shown in Figure 1);
Cycle-index n=8 (relative to n=7, cycle-index increases by 1 time) is set, battery C is complete according to above-mentioned electrolyte filling method After fluid injection, observes at battery liquid-filling hole without flowable electrolyte residual (i.e. without spill liquid phenomenon), determine the model lithium-ion electric The cycle-index in pond is 8 times.
As cycle-index n=8, for the lithium ion battery of the model, time T=that entire injection process is consumed 24.2min, and electroless liquid remains.
For the lithium ion battery of the model, produced in batches using the electrolyte filling method (n=8) of the present embodiment, fluid injection The fluid injection time is counted after the completion, the results are shown in Figure 2, and (abscissa of Fig. 2 is that experiment number (corresponds to one respectively every time Battery), as experimental cell number).Wherein, comparative example is existing liquid injection process.Figure it is seen that the note of the present embodiment Total fluid injection time that liquid method is consumed is obviously shortened compared to prior art.
Existing liquid injection process is such as set to use identical fluid injection time (24min), then what existing liquid injection process occurred spills liquid feelings The battery percentage of condition (there are electrolyte spillovers at battery liquid-filling hole) is 34%, and the electrolyte filling method of the present embodiment The battery that liquid situation is spilt in the presence of appearance is only 1.2%, compares prior art (irregular fluid injection, evacuation cycle mode), It has been obviously improved fluid injection efficiency and effect.
Embodiment 2
The electrolyte filling method of the lithium ion battery of the present embodiment, as shown in Figure 1, including the following steps:
1) it is -90KPa, the time T vacuumized to be evacuated to vacuum degree to battery case inside1=40s;
2) it is -90KPa, dwell time T to maintain condition of high vacuum degree inside battery case2=2s;
3) electrolyte, injection process time T are injected into battery case3=35s, injection process time are slightly shorter than step 1) In time for vacuumizing;
4) dry air pressure release is passed through to atmospheric pressure, venting duration T to battery case4=1s;
5) with what follows pressurization, pressure release, vacuumize, pressure release be one cycle, carry out cycle standing:
Charged pressure is that the nitrogen of 0.035MPa carries out pressurization 60s inside to battery case, leads to air 1s and carries out pressure release, then It is -75KPaKPa to vacuumize 60s to vacuum degree to battery case inside, leads to air 1s and carries out pressure release;The time T of one cycle5 =122s;
Cycle-index is n, and the time for recycling standing is n × T5
6) it pressurizes to the nitrogen that charged pressure inside battery case is 0.035MPa, pressing time T6=50s;
7) battery case is led into dry air 1s and carries out pressure release (i.e. venting duration T7=1s), that is, complete fluid injection.
In above-mentioned electrolyte filling method, time T=T that entire injection process is consumed1+T2+T3+T4+n×T5+T6+T7, wherein n For cycle-index.
Initial setting cycle frequency n=8 after battery A completes fluid injection according to above-mentioned electrolyte filling method, are observed at battery liquid-filling hole There are electrolyte spillovers (to exist and spill liquid phenomenon), and judgement should increase cycle-index (as shown in Figure 1);
Cycle-index n=9 (relative to n=8, cycle-index increases by 1 time) is set, battery B is complete according to above-mentioned electrolyte filling method There are electrolyte spillovers (to exist and spill liquid phenomenon) after fluid injection, at observation battery liquid-filling hole, and judgement should increase cycle time Number (as shown in Figure 1);
Cycle-index n=10 (relative to n=9, cycle-index increases by 1 time) is set, battery C is complete according to above-mentioned electrolyte filling method After fluid injection, observes at battery liquid-filling hole without flowable electrolyte residual (i.e. without spill liquid phenomenon), determine the model lithium-ion electric The cycle-index in pond is 10 times.
As cycle-index n=10, for the lithium ion battery of the model, time T=that entire injection process is consumed 22.5min, and electroless liquid remains.

Claims (7)

1. a kind of electrolyte filling method of lithium ion battery, it is characterised in that:Include the following steps:
1)It is -90KPa~-95KPa to be evacuated to vacuum degree to battery case inside;
2)Maintenance battery case internal vacuum is -90KPa~1~2s of -95KPa pressurizes;
3)Electrolyte is injected into battery case;
4)By battery case pressure release;
5)With what follows pressurization, pressure release, vacuumize, pressure release be one cycle, carry out cycle standing:
60~80s of pressurization is carried out to the nitrogen that charged pressure inside battery case is 0.020~0.035MPa, pressure release, then to electricity It is -65KPa~-90KPa, pressure release that pond enclosure interior, which is evacuated to vacuum degree,;
6)The nitrogen and 30~80s of holding that charged pressure is 0.020~0.035MPa inside to battery case;
7)By battery case pressure release, that is, complete fluid injection;
Step 5)In, the time vacuumized is 60~80s;
Step 5)In, cycle-index is according to step 7)Liquid injection port is set with the presence or absence of liquid situation is spilt after completing fluid injection;It such as completes to note Liquid injection port, which exists, after liquid spills liquid situation, then increases cycle-index;Liquid injection port then reduces cycle without liquid situation is spilt after such as completing fluid injection Number.
2. the electrolyte filling method of lithium ion battery according to claim 1, it is characterised in that:Step 1)In, vacuumize when Between be 35~75s.
3. the electrolyte filling method of lithium ion battery according to claim 2, it is characterised in that:Step 3)In, when injection process Between be no longer than step 1)In time for vacuumizing.
4. the electrolyte filling method of lithium ion battery according to claim 3, it is characterised in that:Step 3)In, when injection process Between be 30~70s.
5. the electrolyte filling method of lithium ion battery according to claim 1, it is characterised in that:Step 4)In, the pressure release Time is 1~2s.
6. the electrolyte filling method of lithium ion battery according to claim 1, it is characterised in that:Step 5)In, the pressure release Time is 1~2s.
7. the electrolyte filling method of lithium ion battery according to claim 1, it is characterised in that:Step 7)In, the pressure release Time is 1~2s.
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CN106941194A (en) * 2017-03-10 2017-07-11 江西佳沃新能源有限公司 A kind of lithium ion battery liquid injection method
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CN110943196A (en) * 2019-12-28 2020-03-31 泰兴市宁辉锂电池有限公司 Lithium battery liquid injection method
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