CN102368571A - Precharge method of lithium ion batteries - Google Patents
Precharge method of lithium ion batteries Download PDFInfo
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- CN102368571A CN102368571A CN2011102691284A CN201110269128A CN102368571A CN 102368571 A CN102368571 A CN 102368571A CN 2011102691284 A CN2011102691284 A CN 2011102691284A CN 201110269128 A CN201110269128 A CN 201110269128A CN 102368571 A CN102368571 A CN 102368571A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of lithium ion batteries, especially to a rapid precharge method of lithium ion batteries. The precharge method provided by the invention comprises the following steps of: (1) letting a liquid injection stand, placing an electrical core between two flat plates and applying pressure; (2) precharging the electrical core with heavy current; (3) carrying out vacuum pumping and packaging. The method provided by the invention is used to charge with heavy current under a certain pressure, thus guaranteeing good internal pole piece interface of the electrical core, reducing polarization during the precharging of the electrical core with heavy current, preventing local over-charge of the negative electrode, simultaneously shortening the formation time, guaranteeing the smooth discharge of gas generated during the formation and forming a uniform SEI membrane when precharging the electrical core with heavy current. Therefore, the performance of the electrical core is improved.
Description
Technical field
The present invention relates to the technical field of lithium ion battery, relate in particular to a kind of quick pre-charge method of lithium ion battery.
Background technology
Lithium rechargeable battery is as a kind of environmental protection battery; Have advantages such as operating voltage height, specific energy is high and have extended cycle life; Obtained in recent years developing rapidly, the application in mobile devices such as mobile phone, ups power, notebook computer, electric tool, electric bicycle and electric automobile more and more widely.The continuous increase of lithium battery demand impels the battery production merchant must simplify technological process, and the reduction activity time is enhanced productivity and satisfied market demands.
The step that changes into of lithium ion battery is the important procedure that battery is made, and is related to the performance of the aspects such as capacity height, cycle life length, high temperature storage of battery.It is initial charge that lithium battery is carried out precharge, forms a kind of solid electrolyte interface or claims the process of SEI (Solid Electrolyte Interface) film in negative terminal surface, is also referred to as formation process.When negative pole forms the SEI film, follow side reaction gas to produce, the gas of generation needs in time to discharge, otherwise these gases gather in electric in-core portion and cause electric core bulging, casing deformation even produce blast.If formation process gas produces not exclusively, in follow-up charge and discharge process, can continue aerogenesis in addition, have a strong impact on the electrical property and the security performance of electric core.In order to obtain SEI film preferably, it is to adopt little electric current to reach tens of hours charging that tradition changes into, and production efficiency is extremely low.
Also disclose some technical schemes in the prior art and shortened the time of changing into, the world patent WO2010/081422A1 of bulletin quickened to produce side reaction gas through introducing two step precharge like on July 22nd, 2010.But this technology does not overcome the polarization problem that large current charge causes, and charging effect is unsatisfactory, and electric core cryogenic property is relatively poor relatively.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, a kind of easy to operate, simple pre-charge method of technical process is provided.Can reach the effect same that changes into for a long time with little electric current, shorten changing into the time simultaneously greatly, increase substantially production capacity, have bigger economic benefit.
For realizing above-mentioned purpose, technical scheme provided by the invention is following:
A kind of pre-charge method of lithium ion battery, under 10～60 ℃ of environment, carry out following steps: (1) is left standstill the electric core in back with fluid injection and is put into two flat boards and exert pressure; (2) electric core is carried out big pre-charge; (3) vacuum suction and encapsulation.
Executing in the said step (1) in the pressure of electric wicking surface size and be 0.01Mpa～1.2Mpa, is to guarantee that electric in-core portion pole piece interface is good, and the polarization when reducing big pre-charge electricity prevents that the negative pole part from overcharging.
Can adopt anchor clamps to exert pressure in the said step (1), it is smooth that anchor clamps have the interface, easy to use; Can also adopt simultaneously cylinder to cooperate and exert pressure, so that the size of controlled pressure.
Big pre-charge electricity is the single step constant current charge in the said step (2), and the preliminary filling electric weight is 8%～70% of the total electric weight of electric core.
Big pre-charge electricity is the multistep charging in the said step (2), and total preliminary filling electric weight is 8%～70% of the total electric weight of electric core.
Charging current is 0.05C～2C in the said step (2), and the charging interval is 5～120Min.
Precharge is under 10～60 ℃ of borders, to carry out in the said step (2).
The encapsulation of said step (3) vacuum suction is to discharge as far as possible fully for the gas that precharge is produced, and prevents electric core high temperature bulging.
Beneficial effect of the present invention:
The inventor finds, adopts traditional little electric current to change into for a long time or when directly changing into big electric current, and along with the carrying out of charging process, the gas of generation gathers more and morely in the battery, and is that about 10% of battery total capacity reaches maximum at charge volume.The portion gas that produces can remain between the positive/negative plate; Hindered the ionic conduction between the both positive and negative polarity; Cause in follow-up charging process the negative pole charging inhomogeneous, charge efficiency is low, and finds that when large current charge negative terminal surface has Li dendrite; Bulging distortion situation appears in battery simultaneously, and battery performance descends.So it is the key that realizes large current charge that the gas when overcoming electric core and changing between the positive/negative plate hinders, exerts pressure with anchor clamps at electric wicking surface when changing into and to realize that big electric current changes into.
Utilize pre-charge method of the present invention,, under the good situation in the electric in-core of assurance portion pole piece interface, carry out big pre-charge through applying certain pressure on electric core two sides.The polarization that the method has produced when having eliminated with big pre-charge electricity and the charging problem of non-uniform that causes, and form uniform SEI film in negative terminal surface.The electric core that obtains through the method reaches and the long-time similar even better electrical property of electric core that charges of traditional little electric current, shortens pre-charging time simultaneously greatly, improves process efficiency, reduces production costs.
Description of drawings
Fig. 1 is pre-charge method of the present invention voltage-time curve figure when 0.5C precharge
Embodiment
Following embodiment all selects for use flexible package 053450 size battery that the present invention is further described:
Embodiment 1:
With cobalt acid lithium be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 0.8Mpa; Under 45 ℃ of ambient temperatures with 0.5C current charges 15min; The preliminary filling electric weight is 12.5% of the total electric weight of electric core, forms the SEI film in negative terminal surface, vacuumizes encapsulation afterwards; Carry out capacity and loop test then, content measurement is seen table 1.
Embodiment 2:
With cobalt acid lithium be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 1.2Mpa, and with 0.3C current charges 30min, the preliminary filling electric weight is 15% of the total electric weight of electric core under 23 ℃ of ambient temperatures; Form the SEI film in negative terminal surface; Vacuumize encapsulation afterwards, carry out capacity and loop test then, content measurement is seen table 1.
Embodiment 3:
With the LiMn2O4 be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 0.01Mpa; Under 10 ℃ of ambient temperatures with 0.05C current charges 120min; The preliminary filling electric weight is 10% of the total electric weight of electric core, forms the SEI film in negative terminal surface, vacuumizes encapsulation afterwards; Carry out capacity and loop test then, content measurement is seen table 1.
Embodiment 4:
With the LiFePO4 be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 0.8Mpa, and with 1C current charges 42min, the preliminary filling electric weight is 70% of the total electric weight of electric core under 60 ℃ of ambient temperatures; Form the SEI film in negative terminal surface; Vacuumize encapsulation afterwards, carry out capacity and loop test then, content measurement is seen table 1.
Embodiment 5:
With the nickle cobalt lithium manganate be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 0.5Mpa, and with 2C current charges 15min, the preliminary filling electric weight is 50% of the total electric weight of electric core under 45 ℃ of ambient temperatures; Form the SEI film in negative terminal surface; Vacuumize encapsulation afterwards, carry out capacity and loop test then, content measurement is seen table 1.
Embodiment 6:
With cobalt acid lithium be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 0.1Mpa; Under 23 ℃ of ambient temperatures with 0.5C current charges 45min; The preliminary filling electric weight is 37.5% of the total electric weight of electric core, forms the SEI film in negative terminal surface, vacuumizes encapsulation afterwards; Carry out capacity and loop test then, content measurement is seen table 1.
Embodiment 7:
With cobalt acid lithium be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is put into two flat boards and imposed the pressure of 0.5Mpa; Behind the 10min that charges with 0.2C earlier under 23 ℃ of ambient temperatures, use 0.5C current charges 10min again; The preliminary filling electric weight is 10% of the total electric weight of electric core, forms the SEI film in negative terminal surface, vacuumizes encapsulation afterwards; Carry out capacity and loop test then, content measurement is seen table 1.
Comparative example 1:
With cobalt acid lithium be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is not exerted pressure, and with 0.5C current charges 15min, charging vacuumizes encapsulation after finishing, and carries out capacity and loop test then under 45 ℃ of ambient temperatures.
Comparative example 2:
With cobalt acid lithium be positive electrode active materials, graphite be negative active core-shell material make both positive and negative polarity pole piece and barrier film process naked electric core through lamination or coiling, then electric core is packed in the pack case, in it, inject the LiPF of 1mol/L
6/ (EC+PC+DEC) electrolyte is made battery.Wherein the volume ratio of ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC) is 1: 1: 1.The battery that makes is not exerted pressure, and with 0.035C current charges 900min, charging vacuumizes encapsulation after finishing, and carries out capacity and loop test then under 45 degree ambient temperatures.
Battery performance test
1. charging curve relatively
Fig. 1 be the charging curve of embodiment 1 when charging the identical time (15min) with comparative example 1 usefulness same current (0.5C) relatively.As can be seen from the figure relatively example 1 is little for embodiment 1 voltage ascensional range; Be illustrated in the polarization in the time of to eliminate big pre-charge electricity under the situation of exerting pressure of electric wicking surface; Play preventing that the negative pole part from overcharging effect, can form uniform SEI film, improve electric core performance.
2. low temperature is tested in proper order
The battery of embodiment and comparative example preparation is placed in the low temperature environment (10 ℃) carries out the capacity loop test; Method of testing: to 4.2V, change constant voltage charge with the 0.5C constant current charge; To an electric current 0.05C, be discharged to 3V with 0.5C then, and repeat 100 circulations; Obtain the battery capacity conservation rate, the result sees table 1.Can find out that from table 1 comparative example 1 is directly relatively poor with the low temperature cycle performance of big pre-charge electricity, and the circulation of embodiment low temperature can be better, to change into electric core suitable with comparative example 2 traditional little electric currents.
3. normal temperature and high temperature circulation test
The battery of embodiment and comparative example preparation is placed on respectively in normal temperature (25 ℃) and high temperature (45 ℃) environment carries out the capacity loop test; Method of testing: to 4.2V, change constant voltage charge with the 1C constant current charge; To electric current 0.05C, be discharged to 3V with 1C then, and repeat 500 circulations; Obtain battery capacity conservation rate and electric core expansion data, the result sees table 1.Can find out that from table 1 high temperature cyclic performance of comparative example 1 is relatively poor, and the embodiment high temperature circulation can be better, to change into electric core suitable with comparative example 2 traditional little electric currents.
Table 1
Utilize pre-charge method of the present invention, through applying certain pressure on electric core two sides, the polarization that has produced when having eliminated and the charging problem of non-uniform that causes with big pre-charge electricity, and form uniform SEI film in negative terminal surface.The electric core that obtains through the method reaches and the long-time similar even better electrical property of electric core that charges of traditional little electric current, shortens pre-charging time simultaneously greatly, improves process efficiency, reduces production costs.Need to prove that according to other execution modes of the present invention, positive active material also can be Li
zCoO
2, Li
zNiO
2, Li
zMnO
2, Li
zCo
1-(x+y)Ni
xMn
yO
2, Li
zNi
xMn
1-xO
2, Li
zCo
xNi
1-xO
2, LiVPO
4, Li
2MnO
3Or Li
zMn
xM
1-xO
4Deng in (wherein: x, y, x+y＜1, z>=1) one or several.Negative electrode active material also can be hard carbon, soft carbon, Li
4Ti
5O
12, Sn, Si or its arbitrary proportion mixture.Barrier film can be a polypropylene diaphragm; The polyethylene barrier film; Or polypropylene and polyethylene composite high-molecular barrier film; Or the polymer gel attitude barrier film that forms of polyvinylidene fluoride, vinylidene difluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene glycol, or the composite isolated film of aforementioned composite high-molecular barrier film and aforementioned polymer gel state barrier film.Electrolytic salt in the electrolyte can be LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiCl, LiBr, LiBOB, CF
3SO
3Li, CH
3SO
3Li, LiB (C
6H
5)
4Or its combination; Organic solvent in the electrolyte can be EC, PC, DEC, DMC, oxolane, gamma-butyrolacton, diethyl ethyl phosphonate, sulfoxide, methyl sulfoxide, dioxolane, acetonitrile or its combination.
Need to prove that according to the announcement and the instruction of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention equivalent modifications more of the present invention and change.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (8)
1. the pre-charge method of a lithium ion battery is characterized in that: comprise the steps:
(1) the electric core in back being left standstill in fluid injection puts into two flat boards and exerts pressure;
(2) electric core is carried out big pre-charge;
(3) charging is finished the electric core in back and carry out vacuum suction and encapsulation.
2. the pre-charge method of a kind of lithium ion battery as claimed in claim 1 is characterized in that: the big or small 0.01Mpa～1.2Mpa of being of pressure that is applied to electric wicking surface in the step (1).
3. the pre-charge method of a kind of lithium ion battery as claimed in claim 1 is characterized in that: big pre-charge electricity is the single step constant current charge in the step (2), and the preliminary filling electric weight is 8%～70% of the total electric weight of electric core.
4. the pre-charge method of a kind of lithium ion battery as claimed in claim 1 is characterized in that: big pre-charge electricity is the multistep charging in the step (2), and always the preliminary filling electric weight is 8%～70% of the total electric weight of electric core.
5. the pre-charge method of a kind of lithium ion battery as claimed in claim 1 is characterized in that: charging current is 0.05C～2C in the step (2), and the charging interval is 5～120Min.
6. the pre-charge method of a kind of lithium ion battery as claimed in claim 1 is characterized in that: precharge is under 10～60 ℃ of borders, to carry out in the step (2).
7. the pre-charge method of a kind of lithium ion battery as claimed in claim 1, it is characterized in that: said step (1) middle plateform is anchor clamps.
8. the pre-charge method of a kind of lithium ion battery of stating like claim 7, it is characterized in that: said anchor clamps also are combined with cylinder.
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| CN2011102691284A CN102368571A (en) | 2011-09-05 | 2011-09-05 | Precharge method of lithium ion batteries |
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Family
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102646809A (en) * | 2012-04-23 | 2012-08-22 | 宁德新能源科技有限公司 | Filling and activating method for flexible-packaging lithium ion battery |
| CN104167566A (en) * | 2014-08-06 | 2014-11-26 | 苏州星恒电源有限公司 | Sealing forming method of lithium ion battery |
| CN104393348A (en) * | 2014-10-29 | 2015-03-04 | 山东神工海特电子科技有限公司 | Preparation method of laminated flexible-package lithium-ion battery |
| CN104600385A (en) * | 2015-01-10 | 2015-05-06 | 鸿德新能源科技有限公司 | Quick forming method of power type soft packaging polymer battery |
| CN104715926A (en) * | 2013-12-16 | 2015-06-17 | 西门子公司 | Removing faults from a self-healing film capacitor |
| CN105161767A (en) * | 2015-08-06 | 2015-12-16 | 孙杰 | Lithium ion power battery and fabrication method and application thereof |
| CN105406130A (en) * | 2015-11-30 | 2016-03-16 | 山东精工电子科技有限公司 | Soft package lithium-ion battery formation method |
| CN105449286A (en) * | 2015-07-30 | 2016-03-30 | 万向A一二三系统有限公司 | Soft package lithium-ion battery activation method |
| CN106025365A (en) * | 2016-07-05 | 2016-10-12 | 深圳市海太阳实业有限公司 | Making method of battery and battery |
| CN106684426A (en) * | 2016-12-29 | 2017-05-17 | 多氟多（焦作）新能源科技有限公司 | Formation method of softly-packed lithium ion battery |
| CN107732314A (en) * | 2017-11-13 | 2018-02-23 | 桑顿新能源科技有限公司 | A kind of quick formation processing method for improving cycle performance of lithium ion battery |
| CN107860810A (en) * | 2017-10-20 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of sign formation of SEI films and the electrochemical method of decomposable process and system |
| CN109346776A (en) * | 2018-11-12 | 2019-02-15 | 上海力信能源科技有限责任公司 | A kind of chemical synthesizing method of soft bag lithium ionic cell, soft bag lithium ionic cell |
| CN111492512A (en) * | 2017-12-07 | 2020-08-04 | 新强能电池公司 | Method of forming an electrochemical cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102646809A (en) * | 2012-04-23 | 2012-08-22 | 宁德新能源科技有限公司 | Filling and activating method for flexible-packaging lithium ion battery |
| CN102646809B (en) * | 2012-04-23 | 2014-07-30 | 宁德新能源科技有限公司 | Filling and activating method for flexible-packaging lithium ion battery |
| CN104715926B (en) * | 2013-12-16 | 2019-01-01 | 西门子公司 | Failure is removed from selfreparing thin film capacitor |
| CN104715926A (en) * | 2013-12-16 | 2015-06-17 | 西门子公司 | Removing faults from a self-healing film capacitor |
| CN104167566A (en) * | 2014-08-06 | 2014-11-26 | 苏州星恒电源有限公司 | Sealing forming method of lithium ion battery |
| CN104167566B (en) * | 2014-08-06 | 2017-03-15 | 星恒电源股份有限公司 | A kind of sealing chemical synthesizing method of lithium ion battery |
| CN104393348A (en) * | 2014-10-29 | 2015-03-04 | 山东神工海特电子科技有限公司 | Preparation method of laminated flexible-package lithium-ion battery |
| CN104600385A (en) * | 2015-01-10 | 2015-05-06 | 鸿德新能源科技有限公司 | Quick forming method of power type soft packaging polymer battery |
| CN105449286A (en) * | 2015-07-30 | 2016-03-30 | 万向A一二三系统有限公司 | Soft package lithium-ion battery activation method |
| CN105161767B (en) * | 2015-08-06 | 2018-01-05 | 孙杰 | A kind of lithium-ion-power cell and its manufacture method and application |
| CN105161767A (en) * | 2015-08-06 | 2015-12-16 | 孙杰 | Lithium ion power battery and fabrication method and application thereof |
| CN105406130A (en) * | 2015-11-30 | 2016-03-16 | 山东精工电子科技有限公司 | Soft package lithium-ion battery formation method |
| CN106025365A (en) * | 2016-07-05 | 2016-10-12 | 深圳市海太阳实业有限公司 | Making method of battery and battery |
| CN106684426A (en) * | 2016-12-29 | 2017-05-17 | 多氟多（焦作）新能源科技有限公司 | Formation method of softly-packed lithium ion battery |
| CN107860810A (en) * | 2017-10-20 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of sign formation of SEI films and the electrochemical method of decomposable process and system |
| CN107860810B (en) * | 2017-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Electrochemical method and system for representing SEI film forming and decomposing processes |
| CN107732314A (en) * | 2017-11-13 | 2018-02-23 | 桑顿新能源科技有限公司 | A kind of quick formation processing method for improving cycle performance of lithium ion battery |
| CN111492512A (en) * | 2017-12-07 | 2020-08-04 | 新强能电池公司 | Method of forming an electrochemical cell |
| CN111492512B (en) * | 2017-12-07 | 2023-10-20 | 新强能电池公司 | Method of forming an electrochemical cell |
| CN109346776A (en) * | 2018-11-12 | 2019-02-15 | 上海力信能源科技有限责任公司 | A kind of chemical synthesizing method of soft bag lithium ionic cell, soft bag lithium ionic cell |
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Application publication date: 20120307 |