CN102376972A - Lithium ion battery and method for improving high-temperature storage performance of same - Google Patents
Lithium ion battery and method for improving high-temperature storage performance of same Download PDFInfo
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- CN102376972A CN102376972A CN2010102589296A CN201010258929A CN102376972A CN 102376972 A CN102376972 A CN 102376972A CN 2010102589296 A CN2010102589296 A CN 2010102589296A CN 201010258929 A CN201010258929 A CN 201010258929A CN 102376972 A CN102376972 A CN 102376972A
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- 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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- 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
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Abstract
The invention discloses a lithium ion battery and a method for improving high-temperature storage performance of the same. According to the invention, a high temperature formation process is utilized in the method to allow the surface of cathode active substances to form an SEI membrane at high temperature, and the high temperature formation process comprises the following steps: (1) carrying out high temperature aging, i.e., subjecting electrical cores after liquid injection to aging for 1 to 20 h at a temperature of 40 to 70 DEG C; (2) carrying out high temperature pre-charging, i.e., pre-charging the electrical cores after high temperature aging at a temperature of 40 to 70 DEG C, cooling the electrical cores after pre-charging and sealing the electrical cores. The SEI membrane in the invention is generated by interaction between an electrolyte and electrode materials at high temperature, has high stability at high temperature and good high temperature performance and enables high-temperature storage performance of the lithium ion battery to be improved. The method has the advantages of no need of great modification of conventional preparation equipment and process for lithium ion batteries, strong adaptability, a simple process and easy control.
Description
Technical field
The present invention relates to lithium ion battery and make the field, specifically relate to a kind of method that improves the lithium ion battery high-temperature storage performance.
Background technology
Characteristics such as lithium ion battery was introduced to the market by sony corporation of japan the nineties in 20th century, and is high because of the battery operated voltage of monomer whose, that energy density is big, have extended cycle life are used widely in small-sized portable power source fields such as mobile phone, notebook computers.Along with the further lifting of lithium ion battery energy density and power density, it has been regarded as the ideal source of hybrid vehicle and electric automobile, is one type of energy storage device with broad prospect of application.
Lithium ion battery is in high temperature storage after a period of time, the phenomenon that battery case bulging, thickness significantly increase can occur.Though cooling back cell thickness can decrease; But the capacity of lithium ion battery decline at this moment is (capacity attenuation can reach 15%) obviously; And because the gas that also residual a large amount of electrolyte at high temperature of inside battery and electrode reaction produce; Increase inner pressure of battery, had a strong impact on the cycle life of battery, and brought potential safety hazard.
For improving the high-temperature storage performance of battery, the researcher sets about improving from electrolyte mostly in the prior art.High temperature resistant electrolyte promptly is through in electrolyte, introducing the resistance to elevated temperatures that additive improves battery.For example common high temperature resistant electrolyte E231A is exactly in electrolyte, to add a certain amount of propylene sulfite PS to improve the high-temperature storage performance of battery.Though the introducing of additive can improve the high-temperature storage performance of lithium ion battery, can reduce battery charge/discharge capacity at low temperatures.In addition, the introducing of additive makes the chemical reaction of battery in the first charge-discharge process complicated, has increased the difficulty of battery quality control.
Summary of the invention
The technical problem that the present invention will solve is to overcome above defective, from the precharging technique for forming of battery, proposes a kind of method that improves the lithium ion battery high-temperature storage performance.
The present invention also proposes a kind of lithium ion battery, has good high-temperature memory property and high temperature cyclic performance.
Lithium ion battery battery case bulging problem at high temperature is because passivation layer SEI (the solid electrolyte interface) film that negative terminal surface forms under the normal temperature is at high temperature unstable essentially, the reconstruct with the electrolyte reaction.The reconstruct reaction can discharge a large amount of gases, causes phenomenons such as inner pressure of battery raises, battery drum shell.If SEI itself at high temperature forms, stable performance at high temperature, reconstruct instead would not take place, and have effectively suppressed disengaging of gas.Based on this, the inventor proposes to solve a kind of new approaches of battery resistance to elevated temperatures.
Technical problem of the present invention is achieved through following technical scheme.
The method of this raising lithium ion battery high-temperature storage performance adopts the high temperature chemical synthesis technology; Make the negative electrode active material surface at high temperature form the SEI film; Said high temperature chemical synthesis technology comprises: step (1), the high temperature ageing, with the electric core after the fluid injection in 40～70 ℃ of following ageings 1～20 hour; Step (2), the high temperature preliminary filling, in 40～70 ℃ of following precharge, preliminary filling finishes, and cool off the back, electric core seals with the electric core after the high temperature ageing.
In the preferred scheme, in the said step (2) during precharge temperature be 45～55 ℃.
The ageing temperature is 40～50 ℃ in the said step (1), and digestion time is 4～8 hours.
Preliminary filling electric current in the said step (2) is 0.02C～0.5C, and pre-charging time is 1～20 hour.
Preliminary filling electric current in the said step (2) is 0.1C～0.2C, and pre-charging time is 3～6 hours.
This lithium ion battery that the present invention proposes has adopted the method for above-mentioned raising lithium ion battery high-temperature storage performance among its preparation technology.
The beneficial effect that the present invention and prior art contrast are had is:
Electrolyte at high temperature viscosity diminishes, and the high temperature ageing can be quickened the infiltration of electrolyte and electrode material, effectively shortens digestion time; Because of the SEI film is that at high temperature electrolyte and electrode material effect generate, it at high temperature has advantages of higher stability, and high-temperature behavior is good.And the solubility with temperature of majority of gas in liquid raises and reduces.Preliminary filling under the normal temperature, though but extrusion process exclusive segment preliminary filling aerogenesis still has portion gas to be dissolved in the electrolyte; Influence cycle performance of battery and security performance; And preliminary filling at high temperature remains in the gas in the battery case after can effectively reducing preliminary filling, improves battery performance.The present invention need not battery making apparatus and technology are carried out big change, and adaptability is strong, and it is simple to have technology, the characteristics that are easy to control.
Embodiment
To prepare 5 groups of models in this execution mode is that 423048AH, nominal capacity are the lithium ion battery of 650mAh, comprises 1 group on 4 groups on embodiment battery and Comparative Examples battery.Wherein will adopt method of the present invention in the manufacturing process of embodiment battery, promptly at high temperature electric core changed into.
The concrete preparation process of preparation process of electricity core is following.
1) batching.With positive active material cobalt acid lithium LiCoO
2, anodal conductive agent acetylene black (adopting Cabot CABOT superconduct carbon black BP2000), anodal adhesive PVDF (model RC10214) and solvent NMP mixing and stirring, process anode sizing agent.Negative electrode active material native graphite, cathode conductive agent acetylene black are mixed, be dispersed in then in the sodium carboxymethylcellulose CMC aqueous solution for preparing, and styrene butadiene rubber sbr is added wherein as binding agent, evenly stir the back and form cathode size.
2) apply.Anode sizing agent is coated on 16 μ m thickness plus plate current-collecting body aluminium foils two-sided, and positive plate is processed in dry and roll-in, positive plate is cut into the anodal small pieces of certain size, and welding aluminium strip on the anodal small pieces.Cathode size is coated on the negative current collector Copper Foil of 10 μ m thickness, negative plate is processed in dry and roll-in, negative plate is cut into the negative pole small pieces of certain size, and welding nickel strap on the negative pole small pieces.
3) preparing electrolyte.With lithium salts LiPF
6Be dissolved in the lithium salts solvent, solvent adopts EC, EMC, DMC mixed solvent, and three's mass ratio is EC: EMC: DMC=1: 1: 1.
4) assembling.Anodal small pieces, barrier film and the negative pole small pieces that branch is cut stacked or reel after pack in the aluminum metal battery case, battery case and cap assembly are carried out welded seal, with the electrolyte injection aluminum hull for preparing.
Embodiment 1
Get 50 above-mentioned electric cores of having annotated electrolyte and change into, may further comprise the steps:
(101) with the electric core after the fluid injection in 40 ℃ of following ageings 8 hours, electrolyte is fully contacted with electrode material, electrolyte fully soaks into electrode material.
(102) with the precharge in 45 ℃ of following constant temperature ovens of the electric core after the high temperature ageing, adopted the 0.02C pre-charge 5 hours earlier, adopt the 0.5C current charges to 4.2V again.Be cooled to room temperature after preliminary filling finishes, to electric core shaping, seal.
Battery is carried out high-temperature behavior investigate test, divide two kinds of test conditions to carry out, first kind is storage test in 60 ℃/7 days, and method is following:
A) get electric core after the precharge, capacity is designated as C1, electric core gauge T1;
The electric core that b) will be full of electricity is put into 60 ± 2 ℃ insulating box, stores 7 days;
C) to the electric core after the storage after measuring gauge T2 under 60 ℃ of conditions, measure electric core thickness T 3 again after at room temperature placing 2h;
D) the 1C discharge under 23 ± 2 ℃ of environment of electric core is obtained capacity C 2, after the 1C charging once more the 1C discharge obtain capacity C 3;
E) calculate following performance index:
Size changing rate (heat is surveyed)=(T2-T1)/T1;
Size changing rate (cold survey)=(T3-T1)/T1;
Capability retention=C2/C1;
Capacity restoration rate=C3/C1.
The average result of the high-temperature behavior test data of gained is seen shown in the table 1.
The another kind of test condition that battery high-temperature behavior is investigated test is storage test in 70 ℃/2 days, is that with the difference of first method step b) is that the electric core that will be full of electricity is put into 70 ± 2 ℃ insulating box, stores 2 days, and other steps are identical.The average result of the high-temperature behavior test data of gained is seen shown in the table 1.
Embodiment 2
Get 50 above-mentioned electric cores of having annotated electrolyte and change into, may further comprise the steps:
(201) with the electric core after the fluid injection in 70 ℃ of following ageings 1 hour, electrolyte is fully contacted with electrode material, electrolyte fully soaks into electrode material.
(202) with the precharge in 55 ℃ of following constant temperature ovens of the electric core after the high temperature ageing, adopted the 0.1C pre-charge 1 hour earlier, adopt the 0.2C current charges to 4.2V again.Be cooled to room temperature after preliminary filling finishes, to electric core shaping, seal.
Battery is carried out high-temperature behavior investigates test, divide two kinds of test conditions to carry out, identical with condition step among the embodiment 1, the result see shown in the table 1.
Embodiment 3
Get 50 above-mentioned electric cores of having annotated electrolyte and change into, may further comprise the steps:
(301) with the electric core after the fluid injection in 50 ℃ of following ageings 4 hours, electrolyte is fully contacted with electrode material, electrolyte fully soaks into electrode material.
(302) with the precharge in 70 ℃ of following constant temperature ovens of the electric core after the high temperature ageing, adopted the 0.1C pre-charge 1 hour earlier, adopt the 0.4C current charges to 4.2V again.Be cooled to room temperature after preliminary filling finishes, to electric core shaping, seal.
Battery is carried out high-temperature behavior investigates test, divide two kinds of test conditions to carry out, identical with condition step among the embodiment 1, the result see shown in the table 1.
Embodiment 4
Get 50 above-mentioned electric cores of having annotated electrolyte and change into, may further comprise the steps:
(401) with the electric core after the fluid injection in 40 ℃ of following ageings 20 hours, electrolyte is fully contacted with electrode material, electrolyte fully soaks into electrode material.
(402) with the precharge in 40 ℃ of following constant temperature ovens of the electric core after the high temperature ageing, adopted the 0.1C pre-charge 1 hour earlier, adopt the 0.2C current charges to 4.2V again.Be cooled to room temperature after preliminary filling finishes, to electric core shaping, seal.
Battery is carried out high-temperature behavior investigates test, divide two kinds of test conditions to carry out, identical with condition step among the embodiment 1, the result see shown in the table 1.
Comparative Examples 1
Getting 50 above-mentioned electric cores of having annotated electrolyte changes into: electric core in room temperature (15～30 ℃) precharge down, was adopted the 0.1C pre-charge 1 hour earlier, adopt the 0.2C current charges to 4.2V again.Be cooled to room temperature after preliminary filling finishes, to electric core shaping, seal.
Battery is carried out high-temperature behavior investigates test, divide two kinds of test conditions to carry out, identical with condition step among the embodiment 1, the result see shown in the table 1.
Comparative Examples 2
At first adopting E231A electrolyte to prepare model is 423048AH, and nominal capacity is the lithium ion battery of 650mAh, and the concrete preparation process of its electric core is following.
1) batching.With positive active material cobalt acid lithium LiCoO
2, anodal conductive agent acetylene black (adopting Cabot CABOT superconduct carbon black BP2000), anodal adhesive PVDF (model RC10214) and solvent NMP mixing and stirring, process anode sizing agent.Negative electrode active material native graphite, cathode conductive agent acetylene black are mixed, be dispersed in then in the sodium carboxymethylcellulose CMC aqueous solution for preparing, and styrene butadiene rubber sbr is added wherein as binding agent, evenly stir the back and form cathode size.
2) apply.Anode sizing agent is coated on 16 μ m thickness plus plate current-collecting body aluminium foils two-sided, and positive plate is processed in dry and roll-in, positive plate is cut into the anodal small pieces of certain size, and welding aluminium strip on the anodal small pieces.Cathode size is coated on the negative current collector Copper Foil of 10 μ m thickness, negative plate is processed in dry and roll-in, negative plate is cut into the negative pole small pieces of certain size, and welding nickel strap on the negative pole small pieces.
3) preparing electrolyte.With lithium salts LiPF
6Be dissolved in the lithium salts solvent, solvent adopts EC, EMC, DMC mixed solvent, and three's mass ratio is EC: EMC: DMC=1: 1: 1, and interpolation accounts for the propylene sulfite PS of weight of solvent part 2%.
4) assembling.Anodal small pieces, barrier film and the negative pole small pieces that branch is cut stacked or reel after pack in the aluminum metal battery case, battery case and cap assembly are carried out welded seal, with the electrolyte injection aluminum hull for preparing.
Getting 50 above-mentioned electric cores of having annotated electrolyte changes into: electric core in room temperature (15～30 ℃) precharge down, was adopted the 0.1C pre-charge 1 hour earlier, adopt the 0.2C current charges to 4.2V again.Be cooled to room temperature after preliminary filling finishes, to electric core shaping, seal.
Battery is carried out high-temperature behavior investigates test, divide two kinds of test conditions to carry out, identical with condition step among the embodiment 1, the result see shown in the table 1.
Table 1
Can find out that from table 1 after employing high temperature changed into mode, owing to remain in the gas in the battery case after can effectively reducing preliminary filling, the high-temperature storage performance of battery was significantly improved.
Above content is to combine concrete execution mode to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (6)
1. a method that improves the lithium ion battery high-temperature storage performance is characterized in that, adopts the high temperature chemical synthesis technology, makes the negative electrode active material surface at high temperature form the SEI film, and said high temperature chemical synthesis technology comprises:
Step (1), the high temperature ageing, with the electric core after the fluid injection in 40～70 ℃ of following ageings 1～20 hour;
Step (2), the high temperature preliminary filling, in 40～70 ℃ of following precharge, preliminary filling finishes, and cool off the back, electric core seals with the electric core after the high temperature ageing.
2. the method for raising lithium ion battery high-temperature storage performance as claimed in claim 1 is characterized in that, in the said step (2) during precharge temperature be 45～55 ℃.
3. the method for raising lithium ion battery high-temperature storage performance as claimed in claim 2 is characterized in that, the ageing temperature is 40～50 ℃ in the said step (1), and digestion time is 4～8 hours.
4. like the method for any described raising lithium ion battery high-temperature storage performance in the claim 1 to 3, it is characterized in that the preliminary filling electric current in the said step (2) is 0.02C～0.5C, pre-charging time is 1～20 hour.
5. the method for raising lithium ion battery high-temperature storage performance as claimed in claim 4 is characterized in that, the preliminary filling electric current in the said step (2) is 0.1C～0.2C, and pre-charging time is 3～6 hours.
6. lithium ion battery adopts the method for any described raising lithium ion battery high-temperature storage performance in the claim 1 to 5 among its preparation technology.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694178A (en) * | 2012-06-21 | 2012-09-26 | 奇瑞汽车股份有限公司 | Cathode material for batteries, battery and preparation method thereof |
| CN103915643A (en) * | 2013-01-04 | 2014-07-09 | 深圳市鼎力源科技有限公司 | Method for improving performance of square aluminum-shell battery |
| CN106848408A (en) * | 2016-12-16 | 2017-06-13 | 国轩新能源（苏州）有限公司 | It is a kind of to improve the method that Soft Roll square high-temperature lithium ion battery stores gas production |
| CN107946661A (en) * | 2017-11-17 | 2018-04-20 | 中山市电赢科技有限公司 | A kind of cell manufacturing method for improving battery high-temperature storage performance |
| CN108565496A (en) * | 2018-03-22 | 2018-09-21 | 天津市捷威动力工业有限公司 | A kind of method and battery preparation method of advance judgement lithium ion power battery electrolyte distribution |
| WO2018201427A1 (en) * | 2017-05-05 | 2018-11-08 | Robert Bosch Gmbh | Lithium ion battery and prelithiation method of anode |
| CN109459463A (en) * | 2017-12-05 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of quick evaluation method of anode material for lithium-ion batteries hot storage stability |
| WO2024000857A1 (en) * | 2022-07-01 | 2024-01-04 | 江苏时代新能源科技有限公司 | Battery shell flatness adjustment method and device, and battery manufacturing system |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694178A (en) * | 2012-06-21 | 2012-09-26 | 奇瑞汽车股份有限公司 | Cathode material for batteries, battery and preparation method thereof |
| CN102694178B (en) * | 2012-06-21 | 2015-11-25 | 奇瑞汽车股份有限公司 | The positive electrode, battery and preparation method thereof of battery |
| CN103915643A (en) * | 2013-01-04 | 2014-07-09 | 深圳市鼎力源科技有限公司 | Method for improving performance of square aluminum-shell battery |
| CN106848408A (en) * | 2016-12-16 | 2017-06-13 | 国轩新能源（苏州）有限公司 | It is a kind of to improve the method that Soft Roll square high-temperature lithium ion battery stores gas production |
| WO2018201427A1 (en) * | 2017-05-05 | 2018-11-08 | Robert Bosch Gmbh | Lithium ion battery and prelithiation method of anode |
| CN110710043A (en) * | 2017-05-05 | 2020-01-17 | 罗伯特·博世有限公司 | Lithium ion battery and method for prelithiation of anode |
| JP2020518991A (en) * | 2017-05-05 | 2020-06-25 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ | Lithium ion battery and method for prelithiation of anode |
| US11769900B2 (en) | 2017-05-05 | 2023-09-26 | Robert Bosch Gmbh | Lithium ion battery and prelithiation method of anode |
| CN107946661A (en) * | 2017-11-17 | 2018-04-20 | 中山市电赢科技有限公司 | A kind of cell manufacturing method for improving battery high-temperature storage performance |
| CN109459463A (en) * | 2017-12-05 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of quick evaluation method of anode material for lithium-ion batteries hot storage stability |
| CN108565496A (en) * | 2018-03-22 | 2018-09-21 | 天津市捷威动力工业有限公司 | A kind of method and battery preparation method of advance judgement lithium ion power battery electrolyte distribution |
| WO2024000857A1 (en) * | 2022-07-01 | 2024-01-04 | 江苏时代新能源科技有限公司 | Battery shell flatness adjustment method and device, and battery manufacturing system |
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