CN102544591A - Method for improving high-temperature storage performance of lithium ion battery - Google Patents
Method for improving high-temperature storage performance of lithium ion battery Download PDFInfo
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- CN102544591A CN102544591A CN2012100310668A CN201210031066A CN102544591A CN 102544591 A CN102544591 A CN 102544591A CN 2012100310668 A CN2012100310668 A CN 2012100310668A CN 201210031066 A CN201210031066 A CN 201210031066A CN 102544591 A CN102544591 A CN 102544591A
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- 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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- 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
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for improving the high-temperature storage performance of a battery on the premise that the battery cycle performance of the battery is not influenced. The method comprises the following steps of: 1, winding a cathode plate, a diaphragm and an anode plate to form a battery core, putting the battery core into a package bag, injecting electrolyte into the package bag, and performing reduction, shaping and capacity measurement to obtain a lithium ion battery, wherein the electrolyte comprises fluoro ethylene carbonate and organic dinitrile substances; and 2, fully charging the lithium ion battery which is obtained in the step 1, and preheating the fully-charged lithium ion battery at a temperature of between 55 and 80 DEG C. Compared with the prior art, the method overcomes the defects that when the organic dinitrile type substances and the fluoro ethylene carbonate (FEC) serving as additives are added into the electrolyte at the same time, the cycle performance and the high-temperature storage performance of the battery core cannot be improved at the same time; and the high-temperature storage performance of the battery is further improved on the premise that the cycle performance of the battery core is not influenced. Besides, the method also has the advantages of simple operation, easy control and the like.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly under the prerequisite that does not influence cycle performance of battery, improve the method for the high-temperature storage performance of battery.
Background technology
Along with the continuous development of modern society with science and technology, electronic products such as notebook computer, panel computer and mobile phone obtain using more widely.And lithium ion battery is as a kind of green power supply, and is high because of its energy density, have extended cycle life and advantage such as self-discharge rate is low, is widely used in the various electronic products.
Yet the competition of current electronic product is growing more intense, and the client improves constantly the requirement of energy density.And the layer structure that currently marketed high-energy-density graphite is comparison rule receives the common embedding of propene carbonate in the electrolyte (PC) to cause peeling off easily, causes the cycle performance of battery to worsen.For addressing this problem, need in electrolyte, add fluorinated ethylene carbonate (FEC) as additive, with film forming on anode better, thereby suppress peeling off of graphite.Yet, the interpolation of FEC, but quickened the thickness swelling of battery when higher temperature storage (for example 85 ℃ under storage): battery will produce a large amount of gas under higher temperature, battery will be no longer available.
And the lithium ion battery that is applied in the electronic product need use under higher temperature sometimes inevitably.The lithium ion battery that uses with notebook computer is example; Because notebook computer usually is placed on ambient temperature and uses than under the conditions of higher; For example in the summer of sweltering heat, use if notebook computer is placed in the car, the environment for use temperature of lithium ion battery in addition up to 85 ℃ or more than; Battery is stored in such hot environment, and battery can not use very fast flatulence.
In order to solve the flatulence problem of lithium ion battery in the high temperature storage process that contains the fluorinated ethylene carbonate additive, application number is that the Chinese patent of CN201110157665 is employed in the electrolyte through adding organic dintrile class material (NC-(CH
2) n-CN, wherein n=2～4) and method.Though this method can be improved the high-temperature storage performance of lithium ion battery to a certain extent, this method receives certain restriction.For example when requiring cycle performance and high-temperature storage performance further to improve simultaneously; Contradiction can appear in these two kinds of results: when the fluorinated ethylene carbonate content of additive increases; Though the cycle performance of battery can improve, the high-temperature storage performance of battery is along with the addition of FEC increases and constantly worsens; If but increased the content of organic two nitrile materials for the high-temperature storage performance that guarantees battery is unaffected, cycle performance again could variation.
In view of this, necessaryly provide a kind of under the prerequisite that does not influence cycle performance of battery, improve the method for the high-temperature storage performance of battery.
Summary of the invention
The objective of the invention is to: to the deficiency of prior art, and provide a kind of under the prerequisite that does not influence electric core cycle performance, improve the method for the high-temperature storage performance of electric core.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of method of improving the lithium ion battery high-temperature storage performance may further comprise the steps:
The first step is wound into electric core with positive plate, barrier film and negative plate, and electric core is packed in the packaging bag, injects electrolyte, change into, and shaping, capacity obtains lithium ion battery, and said electrolyte contains fluorinated ethylene carbonate (FEC) and organic two nitrile materials;
In second step, after the lithium ion battery that step 1 is obtained completely fills, place under 55 ℃～80 ℃ the temperature and carry out The pre-heat treatment.
Need to prove that these two kinds of parameters of the temperature of The pre-heat treatment and warm-up time is provided with all and with fluorinated ethylene carbonate (FEC) content of additive certain relation is arranged among the present invention.Fluorinated ethylene carbonate content is many more, and the preheat temperature setting should be low more, need confirm according to the The pre-heat treatment temperature that is provided with warm-up time: when preheat temperature was lower than 60 ℃ (containing 60 ℃), the The pre-heat treatment time can increase and suitably increase along with the FEC amount; But when preheat temperature was higher than 60 ℃, the The pre-heat treatment time should reduce along with the increase of temperature.
The The pre-heat treatment temperature can be single temperature spot (as 60 ℃), also can preheat temperature be arranged in a plurality of temperature range scopes, and treatment temperature is jumped in the several temperature scope (as between 60 ℃-65 ℃-70 ℃, jumping back and forth) back and forth.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, the content of said fluorinated ethylene carbonate (FEC) is the 1wt%～5wt% of electrolyte total weight.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, the general formula of said organic two nitrile materials is NC-(CH
2) n-CN, wherein n=2～4.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, the content of said organic two nitrile materials is the 1wt%～5wt% of electrolyte total weight.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, the time of said The pre-heat treatment is 3 hours to 7 days.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention; When the content of fluorinated ethylene carbonate in the electrolyte (FEC) is the 1wt%～3wt% of electrolyte total weight; The temperature of said The pre-heat treatment is 55 ℃～80 ℃, and the time of The pre-heat treatment is 3 days.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, when the content of FEC in the electrolyte was the 1wt%～3wt% of electrolyte total weight, the temperature of said The pre-heat treatment was 60 ℃, and the time of The pre-heat treatment is 3 days.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention; When the content of fluorinated ethylene carbonate in the electrolyte (FEC) is the 3wt%～5wt% of electrolyte total weight; The temperature of said The pre-heat treatment is 55 ℃～65 ℃, and the time of The pre-heat treatment is 4 days.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, when the content of FEC in the electrolyte was the 3wt%～5wt% of electrolyte total weight, the temperature of said The pre-heat treatment was 60 ℃, and the time of The pre-heat treatment is 4 days.
Improve a kind of improvement of the method for lithium ion battery high-temperature storage performance as the present invention, when the temperature of said The pre-heat treatment is 70 ℃～80 ℃, after The pre-heat treatment is accomplished, lithium ion battery is cooled to normal temperature immediately also kept at normal temperatures 1～3 day.
With respect to prior art; The present invention has overcome when in electrolyte, adding organic dintrile class material and fluorinated ethylene carbonate (FEC) as additive simultaneously; Can not improve the cycle performance of battery and the shortcoming of high-temperature storage performance simultaneously; Under the prerequisite that does not influence cycle performance of battery, further reduce the flatulence of battery when higher temperature is stored and expand, thus the high-temperature storage performance of raising battery; Lithium ion battery can be used under higher temperature, expanded the range of application of lithium ion battery.In addition, the present invention also have method simple, easy and simple to handle, be easy to advantages such as control.
Embodiment
Be further described below in conjunction with embodiment specific embodiments of the invention and beneficial effect:
Embodiment 1
The preparation of positive plate:
With positive electrode active materials cobalt acid lithium (LiCoO
2), conductive agent acetylene black, bonding agent Kynoar (PVDF) makes anode sizing agent according to being uniformly dispersed in mass ratio adding in 96: 1.5: the 2.5 solvent N-methyl pyrrolidone (NMP).Then anode sizing agent is coated on the Al paper tinsel (thickness is 12 μ m), carries out operations such as roll-in, section and oven dry then, make positive plate.
The preparation of negative plate:
With negative electrode active material graphite, conductive agent acetylene black, bonding agent SBR emulsion and thickener sodium carboxymethylcellulose according to mass ratio 94: 1.5: 2.5: 2 add in the aqueous solvent and mix, and make cathode size after stirring.Then cathode size is coated on the Cu paper tinsel (thickness is 16 μ m), carries out operations such as roll-in, section and oven dry then, make negative plate.
It is polypropylene (PP) microporous barrier of 16 μ m that barrier film adopts thickness.
The preparation of lithium ion battery:
Above-mentioned positive plate, negative plate and barrier film are made into electric core through coiling or lamination technology; Then electric core is packed in the packaging bag; And carry out vacuum bakeout, perfusion contains fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 3wt% and the electrolyte that accounts for the succinonitrile of electrolyte total weight 2wt% then, then electric core is carried out Vacuum Package; Through change into, operation such as shaping and capacity, promptly obtain lithium ion battery.
Above-mentioned lithium ion battery is carried out following The pre-heat treatment: electric core completely is charged to 4.2V with the rate of charge of 0.5C, in 60 ℃ baking oven, left standstill 3 days then, leave standstill after the end electric core placed and cool off a period of time at normal temperatures, make it to return to room temperature.
Embodiment 2
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 1wt% and the adiponitrile that accounts for electrolyte total weight 1wt%.
The The pre-heat treatment condition is: electric core is placed in 80 ℃ the baking oven and leaves standstill 3h, be cooled to normal temperature immediately and kept at normal temperatures 3 days.
Other are identical with embodiment 1, repeat no more here.
Embodiment 3
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 5wt% and the glutaronitrile that accounts for electrolyte total weight 5wt%.
The The pre-heat treatment condition is: electric core is placed in 55 ℃ the baking oven and leaves standstill 7 days, and be cooled to room temperature.
Other are identical with embodiment 1, repeat no more here.
Embodiment 4
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 2wt% and the succinonitrile that accounts for electrolyte total weight 3wt%.
The The pre-heat treatment condition is: electric core is placed in 60 ℃ the baking oven and left standstill earlier 2 days, be cooled to room temperature after, then in 75 ℃ baking oven, left standstill 4 hours, and be cooled to room temperature immediately again.
Other are identical with embodiment 1, repeat no more here.
Embodiment 5
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 4wt% and the glutaronitrile that accounts for electrolyte total weight 4wt%.
The The pre-heat treatment condition is: electric core is placed in 60 ℃ the baking oven and leaves standstill 4 days, and be cooled to room temperature.
Other are identical with embodiment 1, repeat no more here.
Embodiment 6
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 5wt% and the glutaronitrile that accounts for electrolyte total weight 3wt%.
The The pre-heat treatment condition is: electric core is placed in 55 ℃ the baking oven and leaves standstill 7 days, and be cooled to room temperature.
Other are identical with embodiment 1, repeat no more here.
Embodiment 7
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 2wt% and the glutaronitrile that accounts for electrolyte total weight 3wt%.
The The pre-heat treatment condition is: electric core is placed in 60 ℃ the baking oven and leaves standstill 3 days, and be cooled to room temperature.
Other are identical with embodiment 1, repeat no more here.
Embodiment 8
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 2wt% and the adiponitrile that accounts for electrolyte total weight 3wt%.
The The pre-heat treatment condition is: electric core is placed in 60 ℃ the baking oven and leaves standstill 6 days, and be cooled to room temperature.
Other are identical with embodiment 1, repeat no more here.
Embodiment 9
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 1.5wt% and the adiponitrile that accounts for electrolyte total weight 3wt%.
The The pre-heat treatment condition is: electric core is placed in 75 ℃ the baking oven and left standstill 1 day, be cooled to normal temperature immediately and kept at normal temperatures 2 days.
Embodiment 10
Different with embodiment 1 is that the additive in the electrolyte is fluorinated ethylene carbonate (FEC) that accounts for electrolyte total weight 4wt% and the adiponitrile that accounts for electrolyte total weight 4wt%.
The The pre-heat treatment condition is: electric core is placed in 65 ℃ the baking oven and left standstill 5 days, be cooled to normal temperature.
Other are identical with embodiment 1, repeat no more here.
Comparative Examples 1
Different with embodiment 1 is do not contain fluorinated ethylene carbonate (FEC) and organic two nitrile materials in the electrolyte, and the lithium ion battery that makes not to be done any The pre-heat treatment.
Other are identical with embodiment 1, repeat no more here.
Comparative Examples 2
Different with embodiment 1 is that the lithium ion battery that makes is not done any The pre-heat treatment.
Other are identical with embodiment 1, repeat no more here.
The test of lithium ion battery high temperature storage:
The lithium ion battery of embodiment 1 to 10 and Comparative Examples 1 and 2 completely is charged to 4.2V with the rate of charge of 0.5C; The cell thickness of test this moment for storing preceding cell thickness, was put in 85 ℃ the baking oven baking 4 hours with battery then; Baking finishes the back and takes out battery; Test battery thickness immediately is to store the back cell thickness while hot, calculates the expansion rate of cell thickness before and after the storage.The computing formula of thickness swelling is following:
Cell thickness * 100% before thickness swelling=(cell thickness before storage back cell thickness-storage)/storage
The gained result is shown in table 1.
The lithium ion battery high temperature storage result of experiment of table 1: embodiment 1 to 10 and Comparative Examples 1 and 2
Can find out significantly that by table 1 when not containing additive such as fluoro ethylene carbonate (FEC) and organic two nitrile materials in the electrolyte of battery, after 85 ℃ of 4h high temperature storage tests, the expansion of battery is very serious, reaches 120% (seeing comparative example 1); And added additives such as fluorinated ethylene carbonate (FEC) and organic two nitrile materials, but battery is not when doing any The pre-heat treatment, and after 85 ℃ of 4h high temperature storage tests, battery flatulence is still relatively more serious, reaches and (sees comparative example 2) more than 69%; And through after the The pre-heat treatment; Battery high-temperature storage flatulence condition improved is apparent in view, and when FEC content is 3%, the content of organic two nitrile materials is 2% o'clock; After 60 ℃ of 3 days The pre-heat treatment; When battery was done 85 ℃ of 4h high temperature storage, thickness swelling was merely 9%, the high-temperature storage performance when greatly having improved FEC and organic two nitrile additives and existing; After through 80 ℃ of 3h The pre-heat treatment; Battery has slight aerogenesis to a certain degree; But battery left standstill a period of time in normal temperature environment after, the gas of generation will fade away, when battery is done 85 ℃ of 4h high temperature storage tests again; This moment, the cell thickness expansion was less, had improved high temperature storage significantly.
Explanation and instruction according to above-mentioned specification; Those skilled in the art in the invention can also make amendment and change above-mentioned execution mode; Therefore the present invention is not limited to top described embodiment, also should drop into protection range of claim of the present invention and so on to modifications more of the present invention with change.In addition, although used some particular term in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (10)
1. a method of improving the lithium ion battery high-temperature storage performance is characterized in that, may further comprise the steps:
The first step is wound into electric core with positive plate, barrier film and negative plate, and electric core is packed in the packaging bag, injects electrolyte, change into, and shaping, capacity obtains lithium ion battery, and said electrolyte contains fluorinated ethylene carbonate (FEC) and organic two nitrile materials;
In second step, after the lithium ion battery that step 1 is obtained completely fills, place under 55 ℃～80 ℃ the temperature and carry out The pre-heat treatment.
2. the method for improving the lithium ion battery high-temperature storage performance according to claim 1 is characterized in that: the content of said fluorinated ethylene carbonate (FEC) is the 1wt%～5wt% of electrolyte total weight.
3. the method for improving the lithium ion battery high-temperature storage performance according to claim 1 is characterized in that: the general formula of said organic two nitrile materials is NC-(CH
2) n-CN, wherein n=2～4.
4. the method for improving the lithium ion battery high-temperature storage performance according to claim 3 is characterized in that: the content of said organic two nitrile materials is the 1wt%～5wt% of electrolyte total weight.
5. the method for improving the lithium ion battery high-temperature storage performance according to claim 1 is characterized in that: the time of said The pre-heat treatment is 3 hours to 7 days.
6. the method for improving the lithium ion battery high-temperature storage performance according to claim 4; It is characterized in that: when the content of FEC in the electrolyte is the 1wt%～3wt% of electrolyte total weight; The temperature of said The pre-heat treatment is 55 ℃～80 ℃, and the time of The pre-heat treatment is 3 days.
7. the method for improving the lithium ion battery high-temperature storage performance according to claim 6; It is characterized in that: when the content of FEC in the electrolyte is the 1wt%～3wt% of electrolyte total weight; The temperature of said The pre-heat treatment is 60 ℃, and the time of The pre-heat treatment is 3 days.
8. the method for improving the lithium ion battery high-temperature storage performance according to claim 4; It is characterized in that: when the content of FEC in the electrolyte is the 3wt%～5wt% of electrolyte total weight; The temperature of said The pre-heat treatment is 55 ℃～65 ℃, and the time of The pre-heat treatment is 4 days.
9. the method for improving the lithium ion battery high-temperature storage performance according to claim 4; It is characterized in that: when the content of FEC in the electrolyte is the 3wt%～5wt% of electrolyte total weight; The temperature of said The pre-heat treatment is 60 ℃, and the time of The pre-heat treatment is 4 days.
10. the method for improving the lithium ion battery high-temperature storage performance according to claim 1; It is characterized in that: when the temperature of said The pre-heat treatment is 70 ℃～80 ℃; After The pre-heat treatment is accomplished, lithium ion battery is cooled to normal temperature immediately also kept at normal temperatures 1～3 day.
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| CN105720307A (en) * | 2016-02-23 | 2016-06-29 | 东莞锂威能源科技有限公司 | Method for improving self discharge of lithium ion battery core |
| 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 |
| CN115275103A (en) * | 2022-09-26 | 2022-11-01 | 比亚迪股份有限公司 | Lithium battery and electric equipment |
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| CN102244296A (en) * | 2011-06-14 | 2011-11-16 | 东莞新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
| US20110281179A1 (en) * | 2008-11-21 | 2011-11-17 | Ube Industries, Ltd. | Non-aqueous electrolytic solution, and lithium battery comprising same |
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| WO2011081113A1 (en) * | 2009-12-29 | 2011-07-07 | ソニー株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte battery |
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| 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 |
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| CN102544591B (en) | 2014-07-16 |
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