CN103117382B - Preparation method of lithium ion battery negative pole material capable of improving safety performance - Google Patents
Preparation method of lithium ion battery negative pole material capable of improving safety performance Download PDFInfo
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- CN103117382B CN103117382B CN201310058511.4A CN201310058511A CN103117382B CN 103117382 B CN103117382 B CN 103117382B CN 201310058511 A CN201310058511 A CN 201310058511A CN 103117382 B CN103117382 B CN 103117382B
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of a lithium ion battery negative pole material capable of improving the safety performance. The method comprises the following steps of: (1) slurry configuration, (2) coating, and (3) roasting and drying. According to the invention, as a negative pole tab is coated with a lithium metaaluminate film, which not only has a good electronic insulation effect, but also can effectively obstruct battery short circuit after a battery diaphragm PP (Polypropylene) or PE (polyethylene) is punctured, and at the same time the lithium metaaluminate has good ionic conductivity, thus increasing the transmission velocity of the lithium ion battery, and reducing the probability that dendritic crystal generated by lithium separation of the lithium ion battery pierces the diaphragm. The composite negative pole tab prepared by the method plays a very important role in improving high-capacity lithium ion batteries.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind ofly improve the method for lithium ion battery safety performance and prepared lithium ion battery thereof.
Background technology
Ferric phosphate lithium cell is a kind of novel energy-storing element grown up in recent years, and, environmental protection cheap with it, has extended cycle life and be subject to the favor in market.Simultaneously along with the continuous increase of battery energy density, the thermal stability of battery worse and worse, and constantly occur along with the battery door event of the company such as Sony, everything, while the high-energy-density ensureing lithium ion battery, ensure that again the safety and stability performance of battery becomes a major challenge of industry.And the security and stability of battery is mainly because the thermal runaway of lithium ion battery causes, and battery short circuit causes batteries caught fire, blast causes.The fail safe of current raising battery mainly passes through the following aspects: optimize electrolyte prescription, adopts ceramic diaphragm, provides the lithium ion positive and negative pole material of fail safe; But these methods are limited to the security performance improving battery.
Summary of the invention
For the deficiency of existing lithium ion battery, the object of the present invention is to provide a kind of lithium ion battery improving security performance and preparation method thereof, at the certain thickness lithium metaaluminate slurry of cathode pole piece surface-coated by spraying process, obtain the cathode pole piece containing lithium metaaluminate by techniques such as drying, bakings, finally prepare high security lithium ion battery.
Technical scheme of the present invention is achieved in the following ways: a kind of preparation method that can improve the lithium ion battery negative material of security performance, comprises the following steps; 1) slurry configuration, 2) coating, 3) baking drying; It is characterized in that:
1), slurry configuration: by quality ratio, get lithium metaaluminate: LA132 binding agent: CMC binding agent: conductive agent=100 ~ 50: the ratio of 10 ~ 1: 5 ~ 1: 1, be configured to redistilled water the lithium metaaluminate slurry that concentration is 1% ~ 40%;
The chemical molecular formula of described lithium metaaluminate is LiAlO
2, the Main Ingredients and Appearance of LA132 binding agent is polyacrylic acid, and the chemistry of CMC binding agent is called sodium carboxymethylcellulose, and conductive agent is Super-P;
The pore size of described lithium metaaluminate is 0.05 ~ 0.15 μm, and porosity is 40 ~ 50%;
2), be coated with: above-mentioned slurry is adopted the cathode pole piece surface-coated of ultrasonic spraying process after roll-in, its coating thickness is 1 ~ 10 μm, and the spraying frequency of ultrasonic spraying process is 1KHz ~ 1MHz;
3), baking is dry: by the cathode pole piece after above-mentioned surface-coated under temperature is 40 ~ 80 DEG C of conditions, toast 0.5 ~ 2 hour, drying obtains the cathode pole piece of surface containing lithium metaaluminate film.
The present invention; the pore size of lithium metaaluminate and porosity can ensure good lithium ion penetrability; film is carried out by anticathode pole piece; negative electrode active material-graphite in cyclic process is made to be unlikely to structural collapse; and be conducive to the stable of negative terminal surface SEI film; negative pole, carrying out obtaining effective protection in the process circulated, improves fail safe and the cycle performance of lithium ion battery.Utilize lithium ion battery LiAlO in charge and discharge process simultaneously
2the characteristic of ionic conductivity, improves the conduction velocity of lithium ion battery, reduces lithium ion battery and analyses the dendrite that lithium produces and puncture the probability of barrier film, improve the security performance of battery; Make use of LiAlO again
2heat-resisting, high temperature resistant, the characteristic of insulation, makes it prevent battery temperature in cell reaction process too high, and some the thermal runaway point expansion formation overall thermal reduced in battery is out of control, reduces battery short circuit probability.
Accompanying drawing explanation
Fig. 1 is that material prepared by embodiment 1 is assembled into the multiplying power discharging figure of battery A.
Fig. 2 is the multiplying power discharging figure that material prepared by prior art is assembled into battery B.
Embodiment
The embodiment of the present invention provides a kind of and improves the method for lithium ion battery safety performance and prepared lithium ion battery thereof, when being intended to solve non-normal use lithium rechargeable battery, easily cause internal short-circuit of battery and the problem on fire that sets off an explosion, for this reason, the method that the embodiment of the present invention adopts is: adopt the cathode pole piece surface-coated one deck LiAlO of spraying process after roll-in
2material, prepares composite negative pole pole piece, and as the cathode pole piece of lithium ion battery, prepares ferric phosphate lithium cell.
Embodiment 1:
After cathode pole piece roll-in, ultrasonic spraying process is adopted to apply one deck LiAlO in its negative terminal surface
2film; Its step is as follows: 1) slurry configuration, takes 100 grams of LiAlO
2, 10 grams of LA132 binding agents, 2 grams of CMC binding agents, 1 gram of SP conductive agent, 640 grams of redistilled waters, are configured to the lithium metaaluminate slurry of 15% concentration; 2) be coated with: adopted by its above-mentioned slurry ultrasonic spraying process (its device frequency is 500KHz) at cathode pole piece surface-coated lithium metaaluminate material, toast 1 hour afterwards under temperature is 50 DEG C of conditions, drying finally obtains the LiAlO that surface-coated thickness is 2 μm
2the cathode pole piece of film.The Main Ingredients and Appearance of LA132 binding agent is polyacrylic acid, and the chemistry of CMC binding agent is called sodium carboxymethylcellulose, and conductive agent is Super-P.
Embodiment 2:
The lithium ion battery production technology that the present embodiment provides is identical with the production technology that this area is commonly used, and difference is: after cathode pole piece roll-in, adopts ultrasonic spraying process to apply one deck LiAlO in its negative terminal surface
2film; 1) slurry configuration, takes 100 grams of LiAlO
2, 5 grams of LA132 binding agents, 2 grams of CMC binding agents, 1 gram of SP conductive agent, 2052 grams of redistilled waters, are configured to the lithium metaaluminate slurry of 5% concentration; 2) be coated with: adopted by its above-mentioned slurry ultrasonic spraying process (its device frequency is 1MHz) at cathode pole piece surface-coated lithium metaaluminate material, toast 2 hours afterwards under temperature is 40 DEG C of conditions, drying finally obtains the LiAlO that surface-coated thickness is 1 μm
2the cathode pole piece of film.
Embodiment 3:
After cathode pole piece roll-in, ultrasonic spraying process is adopted to apply one deck LiAlO2 film in its negative terminal surface; Its process is as follows: 1) slurry configuration, takes 50 grams of LiAlO
2, 10 grams of LA132 binding agents, 1 gram of CMC, 1 gram of SP conductive agent, 93 grams of redistilled waters, are configured to the lithium metaaluminate slurry of 40% concentration; 2) be coated with: adopted by its above-mentioned slurry ultrasonic spraying process (its device frequency is 1MHz) at cathode pole piece surface-coated lithium metaaluminate material, toast 2h afterwards under temperature is 80 DEG C of conditions, drying finally obtains the LiAlO that surface-coated thickness is 10 μm
2the cathode pole piece of film.
electrochemical property test
Being known by Fig. 1, is the rate discharge curves figure of embodiment 1 battery.Take LiFePO4 as positive electrode, with the composite negative pole material of embodiment 1 preparation for battery cathode, with LiPF
6/ EC+DEC(volume ratio 1: 1) be electrolyte, Celgard2400 film is barrier film, prepares 5AH soft-package battery A.Test the voltage-capacity discharge curve of its material under different multiplying afterwards.
Being known by Fig. 2, is the rate discharge curves figure battery as a comparison of comparative example battery.Being positive electrode with LiFePO4, take Delanium as negative material, adopts LiPF
6/ EC+DEC(volume ratio 1: 1) be electrolyte, Celgard2400 film is barrier film, prepares 5AH soft-package battery B.Test the voltage-capacity discharge curve of its material under different multiplying afterwards.
Under equal conditions test the DC internal resistance of its battery A and battery B, battery A DC internal resistance is 4.18m Ω, and the DC internal resistance of battery B is 5.31m Ω, and therefore the DC internal resistance of battery A is less than the DC internal resistance of battery B; The under equal conditions high rate performance of test battery A and battery B, battery is under 8.0C condition, the capability retention of battery A is 95.2%, and the capability retention of battery B is 91.0%, and random selecting 10 5AH soft-package battery A and 10 5AH soft-package battery B, respectively to 10 battery A, 10 battery B, carry out acupuncture short circuit experiment: result shows, in 10 battery A acupuncture experiments, acupuncture short circuit is caught fire 1, and in 10 battery B acupuncture experiments, acupuncture short circuit is caught fire 4.Therefore the security performance of battery A is better than the security performance of battery B.
The present invention, had both ensured that battery was under thermal runaway state, relied on LiAlO
2the insulating barrier that film is good, serves the effect of two-layer separator, after in battery, PP or PE barrier film is pierced, and LiAlO
2film can prevent internal short-circuit of battery effectively, particularly when PP or PE barrier film local is pierced, and LiAlO
2insulating effect more obvious, make the rapid diffusion of its cell heat, reduce the thawing probability of barrier film, thus reduce the short circuit probability of battery; LiAlO simultaneously
2have again better ionic conductivity, make it not increase at the resistance of battery in use battery, thus improve heat dispersion and the high rate performance of battery, preventing battery under acupuncture, the exceedingly odious condition such as falling, there is on fire, blast in battery.
Claims (1)
1. can improve a preparation method for the lithium ion battery negative material of security performance, comprise the following steps; 1) slurry configuration, 2) coating, 3) baking drying; It is characterized in that:
1), slurry configuration: by quality ratio, get lithium metaaluminate: LA132 binding agent: CMC binding agent: conductive agent=100 ~ 50: the ratio of 10 ~ 1: 5 ~ 1: 1, be configured to redistilled water the lithium metaaluminate slurry that concentration is 1% ~ 40%;
The chemical molecular formula of described lithium metaaluminate is LiAlO
2, the Main Ingredients and Appearance of LA132 binding agent is polyacrylic acid, and the chemistry of CMC binding agent is called sodium carboxymethylcellulose, and conductive agent is Super-P;
The pore size of described lithium metaaluminate is 0.05 ~ 0.15 μm, and porosity is 40 ~ 50%;
2), be coated with: above-mentioned slurry is adopted the cathode pole piece surface-coated of ultrasonic spraying process after roll-in, its coating thickness is 1 ~ 10 μm, and the spraying frequency of ultrasonic spraying process is 1KHz ~ 1MHz;
3), baking is dry: by the cathode pole piece after above-mentioned surface-coated under temperature is 40 ~ 80 DEG C of conditions, toast 0.5 ~ 2 hour, drying obtains the cathode pole piece of surface containing lithium metaaluminate film.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104332588B (en) * | 2014-08-21 | 2017-03-22 | 中航锂电（洛阳）有限公司 | High safety lithium ion battery negative electrode plate, preparation method and applications thereof |
| CN105226234B (en) * | 2015-09-01 | 2017-10-10 | 中航锂电（洛阳）有限公司 | Lithium battery anode composite piece, lithium battery composite negative plate and preparation method thereof, lithium battery |
| CN106486651A (en) * | 2015-09-29 | 2017-03-08 | 上海杉杉科技有限公司 | A kind of lithium ion battery negative material of high safety performance and preparation method thereof |
| CN105633340A (en) * | 2015-12-17 | 2016-06-01 | 佛山市南海区欣源电子有限公司 | Composite pole plate of lithium ion battery and preparation method of composite pole plate |
| CN105591070B (en) * | 2016-03-16 | 2017-11-03 | 江苏乐能电池股份有限公司 | A kind of preparation method of high-energy-density cathode pole piece and its lithium ion battery |
| CN106159201B (en) * | 2016-07-28 | 2019-02-12 | 深圳博磊达新能源科技有限公司 | A kind of lithium ion battery lithium composite sheet and preparation method thereof, lithium ion battery |
| CN106229447A (en) * | 2016-08-10 | 2016-12-14 | 东莞永蓝电子科技有限公司 | A kind of lithium ion battery |
| CN106129315B (en) * | 2016-08-19 | 2019-06-25 | 洛阳力容新能源科技有限公司 | A kind of lithium ion battery composite separation membrane and preparation method thereof, lithium ion battery |
| CN106252626B (en) * | 2016-08-26 | 2019-03-26 | 深圳博磊达新能源科技有限公司 | Have lithium titanate electrode material, the preparation method and application of core-shell structure |
| CN106159236A (en) * | 2016-08-26 | 2016-11-23 | 深圳博磊达新能源科技有限公司 | A kind of quick charge lithium titanate composite negative pole pole piece and lithium ion battery |
| CN106099041B (en) * | 2016-08-26 | 2020-05-29 | 深圳博磊达新能源科技有限公司 | Lithium titanate composite negative electrode piece and lithium titanate battery |
| CN106252598B (en) * | 2016-08-29 | 2019-11-05 | 深圳博磊达新能源科技有限公司 | A kind of high capacity, high security lithium ion battery cathode composite pole piece and preparation method thereof, lithium ion battery |
| CN106450166A (en) * | 2016-11-10 | 2017-02-22 | 厦门日臻动力电源科技有限公司 | Preparation method of lithium ion battery negative electrode composite pole piece |
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