CN109616709B - High-temperature formation process of high-voltage polymer lithium ion battery - Google Patents
High-temperature formation process of high-voltage polymer lithium ion battery Download PDFInfo
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- CN109616709B CN109616709B CN201710925998.XA CN201710925998A CN109616709B CN 109616709 B CN109616709 B CN 109616709B CN 201710925998 A CN201710925998 A CN 201710925998A CN 109616709 B CN109616709 B CN 109616709B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- 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
Abstract
The invention discloses a high-temperature formation process of a high-voltage polymer lithium ion battery, which comprises the following steps: (1) standing the battery at 45 ℃ for 8-12 h; (2) baking for 2-3h under the pressure of 0.6-1.0 Mpa and the temperature of 75-85 ℃ in a high-temperature pressure formation machine; (3) cooling to 60-70 ℃, and then carrying out formation under the pressure of 0.2-0.4 Mpa; (4) heating to 75-85 ℃, and then baking for 2 hours under the pressure of 0.6-1.0 Mpa; (5) and cooling to room temperature and taking out. The invention adopts segmented temperature and pressure control, high-temperature pressure formation and thermal compounding to realize stable thermal compounding of the pole piece/ceramic isolating membrane interface, is beneficial to forming a stable SEI (solid electrolyte interphase) membrane on the surfaces of a positive electrode material and a negative electrode material by a composite film-forming additive, improves the interface stability, the flatness and the hardness of the battery, and obviously improves the high-voltage resistance, the high-temperature resistance, the cycle performance and the safety performance of the battery.
Description
Technical Field
The invention belongs to the technical field of polymer lithium ion battery manufacturing, and particularly relates to a high-temperature formation process of a high-voltage polymer lithium ion battery.
Background
In order to exert higher capacity in a limited space and improve the energy density of the polymer lithium ion battery, the polymer lithium ion battery for the portable electronic product is mainly tried to use a positive and negative electrode material with high specific capacity, a high-energy electrolyte, an ultrathin isolating film (the thinnest is 8 micrometers at present), a thin copper foil (8 micrometers), a thin aluminum foil (10 micrometers), a thin aluminum-plastic packaging film (seventy-few micrometers) and the like, and when the measures are applied to the limit, people begin to pursue higher charging cut-off voltage of the polymer lithium ion battery, and the capacity and the energy density of the battery are further improved by improving the voltage working range of the polymer lithium ion battery. The charging of the polymer lithium ion battery is cut off to the voltage from 4.2V to 4.3V (the cell for an apple iPhone5 mobile phone) to 4.35V (the cell for some mobile phone models such as apple iPhone6, Samsung and Huashi) to 4.4V (apple iPhone7 and the like), the technology and the market of the polymer lithium ion battery with the charging cut off to the voltage of 4.35V and 4.4V are already mature, and the market application of the polymer lithium ion battery is continuously expanded and is in the way of being popularized. And polymer lithium ion batteries with 4.45V and 4.5V charge cutoff voltages are also currently under development.
The batteries of the high-end electronic products of the new generation of apple and samsung have been updated and replaced by high-voltage polymer lithium ion batteries with the charging cut-off voltage of 4.35V or 4.4V. Along with the increase of charging voltage, the energy density of the battery is obviously improved, the requirements on higher volumetric specific energy and endurance capacity of high-end portable equipment are greatly met, and the battery has a wide market prospect.
However, since high voltage polymer lithium ion batteries tend to be ultra thin and high energy density designs, the flatness and hardness requirements of the batteries are high. In order to obtain good performance, the traditional liquid flexible package polymer lithium ion battery is usually higher in electrolyte filling amount, softer and poorer in flatness, and is difficult to meet the hardness requirement of customer assembly such as mobile phones and tablet computers, so that improvement is needed.
Disclosure of Invention
The invention aims to overcome the defects and provide a high-temperature forming process of a high-voltage polymer lithium ion battery, which can improve the energy density of the battery, obtain good battery hardness and flatness and simultaneously keep good battery performance.
The technical scheme adopted by the invention is as follows:
a high-temperature formation process of a high-voltage polymer lithium ion battery comprises the following steps:
(1) standing the high-voltage polymer lithium ion battery which is prepared by adopting the ceramic isolating membrane and is filled with the electrolyte at the high temperature of 45 ℃ for 8-12 h; the high-temperature standing can fully soak the electrolyte in the pole piece and the isolating membrane;
(2) placing the battery in a high-temperature pressure formation machine, and continuously baking for 2-3h under the pressure of 0.6-1.0 Mpa and the temperature of 75-85 ℃;
(3) cooling the high-temperature pressure formation machine to 60-70 ℃, and then forming the battery under the pressure of 0.2-0.4 Mpa according to the formation flow;
(4) after formation, heating the high-temperature pressure formation machine to 75-85 ℃, and then continuously baking for 2 hours under the pressure of 0.6-1.0 Mpa;
(5) and cooling the high-temperature pressure formation machine to room temperature, and taking out the battery to complete high-temperature formation.
Preferably, the formation process comprises: step one, charging to 3.5V at 0.1C constant current under 0.2 Mpa; step two, charging to 3.5V at a constant current of 0.2C under the pressure of 0.3-0.4 Mpa; thirdly, charging to 4.35V at a constant current of 0.5C under the pressure of 0.2 Mpa; and fourthly, discharging to 3.9V at a constant current of 0.5 ℃ under the pressure of 0.2 Mpa.
Preferably, the electrolyte is a high temperature electrolyte. The high-temperature electrolyte can ensure that the electrolyte characteristics can not be damaged when the high-voltage polymer lithium ion battery is subjected to pressure formation under the high-temperature condition, so that the battery performance is deteriorated.
Preferably, the ceramic isolating membrane is mixed coated with Al2O3the/PVDF (polyvinylidene fluoride) composite ceramic isolating membrane.
Compared with the prior art, the invention has the beneficial effects that:
the thermal compounding and formation process adopts segmented temperature and pressure control high-temperature pressure formation and thermal compounding, and can control the positive plate/(Al) according to the generated amount of the formed gas2O3The interface film contact between the PVDF composite ceramic isolating film and the negative plate is beneficial to realizing stable thermal compounding of the pole plate/ceramic isolating film interface and also beneficial to realizing stable SEI (solid electrolyte interface film) of the composite film forming additive in the high-temperature electrolyte on the surfaces of the positive and negative materials, thereby improving the interface stability, the flatness and the hardness of the battery and obviously improving the high voltage resistance, the high temperature resistance, the cycle performance and the safety performance of the polymer lithium ion battery.
Drawings
FIG. 1 is a comparison of the 1C charge-discharge 300 cycle curves of example 2 and comparative example.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1:
in the embodiment of the invention, the high-temperature formation process of the high-voltage polymer lithium ion battery comprises the following steps:
(1) standing the high-voltage polymer lithium ion battery which is prepared by adopting the ceramic isolating membrane and is filled with the electrolyte at the high temperature of 45 ℃ for 8 hours; the high-temperature standing can fully soak the electrolyte in the pole piece and the isolating membrane;
(2) placing the battery in a high-temperature pressure formation machine, and continuously baking for 2h under the pressure of 0.6MpaMpa and the temperature of 75 ℃;
(3) cooling the high-temperature pressure formation machine to 60 ℃, and then forming the battery under the pressure of 0.2Mpa according to the formation process;
(4) heating the high-temperature pressure formation machine to 75 ℃ after formation, and continuously baking for 2 hours under the pressure of 0.6 Mpa;
(5) and cooling the high-temperature pressure formation machine to room temperature, and taking out the battery to complete high-temperature formation.
The formation process comprises the following steps: step one, charging to 3.5V at 0.1C constant current under 0.2 Mpa; step two, charging to 3.5V at a constant current of 0.2C under the pressure of 0.3 Mpa; thirdly, charging to 4.35V at a constant current of 0.5C under the pressure of 0.2 Mpa; and fourthly, discharging to 3.9V at a constant current of 0.5 ℃ under the pressure of 0.2 Mpa.
30 high-voltage polymer lithium ion batteries with model number of 2949119 and nominal capacity of 2750mAh and number of 1# -30 are prepared by the chemical synthesis process.
Example 2:
in the embodiment of the invention, the high-temperature formation process of the high-voltage polymer lithium ion battery comprises the following steps:
(1) standing the high-voltage polymer lithium ion battery which is prepared by adopting the ceramic isolating membrane and is filled with the electrolyte at the high temperature of 45 ℃ for 10 hours; the high-temperature standing can fully soak the electrolyte in the pole piece and the isolating membrane;
(2) placing the battery in a high-temperature pressure formation machine, and continuously baking for 2.5h under the pressure of 0.8Mpa and the temperature of 80 ℃;
(3) cooling the high-temperature pressure formation machine to 65 ℃, and then forming the battery under the pressure of 0.3Mpa according to the formation process;
(4) heating the high-temperature pressure formation machine to 80 ℃ after formation, and continuously baking for 2 hours under the pressure of 0.8 Mpa;
(5) and cooling the high-temperature pressure formation machine to room temperature, and taking out the battery to complete high-temperature formation.
The formation process comprises the following steps: step one, charging to 3.5V at 0.1C constant current under 0.2 Mpa; step two, charging to 3.5V at a constant current of 0.2C under the pressure of 0.35 Mpa; thirdly, charging to 4.35V at a constant current of 0.5C under the pressure of 0.2 Mpa; and fourthly, discharging to 3.9V at a constant current of 0.5 ℃ under the pressure of 0.2 Mpa.
30 high-voltage polymer lithium ion batteries with model number of 2949119 and nominal capacity of 2750mAh and number of 31# -60# are prepared by the chemical synthesis process.
Example 3:
in the embodiment of the invention, the high-temperature formation process of the high-voltage polymer lithium ion battery comprises the following steps:
(1) standing the high-voltage polymer lithium ion battery prepared by adopting the ceramic isolating membrane and filled with the electrolyte at a high temperature of 45 ℃ for 12 hours; the high-temperature standing can fully soak the electrolyte in the pole piece and the isolating membrane;
(2) placing the battery in a high-temperature pressure formation machine, and continuously baking for 3h under the pressure of 1.0Mpa and the temperature of 85 ℃;
(3) cooling the high-temperature pressure formation machine to 70 ℃, and then forming the battery under the pressure of 0.4Mpa according to the formation process;
(4) heating the high-temperature pressure formation machine to 85 ℃ after formation, and continuously baking for 2 hours under the pressure of 1.0 Mpa;
(5) and cooling the high-temperature pressure formation machine to room temperature, and taking out the battery to complete high-temperature formation.
The formation process comprises the following steps: step one, charging to 3.5V at 0.1C constant current under 0.2 Mpa; step two, charging to 3.5V at a constant current of 0.2C under the pressure of 0.4 Mpa; thirdly, charging to 4.35V at a constant current of 0.5C under the pressure of 0.2 Mpa; and fourthly, discharging to 3.9V at a constant current of 0.5 ℃ under the pressure of 0.2 Mpa.
30 high-voltage polymer lithium ion batteries with model number of 2949119 and nominal capacity of 2750mAh and number of 61# -90# are prepared by the chemical synthesis process.
Comparative example:
in this comparative example, a conventional formation process of a high voltage polymer lithium ion battery includes the following steps:
(1) standing a high-voltage polymer lithium ion battery (adopting a wet-process diaphragm which is not coated with ceramic) at normal temperature for 24 hours;
(2) placing the battery in a high-temperature pressure formation machine, heating to 50 ℃, and forming under the pressure of 0.35 Mpa;
(3) and cooling the high-temperature pressure formation machine to room temperature, and taking out the battery to complete high-temperature formation.
30 high-voltage polymer lithium ion batteries with model number of 2949119 and nominal capacity of 2750mAh and number of 91-120 are prepared by the chemical synthesis process.
Table 1 compares the main properties of each example and comparative example.
Fig. 1 shows a comparison of the 1C charge-discharge 300-cycle curves of example 2 and comparative example, and example 2 has more excellent 1C charge-discharge cycle performance than comparative example.
As can be seen from table 1 and fig. 1, the battery prepared by the high-temperature formation process of the high-voltage polymer lithium ion battery according to the present invention has good hardness, flatness and interface stability compared to the comparative example, and the battery obtained by the high-temperature formation process of the high-voltage polymer lithium ion battery has good adhesion between the internal electrode plate and the separator of the battery and has more excellent cycle performance.
The invention has the beneficial effects that: the thermal compounding and formation process adopts segmented temperature and pressure control high-temperature pressure formation and thermal compounding, and can control the positive plate/(Al) according to the generated amount of the formed gas2O3The interface film contact among the PVDF composite ceramic isolating film)/the negative plate is beneficial to realizing the stable thermal compounding of the pole plate/ceramic isolating film interface and the high-temperature electrolyteThe medium composite film-forming additive realizes a stable SEI film on the surfaces of the positive and negative electrode materials, thereby improving the interface stability, the flatness and the hardness of the battery, and obviously improving the high voltage resistance, the high temperature resistance, the cycle performance and the safety performance of the polymer lithium ion battery.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (3)
1. A high-temperature formation method of a high-voltage polymer lithium ion battery is characterized by comprising the following steps:
(1) standing the high-voltage polymer lithium ion battery which is prepared by adopting the ceramic isolating membrane and is filled with the electrolyte at the high temperature of 45 ℃ for 8-12 h;
(2) placing the battery in a high-temperature pressure formation machine, and continuously baking for 2-3h under the pressure of 0.6-1.0 Mpa and the temperature of 75-85 ℃;
(3) cooling the high-temperature pressure formation machine to 60-70 ℃, and then forming the battery under the pressure of 0.2-0.4 Mpa according to the formation flow;
(4) after formation, heating the high-temperature pressure formation machine to 75-85 ℃, and then continuously baking for 2 hours under the pressure of 0.6-1.0 Mpa;
(5) cooling the high-temperature pressure formation machine to room temperature, and taking out the battery to complete high-temperature formation;
wherein the formation process comprises the following steps: step one, charging to 3.5V at 0.1C constant current under 0.2 Mpa; step two, charging to 3.5V at a constant current of 0.2C under the pressure of 0.3-0.4 Mpa; thirdly, charging to 4.35V at a constant current of 0.5C under the pressure of 0.2 Mpa; and fourthly, discharging to 3.9V at a constant current of 0.5 ℃ under the pressure of 0.2 Mpa.
2. The high-temperature formation method of the high-voltage polymer lithium ion battery according to claim 1, wherein the electrolyte is a high-temperature electrolyte.
3. The high-temperature formation method of the high-voltage polymer lithium ion battery according to claim 1, wherein the ceramic isolation film is a mixed coating Al2O3The PVDF composite ceramic isolating membrane.
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| CN110518301B (en) * | 2019-08-05 | 2022-11-08 | 东莞维科电池有限公司 | Soft package lithium ion battery formation method |
| CN112701368B (en) * | 2020-12-29 | 2022-06-14 | 惠州亿纬创能电池有限公司 | Formation method and lithium ion battery |
| CN114597499A (en) * | 2022-02-25 | 2022-06-07 | 惠州锂威新能源科技有限公司 | Formation method and preparation method of lithium ion battery and lithium ion battery |
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| US9553303B2 (en) * | 2010-01-18 | 2017-01-24 | Enevate Corporation | Silicon particles for battery electrodes |
| CN104269584B (en) * | 2014-10-16 | 2016-06-22 | 保定风帆新能源有限公司 | A kind of chemical synthesizing method of poly-lithium battery |
| CN104485482A (en) * | 2014-12-31 | 2015-04-01 | 东莞市安德丰电池有限公司 | Manufacturing method for high-voltage soft-package lithium-ion battery |
| JP2017027768A (en) * | 2015-07-22 | 2017-02-02 | コニカミノルタ株式会社 | Slurry composition and method of manufacturing positive electrode for lithium ion secondary battery |
| CN106785052B (en) * | 2015-11-23 | 2020-07-17 | 天津荣盛盟固利新能源科技有限公司 | Formation method of lithium titanate battery |
| CN105489943A (en) * | 2015-11-25 | 2016-04-13 | 百顺松涛（天津）动力电池科技发展有限公司 | Lithium-ion battery formation method |
| CN105406110A (en) * | 2015-12-17 | 2016-03-16 | 山东精工电子科技有限公司 | Long-circulation high-safety square ternary polymer lithium ion power battery |
| CN105720307B (en) * | 2016-02-23 | 2017-11-24 | 东莞锂威能源科技有限公司 | A kind of method for improving lithium-ion electric core self discharge |
| CN106099202B (en) * | 2016-08-19 | 2017-09-22 | 骆驼集团新能源电池有限公司 | A kind of lamination flexible packing lithium ion battery rapid forming method |
| CN106299514B (en) * | 2016-08-31 | 2019-04-26 | 浙江超威创元实业有限公司 | A kind of compound method for lithium ion battery |
| CN106299461B (en) * | 2016-09-20 | 2018-10-12 | 东莞锂威能源科技有限公司 | A kind of high energy density lithium ion battery core chemical synthesis technology |
| CN106505194B (en) * | 2016-12-19 | 2020-10-27 | 惠州亿纬创能电池有限公司 | Modified lithium cobaltate and preparation method thereof, lithium ion battery and formation method thereof |
| CN106602161B (en) * | 2016-12-29 | 2020-03-20 | 惠州亿纬创能电池有限公司 | Formation method of lithium ion battery and lithium ion battery |
| CN106684457B (en) * | 2017-01-18 | 2019-03-29 | 合肥国轩高科动力能源有限公司 | A kind of chemical synthesizing method of high-voltage lithium ion soft-package battery |
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Effective date of registration: 20221020 Address after: 523000 Building 9, Dasheng Industrial City, No. 1438, Provincial Road S358, Shangsha Community, Chang'an Town, Dongguan City, Guangdong Province Patentee after: Dongguan Grind Energy Co.,Ltd. Address before: 518105 4th Floor, Building A2, Liyuan Bay Industrial Park, 168 Honghu Road, Yanchuan, Songgang, Baoan District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN GRAND POWERSOURCE Co.,Ltd. |
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