CN109616709A - A kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology - Google Patents

A kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology Download PDF

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Publication number
CN109616709A
CN109616709A CN201710925998.XA CN201710925998A CN109616709A CN 109616709 A CN109616709 A CN 109616709A CN 201710925998 A CN201710925998 A CN 201710925998A CN 109616709 A CN109616709 A CN 109616709A
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high temperature
pressure
battery
chemical conversion
ion battery
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CN109616709B (en
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刘小虹
李国敏
李露
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Dongguan Grind Energy Co ltd
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Shenzhen Greende Energy Group Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • H01M10/446Initial charging measures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of high voltage polymer Li-ion battery high temperature chemical synthesis technologies, include the following steps: 45 DEG C of 8~12h quiescence in high temperatures of (1) battery;(2) pressure of 0.6Mpa ~ 1.0Mpa and 75 DEG C ~ 85 DEG C at a temperature ofs, toast 2-3h in high temperature pressure chemical conversion machine;(3) it is melted under the pressure of 0.2Mpa ~ 0.4Mpa after being cooled to 60 DEG C ~ 70 DEG C;(4) 2h is toasted under the pressure of 0.6Mpa ~ 1.0Mpa after being warming up to 75 DEG C ~ 85 DEG C;(5) it is taken out after being cooled to room temperature.The present invention is compound using the chemical conversion of sectional temperature-controlled pressure control high temperature pressure and heat, realize that stable pole piece/ceramics isolation membrane interface heat is compound, be conducive to composite membrane-forming additive and form stable SEI film on positive and negative pole material surface, interface stability, flatness and the hardness of battery are improved, and significantly improves the high voltage withstanding of battery, high temperature resistance, cycle performance and security performance.

Description

A kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology
Technical field
The invention belongs to polymer Li-ion battery manufacturing technology field, specifically a kind of high voltage polymer Li-ion electricity Pond high temperature chemical synthesis technology.
Background technique
Portable electronic product is charged with polymer Li-ion battery and is generally 4.2V by voltage, in order in limited sky Between in play higher capacity, improve the energy density of polymer Li-ion battery, portable electronic product polymer lithium Ion battery is mainly attempting positive and negative pole material, high energy electrolyte, ultra-thin isolation film (industrialization at present using height ratio capacity Most thin is 8 microns), thin copper foil (8 microns) and thin aluminium foil (10 microns), thin plastic-aluminum packaging film (seventies microns) etc., After these measures apply to the limit, people start to pursue the higher charging of polymer Li-ion battery by voltage, by mentioning The voltage power supply range of high polymer lithium ion battery further increases the capacity and energy density of battery.Polymer Li-ion Battery charging by voltage by 4.2V to 4.3V(apple iPhone5 battery for mobile phone) to 4.35V(apple iPhone6, Samsung and Some mobile phone model batteries such as Huawei) 4.4V(apple iPhone7 etc. is arrived again), 4.35V and 4.4V charging at present is by voltage Polymer Li-ion battery technology and market have begun maturation, market application will continue to expand, and just in the air.And 4.45V and 4.5V charging by voltage polymer Li-ion battery at present also under development.
Apple, Samsung a new generation high-end electronic product battery updated for charging by voltage be 4.35V Or the high voltage polymer Li-ion battery of 4.4V.With the promotion of charging voltage, the energy density of battery has significantly It is promoted, requires meaning very great to the higher energy density per unit volume of high-end portable formula equipment and cruising ability is met, this field Also vast market prospect will be had.
However, since often super-thin high-energy metric density designs high voltage polymer Li-ion battery, to the flatness of battery It is very high with hardness requirement.Traditional liquid flexible packing polymer Li-ion battery is in order to obtain good performance, often electrolyte Groundwater increment is more, and battery is relatively soft, and flatness is poor, it is difficult to reach the hardness requirement of the clients such as mobile phone, tablet computer assembly, Therefore it needs to be improved.
Summary of the invention
It is an object of the invention to the shortcomings more than overcoming, and provide a kind of high voltage polymer Li-ion battery high temperature Chemical synthesis technology can obtain good battery hardness and flatness while improving the energy density of battery, while battery Performance is still good.
The technical solution adopted by the present invention is that:
A kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology, includes the following steps:
(1) 45 DEG C of high temperature will be carried out using the high voltage polymer Li-ion battery after perfusion electrolyte made of ceramic isolation film The quiescence in high temperature of 8~12h;This quiescence in high temperature can be such that electrolyte is sufficiently infiltrated in pole piece and isolation film;
(2) battery is placed in high temperature pressure chemical conversion machine, is continued at a temperature of the pressure of 0.6Mpa ~ 1.0Mpa and 75 DEG C ~ 85 DEG C Toast 2-3h;
(3) high temperature pressure chemical conversion machine is cooled to after 60 DEG C ~ 70 DEG C under the pressure of 0.2Mpa ~ 0.4Mpa according to chemical conversion process pair Battery is melted into;
(4) high temperature pressure chemical conversion machine is warming up to after 75 DEG C ~ 85 DEG C after being melted into and is persistently toasted under the pressure of 0.6Mpa ~ 1.0Mpa 2h;
(5) high temperature pressure chemical conversion machine is cooled to after room temperature and takes out battery completion high temperature chemical conversion.
Preferably, the chemical conversion process are as follows: the first step, 0.1C constant-current charge is to 3.5V under 0.2Mpa pressure;The Two steps, 0.2C constant-current charge is to 3.5V under 0.3-0.4Mpa pressure;Third step, 0.5C constant-current charge is extremely under 0.2Mpa pressure 4.35V;4th step, 0.5C constant-current discharge is to 3.9V under 0.2Mpa pressure.
Preferably, the electrolyte is high-temperature electrolyte.High-temperature electrolyte can ensure that high voltage polymer Li-ion Electrolyte characteristic will not be able to destroy and battery performance is caused to deteriorate when battery carries out pressure chemical conversion under the high temperature conditions.
Preferably, the ceramics isolation film is mixing coating Al2O3/ PVDF(Kynoar) composite ceramics isolation Film.
Compared with prior art, the beneficial effects of the present invention are:
Heat is compound and chemical synthesis technology is compound using the chemical conversion of sectional temperature-controlled pressure control high temperature pressure and heat, can be generated according to formation gas Amount number control positive plate/(Al2O3/ PVDF composite ceramics isolation film) contact of interfacial film between three kinds of/negative electrode tab, have Conducive to realizing that stable pole piece/ceramics isolation membrane interface heat is compound, it is also beneficial to composite membrane-forming additive in high-temperature electrolyte and exists Stable SEI film (solid electrolyte interface film) is realized on positive and negative pole material surface, to improve the interface stability of battery, smooth Degree and hardness, and significantly improve the high voltage withstanding of polymer Li-ion battery, high temperature resistance, cycle performance and security performance.
Detailed description of the invention
Fig. 1 is 300 cyclic curve comparisons of 1C charge and discharge of embodiment 2 and comparative example.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that retouched The embodiment stated is only a part of the embodiment of the present invention, instead of all the embodiments.
Embodiment 1:
In the embodiment of the present invention, a kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology includes the following steps:
(1) 45 DEG C of high temperature will be carried out using the high voltage polymer Li-ion battery after perfusion electrolyte made of ceramic isolation film The quiescence in high temperature of 8h;This quiescence in high temperature can be such that electrolyte is sufficiently infiltrated in pole piece and isolation film;
(2) battery is placed in high temperature pressure chemical conversion machine, persistently toasts 2h at a temperature of the pressure of 0.6MpaMpa and 75 DEG C;
(3) high temperature pressure is melted into after machine is cooled to 60 DEG C under the pressure of 0.2Mpa according to chemical conversion process to battery At;
(4) 2h is persistently toasted under the pressure of 0.6Mpa after high temperature pressure chemical conversion machine is warming up to 75 DEG C after being melted into;
(5) high temperature pressure chemical conversion machine is cooled to after room temperature and takes out battery completion high temperature chemical conversion.
The chemical conversion process are as follows: the first step, 0.1C constant-current charge is to 3.5V under 0.2Mpa pressure;Second step, 0.2C constant-current charge is to 3.5V under 0.3Mpa pressure;Third step, 0.5C constant-current charge is to 4.35V under 0.2Mpa pressure;4th Step, 0.5C constant-current discharge is to 3.9V under 0.2Mpa pressure.
Model 2949119 is prepared using above-mentioned chemical synthesis technology, the 4.35V high voltage that nominal capacity is 2750mAh polymerize Object lithium ion battery 30, number 1#-30#.
Embodiment 2:
In the embodiment of the present invention, a kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology includes the following steps:
(1) 45 DEG C of high temperature will be carried out using the high voltage polymer Li-ion battery after perfusion electrolyte made of ceramic isolation film The quiescence in high temperature of 10h;This quiescence in high temperature can be such that electrolyte is sufficiently infiltrated in pole piece and isolation film;
(2) battery is placed in high temperature pressure chemical conversion machine, persistently toasts 2.5h at a temperature of the pressure of 0.8Mpa and 80 DEG C;
(3) high temperature pressure is melted into after machine is cooled to 65 DEG C under the pressure of 0.3Mpa according to chemical conversion process to battery At;
(4) 2h is persistently toasted under the pressure of 0.8Mpa after high temperature pressure chemical conversion machine is warming up to 80 DEG C after being melted into;
(5) high temperature pressure chemical conversion machine is cooled to after room temperature and takes out battery completion high temperature chemical conversion.
The chemical conversion process are as follows: the first step, 0.1C constant-current charge is to 3.5V under 0.2Mpa pressure;Second step, 0.2C constant-current charge is to 3.5V under 0.35Mpa pressure;Third step, 0.5C constant-current charge is to 4.35V under 0.2Mpa pressure;4th Step, 0.5C constant-current discharge is to 3.9V under 0.2Mpa pressure.
Model 2949119 is prepared using above-mentioned chemical synthesis technology, the 4.35V high voltage that nominal capacity is 2750mAh polymerize Object lithium ion battery 30, number 31#-60#.
Embodiment 3:
In the embodiment of the present invention, a kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology includes the following steps:
(1) 45 DEG C of high temperature will be carried out using the high voltage polymer Li-ion battery after perfusion electrolyte made of ceramic isolation film The quiescence in high temperature of 12h;This quiescence in high temperature can be such that electrolyte is sufficiently infiltrated in pole piece and isolation film;
(2) battery is placed in high temperature pressure chemical conversion machine, persistently toasts 3h at a temperature of the pressure of 1.0Mpa and 85 DEG C;
(3) high temperature pressure is melted into after machine is cooled to 70 DEG C under the pressure of 0.4Mpa according to chemical conversion process to battery At;
(4) 2h is persistently toasted under the pressure of 1.0Mpa after high temperature pressure chemical conversion machine is warming up to 85 DEG C after being melted into;
(5) high temperature pressure chemical conversion machine is cooled to after room temperature and takes out battery completion high temperature chemical conversion.
The chemical conversion process are as follows: the first step, 0.1C constant-current charge is to 3.5V under 0.2Mpa pressure;Second step, 0.2C constant-current charge is to 3.5V under 0.4Mpa pressure;Third step, 0.5C constant-current charge is to 4.35V under 0.2Mpa pressure;4th Step, 0.5C constant-current discharge is to 3.9V under 0.2Mpa pressure.
Model 2949119 is prepared using above-mentioned chemical synthesis technology, the 4.35V high voltage that nominal capacity is 2750mAh polymerize Object lithium ion battery 30, number 61#-90#.
Comparative example:
In this comparative example, a kind of high voltage polymer Li-ion battery routine chemical synthesis technology includes the following steps:
(1) high voltage polymer Li-ion battery (using the wet process diaphragm of uncoated ceramics) room temperature is stood for 24 hours;
(2) battery is placed in high temperature pressure chemical conversion machine, is will heat up to being melted under the pressure of 0.35Mpa after 50 DEG C;
(3) high temperature pressure chemical conversion machine is cooled to after room temperature and takes out battery completion high temperature chemical conversion.
Model 2949119 is prepared using above-mentioned chemical synthesis technology, the 4.35V high voltage that nominal capacity is 2750mAh polymerize Object lithium ion battery 30, number 91#-120#.
Table 1 is each embodiment and the comparison of comparative example main performance.
Fig. 1 is 300 cyclic curve comparisons of 1C charge and discharge of embodiment 2 and comparative example, and embodiment 2 has relative to comparative example Superior 1C charge-discharge cycle performance.
It can be seen that prepared by a kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology of the present invention from table 1 and Fig. 1 For battery relative to comparative example, the battery obtained in the case where capacity plays opposite has good hardness, flatness and interface Stability, inside battery pole piece and diaphragm bonding are good, while having superior cycle performance.
The beneficial effects of the present invention are: heat is compound and chemical synthesis technology is multiple using the chemical conversion of sectional temperature-controlled pressure control high temperature pressure and heat Close, can according to formation gas yield number control positive plate/(Al2O3/ PVDF composite ceramics isolation film)/negative electrode tab The contact of interfacial film between three kinds, it is compound to be advantageously implemented stable pole piece/ceramics isolation membrane interface heat, is also beneficial to high-temperature electric Solution liquid in composite membrane-forming additive stable SEI film is realized on positive and negative pole material surface, thus improve the interface stability of battery, Flatness and hardness, and significantly improve the high voltage withstanding of polymer Li-ion battery, high temperature resistance, cycle performance and safety Energy.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention Design or beyond the scope defined by this claim, be within the scope of protection of the invention.

Claims (4)

1. a kind of high voltage polymer Li-ion battery high temperature chemical synthesis technology, which is characterized in that the technique includes the following steps:
(1) 45 DEG C of high temperature will be carried out using the high voltage polymer Li-ion battery after perfusion electrolyte made of ceramic isolation film The quiescence in high temperature of 8~12h;
(2) battery is placed in high temperature pressure chemical conversion machine, is continued at a temperature of the pressure of 0.6Mpa ~ 1.0Mpa and 75 DEG C ~ 85 DEG C Toast 2-3h;
(3) high temperature pressure chemical conversion machine is cooled to after 60 DEG C ~ 70 DEG C under the pressure of 0.2Mpa ~ 0.4Mpa according to chemical conversion process pair Battery is melted into;
(4) high temperature pressure chemical conversion machine is warming up to after 75 DEG C ~ 85 DEG C after being melted into and is persistently toasted under the pressure of 0.6Mpa ~ 1.0Mpa 2h;
(5) high temperature pressure chemical conversion machine is cooled to after room temperature and takes out battery completion high temperature chemical conversion.
2. a kind of according to claim 1, high voltage polymer Li-ion battery high temperature chemical synthesis technology, which is characterized in that The chemical conversion process are as follows: the first step, 0.1C constant-current charge is to 3.5V under 0.2Mpa pressure;Second step is pressed in 0.3-0.4Mpa 0.2C constant-current charge is to 3.5V under power;Third step, 0.5C constant-current charge is to 4.35V under 0.2Mpa pressure;4th step, 0.5C constant-current discharge is to 3.9V under 0.2Mpa pressure.
3. a kind of according to claim 1, high voltage polymer Li-ion battery high temperature chemical synthesis technology, which is characterized in that The electrolyte is high-temperature electrolyte.
4. a kind of according to claim 1, high voltage polymer Li-ion battery high temperature chemical synthesis technology, which is characterized in that The ceramics isolation film is mixing coating Al2O3/ PVDF composite ceramics isolation film.
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Cited By (3)

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CN112701368A (en) * 2020-12-29 2021-04-23 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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