CN111628222A - Battery cell baking method - Google Patents

Battery cell baking method Download PDF

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Publication number
CN111628222A
CN111628222A CN202010327342.XA CN202010327342A CN111628222A CN 111628222 A CN111628222 A CN 111628222A CN 202010327342 A CN202010327342 A CN 202010327342A CN 111628222 A CN111628222 A CN 111628222A
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Prior art keywords
battery cell
ethanol
baking
cell
water
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CN202010327342.XA
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Chinese (zh)
Inventor
黄泽伟
郑昌生
胡清平
陶芝勇
曾坚义
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Guizhou Jiaying Technology Co.,Ltd.
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Herewin Technology Co ltd
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Priority to CN202010327342.XA priority Critical patent/CN111628222A/en
Publication of CN111628222A publication Critical patent/CN111628222A/en
Pending legal-status Critical Current

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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
    • H01M10/058—Construction or manufacture
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/005—Drying solid materials or objects by processes not involving the application of heat by dipping them into or mixing them with a chemical liquid, e.g. organic; chemical, e.g. organic, dewatering aids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of lithium ion batteries, and particularly relates to a battery cell baking method which comprises the following steps of S1, placing a battery cell in a closed space, spraying liquid ethanol in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol; s2, standing the battery cell until the exchange of the ethanol and the water in the battery cell is completed; and S3, baking the battery cell in vacuum until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized. According to the invention, by adopting a scheme of co-solvent of water and alcohol, the formed azeotropic point is lower than the boiling point of ethanol and the boiling point of water, so that the water content of the pole piece after the lithium iron phosphate cell is baked is greatly improved, hydrofluoric acid gas generated by water in the cell and electrolyte is avoided, the internal pressure of the battery is reduced, the situations of stress deformation, battery swelling, liquid leakage and the like of the battery are avoided, and the storage performance, the cycle performance and the high-temperature performance of the cell are effectively improved.

Description

Battery cell baking method
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a battery cell baking method.
Background
Lithium ion batteries have the advantages of light weight, good safety performance and the like, so that the lithium ion batteries are applied to the fields of mobile electronic equipment such as Bluetooth headsets, mobile phones, notebook computers, tablet computers and cameras, portable mobile power supplies and the like. Meanwhile, lithium ion batteries have also been applied in the fields of electric motorcycles, electric automobiles, and the like in batches.
About 80% of the energy storage lithium ion cell adopts a lithium iron phosphate system, and the specific surface area of the lithium iron phosphate is large and reaches 10-25 m2However, the carbon material for protecting the surface of the lithium iron phosphate contains abundant polar functional groups, so that the lithium iron phosphate core is very easy to absorb water in the manufacturing process and is difficult to dry.
If the moisture in the lithium ion battery is too high, the lithium ion battery reacts with the electrolyte to generate hydrofluoric acid, so that metal parts in the battery are corroded, and the leakage of a battery core is caused; moreover, hydrofluoric acid also destroys the SEI film; in addition, LiF precipitates are generated in the battery, lithium ions undergo an irreversible chemical reaction in the battery negative electrode sheet, active lithium ions are consumed, and the energy of the battery is greatly reduced. When the moisture is sufficient, the generated gas is large, and the pressure inside the battery is increased, so that the battery is forced to deform, and the danger of battery swelling, liquid leakage and the like is caused.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the battery cell baking method is provided, so that the moisture in a battery cell pole piece can be greatly reduced, the electrical property of the lithium ion battery is improved, and accidents such as bulging, liquid leakage and the like are avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a battery cell baking method comprises the following steps:
s1, placing the battery cell in a closed space, spraying liquid ethanol in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol;
s2, standing the battery cell until the exchange of the ethanol and the water in the battery cell is completed;
and S3, baking the battery cell in vacuum until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
The principle of the invention is that the boiling point of ethanol is 78.4 ℃ and the boiling point of water is 100 ℃ at room temperature, but the azeotropic point of the cosolvent is 78.2 ℃ and is lower than the boiling points of the ethanol and water which form the cosolvent, so that the moisture in the battery cell can be evaporated as long as the baking temperature reaches the azeotropic point, and the reduction range of the azeotropic point is large, so that the limit water content of the battery cell after being baked is greatly reduced.
As an improvement of the battery cell baking method, the closed space is also provided with an open container filled with ethanol. The open container can ensure that the ethanol is always in an evaporation state, so that the vapor pressure of the ethanol in the closed space is always kept in a saturated state.
As an improvement of the cell baking method according to the present invention, in S1, the air inside the sealed space forms a convection circulation. And the opposite sides of the closed space are respectively provided with the ventilating air cylinders, so that the air in the closed space forms convection circulation, and the exchange speed of ethanol and moisture can be accelerated.
As an improvement of the cell baking method of the present invention, in S3, the vacuum baking further includes performing a cycle of vacuum pumping, time-delay processing, vacuum unloading, and time-delay processing on the enclosed space, and the cycle is repeated. Specifically, the vacuumizing is performed firstly, the delay processing is performed when the vacuum degree in the closed space reaches the set vacuum degree, then the vacuum unloading operation is performed, the delay processing is performed when the vacuum degree reaches the set vacuum degree, and the circulation is performed, so that the evaporation of the water is facilitated.
As an improvement of the battery core baking method, the time of the time delay treatment is 10-20 min, the cycle time is 2-10 times, and the circulated gas is ethanol saturated steam.
As an improvement of the battery cell baking method of the present invention, the enclosed space is a baking oven or a drying oven.
As an improvement of the battery cell baking method, the standing time is 24-72 hours. After standing, the ethanol gas permeates into the electric core at room temperature and completes standing exchange with the water in the pole piece. The standing time is adjusted by the size of the battery core.
As an improvement of the battery cell baking method, the vacuum degree during baking is 95-100 KPa. The vacuum baking is favorable for quickly removing the moisture in the pole piece.
As an improvement of the battery cell baking method, the baking temperature is 85-95 ℃. The boiling point of the cosolvent formed by the ethanol and the water is in the range, so that the boiling point of the water is reduced, and the water in the battery cell can be effectively removed. The baking temperature of the conventional method is 100 ℃ to reach the boiling point of water, so as to promote the evaporation of water. However, too high a temperature may also have some effect on the strength of the current collector, and too high a temperature may also affect the adhesive strength between the current collector and the active material layer.
As an improvement of the battery cell baking method, the concentration of the ethanol is 95-99%. The concentration of the sprayed ethanol is higher, otherwise the ethanol can introduce new moisture into the cell.
The beneficial effects of the invention include but are not limited to: according to the invention, by adopting a scheme of co-solvent of water and alcohol, the formed azeotropic point is lower than the boiling point of ethanol and the boiling point of water, so that the water content of the pole piece after the lithium iron phosphate cell is baked is greatly improved, hydrofluoric acid gas generated by water in the cell and electrolyte is avoided, the internal pressure of the battery is reduced, the situations of stress deformation, battery swelling, liquid leakage and the like of the battery are avoided, and the storage performance, the cycle performance and the high-temperature performance of the cell are effectively improved.
Detailed Description
As used in the specification and in the claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, within which a person skilled in the art can solve the technical problem to substantially achieve the technical result.
The invention provides a battery cell baking method, which comprises the following steps:
s1, placing the battery cell in a closed space, spraying liquid ethanol in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol;
s2, standing the battery cell until the ethanol and the water in the battery cell are exchanged;
and S3, baking the battery cell in vacuum until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
The principle of the invention is that the boiling point of ethanol is 78.4 ℃ and the boiling point of water is 100 ℃ at room temperature, but the boiling point temperature of the azeotropic point is 78.2 ℃, and is lower than the boiling points of the ethanol and water which form the components, the azeotropic point is greatly reduced, and as long as the baking temperature reaches the azeotropic point, the water in the battery cell can be evaporated, so that the limit water content of the battery cell after being baked is greatly reduced.
Preferably, the closed space is further provided with an open container filled with ethanol. The open container can ensure that the ethanol is always in an evaporation state, so that the vapor pressure of the ethanol in the closed space is always kept in a saturated state.
Preferably, in S1, the air inside the sealed space forms a convective circulation. And the opposite sides of the closed space are respectively provided with the ventilating air cylinders, so that the air in the closed space forms convection circulation, and the exchange speed of ethanol and moisture can be accelerated.
Preferably, in S3, the vacuum baking further includes performing a cycle of vacuum-pumping, time-delay treatment, vacuum-releasing, time-delay treatment on the enclosed space, and so on. Specifically, vacuumizing is performed firstly, when the vacuum degree in the closed space reaches a set vacuum degree, delay processing is performed, then vacuum unloading is performed, when the vacuum degree reaches the set vacuum degree, delay processing is performed, and the process is circulated.
Preferably, the time delay treatment time is 10-20 min, the cycle time is 2-10 times, and the circulated gas is ethanol saturated steam.
Preferably, the enclosed space is a baking oven or a drying oven.
Preferably, the standing time is 24-72 hours. After standing, the ethanol gas permeates into the electric core at room temperature and completes standing exchange with the water in the pole piece. The standing time is adjusted by the size of the battery core.
Preferably, the vacuum degree during baking is 95 to 100 KPa. The vacuum baking is favorable for quickly removing the moisture in the pole piece.
Preferably, the baking temperature is 85-95 ℃. The boiling point of the cosolvent formed by the ethanol and the water is in the range, so that the boiling point of the water is reduced, and the water in the battery cell can be effectively removed. The baking temperature of the conventional method is 100 ℃ to reach the boiling point of water, so as to promote the evaporation of water. However, too high a temperature may also have some effect on the strength of the current collector, and too high a temperature may also affect the adhesive strength between the current collector and the active material layer.
Preferably, the concentration of the ethanol is 95-99%. The concentration of the sprayed ethanol is higher, otherwise the ethanol can introduce new moisture into the cell.
Example 1
The embodiment provides a battery cell baking method:
preparing F12213245 lithium iron phosphate core, placing the core in a packaging shell, sealing three sides, and leaving an opening on one side for drying moisture and filling electrolyte;
s1, placing the battery cell in a closed space (namely a baking oven or a drying oven), spraying liquid ethanol with the concentration of 99% in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol;
s2, standing the battery cell for 48 hours until the ethanol and the water in the battery cell are exchanged;
and S3, baking the battery cell in vacuum at the baking temperature of 90 ℃ and the vacuum degree of 95KPa until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
Example 2
The embodiment provides a battery cell baking method: in contrast to the embodiment 1, the process of the invention,
in S1, an open container containing ethanol is further provided in the sealed space.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The embodiment provides a battery cell baking method: in contrast to the embodiment 1, the process of the invention,
in S1, the air inside the sealed space forms a convective circulation.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The embodiment provides a battery cell baking method: in contrast to the embodiment 1, the process of the invention,
in S3, the vacuum baking further includes performing a cycle of vacuum-pumping, time-delay processing, vacuum-releasing, and time-delay processing on the enclosed space, and so on. Wherein the time delay treatment time is 10-20 min, the cycle time is 2-10 times, and the circulated gas is ethanol saturated steam.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The embodiment provides a battery cell baking method: in contrast to the embodiment 1, the process of the invention,
s1, placing the battery cell in a closed space (namely a baking oven or a drying oven), spraying liquid ethanol with the concentration of 99%, wherein the closed space is also provided with an open container filled with ethanol, setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol, and forming convection circulation by the air in the closed space;
s2, standing the battery cell for 48 hours until the ethanol and the water in the battery cell are exchanged;
and S3, performing cycle actions of vacuumizing the closed space, delaying for 10 minutes, vacuumizing, delaying for 10 minutes, and circulating for 10 times, wherein the gas filled into the closed space during vacuumizing is ethanol saturated steam, and the battery cell is vacuum-baked at the baking temperature of 90 ℃ and the vacuum degree of 95KPa until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
Example 6
The embodiment provides a battery cell baking method: in contrast to the embodiment 1, the process of the invention,
s1, placing the battery cell in a closed space (namely a baking oven or a drying oven), spraying liquid ethanol with the concentration of 95% in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol;
s2, standing the battery cell for 24 hours until the ethanol and the water in the battery cell are exchanged;
and S3, baking the battery cell in vacuum at the baking temperature of 85 ℃ and the vacuum degree of 95KPa until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The embodiment provides a battery cell baking method: in contrast to the embodiment 1, the process of the invention,
s1, placing the battery cell in a closed space (namely a baking oven or a drying oven), spraying liquid ethanol with the concentration of 97% in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol;
s2, standing the battery cell for 72 hours until the ethanol and the water in the battery cell are exchanged;
and S3, baking the battery cell in vacuum at the baking temperature of 95 ℃ and the vacuum degree of 100KPa until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The comparative example provides a cell baking method:
preparing F12213245 lithium iron phosphate core, placing the core in a packaging shell, sealing three sides, and leaving an opening on one side for drying moisture and filling electrolyte;
s1, placing the battery cell in a closed space (namely a baking oven or a drying oven);
and S2, vacuum baking the battery cell, wherein the baking temperature is 90 ℃, and the vacuum degree is 95 KPa.
And (3) performing a water content test, a cycle performance test and a high-temperature performance test on the positive pole piece of the F12213245 battery cell, wherein test results are shown in Table 1.
TABLE 1
Figure BDA0002463691590000091
As can be seen from example 1 and comparative example 1, in example 1, ethanol and water form a cosolvent by spraying ethanol in the sealed space, so that the boiling point of the system is reduced, and the water content in the battery cell is greatly reduced.
As can be seen from the embodiments 1 and 2 to 5, the opening container filled with ethanol is further arranged in the sealed space, so that the vapor pressure of ethanol in the sealed space is always kept in a saturated state, the air in the sealed space forms a convection circulation, and the sealed space is subjected to cyclic actions of vacuumizing, time-delay treatment, vacuum unloading and time-delay treatment, and the operations are used cooperatively, so that the water content in the battery cell can be greatly reduced, and various electrical properties of the lithium ion battery are improved.
In conclusion, the invention adopts the scheme of the co-solvent of water and alcohol, the formed co-boiling point is lower than the boiling point of ethanol and the boiling point of water at the same time, the water content of the pole piece after the lithium iron phosphate cell is baked is greatly improved, the hydrofluoric acid gas generated by the water in the cell and the electrolyte is avoided, the internal pressure of the battery is reduced, the situations of stress deformation, battery swelling, liquid leakage and the like of the battery are avoided, and the storage performance, the cycle performance and the high-temperature performance of the cell are effectively improved.
In addition, the invention is not limited to the lithium iron phosphate core, and can also comprise common lithium ion batteries in the field such as lithium nickelate, lithium cobaltate, lithium nickel cobalt manganese oxide and the like.
The foregoing description shows and describes several preferred embodiments of the invention, but as aforementioned, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The battery cell baking method is characterized by comprising the following steps:
s1, placing the battery cell in a closed space, spraying liquid ethanol in the closed space, and setting the air pressure in the closed space to be the saturated vapor pressure of the ethanol;
s2, standing the battery cell until the exchange of the ethanol and the water in the battery cell is completed;
and S3, baking the battery cell in vacuum until the ethanol and the water in the battery cell form an azeotropic solvent and are completely volatilized.
2. The cell baking method according to claim 1, wherein the closed space is further provided with an open container filled with ethanol.
3. The cell baking method according to claim 1, wherein in S1, the air inside the enclosed space forms a convection circulation.
4. The cell baking method of claim 1, wherein in S3, the vacuum baking further includes performing a cycle of evacuation, time-delay treatment, vacuum unloading, and time-delay treatment on the enclosed space, and so on.
5. The battery cell baking method according to claim 4, wherein the time delay treatment is 10-20 min, the cycle number is 2-10, and the circulated gas is ethanol saturated steam.
6. The cell baking method according to claim 1, wherein the enclosed space is a baking oven or a drying oven.
7. The cell baking method according to claim 1, wherein the standing time is 24-72 hours.
8. The battery cell baking method according to claim 1, wherein the vacuum degree during baking is 95-100 KPa.
9. The battery cell baking method according to claim 1, wherein the baking temperature is 85-95 ℃.
10. The cell baking method according to claim 1, wherein the ethanol concentration is 95-99%.
CN202010327342.XA 2020-04-23 2020-04-23 Battery cell baking method Pending CN111628222A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102809264A (en) * 2011-06-01 2012-12-05 微宏动力系统（湖州）有限公司 Drying method for lithium ion battery manufacture
CN103868330A (en) * 2014-03-27 2014-06-18 威格高纯气体设备科技（苏州工业园区）有限公司 Deep drying and dewatering method
CN105115250A (en) * 2015-07-27 2015-12-02 山东精工电子科技有限公司 Rapid drying method for lithium ion battery cell
US20150364737A1 (en) * 2014-06-11 2015-12-17 Jtekt Corporation Method for drying separator for non-aqueous electric storage device and method for manufacturing electric storage apparatus
CN107726737A (en) * 2017-06-06 2018-02-23 东莞市创明电池技术有限公司 Cylindrical battery core and its baking method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102809264A (en) * 2011-06-01 2012-12-05 微宏动力系统（湖州）有限公司 Drying method for lithium ion battery manufacture
CN103868330A (en) * 2014-03-27 2014-06-18 威格高纯气体设备科技（苏州工业园区）有限公司 Deep drying and dewatering method
US20150364737A1 (en) * 2014-06-11 2015-12-17 Jtekt Corporation Method for drying separator for non-aqueous electric storage device and method for manufacturing electric storage apparatus
CN105115250A (en) * 2015-07-27 2015-12-02 山东精工电子科技有限公司 Rapid drying method for lithium ion battery cell
CN107726737A (en) * 2017-06-06 2018-02-23 东莞市创明电池技术有限公司 Cylindrical battery core and its baking method

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