CN109962295A - A kind of temperature-control pressure-control formula formation of Li-ion batteries method - Google Patents
A kind of temperature-control pressure-control formula formation of Li-ion batteries method Download PDFInfo
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- CN109962295A CN109962295A CN201711336837.3A CN201711336837A CN109962295A CN 109962295 A CN109962295 A CN 109962295A CN 201711336837 A CN201711336837 A CN 201711336837A CN 109962295 A CN109962295 A CN 109962295A
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- temperature
- pressure
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- lithium battery
- ion batteries
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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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of temperature-control pressure-control formula formation of Li-ion batteries methods, using the controllable isotropic media environment of temperature and pressure, and closed lithium battery are placed in the media environment, are controlled by temperature and pressure to carry out formation of Li-ion batteries.The chemical synthesizing method can simplify formation of Li-ion batteries process and fixture heating pressure method when firmly contact and pressure, non-uniform temperature caused by a series of various problems, be worthy to be popularized.
Description
Technical field
The present invention relates to formation of Li-ion batteries technologies, more specifically refer to a kind of temperature-control pressure-control formula formation of Li-ion batteries method.
Background technique
Formation of Li-ion batteries refer to the process of lithium ion lithium battery group dress after by lithium battery carry out charge and discharge, should during
Lithium battery system will be activated, therefore the link that manufacturing process is particularly important.By chemical conversion, the material surface of lithium battery will
Form one layer of solid electrolyte interface passivation layer, i.e. SEI film.
Traditional chemical synthesis technology is to allow lithium battery to be stablized under equilibrium temperature, pressure by trickle charge and discharge and form a film, sufficiently
Film forming.However the SEI membrane structure that this method is formed is close, and hole is small, it is therefore desirable to and SEI film is recombinated by high temperature ageing,
To form loose porous film.Because the stability of SEI film determines whether lithium battery material will continue in following cycle
Side reaction occurs, so the technology of chemical conversion, aging directly determines the subsequent service life of lithium battery, is needed into especially for positive and negative anodes
The lithium battery system that film could be stabilized.Since the process of aging and chemical conversion makes that progress can be intersected, will recycle second round below
Preceding chemical conversion and aging process is referred to as formation process.Traditional formation process period is long, energy consumption is big, takes up a large area, therefore
Have become a high-cost process bottleneck in lithium battery large-scale production.
Recently as the development of lithium battery technology, there is the chemical synthesizing method of heating pressurization, such as Publication No.
The patents such as CN104538675A, CN104577206A keep lithium battery fast by applying pressure and temperature to additional fixture
Fast, stable film forming.However, can solve above-mentioned conventional method in scale after using above-mentioned heating pressurization chemical synthesizing method
Defect, but occur the problem that
1, when lithium battery pole group superior pole piece is in uneven thickness, using the application pressure of fixture mode will lead in the group of pole by
Power is uneven, and stress is mainly born by thick place, therefore electrolyte in lithium battery is caused to be unevenly distributed.Equally, pressure and
Being unevenly distributed for temperature keeps pole distance between commutator segments inconsistent, and it is uneven that when chemical conversion will appear electric field, to generate, capacity is low, embedding lithium
Uneven even analysis lithium.
2, fixture mode will appear fixture and contact firmly with lithium battery large area, and lithium battery is caused surface contamination, fold occur
The phenomenon that out-of-flatness and lithium battery deform.
3, it heats rear jig and lithium battery temperature fall time is longer.
4, the carrying for realizing lithium battery by a large amount of mechanical mechanism is needed using fixture mode and shelved, therefore is certain
Lithium battery, for example, three at even four the Soft Roll that can not put forth effort, will receive limitation in large-scale production.
The patent of Publication No. CN104577204A disclose it is a kind of with 0.15-0.4MPa high pressure gas to 0-80 degree heat
The method that lithium battery afterwards carries out pressurization chemical conversion.Battery is in open state, therefore inside battery pressure in this method formation process
Power is not at a kind of Deng static pressure states.The heating means referred in this method are to be heated using heater strip to battery, are deposited
The phenomenon that has that temperature distribution is non-uniform in temperature control low efficiency and medium, and do not refer in this method and being carried out in formation process
The temperature change of medium and utilize medium carry out pressure change.And the present invention controls battery by medium in formation process
Temperature, pressure is transmitted by equal static pressure mode, and principle and the invention have significant difference.
Summary of the invention
The purpose of the present invention is in view of the foregoing drawbacks, providing a kind of temperature-control pressure-control formula formation of Li-ion batteries method, can simplify
Formation of Li-ion batteries process, but when can solve fixture heating pressure method firmly contact and pressure it is uneven caused by a series of various ask
Topic.
To achieve the goals above, the present invention uses following technical scheme.
On the one hand, a kind of temperature-control pressure-control formula formation of Li-ion batteries method, using controllable isotropic Jie of temperature and pressure
Matter environment, and closed lithium battery is placed in the media environment, it is controlled by temperature and pressure to carry out formation of Li-ion batteries.
The medium is mobility medium.
The mobility medium is dry air, argon gas, conduction oil or retardant solution.
The lithium battery is the lithium battery that can receive pressure, temperature variation, considers when being included in design and produces gas storage
The battery sending one's regards to the battery of topic or being melted into advance excessively.
The lithium battery is liquid ion lithium battery, poly-lithium battery or solid state lithium battery.
The lithium battery have can average conduction pressure or orient conducting pressure packaging.
The lithium battery can be externally provided with an anti-short circuit or antipollution protective layer according to demand.
The temperature controlled range is at -40~300 DEG C.
The range of the pressure control is 10-4Pa~20MPa.
The temperature and pressure control is matched with the charge and discharge process of lithium battery.
While formation process, additionally it is possible to it carries out lithium battery electrochemical property test and security performance is tested, and according to
Test data classifies lithium battery.
While formation process, additionally it is possible to be surveyed by detecting the composition transfer of medium with carrying out lithium battery packaging leak detection
Examination.
On the other hand, the detection test side of a kind of temperature-control pressure-control formula lithium battery chemical property, security performance or/and packaging
Method, it is characterised in that: using the controllable isotropic media environment of temperature and pressure, and closed lithium battery is placed in Jie
In matter environment, corresponding test is realized by the control of cooperation temperature and pressure.
In above-mentioned technical proposal of the invention, using the method has the advantages that
1, when lithium battery pole group superior pole piece is in uneven thickness, the mode of temperature-control pressure-control and packaged combination can make lithium battery
Internal pressure, temperature uniform, controllable.
2, the medium of temperature-control pressure-control is mobility medium, has shaping operation to lithium battery, keeps lithium battery surface free from smutting residual
It stays, surfacing corrugationless.
3, the mode of mobility medium source keeps temperature control and pressure control quickly controllable, and changeability is strong.
4, any same tropism of mobility medium can allow the random orientation angle of lithium battery to be placed, to make large-scale production
More easily realize.
5. the side of chemical property detection, security performance test and packaging detection test can be carried out under controllable media environment
Method has higher safety guarantee.
Detailed description of the invention
Fig. 1 is the flow chart of temperature-control pressure-control formula formation of Li-ion batteries method of the invention.
Specific embodiment
Technical solution of the present invention is further illustrated with reference to the accompanying drawing.
As shown in Figure 1, temperature-control pressure-control formula formation of Li-ion batteries method of the invention, using controllable each to same of temperature and pressure
The media environment of property, and closed lithium battery is placed in the media environment, it is controlled by temperature and pressure to carry out lithium battery
Chemical conversion.
As one embodiment, the medium is any mobility medium, preferably dry air, argon gas, conduction oil
(such as bromine system, phosphorus nitrogen system, nitrogen system and red phosphorus and compound are generation for (such as benzenoid form or mineral type), organic or inorganic retardant solution
Some fire retardants of table, inorganic mainly antimony oxide, magnesium hydroxide, aluminium hydroxide, the flame-retardant systems such as silicon systems).
As one embodiment, the lithium battery is the lithium battery that can receive pressure, temperature variation, as liquid from
Sub- lithium battery, poly-lithium battery or solid state lithium battery etc..
As one embodiment, the lithium battery have can average conduction pressure or orient conducting pressure packaging.
As one embodiment, the lithium battery can also be externally provided with as needed in different mobility media
The protective layer of one anti-lithium battery short circuit or the pollution of anti-lithium battery, such as wrapped up using PE plastics, aluminum plastic film.
As one embodiment, the temperature control can be heating or refrigeration, and program setting can be used in temperature control
Mode, range is at -40~300 DEG C, preferably -30~160 DEG C.
As one embodiment, the pressure control can be positive pressure or negative pressure, and program setting can be used in pressure value
Mode, range is any, and preferably 10-4Pa~20MPa.
As one embodiment, the importing and release of the media environment and temperature and pressure control and lithium battery
Charge and discharge process match.The setting that the setting of charging and discharging lithium battery includes the arbitrary size of voltage and current, is arbitrarily segmented.
Cooperation can carry out pressure control or not pressure control, temperature control or the not accordingly control such as temperature control according to being set in during charge and discharge section.
In addition, while formation of Li-ion batteries process, additionally it is possible to carry out such as testing current, voltage tester and inner walkway
Equal lithium batteries electrochemical property test and such as static pressure short circuit security performance test, and lithium battery can be carried out according to test data
Classification.Also, while formation process, additionally it is possible to be surveyed by detecting the composition transfer of medium with carrying out lithium battery packaging leak detection
Examination.
Accordingly, additionally it is possible to special charging and discharging lithium battery Testing Method of Safety can be derived, can be arranged according to demand
The environment of charge and discharge, such as temperature, pressure even puncture, especially under liquid environment, it is possible to reduce to the external world when battery short circuit
Danger.The detection test method such as special lithium battery chemical property, packaging can also similarly be derived
Embodiment 1
It is preferred that features described above item forms a kind of chemical synthesizing method of constant temperature and pressure after package, specific embodiment is as follows:
LiFePO4-graphite soft bag lithium ionic cell is wrapped up to the alkyl for being placed on 45 DEG C, 600KPa with PE polybag
In biphenyl ether type conduction oil, the temperature and pressure is kept, lithium battery is pressed into 0.5C constant-current charge 3.5V, stands 30 minutes, then
0.5C constant-current discharge is to 2V.Pressure release cooling takes out lithium battery and removes package after the completion.
Embodiment 2
It is preferred that features described above item forms a kind of chemical synthesizing method of constant temperature and pressure after being melted into advance, specific embodiment is as follows:
The ternary of pre- chemical conversion to 3.8V-graphite soft bag lithium ionic cell rubber package is placed on 45 DEG C, 700KPa
In alkyl biphenyl ether type conduction oil, the temperature and pressure is kept, lithium battery is pressed into 0.2C constant-current charge 4.2V, stands 30 minutes,
Then 0.5C constant-current discharge is to 2.8V.Pressure release cooling takes out lithium battery and removes package after the completion.
Embodiment 3
It is preferred that features described above item form a kind of package after, the chemical synthesizing method of temperature transformation, specific embodiment is as follows:
By LiFePO4-graphite soft bag lithium ionic cell aluminum plastic film package is placed on-20 DEG C, the low temperature of 600KPa leads
Hot oil, such as U.S. Therminol-VP-1, Dowtherm-A, Japan Therm-S-300, Germany Diphyl or the long star Y-DS of China
In road oil generation, lithium battery is pressed into 0.5C constant-current charge 2.8V, temperature and pressure is kept to stand 30 minutes；Then pressure release changes 45 into
DEG C, the flame retardant solution of 400KPa, then keep temperature and pressure 0.5C constant-current charge to 3.5V；Then same environment 0.5C constant current
It is discharged to 2V, last pressure release changes the low temperature conduction oil of -30 DEG C, 100KPa into, keeps temperature and pressure to stand for 24 hours, lets out after the completion
Pressure heating takes out lithium battery and removes package.
Embodiment 4
It is preferred that features described above item formed it is a kind of do not wrap up, after high temperature and pressure, the chemical synthesizing method of alternating temperature transformation, specific implementation
Scheme is as follows:
Ternary-graphite solid lithium ion battery is placed in 300 DEG C, is kept in the alkyl biphenyl ether type conduction oil of 20MPa
Temperature and pressure stands 5 minutes.It is then cooled to 65 DEG C, is depressurized to 2MPa, keeping temperature and pressure that lithium battery is permanent by 0.5C
Current charge 3.7V, and save at pressure and temperature for 24 hours, subsequent pressure release changes the conduction oil holding temperature of 45 DEG C, 200KPa into
With pressure by 0.5C constant-current charge to 4.2V, then identical environment stands after 48h 0.5C constant-current discharge to 3V.Last pressure release cooling
Take out lithium battery clean surface.
Embodiment 5
It is preferred that features described above item carries out the chemical synthesizing method of electrochemical property test while being formed in temperature-control pressure-control, it is specific
Embodiment is as follows:
LiFePO4-graphite solid lithium ion battery is placed in 55 DEG C, in the argon gas of 1.2MPa, keeps temperature and pressure
Lithium battery is pressed into 0.5C constant-current charge 3.5V, stands 30 minutes, then 0.5C constant-current discharge to 2V.Pass through simultaneously in whole process
Equipment carries out the testing impedance of lithium battery, and records data.Lithium battery clean surface is taken out in pressure release cooling after the completion.
Embodiment 6
It is preferred that features described above item forms a kind of method that can carry out packaging leak detection in formation process, specific embodiment party
Case is as follows:
Ternary-graphite soft bag lithium ionic cell is put into 70 DEG C, in the drying at room temperature air of 5MPa, keeps temperature and pressure
Power simultaneously presses 0.2C constant-current charge 3.7V, is then taken into 10-4Whether pa vacuum state detects in the ingredient of gas bleeding containing electrolysis
Liquid ingredient.After confirmation packaging is without leakage, medium is replaced as to the drying at room temperature air of 45 DEG C, 5MPa, temperature and pressure is kept to press
0.5C constant-current charge is to 4.2V, and then identical environment stands after 48h 0.5C constant-current discharge to 3V.Lithium electricity is taken out in last pressure release cooling
Pond.
Embodiment 7
It is preferred that features described above item forms a kind of chemical synthesizing method of constant temperature and pressure in aqueous solvent, specific embodiment is such as
Under:
LiFePO4-graphite soft bag lithium ionic cell tab and extraneous power supply connected component are subjected to waterproof insulation guarantor
Then shield places it in the in the mixed solvent of 45 DEG C, the water of 600KPa, ethyl alcohol, formaldehyde, acetone, keep temperature and pressure by lithium
Battery presses 0.5C constant-current charge 3.5V, stands 30 minutes, then 0.5C constant-current discharge to 2V.Lithium electricity is taken out in pressure release cooling after the completion
Pond.
Embodiment 8
It is preferred that features described above item forms a kind of method that positive/negative-pressure variation, temperature control chemical conversion can be carried out in formation process,
Its specific embodiment is as follows:
Ternary-graphite solid lithium ion battery is put into 70 DEG C, in the drying at room temperature air of 5MPa, keeps temperature and pressure
Power, and press 0.2C constant-current charge 3.7V.Vacuum is then extracted to 10-4Pa, and kept for 70 DEG C, detecting in the ingredient of gas bleeding is
It is no to contain electrolyte composition.Confirmation packaging without 45 DEG C are cooled to after leakage, 10-4By 0.5C constant-current charge to 4.2V under the conditions of Pa,
Then identical environment stands 48h, 0.5C constant-current discharge to 3V.Lithium battery is taken out in last pressure release cooling.
Embodiment 9
It is preferred that features described above item formed it is a kind of chemical conversion and meanwhile carry out static pressure short circuit safety test and complete the side of cell classification
Method, specific embodiment are as follows:
LiFePO4-graphite soft bag lithium ionic cell is placed in 45 DEG C, in the alkyl biphenyl ether type conduction oil of 600KPa,
Then keep temperature and pressure that lithium battery is pressed 0.5C constant-current charge 3.5V.It is then ladder by pressure 200KPa, from 600KPa
5MPa is risen to, keeps temperature and pressure to stand 30 minutes on every step, tests its resistance variations, when internal resistance is less than preset value 15
It is shut down procedure when milliohm, then 0.5C constant-current discharge to 2V.After the completion, battery is taken out in pressure release, will according to test step and internal resistance
Cell classification.
Embodiment 10
It is preferred that features described above item forms a kind of safety detecting method for carrying out the short circuit of lithium battery static pressure, specific embodiment
It is as follows:
LiFePO4-graphite soft bag lithium ionic cell is placed in 45 DEG C, in the alkyl biphenyl ether type conduction oil of 600KPa,
Then keep temperature and pressure that lithium battery is pressed 0.5C constant-current charge 3.5V.It is then ladder by pressure 200KPa, from 600KPa
200MPa is risen to, keeps temperature and pressure to stand 30 minutes on every step, its resistance is tested, until short circuit.After the completion, pressure release
Battery is taken out, is analyzed.
In conclusion temperature-control pressure-control formula formation of Li-ion batteries method of the invention, by using controllable each of temperature and pressure
The formation of Li-ion batteries that temperature-control pressure-control is carried out to the media environment of the same sex can simplify formation of Li-ion batteries process and folder
When tool heating pressure method firmly contact and pressure it is uneven caused by a series of various problems, be worthy to be popularized.
Those of ordinary skill in the art it should be appreciated that more than embodiment be intended merely to illustrate the present invention,
And be not used as limitation of the invention, as long as the change in spirit of the invention, to embodiment described above
Change, modification will all be fallen within the scope of claims of the present invention.
Claims (12)
1. a kind of temperature-control pressure-control formula formation of Li-ion batteries method, it is characterised in that: using controllable isotropic of temperature and pressure
Media environment, and closed lithium battery is placed in the media environment, it is controlled by temperature and pressure to carry out formation of Li-ion batteries.
2. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: the medium is stream
Dynamic property medium.
3. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as claimed in claim 2, it is characterised in that: the mobility is situated between
Matter is dry air, argon gas, conduction oil or retardant solution.
4. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: the lithium battery is
It can receive the lithium battery of pressure, temperature variation.
5. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as claimed in claim 4, it is characterised in that: the lithium battery is
Liquid ion lithium battery, poly-lithium battery or solid state lithium battery.
6. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as claimed in claim 1 or 5, it is characterised in that: the lithium electricity
Pond have can average conduction pressure or orient conducting pressure packaging.
7. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: the temperature control
Range at -40~300 DEG C.
8. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: the pressure control
Range 10-4Pa~20MPa.
9. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: the temperature and pressure
Power control is matched with the charge and discharge process of lithium battery.
10. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: in formation process
Simultaneously, additionally it is possible to carry out lithium battery electrochemical property test and security performance test, and be carried out lithium battery according to test data
Classification.
11. a kind of temperature-control pressure-control formula formation of Li-ion batteries method as described in claim 1, it is characterised in that: in formation process
Simultaneously, additionally it is possible to by detecting the composition transfer of medium to carry out lithium battery packaging leak detection test.
12. the detection test method of a kind of temperature-control pressure-control formula lithium battery chemical property, security performance or/and packaging, feature
It is: using the controllable isotropic media environment of temperature and pressure, and closed lithium battery is placed in the media environment,
Corresponding test is realized by the control of cooperation temperature and pressure.
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| CN201711336837.3A CN109962295A (en) | 2017-12-14 | 2017-12-14 | A kind of temperature-control pressure-control formula formation of Li-ion batteries method |
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| CN201711336837.3A CN109962295A (en) | 2017-12-14 | 2017-12-14 | A kind of temperature-control pressure-control formula formation of Li-ion batteries method |
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Cited By (3)
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| CN112582678A (en) * | 2019-09-29 | 2021-03-30 | 广州汽车集团股份有限公司 | Naked battery cell and preparation method and application thereof |
| CN113447837A (en) * | 2021-09-01 | 2021-09-28 | 深圳联钜自控科技有限公司 | Temperature measurement and control system for high-temperature formation process of soft package lithium battery |
| CN115344074A (en) * | 2022-10-18 | 2022-11-15 | 杭州科工电子科技有限公司 | Lithium battery constant temperature control system based on big data |
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| CN115344074B (en) * | 2022-10-18 | 2023-01-17 | 杭州科工电子科技有限公司 | Lithium battery constant temperature control system based on big data |
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