CN109244567A - A kind of macromolecule heat-seal electrode coating improving lithium ion battery security - Google Patents
A kind of macromolecule heat-seal electrode coating improving lithium ion battery security Download PDFInfo
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- CN109244567A CN109244567A CN201810721311.5A CN201810721311A CN109244567A CN 109244567 A CN109244567 A CN 109244567A CN 201810721311 A CN201810721311 A CN 201810721311A CN 109244567 A CN109244567 A CN 109244567A
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- heat
- lithium ion
- ion battery
- electrode coating
- battery security
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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
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses technical field of lithium ion, specific field is a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security, it includes thermally sensitive layer that it, which is formed, heat-stable ceramic layer, overcharge protection additives and fire retardant, on the anode electrode using thermally sensitive layer coating, the first line of defence as battery thermal runaway, when lithium ion battery is overheated because of mechanical stamping or short circuit, when internal temperature is higher than critical-temperature, that is, internal temperature higher than thermally sensitive layer fusing point, polymer beads of uniform size form insulating layer by heat deflection process (fusing) on anode, to block the channel that lithium ion continues disengaging electrode, lithium ion battery is set to stop working, high-temperature machinery stability is provided using heat-stable ceramic layer, reduce internal short-circuit chance, in the case of making battery that there is localized hyperthermia using overcharge protection additives and fire retardant, Electrolyte is also able to maintain its stability.
Description
Technical field
The present invention relates to technical field of lithium ion, specific field is a kind of high score for improving lithium ion battery security
Sub- heat-seal electrode coating.
Background technique
More energy can be put into smaller, lighter unit of weight in contrast to other kinds of battery by lithium ion battery, because
This lithium ion battery is widely used in mobile phone, laptop and other portable electronic devices, however, with lithium-ion electric
Portable electronic product occur for pond being widely used in the world catch fire phenomenon and to occur to exist because using lithium ion battery
Battery event on Boeing has caused concern of the people to its safety problem, and causes fire or explosive event most
It is related with lithium ion battery overheat；In a typical thermal runaway environment, initial overheat be, overcharge excessive by electric current,
Caused by high external temperature or mechanical damage (such as extruding, punching press)；
Currently, commercial li-ion battery generallys use pressure limiting valve design, additional PTC resistor is housed on shell
(PTC), however, these external equipments may cannot respond to, and related work report is shown when hazardous reaction occurs, one
1500 milliamperes of batteries will rupture before the charging of 1A electric current shows that maximum internal temperature is 199 DEG C, maximum at this time external
Temperature is only 106.4 DEG C, and 92.6 DEG C of the temperature difference cause external equipment that can not timely respond to；
In order to seek better security control, people have been devoted to inside lithium ion cell and end mechanism from heating
Many diaphragms of research, lithium ion battery design all have heat shutoff characteristic, but are irreversible, once thermal starting will be led
Send a telegraph pond permanent damages；For example, shutdown separator is usually by polyethylene-polypropylene bilayer or polypropylene-polyethylene-polypropylene three
Layer structure composition, more than critical-temperature, porous polyethylene layer softening, membrane pores are collapsed, and prevent ionic conduction, polypropylene layer mentions
For mechanical support, however support force is limited, when internal temperature of battery rises to the softening temperature of partition, turns off the contraction of separator
Density variation between film and the crystallization and amorphous phase of diaphragm material during stretching caused by residual stress, this will lead to
The electrode interior short circuit of failure and the exposure of the shutdown separator；For another example other protective coatings are used in polypropylene separator,
Such as Al2O3 coating, cathode anode is isolated with pinning method, such method can only be protected when (such as 1000 milliamperes) lower in battery capacity
Battery, ceramic coating cannot prevent 18650 lithium batteries from exploding, because reaction speed is fast, gas escapes in cylindrical battery, no
High pressure in rust steel steel cylinder will lead to battery explosion；For another example SEI layers, Faulty Temperature is at 80 DEG C, once this layer disassembles
Begin, exothermic reaction occurs for electrolyte and anode, and temperature further increases, and therewith, the heat that anode reaction generates will lead to organic
The release of the decomposition of solvent and inflammable hydrocarbon gas (such as ethane and methane), this usually occurs at 70~110 DEG C, and temperature rises to
135 DEG C, membrane for polymer thawing, cause short circuit, and the heat that electrolyte decomposition generates leads to hitting for metal oxide cathode materials
The release with oxygen is worn, the burning of the electrolyte and gas of inside battery is promoted, the cathode of lithium and cobalt oxides battery, which is hit, to be started from
About 200 DEG C, the pressure of inside battery is increasing, to generate explosion；In conclusion single technology can not solve complexity
Thermal runaway problem.
Summary of the invention
The purpose of the present invention is to provide it is a kind of improve lithium ion battery security macromolecule heat-seal electrode coating, with
Solve the problems mentioned above in the background art.
To achieve the above object, the invention provides the following technical scheme: a kind of high score for improving lithium ion battery security
Sub- heat-seal electrode coating, composition include thermally sensitive layer, heat-stable ceramic layer, overcharge protection additives and fire retardant, the heat
Sensitive layer includes that weight percent is 80%~100% polymer beads and 0~20% adhesive, the heat-stable ceramic layer
It is 80%~100% heat-stable ceramic particle and 0~20% adhesive, the overcharge protection additives including weight percent
Account for the 1%~12% and 1%~10% of the gross mass of lithium-ion battery electrolytes respectively with the fire retardant.
Preferably, for the thermally sensitive layer with a thickness of 500nm~50 μm, the polymer beads partial size is 100nm~30 μm.
Preferably, for the heat-stable ceramic layer with a thickness of 500nm~10 μm, the heat-stable ceramic grain diameter is 100nm~3
μm。
Preferably, the polymer beads by one of polyethylene, polypropylene and Kynoar or a variety of form.
Preferably, the heat-stable ceramic particle is by one in aluminum oxide, aluminium hydroxide, silica and titanium dioxide
Kind or a variety of compositions.
Preferably, described adhesive is by Kynoar, polyurethane, polyethylene glycol oxide, polyacrylic acid, carboxymethyl cellulose
Element, polyacrylonitrile, polymethacrylates, polyacrylamide, polyvinyl acetate, Pioloform, polyvinyl acetal, polyvinylpyrrolidine
Ketone, polyvinyl alcohol polytetrafluoroethylene (PTFE), diethylene glycol dilaurate, fluoropropene, one or more compositions in chlorotrifluoroethylene.
Preferably, the thermally sensitive layer and the heat-stable ceramic layer are respectively coated by way of spraying, scraper or die casting
On anode and cathode electrode.
Preferably, the overcharge protection additives are by cyclohexyl benzene, dimethoxydiphenylsilane, biphenyl or tert-amyl benzene
In one or more compositions.
Preferably, the fire retardant is five fluorine ethyoxyl phosphonitriles.
Compared with prior art, the beneficial effects of the present invention are: a kind of macromolecule heat for improving lithium ion battery security
Enclosed-electrode coating, battery thermal runaway since anode, are coated on the anode electrode, as battery heat at first using thermally sensitive layer
The first line of defence out of control, when lithium ion battery is overheated because of mechanical stamping or short circuit, internal temperature is higher than in critical-temperature i.e.
When portion's temperature is higher than thermally sensitive layer fusing point, polymer beads of uniform size are formed on anode by heat deflection process (fusing)
Insulating layer continues to pass in and out the channel of electrode, so that lithium ion battery is stopped working, enable lithium ion battery from pass to block lithium ion
It closes, reduces the generation of heat, prevent lithium ion battery explosion or on fire；High-temperature machinery stability is provided using heat-stable ceramic layer,
Internal short-circuit chance is reduced, this protection will reduce the generation of heat and reduce the probability of thermal runaway；It is added using protection is overcharged
In the case of agent and fire retardant make battery have localized hyperthermia, electrolyte is also able to maintain its stability；In conclusion using three kinds of sides
Formula can solve the problems, such as the thermal runaway of lithium ion battery, that is, prevent lithium ion battery explosion while avoiding its internal short-circuit.
Detailed description of the invention
Fig. 1 is the safety battery loop-around data using the technology of the present invention.
Fig. 2 is to penetrate lower control battery Fig. 2 (a) in nail and test feelings using safety battery Fig. 2 (b) of the technology of the present invention
Condition.
Fig. 3 is to control battery Fig. 3 (a) and safety battery Fig. 3 (b) overcharge test situation using the technology of the present invention.
Fig. 4 is that nail penetrates 18650 battery Fig. 4 (a) of lower control and 18650 battery Fig. 4 of safety using the technology of the present invention
(b) test case.
Fig. 5 is the 18650 battery overcharge test charts 5 (a) of safety and short-circuit test Fig. 5 (b) using the technology of the present invention.
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 institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
Embodiment 1:
It is a kind of improve lithium ion battery security macromolecule heat-seal electrode coating, including 500nm thermally sensitive layer and
500nm heat-stable ceramic layer, thermally sensitive layer include weight percent be 80% partial size be 100nm polyethylene particle and 20% it is poly-
Vinylidene, heat-stable ceramic layer include weight percent be 80% partial size be 100nm aluminum oxide particle and 20% it is poly-
Thermally sensitive layer and heat-stable ceramic layer are respectively coated on the anode and cathode electrode of lithium ion battery by urethane by way of spraying
On, into lithium-ion battery electrolytes, addition weight ratio is 1% overcharge protection additives and weight ratio is 1% fire retardant.
Embodiment 2:
It is a kind of improve lithium ion battery security macromolecule heat-seal electrode coating, including 1 μm of thermally sensitive layer and 1 μm it is resistance to
Thermal Ceramics layer, thermally sensitive layer include weight percent be 90% partial size be 500nm PP GRANULES and 10% polyoxyethylene
Alkene, heat-stable ceramic layer include weight percent be 90% partial size be 500nm aluminum hydroxide particles and 10% polyacrylic acid, will
Thermally sensitive layer and heat-stable ceramic layer are respectively coated on the anode and cathode electrode of lithium ion battery by way of scraper, Xiang Li
Addition weight ratio is 6% overcharge protection additives in ion battery electrolyte and weight ratio is 5% fire retardant.
Embodiment 3:
A kind of macromolecule heat-seal electrode coating improving lithium ion battery security, including 50 μm of thermally sensitive layers and 10 μm
Heat-stable ceramic layer, thermally sensitive layer include weight percent be 100% partial size be 50 μm of Kynoar particles, heat-stable ceramic layer
The partial size for being 100% including weight percent is 3 μm of silica dioxide granules, and thermally sensitive layer and heat-stable ceramic layer are passed through die casting
Mode is respectively coated on the anode and cathode electrode of lithium ion battery, and weight ratio is added into lithium-ion battery electrolytes and is
12% overcharge protection additives and weight ratio are 10% fire retardant.
In conjunction with the embodiments and attached drawing, nail penetration test is carried out using MTI hydraulic-driven crusher and degree of hammering into instrument, selection is straight
Diameter is the nail of 3mm, and nail speed is set in 10mm/s, and Fig. 2 (a) shows control battery and batteries caught fire after nail penetrates, Fig. 2
(b) display can penetrate nail using the safety battery of the technology of the present invention, and battery keeps complete；Fig. 3 (a) display overcharges electric control
The temperature of battery rises above 450 DEG C, and Fig. 3 (b) display is increased using the safety battery temperature of the technology of the present invention and is lower than 70C,
This shows that overcharge test can be passed through using the safety battery of the technology of the present invention；Fig. 4 shows 18650 batteries (Fig. 4 a) of control
With the nail penetration test for 18650 batteries (Fig. 4 b) of safety for using the technology of the present invention, 18650 batteries of all controls are worn in nail
It explodes immediately after thoroughly, all 18650 batteries of safety using the technology of the present invention are lower than 100 DEG C by test and temperature；Use this
18650 batteries of safety of inventive technique pass through overcharge (Fig. 5 a) and short-circuit test (Fig. 5 b).
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security, it is characterised in that: it includes heat that it, which is formed,
Sensitive layer, heat-stable ceramic layer, overcharge protection additives and fire retardant, the thermally sensitive layer include weight percent be 80%~
100% polymer beads and 0~20% adhesive, the heat-stable ceramic layer include weight percent be 80%~100%
Heat-stable ceramic particle and 0~20% adhesive, the overcharge protection additives and the fire retardant account for lithium-ion electric respectively
The 1%~12% of the gross mass of pond electrolyte and 1%~10%.
2. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: for the thermally sensitive layer with a thickness of 500nm~50 μm, the polymer beads partial size is 100nm~30 μm.
3. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: for the heat-stable ceramic layer with a thickness of 500nm~10 μm, the heat-stable ceramic grain diameter is 100nm~3 μm.
4. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: the polymer beads are by one of polyethylene, polypropylene and Kynoar or a variety of form.
5. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: the heat-stable ceramic particle is by one of aluminum oxide, aluminium hydroxide, silica and titanium dioxide or a variety of
Composition.
6. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: described adhesive is by Kynoar, polyurethane, polyethylene glycol oxide, polyacrylic acid, carboxymethyl cellulose, polypropylene
Nitrile, polymethacrylates, polyacrylamide, polyvinyl acetate, Pioloform, polyvinyl acetal, polyvinylpyrrolidone, polyethylene
Alcohol polytetrafluoroethylene (PTFE), diethylene glycol dilaurate, fluoropropene, one or more compositions in chlorotrifluoroethylene.
7. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: the thermally sensitive layer and the heat-stable ceramic layer be respectively coated on by way of spraying, scraper or die casting anode and
On cathode electrode.
8. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: the overcharge protection additives by a kind of in cyclohexyl benzene, dimethoxydiphenylsilane, biphenyl or tert-amyl benzene or
A variety of compositions.
9. a kind of macromolecule heat-seal electrode coating for improving lithium ion battery security according to claim 1, special
Sign is: the fire retardant is five fluorine ethyoxyl phosphonitriles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810721311.5A CN109244567A (en) | 2018-06-28 | 2018-06-28 | A kind of macromolecule heat-seal electrode coating improving lithium ion battery security |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810721311.5A CN109244567A (en) | 2018-06-28 | 2018-06-28 | A kind of macromolecule heat-seal electrode coating improving lithium ion battery security |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569703A (en) * | 2012-02-01 | 2012-07-11 | 天津市捷威动力工业有限公司 | Diaphragm and lithium ion battery applying diaphragm |
| CN103715458A (en) * | 2013-10-23 | 2014-04-09 | 江西优锂新材股份有限公司 | Preparation method of electrolyte used for lithium manganate power battery at high temperature |
| JP2014164801A (en) * | 2013-02-21 | 2014-09-08 | Shin Kobe Electric Mach Co Ltd | Nonaqueous electrolyte, nonaqueous electrolyte secondary battery using the same, and secondary battery system with nonaqueous electrolyte secondary battery |
| CN104157811A (en) * | 2013-12-11 | 2014-11-19 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite diaphragm and preparation method and application thereof |
| CN109841783A (en) * | 2017-11-28 | 2019-06-04 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and isolating membrane thereof |
-
2018
- 2018-06-28 CN CN201810721311.5A patent/CN109244567A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569703A (en) * | 2012-02-01 | 2012-07-11 | 天津市捷威动力工业有限公司 | Diaphragm and lithium ion battery applying diaphragm |
| JP2014164801A (en) * | 2013-02-21 | 2014-09-08 | Shin Kobe Electric Mach Co Ltd | Nonaqueous electrolyte, nonaqueous electrolyte secondary battery using the same, and secondary battery system with nonaqueous electrolyte secondary battery |
| CN103715458A (en) * | 2013-10-23 | 2014-04-09 | 江西优锂新材股份有限公司 | Preparation method of electrolyte used for lithium manganate power battery at high temperature |
| CN104157811A (en) * | 2013-12-11 | 2014-11-19 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite diaphragm and preparation method and application thereof |
| CN109841783A (en) * | 2017-11-28 | 2019-06-04 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and isolating membrane thereof |
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Application publication date: 20190118 |
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