CN108666465A - A kind of fire-retardant wrapper and its lithium ion battery - Google Patents
A kind of fire-retardant wrapper and its lithium ion battery Download PDFInfo
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- CN108666465A CN108666465A CN201710210733.1A CN201710210733A CN108666465A CN 108666465 A CN108666465 A CN 108666465A CN 201710210733 A CN201710210733 A CN 201710210733A CN 108666465 A CN108666465 A CN 108666465A
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- Prior art keywords
- wrapper
- fire
- sealing
- diaphragm seal
- retardant
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Present disclose provides a kind of fire-retardant wrappers, including encapsulation containment wall and the fire retardant matter being wrapped in wrapper, and the encapsulation containment wall includes the diaphragm seal item with sealing and the outer membrane insoluble in electrolyte and the closing sealing；The encapsulation containment wall holding structure can be stablized so that the fire retardant matter to be wrapped in the wrapper at a temperature of less than 100 DEG C, and the diaphragm seal item can occur to soften at 100~170 DEG C and rupture, ruptured so as to cause the encapsulation containment wall and the fire retardant matter in the wrapper be discharged to outside the wrapper.The disclosure additionally provides a kind of lithium ion battery of the preparation method and the wrapper provided containing the disclosure of the fire-retardant wrapper, and fire retardant matter can be released into lithium battery by the lithium ion battery before thermal runaway, greatly reduce the generation of safety accident.
Description
Technical field
This disclosure relates to battery technology field, and in particular, to a kind of fire-retardant wrapper and its lithium ion battery.
Background technology
Application of the lithium ion battery in new-energy automobile field is increasingly extensive, however the report of lithium ion battery safety accident
Also showed increased, the cause that safety accident occurs for lithium ion battery are generally internal short-circuit of battery caused by machinery abuse, long-term
In the high temperature environment or battery thermal runaway etc. caused by super-charge super-discharge.Disclosed in CN201310486020.X it is a kind of by
The encapsulation capsule of phosphorous system's flame-retardant additive built in battery encapsulates the cyst wall hair of capsule when thermal runaway occurs for lithium ion battery
Raw rupture is so that core materials, that is, phosphorous flame-retardant additive of encapsulation capsule is released to realize fire-retardant and improve lithium ion
The security performance of battery.
But the encapsulation capsule of phosphorous system's flame-retardant additive can not just eliminate battery thermal runaway before battery thermal runaway
Danger is only capable of delaying the process of thermal runaway, still has the test battery of the phosphorous system's flame-retardant additive encapsulation capsule in part to occur
Fire.The encapsulation capsule of phosphorous system's flame-retardant additive cannot effectively be organized to be the fire-retardant of phosphorous flame-retardant additive the reason of thermal runaway
Mechanism is free radical fire retardant mechanism, and the boiling point of phosphorous flame-retardant additive is generally 200 DEG C, this means that battery has occurred and that heat
Fire retardant out of control can just have an effect.
Therefore, there is an urgent need for a kind of new technical solutions to eliminate the danger of lithium ion battery thermal runaway.
Invention content
Purpose of this disclosure is to provide a kind of lithium ion battery, the probability which occurs thermal runaway is extremely low.
To achieve the goals above, the disclosure provides a kind of fire-retardant wrapper, including encapsulates containment wall and be wrapped in wrapper
Interior fire retardant matter, the encapsulation containment wall include with sealing and the outer membrane insoluble in electrolyte and closing the close of the sealing
Sealer item；The encapsulation containment wall holding structure can be stablized so that the fire retardant matter to be wrapped at a temperature of less than 100 DEG C
In the wrapper, and the diaphragm seal item can occur to soften and rupture at 100~170 DEG C, so as to cause the wrapper
Wall ruptures and the fire retardant matter in the wrapper is discharged to outside the wrapper.
The disclosure additionally provides a kind of preparation method of fire-retardant wrapper, which includes the following steps：
S1, the outer membrane doubling that a piece of at least partly edge is combined with to diaphragm seal item are bonded, then partially enclosed correspondence
Edge, while reserved unclosed sealing, form prefabricated membrane bag；Alternatively, two panels at least partly edge is combined with diaphragm seal item
Outer membrane be bonded each other, then partially enclosed corresponding edge, while reserved unclosed sealing forms prefabricated membrane bag；
Wherein, the diaphragm seal item (2) in non-closed state is provided in unclosed sealing (3)；
Some or all of described diaphragm seal item (2) in non-closed state only with the unclosed sealing (3)
Side inner surface combines, without being combined with the other side inner surface of the unclosed sealing (3)；
S2, fire retardant matter is inserted in the prefabricated membrane bag；
S3, the unclosed sealing (3) is closed by hot pressing, form encapsulation containment wall；
Wherein, the encapsulation containment wall holding structure can be stablized with by the fire retardant matter at a temperature of less than 100 DEG C
(4) it is wrapped in the wrapper, and the diaphragm seal item (2) can occur to soften and rupture at 100~170 DEG C, to lead
The encapsulation containment wall is caused to rupture and the fire retardant matter in the wrapper is discharged to outside the wrapper.
The disclosure additionally provides the fire-retardant wrapper that preparation method as described above is prepared.
The disclosure additionally provides a kind of lithium ion battery containing above-mentioned wrapper.The lithium ion battery contains in addition to interior
Can also include shell and the battery core being contained in housing, nonaqueous electrolytic solution outside above-mentioned wrapper, battery core includes anode, cathode
And the diaphragm between positive electrode and negative electrode.
Through the above technical solutions, envelope is prepared in the diaphragm seal item closing sealing for the encapsulation containment wall that the disclosure provides
Dress packet, the wrapper can soften under the conditions of 100~170 DEG C, in the temperature for reaching battery maximum probability generation thermal runaway
Make wrapper that the fire retardant matter that rupture releases in capsule-core occur before degree and reduces peace to increase the safety of lithium ion battery
The generation of full accident.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is for providing further understanding of the disclosure, and a part for constitution instruction, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings：
Fig. 1 is wrapper cross-sectional structure figure.
Reference sign
1 outer membrane, 2 diaphragm seal item
34 fire retardant matters of sealing
Specific implementation mode
The specific implementation mode of the disclosure is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
In the disclosure, in the absence of explanation to the contrary, the noun of locality used such as " inside and outside " refers to the interior of wrapper
Outside.
Disclosure first aspect provides a kind of fire-retardant wrapper, including encapsulates containment wall and be wrapped in fire-retardant in wrapper
Substance 4, it is described encapsulation containment wall include with sealing 3 and the outer membrane 1 insoluble in electrolyte and close it is described seal 3 diaphragm seal
Item 2；The encapsulation containment wall holding structure can be stablized so that the fire retardant matter 4 is wrapped in institute at a temperature of less than 100 DEG C
It states in wrapper, and the diaphragm seal item 2 can occur to soften and rupture at 100~170 DEG C, so as to cause the encapsulation containment wall
It ruptures and the fire retardant matter in the wrapper is discharged to outside the wrapper.
Through the above technical solutions, the diaphragm seal item can be by thermal welding described in the closing of the inside of the outer membrane
Wrapper allows the wrapper to be melted under the conditions of 100~170 DEG C, and thermal runaway occurs reaching battery maximum probability
Temperature before make wrapper that the fire retardant matter that releases in capsule-core of rupture occur to increase the safety of lithium ion battery to subtract
The generation of few safety accident.
According to the disclosure in a first aspect, in order to remain potted the stability of packet under normal use, the outer membrane
Tensile strength can be higher than the tensile strength of the diaphragm seal item；The tensile strength of the outer membrane can be 50~4000MPa；
The softening temperature of the diaphragm seal item can be 100~170 DEG C.
The tensile strength of the outer membrane is according to GBT13022-1991《Stretched plastic film method for testing performance》Rule
It is fixed, it is measured under conditions of humidity is 20%, temperature is 25 DEG C and tensile speed is 25mm/min.The diaphragm seal item it is soft
It is according to GB/T1633 to change temperature《The measurement of thermoplastic softening temperature (VST)》Regulation, using 10N power, heating
Rate measures under conditions of being 50 DEG C/h.
According to the disclosure in a first aspect, in order to keep the performance of the wrapper, the material of the outer membrane that can be selected from
At least one of polyethylene terephthalate, polyurethane, polyimides and polypropylene；The material of the diaphragm seal item can
To be selected from least one of polyethylene, polyvinyl chloride and olefin copolymer；Select polymer compound film made of above-mentioned material
Tensile strength and diaphragm seal softening temperature be suitable for make wrapper.
According to the disclosure in a first aspect, the outer membrane 1 is formed to have the prefabricated membrane bag for sealing 3 and being bag shaped structure
And it is filled with the fire retardant matter 4, and the both sides inner surface of the sealing 3 is incorporated in the both sides appearance of the diaphragm seal item 2
On face；
Under preferable case, the prefabricated membrane bag be a piece of outer membrane doubling fitting and partially enclosed corresponding edge simultaneously
The prefabricated membrane bag formed after reserved unclosed sealing 3；
Alternatively, the prefabricated membrane bag is bonded each other for outer membrane described in two panels and partially enclosed corresponding edge is reserved simultaneously not
The prefabricated membrane bag formed after closed sealing 3；
Wherein, it is provided with the diaphragm seal item 2 in non-closed state in unclosed sealing 3；
Side of some or all of the described diaphragm seal item 2 in non-closed state only with the unclosed sealing 3
Inner surface combines, without being combined with the other side inner surface of the unclosed sealing 3.
According to the disclosure in a first aspect, in order to prevent in battery solvent volatilize flash burn, the preferred tricresyl phosphate of fire retardant matter
Methyl esters, methyl-phosphoric acid dimethyl ester, three-(2,2,2)-trifluoroethyl phosphite ester, three-(2,2,2)-trifluoroethyl phosphate and phosphine
At least one of nitrile；It is in terms of 100% by the weight of the wrapper, the content of the fire retardant matter is 10-50%；The dosage
Three-(2,2,2)-trifluoroethyl phosphite esters can reach preferable flame retardant effect, and three-(2,2,2)-trifluoroethyls are sub-
Phosphate does not influence the safety of lithium ion battery.
According to the disclosure in a first aspect, another preferably technical solution as the disclosure, in order to make battery be lost in heat
Can be risen brokenly failure before control, and the fire retardant matter also contains the substance that can be decomposed at 100-130 DEG C and generate carbon dioxide；It is preferred that
Ground, it is described by the weight of the wrapper be 100% in terms of, it is described can decompose generate carbon dioxide material content can be 10
~50%.
According to the disclosure in a first aspect, the substance that can decompose generation carbon dioxide can be selected from acetic anhydride, carbonic acid
At least one of ammonium, sodium bicarbonate, malonic acid and basic copper carbonate.
Disclosure second aspect provides a kind of preparation method of fire-retardant wrapper, which includes the following steps：
S1, the outer membrane doubling that a piece of at least partly edge is combined with to diaphragm seal item are bonded, then partially enclosed correspondence
Edge, while reserved unclosed sealing, form prefabricated membrane bag；Alternatively, two panels at least partly edge is combined with diaphragm seal item
Outer membrane be bonded each other, then partially enclosed corresponding edge, while reserved unclosed sealing forms prefabricated membrane bag；
Wherein, it is provided with the diaphragm seal item 2 in non-closed state in unclosed sealing 3；
Side of some or all of the described diaphragm seal item 2 in non-closed state only with the unclosed sealing 3
Inner surface combines, without being combined with the other side inner surface of the unclosed sealing 3；
S2, fire retardant matter is inserted in the prefabricated membrane bag；
S3, the unclosed sealing 3 is closed by hot pressing, form encapsulation containment wall；
Wherein, the encapsulation containment wall holding structure can be stablized with by the fire retardant matter 4 at a temperature of less than 100 DEG C
It is wrapped in the wrapper, and the diaphragm seal item 2 can occur to soften and rupture at 100~170 DEG C, so as to cause described
Encapsulation containment wall ruptures and the fire retardant matter in the wrapper is discharged to outside the wrapper.
According to disclosure second aspect, in order to remain potted the stability of packet under normal use, the outer membrane
Tensile strength can be higher than the tensile strength of the diaphragm seal item；The tensile strength of the outer membrane can be 50~4000MPa；
The softening temperature of the diaphragm seal item can be 100~170 DEG C.
According to disclosure second aspect, in order to keep the performance of the wrapper, the material of the outer membrane that can be selected from
At least one of polyethylene terephthalate, polyurethane, polyimides and polypropylene；The material of the diaphragm seal item can
To be selected from least one of polyethylene, polyvinyl chloride and olefin copolymer；Select polymer compound film made of above-mentioned material
Tensile strength and diaphragm seal softening temperature be suitable for make wrapper.
According to disclosure second aspect, in order to prevent in battery solvent volatilize flash burn, the preferred tricresyl phosphate of fire retardant matter
Methyl esters, methyl-phosphoric acid dimethyl ester, three-(2,2,2)-trifluoroethyl phosphite ester, three-(2,2,2)-trifluoroethyl phosphate and phosphine
At least one of nitrile；It is in terms of 100% by the weight of the wrapper, the content of the fire retardant matter is 10-50%；The dosage
Three-(2,2,2)-trifluoroethyl phosphite esters can reach preferable flame retardant effect, and three-(2,2,2)-trifluoroethyls are sub-
Phosphate does not influence the safety of lithium ion battery.
According to disclosure second aspect, as another preferably technical solution of the disclosure, in order to make battery be lost in heat
Can be risen brokenly failure before control, and the fire retardant matter also contains the substance that can be decomposed at 100~130 DEG C and generate carbon dioxide；It is excellent
Selection of land, it is described by the weight of the wrapper be 100% in terms of, it is described can decompose generate carbon dioxide material content can be
10~50%.
According to disclosure second aspect, the substance that can decompose generation carbon dioxide can be selected from acetic anhydride, carbonic acid
At least one of ammonium, sodium bicarbonate, malonic acid and basic copper carbonate.
The disclosure third aspect provides a kind of fire-retardant wrapper being prepared using preparation method as described above.
Disclosure fourth aspect provides a kind of lithium ion battery containing above-mentioned wrapper.
The lithium ion battery in addition to it is interior containing above-mentioned wrapper other than, can also include shell and the electricity that is contained in housing
Core, nonaqueous electrolytic solution, battery core include anode, cathode and the diaphragm between positive electrode and negative electrode.Wherein lithium ion battery is being just
It is conventional use of each that those skilled in the art may be used in pole piece, the preparation of negative plate and diaphragm and the assembling of lithium ion battery
Kind method, the disclosure are not particularly limited this.
According to disclosure fourth aspect, in order to make the security performance of lithium ion battery improve, while to lithium ion battery
Energy density does not generate big influence, and the weight ratio of the wrapper and lithium-ion battery electrolytes is 1：(4~99)；It is preferred that
The weight ratio of ground, the wrapper and lithium-ion battery electrolytes is 1：(5~19).
The disclosure is further illustrated below by embodiment, but the disclosure is not therefore any way limited.
Embodiment 1
(1) preparation of wrapper：
Using a piece of rectangle thickness be 50 μm of tensile strengths be 3000MPa polyethylene terephthalate film as outer
Tunic, it is hot-forming after doubling that the prefabricated membrane bag on one side with sealing is made；It is 30 μm soft that thickness is preset on the inside of the sealing
Change the polyethylene film item that temperature is 120 DEG C；1.2g tri--(2,2,2)-trifluoroethyl phosphite ester is injected into the prefabricated membrane bag
Afterwards, the wrapper for sealing and the present embodiment being prepared is closed in thermal welding.
(2) preparation of positive plate：
By LiCoO285 are pressed with acetylene black, Kynoar：10：5 weight ratio is uniformly mixed, and solvent is added, is made just
Pole slurry, is uniformly coated on aluminium foil, and positive plate is made in dry and rolling.
(3) preparation of negative plate：
By P15B graphite and butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) with 100：3：2 weight ratio is uniformly mixed,
Solvent is added, negative electrode slurry is made, is uniformly coated on copper foil, dry and roll-in is worth negative plate.
(4) preparation of electrolyte：
Fluorinated ethylene carbonate (FEC), diethyl carbonate (DEC), ethylene carbonate (EC), methyl ethyl carbonate (EMC), carbon
Vinyl acetate (VC) is with 5：45：25：23：Solute LiPF is added in the in the mixed solvent in 2 mass ratio mixing6It is made
The electrolyte of 1.0mol/L.
(5) assembly of battery
It is prepared by soft-package battery：By the positive plate being prepared in the present embodiment, negative plate, electrolyte and Celgard2300
Type micro-pore septum is assembled into soft-package battery；The wrapper prepared in the present embodiment (1) step is added in argon gas glove box, it is close
It is honored as a queen and the lithium ion battery containing wrapper of the present embodiment is prepared.
Embodiment 2
(1) preparation of wrapper：
Using a piece of rectangle thickness be 60 μm of tensile strengths be 4000MPa polyethylene terephthalate film as outer
Tunic, it is hot-forming after doubling that the prefabricated membrane bag on one side with sealing is made；It is 20 μm soft that thickness is preset on the inside of the sealing
Change the polyethylene film item that temperature is 120 DEG C；After 0.1g ammonium carbonates and 1.3g trimethyl phosphates being injected into the prefabricated membrane bag, heat
The wrapper for sealing and the present embodiment being prepared is closed in welding.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, and the present embodiment is prepared
The lithium ion battery containing wrapper.
Embodiment 3
(1) preparation of wrapper：
Using a piece of rectangle thickness be 80 μm of tensile strengths be 4000MPa polyethylene terephthalate film as outer
Tunic, it is hot-forming after doubling that the prefabricated membrane bag on one side with sealing is made；It is 20 μm soft that thickness is preset on the inside of the sealing
Change the polyethylene film item that temperature is 120 DEG C；0.3g acetic anhydrides and 1.1g methyl-phosphoric acid dimethyl esters are injected into the prefabricated membrane bag
Afterwards, the wrapper for sealing and the present embodiment being prepared is closed in thermal welding.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, and the present embodiment is prepared
The lithium ion battery containing wrapper.
Embodiment 4
(1) preparation of wrapper：
Using a piece of rectangle thickness be 80 μm of tensile strengths be 4000MPa polyethylene terephthalate film as outer
Tunic, it is hot-forming after doubling that the prefabricated membrane bag on one side with sealing is made；It is 10 μm soft that thickness is preset on the inside of the sealing
Change the polyethylene film item that temperature is 120 DEG C；After 0.2g sodium bicarbonates and 1.2g phosphine nitriles being injected into the prefabricated membrane bag, thermal welding
Close the wrapper for sealing and the present embodiment being prepared.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, and the present embodiment is prepared
The lithium ion battery containing wrapper.
Embodiment 5
(1) preparation of wrapper：
Using a piece of rectangle thickness be 70 μm of tensile strengths be 2000MPa polyurethane film as outer membrane, it is hot after doubling
It is molded that the prefabricated membrane bag on one side with sealing is made；It is 100 DEG C that preset thickness on the inside of the sealing, which be 20 μm of softening temperatures,
Polychloroethylene film item；0.2g malonic acid and 1.3g tri--(2,2,2)-trifluoroethyl phosphorous acid are injected into the prefabricated membrane bag
After ester, the wrapper for sealing and the present embodiment being prepared is closed in thermal welding.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, this comparative example is prepared
The lithium ion battery containing wrapper.
Embodiment 6
(1) preparation of wrapper：
Using a piece of rectangle thickness be 60 μm of tensile strengths be 4000MPa polyimide film as outer membrane, after doubling
It is hot-forming that the prefabricated membrane bag on one side with sealing is made；It is 120 that preset thickness on the inside of the sealing, which be 20 μm of softening temperatures,
DEG C polyethylene film item；0.1g ammonium carbonates and 1.2g tri--(2,2,2)-trifluoroethyl phosphorous acid are injected into the prefabricated membrane bag
After ester, the wrapper for sealing and the present embodiment being prepared is closed in thermal welding.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, and the present embodiment is prepared
The lithium ion battery containing wrapper.
Embodiment 7
(1) preparation of wrapper：
Using a piece of rectangle thickness be 60 μm of tensile strengths be 500MPa polypropylene screen as outer membrane, hot pressing after doubling
The prefabricated membrane bag on one side with sealing is made in molding；It is 120 DEG C that preset thickness on the inside of the sealing, which be 20 μm of softening temperatures,
Polyethylene film item；After 0.1g ammonium carbonates and 1.2g tri--(2,2,2)-trifluoroethyl phosphite ester being injected into the prefabricated membrane bag,
The wrapper for sealing and the present embodiment being prepared is closed in thermal welding.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, and the present embodiment is prepared
The lithium ion battery containing wrapper.
Embodiment 8
(1) preparation of wrapper：
Using a piece of rectangle thickness be 60 μm of tensile strengths be 500MPa polypropylene screen as outer membrane, hot pressing after doubling
The prefabricated membrane bag on one side with sealing is made in molding；It is 100 DEG C that preset thickness on the inside of the sealing, which be 20 μm of softening temperatures,
Polychloroethylene film item；0.1g ammonium carbonates and 1.2g tri--(2,2,2)-trifluoroethyl phosphite ester are injected into the prefabricated membrane bag
Afterwards, the wrapper for sealing and the present embodiment being prepared is closed in thermal welding.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, and the present embodiment is prepared
The lithium ion battery containing wrapper.
Comparative example 1
Positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, this comparative example is prepared
Lithium ion battery without containing wrapper.
Comparative example 2
(1) preparation of wrapper：
It is hot-forming to be prepared into one after by a piece of rectangle thickness being the polyethylene film doubling that 90 μm of tensile strengths are 6Mpa
Side has the prefabricated membrane bag of sealing；0.2g sodium bicarbonates and 1.2g tri--(2,2,2)-trifluoroethyl phosphite ester injection is prefabricated
In film bag；The sealing of the prefabricated membrane bag is closed in heat-sealing, and the wrapper of this comparative example is prepared.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, this comparative example is prepared
The lithium ion battery containing wrapper.
Comparative example 3
(1) preparation of wrapper：
It is the polyethylene terephthalate film doubling that 90 μm of tensile strengths are 4000Mpa by a piece of rectangle thickness
Afterwards, the hot-forming side that is prepared into has the prefabricated membrane bag of sealing；By 0.2g sodium bicarbonates and 1.2g tri--(2,2,2)-trifluoro second
Base phosphite ester injects in prefabricated membrane bag；The sealing of the prefabricated membrane bag is closed in heat-sealing, and the wrapper of this comparative example is prepared.
(2) positive plate, negative plate, the preparation of electrolyte and battery assembly are same as Example 1, this comparative example is prepared
The lithium ion battery containing wrapper.
Testing example 1
This testing example was used to measure in the expiring and fill of the lithium ion battery obtained in embodiment 1-8 and comparative example 1-3
Resistance, battery capacity and security performance.
Completely fill inner walkway：Under conditions of 25 ± 3 DEG C, lithium ion battery is charged to the continuous current of 0.1C
100%SOC, 4h is stood after the completion of to be charged, is then used the internal resistance of internal resistance instrument test 1000Hz lithium ion batteries, is taken test
The average value of the 1000Hz internal resistances of all lithium ion batteries fills internal resistance to weigh expiring for lithium ion battery.Concrete outcome is shown in Table 1.
Volume test：Under conditions of 25 ± 3 DEG C, with 0.5C constant-current charge 2h, constant-voltage charge is then carried out again to electric current
It is reduced to 0.05C；Then stand 5min, then in a manner of constant-current discharge (wherein, discharge current 1C, discharge time 1h) into
The discharge capacity that lithium ion battery is tested after row electric discharge, takes being averaged for the 1C discharge capacities for all lithium ion batteries that test obtains
Value weighs the capacity of lithium ion battery.Concrete outcome is shown in Table 1.
Safety test is divided into lancing test, furnace temperature test and squeezes test.
Lancing test：Under conditions of 25 ± 3 DEG C, lithium ion battery is charged to 100% with the continuous current of 0.1C
SOC carries out lancing test using the needle of a diameter of 8mm through lithium ion battery；
Furnace temperature is tested：Under conditions of 25 ± 2 DEG C, lithium ion battery is charged to 100% with the continuous current of 0.1C
SOC, by sample be put into oven with 5 ± 2 DEG C of rates per minute be warming up to 170 ± 2 DEG C switch to constant temperature and keep 60 minutes；
Squeeze test：Under conditions of 25 ± 3 DEG C, lithium ion battery is charged to 100% with the continuous current of 0.1C
SOC places it in extrusion equipment (its pressure is 50 tons) and carries out extruding test；
The criterion of lithium ion battery safety test is：As pass through without explosion, without on fire, statistics passes through safety test
The number of lithium ion battery can be used for analyzing.Concrete outcome is shown in Table 1.
Table 1
Through embodiment 1-8 in table 1 compared with comparative example 1-3 it can be seen that the lithium with wrapper that is prepared of the disclosure from
Sub- battery makes wrapper occur to rupture the flame retardant released in capsule-core before the temperature for reaching battery maximum probability generation thermal runaway
Matter reduces the generation of safety accident, especially capsule-core and generates dioxy added with decomposition to increase the safety of lithium ion battery
Changing the lithium ion battery of the substance of carbon can rise brokenly by battery before thermal runaway, and obtained lithium ion battery safety performance is more
It is excellent.
The preferred embodiment of the disclosure is described in detail above in association with attached drawing, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection domain of the disclosure.Such as.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the disclosure to it is various can
The combination of energy no longer separately illustrates.
In addition, arbitrary combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (17)
1. a kind of fire-retardant wrapper, including encapsulation containment wall and the fire retardant matter (4) that is wrapped in wrapper, which is characterized in that institute
State the diaphragm seal item that encapsulation containment wall includes the outer membrane (1) and the closing sealing (3) with sealing (3) and insoluble in electrolyte
(2)；The encapsulation containment wall holding structure can be stablized so that the fire retardant matter (4) to be wrapped at a temperature of less than 100 DEG C
In the wrapper, and the diaphragm seal item (2) can occur to soften and rupture at 100~170 DEG C, so as to cause the encapsulation
Containment wall ruptures and the fire retardant matter in the wrapper is discharged to outside the wrapper.
2. fire-retardant wrapper according to claim 1, wherein the tensile strength of the outer membrane (1) is higher than the sealing
The tensile strength of film item (2)；The tensile strength of the outer membrane (1) is 50~4000MPa.
3. fire-retardant wrapper according to claim 1, wherein the softening temperature of the diaphragm seal item (2) is 100~170
℃。
4. fire-retardant wrapper according to claim 1, wherein the material of the outer membrane (1) is selected from poly terephthalic acid
At least one of glycol ester, polyurethane, polyimides and polypropylene；The material of the diaphragm seal item (2) be selected from polyethylene,
At least one of polyvinyl chloride and olefin copolymer.
5. fire-retardant wrapper according to claim 1, wherein the outer membrane (1) is formed to have sealing (3) and is bag
The prefabricated membrane bag of shape structure is simultaneously filled with the fire retardant matter (4), and the both sides inner surface of the sealing (3) be incorporated in it is described
On two side external surfaces of diaphragm seal item (2).
6. fire-retardant wrapper according to claim 5, wherein the prefabricated membrane bag is a piece of outer membrane doubling fitting
And the prefabricated membrane bag that unclosed sealing (3) is formed afterwards is reserved in partially enclosed corresponding edge simultaneously；
Alternatively, the prefabricated membrane bag is bonded each other for outer membrane described in two panels and partially enclosed corresponding edge is reserved simultaneously unclosed
The prefabricated membrane bag that is formed afterwards of sealing (3)；
Wherein, the diaphragm seal item (2) in non-closed state is provided in unclosed sealing (3)；
Side of some or all of the described diaphragm seal item (2) in non-closed state only with the unclosed sealing (3)
Inner surface combines, without being combined with the other side inner surface of the unclosed sealing (3).
7. fire-retardant wrapper according to claim 1, wherein the fire retardant matter contains trimethyl phosphate, methyl acid phosphate
At least one in dimethyl ester, three-(2,2,2)-trifluoroethyl phosphite ester, three-(2,2,2)-trifluoroethyl phosphate and phosphine nitrile
Kind；It is in terms of 100% by the weight of the wrapper, the content of the fire retardant matter is 10~90%.
8. fire-retardant wrapper according to claim 1, wherein the fire retardant matter also contains can be at 100-130 DEG C point
Solution generates the substance of carbon dioxide；Preferably, described to decompose generation dioxy in terms of by the weight of the wrapper for 100%
The content for changing carbonizable substance is 10~80%；It is highly preferred that the substance for generating carbon dioxide that can decompose is selected from acetic anhydride, carbon
At least one of sour ammonium, sodium bicarbonate, malonic acid and basic copper carbonate.
9. a kind of preparation method of fire-retardant wrapper, which is characterized in that the preparation method includes the following steps：
S1, the outer membrane doubling that a piece of at least partly edge is combined with to diaphragm seal item are bonded, then partially enclosed corresponding edge,
Reserved unclosed sealing simultaneously, forms prefabricated membrane bag；Alternatively, two panels at least partly edge to be combined with to the outer layer of diaphragm seal item
Film is bonded each other, then partially enclosed corresponding edge, while reserved unclosed sealing, forms prefabricated membrane bag；
Wherein, the diaphragm seal item (2) in non-closed state is provided in unclosed sealing (3)；
Side of some or all of the described diaphragm seal item (2) in non-closed state only with the unclosed sealing (3)
Inner surface combines, without being combined with the other side inner surface of the unclosed sealing (3)；
S2, fire retardant matter is inserted in the prefabricated membrane bag；
S3, the unclosed sealing (3) is closed by hot pressing, form encapsulation containment wall；
Wherein, the encapsulation containment wall holding structure can be stablized to wrap the fire retardant matter (4) at a temperature of less than 100 DEG C
It is rolled in the wrapper, and the diaphragm seal item (2) can occur to soften and rupture at 100~170 DEG C, so as to cause described
Encapsulation containment wall ruptures and the fire retardant matter in the wrapper is discharged to outside the wrapper.
10. preparation method according to claim 9, wherein the tensile strength of the outer membrane (1) is higher than the diaphragm seal
The tensile strength of item (2)；The tensile strength of the outer membrane (1) is 50~4000MPa.
11. preparation method according to claim 9, wherein the softening temperature of the diaphragm seal item (2) is 100~170
℃。
12. preparation method according to claim 9, wherein the material of the outer membrane (1) is selected from poly terephthalic acid second
At least one of diol ester, polyurethane, polyimides and polypropylene；The material of the diaphragm seal item (2) is selected from polyethylene, gathers
At least one of vinyl chloride and olefin copolymer.
13. preparation method according to claim 9, wherein the fire retardant matter contains trimethyl phosphate, methyl acid phosphate two
Methyl esters, three-(2,2,2)-trifluoroethyl phosphite ester, three-(2,2,2)-at least one of trifluoroethyl phosphate and phosphine nitrile；
It is in terms of 100% by the weight of the wrapper, the content of the fire retardant matter is 10~90%.
14. preparation method according to claim 9, wherein the fire retardant matter, which also contains, to be decomposed at 100-130 DEG C
Generate the substance of carbon dioxide；Preferably, described to decompose generation titanium dioxide in terms of by the weight of the wrapper for 100%
The content of carbonizable substance is 10~80%；It is highly preferred that the substance for generating carbon dioxide that can decompose is selected from acetic anhydride, carbonic acid
At least one of ammonium, sodium bicarbonate, malonic acid and basic copper carbonate.
15. the fire-retardant wrapper that the preparation method described in any one of claim 9-14 is prepared.
16. a kind of lithium ion battery containing the fire-retardant wrapper described in any one of claim 1-8 and claim 15.
17. lithium ion battery according to claim 16, wherein the fire-retardant wrapper and lithium-ion battery electrolytes
Weight ratio is 1：(4~99)；Preferably, the weight ratio of the fire-retardant wrapper and lithium-ion battery electrolytes is 1：(5~19).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710210733.1A CN108666465A (en) | 2017-03-31 | 2017-03-31 | A kind of fire-retardant wrapper and its lithium ion battery |
| PCT/CN2018/071493 WO2018176980A1 (en) | 2017-03-31 | 2018-01-05 | Flame-retardant package and lithium-ion battery thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710210733.1A CN108666465A (en) | 2017-03-31 | 2017-03-31 | A kind of fire-retardant wrapper and its lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108666465A true CN108666465A (en) | 2018-10-16 |
Family
ID=63674255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710210733.1A Pending CN108666465A (en) | 2017-03-31 | 2017-03-31 | A kind of fire-retardant wrapper and its lithium ion battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108666465A (en) |
| WO (1) | WO2018176980A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433419A (en) * | 2019-06-28 | 2019-11-12 | 浙江南都电源动力股份有限公司 | Lithium electric heating uncontrolled fire inhibits capsule and lithium ion battery |
| CN111584926A (en) * | 2020-05-07 | 2020-08-25 | 珠海冠宇动力电池有限公司 | Lithium ion battery and preparation method thereof |
| WO2023070546A1 (en) * | 2021-10-29 | 2023-05-04 | 宁德时代新能源科技股份有限公司 | Slow-release device for battery, and secondary battery comprising same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114552013B (en) * | 2022-02-25 | 2023-08-22 | 蜂巢能源科技股份有限公司 | Flame-retardant electrolyte and preparation method and application thereof |
| CN115160689B (en) * | 2022-06-29 | 2023-09-29 | 国网浙江省电力有限公司湖州供电公司 | Flame retardant material for lithium ion battery packaging and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018176980A1 (en) | 2018-10-04 |
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Application publication date: 20181016 |