CN101471434A - Capsule and battery containing the same - Google Patents
Capsule and battery containing the same Download PDFInfo
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- CN101471434A CN101471434A CNA2007103014862A CN200710301486A CN101471434A CN 101471434 A CN101471434 A CN 101471434A CN A2007103014862 A CNA2007103014862 A CN A2007103014862A CN 200710301486 A CN200710301486 A CN 200710301486A CN 101471434 A CN101471434 A CN 101471434A
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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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Abstract
The invention provides a capsule, which comprises a shell and a material in the shell, wherein the shell is made of a incombustible material with a melting point of 100 to 130 DEG C and capable of stably existing in the a battery electrolyte; and the gasification temperature of the material in the shell is lower than the melting point of the shell, and can generate a fire retardant gas when being gasified. The invention also provides a battery, which comprises an electrode core, an electrolyte and a battery shell, which the electrode core and the electrolyte are arranged in the battery shell; the electrode core includes a positive electrode, a negative electrode and a diaphragm between the positive electrode and the negative electrode; the positive electrode contains a positive current collector and a negative active material attached on the positive current collector; and the negative electrode includes a negative current collector and a negative active material attached on the negative current collector. The battery also includes the capsule provided in the invention, wherein the capsule is arranged in the battery shell. An anti-explosion hole of the battery having the capsule can be opened to respond to the melting temperature of the capsule shell material to achieve more sensitive battery discharge response.
Description
Technical field
The present invention relates to a kind of capsule and the battery that comprises this capsule.
Background technology
It is little that lithium ion battery has a volume, the energy height, and advantage such as pollution-free has been applied to mobile phone, portable electronic products such as digital camera more and more widely.
Along with the extensive use of lithium ion battery, the security performance of lithium ion battery also more and more comes into one's own.The contingent safety problem of lithium ion battery mainly is: because improper use or other reasons cause inside battery to overcharge; Perhaps under exceedingly odious environment,, cause the local micro-short circuit of inside battery such as unexpected high temperature, bump etc.; The unusual intensification, the material generation chemical reaction in the battery, normally pyrolysis causes temperature further to raise.At high temperature, normally more than 120 ℃ (battery outside wall temperature), various reactions taking place generate a large amount of gases, might cause air pressure inside to increase rapidly, break through the battery shell wall, causes blast; After shell wall breaks, external oxygen and electrolyte inside and the reaction of various material, it is on fire to burn; Above situation is commonly referred to as thermal runaway.It is breakneck thermal runaway occurring.
At present, the main means that prevent battery generation thermal runaway have: adopt PTC material (PTC) thermistor, diaphragm paper and explosionproof hole.
PTC thermistor and diaphragm paper mechanism of action are similar, promptly fuse at a certain temperature or the fusion closed pore, cut off external charge current.These two kinds of modes that method all is temperature responses, reaction are relatively sensitiveer.Although these two kinds of methods can be cut off battery and outside getting in touch, can not stop this inside battery to continue to react and the danger that may cause.Therefore, only there is potential safety hazard in the safety device of response temperature.
Explosionproof hole as explosion-proof impression and explosion-proof valve, generally is meant thinner region on the cover board.Explosionproof hole is the safety device of response inside battery air pressure.When the air pressure of the gas that produces when inside battery met or exceeded the critical value of explosionproof hole, explosionproof hole was opened, and gas release is come out, and reduces the pressure of inside battery, broke and blasted thereby avoid occurring the battery shell wall.
What explosionproof hole responded is inside battery air pressure, and gas flow and temperature decision that air pressure is generated by reaction.In some cases, internal temperature of battery is very high, and under the few situation of the gas flow that generates, inside battery air pressure does not also reach the critical value of explosionproof hole.Yet because at high temperature reaction pyrolysis normally, along with reaction is carried out, temperature continues to raise.When reaching certain high temperature, many decomposition reactions are carried out simultaneously, thereby produce a large amount of gases in very short time, and pressure increases sharply, thereby has caused thermal runaway.In addition, even explosionproof hole is in time opened, still there is unsafe factor.Because under the situation that the battery internal and external environment communicates, external oxygen might enter inside battery, at high temperature burns on fire with inner combustible.Although the area of explosionproof hole is very little, this being still within the bounds of possibility.Therefore, only also there is potential safety hazard in the safety device of response pressure.
Summary of the invention
The objective of the invention is in order to overcome the relatively poor defective of battery thermal safety that prior art provides, a kind of battery that makes battery have the high capsule of thermal safety and comprise this capsule is provided.
The invention provides a kind of capsule, this capsule comprises shell and parcel material in the enclosure, wherein, described shell is that 100-130 ℃ and incombustible that can stable existence in battery electrolyte form by fusing point, the gasification temperature of described parcel material in the enclosure is lower than the fusing point of described shell, and the gas that gasification forms is anti-flammability gas.
The present invention also provides a kind of battery, this battery comprises pole piece, electrolyte and battery case, described pole piece and electrolyte level are in battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises plus plate current-collecting body and attached to the positive electrode active materials on the plus plate current-collecting body, described negative pole comprises negative current collector and attached to the negative active core-shell material on the negative current collector, wherein, described battery also wraps capsule provided by the invention, and described capsule is positioned at battery case.
Capsule provided by the invention, because the fusing point that forms its outer shell matter is lower than the temperature of common generation thermal runaway at 100-130 ℃, and the gasification temperature of parcel material in the enclosure is lower slightly than the melting temperature of corresponding outer shell matter, as 90-120 ℃.Therefore, when using capsule provided by the invention in battery, during the melting temperature of shell matter, on the one hand, shell begins to melt the shell wall attenuation when the temperature of inside battery reaches outside; On the other hand, because the continuous endothermic gasification of material in the capsule, the capsule internal pressure increases sharply, so capsule breaks very soon.Capsules break discharges a large amount of non-flammable gases, and a large amount of non-flammable gases increases sharply inside battery air pressure and reaches the explosionproof hole critical value very soon, and explosionproof hole is opened, the battery pressure release.Therefore, the temperature of inside battery has directly determined opening of explosionproof hole, adopts this control methods, makes the pressure release response sensitiveer, has avoided the generation of some fortuitous events.
In a preferred embodiment of the present invention, capsule discharges a large amount of non-flammable gases when breaking be anti-flammability gas methylene bromide.Methylene bromide can generate the Br free radical, can with battery in and cause in the oxygen battery catch fire the blast the hydroxyl free radical combination, thereby stop the hydroxyl free radical chain reaction, end the reaction of inside battery, thereby avoided because the danger that inside battery continues to react and causes.On the other hand, after explosionproof hole is opened, the fire-retardant gas such as the methylene bromide that discharge in the capsule cover around the battery, have avoided air to enter in the battery by explosionproof hole, thereby have avoided the gas in the battery because the situation that may occur of burning takes place in the oxygen contact.
Embodiment
Capsule provided by the invention comprises shell and parcel material in the enclosure, wherein, described shell is that 100-130 ℃ and incombustible that can stable existence in electrolyte form by fusing point, the gasification temperature of described parcel material in the enclosure is 90-120 ℃, and the gas that gasification forms is fire-retardant gas.
According to capsule provided by the invention, although can realize purpose of the present invention as long as the gasification temperature of described parcel material in the enclosure is lower than the fusing point of described shell, but under the preferable case, the gasification temperature of described parcel material in the enclosure hangs down 3-10 ℃ than the fusing point of described shell, can guarantee more effectively that like this thermal runaway does not take place battery, control internal temperature of battery (internal temperature of battery is usually than the high 10-30 of battery outside wall temperature ℃) usually below 130 ℃.This is that the interior temperature of capsule also is lower than this melting temperature because when temperature reaches in the battery outside during the melting temperature of shell matter; Because gasification substance is the process of heat absorption, have only the external world that heat can constantly be provided again, constantly gasification of material.Therefore, material when the melting temperature that makes the gasification temperature of material in the capsule be lower than outer shell matter slightly helps guaranteeing the melting point values of shell matter outside temperature reaches in battery in the capsule gasifies, thereby guarantee when capsules break, material all becomes anti-flammability gas in the capsule, the pressure of inside battery is increased sharply, help like this realizing that temperature accurately regulates pressure release.
In the present invention, described shell can be 1:4-4:1 with the weight ratio of parcel material in the enclosure, is preferably 1:3-3:1.
Described capsule particle average particle diameter can be the 150-500 micron, is preferably the 150-300 micron.
The wall thickness of described shell can be the 3-100 micron, is preferably the 5-50 micron.
In the present invention, described material that can stable existence in electrolyte is meant at normal temperature and high temperature, as below 130 ℃, not with existing any electrolyte in any material react, and,, also be not dissolved in existing any electrolyte as below 130 ℃ at normal temperature and high temperature.These materials all can be commercially available, can be some macromolecular materials as the Main Ingredients and Appearance that forms shell, as being selected from epoxy resin, gelatin and the Arabic gum one or more; As the auxiliary composition such as the emulsifying agent that form shell, can be selected from sorbester p17, formaldehyde, glutaraldehyde and the Meng alkane diamines one or more.Wherein, account for 1-10 weight % as the auxiliary composition that forms shell as the weight of the Main Ingredients and Appearance that forms shell.With the shell that above-mentioned substance and proportioning form, its fusing point is between 100-130 ℃.
Described battery electrolyte can be a various battery electrolyte of the prior art, for example, can be electrolyte of lithium-ion secondary battery or lithium ion polymer battery electrolyte.
As a kind of preferred embodiment, capsule provided by the invention discharges a large amount of non-flammable gases when breaking be anti-flammability gas, as, methylene bromide.Methylene bromide can generate the Br free radical, can with battery in and cause in the oxygen battery catch fire the blast the hydroxyl free radical combination, thereby stop the hydroxyl free radical chain reaction, end the reaction of inside battery, thereby avoided because the danger that inside battery continues to react and causes.On the other hand, after explosionproof hole is opened, the fire-retardant gas such as the methylene bromide that discharge in the capsule cover around the battery, have avoided air to enter in the battery by explosionproof hole, thereby have avoided the gas in the battery because the situation that may occur of burning takes place in the oxygen contact.
Can prepare capsule of the present invention according to the method for preparing capsule of routine, mix earlier with parcel material in the enclosure as the Main Ingredients and Appearance that will form shell, then under 60-90 ℃, pressure is to mix under the 2-4 MPa, add the auxiliary composition that forms shell again, continuing to mix, is 25-50 ℃ of cooling down under the 2-4 MPa at pressure at last, forms capsule.Wherein, the material that forms shell is 1:4-4:1 with the weight ratio of wrapping up material in the enclosure, is preferably 1:3-3:1.Formed capsule particle average particle diameter can be the 150-500 micron, is preferably the 150-300 micron.The wall thickness of formed capsule particle shell can be the 3-100 micron, is preferably the 5-50 micron.The material of described formation shell can be in epoxy resin, gelatin and the Arabic gum one or more; Parcel material in the enclosure is preferably methylene bromide.The auxiliary composition of described formation shell can be an emulsifying agent, as being in sorbester p17, formaldehyde, glutaraldehyde and the Meng alkane diamines one or more.
Method according to routine prepares battery, as preparation lithium rechargeable battery or lithium ion polymer battery.Battery provided by the invention comprises pole piece, electrolyte and battery case, described pole piece and electrolyte level are in battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises plus plate current-collecting body and attached to the positive electrode active materials on the plus plate current-collecting body, described negative pole comprises negative current collector and attached to the negative active core-shell material on the negative current collector, wherein, described battery also comprises capsule provided by the invention, and described capsule is positioned at battery case.
In the present invention, the content of described capsule discharges capsulated material when this capsules break the formed air pressure of gas is not less than the critical value of explosionproof hole, and the weight of preferred capsule and volume of battery are than being 5-50 gram/rice
3
The mean particle diameter of the capsule that battery provided by the invention comprises is the 150-500 micron.
Described capsule can be positioned on the surface of not adhering to positive electrode active materials of plus plate current-collecting body, also can be positioned on the surface of not adhering to negative active core-shell material of negative current collector; Described capsule also can be positioned on the internal surface of battery shell.When capsule attached to collector on or during internal surface of battery shell, with described capsule and solvent and adhesive mixing, make slurry, be coated on the described collector or on the internal surface of battery shell.Used solvent can be an any or multiple solvent used in the battery, as, n-formyl sarcolysine base pyrrolidones, dimethylformamide, one or more in dimethylacetylamide and the water; Used adhesive can be an any or multiple adhesive used in the battery, as polyvinylidene fluoride, and poly-difluoroethylene and butadiene-styrene rubber etc.
Can by conventional method with described capsules disperse in electrolyte, as, stir or ultrasonic.
In battery provided by the invention, the battery safety that contains capsule provided by the invention in the electrolyte is best.This be because internal temperature of battery from electric in-core portion to the battery inwall, temperature presents decline trend.Because electrolyte and electric core are the most approaching, the capsules break temperature is more near the inside battery actual temperature, and therefore the response time that explosionproof hole is opened is safest also early.
Embodiment 1
This enforcement is used to illustrate capsule provided by the invention and preparation method thereof.
With bisphenol A type epoxy resin E-51 (epoxide equivalent 190, Shanghai Resin Factory) and methylene bromide mix, under 60 ℃, pressure is to mix under 2 MPas, add then sorbester p17 (Guangzhou rapid development trade Co., Ltd) and the Meng alkane diamines, continue to mix, 30 ℃ of coolings down under 2 MPas at last form capsule.Wherein, the total weight of the material of formation capsule shell and the weight ratio of methylene bromide are 1:4, and sorbester p17 accounts for 1 weight % of bisphenol A type epoxy resin E-51 weight, and the Meng, the alkane diamines accounted for 8 weight % of bisphenol A type epoxy resin E-51 weight.The average particle diameter of capsule particle is 200 microns, and outer casing thickness is 5 microns.(capsule broken wall temperature herein is exactly the temperature of capsule wall when breaking to capsule broken wall temperature.) be 115 ℃.
Embodiment 2
This enforcement is used to illustrate capsule provided by the invention and preparation method thereof.
Gelatin (east, Cangzhou beeswax glue industry Co., Ltd) and methylene bromide are mixed, under 70 ℃, pressure is to mix under 3 MPas, add sorbester p17 (Guangzhou rapid development trade Co., Ltd) and glutaraldehyde then, continue to mix, 35 ℃ of coolings down under 3 MPas at last form capsule.Wherein, the total weight of the material of formation capsule shell and the weight ratio of methylene bromide are 2:3, and sorbester p17 accounts for 1 weight % of gelatin weight, and glutaraldehyde accounts for 8 weight % of gelatin weight.500 microns of capsule diameter, outer casing thickness are 100 microns.Capsule broken wall temperature is 125 ℃.
Embodiment 3
This enforcement is used to illustrate capsule provided by the invention and preparation method thereof.
With bisphenol A type epoxy resin E-51 (epoxide equivalent 190, Shanghai Resin Factory) and methylene bromide mix, under 80 ℃, pressure is to mix under 4 MPas, add then sorbester p17 (Guangzhou rapid development trade Co., Ltd) and the Meng alkane diamines, continue to mix, 40 ℃ of coolings down under 4 MPas at last form capsule.Wherein, the total weight of the material of formation capsule shell and the weight ratio of methylene bromide are 3:2, and sorbester p17 accounts for 1 weight % of bisphenol A type epoxy resin E-51 weight, and the Meng, the alkane diamines accounted for 8 weight % of bisphenol A type epoxy resin E-51 weight.150 microns of capsule diameter, outer casing thickness are 30 microns.Capsule broken wall temperature is 120 ℃.
Embodiment 4
This enforcement is used to illustrate capsule provided by the invention and preparation method thereof.
Arabic gum (east, Cangzhou beeswax glue industry Co., Ltd) and methylene bromide are mixed, under 90 ℃, pressure is to mix under 4 MPas, add sorbester p17 (Guangzhou rapid development trade Co., Ltd) and formaldehyde then, continue to mix, 50 ℃ of coolings down under 4 MPas at last form capsule.Wherein, the total weight of the material of formation capsule shell and the weight ratio of methylene bromide are 7:3, and sorbester p17 accounts for 1 weight % of Arabic gum weight, and formaldehyde accounts for 8 weight % of Arabic gum weight.300 microns of capsule diameter, outer casing thickness are 70 microns.Capsule broken wall temperature is 120 ℃.
Embodiment 5
Present embodiment is used to illustrate lithium ion battery that comprises by capsule provided by the invention and preparation method thereof.
(1) Zheng Ji preparation
With 100 weight portion positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive polyvinylidene fluoride (PVDF), 5 weight portion conductive agent acetylene blacks join in the 40 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 40 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.9 gram negative pole compounds.
Wherein, the weight ratio of positive active material and negative electrode active material is 1.4.
(3) preparation of electrolyte
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1:1) of 1.0 mol, obtains nonaqueous electrolytic solution.Capsule and the above-mentioned nonaqueous electrolytic solution that makes that embodiment 1 is made mix.
(4) assembling of battery
The negative pole that the positive pole that (1) is obtained, membrane layer and (2) obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the LP053450 battery case of an end opening, and add 3.5 nonaqueous electrolytic solutions that contain capsule provided by the invention that restrain, make lithium ion battery after the sealing.Wherein, the battery nominal capacity is 1200 MAHs, and the weight of capsule and battery volume ratio are 33:1 gram/rice
3Make 1000 altogether, form battery pack A1.
Comparative Examples 1
Method according to embodiment 5 is carried out, and different is, does not add capsule of the present invention in the electrolyte, obtains reference cell group CA.
Embodiment 6
Present embodiment is used to illustrate lithium ion battery that comprises by capsule provided by the invention and preparation method thereof.
Method according to embodiment 5 is carried out, and different is that the capsule of employing is the capsule that embodiment 2 makes.And the weight of capsule and battery volume ratio are 50:1 gram/rice
3Make 1000 altogether, form battery pack A2.
Embodiment 7
Present embodiment is used to illustrate lithium ion battery that comprises by capsule provided by the invention and preparation method thereof.
Method according to embodiment 5 is carried out, and different is that the capsule of employing is the capsule that embodiment 3 makes.And the weight of capsule and battery volume ratio are 40:1 gram/rice
3Make 1000 altogether, form battery pack A3.
Embodiment 8
Present embodiment is used to illustrate lithium ion battery that comprises by capsule provided by the invention and preparation method thereof.
Method according to embodiment 5 is carried out, and different is that the capsule of employing is the capsule that embodiment 4 makes.And the weight of capsule and battery volume ratio are 20:1 gram/rice
3Make 1000 altogether, form battery pack A4.
Embodiment 9
This enforcement is used to illustrate battery that comprises by capsule provided by the invention and preparation method thereof.
Method according to embodiment 5 is carried out, and different is, after being coated with anode sizing agent, capsule, PVDF and the NMP of embodiment 1 preparation are mixed by weight 100:4:100, make slurry, be coated near the collector of the non-activity material of positive pole ear, surface covered is 250 millimeters
2, about 0.5 millimeter of thickness.120 ℃ of oven dry then, roll-in is cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards, wherein contains 4.8 gram cathode mixtures.The weight of coated capsule and battery volume ratio are 33:1 gram/rice
3Make 1000 altogether, form battery pack A5.
Embodiment 10
This enforcement is used to illustrate battery that comprises by capsule provided by the invention and preparation method thereof.
Method according to embodiment 5 is carried out, and different is, after being coated with cathode size, capsule, PVDF and the NMP of embodiment 1 preparation are mixed by weight 100:4:100, make slurry, be coated near the collector of the non-activity material of negative lug, surface covered is 250 millimeters
2, about 0.5 millimeter of thickness.120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns negative pole afterwards then, wherein contain 2.9 gram negative pole compounds.The weight of coated capsule and battery volume ratio are 33:1 gram/rice
3Make 1000 altogether, form battery pack A6.
Embodiment 11
This enforcement is used to illustrate battery that comprises by capsule provided by the invention and preparation method thereof.
Method according to embodiment 5 is carried out, and different is, used LP053450 battery case is coated with capsule, PVDF and NMP by embodiment 1 preparation by weight the mixture for the 100:4:100 mixing.The weight of coated capsule and battery volume ratio are 5:1 gram/rice
3Make 1000 altogether, form battery pack A7.
Embodiment 12-18
These embodiment are used to detect the performance of the battery of embodiment 5-11 preparation.
(1) internal resistance of cell test: the battery that embodiment 5-11 is made, be under 20 ± 5 ℃ the condition in ambient temperature, with 0.1C (120 milliamperes) charging 16 hours, after charging finishes, shelved 1 hour, and used BS-VR internal resistance of cell tester (a day company is held up in Guangzhou) to measure interchange (AC) resistance of battery then.
(2) battery capacity method of testing: the battery with embodiment 5-11 makes, charge with constant current 1C constant voltage 4.2V charging modes, the restriction electric current is 0.1C (120 milliamperes), final voltage is 4.2 volts; Discharge in the constant-current discharge mode, discharging current is 1C (1200 milliamperes), and the cut-ff voltage of discharge is 3.1 volts, and is recorded in the discharge voltage of the mid point of discharge curve.
(3) security performance test:,, establish cut-ff voltage and overcharge test for 12 volts with 2.85 amperes of constant current charges with the battery that embodiment 5-11 makes.There are not blast, on fire, burning for by test.The explosionproof hole break temperature that the temperature of battery case was represented when record was opened with explosionproof hole, test result is listed in the table 1.
Comparative Examples 2
Carry out according to the described method of embodiment 12-18, different is, battery adopt Comparative Examples lithium ion battery be the reference cell group.Test result is listed in the table 1.
Table 1
| Group | Average internal resistance (milliohm) | Capacity (milliampere-hour) | Test number (propping up) | By number (propping up) | Percent of pass | Explosionproof hole open mean temperature (℃) |
| A1 | 45 | 1205 | 1000 | 1000 | 100％ | 109.3 |
| A2 | 50 | 1201 | 1000 | 1000 | 100％ | 116.4 |
| A3 | 48 | 1204 | 1000 | 1000 | 100％ | 113.7 |
| A4 | 44 | 1210 | 1000 | 1000 | 100％ | 114.3 |
| A5 | 44 | 1223 | 1000 | 1000 | 100％ | 112.0 |
| A6 | 42 | 1219 | 1000 | 1000 | 100％ | 112.6 |
| A7 | 41 | 1225 | 1000 | 1000 | 100％ | 115.4 |
| CA | 42 | 1217 | 1000 | 654 | 63.4％ | / |
As can be seen from Table 1, used the battery of capsule provided by the invention, the performance of battery itself does not have to change substantially, and its to overcharge the fail safe percent of pass be 100%; And the fail safe percent of pass that overcharges of reference cell only is 63.4%.Temperature that explosionproof hole is opened and capsules break temperature are inconsistent, are because in this experiment, and the temperature that explosionproof hole is opened is that the temperature of battery case is represented when opening with explosionproof hole.The battery case temperature can be lower than about the about 10-30 of internal temperature of battery ℃ usually.And internal temperature of battery from electric in-core portion to the battery inwall, also present decline trend.The closer to electric in-core portion, temperature is high more, and just electric in-core portion and battery case difference are big more; The closer to the battery inwall, temperature is low more, and is more little with battery case difference.Therefore, even capsule all breaks at 120 ℃, the battery case temperature that presents is difference to some extent also.This also shows, the capsule of interpolation is the closer to battery battery core inside, and the capsules break temperature is more near the inside battery actual temperature, the response time that explosionproof hole is opened more early, also so safer.
Claims (14)
1, a kind of capsule, this capsule comprises shell and parcel material in the enclosure, it is characterized in that, described shell is that 100-130 ℃ and incombustible that can stable existence in battery electrolyte form by fusing point, the gasification temperature of described parcel material in the enclosure is lower than the fusing point of described shell, and the gas that gasification forms is non-flammable gases.
2, capsule according to claim 1, wherein, the gasification temperature of described parcel material in the enclosure hangs down 3-10 ℃ than the fusing point of described shell.
3, capsule according to claim 1, wherein, described shell is 1:4-4:1 with the weight ratio of parcel material in the enclosure.
4, according to any described capsule among the claim 1-3, wherein, the wall thickness of described shell is the 3-100 micron.
5, according to any described capsule among the claim 1-3, wherein, the material that forms described shell is selected from one or more in epoxy resin, gelatin and the gum arabic.
6, according to any described capsule among the claim 1-3, wherein, described parcel material in the enclosure is a methylene bromide.
7, capsule according to claim 1, wherein, described battery electrolyte is electrolyte of lithium-ion secondary battery or lithium ion polymer battery electrolyte.
8, a kind of battery, this battery comprises pole piece, electrolyte and battery case, described pole piece and electrolyte level are in battery case, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises plus plate current-collecting body and attached to the positive electrode active materials on the plus plate current-collecting body, described negative pole comprises negative current collector and attached to the negative active core-shell material on the negative current collector, it is characterized in that, described battery also comprises any described capsule among the claim 1-6, and described capsule is positioned at battery case.
9, battery according to claim 8, wherein, the weight that the content of described capsule makes capsule and volume of battery are than being 5-50 gram/rice
3
10, battery according to claim 8, wherein, the mean particle diameter of described capsule is the 150-500 micron.
11, according to Claim 8 any described battery-10, wherein, described capsule is positioned on the surface of not adhering to positive electrode active materials of plus plate current-collecting body.
12, according to Claim 8 any described battery-10, wherein, described capsule is positioned on the surface of not adhering to negative active core-shell material of negative current collector.
13, according to Claim 8 any described battery-10, wherein, described capsule is positioned on the internal surface of battery shell.
14, according to Claim 8 any described battery-10, wherein, described capsules disperse is in electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103014862A CN101471434A (en) | 2007-12-27 | 2007-12-27 | Capsule and battery containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007103014862A CN101471434A (en) | 2007-12-27 | 2007-12-27 | Capsule and battery containing the same |
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| CN101471434A true CN101471434A (en) | 2009-07-01 |
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| CNA2007103014862A Pending CN101471434A (en) | 2007-12-27 | 2007-12-27 | Capsule and battery containing the same |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500806A (en) * | 2013-10-17 | 2014-01-08 | 宁德新能源科技有限公司 | Capsule and lithium ion battery |
| CN103811711A (en) * | 2014-02-27 | 2014-05-21 | 深圳市格瑞普电池有限公司 | Lithium ion battery with capsule |
| CN103931041A (en) * | 2011-11-10 | 2014-07-16 | 三菱自动车工业株式会社 | Secondary cell |
| CN104979581A (en) * | 2014-04-11 | 2015-10-14 | 宁德时代新能源科技有限公司 | Capsule and lithium ion battery |
| CN105742728A (en) * | 2014-12-09 | 2016-07-06 | 北京有色金属研究总院 | Lithium-ion secondary battery |
| CN106384802A (en) * | 2016-11-08 | 2017-02-08 | 曙鹏科技（深圳）有限公司 | Battery diaphragm and preparation method thereof as well as lithium ion battery |
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| CN103931041B (en) * | 2011-11-10 | 2016-06-15 | 三菱自动车工业株式会社 | Secondary cell |
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| CN105742728A (en) * | 2014-12-09 | 2016-07-06 | 北京有色金属研究总院 | Lithium-ion secondary battery |
| CN106469794B (en) * | 2015-08-20 | 2019-10-15 | 江苏海四达电源股份有限公司 | A kind of method of high specific energy batteries packet internal ignition resistant cooling |
| CN106469794A (en) * | 2015-08-20 | 2017-03-01 | 江苏海四达电源股份有限公司 | A kind of method of high specific energy batteries bag internal ignition resistant cooling |
| CN106384802A (en) * | 2016-11-08 | 2017-02-08 | 曙鹏科技（深圳）有限公司 | Battery diaphragm and preparation method thereof as well as lithium ion battery |
| CN108666454A (en) * | 2017-03-31 | 2018-10-16 | 比亚迪股份有限公司 | A kind of fire-retardant wrapper and its lithium ion battery |
| CN108666454B (en) * | 2017-03-31 | 2020-10-23 | 比亚迪股份有限公司 | Flame-retardant packaging bag and lithium ion battery thereof |
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| CN109461938B (en) * | 2018-11-08 | 2022-02-18 | 桑顿新能源科技有限公司 | Microcapsule, preparation method thereof and lithium ion battery |
| 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 |
| CN112018390A (en) * | 2020-07-17 | 2020-12-01 | 清华大学 | Sandwich electrode and battery |
| CN112018445A (en) * | 2020-07-17 | 2020-12-01 | 清华大学 | Self-destruction structure, electrolyte, electrode, diaphragm and battery |
| CN112029343A (en) * | 2020-07-17 | 2020-12-04 | 清华大学 | Coating, positive plate, negative plate, diaphragm and lithium ion battery for inhibiting thermal runaway of lithium ion battery |
| CN112018390B (en) * | 2020-07-17 | 2021-09-14 | 清华大学 | Sandwich electrode and battery |
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