CN110098371A - Secondary cell and top insulator for secondary cell - Google Patents
Secondary cell and top insulator for secondary cell Download PDFInfo
- Publication number
- CN110098371A CN110098371A CN201910080012.2A CN201910080012A CN110098371A CN 110098371 A CN110098371 A CN 110098371A CN 201910080012 A CN201910080012 A CN 201910080012A CN 110098371 A CN110098371 A CN 110098371A
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- China
- Prior art keywords
- silicon rubber
- top insulator
- insulator
- fabric
- secondary cell
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Classifications
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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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
-
- 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
- H01M10/04—Construction or manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of secondary cell and the top insulator for secondary cell are disclosed, wherein the top insulator for secondary cell includes: the glass fabric formed by the weft yarn and warp thread of intermeshed glass fibers raw yarn；With the silicon rubber of coating at least one surface of glass fabric.Therefore, the characteristic of such as heat resistance and chemical resistance etc can be improved, can continuous production product, increasing yield and reduces manufacturing cost.
Description
Cross reference to related applications
This application claims on January 29th, 2018 South Korea patent application submitted the 10-2018-0010900th and in
On October 19th, 2018 South Korea patent application submitted the 10-2018-0125529th priority, will be above-mentioned special by reference
Benefit application is integrally joined to this.
Technical field
The present invention relates to a kind of top insulators and its manufacturing method for secondary cell, more specifically to one
Kind is improved in terms of the characteristic of such as heat resistance and chemical resistance etc and is inhibited during punching press (punching)
The secondary cell of the generation of dust and top insulator for secondary cell.
Background technique
In general, secondary cell includes nickel-cadmium cell, nickel-metal hydride battery, lithium ion battery and lithium ion polymer battery.
This secondary cell is just being applied to such as digital camera, P-DVD, MP3P, mobile phone, PDA, portable type game device, is moving
The small sized product of power tool, electric bicycle or the like, and such as electric vehicle and hybrid vehicle etc need height
The large product of power, energy storage device and spare energy storage device for storing excess power or renewable energy.
In general, in order to manufacture lithium secondary battery, firstly, electrode active material slurry is coated to anode current collector and
Negative electrode current collector, with manufacture anode and cathode.Then, by these electrode stacks on the two sides of partition, to form electrode assembly.
In addition, electrode assembly is accommodated in the cell housing, electrolyte is injected, is then sealed.
According to the material of the shell of accommodate electrod component, this secondary cell is divided into bag type secondary battery and the secondary electricity of pot
Pond.In bag type secondary battery, electrode assembly is accommodated in the bag made of the flexible polymer material with shape-variable.
In addition, electrode assembly is accommodated in the shell made of the metal or plastic material with predetermined shape in can type secondary battery
In body.
According to the shape of battery case, can type secondary battery, which is divided into wherein shell, has the prismatic of polygonal shape secondary
Battery and wherein battery case have the cylinder type secondary battery of cylindrical shape.
Fig. 1 is the partial cross section view according to the column secondary battery 2 of the relevant technologies.
In general, as shown in fig. 1, column secondary battery 2 includes: cylindrical battery tank 12, is contained in battery can
Jellyroll (jelly-roll) type electrode assembly 13 in 12, be coupled to battery can 12 top cap assemblies 11, be arranged in electricity
The front end of pond tank 12 is to install the flanging part (beadingpart) 14 of cap assemblies 11 and for the crimping of sealed cell tank 12
Portion (crimping part) 15.
Cap assemblies 11 have wherein top cover 111, PTC element 112, safety exhaust portion 113, CID washer 114 and CID filtering
The structure that device 115 stacks in order, the opening of 111 sealed cell tank 12 of top cover simultaneously form positive terminal, and PTC element 112 passes through
Increase resistance when the internal temperature of battery increases and carry out interruptive current, safety exhaust portion 113 battery internal pressure due to different
Normal electric current and interruptive current and internal gas is discharged when increasing, in addition to specific part, CID washer 114 by safety exhaust portion with
CID filter (filter) 115 is electrically isolated, CID filter 115 be connected to the positive positive wire connecting, when being produced in battery
When raw high pressure, 115 interruptive current of CID filter.
In addition, cap assemblies 11 are mounted on the flanging part 14 of battery can 12 with the state being mounted on crimping washer 116.Cause
This, in normal operation condition, the anode of electrode assembly 13 is via positive wire 131, CID filter 115, safety exhaust portion
113 and PTC element 112 be electrically connected to top cover 111.
Insulator 26 is arranged in each of the top and bottom of electrode assembly 13.Here, the top of upper end is arranged in
Insulator 26 insulate electrode assembly 13 and cap assemblies 11, and the bottom insulator (not shown) of lower end is arranged in by electrode assembly 13
With the bottom insulation of battery can 12.
However, top insulator is by with insulation characterisitic in the situation according to the column secondary battery 2 of the relevant technologies
With electrolyte-resistant and the excellent thermoplastic resin of punch process, such as polyethylene or polypropylene are made.However, thermoplasticity
Resin has rather low 200 DEG C to 250 DEG C of fusing point.Additionally, there are following problems: when the internal temperature of secondary cell 2 is anxious
When play is increased over 250 DEG C, top insulator 26 melts and causes short circuit.In order to solve this problem, although having been proposed
Increase the technology of the thickness of top insulator 26, but existing leads to battery since the inner space of secondary cell 2 reduces
The problem of capacity and efficiency decline.
In recent years it has been proposed that a kind of made by coating the phenol for being used as thermosetting resin to glass fabric
Make the technology of top insulator 26.However, the fusing point of phenol itself is very low in 40 DEG C of temperature, and even if coated
To glass fabric, there is also reduce quality due to being oxidized to carbon dioxide or carbon monoxide in 600 DEG C of temperature
The problem of.In addition, when being then stamped into disc-shape, generating a large amount of dust when glass fabric is applied phenol.Cause
This, is difficult continuous production product, leads to the decline of yield and the increase of manufacturing cost.
Summary of the invention
Technical problem
It is to be solved in order to solve the problems, such as, the object of the present invention is to provide one kind such as heat resistance and chemical resistance it
Improved and inhibited in punching course the secondary cell of the generation of dust in terms of the characteristic of class and for secondary cell
Top insulator.
The purpose of the present invention is not limited to above-mentioned purpose, and those skilled in the art are clearly understood that herein from following description
The other purposes not described.
Technical solution
To solve the above-mentioned problems, according to the present invention embodiment be inserted into the shell of secondary cell for secondary
The top insulator of battery includes: the glass fabric formed by the weft yarn and warp thread of intermeshed glass fibers raw yarn；And painting
It covers to the silicon rubber at least one surface of the glass fabric.
In addition, silicon rubber can include: the first silicon rubber, first silicon rubber are attached to the glass fibre raw yarn；With
Second silicon rubber, second silicon rubber are inserted into the hole being formed between the glass fibre raw yarn.
In addition, the glass fibre raw yarn can be handed over each other with wherein glass fibre raw yarn shape perpendicular to one another
It knits, and second silicon rubber can be plugged into the hole for being formed in and being formed between the glass fibre raw yarn perpendicular to one another
In.
In addition, top insulator can have thickness identical with the glass fabric.
In addition, the silicon rubber can include: the first silicon rubber, first Silicone Rubber Coated to the glass fabric
At least one described surface；With the second silicon rubber, second Silicone Rubber Coated to first silicon rubber.
In addition, first silicon rubber may be stacked at least one described surface of the glass fabric, and
Second silicon rubber may be stacked on first silicon rubber.
In addition, the silicon rubber may be stacked at least one described surface of the glass fabric.
In addition, the glass fabric can have disc-shape.
In addition, the silicon rubber can coat the institute to the glass fabric there are two surface.
In addition, the glass fabric can have the ratio of components of 70wt% to 80wt%, and the silicon rubber can have
There is the ratio of components of 20wt% to 30wt%.
In addition, the silicon rubber may include silicone polymer and fire retardant.
In addition, the silicone polymer can have the ratio of components of 10wt% to 20wt%, and the fire retardant can have
The ratio of components of 10wt% to 15wt%.
In addition, the silicon rubber can further comprise pigment.
In addition, the pigment can have 5wt% or lower ratio of components.
To solve the above-mentioned problems, the secondary cell of embodiment includes: cylindrical battery tank according to the present invention；It is contained in
Jelly roll electrode assembly in the battery can；It is coupled to the cap assemblies on the top of the battery can；It is arranged in the battery
The front end of tank is to install the flanging parts of the cap assemblies；It is configured to seal the pressure contact portion of the battery can；Be configured to will be described
The insulator of electrode assembly insulation, wherein the insulator includes: to be formed by the weft yarn and warp thread of intermeshed glass fibers raw yarn
Glass fabric；With the silicon rubber of coating at least one surface of the glass fabric.
In addition, the insulator may include the top insulator being arranged between the electrode assembly and the cap assemblies.
In addition, the insulator may include that the bottom that is arranged between the electrode assembly and the bottom of the battery can is exhausted
Edge body.
It include the feature of other embodiments in the detailed description and the accompanying drawings.
Beneficial effect
Embodiments of the present invention can at least have the following effects that.
Thus Silicone Rubber Coated to glass fabric can be improved with manufacturing the top insulator for being used for secondary cell
The characteristic of such as heat resistance and chemical resistance etc.
In addition, can inhibit ash when by top insulator fabric punching press to manufacture the top insulator for being used for secondary cell
The generation of dirt increases yield and reduces manufacturing cost so as to continuous production product.
In addition, top insulator fabric can have flexibility and be easy to roll, thus parent roll (mother easy to form
It roll), therefore, can the top insulator easy to manufacture for secondary cell.
Effect of the invention is not limited by the foregoing description, therefore, the effect of more evolutions involved in the application.
Detailed description of the invention
Fig. 1 is the partial cross section view according to the column secondary battery of the relevant technologies.
Fig. 2 is the flow chart for illustrating the method for manufacture top insulator according to an embodiment of the present invention.
Fig. 3 is the partial cross section view of column secondary battery according to an embodiment of the present invention.
Fig. 4 is the plan view of top insulator according to an embodiment of the present invention.
Fig. 5 is the side view of top insulator according to an embodiment of the present invention.
Fig. 6 is the flow chart for illustrating the method for manufacture top insulator of another embodiment according to the present invention.
Fig. 7 is the partial cross section view of the column secondary battery of another embodiment according to the present invention.
Fig. 8 is the side view of the top insulator of another embodiment according to the present invention.
Fig. 9 is the partial cross section view of the column secondary battery of another embodiment according to the present invention.
Figure 10 is to illustrate wherein the first silicon rubber of another embodiment according to the present invention to be applied to glass fabric
State schematic diagram.
Figure 11 is to illustrate wherein the second silicon rubber of another embodiment according to the present invention to be applied to glass fabric
State schematic diagram.
Figure 12 is the cross section for the top insulator that the line A-A' along Figure 11 of another embodiment according to the present invention is intercepted
Figure.
Figure 13 is the SEM photograph that the practical top insulator manufactured of another embodiment amplifies 1,500 times according to the present invention.
Figure 14 is the SEM photograph that the practical top insulator manufactured of another embodiment amplifies 1,000 times according to the present invention.
Figure 15 is the SEM photograph that the practical top insulator manufactured of another embodiment amplifies 200 times according to the present invention.
Figure 16 is the SEM photograph that the practical top insulator manufactured of another embodiment amplifies 40 times according to the present invention.
Figure 17 is that diagram is obtained and carrying out heat resistance test to the exemplary top insulator of manufacture according to the present invention
Result curve graph.
Figure 18 is illustrated by carrying out heat resistance test according to the top insulator of comparative example 2 and the song of result that obtains
Line chart.
Figure 19 is the photo of the state of each electrolyte sample after being shown in chemical resistance test.
Figure 20 is the curve graph for illustrating the GC-MS test result of each electrolyte sample.
Figure 21 is diagram secondary cell of the manufacture example set equipped with top insulator according to the present invention in stability test
The photo of decomposing state later.
Figure 22 is to illustrate to be assembled with decomposition of the secondary cell of top insulator after stability test according to comparative example 1
The photo of state.
Figure 23 is to illustrate to be assembled with decomposition of the secondary cell of top insulator after stability test according to comparative example 2
The photo of state.
Specific embodiment
By the embodiment described referring to the drawings, by the advantages of illustrating present disclosure and feature and its realization side
Method.However, the present invention can be implemented in different forms, embodiment set forth herein should not be construed as limited to.But it mentions
It is and the scope of the present invention sufficiently to be passed to this field skill to keep present disclosure full and complete for these embodiments
Art personnel.In addition, the present invention is limited solely by the scope of the following claims.Similar reference number indicates similar element in the whole text.
Unless term used in the definition present invention in different ways, otherwise all terms used herein (including technology
Term and scientific term) there is meaning identical with the normally understood meaning of those skilled in the art.In addition, unless in specification
In it is clear and significantly define, otherwise the term defined in common dictionary is not construed to form ideally or exceedingly
Meaning.
In the following description, technical term is only used for explaining specific illustrative embodiment, rather than limits the present invention.?
In the application, unless specifically mentioned otherwise, the term of singular may include plural form.The meaning of " comprising " is not excluded for except institute
Other component except the component referred to.
Hereinafter, preferred embodiment is described in detail with reference to the accompanying drawings.
Fig. 2 is the flow chart for illustrating the method for manufacture top insulator 16 according to an embodiment of the present invention.
Top according to an embodiment of the present invention is manufactured by coating silicon rubber 162 to glass fabric 161
Insulator 16.Therefore, the characteristic of such as heat resistance and chemical resistance etc can be improved.In addition, when top insulator fabric is rushed
When pressure is to manufacture the top insulator 16 for secondary cell, the generation of dust can inhibit, so as to continuous production product, increase
Add yield and reduces manufacturing cost.In addition, top insulator fabric can have flexibility and be easy to wind with parent roll easy to form,
It therefore, can the top insulator 16 easy to manufacture for secondary cell.
Hereinafter, the particular content of each step shown in the flowchart of Fig. 2 will be described referring to Fig. 3 to Fig. 5.
Fig. 3 is the partial cross section view of column secondary battery 1 according to an embodiment of the present invention.
As shown in Figure 3, column secondary battery 1 according to an embodiment of the present invention includes: battery can 12；It is contained in
Jelly roll electrode assembly 13 in battery can 12, be coupled to battery can 12 top cap assemblies 11, be arranged in battery can 12
Front end to install the flanging part 14 of cap assemblies 11 and for the pressure contact portion 15 of sealed cell tank 12.Column secondary battery 1
Can be used as mobile phone, laptop, electric vehicle etc. steadily provides the power supply of constant output.
Battery can 12 can be made of lightweight conductive metal material, such as aluminium, nickel, stainless steel or its alloy.Battery can 12 can
With open top and the closed bottom opposite with top.Electrolyte can be accommodated in together battery can with electrode assembly 13
In 12 inner space.Although battery can 12 has cylindrical shape, but the invention is not restricted to this.For example, in addition to cylindrical shape
Except, battery can 12 can also have the various shape of such as prism shape etc.
Electrode assembly 13 can have the stacking knot of two electrode plates and partition including such as positive plate and negative plate etc
Structure, each electrode plate have the broad plate shape of roll form, and partition is arranged between electrode plate so that electrode plate is exhausted each other
The left or right side of an electrode plate is arranged in edge or partition.Stacked structure can have various shape, for example, stacked structure can
To be wound in the form of jellyroll, or can be with wherein each positive plate and negative plate with predetermined size two
It is stacked between person with the shape stacked in the case where partition.Each of two electrode plates has wherein active material
Slurry is applied to the structure of metal foil or mesh current collector including aluminium and copper.It usually can be by the case where adding solvent
Granulated activated material, auxiliary conductor, adhesive and plasticizer are stirred to form slurry.Solvent can be removed in the subsequent process.
The starting point of current-collector on the direction of electrode plate winding and the uncoated portion of the settable slurry uncoated thereon of far-end.
The a pair of lead wires for corresponding respectively to electrode plate is attached to uncoated portion.It is attached to the positive wire of the upper end of electrode assembly 13
131 may be electrically connected to cap assemblies 11, and the negative wire (not shown) for being attached to the lower end of electrode assembly 13 can be connected to battery can
12 bottom surface.However, the present invention is not limited thereto.For example, all positive wires 131 and negative wire can be in cap assemblies 11
Side be drawn upwardly out.
The each of the top and bottom of electrode assembly 13 is arranged in the insulator 16 of each insulation of electrode assembly 13
On a.Here, the top insulator 16 that upper end is arranged in is arranged between electrode assembly 13 and cap assemblies 11, by electrode assembly
13 insulation, the bottom insulator (not shown) that lower end is arranged in are arranged between electrode assembly 13 and the bottom of battery can 12, with
Electrode assembly 13 is insulated.As shown in Figure 3, insulator 16 according to an embodiment of the present invention, which can be, is arranged in electrode group
The top insulator 16 on the top of part, but it is not limited to this.For example, insulator 16 can be the lower part that electrode assembly is arranged in
Bottom insulator (not shown).Top insulator 16 by description according to an embodiment of the present invention later.
Prevent the expansion of electrode assembly 13 wound with jelly roll form and the movement routine as the gas in secondary cell 1
Centrepin (not shown) can be plugged into the center of battery can 12.
The electrolyte being filled into battery can 12 can move the electricity by electrode plate during the charging and discharging of secondary cell 1
Lithium ion caused by chemically reacting.Electrolyte may include as the non-aqueous organic of the mixture of lithium salts and high-purity organic solvent
Electrolyte or the polymer for using polymer dielectric.
Cap assemblies 11 may be coupled to the opening being formed in the upper end of battery can 12, with the opening of sealed cell tank 12.Root
According to the shape of battery can 12, cap assemblies 11 can have various shape, such as cylindrical shape or prism shape.According to an embodiment party
Formula, battery can 12 have cylindrical shape.In this case, cap assemblies 11 can also have circle corresponding with the shape of battery can 12
Disk shape.
According to an embodiment of the present invention, cap assemblies 11 can have wherein top cover 111, safety exhaust portion 113 and current interruptions
The structure that device stacks in order, the opening of 111 sealed cell tank 12 of top cover simultaneously form positive terminal, and safety exhaust portion 113 exists
The internal pressure of battery interruptive current and the gas in battery is discharged due to abnormal current and when increasing, and current interrupt device connects
It is connected to the positive wire 131 connecting with the anode of electrode assembly 13, and when generating high pressure in battery, in current interrupt device
Power-off stream.In addition, cap assemblies 11 are mounted on the flanging part 14 of battery can 12 with the state being mounted on crimping washer 116.Cause
This, in normal operation condition, the anode of electrode assembly 13 is via positive wire 131, current interrupt device, safety exhaust portion
113 and PTC element 112 be electrically connected to top cover 111.
The topmost of cap assemblies 11 is arranged in the shape projected upwards for top cover 111, to form anode.Therefore, top cover 111
It may be electrically connected to load or external device (ED), such as charging unit.Stomata 1111 can be formed in top cover 111, produced in secondary cell 1
Raw gas is discharged by the stomata 1111.Therefore, in causing when the generation gas of electrode assembly 13 due to overcharge etc.
When portion's pressure increase, the CID filter 115 and safety exhaust portion 113 of current interrupt device are rupturable, and therefore, internal gas can
It is externally discharged by broken portion and stomata 1111.Therefore, it no longer charges and discharges, to ensure the peace of secondary cell 1
Quan Xing.Top cover 111 can be made of the metal material of such as stainless steel or aluminium etc.
The part of top cover 111 contacted with safety exhaust portion 113 can be not particularly limited on thickness, as long as top cover 111
The part protect all parts of cap assemblies 11 from outside apply pressure influence, that is, the part of top cover 111
There can be the thickness of 0.3mm to 0.5mm.When the thickness of the part of top cover 111 is too thin, it is difficult to show mechanical rigid.Separately
On the one hand, when the thickness of the part of top cover 111 is too thick, compared with same size, due to the increase of size and weight, battery
Capacity can reduce.
Safety exhaust portion 113 can be used for interruptive current or discharge when the internal pressure of battery increases due to abnormal current
Gas, and can be made of metal material.The thickness of safety exhaust portion 113 can change according to its material, structure etc..Namely
It says, the thickness of safety exhaust portion 113 is not particularly limited, as long as safety exhaust portion 113 exists when generating predetermined high pressure in battery
Gas is discharged while rupture.For example, safety exhaust portion 113 can have the thickness of 0.2mm to 0.6mm.
Current interrupt device (CID) may be provided between safety exhaust portion 113 and electrode assembly 13, by electrode assembly 13
It is electrically connected to safety exhaust portion 113.Current interrupt device includes CID filter 115 and CID washer 114, and CID filter 115 connects
Touching safety exhaust portion 113 to transmit electric current, CID washer 114 spatially by CID filter 115 and safety exhaust portion 113 each other
It separates and separates.
Therefore, the electric current generated from electrode assembly 13 is in normal state via positive wire 131 and CID filter 115
Safety exhaust portion 113 is flowed into, so that secondary cell is discharged.However, when secondary cell 1 internal pressure due to abnormal current and
When increase, since abnormal current leads to the gas generated in secondary cell 1, the internal pressure of battery can increase.Therefore, safety row
Connection between gas portion 113 and CID filter 115 can be interrupted or CID filter 115 is rupturable.Therefore, safety exhaust portion
Being electrically connected between 113 and electrode assembly 13 can be interrupted, to ensure safety property.
Cap assemblies 11 can further comprise positive temperature coefficient (PTC) element between safety exhaust portion 113 and top cover 111
112.PTC element 112 can increase cell resistance when internal temperature increases, with interruptive current.That is, PTC element 112 exists
Top cover 111 is electrically connected to safety exhaust portion 113 under normal condition.However, under abnormality, for example, working as temperature anomaly liter
Gao Shi, PTC element 112 interrupt being electrically connected between top cover 111 and safety exhaust portion 113.PTC element 112 can also on thickness
Changed according to its material, structure etc., for example, PTC element 112 there can be the thickness of 0.2mm to 0.4mm.When PTC element 112
When with the thickness for being greater than 0.4mm, internal resistance can increase, in addition, battery can dimensionally increase when compared with same size
Add, to reduce battery capacity.On the other hand, when PTC element 112 has the thickness less than 0.2mm, it is difficult to table at high temperature
Reveal current interruptions effect, and PTC element 112 can be destroyed by weaker external impact.Therefore, these aspects can be comprehensively considered
The thickness of PTC element 112 is suitably determined in above-mentioned thickness range.
Even when the secondary cell 1 including above-mentioned cap assemblies 11 is used as the power supply of the power tool of such as electric drill etc,
Secondary cell 1 can also provide high output moment, and be steady for the external physical impact for such as vibrating and falling etc
Fixed.
It may be formed at the top of battery can 12 externally to interior curved flanging part 14.Flanging part 14 can make to be stacked with thereon
Top cover 111, PTC element 112, safety exhaust portion 113 and current interrupt device cap assemblies 11 upper end of battery can 12 is set,
To prevent electrode assembly 13 from vertically moving.
As described above, cap assemblies 11 are mounted on the flanging part 14 of battery can 12 with the state being mounted on crimping washer 116
On.Crimping washer 116 can have the cylindrical shape including two open ends.As shown in Figure 3, crimp washer 116 towards electricity
One end inside pond tank 12 can be generally perpendicularly bent first towards central axis, then secondary vertical towards the inside of battery can 12
Ground is bent and is placed on flanging part 14.It is initially upwardly extended in the side for being parallel to central axis in addition, crimping washer 116 has
The other end.However, when after execute coupling cap assemblies 11 and press battery can 12 upper end outer wall to form pressure contact portion 15
Technique when, crimping washer 116 can be bent in generally perpendicular direction along the shape of pressure contact portion 15, to be directed toward central axis.
Therefore, crimping washer 116 have tight attachment to cap assemblies 111 inner peripheral surface and tight attachment to battery can 12 interior weekly form
The peripheral surface in face.
Fig. 4 is the plan view of top insulator 16 according to an embodiment of the present invention.
The top for secondary cell 1 in the shell for being inserted into secondary cell 1 according to an embodiment of the present invention is exhausted
Edge body 16 includes: to be knitted by the discoid of glass fibre 161 that the weft yarn and warp thread of the raw yarn of intermeshed glass fibers 161 are formed
Object；With the silicon rubber 162 at least one surface of the fabric of coating to glass fibre 161.In addition, silicon rubber 162 is stacked on glass
On at least one surface of the fabric of glass fiber 161.
Glass fibre 161 is by the fusing glass in platinum furnace (platinum furnace) and to pass through the glass of fusing
Small diameter bore pulls out and is made into long fibre shape.Glass fibre can have excellent heat resistance, durability, sound absorption properties, electricity absolutely
Edge, rust-preventing characteristic and workability, therefore be mainly used for structural insulated material, air filting material, electrically insulating material etc..According to
An embodiment of the present invention, the weft yarn and warp thread of the raw yarn of glass fibre 161 can be interlaced with one another, to prepare glass fibre 161
Fabric, and silicon rubber 162 is coated to the fabric of glass fibre 161.Preferably, it is knitted from the fabric solution of glass fibre 161
(loosen) cross section of one yarn has about 4 μm to 15 μm of diameter.
Silicon rubber 162 is siliceous rubber.Silicon rubber can have excellent heat resistance and chemical resistance.Therefore, though
After placing 3 days at a temperature of 250 DEG C, the intensity and elongation percentage of silicon rubber be may remain within 10%, and in -45 DEG C of temperature
The elasticity of silicon rubber can also be kept under degree.Since electrology characteristic is to temperature-insensitive, thus silicon rubber be widely used in need it is heat-resisting
In the electrical of property, electronics and the communications field.Silicon rubber 162 is prepared by mixing a variety of materials.For example, such as organic poly- silicon
The silicone polymer of oxygen alkane etc is used as raw material.Silica-based filler, the expanding material for increasing volume, Zhu Ruyou can be mixed
The vulcanizing agent of machine peroxide etc, the rapidoprint of such as low molecular weight silicone oligomer etc or such as BaO, CaO, MgO
With the various performance improvement agents of ZnO etc.In addition, can further include such as Al (OH) to improve anti-flammability3、Mg(OH)2
And BH3O3Etc fire retardant, or pigment can be further included, in order to the naked eye carry out quality inspection.In addition, can lead to
It crosses and is mixed and heated above-mentioned material, then vulcanized and be dried to prepare silicon rubber 162.Such as benzoyl peroxide first
The peroxide of acyl, cumyl peroxide or the like can be used for vulcanizing treatment.
In order to manufacture the top insulator 16 for secondary cell according to an embodiment of the present invention, firstly, will contain
The a variety of materials of silicone polymer are dissolved in specific solvent before mixing and solidification, to prepare solution.Solvent is preferably capable of
Enough organic solvents for being easy dissolution above-mentioned material.For example, solvent includes toluene, dimethylbenzene, MEK etc..
According to the concentration that silicone polymer dissolves, prepared solution has different viscosity.Here, if viscosity too
It is low, then the weft yarn of glass fibre 161 and warp thread can solution knit, the effect of coating can be less obvious.On the other hand, if viscosity too
Height, then solution can not penetrate into the hole 3 between the weft yarn and warp thread of glass fibre 161, and hole 3 will not be filled.Solution
Viscosity can by experimental selection be optimum viscosity.
In addition, prepared solution is coated to the fabric of glass fibre 161 (S201), then drying (S202).Work as painting
It, can will be on the fabric of solution spraying to glass fibre 161 by using sprayer when covering solution.However, it is preferable that by glass
The fabric of fiber 161 immerses in the container containing the solution.As a result, tank solution can be coated quickly to glass fibre 161
Fabric.When coating solution and drying, solvent evaporation, thus silicon rubber 162 is applied to the fabric of glass fibre 161, thus
It is formed top insulator fabric (S203).In addition, top insulator fabric is struck out specific shape, produce according to the present invention
The top insulator 16 (S204) of one embodiment.Here, when top insulator 16 is mounted in column secondary battery 1
When, as shown in figure 4, top insulator fabric is preferably stamped into disc-shape, so that top insulator 16 is easily inserted into circle
In the battery can 12 of cylindrical secondary battery 1.It therefore, generally speaking, can be by the way that the coating of silicon rubber 162 be extremely had disc-shape
The fabric of glass fibre 161 manufactures top insulator 16.
Fig. 5 is the side view of top insulator 16 according to an embodiment of the present invention.
As shown in figure 5, top insulator 16 according to an embodiment of the present invention is applied to wherein silicon rubber 162
The shape that multiple layers are stacked while at least one surface of the fabric of glass fibre 161.
Solution can be coated only to a surface of the fabric of glass fibre 161.However, according to an embodiment of the present invention,
Solution preferably coats the institute to the fabric of glass fibre 161 there are two surface.As a result, silicon rubber 162 can be applied to glass
Two surfaces of the fabric of fiber 161, so that top insulator 16 according to an embodiment of the present invention has plurality of layer
The shape stacked.Although stacking three layers in Fig. 5, embodiments of the present invention are not limited to this.For example, can be in glass
Separation layer is further set between the fabric and silicon rubber 162 of glass fiber 161.
Fig. 6 is the flow chart for illustrating the method for manufacture top insulator 16 of another embodiment according to the present invention.
Top insulator 16 according to an embodiment of the present invention is by by 162 primary coating of silicon rubber to glass fibre
At least one surface of 161 fabric manufactures.On the other hand, the top insulator of another embodiment according to the present invention
16a is manufactured by being coated silicon rubber 162a for several times at least one surface of the fabric of glass fibre 161a.
Hereinafter, the particular content of each step shown in the flowchart of Fig. 6 will be described referring to Fig. 7 to Fig. 8.
Fig. 7 is the partial cross section view of the column secondary battery 1a of another embodiment according to the present invention.
Hereinafter, the column secondary battery 1a and top insulator 16a of another embodiment according to the present invention will be omitted
With the secondary cell repetitive description of above embodiment according to the present invention.This is for ease of description, it is no intended to limitation power
The range of benefit.
The each of the top and bottom of electrode assembly 13 is arranged in the insulator 16a of each insulation of electrode assembly 13
On a.As shown in Figure 7, the insulator 16a of another embodiment can be the top that electrode assembly is arranged according to the present invention
Top insulator 16a, but it is not limited to this.For example, insulator 16a can be arranged in the lower part of electrode assembly bottom it is exhausted
Edge body (not shown).
The top for secondary cell 1a in the shell for being inserted into secondary cell 1a of another embodiment according to the present invention
Portion insulator 16a includes: knitting for the glass fibre 161a formed by the weft yarn and warp thread of the raw yarn of intermeshed glass fibers 161a
Object；With the silicon rubber 162a at least one surface of the fabric of coating to glass fibre 161a.In addition, silicon rubber 162a includes:
It is coated first to the first silicon rubber 1621a at least one surface of the fabric of glass fibre 161a；With coating to the first silicon rubber
The second silicon rubber 1622a of glue 1621a.In order to manufacture the top insulator 16a of another embodiment according to the present invention, firstly,
A variety of materials containing silicone polymer are dissolved in specific solvent before mixing and solidification, to prepare the first solution and the
Two solution.
Specifically, the first silicone polymer is dissolved in the first solvent, to prepare the first solution, by the second silicone polymer
Object is dissolved in the second solvent, to prepare the second solution.According to the concentration that silicone polymer dissolves, prepared solution has not
Same viscosity.Here, it is preferable that the first solution has the viscosity bigger than the viscosity of the second solution.
In addition, the first prepared solution is coated at least one surface (S601) of the fabric of glass fibre 161a,
Then dry (S602).First solution can be coated only to a surface of the fabric of glass fibre 161a.However, according to the present invention
Another embodiment, solution preferably coats the institute to the fabric of glass fibre 161a there are two surface.When coating first is molten
Liquid and when drying, the evaporation of the first solvent, thus the first silicon rubber 1621a is applied to the fabric (S603) of glass fibre 161a.
Later, the second prepared solution is coated at least one surface (S604) for being coated the first silicon rubber 1621a, then
Dry (S605).When coating the second solution and when drying, the evaporation of the second solvent, thus the second silicon rubber 1622a is applied to the
One silicon rubber 1621a (S606).As a result, preparing top insulator fabric.
Due to the first solution have low viscosity, so the first solution can the readily permeable fabric to glass fibre 161a latitude
In hole 3 between yarn and warp thread, with filling pore 3.On the other hand, the second solution has high viscosity, to fix glass fibre
The weft yarn and warp thread of the fabric of 161a are knitted without solution, to increase retentivity.Therefore, in another embodiment according to the present invention
Top insulator 16a in, silicon rubber 162a can be mixed preferably with glass fibre 161a, to increase retentivity.
Top insulator fabric is struck out into specific shape, produces the top insulation of another embodiment according to the present invention
Body 16a (S607).Here, top insulator fabric is excellent when top insulator 16a to be mounted in column secondary battery 1a
Choosing is stamped into disc-shape, so that top insulator 16a is easily inserted into the battery can of column secondary battery 1a.
Fig. 8 is the side view of the top insulator 16a of another embodiment according to the present invention.
As shown in Figure 8, in the top insulator 16a of another embodiment according to the present invention, the first silicon rubber 1621a
It is stacked at least one surface of the fabric of glass fibre 161a, the second silicon rubber 1622a is stacked on the first silicon rubber 1621a
On.That is, the first silicon rubber 1621a and the second silicon rubber 1622a sequence stack, stacked with forming plurality of layer
Shape.
First solution and the second solution can be coated only to a surface of the fabric of glass fibre 161a.However, according to this
Invention another embodiment, solution preferably coat to the fabric of glass fibre 161a institute there are two surface.As a result, first
Silicon rubber 1621a and the second silicon rubber 1622a can be coated to two surfaces of the fabric of glass fibre 161a, so that according to this hair
The shape that there is the top insulator 161a of bright another embodiment plurality of layer to be stacked.Specifically, due to coating
The first silicon rubber 1621a is coated before second silicon rubber 1622a, so the first silicon rubber 1621a is stacked on the second silicon rubber
On the inside of 1622a, the second silicon rubber 1622a is stacked on the outside of the first silicon rubber 1621a.Although being stacked in fig. 8 there are five layer,
Embodiments of the present invention are not limited to this.For example, can glass fibre 161a fabric and silicon rubber 1621a and 1621a it
Between separation layer is further set.
Fig. 9 is the partial cross section view of the column secondary battery 1b of another embodiment according to the present invention.
In the top insulator 16a of another embodiment according to the present invention, each of silicon rubber 162 and 162a are applied
It covers at least one surface of the fabric of each of glass fibre 161 and 161a, is stacked with to form plurality of layer
Shape.However, silicon rubber 162b is not stacked on glass fibers in the top insulator 16b of another embodiment according to the present invention
On the fabric for tieing up 161b, therefore, top insulator 16b has thickness identical with the fabric of glass fibre 161b.
However, according to the present invention the method for the manufacture top insulator 16b of another embodiment with according to another embodiment party
The method of the manufacture top insulator 16a of formula is similar, therefore, will be described again shown in the flow chart of Fig. 6 referring to Fig. 9 to Figure 16
Each step particular content.Hereinafter, will omit according to the present invention the column secondary battery 1b of another embodiment and
The secondary cell repetitive description of top insulator 16b and above embodiment according to the present invention.This be for ease of description, and
It is not intended to the range of limitation right.
The top for secondary cell of another embodiment being inserted into the shell of secondary cell is exhausted according to the present invention
Edge body 16b includes: the fabric of the glass fibre 161b formed by the weft yarn and warp thread of the raw yarn of intermeshed glass fibers 161b；With
It coats to the silicon rubber 162b at least one surface of the fabric of glass fibre 161b.In addition, silicon rubber 162b includes: to be attached to
First silicon rubber 1621b of the raw yarn of glass fibre 161b；And it is inserted into the hole being formed between the raw yarn of glass fibre 161b
The second silicon rubber 1622b in gap 3.
In order to manufacture the top insulator 16b of another embodiment according to the present invention, the first solution is coated to glass fibers
At least one surface (S601) of the fabric of 161b is tieed up, then dry (S602).Another embodiment according to the present invention, preferably
Be that there are two on surface for the institute that coats the first solution to the fabric of glass fibre 16b.
Figure 10 is to illustrate wherein the first silicon rubber 1621b of another embodiment according to the present invention to be applied to glass fibre
The schematic diagram of the state of the fabric of 161b.
The fabric that glass fibre 161b is formed by the raw yarn of intermeshed glass fibers 161b, glass fibre 161b each other
Hole 3 is formed between vertical raw yarn.Here, the first solution has the viscosity smaller than the viscosity of the second solution and further
Less than the viscosity of the first solution of another embodiment according to the present invention.Therefore, the first solution only can be adhered to form glass fibers
Tie up the raw yarn periphery of the glass fibre 161b of the fabric of 161b.
After coating the first solution, with the fabric of the scrapings glass fibre such as knife 161b.Therefore, glass can be adjusted on thickness
The fabric of glass fiber 161b.In addition, the fabric surface of glass fibre 161b can be made smooth.In addition, when dry first solution
(S602), the first solvent evaporates.As shown in Figure 10, the first silicon rubber 1621b is applied to the fabric of glass fibre 161b
(S603).Here, another embodiment according to the present invention, since the first silicon rubber 1621b closely adheres to be only adhered to
The raw yarn of glass fibre 161b, so forming hole 3 between the raw yarn perpendicular to one another of glass fibre 161b.
Figure 11 is to illustrate wherein the second silicon rubber 1622b of another embodiment according to the present invention to be applied to glass fibre
The schematic diagram of the state of the fabric of 161b.
Later, the second solution is coated at least one surface (S604) of the fabric of glass fibre 161b, is then dried
(S605).Here, the second solution is molten with second than the viscosity of the first solution greatly but than another embodiment according to the present invention
The small viscosity of the viscosity of liquid.Therefore, the second solution is inserted into the hole 3 being formed between the raw yarn of glass fibre 161b.
After coating the second solution, with the fabric of the scraping glass fibre 161b again such as knife.Therefore, it can be raised in thickness
Save the fabric of glass fibre 161b.In addition, the smooth surface of the fabric of glass fibre 161b can be made.In addition, when drying second is molten
When liquid (S605), the evaporation of the second solvent.As shown in Figure 11, the second silicon rubber 1622b is applied to knitting for glass fibre 161b
Object (S606).Here, another embodiment according to the present invention, the second silicon rubber 1622b, which is inserted into, is formed in glass fibre
In hole 3 between the raw yarn perpendicular to one another of 161b, with filling pore 3.As a result, preparing top insulator fabric.
Top insulator fabric is struck out into specific shape, produces the top insulation of another embodiment according to the present invention
Body 16b (S607).Here, top insulator fabric is excellent when top insulator 16b to be mounted in column secondary battery 1b
Choosing is stamped into disc-shape, so that top insulator 16b is easily inserted into the battery can 12 of column secondary battery 1b.
Figure 12 is the transversal of the top insulator 16b that the line A-A' along Figure 11 of another embodiment according to the present invention is intercepted
Face figure.
In the top insulator 16b of another embodiment according to the present invention, as shown in Figure 12, the first and second silicon rubbers
Glue 162b is not formed into individual layer.That is, the first silicon rubber 1621b close attachment is to be only adhered to glass fibre 161b
Raw yarn, the second silicon rubber 1622b is inserted into the hole 3 being formed between the raw yarn of glass fibre 161b.Therefore, because the
One and second silicon rubber 162b be not formed into individual layer, so complete top insulator 16b have and uncoated silicon rubber
The thickness of the fabric of the glass fibre 161b of 162b is equal or similar thickness.
As described above, by electrode assembly 13 each insulation insulator 16b be arranged in electrode assembly 13 upper end and
In each of lower end.As shown in Figure 9, insulator 16b according to an embodiment of the present invention, which can be, is arranged in electrode group
The top insulator 16b on the top of part, but it is not limited to this.For example, insulator 16b, which can be, is arranged in electrode assembly lower part
Bottom insulator (not shown).
When the insulator 16b of another embodiment according to the present invention is used as top insulator 16b, can improve such as heat-resisting
The characteristic of property and chemical resistance etc, to ensure thermal stability and chemical stability.On the other hand, when insulator 16b is used as bottom
When portion's insulator, it can be ensured that thermal stability and chemical stability can also block the heat from the lower part of electrode assembly 13 diffusion heat
Transmission path.According to the relevant technologies, bottom baffles can due to the negative tab of electrode assembly 13 thermal diffusion and be lost, to lead
Cause the edge shorting of 13 lower part of electrode assembly.However, to can be used as bottom exhausted by the insulator 16b of another embodiment according to the present invention
Thus edge body prevents the lower part of electrode assembly 13 with the heat transfer path that intercept heat is spread to the lower part of electrode assembly 13
Edge shorting.
Figure 13 is that the SEM that the practical top insulator 16b manufactured of another embodiment amplifies 1,500 times according to the present invention shines
Piece, Figure 14 are the SEM photograph that the practical top insulator 16b manufactured of another embodiment amplifies 1,000 times according to the present invention, figure
15 be the SEM photograph that the practical top insulator 16b manufactured of another embodiment amplifies 200 times according to the present invention, and Figure 16 is root
Amplify 40 times of SEM photograph according to the practical top insulator 16b manufactured of a further embodiment of this invention.
In figs. 13 and 14, biggish rounded form is the cross section of the raw yarn of glass fibre 161b, is attached to glass
Material around the raw yarn of fiber 161b is silicon rubber 162b.
As shown in figure 13 and figure 14, the first silicon rubber 1621b close attachment is to be adhered to the raw yarn of glass fibre 161b
Between.In addition, as shown in figs. 15 and 16, silicon rubber 162b is not formed into individual layer.
In Figure 13 into Figure 16, the hole 3 and the second silicon rubber between the raw yarn of glass fibre 161b are not taken
1622b is inserted into the state in hole 3.Although considering to coat the second silicon rubber 1622b to glass fibre 161b however, working as,
But when the not formed individual layer of silicon rubber 162b, it may be determined that the second silicon rubber 1622b is inserted into hole 3.
After actually producing the top insulator 16b of another embodiment according to the present invention, ratio of components is measured as follows.
[table 1]
Table 1 is shown according to the ratio of components for manufacturing exemplary top insulator.
As shown in table 1, glass fibre has the ratio of components of 70wt% to 80wt%, and silicon rubber has 20wt% extremely
The ratio of components of 30wt%.Specifically, as the main chain of silicone polymer, the dimethyl siloxane of ethenyl blocking and containing for silicone
Measuring is 10wt% to 15wt%, and the content of dimethyl ethenyl and trimethylated silica is 0wt% to 5wt%.Also
It is to say, the total composition ratio of silicone polymer is 10wt% to 20wt%.In addition, the content of three aluminium hydroxides as fire retardant is
10wt% to 15wt%, the content of the titanium dioxide as pigment are 0wt% to 5wt%.That is, due to dimethylvinylsiloxy
The minimum value of base and trimethylated silica and titanium dioxide be 0wt%, therefore do not need at all containing.
The top insulator for secondary cell of embodiment being inserted into the shell of secondary cell according to the present invention
It include: the glass fabric formed by the weft yarn and warp thread of the raw yarn of intermeshed glass fibers；It is knitted with coating to glass fibre
The silicon rubber at least one surface of object.
When the top insulator for secondary cell is heated to 600 DEG C or higher, or even 950 DEG C or higher temperature
When spending, since mass loss caused by being pyrolyzed can be 10wt% to 15wt%, preferably 12wt% to 14wt%.Therefore, according to
The top insulator for secondary cell of embodiment of the present invention is excellent in terms of heat resistance.
In addition, the top insulator for being used for secondary cell to be impregnated into bis- (fluorosulfonyl) acyls containing 10wt% or more
In the electrolyte of imine lithium (lithium bis (fluorosulfony) imide, LIFSI), and 72 DEG C at a temperature of store 1
Week or longer time, the reduction amount of bis- (fluorosulfonyl) imide lis (LIFSI) can be 1wt% to 3wt%, preferably
1.5wt% to 2.5wt%.Therefore, according to the present invention the top insulator for secondary cell of embodiment in chemical resistance
Aspect is excellent.
In addition, working as the top insulator for secondary cell using embodiment according to the present invention to manufacture secondary cell
When, when secondary cell be heated under 600 DEG C or higher temperature and therefore explosion time, not will form pin hole in the cell housing
(pinhole).Therefore, the top insulator for secondary cell of embodiment is excellent in terms of safety according to the present invention.
In addition, being stretched when the top insulator for secondary cell of embodiment according to the present invention is to two side stretchings
Intensity can be 120N/mm2To 150N/mm2, preferably 130N/mm2To 140N/mm2, and elongation percentage can be 5% to 10%,
Preferably 7% to 8%.Therefore, according to the present invention the top insulator for secondary cell of embodiment in tensile strength and
It is excellent in terms of elongation percentage.
Manufacture example
Prepare the glass fabric with 1,040mm width, 300,000mm length and 0.3mm thickness.In addition, will
The dimethyl siloxane and silicone of the ethenyl blocking of 12kg and the dimethyl ethenyl and trimethylated silica of 4kg
Main chain as silicone polymer is added in the toluene solvant of 20kg, and three aluminium hydroxides of 13kg are added as fire retardant.
In addition, further the titanium dioxide of addition 3kg is as pigment, to prepare the first solution of 52kg.
After on the two sides that glass fabric is arranged in roller, knife is set in the upper end of each roller.In addition, by first
Solution fills in a reservoir, and rotating roller is so that glass fabric immerses in the first solution.When roller is reversely rotated to remove glass fibers
When tieing up fabric, the first solution on the surface for staying in glass fabric is wiped off by knife.In addition, glass fabric is inserted into
In drying oven, by the first solution 170 DEG C at a temperature of it is 5 minutes dry.
Then, by the dimethyl ethenylization of the dimethyl siloxane of the ethenyl blocking of 12kg and silicone and 4kg and
Trimethylated silica is added in the toluene solvant of 10kg as the main chain of silicone polymer, and three hydrogen-oxygens of 13kg are added
Change aluminium as fire retardant.In addition, further the titanium dioxide of addition 3kg is as pigment, to prepare the second solution of 41kg.
After on the two sides that glass fabric is arranged in roller, knife is set in the upper end of each roller.In addition, by second
Solution fills in a reservoir, and rotating roller is so that glass fabric immerses in the second solution.When roller is reversely rotated to remove glass fibers
When tieing up fabric, the second solution on the surface for staying in glass fabric is wiped off by knife.In addition, glass fabric is inserted into
In drying oven, by the second solution 170 DEG C at a temperature of it is 5 minutes dry.
When preparing top insulator fabric as described above, it is inserted into press machine, top insulator fabric is struck out
Disc-shape with 20mm diameter, to prepare according to the exemplary top insulator of manufacture.
Comparative example 1
By method of electrostatic spinning using PET raw material prepare width be 30mm, length 30mm, having with a thickness of 0.3mm
The PET of non-woven fabrics.
When preparing top insulator fabric as described above, it is inserted into press machine, top insulator fabric is struck out
Disc-shape with 20mm diameter, to prepare the top insulator according to comparative example 1.
Comparative example 2
Prepare the glass fabric with 270mm width, 270mm length and 0.3mm thickness.In addition, by the phenolic aldehyde of 5kg
Three aluminium hydroxides of resin and 5kg are added in the toluene solvant of 10kg, to prepare the solution of 20kg.
The fabric of three pieces dipping is stacked, and heat and pressure are applied by using hot pressing, to prepare at the top of cured phenolic aldehyde
Insulator.
When preparing top insulator fabric as described above, it is inserted into press machine, top insulator fabric is struck out
Disc-shape with 20mm diameter, to prepare the top insulator according to comparative example 2.
The method for measuring physical characteristic
1. heat resistance
By according to aforementioned manufacture example, each top insulator of comparative example 1 and comparative example 2 be inserted by
In the heat resistance tester (model: TGA Q500) of TAInstruments Co. manufacture, and in 25 DEG C to 950 DEG C of temperature
It is gradually heated up under the heating rate of 10 DEG C/min.In addition, the quality of each top insulator of real-time measurement, and confirm due to heat
The amount of mass loss caused by solving.
2. chemical resistance
Salt and additive are mixed with solvent, to prepare electrolyte.By by ethylene carbonate (EC), dimethyl carbonate
(DMC) it is mixed with each other with methyl ethyl carbonate (EMC) and prepares solvent, and mix as the lithium hexafluoro phosphate (LiFF6) of salt and double
(fluorosulfonyl) imide li and various additives.
It will be impregnated into prepared electrolyte according to each top insulator of manufacture example, comparative example 1 and comparative example 2
And 72 DEG C at a temperature of store 1 week.In addition, electrolyte sample is injected NMR equipment after removing each top insulator
(being manufactured by Varian, model name EQC-0279) and GC-MS equipment (are manufactured, model GC2010Plus/ by SHIMADZU
QP2020, EQC-0291) in, to carry out NMR and GC analysis, to analyze the ratio of components and reaction by-product of each electrolyte sample
Object.
3. flame propagation (flame Propagation)
In the test, the top insulator according to comparative example 1 and comparative example 2 is not tested, is only tested according to manufacture example
Top insulator.Therefore, it was confirmed that meet flame propagation performance standard according to exemplary top insulator is manufactured.Testing standard
Dependent on IMO RESOLUTION MSC.307 (88).
Specifically, it will be mounted in the equipment with main heat source and auxiliary thermal source according to the exemplary top insulator of manufacture,
And apply flame.The methane gas with 99.99% purity is used in the radiant panel with 483mm width and 284mm length
The flame as main heat source is generated as fuel.Here, heat is 50.5kW/m at the point of 50mm2, heat is at the point of 350mm
23.9kW/m2.In addition, having the length of about 230mm as the pilot flame of auxiliary thermal source, and made by using propane gas
Flame is generated for fuel.
Firstly, in order to standardize the service condition of equipment, installation calibrating test specimen lights radiant panel and pilot flame, really
It is at least 180 seconds continual and steady to recognize chimney signal value (chimney signal value).When signal value becomes stable, school is removed
Quasi- test specimen, and install in 10 seconds according to the exemplary top insulator of manufacture.In addition, test constantly chimney signal value, and
Record flame tip reach according to each time of point for the 50mm for manufacturing exemplary top insulator and the point of fray-out of flame and
The time of fray-out of flame.
If there is no igniting within 600 seconds after test starts, or then remove root by 180 seconds after fray-out of flame
According to the exemplary top insulator of manufacture, and standard specimen is installed again.It has manufactured exhausted at the top of exemplary a total of three according to manufacturing
Edge body, and the process is in total in triplicate.
4. stability
Secondary cell is manufactured by using according to the top insulator of manufacture example, comparative example 1 and comparative example 2, then
It is fully charged.In addition, when secondary cell to be put into temperature being maintained in 600 DEG C of heating furnace and heating 3 minutes to 5 minutes,
Secondary cell explosion.In addition, the secondary cell of explosion is cooled down at room temperature, cap assemblies are then dismantled, to confirm in battery can
Top edge whether there is pin hole.
5. tensile strength and elongation percentage
The each top insulator manufactured according to manufacture example, comparative example 1 and comparative example 2 is fixed to by Instron system
The upper fixture for the universal testing machine (UTM, model 3340) made and lower fixture.In addition, with the same of the speed tensile of 300mm/min
When measurement needed for power, which is be evaluated as tensile strength.In addition, the ratio of tensile elongation and tensile strength is be evaluated as extending
Rate.It is tested twice, calculates the average value of each result.
Physical characteristic measurement result
1. heat resistance
[table 2]
Figure 17 is that diagram is obtained and carrying out heat resistance test to the exemplary top insulator of manufacture according to the present invention
Result curve graph, Figure 18 be illustrate by according to the top insulator of comparative example 2 carry out heat resistance test and obtain
As a result curve graph.In addition, table 2 is shown based on temperature range, the amount of the mass loss of each top insulator and remaining matter
Amount.
As shown in Figure 17, it is gradually decreased stage by stage according to the exemplary top insulator of manufacture.In addition, reduced quality is wide
It spends shown in table 2 as above.As shown in table 2, can confirm according to the exemplary top insulator of manufacture in the range of 0 DEG C to 320 DEG C
Mass loss with 3.8wt%, with the mass loss of 9.3wt% in the range of 320 DEG C to 600 DEG C, and at 600 DEG C
With the mass loss of 0.3wt% in the range of to 700 DEG C.
On the other hand, as shown in Figure 18, according to the quality of the top insulator of comparative example 2 until 600 DEG C of temperature
Until continue to decline, and the quality of top insulator declines rapidly in the range of 320 DEG C to 600 DEG C.As shown in table 2,
It can confirm mass loss in the range of 0 DEG C to 600 DEG C according to the top insulator of comparative example 2 with 40.5wt%.
When having 600 DEG C of temperature according to the top insulator of comparative example 1, it is completely consumed and has lost
The quality of 100wt%, since it quickly burns and is being not shown in the figure.
Therefore, it was confirmed that had under 600 DEG C or higher temperature due to pyrolysis according to the exemplary top insulator of manufacture
Caused minimum mass loss amount 13.4wt%, or even still there is thermal stability until 950 DEG C of temperature.
2. chemical resistance
[table 3]
| LiPF6 | LiFSI | Remaining component | |
| Benchmark | 9.5 | 11.4 | 79.1 |
| Manufacture example | 6.5 | 9.3 | 84.2 |
| Comparative example 1 | 9.4 | 11.1 | 79.5 |
| Comparative example 2 | 7.8 | 0.8 | 91.4 |
Figure 19 is the photo of the state of each electrolyte sample after being shown in chemical resistance test, and Figure 20 is that diagram is each
The curve graph of the GC-MS test result of electrolyte sample.In addition, table 3 shows the ratio of components of the component of each electrolyte sample.
As shown in table 3, LiPF6 and LiFSI is opposite in all samples is reduced, remaining component tends to relative increase.
However, this is not meant to that LiPF6 and LiFSI are decomposed and become remaining component of electrolyte, because absolute mass does not change
Become.The numerical value as shown in table 3 is relative mass ratio, therefore meaning that LiPF6 and LiFSI are more decomposed relatively.
As shown in table 3, in the exemplary top insulator of manufacture according to the present invention, when compared with benchmark, LiPF6 subtracts
3wt% is lacked, LiFSI reduces 2.1wt%.However, LiPF6 and LiFSI divide in the top insulator according to comparative example 1
0.1wt% and 0.3wt% are not reduced, in the top insulator according to comparative example 2, LiPF6 reduces 1.7wt%, LiFSI
Reduce 10.6wt%.That is, it can be seen that LiFSI is reduced at most in the top insulator according to comparative example 2, this
Show that according to the top insulator of comparative example 2 be most active.
9 photo referring to Fig.1, range estimation confirmation, becomes according to the color for the electrolyte for including in the top insulator of comparative example 2
Change maximum.In addition, in the curve graph of Figure 20, it can be verified that most weak chemical resistance is had according to the top insulator of comparative example 2,
Because detecting a large amount of by-products being initially not present in the electrolyte comprising the top insulator according to comparative example 2.
Therefore, can confirm, according to the exemplary top insulator of manufacture than the top according to comparative example 2 in terms of chemical resistance
Insulator is more excellent.
However, there is highest chemical resistance according to the top insulator of comparative example 1.However, in heat resistance test, it can
Confirm that minimum heat resistance is had according to the top insulator of comparative example 1, therefore, according to the exemplary top insulator of manufacture resistance to
It is excellent in terms of hot and chemical resistance.
3. flame propagation
[table 4]
[table 5]
Table 4 is shown for according to manufacturing for exemplary top insulator, critical flux, total heat dissipation capacity when extinguishing,
It is that whether exothermic maximum rate and flame drip as a result, table 5 is shown for putting down according to manufacturing for exemplary top insulator
The result of equal combustion continuation heat.
Combustion continuation heat be by the way that time when flame tip reaches at every will be played from initial exposure sample, multiplied by
It is worth obtained from the radiation heat flux of same point radiation corresponding with non-combustible calibration plate.In addition, average combustion continues heat is
The average value for the characteristic value that combustion continuation heat measures at different locations.As shown in table 5, exhausted according to exemplary top is manufactured
The average combustion of edge body continues heat less than 1.5, that is, when flame reaches a reference value when distance is 50mm or 100mm.
However, igniting started at 13 seconds, 12 seconds and 13 seconds respectively in the top insulator according to manufacture example 1 to 3.
However, flame extinguished at 54 seconds, 31 seconds and 50 seconds respectively, then top insulator is no longer ignited.Therefore, it can confirm flame not
It is maintained in top insulator, because even average combustion continues that heat is lower, and flame is also put out in a short time during burning
It goes out.That is, it can be verified that flame is not easy to travel to around it, so that it is guaranteed that safety.
Critical flux when extinguishing refers to that flame is propagated from the center line of burning sample at the farthest position to stop
Heat flow velocity.The heat flux of record is obtained via the calibration test of test machine by using calibration plate.As shown in table 4,
It is 48.6kW/m according to the average value for manufacturing critical flux when exemplary top insulator is extinguished2, it is greater than 20.0kW/m2's
A reference value, therefore meet standard.
Total heat dissipation capacity refers to that total heat dissipation capacity during test, exothermic maximum rate refer to the exothermic maximum rate during test.Such as
Shown in table 4, it is 0.03MJ according to the average value for the total heat dissipation capacity for manufacturing exemplary top insulator, is less than and is used as a reference value
0.7MJ, and the average value of exothermic maximum rate is 0.21kW, is less than 4.0kW as a reference value.
4. stability
[table 6]
| Sum | There is the number of pin hole | Pin hole incidence | |
| Manufacture example | 41 | 0 | 0% |
| Comparative example 1 | 15 | 3 | 20% |
| Comparative example 2 | 15 | 0 | 0% |
Figure 21 is diagram secondary cell of the manufacture example set equipped with top insulator according to the present invention in stability test
The photo of decomposing state later, Figure 22 are to illustrate to be assembled with the secondary cell of top insulator in stability according to comparative example 1
The photo of decomposing state after test, Figure 23 are to illustrate to be assembled with the secondary cell of top insulator steady according to comparative example 2
The photo of decomposing state after qualitative test.In addition, table 6 shows the number and ratio of the appearance pin hole of each top insulator
Rate.
As shown in Figure 22, pin hole is generated being wherein assembled in the secondary cell according to the top insulator of comparative example 1.
Specifically, as shown in table 6, it is being assembled in 15 secondary cells according to the top insulator of comparative example 1, at three two
Pin hole is generated in primary cell.
On the other hand, as shown in Figure 21 and Figure 23, it can be verified that according to manufacturing exemplary top insulator and according to comparing
The top insulator of example 2 is at all without generating pin hole, the optimum stabilization with electrical resistance method explosion.
However, due to the top insulator according to comparative example 2 in terms of heat resistance, chemical resistance and stability ratio according to system
It is weak to make exemplary top insulator, so susceptible of proof is according to manufacturing exemplary top insulator in heat resistance, chemical resistance and steady
Qualitative all aspects are all excellent.
5. tensile strength and elongation percentage
[table 7]
Table 7 shows the tensile strength and elongation percentage of each top insulator.
As shown in table 7, according to the exemplary top insulator of manufacture in 133.64N/mm2Average tensile strength when it is broken
It splits.In addition, the average value of elongation percentage at this time is 7.13%.
However, according to the top insulator of comparative example 1 in 56.9N/mm2Average tensile strength when rupture.In addition, at this time
Elongation percentage average value be 49.0%.
In addition, not being stretched to 1000N at all according to the top insulator of comparative example 2, this is the maximum of universal testing machine
Allow weight.Therefore, unmeasured tensile strength, the average value of elongation percentage are 0%.
Therefore, have and be easy because smaller due to low tensile strength and high-elongation according to the top insulator of comparative example 1
Power and the problem of deform.Further, since not having tensile properties according to the top insulator of comparative example 2, so it is without legal system
At roll.Therefore, because top insulator is not in line, thus continuous production be it is impossible, productivity can reduce.So
And the energy stretched according to exemplary top insulator is manufactured due to its high tensile and low elongation and to a certain extent
Power, so may be produced that wherein top insulator is rolls-up onto the roll of side.
As described above, with according to the relevant technologies the case where being coated with thermoplastic resin or phenol compared with, work as glass fibre
161 when being applied silicon rubber 162, and the top insulator 16 of secondary cell is used for by manufacturing, and can improve such as heat resistance and resistance to
Characteristic chemically etc.Specifically, it is the chain type bonding scheme of carbon (C) that phenol, which has wherein central element, and as silicon rubber
The silicone polymer of the primary raw material of glue 162 have wherein central element be silicon chain type bonding scheme.Therefore, it can get higher
Thermal stability.In addition, can inhibit the generation of dust in 16 punching press of top insulator that will be used for secondary cell, so as to
Enough continuous production products increase yield and reduce manufacturing cost.In addition, being stamped in the top insulator 16 for secondary cell
Before, top insulator fabric can have flexibility and be easy to roll, thus therefore parent roll easy to form easy to manufacture can be used
In the top insulator 16 of secondary cell.
Technical field ordinarily skilled artisan will understand that, in the case where not changing technical concept or inner characteristic
The present invention can be implemented in other specific forms.Therefore, above embodiment is considered illustrative and not restrictive.Cause
This, the scope of the present invention is defined by the following claims, rather than exemplary embodiment party as described in the description of front and its
Formula limits.The various modifications carried out in scope of the presently claimed invention and its within the scope of equivalents are considered falling in this hair
In bright range.
Claims (17)
1. a kind of top insulator for secondary cell being inserted into the shell of secondary cell, the top insulator packet
It includes:
The glass fabric formed by the weft yarn and warp thread of intermeshed glass fibers raw yarn；With
It coats to the silicon rubber at least one surface of the glass fabric.
2. top insulator as described in claim 1, wherein the silicon rubber includes:
First silicon rubber, first silicon rubber are attached to the glass fibre raw yarn；With
Second silicon rubber, second silicon rubber are inserted into the hole being formed between the glass fibre raw yarn.
3. top insulator as claimed in claim 2, wherein the glass fibre raw yarn is with the wherein glass fibre raw yarn
Shape perpendicular to one another is interlaced with one another, and
Second silicon rubber is inserted into the hole being formed between the glass fibre raw yarn perpendicular to one another.
4. top insulator as claimed in claim 2, wherein the top insulator has and the glass fabric phase
Same thickness.
5. top insulator as described in claim 1, wherein the silicon rubber includes:
First silicon rubber, at least one surface described in first Silicone Rubber Coated to the glass fabric；With
Second silicon rubber, second Silicone Rubber Coated to first silicon rubber.
6. top insulator as claimed in claim 5, wherein first silicon rubber is stacked on the glass fabric
On at least one described surface, and
Second silicon rubber is stacked on first silicon rubber.
7. top insulator as described in claim 1, wherein the silicon rubber is stacked on the described of the glass fabric
On at least one surface.
8. top insulator as described in claim 1, wherein the glass fabric has disc-shape.
9. top insulator as described in claim 1, wherein the Silicone Rubber Coated owning to the glass fabric
Two surfaces.
10. top insulator as described in claim 1, wherein the glass fabric has the group of 70wt% to 80wt%
At than, and
The silicon rubber has the ratio of components of 20wt% to 30wt%.
11. top insulator as claimed in claim 10, wherein the silicon rubber includes silicone polymer and fire retardant.
12. top insulator as claimed in claim 11, wherein the silicone polymer has the group of 10wt% to 20wt%
At than, and
The fire retardant has the ratio of components of 10wt% to 15wt%.
13. top insulator as claimed in claim 12, wherein the silicon rubber further comprises pigment.
14. top insulator as claimed in claim 13, wherein the pigment has 5wt% or lower ratio of components.
15. a kind of secondary cell, comprising:
Cylindrical battery tank；
The jelly roll electrode assembly being contained in the battery can；
It is coupled to the cap assemblies on the top of the battery can；
The front end of the battery can is set to install the flanging part of the cap assemblies；
It is configured to seal the pressure contact portion of the battery can；With
It is configured to the insulator that the electrode assembly insulate,
Wherein the insulator includes:
The glass fabric formed by the weft yarn and warp thread of intermeshed glass fibers raw yarn；With
It coats to the silicon rubber at least one surface of the glass fabric.
16. secondary cell as claimed in claim 15, wherein the insulator include setting the electrode assembly with it is described
Top insulator between cap assemblies.
17. secondary cell as claimed in claim 15, wherein the insulator include setting the electrode assembly with it is described
Bottom insulator between the bottom of battery can.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20180010900 | 2018-01-29 | ||
| KR10-2018-0010900 | 2018-01-29 | ||
| KR10-2018-0125529 | 2018-10-19 | ||
| KR1020180125529A KR102242251B1 (en) | 2018-01-29 | 2018-10-19 | The Secondary Battery And Top Insulator For Secondary Battery |
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| CN110098371A true CN110098371A (en) | 2019-08-06 |
| CN110098371B CN110098371B (en) | 2020-08-14 |
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| CN201910080012.2A Active CN110098371B (en) | 2018-01-29 | 2019-01-28 | Secondary battery and top insulator for secondary battery |
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| WO (1) | WO2019146926A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114424381A (en) * | 2019-11-20 | 2022-04-29 | 株式会社Lg新能源 | Secondary battery and device including the same |
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| Publication number | Publication date |
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| CN110098371B (en) | 2020-08-14 |
| WO2019146926A1 (en) | 2019-08-01 |
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