CN106299210B - A kind of non-aqueous secondary battery isolation film production method and equipment - Google Patents
A kind of non-aqueous secondary battery isolation film production method and equipment Download PDFInfo
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- CN106299210B CN106299210B CN201610943277.7A CN201610943277A CN106299210B CN 106299210 B CN106299210 B CN 106299210B CN 201610943277 A CN201610943277 A CN 201610943277A CN 106299210 B CN106299210 B CN 106299210B
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- isolation film
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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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
Abstract
This application involves a kind of non-aqueous secondary battery isolation film production methods, comprising: Step 1: being coated with one layer of coating fluid in isolation film surface；Step 2: the isolation film that surface is coated with coating fluid is imported in solidification liquid, and to isolation film surface pressure, make coating fluid and solidification liquid that mass exchange occur；And Step 3: the isolation film that mass exchange occurs for coating fluid and solidification liquid is exported into solidification liquid.Non-aqueous secondary battery isolation film production method provided herein, by applying active force to the isolation film imported in solidification liquid, promote coating fluid and solidification liquid quickly to occur mutually to spread and then inversion of phases occurs, it avoids because coating fluid and solidification liquid spread the unfavorable lesser cementability porous layer in formation aperture, and then it avoids the lesser cementability porous layer in aperture in heat pressing process and avalanche occurs, the ionic conductivity of isolation film is effectively improved, battery polarization is reduced.
Description
Technical field
This application involves battery technology field, more particularly to a kind of it can promote the non-of solidification liquid and coating fluid phase counterdiffusion
Aqoue seconary battery isolation film production method and equipment.
Background technique
Non-aqueous secondary battery especially lithium ion secondary battery is with characteristics such as its energy density height, good rate capabilities, extensively
It is general to be used for as the power supply of the mancarried electronic aids such as laptop, digital camera, video camera and mobile phone.With lithium battery technology
Development, lithium ion secondary battery can also be used as the power supply of new-energy automobile.In order to further increase lithium ion secondary electricity
The energy density in pond generallys use the compound soft-package battery of aluminium.However in the cyclic process of battery charging and discharging, along with charge and discharge
Progress, will form gap between the electrode and isolation film of inside battery, cause circulation volume to reduce and influence service life of battery.
The prior art uses on the micro- porous isolating membrane of polyolefin, constitutes cementability porous layer using Kynoar (PVDF) resin.
In secondary cell manufacturing process, injection electrolyte encapsulation is carried out after electrode and isolation film winding, hot pressing is then carried out, utilizes
PVDF resin layer is bonded electrode and isolation film, solves the clearance issues generated by battery charging and discharging circulation.
During carrying out cured to coating fluid using solidification liquid, coating fluid has just started and contact solidification liquid the prior art
When, it will form one layer of finer and close cortex and solidification liquid and coating fluid hindered to spread, slow down process of setting.And in order to reduce cortex shape
At the prior art can be using the method for delaying cortex to solidify, and these methods can equally hinder the process of setting of coating fluid entirety.
And since in the forming process of cementability porous layer, solidification liquid and coating fluid phase counterdiffusion are slow, it is unfavorable for coating fluid
Solidification, and then the cementability porous layer aperture resulted in is smaller, in heat pressing process, the lesser cementability porous layer in aperture holds
Easily there is avalanche, thereby reduce the ionic conductivity of isolation film, increase battery polarization, furthermore there is also solidifications for the prior art
The defects such as the time is long, and solidification liquid consumption is big, production efficiency is low.
In consideration of it, special propose the application.
Summary of the invention
The primary goal of the invention of the application is to provide a kind of non-aqueous secondary battery isolation film production method.
The second goal of the invention of the application is to provide the non-aqueous secondary battery isolation film making apparatus for realizing the above method.
In order to complete the purpose of the application, the technical solution of use are as follows:
This application involves a kind of non-aqueous secondary battery isolation film production methods, comprising:
Step 1: being coated with one layer of coating fluid in isolation film surface；
Step 2: the isolation film that surface is coated with coating fluid is imported in solidification liquid, and to isolation film surface pressure；And
Step 3: the isolation film that mass exchange occurs for coating fluid and solidification liquid is exported solidification liquid.
Preferably, repeatedly to isolation film surface pressure in step 2, number≤5 time preferably to press.
Preferably, when repeatedly pressing to isolation film surface in step 2, the adjacent time interval for applying active force twice is
0.2~3s.
Preferably, tape transport tension when isolation film transmits is 40~90N/m.
Preferably, tape running speed when isolation film transmits is 2~4m/min；More preferable isolation film passes through entire solidification liquid
Time is 30~60s.
Preferably, vertical with the direction of transfer of isolation film to the force direction of isolation film application.
The application further relates to a kind of non-aqueous secondary battery isolation film making apparatus, including pressing mechanism and solidification liquid contain
Mechanism, the solidification liquid contain mechanism and contain in mechanism for containing solidification liquid, the pressing mechanism setting in the solidification liquid,
For applying active force to isolation film surface.
Preferably, the preferably described pressing mechanism is multiple, and multiple pressing mechanisms are arranged at intervals on the solidification liquid and contain
The isolation film is transmitted with cooperation in mounting mechanism, the more preferable pressing mechanism is roll structure.
It preferably, further include bindiny mechanism, the bindiny mechanism is vertical relative to horizontal direction or is inclined at described
In solidification liquid apparatus for placing, the both ends of the bindiny mechanism are separately connected the pressing mechanism, in the bindiny mechanism
Portion is mutually fixed with the solidification liquid apparatus for placing, and the bindiny mechanism and pressing mechanism cooperation enable the isolation film edge
The transmission of the path S.
Preferably, the pressing mechanism is roll structure.
Technical solution provided by the present application can achieve it is following the utility model has the advantages that
Non-aqueous secondary battery isolation film production method provided herein, by the isolation film imported in solidification liquid
Apply active force, during active force applies with cancelling, the coating fluid of film surface is isolated and solidification liquid quickly carries out mutually
Inversion of phases is spread and then occurs, so as to avoid to spread the lesser cementability in unfavorable formation aperture porous because of coating fluid and solidification liquid
Layer, efficiently solve the problems, such as existing isolation film in the production process solidification liquid spread with coating fluid it is slow.And then it avoids
There is avalanche in the lesser cementability porous layer in aperture in heat pressing process, effectively increases the ionic conductivity of isolation film, reduces
Battery polarization.
It should be understood that the above general description and the following detailed description are merely exemplary, this can not be limited
Application.
Detailed description of the invention
Fig. 1 is the schematic diagram one of non-aqueous secondary battery isolation film making apparatus provided by the embodiment of the present application one；
Fig. 2 is the schematic diagram of non-aqueous secondary battery isolation film making apparatus provided by the embodiment of the present application two；
Fig. 3 is the schematic diagram of non-aqueous secondary battery isolation film making apparatus provided by the embodiment of the present application three；
Fig. 4 is the schematic diagram of non-aqueous secondary battery isolation film making apparatus provided by the embodiment of the present application four；
Fig. 5 is the SEM figure of the isolation film of the processing of non-aqueous secondary battery isolation film making apparatus provided by embodiment one；
Fig. 6 is that the prior art (comparative example one) is not added using the non-aqueous secondary battery isolation film making apparatus of pressing mechanism
The SEM of the isolation film of work schemes；
Fig. 7 is the isolation film of the processing of non-aqueous secondary battery isolation film making apparatus provided by the application comparative example two
SEM figure；
Fig. 8 is the isolation film of the processing of non-aqueous secondary battery isolation film making apparatus provided by the application comparative example three
SEM figure；
Fig. 9 is the SEM figure of the isolation film of the processing of non-aqueous secondary battery isolation film making apparatus provided by embodiment three.
Wherein: 1, pressing mechanism；2, solidification liquid contains mechanism；3, unreeling structure；4, rolling-up mechanism；5, introducing mechanism；6,
Export agency；7, bindiny mechanism；8, coating mechanism；9, water lotion contains mechanism；10, isolation film；11, baking oven.
The drawings herein are incorporated into the specification and forms part of this specification, and shows the implementation for meeting the application
Example, and together with specification it is used to explain the principle of the application.
Specific embodiment
The application is described in further detail below by specific embodiment and in conjunction with attached drawing." preceding " in text,
" rear ", "left", "right", "upper", "lower" are with the placement status of the non-aqueous secondary battery isolation film making apparatus in attached drawing
Reference.
This application involves a kind of non-aqueous secondary battery isolation film production methods, comprising the following steps:
Step 1: one layer of coating fluid is coated in isolation film surface.
After the completion of the coating of step 1, coated face is avoided prematurely to contact with roller.The time interval of the two is at least big
In 3s, a large amount of losses of coating fluid are caused to avoid too early extruding.The time that isolation film enters solidification liquid is not needed strictly
It limits, solidification liquid can be immediately entered after coating, solidification liquid can also be entered back by interval of time.To prevent
Coating fluid is completely dried solidification, which should control within 20s.
After the completion of coating, step 2 is carried out: the isolation film that surface is coated with coating fluid being imported in solidification liquid, and to isolation
Film surface pressure makes coating fluid and solidification liquid that mass exchange occur.
Specifically, it is resin and ceramic powder that the main component of coating fluid, which is Kynoar (PVDF), with N- methyl pyrrole
Pyrrolidone (NMP) is solvent.Solidification liquid is the aqueous solution of NMP.Coating fluid and the process that mass exchange occurs for solidification liquid are as follows: logical
It crosses to isolation film surface pressure, keeps coating fluid coating thinning, the organic solvent NMP in coating fluid expands from coating to solidification liquid
It dissipates, leaves hole in the coating.After removing pressure, the original thickness of coating fluid coat resuming, the water in solidification liquid is diffused into
Enter the position that original NMP is occupied in coating fluid coating, completes the mass exchange of both coating fluid and solidification liquid.To export solidification liquid
Isolation film be dried, obtained coating have smooth surface and good pore structure.The application utilizes application and revocation
The pressure of isolation film is acted on, the phase counterdiffusion between coating fluid and solidification liquid is promoted, to improve setting rate, is promoted in coating
The formation of pore structure.Simultaneously in extrusion process, replace the water in NMP and solidification liquid in coating, then pass through drying
Moisture is removed, is not present in toxic NMP in dry coating, increases the safety of operation.
As a kind of improvement of the application isolation film production method, can repeatedly press to isolation film surface in step 2,
Keep the diffusion between coating fluid and solidification liquid more abundant.The number repeatedly to press is usually no more than 5 times.The number that presses is very few,
It is unobvious to the influence for improving diffusion；The number that presses is excessive, is easily damaged coating, causes the avalanche of pore structure.
As a kind of improvement of the application isolation film production method, when repeatedly pressing to isolation film surface in step 2, phase
The adjacent preferred 0.2-3s of time interval for applying active force twice.If the adjacent time interval for applying active force twice is too short, by
The coating fluid coating of extruding also has not enough time to restore just to be pressed again, then will affect the mutual expansion between coating fluid and solidification liquid
It dissipates, loses the meaning repeatedly to press, be also easily damaged coating；If time interval is too long, isolation film can be extended in solidification liquid
In time, be not achieved the application shorten working hour effect.
In entire transmit process, transmission speed is consistent isolation film.Multiple rollers can be set in transmitting path, with
Play the role of extruding and transmission isolation film.Preferably, with cross roller number increase, tape transport tension can increase accordingly, for every
It is also just increasing from the active force that film applies, squeezing effect can be enhanced in this way, preferably promote coating fluid and solidification liquid
Diffusion.
After the completion of extruding, step 3 is carried out: the isolation film that mass exchange occurs for coating fluid and solidification liquid is exported into solidification liquid.
As a kind of improvement of the application isolation film production method, after step 3, return step two.Repeatedly will
The isolation film that surface is coated with coating fluid, which imports in solidification liquid, to press.Effect is the object being repeatedly coated between liquid and solidification liquid
Mass transter obtains the coating with higher porosity.
As a kind of improvement of the application isolation film production method, tape transport tension when isolation film transmits is 40~90N/m,
Tension is too small, does not have the effect to isolation film pressure；Overtension is easily damaged isolation film.It is preferred that tape running speed is 2~4m/
Min, the time by entire solidification liquid are 30~60s.Active force is not being applied in the prior art to isolation film, isolation film is logical
The time for crossing entire solidification liquid is 1~2min.Using method provided by the present application can reduce isolation film by solidification liquid when
Between, shorten machining period, while the porous layer obtained has biggish porosity and stability.
It is further preferred that the isolation film with a thickness of 12 μm uses the tape transport tension of 80-90N/m, with a thickness of 9 μm of isolation film
Using the tape transport tension of 60-70N/m, the tape transport tension of 50-60N/m is used, with a thickness of 7 μm of isolation films with a thickness of 5 μm of isolation
Film uses the tape transport tension of 40-50N/m.Usually tape transport tension is bigger, and the active force applied for isolation film is bigger, more
Be conducive to coating fluid and mass exchange occurs for solidification liquid.But isolation film is easily deformed or is broken when overtension, therefore right
In relatively thin isolation film, tape transport tension should be suitably reduced.
Preferably, to isolation film apply force direction it is vertical with the direction of transfer of isolation film, with promote coating fluid and
Solidification liquid is diffused along shortest path, reduces time of the isolation film in solidification liquid.
As shown in Figs 1-4, present invention also provides a kind of non-aqueous secondary battery isolation film making apparatus, including extruder
Structure 1 and solidification liquid contain mechanism 2.Wherein solidification liquid contains mechanism 2 for containing solidification liquid, and solidification liquid (not indicating in figure) is used for
The coating fluid (not indicating in figure) on the isolation film 10 of mechanism 2, which is contained, with importing solidification liquid carries out inversion of phases in isolation film 10
Surface forms cementability porous layer.The setting of pressing mechanism 1 contains in mechanism 2 in solidification liquid, and pressing mechanism 1 passes through to isolation film 10
Promote coating fluid that phase counterdiffusion occurs with solidification liquid during applying active force and revocation active force.When solidification liquid contains mechanism
When being loaded with the solidification liquid enough with the coating fluid progress inversion of phases on the isolation film 10 of importing solidification liquid in 2, it is located at solidification liquid
Liquid level pressing mechanism 1 below can directly act on isolation film 10, and promote to apply by applying active force to its surface
Inversion of phases occurs for cloth liquid and solidification liquid.
As a kind of improvement of the application isolation film making apparatus, the application further includes unreeling structure 3 and rolling-up mechanism 4,
Unreeling structure 3 and rolling-up mechanism 4 are for discharging and collecting isolation film 10 and isolation film 10 is driven to move along transmitting path, unreeling machine
Structure 3 and rolling-up mechanism 4 are located at solidification liquid and contain the downstream and upstream of mechanism 2, and connect with pressing mechanism 1.Unreeling machine
Structure 3 and rolling-up mechanism 4 all have speed and adjust component (not shown), for adjusting the release of isolation film 10 and collecting speed
Degree.Pressing mechanism 1 can use roll structure, and roll structure is located in transmitting path.Unreeling structure 3 and rolling-up mechanism 4 pass through speed
It adjusts component control and unreels speed and rolling speed, and then control the transmission of the transmission speed and isolation film 10 of isolation film 10
Power is located in the transmitting path of isolation film 10 due to roll structure and is in contact with isolation film 10, when isolation film 10 starts transmission,
Occur therebetween when being contacted with each other to isolation film 10 there are stretching action, roll structure and isolation film 10 due to transmission tension mutual
Active force, roll structure apply active force and squeeze isolation film 10 in contact.When the part isolation film 10 continue transmission without
When being in contact again with roll structure, roll structure no longer applies active force to the part isolation film 10, is equivalent to active force and is revoked.It is logical
The application and revocation of active force suffered by isolation film 10 are crossed, solidification liquid contains solidification liquid and 10 surface of isolation film in mechanism 2
The phase counterdiffusion of coating fluid is promoted and accelerates the inversion of phases between solidification liquid and coating fluid.
As a kind of improvement of the application isolation film making apparatus, the application further includes introducing mechanism 5 and export agency 6,
The two cooperation pressing mechanism 1 is provided commonly for transmission isolation film 10.Wherein the setting of introducing mechanism 5 is contained in unreeling structure 3 and solidification liquid
Between mounting mechanism 2, the setting of export agency 6 contains between mechanism 2 and rolling-up mechanism 4 in solidification liquid, introducing mechanism 5 and export agency
6 are above the open end setting that solidification liquid contains mechanism 2, after unreeling structure 3 discharges isolation film 10, the traction isolation of rolling-up mechanism 4
Film 10 moves, and isolation film 10 is directed into solidification liquid and contained in mechanism 2 by introducing mechanism 5.It is immersed in solidification liquid in isolation film 10, and
After inversion of phases occurs for the coating fluid and solidification liquid on 10 surface of isolation film, isolation film 10 is exported solidification liquid and contains machine by export agency 6
Structure 2, and collected the isolation film 10 completed the process by rolling-up mechanism 4.The setting of pressing mechanism 1 contains mechanism 2 in solidification liquid
Interior, the isolation film 10 that mechanism 2 can be contained in order to import solidification liquid can be sufficiently immersed in solidification liquid, introducing mechanism 5 and be led
Mechanism 6 is distributed in the two sides of pressing mechanism 1 relative to pressing mechanism 1 out, and guiding structure, extrusion structure and derived type structure are formed
Transmitting path can be U-shaped.
In order to repeatedly apply active force to isolation film 10, keep the diffusion between coating fluid and solidification liquid more abundant, this Shen
Pressing mechanism 1 please can be it is multiple, multiple pressing mechanisms 1 be arranged at intervals on solidification liquid contain mechanism 2 in.Multiple pressing mechanisms
1 can just be spaced setting, so that isolation film 10 is transmitted along waveform path with cooperation.The number of pressure is usually no more than 5
It is secondary, apply the preferred 0.2-3s in interval of active force every time, the distance that can arrange by adjusting tape running speed or roller controls
The time interval.If the interval for applying active force is too short, extruded coating fluid coating also has not enough time to restore just by again
Pressure, then will affect the phase counterdiffusion between coating fluid and solidification liquid.
As a kind of improvement of the application isolation film making apparatus, for the ease of there is the isolation film of coating fluid to dual coating
10 are squeezed, and the application further includes bindiny mechanism 7, and bindiny mechanism 7 tilts relative to the short transverse of solidification liquid apparatus for placing
It is arranged in solidification liquid apparatus for placing.The both ends of bindiny mechanism 7 are separately connected a pressing mechanism 1, the middle part of bindiny mechanism 7 with
Solidification liquid apparatus for placing is mutually fixed, and bindiny mechanism 7 and the cooperation of pressing mechanism 1 enable isolation film 10 to transmit along the path S.With position
When pressing mechanism 1 in 7 both ends of bindiny mechanism contacts respectively, pressing mechanism 1 can respectively apply the both side surface of isolation film 10
Active force, to promote the phase counterdiffusion between the coating fluid and solidification liquid of 10 both side surface of isolation film.
As a kind of improvement of the application isolation film making apparatus, for the ease of the painting of the coating fluid on 10 surface of isolation film
Cloth, the application further include coating mechanism 8, and coating mechanism 8 connects with introducing mechanism 5 and the upstream of introducing mechanism 5 is arranged in.Every
Before importing solidification liquid splendid attire mechanism 2 from film 10, coating mechanism 8 can coat coating fluid in the side of isolation film 10.In the application
Isolation film 10 can be side coating coating fluid, be also possible to two sides coating coating fluid.It is all coated in the two sides of isolation film 10
It, can be using the pressing mechanism 1 of the path S setting, before isolation film 10 imports solidification liquid splendid attire mechanism 2, coating mechanism 8 when cloth liquid
Can the side of isolation film 10 coat coating fluid, introducing mechanism 5, pressing mechanism 1 and export agency 6 be collectively formed transmission every
Transmission plane from film 10.In the transmitting path of isolation film 10, the pressing mechanism 1 adjacent with introducing mechanism 5 is set with coating mechanism 8
It sets and active force is applied with the side for coating coating fluid to isolation film 10 in the ipsilateral of transmission plane.Since pressing mechanism 1 directly acts on
It is coated with the side of coating fluid in isolation film 10 and coating fluid is realized and sufficiently squeeze, be conducive to the good of coating fluid and solidification liquid
It spreads and then forms structurally stable cementability porous layer, avoid in heat pressing process because coating fluid and solidification liquid diffusion are bad
There is avalanche in the lesser cementability porous layer in the aperture resulted in.
As a kind of improvement of the application isolation film making apparatus, in order to enhance the coagulation result of coating fluid, in the application
Solidification liquid contain the quantity of mechanism 2 and can be 2-3.Each solidification liquid contains mechanism 2 and is arranged successively, and each solidification liquid contains machine
One pressing mechanism 1 is at least set in structure 2, to realize the multiple extruding to isolation film 10, and then promotes coating fluid and solidification liquid
Phase counterdiffusion accelerate inversion of phases between the two, so that isolation film 10 surface be promoted to form cementability porous layer.Due to applying
Cloth liquid and solidification liquid diffusion effect are good, so that the cementability porous layer formed can either realize the good of electrode and isolation film 10
Bonding, while porous structure stabilization can also be maintained in hot pressing, avalanche do not occur, so that battery polarization be effectively reduced.
As a kind of improvement of the application isolation film making apparatus, in order to reduce, in coating fluid, surface is attached in process of setting
Organic solvent isolation film 10 is had an impact, the application further include water lotion contain mechanism 9, water lotion contain mechanism 9 use
The removal of organic solvent is carried out in the isolation film 10 for containing mechanism 2 to export solidification liquid, water lotion contains mechanism 9 and solidification liquid is contained
Mounting mechanism 2 is connected, and the downstream that solidification liquid contains mechanism 2 is arranged in, and the quantity that water lotion contains mechanism 9 can be 1-3.
As a kind of improvement of the application isolation film making apparatus, in order to accelerate the rate of drying of isolation film 10, the application
It can also include drying mechanism.Drying mechanism can be baking oven 11, contains mechanism 9 with water lotion and connects, and is arranged in water lotion
The downstream of mechanism 9 is contained, isolation film 10 is directed into drying in baking oven 11 after completing washing.
Non-aqueous secondary battery isolation film making apparatus provided herein is set by containing in mechanism 2 in solidification liquid
Pressing mechanism 1 is set, the isolation film 10 imported in solidification liquid splendid attire mechanism 2 by 1 Dui of pressing mechanism applies active force, in isolation film
During active force suffered by 10 applies with revocation, phase counterdiffusion quickly occurs with solidification liquid for the coating fluid on 10 surface of isolation film
And then inversion of phases occurs, the unfavorable lesser cementability porous layer in formation aperture is spread so as to avoid because of coating fluid and solidification liquid,
And then avoid the lesser cementability porous layer in the aperture in heat pressing process and avalanche occur, effectively increase the ion of isolation film 10
Conductibility reduces battery polarization.
Specifically, the application is directed to the tape transport tension that isolation film 10 transmits and the time for passing through solidification liquid is porous to cementability
The influence that the formation of layer generates has carried out corresponding research, and the common isolation film making apparatus that will not have pressing mechanism 1
As a comparison case, specific process is as follows:
Embodiment one:
The coating fluid of the present embodiment can be using Kynoar (PVDF) system tree of Sol dimension group (Solvay) production
Rouge (Hylar460) and Al2O3Ceramic powder, with N-Methyl pyrrolidone (NMP) for solvent, according to mass ratio PVDF:Al2O3:
The ratio mixed dissolution of NMP=7:10:93 is made.Wherein, solidification liquid use weight percent for 30% NMP aqueous solution,
The temperature of coating fluid and solidification liquid is selected as 25 DEG C.Using blade coating by coating liquid in isolation film (12 μ m thicks, hole
Rate 38.4%, Gurley value 241s/100cc, the production of toray company) on.Using process equipment as shown in Figure 1, control
The tape transport tension of isolation film transmission is 80N/m, tape running speed 2m/min, and the time by entire solidification liquid is 50s.It is being isolated
Film is immersed in solidification liquid and is squeezed by pressurizing unit it, is squeezed using the interaction between tape transport tension and roller
Drying in oven of the surface of isolation film to promote the exchange of solidification liquid and coating fluid, under the conditions of isolation film is placed in 70 DEG C.
Comparative example one:
Pressing mechanism is not used.Coating fluid composition and coating process as in the first embodiment, only isolation film is placed in solidification liquid,
The exchange of liquid and solidification liquid is coated by diffusion.
Comparative example two:
The tape transport tension that isolation film transmits is set as 10N/m, remaining processing conditions is the same as embodiment one.Due to tape transport tension
After reduction, the squeeze pressure for crossing roller generation is very small, can be ignored.
Comparative example three:
Isolation film is set as 10min by the time of solidification liquid, remaining processing conditions is the same as comparative example two.
To above-mentioned change tape transport tension and pass through the isolation film surface of solidification liquid time using scanning electron microscope (SEM)
The cementability porous layer of formation is scanned, and obtains SEM figure.As viewed in figures 5-8, wherein Fig. 5 be one isolation film of embodiment SEM
Figure, Fig. 6 are that the SEM of one isolation film of comparative example schemes, and Fig. 7 is the SEM figure of the isolation film of comparative example two, and Fig. 8 is the isolation of comparative example three
The SEM of film schemes.It by comparison diagram 5 and Fig. 6, Fig. 5 and Fig. 7, Fig. 5 and Fig. 8, can clearly obtain: in embodiment one, in isolation film
Surface forms the cementability porous layer with good pore structure；In comparative example one, film surface has the PVDF resin being precipitated,
Structure is more loose, and pore structure is almost invisible；In comparative example two, in the case where reducing the tape transport tension of isolation film, isolation
Film surface has the PVDF resin being precipitated, and the hole number formed is less, can not form required cementability honeycomb sandwich；It is right
In ratio three, close to embodiment one, the quantity and density in hole do not increase significantly the surface topography of isolation film, illustrate not adopt
With pressure structure, only extends time of the isolation film by solidification liquid, the formation of cementability porous layer can also be promoted.Therefore this Shen
Please by the effect of pressing mechanism, phase counterdiffusion of the coating fluid with solidification liquid has been dramatically speeded up.By in isolation film immersion solidification
Apply pressure during liquid, the formation of cementability honeycomb sandwich can be effectively facilitated, reduce setting time.
The cementability porous layer thickness and Gurley value of isolation film surface are tested respectively, in which:
Film thickness test is isolated: using calibrator (production of Naitutoyo company, VL-50 type LITEMATIC), using 5mm
Flat probe, control probe travel speed is 50mm/min, and each coated film sample measures 60 thickness points, takes thickness average value
As measured value.
The test of Gurley value: cutting the diaphragm sample of 100mm × 100mm, is tested using U.S.'s Gurley4110N air permeability
Instrument, test gas volume are 100cc, and test gas is all passed through the time of diaphragm as Gurley value.Gurley value is used to
Air penetrability is characterized, refers to that the air of specific quantity passes through the time required for the diaphragm of particular area at a certain pressure, is weighing apparatus
Measure a measurement of diaphragm permeability quality.
Embodiment one, the test result of comparative example one to comparative example three are shown in Table 1.
Table 1
| Cementability porous layer thickness (μm) | Gurley value (s/100cc) | |
| Embodiment one | 2.2 | 271 |
| Comparative example one | 1.5 | 589 |
| Comparative example two | 1.9 | 422 |
| Comparative example three | 2.1 | 290 |
Under the premise of coating fluid weight is identical on isolation film in embodiment and comparative example, coating layer thickness is bigger after drying,
Illustrate that coating is more loose, porosity is higher；Otherwise coating layer thickness is smaller, illustrates that coating is finer and close, porosity is lower.Such as 1 institute of table
Show, the thickness and air permeability values of the cementability porous layer formed by comparison isolation film surface can be learnt:
In embodiment one, the cementability porous layer thickness that isolation film surface is formed is maximum, it is meant that its coating porosity is most
Height, and it also illustrates that the caking property coating of isolation film forms perfect porous structure with the smallest Gurley value, gas
Through performance is good；
In comparative example one, the cementability porous layer thickness that isolation film surface is formed is minimum, it is meant that and its porosity is minimum, and
It also illustrates the caking property coating of isolation film with maximum Gurley value almost without porous structure is formed；
In comparative example two, isolation film surface formed cementability porous layer thickness it is smaller, Gurley value is larger, illustrate every
When tape transport tension from film is smaller, the cementability honeycomb sandwich that isolation film surface is formed is relatively thin finer and close, and air permeability effect is poor,
Required porous structure can not be formed；
In comparative example three, the cementability porous layer thickness that isolation film surface is formed is less than cementability porous layer in embodiment one
Thickness, Gurley value be greater than embodiment one and be much smaller than comparative example two, illustrate extension time of the isolation film by solidification liquid
When, the hole count and density that membrane coat is isolated are not subject to a significant impact.
Embodiment two:
The present embodiment is set as multiple on the basis of example 1, by pressing mechanism 1, and isolation film 10 can use single side
Coating or dual coating, as shown in Figure 2.
Specifically, the Kynoar (PVDF) that ARKEN production can be used in the coating fluid of the present embodiment is resin
(KYNAR2851) it is dissolved in dimethylacetamide solvent and makes coating fluid, wherein the solid content of resin can be 7%.It will apply
Cloth liquid is coated on the surface of isolation film, then by the way that isolation film is immersed in solidification liquid the phase induced between coating fluid and solidification liquid
Conversion promotes coating fluid to solidify.Wherein, the temperature of coating fluid and solidification liquid can be 25 DEG C.Solidification liquid is immersed in isolation film 10
When middle, isolation film 10 is squeezed using multiple pressing mechanisms 1, by changing tape transport tension, isolation film 10 is applied to change
The size of the active force added.Isolation film 10 can be 1s by the extrusion time of each pressing mechanism 1, what pressing mechanism 1 acted on
Initial time is to immerse in solidification liquid to start after 5s in isolation film 10, and after application extruding squeezes 5 times with revocation, isolation film 10 is set
40min is dried in baking oven 11 under the conditions of 60 DEG C, the total time of submergence of the isolation film 10 in solidification liquid is 30s.
The selection of isolation film and source are as follows in embodiment two:
The isolation film of (1) 5 μ m thick: porosity 29.8%, Gurley value are 135s/100cc, and SK company, South Korea is raw
It produces；
The isolation film of (2) 7 μ m thicks: porosity 42.5%, Gurley value are 105s/100cc, Japanese Asahi Kasei Corporation
Production；
The isolation film of (3) 9 μ m thicks: porosity 38.7%, Gurley value are 164s/100cc, and SK company, South Korea is raw
It produces；
The isolation film of (4) 12 μ m thicks: porosity 38.4, Gurley value are 241s/100cc, and toray company is raw
It produces.
Be isolated film thickness, tape transport tension and speed setting, and isolation film surface cementability porous layer thickness and
The test result of Gurley value is shown in Table 2.
Table 2
Through table 2 it is found that compared with embodiment one, the porosity that can effectively improve cementability porous layer is repeatedly squeezed,
The diffusion of coating fluid and solidification liquid is uniform, and pore-size is uniform, enhances the stability of coating structure.Tape transport tension is to coating
The influence of energy is maximum, and 12 μm of isolation films are used with the tape transport tension of 80-90N/m, uses 60- with a thickness of 9 μm of isolation films
The tape transport tension of 70N/m uses the tape transport tension of 50-60N/m with a thickness of 7 μm of isolation films, uses with a thickness of 5 μm of isolation films
The tape transport tension of 40-50N/m, obtained coating structure are preferable.
Embodiment three:
The coating fluid of the application can also be using Kynoar (PVDF) system tree of Sol dimension group (Solvay) production
Rouge (Hylar460) and Al2O3Ceramic powder, with N-Methyl pyrrolidone (NMP) for solvent, according to mass ratio PVDF:Al2O3:
The ratio mixed dissolution of NMP=4:6:93 is made.Wherein, solidification liquid use weight percent for 30% NMP aqueous solution, apply
Cloth liquid and solidification liquid temperature are 25 DEG C.Using dip-coating by coating liquid in isolation film 10 (12 μ m thicks, porosity 38%,
The production of M824, Celgard company) on, the tape transport tension that control isolation film 10 transmits is 80N/m, and tape running speed can be 2m/
min.It is immersed in solidification liquid and the pressing mechanism 1 by the way that 7 both ends of bindiny mechanism are arranged in isolation film 10, specifically can be roller
Structure transmits isolation film 10 along the path S, extruding by above-mentioned roll structure to isolation film 10, using tape transport tension and roller it
Between interaction squeeze the surface of isolation film 10 to promote the exchange of solidification liquid and coating fluid, as shown in Figure 3.Its coating layer thickness
Similar to embodiment one and embodiment two with pore structure, the SEM figure that film surface is isolated is as shown in Figure 9.
10 making apparatus of non-aqueous secondary battery isolation film provided herein, by being contained in mechanism 2 in solidification liquid
Pressing mechanism 1 is set, and the isolation film 10 imported in solidification liquid splendid attire mechanism 2 by 1 Dui of pressing mechanism applies active force, is being isolated
During active force suffered by film 10 applies with revocation, the coating fluid and solidification liquid on 10 surface of isolation film quickly occur mutually to expand
Inversion of phases is dissipated and then occurs, so as to avoid to spread the lesser cementability in unfavorable formation aperture porous because of coating fluid and solidification liquid
Layer, and then avoid the lesser cementability porous layer in the aperture in heat pressing process and avalanche occur, effectively increase isolation film 10
Ionic conductivity reduces battery polarization.
The above is only preferred embodiment of the present application, are not intended to limit this application, for those skilled in the art
For member, various changes and changes are possible in this application.Within the spirit and principles of this application, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (9)
1. a kind of non-aqueous secondary battery isolation film production method characterized by comprising
Step 1: being coated with one layer of coating fluid in isolation film surface；
Step 2: the isolation film that surface is coated with coating fluid is imported in solidification liquid, and to isolation film surface pressure；And
Step 3: the isolation film that mass exchange occurs for coating fluid and solidification liquid is exported into solidification liquid,
It wherein, is 2 to 5 times to the number of isolation film surface pressure in step 2；And to isolation film surface pressure in step 2
When, the adjacent time interval for applying active force twice is 0.2~3s.
2. non-aqueous secondary battery isolation film production method according to claim 1, which is characterized in that when isolation film transmits
Tape transport tension be 40~90N/m.
3. non-aqueous secondary battery isolation film production method according to claim 1, which is characterized in that when isolation film transmits
Tape running speed be 2~4m/min.
4. non-aqueous secondary battery isolation film production method according to claim 3, which is characterized in that isolation film passes through whole
The time of a solidification liquid is 30~60s.
5. non-aqueous secondary battery isolation film production method according to claim 1, which is characterized in that apply to isolation film
Force direction it is vertical with the direction of transfer of isolation film.
6. a kind of non-aqueous secondary battery isolation film making apparatus for any one of claim 1 to 5 the method, feature
It is, including pressing mechanism and solidification liquid contain mechanism, the solidification liquid contains mechanism for containing solidification liquid, the extruder
Structure setting contains in mechanism in the solidification liquid, for applying active force to isolation film surface.
7. non-aqueous secondary battery isolation film making apparatus according to claim 6, which is characterized in that the pressing mechanism
To be multiple, multiple pressing mechanisms are arranged at intervals on the solidification liquid and contain in mechanism with the cooperation transmission isolation film.
8. non-aqueous secondary battery isolation film making apparatus according to claim 7, which is characterized in that further include connection machine
Structure, the bindiny mechanism is vertical relative to horizontal direction or is inclined in solidification liquid splendid attire mechanism, the connection machine
The both ends of structure are separately connected the pressing mechanism, and the middle part of the bindiny mechanism contains mechanism mutually admittedly with the solidification liquid
Fixed, the bindiny mechanism and pressing mechanism cooperation enable the isolation film to transmit along the path S.
9. non-aqueous secondary battery isolation film making apparatus according to claim 7 or 8, which is characterized in that the extruding
Mechanism is roll structure.
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| CN103201024A (en) * | 2010-11-05 | 2013-07-10 | 日东电工株式会社 | Method for manufacturing sheet-shaped separation membrane |
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| CN1408466A (en) * | 2001-09-28 | 2003-04-09 | 帝人株式会社 | Method for producing composite porous film |
| CN103201024A (en) * | 2010-11-05 | 2013-07-10 | 日东电工株式会社 | Method for manufacturing sheet-shaped separation membrane |
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