CN106099017B - A kind of preparation method of lithium battery diaphragm - Google Patents
A kind of preparation method of lithium battery diaphragm Download PDFInfo
- Publication number
- CN106099017B CN106099017B CN201610509124.1A CN201610509124A CN106099017B CN 106099017 B CN106099017 B CN 106099017B CN 201610509124 A CN201610509124 A CN 201610509124A CN 106099017 B CN106099017 B CN 106099017B
- Authority
- CN
- China
- Prior art keywords
- diaphragm
- blast pipe
- preparation
- lithium battery
- baking oven
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims abstract description 9
- 230000037303 wrinkles Effects 0.000 claims description 15
- 238000009499 grossing Methods 0.000 claims description 14
- 230000007704 transition Effects 0.000 claims description 9
- 230000007246 mechanism Effects 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 description 38
- 239000011248 coating agent Substances 0.000 description 30
- 239000002033 PVDF binder Substances 0.000 description 24
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 238000003618 dip coating Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229910052574 oxide ceramic Inorganic materials 0.000 description 6
- 239000011224 oxide ceramic Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 241000238367 Mya arenaria Species 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
A kind of preparation method of lithium battery diaphragm, includes the following steps：Prepare ceramic slurry；Barrier film base material is soaked in slurry pool and is coated；Barrier film base material is promoted in baking oven and is dried；In the baking oven multiple blast pipes are symmetrically arranged in the both sides of diaphragm, the arrangement mode of the blast pipe is m n array form, wherein, m is the quantity of longitudinal upper blast pipe, m >=2, n are the quantity of lateral upper blast pipe, n >=1, air force positioned at the blast pipe of same row is identical, and the air quantity of blast pipe gradually weakens from the bottom up on longitudinal direction.The method of the present invention can improve the heat-shrinkable of diaphragm, improve diaphragm and the cementability of pole piece in the battery, thus can improve the hardness of battery, improve the cycle life of battery.
Description
Technical field
The invention belongs to polymer Li-ion battery technical field more particularly to a kind of forming the net containing ceramic fillers
The preparation method of the diaphragm of network shape PVDF coatings.
Background technology
It is influenced by economic development and population growth, people are continuously increased the consumption figure of the disposable energy, are with oil
The fossil resource of representative is increasingly reduced, and the automobile using oil as raw material is also brought living point to people while facility
The problems such as environmental pollution, greenhouse effects.After since twentieth century leaf, the mankind just begin look for clean alternative energy source with
And energy storage device.
Lithium ion battery has safe and reliable and energy due to the high characteristic of small, light-weight, energy density
The advantages that fast charging and discharging, becomes the hot spot of novel power supply technical research in recent years.Diaphragm in lithium ion battery has partition
Positive/negative plate, the effect for simultaneously turning on lithium ion are to prepare a kind of important material of lithium ion battery.It is usually used in preparing lithium battery
The material of diaphragm has polyolefin, polyimides, non-woven fabrics etc., and the above material is prepared by coating organic or inorganic coating
The composite material arrived.These materials have porous structure and fabulous electrolyte wellability, and the electrolyte being stored in diaphragm can
Carrier as lithium ion transport.During lithium ion battery use, with the progress of cycle, lithium ion can constantly be disappeared
Consumption, when electrolyte content, which is depleted to, to maintain lithium ion normally to move about, performance of lithium ion battery will deteriorate, so as to cause not
It can normal charge and discharge.Therefore selection Electolyte-absorptive it is good and store electrolyte more than diaphragm be conducive to extend battery use the longevity
Life.
In field of lithium ion battery, it can be divided into hard shell packaging lithium ion battery according to manner of packing and soft shell packs lithium ion
Battery.Hard shell battery refers mainly to the larger box hat or aluminum-shell battery of hardness, and hard shell battery, which has, processes simple, the fixed spy of shape
Point.Soft shell battery refer to use the seal-packed battery of plastic-aluminum packaging film, soft shell battery have appearance it is flexible and changeable, it is light-weight,
The good feature of battery security.Since smart mobile phone, tablet computer and vehicle mounted dynamic battery are just towards thin, wide, light direction
Development, this requires matching lithium ion batteries towards thinner, wider, lighter direction design, and must use Soft Roll
The potting mode of dress improves the design advantage of battery.But flexible-packed battery is influenced by packaging material, there are the drawbacks of just
It is that battery deformation of feeling like jelly easily occurs, causes the deterioration of battery performance.In order to improve the hardness of battery, that takes at present generally arranges
Apply is to coat one layer of PVDF (vinylidene fluoride homopolymer) in membrane surface, but coat PVDF in membrane surface so that diaphragm is being met
It is easily breakdown when to pole piece or foreign matter burr, cause battery performance to deteriorate.
In order to enhance the breakdown characteristics of battery, the prior art coats one layer by the way of intaglio printing in membrane surface
2~6 μm of ceramics or the mixture of ceramics and PVDF, prepare diaphragm in this way, good with pole piece to reach diaphragm
Cementability, multiple coating processes need to be carried out to diaphragm, cost is higher；And the coating method of intaglio printing requires to tense diaphragm
Tension it is bigger, therefore in coating procedure, the diaphragm thin to diaphragm, especially thickness be easy to cause stronger stretcher strain,
To destroy diaphragm, the deterioration of cycle performance of battery is caused.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of lithium battery diaphragm simple for process, that battery performance can be improved
Method, only need carry out primary coating can obtain it is two-sided all contain cated diaphragm, can be improved battery discharge cycle performance,
Security performance and battery hardness performance.
To achieve the goals above, the present invention takes following technical solution：
A kind of preparation method of lithium battery diaphragm, includes the following steps：
Prepare ceramic slurry；
Barrier film base material is soaked in slurry pool and is coated；
Barrier film base material is promoted in baking oven and is dried；
Multiple blast pipes are symmetrically arranged in the both sides of diaphragm in the baking oven, the arrangement mode of the blast pipe is m × n
Array format, wherein m is the quantity of longitudinal upper blast pipe, and m >=2, n are the quantity of lateral upper blast pipe, and n >=1 is located at same
The air force of the blast pipe of row is identical, and the air quantity of blast pipe gradually weakens from the bottom up on longitudinal direction.
More specifically, the blast pipe is obliquely installed relative to diaphragm moving direction.
More specifically, the angle between the air inlet tube hub line and diaphragm moving direction clockwise is 15~75
Degree.
More specifically, diaphragm both sides have been symmetrically arranged discharge pipe above blast pipe in the baking oven.
More specifically, diaphragm both sides have been symmetrically arranged 2~5 discharge pipes above blast pipe in the baking oven.
More specifically, processing speed of the diaphragm in baking oven is 2.5~6.0m/min.
More specifically, 5 × 1 blast pipes are respectively provided with positioned at diaphragm both sides in baking oven, from top to bottom each air inlet
The air volume adjustment ratio of pipe is 8:6:4:2:1.
More specifically, further include smoothing wrinkle step, the smoothing wrinkle step is realized by smoothing wrinkle mechanism, and the smoothing wrinkle mechanism includes
A pair of of transition roller and the oscillating roller being set between the transition roller, the oscillating roller are set to the swing arm that can be swung around the shaft
On, the axis of the shaft is parallel with diaphragm width direction.
More specifically, the swing angle of the swing arm is 15 °.
By above technical scheme it is found that the present invention uses pull-type dipping process coated ceramic slurry in barrier film base material,
Can be formed on diaphragm by PVDF with ceramics mix the coating formed, in the coating containing PVDF form network architecture with
And the ceramic particle of filling in this configuration can ensure enough hardness for thin and big battery, to ensure that battery makes
When consistency, while there is stronger inoxidizability and puncture energy, battery security can be increased.The preparation work of the present invention
Skill realizes primary coating forming, is not required to reprocess diaphragm, effectively increases production efficiency, can obviously reduce cost.
Compared with prior art, the diaphragm that the method for the present invention is prepared has uniform network-like PVDF coatings, and ceramic particle
It is evenly distributed in the network coating of PVDF, improves the heat-shrinkable of diaphragm, improve diaphragm and pole piece in the battery
Cementability, thus the hardness of battery can be improved, improve the cycle life of battery.
Description of the drawings
Fig. 1 is the structural schematic diagram of used baking oven when diaphragm of the present invention is coated with；
Fig. 2 is another angle schematic diagram in baking oven；
Fig. 3 is the structural schematic diagram of smoothing wrinkle of embodiment of the present invention mechanism；
Fig. 4 is the schematic diagram of another angles of Fig. 3.
The specific implementation mode of the present invention is described in more detail below in conjunction with attached drawing.
Specific implementation mode
Present invention will now be described in detail with reference to the accompanying drawings., when describing the embodiments of the present invention, for purposes of illustration only, indicating
The attached drawing of device architecture can disobey general proportion and do partial enlargement, and the schematic diagram is example, should not limit herein
The scope of protection of the invention.It should be noted that attached drawing is using simplified form and uses non-accurate ratio, only to side
Just the purpose of the embodiment of the present invention, is clearly aided in illustrating.
The basic ideas of the method for the present invention are：Using pull-type dipping process on lithium battery diaphragm coated ceramic slurry,
Ceramic slurry is mixed to form organic solution by PVDF powders and solvent, and ceramic powder then is added and size configures, will
Barrier film base material is immersed in progress slurry coating in slurry pool, then carries out lifting drying in an oven, by adjusting drying rate
The size of the grid in the coating formed on the diaphragm surface is controlled, is formed in the barrier film base material finally obtained network-like
PVDF coating structures contain ceramic particle filler in the network-like structure.
It is core of the invention thought above, following will be combined with the drawings in the embodiments of the present invention, to the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are only a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of the every other embodiment that obtains, shall fall within the protection scope of the present invention.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
Implemented different from other manner described here using other, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
The ceramic slurry used in the method for the present invention can be used prior art and be made.When preparing ceramic slurry, organic solution
In PVDF powders can be PVDF or PVDF-HFP or their mixture, the organic solvent of selection can be NMP, acetone,
It is one or more of in DMF, THF, MEK, PVDF powders are dissolved in by way of stirring in organic solvent, macromolecule material is made
The organic solution of material, blender can use double planetary mixer, single blade mixer, ball mill or grinder etc., and mixing time is
20min~120min, the content of PVDF materials is 1%wt~10%wt in organic solution.
Organic solution obtained is sealed, and place 12 in the environment of being positioned over 20~30 DEG C~for 24 hours, then it is added
Ceramic material prepares ceramic slurry, and the content of ceramic powder is 1%wt~30%wt, preferably 6%wt in ceramic slurry, selection
Ceramic powder can be in alundum (Al2O3), silica, boehmite, magnesia, magnesium hydroxide, titanium dioxide or titanium sulfate
The particle D50 of one or more, ceramic powder can be 0.1~10um.
When coating, coating speed is 1m/min~30m/min, preferably 4~5m/min, through the invention coating process preparation
Coating in PVDF grids size be 0.1~50 μm, preferably 1~10 μm, coating layer thickness be 2 μm~20 μm, preferably 3 μm
~6 μm, ceramic content is 50%wt~90%wt, preferably 70%wt in coating.
With specific embodiment, the invention will be further described below：
Embodiment 1
The LBG (the PVDF copolymers containing HFP) of 3%wt contents is added in acetone, blender is opened and stirs 60min, system
At the solution of homogeneous transparent, seal and static 12 in 20~30 DEG C of environment~spare for 24 hours；
The α phase aluminum oxide ceramic powders that weight is solution weight 4.5%wt, the ceramic powder are added in above-mentioned solution
Expect that 50% accumulative diameter D50 is 0.4 μm in particle diameter distribution, opens blender and stirs 60min, stirs evenly, then crosses 80 mesh sieve
Ceramic slurry is made in net；
The ceramic slurry prepared dip-coating formula membrane treatment machine is coated on the polyethylene base material diaphragm of 7 μ m thicks simultaneously
Dry, after coating is dry, coating layer thickness is 5 μm；
It is network-like according to the PVDF that lithium battery diaphragm made from above step is a kind of filler containing aluminum oxide ceramic
The thickness of dual coating diaphragm, the lithium ion battery separator is 12 μm, and wherein polyethylene film thickness is 7 μm, pair of ceramic filler
Torus network shape coating layer thickness is 5 μm, and the aperture size mean value in coating network is 10 μm or so.
In order to prepare the network-like PVDF coatings of even aperture distribution, the present invention changes traditional dipping process
Into, in baking step using multiposition air inlet by the way of diaphragm is dried.The pull-type dip-coating diaphragm of the present embodiment is fast
The coating machine that dry-coated machine is produced using Zhuhai Guang Haojie precision machineries Co., Ltd.Diaphragm dip-coating in slurry pool 20
Afterwards, it is promoted in baking oven 1, as shown in Figure 1, the baking oven that the present invention uses is symmetrical arranged in baking oven 1 positioned at the both sides of diaphragm 10
There are multiple blast pipes 2, blast pipe 2 to dry to the surface of diaphragm.The arrangement mode of blast pipe is m n array form.For the ease of
Description, by the septum inlet prescription of baking oven to being defined as down, diaphragm exit direction is defined as, direction shown in arrow in Fig. 1
For diaphragm moving direction, it is longitudinal to be parallel to the direction of diaphragm moving direction, and the direction for being parallel to diaphragm width direction is laterally.
M is the quantity of longitudinal upper blast pipe, i.e. number of rows, and m >=2, n are the quantity of lateral upper blast pipe, i.e. columns, n >=1.Blast pipe battle array
The air force of blast pipe in row positioned at same row is identical, and the air quantity of blast pipe gradually weakens from the bottom up on longitudinal direction.Such as Fig. 2
Shown, the present embodiment is respectively provided with 5 × 1 blast pipes 2 in baking oven in diaphragm both sides, i.e., discharges into air hose provided with 5, each
It arranges and a blast pipe, i.e. an only row blast pipe is only set, the air volume adjustment ratio of each blast pipe is from top to bottom on longitudinal direction
8:6:4:2:1.Further, blast pipe 2 is obliquely installed relative to diaphragm moving direction, and 2 center line of blast pipe is moved with diaphragm
Angle a between direction clockwise is 15~75 degree.In baking oven above blast pipe diaphragm both sides be symmetrically arranged 2~
5 discharge pipes, the present embodiment septation both sides are respectively provided with 3 discharge pipes, and the air quantity and setting angle of discharge pipe are without spy
It is different to require.The heat distribution of five positions is adjusted by adjusting the air quantity of five blast pipes, so as to adjust the steam in baking oven
Pressure ensures the whole uniformly drying of coating, and forms network-like PVDF coatings.Processing speed of the diaphragm in baking oven be 2.5~
6.0m/min。
Preferably, further include smoothing wrinkle step in diaphragm preparation method of the invention, smoothing wrinkle step is realized by smoothing wrinkle mechanism.
With reference to Fig. 3 and Fig. 4, the smoothing wrinkle mechanism of the present embodiment includes a pair of of transition roller 4 and the oscillating roller being set between transition roller 45,
4 position of transition roller is fixed, and oscillating roller 5 is set in swing arm 6, and swing arm 6 can be under the driving of wobble drive unit (not shown)
It 7 swings around the shaft, the axis of shaft 7 is parallel with diaphragm width direction, i.e., the axis direction of shaft 7 is perpendicular to diaphragm movement side
To.Preferably, the swing angle a of swing arm 6 is 15 °.
The operating principle of smoothing wrinkle mechanism is：Diaphragm bypasses transition roller 4, oscillating roller 5 and transition roller 4 successively, and swing arm 6 is being swung
It 7 swings around the shaft under the control of driving unit, drives oscillating roller 5 to push diaphragm when swing arm 6 is swung, to realize to diaphragm
The smoothing wrinkle on surface.The common driving unit such as motor or cylinder may be used in wobble drive unit, as long as driving pendulum can be realized
Arm waves.
Compared with existing masking technique, diaphragm preparation method of the invention can realize primary coating forming, not have to base material
Diaphragm pre-process and reprocessed to the film after coating, effectively increases coating efficiency, technical process is simple, and can criticize
Quantization production, can handle the ultra-thin polyalkene diaphragm of most thin 3 μ m thick.
Embodiment 2
The HSV900 (PVDF homopolymers) of 6%wt contents is added in NMP, blender is opened and stirs 60min, be made uniformly
Transparent solution a；
The LBG of 1%wt contents is added in acetone, blender is opened and stirs 60min, the solution b of homogeneous transparent is made；
Solution a and solution b is pressed 1:20 ratio is added in agitator tank, stirs 30min, mixed solution；
The α phase aluminum oxide ceramic powder that weight is solution weight 5%wt, the ceramic powder are added into above-mentioned mixed solution
Expect that 50% accumulative diameter D50 is 0.4 μm in particle diameter distribution, opens blender and stirs 60min, stirs evenly, then crosses 80 mesh sieve
Net obtains ceramic slurry；
The above-mentioned ceramic slurry prepared is coated in the polyethylene base material diaphragm of 7 μ m thicks with dip-coating formula membrane treatment machine
It goes up and dries, after coating is dry, coating layer thickness is 4 μm.
According to the mixing PVDF nets that lithium battery diaphragm made from above step is a kind of filler containing aluminum oxide ceramic
Network shape dual coating diaphragm, the lithium ion battery separator overall thickness are 9 μm, and wherein polyethylene film thickness is 5 μm, ceramic filler
Two-sided network-like coating layer thickness is 4 μm, and the aperture size mean value in coating network is 5 μm or so.
Embodiment 3
21216 (the PVDF copolymers containing HFP) of 2%wt contents are added in acetone, blender is opened and stirs 60min,
It is made the solution of homogeneous transparent, seal and static 12 in 20~30 DEG C of environment~spare for 24 hours；
The α phase aluminum oxide ceramic powders that weight is solution weight 8%wt, the ceramic powder are added in above-mentioned solution
50% accumulative diameter D50 is 0.1 μm in particle diameter distribution；It opens blender and stirs 60min, stir evenly, then cross 120 mesh sieve
Net obtains ceramic slurry；
The ceramic slurry prepared dip-coating formula membrane treatment machine is coated on the polyethylene base material diaphragm of 3 μ m thicks simultaneously
Dry, after coating is dry, coating layer thickness is 4 μm.
It is network-like according to the PVDF that lithium battery diaphragm made from above step is a kind of filler containing aluminum oxide ceramic
Dual coating diaphragm, the lithium ion battery separator overall thickness be 7 μm, wherein polyethylene film thickness be 3 μm, ceramic filler it is two-sided
Network-like coating layer thickness is 4 μm, and the aperture size mean value in coating network is 5 μm or so.
With the diaphragm of the diaphragm of coated ceramic slurry in above three embodiments and the uncoated ceramic slurry of same thickness
Thermal contraction test is carried out, diaphragm thermal contraction test step is：Diaphragm is cut into 140mm × 65mm specifications, and measure length and
Width；Two A4 blank sheet of paper of the diaphragm sample cut are sandwiched neatly, are put into 130 DEG C of ovens, 1h is stood；Baking is completed,
After cooling, length and width are measured with Steel Ruler and calculates shrinking percentage；The calculation formula of diaphragm retracts rate is：Laterally (TD)=(baking
Width after width-baking before roasting) preceding width × 100% of/baking, longitudinal (MD)=(length after length-baking before baking)/baking
Preceding length × 100%.Shown in test result table 1, the diaphragm of uncoated ceramic slurry prepares raw material and technique in addition to uncoated
Raw material is prepared with the diaphragm of embodiment 1-3 and technique is identical outside ceramic slurry；
Table 1
The diaphragm of coated ceramic slurry made from above three embodiments and the diaphragm of uncoated ceramic slurry are cut
Afterwards, battery core is made in winding together with positive and negative plate, and the thick 2.9mm of battery core model, wide 87mm, long 110mm, battery core is through supercooling
Pressure, 60 DEG C of hot pressing, pack encapsulation, chemical conversion, 85 DEG C of hot pressing shapings, sealing, partial volume, prepare battery.It will be prepared
Battery using Shenzhen it is great it is prosperous up to Instrument Ltd. production HV-1000 model hardometers carry out diaphragm hardness test, survey
It using the load on of 1kgf when examination, is sampled at multiple positions of battery surface, is then averaged and can be obtained firmly
Test paper is spent, takes the average value of 10 sampled points as hardness number in battery surface in this test.Test result such as 2 institute of table
Show, the diaphragm of uncoated ceramic slurry prepares the diaphragm system of raw material and technique with embodiment 1 other than uncoated ceramic slurry
Standby raw material and technique are identical；
Table 2
By Tables 1 and 2 it is found that the diaphragm coated with the network-like PVDF coatings containing ceramic fillers has preferably heat receipts
Shrinkage and the performance for resisting burr breakdown, the battery prepared using this kind of diaphragm have better hardness performance.
Diaphragm made from diaphragm preparation method of the present invention can have due to the ceramic fillers containing higher proportion in diaphragm
Safety problem caused by effect prevents pole piece or external foreign matter from being pierced through to diaphragm；And the coating work of the pull-type dip-coating using innovation
Skill, it is avoidable that tensile failure is caused to base material diaphragm containing action separate to membrane tension in the manufacture craft, but also can
It discharges base material diaphragm and makes residual stress caused by transportational process, can avoid cell deformation caused by membrane tension, promote battery
Performance；Preparing coated on both sides diaphragm only using the method for pull-type dip-coating simultaneously need to can complete by primary coating, simplify
Technique can obviously reduce cost, improve production efficiency.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to embodiment illustrated herein, and is to fit to consistent with the principles and novel features disclosed in this article
Widest range.
Claims (9)
1. a kind of preparation method of lithium battery diaphragm, includes the following steps：
Prepare ceramic slurry；
Barrier film base material is soaked in slurry pool and is coated；
Barrier film base material is promoted in baking oven and is dried；
It is characterized in that：In the baking oven multiple blast pipes, the arrangement side of the blast pipe are symmetrically arranged in the both sides of diaphragm
Formula is m n array form, wherein m is the quantity of longitudinal upper blast pipe, and m >=2, n are the quantity of lateral upper blast pipe, n >=1,
Air force positioned at the blast pipe of same row is identical, and the air quantity of blast pipe gradually weakens from the bottom up on longitudinal direction.
2. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that：The blast pipe is moved relative to diaphragm
Dynamic direction is obliquely installed.
3. the preparation method of lithium battery diaphragm as claimed in claim 1 or 2, it is characterised in that：The air inlet tube hub line with
Angle between diaphragm moving direction clockwise is 15~75 degree.
4. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that：In the baking oven above blast pipe every
Film both sides have been symmetrically arranged discharge pipe.
5. the preparation method of the lithium battery diaphragm as described in claims 1 or 2 or 4, it is characterised in that：Blast pipe in the baking oven
Top diaphragm both sides have been symmetrically arranged 2~5 discharge pipes.
6. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that：Processing speed of the diaphragm in baking oven
For 2.5~6.0m/min.
7. the preparation method of lithium battery diaphragm as claimed in claim 1 or 2, it is characterised in that：It is located at diaphragm two in baking oven
Side is respectively provided with 5 × 1 blast pipes, and the air volume adjustment ratio of each blast pipe is 8 from top to bottom:6:4:2:1.
8. the preparation method of lithium battery diaphragm as described in claim 1, it is characterised in that：Further include smoothing wrinkle step, it is described to remove
Wrinkle step realizes that the smoothing wrinkle mechanism includes a pair of of transition roller and the pendulum that is set between the transition roller by smoothing wrinkle mechanism
Dynamic roller, the oscillating roller are set in the swing arm that can be swung around the shaft, and the axis of the shaft is parallel with diaphragm width direction.
9. the preparation method of lithium battery diaphragm as claimed in claim 8, it is characterised in that：The swing angle of the swing arm is
15°。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610509124.1A CN106099017B (en) | 2016-06-29 | 2016-06-29 | A kind of preparation method of lithium battery diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610509124.1A CN106099017B (en) | 2016-06-29 | 2016-06-29 | A kind of preparation method of lithium battery diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106099017A CN106099017A (en) | 2016-11-09 |
| CN106099017B true CN106099017B (en) | 2018-08-03 |
Family
ID=57211659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610509124.1A Active CN106099017B (en) | 2016-06-29 | 2016-06-29 | A kind of preparation method of lithium battery diaphragm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106099017B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107342394B (en) * | 2017-07-26 | 2023-07-04 | 湖北猛狮新能源科技有限公司 | Double-sided continuous coating equipment and coating method for lithium ion battery |
| CN108878749A (en) * | 2018-06-29 | 2018-11-23 | 珠海光宇电池有限公司 | A kind of diaphragm and preparation method thereof and lithium-sulfur cell using the diaphragm |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202591058U (en) * | 2012-05-22 | 2012-12-12 | 余艳 | Membrane coating machine |
| CN103515563A (en) * | 2013-10-15 | 2014-01-15 | 杨海燕 | Method for manufacturing ceramic diaphragm for high-safety lithium ion battery |
| CN103691626A (en) * | 2012-09-27 | 2014-04-02 | 天津力好科技发展有限公司 | Isolated film coater |
| CN203620870U (en) * | 2013-12-06 | 2014-06-04 | 珠海市广浩捷精密机械有限公司 | Environment-friendly high-precision lithium ion battery diaphragm coater |
| CN105514328A (en) * | 2016-01-13 | 2016-04-20 | 浙江天能能源科技有限公司 | Ceramic diaphragm for lithium ion battery and preparation method of ceramic diaphragm |
| JP2016072139A (en) * | 2014-09-30 | 2016-05-09 | 株式会社日立ハイテクファインシステムズ | Inorganic porous thin film manufacturing device and method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6387692B2 (en) * | 2014-06-11 | 2018-09-12 | 株式会社ジェイテクト | Nonaqueous storage device separator drying method, and storage device manufacturing method |
-
2016
- 2016-06-29 CN CN201610509124.1A patent/CN106099017B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202591058U (en) * | 2012-05-22 | 2012-12-12 | 余艳 | Membrane coating machine |
| CN103691626A (en) * | 2012-09-27 | 2014-04-02 | 天津力好科技发展有限公司 | Isolated film coater |
| CN103515563A (en) * | 2013-10-15 | 2014-01-15 | 杨海燕 | Method for manufacturing ceramic diaphragm for high-safety lithium ion battery |
| CN203620870U (en) * | 2013-12-06 | 2014-06-04 | 珠海市广浩捷精密机械有限公司 | Environment-friendly high-precision lithium ion battery diaphragm coater |
| JP2016072139A (en) * | 2014-09-30 | 2016-05-09 | 株式会社日立ハイテクファインシステムズ | Inorganic porous thin film manufacturing device and method |
| CN105514328A (en) * | 2016-01-13 | 2016-04-20 | 浙江天能能源科技有限公司 | Ceramic diaphragm for lithium ion battery and preparation method of ceramic diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106099017A (en) | 2016-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106953050B (en) | A kind of high temperature resistance multilayer diaphragm composite lithium ion cell diaphragm and preparation method thereof | |
| Kamat | Lithium-ion batteries and beyond: Celebrating the 2019 Nobel Prize in chemistry–a virtual issue | |
| Yang et al. | Batwing-like polymer membrane consisting of PMMA-grafted electrospun PVdF–SiO2 nanocomposite fibers for lithium-ion batteries | |
| CN103840112B (en) | PVDF-HFP-based composite porous polymer diaphragm and preparation method thereof | |
| CN106784542B (en) | A kind of lithium ion battery separator and preparation method thereof of a variety of coatings of high temperature resistant | |
| CN1274036C (en) | Electrochemical battery using multicomponent composite membrane | |
| Kotobuki et al. | Effect of sol composition on solid electrode/solid electrolyte interface for all-solid-state lithium ion battery | |
| CN106654119A (en) | Mixed coating diaphragm and preparation method and application thereof | |
| CN104650375B (en) | Preparation method of composite polymer electrolyte membrane | |
| CN105932209B (en) | Ceramic coating diaphragm for lithium ion battery and preparation method thereof | |
| CN106532104B (en) | A kind of lithium-sulfur cell gel electrolyte porous electrode and its preparation and application | |
| CN103474609A (en) | Overlapped coating composite lithium battery diaphragm and preparation method thereof | |
| WO2018113486A1 (en) | Slurry for lithium-ion battery and preparation method therefor | |
| CN109786817A (en) | Solid state lithium battery and its application and the method for preparing the solid electrolyte membrane that non-woven fabrics enhances | |
| CN107275670A (en) | The preparation method of lithium-ion-power cell and preparation method thereof, its barrier film and barrier film, and for forming the slurry of barrier film | |
| CN106099017B (en) | A kind of preparation method of lithium battery diaphragm | |
| CN107673350A (en) | A kind of polyethyleneimine-modified biomass carbon material, preparation method and the application in lithium-sulfur cell diagram modification | |
| CN108365269A (en) | A kind of coating processes of wet coating dielectric film coating machine | |
| CN113206223A (en) | Lithium battery pole piece processing method and lithium battery preparation method | |
| CN107681147A (en) | A kind of preparation method of solid electrolyte coating modification anode material for lithium-ion batteries and application | |
| CN113921986A (en) | Composite diaphragm and battery comprising same | |
| CN104332618A (en) | Nickel-cobalt-lithium manganese positive electrode material with boron-lithium composite oxide clad on surface, and preparation method thereof | |
| CN101872852A (en) | Preparation method of cell diaphragm based on aramid fiber | |
| WO2010101308A2 (en) | Positive electrode active material and lithium secondary battery | |
| CN103956476B (en) | Rich lithium manganese material, preparation method and the application in lithium ion battery of a kind of surface modification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Patentee after: Zhuhai CosMX Battery Co.,Ltd. Address before: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Patentee before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address after: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Patentee after: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address before: 519180 Guangdong Province, Zhuhai city Doumen District Xinqing Technology Industrial Park Mount Everest Road No. nine Patentee before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |