CN109004164A - A kind of lithium-ion-power cell pressure sensitive composite diaphragm - Google Patents
A kind of lithium-ion-power cell pressure sensitive composite diaphragm Download PDFInfo
- Publication number
- CN109004164A CN109004164A CN201810832412.XA CN201810832412A CN109004164A CN 109004164 A CN109004164 A CN 109004164A CN 201810832412 A CN201810832412 A CN 201810832412A CN 109004164 A CN109004164 A CN 109004164A
- Authority
- CN
- China
- Prior art keywords
- organic
- inorganic
- coating
- diaphragm
- lithium
- 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.)
- Pending
Links
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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to lithium ion power battery technology fields, it is related to a kind of lithium-ion-power cell pressure sensitive composite diaphragm, including MIcroporous polyolefin film, inorganic-organic coating coated at least one surface of MIcroporous polyolefin film, and the pressure sensitive Organic-inorganic composite coating being distributed coated in MIcroporous polyolefin film and/or inorganic-organic coating surface rule island.Inorganic-organic coating is made of particles of inorganic material and organic polymeric binder, improves the thermal stability of MIcroporous polyolefin film, reduces high temperature thermal contraction；Pressure sensitive Organic-inorganic composite coating is made of polymer hot melting glue, organic polymeric binder and particles of inorganic material, wherein polymer hot melting glue provides the adhesive attraction between electrode and diaphragm, particles of inorganic material provides the lithium ion tunnel in the coating, while the pressure sensitive organic and inorganic coating of regular island distribution ensure that electrode and diaphragm bond, diaphragm has lower air permeability, does not influence the high-multiplying power discharge of battery.
Description
Technical field
The invention belongs to lithium ion power battery technology fields, and in particular to a kind of lithium-ion-power cell is multiple with pressure sensitive
Close diaphragm.
Background technique
With the continuous improvement that country requires battery energy density, while being also the needs of market development, needs mentioning
Production cost is reduced while high battery production efficiency, the advanced battery production enterprise such as Japan and Korea S selects winding process, the work
The battery core that the battery core of skill production has many advantages, such as the high consistency of high efficiency, but prepares is in double arches, and the convex both sides in centre are recessed, need into
Row Shape correction.Under certain condition, battery positive/negative plate is pressed integral and will not rebounded, it is aobvious by pressure merely
It can not so accomplish, then just needing to provide between each interface, there is the coating of certain viscosity to play bonding effect, think in the industry most
Good mode is to carry out sticky processing in membrane surface.Since ceramic diaphragm has been popularized, high-temperature stability is excellent, energy
The security performance for enough improving battery, by demonstration, viscosity processing is carried out on the basis of ceramic diaphragm can retain the high temperature of diaphragm
Stability, while its effect for bonding positive/negative plate is assigned, the battery core after pressing can reduce assembly difficulty and production process
Scrappage, while improving inside battery interface, improve cycle performance.
Existing some technologies are to coat one layer of organic matter coating on conventional polyolefin ceramic diaphragm surface, cold using battery core
Hot-press arrangement carries out hot pressing shaping to battery core, and organic matter softens the bonding to be formed between diaphragm and pole piece, the problem is that having
The excessively high diaphragm that will affect of machine object coating coverage is breathed freely, and then influences the rate charge-discharge performance of battery, the covering of organic matter coating
Rate is too low, is not achieved the bond effect of diaphragm and pole piece, cohesive force and diaphragm it is ventilative between balance be difficult to hold, and technique
It is difficult to precisely realize.
Summary of the invention
The object of the present invention is to provide a kind of lithium-ion power battery dissepiment, overcome current conventional polyolefin ceramic diaphragm without
Method bonding and organic matter coating bonding and ventilative the shortcomings that cannot be considered in terms of, while guaranteeing that diaphragm and pole piece have enough cohesive forces,
There are also higher gas permeabilities for diaphragm, do not influence the high-rate charge-discharge capability of battery.
Lithium-ion-power cell of the invention pressure sensitive composite diaphragm, including MIcroporous polyolefin film；Coated in polyolefin
The inorganic-organic coating at least one surface of microporous barrier；Coated in the MIcroporous polyolefin film and/or inorganic-organic coating table
The pressure sensitive Organic-inorganic composite coating of the regular island distribution in face；
The MIcroporous polyolefin film is with a thickness of 5~25 μm；
The inorganic-organic coating layer thickness coated at least one surface of MIcroporous polyolefin film is 1~10 μm；It is described
Inorganic-organic coating coating method is intaglio printing；
The inorganic-organic coating includes particles of inorganic material and organic polymeric binder, by mass percentage, inorganic
Composition granule dosage is 80%~99%, and organic polymeric binder dosage is 1%~20%, is preferably in a proportion of particles of inorganic material
95%~98%, organic polymeric binder 2%~5%；
The particles of inorganic material be one of aluminum oxide, silica, zirconium dioxide, boehmite, barium sulfate or
It is several；The organic polymeric binder is polyvinylidene fluoride (PVDF), polyvinyl alcohol, polyurethane, sodium carboxymethylcellulose
(CMC), butadiene-styrene rubber (SBR), polyacrylate, polyacrylonitrile, polyacrylamide, in ethylene-vinyl acetate copolymer emulsion
One or more；
The organic and inorganic coating includes polymer hot melting glue, organic polymeric binder and particles of inorganic material, by quality
Percentage, polymer hot melting glue ratio are 50%~98%, and organic polymeric binder ratio is 1%~10%, inorganic matter
Grain ratio is 1%~49%；Preferred polymers hot melt adhesive ratio is 70%~98%, and organic polymeric binder ratio is 1%
~10%, particles of inorganic material ratio is 1%~29%；Organic and inorganic coating layer thickness is 0.5~6 μm.
The organic and inorganic coating coating method is flexographic printing, silk-screen printing；
The method of the present invention by flexographic printing roller carve different area, different shape and different meshes salient point, or
Realize the area on island and the control of island distance in the hole that person carves different area, different shape and different meshes on screen printing plate
System is adjusted by the pressure between slurry solid content and viscosity and printing plate cylinder and MIcroporous polyolefin film and realizes that island height and side are thrown
The control of shadow shape.Hole shape on salient point or screen printing plate on flexographic printing roller is set for round, ellipse, three
Angular or regular/irregular polygon etc.；Salient point and salient point or the center Kong Yukong spacing are 60 μm~600 μm, salient point or hole
Area is 1.9625 × 10-5cm2~2.826 × 10-3cm2, so that organic and inorganic coating is in regular island distribution, island it is vertical
Projection of shape is round, oval, triangle or rule/irregular polygon etc., and the preferably upright projection shape on island is circle,
Center spacing between the island Dao He are as follows: 60 μm~600 μm, preferably the center spacing between the island Dao He are as follows: 150 μm~500 μm；Island
Planimetric area size is 7.85 × 10-5cm2~7.065 × 10-4cm2；Pressure between printing plate cylinder and MIcroporous polyolefin film
For 0.1kg~2kg, so that lateral projection's shape on island is rectangle, triangle, rule/irregular polygon or steamed bun shape etc., it is excellent
The lateral projection's shape for selecting island is rectangle or steamed bun shape；Island height is 0.5~6 μm, and preferably island height is 1.5~3 μm.
Organic moiety in organic and inorganic coating provides the adhesive attraction between electrode and diaphragm, and inorganic particle provides
Lithium ion tunnel, especially circulating battery later period prevent the defect of polymer hot melting glue complete swelling plug-hole；Regular island point
While the pressure sensitive organic and inorganic coating of cloth ensure that electrode and diaphragm bond, diaphragm has lower air permeability, does not influence
The high-multiplying power discharge of battery.Because the presence in the gap for having island to divide between pole piece and basement membrane, acts as imbibition after battery core hot pressing
With the channel of exhaust, fluid injection and pumping are easier, while expanding reserved space to positive and negative anodes especially cathode, are unlikely to cause electricity
Core deforms bulging, causes circulating battery decaying too fast.
The polymer hot melting glue is the polyvinylidene fluoride (PVDF) that softening point is 60 DEG C~140 DEG C, polymethyl
Sour methyl esters (PMMA), polystyrene (PS), polyethylene (PE), vinyl-vinyl acetate copolymer (EVA), polyethylene glycol oxide
One or more of (PEO)；The organic polymeric binder be polyvinylidene fluoride (PVDF), polyvinyl alcohol, polyurethane,
Sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR), polyacrylate, polyacrylonitrile, polyacrylamide, ethyl vinyl acetate second
One or more of alkene copolymer lotion；The particles of inorganic material is aluminum oxide, silica, zirconium dioxide, Bo Mu
One or more of stone, barium sulfate；
First coating inorganic organic coating can be improved the dimensional stability of diaphragm, reduces high temperature and is heat-shrinked, ensures battery
Safety, re-coating organic-inorganic coating can be realized the bonding of diaphragm and pole piece, while guarantee that diaphragm air permeability is unaffected.
The present invention also provides the application of lithium-ion-power cell diaphragm, the diaphragm is for assembling lithium ion power electricity
Pond, assemble method are as follows: positive plate, negative electrode tab and the diaphragm being set between positive/negative plate are fabricated to electricity using winding method
Battery core is fitted into aluminum plastic film or metal-back outer packing, reinjects electrolyte, be fabricated to lithium-ion-power cell, wherein institute by core
Stating diaphragm is above-mentioned lithium-ion-power cell diaphragm.
Beneficial effects of the present invention:
1, contain particles of inorganic material in organic and inorganic coating of the invention, can be uniformly distributed in hot melt adhesive, heat when hot pressing
Melten gel and pole piece bonding, and the presence of particles of inorganic material is able to maintain ion channel, can play the role of pore-creating, realizes low
Gas value added, the ventilative of bonding point does not increase after especially ensure that long circulating, realizes high rate charge-discharge and the long-life is followed
Ring；Organic and inorganic coating is in island distribution simultaneously, and island size and spacing-controllable, coverage rate is controllable, to the coverage rate of diaphragm compared with
It is low, more facilitate the long-acting circulation of battery, regular island is distributed with conducive to membrane thicknesses, the control of air permeability consistency, favorably
In the promotion of battery consistency；
2, lithium-ion-power cell diaphragm of the invention, including MIcroporous polyolefin film；Extremely coated in MIcroporous polyolefin film
The inorganic-organic coating on a few surface；Regular island coated in MIcroporous polyolefin film and/or inorganic-organic coating surface
The organic and inorganic coating of distribution, the high temperature resistance of the diaphragm is more preferable, and the cycle life of battery is longer；After battery core hot pressing because
The presence in the gap for having island to divide between pole piece and basement membrane, acts as the channel of imbibition and exhaust, fluid injection and pumping are easier.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of comparative example 1, comparative example 2 and embodiment 1-4 diaphragm；
Fig. 2 is the electric discharge DC internal resistance test result of comparative example 1-3 and embodiment 1-4 battery；
Fig. 3 is the rate discharge curves of comparative example 1-3 and embodiment 1-4 battery.
Specific embodiment
Embodiment 1
The present embodiment positive plate the preparation method comprises the following steps: positive electrode, PVDF and SP are weighed material according to the ratio of 95:3:2,
And be uniformly mixed using double planetary mixer, obtain anode sizing agent.Anode sizing agent is coated on aluminium foil using transfer coated mode,
Positive plate is formed by roll-in, cross cutting.
The present embodiment negative electrode tab is the preparation method comprises the following steps: claim negative electrode material, LA133, CMC and SP according to the ratio of 95:3:1:1
Material is taken, and is uniformly mixed using double planetary mixer, negative electrode slurry is obtained.Negative electrode slurry is coated on using transfer coated mode
On copper foil, negative electrode tab is formed by roll-in, cross cutting.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: weigh aluminium oxide and polyacrylate according to the ratio of 96:4
Material is uniformly mixed using double planetary mixer, then ceramic slurry is ground 10 times to obtain using sand mill, using intaglio printing side
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by formula, and coating layer thickness is 3 μm；Step 2: PVDF, oxidation
Aluminium and polyacrylonitrile weigh material according to the ratio of 90:5:5, are uniformly mixed using double planetary mixer, then use sand mill
Organic ink is ground 10 times to obtain, organic ink is coated in two surfaces of diaphragm made from the first step using flexographic printing mode,
Obtain diaphragm finished product, wherein printing plate cylinder convexity dot shape is circle, and area is 7.85 × 10-5cm2, salient point center spacing is 200
μm, the pressure between printing plate cylinder and MIcroporous polyolefin film is 1kg.Forming upright projection is circle, and side projection is rectangular
Island, island planimetric area size are 7.85 × 10-5cm2, 200 μm of island center spacing, 2.5 μm of island height.
Electrolyte is that 1mol/l LiPF6+EC+DMC+DEC+EMC is formulated.
The production method of battery core is winding, and battery core passes through 80 DEG C, 1Mpa, 60S hot pressing.
Battery case is aluminum hull.
Embodiment 2
The present embodiment positive plate the preparation method comprises the following steps: positive electrode, PVDF and SP are weighed material according to the ratio of 95:3:2,
And be uniformly mixed using double planetary mixer, obtain anode sizing agent.Anode sizing agent is coated on aluminium foil using transfer coated mode,
Positive plate is formed by roll-in, cross cutting.
The present embodiment negative electrode tab is the preparation method comprises the following steps: claim negative electrode material, LA133, CMC and SP according to the ratio of 95:3:1:1
Material is taken, and is uniformly mixed using double planetary mixer, negative electrode slurry is obtained.Negative electrode slurry is coated on using transfer coated mode
On copper foil, negative electrode tab is formed by roll-in, cross cutting.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: weigh aluminium oxide and polyacrylate according to the ratio of 96:4
Material is uniformly mixed using double planetary mixer, then ceramic slurry is ground 10 times to obtain using sand mill, using intaglio printing side
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by formula, and coating layer thickness is 3 μm；Step 2: PVDF, oxidation
Aluminium and polyacrylonitrile weigh material according to the ratio of 90:5:5, are uniformly mixed using double planetary mixer, then use sand mill
Organic ink is ground 10 times to obtain, organic ink is coated in two surfaces of diaphragm made from the first step using flexographic printing mode,
Obtain diaphragm finished product, wherein printing plate cylinder convexity dot shape is circle, and area is 3.14 × 10-4cm2, salient point center spacing is 400
μm, the pressure between printing plate cylinder and MIcroporous polyolefin film is 0.5kg.Forming upright projection is circle, and side projection is steamed bun shape
Island, island planimetric area size be 3.14 × 10-4cm2, 400 μm of island center spacing, 3 μm of island height.
Electrolyte is that 1mol/l LiPF6+EC+DMC+DEC+EMC is formulated.
The production method of battery core is winding, and battery core passes through 80 DEG C, 1Mpa, 60S hot pressing.
Battery case is aluminum hull.
Embodiment 3
The preparation method is the same as that of Example 1 for positive plate and negative electrode tab, and the production method of electrolyte and battery core is also the same as embodiment 1.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: claim silica and polyacrylamide according to the ratio of 95:5
Material is taken, is uniformly mixed using double planetary mixer, ceramic slurry is then ground 10 times to obtain using sand mill, using intaglio printing
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by mode, and coating layer thickness is 3 μm；Step 2: poly- methyl
Methyl acrylate, zirconium dioxide and butadiene-styrene rubber weigh material according to the ratio of 92:4:4, are mixed using double planetary mixer equal
It is even, organic ink is then ground 10 times to obtain using sand mill, organic ink is coated in first step system using flexographic printing mode
Two surfaces of diaphragm obtained, obtain diaphragm finished product, wherein printing plate cylinder convexity dot shape is circle, and area is 3.14 × 10-4cm2,
Salient point center spacing is 300 μm, and the pressure between printing plate cylinder and MIcroporous polyolefin film is 1kg.Forming upright projection is circle, side
Face is projected as rectangular island, and island planimetric area size is 3.14 × 10-4cm2, 300 μm of island center spacing, island height 2.5
μm。
Battery case is aluminum hull.
Embodiment 4
The preparation method is the same as that of Example 1 for positive plate and negative electrode tab, and the production method of electrolyte and battery core is also the same as embodiment 1.
The present embodiment diaphragm the preparation method comprises the following steps: step 1: barium sulfate and polyurethane are weighed material according to the ratio of 92:8,
It is uniformly mixed using double planetary mixer, ceramic slurry is then ground 10 times to obtain using sand mill, it will using intaglio printing mode
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films, and coating layer thickness is 3 μm；Step 2: polystyrene, Bo Mu
Stone and polyacrylamide weigh material according to the ratio of 94:3:3, are uniformly mixed using double planetary mixer, then using being sanded
Machine grinds 10 times to obtain organic ink, and organic ink is coated in two tables of diaphragm made from the first step using flexographic printing mode
Face obtains diaphragm finished product, wherein printing plate cylinder convexity dot shape is circle, and area is 1.256 × 10-3cm2, salient point center spacing
It is 400 μm, the pressure between printing plate cylinder and MIcroporous polyolefin film is 0.5kg.Forming upright projection is circle, and side projection is steamed bun
The island of capitiform, island planimetric area size are 1.256 × 10-3cm2, 600 μm of island center spacing, 2 μm of island height.
Battery case is aluminum hull.
Embodiment 5
The preparation method is the same as that of Example 1 for positive plate and negative electrode tab, and the production method of electrolyte and battery core is also the same as embodiment 1.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: weigh zirconium dioxide and polyvinyl alcohol according to the ratio of 92:8
Material is uniformly mixed using double planetary mixer, then ceramic slurry is ground 10 times to obtain using sand mill, using intaglio printing side
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by formula, and coating layer thickness is 3 μm；Step 2: polyoxyethylene
Alkene, boehmite and vinyl-vinyl acetate copolymer weigh material according to the ratio of 94:3:3, are mixed using double planetary mixer
Uniformly, organic ink is then ground 10 times to obtain using sand mill, organic ink is coated in the first step using screen printing mode
Two surfaces of diaphragm obtained, obtain diaphragm finished product, wherein hole shape is circle on screen printing plate, and area is 1.256 × 10- 3cm2, hole center spacing is 400 μm, and the pressure between printing plate cylinder and MIcroporous polyolefin film is 0.5kg.Forming upright projection is circle
Shape, side projection are the island of steamed bun shape, and island planimetric area size is 1.256 × 10-3cm2, 600 μm of island center spacing, island
Highly 2 μm.
Battery case is aluminum hull.
Comparative example 1
The present embodiment positive plate the preparation method comprises the following steps: positive electrode, PVDF and SP are weighed material according to the ratio of 95:3:2,
And be uniformly mixed using double planetary mixer, obtain anode sizing agent.Anode sizing agent is coated on aluminium foil using transfer coated mode,
Positive plate is formed by roll-in, cross cutting.
The present embodiment negative electrode tab is the preparation method comprises the following steps: claim negative electrode material, LA133, CMC and SP according to the ratio of 95:3:1:1
Material is taken, and is uniformly mixed using double planetary mixer, negative electrode slurry is obtained.Negative electrode slurry is coated on using transfer coated mode
On copper foil, negative electrode tab is formed by roll-in, cross cutting.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: weigh aluminium oxide and polyacrylate according to the ratio of 96:4
Material is uniformly mixed using double planetary mixer, then ceramic slurry is ground 10 times to obtain using sand mill, using intaglio printing side
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by formula, and coating layer thickness is 3 μm；Step 2: PVDF, oxidation
Aluminium and polyacrylonitrile weigh material according to the ratio of 90:5:5, are uniformly mixed using double planetary mixer, then use sand mill
Organic ink is ground 10 times to obtain, two by organic-inorganic slurry using intaglio printing mode coated in diaphragm made from the first step
Surface obtains diaphragm finished product.
Electrolyte is that 1mol/l LiPF6+EC+DMC+DEC+EMC is formulated.
The production method of battery core is winding, and battery core passes through 80 DEG C, 1Mpa, 60S hot pressing.
Battery case is aluminum hull.
Comparative example 2
The present embodiment positive plate the preparation method comprises the following steps: positive electrode, PVDF and SP are weighed material according to the ratio of 95:3:2,
And be uniformly mixed using double planetary mixer, obtain anode sizing agent.Anode sizing agent is coated on aluminium foil using transfer coated mode,
Positive plate is formed by roll-in, cross cutting.
The present embodiment negative electrode tab is the preparation method comprises the following steps: claim negative electrode material, LA133, CMC and SP according to the ratio of 95:3:1:1
Material is taken, and is uniformly mixed using double planetary mixer, negative electrode slurry is obtained.Negative electrode slurry is coated on using transfer coated mode
On copper foil, negative electrode tab is formed by roll-in, cross cutting.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: weigh aluminium oxide and polyacrylate according to the ratio of 96:4
Material is uniformly mixed using double planetary mixer, then ceramic slurry is ground 10 times to obtain using sand mill, using intaglio printing side
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by formula, and coating layer thickness is 3 μm；Step 2: PVDF, oxidation
Aluminium and polyacrylonitrile weigh material according to the ratio of 90:5:5, are uniformly mixed using double planetary mixer, then use sand mill
Organic ink is ground 10 times to obtain, organic-inorganic slurry is coated in two tables of diaphragm made from the first step using spraying method
Face obtains diaphragm finished product.
Electrolyte is that 1mol/l LiPF6+EC+DMC+DEC+EMC is formulated.
The production method of battery core is winding, and battery core passes through 80 DEG C, 1Mpa, 60S hot pressing.
Battery case is aluminum hull.
Comparative example 3
The preparation method is the same as that of Example 1 for the present embodiment positive plate and negative electrode tab.
The present embodiment diaphragm is the preparation method comprises the following steps: step 1: weigh aluminium oxide and polyacrylate according to the ratio of 96:4
Material is uniformly mixed using double planetary mixer, then ceramic slurry is ground 10 times to obtain using sand mill, using intaglio printing side
Ceramic slurry is coated on a surface of 12 μm of MIcroporous polyolefin films by formula, and coating layer thickness is 3 μm；Step 2: PVDF and gathering
Acrylonitrile weighs material according to the ratio of 95:5, is uniformly mixed using double planetary mixer, is then ground 10 times using sand mill
Organic ink, by organic ink using flexographic printing mode be coated in the first step made from two surfaces of diaphragm, obtain diaphragm at
Product, wherein printing plate cylinder convexity dot shape is circle, and area is 7.85 × 10-5cm2, salient point center spacing is 200 μm, galley
Pressure between roller and MIcroporous polyolefin film is 1kg.Forming upright projection is circle, and side projection is rectangular island, and island is vertical
Projected area size is 7.85 × 10-5cm2, 200 μm of island center spacing, 2.5 μm of island height.
Electrolyte is that 1mol/l LiPF6+EC+DMC+DEC+EMC is formulated.
The production method of battery core is winding, and battery core passes through 80 DEG C, 1Mpa, 60S hot pressing.
Battery case is aluminum hull.
Diaphragm made from the measurement of test example 1 comparative example 1, comparative example 2, embodiment 1, embodiment 2, embodiment 3 and embodiment 4
Microscopic appearance, show as shown in Figure 1: diaphragm of the present invention organic and inorganic coating island distribution controllability it is excellent.
Test example 2 measures comparative example 1, comparative example 2, comparative example 3, embodiment 1, embodiment 2, embodiment 3,4 and of embodiment
The different location thickness (test value for referring to diaphragm difference) of diaphragm made from embodiment 5, is shown in Table 1, shows diaphragm of the present invention
Organic and inorganic island coating layer thickness consistency it is good.
Table 1
Test example 3 measures comparative example 1, comparative example 2, comparative example 3, embodiment 1, embodiment 2, embodiment 3,4 and of embodiment
The air permeability (test value for referring to diaphragm difference) of diaphragm different location made from embodiment 5, is shown in Table 2, shows of the invention
Diaphragm good permeability, higher to the coverage rate of barrier film base material using the organic and inorganic coating of intaglio plate coating, island distribution has
Machine-inorganic coating is lower to barrier film base material coverage rate, smaller on the ventilative influence of diaphragm.
Table 2
Test example 4 measures comparative example 1, comparative example 2, comparative example 3, embodiment 1, embodiment 2, embodiment 3,4 and of embodiment
5 battery core hot pressing metacneme gas permeability of embodiment is shown in Table 3 to characterize influence of the pressure sensitive coating to diaphragm gas permeability after hot pressing.It surveys
Test result show after regular organic and inorganic island coating hot-pressing of the invention it is ventilative on diaphragm influence it is minimum.
Table 3
Test example 5 measures comparative example 1, comparative example 2, comparative example 3, embodiment 1,4 electricity of embodiment 2, embodiment 3 and embodiment
The DC internal resistance DCR (Fig. 2) in pond, discharge-rate performance (Fig. 3) test result show diaphragm of the invention relative to organic coating
Diaphragm, smaller on the influence of the performance of battery, regular island organic and inorganic coated separator of the invention is organic relative to regular island
Coated separator ion channel is more, and it is smaller to recycle later period plug-hole risk；And it is distributed coated separator relative to irregular island, it is thick
Degree consistency is more preferable, and coating coverage is lower and controllable, and ion channel is also more, is conducive to battery multiplying power discharging.
Claims (9)
1. a kind of lithium-ion-power cell diaphragm, it is characterised in that: the diaphragm includes MIcroporous polyolefin film；Coated in polyene
The inorganic-organic coating at least one surface of hydrocarbon microporous barrier；Coated in MIcroporous polyolefin film and/or inorganic-organic coating surface
Regular island distribution pressure sensitive Organic-inorganic composite coating；Wherein, inorganic-organic coating coating method is intaglio printing；
Organic and inorganic coating coating method is flexographic printing or silk-screen printing, and the pressure between printing plate cylinder and MIcroporous polyolefin film is
0.1kg~2kg.
2. lithium-ion-power cell diaphragm according to claim 1, it is characterised in that: the polyolefin micropore film thickness
It is 5~25 μm；Inorganic-organic coating layer thickness is 1~10 μm；Organic and inorganic coating layer thickness is 0.5~6 μm.
3. lithium-ion-power cell diaphragm according to claim 1, it is characterised in that: the inorganic-organic coating
Be made of particles of inorganic material and organic polymeric binder, wherein by mass percentage, particles of inorganic material dosage be 80%~
99%, organic polymeric binder dosage is 1%~20%.
4. lithium-ion-power cell diaphragm according to claim 3, it is characterised in that: the particles of inorganic material is three oxygen
Change one or more of two aluminium, silica, zirconium dioxide, boehmite, barium sulfate；The organic polymeric binder is poly-
Vinylidene fluoride (PVDF), polyvinyl alcohol, polyurethane, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR), polyacrylic acid
One or more of ester, polyacrylonitrile, polyacrylamide, ethylene-vinyl acetate copolymer emulsion.
5. lithium-ion-power cell diaphragm according to claim 1, it is characterised in that: the organic and inorganic coating
It being distributed in regular island, wherein the upright projection shape on island is round, ellipse, triangle or rule/irregular polygon,
Lateral projection's shape on island is rectangle, triangle, rule/irregular polygon or steamed bun shape.
6. lithium-ion-power cell diaphragm according to claim 5, it is characterised in that: the island planimetric area is big
Small is 1.9625 × 10-5cm2~2.826 × 10-3cm2, island height is 0.5~6 μm, the center spacing between the island Dao He are as follows: 60 μ
M~600 μm.
7. lithium-ion-power cell diaphragm according to claim 1, it is characterised in that: the organic and inorganic coating by
Polymer hot melting glue, organic polymeric binder and particles of inorganic material composition, wherein by mass percentage, polymer hot melting glue
Dosage is 50%~98%, and organic polymeric binder dosage is 1%~10%, and particles of inorganic material dosage is 1%~49%.
8. lithium-ion-power cell diaphragm according to claim 7, it is characterised in that: the polymer hot melting glue is soft
Change the polyvinylidene fluoride (PVDF) that point is 60 DEG C~140 DEG C, polymethyl methacrylate (PMMA), polystyrene (PS), gather
One or more of ethylene (PE), vinyl-vinyl acetate copolymer (EVA), polyethylene glycol oxide (PEO)；It is described organic poly-
Closing object binder is polyvinylidene fluoride (PVDF), polyvinyl alcohol, polyurethane, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber
(SBR), one or more of polyacrylate, polyacrylonitrile, polyacrylamide, ethylene-vinyl acetate copolymer emulsion；Institute
Stating particles of inorganic material is one or more of aluminum oxide, silica, zirconium dioxide, boehmite, barium sulfate.
9. a kind of application of lithium-ion-power cell diaphragm according to claim 1, it is characterised in that: the diaphragm is used
In assembling lithium-ion-power cell, assemble method are as follows: by positive plate, negative electrode tab, the diaphragm and electricity being set between positive/negative plate
Solution liquid and aluminum plastic film or metal-back outer packing are assembled, wherein the diaphragm is that lithium ion described in claim 1 is dynamic
Power battery diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810832412.XA CN109004164A (en) | 2018-07-26 | 2018-07-26 | A kind of lithium-ion-power cell pressure sensitive composite diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810832412.XA CN109004164A (en) | 2018-07-26 | 2018-07-26 | A kind of lithium-ion-power cell pressure sensitive composite diaphragm |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109004164A true CN109004164A (en) | 2018-12-14 |
Family
ID=64597514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810832412.XA Pending CN109004164A (en) | 2018-07-26 | 2018-07-26 | A kind of lithium-ion-power cell pressure sensitive composite diaphragm |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109004164A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110277594A (en) * | 2019-06-11 | 2019-09-24 | 北京小米移动软件有限公司 | Soft-package battery expansion monitoring device, soft-package battery, terminal and electric product |
| CN111900311A (en) * | 2020-03-30 | 2020-11-06 | 明基材料（芜湖）有限公司 | Isolating membrane and manufacturing method thereof |
| CN114649638A (en) * | 2022-05-20 | 2022-06-21 | 宁德卓高新材料科技有限公司 | Coated diaphragm and preparation method and application thereof |
| WO2023179333A1 (en) * | 2022-03-25 | 2023-09-28 | 宁德时代新能源科技股份有限公司 | Separator and preparation method therefor, battery, and electric apparatus |
| CN117937044A (en) * | 2024-03-22 | 2024-04-26 | 深圳市旭然电子有限公司 | Battery diaphragm coating process and battery diaphragm prepared by same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441230A (en) * | 2013-08-21 | 2013-12-11 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane, preparation method thereof and electrochemical device |
| CN105251375A (en) * | 2015-11-19 | 2016-01-20 | 肖汉宁 | Preparation method of multilayered gradient ceramic membrane |
| JP2016197505A (en) * | 2015-04-02 | 2016-11-24 | 旭化成株式会社 | Wound body |
| CN107316968A (en) * | 2017-05-11 | 2017-11-03 | 东莞市赛普克电子科技有限公司 | A kind of sticky battery diaphragm and the lithium ion battery using the barrier film |
| CN108079788A (en) * | 2017-12-27 | 2018-05-29 | 肖汉宁 | A kind of preparation method of asymmetric flat ceramic NF membrane |
| CN108305976A (en) * | 2018-02-01 | 2018-07-20 | 中航锂电技术研究院有限公司 | A kind of lithium-ion-power cell and its diaphragm |
-
2018
- 2018-07-26 CN CN201810832412.XA patent/CN109004164A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103441230A (en) * | 2013-08-21 | 2013-12-11 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane, preparation method thereof and electrochemical device |
| JP2016197505A (en) * | 2015-04-02 | 2016-11-24 | 旭化成株式会社 | Wound body |
| CN105251375A (en) * | 2015-11-19 | 2016-01-20 | 肖汉宁 | Preparation method of multilayered gradient ceramic membrane |
| CN107316968A (en) * | 2017-05-11 | 2017-11-03 | 东莞市赛普克电子科技有限公司 | A kind of sticky battery diaphragm and the lithium ion battery using the barrier film |
| CN108079788A (en) * | 2017-12-27 | 2018-05-29 | 肖汉宁 | A kind of preparation method of asymmetric flat ceramic NF membrane |
| CN108305976A (en) * | 2018-02-01 | 2018-07-20 | 中航锂电技术研究院有限公司 | A kind of lithium-ion-power cell and its diaphragm |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110277594A (en) * | 2019-06-11 | 2019-09-24 | 北京小米移动软件有限公司 | Soft-package battery expansion monitoring device, soft-package battery, terminal and electric product |
| CN111900311A (en) * | 2020-03-30 | 2020-11-06 | 明基材料（芜湖）有限公司 | Isolating membrane and manufacturing method thereof |
| WO2023179333A1 (en) * | 2022-03-25 | 2023-09-28 | 宁德时代新能源科技股份有限公司 | Separator and preparation method therefor, battery, and electric apparatus |
| CN114649638A (en) * | 2022-05-20 | 2022-06-21 | 宁德卓高新材料科技有限公司 | Coated diaphragm and preparation method and application thereof |
| CN117937044A (en) * | 2024-03-22 | 2024-04-26 | 深圳市旭然电子有限公司 | Battery diaphragm coating process and battery diaphragm prepared by same |
| CN117937044B (en) * | 2024-03-22 | 2024-06-11 | 深圳市旭然电子有限公司 | Battery diaphragm coating process and battery diaphragm prepared by same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004164A (en) | A kind of lithium-ion-power cell pressure sensitive composite diaphragm | |
| CN108305976A (en) | A kind of lithium-ion-power cell and its diaphragm | |
| US10497914B2 (en) | Water-based composition used for modifying diaphragm for lithium batteries and modified diaphragm and batteries | |
| CN110071293B (en) | Battery cell and battery, liquid-retaining coating and battery pole piece and preparation method thereof | |
| CN105304907B (en) | Lithium ion battery composite pole piece binding agent and preparation method thereof, composite pole piece, battery core, lithium ion battery | |
| CN108963153A (en) | A kind of lithium ion battery separator and preparation method thereof | |
| CN109950459A (en) | A kind of lithium ion battery separator of richness lithium | |
| CN110752345A (en) | Pole piece, preparation method thereof and lithium ion battery | |
| CN104979516A (en) | Electrochemical apparatus, isolation membrane used therein and preparation method of the isolation membrane | |
| CN109088031A (en) | Ceramic coating membrane slurry, Ceramic Composite diaphragm and its preparation method and application | |
| CN111599971A (en) | High-safety regular matrix coating adhesive lithium ion battery diaphragm and preparation method and application thereof | |
| CN110911622A (en) | Coated diaphragm slurry, composite diaphragm and preparation method thereof | |
| CN107706341B (en) | Preparation process of composite diaphragm | |
| CN107681113B (en) | Positive plate, preparation method thereof and secondary battery | |
| CN104979512A (en) | Electrochemical apparatus, isolation membrane used therein and preparation method of the isolation membrane | |
| CN111525074A (en) | PTFE-PVDF (polytetrafluoroethylene-polyvinylidene fluoride) blended and sprayed lithium battery diaphragm and preparation method thereof | |
| CN110707266A (en) | PVDF (polyvinylidene fluoride) mixed coating slurry, preparation method thereof and diaphragm | |
| CN114597590A (en) | Special edge-coated diaphragm and application thereof | |
| CN105870403A (en) | Lithium-ion battery cathode sheet, preparation method thereof as well as super capacitor composite battery comprising lithium-ion battery cathode sheet | |
| CN111244364B (en) | PVDF (polyvinylidene fluoride) coated diaphragm, preparation method thereof and lithium ion battery | |
| CN117497835A (en) | Solid-state battery cell, preparation method thereof and solid-state battery | |
| CN111584796B (en) | Composite coating diaphragm and preparation method and application thereof | |
| CN111785899A (en) | Lithium ion battery diaphragm and lithium ion battery containing same | |
| CN106450333A (en) | Lithium battery anode slurry and slurry mixing method thereof | |
| CN111987273A (en) | PVDF&Al2O3Mixed coating slurry, preparation method thereof, lithium ion battery diaphragm and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181214 |
|
| RJ01 | Rejection of invention patent application after publication |