CN109004159A - Preparation method, lithium ion battery separator and the lithium ion battery of lithium ion battery separator - Google Patents
Preparation method, lithium ion battery separator and the lithium ion battery of lithium ion battery separator Download PDFInfo
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- CN109004159A CN109004159A CN201811072376.8A CN201811072376A CN109004159A CN 109004159 A CN109004159 A CN 109004159A CN 201811072376 A CN201811072376 A CN 201811072376A CN 109004159 A CN109004159 A CN 109004159A
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- lithium ion
- ion battery
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to technical field of lithium ion, are related to preparation method, lithium ion battery separator and the lithium ion battery of lithium ion battery separator.Preparation method of the invention includes: that basis material is fixed in the intracorporal unreeling structure of vacuum reaction chamber, and optional coating material plasma gas is passed through into vacuum reaction chamber body；Coating material is gasified into vacuum reaction cavity using vapor deposition apparatus, and coating material is deposited on basis material by vapour deposition process；The basis material that surface deposited coating material closes in rolling-up mechanism；Chill roll is additionally provided between unreeling structure and rolling-up mechanism, which is located at the top of vapor deposition apparatus.The present invention substantially reduces relative to traditional handicraft coating layer thickness, and the good permeability of coating, homogeneity are good；Equipment cleaning degree is high, and the amount for introducing impurity declines to a great extent, and without preparing slurry, can reduce environmental pollution；It is additive-free in coating, in high temperature and pressure system, there is excellent thermal stability and inoxidizability.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of lithium ion battery separator, lithium
Ion battery diaphragm and lithium ion battery.
Background technique
Lithium ion battery includes anode, cathode, electrolyte and diaphragm, wherein diaphragm is between anode and cathode
Diaphragm material, be crucial one of interior layer assembly, determine interfacial structure, internal resistance of battery etc..Diaphragm can guarantee electrolyte
Intermediate ion passes through, the problems such as preventing self discharging and short-circuit the two poles of the earth of battery.
In recent years, increasingly extensive with lithium ion battery applications, the comprehensive performance of lithium ion battery also proposed more
High requirement.Generally, the porosity of diaphragm is improved, membrane thicknesses is reduced ionic conduction between positive and negative anodes can be improved, improves electricity
The high rate performance in pond；Battery with two side terminals can be improved in the consistency for improving diaphragm, for extending the service life of battery, improving
The security performance of battery all has great importance.However existing coating diaphragm mode mostly uses and prints similar dimple version
Roller coating, existing diaphragm preparation process are mainly formed by unreeling, coating, dry, winding four processes.For coating process, slurry
Material by air pump enters slurry box by feed system, from dimple roller rotate and with scraper coat with a thickness of 2~5 in membrane surface
μm coating, coating just forms final products after baking oven for drying solidification.
Current dimple version roller coating technology is formed by coating, has the following disadvantages: (1) due to feed system gas
The influence of the factors such as voltage-controlled system, the abrasion condition of roll surface cleaning degree, roller and scraper, oven temperature control and speed control,
One property is simultaneously unstable.(2) machinery equipment cleaning be more troublesome, and coating speed due to the processes such as baking oven limitation relatively
Slowly.(3) coating need to configure slurry: firstly, various chemical reagent used by configuration slurry can cause environmental pollution, secondly,
When customer demand changes, adjustment is also more troublesome with slurry ratio；The slurry configured each time complete one is not ensured that
It causes.(4) the obtained coating of traditional handicraft in the micron-scale, is unfavorable for the promotion of battery energy density；In addition, the biggish painting of thickness
Layer can make the permeability of diaphragm have decline by a relatively large margin.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of lithium ion battery separator, and this method is relative to tradition
Technique coating layer thickness can substantially reduce, the good permeability of coating, and coating uniformity obtained is fabulous；And equipment cleaning degree is high, draws
The amount for entering impurity declines to a great extent, and without preparing slurry, reduces environmental pollution, environmental benefit is good.
The second object of the present invention is to provide a kind of lithium ion battery separator, is prepared using method of the invention
Diaphragm coating layer thickness can substantially reduce, and the good permeability of coating, coating uniformity is fabulous, help to improve making for lithium ion battery
With the service life, and improve the safety of battery.
The third object of the present invention is to provide a kind of lithium ion battery, the lithium battery diaphragm is applied in lithium ion
In battery, the high rate performance of battery is helped to improve, improve the service life of lithium ion battery and improves the safety of battery.
The fourth object of the present invention be to provide a kind of electronic device comprising the lithium ion battery, electric tool,
Electric vehicle or electric power storage system have above-mentioned lithium ion battery in these products, thus at least have and above-mentioned lithium ion
The identical advantage of battery.
To achieve the above object, the technical solution adopted by the present invention are as follows:
According to an aspect of the present invention, the present invention provides a kind of preparation method of lithium ion battery separator, including following
Step:
Basis material is fixed in the intracorporal unreeling structure of vacuum reaction chamber, is passed through into vacuum reaction chamber body optional
Coating material plasma gas；
Coating material is gasified into vacuum reaction cavity using vapor deposition apparatus, and coating material is sunk by gas phase
Area method is deposited on basis material；
The basis material that surface deposited coating material closes in rolling-up mechanism；
Wherein, chill roll is additionally provided between unreeling structure and rolling-up mechanism, which is located at the upper of vapor deposition apparatus
Side, for preventing basis material is heated from generating deformation.
As further preferred technical solution, the vacuum degree of the vacuum reaction cavity is 2 × 10- 2Pa or less；
Preferably, the vacuum degree of the vacuum reaction cavity is 1 × 10- 3~1 × 10- 7Pa。
As further preferred technical solution, the heating temperature of the vapor deposition apparatus is 200~1500 DEG C, preferably
It is 450~1250 DEG C；
Preferably, the temperature of the chill roll is -30~0 DEG C, preferably -25~-15 DEG C.
As further preferred technical solution, the vapour deposition process includes physical vapour deposition (PVD) and/or chemical vapor deposition
Product；
Preferably, the vapour deposition process is arc evaporation, sputter vaporization, ion beam bombardment, pulse laser deposition and heat
At least one of evaporation.
As further preferred technical solution, described matrix material include polyethylene, polypropylene, polyamide, polyimides,
At least one of polyethylene terephthalate, non-woven fabrics or fiber.
As further preferred technical solution, the coating material includes metal and/or polymer；
Preferably, the coating material includes silica, aluminum oxide, titanium dioxide, zirconium oxide, zinc oxide, oxygen
Change magnesium, boron nitride, boehmite, Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropylene copolymer or polyacrylonitrile
At least one of.
As further preferred technical solution, be deposited on the coating on basis material with a thickness of
According to another aspect of the present invention, the present invention provides a kind of lithium ion battery separator, using above-mentioned lithium ion
The preparation method of battery diaphragm is prepared.
According to another aspect of the present invention, the present invention also provides a kind of lithium ion batteries, including above-mentioned lithium-ion electric
Pond diaphragm.
According to another aspect of the present invention, the present invention also provides a kind of, and the electronics comprising the lithium ion battery fills
It sets, electric tool, electric vehicle or electric power storage system.
Compared with prior art, the beneficial effects of the present invention are:
1, the preparation method of lithium ion battery separator of the invention is gasified coating material to true using gas phase deposition technology
In empty reaction cavity, and it is deposited on substrate material surface, not only ensure that the uniformity and consistency of coating, but also reduces lithium ion
The percent thermal shrinkage of battery diaphragm, it is solid and reliable, the gas permeability of diaphragm is also improved, internal resistance is reduced, there is diaphragm good
Comprehensive performance；Preparation method is safe and efficient, environmentally friendly, reduces the requirement to basis material and coating material, has been effectively relieved existing
The problems of traditional handicrafts such as some dimple version roller coating technologies.
2, present invention process condition is simple and easy, facilitates control, pollution-free, environmental-friendly, high-efficient, equipment cleaning degree
Height greatly reduces the impurity level of introducing；And separator product coating uniformity obtained is good, coating layer thickness can be controlled in nanometer
Or micron order, reduce the thickness of coating, good permeability, stability is good, is convenient for large-scale industrial production, in lithium-ion electric
It is had a good application prospect on pond.
3, the lithium ion battery separator being prepared by means of the present invention, coating is with excellent uniformity and unanimously
Property, coating layer thickness can be controlled in nanometer or micron order, ensure that the air penetrability of diaphragm, reduce internal resistance, solid and reliable, make every
Film has good comprehensive performance.Compared with traditional handicraft, the present invention is the case where the coating layer thickness of diaphragm reduces 85~95%
Under, percent thermal shrinkage increase still can control within 5%.
4, lithium ion battery provided by the invention is provided with lithium ion battery separator of the invention between anode, cathode,
Its excellent reduced performance short circuit probability of lithium ion battery, improves the high rate performance of battery, improves lithium ion battery
Service life and safety in utilization, while showing excellent chemical property.It also, include lithium ion battery of the invention
Electronic device, electric tool, electric vehicle or electric power storage system, at least have it is identical with above-mentioned lithium ion battery excellent
Gesture.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the preparation method process schematic illustration of lithium ion battery separator provided in an embodiment of the present invention；
Fig. 2 is the preparation method process schematic illustration for the lithium ion battery separator that comparative example of the present invention provides.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.
In a first aspect, providing a kind of preparation method of lithium ion battery separator in some embodiments, comprising the following steps:
Basis material is fixed in the intracorporal unreeling structure of vacuum reaction chamber, is passed through into vacuum reaction chamber body optional
Coating material plasma gas；
Coating material is gasified into vacuum reaction cavity using vapor deposition apparatus, and coating material is sunk by gas phase
Area method is deposited on basis material；
The basis material that surface deposited coating material closes in rolling-up mechanism；
Wherein, chill roll is additionally provided between unreeling structure and rolling-up mechanism, which is located at the upper of vapor deposition apparatus
Side, for preventing basis material is heated from generating deformation.
Preparation method of the invention is utilized gas phase deposition technology and coating material gasifies and diffuses to vacuum reaction cavity
In, subsequent coating material is deposited on substrate material surface with molecular forms, it both ensure that the uniformity and consistency of coating in this way,
The percent thermal shrinkage of lithium ion battery separator is reduced again, and solid and reliable, coating layer thickness can be controlled in nanometer or micron order, relatively
The thickness of coating can be made substantially to reduce in traditional handicraft, improve the gas permeability of diaphragm, reduce internal resistance, there is diaphragm good
Comprehensive performance, and then for improve lithium ion battery service life, improve the safety of battery and improve battery again
Rate performance etc., which has, is greatly promoted effect；And it is additive-free in diaphragm coating layer, in high temperature and pressure system, have excellent
Thermal stability and inoxidizability.
Meanwhile it is above-mentioned preparation method is simple, facilitate control, high-efficient, equipment cleaning degree is high, greatly reduces and draws
Coating material is directly placed in vapor deposition apparatus and heats by the impurity level entered, and without preparing slurry, it is dirty to reduce environment
Dye, environmental benefit are good, it is easy to accomplish industrial-scale production.
It should be noted that above-mentioned " optional coating material plasma gas " refers in the vacuum reaction cavity
It can be passed through plasma gas, plasma gas can not also be passed through, determined according to selected coating material, such as needed for
When the coating wanted is simple substance, then do not need to be passed through plasma gas, and when required coating is compound, then it needs to be passed through
Ionized gas.
Preparation method according to the present invention, the present invention do not have coating material and basis material special limitation, can be with
For coating material and basis material commonly used in the art, the requirement to basis material and coating material is reduced.
Preparation method according to the present invention, the present invention can be ability for plasma gas also not special limitation
The common plasma gas in domain, for example, can be air, oxygen, nitrogen, helium, neon, argon gas, in Krypton any one or
Several mixed gas in practical application, according to used coating material, selects corresponding plasma gas.
Optionally, the flow that is passed through of plasma gas is 10~1000sccm.Sccm is volume flow unit, for mark condition milli
Liter Per Minute.The present invention is passed through the also not special limitation of flow or intake for plasma gas, according to actual work
The adjustment that skill operational requirements are suitable in the range
In a preferred embodiment, the vacuum degree of the vacuum reaction cavity is 2 × 10- 2Pa or less；
Preferably, the vacuum degree of the vacuum reaction cavity is 1 × 10- 3~1 × 10- 7Pa.It is typical but non-limiting,
The vacuum degree of vacuum reaction cavity can be 2 × 10- 2Pa、1× 10- 2Pa、9×10- 3Pa、5×10- 3Pa、2×10- 3Pa、1
×10- 3Pa、1×10- 4Pa、1 ×10- 5Pa、1×10- 6Pa or 1 × 10- 7Pa.It can be gasified according to selected coating material
It is difficult to degree, the vacuum degree of adaptable adjustment vacuum reaction cavity.
In a preferred embodiment, the heating temperature of the vapor deposition apparatus is 200~1500 DEG C, preferably
It is 450~1250 DEG C；Typical but unrestricted, heating temperature can be 200 DEG C, 300 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 600
DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, 1200 DEG C, 1250 DEG C, 1300 DEG C, 1400 DEG C or 1500
℃；The present invention makes coating material gasify heating temperature, the sputtering power etc. of the vapor deposition apparatus where coating material
Operating condition, not special limitation add according to selected coating material or the difference of the specific embodiment of vapor deposition
Hot temperature is also required to make adaptable adjustment.
In a preferred embodiment, the vapour deposition process includes physical vapour deposition (PVD) and/or chemical vapor deposition
Product；
Preferably, the vapour deposition process is arc evaporation, sputter vaporization, ion beam bombardment, pulse laser deposition and heat
At least one of evaporation.
The present invention does not do special restriction for the embodiment that is specifically vapor-deposited, and including but not limited to physical vapor is heavy
Product, chemical vapor deposition, coating material is gasified to vacuum or contain plasma (orifice) gas using existing vapor deposition apparatus
In the reaction cavity of body, the intracorporal vacuum pressure of reaction chamber is generally 1 × 10- 3~1 × 10- 7Pa, so that coating material gasification
Mode includes but is not limited to any one in arc evaporation, sputter vaporization, ion beam bombardment, pulse laser deposition and thermal evaporation
Or it is a variety of, it can also be other vapor deposition modes commonly used in the art.
Using above-mentioned gas phase deposition technology carry out plated film, can according to the difference of coating material, in specific atmosphere into
Row reactive deposition, technical process is simple, pollution-free, environmental-friendly, and consumptive material is few, escapable cost, and the even compact that forms a film, one
Cause property is good, strong with the binding force of basis material, solid and reliable.
In a preferred embodiment, the temperature of the chill roll be -30~0 DEG C, preferably -25~-15
℃；Typical but non-limiting, the temperature of chill roll can be -30 DEG C, -25 DEG C, -20 DEG C, -15 DEG C, -10 DEG C, -5
DEG C or 0 DEG C.
The present invention is also provided with chill roll between unreeling structure and rolling-up mechanism, and the chill roll has been additionally arranged at gas phase
The surface of depositing device.When diaphragm passes through right above vapor deposition apparatus, to prevent diaphragm is heated from generating deformation, and protect
Hold basis material and be in flat, the present invention is provided with chill roll here, the temperature of chill roll generally at -20 DEG C or so,
In this way, basis material can either be kept to be in flat, heated generation deformation is prevented, and can further ensure that the equal of coating
Even property, consistency, highly-safe, stability is good.
In a preferred embodiment, unreeling structure, chill roll, vapor deposition apparatus and rolling-up mechanism are all located at close
In the vacuum reaction cavity closed.That is, it is of the invention unreel, plated film and winding are completed in closed cavity, in this way may be used
It is pollution-free to improve coating effects, facilitate control, reduce energy consumption, reduce the processing time, improves working efficiency.
Coating speed of the invention can reach 10~20m/s, preferably 12~18m/s, and the reaction time is short, speed is fast, work
Make high-efficient.
In a preferred embodiment, described matrix material include polyethylene, polypropylene, polyamide, polyimides,
At least one of polyethylene terephthalate, non-woven fabrics or fiber.
The present invention does not have basis material special limitation, using basis material commonly used in the art, including
But it is not limited to polyethylene (PE), polypropylene (PP), polyamide (PA), polyimides (PI), polyethylene terephthalate
(PET), one of non-woven fabrics or fiber or a variety of combinations can also be polytetrafluoroethylene (PTFE) or polytetrafluoroethylene (PTFE) and above-mentioned height
The materials such as the combination of Molecularly Imprinted Polymer.These basis materials are at low cost, and manufacture craft is simple, and intensity is high, and heat resistance is good, can mention
For good mechanical support, humidification can be played.
Optionally, it is the adhesion and firmness that further increase coating, basis material can also be surface-treated,
Including surface treatment methods such as corona, ion beam bombardments, to eliminate the electrostatic of basis material, the surface of basis material is improved
Power improves the binding force of basis material and coating.
In a preferred embodiment, the coating material includes metal and/or polymer；
Preferably, the coating material includes silica, aluminum oxide, titanium dioxide, zirconium oxide, zinc oxide, oxygen
Change magnesium, boron nitride, boehmite, Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropylene copolymer or polyacrylonitrile
At least one of.
The present invention does not have coating material special limitation, using coating material commonly used in the art, including
But the ceramic materials such as silica, aluminum oxide, titanium dioxide, zirconium oxide, zinc oxide, magnesia are not limited to, and nitridation
Boron, boehmite and Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropylene copolymer or polyacrylonitrile etc. are organic
The mixture of any one or more in polymer.
In a preferred embodiment, be deposited on the coating on basis material with a thickness of
Above-mentioned preparation method, first coating material are superheated to evaporation, and (including but not limited to traditional heating and electron beam adds
Heat etc.) it forms gas and diffuses in vacuum or reaction cavity containing a small amount of plasma gas, coating material can be gold
Category is also possible to polymer, and subsequent coating material is attached to substrate material surface with molecular forms.For example, being Al with coating2O3For
Example, the Al material for evaporation are diffused in after evaporating containing O through heat2Plasma gas reaction cavity in, occur therewith
Chemical reaction generates Al2O3, subsequent Al2O3It is attached on basis material and is formed with either as singular molecular entitiesThickness
The coating controllable, homogeneity is fabulous, this method greatly reduce the thickness of coating relative to traditional handicraft, improve diaphragm
Gas permeability, reduce internal resistance, make diaphragm have good comprehensive performance.In addition, diaphragm leads to right above vapor deposition apparatus
It crosses, deformation is generated to prevent diaphragm from receiving heat, and basis material is kept to be in flat, in the surface of vapor deposition apparatus
Equipped with a chill roll, temperature is -20 DEG C or so.And it unreels, plated film and winding are all completed in closed cavity.
Second aspect provides a kind of lithium ion battery separator in some embodiments, using the upper lithium ion battery
The preparation method of diaphragm is prepared.
Using technique diaphragm produced of the invention, since coating material dosage accurately controls, coating material gasification
After be dispersed in cavity, so coating layer thickness can be controlled in nanometer or micron order, coating uniformity is fabulous, floating range
Only 3% or so.Also, coating speed can reach 16~18m/s, and the reaction time is short, speed is fast, and work efficiency is high.Without matching
Slurry is set, is not polluted the environment.Equipment cleaning degree is high, introduces impurity level and declines to a great extent.And compared to traditional handicraft coating layer thickness
Substantially reduce, improve the permeability of diaphragm, reduce internal resistance, makes diaphragm that there is good comprehensive performance.
Compared with traditional handicraft, in the case where the coating layer thickness of diaphragm reduces 85~95%, percent thermal shrinkage increases the present invention
Adding still can control within 5%.
The third aspect provides a kind of lithium ion battery in some embodiments, including above-mentioned lithium ion battery separator.
It should be understood that the core of the lithium ion battery is to include septum for lithium ion battery of the invention, lithium ion
Remaining each component of battery and whole preparation process are using existing.
Fourth aspect provides a kind of electronic device comprising the lithium ion battery, electronic work in some embodiments
Tool, electric vehicle or electric power storage system.
Lithium ion battery provided by the invention is provided with lithium ion battery separator of the invention between anode, cathode,
The excellent reduced performance short circuit probability of lithium ion battery, improves the high rate performance of battery, improves lithium ion battery
Service life and safety in utilization, while showing excellent chemical property.It also, include lithium ion battery of the invention
Electronic device, electric tool, electric vehicle or electric power storage system at least have advantage identical with above-mentioned lithium ion battery.
Wherein, electronic device, which can be, uses lithium ion battery to perform various functions as the power supply of operation (for example, playing
Music) electronic device.Electric tool can be use lithium ion battery as driving power move moving parts (for example,
Drill bit) electric tool.Electric vehicle can be the electric vehicle run by lithium ion battery as driving power, and can
To be the automobile (including hybrid electric vehicle) for being also equipped with other driving sources other than lithium ion battery.Electric power storage system can
To be to use lithium ion battery as the electric power storage system of electric power storage source.For example, making electricity in household power stocking system
Power is stored in the lithium ion battery as electric power storage source, and consumes the electric power being stored in lithium ion battery as needed
To be able to use the various devices of such as domestic electronic appliances.
Combined with specific embodiments below, comparative example and attached drawing, the invention will be further described.
Embodiment 1
Fig. 1 is the preparation method process schematic illustration of lithium ion battery separator provided in an embodiment of the present invention, such as Fig. 1 institute
Show, the preparation method of the lithium ion battery separator, including is in the intracorporal unreeling structure of vacuum reaction chamber, chill roll, gas phase
Depositing device and winding device, wherein chill roll is located at vapor deposition apparatus between unreeling structure and rolling-up mechanism
Surface；
It include: that basis material is fixed in unreeling structure using the process that above-mentioned apparatus prepares diaphragm, to vacuum reaction
Optional coating material plasma gas is passed through in cavity；After adjusting certain vacuum degree and other filming parameters, unlatching is unreeled
Mechanism and rolling-up mechanism carry out continuous coating according to certain linear velocity；
Coating material is gasified using vapor deposition apparatus and is diffused in vacuum reaction cavity, subsequent coating material is to divide
Sub- form is deposited on substrate material surface；
Meanwhile diaphragm passes through right above vapor deposition apparatus, also have passed through the cooling of -20 DEG C or so of chill roll；
It is closed in rolling-up mechanism with the basis material that rear surface deposited coating material.
In the present embodiment, using the vapour deposition process (PVD) of thermal evaporation；
Basis material is PE, coating material Al2O3, the material for evaporation is Al, plasma gas O2；
The vacuum degree of vacuum reaction cavity is 1 × 10- 3Pa, heating temperature are 1100~1300 DEG C；
Basis material with a thickness of 12~25 μm, coating with a thickness of
The present embodiment obtains the lithium ion battery separator after plated film, in mechanical properties: percent thermal shrinkage decline 0.1%~
20% (test condition of percent thermal shrinkage be 105 DEG C, 1h, similarly hereinafter), the Gurleyvalue for characterizing permeability increases 0~
15。
In terms of chemical property: diaphragm surface resistance reduces by 2%~20%, 20% is improved to guarantor's liquid rate of electrolyte~
40%.
The lithium ion battery separator of this implementation is applied in lithium ion battery: compared to the battery for using basement membrane, battery
Cycle performance, service life and stability increase, wherein under the conditions of trickle charge, using the time extend longest up to 6
Times, leakage current reduces at most up to 50%, more aobvious to the promotion of battery performance especially when applying in high pressure soft-package battery
It writes.
Embodiment 2
A kind of preparation method of lithium ion battery separator, the difference from embodiment 1 is that:
In the present embodiment, basis material PP, coating material Al2O3, plasma gas O2, plated film mode useization
Learn vapor deposition (CVD)；
The vacuum degree of vacuum reaction cavity is 1 × 10- 3Pa, heating temperature are 1250 DEG C；
Basis material with a thickness of 12~25 μm, coating with a thickness of 1nm~115nm.
The present embodiment obtains the lithium ion battery separator after plated film, in mechanical properties: percent thermal shrinkage decline 0.1%~
15%, the Gurleyvalue for characterizing permeability increases 0~20.
In terms of chemical property: diaphragm surface resistance reduces by 4%~20%, 20 is improved to guarantor's liquid rate of electrolyte~
40%.
The lithium ion battery separator of this implementation is applied in lithium ion battery: compared to the battery for using basement membrane, battery
Cycle performance, service life and stability increase, wherein under the conditions of trickle charge, using the time extend longest up to 5
Times, leakage current reduces at most up to 30%, more aobvious to the promotion of battery performance especially when applying in high pressure soft-package battery
It writes.
Embodiment 3
A kind of preparation method of lithium ion battery separator, the difference from embodiment 1 is that:
In the present embodiment, basis material PE, coating material Al；
The vacuum degree of vacuum reaction cavity is 1 × 10- 4Pa, heating temperature are 1100~1300 DEG C；
Basis material with a thickness of 12~25 μm, coating with a thickness of
The present embodiment obtains the lithium ion battery separator after plated film, in mechanical properties: percent thermal shrinkage decline 0.1%~
30%, the Gurley value for characterizing permeability increases 0~20.
In terms of chemical property: diaphragm surface resistance can at most decline 20%.
The lithium ion battery separator of this implementation is applied in lithium ion battery: compared to the battery for using basement membrane, battery
Cycle performance, service life and stability increase, wherein under the conditions of trickle charge, using the time extend longest up to 6
Times, leakage current reduces at most up to 30%, more aobvious to the promotion of battery performance especially when applying in high pressure soft-package battery
It writes.
Embodiment 4
A kind of preparation method of lithium ion battery separator, the difference from embodiment 1 is that:
In the present embodiment, basis material PP, coating material Au；
The vacuum degree of vacuum reaction cavity is 1 × 10- 5Pa, heating temperature are 1100~1300 DEG C；
Basis material with a thickness of 12~25 μm, coating with a thickness of
The present embodiment obtains the lithium ion battery separator after plated film, in mechanical properties: percent thermal shrinkage decline 0.1%~
30%, the Gurleyvalue for characterizing permeability increases 0~20.
In terms of chemical property: diaphragm surface resistance can at most decline 20%.
The lithium ion battery separator of this implementation is applied in lithium ion battery: compared to the battery for using basement membrane, battery
Cycle performance, service life and stability increase, wherein under the conditions of trickle charge, using the time extend longest it is reachable
50~100 times, leakage current reduces at most up to 30%, especially when applying in high pressure soft-package battery, mentions to battery performance
It rises more significant.
Comparative example 1
Fig. 2 is the preparation method process schematic illustration for the lithium ion battery separator that comparative example of the present invention provides, such as Fig. 2 institute
Show, the preparation method of the lithium ion battery separator of this comparative example, using traditional preparation unreel, coat, dry, wound
Technique；
Wherein, basis material is PE or PP, coating material Al2O3；
Basis material with a thickness of 12~25 μm, coating with a thickness of 2000nm~4000nm.
Diaphragm after the coating that this comparative example obtains, in mechanical properties: percent thermal shrinkage decline 25%~35% is used
40~60 are increased in the Gurleyvalue of characterization permeability.
In terms of chemical property: diaphragm surface resistance increases 20%~40%.
In terms of lithium ion battery applications, conventional ceramic coating diaphragm can not be applied in high pressure soft-package battery.Battery can be
Failure in short time.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of lithium ion battery separator, which comprises the following steps:
Basis material is fixed in the intracorporal unreeling structure of vacuum reaction chamber, optional coating is passed through into vacuum reaction chamber body
Material plasma gas；
Coating material is gasified into vacuum reaction cavity using vapor deposition apparatus, and coating material is passed through into vapour deposition process
It is deposited on basis material；
The basis material that surface deposited coating material closes in rolling-up mechanism；
Wherein, chill roll is additionally provided between unreeling structure and rolling-up mechanism, which is located at the top of vapor deposition apparatus, uses
In preventing, basis material is heated to generate deformation.
2. the preparation method of lithium ion battery separator according to claim 1, which is characterized in that the vacuum reaction cavity
Vacuum degree 2 × 10- 2Pa or less；
Preferably, the vacuum degree of the vacuum reaction cavity is 1 × 10- 3~1 × 10- 7Pa。
3. the preparation method of lithium ion battery separator according to claim 1, which is characterized in that the vapor deposition apparatus
Heating temperature be 200~1500 DEG C, preferably 450~1250 DEG C；
Preferably, the temperature of the chill roll is -30~0 DEG C, preferably -25~-15 DEG C.
4. the preparation method of lithium ion battery separator according to claim 1, which is characterized in that the vapour deposition process packet
Include physical vapour deposition (PVD) and/or chemical vapor deposition；
Preferably, the vapour deposition process is arc evaporation, sputter vaporization, ion beam bombardment, pulse laser deposition and thermal evaporation
At least one of.
5. the preparation method of lithium ion battery separator according to claim 1, which is characterized in that described matrix material includes
At least one of polyethylene, polypropylene, polyamide, polyimides, polyethylene terephthalate, non-woven fabrics or fiber.
6. the preparation method of lithium ion battery separator according to claim 1, which is characterized in that the coating material includes
Metal and/or polymer；
Preferably, the coating material include silica, aluminum oxide, titanium dioxide, zirconium oxide, zinc oxide, magnesia,
In boron nitride, boehmite, Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropylene copolymer or polyacrylonitrile
It is at least one.
7. the preparation method of described in any item lithium ion battery separators according to claim 1~6, which is characterized in that be deposited on
Coating on basis material with a thickness of
8. a kind of lithium ion battery separator, which is characterized in that using the described in any item lithium ion batteries of claim 1~7 every
The preparation method of film is prepared.
9. a kind of lithium ion battery, which is characterized in that including lithium ion battery separator according to any one of claims 8.
10. electronic device, electric tool, electric vehicle comprising lithium ion battery as claimed in claim 9 or electric power storage system
System.
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Cited By (6)
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| CN108258226A (en) * | 2018-01-25 | 2018-07-06 | 深圳市德方纳米科技股份有限公司 | A kind of carbon coating tertiary cathode material and preparation method thereof |
| CN109626053A (en) * | 2018-12-28 | 2019-04-16 | 南京坚泰普新材料有限公司 | A kind of small-sized rewinding machine band heating and vacuumized |
| CN112002863A (en) * | 2020-09-02 | 2020-11-27 | 溧阳月泉电能源有限公司 | Preparation method of battery diaphragm |
| CN113346038A (en) * | 2020-03-03 | 2021-09-03 | 宁德新能源科技有限公司 | Preparation method and preparation device of composite current collector |
| CN113544904A (en) * | 2019-01-04 | 2021-10-22 | 赛尔格有限责任公司 | Battery separator comprising microporous membrane and coating |
| CN115275507A (en) * | 2022-08-09 | 2022-11-01 | 南木纳米科技(北京)有限公司 | Dry method diaphragm coating machine |
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| US9127344B2 (en) * | 2011-11-08 | 2015-09-08 | Sakti3, Inc. | Thermal evaporation process for manufacture of solid state battery devices |
| CN105958000A (en) * | 2016-07-11 | 2016-09-21 | 东莞市魔方新能源科技有限公司 | Lithium ion battery composite membrane and preparation method thereof |
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| CN103137929A (en) * | 2011-11-24 | 2013-06-05 | 比亚迪股份有限公司 | Lithium ion battery diaphragm, preparation method of the lithium ion battery diaphragm, and lithium ion battery containing the lithium ion battery diaphragm |
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| CN108258226A (en) * | 2018-01-25 | 2018-07-06 | 深圳市德方纳米科技股份有限公司 | A kind of carbon coating tertiary cathode material and preparation method thereof |
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| CN113544904A (en) * | 2019-01-04 | 2021-10-22 | 赛尔格有限责任公司 | Battery separator comprising microporous membrane and coating |
| CN113346038A (en) * | 2020-03-03 | 2021-09-03 | 宁德新能源科技有限公司 | Preparation method and preparation device of composite current collector |
| CN112002863A (en) * | 2020-09-02 | 2020-11-27 | 溧阳月泉电能源有限公司 | Preparation method of battery diaphragm |
| CN115275507A (en) * | 2022-08-09 | 2022-11-01 | 南木纳米科技(北京)有限公司 | Dry method diaphragm coating machine |
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