CN108417762A - Lithium ion battery separator and preparation method thereof, lithium ion battery - Google Patents
Lithium ion battery separator and preparation method thereof, lithium ion battery Download PDFInfo
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- CN108417762A CN108417762A CN201810169305.3A CN201810169305A CN108417762A CN 108417762 A CN108417762 A CN 108417762A CN 201810169305 A CN201810169305 A CN 201810169305A CN 108417762 A CN108417762 A CN 108417762A
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- lithium ion
- cyclodextrin
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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
- 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
- H01M50/403—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
- 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
- H01M50/411—Organic 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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- Cell Separators (AREA)
Abstract
The invention discloses a kind of lithium ion battery separator and preparation method thereof, lithium ion batteries, are related to technical field of lithium ion.Lithium ion battery separator includes the cyclodextrin layer of PP/PE/PP porous membrane substrates and PP/PE/PP porous membrane substrates surface.The preparation method of lithium ion battery separator includes the following steps：Cyclodextrin slurry is evenly applied on PP/PE/PP porous membrane substrates, cyclodextrin layer is formed, lithium ion battery separator is obtained after dry；Cyclodextrin slurry includes cyclodextrin and water.The defect that the present invention alleviates conventional membrane basis material non-refractory, safety is poor and ceramic coating membrane is easily damaged, the lithium ion battery separator cyclodextrin layer of the present invention is not easily to fall off, diaphragm after coating has preferable chemical property and mechanical property, diaphragm percent thermal shrinkage is low, it has a safety feature, is suitble to high power charging-discharging.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of lithium ion battery separator and its preparation
Method, lithium ion battery.
Background technology
Lithium ion battery is a kind of secondary cell with higher energy density.As time goes on, its cost is gradually low,
Using being also promoted, especially in electric vehicle and energy storage field.The safety of lithium ion battery constrains it further
Development and application.
Diaphragm is the important composition component of lithium ion battery, and main function of the diaphragm in lithium ion battery makes battery
Positive and negative electrode is separated, and prevents the two poles of the earth from contacting and short-circuit, is one of the interior layer assembly of key.The performance of diaphragm determines battery
Interfacial structure, internal resistance etc., directly affect the characteristics such as the capacity, cycle performance and safety of battery, the diaphragm pair haveing excellent performance
The comprehensive performance for improving lithium ion battery plays an important role.
Common lithium ion battery separator basis material includes mainly polypropylene, polythene material and additive.But due to
The defects of there are non-refractories, making the safety of lithium ion, there are larger hidden danger.The heat resistanceheat resistant contractility for improving diaphragm, can be with
The Joule heat that the internal short-circuit caused by diaphragm short circuit generates is effectively reduced, is the important method for improving battery thermal shock resistance.
There is ceramic coating membrane later, but ceramics are a kind of materials of strong resistance to thermal contraction, when with the lithium battery diaphragm that is easy to contraction
Material coating together when, two bed boundarys are due to being subjected to differing for a long time larger thermal shrinkage stress and generating inevitable strain causes
Diaphragm is impaired.
In view of this, special propose the present invention.
Invention content
One of the objects of the present invention is to provide a kind of lithium ion battery separator, using PP/PE/PP sandwich diaphragms as more
Hole film base material is coated with cyclodextrin layer on film base material, acted between cyclodextrin and porous membrane substrate it is strong, be not easy
It falls off, the diaphragm air permeability after coating is good, aperture is intensive, and aperture is more uniform, and surface is more smooth, has preferable chemical property
And mechanical property.Diaphragm percent thermal shrinkage is low, and during battery high power charging-discharging, which melts from micropore closed pore to diaphragm
Melt break temperature wider range, has a safety feature.
The second object of the present invention is to provide a kind of preparation method of lithium ion battery separator, the lithium that this method obtains from
Sub- battery diaphragm aperture parameters are good, and aperture is intensive, uniform, and air permeability is good, have preferable chemical property, mechanical property and peace
Full performance.In addition, this method is easy to operate, it is convenient for industrialized production.
The third object of the present invention be to provide it is a kind of comprising above-mentioned lithium ion battery separator or above-mentioned lithium ion battery every
The lithium ion battery for the lithium ion battery separator that the preparation method of film is prepared has advantage identical with above-mentioned diaphragm, obtains
The lithium ion battery safety performance arrived is good.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
In a first aspect, provide a kind of lithium ion battery separator, including PP/PE/PP porous membrane substrates and PP/PE/PP it is more
The cyclodextrin layer of pore membrane substrate surface.
Preferably, on the basis of technical solution provided by the invention, the thickness of the PP/PE/PP porous membrane substrates is
10-20 μm, preferably 15-18 μm, further preferred 16-18 μm；
Preferably, the air permeability of the PP/PE/PP porous membrane substrates is 180-200s/100mL；
Preferably, the aperture of the PP/PE/PP porous membrane substrates is 0.03-0.05 μm；
Preferably, the porosity of the PP/PE/PP porous membrane substrates is 35-50%.
Preferably, on the basis of technical solution provided by the invention, the thickness of the cyclodextrin layer is 0.5-
10 μm, preferably 1-10 μm, further preferred 1-5 μm.
Preferably, on the basis of technical solution provided by the invention, coating slurry used in the cyclodextrin layer
Following component including parts by weight：10-25 parts of cyclodextrin, 0.5-2 parts optional of binder, is appointed at 60-100 parts of water
0.1-3 parts of the aqueous dispersion of choosing and 0.1-2 parts optional of surfactant；
Preferably, binder includes butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer or poly- ammonia
One kind in ester or at least two combination；
Preferably, aqueous dispersion includes metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate or poly-
One kind in potassium acrylate or at least two combination；
Preferably, surfactant includes fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxy
One kind in vinethene, fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy ether or at least two combination.
Preferably, on the basis of technical solution provided by the invention, coating slurry used in the cyclodextrin layer
In further include ceramic powder 1-10 parts by weight.
Second aspect provides a kind of preparation method of lithium ion battery separator, includes the following steps：
Cyclodextrin slurry is evenly applied on PP/PE/PP porous membrane substrates, cyclodextrin layer is formed,
Lithium ion battery separator is obtained after drying；
The cyclodextrin slurry includes cyclodextrin and water.
Preferably, described applied to single side coating or dual coating on the basis of technical solution provided by the invention.
Preferably, on the basis of technical solution provided by the invention, the cyclodextrin slurry includes parts by weight
Several following components：10-25 parts of cyclodextrin, 60-100 parts of water, 0.5-2 parts of binder, 0.1-3 parts of aqueous dispersion and
0.1-2 parts of surfactant；
Preferably, binder includes butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer or poly- ammonia
One kind in ester or at least two combination；
Preferably, aqueous dispersion includes metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate or poly-
One kind in potassium acrylate or at least two combination；
Preferably, surfactant includes fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxy
One kind in vinethene, fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy ether or at least two combination.
Preferably, further include pottery on the basis of technical solution provided by the invention, in the cyclodextrin slurry
Porcelain powder 1-10 parts by weight.
The third aspect provides a kind of preparation side comprising above-mentioned lithium ion battery separator or above-mentioned lithium ion battery separator
The lithium ion battery for the lithium ion battery separator that method is prepared.
Compared with the prior art, the present invention has the advantages that：
(1) lithium ion battery separator of the invention includes the cyclodextrin of PP/PE/PP porous membrane substrates and its surface
Layer is coated with cyclodextrin layer, cyclodextrin polymerization using PP/PE/PP sandwich diaphragms as porous membrane substrate on film base material
Act on strong, not easily to fall off between object and porous membrane substrate, advantageously reduce the percent thermal shrinkage of diaphragm, improve battery safety and
Persistence.The lithium ion battery separator aperture of the present invention is intensive, and air permeability is good, is suitable for multi-multiplying power charging-discharging lithium ion battery,
It can inhibit corrosion of the gas generation to electrode in charge and discharge process, thus high-multiplying power discharge capacity reduces less.Membrane pore size compared with
Uniformly, surface is more smooth, thus shows preferable chemical property.Using diaphragm of the present invention in battery high power charging-discharging process
In, from micropore closed pore to diaphragm melt fracture wider range, remained within the scope of the wider temperature of failure of current the latter
Preferable mechanical property is kept, thus is had a safety feature.
(2) diaphragm is made to have due to hydrophilic highly polar group hydroxy by the diaphragm that cyclodextrin coats
Preferable electrolyte wellability, improves diaphragm imbibition rate, can effectively reduce the capacity attenuation of battery.
(3) preparation method of lithium ion battery separator of the invention uniformly applies shroud on PP/PE/PP porous membrane substrates surface
Dextrin polymer paste, the lithium ion battery separator aperture that this method obtains is intensive, uniform, and air permeability is good, has preferable electricity
Chemical property, mechanical property and security performance.In addition, this method is easy to operate, it is convenient for industrialized production.The ring paste used simultaneously
Smart polymer paste uses water as solvent, avoids using the pollution and harm caused by organic solution, avoids organic solvent
It is uneven and uncertain caused by volatilization.
Description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepare lithium ion battery separator scanning electron microscope (SEM) photograph ((a) be a lithium ion battery
Diaphragm scanning electron microscope (SEM) photograph；(b) it is another lithium ion battery separator scanning electron microscope (SEM) photograph)；
Fig. 2 is the lithium ion battery charge and discharge electrograph of the lithium ion battery separator prepared using the embodiment of the present invention 1.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, a kind of lithium ion battery separator, including PP/PE/PP perforated membrane bases are provided
The cyclodextrin layer of material and PP/PE/PP porous membrane substrates surface.
The meaning of the expression sum of "/" in PP/PE/PP porous membrane substrates, i.e. PP/PE/PP (polypropylene, polyethylene/poly- third
Alkene) perforated membrane that is combined of three-decker.
Typical but non-limiting PP/PE/PP porous membrane substrates are, for example, 16 μm of diaphragms of Celguard.
PP/PE/PP perforated membranes combine PP, PE film advantage, and mechanical strength is good, safety higher.
Cyclodextrin layer refers to the coating that principal component is cyclodextrin, and cyclodextrin is pasted by multiple rings
Smart unit, which is present on macromolecular chain, constitutes cyclodextrin (high polymer, CDP)
Typical cyclodextrin is beta-cyclodextrin cross-linked polymer, is that host cyclodextrin passes through cross-linking agents appropriate
It obtains afterwards, the source of beta-cyclodextrin cross-linked polymer is not construed as limiting, commercially available beta-cyclodextrin cross-linked polymer can be used, such as β-ring
Dextrin cross-linked polymer, or be prepared using conventional method.
Cyclodextrin makes diaphragm be infiltrated with preferable electrolyte due to hydrophilic highly polar group hydroxy
Property, diaphragm imbibition rate is improved, the capacity attenuation of battery can be effectively reduced.
The lithium ion battery separator of the present invention is coated using PP/PE/PP sandwich diaphragms as porous membrane substrate on film base material
There is cyclodextrin layer, PP/PE/PP perforated membranes and cyclodextrin are organic material, and cyclodextrin bonds
Property is strong, enhances the effect between coating and porous membrane substrate, cyclodextrin coating is not easily to fall off, advantageously reduces diaphragm
Percent thermal shrinkage, improve safety and the persistence of battery.Coating particle accumulation is neat, is uniformly dispersed, soilless sticking phenomenon, unanimously
Property it is good, will not plug-hole, aperture is intensive, and air permeability is relatively low, and imbibition rate is high, is suitable for multi-multiplying power charging-discharging lithium ion battery, can
To inhibit corrosion of the gas generation to electrode in charge and discharge process, thus high-multiplying power discharge capacity reduces less.Membrane pore size is more equal
Even, surface is more smooth, thus shows preferable chemical property.Using diaphragm of the present invention in battery high power charging-discharging process
In, from micropore closed pore to diaphragm melt fracture wider range, remained within the scope of the wider temperature of failure of current the latter
Preferable mechanical property is kept, thus is had a safety feature.
In a preferred embodiment, the thickness of PP/PE/PP porous membrane substrates be 10-20 μm, preferably 15-18 μm,
Further preferably 16-18 μm.
The typical but non-limiting thickness of PP/PE/PP porous membrane substrates is, for example, 10 μm, 12 μm, 14 μm, 15 μm, 16 μ
M, 18 μm or 20 μm.
In a preferred embodiment, the air permeability of PP/PE/PP porous membrane substrates is 180-200s/100mL, example
Such as 180s/100mL, 190s/100mL or 200s/100mL.
In a preferred embodiment, the aperture of PP/PE/PP porous membrane substrates is 0.03-0.05 μm, such as 0.03
μm, 0.04 μm or 0.05 μm.
In a preferred embodiment, the porosity of PP/PE/PP porous membrane substrates is 35-50%.Such as 35%,
40%, 45% or 50%.
The good PP/PE/PP porous membrane substrates of consistency are selected, it is smaller in certain mechanical strength lower diaphragm plate thickness, reduce
Internal resistance, can high-power charge and discharge.Uniform pore diameter, porosity are suitable, ensure lower resistance and higher ionic conductivity, improve
Cell potential density promotes charge-discharge performance.Air permeability is relatively low, and aperture is intensive can to inhibit gas generation pair in charge and discharge process
The corrosion of electrode, high-multiplying power discharge capacity reduce few.
In a preferred embodiment, the thickness of cyclodextrin layer be 0.5-10 μm, preferably 1-10 μm, into one
Walk preferred 1-5 μm.
It is, for example, 0.5 μm that the thickness of cyclodextrin layer is typical but non-limiting, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6
μm, 7 μm, 8 μm, 9 μm or 10 μm.
The thinner thickness of cyclodextrin layer is unfavorable for more efficiently reducing the percent thermal shrinkage of diaphragm, improves battery
Safety and persistence, the wellability of diaphragm can not be effectively improved.The thickness of cyclodextrin layer is thicker, and cyclodextrin is poly-
It closes nitride layer to be easy to fall off, influences safety and persistence.
In a preferred embodiment, coating slurry used in cyclodextrin layer includes parts by weight such as the following group
Point：10-25 parts of cyclodextrin, 60-100 parts of water, 0.5-2 parts optional of binder, 0.1-3 parts optional of aqueous dispersion
With 0.1-2 parts optional of surfactant.
The typical but non-limiting parts by weight of cyclodextrin are, for example, 10 parts, 15 parts, 20 parts or 25 parts.
The typical but non-limiting parts by weight of water are, for example, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts.
Binder is optional component, and binder, which is added, can further enhance the adhesive force of cyclodextrin and diaphragm.
The typical but non-limiting parts by weight of binder are, for example, 0.5 part, 1 part or 2 parts.
Preferably, binder includes butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer or poly- ammonia
One kind in ester or at least two combination.
Aqueous dispersion is optional component, and aqueous dispersion, which is added, can be such that cyclodextrin preferably divides in water
It dissipates, keeps the cyclodextrin layer after coating more uniform.
The typical but non-limiting parts by weight of aqueous dispersion are, for example, 0.1 part, 1 part, 2 parts or 3 parts.
Preferably, aqueous dispersion includes metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate or poly-
One kind in potassium acrylate or at least two combination.
Surfactant is optional component, and surfactant, which is added, can play the role of adjusting slurry surface tension, if
Slurry surface tension is excessively high, then slurry is not easy on PP/PE/PP diaphragms extravagant, causes application difficulties；If slurry surface tension is too
Low, then slurry is easy blistering in transfer process, in drying process lather collapse cause holiday.
The typical but non-limiting parts by weight of surfactant are, for example, 0.1 part, 0.5 part, 1 part or 2 parts.
Preferably, surfactant includes fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxy
One kind in vinethene, fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy ether or at least two combination.
Cyclodextrin is mixed with water with special ratios, the suitable slurry of concentration is obtained, uniformity is good after coating, and
Being preferably added to binder, aqueous dispersion and surfactant can make slurry dispersibility more preferable, the cyclodextrin obtained after coating
Polymer coating property is more preferable.
In a preferred embodiment, in coating slurry used in cyclodextrin layer further include ceramic powder 1-10 weights
Measure part.
Ceramic is a kind of lightweight non-metallic multifunctional material, and main component is SiO2And Al2O3, ceramic typical case
But unrestricted parts by weight are, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
Rigid backbone is then formed in composite membrane by the way that inorganic ceramic particle is added, and further prevents diaphragm in hot conditions
Under shrink even melt, further promote battery safety.
According to the second aspect of the invention, a kind of preparation method of lithium ion battery separator, including following step are provided
Suddenly：
Cyclodextrin slurry is evenly applied on PP/PE/PP porous membrane substrates, cyclodextrin layer is formed,
Lithium ion battery separator is obtained after drying；
Cyclodextrin slurry includes cyclodextrin and water.
Cyclodextrin slurry is that beta-cyclodextrin cross-linked polymer is dissolved or dispersed in water and obtains, and can form gel
State fluid, the viscosity of preferred cyclodextrin polymer paste are 50-500mPas, such as 50mPas, 100mPas,
120mPas, 150mPas, 200mPas, 300mPas, 400mPas or 500mPas.
Cyclodextrin is preferably beta-cyclodextrin cross-linked polymer, be host cyclodextrin by cross-linking agents appropriate after
It obtains, the source of beta-cyclodextrin cross-linked polymer is not construed as limiting, commercially available beta-cyclodextrin cross-linked polymer can be used, such as β-ring paste
Smart cross-linked polymer, or be prepared using conventional method.
Preferably, beta-cyclodextrin cross-linked polymer is prepared using epoxychloropropane with beta-cyclodextrin cross-linking reaction.It is typical
Preparation method is as follows：Beta-cyclodextrin is dissolved in 20% sodium hydroxide solution, under constant stirring press certain speed instill 30~
40mL epoxychloropropane after system reaches certain viscosity, stops stirring, and the reaction was continued occurs to the hard cake mass of gel, takes out
It is washed until not chloride ion-containing with water and acetone, filtration drying, the granular beta-cyclodextrin cross-linked polymer after grinding.
Beta-cyclodextrin cross-linked polymer has tridimensional network, can effectively prevent reuniting, and dispersing uniformity is good, and coating is laggard
One step promotes the performances such as surface nature, pore passage structure, the mechanical strength of diaphragm.
Cyclodextrin layer is formed after coating cyclodextrin slurry, the thickness of this layer is, for example, 0.5 μm, 1 μm, 2 μ
M, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
The preparation method of the lithium ion battery separator of the present invention uniformly applies shroud paste on PP/PE/PP porous membrane substrates surface
Smart polymer paste, the lithium ion battery separator aperture obtained after coating is intensive, uniform, and air permeability is good, chemical property, mechanics
Performance and security performance are outstanding.In addition, this method is easy to operate, it is convenient for industrialized production.The cyclodextrin used simultaneously
Slurry uses water as solvent, avoids using the pollution and harm caused by organic solution, avoids organic solvent volatilization and is made
At it is uneven and uncertain.
Preferably, single side coating or dual coating are applied to.
Cyclodextrin slurry can be coated on the one side that PP/PE/PP basement membranes are in contact with battery anode slice when coating
On the two sides being in contact in the one side being in contact above or with the negative plate of battery or with the positive and negative anodes pole piece of battery.
In a preferred embodiment, cyclodextrin slurry includes the following component of parts by weight：Cyclodextrin
0.1-2 parts of 10-25 parts of polymer, 60-100 parts of water, 0.5-2 parts of binder, 0.1-3 parts of aqueous dispersion and surfactant.
The typical but non-limiting parts by weight of cyclodextrin are, for example, 10 parts, 15 parts, 20 parts or 25 parts.
The typical but non-limiting parts by weight of water are, for example, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts.
Typical but non-limiting binder is, for example, butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethene-vinyl acetate
Copolymer or polyurethane etc., weight of binder part are, for example, 0.5 part, 1 part or 2 parts.
Typical but non-limiting aqueous dispersion is, for example, Barbiturates fluorine dispersant, Sulfonates fluorine dispersant, poly- third
Olefin(e) acid sodium or polyacrylic acid potassium etc., aqueous dispersion parts by weight are, for example, 0.1 part, 1 part, 2 parts or 3 parts.
Typical but non-limiting surfactant is, for example, fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether
Alcohol, alkyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy ether etc., surfactant typical case but non-limit
Property processed is, for example, 0.1 part, 0.5 part, 1 part or 2 parts.
It is starched made of the cyclodextrin of certain content, binder, aqueous dispersion, surfactant and water
Material property is uniform, modest viscosity, and the cyclodextrin coating performance obtained after coating is more preferable.
In a preferred embodiment, in coating slurry used in cyclodextrin layer further include ceramic powder 1-10 weights
Measure part.
The typical but non-limiting parts by weight of ceramic powder are, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts
Or 10 parts.
Rigid backbone can be formed in composite membrane by the way that inorganic ceramic particle is added, and further prevent diaphragm in high temperature item
It shrinks under part and even melts, further promote battery safety.
Preferably, a kind of preparation method of typical lithium ion battery separator, includes the following steps：
(a) binder, aqueous dispersion and surfactant are dissolved in the water of part, obtain solution A；
(b) cyclodextrin is dissolved in remaining water, obtains solution B；
(c) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(d) cyclodextrin slurry is evenly applied on the one or both sides of PP/PE/PP porous membrane substrates, it is dry
The lithium ion battery separator coated with cyclodextrin layer is obtained afterwards；The thickness of PP/PE/PP porous membrane substrates is 10-20 μm；
The thickness of cyclodextrin layer is 0.5-10 μm.
The preparation method of the typical lithium ion battery separator by first prepare respectively cyclodextrin solution and its
His compounding agent solution, then the two is mixed and made into slurry, obtained slurry stable uniform, caking property is good, the diaphragm obtained after coating
Surfacing is conducive to obtain the good battery diaphragm of chemical property, security performance.
According to the third aspect of the present invention, it includes above-mentioned lithium ion battery separator or above-mentioned lithium-ion electric to provide a kind of
The lithium ion battery for the lithium ion battery separator that the preparation method of pond diaphragm is prepared.
Lithium ion battery has advantage identical with above-mentioned diaphragm, obtained lithium ion battery safety performance good.
Hereinafter, the present invention will be more fully described according to following specific embodiment and comparative example.However, providing following
Embodiment and comparative example be only used for illustrate the present invention, the scope of the present invention is not limited thereto, each raw material of the present invention
Pass through commercially available acquisition.
Embodiment 1
A kind of lithium ion battery separator, including 16 μm of barrier film base material tables of 16 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin layer in face, cyclodextrin layer is 1 μm.
The preparation method of lithium ion battery separator, includes the following steps：
(1) surfactant of the binder of 0.5 parts by weight, the aqueous dispersion of 3 parts by weight and 0.1 parts by weight is dissolved in
In the water of 50 parts by weight, solution A is obtained；
(2) cyclodextrin of 25 parts by weight is dissolved in the water of remaining 50 parts by weight, obtains solution B；
(3) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(4) cyclodextrin slurry is evenly applied in the one side of 16 μm of barrier film base materials of Celguard, is obtained after dry
To the lithium ion battery separator coated with cyclodextrin layer.
Embodiment 2
A kind of lithium ion battery separator, including 10 μm of barrier film base material tables of 10 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin layer in face, cyclodextrin layer is 0.5 μm.
The preparation method of lithium ion battery separator, includes the following steps：
(1) surfactant of the binder of 2 parts by weight, the aqueous dispersion of 0.1 parts by weight and 2 parts by weight is dissolved in 30
In the water of parts by weight, solution A is obtained；
(2) cyclodextrin of 10 parts by weight is dissolved in the water of remaining 30 parts by weight, obtains solution B；
(3) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(4) cyclodextrin slurry is evenly applied in the one side of 10 μm of barrier film base materials of Celguard, is obtained after dry
To the lithium ion battery separator coated with cyclodextrin layer.
Embodiment 3
A kind of lithium ion battery separator, including 20 μm of barrier film base material tables of 20 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin layer in face, cyclodextrin layer is 2 μm.
The preparation method of lithium ion battery separator, includes the following steps：
(1) surfactant of the binder of 1 parts by weight, the aqueous dispersion of 1 parts by weight and 1.5 parts by weight is dissolved in 30
In the water of parts by weight, solution A is obtained；
(2) cyclodextrin of 15 parts by weight is dissolved in the water of remaining 40 parts by weight, obtains solution B；
(3) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(4) cyclodextrin slurry is evenly applied in the one side of 20 μm of barrier film base materials of Celguard, is obtained after dry
To the lithium ion battery separator coated with cyclodextrin layer.
Embodiment 4
A kind of lithium ion battery separator, including 15 μm of barrier film base material tables of 15 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin layer in face, cyclodextrin layer is 3 μm.
The preparation method of lithium ion battery separator, includes the following steps：
(1) surfactant of the binder of 1.5 parts by weight, the aqueous dispersion of 2 parts by weight and 1 parts by weight is dissolved in 40
In the water of parts by weight, solution A is obtained；
(2) cyclodextrin of 12 parts by weight is dissolved in the water of remaining 40 parts by weight, obtains solution B；
(3) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(4) cyclodextrin slurry is evenly applied in the one side of 15 μm of barrier film base materials of Celguard, is obtained after dry
To the lithium ion battery separator coated with cyclodextrin layer.
Embodiment 5
A kind of lithium ion battery separator, including 18 μm of barrier film base material tables of 18 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin layer in face, cyclodextrin layer is 4 μm.
The preparation method of lithium ion battery separator, includes the following steps：
(1) surfactant of the binder of 1.8 parts by weight, the aqueous dispersion of 2.5 parts by weight and 0.5 parts by weight is molten
In the water of 50 parts by weight, solution A is obtained；
(2) cyclodextrin of 20 parts by weight is dissolved in the water of remaining 40 parts by weight, obtains solution B；
(3) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(4) cyclodextrin slurry is evenly applied in the one side of 18 μm of barrier film base materials of Celguard, is obtained after dry
To the lithium ion battery separator coated with cyclodextrin layer.
Embodiment 6
A kind of lithium ion battery separator, including 16 μm of barrier film base material tables of 16 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin layer in face, cyclodextrin layer is 5 μm.
The preparation method of lithium ion battery separator, includes the following steps：
(1) surfactant of the binder of 1.5 parts by weight, the aqueous dispersion of 0.5 parts by weight and 1 parts by weight is dissolved in
In the water of 45 parts by weight, solution A is obtained；
(2) cyclodextrin of 18 parts by weight is dissolved in the water of remaining 40 parts by weight, obtains solution B；
(3) solution A and solution B are uniformly mixed, obtain cyclodextrin slurry；
(4) cyclodextrin slurry is evenly applied in the one side of 16 μm of barrier film base materials of Celguard, is obtained after dry
To the lithium ion battery separator coated with cyclodextrin layer.
Embodiment 7
A kind of lithium ion battery separator, including 16 μm of barrier film base material tables of 16 μm of barrier film base materials of Celguard and Celguard
The thickness of the cyclodextrin-ceramic layer in face, cyclodextrin-ceramic layer is 0.5 μm.
The preparation method of lithium ion battery separator, wherein step (2) are by the cyclodextrin of 25 parts by weight and 2 weights
The ceramic powder of amount part is dissolved in the water of remaining 50 parts by weight, obtains solution B, remaining step is same as Example 1.
Comparative example 1
A kind of lithium ion battery separator, as different from Example 1, this comparative example use the 20 μm of diaphragm conducts of East Airways's photoelectricity
Barrier film base material.
Comparative example 2
A kind of lithium ion battery separator, as different from Example 1, this comparative example is using 23 μm of Xinxiang diaphragm as diaphragm
Base material.
Comparative example 3
A kind of lithium ion battery separator, as different from Example 1, this comparative example using prompt source contain 20 μm of diaphragms be used as every
Film base material.
Comparative example 4
This comparative example uses 16 μm of diaphragms of Celguard, porosity 50%, and without any coating treatment.
Test example 1
The obtained lithium ion battery separator of embodiment 1-7 and comparative example 1-4 is tested, following table is as a result shown in
In 1.
Test includes membrane thicknesses, aperture, porosity, air permeability, imbibition rate, percent thermal shrinkage and punctured resistance, specifically
Test method is as follows：
Thickness：It is measured using non-contact thickness gauge.
Aperture and pore-size distribution：It is measured using mercury injection method, the distributing homogeneity in hole is observed using SEM.
Porosity：For certain electrolyte, the diaphragm with high porosity can reduce the impedance of battery, but hole
Rate is too high, and the mechanical strength of material can be made to be deteriorated, and theoretical porosity is calculated using weight method.
Air permeability：Air permeability is also known as Gurley numbers, reflects the transmission ability of diaphragm.It is examined using sharp (GURLEY) Permeability gauge of lattice
It surveys.
Imbibition rate：It is immersed in after dry type sample is weighed in solution liquid, until absorption equilibrium, further takes out wet diaphragm and dry surface
Electrolyte is weighed, and imbibition rate is calculated.
Percent thermal shrinkage：Diaphragm is placed on 90 DEG C of environment lower 1 hour, sees the area change rate of front and back diaphragm.
Punctured resistance：Diaphragm is fixed with cycle object, takes the needle of certain diameter, it is desirable that needle point is without sharp edge, with one
Fixed speed perpendicular insertion crosses diaphragm, and diaphragm is punctured the puncture resistant power that maximum, force is exactly diaphragm.
Table 1
As shown in table 1, the present invention obtains membrane thicknesses, aperture, porosity, air permeability are good, and imbibition rate is high, and heat is received
Shrinkage is low, and mechanical property punctured resistance is high.
Embodiment 7 is further promoted compared with the imbibition rate and puncture strength of 1 diaphragm of embodiment, and percent thermal shrinkage further decreases.
It can be seen that embodiment 7 increases ceramic powder on the basis of embodiment 1, further improves the imbibition rate of diaphragm, is heat-shrinked
Rate and puncture strength performance.
Comparative example 1-3 compared with Example 1, has replaced barrier film base material, membrane properties especially mechanical property and thermal contraction
Property is decreased obviously, and influences diaphragm safety in utilization, it is seen that can obtain machine as base film using PP/PE/PP sandwich diaphragms
Tool intensity and the better diaphragm of security performance.
Comparative example 4 compared with Example 1, does not carry out coating treatment, and diaphragm imbibition rate is decreased obviously, in addition percent thermal shrinkage and
Mechanical property is also declined, it is seen then that by coating cyclodextrin layer, can significantly improve the imbibition rate of diaphragm, and energy
Enough diaphragms for obtaining more high mechanical properties and security performance.
As it can be seen that the present invention by using PP/PE/PP sandwich diaphragms as porous membrane substrate, and be coated on film base material
Cyclodextrin layer, obtained diaphragm air permeability is good, aperture is intensive, and aperture is more uniform, and surface is more smooth, has preferable electricity
Chemical property and mechanical property.Diaphragm percent thermal shrinkage is low, has a safety feature.
Test example 2
Lithium-ion electric is made in the lithium ion battery separator that the lithium ion battery separator that embodiment 1 obtains is obtained with comparative example
Pond carries out contrast experiment.
Wherein positive electrode slurry includes LiFePO4：Conductive agent：Binder：Dispersant=92.14%：3.50%：
4.00%：0.36%；Negative material is artificial graphite；Electrolyte LiPF6A concentration of 1mol/L, EC：EMC：DMC=1:1:1.
It is 1185.8mAh (0.5C) as a result, it has been found that capacity of lithium ion battery height is made using 1 diaphragm of embodiment, internal resistance is low,
For 37.8m Ω.
Fig. 1 is lithium ion battery separator scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1；Fig. 2 is to be implemented using the present invention
The lithium ion battery charge and discharge electrograph of lithium ion battery separator prepared by example 1.
For embodiment 1 compared with comparative example 1-3,16 μm of diaphragms of Celguard are tri- laminated spelling diaphragm papers of PP/PE/PP, other
It is single layer PP diaphragms.As shown in Fig. 2, reaching 90% using battery 40C efficiency for charge-discharges made of 1 diaphragm of embodiment, put
Electric platform voltage reaches 2.5V, and without apparent polarization phenomena.As discharge-rate increases, capacity reduction is less, is seen by 1 gas permeability of table
It can inhibit corrosion of the gas generation to electrode in charge and discharge process to membrane pore size is intensive, thus high-multiplying power discharge capacity reduces
It is few.Membrane pore size is more uniform, and surface is more smooth, thus shows preferable chemical property.As shown in Figure 1, scanning electron microscope (SEM) photograph is seen
It is independent, simple tension to membranes pores, and during battery high power charging-discharging, since discharge current is big, due to ohm
Fuel factor, inside battery generate prodigious heat, and excessively high temperature produces a very large impact diaphragm high rate during charging-discharging, this
The diaphragm of inventive embodiments 1 is wider in failure of current the latter from micropore closed pore to diaphragm melt fracture wider range
It remains to keep preferable mechanical property in temperature range, have a safety feature.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that wrapping in the following claims
Include all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. a kind of lithium ion battery separator, which is characterized in that including PP/PE/PP porous membrane substrates and PP/PE/PP perforated membrane bases
The cyclodextrin layer on material surface.
2. lithium ion battery separator described in accordance with the claim 1, which is characterized in that the thickness of the PP/PE/PP porous membrane substrates
Degree is 10-20 μm, preferably 15-18 μm, further preferred 16-18 μm；
Preferably, the air permeability of the PP/PE/PP porous membrane substrates is 180-200s/100mL；
Preferably, the aperture of the PP/PE/PP porous membrane substrates is 0.03-0.05 μm；
Preferably, the porosity of the PP/PE/PP porous membrane substrates is 35-50%.
3. lithium ion battery separator described in accordance with the claim 1, which is characterized in that the thickness of the cyclodextrin layer is
0.5-10 μm, preferably 1-10 μm, further preferred 1-5 μm.
4. according to claim 1-3 any one of them lithium ion battery separators, which is characterized in that the cyclodextrin layer
Coating slurry used includes the following component of parts by weight：10-25 parts of cyclodextrin, 60-100 parts of water, optional bonding
0.5-2 parts of agent, 0.1-3 parts optional of aqueous dispersion and 0.1-2 parts optional of surfactant；
Preferably, binder includes in butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer or polyurethane
One kind or at least two combination；
Preferably, aqueous dispersion includes metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate or polypropylene
One kind in sour potassium or at least two combination；
Preferably, surfactant includes fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkylphenol-polyethenoxy
One kind in ether, fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy ether or at least two combination.
5. lithium ion battery separator according to claim 4, which is characterized in that cyclodextrin layer coating used
Further include ceramic powder 1-10 parts by weight in slurry.
6. a kind of preparation method of claim 1-5 any one of them lithium ion battery separators, which is characterized in that including following
Step：
Cyclodextrin slurry is evenly applied on PP/PE/PP porous membrane substrates, cyclodextrin layer is formed, it is dry
After obtain lithium ion battery separator；
The cyclodextrin slurry includes cyclodextrin and water.
7. the preparation method of lithium ion battery separator according to claim 6, which is characterized in that described to be applied applied to single side
It covers or dual coating.
8. according to the preparation method of the lithium ion battery separator described in claim 6 or 7, which is characterized in that the cyclodextrin is poly-
Close the following component that object slurry includes parts by weight：10-25 parts of cyclodextrin, 60-100 parts of water, 0.5-2 parts of binder,
0.1-2 parts of 0.1-3 parts of aqueous dispersion and surfactant；
Preferably, binder includes in butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer or polyurethane
One kind or at least two combination；
Preferably, aqueous dispersion includes metal carboxylate fluorine dispersant, Sulfonates fluorine dispersant, Sodium Polyacrylate or polypropylene
One kind in sour potassium or at least two combination；
Preferably, surfactant includes fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkylphenol-polyethenoxy
One kind in ether, fatty alcohol polyoxyethylene ether or aliphatic acid polyethenoxy ether or at least two combination.
9. the preparation method of lithium ion battery separator according to claim 8, which is characterized in that the cyclodextrin
Further include ceramic powder 1-10 parts by weight in slurry.
10. comprising claim 1-5 any one of them lithium ion battery separator or claim 6-9 any one of them lithium from
The lithium ion battery for the lithium ion battery separator that the preparation method of sub- battery diaphragm is prepared.
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| CN109244325A (en) * | 2018-09-25 | 2019-01-18 | 合肥先杰新能源科技有限公司 | lithium battery diaphragm and preparation method thereof |
| CN109273649A (en) * | 2018-09-25 | 2019-01-25 | 合肥先杰新能源科技有限公司 | Lithium battery micro-pore septum and preparation method thereof |
| CN109546053A (en) * | 2018-11-01 | 2019-03-29 | 合肥国轩高科动力能源有限公司 | Nano modified lithium ion battery diaphragm, preparation method thereof and product containing nano modified lithium ion battery diaphragm |
| CN110690400A (en) * | 2019-11-10 | 2020-01-14 | 苏州欧纳克纳米科技有限公司 | High-wettability composite diaphragm for lithium ion battery |
| CN110783515A (en) * | 2019-11-10 | 2020-02-11 | 苏州欧纳克纳米科技有限公司 | High-wettability lithium ion battery diaphragm |
| CN111430641A (en) * | 2020-03-31 | 2020-07-17 | 石狮申泰新材料科技有限公司 | Production method of lithium battery diaphragm |
| CN112635765A (en) * | 2020-12-17 | 2021-04-09 | 中国科学院宁波材料技术与工程研究所 | Metal lithium battery cathode, preparation method thereof and lithium secondary battery |
| CN112928385A (en) * | 2021-03-23 | 2021-06-08 | 华中科技大学 | Diaphragm coating for lithium metal negative electrode protection and preparation method and application thereof |
| CN116042022A (en) * | 2023-03-30 | 2023-05-02 | 江苏正力新能电池技术有限公司 | Explosion-proof coating and application thereof in sodium ion battery |
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| CN109244325A (en) * | 2018-09-25 | 2019-01-18 | 合肥先杰新能源科技有限公司 | lithium battery diaphragm and preparation method thereof |
| CN109273649A (en) * | 2018-09-25 | 2019-01-25 | 合肥先杰新能源科技有限公司 | Lithium battery micro-pore septum and preparation method thereof |
| CN109546053A (en) * | 2018-11-01 | 2019-03-29 | 合肥国轩高科动力能源有限公司 | Nano modified lithium ion battery diaphragm, preparation method thereof and product containing nano modified lithium ion battery diaphragm |
| CN109546053B (en) * | 2018-11-01 | 2021-04-16 | 合肥国轩高科动力能源有限公司 | Nano modified lithium ion battery diaphragm, preparation method thereof and product containing nano modified lithium ion battery diaphragm |
| CN110690400A (en) * | 2019-11-10 | 2020-01-14 | 苏州欧纳克纳米科技有限公司 | High-wettability composite diaphragm for lithium ion battery |
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| CN111430641A (en) * | 2020-03-31 | 2020-07-17 | 石狮申泰新材料科技有限公司 | Production method of lithium battery diaphragm |
| CN112635765A (en) * | 2020-12-17 | 2021-04-09 | 中国科学院宁波材料技术与工程研究所 | Metal lithium battery cathode, preparation method thereof and lithium secondary battery |
| CN112928385A (en) * | 2021-03-23 | 2021-06-08 | 华中科技大学 | Diaphragm coating for lithium metal negative electrode protection and preparation method and application thereof |
| CN116042022A (en) * | 2023-03-30 | 2023-05-02 | 江苏正力新能电池技术有限公司 | Explosion-proof coating and application thereof in sodium ion battery |
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Application publication date: 20180817 |