CN110364664A - A kind of Water based metal ion secondary battery diaphragm and its preparation method and application - Google Patents
A kind of Water based metal ion secondary battery diaphragm and its preparation method and application Download PDFInfo
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- CN110364664A CN110364664A CN201910649294.3A CN201910649294A CN110364664A CN 110364664 A CN110364664 A CN 110364664A CN 201910649294 A CN201910649294 A CN 201910649294A CN 110364664 A CN110364664 A CN 110364664A
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of Water based metal ion secondary battery diaphragms and its preparation method and application, belong to lithium battery diaphragm technical field.The surface of a kind of Water based metal ion secondary battery diaphragm of the invention, including porous basement membrane, porous basement membrane is coated with hydrophobic coating, and the surface grafting of the hydrophobic coating has hydrophilic coating；The hydrophilic coating grafts on the surface of hydrophobic coating by the method for laser emission surface grafting, and radiation light beam wavelength is 9.1 μm~10.6 μm, and irradiation duration is 100~500ns, preferably 100~200ns.The wellability and liquid retention of diaphragm can be effectively improved, to meet the requirement of Water based metal ion secondary battery diaphragm on the basis of keeping the original good physical of membrane for polymer and conduction, cycle performance using technical solution of the present invention.
Description
Technical field
The invention belongs to lithium battery diaphragm technical fields, more specifically to a kind of Water based metal ion secondary battery
Diaphragm and its preparation method and application.
Background technique
In recent years, lithium ion battery is because having high-energy density, long circulation life, low self-discharge rate, high open circuit voltage, nothing
The advantages that heavy metal pollution and memory-less effect, becomes important electrical source of power, and is therefore widely used as notebook type
The power supply of people's computer, mobile phone and other mancarried devices.Lithium battery diaphragm is one of important component of lithium battery, effect
It is to separate positive and negative anodes and can guarantee the normal migration of lithium ion simultaneously to realize charge and discharge, the performance quality of lithium battery diaphragm is straight
Connect the service performance for influencing lithium ion battery.
Water based metal ion secondary battery is concerned because of its safer environmental protection, existing Water based metal ion secondary battery
The material of diaphragm mainly has: non-woven fabrics, glass fibre (AGM), dust-free paper, polyethylene (PE) and polypropylene (PP).But it is above-mentioned every
Film all has certain defect, such as non-woven fabrics, glass fibre and dust-free paper are as diaphragm its tensile strength, anti-tensile puncture intensity
It is not able to satisfy the demand of present battery, while the porosity of above-mentioned material is high (60%~80%), aperture is big (20~100 μm)
And it is uneven, cause self-discharge of battery larger, and be easy to cause short circuit.The diaphragm of polymer material such as polyethylene (PE) and poly-
The chemical stability and high mechanical strength of propylene (PP) diaphragm, porosity is moderate and uniform pore diameter, but the hydrophobic performance of itself
Cause it poor to the wellability and water retainability of aqueous electrolyte, to influence its answering in Water based metal ion secondary battery
With.
The lyophily of diaphragm can be improved by carrying out hydrophilic modifying processing to hydrophobic membrane, improve battery performance, therefore, existing lithium
Battery diaphragm manufacturer is usually all by being all that the hydrophobic membranes such as polyolefin are carried out with hydrophilic modifying processing to improve its infiltration
Property and liquid retention.The method for carrying out hydrophilic modifying to hydrophobic membrane at present mainly has surface coating hydrophilic polymer method, surface to connect
Branch hydrophilic polymer method and hydrophilic polymer blending method and surfactant facture etc..Wherein, parent is coated using surface
When waterborne polymeric method is modified processing, hydrophilic polymer and hydrophobic polymer interaction force are undesirable, use
Hydrophilic polymer is easy to fall off in journey.It is to match polymeric and hydrophilic macromolecule with hydrophilic polymer blending method
Uniform solution is made to form a film together later, two kinds of macromolecules are wound mutually, but there is no crosslinking, membrane material may occur
Separation, and hydrophilic polymer dosage is larger.Surfactant facture is that surfactant is coated on to porous hydrophobic basement membrane
Surface, but its timeliness is not grown, surfactant is easy to peel off.
Existing surface grafting hydrophilic polymer method is usually to use ultraviolet light, plasma etc. in advance to hydrophobicity basement membrane
Surface directly carries out radiation treatment, and hydroaropic substance is then grafted on membrane surface, hydroaropic substance and hydrophobicity basement membrane
In conjunction with relatively securely.Such as, the application case that Chinese Patent Application No. is 201410471524.9 discloses a kind of hydrophilic lithium-ion electric
Pond diaphragm, the diaphragm of this application be by MIcroporous polyolefin film carry out crosslinking electron beam irradiation after with uncrosslinked polyolefin micropore
Film is compounded to form composite diaphragm, then through prepared by via radiation grafting modification after the composite diaphragm is handled with hydrophilic modifier.It should
Application case can be improved the wetability of electrolyte by carrying out hydroaropic substance graft modification processing to diaphragm in certain journey, have
Help passing through for lithium ion, improves battery efficiency.
But using existing surface grafting hydrophilic polymer method processing is modified to battery diaphragm when, porous basement membrane it is micro-
Pore structure inevitably will receive destruction, so as to cause the physical property (air permeability, tensile strength, puncture strength etc.) of basement membrane
Decline.Therefore, research and development prepare one kind and are able to maintain thin polymer film good physical and electric conductivity, while having height again
The diaphragm for being more suitable for Water based metal ion secondary battery of wellability and Gao Bao liquid rate just has great importance.
Summary of the invention
1. to solve the problems, such as
It is an object of the invention to overcome lyophily existing for existing Water based metal ion secondary battery diaphragm relatively poor
Or the physical properties such as unstable or diaphragm gas permeability, intensity are difficult to meet the deficiency of requirement, provide a kind of Water based metal
Ion secondary battery diaphragm and its preparation method and application.Membrane for polymer can kept former using technical solution of the present invention
On the basis of having good physical and conductive, cycle performance, the wellability and liquid retention of diaphragm are effectively improved, to meet water
It is the requirement of metal ion secondary battery membrane.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
First, a kind of Water based metal ion secondary battery diaphragm of the invention, including porous basement membrane, the surface of porous basement membrane
Coated with hydrophobic coating, the surface grafting of the hydrophobic coating has hydrophilic coating.
Further, the selection of lyophobic dust used in hydrophobic coating carbomer, Arabic gum, sodium alginate,
Povidone, sodium carboxymethylcellulose, carboxymethyl cellulose, hydroxypropyl methylcellulose, dimethyl silicone polymer, cyclomethicone,
Amino silicone, at least one of polymethylphenylsiloxane and polyether siloxane copolymer.
Further, the hydrophobic coating with a thickness of 200nm~5 μm, preferably 1~2 μm.
Further, the coating of the hydrophilic coating includes solvent and hydroaropic substance, the hydroaropic substance choosing
With acrylic monomers, Acrylic Acid-sodium Acrylate Copolymers, acrylic-ethylene alcohol copolymer, acrylic acid-acrylamide copolymerization
At least one of object, SMAS-AA-AM copolymer.
Further, the solvent is at least one of ethyl alcohol, methanol, isopropanol and normal propyl alcohol, and solvent and parent
The proportion of aqueous substance is 1:1~9:1, preferably 3:1~5:1.
Further, the hydrophilic coating grafts on hydrophobic coating by the method for laser emission surface grafting
Surface, radiation light beam wavelength is 9.1 μm~10.6 μm, and irradiation duration is 100~500ns, preferably 100~200ns.
Second, a kind of preparation method of Water based metal ion secondary battery diaphragm of the invention, comprising the following steps:
Step 1: coating hydrophobic coating on the surface of porous basement membrane；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing；
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, dried later i.e.
Obtain the Water based metal ion secondary battery diaphragm.
Further, the hydrophobic coating is coated on the one side of basement membrane by spraying, dimple coating or dip coating manner
Or two sides.
Further, first basement membrane is placed in acetone in the step 3 and carries out rinse, be put into distilled water later with
Wash away extra acetone；The temperature of the vacuum drying constant weight processing is 30-65 DEG C, time 0.5-1.5h；In the step 4
The temperature of hydrophilic coating is 30~55 DEG C, grafting time 1.5-2.5h；Drying temperature is 45~55 DEG C, drying time 0.5
~1.0h.
Further, the material of the porous basement membrane is polyethylene, polypropylene, polyethylene terephthalate and gathers
One or more of acid imide.
Third, the application of Water based metal ion secondary battery diaphragm of the invention in Water based metal ion secondary battery.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) surface of a kind of Water based metal ion secondary battery diaphragm of the invention, porous basement membrane is applied coated with hydrophobicity
Layer, the surface grafting of hydrophobic coating have hydrophilic coating, can effectively improve battery by the grafting processing of hydrophilic coating
The wellability and liquid retention of diaphragm, and the coating of hydrophobic coating is then it is possible to prevente effectively to more when hydrophilic coating grafting is handled
Hole basement membrane itself damages, and the physical properties such as its air permeability, micropore size, voidage, tensile strength, puncture strength occur
Decline.
(2) a kind of Water based metal ion secondary battery diaphragm of the invention, by hydrophobicity object used in hydrophobic coating
The type of matter optimizes, on the one hand can guarantee have between the hydrophobic grouping of lyophobic dust and porous basement membrane
Good adhesive property guarantees that it is firmly combined, do not fall off, and on the other hand the lyophobic dust also has excellent resistance to
High temperature performance and oxidation resistent susceptibility, to guarantee the service performance of battery diaphragm；Meanwhile lyophobic dust used in the present invention
Resistance to heat rating is big, can effectively increase the thermal contraction ability of diaphragm.
(3) a kind of Water based metal ion secondary battery diaphragm of the invention is carried out excellent by the composition to hydrophilic coating
Change design, on the one hand can effectively improve the hydrophilicity of porous basement membrane, on the other hand can also effectively avoid polarizing
Or side reaction occurs under high charge-discharge magnification, to cause other negative effects to battery.
(4) a kind of Water based metal ion secondary battery diaphragm of the invention, the hydrophilic coating pass through laser emission table
The method of face grafting grafts on the surface of hydrophobic coating, and optimizes to the specific process parameter of laser emission, from
And on the one hand can guarantee that the segment in hydrophobic grouping is sufficiently opened, be allowed to rear hydrophilic group may be coupled to it is modified every
On film, and improve its grafting rate；On the other hand laser emission damage caused by porous basement membrane can also be further avoided.
(5) preparation method of a kind of Water based metal ion secondary battery diaphragm of the invention, by elder generation in porous basement membrane
Surface coat one layer of hydrophobic coating, then carry out hydrophilic coating grafting processing again, thus both can effectively improve gained every
The lyophily of film makes it have higher wellability and liquid retention, while can also effectively avoid directly carrying out in membrane surface
Damage of the radiation grafting processing to basement membrane physical property itself, therefore gained diaphragm can satisfy Water based metal ion secondary battery
The use demand of diaphragm.
(6) preparation method of a kind of Water based metal ion secondary battery diaphragm of the invention, the hole of preparation gained diaphragm
Uniformly, porosity is maintained on the basis of original aperture, and imbibition rate can reach 110%~150%, protect liquid rate can reach 50%~
90%, for contact angle between 5 °~15 °, the rate of liquid aspiration of diaphragm also has very big promotion, rate of liquid aspiration compared with traditional polymer diaphragm
1.0~5.0cm of 30mins lifting height.
Detailed description of the invention
Fig. 1 is the SEM schematic diagram of the 1 hydrophilic porous diaphragm of gained of embodiment；
Fig. 2 is embodiment 1, the lyophily parameter comparison of embodiment 2 and conventional polyethylene diaphragm；
Fig. 3 is that the tensile strength data of embodiment 1, embodiment 2 and conventional membrane compares.
Specific embodiment
A kind of Water based metal ion secondary battery diaphragm of the invention, including porous basement membrane, the surface of the porous basement membrane
Coated with hydrophobic coating, the surface grafting of the hydrophobic coating has hydrophilic coating.It is hydrophobic used in the hydrophobic coating
Property substance select carbomer, Arabic gum, sodium alginate, povidone, sodium carboxymethylcellulose, carboxymethyl cellulose, hydroxypropyl first
Cellulose, dimethyl silicone polymer, cyclomethicone, amino silicone, polymethylphenylsiloxane and polyether silicone are total
At least one of polymers, the hydrophobic coating with a thickness of 200nm~5 μm, preferably 1~2 μm.The painting of the hydrophilic coating
Material includes solvent and hydroaropic substance, and wherein hydroaropic substance selects acrylic monomers, Acrylic Acid-sodium Acrylate Copolymers, third
At least one of olefin(e) acid-ethenol copolymer, acrylic acid-acrylamide copolymer, SMAS-AA-AM copolymer, solvent is
At least one of ethyl alcohol, methanol, isopropanol and normal propyl alcohol, and the proportion of solvent and hydroaropic substance is 1:1~9:1, preferably
3:1~5:1.
For existing non-woven fabrics, glass fibre (AGM), dust-free paper, polyethylene (PE) and polypropylene (PP) Water based metal from
Deficiency existing for sub- secondary battery membrane, currently, existing diaphragm manufacturer is usually to use ultraviolet light, plasma or electronics
Beam directly radiates hydrophobicity membrane surface, so that hydroaropic substance is grafted in hydrophobicity membrane surface, to meet water system
Demand of the metal ion secondary battery membrane to lyophily.But above-mentioned processing method easily damages basement membrane itself, makes porous
The microcellular structure of basement membrane is destroyed, so as to cause the physical property of basement membrane, such as air permeability, tensile strength, the hair such as puncture strength
It is raw to weaken, influence the service performance of diaphragm.Based on problem above, the application by coating one layer in hydrophobicity membrane surface in advance
Presoma (hydrophobic coating) carries out hydroaropic substance grafting, then so as to effectively avoid direct radiation treatment to basement membrane
It is damaged caused by this body structure and performance.Compared to non-woven fabrics, glass fibre, these traditional Water based metal ions two of dust-free paper
Primary cell diaphragm, porous, hydrophilic diaphragm of the invention are capable of providing better tensile strength, and tensile strength promotes at least 10
Times, and the pore-size distribution of the diaphragm is more uniform, thickness is smaller.And these traditional water systems compared to thin polymer film (PE/PP)
Metal ion secondary cell film, porous, hydrophilic diaphragm of the invention are capable of providing more excellent wellability and liquid retention, and
Its contact angle is smaller.
It should be noted that there is high requirement to the selection of the type of lyophobic dust in the present invention, the present invention by pair
The type of lyophobic dust optimizes, to guarantee that the hydrophobic coating of membrane surface had both had excellent hydrophobic performance, rises
To the effect of the porous basement membrane ontology of effective protection, at the same also have certain cementability, thus can steadily with basement membrane
Ontology is attached together, and prevents to fall off.In addition, hydrophobic coating of the invention also has good high and low temperature resistance,
Its resistance to heat rating is big, therefore can increase the thermal contraction ability of diaphragm, guarantees the service performance of battery diaphragm entirety.The present invention is logical
It crosses and the composition of hydrophilic coating coating is optimized, especially by the selection of acrylic compounds hydroaropic substance, so as to
The hydrophilicity of battery diaphragm is effectively improved, and its stability is preferable, in battery use process, such as polarized or height fills
The generation of side reaction is not had when discharge-rate, therefore other negative effects will not be caused to battery.
Specifically, hydrophilic coating by the method for laser emission surface grafting grafts on hydrophobic coating in the present invention
Surface, radiation light beam wavelength is 9.1 μm~10.6 μm, and irradiation duration is 100~500ns, preferably 100~200ns.Swash
Light irradiation can produce with certain energy density, the energy of high directivity and coherence, be easy to keep hydrophobic grouping segment abundant
It opens, but laser irradiation intensity is higher, easily causes to damage to diaphragm, therefore the protection that one aspect of the present invention passes through hydrophobic coating
Effect, on the other hand by the design parameter to laser emission, especially optimizes control to light beam wavelength, thus on the one hand
Hydrophobic grouping segment can be made sufficiently to open, be conducive to the grafting rate for improving hydroaropic substance, guarantee the infiltration of grafting metacneme
Property, liquid retention and contact angle, on the other hand can effectively avoid damage of the laser emission to diaphragm basement membrane.
Polyethylene, polypropylene, polyethylene terephthalate and polyamides can be used in the material of porous basement membrane in the present invention
One or more of imines, the preparation process of the porous basement membrane are as follows: by thin-film material melting extrusion, then according to thermotropic phase point
It from (TIPS) or stretches as porous film, porous film can also be become by melt-blown or electrostatic spinning, most preferably
For Thermal inactive (TIPS), wherein key process parameter are as follows: extruder temperature: 170-220 DEG C；Melt temperature: 160-205
℃；Casting temperature: 10-60 DEG C；Draft temperature: 70-130 DEG C；Stretching speed ratio: 4-8.5 times.The porous membrane has following spy
Sign: thickness: 5~100 μm；Porosity: 20%~80%；Air permeability: 0~300s/100cc；Intensity: greater than be equal to 35Mpa；It is bent
Folding degree: 1~50；Aperture: 10nm~500nm；Most preferably porosity is 30~50%；Tortuosity is 3~20；Aperture be 10~
50nm。
The preparation method of Water based metal ion secondary battery diaphragm of the invention, comprising the following steps:
Step 1: hydrophobic in the one or both sides coating of porous basement membrane by spraying, dimple coating, dip-coating or other modes
Property coating；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing, radiation light beam wavelength is 9.1 μ
M~10.6 μm, irradiation duration are 100~500ns, preferably 100~200ns.
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；Specifically, first basement membrane is set
Rinse is carried out in acetone, is put into distilled water later to wash away extra acetone；Then film extracted is placed in vacuum ring
0.5-1.5h is handled in 30-65 degrees Celsius of dry constant weight under border；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, the temperature of hydrophilic coating
Degree is 30~55 DEG C, grafting time 1.5-2.5h；45~55 DEG C of 0.5~1.0h of drying that are placed on obtain water system gold
Belong to ion secondary battery diaphragm.
For the ease of more fully understanding the present invention, it is illustrated now in conjunction with some embodiments.
Embodiment 1
A kind of Water based metal ion secondary battery diaphragm of the present embodiment, including polyethylene porous basement membrane (melt polyethylene
Melt extrusion, then obtained according to Thermal inactive (TIPS) stretching), the surface of the polyethylene porous basement membrane is coated with hydrophobicity
The surface grafting of coating, the hydrophobic coating has hydrophilic coating.Lyophobic dust used in the hydrophobic coating is carboxylic first
Base cellulose, the hydrophobic coating with a thickness of 1 μm.The coating of the hydrophilic coating includes solvent and hydroaropic substance,
Middle hydroaropic substance selects acrylic monomers, and solvent is ethyl alcohol, and the proportion of solvent and hydroaropic substance is 3:1.
The preparation method of the Water based metal ion secondary battery diaphragm of the present embodiment, comprising the following steps:
Step 1: the one side by spraying method in porous basement membrane coats hydrophobic coating；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing, radiation light beam wavelength is 10 μ
M, irradiation duration 100ns.
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；Specifically, first basement membrane is set
Rinse is carried out in acetone, is put into distilled water later to wash away extra acetone；Then film extracted is placed in vacuum ring
1h is handled in 50 degrees Celsius of dry constant weights under border；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, the temperature of hydrophilic coating
Degree is 55 DEG C, grafting time 2h；The 55 DEG C of drying 1.0h that are placed on obtain the Water based metal ion secondary battery diaphragm.
It is as shown in Figure 1 the SEM picture of diaphragm obtained by the present embodiment, as seen from the figure, is carried out using the method for the present embodiment hydrophilic
Property grafting processing after, the hole of gained diaphragm is uniform, and porosity stills remain on the basis of original aperture.
Embodiment 2
A kind of Water based metal ion secondary battery diaphragm of the present embodiment, including polyethylene porous basement membrane, the polyethylene
The surface of porous basement membrane is coated with hydrophobic coating, and the surface grafting of the hydrophobic coating has hydrophilic coating.It is described hydrophobic
Property coating used in lyophobic dust select cyclomethicone, the hydrophobic coating with a thickness of 2 μm.The hydrophilic coating
Coating includes solvent and hydroaropic substance, and wherein hydroaropic substance selects Acrylic Acid-sodium Acrylate Copolymers, and solvent is methanol,
And the proportion of solvent and hydroaropic substance is 5:1.
The preparation method of the Water based metal ion secondary battery diaphragm of the present embodiment, comprising the following steps:
Step 1: dip coating manner coats hydrophobic coating on the two sides of porous basement membrane；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing, radiation light beam wavelength is 9.1 μ
M, irradiation duration 200ns.
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；Specifically, first basement membrane is set
Rinse is carried out in acetone, is put into distilled water later to wash away extra acetone；Then film extracted is placed in vacuum ring
1.5h is handled in 30 degrees Celsius of dry constant weights under border；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, the temperature of hydrophilic coating
Degree is 30 DEG C, grafting time 2.5h；Be placed on 45 DEG C of drying 0.5h obtain the Water based metal ion secondary battery every
Film.
Embodiment 1 and the hydrophilic porous diaphragm of 2 gained of embodiment and the polyethylene diagrams for not carrying out any processing are distinguished
Lyophily test is carried out, test is water with solvent, and electrolyte is lithium sulfate, matches 1:1, as a result as shown in Fig. 2, can be with by Fig. 2
Find out, after hydrophily processing of the invention, gained diaphragm can effectively improve its suction on the basis of possessing pre-existent pore rate
Liquid rate and guarantor's liquid rate, and the rate of liquid aspiration of gained diaphragm also has very big promotion compared with traditional polymer diaphragm.As shown in figure 3, implementing
Example 1 and the hydrophilic porous diaphragm of the preparation gained of embodiment 2 are compared to traditional non-woven fabrics, glass fibre (AGM) diaphragm, dust-free paper
Also there is excellent voidage, tensile strength and puncture strength.
Embodiment 3
A kind of Water based metal ion secondary battery diaphragm of the present embodiment, including the porous basement membrane of polypropylene, the polypropylene
The surface of porous basement membrane is coated with hydrophobic coating, and the surface grafting of the hydrophobic coating has hydrophilic coating.It is described hydrophobic
Property coating used in lyophobic dust select amino silicone and polymethylphenylsiloxane combination, the thickness of the hydrophobic coating
It is 1.5 μm.The coating of the hydrophilic coating includes solvent and hydroaropic substance, and wherein hydroaropic substance selects acrylic monomers
With the combination of acrylic acid-acrylamide copolymer, solvent is isopropanol, and the proportion of solvent and hydroaropic substance is 4:1.
The preparation method of the Water based metal ion secondary battery diaphragm of the present embodiment, comprising the following steps:
Step 1: coating hydrophobic coating on the two sides of porous basement membrane by dimple coating method；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing, radiation light beam wavelength is 10.6
μm, irradiation duration 160ns.
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；Specifically, first basement membrane is set
Rinse is carried out in acetone, is put into distilled water later to wash away extra acetone；Then film extracted is placed in vacuum ring
0.5h is handled in 65 degrees Celsius of dry constant weights under border；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, the temperature of hydrophilic coating
Degree is 40 DEG C, grafting time 2h；The 48 DEG C of drying 0.7h that are placed on obtain the Water based metal ion secondary battery diaphragm,
The porosity of the diaphragm is 30%, and imbibition rate can reach 140%, and protecting liquid rate can reach 90%, and contact angle is 5 °, the imbibition of diaphragm
Speed 30mins lifting height 5.0cm.
Embodiment 4
A kind of Water based metal ion secondary battery diaphragm of the present embodiment, including the porous base of polyethylene terephthalate
The surface of film, the porous basement membrane is coated with hydrophobic coating, and the surface grafting of the hydrophobic coating has hydrophilic coating.Institute
State lyophobic dust used in hydrophobic coating select carbomer, the hydrophobic coating with a thickness of 5 μm.The hydrophilic coating
Coating includes solvent and hydroaropic substance, and wherein hydroaropic substance selects SMAS-AA-AM copolymer, and solvent is normal propyl alcohol, and molten
The proportion of agent and hydroaropic substance is 1:1.
The preparation method of the Water based metal ion secondary battery diaphragm of the present embodiment, comprising the following steps:
Step 1: the one side by spraying method in porous basement membrane coats hydrophobic coating；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing, radiation light beam wavelength is 9.5 μ
M, irradiation duration 500ns.
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；Specifically, first basement membrane is set
Rinse is carried out in acetone, is put into distilled water later to wash away extra acetone；Then film extracted is placed in vacuum ring
1.2h is handled in 35 degrees Celsius of dry constant weights under border；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, the temperature of hydrophilic coating
Degree is 45 DEG C, grafting time 1.8h；Be placed on 50 DEG C of drying 1.0h obtain the Water based metal ion secondary battery every
Film, the imbibition rate of the diaphragm can reach 110%, and protecting liquid rate can reach 50%, and contact angle is 15 °, the rate of liquid aspiration of diaphragm
30mins lifting height 1.0cm.
Embodiment 5
A kind of Water based metal ion secondary battery diaphragm of the present embodiment, including polyimide foraminous basement membrane, the polyamides
The surface of the porous basement membrane of imines is coated with hydrophobic coating, and the surface grafting of the hydrophobic coating has hydrophilic coating.It is described
Lyophobic dust used in hydrophobic coating selects sodium alginate and sodium carboxymethylcellulose, the hydrophobic coating with a thickness of
200nm.The coating of the hydrophilic coating includes solvent and hydroaropic substance, and wherein hydroaropic substance selects acrylic acid-acrylic
Amide copolymer, solvent is ethyl alcohol, and the proportion of solvent and hydroaropic substance is 9:1.
The preparation method of the Water based metal ion secondary battery diaphragm of the present embodiment, comprising the following steps:
Step 1: the one or both sides by spraying method in porous basement membrane coat hydrophobic coating；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing, radiation light beam wavelength is 10 μ
M, irradiation duration 300ns.
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；Specifically, first basement membrane is set
Rinse is carried out in acetone, is put into distilled water later to wash away extra acetone；Then film extracted is placed in vacuum ring
0.5h is handled in 65 degrees Celsius of dry constant weights under border；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, the temperature of hydrophilic coating
Degree is 48 DEG C, grafting time 1.5h；Be placed on 55 DEG C of drying 0.5h obtain the Water based metal ion secondary battery every
Film.The imbibition rate of the diaphragm can reach 150%, and protecting liquid rate can reach 850%, and contact angle is 13 °, the rate of liquid aspiration of diaphragm
30mins lifting height 3cm.
Claims (10)
1. a kind of Water based metal ion secondary battery diaphragm, it is characterised in that: including porous basement membrane, the surface of porous basement membrane is coated
There is hydrophobic coating, the surface grafting of the hydrophobic coating has hydrophilic coating.
2. a kind of Water based metal ion secondary battery diaphragm according to claim 1, it is characterised in that: the hydrophobicity applies
Lyophobic dust used in layer selects carbomer, Arabic gum, sodium alginate, povidone, sodium carboxymethylcellulose, carboxymethyl cellulose
Element, hydroxypropyl methylcellulose, dimethyl silicone polymer, cyclomethicone, amino silicone, polymethylphenylsiloxane and polyethers
At least one of silicone copolymers.
3. a kind of Water based metal ion secondary battery diaphragm according to claim 2, it is characterised in that: the hydrophobicity applies
Layer with a thickness of 200nm~5 μm, preferably 1~2 μm.
4. a kind of Water based metal ion secondary battery diaphragm according to any one of claim 1-3, it is characterised in that: institute
The coating for stating hydrophilic coating includes solvent and hydroaropic substance, and the hydroaropic substance selects acrylic monomers, acrylic acid-
Sodium acrylate copolymer, acrylic-ethylene alcohol copolymer, acrylic acid-acrylamide copolymer, in SMAS-AA-AM copolymer
At least one.
5. a kind of Water based metal ion secondary battery diaphragm according to claim 4, it is characterised in that: the solvent is second
At least one of alcohol, methanol, isopropanol and normal propyl alcohol, and the proportion of solvent and hydroaropic substance is 1:1~9:1, preferably 3:1
~5:1.
6. a kind of Water based metal ion secondary battery diaphragm according to claim 4, it is characterised in that: the hydrophily applies
Layer grafts on the surface of hydrophobic coating by the method for laser emission surface grafting, radiation with light beam wavelength for 9.1 μm~
10.6 μm, irradiation duration is 100~500ns, preferably 100~200ns.
7. a kind of preparation method of such as Water based metal ion secondary battery diaphragm of any of claims 1-6, special
Sign is, comprising the following steps:
Step 1: coating hydrophobic coating on the surface of porous basement membrane；
Step 2: carrying out CO to the membrane surface after coating2Pulsed laser radiation processing；
Step 3: being cleaned and being dried in vacuo constant weight processing for the basement membrane after radiation treatment；
Step 4: will dry constant weight treated that basement membrane is placed in hydrophilic coating is grafted, carry out obtained by drying arrive later
The Water based metal ion secondary battery diaphragm.
8. a kind of preparation method of Water based metal ion secondary battery diaphragm according to claim 7, it is characterised in that: institute
The material for stating porous basement membrane is one or more of polyethylene, polypropylene, polyethylene terephthalate and polyimides；
The hydrophobic coating is coated on the one or both sides of basement membrane by spraying, dimple coating or dip coating manner.
9. a kind of preparation method of Water based metal ion secondary battery diaphragm according to claim 7, it is characterised in that: institute
It states that first basement membrane is placed in acetone in step 3 and carries out rinse, be put into distilled water later to wash away extra acetone；The vacuum
The temperature of dry constant weight processing is 30-65 DEG C, time 0.5-1.5h；In the step 4 temperature of hydrophilic coating be 30~
55 DEG C, grafting time 1.5-2.5h；Drying temperature is 45~55 DEG C, 0.5~1.0h of drying time.
10. a kind of if Water based metal ion secondary battery diaphragm of any of claims 1-6 is in Water based metal ion
Application in secondary cell.
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| CN114361708A (en) * | 2022-01-05 | 2022-04-15 | 池州精研新能源科技有限公司 | Environment-friendly water-based battery and preparation method thereof |
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