CN109411680A - A kind of aramid fiber resin base micropore lithium electric separator and preparation method thereof - Google Patents
A kind of aramid fiber resin base micropore lithium electric separator and preparation method thereof Download PDFInfo
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- CN109411680A CN109411680A CN201811265042.2A CN201811265042A CN109411680A CN 109411680 A CN109411680 A CN 109411680A CN 201811265042 A CN201811265042 A CN 201811265042A CN 109411680 A CN109411680 A CN 109411680A
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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
- H01M50/44—Fibrous 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
- H01M50/411—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
- H01M50/403—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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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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Abstract
The present invention provides a kind of aramid fiber resin base micropore lithium electric separators and preparation method thereof, the diaphragm includes aramid fiber resin and diagram modification material, with three-dimensional micro-nano cellular structure, average pore size is adjustable in 20-1000 nanometer range, with a thickness of 12-60 microns, porosity is more than 50%, and diaphragm shows good electrolyte compatibility, heat-resisting quantity and mechanical strength.The preparation step of aramid fiber resin base micropore lithium electric separator of the present invention includes: the processing of (1) film forming raw material；(2) preparation of film forming solution；(3) knifing and film inversion of phases pore-forming；(4) post-processing of wet film, roll-in, drying, is eventually fabricated battery diaphragm.Aramid fiber resin base micropore lithium electric separator of the present invention has excellent comprehensive performance, better than conventional application type aramid fiber complex lithium electric separator, there is remarkable effect for high rate during charging-discharging, the thermal safety for promoting battery etc. that improve battery, and preparation method of the invention have environmental-friendly, at low cost, simple process, be convenient for continuous production the features such as.
Description
Technical field
The invention belongs to the preparation fields of diaphragm for lithium ion battery material, and in particular to a kind of aramid fiber resin base micropore lithium
Electric separator and preparation method thereof
Background technique
Lithium ion battery is the novel green secondary cell succeeded in developing the 1990s, has energy density height, follows
The ring service life is long, it is environmental-friendly, reliable and can fast charging and discharging the advantages that, be widely used in various digital products at present, and
It is also constantly being expanded in the application of new energy field.Diaphragm is one of core key material of lithium ion battery, is mainly determined
The safety of battery and charge-discharge performance.The today being continuously improved is required diaphragm in dynamic lithium battery, and there is more Gao An
Quan Xing, more resistant to electrochemical stability, the diaphragm of more preferable absorbency and more excellent homogeneity becomes the emphasis studied at present.
Function of the diaphragm in lithium ion battery is mainly reflected in two aspects, first is that safety, diaphragm need to have well
Insulating properties to prevent positive and negative anodes contact from short circuit occurs, should also have certain mechanical strength, prevent dendrite, burr, miscellaneous
Matter particle pierces through and the short circuit of appearance, in addition, the guarantee dimensional stability under the hot environment that happens suddenly is also that battery is avoided to generate
The necessary condition of large area short circuit and thermal runaway；On the other hand, diaphragm will have certain porosity and uniform pore-size distribution,
To provide the micro channel for realizing lithium ion battery charging/discharging function and good high rate performance.
The lithium electric separator being commercialized at present is mainly that polyolefins, polyolefin-Ceramic Composite diaphragm and polyolefin-resin apply
Cover diaphragm.The former will appear apparent dimensional contraction phenomenon since thermal stability is poor more than high temperature of 120 DEG C, use in battery
There can be bigger security risk in the process, the latter coats one layer of ceramic particle or fire resistant resin coating in polyolefin surfaces
Afterwards, the thermal stability and electrolyte wetability of diaphragm are improved to a certain extent, but there is also ceramic particle or resins simultaneously
The disadvantage that layer falls off (picking) and homogeneity (aperture, hole pattern) is uncontrollable.As it can be seen that using conventional polyolefins diaphragm as base
Film is still difficult to fundamentally improve the performance of diaphragm, is still not enough to increase substantially lithium by the modified methods such as simply coating
The safety of ion battery.
Summary of the invention
Based on the above issues, the present invention develops a kind of novel using diaphragm composition material and microstructure design as starting point
Diaphragm material, fundamentally solve the disadvantage that conventional polyolefins diaphragm and polyolefin modified diaphragm, meet each application neck
Needs of the domain to high security lithium ion battery.
It is an object of the present invention to provide a kind of diaphragm material, the raw material for preparing of the diaphragm material includes aramid fiber tree
Rouge, modified material and the substance containing lithium ion.
Specifically, the diaphragm material further includes following 1) -7) described at least one:
1) diaphragm material is 20-1000 nanometers with a thickness of 12-60 microns, average pore size, and/or porosity is 50%
More than；
2) diaphragm material further includes 3 D pore canal and/or network structure；
Specifically, the 3 D pore canal and/or network structure include micron openings and nano-pore, the micron openings includes by virtue
The hole formed after synthetic fibre resin inversion of phases, the nano-pore include the hole formed by the gap between aramid fiber resin and modified material,
Micron openings is mutually nested with nano-pore, forms three-dimensional network cellular structure；
Again specifically, the substance containing lithium ion is distributed in micron openings and/or nano-pore；
3) modified material includes nano inorganic ceramic particle and/or nano inorganic ceramic fibre；
4) the aramid fiber resin includes p-aramid fiber resin and/or meta-aramid resin；
5) the aramid fiber resin and the mass ratio of modified material are 10:1~10:10；
6) diaphragm material has heat-resisting quantity；
Specifically, the heat-resisting quantity includes, under 150 DEG C, the heat treatment condition of 1h, the size of the diaphragm material is received
Shrinkage is 0%；
7) electrolyte of the diaphragm material absorbs and/or holding capacity is strong；
Specifically, the electrolyte absorbs and/or holding capacity includes that the electrolyte absorptivity of the diaphragm material is by force
200% or more.
Specifically, when the modified material includes nano inorganic ceramic particle and/or nano inorganic ceramic fibre, it is described
Nano inorganic ceramic particle includes nano-aluminium oxide, nano silica and/or nano-titanium oxide；The nano inorganic pottery
Porcelain fiber includes alumina fibre, mullite fiber, titanium nitride fiber and/or silicon carbide fibre.
Specifically, the preparation method of the diaphragm material includes:
1) after aramid fiber resin and modified material being mixed and/or dispersed in a solvent, deaeration handles to obtain casting solution；
2) casting solution is prepared into membrane structure, split-phase in coagulating bath is immersed after standing and is formed a film to get wet film；
3) it takes out, is drying to obtain after impregnating the wet film in lithium salts treatment fluid.
Specifically, the preparation method of the diaphragm material further includes following 1) -11) described at least one:
1) preparation method further includes the pretreatment of aramid fiber resin and modified material, and the pretreatment includes going to clean
Matter；Specifically, the pretreatment of the aramid fiber resin includes using dry after dehydrated alcohol and/or acetone washing；The modified material
The pretreatment of material includes using dry after water, ethyl alcohol and/or alkaline wash；
2) solvent includes dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, and/or N- first
Base pyrrolidones；
3) mixing and/or dispersion include being mixed and/or being divided by ultrasonic treatment, mechanical stirring, and/or ball milling
It dissipates；
4) the deaeration processing includes that vacuum defoamation is handled；Specifically, the vacuum defoamation processing is vacuum at room temperature
Deaeration is handled under conditions of degree is 15-60kPa；
5) it is described by the casting solution be prepared into membrane structure include: by casting solution cleaned glass plate surface striking form a film；
6) membrane structure with a thickness of 20 microns -200 microns；
7) described stand including dwell temperature is 10 DEG C -60 DEG C；
8) described stand including time of repose is 5s-150s；
9) described stand includes standing humidity as 30%-90%；
10) coagulating bath includes deionized water, ethyl alcohol, and/or acetone；
11) the lithium salts treatment fluid includes water lithium chloride solution, lithium perchlorate aqueous solution, lithium bromide water solution.
It is a further object to provide a kind of preparation methods of diaphragm material, which comprises
1) after aramid fiber resin and modified material being mixed and/or dispersed in a solvent, deaeration handles to obtain casting solution；
2) casting solution is prepared into membrane structure, split-phase in coagulating bath is immersed after standing and is formed a film to get wet film；
3) it takes out, is drying to obtain after impregnating the wet film in lithium salts treatment fluid.
Specifically, the method also includes following 1) -14) described at least one:
1) preparation method further includes the pretreatment of aramid fiber resin and modified material, and the pretreatment includes going to clean
Matter；
Specifically, the pretreatment of the aramid fiber resin includes using dry after dehydrated alcohol and/or acetone washing；It is described to change
Property material pretreatment include using dry after water, ethyl alcohol and/or alkaline wash；
2) solvent includes dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, and/or N- first
Base pyrrolidones；
3) mixing and/or dispersion include being mixed and/or being divided by ultrasonic treatment, mechanical stirring, and/or ball milling
It dissipates；
4) the deaeration processing includes that vacuum defoamation is handled；
Specifically, the vacuum defoamation processing is at room temperature, deaeration is handled under conditions of vacuum degree is 15-60kPa；
5) it is described by the casting solution be prepared into membrane structure include: by casting solution cleaned glass plate surface striking form a film；
6) membrane structure with a thickness of 20 microns -200 microns；
7) described stand including dwell temperature is 10 DEG C -60 DEG C；
8) described stand including time of repose is 5s-150s；
9) described stand includes standing humidity as 30%-90%；
10) coagulating bath includes deionized water, ethyl alcohol, and/or acetone；
11) the lithium salts treatment fluid includes water lithium chloride solution, lithium perchlorate aqueous solution, lithium bromide water solution；
12) modified material includes nano inorganic ceramic particle and/or nano inorganic ceramic fibre；
13) the aramid fiber resin and the mass ratio of modified material are 10:1-10:10；
14) the aramid fiber resin includes p-aramid fiber resin and/or meta-aramid resin.
Specifically, when the modified material includes nano inorganic ceramic particle and/or nano inorganic ceramic fibre, it is described
Nano inorganic ceramic particle includes nano-aluminium oxide, nano silica and/or nano-titanium oxide；The nano inorganic pottery
Porcelain fiber includes alumina fibre, mullite fiber, titanium nitride fiber and/or silicon carbide fibre.
It is also another object of the present invention to provide any diaphragm materials of the present invention, any preparation of the present invention
The application for the diaphragm material that any preparation method of method, the present invention is directly prepared.
At least one of specifically, the application includes following 1) -3) described:
1) as the diaphragm material of lithium ion battery；
2) product and/or its Related product of the diaphragm material as lithium ion battery are used to prepare；
3) lithium ion battery and/or its Related product are used to prepare.
A kind of aramid fiber resin base micropore lithium electric separator material provided by the invention mainly includes aramid fiber resin and diagram modification
Material, wherein resin constitutes the overall skeleton of diaphragm, forms macropore microcellular structure, meets battery to diaphragm mechanical strength, flexible
Property etc. require, modified material intercouples by the inversion of phases speed of regulation resin and with resin split-phase micropore, reinforcing diaphragm
Micro-nano pore distribution, improve diaphragm electrolyte absorb and holding capacity.It is final micro- prepared by the embodiment of the present invention
Hole lithium electric separator material is film-like material, with a thickness of 12-60 μm.
A kind of lithium ion battery provided by the invention aramid fiber resin base micropore lithium electric separator material and preparation method thereof, until
It has the advantage that less
Aramid fiber resin base micropore lithium electric separator material provided by the invention has excellent comprehensive performance, shows higher
Heat resistance and good electrolyte is affine, holding capacity, better than conventional application type aramid fiber complex lithium electric separator, for improving electricity
The high rate during charging-discharging in pond, the thermal safety for promoting battery etc. have remarkable effect, have in lithium ion battery good
Good application prospect；And simple production process of the present invention, process cycle are short, at low cost, energy conservation and environmental protection, environmental-friendly, can meet
The needs of large-scale industrial production.
Specifically, relative to commercially available polyalkene diaphragm, diaphragm material that the following embodiments of the present invention are specifically prepared
Temperature tolerance can be improved 50 DEG C or more, can ensure the applied at elevated temperature safety of lithium ion battery to greatest extent；The present invention is following
The electrolyte of the diaphragm material that embodiment is specifically prepared absorbs and the more commercially available polyalkene diaphragm of holding capacity improve 100% with
On, the multiplying power discharging capacity retention and circulation volume retentivity of battery can be effectively improved；Have using the following embodiments of the present invention
The lithium ion battery for the diaphragm material preparation that body is prepared, battery discharge holds under the conditions of 0.5C charge and discharge, after circulation 100 times
5% or less amount decaying；The battery for the diaphragm material assembly being specifically prepared using the following embodiments of the present invention simultaneously is at 4C times
Charge and discharge under rate, discharge capacity still keep 75% or more under 0.5C.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, not
Constitute the improper restriction to the application.In the accompanying drawings:
Fig. 1 is the electron microscope of diaphragm material prepared by the embodiment of the present invention 2.
Specific embodiment
Made in following embodiments, experimental method is conventional method unless otherwise specified.
Material as used in the following examples etc., is commercially available unless otherwise specified.
Following embodiments and its illustrate for explanation and understanding the present invention, do not constitute to improper limit of the invention
It is fixed.
In following embodiments unless otherwise specified, the percentage being related to is mass percent.
Embodiment 1
8 grams of p-aramid fiber resin fibres are weighed, and are cut into the staple fiber that length is 3-5mm, by it respectively in excessive nothing
Using ultrasonic vibration 10 minutes that frequency is 60khz in water-ethanol and acetone, then dry at 120 DEG C, treated for acquisition
Aramid fiber resin；The aluminum oxide particle that partial size is 200nm is ultrasonically treated 30min in ethanol, it is then true at 100 DEG C
(vacuum degree 60kPa) is dry in empty baking oven.
3.6 grams of aramid fiber resins are added in the n,N-Dimethylformamide (DMF) of 95.2ml, is then sealed against and stands
In 80 DEG C of environment, keeps obtaining clear resin solution afterwards for 24 hours, 1.2 grams of aluminum oxide nanometers are added in resin solution
Particle, the strong stirring 4h at 600 turns/min, and in the case where vacuum degree is 45kPa, deaeration handles 2h, finally obtains finely dispersed
Casting solution.
In the cleaned glass plate surface with a thickness of 3mm, by the above-mentioned casting solution being prepared using scraper striking at thickness
For 90 μm of wet film, temperature is 40 DEG C, humidity is to stand 25s under 60% environment, then wet film was immersed together with glass plate
In the ethanol solution of amount, 6h is kept, wet film is then immersed into the water lithium chloride solution that concentration is 12%, continues to keep 2h,
Final to take out diaphragm, drying for 24 hours, obtains diaphragm material of the invention at 80 DEG C.
Routine test and battery performance test are carried out to diaphragm material prepared by the present embodiment, test result is as follows institute
It states.
Cellular structure test: average pore size 360nm, porosity 72%, with a thickness of 25 μm.
Heat resistance and lyophily test: under 150 DEG C, the heat treatment condition of 1h, diaphragm material ruler manufactured in the present embodiment
Very little shrinking percentage is 0%；The shrinking percentage of commercial polypropylene diaphragm is more than 40%；The electrolyte of diaphragm material manufactured in the present embodiment is inhaled
Yield is 342%, and the imbibition rate of commercial polypropylene diaphragm is only 115%.
Cycle performance of battery test: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Battery utilizes commercial polypropylene diaphragm under the conditions of 0.5C charge and discharge, discharge capacity of the cell decaying 3.6% after circulation 200 times
The battery of preparation, battery capacity decaying about 5.8%.
The test of battery high rate performance: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Under the conditions of the 4C charge and discharge of battery, discharge capacity still keeps 80% under 0.5C, and utilizes the electricity of commercial polypropylene diaphragm preparation
Pond, the discharge capacity of battery only keep 56% or so under 0.5C.
Embodiment 2
8 grams of p-aramid fiber resin fibres are weighed, and are cut into the staple fiber that length is 5-10mm, by it respectively in excessive nothing
Using ultrasonic vibration 30 minutes that frequency is 60khz in water-ethanol and acetone, then dry at 120 DEG C, treated for acquisition
Aramid fiber resin；The silicon dioxide granule that partial size is 120nm is ultrasonically treated 30min in ethanol, then the vacuum at 150 DEG C
(vacuum degree 60kPa) is dry in baking oven.
3.2 grams of aramid fiber resins are added in the n,N-Dimethylformamide (DMF) of 95.2ml, is then sealed against and stands
In 90 DEG C of environment, clear resin solution is obtained after keeping 16h, 1.6 grams of silica dioxide nano particles are added in resin solution
Son, the ball grinding stirring 2h at 400 turns/min, and in the case where vacuum degree is 30kPa, deaeration handles 1h, finally obtains finely dispersed casting
Film liquid.
In the cleaned glass plate surface with a thickness of 3mm, by the above-mentioned casting solution being prepared using scraper striking at thickness
For 65 μm of wet film, temperature is 20 DEG C, humidity is to stand 15s under 85% environment, then wet film was immersed together with glass plate
In the deionized water of amount, 8h is kept, wet film is then immersed into the lithium bromide water solution that concentration is 15%, continues to keep 3h, finally
Diaphragm is taken out, drying for 24 hours, obtains diaphragm material of the invention at 100 DEG C.
Routine test and battery performance test are carried out to diaphragm material prepared by the present embodiment, test result is as follows institute
It states.
Cellular structure test: average pore size 240nm, porosity 68%, with a thickness of 22 μm.
Heat resistance and lyophily test: under 150 DEG C, the heat treatment condition of 1h, diaphragm material ruler manufactured in the present embodiment
Very little shrinking percentage is 0%；The shrinking percentage of commercial polypropylene diaphragm is more than 40%；The electrolyte of diaphragm material manufactured in the present embodiment is inhaled
Yield is 315%, and the imbibition rate of commercial polypropylene diaphragm is only 115%.
Cycle performance of battery test: comparing under similarity condition, this utilizes the electricity of diaphragm material manufactured in the present embodiment assembly
Pond, battery under the conditions of 0.5C charge and discharge, circulation 200 times after discharge capacity of the cell decaying 2.4%, and use commercial polypropylene every
The battery of film, battery capacity decaying about 5.8%.
The test of battery high rate performance: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Under the conditions of the 4C charge and discharge of battery, discharge capacity still keeps 77% under 0.5C, and uses the battery of commercial polypropylene diaphragm, electricity
Tank discharge capacity only keeps 56% or so under 0.5C.
Embodiment 3
10 grams of meta-aramid toners are weighed, are using frequency in excessive dehydrated alcohol and acetone respectively by it
The ultrasonic vibration of 60khz 10 minutes, then dry at 120 DEG C, the aramid fiber resin that obtains that treated；It is 0.3 μm by diameter, long
Degree is ultrasonically treated 10min and 30min for 30 μm of mullite fiber in 5% sodium hydroxide solution and deionized water respectively,
Then (vacuum degree 60kPa) is dry in the vacuum drying oven at 120 DEG C.
2.8 grams of aramid fiber resins are added in the n,N-Dimethylformamide (DMF) of 94.4ml, is then sealed against and stands
In 100 DEG C of environment, clear resin solution is obtained after keeping 8h, 2.8 grams of mullite fibers are added in resin solution, in frequency
40min is shaken under the ultrasound that rate is 60khz, and deaeration handles 1h in the case where vacuum degree is 20kPa, finally obtains finely dispersed casting
Film liquid.
In the cleaned glass plate surface with a thickness of 3mm, by the above-mentioned casting solution being prepared using scraper striking at thickness
For 60 μm of wet film, temperature is 20 DEG C, humidity is to stand 60s under 90% environment, then wet film was immersed together with glass plate
In the deionized water of amount, 16h is kept, wet film is then immersed into the lithium perchlorate aqueous solution that concentration is 10%, continues to keep 2h, most
Diaphragm is taken out eventually, and drying for 24 hours, obtains diaphragm material of the invention at 100 DEG C.
Routine test and battery performance test are carried out to diaphragm material prepared by the present embodiment, test result is as follows institute
It states.
Cellular structure test: average pore size 514nm, porosity 79%, with a thickness of 28 μm.
Heat resistance and lyophily test: under 150 DEG C, the heat treatment condition of 1h, diaphragm material ruler manufactured in the present embodiment
Very little shrinking percentage is 0%；The shrinking percentage of commercial polypropylene diaphragm is more than 40%；The electrolyte of diaphragm material manufactured in the present embodiment is inhaled
Yield is 366%, and the imbibition rate of commercial polypropylene diaphragm is only 115%.
Cycle performance of battery test: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Battery uses commercial polypropylene diaphragm under the conditions of 0.5C charge and discharge, discharge capacity of the cell decaying 2.7% after circulation 200 times
Battery, battery capacity decaying about 5.8%.
The test of battery high rate performance: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Under the conditions of the 4C charge and discharge of battery, discharge capacity still keeps 73% under 0.5C, and uses the battery of commercial polypropylene diaphragm, electricity
Tank discharge capacity only keeps 56% or so under 0.5C.
Embodiment 4
10 grams of meta-aramid toners are weighed, are using frequency in excessive dehydrated alcohol and acetone respectively by it
The ultrasonic vibration of 60khz 10 minutes, then dry at 120 DEG C, the aramid fiber resin that obtains that treated；It is 0.2 μm by diameter, long
Degree is ultrasonically treated 5min and 20min for 55 μm of silicon carbide fibre in 10% sodium hydroxide solution and deionized water respectively,
Then (vacuum degree 60kPa) is dry in the vacuum drying oven at 120 DEG C.
4.0 grams of aramid fiber resins are added in the n,N-Dimethylformamide (DMF) of 95.0ml, is then sealed against and stands
In 80 DEG C of environment, clear resin solution is obtained after keeping 12h, 1.0 grams of silicon carbide fibres are added in resin solution, turned
Speed is 500 turns/min mechanical stirring 120min, and in the case where vacuum degree is 55kPa, deaeration handles 2h, finally obtains finely dispersed
Casting solution.
In the cleaned glass plate surface with a thickness of 3mm, by the above-mentioned casting solution being prepared using scraper striking at thickness
For 135 μm of wet film, temperature is 10 DEG C, humidity is to stand 100s under 30% environment, then wet film is immersed together with glass plate
It in excessive deionized water, keeps for 24 hours, wet film then being immersed the water lithium chloride solution that concentration is 6%, continues to keep 2h, most
Diaphragm is taken out eventually, and drying for 24 hours, obtains diaphragm material of the invention at 100 DEG C.
Routine test and battery performance test are carried out to diaphragm material prepared by the present embodiment, test result is as follows institute
It states.
Cellular structure test: average pore size 220nm, porosity 65%, with a thickness of 32 μm.
Heat resistance and lyophily test: under 150 DEG C, the heat treatment condition of 1h, diaphragm material ruler manufactured in the present embodiment
Very little shrinking percentage is 0%；The shrinking percentage of commercial polypropylene diaphragm is more than 40%；The electrolyte of diaphragm material manufactured in the present embodiment is inhaled
Yield is 305%, and the imbibition rate of commercial polypropylene diaphragm is only 115%.
Cycle performance of battery test: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Battery utilizes commercial polypropylene diaphragm under the conditions of 0.5C charge and discharge, discharge capacity of the cell decaying 1.9% after circulation 200 times
The battery of preparation, battery capacity decaying about 5.8%.
The test of battery high rate performance: comparing under similarity condition, the battery assembled using diaphragm material manufactured in the present embodiment,
Under the conditions of the 4C charge and discharge of battery, discharge capacity still keeps 77% under 0.5C, and utilizes the electricity of commercial polypropylene diaphragm preparation
Pond, the discharge capacity of battery only keep 56% or so under 0.5C.
Above-described embodiment the result shows that, a kind of lithium ion battery micropore lithium electric separator material and its system provided by the invention
Preparation Method, overcomes that conventional polyolefins diaphragm material heat-resisting quantity is poor, problem of electrolyte compatibility deficiency, and it is comprehensive to realize battery
The raising for closing performance, using lithium ion battery prepared by diaphragm material of the present invention in circulation volume retentivity, safety and again
Rate performance etc. is better than conventional batteries, and has many advantages, such as that preparation process is simple, at low cost, sets without expensive production
Standby, easy to operate, high production efficiency is, it can be achieved that large-scale industrial production.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (10)
1. a kind of diaphragm material, which is characterized in that the raw material for preparing of the diaphragm material includes aramid fiber resin, modified material and contains
The substance of lithium ion.
2. diaphragm material according to claim 1, which is characterized in that the diaphragm material further includes following 1) -7) in institute
At least one stated:
1) diaphragm material with a thickness of 12-60 microns, average pore size be 20-1000 nanometers, and/or porosity be 50% with
On；
2) diaphragm material further includes 3 D pore canal and/or network structure；
Specifically, the 3 D pore canal and/or network structure include micron openings and nano-pore, the micron openings includes by aramid fiber tree
The hole formed after lipid phase conversion, the nano-pore includes the hole formed by the gap between aramid fiber resin and modified material, micron
Hole is mutually nested with nano-pore, forms three-dimensional network cellular structure；
Again specifically, the substance containing lithium ion is distributed in micron openings and/or nano-pore；
3) modified material includes nano inorganic ceramic particle and/or nano inorganic ceramic fibre；
4) the aramid fiber resin includes p-aramid fiber resin and/or meta-aramid resin；
5) the aramid fiber resin and the mass ratio of modified material are 10:1~10:10；
6) diaphragm material has heat-resisting quantity；
Specifically, the heat-resisting quantity includes, under 150 DEG C, the heat treatment condition of 1h, the dimensional contraction rate of the diaphragm material
It is 0%；
7) electrolyte of the diaphragm material absorbs and/or holding capacity is strong；
Specifically, the electrolyte absorbs and/or holding capacity includes that the electrolyte absorptivity of the diaphragm material is by force
200% or more.
3. diaphragm material according to claim 2, which is characterized in that when the modified material includes nano inorganic ceramics grain
When son and/or nano inorganic ceramic fibre, the nano inorganic ceramic particle includes nano-aluminium oxide, nano silica
And/or nano-titanium oxide；The nano inorganic ceramic fibre include alumina fibre, mullite fiber, titanium nitride fiber and/or
Silicon carbide fibre.
4. according to claim 1,2 and/or 3 any diaphragm material, which is characterized in that the preparation side of the diaphragm material
Method includes:
1) after aramid fiber resin and modified material being mixed and/or dispersed in a solvent, deaeration handles to obtain casting solution；
2) casting solution is prepared into membrane structure, split-phase in coagulating bath is immersed after standing and is formed a film to get wet film；
3) it takes out, is drying to obtain after impregnating the wet film in lithium salts treatment fluid.
5. diaphragm material according to claim 4, which is characterized in that the preparation method of the diaphragm material further includes following
1) at least one described in -11):
1) preparation method further includes the pretreatment of aramid fiber resin and modified material, and the pretreatment includes removal impurity；
2) solvent includes dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, and/or N- methyl pyrrole
Pyrrolidone；
3) mixing and/or dispersion include being mixed and/or being dispersed by ultrasonic treatment, mechanical stirring, and/or ball milling；
4) the deaeration processing includes that vacuum defoamation is handled；
5) it is described by the casting solution be prepared into membrane structure include: by casting solution cleaned glass plate surface striking form a film；
6) membrane structure with a thickness of 20 microns -200 microns；
7) described stand including dwell temperature is 10 DEG C -60 DEG C；
8) described stand including time of repose is 5s-150s；
9) described stand includes standing humidity as 30%-90%；
10) coagulating bath includes deionized water, ethyl alcohol, and/or acetone；
11) the lithium salts treatment fluid includes water lithium chloride solution, lithium perchlorate aqueous solution, lithium bromide water solution.
6. a kind of preparation method of diaphragm material, which is characterized in that the described method includes:
1) after aramid fiber resin and modified material being mixed and/or dispersed in a solvent, deaeration handles to obtain casting solution；
2) casting solution is prepared into membrane structure, split-phase in coagulating bath is immersed after standing and is formed a film to get wet film；
3) it takes out, is drying to obtain after impregnating the wet film in lithium salts treatment fluid.
7. preparation method according to claim 6, which is characterized in that the method also includes following 1) -14) described in
It is at least one:
1) preparation method further includes the pretreatment of aramid fiber resin and modified material, and the pretreatment includes removal impurity；
2) solvent includes dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, and/or N- methyl pyrrole
Pyrrolidone；
3) mixing and/or dispersion include being mixed and/or being dispersed by ultrasonic treatment, mechanical stirring, and/or ball milling；
4) the deaeration processing includes that vacuum defoamation is handled；
5) it is described by the casting solution be prepared into membrane structure include: by casting solution cleaned glass plate surface striking form a film；
6) membrane structure with a thickness of 20 microns -200 microns；
7) described stand including dwell temperature is 10 DEG C -60 DEG C；
8) described stand including time of repose is 5s-150s；
9) described stand includes standing humidity as 30%-90%；
10) coagulating bath includes deionized water, ethyl alcohol, and/or acetone；
11) the lithium salts treatment fluid includes water lithium chloride solution, lithium perchlorate aqueous solution, lithium bromide water solution；
12) modified material includes nano inorganic ceramic particle and/or nano inorganic ceramic fibre；
13) the aramid fiber resin and the mass ratio of modified material are 10:1-10:10；
14) the aramid fiber resin includes p-aramid fiber resin and/or meta-aramid resin.
8. preparation method according to claim 7, which is characterized in that when the modified material includes nano inorganic ceramics grain
When son and/or nano inorganic ceramic fibre, the nano inorganic ceramic particle includes nano-aluminium oxide, nano silica
And/or nano-titanium oxide；The nano inorganic ceramic fibre include alumina fibre, mullite fiber, titanium nitride fiber and/or
Silicon carbide fibre.
9. diaphragm material described in claim 1,2,3,4 and/or 5, preparation method described in claim 6,7 and/or 8, power
Benefit require 6,7 and/or 8 described in the application of diaphragm material that is directly prepared of preparation method.
10. application according to claim 9, which is characterized in that the application includes following 1) -3) it is described at least one
Kind:
1) as the diaphragm material of lithium ion battery；
2) product and/or its Related product of the diaphragm material as lithium ion battery are used to prepare；
3) lithium ion battery and/or its Related product are used to prepare.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477816A (en) * | 2020-04-13 | 2020-07-31 | 华鼎国联四川动力电池有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN112909433A (en) * | 2021-01-28 | 2021-06-04 | 山东大学 | Silicon monoxide/polyacrylic acid modified high-safety battery diaphragm and preparation method and application thereof |
| WO2022127148A1 (en) * | 2020-12-16 | 2022-06-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymerization liquid, coating slurry, lithium battery separator and preparation method therefor |
| CN114725616A (en) * | 2022-04-15 | 2022-07-08 | 青岛科技大学 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
| EP4322306A3 (en) * | 2023-07-06 | 2024-06-05 | Yantai Tayho Advanced Materials Research Institute Co. ,Ltd | Composite slurry, and preparation method and use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102122704A (en) * | 2010-12-29 | 2011-07-13 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
| US20110183203A1 (en) * | 2010-01-27 | 2011-07-28 | Molecular Nanosystems, Inc. | Polymer supported electrodes |
| CN103855349A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Diaphragm of lithium-sulfur battery |
| CN105390643A (en) * | 2014-09-05 | 2016-03-09 | 北京师范大学 | Lithium ion battery composite separation membrane and lithium ion battery containing lithium ion battery composite separation membrane |
| CN105449142A (en) * | 2015-12-30 | 2016-03-30 | 吉林省聚科高新材料有限公司 | Polyimide/nano-silica composite porous film containing carboxyl structure and preparation method thereof |
| CN106876633A (en) * | 2017-02-22 | 2017-06-20 | 北京卫蓝新能源科技有限公司 | A kind of composite diaphragm, lithium battery and preparation method thereof |
-
2018
- 2018-10-29 CN CN201811265042.2A patent/CN109411680A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110183203A1 (en) * | 2010-01-27 | 2011-07-28 | Molecular Nanosystems, Inc. | Polymer supported electrodes |
| CN102122704A (en) * | 2010-12-29 | 2011-07-13 | 中科院广州化学有限公司 | Composite microporous membrane used as lithium ion battery diaphragm as well as preparation method and application thereof |
| CN103855349A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Diaphragm of lithium-sulfur battery |
| CN105390643A (en) * | 2014-09-05 | 2016-03-09 | 北京师范大学 | Lithium ion battery composite separation membrane and lithium ion battery containing lithium ion battery composite separation membrane |
| CN105449142A (en) * | 2015-12-30 | 2016-03-30 | 吉林省聚科高新材料有限公司 | Polyimide/nano-silica composite porous film containing carboxyl structure and preparation method thereof |
| CN106876633A (en) * | 2017-02-22 | 2017-06-20 | 北京卫蓝新能源科技有限公司 | A kind of composite diaphragm, lithium battery and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477816A (en) * | 2020-04-13 | 2020-07-31 | 华鼎国联四川动力电池有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| WO2022127148A1 (en) * | 2020-12-16 | 2022-06-23 | 烟台泰和新材料股份有限公司 | Modified para-aramid polymerization liquid, coating slurry, lithium battery separator and preparation method therefor |
| CN112909433A (en) * | 2021-01-28 | 2021-06-04 | 山东大学 | Silicon monoxide/polyacrylic acid modified high-safety battery diaphragm and preparation method and application thereof |
| CN112909433B (en) * | 2021-01-28 | 2022-12-16 | 山东大学 | Silicon monoxide/polyacrylic acid modified high-safety battery diaphragm and preparation method and application thereof |
| CN114725616A (en) * | 2022-04-15 | 2022-07-08 | 青岛科技大学 | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery |
| EP4322306A3 (en) * | 2023-07-06 | 2024-06-05 | Yantai Tayho Advanced Materials Research Institute Co. ,Ltd | Composite slurry, and preparation method and use thereof |
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Application publication date: 20190301 |