CN106784541A - A kind of lithium battery diaphragm nano alumina powder jointed material and lithium battery diaphragm therefrom - Google Patents
A kind of lithium battery diaphragm nano alumina powder jointed material and lithium battery diaphragm therefrom Download PDFInfo
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- CN106784541A CN106784541A CN201710069680.6A CN201710069680A CN106784541A CN 106784541 A CN106784541 A CN 106784541A CN 201710069680 A CN201710069680 A CN 201710069680A CN 106784541 A CN106784541 A CN 106784541A
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- lithium battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—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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- 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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- 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
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- 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 nano alumina powder jointed material of lithium battery diaphragm, the powder body material is coated with sulfonated polyether amine layer and polyetheramine hyperbranched poly pyrrole throat copolymer layer successively with nano aluminium oxide as kernel, and from inside to outside.Lithium battery diaphragm using nano alumina powder jointed material of the invention has heat endurance higher, more preferable mechanical performance and more preferably pore-size distribution.
Description
Technical field
The invention belongs to nano-powder technical field, more particularly it relates to a kind of lithium battery diaphragm nano oxygen
Change aluminium powder body material and lithium battery diaphragm therefrom.
Background technology
Lithium battery is widely used in the electronics fields such as mobile phone, portable computer, camera, video camera.It has energy
Metric density is high, voltage is high, have extended cycle life, self-discharge rate is low, memory-less effect, discharge voltage stable, discharge and recharge is quick and ring
The advantages of guarantor.Barrier film is the core component of lithium ion battery, and the quality of its performance directly affects the battery capacity of lithium battery, circulation
Service life and security performance.
At present, the lithium battery diaphragm of commercialization is mainly the MIcroporous polyolefin film with polyethylene and polypropylene as material.This
The fusing point of a little conventional polyolefins barrier films is relatively low, and contraction occurs after being heated, and causes battery plus-negative plate contact short circuit；In addition, polyene
Hydro carbons barrier film mechanical performance in itself is also bad.It is modified by adding inorganic particle, such as aluminum oxide, can be to a certain extent
Resistance to heat problem is solved, but it there are problems that always with the compatibility of film, frequently result in the decline of mechanical strength, and easily cause hole
The problem that gap rate is low and pore-size distribution is uneven.
Accordingly, it would be desirable to carry out technological improvement to inorganic particle, there is more preferable mechanical performance and more preferably hole to prepare
The septum for lithium ion battery of footpath distribution.
The content of the invention
In order to solve the above problems, one aspect of the present invention provides a kind of nano alumina powder jointed material of lithium battery diaphragm
Material, it is characterised in that the powder body material is coated with sulfonated polyether amine successively with nano aluminium oxide as kernel, and from inside to outside
Layer and polyetheramine-hyperbranched poly pyrrole throat copolymer layer.
In one embodiment, the particle diameter of the nano aluminium oxide is 10-100 nanometers；Preferably, it is described nano oxidized
The particle diameter of aluminium is 20-80 nanometers；It is highly preferred that the particle diameter of the nano aluminium oxide is 30 nanometers.
In one embodiment, the nano aluminium oxide be sheet, and the flake nano aluminum oxide preparation method
For：
（1) it is 2.5 liters the aluminium powder that granularity is 100 μm to be put into volume, and power is the rolling-vibrating grinding machine of 0.3kW, grinds 3h；
（2) aluminium powder for preparing step 1 compares 1: 15 and mixes with running water according to weight, is then placed in ultrasonator, ultrasound point
3h is dissipated, the colloids of white " milky " Al (OH) 3 are prepared；
（3) colloids of white " milky " Al (OH) 3 for preparing step 2, are put into thermostatic drying chamber after press filtration, 80 DEG C dry 16h, obtain
The powder of Al (OH) 3；
（4) powder of Al (OH) 3 for finally obtaining step 3 is put into chamber type electric resistance furnace, and 210 DEG C of freeze-day with constant temperature 4h take out and are piece
Shape nano-scale alumina.
In one embodiment, the thickness of the sulfonated polyether amine layer is 1-10 microns；Preferably, the sulfonated polyether
The thickness of amine layer is 2-8 microns；It is highly preferred that the thickness of the sulfonated polyether amine layer is 5.1 microns.
In one embodiment, the sulfonated polyether amine is prepared from by following methods：
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.255mol benzylamine and 500 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 150mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration
And collected polymer, in vacuum drying oven, 60 DEG C of dryings 20 hours obtain polyetheramine；
In the dry three-necked bottles of 100mL, the dense sulphur of 1 gram of above-mentioned polyetheramine and the mass fraction 98% of 10mL is sequentially added
Acid, under nitrogen protection, after stirring 60min at 25 DEG C, is poured into frozen water, and with after the frozen water cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 80 DEG C of dryings obtain final product sulfonated polyether amine in 24 hours.
In one embodiment, the thickness of the polyetheramine-hyperbranched poly pyrrole throat copolymer layer is 1-10 microns；It is preferred that
Ground, the thickness of the polyetheramine-hyperbranched poly pyrrole throat copolymer layer is 3-7 microns；It is highly preferred that the polyetheramine-hyperbranched
The thickness of poly- pyrrole throat copolymer layer is 4.2 microns.
In one embodiment, the polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（2）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25mL metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（3）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer.
Another aspect of the present invention provides a kind of lithium battery diaphragm, and it uses polypropylene for basement membrane and doped with described lithium
The nano alumina powder jointed material of battery diaphragm.
The method of the lithium battery diaphragm described in another aspect of the invention, comprises the following steps：
(1) described lithium battery diaphragm is uniformly blended into polypropylene with nano alumina powder jointed material, addition is polypropylene
The 1%-5% of quality, melts to raw material, using biaxial tension legal system film forming, the film being made through 70~155 DEG C, 10min~
30h anneals；
(2) by above-mentioned film 100~150 DEG C, draw speed be 5~10m/min, draw ratio be 2~4 times under conditions of drawn
Stretch and obtain lithium battery diaphragm.
Compared with prior art, beneficial effects of the present invention are：
1st, sulfonated polyether amine contains great amount of hydroxy group, with its coated inorganic thing, can greatly improve the cohesive force with inorganic material, and
The compatibility of inorganic matter and membrane material is improved, additionally, sulfonic group can also occur ionomer with poly- pyrrole throat, crosslink density is improved, this
The introducing of a large amount of rigidity phenyl ring, can improve molecule chain rigidity on outside chain, and certain interpenetrating networks knot is formed with polypropylene
Structure, improves film strength, so as to provide Advantageous Effects of the invention.
2nd, the addition of polyetheramine-hyperbranched poly pyrrole throat copolymer can both provide excellent weatherability, intensity higher, and
Rigidity, the stronger inierpeneirating network structure of formation, the significantly service life and intensity of film, so as to provide can be further improved again
Advantageous Effects of the invention.
Specific embodiment
Raw material:
Tetramine is purchased from CTI, SigmaAldrich, AlfaAesar or SCRC, and directly uses, without being further purified.Sheet
Nano aluminium oxide（30 nanometers of average grain diameter, model SH-A01）Self-control, other raw materials are purchased from Aladdin reagent Co., Ltd.
Specific raw material is as follows：
A1：Nano aluminium oxide, average grain diameter is 10 nanometers
A2：Nano aluminium oxide, average grain diameter is 100 nanometers
A3：Nano aluminium oxide, average grain diameter is 30 nanometers
A4：Flake nano aluminum oxide, average grain diameter is 30 nanometers, and its preparation method is：
（1) it is 2.5 liters the aluminium powder that granularity is 100 μm to be put into volume, and power is the rolling-vibrating grinding machine of 0.3kW, grinds 3h；
（2) aluminium powder for preparing step 1 compares 1: 15 and mixes with running water according to weight, is then placed in ultrasonator, ultrasound point
3h is dissipated, the colloids of white " milky " Al (OH) 3 are prepared；
（3) colloids of white " milky " Al (OH) 3 for preparing step 2 are put into thermostatic drying chamber, and 80 DEG C dry 16h, obtain Al (OH) 3
Powder；
（4) powder of Al (OH) 3 for finally obtaining step 3 is put into chamber type electric resistance furnace, and 210 DEG C of freeze-day with constant temperature 4h take out and are piece
Shape nano-scale alumina.
B1：Polyetheramine is prepared from by following methods：
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.255mol benzylamine and 500 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 150mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration
And collected polymer, in vacuum drying oven, 60 DEG C of dryings 20 hours obtain polyetheramine.
B2：Sulfonated polyether amine is prepared from by following methods：
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.255mol benzylamine and 500 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 150mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration
And collected polymer, in vacuum drying oven, 60 DEG C of dryings 20 hours obtain polyetheramine；
In the dry three-necked bottles of 100mL, the dense sulphur of 1 gram of above-mentioned polyetheramine and the mass fraction 98% of 10mL is sequentially added
Acid, under nitrogen protection, after stirring 60min at 25 DEG C, is poured into frozen water, and with after the frozen water cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 80 DEG C of dryings obtain final product sulfonated polyether amine in 24 hours.
C1：Hyperbranched poly pyrrole throat, is prepared from by following methods：
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25mL metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride.
C2：Polyetheramine-hyperbranched poly pyrrole throat copolymer, is prepared from by following methods：
（1）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（2）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25mL metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（3）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer.
D1：Polypropylene, model SFC-750R carefree purchased from South Korea
Embodiment 1
（1）1 gram of B1 is dissolved in the propylene glycol monomethyl ether of 35ml, 5 grams of A1 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）1 gram of C1 is dissolved in the metacresol of 30ml, 5 grams of above-mentioned individual layer cladding nano aluminium oxide, 40 DEG C is subsequently adding
Under, after stirring 60min, suction filtration, and product is collected, and in vacuum drying oven, the product is dried 15 hours at 120 DEG C, obtain
The nano alumina powder jointed material of double-coating nano aluminium oxide, as lithium battery diaphragm；
（3）Above-mentioned lithium battery diaphragm is taken to be uniformly blended into 100Kg D1 with nano alumina powder jointed material 2Kg, it is former to above-mentioned mixing
Material is melted, and melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h enters the film being made
Row annealing；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Embodiment 2
（1）1 gram of B2 is dissolved in the propylene glycol monomethyl ether of 35ml, 5 grams of A1 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）1 gram of C2 is dissolved in the metacresol of 30ml, 5 grams of above-mentioned individual layer cladding nano aluminium oxide, 40 DEG C is subsequently adding
Under, after stirring 60min, suction filtration, and product is collected, and in vacuum drying oven, the product is dried 15 hours at 120 DEG C, obtain
The nano alumina powder jointed material of double-coating nano aluminium oxide, as lithium battery diaphragm；
（3）Above-mentioned lithium battery diaphragm is taken to be uniformly blended into 100Kg D1 with nano alumina powder jointed material 2Kg, it is former to above-mentioned mixing
Material is melted, and melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h enters the film being made
Row annealing；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Embodiment 3
（1）1 gram of B2 is dissolved in the propylene glycol monomethyl ether of 35ml, 5 grams of A2 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）1 gram of C2 is dissolved in the metacresol of 30ml, 5 grams of above-mentioned individual layer cladding nano aluminium oxide, 40 DEG C is subsequently adding
Under, after stirring 60min, suction filtration, and product is collected, and in vacuum drying oven, the product is dried 15 hours at 120 DEG C, obtain
The nano alumina powder jointed material of double-coating nano aluminium oxide, as lithium battery diaphragm；
（3）Above-mentioned lithium battery diaphragm is taken to be uniformly blended into 100Kg D1 with nano alumina powder jointed material 2Kg, it is former to above-mentioned mixing
Material is melted, and melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h enters the film being made
Row annealing；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Embodiment 4
（1）1 gram of B2 is dissolved in the propylene glycol monomethyl ether of 35ml, 5 grams of A3 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）1 gram of C2 is dissolved in the metacresol of 30ml, 5 grams of above-mentioned individual layer cladding nano aluminium oxide, 40 DEG C is subsequently adding
Under, after stirring 60min, suction filtration, and product is collected, and in vacuum drying oven, the product is dried 15 hours at 120 DEG C, obtain
The nano alumina powder jointed material of double-coating nano aluminium oxide, as lithium battery diaphragm；
（3）Above-mentioned lithium battery diaphragm is taken to be uniformly blended into 100Kg D1 with nano alumina powder jointed material 2Kg, it is former to above-mentioned mixing
Material is melted, and melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h enters the film being made
Row annealing；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Embodiment 5
（1）1 gram of B2 is dissolved in the propylene glycol monomethyl ether of 10ml, 5 grams of A3 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）1 gram of C2 is dissolved in the metacresol of 10ml, 5 grams of above-mentioned individual layer cladding nano aluminium oxide, 40 DEG C is subsequently adding
Under, after stirring 60min, suction filtration, and product is collected, and in vacuum drying oven, the product is dried 15 hours at 120 DEG C, obtain
The nano alumina powder jointed material of double-coating nano aluminium oxide, as lithium battery diaphragm；
（3）Above-mentioned lithium battery diaphragm is taken to be uniformly blended into 100Kg D1 with nano alumina powder jointed material 2Kg, it is former to above-mentioned mixing
Material is melted, and melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h enters the film being made
Row annealing；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Embodiment 6
（1）1 gram of B2 is dissolved in the propylene glycol monomethyl ether of 20ml, 5 grams of A4 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）1 gram of C2 is dissolved in the metacresol of 16ml, 5 grams of above-mentioned individual layer cladding nano aluminium oxide, 40 DEG C is subsequently adding
Under, after stirring 60min, suction filtration, and product is collected, and in vacuum drying oven, the product is dried 15 hours at 120 DEG C, obtain
The nano alumina powder jointed material of double-coating nano aluminium oxide, as lithium battery diaphragm；
（3）Above-mentioned lithium battery diaphragm is taken to be uniformly blended into 100Kg D1 with nano alumina powder jointed material 2Kg, it is former to above-mentioned mixing
Material is melted, and melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h enters the film being made
Row annealing；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Comparative example 1
（1）1 gram of B2 is dissolved in the propylene glycol monomethyl ether of 20ml, 5 grams of A3 is subsequently adding, at 40 DEG C, after stirring 30min, taken out
Filter, and product is collected, in vacuum drying oven, the product is dried 10 hours at 60 DEG C, obtain individual layer cladding nano aluminium oxide；
（2）Take above-mentioned individual layer cladding nano aluminium oxide 2Kg to be uniformly blended into 100Kg D1, above-mentioned mixed material melted,
Melt temperature is 220 DEG C, and using biaxial tension legal system film forming, through controlling temperature at 85 DEG C, 3h's film being made is annealed；
（3）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Comparative example 2
Take A3 2Kg to be uniformly blended into 100Kg D1, above-mentioned mixed material is melted, melt temperature is 220 DEG C, using double
Film is made to pulling method, through controlling temperature at 85 DEG C, 3h's film being made is annealed；
（4）By above-mentioned film 115 DEG C, draw speed be 6m/min, draw ratio be 3 times under conditions of stretch obtaining lithium battery
Barrier film.
Test condition
Barrier film to embodiment 1-6 and comparative example 1-2 carries out performance test.
（1）Elastic recovery rate
Using electronic universal tester（CMT-4502, beautiful this secret service industry System Co., Ltd）Determine the elastic recovery rate of basement membrane.
Film is placed on fixture, the gauge length of working portion is 100mm, after stretching 50mm with 50% rate of straining, then with same speed
Degree is return, and measures the expendable length of sample and calculates ER elastic recovery rates by following formula（ER）Value：
ER=(100-l)/100×100%
In formula, l is the expendable length of sample, mm after stretching 50mm.
（2）Air penetrability
Using permeability apparatus（4110 types, Gurley companies of the U.S.）Determine the Gurley values of microporous barrier.Gurley values refer to
The air of specified quantitative is at a certain pressure by the time required for the microporous barrier of particular area, and Gurley values are smaller, breathes freely
Rate is higher.Condition determination is：Operating pressure 8.5KPa, test area 645.2mm2。
（3）Porosity and size distribution
The full-automatic mercury injection apparatuses of PoreMaster-60 produced using Kang Ta instrument companies of the U.S. determine the hole of microporous polypropylene membrane
Rate and size distribution.According to pore volume and the relation curve in aperture, average pore size is obtained；With average pore size as intermediate value, ±
25nm is bound, and even aperture distribution is represented with the percentage that aperture pore volume within the range is shared in total pore volume,
The percentage is higher, represents that pore-size distribution is more uniform.
Test result is shown in Table 1.
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 |
| Internal layer thickness | 1.2 microns | 1.1 microns | 1.2 microns | 1.3 microns | 8.9 microns | 5.1 microns | 5.3 microns | - |
| Outer layer thickness | 1.0 microns | 1.3 microns | 1.2 microns | 1.2 microns | 1.1 microns | 4.2 microns | - | - |
| Elastic recovery rate | 75% | 82% | 80% | 87% | 90% | 98% | 70% | 60% |
| Tensile strength | 42Mpa | 63Mpa | 60Mpa | 65Mpa | 67Mpa | 73Mpa | 48Mpa | 32Mpa |
| Gurley values | 258 | 190 | 185 | 147 | 133 | 120 | 235 | 306 |
| Porosity | 39% | 50% | 52% | 58% | 60% | 63% | 43% | 32% |
| Average pore size | 43 nanometers | 45 nanometers | 46 nanometers | 44 nanometers | 43 nanometers | 45 nanometers | 47 nanometers | 48 nanometers |
| Pore-size distribution | 51% | 67% | 65% | 68% | 71% | 85% | 58% | 32% |
Data above can be seen that compared with the barrier film of double-coating nano aluminium oxide is not used, and barrier film of the invention has bright
Aobvious better performance, is thus provided that Advantageous Effects of the invention.
Claims (8)
1. the nano alumina powder jointed material of a kind of lithium battery diaphragm, it is characterised in that the powder body material is with nano aluminium oxide
It is kernel, and from inside to outside, sulfonated polyether amine layer and polyetheramine-hyperbranched poly pyrrole throat copolymer layer is coated with successively.
2. the nano alumina powder jointed material of lithium battery diaphragm according to claim 1, it is characterised in that the nano oxygen
The particle diameter for changing aluminium is 10-100 nanometers.
3. the nano alumina powder jointed material of lithium battery diaphragm according to claim 1, it is characterised in that the sulfonation gathers
The thickness of ether amines layer is 1-10 microns.
4. the nano alumina powder jointed material of lithium battery diaphragm according to claim 1, it is characterised in that the sulfonation gathers
Ether amines are prepared from by following methods：
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.255mol benzylamine and 500 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 150mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration
And collected polymer, in vacuum drying oven, 60 DEG C of dryings 20 hours obtain polyetheramine；
In the dry three-necked bottles of 100mL, the dense sulphur of 1 gram of above-mentioned polyetheramine and the mass fraction 98% of 10mL is sequentially added
Acid, under nitrogen protection, after stirring 60min at 25 DEG C, is poured into frozen water, and with after the frozen water cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 80 DEG C of dryings obtain final product sulfonated polyether amine in 24 hours.
5. the nano alumina powder jointed material of lithium battery diaphragm according to claim 1, it is characterised in that
The thickness of the polyetheramine-hyperbranched poly pyrrole throat copolymer layer is 1-10 microns.
6. the nano alumina powder jointed material of lithium battery diaphragm according to claim 1, it is characterised in that the polyethers
Amine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（2）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25mL metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（3）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer.
7. a kind of lithium battery diaphragm, it is characterised in that using polypropylene for basement membrane and doped with any one of claim 1-6 institutes
The nano alumina powder jointed material of the lithium battery diaphragm stated.
8. a kind of method for preparing lithium battery diaphragm as claimed in claim 7, it is characterised in that comprise the following steps：
(1) lithium battery diaphragm any one of claim 1-6 is uniformly blended into poly- third with nano alumina powder jointed material
In alkene, addition is the 1%-5% of polypropylene quality, raw material is melted, using biaxial tension legal system film forming, the film being made
Through 70~155 DEG C, 10min~30h annealing；
(2) by above-mentioned film 100~150 DEG C, draw speed be 5~10m/min, draw ratio be 2~4 times under conditions of drawn
Stretch and obtain lithium battery diaphragm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403661A (en) * | 2020-03-23 | 2020-07-10 | 南京航空航天大学 | Composite diaphragm for power lithium ion battery and preparation method thereof |
| US11581614B2 (en) * | 2018-05-24 | 2023-02-14 | Lg Energy Solution, Ltd. | Separator including coating layer with polymer having main chain with non-covalent electron pair and aromatic side chain and lithium-sulfur battery having the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367172A (en) * | 2011-10-17 | 2012-03-07 | 中科院广州化学有限公司 | Modified silicon dioxide and high-property lithium ion battery diaphragm and application thereof |
| CN104900833A (en) * | 2015-07-07 | 2015-09-09 | 佛山市盈博莱科技有限公司 | Lithium ion battery separator and preparation method thereof |
| CN105754431A (en) * | 2016-04-01 | 2016-07-13 | 云南佑琳生科技有限公司 | Exterior wall coating material capable of finishing working through one-time painting |
| CN106116095A (en) * | 2016-08-01 | 2016-11-16 | 郑经耀 | A kind of sludge dryer and the method using this drying machine drying mud |
-
2017
- 2017-02-08 CN CN201710069680.6A patent/CN106784541A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367172A (en) * | 2011-10-17 | 2012-03-07 | 中科院广州化学有限公司 | Modified silicon dioxide and high-property lithium ion battery diaphragm and application thereof |
| CN104900833A (en) * | 2015-07-07 | 2015-09-09 | 佛山市盈博莱科技有限公司 | Lithium ion battery separator and preparation method thereof |
| CN105754431A (en) * | 2016-04-01 | 2016-07-13 | 云南佑琳生科技有限公司 | Exterior wall coating material capable of finishing working through one-time painting |
| CN106116095A (en) * | 2016-08-01 | 2016-11-16 | 郑经耀 | A kind of sludge dryer and the method using this drying machine drying mud |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11581614B2 (en) * | 2018-05-24 | 2023-02-14 | Lg Energy Solution, Ltd. | Separator including coating layer with polymer having main chain with non-covalent electron pair and aromatic side chain and lithium-sulfur battery having the same |
| CN111403661A (en) * | 2020-03-23 | 2020-07-10 | 南京航空航天大学 | Composite diaphragm for power lithium ion battery and preparation method thereof |
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