CN108172743A - Polyimides lithium battery diaphragm and preparation method thereof - Google Patents
Polyimides lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN108172743A CN108172743A CN201711443141.0A CN201711443141A CN108172743A CN 108172743 A CN108172743 A CN 108172743A CN 201711443141 A CN201711443141 A CN 201711443141A CN 108172743 A CN108172743 A CN 108172743A
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- pore former
- lithium battery
- dianhydride
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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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- 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
Abstract
The present invention relates to a kind of polyimides lithium battery diaphragms for improving polyimide diaphragm production efficiency and preparation method thereof, the material for preparing polyimides lithium battery diaphragm includes the pore former of all gas of reaction product under low boiling point solvent, polyimide resin, high temperature, polyimide resin is synthesized by dianhydride and diamines, the molar ratio 0.98 of dianhydride and diamines:1~1.2:1；On the basis of the gross mass of polyimide resin and low boiling point solvent, the content of the low boiling point solvent is 75% ~ 92%, and polyimide resin content is 8% ~ 25%；On the basis of the gross mass of polyimide resin, the content of pore former is 30% ~ 60%, compared with existing polyimide diaphragm and preparation method thereof, removes pore former without excess step, substantially increases the production efficiency of polyimide diaphragm.
Description
Technical field
The present invention relates to a kind of battery diaphragms, and in particular to a kind of polyimide diaphragm production efficiency of can greatly improving
Polyimides lithium battery diaphragm and preparation method thereof.
Background technology
Diaphragm is the important component of lithium ion battery, effect mainly isolation positive and negative electrode, make in electrolyte from
Son passes through between positive and negative anodes and limits electronics and pass freely through.In addition to this, diaphragm also has a major impact the safety of battery.
Battery is in the case of the improper use in the case of inside battery or external overheat, and traditional polyalkene diaphragm is in battery temperature
Can fuse during more than 160 DEG C, cause positive and negative anodes contact and it is short-circuit, so as to cause batteries caught fire or explosion, seriously jeopardize use
The life security of person.
Polyimides is a kind of good insulating materials of comprehensive performance, has excellent thermal stability and mechanical performance,
Temperature is used for a long time and may be up to 300 DEG C or more, is ideal battery diaphragm material.The system of polyimide battery diaphragm is prepared at present
Preparation Method has method of electrostatic spinning, phase inversion method and inorganic filler removal method, and there are certain drawbacks, such as Static Spinning for the prior art
Silk method, low production efficiency, equipment cost is high, and complex process etc., phase inversion method and inorganic filler method can all make in preparation process
With coagulator, inorganic filler remover etc., in the preparation method of common polyimide battery diaphragm, coagulator and inorganic filler
The use of remover etc. also affects the production efficiency of polyimide battery diaphragm.
As disclosed a kind of preparation method of polyimide diaphragm in Chinese invention patent CN 102354733, this method makes
By the use of inorganic matters such as lithias as pore former, lithia is dispersed in polyamic acid solution, is contained after plastic film mulch imidization
Then the Kapton of lithia with dilute hydrochloric acid cleans removing lithia and obtains porous polyimide diaphragm repeatedly.It should
After method obtains Kapton, the last handling process of multistep is needed, increases time cost, seriously affected the life of diaphragm
Produce efficiency.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art and to provide a kind of good product quality, performance steady
Fixed, at low cost, production efficiency is high polyimides lithium battery diaphragm and preparation method thereof, with existing polyimide diaphragm and its system
Preparation Method is compared, and is removed pore former without excess step, is substantially increased the production efficiency of polyimide diaphragm.
The object of the present invention is achieved like this：
A kind of polyimides lithium battery diaphragm, which is characterized in that the material for preparing polyimides lithium battery diaphragm includes low
The pore former of all gas of reaction product under boiling point solvent, polyimide resin, high temperature, wherein the polyimide resin by
The molar ratio of dianhydride and diamines synthesis, dianhydride and diamines is 0.98:1~1.2:1；With polyimide resin and low boiling point solvent
On the basis of gross mass, the content of the low boiling point solvent is 75% ~ 92%, and polyimide resin content is 8% ~ 25%；With polyamides Asia
On the basis of the gross mass of polyimide resin, the content of the pore former is 30% ~ 60%.
The low boiling point solvent is the low boiling point solvent that can dissolve polyamic acid, specially methanol, ethyl alcohol, tetrahydrofuran
One or more combinations, when multi-solvents are used in mixed way, on the basis of the gross mass of methanol, ethyl alcohol and tetrahydrofuran, institute
Be 70% ~ 80% with the content of tetrahydrofuran, the total content of methanol and ethyl alcohol used is 20% ~ 30%, wherein account for solvent content 20% ~
It is mixed between 30% methanol and ethyl alcohol with arbitrary proportion.
The dianhydride is the monomer of common synthesis of polyimides, including pyromellitic dianhydride, 3,3 ', 4, and 4 '-biphenyl four
One kind in formic acid dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), Bisphenol A Type Diether Dianhydride or
Several arbitrary combinations.
The diamines is the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3,4 '-diamino
Diphenyl ether p-phenylenediamine, m-phenylene diamine (MPD), 5,4 '-diamino -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 amino benzo miaows
The arbitrary combination of one or more of azoles, 4,4 '-diamino -2,2 '-dimethyl -1,1 '-biphenyl, 4,4 '-benzidine.
The pore former is the substance of all gas of reaction product under high temperature, and specific decomposition temperature is described less than 400 DEG C
The average grain diameter of pore former is 0.03 ~ 2.5 micron, and the pore former is selected from ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, nitre
The arbitrary combination of one or more of sour ammonium, inferior ammonium nitrate, ammonium ceric nitrate.
A kind of preparation method of above-mentioned polyimides lithium battery diaphragm, which is characterized in that the polyimides lithium battery
The preparation method of diaphragm, includes the following steps：
Step 1）, at low temperature pore former is uniformly dispersed in it is spare in low boiling point solvent；
Step 2）, first diamines is dissolved in the low boiling point solvent for being dispersed with pore former under similary low temperature, be slow added into dianhydride, it is low
After the lower stirring of temperature 2 ~ 24 hours, after vacuum outgas, the polyamic acid solution containing pore former is obtained；
Step 3）, by polyamic acid solution plastic film mulch on a glass, then in the imidization that gradually heats up, after pore former is thermally decomposed
Obtain polyimide foraminous diaphragm.
In step 1）In, the dispersion temperature of the pore former is -10 ~ 5 DEG C.
In step 3）In, by polyamic acid solution plastic film mulch on a glass, then gradually heat up imidization, and gradually heating is sub-
The process of amination is under 40 ~ 60 DEG C of lower temperature, is handled 0.5 ~ 4 hour, then 0.5 ~ 2 is handled at a temperature of 90 ~ 150 DEG C
Hour, it secondly handles 0.5 ~ 2 hour at 180 ~ 250 DEG C, is finally handled 0.3 ~ 1.5 hour at 300 ~ 400 DEG C.
The selection of above-mentioned heat treatment temperature depending on the heat decomposition temperature of selected pore former, the selection of actual temp be into
Hole agent cures polyamide acid film before decomposing, then the Temperature Treatment more than the heat decomposition temperature of pore former 0.5 ~ 2 hour.
Compared with prior art, the method have the characteristics that：
1st, the pore former that the present invention uses is the labile substance that is heated, which is heat-treated less than polyimides imidization
It can be thermally decomposed in temperature, all gas of reaction product, its position will pore-forming after pore former is thermally decomposed.With biography
The method for doing pore former using inorganic filler of system is compared, and pore-forming is removed without using the extra step such as inorganic filler remover
Agent substantially increases production efficiency, has saved production cost.
2nd, solvent for use of the present invention is less than 100 DEG C of low boiling point solvent for boiling point, and boiling point is less than the decomposition temperature of pore former
Degree, the quick volatilization of solvent, polyamic acid rapid curing film forming, pore former are fixed in polyamide acid film, further high temperature
Imidization, pore former gasification pore-forming, pore-forming can be very good that the original shape of pore former is presented.
3rd, the pore former of different-grain diameter, different shape, different content can be very easily selected as needed, and aperture is made
It it is 0.03 ~ 2.5 micron, porosity is 30% ~ 60% polyimide porous membrane, can be reached by adjusting pore former to polyamides Asia
The purpose that the pore size of amine diaphragm, porosity, the shape in hole are adjusted.
4th, patent of the present invention removes inorganic filler without using reagent, reduces the pollution to environment, is beneficial to protection behaviour
Make the health of personnel.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but
The present invention is not limited to following embodiments.
A kind of polyimides lithium battery diaphragm, which is characterized in that the material packet for preparing polyimides lithium battery diaphragm
The pore former of all gas of reaction product under low boiling point solvent, polyimide resin, high temperature is included, wherein the polyimides tree
Fat is synthesized by dianhydride and diamines, and the molar ratio of dianhydride and diamines is 0.98:1~1.2:1；（Here it is one section of word, should not is two sections）
On the basis of the gross mass of polyimide resin and low boiling point solvent, the content of the low boiling point solvent is 75%-92%, and polyamides is sub-
Polyimide resin content is 8% ~ 25%；On the basis of the gross mass of polyimide resin, the content of the pore former is 30% ~ 60%.
The low boiling point solvent is the low boiling point solvent that can dissolve polyamic acid, specially methanol, ethyl alcohol, tetrahydrofuran
One or more combinations, when multi-solvents are used in mixed way, on the basis of the gross mass of methanol, ethyl alcohol and tetrahydrofuran, institute
Be 70% ~ 80% with the content of tetrahydrofuran, the total content of methanol and ethyl alcohol used is 20% ~ 30%, wherein account for solvent content 20% ~
It is mixed between 30% methanol and ethyl alcohol with arbitrary proportion.
The dianhydride is the monomer of common synthesis of polyimides, including pyromellitic dianhydride, 3,3 ', 4, and 4 '-biphenyl four
One kind in formic acid dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), Bisphenol A Type Diether Dianhydride or
Several arbitrary combinations.
The diamines is the monomer of common synthesis of polyimides, including 4,4 '-diaminodiphenyl ether, 3,4 '-diamino
Diphenyl ether p-phenylenediamine, m-phenylene diamine (MPD), 5,4 '-diamino -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 amino benzo miaows
The arbitrary combination of one or more of azoles, 4,4 '-diamino -2,2 '-dimethyl -1,1 '-biphenyl, 4,4 '-benzidine.
The pore former is the substance of all gas of reaction product under high temperature, and specific decomposition temperature is described less than 400 DEG C
The average grain diameter of pore former is 0.03 ~ 2.5 micron, and the pore former is selected from ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, nitre
The arbitrary combination of one or more of sour ammonium, inferior ammonium nitrate, ammonium ceric nitrate.
Embodiment 1:
Pore former is selected first, that is, weighs the ammonium carbonate (NH that 18g average grain diameters are 2.5 microns4)2CO3 As pore former ,-
The tetrahydrofuran of 270g is uniformly dispersed in 10 DEG C of environment（THF）And methanol（Me）The mixing of two kinds of low boiling point solvent compositions
In solvent, the mass ratio between both low boiling point solvents is（THF：Me=7:3, w：w）, it is spare, then select diamines and two
Acid anhydride, i.e., by the 4 of 14.36g, 4 '-diaminodiphenyl ether（ODA）It is dissolved in a low temperature of similary and is dispersed with ammonium carbonate (NH4)2CO3
Low boiling point solvent in, by the pyromellitic dianhydride of 15.64g（PMDA）It is slowly added in above-mentioned low boiling point solvent, is stirred under low temperature
It mixes 2 hours, after vacuum outgas, obtains the polyamic acid solution containing pore former.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 40 DEG C 4 hours, 90 DEG C of processing
0.5 hour, 180 DEG C were handled 0.5 hour, and 300 DEG C are handled 1 hour, and it is 2.4 microns that average pore size is obtained after imidization, porosity
For 55.6% polyimide diaphragm.
Embodiment 2：
Pore former is selected first, that is, weighs the ammonium chloride NH that 12g average grain diameters are 1 micron4Cl is as pore former, in 0 DEG C of ring
The tetrahydrofuran of 270g is uniformly dispersed in border（THF）And methanol（Me）The in the mixed solvent of two kinds of low boiling point solvent compositions,
Mass ratio is between both low boiling point solvents（THF：Me=8:2, w：w）, it is spare, diamines and dianhydride are then selected, by 14.36g
4,4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 15.64g
（PMDA）Substep is slowly added in above-mentioned solvent, and low temperature 4 hours after vacuum outgas, obtains the polyamides containing pore former
Amino acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled 1 hour at 60 DEG C, at 90 DEG C of processing
Reason 2 hours, 180 DEG C are handled 0.5 hour, and 250 DEG C are handled 0.5 hour, and 300 DEG C are handled 0.5 hour, and 400 DEG C are handled 1.5 hours,
It is 0.9 micron that average pore size is obtained after imidization, and porosity is 35.3% polyimide diaphragm.
Embodiment 3：
Pore former is selected first, that is, weighs the ammonium oxalate (NH that 9g average grain diameters are 0.03 micron4)2C2O4As pore former, 5
DEG C environment in be uniformly dispersed in the tetrahydrofuran of 270g（THF）And ethyl alcohol（Et）In the mixed solvent（THF：Et=8:2, w：
w）, it is spare, then by the 4 of 14.36g, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, it, will after two amine solvents
15.64g pyromellitic dianhydride（PMDA）Substep is added in above-mentioned solvent, and low temperature 3 hours after vacuum outgas, obtains
Polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 2 hours, 100 DEG C of processing
0.5 hour, 180 DEG C were handled 2 hours, and 350 DEG C are handled 1 hour, and it is 0.028 micron that average pore size is obtained after imidization, porosity
For 29.4% polyimide diaphragm.
Embodiment 4：
Pore former is selected first, that is, weighs the ammonium carbonate (NH that 5g average grain diameters are 0.08 micron4)2CO3With 5.5g average grain diameters
For 0.08 micron of ammonium chloride NH4Cl is uniformly dispersed in the tetrahydrofuran of 270g as pore former in -10 DEG C of environment
（THF）And ethyl alcohol（Et）In the mixed solvent（THF：Et=7:3, w：w）, it is spare, then by the 4 of 14.36g, 4 '-diamino two
Phenylate（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 15.64g（PMDA）Substep adds in above-mentioned
In solvent, low temperature 4 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 50 DEG C 2 hours, 90 DEG C of processing 0.5
Hour, 200 DEG C are handled 0.5 hour, and 300 DEG C are handled 0.5 hour, and 400 DEG C are handled 1 hour, and average pore size is obtained after imidization is
0.073 micron, porosity is 33.6% polyimide diaphragm.
Embodiment 5：
Pore former is selected first, that is, weighs the ammonium oxalate (NH that 8g average grain diameters are 1.5 microns4)2C2O4It is with 7g average grain diameters
1.5 microns of ammonium chloride NH4Cl is uniformly dispersed in the tetrahydrofuran of 270g as pore former in 0 DEG C of environment（THF）、
Methanol and ethyl alcohol（Et）In the mixed solvent（THF：Me：Et=7:2:1, w：w：w）, it is spare, then by the 4 of 14.36g, 4 '-two
Amino-diphenylethers（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 15.64g（PMDA）Substep adds
Enter in above-mentioned solvent, low temperature 4 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 2 hours, 90 DEG C of processing 0.5
Hour, 190 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and 400 DEG C are handled 0.5 hour, and average pore size 1.4 is obtained after imidization
Micron, porosity are 48.1% polyimide diaphragm.
Embodiment 6：
Pore former is selected first, that is, weighs the ammonium oxalate (NH that 6g average grain diameters are 2 microns4)2C2O4It is 2 with 7.5g average grain diameters
Ammonium carbonate (the NH of micron4)2CO3As pore former, the tetrahydrofuran of 270g is uniformly dispersed in 0 DEG C of environment（THF）、
Methanol and ethyl alcohol（Et）In the mixed solvent（THF：Me：Et=8:1:1, w：w：w）, it is spare, then by the 4 of 14.36g, 4 '-two
Amino-diphenylethers（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 15.64g（PMDA）Substep adds
Enter in above-mentioned solvent, low temperature 4 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 40 DEG C 4 hours, 90 DEG C of processing 0.5
Hour, 190 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and 350 DEG C are handled 0.5 hour, and average pore size 1.8 is obtained after imidization
Micron, porosity are 43.7% polyimide diaphragm.
Embodiment 7：
Pore former is selected first, that is, weighs the ammonium carbonate (NH that 22.5g average grain diameters are 1 micron4)2CO3 As pore former ,-
The tetrahydrofuran of 225g is uniformly dispersed in 10 DEG C of environment（THF）, methanol（Me）And ethyl alcohol（Et）Three kinds of low boiling point solvents
The in the mixed solvent of composition, the mass ratio between these three low boiling point solvents are（THF：Me：Et=7:1:2, w：w）, it is spare, so
Select diamines and dianhydride afterwards, i.e., by the 4 of 35.52g, 4 '-diaminodiphenyl ether（ODA）It is dissolved in and is dispersed in a low temperature of similary
Ammonium carbonate (NH4)2CO3Low boiling point solvent in, by the pyromellitic dianhydride of 39.48g（PMDA）It is molten that substep adds in above-mentioned low boiling point
In agent, low temperature 2 hours after vacuum outgas, obtains the polyamic acid solution containing pore former.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 40 DEG C 4 hours, 90 DEG C of processing
0.5 hour, 180 DEG C were handled 0.5 hour, and 300 DEG C are handled 1 hour, and it is 0.92 micron that average pore size is obtained after imidization, porosity
For 29.6% polyimide diaphragm.
Embodiment 8：
Pore former is selected first, that is, weighs the ammonium chloride NH that 26.25g average grain diameters are 0.8 micron4Cl is as pore former, 0
DEG C environment in be uniformly dispersed in the tetrahydrofuran of 225g（THF）And methanol（Me）The mixing of two kinds of low boiling point solvent compositions is molten
In agent, mass ratio is between both low boiling point solvents（THF：Me=8:2, w：w）, it is spare, diamines and dianhydride are then selected, it will
The 4,4 ' of 32.51g-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, after two amine solvents, by the equal benzene tetramethyl of 42.49g
Acid anhydrides（PMDA）Substep is slowly added in above-mentioned solvent, and low temperature 4 hours after vacuum outgas, is obtained containing pore former
Polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled 1 hour at 60 DEG C, at 90 DEG C of processing
Reason 2 hours, 180 DEG C are handled 0.5 hour, and 250 DEG C are handled 0.5 hour, and 300 DEG C are handled 0.5 hour, and 400 DEG C are handled 1.5 hours,
It is 0.76 micron that average pore size is obtained after imidization, and porosity is 34.7% polyimide diaphragm.
Embodiment 9：
Pore former is selected first, that is, weighs the ammonium oxalate (NH that 3g average grain diameters are 0.5 micron4)2C2O4It is with 3.2g average grain diameters
0.5 micron of ammonium carbonate (NH4)2CO3With the ammonium chloride NH that 4g average grain diameters are 0.5 micron4Cl is as pore former, at 0 DEG C
The tetrahydrofuran of 276g is uniformly dispersed in environment（THF）, methanol and ethyl alcohol（Et）In the mixed solvent（THF：Me：Et=8:
1:1, w：w：w）, it is spare, then by the 4 of 11.49g, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats two amine solvents
Afterwards, by the pyromellitic dianhydride of 12.51g（PMDA）Substep is added in above-mentioned solvent, low temperature 4 hours, after vacuum outgas,
Obtain polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 40 DEG C 2 hours, 90 DEG C of processing 1 are small
When, 190 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and 400 DEG C are handled 0.5 hour, and average pore size 0.46 is obtained after imidization
Micron, porosity are 44.7% polyimide diaphragm.
Comparative example 1：The lithia that average grain diameter is 1 micron is uniformly dispersed in n,N-dimethylacetamide solvent,
4,4 '-diaminodiphenyl ether of 14.36g is added in into solvent（ODA）, after and after amine solvent, by the Pyromellitic Acid of 15.64g
Acid anhydride（PMDA）Substep is added in above-mentioned solvent, and low temperature 4 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, it is thin gradually polyimides to be obtained after imidization in an oven
Film.
Above-mentioned film with dilute hydrochloric acid solution is extracted repeatedly, lithia is removed, is then cleaned with distilled water to neutrality, and put
Baking oven drying is put, obtains porous polyimide diaphragm.
Embodiment 10:
Pore former is selected first, that is, weighs 18g average grain diameters as 1.2 microns of ammonium nitrate NH4NO3As pore former, at 0 DEG C
The tetrahydrofuran of 264g is uniformly dispersed in environment（THF）, methanol and ethyl alcohol（Et）In the mixed solvent（THF：Me：Et=7:
2:1, w：w：w）, it is spare, then by the 4 of 17.05g, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, treats two amine solvents
Afterwards, by the pyromellitic dianhydride of 18.95g（PMDA）Substep is added in above-mentioned solvent, low temperature 2.5 hours, vacuum outgas
Afterwards, polyamic acid solution is obtained.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 0.5 hour, 90 DEG C of processing
0.5 hour, 200 DEG C were handled 1 hour, and 250 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and average pore size is obtained after imidization
1.1 microns, porosity is 47.4% polyimide diaphragm.
Embodiment 11:
Pore former is selected first, that is, weighs the ammonium chloride NH that 10g average grain diameters are 1.8 microns4Cl and average grain diameter are 1.8 microns
8.9g NH4NO3As pore former, the tetrahydrofuran of 255g is uniformly dispersed in 0 DEG C of environment（THF）, methanol and second
Alcohol（Et）In the mixed solvent（THF：Me：Et=8:1:1, w：w：w）, it is spare, then by the 4 of 20.99g, 4 '-diamino hexichol
Ether（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 24.01g（PMDA）Substep adds in above-mentioned molten
In agent, low temperature 3 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 60 DEG C 0.5 hour, 90 DEG C of processing
0.5 hour, 200 DEG C were handled 1 hour, and 250 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and 350 DEG C are handled 0.5 hour, imines
1.7 microns of average pore size is obtained after change, porosity is 40.8% polyimide diaphragm.
Embodiment 12:
Pore former is selected first, that is, weighs the ammonium oxalate (NH that 10g average grain diameters are 2.2 microns4)2C2O4With 8.9g average grain diameters
For 0.5 micron of ammonium carbonate (NH4)2CO3As pore former, the tetrahydrofuran of 276g is uniformly dispersed in 0 DEG C of environment
（THF）, methanol in the mixed solvent（THF：Me=7:3, w：w）, it is spare, then by the 4 of 24.57g, 4 '-diaminodiphenyl ether
（ODA）It adds in above-mentioned solvent, after two amine solvents, by the pyromellitic dianhydride of 29.43g（PMDA）Substep adds in above-mentioned solvent
In, low temperature 3.5 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 40 DEG C 4 hours, 90 DEG C of processing 0.5
Hour, 190 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and 350 DEG C are handled 0.5 hour, and average pore size 2.1 is obtained after imidization
Micron, porosity are 33.9% polyimide diaphragm.
Embodiment 13:
Pore former is selected first, that is, weighs the ammonium oxalate (NH that 7g average grain diameters are 0.06 micron4)2C2O4It is with 7g average grain diameters
0.06 micron of ammonium carbonate (NH4)2CO3With the ammonium chloride NH that 7g average grain diameters are 0.06 micron4Cl is as pore former, at 0 DEG C
Environment in be uniformly dispersed in the tetrahydrofuran of 240g（THF）And ethyl alcohol（Et）In the mixed solvent（THF： Et=8:2, w：
w）, it is spare, then by the 4 of 26.63g, 4 '-diaminodiphenyl ether（ODA）It adds in above-mentioned solvent, it, will after two amine solvents
33.37g pyromellitic dianhydride（PMDA）Substep is added in above-mentioned solvent, and low temperature 4 hours after vacuum outgas, obtains
Polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, baking oven is put into, is handled at 40 DEG C 2 hours, 90 DEG C of processing 1 are small
When, 190 DEG C are handled 1 hour, and 300 DEG C are handled 0.5 hour, and 400 DEG C are handled 0.5 hour, and average pore size 0.051 is obtained after imidization
Micron, porosity are 33.7% polyimide diaphragm.
Comparative example 1：The lithia that average grain diameter is 1 micron is uniformly dispersed in n,N-dimethylacetamide solvent,
4,4 '-diaminodiphenyl ether of 14.36g is added in into solvent（ODA）, after and after amine solvent, by the Pyromellitic Acid of 15.64g
Acid anhydride（PMDA）Substep is added in above-mentioned solvent, and low temperature 4 hours after vacuum outgas, obtains polyamic acid solution.
By above-mentioned polyamic acid solution plastic film mulch on a glass, it is thin gradually polyimides to be obtained after imidization in an oven
Film.Above-mentioned film with dilute hydrochloric acid solution is extracted repeatedly, lithia is removed, is then cleaned with distilled water to neutrality, and place baking
Case is dried, and obtains porous polyimide diaphragm.
Claims (9)
1. a kind of polyimides lithium battery diaphragm, which is characterized in that the material for preparing polyimides lithium battery diaphragm includes
The pore former of all gas of reaction product under low boiling point solvent, polyimide resin, high temperature, wherein the polyimide resin
It is synthesized by dianhydride and diamines, the molar ratio of dianhydride and diamines is 0.98:1~1.2:1；With polyimide resin and low boiling point solvent
Gross mass on the basis of, the content of the low boiling point solvent is 75% ~ 92%, and polyimide resin content is 8% ~ 25%；With polyamides
On the basis of the gross mass of imide resin, the content of the pore former is 30% ~ 60%.
2. polyimides lithium battery diaphragm according to claim 1, which is characterized in that the low boiling point solvent is can be molten
One or more combinations of the low boiling point solvent, specially methanol, ethyl alcohol, tetrahydrofuran of polyamic acid are solved, when multi-solvents mix
It closes in use, on the basis of the gross mass of methanol, ethyl alcohol and tetrahydrofuran, the content of tetrahydrofuran used is 70% ~ 80%, used
The total content of methanol and ethyl alcohol is 20% ~ 30%, wherein being mixed between accounting for the methanol and ethyl alcohol of solvent content 20% ~ 30% with arbitrary proportion
It closes.
3. polyimides lithium battery diaphragm according to claim 1, which is characterized in that the dianhydride is poly- for common synthesis
Imido monomer, including pyromellitic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic
The arbitrary combination of one or more of dianhydride, benzophenone tetracarboxylic dianhydride (BTDA), Bisphenol A Type Diether Dianhydride.
4. polyimides lithium battery diaphragm according to claim 1, which is characterized in that the diamines is poly- for common synthesis
Imido monomer, including 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether is to this diamines, m-phenylene diamine (MPD), 5, and 4 '-two
Amino -2- phenyl benzoxazoles, 2-（4- aminophenyls）- 5 aminobenzimidazoles, 4,4 '-diamino -2,2 '-dimethyl -1,
The arbitrary combination of one or more of 1 '-biphenyl, 4,4 '-benzidine.
5. polyimides lithium battery diaphragm according to claim 1, which is characterized in that the pore former is to be reacted under high temperature
The substance of all gas of product, specific decomposition temperature are less than 400 DEG C, and the average grain diameter of the pore former is micro- for 0.03 ~ 2.5
Rice, the pore former in ammonium oxalate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, inferior ammonium nitrate, ammonium ceric nitrate one
Kind or several arbitrary combinations.
6. a kind of preparation method of polyimides lithium battery diaphragm as described in claim 1, which is characterized in that the polyamides is sub-
The preparation method of amine lithium battery diaphragm, includes the following steps：
Step 1）, at low temperature pore former is uniformly dispersed in it is spare in low boiling point solvent；
Step 2）, first diamines is dissolved in the low boiling point solvent for being dispersed with pore former under similary low temperature, be slow added into dianhydride, it is low
After the lower stirring of temperature 2 ~ 24 hours, after vacuum outgas, the polyamic acid solution containing pore former is obtained；
Step 3）, by polyamic acid solution plastic film mulch on a glass, then in the imidization that gradually heats up, after pore former is thermally decomposed
Obtain polyimide foraminous diaphragm.
7. the preparation method of a kind of polyimides lithium battery diaphragm according to claim 6, which is characterized in that in step 1）
In, the dispersion temperature of the pore former is -10 ~ 5 DEG C.
8. the preparation method of a kind of polyimides lithium battery diaphragm according to claim 6, which is characterized in that in step 3）
In, by polyamic acid solution plastic film mulch on a glass, then gradually heat up imidization, and the process for the imidization that gradually heats up is 40
Under ~ 60 DEG C of lower temperature, handle 0.5 ~ 4 hour, then handle 0.5 ~ 2 hour at a temperature of 90 ~ 150 DEG C, next 180 ~
250 DEG C are handled 0.5 ~ 2 hour, are finally handled 0.3 ~ 1.5 hour at 300 ~ 400 DEG C.
9. the preparation method of a kind of polyimides lithium battery diaphragm according to claim 8, which is characterized in that at above-mentioned heat
The selection of temperature is managed depending on the heat decomposition temperature of selected pore former, the selection of actual temp is to make to gather before pore former decomposition
Amide sorrel cures, then the Temperature Treatment more than the heat decomposition temperature of pore former 0.5 ~ 2 hour.
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| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN111584808A (en) * | 2020-04-16 | 2020-08-25 | 山东工业陶瓷研究设计院有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN111883722A (en) * | 2020-07-22 | 2020-11-03 | 江西师范大学 | Preparation method of double-structure polyimide composite battery diaphragm |
| CN113121857A (en) * | 2021-06-01 | 2021-07-16 | 桂林电器科学研究院有限公司 | Low-dielectric-property polyimide film and preparation method thereof |
| CN116063709A (en) * | 2021-11-01 | 2023-05-05 | 宁德时代新能源科技股份有限公司 | Composite polyimide diaphragm, preparation method thereof and secondary battery |
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