CN108767174A - A kind of preparation method of Organic-inorganic composite lithium battery diaphragm - Google Patents
A kind of preparation method of Organic-inorganic composite lithium battery diaphragm Download PDFInfo
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- CN108767174A CN108767174A CN201810593265.5A CN201810593265A CN108767174A CN 108767174 A CN108767174 A CN 108767174A CN 201810593265 A CN201810593265 A CN 201810593265A CN 108767174 A CN108767174 A CN 108767174A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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 preparation methods of Organic-inorganic composite lithium battery diaphragm, belong to new energy battery material technical field.The present invention first will be after sepiolite mechanical crushing, sieving, after sepiolite powder, water and Tea Saponin are mixed again, hydro-thermal reaction, filtering, obtains pretreatment sepiolite, after pretreatment sepiolite is scattered in absolute ethyl alcohol again, thionyl chloride, urea and plasticizer are sequentially added, heating stirring reaction obtains modified meerschaum dispersion liquid；After sodium alginate and water are then mixed swelling, heating stirring dissolving adds sodium metaperiodate, and heating stirring reaction obtains modified sodium alginate dispersion liquid；Again by itself and cellulose dispersion liquid, the raw materials such as modified meerschaum dispersion liquid stir to form homogeneous phase solution, cooling after homogeneous phase solution is hot pressed into plate membrane, stretch, dry, take off film to get Organic-inorganic composite lithium battery diaphragm.Gained Organic-inorganic composite lithium battery diaphragm of the invention has excellent mechanical property and thermal stability.
Description
Technical field
The invention discloses a kind of preparation methods of Organic-inorganic composite lithium battery diaphragm, belong to new energy battery material
Technical field.
Background technology
Lithium ion battery is widely used to 3C Product（Refer to computer, communication, consumer electronics product）It is common mobile
Power supply.In recent years, due to haze problem getting worse, the requirement to environmental protection is higher and higher and government accelerates new energy
The guiding of the relevant policies of source development of automobile, therefore increase the demand to new-energy automobile.It is counted according to auto industry association,
It produces new-energy automobile 3.7 ten thousand in May, 2016, sells 3.5 ten thousand, compared with the same period of last year, increase by 131.3% He respectively
128.0%.Wherein, pure electric automobile production, sales volume 2.9,2.6 ten thousand, increase 177.0%, 161.6% respectively, but also will be after
The situation of rapid growth is held in continuation of insurance.Under the promotion of new-energy automobile market demand, need accelerate dynamic lithium battery development and
Its performance is further promoted, and the membrane properties as lithium battery critical material are also required to be substantially improved.Therefore, dynamic lithium battery
The study on the modification of diaphragm is concerned.
The effect of lithium ion battery separator is to separate the positive and negative anodes of battery, prevents positive and negative anodes from contacting and causing short circuit, is permitted
Perhaps ion is by without allowing electronics to pass through, to complete quick transmission of the lithium ion between positive and negative anodes in charge and discharge process.
Currently, the production technology of lithium ion battery separator mainly has dry method simple tension, dry method biaxial tension and wet processing, product master
If monolayer polyethylene（PE）Diaphragm, single-layer polypropylene（PP）Diaphragm, bilayer PP/PE diaphragms, bilayer PP/PP diaphragms, three layers of PP/
PE/PP composite diaphragms.The diaphragm material that lithium battery for automobile power uses with three layers of PP/PE/PP composite diaphragms, bilayer PP/PE every
Based on film.There is also the bad problems of mechanical property and thermal stability for traditional lithium battery diaphragm at present, thus also need to its into
Row research.
Invention content
The present invention solves the technical problem of：It is bad for traditional lithium battery diaphragm mechanical property and thermal stability
Problem provides a kind of preparation method of Organic-inorganic composite lithium battery diaphragm.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）After sepiolite mechanical crushing, sieving obtains sepiolite powder, counts in parts by weight, takes 30~40 parts of sepiolites successively
Powder, 100~200 parts of water, 8~10 parts of Tea Saponins, 10~20 parts of hydrochloric acid, after mixing, 4~6h of hydro-thermal reaction, filtering must pre-process
Sepiolite；
（2）It counts in parts by weight, takes 30~40 parts of pretreatment sepiolites, 80~120 parts of absolute ethyl alcohols, 8~10 parts of chlorinations successively
Sulfoxide, 2~4 parts of urea, 3~5 parts of plasticizer will first pre-process sepiolite ultrasonic disperse in absolute ethyl alcohol, and add chlorination
Sulfoxide, urea and plasticizer, heating stirring reaction, obtain modified meerschaum dispersion liquid；
（3）It counts in parts by weight, 30~45 parts of sodium alginates, 200~250 parts of water, 8~10 parts of sodium metaperiodates is taken first will successively
After sodium alginate and water mixing swelling, heating stirring dissolving adds sodium metaperiodate, and heating stirring reaction obtains modified alginic acid
Sodium dispersion liquid；
（4）It counts in parts by weight, takes 60~80 parts of cellulose dispersion liquids successively, 30~40 parts of modified meerschaum dispersion liquids, 50~
60 parts of modified sodium alginate dispersion liquids, 2~6 parts of polyacrylic acid zinc, 4~6 parts of antifoaming agent, under the conditions of temperature is 120~130 DEG C
Stirring forms homogeneous phase solution；
（5）The plate membrane that thickness is 8~18 μm is hot pressed under the conditions of being 160~180 DEG C in temperature by homogeneous phase solution, it is right after cooling
Plate membrane is stretched, then through drying, takes off film to get Organic-inorganic composite lithium battery diaphragm.
Step（1）The sieving was 325 mesh sieve.
Step（2）The plasticizer is dibutyl phthalate, two fourth of dioctyl phthalate and phthalic acid
Any one in benzyl ester.
Step（4）The cellulose dispersion liquid configuration process is：It is 1 in mass ratio by sodium cellulosate and water：10~1：12
After mixing, ultrasonic disperse is heated, cellulose dispersion liquid is obtained.
Step（4）The antifoaming agent is silicone emulsion, appointing in dimethyl silicone polymer or polyoxyethylene oxygen propyl alcohol amidogen ether
Meaning is a kind of.
The beneficial effects of the invention are as follows：
（1）For conventionally employed organic resin, inorganic particulate and diluent hot pressing stretch the lithium battery diaphragm being prepared,
Although its product porosity is easy to control and high-temperature stability is good, the binding force between organic resin and inorganic particulate is not
Good, product mechanical property is insufficient, and organic resin hydrophily is poor, causes the liquid holdup of product not high, and the application is based on this not
Cellulose dispersion liquid, modified meerschaum dispersion liquid and modified sodium alginate dispersion liquid are principle active component, realize production by foot
The combination of organic and inorganic particle in product, while so that product mechanical property is got a promotion, thermal stability further increases,
And the liquid holdup of product effectively improves；
（2）The present invention first carries out it mechanical crushing during sodium alginate-modified, and mechanical crushing is easy to cause sepiolite knot
More defect sturcture is generated in structure, to be conducive in drawing process, forms hole, in addition, sepiolite is chain stratiform silicon
Hydrochlorate, in preprocessing process, under the good surface-active of Tea Saponin and hydrochloric acid effect, interlamellar spacing is widened, and
Make metal ion and hydrogen ion in its interlayer structure that ion exchange occur, more active silicone hydroxyl is formed, successive modified
In the process, thionyl chloride can be reacted with the carboxyl in Tea Saponin molecular structure, form acyl chlorides, and acid chloride group is lived with higher reaction
Property, covalent bonding can be formed between sepiolite, Tea Saponin, urea and plasticizer, make four formation organic wholes, on the one hand,
Be conducive to the fine dispersion of sepiolite, on the other hand, be conducive to form chemical bond between sepiolite and cellulose and sodium alginate
It closes, to make product mechanical property effectively improve, furthermore, effective fixation of plasticizer can avoid processing and using
The loss of plasticizer in journey, enables the stability of product mechanical property to be promoted；
（3）The present invention is coordinated using modified sodium alginate and cellulose, under sodium metaperiodate effect, in sodium alginate molecular structure
Part of hydroxyl is converted to aldehyde radical, and the aldehyde radical in molecular structure is during product following process, and in cellulose molecular structure
Hydroxyl aldol condensation occurs, form hemiacetal structure, the formation of hemiacetal structure further improves the thermal stability of product
Can, and the inorganic particulate in system is effectively fixed in hemiacetal structure, so that product mechanical property is further promoted.
Specific implementation mode
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 30~40 parts of sepiolite powders successively, 100~200 parts of water, 8~10 parts of Tea Saponins, 10~20 parts of hydrochloric acid, mixing pours into water heating kettle
In, it is 170~180 DEG C in temperature, under the conditions of pressure is 1.2~1.6MPa, after 4~6h of hydro-thermal reaction, filtering must pre-process sea
Afrodite；It counts in parts by weight, takes 30~40 parts of pretreatment sepiolites, 80~120 parts of absolute ethyl alcohols, 8~10 parts of protochlorides successively
Pretreatment sepiolite and absolute ethyl alcohol are first mixed and are poured into No. 1 beaker by sulfone, 2~4 parts of urea, 3~5 parts of plasticizer, and by 1
Number beaker moves into ultrasonic disperse instrument, under the conditions of supersonic frequency is 45~60kHz, after 45~60min of ultrasonic disperse, then by No. 1
Material pours into reaction kettle in beaker, and is sequentially added into reaction kettle into thionyl chloride, urea and plasticizer, then in temperature
It it is 75~80 DEG C, under the conditions of rotating speed is 400~800r/min, heating stirring reacts 4~6h, obtains modified meerschaum dispersion liquid；It presses
Parts by weight meter, takes 30~45 parts of sodium alginates successively, 200~250 parts of water, 8~10 parts of sodium metaperiodates, first by sodium alginate and
Water pours into No. 2 beakers, after being stirred 10~20min with glass bar, is swollen 4~6h in standing under room temperature, then by No. 2
Beaker moves into digital display and tests the speed in constant temperature blender with magnetic force, in temperature be 65~75 DEG C, under the conditions of rotating speed is 400~600r/min,
Heating stirring dissolves 1~3h, and under constant temperature stirring, sodium metaperiodate is added into No. 2 beakers, continues heating stirring reaction
2~3h obtains modified sodium alginate dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：10~1：After 12 mixing, it is in temperature
65~80 DEG C, under the conditions of supersonic frequency is 55~60kHz, 45~60min of ultrasonic disperse is heated, cellulose dispersion liquid is obtained；By weight
Number meter is measured, takes 60~80 parts of cellulose dispersion liquids, 30~40 parts of modified meerschaum dispersion liquids, 50~60 parts of modified seaweed successively
Sour sodium dispersion liquid, 2~6 parts of polyacrylic acid zinc, 4~6 parts of antifoaming agent are 300~600r/min in rotating speed, and temperature is 120~130
Stirring forms homogeneous phase solution under the conditions of DEG C, then by homogeneous phase solution be 160~180 DEG C in temperature under the conditions of be hot pressed into thickness be 8~
18 μm of plate membrane, and be cooled to room temperature to tablet film surface flushing liquor nitrogen, then plate membrane after cooling is stretched, it controls
It is 0.8~1.9 μm to stretch rear plate film thickness, then the plate membrane after stretching is placed in baking oven, is dried under vacuum to constant weight, takes off
Film is to get Organic-inorganic composite lithium battery diaphragm.The plasticizer is dibutyl phthalate, dioctyl phthalate
With any one in two butyl benzyl of phthalic acid.The antifoaming agent is silicone emulsion, dimethyl silicone polymer or polyoxyethylene
Any one in oxygen propyl alcohol amidogen ether.
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 40 parts of sepiolite powders successively, 200 parts of water, 10 parts of Tea Saponins, 20 parts of hydrochloric acid, mixing pours into water heating kettle, in temperature be 180
DEG C, under the conditions of pressure is 1.6MPa, after hydro-thermal reaction 6h, filtering obtains pretreatment sepiolite；It counts in parts by weight, takes 40 successively
Part pretreatment sepiolite, 120 parts of absolute ethyl alcohols, 10 parts of thionyl chlorides, 4 parts of urea, 5 parts of plasticizer will first pre-process sepiolite
Poured into No. 1 beaker with absolute ethyl alcohol mixing, and No. 1 beaker moved into ultrasonic disperse instrument, in supersonic frequency be 60kHz conditions
Under, after ultrasonic disperse 60min, then material in No. 1 beaker poured into reaction kettle, and sequentially added into reaction kettle into protochloride
Sulfone, urea and plasticizer are then 80 DEG C in temperature, and under the conditions of rotating speed is 800r/min, heating stirring reacts 6h, must be modified sea
Afrodite dispersion liquid；It counts in parts by weight, takes 45 parts of sodium alginates, 250 parts of water, 10 parts of sodium metaperiodates, first by sodium alginate successively
It is poured into No. 2 beakers with water, after being stirred 20min with glass bar, in standing swelling 6h under room temperature, then by No. 2 beakers
Immigration digital display tests the speed in constant temperature blender with magnetic force, is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, heating stirring dissolves
Sodium metaperiodate is added into No. 2 beakers under constant temperature stirring by 3h, continues heating stirring and reacts 3h, obtains modified alginic acid
Sodium dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：It it is 80 DEG C in temperature, supersonic frequency is 60kHz conditions after 12 mixing
Under, ultrasonic disperse 60min is heated, cellulose dispersion liquid is obtained；It counts in parts by weight, takes 80 parts of cellulose dispersion liquids successively, 40 parts
Modified meerschaum dispersion liquid, 60 parts of modified sodium alginate dispersion liquids, 6 parts of polyacrylic acid zinc, 6 parts of antifoaming agent, in rotating speed be 600r/
Min, under the conditions of temperature is 130 DEG C stirring form homogeneous phase solution, then by homogeneous phase solution be 180 DEG C in temperature under the conditions of be hot pressed into thickness
Degree is 18 μm of plate membrane, and is cooled to room temperature to tablet film surface flushing liquor nitrogen, then plate membrane after cooling is stretched,
It is 1.9 μm that control, which stretches rear plate film thickness, then the plate membrane after stretching is placed in baking oven, is dried under vacuum to constant weight, takes off film,
Up to Organic-inorganic composite lithium battery diaphragm.The plasticizer is dibutyl phthalate.The antifoaming agent is emulsification silicon
Oil.
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 40 parts of sepiolite powders successively, 200 parts of water, 10 parts of Tea Saponins, 20 parts of hydrochloric acid, mixing pours into water heating kettle, in temperature be 180
DEG C, under the conditions of pressure is 1.6MPa, after hydro-thermal reaction 6h, filtering obtains pretreatment sepiolite；It counts in parts by weight, takes 45 successively
Part sodium alginate, 250 parts of water, 10 parts of sodium metaperiodates first pour into sodium alginate and water in No. 2 beakers, are stirred with glass bar mixed
After closing 20min, in standing swelling 6h under room temperature, then No. 2 beakers is moved into digital displays and are tested the speed in constant temperature blender with magnetic force, Yu Wen
Degree is 75 DEG C, and under the conditions of rotating speed is 600r/min, heating stirring dissolves 3h, under constant temperature stirring, is added into No. 2 beakers
Enter sodium metaperiodate, continues heating stirring and react 3h, obtain modified sodium alginate dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：
After 12 mixing, it is 80 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, heats ultrasonic disperse 60min, obtain cellulose dispersion liquid；
It counts in parts by weight, takes 80 parts of cellulose dispersion liquids successively, 40 parts of pretreatment sepiolites, 60 parts of modified sodium alginate dispersion liquids, 6
Part polyacrylic acid zinc, 6 parts of antifoaming agent are 600r/min in rotating speed, and temperature stirs under the conditions of being 130 DEG C and forms homogeneous phase solution, then
It is hot pressed into the plate membrane that thickness is 18 μm under the conditions of being 180 DEG C in temperature by homogeneous phase solution, and to tablet film surface flushing liquor nitrogen
It is cooled to room temperature, then plate membrane after cooling is stretched, it is 1.9 μm that control, which stretches rear plate film thickness, then will be after stretching
Plate membrane be placed in baking oven, be dried under vacuum to constant weight, take off film to get Organic-inorganic composite lithium battery diaphragm.The plasticizer
For dibutyl phthalate.The antifoaming agent is silicone emulsion.
It counts in parts by weight, takes 45 parts of sodium alginates, 250 parts of water, 10 parts of sodium metaperiodates, first by sodium alginate and water successively
It pours into No. 2 beakers, after being stirred 20min with glass bar, is swollen 6h in standing under room temperature, then No. 2 beakers are moved into
Digital display tests the speed in constant temperature blender with magnetic force, is 75 DEG C in temperature, and under the conditions of rotating speed is 600r/min, heating stirring dissolves 3h, then
Under constant temperature stirring, sodium metaperiodate is added into No. 2 beakers, continues heating stirring and reacts 3h, obtain modified sodium alginate point
Dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：After 12 mixing, it is 80 DEG C in temperature, under the conditions of supersonic frequency is 60kHz, adds
Hot ultrasonic disperse 60min, obtains cellulose dispersion liquid；It counts in parts by weight, takes 80 parts of cellulose dispersion liquids, 40 parts of Hai Pao successively
Stone, 60 parts of modified sodium alginate dispersion liquids, 6 parts of polyacrylic acid zinc, 6 parts of antifoaming agent, in rotating speed be 600r/min, temperature 130
Stirring forms homogeneous phase solution under the conditions of DEG C, then by homogeneous phase solution be 180 DEG C in temperature under the conditions of to be hot pressed into thickness be 18 μm flat
Plate film, and be cooled to room temperature to tablet film surface flushing liquor nitrogen, then plate membrane after cooling is stretched, control is put down after stretching
Plate film thickness is 1.9 μm, then the plate membrane after stretching is placed in baking oven, is dried under vacuum to constant weight, takes off film to get organic-nothing
Machine composite lithium battery membrane.The plasticizer is dibutyl phthalate.The antifoaming agent is silicone emulsion.
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 40 parts of sepiolite powders successively, 200 parts of water, 10 parts of Tea Saponins, 20 parts of hydrochloric acid, mixing pours into water heating kettle, in temperature be 180
DEG C, under the conditions of pressure is 1.6MPa, after hydro-thermal reaction 6h, filtering obtains pretreatment sepiolite；It counts in parts by weight, takes 40 successively
Part pretreatment sepiolite, 120 parts of absolute ethyl alcohols, 10 parts of thionyl chlorides, 4 parts of urea, 5 parts of plasticizer will first pre-process sepiolite
Poured into No. 1 beaker with absolute ethyl alcohol mixing, and No. 1 beaker moved into ultrasonic disperse instrument, in supersonic frequency be 60kHz conditions
Under, after ultrasonic disperse 60min, then material in No. 1 beaker poured into reaction kettle, and sequentially added into reaction kettle into protochloride
Sulfone, urea and plasticizer are then 80 DEG C in temperature, and under the conditions of rotating speed is 800r/min, heating stirring reacts 6h, must be modified sea
Afrodite dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：It it is 80 DEG C in temperature, supersonic frequency is 60kHz items after 12 mixing
Under part, ultrasonic disperse 60min is heated, cellulose dispersion liquid is obtained；It counts in parts by weight, takes 80 parts of cellulose dispersion liquids successively, 40
Part modified meerschaum dispersion liquid, 6 parts of polyacrylic acid zinc, 6 parts of antifoaming agent, in rotating speed be 600r/min, under the conditions of temperature is 130 DEG C
Stirring forms homogeneous phase solution, then by homogeneous phase solution be 180 DEG C in temperature under the conditions of be hot pressed into the plate membrane that thickness is 18 μm, and to
Tablet film surface flushing liquor nitrogen is cooled to room temperature, then plate membrane after cooling is stretched, and control stretches rear plate film thickness
It is 1.9 μm, then the plate membrane after stretching is placed in baking oven, be dried under vacuum to constant weight, takes off film to get Organic-inorganic composite lithium
Battery diaphragm.The plasticizer is dibutyl phthalate.The antifoaming agent is silicone emulsion.
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 40 parts of sepiolite powders successively, 200 parts of water, 10 parts of Tea Saponins, 20 parts of hydrochloric acid, mixing pours into water heating kettle, in temperature be 180
DEG C, under the conditions of pressure is 1.6MPa, after hydro-thermal reaction 6h, filtering obtains pretreatment sepiolite；It counts in parts by weight, takes 40 successively
Part pretreatment sepiolite, 120 parts of absolute ethyl alcohols, 10 parts of thionyl chlorides, 4 parts of urea, 5 parts of plasticizer will first pre-process sepiolite
Poured into No. 1 beaker with absolute ethyl alcohol mixing, and No. 1 beaker moved into ultrasonic disperse instrument, in supersonic frequency be 60kHz conditions
Under, after ultrasonic disperse 60min, then material in No. 1 beaker poured into reaction kettle, and sequentially added into reaction kettle into protochloride
Sulfone, urea and plasticizer are then 80 DEG C in temperature, and under the conditions of rotating speed is 800r/min, heating stirring reacts 6h, must be modified sea
Afrodite dispersion liquid；It counts in parts by weight, takes 45 parts of sodium alginates, 250 parts of water that sodium alginate and water are first poured into No. 2 burnings successively
In cup, after being stirred 20min with glass bar, in standing swelling 6h under room temperature, then No. 2 beakers is moved into digital displays and are tested the speed perseverance
It it is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, heating stirring dissolves 3h, obtains modified alginic acid in warm magnetic stirring apparatus
Sodium dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：It it is 80 DEG C in temperature, supersonic frequency is 60kHz conditions after 12 mixing
Under, ultrasonic disperse 60min is heated, cellulose dispersion liquid is obtained；It counts in parts by weight, takes 80 parts of cellulose dispersion liquids successively, 40 parts
Modified meerschaum dispersion liquid, 60 parts of modified sodium alginate dispersion liquids, 6 parts of polyacrylic acid zinc, 6 parts of antifoaming agent, in rotating speed be 600r/
Min, under the conditions of temperature is 130 DEG C stirring form homogeneous phase solution, then by homogeneous phase solution be 180 DEG C in temperature under the conditions of be hot pressed into thickness
Degree is 18 μm of plate membrane, and is cooled to room temperature to tablet film surface flushing liquor nitrogen, then plate membrane after cooling is stretched,
It is 1.9 μm that control, which stretches rear plate film thickness, then the plate membrane after stretching is placed in baking oven, is dried under vacuum to constant weight, takes off film,
Up to Organic-inorganic composite lithium battery diaphragm.The plasticizer is dibutyl phthalate.The antifoaming agent is emulsification silicon
Oil.
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 40 parts of sepiolite powders successively, 200 parts of water, 10 parts of Tea Saponins, 20 parts of hydrochloric acid, mixing pours into water heating kettle, in temperature be 180
DEG C, under the conditions of pressure is 1.6MPa, after hydro-thermal reaction 6h, filtering obtains pretreatment sepiolite；It counts in parts by weight, takes 40 successively
Part pretreatment sepiolite, 120 parts of absolute ethyl alcohols, 10 parts of thionyl chlorides, 4 parts of urea, 5 parts of plasticizer will first pre-process sepiolite
Poured into No. 1 beaker with absolute ethyl alcohol mixing, and No. 1 beaker moved into ultrasonic disperse instrument, in supersonic frequency be 60kHz conditions
Under, after ultrasonic disperse 60min, then material in No. 1 beaker poured into reaction kettle, and sequentially added into reaction kettle into protochloride
Sulfone, urea and plasticizer are then 80 DEG C in temperature, and under the conditions of rotating speed is 800r/min, heating stirring reacts 6h, must be modified sea
Afrodite dispersion liquid；It counts in parts by weight, takes 45 parts of sodium alginates, 250 parts of water, 10 parts of sodium metaperiodates, first by sodium alginate successively
It is poured into No. 2 beakers with water, after being stirred 20min with glass bar, in standing swelling 6h under room temperature, then by No. 2 beakers
Immigration digital display tests the speed in constant temperature blender with magnetic force, is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, heating stirring dissolves
Sodium metaperiodate is added into No. 2 beakers under constant temperature stirring by 3h, continues heating stirring and reacts 3h, obtains modified alginic acid
Sodium dispersion liquid；It is 1 in mass ratio by sodium cellulosate and water：It it is 80 DEG C in temperature, supersonic frequency is 60kHz conditions after 12 mixing
Under, ultrasonic disperse 60min is heated, cellulose dispersion liquid is obtained；It counts in parts by weight, takes 80 parts of cellulose dispersion liquids successively, 40 parts
Modified meerschaum dispersion liquid, 60 parts of modified sodium alginate dispersion liquids, 6 parts of antifoaming agent, in rotating speed be 600r/min, temperature 130
Stirring forms homogeneous phase solution under the conditions of DEG C, then by homogeneous phase solution be 180 DEG C in temperature under the conditions of to be hot pressed into thickness be 18 μm flat
Plate film, and be cooled to room temperature to tablet film surface flushing liquor nitrogen, then plate membrane after cooling is stretched, control is put down after stretching
Plate film thickness is 1.9 μm, then the plate membrane after stretching is placed in baking oven, is dried under vacuum to constant weight, takes off film to get organic-nothing
Machine composite lithium battery membrane.The plasticizer is dibutyl phthalate.The antifoaming agent is silicone emulsion.
Sepiolite is poured into pulverizer, after mechanical crushing, 325 mesh sieve is crossed, obtains sepiolite powder, then count in parts by weight,
Take 40 parts of sepiolite powders successively, 200 parts of water, 10 parts of Tea Saponins, 20 parts of hydrochloric acid, mixing pours into water heating kettle, in temperature be 180
DEG C, under the conditions of pressure is 1.6MPa, after hydro-thermal reaction 6h, filtering obtains pretreatment sepiolite；It counts in parts by weight, takes 40 successively
Part pretreatment sepiolite, 120 parts of absolute ethyl alcohols, 10 parts of thionyl chlorides, 4 parts of urea, 5 parts of plasticizer will first pre-process sepiolite
Poured into No. 1 beaker with absolute ethyl alcohol mixing, and No. 1 beaker moved into ultrasonic disperse instrument, in supersonic frequency be 60kHz conditions
Under, after ultrasonic disperse 60min, then material in No. 1 beaker poured into reaction kettle, and sequentially added into reaction kettle into protochloride
Sulfone, urea and plasticizer are then 80 DEG C in temperature, and under the conditions of rotating speed is 800r/min, heating stirring reacts 6h, must be modified sea
Afrodite dispersion liquid；It counts in parts by weight, takes 45 parts of sodium alginates, 250 parts of water, 10 parts of sodium metaperiodates, first by sodium alginate successively
It is poured into No. 2 beakers with water, after being stirred 20min with glass bar, in standing swelling 6h under room temperature, then by No. 2 beakers
Immigration digital display tests the speed in constant temperature blender with magnetic force, is 75 DEG C in temperature, under the conditions of rotating speed is 600r/min, heating stirring dissolves
Sodium metaperiodate is added into No. 2 beakers under constant temperature stirring by 3h, continues heating stirring and reacts 3h, obtains modified alginic acid
Sodium dispersion liquid；It is 1 in mass ratio by cellulose and water：12 mixing after, in temperature be 80 DEG C, supersonic frequency be 60kHz under the conditions of,
Ultrasonic disperse 60min is heated, cellulose dispersion liquid is obtained；It counts in parts by weight, takes 80 parts of cellulose dispersion liquids, 40 parts of modifications successively
Sepiolite dispersion liquid, 60 parts of modified sodium alginate dispersion liquids, 6 parts of polyacrylic acid zinc, 6 parts of antifoaming agent, in rotating speed be 600r/min,
Stirring forms homogeneous phase solution under the conditions of temperature is 130 DEG C, then by homogeneous phase solution be 180 DEG C in temperature under the conditions of be hot pressed into thickness and be
18 μm of plate membrane, and be cooled to room temperature to tablet film surface flushing liquor nitrogen, then plate membrane after cooling is stretched, it controls
It is 1.9 μm to stretch rear plate film thickness, then the plate membrane after stretching is placed in baking oven, and constant weight is dried under vacuum to, take off film to get
Organic-inorganic composite lithium battery diaphragm.The plasticizer is dibutyl phthalate.The antifoaming agent is silicone emulsion.
Comparative example：The lithium battery diaphragm of Environmental Protection Technology Co., Ltd of Shenzhen production.
1 to 7 gained lithium battery diaphragm of example and comparative example product are subjected to performance detection, specific testing result such as 1 institute of table
Show：
Table 1：Performance detection table
| Detection content | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative example |
| Longitudinal fracture intensity/MPa | 167 | 134 | 138 | 141 | 132 | 143 | 135 | 100 |
| Cross-breaking strength/MPa | 14 | 11 | 10 | 11 | 10 | 12 | 11 | 8 |
| Elongation at break/% | 82 | 68 | 65 | 70 | 72 | 71 | 68 | 50 |
| Percent thermal shrinkage/% | 2.1 | 3.5 | 3.2 | 3.4 | 3.4 | 3.2 | 3.5 | 4.8 |
By 1 testing result of table it is found that present invention gained Organic-inorganic composite lithium battery diaphragm has excellent mechanical property and heat
Stability.
Claims (5)
1. a kind of preparation method of Organic-inorganic composite lithium battery diaphragm, it is characterised in that specifically preparation process is；
（1）After sepiolite mechanical crushing, sieving obtains sepiolite powder, counts in parts by weight, takes 30~40 parts of sepiolites successively
Powder, 100~200 parts of water, 8~10 parts of Tea Saponins, 10~20 parts of hydrochloric acid, after mixing, 4~6h of hydro-thermal reaction, filtering must pre-process
Sepiolite；
（2）It counts in parts by weight, takes 30~40 parts of pretreatment sepiolites, 80~120 parts of absolute ethyl alcohols, 8~10 parts of chlorinations successively
Sulfoxide, 2~4 parts of urea, 3~5 parts of plasticizer will first pre-process sepiolite ultrasonic disperse in absolute ethyl alcohol, and add chlorination
Sulfoxide, urea and plasticizer, heating stirring reaction, obtain modified meerschaum dispersion liquid；
（3）It counts in parts by weight, 30~45 parts of sodium alginates, 200~250 parts of water, 8~10 parts of sodium metaperiodates is taken first will successively
After sodium alginate and water mixing swelling, heating stirring dissolving adds sodium metaperiodate, and heating stirring reaction obtains modified alginic acid
Sodium dispersion liquid；
（4）It counts in parts by weight, takes 60~80 parts of cellulose dispersion liquids successively, 30~40 parts of modified meerschaum dispersion liquids, 50~
60 parts of modified sodium alginate dispersion liquids, 2~6 parts of polyacrylic acid zinc, 4~6 parts of antifoaming agent, under the conditions of temperature is 120~130 DEG C
Stirring forms homogeneous phase solution；
（5）The plate membrane that thickness is 8~18 μm is hot pressed under the conditions of being 160~180 DEG C in temperature by homogeneous phase solution, it is right after cooling
Plate membrane is stretched, then through drying, takes off film to get Organic-inorganic composite lithium battery diaphragm.
2. a kind of preparation method of Organic-inorganic composite lithium battery diaphragm according to claim 1, which is characterized in that step
Suddenly（1）The sieving was 325 mesh sieve.
3. a kind of preparation method of Organic-inorganic composite lithium battery diaphragm according to claim 1, which is characterized in that step
Suddenly（2）The plasticizer is dibutyl phthalate, arbitrary in two butyl benzyl of dioctyl phthalate and phthalic acid
It is a kind of.
4. a kind of preparation method of Organic-inorganic composite lithium battery diaphragm according to claim 1, which is characterized in that step
Suddenly（4）The cellulose dispersion liquid configuration process is：It is 1 in mass ratio by sodium cellulosate and water：10~1：After 12 mixing, heating
Ultrasonic disperse obtains cellulose dispersion liquid.
5. a kind of preparation method of Organic-inorganic composite lithium battery diaphragm according to claim 1, which is characterized in that step
Suddenly（4）The antifoaming agent is silicone emulsion, any one in dimethyl silicone polymer or polyoxyethylene oxygen propyl alcohol amidogen ether.
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