CN109244331A - A kind of preparation method of lithium ion battery separator - Google Patents
A kind of preparation method of lithium ion battery separator Download PDFInfo
- Publication number
- CN109244331A CN109244331A CN201811142760.0A CN201811142760A CN109244331A CN 109244331 A CN109244331 A CN 109244331A CN 201811142760 A CN201811142760 A CN 201811142760A CN 109244331 A CN109244331 A CN 109244331A
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- China
- Prior art keywords
- polycarbonate
- ptfe
- polytetrafluoroethylene
- ion battery
- lithium ion
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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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to a kind of lithium ion battery separator, which is polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane；Based on mass fraction, polytetrafluoroethylene (PTFE) 70%~95% is contained in polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane, contains polycarbonate 5%~30%；The polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane is prepared by method of electrostatic spinning, weighs polytetrafluoroethylene (PTFE) and polycarbonate, stirring and dissolving is in DMF；It takes appropriate solution to carry out electrostatic spinning and polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane is made.With cellular structure abundant and higher porosity, there is good gas permeability, conducive to the absorption and holding of electrolyte, and be conducive to transmission of the ion in diaphragm, improve the efficiency for charge-discharge of lithium ion battery.Therefore, lithium ion battery separator of the invention shows excellent gas permeability and thermal stability, significantly improves the compatibility with electrolyte, more excellent to the contact angle and imbibition rate of electrolyte.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of preparation method of lithium ion battery separator.
Background technique
Lithium ion battery (LIBs) has voltage height, specific energy height, service life length, memory-less effect, environmental-friendly, charging speed
The advantages such as degree is fast, self-discharge rate is low, already become of greatest concern, the highest consumer battery kind of yield at present.Lithium-ion electric
Pond diaphragm has the important function for avoiding the contact of battery positive and negative electrode, possessing electrolyte, lithium ion being allowed to pass through, and performance can be right
The chemical property of lithium ion battery has an immense impact on.Therefore, battery diaphragm researched and developed, improve membrane properties general
It is a pith of the following lithium ion battery development.
Diaphragm used in lithium ion battery should have the characteristic of electronic isolation and electrolyte ion conductor simultaneously, and necessary
Have good mechanical property and chemistry, electrochemical stability, and can be protected always during the iterative cycles of charge and discharge
It holds to good wellability of electrolyte etc..Although diaphragm will not influence energy storage and the output of battery, but diaphragm is to battery
Interfacial structure, internal resistance, capacity, circulation and safety suffer from vital effect.At present business lithium battery diaphragm apply than
Wide is MIcroporous polyolefin film, and such as polyethylene and polypropylene diaphragm, but the thermal stability of this diaphragm is poor, wetability,
Porosity and the absorptivity of electrolyte etc. are all relatively low, and there are security risks, are insufficient for the requirement of people.
Chinese invention patent 201410147627X discloses a kind of preparation side of polyimide nano lithium ion battery separator
Method, including prepare polyamic acid solution and its melt, then by obtained melt through melt spinning, recrystallization, cold and hot stretching and
The series of process such as thermal finalization handle to obtain product, have excellent electrochemical stability and thermal contraction performance.But the invention needs
Strict control diaphragm preparation-fusion drawn technological parameter and condition are wanted, brings difficulty in actual operation.
Chinese invention patent 201610363502X discloses a kind of preparation method of diaphragm for lithium ion battery, by poly- second
Alkene, polycarbonate, maleic resin, hydroxyethyl methacrylate, titanium dioxide, polylactic acid, polycyclic lactone and plasticising
Agent heating stirring, film extrusion obtain base film；It is then immersed in by hydroxypropyl methylcellulose, polyethylene glycol, white carbon black and oxidation
In the mixed solution of zirconium composition；Obtain diaphragm for lithium ion battery；Raw material and auxiliary agent needed for this method are many kinds of, but only mention
The high mechanical performance and electric property of product.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of preparation method of lithium ion battery separator is provided,
Can while realizing that diaphragm thermal stability improves gas permeability with higher, the imbibition rate of wetability and electrolyte, it is comprehensive
Conjunction is had excellent performance, and can be widely applied for meeting higher requirement in lithium ion battery, and this method is easy to operate, is convenient for
Industrialized production.
The present invention provides a kind of preparation method of lithium ion battery separator, which is polytetrafluoroethylene (PTFE)/polycarbonate
Composite cellulosic membrane is prepared by following steps:
7.0g~9.0g polytetrafluoroethylene (PTFE) and 0.5g~3.0g polycarbonate are weighed, stirring and dissolving is in 60g~100g DMF
In；Take appropriate solution to carry out electrostatic spinning, electrospinning parameters are as follows: spinning voltage 20kV, propulsion rate are 0.02mL/
Min, it is 20cm, syringe needle 8# that spinning, which receives distance, and polytetrafluoroethylene (PTFE)/poly- carbonic acid is made in spinning 4-12h at room temperature
Ester composite cellulosic membrane.
In the present invention, based on mass fraction, polytetrafluoroethylene (PTFE) is contained in the polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane
70%~95%, contain polycarbonate 5%~30%.
In the present invention, the polycarbonate is aromatic copolycarbonate.
Preferably, polycarbonate is selected from bisphenol-a polycarbonate, tetrachlorobisphenol A polycarbonate, tetrabromobisphenol a polycarbonate
One of.
The object of the invention is also to provide the above methods to prepare the application in lithium ion battery separator.
The present invention is prepared for polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane by method of electrostatic spinning, has hole abundant
Road structure and higher porosity have good gas permeability, conducive to the absorption and holding of electrolyte, and are conducive to ion and exist
Transmission in diaphragm improves the efficiency for charge-discharge of lithium ion battery.The polytetrafluoroethylene (PTFE) that the present invention uses has thermal stability
Good advantage.In addition, the polycarbonate that the present invention uses has the effect of fire-retardant, while polycarbonate and lithium ion battery are electrolysed
Liquid compatibility with higher, by polycarbonate and it is polytetrafluoroethylblended blended after prepare diaphragm, keep diaphragm thermal stability it is good
While, electrolyte is significantly reduced in the contact angle of membrane surface, is significantly improved between diaphragm and lithium-ion battery electrolytes
Compatibility, and effectively increase diaphragm to guarantor's liquid rate of electrolyte.
Compared with prior art, technical solution of the present invention has the following advantages that and improves:
The preparation method simple process of lithium ion battery separator provided by the invention, it is easily operated, the lithium being prepared from
Sub- battery separator shows excellent gas permeability, compatibility and thermal stability with electrolyte, significantly improves conventional membrane
Compatibility between lithium-ion battery electrolytes is more excellent to the contact angle and imbibition rate of electrolyte.
Specific embodiment
Embodiment of the present invention is described in detail below with reference to embodiment, actual conditions are not specified in embodiment
Person carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument are that can be obtained by commercially available purchase
Conventional products.
Embodiment 1
7.0g polytetrafluoroethylene (PTFE) and 3.0g tetrachlorobisphenol A polycarbonate are weighed, stirring and dissolving is in 80g DMF；It takes appropriate
Solution carries out electrostatic spinning, and electrospinning parameters are as follows: spinning voltage 20kV, propulsion rate are 0.02mL/min, and spinning connects
Receiving distance is 20cm, syringe needle 8#, and polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane is made in spinning 6h at room temperature.
Embodiment 2
8.3g polytetrafluoroethylene (PTFE) and 1.7g bisphenol-a polycarbonate are weighed, stirring and dissolving is in 60g DMF；Take appropriate solution
Carry out electrostatic spinning, electrospinning parameters are as follows: spinning voltage 20kV, propulsions rate are 0.02mL/min, spinning reception away from
From for 20cm, syringe needle 8#, polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane is made in spinning 4h at room temperature.
Embodiment 3
9.5g polytetrafluoroethylene (PTFE) and 0.5g tetrabromobisphenol a polycarbonate are weighed, stirring and dissolving is in 100g DMF；It takes appropriate
Solution carries out electrostatic spinning, and electrospinning parameters are as follows: spinning voltage 20kV, propulsion rate are 0.02mL/min, and spinning connects
Receiving distance is 20cm, syringe needle 8#, and polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane is made in spinning 12h at room temperature.
Embodiment 1
9.0g polytetrafluoroethylene (PTFE) and 1.0g tetrachlorobisphenol A polycarbonate are weighed, stirring and dissolving is in 80g DMF；It takes appropriate
Solution carries out electrostatic spinning, and electrospinning parameters are as follows: spinning voltage 20kV, propulsion rate are 0.02mL/min, and spinning connects
Receiving distance is 20cm, syringe needle 8#, and polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane is made in spinning 10h at room temperature.
Comparative example 1
7.0g Teflon stir is weighed to be dissolved in 80g DMF；Appropriate solution is taken to carry out electrostatic spinning, electrostatic spinning
Parameter is as follows: spinning voltage 20kV, and propulsion rate is 0.02mL/min, and it is 20cm that spinning, which receives distance, and syringe needle is
8#, polytetrafluoroethylfiber fiber film is made in spinning 6h at room temperature；As lithium ion battery separator.
Membrane properties test
To diaphragm provided by diaphragm provided by the commercial diaphragm of U.S. Celgard 2400, comparative example 1, Examples 1 to 4
It is tested for the property, including gas permeability, contact angle, imbibition rate, percent thermal shrinkage, the results are shown in Table 1.Contact angle and imbibition rate test are adopted
Electrolyte is lithium hexafluorophosphate electrolyte solution, consisting of the volume ratio of ethylene carbonate and diethyl carbonate is l:1, wherein
Dissolve the lithium hexafluoro phosphate of 1mol/L.Percent thermal shrinkage test tests 30min at 200 DEG C.
1 membrane properties test result of table
As seen from the results in Table 1, polytetrafluoroethylene (PTFE) prepared by the present invention/polycarbonate composite cellulosic membrane is used as lithium ion battery
Diaphragm shows excellent gas permeability, compatibility and thermal stability with electrolyte.The polytetrafluoroethylene (PTFE) provided with comparative example 1
Battery diaphragm is compared, and polytetrafluoroethylene (PTFE) provided by the invention/polycarbonate composite cellulosic membrane containing polycarbonate due to significantly mentioning
The high compatibility between lithium-ion battery electrolytes is more excellent to the contact angle and imbibition rate of electrolyte.
Claims (5)
1. a kind of preparation method of lithium ion battery separator, which is characterized in that the diaphragm is that polytetrafluoroethylene (PTFE)/polycarbonate is multiple
Condensating fiber film, is prepared by following steps:
7.0g~9.0g polytetrafluoroethylene (PTFE) and 0.5g~3.0g polycarbonate are weighed, stirring and dissolving is in 60g~100gDMF；It takes
Appropriate solution carries out electrostatic spinning, and electrospinning parameters are as follows: spinning voltage 20kV, and propulsion rate is 0.02mL/min, spins
It is 20cm, syringe needle 8# that silk, which receives distance, and it is compound that polytetrafluoroethylene (PTFE)/polycarbonate is made in spinning 4-12h at room temperature
Tunica fibrosa.
2. a kind of preparation method of lithium ion battery separator according to claim 1, which is characterized in that with mass fraction
It counts, polytetrafluoroethylene (PTFE) 70%~95% is contained in the polytetrafluoroethylene (PTFE)/polycarbonate composite cellulosic membrane, containing polycarbonate 5%~
30%.
3. a kind of preparation method of lithium ion battery separator according to claim 1, which is characterized in that the polycarbonate
For aromatic copolycarbonate.
4. a kind of preparation method of lithium ion battery separator according to claim 3, which is characterized in that the polycarbonate
Selected from one of bisphenol-a polycarbonate, tetrachlorobisphenol A polycarbonate, tetrabromobisphenol a polycarbonate.
5. any one of claim 1-4 the method is preparing the application in lithium ion battery separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811142760.0A CN109244331A (en) | 2018-09-28 | 2018-09-28 | A kind of preparation method of lithium ion battery separator |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811142760.0A CN109244331A (en) | 2018-09-28 | 2018-09-28 | A kind of preparation method of lithium ion battery separator |
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| Publication Number | Publication Date |
|---|---|
| CN109244331A true CN109244331A (en) | 2019-01-18 |
Family
ID=65054425
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811142760.0A Pending CN109244331A (en) | 2018-09-28 | 2018-09-28 | A kind of preparation method of lithium ion battery separator |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453372A (en) * | 2019-08-01 | 2019-11-15 | 合肥国轩高科动力能源有限公司 | Composite diaphragm and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5250544A (en) * | 1975-10-20 | 1977-04-22 | Nitto Electric Ind Co | Secondary battery separator |
| CN1930344A (en) * | 2004-03-12 | 2007-03-14 | 三菱制纸株式会社 | Heat resistant non-woven fabric |
| CN203659968U (en) * | 2013-12-20 | 2014-06-18 | 襄阳锦翔光电科技股份有限公司 | Lithium ion battery composite diaphragm with high liquid absorptivity |
| CN102779964B (en) * | 2012-08-08 | 2015-03-04 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN105970484A (en) * | 2016-05-27 | 2016-09-28 | 江西先材纳米纤维科技有限公司 | PTFE/PI composite-nanometer-fiber porous membrane and preparing method thereof |
-
2018
- 2018-09-28 CN CN201811142760.0A patent/CN109244331A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5250544A (en) * | 1975-10-20 | 1977-04-22 | Nitto Electric Ind Co | Secondary battery separator |
| CN1930344A (en) * | 2004-03-12 | 2007-03-14 | 三菱制纸株式会社 | Heat resistant non-woven fabric |
| CN102779964B (en) * | 2012-08-08 | 2015-03-04 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN203659968U (en) * | 2013-12-20 | 2014-06-18 | 襄阳锦翔光电科技股份有限公司 | Lithium ion battery composite diaphragm with high liquid absorptivity |
| CN105970484A (en) * | 2016-05-27 | 2016-09-28 | 江西先材纳米纤维科技有限公司 | PTFE/PI composite-nanometer-fiber porous membrane and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453372A (en) * | 2019-08-01 | 2019-11-15 | 合肥国轩高科动力能源有限公司 | Composite diaphragm and preparation method and application thereof |
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Application publication date: 20190118 |
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