CN109065809A - A kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material - Google Patents
A kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material Download PDFInfo
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- CN109065809A CN109065809A CN201810907255.4A CN201810907255A CN109065809A CN 109065809 A CN109065809 A CN 109065809A CN 201810907255 A CN201810907255 A CN 201810907255A CN 109065809 A CN109065809 A CN 109065809A
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- lithium ion
- diaphragm
- diatomite
- parts
- diatomaceous earth
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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
- H01M50/431—Inorganic 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)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to a kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material, belongs to diaphragm material field.The present invention is first heat-treated diatomaceous earth sample, improve the porosity of diatomite, activated diatomaceous earth surface functional group, it again disperses activated diatomaceous earth and basalt chopped fiber, modifying agent, segregation vinyl fluoride (PVDF) in N-N dimethylformamide (DMF) solvent, phase transfer method is recycled to obtain the diaphragm material that porosity is big, liquid absorption amount is big.The filling of diatomite effectively can inhibit PVDF to crystallize, and promote diaphragm pore-forming.Meanwhile the diatomite of porous structure can enough produce the porous structure that duct is flourishing, porosity is high in PVDF matrix, to promote lithium ion in transmission wherein, reduce the internal resistance of cell, improve the high rate performance and cycle performance of battery.The preparation method that the present invention illustrates is simple, equipment requirement is not high, cost of material is lower, has the stronger market competitiveness.
Description
Technical field:
The invention belongs to lithium ion battery separator technical field, it is related to a kind of high temperature resistant, is suitble to the dynamic of high current charge-discharge
Power type lithium ion battery separator and preparation method thereof.
Background technique:
Segregation vinyl fluoride (PVDF) is the second largest fluorine material for being only second to polytetrafluoroethylene (PTFE), because having excellent film forming
Energy, higher thermal stability and chemical stability make it one of polymer for preparing lithium ion battery separator most advantage.
But since PVDF has the stronger crystallization trend microcellular structure easy to form containing spherocrystal, biggish cavity is formed between spherocrystal,
Thus there are limitations in terms of PVDF diaphragm micro-hole structure control.Inorganic additive is added in PVDF film forming procedure, it can
The crystallinity of PVDF is effectively reduced, helps to obtain asymmetric or anisotropic microcellular structure.Such as Chinese patent
CN106784534A discloses the preparation method of a kind of PVDF and its copolymer ceramic coating membrane.The use of ceramic packing reduces
The crystallinity of PVDF, while improving the imbibition rate of diaphragm.For another example Chinese patent CN106684296A discloses a kind of safety
Property good PVDF mixing coating diaphragm and preparation method thereof.The invention is by by PVDF and Mg (OH)2Particle directly mixes, Mg
(OH)2The crystallinity for reducing PVDF, improves the amorphous region of lithium ion conduction, improves the multiplying power discharging and cyclicity of lithium battery
Energy.In order to further increase porosity, liquid absorption amount, electrolyte wetability and the mechanical performance of diaphragm, novel inorganic filler is ground
Studying carefully is still current hot issue.
Diatomite is to be turned by unicellular low water plant diatom and other microbody biologies by millions of years placer deposits
With and the biogenic mineral material that is formed, there is natural orderly porous structure.The material is filled in PVDF matrix, it can be effective
Inhibit PVDF crystallization, promotes diaphragm pore-forming.Meanwhile the diatomite of porous structure can enough produce duct hair in PVDF matrix
It reaches, the porous structure that porosity is high, to promote lithium ion in transmission wherein.In addition, diatomite passes through anoxic high-temperature process
Afterwards, a small amount of organic matter therein tends to decompose, and forms fluffy porous structure, improves the porosity of diatomite, and high temperature is living
The diatomite surface functional group of change all has good adaptability to aqueous electrolyte and organic electrolyte, can be improved diaphragm pair
The wetability of different electrolytes improves the high rate performance and cycle performance of battery to reduce battery impedance.Meanwhile in order to mention
The mechanical performance of high diaphragm improves composite diaphragm as reinforcing fiber using basalt chopped fiber in diaphragm preparation process
Mechanical strength and flexibility.In addition, cheap diatomite filling will will be greatly reduced the production cost of composite diaphragm, mention
The high market competitiveness.
Application prospect based on the unique structure feature of diatomite and in lithium ion battery separator field.The present invention proposes one
The method that kind prepares novel lithium ion battery diaphragm as filler filling PVDF matrix using diatomite, this method process is simple,
Raw material is easily obtained, is cheap, effectively facilitates lithium ion battery high rate performance and cycle performance.
Summary of the invention:
The present invention is first heat-treated diatomaceous earth sample, improves the porosity of diatomite, activated diatomaceous earth surface official
It can roll into a ball, then disperse the powder and basalt chopped fiber, modifying agent, PVDF in N-N dimethylformamide (DMF) solvent,
Phase transfer method is recycled to obtain the diaphragm material that porosity is big, liquid absorption amount is big.
The present invention is achieved by the following technical solutions:
A kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material, comprising the following steps:
Diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；Diatom will be activated again
Soil 40~80 parts, 3~5 parts of basalt chopped fiber, 1~5 part of modifying agent, 20~60 parts of Kynoar be scattered in 600 parts
Suspension is obtained in N-N dimethylformamide；On a glass by suspension slurry blade coating finally, and glass plate is slowly submerged
It in the distilled water containing isopropanol, is taken out after being kept for 40 seconds, obtains diaphragm for lithium ion battery material after 40 DEG C of vacuum drying.
SiO in the diatomite2Content be greater than 92%；Modifying agent is titanate coupling agent TMC-201, TMC-
102, any one of TMC-101；Concentration of the isopropanol in distilled water is 2wt%；It is 40 micro- that slurry, which scratches thickness control,
Rice.
Detailed description of the invention
Fig. 1, LiFePO4/lithium battery high rate performance using the composite diaphragm
Fig. 2, LiFePO4/lithium battery cycle performance (1C) using the composite diaphragm
Specific embodiment:
The present invention is described in further detail in conjunction with the embodiments:
A. diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；
B. by 40~80 parts of activated diatomaceous earth, 3~5 parts of basalt chopped fiber, 1~5 part of modifying agent, Kynoar 20
~60 parts are scattered in 600 parts of N-N dimethylformamide, magnetic agitation, obtain suspension；
C. suspension slurry is scratched on a glass using painting hymenotome (it is 40 microns that slurry, which scratches thickness control)；
D. glass plate is slowly immersed in the distilled water containing isopropanol (2wt%), is kept for 40 seconds；
E. diaphragm for lithium ion battery material is obtained after 40 DEG C of the sample taken out vacuum drying.
Embodiment 1
A. diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；
B. it disperses 40 parts of activated diatomaceous earth, 3 parts of basalt chopped fiber, 2 parts of modifying agent, 60 parts of Kynoar in
In 600 parts of N-N dimethylformamide, magnetic agitation obtains suspension；
C. suspension slurry is scratched on a glass using painting hymenotome (it is 40 microns that slurry, which scratches thickness control)；
D. glass plate is slowly immersed in the distilled water containing isopropanol (2wt%), is kept for 40 seconds；
E. diaphragm for lithium ion battery material is obtained after 40 DEG C of the sample taken out vacuum drying.
Using the diaphragm in LiFePO4/lithium battery system, porosity to reach 61%.4C discharge capacity of the cell reaches
106Amh/g is higher than the battery (102Amh/g) using pure PVDF diaphragm.
Embodiment 2
A. diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；
B. it disperses 60 parts of activated diatomaceous earth, 5 parts of basalt chopped fiber, 5 parts of modifying agent, 40 parts of Kynoar in
In 600 parts of N-N dimethylformamide, magnetic agitation obtains suspension；
C. suspension slurry is scratched on a glass using painting hymenotome (it is 40 microns that slurry, which scratches thickness control)；
D. glass plate is slowly immersed in the distilled water containing isopropanol (2wt%), is kept for 40 seconds；
E. diaphragm for lithium ion battery material is obtained after 40 DEG C of the sample taken out vacuum drying.
Using the diaphragm in LiFePO4/lithium battery system, porosity to reach 65%.4C discharge capacity of the cell reaches
111Amh/g is higher than the battery (102Amh/g) using pure PVDF diaphragm.
Embodiment 3
A. diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；
B. it disperses 70 parts of activated diatomaceous earth, 4 parts of basalt chopped fiber, 1 part of modifying agent, 30 parts of Kynoar in
In 600 parts of N-N dimethylformamide, magnetic agitation obtains suspension；
C. suspension slurry is scratched on a glass using painting hymenotome (it is 40 microns that slurry, which scratches thickness control)；
D. glass plate is slowly immersed in the distilled water containing isopropanol (2wt%), is kept for 40 seconds；
E. diaphragm for lithium ion battery material is obtained after 40 DEG C of the sample taken out vacuum drying.
Using the diaphragm in LiFePO4/lithium battery system, porosity to reach 72%.4C discharge capacity of the cell reaches
117Amh/g is higher than the battery (102Amh/g) using pure PVDF diaphragm.
Embodiment 4
A. diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；
B. it disperses 80 parts of activated diatomaceous earth, 5 parts of basalt chopped fiber, 3 parts of modifying agent, 20 parts of Kynoar in
In 600 parts of N-N dimethylformamide, magnetic agitation obtains suspension；
C. suspension slurry is scratched on a glass using painting hymenotome (it is 40 microns that slurry, which scratches thickness control)；
D. glass plate is slowly immersed in the distilled water containing isopropanol (2wt%), is kept for 40 seconds；
E. diaphragm for lithium ion battery material is obtained after 40 DEG C of the sample taken out vacuum drying.
Using the diaphragm in LiFePO4/lithium battery system, porosity to reach 69%.4C discharge capacity of the cell reaches
112Amh/g is higher than the battery (102Amh/g) using pure PVDF diaphragm.
Claims (3)
1. a kind of preparation method of the composite lithium ion cell diaphragm containing tripolite filling material, which is characterized in that including following step
It is rapid:
Diatomite is completely cut off into air, is calcined 4 hours for 400 DEG C in high temperature furnace, obtains activated diatomaceous earth；Again by activated diatomaceous earth 40
~80 parts, 3~5 parts of basalt chopped fiber, 1~5 part of modifying agent, 20~60 parts of Kynoar be scattered in 600 parts of N-N bis-
Suspension is obtained in methylformamide；On a glass by suspension slurry blade coating finally, and glass plate is slowly immersed in and is contained
Have in the distilled water of isopropanol, taken out after being kept for 40 seconds, obtains diaphragm for lithium ion battery material after 40 DEG C of vacuum drying.
2. a kind of preparation method of composite lithium ion cell diaphragm containing tripolite filling material described in accordance with the claim 1,
It is characterized in that, SiO in the diatomite2Content be greater than 92%；Modifying agent is titanate coupling agent TMC-201, TMC-
102, any one of TMC-101；Concentration of the isopropanol in distilled water is 2wt%；It is 40 micro- that slurry, which scratches thickness control,
Rice.
3. a kind of composite lithium ion cell diaphragm containing tripolite filling material, it is characterised in that: any according to claim 1-2
Method is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810907255.4A CN109065809A (en) | 2018-08-07 | 2018-08-07 | A kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810907255.4A CN109065809A (en) | 2018-08-07 | 2018-08-07 | A kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material |
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| CN109065809A true CN109065809A (en) | 2018-12-21 |
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| CN201810907255.4A Pending CN109065809A (en) | 2018-08-07 | 2018-08-07 | A kind of composite lithium ion cell diaphragm and preparation method thereof containing tripolite filling material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102104171A (en) * | 2011-01-18 | 2011-06-22 | 华南师范大学 | Lithium ion battery gel polymer electrolyte, preparation method and application thereof |
| CN104766937A (en) * | 2015-02-10 | 2015-07-08 | 龙岩紫荆创新研究院 | Environment friendly battery diaphragm and preparation method thereof |
| CN107611318A (en) * | 2017-09-04 | 2018-01-19 | 吉林大学 | A kind of diatomite coating non-woven fabrics lithium ion battery separator and preparation method thereof |
| CN108232089A (en) * | 2018-01-05 | 2018-06-29 | 吉林大学 | A kind of lithium ion battery diatomite diaphragm and preparation method thereof |
-
2018
- 2018-08-07 CN CN201810907255.4A patent/CN109065809A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102104171A (en) * | 2011-01-18 | 2011-06-22 | 华南师范大学 | Lithium ion battery gel polymer electrolyte, preparation method and application thereof |
| CN104766937A (en) * | 2015-02-10 | 2015-07-08 | 龙岩紫荆创新研究院 | Environment friendly battery diaphragm and preparation method thereof |
| CN107611318A (en) * | 2017-09-04 | 2018-01-19 | 吉林大学 | A kind of diatomite coating non-woven fabrics lithium ion battery separator and preparation method thereof |
| CN108232089A (en) * | 2018-01-05 | 2018-06-29 | 吉林大学 | A kind of lithium ion battery diatomite diaphragm and preparation method thereof |
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