CN112054146A - Method for producing battery diaphragm by using PPS material and prepared film - Google Patents
Method for producing battery diaphragm by using PPS material and prepared film Download PDFInfo
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- CN112054146A CN112054146A CN202010916395.5A CN202010916395A CN112054146A CN 112054146 A CN112054146 A CN 112054146A CN 202010916395 A CN202010916395 A CN 202010916395A CN 112054146 A CN112054146 A CN 112054146A
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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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- 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
A method for producing a battery diaphragm by using a PPS material comprises the steps of adding the PPS material into PP and PE according to the weight ratio of 1-70%, uniformly mixing, and carrying out film-forming production to obtain a film with greatly improved film breaking temperature, obviously reduced thermal shrinkage and better high-temperature resistance, wherein the film has abundant nano-scale micropores and is suitable for producing the battery diaphragm. The invention relates to a method for producing a PP film PE film by applying PPS material, which mainly utilizes the performance of the PPS material to fill in a film made of PP/PE, improves the film breaking temperature of the film, reduces the high-temperature thermal shrinkage, prevents the problem that the PP/PE film applied to a battery is damaged and melted when the temperature is higher than the melting point of the PP/PE film, ensures the safety performance of the battery using the film as a diaphragm under the condition of not influencing the electron passing rate of the PP/PE film, and improves the industrial value of the battery.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of lithium ion battery manufacturing, in particular to the technical field of battery diaphragm manufacturing by using polyphenylene sulfide materials.
[ background of the invention ]
Lithium batteries have the advantages of high operating voltage, high specific energy, long cycle life, no environmental pollution and the like, and are always regarded as hot technologies of power energy storage systems by industrial people as secondary chemical power sources capable of converting electric energy and chemical energy into each other. The power generation device is not only widely used in mobile communication equipment and portable electronic equipment, but also widely applied to large power equipment such as electric tools, electric bicycles, electric automobiles and the like. However, news such as spontaneous combustion of the electric vehicle, charging and ignition of the electric vehicle and the like are continuously reported, so that the safety performance of the lithium ion battery is still seriously considered, and potential safety hazards exist. How to improve the safety performance of the battery is the main direction of research of various large battery manufacturers at present.
From the view of industrial requirements, the diaphragm of the battery needs to meet the requirements that the diaphragm has higher void ratio and through holes and is used for ions to pass through in a free mode during charging and discharging; but also to meet the requirement of high temperature resistance in order to cope with the problem of heat accumulation which is inevitably generated during rapid charging and discharging. If the porosity and the through hole parameters do not meet the requirements, the diaphragm has high ion blocking degree, low charging and discharging efficiency and low efficiency, and the consumed time is long and does not meet the expectation and the requirements of the high-efficiency society; the heat resistance of the diaphragm is a necessary performance requirement from the use safety angle, energy loss in the form of heat energy is inevitably caused while rapid charging and discharging, temperature rise can be caused by heat energy accumulation, and once the critical value of the heat resistance temperature of the diaphragm is broken through, short circuit can be instantly caused by diaphragm ablation.
At present, the conventional battery diaphragm in the industry is made of polyolefin materials, such as polypropylene (PP) and Polyethylene (PE), the two materials have good film forming property, good porosity and porosity, low price and suitability for industrial mass production, but the high-temperature resistance of the battery diaphragm is general on the whole: wherein the PE melting temperature is 130 ℃, and the industrial application environment temperature is not higher than 110 ℃. The melting temperature of PP is 160 ℃, and the temperature of the industrial application environment is not more than 130 ℃.
If the battery is operated at a temperature higher than the above temperature, a short circuit may occur in the counter electrode inside the battery, and the battery may generate severe heat, resulting in safety accidents such as explosion and the like.
There are patents which propose ceramic fiber separators, such as patent: CN 201210367348.5A lithium ion battery diaphragm and its applied lithium ion battery. There are also patents that propose the use of polytetrafluoroethylene PVDF and inorganic particles to make membranes, such as the patents: CN 201210544045.6A preparation method of a lithium ion battery diaphragm and the lithium ion battery diaphragm. Or the polytetrafluoroethylene PVDF and the polyimide PI are adopted to carry out surface modification on the PE and the PP so as to improve the temperature resistance and the heat resistance.
However, the above patent technologies all have certain defects, complex coating process and other problems, for example, PVDF is toxic, is not friendly to the environment, and does not meet the requirements of a continuously developable strategy; the alumina ceramic powder has high specific gravity; PI has only been reported by related academia to be useful, but in practice, no large quantities of finished products are found in the industrial field.
[ summary of the invention ]
The invention provides a method for producing a battery diaphragm by using a PPS material, and the PPS material is a polyarylsulfone resin product, contains a benzene ring and a sulfenyl group which are stable in heat resistance, has the characteristics of high temperature resistance, flame retardance, excellent mechanical property and the like, and is suitable for being used as a filler material for producing the battery diaphragm by using PP and PE films.
A method for producing a battery diaphragm by using PPS material is characterized by comprising the following steps:
1. selecting polyphenylene sulfide (PPS) high polymer material; preparing PPS material into particle powder with the particle size of 0.1-20 microns, or preparing the PPS material into fiber filaments with the diameter of less than 20 microns and the length of less than 100 microns;
2. adding the PPS material into a polyethylene PE or polypropylene PP material, wherein the PPS material accounts for 1-70% of the weight of the PE or PP material, fully mixing the materials, and extruding and stretching the mixed material into a finished film by a polyethylene PE film-making process or a polypropylene PP film-making process;
the PPS material is added into the PE material and applied to the production process of the wet method, the PPS material is added under the condition that the PE and the paraffin oil are molten, or the PPS material is added into the paraffin oil in advance and premixed in the wet method process, and then added into the PE material together with the paraffin oil; then stirring and fully mixing the materials by a large stirrer, and then producing the film filled with the PPS material and having rich nano-scale micropores by extruding, stretching, extending and other steps according to a PE film forming process;
PPS material is added into PP material, and is applied to dry-process production technology, the PPS material is added into PP dry powder, and the mixture is put into a PP film-forming production line after being uniformly mixed, so that the film filled with the PPS material and having rich nano-scale micropores can be produced.
The PPS material added in the second step accounts for 3 to 60 weight percent of the PE or PP material.
The PPS material added in the second step accounts for 5 to 50 percent of the weight of the PE or PP material.
The PPS material added in the second step accounts for 5 to 30 percent of the weight of the PE or PP material.
The PPS material added in the second step accounts for 8-25% of the weight of the PE or PP material.
The film is applied to lithium ion batteries and hydrogen fuel batteries, the film breaking temperature of the film is obviously improved, the high-temperature thermal shrinkage is obviously reduced, and the film cannot be damaged or melted even if the temperature is higher than the melting point of PE or PP. Because the PPS material is added in a filling mode to play a role in protecting the net-shaped bracket, the battery membrane can still maintain the shape and the structure at the temperature exceeding the melting point of PE and PP.
Compared with the PP or PE film produced by the original process, the temperature of the PP or PE film added with the PPS material for safe work can be greatly increased by 10-80 ℃, and the increase amplitude is related to the proportion of the added PPS material and the shape of the PPS.
In the above-described method, PI may be used instead of or in part instead of PPS material.
Or high-temperature resistant plastic PPSU/PEEK/PA66/PPO is adopted to replace PPS material.
The invention relates to a method for producing a PP film PE film by applying PPS material, which mainly utilizes the performance of the PPS material to fill the film made of PP/PE, improves the film breaking temperature of the film, reduces the high-temperature thermal shrinkage, prevents the problem that the PP/PE film applied to a battery is damaged and melted when the temperature is higher than the melting point of the PP/PE film, ensures the safety performance of the battery using the film as a diaphragm, and improves the industrial value of the battery.
[ detailed description ] embodiments
The present invention will be described in further detail with reference to specific embodiments thereof.
Aiming at the problems that the heat resistance of the battery diaphragm cannot reach the ideal temperature and the heat resistance and shrinkage resistance at high temperature are not ideal, the PP film and the PE film which are commonly used for the battery diaphragm in the industry are modified, the modification process does not involve high polymer modification or chemical modification, but simply adopts the physical principle to modify the physical layer, the consumed material cost and the process difficulty are low, and the industrial mass production and mass production conditions are easy to realize. The method is a great technical innovation for the film making industry and the battery manufacturing industry, and technical iteration and product upgrading of the industry are promoted. Further optimizes and promotes the quality of industrial products, and makes great contribution to the safety and stability of the battery industry.
First, we propose a method for producing a battery separator using a PPS material,
a method for producing a battery diaphragm by using PPS material is characterized by comprising the following steps:
1. selecting polyphenylene sulfide (PPS) high polymer material; preparing PPS material into particle powder with the particle size of 0.1-20 microns, or preparing the PPS material into fiber filaments with the diameter of less than 20 microns and the length of less than 100 microns;
2. adding the PPS material into a polyethylene PE or polypropylene PP material, wherein the PPS material accounts for 1-70% of the weight of the PE or PP material, fully mixing the materials, and extruding and stretching the mixed material into a finished film by a polyethylene PE film-making process or a polypropylene PP film-making process;
the PPS material is added into the PE material, is applied to the production process of a wet method, and is added under the condition that the PE and paraffin oil are molten, or is added into the paraffin oil in advance for premixing and then added into the PE material together with the paraffin oil; then stirring and fully mixing the materials by a large stirrer or stirring the materials by a screw machine, and then producing the film filled with the PPS material and having rich nano-scale micropores by extruding, stretching, extending and other steps according to a PE film forming process;
PPS material is added into PP material, and is applied to a dry-method production process, the PPS material is added into PP dry powder, the mixture is put into a PP film-forming production line after being uniformly mixed, and the film filled with the PPS material and having rich nano-scale micropores is obtained through a PP film production process.
The PPS material added in the second step accounts for 3 to 60 weight percent of the PE or PP material.
The PPS material added in the second step accounts for 5 to 50 percent of the weight of the PE or PP material.
The PPS material added in the second step accounts for 5 to 30 percent of the weight of the PE or PP material.
The PPS material added in the second step accounts for 8-25% of the weight of the PE or PP material.
The film is applied to lithium ion batteries and hydrogen fuel batteries, the high-temperature thermal shrinkage of the film is obviously reduced, and the film cannot be damaged or melted even if the temperature is higher than the melting point of PE or PP. Because the PPS material is added in a filling mode to play a role in protecting the net-shaped bracket, the battery membrane can still maintain the shape and the structure at the temperature exceeding the melting point of PE and PP.
Compared with the PP or PE film produced by the original process, the temperature of the PP or PE film added with the PPS material for safe work can be greatly increased by 10-80 ℃, and the increase amplitude is related to the proportion of the added PPS material and the shape of the PPS.
In the above-described method, PI may be used instead of or in part instead of PPS material.
Or high-temperature resistant plastic PPSU/PEEK/PA66/PPO is adopted to replace PPS material.
Implementation example:
example one, a PE powder used as a battery separator is added with PPS powder having a particle size range of 5 to 15 μm to paraffin oil, and the PPS powder is stirred and dispersed, wherein the addition ratio is 3%, 5%, 8%, 10%, 15%, 20%, 25% of the weight ratio of the PE powder, and the weight ratio of the paraffin oil to the PE powder is 7: 3, stirring and co-extruding a thick film at each temperature zone of 100-250 ℃ by a double screw, then carrying out transverse and longitudinal hot stretching to form a 15-micron film, extracting paraffin oil by dichloromethane, and preparing the PPS filled PE film with various proportions, wherein the visual inspection of the film surface is rough, and the indexes are as follows:
table 1: (PPS particle + PE) coextrusion experimental diaphragm sample
Example two, the PE powder used as a battery separator was added with PPS powder having a particle size range of 0.6 to 2 μm to paraffin oil in a proportion of 3%, 5%, 8%, 10%, 15%, 20%, 25% by weight of the PE powder, and the weight ratio of paraffin oil to PE powder was 7: 3, stirring and co-extruding a thick film at each temperature zone of 100-250 ℃ by a double screw, then carrying out transverse and longitudinal hot stretching to form a 15-micron film, extracting paraffin oil by dichloromethane to obtain the PPS filled PE film under each proportion, visually observing the smoothness and flatness of the surface of the diaphragm, and measuring each index as follows:
table 2: (PPS particle + PE) coextrusion experimental diaphragm sample
Example three, PPs powder with a particle size range of 0.8 to 4 μm is added to PP powder for stirring and dispersing, the adding proportion is respectively 3%, 5%, 8%, 10%, 15%, 20% and 25% of the weight ratio of the PP powder, a thick film is co-extruded by stirring at each temperature zone of 150 to 260 ℃ through a double screw, and then transverse and longitudinal hot stretching is carried out to obtain a 20 μm film, and PPs filled PP films with various proportions are prepared, and the indexes are as follows:
table 3: (PPS particles + PP) Co-extrusion experimental diaphragm sample
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A method for producing a battery diaphragm by using PPS material is characterized by comprising the following steps:
firstly, selecting a polyphenylene sulfide (PPS) high polymer material; preparing PPS material into particle powder with the particle size of 0.1-20 microns, or preparing the PPS material into fiber filaments with the diameter of less than 20 microns and the length of less than 100 microns;
step two, adding the PPS material into a polyethylene PE or polypropylene PP material, wherein the PPS material accounts for 1-70% of the weight of the PE or PP material, fully mixing the materials, and extruding and stretching the mixed material into a finished film through a polyethylene PE film-making process or a polypropylene PP film-making process;
the PPS material is added into the PE material, is applied to the production process of a wet method, and is added under the condition that the PE and paraffin oil are molten, or is added into the paraffin oil in advance for premixing and then added into the PE material together with the paraffin oil; then stirring and fully mixing the materials by a large stirrer, and then producing the film filled with the PPS material and having rich nano-scale micropores by extruding, stretching, extending and other steps according to a PE film forming process;
PPS material is added into PP material, and is applied to dry-process production technology, the PPS material is added into PP dry powder, and the mixture is put into a PP film-forming production line after being uniformly mixed, so that the film filled with the PPS material and having rich nano-scale micropores can be produced.
2. The method for producing the battery separator by using the PPS material as claimed in claim 1, wherein the weight ratio of the PPS material added in the second step to the PE or PP material is 3% -60%.
3. The method for producing the battery separator by using the PPS material as claimed in claim 1, wherein the weight ratio of the PPS material added in the second step to the PE or PP material is 5% -50%.
4. The method for producing the battery separator by using the PPS material as claimed in claim 1, wherein the weight ratio of the PPS material added in the second step to the PE or PP material is 5% -30%.
5. The method for producing the battery separator by using the PPS material as claimed in claim 1, wherein the weight ratio of the PPS material added in the second step to the PE or PP material is 8% -25%.
6. The method for producing a battery separator from PPS material in accordance with claim 1, wherein PI substitution or partial substitution of PPS material is possible in the above-described production method.
7. The PPS material as defined in claim 1, which is used for a membrane of a battery, wherein the membrane is used in a lithium ion battery and a hydrogen fuel cell.
8. The film of claim 7, wherein the film breaking temperature of the film is increased by 10-25%, the high-temperature thermal shrinkage is reduced by 20-30%, and the safe working temperature of the PP or PE film added with the PPS material is greatly increased by 10-80 ℃.
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| CN202010896951 | 2020-08-31 | ||
| CN2020108969517 | 2020-08-31 |
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| CN112054146A true CN112054146A (en) | 2020-12-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115882159A (en) * | 2023-03-08 | 2023-03-31 | 四川中科兴业高新材料有限公司 | Preparation method of sodium battery diaphragm based on PPS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103618058A (en) * | 2013-12-16 | 2014-03-05 | 中国科学院宁波材料技术与工程研究所 | Membrane and preparation method thereof |
| CN103996814A (en) * | 2014-06-04 | 2014-08-20 | 深圳市星源材质科技股份有限公司 | Lithium-ion battery diaphragm with low thermal shrinkage and preparation method thereof |
| CN105489816A (en) * | 2016-01-26 | 2016-04-13 | 湖南中锂新材料有限公司 | Production process for preparing high-specific-energy battery diaphragm |
| CN110289383A (en) * | 2019-06-18 | 2019-09-27 | 深圳昌茂粘胶新材料有限公司 | A kind of lithium battery power battery high-temperature resistant micropore thin film material and preparation method thereof |
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- 2020-09-03 CN CN202010916395.5A patent/CN112054146A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103618058A (en) * | 2013-12-16 | 2014-03-05 | 中国科学院宁波材料技术与工程研究所 | Membrane and preparation method thereof |
| CN103996814A (en) * | 2014-06-04 | 2014-08-20 | 深圳市星源材质科技股份有限公司 | Lithium-ion battery diaphragm with low thermal shrinkage and preparation method thereof |
| CN105489816A (en) * | 2016-01-26 | 2016-04-13 | 湖南中锂新材料有限公司 | Production process for preparing high-specific-energy battery diaphragm |
| CN110289383A (en) * | 2019-06-18 | 2019-09-27 | 深圳昌茂粘胶新材料有限公司 | A kind of lithium battery power battery high-temperature resistant micropore thin film material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115882159A (en) * | 2023-03-08 | 2023-03-31 | 四川中科兴业高新材料有限公司 | Preparation method of sodium battery diaphragm based on PPS |
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Application publication date: 20201208 |