CN110804113B - Ultralow-ash polypropylene and polypropylene lithium battery diaphragm material - Google Patents
Ultralow-ash polypropylene and polypropylene lithium battery diaphragm material Download PDFInfo
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- CN110804113B CN110804113B CN201911095096.3A CN201911095096A CN110804113B CN 110804113 B CN110804113 B CN 110804113B CN 201911095096 A CN201911095096 A CN 201911095096A CN 110804113 B CN110804113 B CN 110804113B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
-
- 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
-
- 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
- H01M50/411—Organic material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an ultra-low ash polypropylene, which is prepared by the following steps: mixing propylene, a Ziegler-Natta catalyst, triethyl aluminum and an electron donor in a hydrogen atmosphere, and reacting to obtain ultra-low ash polypropylene; the Ziegler-Natta catalyst comprises 2.5wt% of Ti, 18.5wt% of Mg, 8.3wt% of diisobutyl phthalate and 2.9wt% of volatile matter; the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is (2-3): 1. the invention relates to an ultra-low ash polypropylene resin obtained by improving the component vegetation of a catalyst, and a diaphragm material of a lithium battery is prepared by utilizing the ultra-low ash polypropylene resin. The diaphragm material prepared by the invention has low tendency and excellent heat resistance.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an ultralow-ash polypropylene and a polypropylene lithium battery diaphragm material.
Background
In the construction of lithium batteries, the separator is one of the key internal components. The performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, safety performance and other characteristics of the battery, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. The separator has a main function of separating the positive electrode and the negative electrode of the battery to prevent short circuit due to contact between the two electrodes, and also has a function of allowing electrolyte ions to pass therethrough. The separator material is non-conductive, and the physical and chemical properties of the separator have a great influence on the performance of the battery. The lithium battery diaphragm material in the current market is mainly prepared by molding polyethylene and polyimide as raw materials.
The polypropylene is used as a general plastic material, has good chemical stability and processability and is relatively cheap, but the common polypropylene has high ash content and poor thermal shrinkage, and a diaphragm can shrink or fuse when the temperature is too high, so that potential safety hazards exist.
Disclosure of Invention
The invention aims to provide an ultralow-ash polypropylene and a polypropylene lithium battery diaphragm material.
The invention provides an ultra-low ash polypropylene, which is prepared by the following steps:
mixing propylene, a Ziegler-Natta catalyst, triethyl aluminum and an electron donor in a hydrogen atmosphere, and reacting to obtain ultra-low ash polypropylene;
the Ziegler-Natta catalyst comprises 2.5wt% of Ti, 18.5wt% of Mg, 8.3wt% of diisobutyl phthalate and 2.9wt% of volatile matter;
the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is (2-3): 1.
preferably, the molar ratio of the triethyl aluminum to the Ti element in the Ziegler-Natta catalyst is (60-70): 1.
preferably, the electron donor is cyclohexylmethyldimethoxysilane;
the molar ratio of triethyl aluminum to electron donors is (3-4): 1.
preferably, the reaction temperature is 70-80 ℃;
the reaction pressure is 3.0-3.5 MPa.
Preferably, the concentration of the hydrogen is 500-1000 ppm.
The invention provides a polypropylene lithium battery diaphragm material which is prepared from the following raw materials in parts by mass:
the ultra-low ash polypropylene of any one of claims 1 to 5: 99.61-99.93%;
main antioxidant: 0.1-0.2%;
auxiliary antioxidant: 0.1-0.2%;
halogen absorbent: 0.01 to 0.05 percent.
Preferably, the primary antioxidant is a phenolic antioxidant;
the auxiliary antioxidant is phosphite antioxidant.
Preferably, the halogen absorbent is zinc stearate and/or hydrotalcite;
the mass ratio of the zinc stearate to the hydrotalcite is 50: (50-60).
Preferably, the polypropylene lithium battery diaphragm is prepared according to the following steps:
weighing the ultra-low ash polypropylene, the main antioxidant, the auxiliary antioxidant and the halogen absorbent according to a formula, blending in a high-speed mixer for 30-35 min, adding into a double-screw extruder for melt blending, extruding and granulating to obtain the polypropylene lithium battery diaphragm material.
Preferably, the temperature of the melt blending is 160-240 ℃.
The invention provides an ultra-low ash polypropylene, which is prepared by the following steps: mixing propylene, a Ziegler-Natta catalyst, triethyl aluminum and an electron donor in a hydrogen atmosphere, and reacting to obtain ultra-low ash polypropylene; the Ziegler-Natta catalyst comprises 2.5wt% of Ti, 18.5wt% of Mg, 8.3wt% of diisobutyl phthalate and 2.9wt% of volatile matter; the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is (2-3): 1. the invention relates to an ultra-low ash polypropylene resin obtained by improving the component vegetation of a catalyst, and a diaphragm material of a lithium battery is prepared by utilizing the ultra-low ash polypropylene resin. Compared with the prior art, the invention has the following beneficial effects:
1. the ultralow-ash polypropylene lithium battery diaphragm material has good moisture resistance, does not absorb water, has a dielectric constant which does not change along with the change of frequency, has small dielectric loss, and realizes the miniaturization and light weight of a capacitor;
2. the polypropylene resin disclosed by the invention is an ultralow-ash polypropylene resin, has better mechanical properties, heat resistance, corrosion resistance and high-temperature micropore closure performance, meets the requirements of a lithium battery diaphragm material, is adjusted and controlled by adjusting the hydrogen concentration so as to enable the ultralow-ash polypropylene resin to have good melt flowability, so that the processing performance of the resin is enhanced, additives such as a slipping agent and the like are prevented from being added in the processing process, low-molecular substances in the lithium battery diaphragm material are reduced, the ultralow-ash polypropylene resin diaphragm material can keep the characteristics in an electrolyte corrosion environment, and has good corrosion resistance.
3. The yellow index and the ash content of the ultra-low ash polypropylene membrane material meet the use requirements of the processability and the electrical property of a lithium battery membrane material. Dielectric loss factor less than or equal to 3.0 x 10-4The prepared lithium battery diaphragm can stably work for a long time, and the ash content in the material is little because no slipping agent is added.
4. The ultra-low ash polypropylene membrane material can realize coarsening, and can be made into a high-capacity oil-immersed power capacitor, which is a direction for the development of the capacitor at present.
5. The dielectric constant of the ultra-low ash polypropylene membrane material does not change along with the change of frequency, which is the main factor of the ultra-low ash polypropylene membrane material in the alternating-frequency capacitor.
Detailed Description
The invention provides an ultra-low ash polypropylene, which is prepared by the following steps:
mixing propylene, a Ziegler-Natta catalyst, triethyl aluminum and an electron donor in a hydrogen atmosphere, and reacting to obtain ultra-low ash polypropylene;
the Ziegler-Natta catalyst comprises 2.5wt% of Ti, 18.5wt% of Mg, 8.3wt% of diisobutyl phthalate and 2.9wt% of volatile matter;
the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is (2-3): 1.
in the invention, the propylene is preferably polymer-grade propylene, the purity of the propylene is 99.6 percent, the moisture content is less than or equal to 10ppm, the sulfur content is less than or equal to 1ppm, the CO content is less than or equal to 5ppm, the CO2 content is less than or equal to 10ppm, the O2 content is less than or equal to 10ppm, the contents of dialkene and alkyne are less than or equal to 5ppm, the propane content is less than or equal to 300ppm, and the content of C4 components is less than or equal to 5mL/m3。
In the present invention, the Ziegler-Natta catalyst comprises MgCl as a main component2And TiCl4Ti content of 2.5wt%, Mg content of 18.5wt%, diisobutyl phthalate (DIBP) content of 8.3wt%, and volatile matter of 2.9 wt%; the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is (2-3): 1, more preferably (2.3 to 2.8): 1, most preferably 2.45: 1.
In the invention, the triethyl aluminum is used as a cocatalyst, and the molar ratio of the triethyl aluminum to the Ti element in the Ziegler-Natta catalyst is preferably (60-70): 1, more preferably (63-68): 1, more preferably 64: 1.
In the present invention, the electron donor is preferably Cyclohexylmethyldimethoxysilane (CMMS); the preferred molar ratio of triethyl aluminum to electron donor is (3-4): 1, more preferably (3.1 to 3.8): 1, most preferably 3.18: 1.
In the invention, the reaction temperature is preferably 70-80 ℃, more preferably 71-76 ℃, and most preferably 71-73 ℃, specifically, in the embodiment of the invention, 72 ℃; the pressure of the reaction is preferably 3.0-3.5 MPa, and more preferably 3.0-3.2 MPa; the concentration of the hydrogen is preferably 500 to 1000ppm, more preferably 600 to 900ppm, and most preferably 700 to 800 ppm. In the present invention, the hydrogen preferably has a purity of > 99.99%, an oxygen content of < 10ppm, CO + CO2The content of (B) is preferably < 10ppm and the water content is preferably < 5 ppm.
The ultra-low ash polypropylene has the melt flow rate of 3.26g/10min (GB/T97.58.1 (230 ℃, 2.16kg)), the yellow index of 7.16 (HG/T3862-.
The invention also provides a polypropylene lithium battery diaphragm material which is prepared from the following raw materials in parts by mass:
the ultra low ash polypropylene described above: 99.61-99.93%;
main antioxidant: 0.1-0.2%;
auxiliary antioxidant: 0.1-0.2%;
halogen absorbent: 0.01 to 0.05 percent.
In the present invention, the ultra-low ash polypropylene is the ultra-low ash polypropylene described above, and the components and the preparation method thereof are not described herein again. The mass fraction of the ultra-low ash polypropylene is preferably 99.7%, 99.72%, 99.74% or 99.76%.
In the present invention, the primary antioxidant is preferably a phenolic antioxidant, more preferably an antioxidant 1010; the mass fraction of the main antioxidant is preferably 0.10-0.2%, more preferably 0.1%, 0.11% or 0.12%; the auxiliary antioxidant is preferably a phosphite antioxidant, and more preferably an antioxidant 168; the mass fraction of the auxiliary antioxidant is preferably 0.1-0.2%, more preferably 0.1%, 0.12%, 0.08% or 0.09%. The mass ratio of the main antioxidant to the auxiliary antioxidant is preferably (40-50): (50-60), more preferably 50: 50. Specifically, in the embodiment of the present invention, the ratio may be 50: 50. 60:40 or 55: 45.
The halogen absorbent is preferably zinc stearate and/or hydrotalcite, and the mass fraction of the halogen absorbent is preferably 0.01-0.05%, and more preferably 0.02-0.04%; the mass ratio of the zinc stearate to the hydrotalcite is preferably 50: (50-60), more preferably 50: 50.
In the invention, the polypropylene lithium battery diaphragm material is preferably prepared according to the following steps:
weighing the ultra-low ash polypropylene, the main antioxidant, the auxiliary antioxidant and the halogen absorbent according to the formula, then placing the materials in a high-speed mixer for blending for 30-35 min, then adding the materials into a double-screw extruder for melt blending, extruding and granulating to obtain the polypropylene lithium battery diaphragm material.
In the invention, the temperature of each section of the extrusion granulation is controlled between 160 ℃ and 240 ℃, and specifically, the temperature of each section is as follows: zone 1: 175 ℃, 2 zone 180 ℃, 3 zone 175 ℃, 4 zone 180 ℃, 5 zone 180 ℃, 6 zone 175 ℃, 7 zone 180 ℃, 8 zone 185 ℃, 190 ℃ die head.
The invention provides an ultra-low ash polypropylene, which is prepared by the following steps: mixing propylene, a Ziegler-Natta catalyst, triethyl aluminum and an electron donor in a hydrogen atmosphere, and reacting to obtain ultra-low ash polypropylene; the Ziegler-Natta catalyst comprises 2.5wt% of Ti, 18.5wt% of Mg, 8.3wt% of diisobutyl phthalate and 2.9wt% of volatile matter; the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is (2-3): 1. the invention relates to an ultra-low ash polypropylene resin obtained by improving the component vegetation of a catalyst, and a diaphragm material of a lithium battery is prepared by utilizing the ultra-low ash polypropylene resin. Compared with the prior art, the invention has the following beneficial effects:
1. the ultralow-ash polypropylene lithium battery diaphragm material has good moisture resistance, does not absorb water, has a dielectric constant which does not change along with the change of frequency, has small dielectric loss, and realizes the miniaturization and light weight of a capacitor;
2. the polypropylene resin disclosed by the invention is an ultralow-ash polypropylene resin, has better mechanical properties, heat resistance, corrosion resistance and high-temperature micropore closure performance, meets the requirements of a lithium battery diaphragm material, is adjusted and controlled by adjusting the hydrogen concentration so as to enable the ultralow-ash polypropylene resin to have good melt flowability, so that the processing performance of the resin is enhanced, additives such as a slipping agent and the like are prevented from being added in the processing process, low-molecular substances in the lithium battery diaphragm material are reduced, the ultralow-ash polypropylene resin diaphragm material can keep the characteristics in an electrolyte corrosion environment, and has good corrosion resistance.
3. The yellow index and the ash content of the ultra-low ash polypropylene membrane material meet the use requirements of the processability and the electrical property of a lithium battery membrane material. Dielectric loss factor less than or equal to 3.0 x 10-4The prepared lithium battery diaphragm can stably work for a long time, and the ash content in the material is little because no slipping agent is added.
4. The ultra-low ash polypropylene membrane material can realize coarsening, and can be made into a high-capacity oil-immersed power capacitor, which is a direction for the development of the capacitor at present.
5. The dielectric constant of the ultra-low ash polypropylene membrane material does not change along with the change of frequency, which is the main factor of the ultra-low ash polypropylene membrane material in the alternating-frequency capacitor.
For further illustration of the present invention, the following examples are provided to describe the ultra-low ash polypropylene and polypropylene lithium battery separator material in detail, but should not be construed as limiting the scope of the present invention.
Example 1 preparation of ultra-low ash polypropylene
The Ziegler Natta catalyst used in this example had a Ti content of 2.5wt%, a Mg content of 18.5wt%, a diisobutyl phthalate (DIBP) content of 8.3wt%, and a volatile content of 2.9 wt%;
adding propylene into a reaction kettle, and adding a Ziegler Natta catalyst, a cocatalyst (triethyl aluminum) and an electron donor (CMMS), wherein the catalyst is added according to the yield of 40kg of polypropylene/g of catalyst, and the triethyl aluminum/Ti (Ti element in the catalyst) is 64
The Ti element/propylene monomer in the catalyst is 2.45, the triethyl aluminium/DONOR is 3.18, the mixture is evenly stirred, the temperature of the reactor is controlled to be 72 +/-1 ℃, the reaction pressure is 3.0-3.2MPa, and the hydrogen concentration is 800 ppm. Thereby obtaining the ultra-low ash polypropylene resin.
The properties of the resulting polypropylene resin are shown in Table 1,
TABLE 1 Properties of the ultra-low ash Polypropylene resin of example 1 of the present application
Examples 2 to 8
According to the proportion in the table 3, adding the ultra-low ash polypropylene resin, the antioxidant and the halogen absorbent into a 10L high-speed stirring mixer, mixing for 30 minutes at normal temperature and normal pressure, then carrying out extrusion granulation by adopting a Kyolon extrusion granulator, wherein the temperature of each section is controlled between 165 ℃ and 240 ℃, and the temperature of each section is shown in the table 2, so as to obtain the polypropylene resin material for the lithium battery diaphragm.
TABLE 2 temperatures of extrusion granulation sections in examples 2 to 8 of the present application
| Region 1 | Zone 2 | Zone 3 | Zone 4 | Zone 5 | Zone 6 | Zone 7 | Zone 8 | Machine head | |
| Temperature/. degree.C | 175 | 180 | 175 | 180 | 180 | 175 | 180 | 185 | 190 |
TABLE 3 component ratios in examples 2 to 8 of the present application
The results of physical and chemical property tests of the polypropylene resin materials for lithium battery separators of examples 2 to 8 are shown in Table 4,
TABLE 4 Performance data of Polypropylene resin materials for lithium batteries in examples 2 to 8 of the present application
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. An ultra-low ash polypropylene is prepared by the following steps:
mixing propylene, a Ziegler-Natta catalyst, triethyl aluminum and an electron donor in a hydrogen atmosphere, and reacting to obtain ultra-low ash polypropylene;
the Ziegler-Natta catalyst comprises 2.5wt% of Ti, 18.5wt% of Mg, 8.3wt% of diisobutyl phthalate and 2.9wt% of volatile matter;
the molar ratio of the Ti element to the propylene in the Ziegler-Natta catalyst is 2.45: 1;
the molar ratio of the triethyl aluminum to the Ti element in the Ziegler-Natta catalyst is 64: 1;
the electron donor is cyclohexyl methyl dimethoxy silane; the molar ratio of the triethyl aluminum to the electron donor is 3.18: 1.
2. the ultra-low ash polypropylene of claim 1, wherein the reaction temperature is 70 to 80 ℃;
the reaction pressure is 3.0-3.5 MPa.
3. The ultra-low ash polypropylene of claim 1, wherein the hydrogen concentration is 500 to 1000 ppm.
4. The polypropylene lithium battery diaphragm material is prepared from the following raw materials in percentage by mass:
the ultra-low ash polypropylene of any one of claims 1 to 3: 99.61-99.93%;
main antioxidant: 0.1-0.2%;
auxiliary antioxidant: 0.1-0.2%;
halogen absorbent: 0.01 to 0.05 percent.
5. The polypropylene lithium battery separator material as claimed in claim 4, wherein the primary antioxidant is a phenolic antioxidant;
the auxiliary antioxidant is phosphite antioxidant.
6. The polypropylene lithium battery separator material according to claim 4, wherein the halogen absorbent is zinc stearate and/or hydrotalcite;
the mass ratio of the zinc stearate to the hydrotalcite is 50: (50-60).
7. The polypropylene lithium battery separator material as claimed in claim 4, wherein the polypropylene lithium battery separator is prepared by the following steps:
weighing the ultra-low ash polypropylene, the main antioxidant, the auxiliary antioxidant and the halogen absorbent according to a formula, blending in a high-speed mixer for 30-35 min, adding into a double-screw extruder for melt blending, extruding and granulating to obtain the polypropylene lithium battery diaphragm material.
8. The polypropylene lithium battery separator material as claimed in claim 7, wherein the melt blending temperature is 160-240 ℃.
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| CN201911095096.3A CN110804113B (en) | 2019-11-11 | 2019-11-11 | Ultralow-ash polypropylene and polypropylene lithium battery diaphragm material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896511A (en) * | 2007-12-14 | 2010-11-24 | 道达尔石油化学产品研究弗吕公司 | Process for the production of a bimodal polypropylene having low ash content |
| CN109306030A (en) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | Lithium battery diaphragm PP Pipe Compound and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896511A (en) * | 2007-12-14 | 2010-11-24 | 道达尔石油化学产品研究弗吕公司 | Process for the production of a bimodal polypropylene having low ash content |
| CN109306030A (en) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | Lithium battery diaphragm PP Pipe Compound and preparation method thereof |
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