CN104059298A - Lithium battery electrolyte-resistant halogen-free flame-retardant polypropylene reinforced composite material and preparation method thereof - Google Patents
Lithium battery electrolyte-resistant halogen-free flame-retardant polypropylene reinforced composite material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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- 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
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Abstract
The invention relates to a lithium battery electrolyte-resistant halogen-free flame-retardant polypropylene reinforced composite material which is characterized by containing the following components in parts by weight: 30-85 parts of polypropylene alloy, 5-20 parts of glass fiber, 10-40 parts of halogen-free flame retardant, 0.1-10 parts of oligomer, 0.1-10 parts of metal oxide and 0.1-10 parts of processing assistant. The preparation method comprises the following steps: (1) preparing the halogen-free flame retardant master batch: uniformly mixing components of the halogen-free flame retardant, adding into an internal mixer, adding the oligomer, uniformly mixing, performing devolatilization treatment, and granulating; (2) preparing the polypropylene alloy: uniformly mixing components of the polypropylene alloy, performing melt extrusion, and granulating; and (3) preparing the composite material: uniformly mixing the prepared polypropylene alloy, the prepared halogen-free flame retardant master batch, the metal oxide and the processing assistant, adding into a double screw extruder, performing melt blending and extrusion, drawing, and granulating.
Description
Technical field
The invention belongs to technical field of polymer materials, be particularly related to, be specifically related to a kind of halogen-free flame-retardant system that adopts resistance to migration, fire-retardant, water-fast, the electrolyte resistance of the case material of composite lithium ion battery move halogen-free polypropylene flame redardant reinforced composite of the resistance to lithium battery electrolytes requiring and preparation method thereof.Product is suitable for the case material as lithium cell.
Background technology
Lithium cell, as Power Component, need to frequently discharge and recharge, and this process can a large amount of heat releases, have potential safety hazard, by adopting fire retardant material to prevent the generation of malignant fire and personal injury, is advanced country's practice one of effective safety prevention measure for many years.The batteries of electric automobile safety standard UL2580 " power cell standard " that on October 13rd, 2011, UL promulgated first, to having proposed clear and definite fire-retardant requirement for the material of housing and casing.
Electromobile adopts clean energy, is green product, and the material first-selection of use is environment-friendly type, and its fire-retardant mode should adopt Non-halogen Flame Retardant Technology, avoids the harm to environment in production, use and offal treatment process of Halogen material.But there is the problem such as poor water resistance, easy migration in traditional polyolefine halogen-free expanded flame-retardant technology (IFR), cannot meet the material requirements of lithium cell battery group.
Chinese patent literature CN102002205A " flame-proof heat-resistant material and preparation method for battery container ", disclosed is the fire-retardant ABS of Halogen, owing to can not using ultrasonic wave heat-sealing technique, has greatly limited its application in lithium cell field.Halogen glass produces a large amount of black smokes while strengthening PP existence burning, even discharges the problem of toxic gas, does not meet the environmental requirement of new-energy automobile.From electrolyte resistance transport property angle, also there is impassable technical problem in Halogen flame-retarded technology.
Lithium cell requires the metallic impurity ions such as iron in material, sodium, potassium and chlorion/bromide anion can not move in electrolytic solution.If iron, sodium, potassium plasma are than lithium ion reduction potential, in process of charging, will more easily embed in carbon negative pole than lithium ion, reduce the reversible capacity of lithium ion battery.The metallic impurity ion of high density also can be separated out simultaneously, causes electrode surface cannot form effective passivation layer, easily battery is damaged.Chlorion/bromide anion may be oxidized to chlorine/bromine, is dissolved in organic electrolyte.Because chlorine and bromine are strong oxidizer, therefore with electrolytic solution in organic solvent while coexisting, can produce potential safety hazard; In addition, the graphite after embedding lithium is strong reductant, with chlorine and bromine, redox reaction fast can occur, and shows to form lithium chloride or the lithiumbromide of electrochemistry inertia at negative pole, disturbs SEI to form, and further affects cycle performance and increases interface impedance.Therefore also there is impassable technical problem in Halogen flame-retarded technology.
It is due to these two bottlenecks of fire-retardant and resistance to migrating technology to a great extent that bittern-free flame-proof material is not applied on new forms of energy dynamic lithium battery shell.Due to " the candle wick effect " of glass, the flame retardant effect of halogen-free expanded flame-retardant technology (IFR) is affected on the one hand, difficult fire-retardant; Lithium ion power cell case material is except requiring good mechanical property requirement on the other hand, also needs there is good water tolerance, resistance to lithium hexafluorophosphate electrolyte solution transport property and thermotolerance, and conventional I FR exists defect.
The case material that dynamic lithium battery is used also needs to meet performance below except fire-retardant, mechanical property:
(1) permeability rate is low: lithium hexafluoro phosphate is very responsive to moisture, and the moisture of trace can make its hydrolysis, produces lithium fluoride and phosphorus pentafluoride.Then phosphorus pentafluoride and water reaction, generate HF and POF3, consumes lithium ion, causes the increase of battery irreversible capacity and interior pressure; Hydrogen fluoride also can react with positive electrode material, causes the dissolving of positive electrode material.
(2) resistance to lithium hexafluorophosphate electrolyte solution performance: dynamic lithium battery electrolysis liquid is by solute and solvent composition, and solvent is methylcarbonate (DMC): NSC 11801 (EC)=1: 1 or DMC: methylethyl carbonic ether (EMC): EC=1: the mixture of 1: 1.Simple compound system and common single component expansion type flame retardant in the past, as the ammonium polyphosphate in compound system, tetramethylolmethane and melamine, triazines nitrogen heterocyclic ring structure in single component expansion type flame retardant, solubleness in lithium hexafluorophosphate electrolyte solution is large, the lithium hexafluorophosphate electrolyte solution of the fire retardant material Long Term Contact deep-etching of producing with this based flame retardant there will be swelling even jaundice, shortens the work-ing life of battery.
(3) thermotolerance: dynamic lithium battery housing requires stopping property excellence normally to work with protection battery.The first-selected technique of the fire-retardant GFRPP housings of advantage right and wrong such as ultrasonic welding is quick owing to having, clean, good sealing effect.No matter be heat-sealing or ultrasonic welding, all require material to have good thermotolerance, to prevent that material degraded occurs and affects sealing-strength in sealing process.At present, the general initial decomposition temperature of halogen-free expansion fire retardant, 220 DEG C of left and right, is difficult to meet the requirement of this technique.
(4) electrolyte resistance transport property: the metallic impurity ion such as iron in material, sodium, potassium and chlorion/bromide anion can not move in electrolytic solution, if iron, sodium, potassium plasma are than lithium ion reduction potential, in process of charging, will more easily embed in carbon negative pole than lithium ion, reduce the reversible capacity of lithium ion battery.The metallic impurity ion of high density also can be separated out simultaneously, causes electrode surface cannot form effective passivation layer, easily battery is damaged.Chlorion/bromide anion may be oxidized to chlorine/bromine, is dissolved in organic electrolyte.Because chlorine and bromine are strong oxidizer, therefore with electrolytic solution in organic solvent while coexisting, can produce potential safety hazard; In addition, the graphite after embedding lithium is strong reductant, with chlorine and bromine, redox reaction fast can occur, and shows to form lithium chloride or the lithiumbromide of electrochemistry inertia at negative pole, disturbs SEI to form, and further affects cycle performance and increases interface impedance.See that from this some Halogen flame-retarded technology also exists impassable technical problem.
Summary of the invention
The technical issues that need to address of the present invention are, a kind of halogen-free flameproof is provided, can reach UL94V0, the halogen-free polypropylene flame redardant reinforced composite of the resistance to lithium battery electrolytes of water-tolerant, low permeability rate, resistance to migration precipitation in lithium battery electrolytes, meets to meet the high requirement of lithium battery casing material.
The halogen-free polypropylene flame redardant reinforced composite of resistance to lithium battery electrolytes of the present invention, the component that contains following weight parts is through being prepared from:
Polypropylene alloy in said components, is prepared from by the component that contains following weight parts:
Halogen-free flame retardants in said components, is prepared from by the component that contains following weight parts:
The halogen-free expansion fire retardant of resistance to migration 80.0-99.6,
Melamine cyanurate (MCA) 0.2-10.0, its median size 4-8 μ m, more than 90% particle is in 1-10 μ m particle size interval,
The close ammonium salt 0.2-10.0 of polyphosphoric acid, its 10% aqeous suspension specific conductivity requirement≤150us/mm, 300 DEG C of x30min thermal weight loss≤2%;
The preparation method of the halogen-free polypropylene flame redardant reinforced composite of resistance to lithium battery electrolytes is as follows:
1. prepare halogen-free flame retardants master batch: each the halogen-free flame retardants of above-mentioned amount component is mixed, add in Banbury mixer, at 120-200 DEG C, add oligopolymer, under kneading effect, the oligopolymer of melting and fire retardant fully mix, carry out devolatilization and process 0.5-3 hour, then add tablets press, obtain diameter 2-5mm, the cylindrical pellet of length 2-5mm;
2. prepare polypropylene alloy: each the polypropylene alloy of above-mentioned amount component is mixed, melt extrude granulation at twin screw extruder, temperature is set respectively: 1 190 DEG C, district, 2 230 DEG C, districts, 3 265 DEG C, districts, 4 265 DEG C, districts, 5 250 DEG C, districts, 6 240 DEG C, districts, 7 240 DEG C, districts, 240 DEG C of head temperatures, rotating speed 200RPM;
3. the preparation of matrix material: by above-mentioned weight part, take the polypropylene alloy preparing, the halogen-free flame retardants master batch, metal oxide and the processing aid that prepare add high mixer to mix, add twin-screw extrusion owner spout, take glass and add people from side spout, jointly extrude at forcing machine melt blending, tie rod pelletizing, temperature is set respectively: 1 150 DEG C, district, 2 160 DEG C, districts, 3 180 DEG C, districts, 4 190 DEG C, districts, 5 195 DEG C, districts, 6 195 DEG C, districts, 7 200 DEG C, districts, 8 190 DEG C, districts, 9 190 DEG C, districts, 10 180 DEG C, districts, 170 DEG C of head temperatures, rotating speed 200RPM.
Described oligopolymer is to contain amino oligopolymer, and molecular weight is at 500-5000.
Preferred metal oxide be zinc oxide, aluminium sesquioxide, magnesian one or more.
Preferred processing aid comprises lubricant and oxidation inhibitor, and wherein lubricant is selected from one or more of polyethylene wax, Poly Propylene Wax, oxidized polyethlene wax; Oxidation inhibitor is 1010 and 168, and both weight ratios are 2: 1.
Compared with prior art, the present invention has increased substantially halogen-free flame-retardant glass fiber reinforced polypropylene material anti-migration precipitation performance in lithium cell electrolyte resistance soak test, can meet the requirement of lithium cell to case material.The halogen-free polypropylene flame redardant reinforced composite of the resistance to lithium battery electrolytes of the present invention, has following technology
Index:
Embodiment
Be further described of the present invention with embodiment below, but the present invention is not limited to these embodiment.
Embodiment 1
The halogen-free polypropylene flame redardant reinforced composite of this routine resistance to lithium battery electrolytes, fill a prescription as follows:
Preparation process is as follows:
1. prepare halogen-free expansion fire retardant master batch: the each component of halogen-free expansion fire retardant of above-mentioned amount mixes, add Banbury mixer, at 160 DEG C, add oligopolymer, under mediating, oligopolymer and the fire retardant of melting fully mix, devolatilization is processed 1.5 hours, enter granulator granulation, obtain diameter 2-5mm, the cylindrical pellet of length 2-5mm;
2. prepare polypropylene alloy: the polypropylene of above-mentioned amount, polyphenylene oxide, glycidyl acrylate grafting and oxidation inhibitor 626 are mixed, melt extrude granulation at twin screw extruder, temperature is set respectively: 1 190 DEG C, district, 2 230 DEG C, districts, 3 265 DEG C, districts, 4 265 DEG C, districts, 5 250 DEG C, districts, 6 240 DEG C, districts, 7 240 DEG C, districts, 240 DEG C of head temperatures.Rotating speed 200RPM.
3. the preparation of matrix material: take described weight part polypropylene alloy, halogen-free flame retardants master batch, metal oxide and processing aid and add high mixer to mix, add twin-screw extrusion owner spout, the glass of described weight part adds people from side spout, jointly extrude at forcing machine melt blending, tie rod pelletizing obtains product.Temperature is set respectively: 1 150 DEG C, district, 2 160 DEG C, districts, 3 180 DEG C, districts, 4 190 DEG C, districts, 5 195 DEG C, districts, 6 195 DEG C, districts, 7 200 DEG C, districts, 8 190 DEG C, districts, 9 190 DEG C, districts, 10 180 DEG C, districts, 170 DEG C of head temperatures, rotating speed 200RPM.
Embodiment 2.5: technique is with embodiment 1, and formula is in table 1.
Table 1: implement 2-5 formula table
Comparative example 1: the halogen-free expansion fire retardant of resistance to migration substitutes with JLS-PNP1, remaining same embodiment 1.JLS-PNP1 is that Hangzhou JLS Flame Retardants Chemical Co., Ltd. produces.
Embodiment and comparative example's performance index are in table 2.
Table 2: embodiment and comparative example's performance comparison table
Testing method:
Tensile strength, elongation at break: GB/T1040-2006
Flexural strength, modulus in flexure: GB/T9341-2008
Socle girder notched Izod impact strength: GB/T1843-2008
HDT(1.80MPa)：GB/T1634-2004
Permeability rate: GB/T1037
Can find that from table 2 data common Halogen system is not owing to itself there is no Fe, k plasma, can meet the requirement of electrolytic solution intermediate ion migration figureofmerit, can not meet lithium cell requirement but air penetrability and electrolytic solution soak rear weight rate.The heat-drawn wire of having added ZnO has improvement, better than magnesian, sees in addition in flame retardant resistance, and that adds zinc oxide is also better than magnesium oxide, and it is helpful to air penetrability and weight rate simultaneously.After oligopolymer is processed flame-retardant system, the consistency of fire retardant and polymkeric substance is improved, helpful to air penetrability, notched Izod impact strength etc.
Claims (4)
1. a halogen-free polypropylene flame redardant reinforced composite for resistance to lithium battery electrolytes, is characterized in that the component that contains following weight parts is through being prepared from:
Polypropylene alloy 30-85,
Glass fibre 5-20,
Halogen-free flame retardants 10-40,
Oligopolymer 0.1-10,
Metal oxide 0.1-10,
Processing aid 0.1-10;
Polypropylene alloy in said components, is prepared from by the component that contains following weight parts:
Polypropylene 30-80, it is copolymerization, the melting index=2-30g/10min under 2.16kg-230 DEG C of condition,
Polyphenylene oxide 0.5-30,
The polypropylene 0.5-10 of glycidyl acrylate grafting,
Oxidation inhibitor 626 0.01-5;
Halogen-free flame retardants in said components, is prepared from by the component that contains following weight parts:
The halogen-free expansion fire retardant of resistance to migration 80.0-99.6,
Melamine cyanurate 0.2-10.0, its median size 4-8 μ m, more than 90% particle is in 1-10 μ m particle size interval,
The close ammonium salt 0.2-10.0 of polyphosphoric acid, its 10% aqeous suspension specific conductivity requirement≤150us/mm, 300 DEG C of x30min thermal weight loss≤2%;
The preparation method of the halogen-free polypropylene flame redardant reinforced composite of resistance to lithium battery electrolytes is as follows:
1. prepare halogen-free flame retardants master batch: each the halogen-free flame retardants of above-mentioned amount component is mixed, add in Banbury mixer, at 120-200 DEG C, add oligopolymer, under kneading effect, the oligopolymer of melting and fire retardant fully mix, carry out devolatilization and process 0.5-3 hour, then add tablets press, obtain diameter 2-5mm, the cylindrical pellet of length 2-5mm;
2. prepare polypropylene alloy: each the polypropylene alloy of above-mentioned amount component is mixed, melt extrude granulation at twin screw extruder, temperature is set respectively: 1 190 DEG C, district, 2 230 DEG C, districts, 3 265 DEG C, districts, 4 265 DEG C, districts, 5 250 DEG C, districts, 6 240 DEG C, districts, 7 240 DEG C, districts, 240 DEG C of head temperatures, rotating speed 200RPM;
3. the preparation of matrix material: by above-mentioned weight part, take the polypropylene alloy preparing, the halogen-free flame retardants master batch preparing, metal oxide and processing aid add high mixer to mix, add twin-screw extrusion owner spout, take glass and add people from side spout, jointly extrude at forcing machine melt blending, tie rod pelletizing, temperature is set respectively: 1 150 DEG C, district, 2 160 DEG C, districts, 3 180 DEG C, districts, 4 190 DEG C, districts, 5 195 DEG C, districts, 6 195 DEG C, districts, 7 200 DEG C, districts, 8 190 DEG C, districts, 9 190 DEG C, districts, 10 180 DEG C, districts, 170 DEG C of head temperatures, rotating speed 200RPM.
2. the halogen-free polypropylene flame redardant reinforced composite of resistance to lithium battery electrolytes according to claim 1, is characterized in that described oligopolymer is to contain amino oligopolymer, and molecular weight is at 500-5000.
3. the halogen-free polypropylene flame redardant reinforced composite of resistance to lithium battery electrolytes according to claim 1 and 2, it is characterized in that described metal oxide be zinc oxide, aluminium sesquioxide, magnesian one or more.
4. the halogen-free polypropylene flame redardant reinforced composite of resistance to lithium battery electrolytes according to claim 1 and 2, it is characterized in that described processing aid comprises lubricant and oxidation inhibitor, wherein lubricant is selected from one or more of polyethylene wax, Poly Propylene Wax, oxidized polyethlene wax; Oxidation inhibitor is 1010 and 168, and both weight ratios are 2:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672612A (en) * | 2015-02-04 | 2015-06-03 | 苏州康华净化系统工程有限公司 | Flame retardant polypropylene material and preparation method thereof |
| CN106633784A (en) * | 2016-12-28 | 2017-05-10 | 宁波优科泰科技发展有限公司 | Battery box containing polyphenyl ether for lithium-ion power battery and energy storage battery and preparation method of battery box |
| CN109096616A (en) * | 2018-08-30 | 2018-12-28 | 杭州捷尔思阻燃化工有限公司 | Long glass fiber reinforced halogen-free polypropylene flame redardant battery case material and preparation method thereof |
| CN112759839A (en) * | 2021-01-22 | 2021-05-07 | 浙江科瑞达塑胶有限公司 | Composite material for AGM storage battery and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0703273A2 (en) * | 1994-09-26 | 1996-03-27 | General Electric Company | Filled blends of polyphenylene ether/polypropylene |
| CN102942738A (en) * | 2012-12-04 | 2013-02-27 | 上海日之升新技术发展有限公司 | High-CTI (Creepage Tracking Index) high-GWIT (Glow-Wire Ignition Temperature) environmental-friendly flame-retardant glass fiber reinforced PP/PPO (Polypropylene/Polyphenylene Oxide) alloy material and preparation method thereof |
| CN103421245A (en) * | 2013-08-23 | 2013-12-04 | 苏州长盛机电有限公司 | Enhanced halogen-free flame-retardant PP/PPO alloy and preparation method thereof |
-
2014
- 2014-05-09 CN CN201410194264.5A patent/CN104059298B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0703273A2 (en) * | 1994-09-26 | 1996-03-27 | General Electric Company | Filled blends of polyphenylene ether/polypropylene |
| CN102942738A (en) * | 2012-12-04 | 2013-02-27 | 上海日之升新技术发展有限公司 | High-CTI (Creepage Tracking Index) high-GWIT (Glow-Wire Ignition Temperature) environmental-friendly flame-retardant glass fiber reinforced PP/PPO (Polypropylene/Polyphenylene Oxide) alloy material and preparation method thereof |
| CN103421245A (en) * | 2013-08-23 | 2013-12-04 | 苏州长盛机电有限公司 | Enhanced halogen-free flame-retardant PP/PPO alloy and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672612A (en) * | 2015-02-04 | 2015-06-03 | 苏州康华净化系统工程有限公司 | Flame retardant polypropylene material and preparation method thereof |
| CN106633784A (en) * | 2016-12-28 | 2017-05-10 | 宁波优科泰科技发展有限公司 | Battery box containing polyphenyl ether for lithium-ion power battery and energy storage battery and preparation method of battery box |
| CN109096616A (en) * | 2018-08-30 | 2018-12-28 | 杭州捷尔思阻燃化工有限公司 | Long glass fiber reinforced halogen-free polypropylene flame redardant battery case material and preparation method thereof |
| CN109096616B (en) * | 2018-08-30 | 2021-08-31 | 杭州捷尔思阻燃化工有限公司 | Long glass fiber reinforced halogen-free flame-retardant polypropylene battery jar material and preparation method thereof |
| CN112759839A (en) * | 2021-01-22 | 2021-05-07 | 浙江科瑞达塑胶有限公司 | Composite material for AGM storage battery and application thereof |
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| CN104059298B (en) | 2016-05-11 |
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