CN102152578A - Method for preparing highly conductive multi-layered composite plate - Google Patents
Method for preparing highly conductive multi-layered composite plate Download PDFInfo
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- CN102152578A CN102152578A CN2010105975673A CN201010597567A CN102152578A CN 102152578 A CN102152578 A CN 102152578A CN 2010105975673 A CN2010105975673 A CN 2010105975673A CN 201010597567 A CN201010597567 A CN 201010597567A CN 102152578 A CN102152578 A CN 102152578A
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Abstract
The invention discloses a method for preparing a highly conductive multi-layered composite plate, which is a carbon plastic conductive composite plate formed by directly fusing and mixing polymer matrix and conductive stuffing in a certain mass ratio and by a multi-layer coextrusion or laminating process, and the resistance of the prepared highly conductive multi-layered composite plate is generally less than 0.5 omega.cm. The types and ratios of the polymer matrix and the conductive stuffing of each layer can be individually designed according o the requirements on conductivity, mechanical property, thickness and the like, the composite can be designed and prepared according to the requirement on the mechanical performance of a battery and the requirement on assembly, and a thin conducting plate can be prepared to fulfill the aim of improving the voltage efficiency of the battery. When the method is used, some structural design of the surface of the highly conductive multi-layered composite can also be performed simply and conveniently to meet the particular demands for application in the field of energy storage.
Description
Technical field
The present invention relates to the preparation method of the high conductive carbon plastic clad plate of a kind of multilayer, this composite plate can be applicable to new energy field, especially the energy-storage battery field.
Background technology
Along with the rise of new forms of energy industry, carbon is moulded the class conducing composite material and more and more is subject to people's attention.Selecting suitable matrix material is a crucial step in the high conducing composite material preparation, and common employed polymeric matrix is a thermoplastic polymer, such as polypropylene, polyethylene etc.Polypropylene generally is better than polyethylene based composition as the prepared conductivity of composite material of matrix, and the polyethylene conductive composite generally has high toughness, and the polypropylene-base composite generally has higher rigidity.General individual layer expressing technique is difficult prepares the composite plate that has multiple material premium properties concurrently, and this will limit the use of composite plate in the energy storage field greatly.
In order to improve the energy efficiency of energy-storage battery, need to reduce as far as possible the thickness of conduction composite plate, reduce the contact resistance between conduction composite plate and electrode material simultaneously.At present, preparing carbon, to mould conduction method that composite plate adopted generally be mould pressing process, Shooting Technique and individual layer extrusion calendaring technology.Yet, use the composite plate that these technologies are prepared, or area is less, or thickness is bigger, even thickness is less, also often can't safe being applied in the energy-storage battery because mechanical performance is relatively poor.Therefore being necessary to propose a kind of new preparation method prepares and has more excellent mechanical property, thinner thickness and the conduction composite plate less with the electrode material surface contact resistance.
Summary of the invention
The object of the present invention is to provide the preparation method of the high conduction of a kind of multilayer composite plate, the multilayer composite sheet that uses this method to prepare is compared general individual layer extrusion board and has high conduction, high-mechanical property, has concurrently advantages such as multiple material premium properties, can arrange in pairs or groups flexibly with energy-storage battery fluid frame simultaneously.
Technical scheme of the present invention is:
High conductive multilayer composite plate provided by the invention is that carbon is moulded the conduction composite plate, it is directly with the polymeric matrix and the conductive filler melting mixing of certain mass proportioning, be prepared from by multi-layer co-extruded or laminating technology, the resistivity of the high conductive multilayer composite plate that makes is generally below 0.5 Ω .cm.
Polymeric matrix of the present invention generally comprises polypropylene, polyethylene and polyvinyl chloride; Conductive filler generally comprises natural flake graphite powder, graphous graphite powder, expanded graphite, carbon black and carbon fiber (powder), CNT; Used polymeric matrix can mix use with arbitrary proportion according to actual needs, also can carry out suitable polarization to polymeric matrix and handle, and also can add suitable compatilizer as required.
High conductive multilayer composite plate of the present invention, the polymeric matrix of each layer and the kind of conductive filler and proportioning can design separately according to the requirement of electric conductivity, mechanical property and thickness etc.
High conductive multilayer composite plate of the present invention is prepared or produces according to following steps: (1) according to the material design of each layer, takes by weighing needed polymeric matrix and conductive filler earlier; (2) carry out mixing respectively to layers of material then; (3) carry out moulding by multi-layer co-extruded or laminating technology at last and prepare multilayer composite sheet.
Of the present invention material is carried out the mixing single screw extrusion machine that adopts banbury, mill, multi-screw extruder or have melting effect; As the material behind banbury and the mill mixing is carried out granulation, can adopt single screw rod or multi-screw extruder.
Multi-layer co-extruded technology of the present invention is to extrude from extruder separately respectively after the granulation of each layer needed raw material, jointly by extrusion die, carries out cooling and shaping through three rollers or multiple roll calendering (press polish) machine then; The temperature of each workspace of extruder is 100-300 ℃, and the temperature of three rollers or multi-rolling mill is controlled at 50-250 ℃, and the speed of carry-over pinch rolls is controlled at 0-5m/min.
Laminating technology of the present invention is with the superimposed lamination of a plurality of laminas, by hot press it is combined into one then; The temperature of hot press is controlled at 100-300 ℃, and pressure is controlled at 0-100MPa, and the press time is 0-100min.
The used lamina of lamination of the present invention can be opened refining back directly calendering or banburying extrusion calendaring moulding preparation by banburying; Banburying is opened in the refining calendering technology, 100-300 ℃ of banburying premix temperature, and the temperature of mill is subsequently compared 0-100 ℃ of banbury intensification, and each stack temperature is controlled at 100-250 ℃.
High conductive multilayer composite plate of the present invention, it can carry out certain surface texture moulding by knurling rolls in two surfaces up and down, also can directly be pressed into flat surface.
Advantage of the present invention and good effect show as: the preparation method of high conductive multilayer composite plate provided by the invention can realize the comprehensive of various material excellent properties, simultaneously when being applied to the energy-storage battery field, can carry out the design and the preparation of composite according to the mechanical performance requirement and the matching requirements of energy-storage battery, can prepare the less conductive plate of thickness, to satisfy the purpose that improves cell voltage efficient.Also can carry out the certain structure design to high conducing composite material surface simply and easily by the present invention, to satisfy the specific demand of using in the energy storage field.
The specific embodiment
Embodiment 1
Mass ratio by 8.5:9:2:0.5 takes by weighing high density polyethylene (HDPE), the synthetic graphite powder, expanded graphite and other fillers, secondly take by weighing COPP according to same ratio, the synthetic graphite powder, expanded graphite and other fillers, putting into banbury respectively carries out mixing, then by the single screw extrusion machine extruding pelletization, two kinds of pellets are rendered to (each warm area temperature of extruder is controlled at 180-260 ℃) in two extruders respectively, can prepare the surface by the co-extrusion calendering and be polypropylene matrix, the centre is the composite conducting plate of the three-layer sandwich structure of high density polyethylene (HDPE) matrix, thickness is 0.5mm, this composite plate has the rigidity of PP composite material and the toughness of composite polyethylene material concurrently, can weld fusion with polypropylene fluid frame.
Embodiment 2
Mass ratio by 4:3:3:0.5 takes by weighing polypropylene, synthetic graphite powder, high conductive black and other fillers, it is mixing that it is directly put into banbury, then by the double screw extruder extruding pelletization, pellet is dropped in two extruders (each warm area temperature of extruder is 200-260 ℃), by co-extrusion, three-roll press-polishing (roller temperature is 90 ℃) can be prepared the connatural high conduction composite plate (thickness 0.6mm) of upper and lower surface.Compare with the single layer composite of general extrusion calendaring technology preparation, this composite plate mechanics performance is more excellent, and bending strength can reach more than the 45MPa, and specific insulation is 0.14 Ω .cm, and conductivity difference is in ± 0.02 Ω .cm everywhere.Change felt wrapped roll into certain surface lines roller, the composite surface of preparing and the contact point of felt significantly increase, and can reduce its contact resistance.This composite plate is applied in the all-vanadium liquid flow energy storage monocell, at 80mA/cm
2Discharge and recharge that the voltage efficiency of monocell reaches 85% under the condition.In the time of in this composite dual-electrode plates being applied to 10kW energy-storage battery heap, under the identical condition that discharges and recharges, the energy efficiency of pile reaches 81%.
Embodiment 3
Mass ratio by 4:3:3 takes by weighing polyvinyl chloride, graphite powder, conductive black etc., put it into mixer mixing (165 ℃ of banbury temperature), then through mill (temperature is 180 ℃), calender (roller temperature is controlled at 170-190 ℃), peel off deflector roll, embossing etc. are prepared has certain thickness conductive sheet, again with the superimposed lamination of sheet material, prepares the laminate (thickness 0.55mm) of high conduction and high-mechanical property.The bending strength of this composite plate is near 50MPa, specific insulation 0.14-0.2 Ω .cm.
Claims (8)
1. the preparation method of a high conductive multilayer composite plate, it is characterized in that: described high conductive multilayer composite plate is that carbon is moulded the conduction composite plate, it is directly with the polymeric matrix and the conductive filler melting mixing of certain mass proportioning, be prepared from by multi-layer co-extruded or laminating technology, the resistivity of the high conductive multilayer composite plate that makes is below 0.5 Ω .cm.
2. the preparation method of high conductive multilayer composite plate according to claim 1 is characterized in that: described polymeric matrix comprises polypropylene, polyethylene and polyvinyl chloride; Conductive filler comprises natural flake graphite powder, graphous graphite powder, expanded graphite, carbon black and carbon fiber (powder), CNT; Used polymeric matrix can mix use with arbitrary proportion according to actual needs, also can carry out suitable polarization to polymeric matrix and handle, and also can add suitable compatilizer as required.
3. the preparation method of high conductive multilayer composite plate according to claim 1, it is characterized in that: described high conductive multilayer composite plate is produced according to following steps: (1) according to the material design of each layer, takes by weighing needed polymeric matrix and conductive filler earlier; (2) carry out mixing respectively to layers of material then; (3) carry out moulding by multi-layer co-extruded or laminating technology at last and prepare multilayer composite sheet.
4. the preparation method of high conductive multilayer composite plate according to claim 3 is characterized in that: described material is carried out the mixing single screw extrusion machine that adopts banbury, mill, multi-screw extruder or have melting effect; As the material behind banbury and the mill mixing is carried out granulation, can adopt single screw rod or multi-screw extruder.
5. the preparation method of high conductive multilayer composite plate according to claim 3, it is characterized in that: described multi-layer co-extruded technology is to extrude from extruder separately respectively after the granulation of each layer needed raw material, common by extrusion die, carry out cooling and shaping through three rollers or multiple roll calendering (press polish) machine then; The temperature of each workspace of extruder is 100-300 ℃, and the temperature of three rollers or multi-rolling mill is controlled at 50-250 ℃, and the speed of carry-over pinch rolls is controlled at 0-5m/min.
6. the preparation method of high conductive multilayer composite plate according to claim 3 is characterized in that: described laminating technology is with the superimposed lamination of a plurality of laminas, by hot press it is combined into one then; The temperature of hot press is controlled at 100-300 ℃, and pressure is controlled at 0-100MPa, and the press time is 0-100min.
7. the preparation method of high conductive multilayer composite plate according to claim 3 is characterized in that: the used lamina of described lamination can be opened refining back directly calendering or banburying extrusion calendaring moulding preparation by banburying; Banburying is opened in the refining calendering technology, 100-300 ℃ of banburying premix temperature, and the temperature of mill is subsequently compared 0-100 ℃ of banbury intensification, and each stack temperature is controlled at 100-250 ℃.
8. the preparation method of high conductive multilayer composite plate according to claim 1 is characterized in that: described high conductive multilayer composite plate, it can carry out certain surface texture moulding by knurling rolls in two surfaces up and down, also can directly be pressed into flat surface.
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| CN2010105975673A CN102152578A (en) | 2010-12-21 | 2010-12-21 | Method for preparing highly conductive multi-layered composite plate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165907A (en) * | 2013-04-03 | 2013-06-19 | 胡国良 | Vanadium battery electrode and preparation method thereof |
| CN108702854A (en) * | 2016-12-19 | 2018-10-23 | Waps株式会社 | The preparation method of cooling fin including double layer of insulation and the cooling fin for utilizing this method |
| CN109640607A (en) * | 2018-10-23 | 2019-04-16 | 苏州铂韬新材料科技有限公司 | A kind of electromagnetic performance can flexible design flame retardant type soft-magnetic composite material and preparation method thereof |
| CN109728319A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of bipolar plate of vanadium cell and its continuous processing device and method |
| CN109728318A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of vanadium cell highly conductive bipolar plates and its continuous processing device and method |
| CN110001176A (en) * | 2019-04-23 | 2019-07-12 | 常熟优锆包装材料有限公司 | A kind of preparation process of colour static mat |
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| CN1203461A (en) * | 1997-03-27 | 1998-12-30 | 埃姆特克磁性公司 | Production of moldings for lithium ion batteries |
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| CN1813314A (en) * | 2003-06-27 | 2006-08-02 | 通用电气公司 | Electrically conductive compositions comprising carbon nanotubes and method of manufacture thereof |
| CN101071876A (en) * | 2007-05-23 | 2007-11-14 | 天津大学 | Fuel cell graphitc composite flow field plate and its manufacturing method |
| CN101308923A (en) * | 2007-05-18 | 2008-11-19 | 中国科学院大连化学物理研究所 | Carbon plastic electricity conductive bipolar board for liquid energy-storing battery and manufacture thereof |
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| CN1203461A (en) * | 1997-03-27 | 1998-12-30 | 埃姆特克磁性公司 | Production of moldings for lithium ion batteries |
| JP2002264272A (en) * | 2002-01-15 | 2002-09-18 | Denki Kagaku Kogyo Kk | Conductive composite plastic sheet and molding |
| CN1813314A (en) * | 2003-06-27 | 2006-08-02 | 通用电气公司 | Electrically conductive compositions comprising carbon nanotubes and method of manufacture thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165907A (en) * | 2013-04-03 | 2013-06-19 | 胡国良 | Vanadium battery electrode and preparation method thereof |
| CN108702854A (en) * | 2016-12-19 | 2018-10-23 | Waps株式会社 | The preparation method of cooling fin including double layer of insulation and the cooling fin for utilizing this method |
| CN109728319A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of bipolar plate of vanadium cell and its continuous processing device and method |
| CN109728318A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院金属研究所 | A kind of vanadium cell highly conductive bipolar plates and its continuous processing device and method |
| CN109728319B (en) * | 2017-10-30 | 2021-10-22 | 中国科学院金属研究所 | Bipolar plate for vanadium battery and continuous processing device and method thereof |
| CN109728318B (en) * | 2017-10-30 | 2021-10-22 | 中国科学院金属研究所 | High-conductivity bipolar plate for vanadium battery and continuous processing device and method thereof |
| CN109640607A (en) * | 2018-10-23 | 2019-04-16 | 苏州铂韬新材料科技有限公司 | A kind of electromagnetic performance can flexible design flame retardant type soft-magnetic composite material and preparation method thereof |
| CN109640607B (en) * | 2018-10-23 | 2020-11-10 | 苏州铂韬新材料科技有限公司 | Flame-retardant soft magnetic composite material with flexibly designed electromagnetic performance |
| CN110001176A (en) * | 2019-04-23 | 2019-07-12 | 常熟优锆包装材料有限公司 | A kind of preparation process of colour static mat |
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Application publication date: 20110817 |