CN115149164A - Plastic part, preparation method thereof and battery cover body assembly - Google Patents
Plastic part, preparation method thereof and battery cover body assembly Download PDFInfo
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- CN115149164A CN115149164A CN202210829919.6A CN202210829919A CN115149164A CN 115149164 A CN115149164 A CN 115149164A CN 202210829919 A CN202210829919 A CN 202210829919A CN 115149164 A CN115149164 A CN 115149164A
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- 239000004033 plastic Substances 0.000 title claims abstract description 186
- 229920003023 plastic Polymers 0.000 title claims abstract description 186
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000002425 crystallisation Methods 0.000 claims abstract description 54
- 230000008025 crystallization Effects 0.000 claims abstract description 54
- 238000012360 testing method Methods 0.000 claims abstract description 43
- 238000000113 differential scanning calorimetry Methods 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000005259 measurement Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 81
- 238000010438 heat treatment Methods 0.000 claims description 70
- 239000000463 material Substances 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003365 glass fiber Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 239000002991 molded plastic Substances 0.000 claims description 20
- 238000001746 injection moulding Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 34
- 239000004734 Polyphenylene sulfide Substances 0.000 description 29
- 229920000069 polyphenylene sulfide Polymers 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 description 17
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- 239000004917 carbon fiber Substances 0.000 description 14
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 7
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- 238000012986 modification Methods 0.000 description 3
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- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
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Images
Classifications
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/147—Lids or covers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
- B29C45/0055—Shaping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
-
- 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
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/147—Lids or covers
- H01M50/155—Lids or covers characterised by the material
- H01M50/16—Organic material
Abstract
The invention belongs to the technical field of battery production and manufacture, and particularly relates to a plastic part, a preparation method thereof and a battery cover body assembly, wherein the plastic part is tested by Differential Scanning Calorimetry (DSC), and the crystallization exothermic peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g; differential scanning calorimetry test is carried out in inert gas atmosphere, the temperature is raised in the temperature range of 25-400 ℃ at the temperature raising speed of 5k/min in the measurement of melting and crystallization temperature and enthalpy, and after the test is finished, the crystallization heat release peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g; the determination of the melting and crystallization temperatures and the enthalpy is carried out using a differential scanning calorimeter under the following test conditions: the test amount is 30mg, and the temperature rise speed is 5k/min; the atmosphere is N2, and the measuring temperature range is 25-400 ℃. The application eliminates secondary crystallization of the plastic part, avoids creep deformation of the plastic part in different degrees under high temperature environment, and accordingly enables the battery cover body assembly using the plastic part to be stable in structure.
Description
Technical Field
The invention belongs to the technical field of battery production and manufacturing, and particularly relates to a plastic part, a preparation method thereof and a battery cover body assembly.
Background
PPS (polyphenylene sulfide) is a novel special engineering plastic with excellent comprehensive performance, has the characteristics of excellent high temperature resistance, corrosion resistance, radiation resistance, flame retardance, balanced physical and mechanical properties, excellent dimensional stability and the like, has a continuous use temperature of 220-240 ℃, a thermal deformation temperature of over 260 ℃, and can be used as a structural component to be widely applied to the field of power battery top covers because the resilience of a bearing sealing element is stabilized by the temperature resistance stability and high structural strength.
Conventional plastic part uses the PPS material to have once crystallization incomplete behind injection moulding, and secondary crystallization's problem can appear under the high temperature environment, and after the plastic part that makes PPS assembled into the battery top cap as power battery structure subassembly, the plastic part can take place the creep of different degrees under the high temperature environment, finally leads to battery top cap structure unstability.
Disclosure of Invention
One of the objects of the present invention is: the plastic part has the advantages that the defects in the prior art are overcome, secondary crystallization cannot occur in the plastic part under a high-temperature environment, and creep deformation in different degrees is avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a plastic part is tested by Differential Scanning Calorimetry (DSC), and the crystallization exothermic peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g;
differential scanning calorimetry test is carried out in inert gas atmosphere, the temperature is raised in the temperature range of 25-400 ℃ at the temperature raising speed of 5k/min in the measurement of melting and crystallization temperature and enthalpy, and after the test is finished, the crystallization heat release peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g;
the determination of the melting and crystallization temperatures and of the enthalpy was carried out using a differential scanning calorimeter under the following test conditions: the test amount is 30mg, and the temperature rise speed is 5k/min; the atmosphere being N 2 The measuring temperature range is 25-400 ℃.
Compared with the prior art, the invention has the beneficial effects that: the application of plastic part is at DCS test: the crystallization exothermic peak intensity of 110-120 ℃ is less than 0.1J/g, and no obvious crystallization exothermic peak exists. Eliminate the secondary crystallization of plastic part, avoid the plastic part to appear creep deformation of different degrees under high temperature environment.
The second purpose of the invention is: the preparation method of the plastic part comprises the following steps:
s1, injection molding of the plastic composite material;
s2, carrying out high-temperature heat treatment on the injection-molded plastic part, wherein the heating temperature is 100-260 ℃, and the heating time is more than or equal to 1h.
Compared with the prior art, the invention has the beneficial effects that: the crystallization exothermic peak intensity of 110-120 ℃ is less than 0.1J/g, wherein the crystallization exothermic peak intensity of less than 0J/g represents that the peak is downward and an endothermic peak exists; a crystallization exotherm peak intensity greater than 0J/g indicates a peak up, with an exotherm peak present. Therefore, the plastic part has no obvious crystallization heat release wave peak, the secondary crystallization of the plastic part is eliminated, and the creep deformation of the plastic part in different degrees under a high-temperature environment is avoided.
As an improvement of the preparation method, in step S1, the raw materials of the plastic composite material comprise PPS resin, glass fiber and an auxiliary agent.
As an improvement of the preparation method, the raw materials of the plastic composite material also comprise a conductive material.
As an improvement of the preparation method, the mass ratio of the PPS resin, the conductive material, the glass fiber and the auxiliary agent is (52.5-57.9), (12-18.4), (29-31) and (0.1-3.5).
As an improvement of the preparation method, the conductive material comprises conductive fibers and conductive carbon particles.
As an improvement of the preparation method, the mass ratio of the conductive fiber to the conductive carbon particles is (12-17.9) to (0-0.5).
As an improvement of the preparation method, the method further comprises the following steps in step S1:
s1-1, weighing raw materials of the plastic composite material according to a ratio, adding the raw materials into a high-speed mixer, mixing to obtain a mixed material, and putting the mixed material into a hopper and stirring;
s1-2, adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
s1-3, extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material;
s1-4, performing high-temperature injection molding on the plastic composite material to obtain a plastic part.
As an improvement of the preparation method, in step S2, the injection molding process comprises: and injecting the molten plastic composite material into a mold, and cooling the plastic composite material in the mold to obtain the plastic part.
As an improvement of the preparation method, the plastic composite material with the temperature of 290-340 ℃ is poured into a mold with the temperature of 140-190 ℃ in the injection molding process.
The third purpose of the invention is that: a battery cover assembly is provided, which comprises the plastic part.
Compared with the prior art, the invention has the beneficial effects that: because the used plastic part is used in a high-temperature environment, secondary crystallization cannot occur, and therefore the structure of the battery cover body assembly using the plastic part is stable.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present invention will be described below with reference to the accompanying drawings.
FIG. 1 is a flow chart of a method for manufacturing a plastic part according to the present invention.
FIG. 2 is a flowchart illustrating a method for manufacturing a plastic part according to the present invention.
FIG. 3 is one of the DSC test charts of the plastic parts of the present invention.
Fig. 4 is a second test chart of DSC of the plastic part of the present invention.
Fig. 5 is a third test chart of a DSC of the plastic part of the present invention.
Fig. 6 is a fourth chart showing DSC of the plastic parts according to the present invention.
FIG. 7 is a fifth chart showing DSC test of the plastic parts of the present invention.
FIG. 8 shows a sixth chart of DSC test of the plastic parts of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, in which it should be noted that: various modifications of the invention in equivalent forms, which would be apparent to those skilled in the art, are possible without departing from the principles of the invention, and are within the scope of the invention as defined in the appended claims.
The invention discloses a plastic part, which is tested by Differential Scanning Calorimetry (DSC), wherein the crystallization exothermic peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g;
differential scanning calorimetry test is carried out in inert gas atmosphere, the temperature is raised in the temperature range of 25-400 ℃ at the temperature raising speed of 5k/min in the measurement of melting and crystallization temperature and enthalpy, and after the test is finished, the crystallization heat release peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g;
the determination of the melting and crystallization temperatures and of the enthalpy was carried out using a differential scanning calorimeter under the following test conditions: the test quantity is 30mg, and the temperature rise speed is 5k/min; the atmosphere is N2, and the measuring temperature range is 25-400 ℃.
Specifically, the differential scanning calorimeter used in the present application is DCS-3. Differential scanning calorimetry testing was performed according to the criteria of GB-T19466.3-2004 Plastic Differential Scanning Calorimetry (DSC) part 3.
The application of plastic part is at DCS test: the crystallization exothermic peak intensity at 110-120 ℃ is less than 0.1J/g, and the crystallization exothermic peak intensity of less than 0J/g shows that the peak is downward and an endothermic peak exists; a crystallization exotherm peak intensity greater than 0J/g indicates a peak up, with an exotherm peak present. Therefore, the plastic part has no obvious crystallization heat release wave peak, the secondary crystallization of the plastic part is eliminated, and the creep deformation of the plastic part in different degrees under a high-temperature environment is avoided.
Referring to fig. 1 to 2, the present invention also discloses a method for preparing a plastic part, comprising the following steps:
s1, injection molding of the plastic composite material;
s2, carrying out high-temperature heat treatment on the injection-molded plastic part, wherein the heating temperature is 100-260 ℃, and the heating time is more than or equal to 1h.
By carrying out high-temperature heat treatment on the injection-molded plastic part, setting the heating temperature of the high-temperature heat treatment to be 100-260 ℃ and the heating time to be more than or equal to 1h, secondary crystallization of the plastic part can be eliminated, creep deformation of the plastic part in different degrees under a high-temperature environment is avoided, and therefore the structure of the battery cover body assembly using the plastic part is stable.
Specifically, the heating temperature of the high-temperature heat treatment is set to be 100-260 ℃, and the heating temperature is selected in a gradient of every 40 ℃. Preferably, the heating temperature of the high-temperature heat treatment is set to be 100-140 ℃, so that secondary crystallization of the plastic part in a high-temperature environment can be better eliminated.
In some embodiments, in step S1, the raw materials of the plastic composite material include PPS resin, glass fiber, and an auxiliary agent.
In these examples, the mechanical properties and heat resistance of the plastic composite material can be significantly improved by adding glass fibers to the PPS resin. The auxiliary agent comprises an antioxidant, a plasticizer, a surface treatment agent and a light stabilizer. The antioxidant in the auxiliary agent can improve the oxidation resistance of the plastic composite material, the plasticizer can increase the flexibility of the plastic composite material, the surface treatment agent can enable the surface flatness of the plastic composite material to be better, and the light stabilizer enables the plastic composite material to eliminate or slow down the possibility of photochemical reaction under the radiation of light, so that the photo-aging process is prevented or delayed, and the purpose of prolonging the service life of a high polymer product is achieved. These auxiliaries are all of the types which are customary and known in the art.
In some embodiments, the plastic composite material further comprises a conductive material.
In the embodiments, the conductive material in the plastic composite material is distributed on the phase interface of the resin matrix formed by the PPS resin, and the conductive material is easy to form a conductive network on the basis of uniform dispersion of the phase interface, so that the conductive performance is remarkably improved, and the volume resistance of the plastic composite material can be reduced by only adding less conductive material.
In some embodiments, the mass ratio of the PPS resin, the conductive material, the glass fiber and the auxiliary agent is (52.5-57.9): (12-18.4): 29-31): 0.1-3.5.
In these examples, by limiting the respective raw material components to the above ranges, the plastic composite material can possess good mechanical properties, heat resistance and electrical conductivity.
In some embodiments, the conductive material includes conductive fibers and conductive carbon particles.
In the embodiments, the conductive fibers can effectively avoid the defect of poor conductivity of the conductive carbon particles in the vertical direction, and the complex formulation of the conductive fibers and the conductive carbon particles can more effectively form a more perfect three-dimensional network structure in PPS, so that the conductive channels can be more favorably formed, and the conductivity of the matrix can be more easily improved.
In some embodiments, the mass ratio of the conductive fibers to the conductive carbon particles is (12-17.9) to (0-0.5).
In the embodiments, the content of the conductive fiber is increased, the content of the conductive carbon particles is reduced, and the conductive fiber and the conductive carbon particles are limited in the above range, so that the shrinkage rate of the material after injection molding can be further reduced, the surface flatness of the plastic part is improved, the conductive integration level is improved, and the stability of the positive electrode bonding resistance is remarkably improved. The conductive fibers may be conductive carbon fibers, carbon nanofibers, carbon nanotubes, or the like.
In some embodiments, step S1 further comprises:
s1-1, weighing raw materials of the plastic composite material according to a ratio, adding the raw materials into a high-speed mixer, mixing to obtain a mixed material, and putting the mixed material into a hopper and stirring;
s1-2, adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
s1-3, extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material;
s1-4, performing high-temperature injection molding on the plastic composite material to obtain a plastic part.
In the embodiments, the plastic composite material and the plastic part are simple in preparation process, and can repeatedly meet the process requirements of injection molding processing.
In some embodiments, in step S2, the injection molding process S2-1 includes: and injecting the molten plastic composite material into a mold, and cooling the plastic composite material in the mold to obtain the plastic part. In these embodiments, the plastic composite material is injected into the mold, which is configured to have the same shape as the desired shape of the battery cover assembly, so that after the plastic composite material is cooled, a plastic structural member having the desired shape can be obtained for assembly of the battery cover assembly. Meanwhile, a metal part in the battery cover body assembly can be placed in the mold, and then the plastic composite material is injected into the mold, so that a mixed injection molding piece of the plastic composite material and the metal part is obtained. In step S2, the high temperature heating process S2-2 includes: and carrying out high-temperature heat treatment on the plastic part, wherein the heating temperature is 100-260 ℃, and the heating time is more than or equal to 1h.
In some embodiments, the plastic composite material with the temperature of 290-340 ℃ is poured into a mold with the temperature of 140-190 ℃ during the injection molding process.
In the embodiments, the temperature of the mold has a great influence on the molding quality and molding efficiency of the plastic part, the plastic composite material is molten when the temperature is 290-340 ℃, and the molten plastic composite material is injected into the mold with the temperature of 140-190 ℃, so that in the mold with the temperature range, the molten plastic composite material has good fluidity, the mold cavity can be filled with the plastic composite material, a plastic structural part with a high-quality appearance surface can be obtained, the solidification time of the plastic composite material can be prevented from being overlong, the crystallization process of the plastic composite material can be facilitated, and the size change of the plastic composite material during storage and use can be reduced.
The invention also discloses a battery cover body assembly which sequentially comprises the pole, the plastic part, the top cover, the sealing ring, the lower plastic and the conductive block from top to bottom. Because the plastic part that uses can not appear creeping under high temperature environment, consequently battery cover body assembly's stable in structure.
The present invention will be further described with reference to the following examples.
Example 1
The preparation process of the plastic part of this embodiment includes:
weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 53.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection molded plastic part, wherein the heating temperature is 100 ℃, and the heating time is 4 hours.
Example 2
Different from the embodiment 1, the embodiment performs high temperature heat treatment on the injection molded plastic part, the heating temperature is 140 ℃, and the heating time is 1 hour.
The remaining steps are the same as in embodiment 1, and are not described herein again.
Example 3
Different from the embodiment 1, the injection molded plastic part is subjected to high temperature heat treatment at 180 ℃ for 1 hour.
The rest of the steps are the same as those in embodiment 1, and are not described herein again.
Example 4
Different from the embodiment 1, the embodiment performs high temperature heat treatment on the injection molded plastic part, the heating temperature is 220 ℃, and the heating time is 1 hour.
The rest of the steps are the same as those in embodiment 1, and are not described herein again.
Example 5
Different from the embodiment 1, the embodiment performs high temperature heat treatment on the injection molded plastic part, the heating temperature is 260 ℃, and the heating time is 1 hour.
The remaining steps are the same as in embodiment 1, and are not described herein again.
Example 6
Different from the embodiment 1, the mass ratio of the PPS resin, the conductive carbon fibers, the conductive carbon particles, the glass fibers and the calcium carbonate in the embodiment is 56.1.
The remaining steps are the same as in embodiment 1, and are not described herein again.
Example 7
Unlike example 6, the injection-molded plastic part was subjected to a high-temperature heat treatment at 140 ℃ for 1 hour.
The rest of the steps are the same as those in embodiment 6, and are not described herein again.
Example 8
Unlike example 6, the injection-molded plastic part was subjected to a high-temperature heat treatment at 180 ℃ for 1 hour.
The remaining steps are the same as in embodiment 6, and are not described herein again.
Example 9
Unlike example 6, the injection-molded plastic part was subjected to a high-temperature heat treatment at 220 ℃ for 1 hour.
The rest of the steps are the same as those in embodiment 6, and are not described herein again.
Example 10
Unlike example 6, the injection-molded plastic part was subjected to a high-temperature heat treatment at 260 ℃ for 1 hour.
The rest of the steps are the same as those in embodiment 6, and are not described herein again.
Example 11
Different from example 1, the mass ratio of the PPS resin, the conductive carbon fibers, the conductive carbon particles, the glass fibers and the calcium carbonate in this example is 56.5.
The rest of the steps are the same as those in embodiment 1, and are not described herein again.
Example 12
Different from the embodiment 1, the PPS resin, the conductive carbon fibers, the conductive carbon particles, the glass fibers and the calcium carbonate in the embodiment are weighed according to a mass ratio of 50.1.
The rest of the steps are the same as those in embodiment 1, and are not described herein again.
Example 13
Different from example 1, the PPS resin, the conductive carbon fibers, the conductive carbon particles, the glass fibers and the calcium carbonate of the present example are weighed according to a mass ratio of 49.6.
The rest of the steps are the same as those in embodiment 1, and are not described herein again.
Example 14
Different from the embodiment 1, the mass ratio of the PPS resin, the conductive carbon fibers, the conductive carbon particles, the glass fibers and the calcium carbonate in the embodiment is 56.
The remaining steps are the same as in embodiment 1, and are not described herein again.
Example 15
Different from the embodiment 1, the PPS resin, the glass fiber and the calcium carbonate in the embodiment are weighed according to a mass ratio of 68.5.
The remaining steps are the same as in embodiment 1, and are not described herein again.
Comparative example 1
The preparation process of the plastic part of the comparative example comprises the following steps:
the preparation method comprises the following steps of (1) weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 53.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection-molded plastic part, wherein the heating temperature is 90 ℃, and the heating time is 1 hour.
Comparative example 2
The preparation process of the plastic part of the comparative example comprises the following steps:
weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 53.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection molded plastic part, wherein the heating temperature is 270 ℃, and the heating time is 1 hour.
Comparative example 3
The preparation process of the plastic part of the comparative example comprises the following steps:
weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 56.1;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection molded plastic part, wherein the heating temperature is 90 ℃, and the heating time is 1 hour.
Comparative example 4
The preparation process of the plastic part of the comparative example comprises the following steps:
weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 56.1;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection molded plastic part, wherein the heating temperature is 270 ℃, and the heating time is 1 hour.
Comparative example 5
The preparation process of the plastic part of the comparative example comprises the following steps:
weighing PPS resin, glass fiber and calcium carbonate according to a mass ratio of 68.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection-molded plastic part, wherein the heating temperature is 90 ℃, and the heating time is 1 hour.
Comparative example 6
The preparation process of the plastic part of the comparative example comprises the following steps:
weighing PPS resin, glass fiber and calcium carbonate according to a mass ratio of 68.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain a plastic composite material;
injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain a plastic part;
and (3) carrying out high-temperature heat treatment on the injection molded plastic part, wherein the heating temperature is 270 ℃, and the heating time is 1 hour.
Comparative example 7
The preparation process of the plastic part of the comparative example comprises the following steps:
the preparation method comprises the following steps of (1) weighing the PPS resin, the conductive carbon fibers, the conductive carbon particles, the glass fibers and the calcium carbonate according to a mass ratio of (56.1);
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material;
and (3) injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain the plastic part.
Comparative example 8
The preparation process of the plastic part of the comparative example comprises the following steps:
the preparation method comprises the following steps of (1) weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 53.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material;
and (3) injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain the plastic part.
Comparative example 9
The preparation process of the plastic part of the comparative example comprises the following steps:
adding PPS resin, glass fiber and calcium carbonate into a high-speed mixer according to a mass ratio of 68.5;
adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material;
and (3) injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain the plastic part.
Performance testing
1. The plastic parts, the poles, the top cover, the sealing rings, the lower plastic and the conductive blocks prepared in the above embodiments 1 to 7 are assembled into a battery cover body assembly, and the anode resistance of the battery cover body assembly is tested in the following manner: and (3) taking the 100Pcs battery cover body assembly, and testing the resistance between the pole and the top cover by using an internal resistance tester.
2. The distance value between the polar column and the top cover in the battery cover body assembly is measured firstly, then the plastic part is baked at different temperatures/time, finally the distance value between the polar column and the top cover is measured, and the difference value of the two distance values is the change value of the plastic part.
3. And (3) carrying out DSC test on the plastic part, and comparing the plastic part with different baking temperatures/time, wherein the DSC test method comprises the following steps: GB-T19466.3-2004 plastics Differential Scanning Calorimetry (DSC) part 3: and (4) measuring the melting and crystallization temperatures and the heat content.
The parts by weight of the raw materials and the properties of the resulting plastic parts of examples 1 to 15 and comparative examples 1 to 9 are shown in Table 1.
TABLE 1
From the above data, it can be seen that the plastic parts injection molded in examples 1 to 15 are first subjected to heat treatment at a high temperature of 100 to 260 ℃ for more than or equal to 1 hour, and then the top cover is assembled, so that the height change of the pole is very stable, the positive electrode resistance consistency is good, and the crystallization heat release peak is minimal (substantially disappeared); compared with the comparative examples 1, 3 and 5, the plastic parts are subjected to heat treatment at a high temperature of 90 ℃ for more than or equal to 1 hour, and then the top cover is assembled, so that the height change of the pole is unstable, the resistance consistency of the positive electrode is poor, and the crystallization heat release peak is very obvious; in comparative examples 2, 4 and 6, the plastic parts are subjected to heat treatment at a high temperature of 270 ℃ for more than or equal to 1h, and then the top cover is assembled, although the crystallization heat release peak disappears, the height change of the post after baking starts to be unstable and the consistency of the positive electrode resistance starts to deteriorate due to the fact that the height change is close to the melting point of PPS; in addition, the plastic parts in comparative examples 7, 8 and 9 are not subjected to high temperature heating treatment after injection molding, and have crystallization heat release peaks at 110-120 ℃, and the plastic parts are unstable under the influence of high temperature: after the top cover is assembled, the height change of the pole is extremely unstable, the consistency of the positive electrode resistance is very poor, and the crystallization heat release peak is also extremely obvious.
Meanwhile, the influence of the heating temperature and the heating time on the secondary crystallization of the plastic part during the high-temperature heat treatment of the injection-molded plastic part is further verified.
The preparation method comprises the following steps of (1) weighing PPS resin, conductive carbon fibers, conductive carbon particles, glass fibers and calcium carbonate according to a mass ratio of 53.5; adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel; extruding, cooling and granulating the uniformly plasticized and mixed materials to obtain a plastic composite material; and (3) injecting the molten plastic composite material with the temperature of 315 ℃ into a mold with the temperature of 165 ℃, and cooling the plastic composite material in the mold to obtain the plastic part.
The 600 injection molding plastic part samples are divided into 6 groups by taking 100 as 1 component, and high temperature heating treatment and DSC test are carried out. By GB-T19466.3-2004 plastics Differential Scanning Calorimetry (DSC) part 3 under an inert gas atmosphere: in the measurement of the melting and crystallization temperatures and the enthalpies, the temperature of each group was raised to the heating temperature shown in Table 2 at a temperature raising rate of 5k/min, and then the temperature was maintained for the heating time shown in Table 2, and the melting and crystallization temperatures and the enthalpies were measured using a differential scanning calorimeter DCS-3 under the following conditions: the test amount is 30mg, and the temperature rise speed is 5k/min; the atmosphere was N2.
TABLE 2
The DSC test charts obtained by the above tests are sequentially shown in fig. 3 to 8 for the first to fifth groups of DSC test charts, and the test charts of the respective groups are sequentially analyzed:
as shown in fig. 3, the first group: baking at the temperature of 90 ℃/48h, and performing normalized:9.84J/g, the peak of crystallization exotherm of the sample is very obvious.
As shown in fig. 4, the second group: baking at 100 ℃/4h, normalized: at 0J/g, the peak of the exothermic crystallization of the sample has completely disappeared.
As shown in fig. 5, the third group: baking at 140 ℃/1h, normalized: at 0J/g, the peak of the exothermic crystallization of the sample has completely disappeared.
As shown in fig. 6, fourth group: baking at 180 ℃/1h, normalized:1.28J/g, the peak of the exothermic crystallization of the sample has completely disappeared.
As shown in fig. 7, fifth group: baking at 220 ℃/1h, normalized: 1.38J/g, the peak of crystallization exotherm of the sample has completely disappeared.
As shown in fig. 8, sixth group: baking at 260 ℃/1h, normalized: 2.26J/g, the peak of the exothermic crystallization of the sample has completely disappeared.
The analysis of the DSC test chart clearly shows that the first group of the heat-insulating materials still have very obvious crystallization heat-release peaks when the heating temperature is lower than 100 ℃ and the high-temperature heating is carried out for 48 hours at 90 ℃; the second, third, fourth, fifth and sixth groups were heated at temperatures greater than 100 ℃ and less than 260 ℃ for shorter heating times than the first group, but the crystallization heat release peak was completely disappeared.
Variations and modifications to the above-described embodiments may become apparent to those skilled in the art to which the invention pertains based upon the disclosure and teachings of the above specification. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (11)
1. The plastic part is characterized in that the plastic part passes through a Differential Scanning Calorimetry (DSC) test, and the DSC test curve has a crystallization exothermic peak intensity of less than 0.1J/g at 110-120 ℃;
the differential scanning calorimetry test is carried out in an inert gas atmosphere, the temperature is increased within the temperature range of 25-400 ℃ at the temperature increasing speed of 5k/min in the measurement of melting and crystallization temperature and enthalpy, and the crystallization exothermic peak intensity of a DSC test curve at 110-120 ℃ is less than 0.1J/g after the test is finished;
the measurement of the melting and crystallization temperatures and enthalpy is carried out using a differential scanning calorimeter under the following test conditions: the test quantity is 30mg, and the temperature rise speed is 5k/min; the atmosphere being N 2 The measuring temperature range is 25-400 ℃.
2. The preparation method of the plastic part is characterized by comprising the following steps:
s1, injection molding of the plastic composite material;
s2, carrying out high-temperature heat treatment on the injection-molded plastic part, wherein the heating temperature is 100-260 ℃, and the heating time is more than or equal to 1h.
3. The method of claim 2, wherein in the step S1, the raw materials of the plastic composite material comprise PPS resin, glass fiber and an auxiliary agent.
4. The method of claim 3, wherein the raw material of the plastic composite material further comprises a conductive material.
5. The method for preparing a plastic part according to claim 4, wherein the mass ratio of the PPS resin, the conductive material, the glass fiber and the auxiliary agent is (52.5-57.9), (12-18.4), (29-31) and (0.1-3.5).
6. The method for preparing a plastic part according to claim 4 or 5, wherein the conductive material comprises conductive fibers and conductive carbon particles.
7. The method for preparing plastic parts according to claim 6, wherein the mass ratio of the conductive fibers to the conductive carbon particles is (12-17.9) to (0-0.5).
8. The method for preparing a plastic part according to claim 2, wherein the step S1 further comprises:
s1-1, weighing the raw materials of the plastic composite material according to a ratio, adding the raw materials into a high-speed mixer, mixing to obtain a mixed material, and putting the mixed material into a hopper and stirring;
s1-2, adding the stirred mixed material into a charging barrel of a double-screw extruder, and plasticizing, mixing and dispersing all the components uniformly in the charging barrel;
s1-3, extruding, cooling and granulating the uniformly plasticized, mixed and dispersed materials to obtain the plastic composite material;
s1-4, performing high-temperature injection molding on the plastic composite material to obtain the plastic part.
9. The method for preparing a plastic part according to claim 2, wherein in the step S2, the injection molding process comprises: and injecting the molten plastic composite material into a mold, and cooling the plastic composite material in the mold to obtain the plastic part.
10. The method of claim 9, wherein the plastic composite material is poured into the mold at a temperature of 140-190 ℃ during the injection molding process, wherein the temperature of the plastic composite material is 290-340 ℃.
11. A battery cover assembly comprising the plastic part produced by the plastic part production method according to any one of claims 2 to 10.
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Effective date of registration: 20240301 Address after: No. 68, Xin'anjiang Road, Southeast Street, Changshu City, Suzhou City, Jiangsu Province, 215000 Applicant after: Jiangsu Zhengli new energy battery technology Co.,Ltd. Country or region after: China Address before: No. 1 Jiayuan Road, Dalang Town, Dongguan City, Guangdong Province, 523000 Applicant before: Dongguan Zhengli New Energy Battery Technology Co.,Ltd. Country or region before: China Applicant before: Jiangsu Zhengli new energy battery technology Co.,Ltd. |