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CN-122025939-A - Surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell and preparation method thereof

CN122025939ACN 122025939 ACN122025939 ACN 122025939ACN-122025939-A

Abstract

The invention provides a surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell and a preparation method thereof, belonging to the technical field of battery shell materials. The invention adopts bisphenol A type polycarbonate as matrix resin to ensure the rigidity and heat resistance of a shell, improves the compatibility and electrolyte corrosion resistance of the whisker and a PC matrix cooperatively by carrying out double-step modification on calcium sulfate whisker, improves the toughness of the protective shell by utilizing a modified elastomer, realizes the balance of rigidity and flexibility by the proportion regulation and control of the modified elastomer and surface modified calcium sulfate whisker, provides continuous interface pressure, introduces nano functional filler, synchronously improves the heat dissipation and puncture resistance, inhibits the high-temperature degradation of bisphenol A type polycarbonate by utilizing an antioxidant, improves the heat stability, improves the flame retardance by using a flame retardant, improves the processing fluidity by using a lubricant, and improves the surface finish of the protective shell to finally obtain the high-performance PC-based composite protective shell adapting to the solid-state battery.

Inventors

  • XIE CHAOXIANG
  • LIU JIAQUAN

Assignees

  • 上海高光新能源科技有限公司

Dates

Publication Date
20260512
Application Date
20260210

Claims (10)

  1. 1. The surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell is characterized by comprising the following raw materials in parts by weight: 95-105 parts of bisphenol A type polycarbonate, 6-14 parts of modified elastomer, 10-20 parts of surface modified calcium sulfate whisker, 2-6 parts of nano aluminum nitride, 1-5 parts of nano zirconium oxide, 0.1-0.5 part of antioxidant, 3-8 parts of flame retardant and 0.2-0.6 part of lubricant; The modified elastomer is hydroxyl-terminated polybutadiene grafted methyl methacrylate elastomer; the surface modified calcium sulfate whisker is obtained by sequentially modifying a borate surfactant and a silane coupling agent by the calcium sulfate whisker.
  2. 2. The surface-modified calcium sulfate whisker PC nanocomposite solid-state battery protective shell according to claim 1, wherein the bisphenol A polycarbonate has a number average molecular weight of 25000 to 32000 and a heat distortion temperature of not less than 150 ℃.
  3. 3. The surface-modified calcium sulfate whisker PC nanocomposite solid state battery protective casing according to claim 1, wherein the preparation method of the modified elastomer comprises the steps of: Mixing hydroxyl-terminated polybutadiene and ethyl acetate, and heating and stirring in a nitrogen atmosphere to obtain a hydroxyl-terminated polybutadiene solution; and in a nitrogen atmosphere, adding methyl methacrylate, an azodiisobutyronitrile initiator and a trimethylolpropane triacrylate crosslinking agent into the hydroxyl-terminated polybutadiene solution to perform graft polymerization reaction to obtain the modified elastomer.
  4. 4. The surface-modified calcium sulfate whisker PC nanocomposite solid state battery protective casing according to claim 1, wherein the preparation method of the surface-modified calcium sulfate whisker comprises the steps of: (S1) sequentially carrying out first vacuum drying and cooling on the calcium sulfate whisker to obtain a pretreated calcium sulfate whisker; (S2) heating and stirring the pretreated calcium sulfate whisker obtained in the step (S1), adding a borate surfactant, and stirring at a constant temperature to obtain a hydrophobically modified whisker; And (S2) cooling the hydrophobic modified whisker obtained in the step (S2) under the condition of stirring, adding a silane coupling agent, and sequentially carrying out stirring treatment, second vacuum drying and second cooling to obtain the surface modified calcium sulfate whisker.
  5. 5. The surface-modified calcium sulfate whisker PC nanocomposite solid-state battery protective shell according to claim 4, wherein in the step (S1), the calcium sulfate whisker is anhydrous, the aspect ratio of the calcium sulfate whisker is 25-35, the diameter is 0.8-2 μm, the strength is not less than 2000MPa, and the modulus is not less than 70GPa.
  6. 6. A method for preparing the surface modified calcium sulfate whisker PC nanocomposite solid-state battery protective shell according to any one of claims 1 to 5, comprising the steps of: (1) Mixing bisphenol A polycarbonate, a modified elastomer, surface modified calcium sulfate whisker, nano aluminum nitride, nano zirconium oxide, an antioxidant, a flame retardant and a lubricant, and stirring to obtain a mixture; (2) Sequentially carrying out melt extrusion and water-cooling granulation on the mixture obtained in the step (1) to obtain composite material particles; (3) And (3) sequentially carrying out vacuum drying, injection molding, temperature keeping and post-treatment on the composite material particles obtained in the step (2) to obtain the surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell.
  7. 7. The method according to claim 6, wherein the parameters of the twin-screw extruder used in the melt extrusion in the step (2) include barrel temperature segmentation setting of 220-230 ℃ in one zone, 240-250 ℃ in two zones, 250-260 ℃ in three zones, 245-255 ℃ in a machine head and screw rotation speed of 130-150 r/min.
  8. 8. The preparation method according to claim 6, wherein the temperature of the vacuum drying in the step (3) is 120-125 ℃, and the time of the vacuum drying is 2-4 hours.
  9. 9. The method according to claim 6, wherein the injection molding parameters in the step (3) include an injection molding temperature of 240-250 ℃, a mold temperature of 80-90 ℃, an injection molding pressure of 80-90 mpa, a holding pressure of 60-70 mpa, a holding time of 2-3 s, and a cooling time of 15-20 s.
  10. 10. The preparation method according to claim 6, wherein the temperature of the heat preservation in the step (3) is 95-110 ℃, and the time of the heat preservation is 1.5-3 hours.

Description

Surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell and preparation method thereof Technical Field The invention relates to the technical field of battery shell materials, in particular to a surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell and a preparation method thereof. Background With the vigorous development of the automobile industry, gasoline is burned in a large amount and causes pollution to the atmosphere, and with the continuous enhancement of environmental awareness of people, the requirements of various countries in the world on the composition of engine fuels are more stringent, and particularly the requirements on the sulfur content in gasoline are more stringent. Thiol is one of main sulfur-containing compounds in gasoline, has malodorous smell and strong reactivity, and is easy to deactivate catalysts in downstream processes, so that the task of removing the thiol compounds in the gasoline is urgent and difficult. Existing gasoline sweetening technologies are divided into hydrodesulfurization technologies and non-hydrodesulfurization technologies. The hydrodesulfurization technology is mature, but deep hydrodesulfurization can lead to low liquid yield and octane number loss, and has the defects of high energy consumption, high hydrogen consumption, high investment and operation cost and the like. In contrast, non-hydrodesulfurization technology has mild reaction conditions and simpler process flow, but is usually discharged by waste lye, and is not environment-friendly, while alkali-free deodorization technology requires continuous addition of an activator and periodic replacement of a fixed bed catalyst, which results in higher operation cost. Disclosure of Invention The invention aims to provide a surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell and a preparation method thereof, the surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell provided by the invention has excellent heat dissipation performance and electrolyte corrosion resistance, can provide continuous interface pressure, and can meet the requirements of high-pressure packaging and light weight. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a surface modified calcium sulfate whisker PC nano composite solid-state battery protective shell which is characterized by comprising the following raw materials in parts by weight: 95-105 parts of bisphenol A type polycarbonate, 6-14 parts of modified elastomer, 10-20 parts of surface modified calcium sulfate whisker, 2-6 parts of nano aluminum nitride, 1-5 parts of nano zirconium oxide, 0.1-0.5 part of antioxidant, 3-8 parts of flame retardant and 0.2-0.6 part of lubricant; The modified elastomer is hydroxyl-terminated polybutadiene grafted methyl methacrylate elastomer; the surface modified calcium sulfate whisker is obtained by sequentially modifying a borate surfactant and a silane coupling agent by the calcium sulfate whisker. Preferably, the number average molecular weight of the bisphenol A type polycarbonate is 25000-32000, and the thermal deformation temperature of the bisphenol A type polycarbonate is more than or equal to 150 ℃. Preferably, the preparation method of the modified elastomer comprises the following steps: Mixing hydroxyl-terminated polybutadiene and ethyl acetate, and heating and stirring in a nitrogen atmosphere to obtain a hydroxyl-terminated polybutadiene solution; and in a nitrogen atmosphere, adding methyl methacrylate, an azodiisobutyronitrile initiator and a trimethylolpropane triacrylate crosslinking agent into the hydroxyl-terminated polybutadiene solution to perform graft polymerization reaction to obtain the modified elastomer. Preferably, the preparation method of the surface modified calcium sulfate whisker comprises the following steps: (S1) sequentially carrying out first vacuum drying and cooling on the calcium sulfate whisker to obtain a pretreated calcium sulfate whisker; (S2) heating and stirring the pretreated calcium sulfate whisker obtained in the step (S1), adding a borate surfactant, and stirring at a constant temperature to obtain a hydrophobically modified whisker; And (S2) cooling the hydrophobic modified whisker obtained in the step (S2) under the condition of stirring, adding a silane coupling agent, and sequentially carrying out stirring treatment, second vacuum drying and second cooling to obtain the surface modified calcium sulfate whisker. Preferably, in the step (S1), the calcium sulfate whisker is anhydrous, the length-diameter ratio of the calcium sulfate whisker is 25-35, the diameter is 0.8-2 mu m, the strength is more than or equal to 2000MPa, and the modulus is more than or equal to 70GPa. The invention also provides a preparation method of the surface modified calcium