Preparation method of fluorine-containing polymer porous nano-micron fibre electrode diaphragm

A technology of fiber electrodes and polymers, which is applied in the direction of circuits, electrical components, battery pack components, etc., can solve the problems of low liquid holding capacity, easy fusion, and poor mechanical strength of non-porous fiber separators, and achieve good thermal stability. Stability and acid and alkali resistance, improved cycle life, and improved power density

Active Publication Date: 2015-07-01
锦州凯美能源有限公司
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Problems solved by technology

[0003] CN 104022245A discloses a polyethylene terephthalate / polyolefin composite fiber prepared by a coaxial melt electrospinning method. The fiber outer layer material is a polyolefin material, which has a certain closed-cell protection function and prevents charging and discharging Thermal runaway occurs during the process, which improves the safety performance of energy storage devices, but the coaxial melt spinning process is difficult, and fusion is prone to occur during the spinning process, destroying the nano-micron structure of the fiber, and the polyester and polyolefin materials used Poor physical and chemical stability affects the cycle life of energy storage devices
[0004] CN 102587040A discloses a method for preparing a polyvinylidene fluoride electrospinning fiber diaphragm. The method is to electrospin an organic solution of polyvinylidene fluoride under a high-voltage electrostatic field to obtain a polyvinylidene fluoride electrospinning fiber Diaphragm: It has the characteristics of simple process and high processing efficiency, but the non-porous structure fiber diaphragm has low liquid holding capacity and poor ion permeability
[0005] CN 103258978A discloses a method for preparing an inorganic composite porous nanofiber diaphragm. The method is to electrospin an organic solution of polyvinylidene fluoride-hexafluoropropylene copolymer, water-soluble polymer and inorganic nanoparticles, and then water-soluble The polymer is removed to obtain a fluorine-containing polymer inorganic composite porous nanofiber diaphragm, thereby improving its hydrophilicity and liquid holding capacity, but adding inorganic nanoparticles in this method reduces the continuous fiber-forming ability of electrospinning, and the mechanical strength is poor. The porosity is low, and the wettability of the organic electrolyte to the separator is not ideal

Method used

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  • Preparation method of fluorine-containing polymer porous nano-micron fibre electrode diaphragm
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  • Preparation method of fluorine-containing polymer porous nano-micron fibre electrode diaphragm

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Embodiment 1

[0032] 1.1. Preparation of spinning precursor

[0033] Dissolve 2.0g of polyvinylidene fluoride (number-average molecular weight: 200,000) and 2.0g of zinc acetate (mass ratio: 1:1) in N,N-dimethylformamide to prepare the mass ratio concentration of polyvinylidene fluoride 20% of the spinning precursor;

[0034] 1.2. Preparation of polyvinylidene fluoride-zinc acetate electrospun fiber membrane

[0035] The prepared spinning precursor is electrospun with the copper mesh as the receiver, the voltage of the electrospinning is 10kV, the distance between the needle and the receiver (spinning spacing) is 10cm, and polyvinylidene fluoride-acetic acid is obtained on the receiver. Zinc electrospun fiber membrane, after 30 minutes of electrospinning, the polyvinylidene fluoride-zinc acetate electrospun fiber membrane was vacuum-dried at 40°C for 24 hours for later use;

[0036] 1.3. Preparation of polyvinylidene fluoride-zinc oxide electrospun fibers

[0037] Add the polyvinylidene ...

Embodiment 2

[0042] 1.1. Preparation of spinning precursor

[0043] Dissolve 2.0 g poly(vinylidene fluoride-co-hexafluoropropylene) (number average molecular weight: 50,000) and 0.4 g copper acetate (mass ratio: 5:1) in N,N-dimethylacetamide / acetone ( In the mixed solution with a mass ratio of 3:7), it is prepared into a spinning precursor whose mass ratio concentration of poly(vinylidene fluoride-co-hexafluoropropylene) is 12%;

[0044] 1.2. Preparation of poly(vinylidene fluoride-co-hexafluoropropylene)-copper acetate electrospun fiber membrane

[0045]The prepared spinning precursor is electrospun with the copper mesh as the receiver, the voltage of the electrospinning is 15kV, the distance between the needle and the receiver is 15cm, and poly(vinylidene fluoride-co-hexafluoropropylene) is obtained on the receiver. )-copper acetate electrospinning fiber membrane, after electrospinning for 80 minutes, the poly(vinylidene fluoride-co-hexafluoropropylene)-copper acetate electrospinning fi...

Embodiment 3

[0052] 1.1. Preparation of spinning precursor

[0053] Dissolve 20.0g poly(vinylidene fluoride-co-trifluoroethylene) (number average molecular weight: 150,000) and 2.0g tin chloride (mass ratio: 10:1) in N-methylpyrrolidone to prepare poly( Vinylidene fluoride-co-trifluoroethylene) mass ratio concentration is the spinning precursor of 5%;

[0054] 1.2. Preparation of poly(vinylidene fluoride-co-trifluoroethylene)-tin chloride electrospun fiber membrane

[0055] The prepared spinning precursor is electrospun with the copper mesh as the receiver, the voltage of the electrospinning is 30kV, and the distance between the needle and the receiver is 20cm, and poly(vinylidene fluoride-co-trifluoroethylene) is obtained on the receiver. )-tin chloride electrospinning fiber membrane, after electrospinning for 120 minutes, the poly(vinylidene fluoride-co-trifluoroethylene)-tin chloride electrospinning fiber membrane was vacuum-dried at 40°C for 24 hours for later use, and measured The B...

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Abstract

The invention relates to a preparation method of a fluorine-containing polymer porous nano-micron fibre electrode diaphragm. The preparation method comprises the following steps: dissolving a fluorine-containing polymer and soluble metal salt in an organic solvent to prepare a spinning precursor, then, preparing a fluorine-containing polymer-metal salt electrostatic spinning fibrous membrane through high-pressure electrostatic spinning, adding a mineralizing agent to carry out hydrothermal reaction so as to obtain a fluorine-containing polymer-metal oxide nano-micron fibrous membrane, carrying out acid treatment by using dilute acid aqueous solution to convert metal oxide nanoparticles in the fluorine-containing polymer-metal oxide nano-micron fibrous membrane into soluble metal salt which is dissolved in inorganic acid aqueous solution, thus obtaining the fluorine-containing polymer porous nano-micron fibre electrode diaphragm. The preparation method disclosed by the invention has the advantages that the liquid holdup, the infiltrating property and the conductive ion migration rate of the diaphragm can be effectively increased; the resistance among the diaphragm, an electrode and electrolyte is reduced; the electrochemical performances of a supercapacitor, such as the power density and the cycle service life, can be increased; and therefore, the supercapacitor having high power density can be obtained.

Description

technical field [0001] The invention belongs to the field of electrode diaphragm preparation, in particular to a method for preparing a fluorine-containing polymer porous nanometer fiber electrode diaphragm for a supercapacitor. Background technique [0002] As a high-power energy storage device, supercapacitors work in continuous charging and discharging under high-power and high-current conditions. The diaphragm is placed between the two poles of the capacitor to separate the positive and negative poles, preventing the direct contact of the active materials of the two poles and causing a short circuit, while not preventing the migration of ions in the capacitor and allowing the ions to pass through freely. The electrospun nano-micron fiber separator can effectively increase the ion migration rate, reduce the concentration polarization, and ensure the supercapacitor's high-capacity, long-term stable charge-discharge mode. [0003] CN 104022245A discloses a polyethylene ter...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M2/16H01M50/403H01M50/411H01M50/44H01M50/443H01M50/489H01M50/491H01M50/497
CPCH01M50/403H01M50/446Y02E60/10
Inventor 何铁石应俊曲蛟魏颖任雪王道林
Owner 锦州凯美能源有限公司
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