Preparation and application of modified ultrathin cellulose diaphragm

A cellulose diaphragm and cellulose technology, applied in the field of electrochemical energy storage, can solve the problems of reducing the specific energy of the aqueous zinc-based energy storage system, the inability of the cellulose diaphragm to be ultra-thin, and the extension of the electrolyte ion transmission distance, etc., to achieve The effect of high stability, low cost and simple preparation method

Pending Publication Date: 2022-07-12
JINAN UNIVERSITY
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  • Abstract
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Problems solved by technology

However, for example, the cellulose separator prepared by solution casting method has limited effect on inhibiting zinc dendrites, at 5mA / cm 2 、2.5mAh / cm 2 Under certain conditions, the cycle life of a symmetrical battery based on its assembly is only 20 hours (Nano Energy, 2021, 89, 106322)
Moreover, due to the need to ensure its inhibitory effect on zinc dendrites, the thickness of the cellulose separator in the prior art cannot be ultra-thin, such as the Chinese patent publication CN 112332026 A, the cellulose-based separator prepared by the coating method , the preferred thickness of the cellulose separator is 100 μm; the thickness of the cellulose separator prepared by Zhou et al. is 140 μm (Energy Storage Materials, 2022, 44, 57-65)
Diaphragm is one of the key components in aqueous zinc-based energy storage devices. The use of large-thickness diaphragms significantly reduces the specific energy (including volume specific energy and mass specific energy) of the aqueous zinc-based energy storage system, and at the same time leads to electrolysis during charging and discharging. The extended transmission distance of liquid ions is not conducive to the realization of fast charging and discharging and high power density, which hinders its industrial application

Method used

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  • Preparation and application of modified ultrathin cellulose diaphragm
  • Preparation and application of modified ultrathin cellulose diaphragm
  • Preparation and application of modified ultrathin cellulose diaphragm

Examples

Experimental program
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Effect test

Embodiment 1

[0045] Preparation of Ultrathin Cellulose Separator

[0046] (1) Disperse commercial hydroxycellulose nanofibers (purchased from Zhejiang Jinjiahao Green Nanomaterials Co., Ltd., model CNF-H1) weighing 12.6, 37.7, and 113.1 mg in deionized water to prepare hydroxycellulose nanofibers. A dispersion liquid with a fiber concentration of 0.5 mg / mL was uniformly dispersed by ultrasound. By the method of vacuum filtration, the above dispersion liquid was suction-filtered onto a mixed cellulose water-based filter membrane (model: Tianjin Jinteng microporous water-based filter membrane, pore size 0.8 μm) substrate. After drying at room temperature for 8 hours, the filter membrane substrate was peeled off to obtain hydroxycellulose nanofibers with loadings of 1, 3, and 9 mg / cm, respectively. 2 of ultra-thin cellulose separators with a loading of 3 mg / cm 2 The thickness of the ultra-thin cellulose separator is about 16 μm, and the thickness cross-sectional diagram is as follows figur...

Embodiment 2

[0051] Preparation of Nanometer Zinc Oxide Modified Ultrathin Cellulose Separator

[0052] (1) Disperse 18.9 mg of hydroxycellulose nanofibers (purchased from Zhejiang Jinjiahao Green Nanomaterials Co., Ltd., model CNF-H1) and 18.9 mg of nano-zinc oxide in deionized water, and the concentration of hydroxycellulose nanofibers is The dispersion liquid with 0.5 mg / mL and nano-zinc oxide concentration of 0.5 mg / mL was uniformly dispersed by ultrasonic. By vacuum filtration, the above mixed dispersion liquid was suction filtered onto a mixed cellulose water-based filter membrane (model: Tianjin Jinteng microporous water-based filter membrane, pore size 0.8 μm) substrate. After drying at room temperature for 8 hours, the filter membrane substrate was peeled off, and the loading of hydroxycellulose nanofibers was 1.5 mg / cm. 2 , the nano-zinc oxide loading is 1.5mg / cm 2 Nano-zinc oxide modified ultrathin cellulose separator.

[0053] (2) A zinc sheet with a diameter of 10 mm and a ...

Embodiment 3

[0056] Preparation of Halloysite Nanotubes Modified Ultrathin Cellulose Separator

[0057](1) 18.9 mg of hydroxycellulose nanofibers (purchased from Zhejiang Jinjiahao Green Nanomaterials Co., Ltd., model CNF-H1) and 18.9 mg of commercial natural halloysite nanotubes (with an outer diameter of about 50 nm and an inner diameter of 15 -20nm, 100-1500nm in length) dispersed in deionized water to prepare a dispersion liquid with hydroxycellulose nanofiber concentration of 0.5mg / mL and halloysite concentration of 0.5mg / mL, and uniformly dispersed by ultrasonic. By vacuum filtration, the above mixed dispersion liquid was suction filtered onto a mixed cellulose water-based filter membrane (model: Tianjin Jinteng microporous water-based filter membrane, pore size 0.8 μm) substrate. After drying at room temperature for 8 hours, the filter membrane substrate was peeled off, and the loading of hydroxycellulose nanofibers was 1.5 mg / cm. 2 , the loading of halloysite nanotubes is 1.5 mg / c...

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Abstract

The invention belongs to the technical field of electrochemical energy storage, and discloses preparation and application of a modified ultrathin cellulose diaphragm. According to the invention, cellulose or functional material modified cellulose is directly sucked and filtered to a filter membrane substrate by adopting a vacuum suction filtration method, and the filter membrane substrate is peeled off after drying, so that the modified ultrathin cellulose diaphragm is constructed. The modified ultrathin cellulose diaphragm has the effects of high puncture strength, promotion of homogenization of a zinc negative electrode surface electric field and an ion field during zinc ion deposition, optimization of zinc deposition crystal face orientation, reduction of a nucleation barrier and the like, so that the effect of inhibiting growth of zinc dendrites is achieved. Therefore, the water-based zinc-based energy storage system with high stability and long cycle life is realized, and the method has important significance in promoting the practical application of the water-based zinc-based energy storage system.

Description

technical field [0001] The invention belongs to the technical field of electrochemical energy storage, and particularly relates to the preparation and application of a modified ultra-thin cellulose diaphragm. Background technique [0002] The rapid development of human society is accompanied by the huge consumption of fossil fuels and the environmental pollution caused by their combustion. Therefore, electrochemical energy storage devices with high energy storage / conversion efficiency and green environmental protection have been increasingly studied. Aqueous batteries have higher safety performance and lower cost due to the use of aqueous solutions of metal salts as electrolytes; and, using aqueous solutions of metal salts as electrolytes, the ionic conductivity is much higher than that of organic electrolytes such as those used in lithium-ion batteries, so aqueous batteries Batteries have broad application prospects in the field of energy storage and are considered as a bat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M50/44H01M50/446H01M50/431H01M50/414H01M50/411H01M50/489H01M50/497H01M10/42H01M50/403H01M10/36C08J5/18C08L1/02
CPCH01M50/44H01M50/446H01M50/431H01M50/414H01M50/411H01M50/489H01M50/497H01M10/4235H01M50/403H01M10/36C08J5/18C08J2301/02Y02E60/10
Inventor 董留兵李扬李许彭新亚容建华
Owner JINAN UNIVERSITY
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