Modified SiO2 nanoparticle, preparation method thereof, nanofiber membrane containing same, gel electrolyte and lithium metal battery

A technology of nanofiber membrane and gel electrolyte, which is applied in the direction of non-aqueous electrolyte batteries, lithium batteries, secondary batteries, etc., can solve the problems of small liquid absorption, battery short circuit, high crystallinity, etc., and achieve large porosity and gas permeability , improve ionic conductivity, improve the effect of interaction

Active Publication Date: 2018-07-13
INST OF PROCESS ENG CHINESE ACAD OF SCI
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Problems solved by technology

However, these diaphragms have the following problems in the assembled batteries: on the one hand, during the charge-discharge cycle of lithium metal batteries, the negative electrode of the lithium sheet is prone to form malignant proliferating dendrite lithium, and the dendrite lithium pierces the diaphragm, and the positive and negative electrodes are in contact with each other. lead to a short circuit in the battery; on the other hand, the liquid electrolyte of the battery may bring some disadvantages, such as electrolyte leakage, and the electrolyte contains more organic solvents, which may cause the battery to catch fire or even explode.
The in-situ polymerization method integrates polymer film formation, pore formation and plasticizer plasticization treatment, which simplifies the operation process, but all raw materials for film production must undergo strict drying treatment, and the film production process is carried out in a glove box. higher requirements
[0004] In addition, PVDF has high crystallinity and contains crystalline phase and amorphous phase. The wetting of the electrolyte is mainly completed between the amorphous phases. The crystalline phase cannot store the electrolyte, causing it to separate from the electrolyte, hindering the migration of lithium ions, and further affecting Battery cycle performance and rate performance
Although the copolymerization of PVDF and amorphous HFP can reduce its crystallization rate, increase its ionic conductivity, and increase its dielectric constant, the high crystallinity of PVDF is still one of the main factors limiting the ionic conductivity of gel electrolytes.
CN106384843A The PVDF-HFP matrix prepared by in-situ polymerization still mainly relies on the amorphous phase of the material to store the electrolyte, its liquid absorption is small, and the ionic conductivity of the obtained gel electrolyte is also low

Method used

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  • Modified SiO2 nanoparticle, preparation method thereof, nanofiber membrane containing same, gel electrolyte and lithium metal battery
  • Modified SiO2 nanoparticle, preparation method thereof, nanofiber membrane containing same, gel electrolyte and lithium metal battery
  • Modified SiO2 nanoparticle, preparation method thereof, nanofiber membrane containing same, gel electrolyte and lithium metal battery

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Embodiment 1

[0079] This embodiment provides a modified nano-SiO 2 particles, including nano-SiO 2 Particles and grafting on nano-SiO 2 Ionic liquids on particles;

[0080] Wherein, the cation of the ionic liquid is 1-propyl(trimethoxy)silane-1-methylpiperidinium, and the anion of the ionic liquid is bistrifluoromethylsulfonimide anion.

[0081] This embodiment modified nano-SiO 2 The preparation method of particles is as follows:

[0082] (1) Dissolve N-methylpiperidine and 3-chloropropyltrimethoxysilane (molar ratio 1:1.1) in DMF respectively, and add N-methylpiperidine solution dropwise under nitrogen protection environment In 3-chloropropyltrimethoxysilane solution, stirred and reacted at 80°C for 1 day, the reaction product was washed, rotary evaporated and dried to obtain 1-propyl(trimethoxy)silane-1-methylpiperidinium Chloride (PPCl);

[0083] (2) PPCl obtained in step (1) is dissolved in water, and SiO is added dropwise 2 Colloid (particle size 20-100nm), stir evenly, react ...

Embodiment 2

[0086] This embodiment provides a modified nano-SiO 2 particles, including nano-SiO 2 Particles and grafting on nano-SiO 2 Ionic liquids on particles;

[0087] Wherein, the cation of the ionic liquid is 1-propyl(trimethoxy)silane-1-methylpiperidinium, and the anion of the ionic liquid is a bisfluorosulfonimide anion.

[0088] This embodiment modified nano-SiO 2 The preparation method of particles is as follows:

[0089] (1) Dissolve N-methylpiperidine and 3-chloropropyltrimethoxysilane (molar ratio 1:1.1) in DMF respectively, and add N-methylpiperidine solution dropwise under nitrogen protection environment In 3-chloropropyltrimethoxysilane solution, stirred and reacted at 75°C for 3 days, the reaction product was washed, rotary evaporated and dried to obtain 1-propyl(trimethoxy)silane-1-methylpiperidinium Chloride (PPCl);

[0090] (2) PPCl obtained in step (1) is dissolved in water, and SiO is added dropwise 2 Colloid (particle size 20-100nm), stir evenly, react at 70°...

Embodiment 3

[0093] This embodiment provides a modified nano-SiO 2 particles, including nano-SiO 2 Particles and grafting on nano-SiO 2 Ionic liquids on particles;

[0094] Wherein, the cation of the ionic liquid is 1-propyl(trimethoxy)silane-1-methylpiperidinium, and the anion of the ionic liquid is difluorooxalate borate anion.

[0095] This embodiment modified nano-SiO 2 The preparation method of particles is as follows:

[0096] (1) Dissolve N-methylpiperidine and 3-chloropropyltrimethoxysilane (molar ratio 1:1.1) in DMF respectively, and add N-methylpiperidine solution dropwise under nitrogen protection environment In 3-chloropropyltrimethoxysilane solution, stirred and reacted at 85°C for 1.5 days, the reaction product was washed, rotary evaporated and dried to obtain 1-propyl(trimethoxy)silane-1-methylpiperidinium Chloride (PPCl);

[0097] (2) PPCl obtained in step (1) is dissolved in water, and SiO is added dropwise 2 Colloid (particle size 20-100nm), stir evenly, react at 9...

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Abstract

The invention provides a modified SiO2 nanoparticle, a preparation method thereof, a nanofiber membrane containing the modified SiO2 nanoparticle, a gel electrolyte and a lithium metal battery. The modified SiO2 nanoparticle comprises an SiO2 nanoparticle and a specific ionic liquid grafted on the SiO2 nanoparticle. The nanofiber membrane is composed of a vinylidene fluoride-hexafluoropropylene copolymer and fiber consisting of the modified SiO2 nanoparticle. The gel electrolyte comprises the nanofiber membrane and a plasticizer adsorbed inside the nanofiber membrane. An electrolyte of the lithium metal battery is the gel electrolyte. According to the modified SiO2 nanoparticle provided by the invention, the mutual effect of the nanofiber membrane and the plasticizer can be strengthened, the transference number of Li+ is increased, the modified SiO2 nanoparticle is matched with the structure of the nanofiber membrane, and the ionic conductivity and specific capacity of the gel electrolyte and the cycling stability under high rate can be further improved.

Description

technical field [0001] The invention belongs to the technical field of lithium metal batteries, in particular to a modified nano-SiO 2 Particles, methods for their preparation, and nanofibrous membranes, gel electrolytes, and lithium metal batteries comprising the same. Background technique [0002] Lithium metal batteries have attracted widespread attention due to their high energy density, high power density, small memory effect, and low environmental pollution, and have become one of the effective energy storage systems for various new energy vehicles. Separator is an important part of lithium metal battery, which affects the electrochemical performance and safety performance of the whole battery. At present, the main battery separators on the market include: polyethylene microporous membrane, polypropylene microporous membrane and their composite membranes. However, these diaphragms have the following problems in the assembled batteries: on the one hand, during the cha...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0565H01M10/052
CPCH01M10/052H01M10/0565Y02E60/10
Inventor 张锁江张兰程源源
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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