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Polyformaldehyde all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and application thereof

An all-solid-state polymer and ring-opening polymerization technology, applied in solid electrolytes, electrolytes, non-aqueous electrolytes, etc., can solve problems such as difficult practical application of lithium batteries, difficulty in compatibility with high-potential positive electrode materials, and low room temperature ionic conductivity. Improved interface stability and long-term cycle performance, excellent room temperature ionic conductivity, and high room temperature ionic conductivity

Active Publication Date: 2020-04-28
QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, when commercial lithium-ion batteries based on liquid electrolytes are abused, short-circuited, or used in extreme conditions, a large amount of heat will be released inside the battery, which will ignite the organic electrolyte, causing safety hazards such as fire and explosion, which greatly threatens the safety and well-being of users. experience, apparently difficult to use widely
Even the American Tesla car, which is currently considered the safest, uses a complex battery management system and protective measures, and there have been many fire and explosion accidents in just a few years after it came out.
In addition, there are still problems with organic electrolytes: limited electrochemical window, difficult to be compatible with metal lithium anodes and newly developed high-potential cathode materials; lithium ions are not the only carriers, and the internal resistance of the battery will be affected by the The appearance of the ion concentration gradient increases (concentration polarization), and the performance of the battery decreases; the working temperature is limited (the operating temperature is 0°C-40°C); it reacts with the negative electrode material to form a solid electrolyte interphase (SEI) layer, resulting in active lithium Continuous consumption, so that the battery capacity continues to decline
CN105826603 A describes an in-situ polymerized vinylene carbonate-based solid-state electrolyte system and its application, which has excellent mechanical properties, but the solid-state electrolyte has low room temperature ionic conductivity and cannot operate at room temperature
[0004] Polyethylene oxide (PEO) / lithium salt electrolytes have been used in solid-state lithium polymer batteries, but there are still some problems to be solved from the practical point of view: linear and grafted polymers have poor mechanical properties, and it is not easy to make independent Supported polymer film, while the conductivity of the network polymer is too small
Therefore, this kind of electrolyte system is only suitable for working under high temperature or low current conditions, and it is difficult to get practical application in lithium batteries working at normal temperature.

Method used

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  • Polyformaldehyde all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and application thereof
  • Polyformaldehyde all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and application thereof
  • Polyformaldehyde all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] In a glove box filled with argon, 4g of paraldehyde and 1.5g of succinonitrile were stirred for 5 minutes on a hot stage at 60°C and mixed evenly, then 0.375g of LiDFOB was added and stirred for 10 minutes to mix evenly, and the above mixed solution was taken 0.15 mL was added dropwise with cellulose as the support material; then LiCoO 2 As the positive electrode and lithium as the negative electrode, the porous support material soaked in the mixture above is placed between the positive and negative electrodes, and the assembled battery is heated at 60°C for 2 hours, and the mixture is polymerized in situ on the porous support material inside the battery to obtain an all-solid state polymer electrolyte (see figure 1 ), and then obtain an all-solid-state polymer lithium battery.

[0038] Depend on figure 1 It can be seen that the formed all-solid electrolyte is evenly attached to the cellulose non-woven separator.

Embodiment 2

[0040] Stir 2.5g 1,3,5-trioxane (TXE) and 1.5g succinonitrile on a hot stage at 80°C in a glove box filled with argon for 5 minutes and mix well, then add 0.375g g LiDFOB and continue stirring for 5 minutes Minutes to mix evenly, take 0.15mL of the above mixed solution and add it dropwise with cellulose as the support material; then use LiFeO 4 As the positive electrode and lithium as the negative electrode, the porous support material soaked in the mixture above is placed between the positive and negative electrodes, and the assembled battery is heated at 80°C for 5 hours, and the mixture is polymerized in situ on the porous support material inside the battery to obtain an all-solid state polymer electrolyte.

[0041] Use the above-mentioned all-solid-state polymer lithium battery to carry out the battery cycle test, the battery charge and discharge range is 2.75V-4V, the charge and discharge rate is 0.3C, and the test temperature is room temperature (see image 3 ). .

[...

Embodiment 3

[0044] Stir 2.5g 1,3,5-trioxane (TXE) and 2.5g succinonitrile on a hot stage at 80°C in a glove box filled with argon for 10 minutes, then add 0.375g LiDFOB and continue stirring for 5 Mix evenly within 1 minute, add 0.15 mL of the above mixed solution dropwise to cellulose as a support material; then use the ternary material as the positive electrode and lithium as the negative electrode, place the porous support material soaked in the mixture between the positive and negative electrodes, and assemble The completed battery is heated at 80°C for 5 hours, and the mixture is polymerized in situ on the porous support material inside the battery to obtain an all-solid polymer electrolyte.

[0045] The above-mentioned all-solid-state polymer lithium battery is used for battery cycle test, the battery charge and discharge range is 2.75V-4.3V, the charge and discharge rate is 0.2C, and the test temperature is room temperature (see Figure 4 ).

[0046] Depend on Figure 4 It can be...

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Abstract

The invention relates to an all-solid-state polymer electrolyte, and particularly relates to a polyformaldehyde all-solid-state polymer electrolyte prepared by in-situ ring-opening polymerization andapplication of the polyformaldehyde all-solid-state polymer electrolyte in forming an all-solid-state secondary lithium battery. The all-solid-state polymer electrolyte is prepared by initiating in-situ ring opening polymerization of a trioxymethylene monomer, an additive and a lithium salt to a porous support material through a catalyst, wherein the thickness ranges from 10[mu]m to 800[mu]m; theroom-temperature ionic conductivity ranges from 4*10<-5>S / cm to 8*10<-3>S / cm, and the electrochemical window is not lower than 4.2V. The all-solid-state polymer electrolyte is easy to prepare and simple to form; the mechanical performance is excellent; and the room-temperature ionic conductivity is high. Meanwhile, the all-solid-state polymer electrolyte can effectively inhibit the growth of lithium dendrites and match with a high-voltage positive electrode material, so that the interface stability, the long cycle performance and the energy density are effectively improved.

Description

technical field [0001] The invention relates to an all-solid polymer electrolyte, in particular to a polyoxymethylene-based all-solid polymer electrolyte prepared by in-situ ring-opening polymerization and its application in forming an all-solid secondary lithium battery. Background technique [0002] Power lithium-ion batteries for electric vehicles, in addition to meeting the requirements of long mileage and high-power charging and discharging, safety performance is particularly important. At present, when commercial lithium-ion batteries based on liquid electrolytes are abused, short-circuited, or used in extreme conditions, a large amount of heat will be released inside the battery, which will ignite the organic electrolyte, causing safety hazards such as fire and explosion, which greatly threatens the safety and well-being of users. Experience, obviously difficult to use widely. Even the American Tesla car, which is currently considered the safest, uses a complex batte...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0565H01M10/058H01M10/0525H01M10/42C08G65/16
CPCH01M10/0565H01M10/058H01M10/0525H01M10/4235C08G65/16H01M2300/0082H01M2300/0091Y02E60/10Y02P70/50C08L59/00C08G2/10C08G2/06H01M10/052C08G61/122
Inventor 崔光磊张建军吴瀚刘亭亭张津宁唐犇于喆徐红霞
Owner QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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