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Method of preparing solid-state lithium ion battery through photocuring 3D printing

A lithium-ion battery, 3D printing technology, applied in the direction of secondary battery, secondary battery manufacturing, 3D object support structure, etc., can solve the problem of poor cycle stability of time-consuming and energy-consuming batteries, cycle stability of time-consuming and energy-consuming batteries Solve problems such as complicated process, achieve the effect of improving interface compatibility, shortening process cycle, and improving ion conductivity

Active Publication Date: 2019-12-13
HUAZHONG UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, due to the presence of solvent water, subsequent freeze-drying and heat treatment are still required to obtain the final electrode, which has the problems of complicated preparation process, time-consuming and energy-consuming, and poor cycle stability of the battery.
[0006] In summary, the existing 3D printing technology to prepare solid-state lithium-ion batteries uses traditional liquid electrolytes, which need to be encapsulated with polymer shells, or require subsequent drying or heat treatment to remove solvents after 3D printing. The preparation process is complex and time-consuming. Poor performance and battery cycle stability

Method used

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  • Method of preparing solid-state lithium ion battery through photocuring 3D printing
  • Method of preparing solid-state lithium ion battery through photocuring 3D printing
  • Method of preparing solid-state lithium ion battery through photocuring 3D printing

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preparation example Construction

[0075] Preparation of photosensitive polymer network matrix: mix photosensitive resin, photoinitiator and polymer matrix according to a certain mass ratio to form semi-IPN, the semi-interpenetrating polymer network framework Semi-IPN, and then mix lithium salt solution and semi-interpenetrating polymer framework Semi-IPN -IPN mixed to obtain a photosensitive polymer network matrix with lithium ion conductivity.

[0076] Preparation of inorganic oxide nano-active fillers: As one of the key improvements of the present invention, the product obtained in this step—ceramic nanoparticles with lithium-ion conductive activity plays an important role in the printing and ionic conductivity of composite solid electrolytes. important influence. The corresponding salts can be added to ethylene glycol in sequence, and then citric acid monohydrate is added to stir to obtain a clear solution; the obtained clear solution is heated to reflux, aged, carbonized, and then calcined at a high temper...

Embodiment 1

[0085] figure 1 It is a schematic diagram of the process flow for preparing a solid-state lithium-ion battery by 3D printing constructed according to the present invention, figure 2 It is a schematic diagram for exemplarily showing the composition and structure of a solid-state lithium-ion battery prepared according to the present invention. Such as figure 1 As shown in , the process mainly includes the following process steps:

[0086] First, the preparation of the photosensitive polymer network matrix.

[0087] In this step, a photosensitive resin (ethoxylated trimethylolpropane triacrylate (ETPTA, Aldrich) containing 1.0 wt% of photoinitiator (2-hydroxy-2-methyl-1-phenyl- 1-acetone (HMPP) and polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP, Sigma, HFP content 6mol%), mixed according to a certain mass ratio (ETPTA / PVdF-HFP=75 / 25 (w / w)) , to form a semi-interpenetrating polymer network skeleton IPN, and then lithium salt solution (1M LiClO 4 solution, th...

Embodiment 2

[0108] A photosensitive polymer network matrix used for photocuring 3D printing to prepare solid-state lithium-ion batteries, the photosensitive polymer network matrix includes a semi-interpenetrating polymer network skeleton and a lithium salt solution; the lithium salt solution is dispersed in the semi- In the interpenetrating polymer network skeleton, wherein: the semi-interpenetrating polymer network skeleton includes a photosensitive resin, a photoinitiator and a polymer matrix, the photosensitive resin has a network crosslinked structure, and the photoinitiator is used to initiate The photosensitive resin undergoes a polymerization reaction; the polymer matrix has a linear non-crosslinked structure; the lithium salt solution is an organic solution obtained by dissolving lithium salt in an organic solvent.

[0109] The lithium salt in the lithium salt organic solution is lithium tetrafluoroborate, the organic solvent is sebaconitrile, and the concentration of the lithium s...

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Abstract

The invention belongs to the technical field of lithium ion battery preparation, and particularly relates to a method of preparing a solid-state lithium ion battery through photocuring 3D printing. According to the method, inorganic oxide active nanofillers with high lithium ion conductivity and positive and negative electrode active materials are compounded with a photosensitive polymer network matrix with a semi-interpenetrating structure respectively, and a compound solid electrolyte and positive and negative electrode paste materials with proper rheological properties and photosensitive properties are obtained. Integrated 3D printing of the solid-state lithium ion battery is realized by adopting a photocuring 3D printing technology, and post-treatment processes such as degreasing, sintering and the like are not needed. The technology can effectively reduce the production cost and the process period. The prepared battery has good mechanical properties, particularly, the solid-stateelectrolyte and the electrodes adopt the same photosensitive polymer network as the matrix, the cured electrode / electrolyte interface has good compatibility, and thus, the interface resistance can beeffectively reduced, and the interface compatibility and the process compatibility among a positive electrode, a negative electrode and a solid electrolyte material are solved.

Description

technical field [0001] The invention belongs to the technical field of lithium-ion battery preparation, and more specifically relates to a method for preparing solid-state lithium-ion batteries (including organic-inorganic composite solid electrolytes and positive and negative electrodes) by photocuring 3D printing. Background technique [0002] As a new type of energy storage device, lithium-ion battery has the characteristics of high energy density, long cycle life, stable output voltage, less self-discharge and no pollution. Lithium-ion batteries are generally composed of positive and negative electrodes, separators and electrolytes. Electrolytes include: aqueous electrolytes, organic electrolytes, ionic liquid electrolytes and solid electrolytes. The electrolyte used in commercial lithium-ion batteries is usually an organic electrolyte, and in order to obtain better overall performance, a variety of organic solvents are generally used to dissolve ionic compounds. Most of...

Claims

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Application Information

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IPC IPC(8): H01M10/0585H01M10/0525H01M10/04B29C64/135B33Y10/00
CPCB33Y10/00B29C64/135H01M10/04H01M10/0525H01M10/0585Y02E60/10Y02P70/50
Inventor 魏璐郭新谢会信吴甲民陈双
Owner HUAZHONG UNIV OF SCI & TECH
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