阅读说明：本技术 普适性的3d打印纳米电极浆料及其制备方法 (Universal 3D printing nano electrode slurry and preparation method thereof ) 是由 田晓聪 靳洪允 侯书恩 唐康 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种普适性的3D打印纳米电极浆料,包括以下组分组成：纳米电极活性材料、导电剂、粘结剂、分散剂,所述纳米电极活性材料、所述导电剂与所述粘结剂的重量比为5～7:2～4:1,所述分散剂的体积与所述纳米电极活性材料、所述导电剂和所述粘结剂总重量的比例为2～5mL:1g,还提供一种普适性的3D打印纳米电极浆料的制备方法。本发明具有提高3D打印纳米电极浆料的流变性和材料分散性的有益效果。(The invention discloses universal 3D printing nano electrode slurry, which comprises the following components: the nano-electrode paste comprises a nano-electrode active material, a conductive agent, a binder and a dispersing agent, wherein the weight ratio of the nano-electrode active material to the conductive agent to the binder is 5-7: 2-4: 1, and the ratio of the volume of the dispersing agent to the total weight of the nano-electrode active material to the conductive agent to the binder is 2-5 mL:1 g. The invention has the beneficial effects of improving the rheological property and material dispersibility of the 3D printing nano-electrode slurry.)

1. The universal 3D printing nano electrode slurry is characterized by comprising the following components: the conductive electrode comprises a nanometer electrode active material, a conductive agent, a binder and a dispersing agent, wherein the weight ratio of the nanometer electrode active material, the conductive agent and the binder is 5-7: 2-4: 1, and the ratio of the volume of the dispersing agent to the total weight of the nanometer electrode active material, the conductive agent and the binder is 2-5 mL:1 g.

2. The universal 3D printing nanoelectrode paste of claim 1, wherein the binder comprises 10% by weight of the total weight of the nanoelectrode active material, the conductive agent, and the binder.

3. The universal 3D printing nanoelectrode paste of claim 1, wherein the nanoelectrode active material is one or more of lithium iron phosphate, lithium titanate, nickel cobalt manganese ternary material, and silicon carbon.

4. The universal 3D printing nanoelectrode paste of claim 1, wherein the conductive agent is one or more of conductive carbon black, multi-walled carbon nanotubes, or graphene.

5. The universal 3D printing nanoelectrode paste as claimed in claim 1, wherein the binder is one of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate and sodium carboxymethylcellulose.

6. The universal 3D printing nanoelectrode paste as claimed in claim 1, wherein the dispersant is one of N-methyl pyrrolidone and pure water.

7. The method for preparing the universal 3D printing nanoelectrode paste according to any one of claims 1 to 6, comprising the following steps: mixing the nano electrode active material, the conductive agent and the binder, grinding, adding the dispersing agent, continuously grinding, and shearing and dispersing to prepare paste-shaped 3D printing nano electrode slurry.

8. The method for preparing universal 3D printing nanoelectrode paste according to claim 7, further comprising: the method for printing the battery electrode by using the 3D printing nano electrode paste is characterized by comprising the following steps of: setting a printing program of a 3D printer, fixing a cylinder to be used on the 3D printer, setting printing parameters of the 3D printer, printing a battery electrode precursor by using 3D printing nano electrode slurry, soaking, taking out, absorbing water, and freeze-drying to obtain the battery electrode.

Technical Field

The present invention relates to the field of electrochemical energy storage. More specifically, the invention relates to universal 3D printing nano-electrode slurry and a preparation method thereof.

Background

The lithium ion battery is a rechargeable battery, mainly works by moving lithium ions between a positive electrode and a negative electrode, and is widely applied to the fields of mobile phones, notebook computers, digital cameras, smart power grids and the like due to the advantages of high energy density, high multiplying power, low cost, no memory effect and the like. The electrode material (anode or cathode) is a core unit component of the lithium ion battery, the nano electrode material is considered as an ideal anode and cathode material due to larger specific surface area, and the reasonable microstructure is another key for improving the electrochemical performance of the nano electrode material and is a guarantee for realizing effective transmission, interface reaction and diffusion of electricity/ions and providing structural support. Therefore, in addition to the nanoelectrode material itself, the manufacturing approach of the nanoelectrode material is another key factor for controlling the reliability and durability of the lithium ion battery.

At present, the traditional preparation method of the nano electrode material, such as a slurry coating method and the like, obtains an electrode structure which is uncontrollable, poor in repeatability and easy to deform. Therefore, the preparation of 3D structured nano-electrode materials is considered as an effective means for achieving high energy density and power density, and 3D printing technology is a typical advanced technology for preparing 3D batteries. On one hand, the 3D printing method can be used for preparing a customizable battery electrode and has the great advantage of flexible application; on the other hand, the technology can provide more active materials by increasing the height of the electrode or changing the shape to obtain higher energy density, and the ion diffusion distance is effectively shortened, so that the self energy density of the prepared 3D battery electrode can be improved without sacrificing the power density.

However, the rheological property of 3D printing paste is required to be high in 3D printing, and the existing 3D printing paste cannot meet the requirement, which seriously restricts the further development of the 3D printing technology in the energy field.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.

The invention also aims to provide the universal 3D printing nano-electrode slurry and a preparation method of the universal 3D printing nano-electrode slurry, and the universal 3D printing nano-electrode slurry has the beneficial effects of improving the rheological property and material dispersibility of the 3D printing nano-electrode slurry.

To achieve these objects and other advantages in accordance with the present invention, there is provided a universal 3D printing nanoelectrode paste comprising the following components: the conductive electrode comprises a nanometer electrode active material, a conductive agent, a binder and a dispersing agent, wherein the weight ratio of the nanometer electrode active material, the conductive agent and the binder is 5-7: 2-4: 1, and the ratio of the volume of the dispersing agent to the total weight of the nanometer electrode active material, the conductive agent and the binder is 2-5 mL:1 g.

Preferably, the weight of the binder is 10% of the total weight of the nanoelectrode active material, the conductive agent and the binder.

Preferably, the nano-electrode active material is one or more of lithium iron phosphate, lithium titanate, nickel-cobalt-manganese ternary material and silicon carbon.

Preferably, the conductive agent is one or more of conductive carbon black, multi-walled carbon nanotubes or graphene.

Preferably, the binder is one of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate and sodium carboxymethylcellulose.

Preferably, the dispersant is one of corresponding N-methyl pyrrolidone and pure water.

Also provides a universal preparation method of the 3D printing nano electrode slurry, which comprises the following steps: mixing the nano electrode active material, the conductive agent and the binder, grinding, adding the dispersing agent, continuously grinding, and preparing paste-like 3D printing nano electrode slurry through self-shearing dispersion.

Preferably, the method further comprises the following steps: a method of printing a battery electrode using 3D printed nano-electrode paste, comprising the steps of: setting a printing program of a 3D printer, fixing a cylinder to be used on the 3D printer, setting printing parameters of the 3D printer, printing a battery electrode precursor by using 3D printing nano electrode slurry, soaking, taking out, absorbing water, and freeze-drying to obtain the battery electrode.

The invention at least comprises the following beneficial effects:

the method comprises the steps of accurately controlling the dosage of a nano electrode active material, a conductive agent, a binder and a dispersing agent to obtain a preceding stage sample of 3D printing nano electrode slurry, further preparing pasty 3D printing nano electrode slurry in a self-shearing dispersion mode, and improving the rheological property and material dispersibility of the printing slurry, so that the preparation of the 3D printing customizable lithium ion battery nano electrode material is universally realized, and the advantages of the 3D printing technology for realizing the controllable manufacturing of a microstructure are fully exerted;

the method for preparing the 3D printing nano electrode slurry has certain universality, is suitable for common nano anode and cathode materials, the obtained slurry is a non-Newtonian fluid with high viscosity and shear thinning property, and the materials of all components in the slurry are uniformly dispersed, so that the slurry extrusion in the 3D printing process is very smooth;

the battery electrode prepared by the 3D printing method has customizability and can be directly used for the anode and the cathode of the battery.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Drawings

FIG. 1 is a graph of the rheological properties of a battery electrode paste prepared by 3D printing according to an embodiment of the invention;

FIG. 2 is a diagram of dispersed objects of 3D grid-shaped 1-4 layers of battery electrodes prepared by 3D printing according to an embodiment of the invention;

fig. 3 is a schematic diagram of the specific capacity and the coulombic efficiency of a battery electrode of a 3D grid-shaped 4-layer nano lithium iron phosphate-based electrode prepared by 3D printing under different current densities according to an embodiment of the invention;

fig. 4 is a battery electrode charge-discharge voltage curve diagram of a 3D grid-shaped 4-layer nano lithium iron phosphate-based nanotube electrode prepared by 3D printing according to an embodiment of the present invention at different current densities;

fig. 5 is a composite image of a 3D "L" shaped lithium titanate-based battery electrode prepared by 3D printing according to an embodiment of the present invention.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.