阅读说明：本技术 一种基于互联气相沉积技术制备复合电极粉末的方法 (Method for preparing composite electrode powder based on interconnected vapor deposition technology ) 是由 陈人杰 罗锐 马一添 潘新慧 于 2020-12-23 设计创作，主要内容包括：一种基于互联气相沉积技术制备复合电极粉末的方法,该方法是将离子束溅射沉积和磁控溅射沉积集成在一台镀膜设备,可以在同一设备不同模块镀膜。按照镀膜设计需要,采取合适的薄膜沉积技术,不但可以提高膜层质量,还可以提高镀膜效率,降低镀膜成本。同时,镀膜过程中粉末颗粒处于振动状态,确保磁性粉末颗粒表面溅射薄膜包覆均匀性,厚度可控性；本发明提出采用离子束和磁控溅射沉积互联技术,选用具有较高离子电导率的靶材(如磷酸锂、LiPON、氧化物等)在电极粉末的颗粒表面镀一层离子导体膜,制备离子导体膜均匀包覆的具有分级核壳结构的复合电极材料,改善传统电极材料与电解质之间的固固接触界面问题,有效增大电极颗粒/电解质界面的接触面积,同时分级核壳结构缩短了离子传输路径,有效抑制循环过程中正极的体积膨胀。(A method for preparing composite electrode powder based on an interconnected vapor deposition technology integrates ion beam sputtering deposition and magnetron sputtering deposition into one coating device, and can coat films on different modules of the same device. According to the design requirement of coating, a proper film deposition technology is adopted, so that the quality of the coating can be improved, the coating efficiency can be improved, and the coating cost can be reduced. Meanwhile, the powder particles are in a vibration state in the coating process, so that the coating uniformity and thickness controllability of the sputtered film on the surface of the magnetic powder particles are ensured; the invention provides a method for preparing a composite electrode material with a hierarchical core-shell structure, which adopts an ion beam and magnetron sputtering deposition interconnection technology, selects a target material (such as lithium phosphate, LiPON, oxide and the like) with higher ionic conductivity to plate a layer of ion conductor film on the particle surface of electrode powder, prepares the composite electrode material with the hierarchical core-shell structure and uniformly coated by the ion conductor film, improves the problem of solid-solid contact interface between the traditional electrode material and electrolyte, effectively increases the contact area of electrode particle/electrolyte interface, shortens an ion transmission path by the hierarchical core-shell structure, and effectively inhibits the volume expansion of a positive electrode in a circulation process.)

1. A method for preparing composite electrode powder based on an interconnected vapor deposition technology is characterized by comprising the following steps:

(1) providing a substrate;

(2) cleaning the surface of the substrate to obtain an atomic-scale clean surface;

(3) selecting a target material according to the requirement, placing the target material on a handle frame connected with a cooling device, placing the powder to be plated on a sample trolley, and transporting the powder to be plated to a powder sample table of an ion beam sputtering module;

(4) an ion beam sputtering deposition module: the air pressure of the working chamber is pumped to 1.0 multiplied by 10^-2Pa～4×10^-2Introducing argon gas of sputtering gas with the purity of 99.99% after Pa, wherein the flow rate of the argon gas is controlled by a gas mass flow meter, introducing 6-12 SCCM of argon gas into the main ion source, introducing 1-6 SCCM of argon gas into the auxiliary ion source, and introducing 1-9 SCCM of nitrogen gas into the auxiliary ion source; the energy of the main ion source is 400-2000 eV, and the energy of the auxiliary ion source is 400-1500 eV; setting the deposition rate of ion beam sputtering, wherein the deposition time is 1-8 h, and the sample temperature is controlled at 300-650 ℃;

(5) the sputtering ion gun and the auxiliary ion gun work simultaneously, and the sputtering ion gun bombards the sputtering target material;

(6) during sputtering coating, the swing frequency of the powder sample table and the vibration power of ultrasonic waves are adjusted, so that each powder particle can maintain a good dispersion state;

(7) after the ion beam sputtering coating is finished, the magnetic powder particles vertically fall into a sample collecting trolley below under the action of gravity and are transported to a magnetron sputtering deposition module;

(8) magnetron sputtering deposition module: sputtering power is 50-500W, sputtering time is 10-300 min, and sample temperature is controlled at 20-300 ℃;

(9) and (5) in the same step (6), finishing coating after the coating of the coating layer is finished.

2. The interconnected vapor deposition-based method for preparing composite electrode powder according to claim 1, wherein the target size in step (3) is 70x70mm, and the thickness is 5-7 mm.

3. The interconnected vapor deposition technology-based method for preparing composite electrode powder according to claim 1 or 2, wherein the cooling device in the step (3) is water-cooled.

4. The interconnected vapor deposition technology-based method for preparing composite electrode powder according to claim 1 or 2, wherein the target plane in step (5) is 45 ° to the sputter ion gun.

Technical Field

The invention belongs to the technical field of interconnected vapor deposition, and particularly relates to the field of ion beam sputtering deposition and magnetron sputtering comprehensive deposition coating.

Background

The interconnection vapor deposition technology is a method for coating a coating or a nano material on the surface of a substrate, can realize the functions of transferring and connecting samples among process modules, depositing thin films and the like in a high-vacuum ultra-clean environment, and is widely applied to the fields of material surface modification, electronic integration, energy sources and the like at present.

Physical vapor deposition is a technique of vaporizing a material source, i.e., a solid or liquid surface, into gaseous atoms, molecules or parts of the gas, ionizing the gaseous atoms, molecules or parts of the gas into ions under vacuum, and depositing a film with a specific function on the surface of a substrate through a low-pressure gas (or plasma) process, and includes vacuum evaporation deposition, magnetron sputtering deposition, ion beam assisted deposition, and the like. Among them, the ion beam sputtering deposition technique has the characteristics of high compactness, high stability and the like, and is widely applied to the preparation of thin film elements, so that people pay attention to the technique and the technique is vigorously developed.

The magnetron sputtering deposition technology is that electrons collide with argon atoms in the process of flying to a matrix under the action of an electric field, so that the argon atoms are ionized to generate argon positive ions and new electrons; the new electron flies to the substrate, argon ions fly to the cathode target under the action of an electric field in an accelerating way, and bombard the surface of the target at high energy, so that the target is sputtered and a film is formed on the surface of the substrate. At present, the most studied by magnetron sputtering deposition technology is to coat a film on a bulk substrate, and the substrate can be in good contact with a thin film substance mostly in a standing state. For the particles, the particle size is small, the specific surface area is large, and the agglomeration phenomenon is easy to generate. If the powder movement treatment is improper, the uniformity of the film is difficult to control, the compactness of the film is poor, and the performance of the film is directly influenced. In order to ensure that each microparticle has an opportunity to fully expose the surface of the microparticle during film growth, a vibration type coating method is adopted, and the method is characterized in that powder particles are in a vibration suspension state in the magnetron sputtering coating process, so that the sputtered film on the surface of the powder particles is uniformly coated. When the electrode without coating is directly exposed to the organic electrolyte, side reaction can occur with the electrolyte, and then a large amount of side reaction products are generated, and the side products can be accumulated on the surface of the electrode and can block the migration of ions at the interface.

In some applications, the advantages of ion beam sputtering deposition and magnetron sputtering deposition interconnection technology need to be comprehensively utilized to realize two or even more than two kinds of film deposition on the same coating element. Currently, for the coating requirement, a part of the film layers are finished in one coating device, and then the film layers of the rest part are finished in another device. The method greatly increases the probability of defects caused inside the element in the processes of loading, taking and vacuumizing for many times, thereby reducing the performance of the film layer; on the other hand, the high vacuum is pumped for many times, so that the film coating efficiency is reduced, and the film coating cost is increased.

Disclosure of Invention

The invention aims to realize the integrated preparation of composite electrode powder by using an ion beam sputtering deposition module and a magnetron sputtering deposition module on the same equipment.

The invention relates to a method for preparing composite electrode powder based on an interconnected vapor deposition technology, which comprises the following steps: (1) providing a substrate;

(2) performing ion beam etching cleaning on the surface of the substrate by using an argon ion beam generated by an auxiliary ion source to obtain an atomic-level clean surface;

(3) the size of the target used for sputtering is 70x70mm, and the thickness is 5-7 mm. The target is rotated and cooled by water, and the plane of the target and the sputtering ion gun form an angle of 45 degrees;

(4) selecting a target material as required, placing the target material on a handle frame connected with a cooling circulating water device, putting the powder to be plated on a sample trolley, and transporting the powder to be plated to a powder sample table of an ion beam sputtering module;

(5) an ion beam sputtering deposition module: the air pressure of the working chamber is pumped to 1.0 multiplied by 10^-2Pa～4×10^-2Introducing argon gas of which the purity is 99.99% into the reactor after Pa, wherein the flow rate of the argon gas is controlled by a gas mass flowmeter, introducing 6-12 SCCM (Standard-state cubic centimetre minute) of argon gas into the main ion source, introducing 1-6 SCCM of argon gas into the auxiliary ion source, and introducing 1-9 SCCM of nitrogen gas into the auxiliary ion source; the energy of the main ion source is 400-2000 eV, and the energy of the auxiliary ion source is 400-1500 eV; setting the deposition rate during ion beam sputtering, wherein the deposition time is 1-8 h, and the sample temperature is controlled at 300-650 ℃;

(6) the sputtering ion gun and the auxiliary ion cavity gun work simultaneously, the sputtering ion gun bombards the sputtering target material, and the included angle between the sputtering target material and the horizontal direction is 45 degrees;

(7) during sputtering coating, the swing frequency of the powder sample table and the vibration power of ultrasonic waves are adjusted, so that each powder particle can maintain a good dispersion state;

(8) after the ion beam sputtering coating is finished, the magnetic powder particles vertically fall into a sample collecting trolley below under the action of gravity and are transported to a magnetron sputtering module;

(9) magnetron sputtering deposition module: sputtering power is 50-500W, sputtering time is 10-300 min, and sample temperature is controlled at 20-300 ℃;

(10) and (7) finishing coating after the coating of the coating layer is finished. The sample is collected by a sample trolley and taken out.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention can respectively use the deposition technology in the process of one-time film coating, and can also select the ion beam sputtering deposition technology and the magnetron sputtering deposition technology according to the design sequence according to the design requirement of the film, thereby realizing the purpose of preparing the composite electrode material by utilizing the ion beam sputtering and the magnetron sputtering deposition technologies;

2. on one hand, the invention can avoid the defects introduced into the film material in the processes of repeatedly loading and taking the material and repeatedly vacuumizing, thereby improving the performance of the film layer; on the other hand, the high vacuum is prevented from being extracted for many times, so that the film coating efficiency is improved, and the film coating cost is reduced;

3. in the vacuum interconnection device, magnetic powder particles after sputtering coating vertically fall into a sample collecting trolley below under the action of gravity, so that the purity of the coating and the service life of an instrument are ensured;

4. in the magnetron sputtering coating process, the powder sample table is in a vibration state, so that the powder particles are in a suspension state, and the surface of the powder particles is ensured to be uniformly coated with a sputtering film.

5. The sample trolley is accurately positioned to collect the magnetic powder, and the position of the conveying trolley can be timely monitored, so that the sample can be accurately conveyed to a specified station.

Drawings

FIG. 1 SEM image for comparing before and after coating

Detailed Description

Embodiment 1 a method for preparing composite electrode powder based on interconnected vapor deposition technology, characterized by the following steps:

(1) providing a substrate;

(2) cleaning the surface of the substrate to obtain an atomic-scale clean surface;

(3) selecting a target material according to the requirement, placing the target material on a handle frame connected with a cooling device, placing the powder to be plated on a sample trolley, and transporting the powder to be plated to a powder sample table of an ion beam sputtering module;

(5) an ion beam sputtering deposition module: the air pressure of the working chamber is pumped to 1.0 multiplied by 10^-2Pa～4×10^-2Introducing argon gas of sputtering gas with the purity of 99.99% after Pa, wherein the flow rate of the argon gas is controlled by a gas mass flow meter, introducing 6-12 SCCM of argon gas into the main ion source, introducing 1-6 SCCM of argon gas into the auxiliary ion source, and introducing 1-9 SCCM of nitrogen gas into the auxiliary ion source; the energy of the main ion source is 400-2000 eV, and the energy of the auxiliary ion source is 400-1500 eV; setting the deposition rate during ion beam sputtering, wherein the deposition time is 1-8 h, and the sample temperature is controlled at 300-650 ℃;

(6) the sputtering ion gun and the auxiliary ion gun work simultaneously, the sputtering ion gun bombards the sputtering target material,

(7) during sputtering coating, the swing frequency of the powder sample table and the vibration power of ultrasonic waves are adjusted, so that each powder particle can maintain a good dispersion state;

(8) after the ion beam sputtering coating is finished, the magnetic powder particles vertically fall into a sample collecting trolley below under the action of gravity and are transported to a magnetron sputtering module;

(9) magnetron sputtering deposition module: sputtering power is 50-500W, sputtering time is 10-300 min, and sample temperature is controlled at 20-300 ℃;

(10) and (7) finishing coating after the coating of the coating layer is finished. The sample is collected by a sample trolley and taken out. As shown in fig. 1.

The invention solves the technical problem of overcoming the defects of the prior art and provides ion beam sputtering deposition and magnetron sputtering comprehensive deposition coating equipment and a comprehensive coating method thereof. Meanwhile, the powder particles are in a suspension state in the magnetron sputtering coating process, so that the coating uniformity and thickness controllability of the sputtered film on the surface of the magnetic powder particles are ensured.

The invention provides a method for preparing a composite electrode material with a hierarchical core-shell structure, which adopts ion sputtering and magnetron sputtering technologies, selects materials with higher ion conductivity (such as lithium phosphate, LiPON, oxides and the like) to plate a layer of insulating film on the particle surface of electrode powder, prepares the composite electrode material uniformly coated by an ion conductor film and has the hierarchical core-shell structure, improves the solid-solid contact problem between the traditional electrode material and electrolyte, effectively increases the contact area of electrode particle/electrolyte interfaces, shortens an ion transmission path by the hierarchical structure, and effectively inhibits the volume expansion of a positive electrode in a circulation process. And collecting the prepared magnetic powder to a sample trolley and transporting the magnetic powder to a magnetron sputtering module.

In order to ensure that the surface of each micro-particle can be fully exposed in the coating process, a vibration type coating method is adopted, and the method is characterized in that the powder particles are in a vibration state in the magnetron sputtering coating process, so that the sputtered film on the surface of the powder particles is uniformly coated. The electrode material particles without coating are directly exposed in the organic electrolyte and are easy to generate side reaction with the electrolyte, so that a large amount of unstable solid electrolyte products are generated, and the products are accumulated on the surface of an electrode to block the migration of interfacial ions, thereby causing the polarization of the battery to be increased continuously. As side reactions occur, the electrolyte in the battery is continuously consumed, resulting in a reduction in the cycle life of the battery. The magnetron sputtering technology can effectively and uniformly coat the film on the surface of the particle, the stability of an electrode/electrolyte interface is improved, and meanwhile, the film coating with high ionic conductivity is beneficial to improving the transmission rate of ions.

The material structure is kept intact and the coating layer is uniform and continuous by carrying out coating layer modification with high ionic conductivity on the surface of the magnetic electrode material; the thickness of the coating film can be controlled, the transmission of the ions of the material can not be influenced in a certain thickness range, and the coating film layer has good binding force with the electrode material of the body and is not easy to pulverize and fall off. The thickness and uniformity of the film prepared by the existing sol-gel method are difficult to control. By adopting the ion beam sputtering deposition and the magnetron sputtering deposition technology, a vibration system device is added, and the phenomena of magnetic powder particle agglomeration and uneven coating in the coating process are effectively avoided.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.