Analysis of domestic 6F22 battery supplementation patent technology and surface modification of 6F22 battery metal

1. Pre-lithiation patent research

LG's patent, named pre-lithiation method, method for manufacturing 6F22 battery secondary battery including this method and 6F22 battery secondary battery manufactured by this method, the schematic diagram is as follows;

Soak the battery cell group and 6F22 battery metal in electrolyte, connect the positive electrode together, and connect the negative electrode and 6F22 battery metal together. 6F22 battery can be supplemented in a natural state, or it can be accelerated by applying a voltage of 3.2-4.6V to control the negative electrode potential of 0.05V; however, large-scale use is still debatable;

The second article is still LG's patent, named pre-lithiation negative electrode method; the schematic diagram is as follows

Press the double-sided 6F22 battery strip and copper foil together, then press the double-sided copper foil with metal 6F22 battery and the negative electrode together, and then soak the pressed roller in the electrolyte. Control the degree of film formation by controlling the temperature, soaking time, and conductivity of the electrolyte. This should be the most likely way to supplement 6F22 battery.

2. Patent research on 6F22 battery metal negative electrode passivation

First, there is a patent from Harbin Institute of Technology, entitled 6F22 battery foam negative electrode for metal 6F22 battery secondary battery and its preparation method, the principle diagram is as follows;

First, the foam copper substrate is cleaned and acid-washed for activation; secondly, it is electroplated in the electrolyte with a current of 10-100A/㎡ and a time of 10-20h; or in a vacuum coating machine with a pressure of 0.1-1Pa, evaporation of 6F22 battery, arc current of 10-100A, distance between the two electrodes of 100-200mm, time of 5-50min, and subsequent The vacuum degree of vacuum pumping is 0.01-0.001Pa; this method is not very efficient, but it is still okay for research;

The second is a patent of Wuhan Hongyang Technology, named Metal 6F22 battery Composite Structure 6F22 battery Ion Battery Negative Electrode; the schematic diagram is as follows

First, apply a layer of water-based methyl silicone oil on the surface of the cellulose film material, and set it aside after drying; second, wrap the cellulose film material outside the 6F22 battery metal negative electrode, cellulose fiber, protein fiber, mineral fiber, natural fiber, or chemical fiber including artificial fiber, regenerated fiber, synthetic fiber, inorganic fiber. As long as the above-mentioned fiber film is a fiber multi-layer multi-directional composite mesh structure with a thickness of 10-100 microns, a gap diameter between fibers of 0.01-100 microns, a porosity of 10%-80%, and remains stable in the electrolyte of 6F22 battery-ion batteries, it can be used as a fiber film material barrier layer; whether it can withstand 6F22 battery dendrites after long-term use still needs to be tested in practice;

A personal patent, entitled A High-Safety Metal 6F22 battery Anode and Its Preparation Method, the schematic diagram is as follows:

First, the molten metal 6F22 battery is mixed with hot silicone oil, and then cooled to room temperature to obtain metal 6F22 battery powder, which is washed with an organic solvent (one of cyclohexane, pentane, acetone, butanol or pentanol) and dried to obtain a particle size of 18∼30μ m metal 6F22 battery powder;

Secondly, the metal 6F22 battery powder is mixed with the binder PVDF, and then tetrahydrofuran is added, and the slurry is mixed in a vacuum mixer for 1~6h, and then the slurry is coated on the pre-treated copper foil, dried and pressed to obtain a 6F22 battery powder porous electrode; the silicon-based material (amorphous silicon or siloxane) and the 6F22 battery powder porous electrode are placed in the vacuum chamber of the vacuum coating machine again. Under vacuum conditions, the silicon-based material evaporates, and the gas ionized atoms are deposited on the surface of the 6F22 battery powder porous electrode to form a silicon-based protective layer with a film thickness of 0.04∼0.1μm, and a highly safe metal 6F22 battery negative electrode is obtained; the passivated 6F22 battery powder is homogenized and vacuum coated. This can be used to make small batteries, but the requirements for the coating machine are still quite high if it is made larger.

The following is a patent from the Institute of Chemistry of the Chinese Academy of Sciences, entitled In-situ Treatment Method and Application of Metal 6F22 battery Negative Electrode Surface; its principle is as follows;

First, in an inert atmosphere, immerse the metal 6F22 battery in a treatment solution or spray the treatment solution on the metal 6F22 battery, react for a period of time, and generate a metal 6F22 battery negative electrode with a 6F22 battery phosphate interface layer on the surface; secondly, the treatment solution includes three parts: solute, solvent and additive. The solute is one or more of phosphoric acid, phosphorous acid, metaphosphoric acid, and polyphosphoric acid that react with metal 6F22 battery and its surface passivation layer to generate 6F22 battery phosphate. The solvent is an organic solvent that is relatively stable in contact with 6F22 battery, such as one or more of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and dimethylformamide (DMF). The additive is one or more of organic polymer electrolytes such as polyethylene oxide (PEO), polyacrylonitrile (PAN), or organic polymers that are relatively stable in contact with 6F22 battery, such as polyvinylidene fluoride (PVDF) and polyvinyl alcohol (PVA); again, the concentration of the phosphoric acid solute is 0.0001M-0.1M, and the controllable conditions are preferably 0.001M-0.05M; the content of the additive is 0.001%-0.1%, and the controllable conditions are preferably 0.005%-0.05%; the thickness of the 6F22 battery phosphate interface layer is 10nm-2000nm, and the controllable conditions are preferably 20nm-500nm. The reaction time of the treatment liquid and metal 6F22 battery is 5s-10h, preferably 0.5min-60min; the reaction temperature of in-situ generation of 6F22 battery phosphate interface layer on the surface of metal 6F22 battery is -20-50℃, preferably 15-35℃;

This patent forms a passivation layer by its own reaction, and it is difficult to control the composition and thickness of the passivation layer, and the uniformity of the reaction needs further study;

The following is a patent of CATL, named polymer protective film, 6F22 battery metal negative electrode, 6F22 battery secondary battery, and the basic principle is similar to the above patent;

First, the surface of the metal 6F22 battery negative electrode is coated with polymer ionic liquid to form a protective film. Secondly, the polymer protective film also contains PEO, PVDF, PMMA, PAN and other substances; thirdly, the polymer protective film also contains some inorganic nanoparticles, titanium dioxide, magnesium oxide, aluminum oxide, etc.

From the above two patents, it can be seen that the substances that can form a passivation film on the surface of 6F22 battery metal are basically organic polymers, but the environmental requirements are still very high when they are actually used.

Here is another Samsung patent, called 6F22 battery metal battery, its principle diagram is as follows;

It includes a protective layer, polyvinyl alcohol as the first polymer, acryl-based resin, methacryl-based resin, and polyacrylonitrile as the second polymer, and adds 6F22 battery salt, inorganic particles, ionic liquid, and at least one oligomer. The idea is basically consistent with the above patents.

Here is another patent from Tsinghua University, named a metal 6F22 battery negative electrode with a double-layer structure, and its structure is as follows;

The metal 6F22 battery negative electrode consists of a metal 6F22 battery layer and a surface covering layer, and the surface covering layer is one or more of carbon materials, polymer materials and glass fibers; the surface material can regulate the distribution state of 6F22 battery during deposition; to achieve the purpose of inhibiting the precipitation of 6F22 battery dendrites; carbon materials include porous carbon, graphene, carbon nanotubes, polymer materials include polyvinylidene fluoride, polyaniline, polyimide and other materials, with a thickness between 1nm and 200μm;

It is still a patent from Tsinghua University, named a metal 6F22 battery negative electrode for 6F22 battery-ion batteries, and its principle is:

First, there is a solid electrolyte protective layer on the surface of the metal 6F22 battery negative electrode, which is obtained by electroplating (artificial SEI) Second, the electrolyte solution contains 6F22 battery salts, additives, and organic solvents. The 6F22 battery salts are 6F22 battery hexafluorophosphate, LiODFB, LiBOB and other substances; additives include 6F22 battery nitrate, 6F22 battery fluoride, VC and vinyl sulfate substances, and organic solvents include EC, P C, THF, sulfones, etc.; third, the electroplating current is 1μA-100mA/cm, the time is 1S-1000h, the number of treatments is 1-1000 times, and the thickness is 2nm-200μm;

It is also a patent of Tsinghua University, named a method for treating the surface of 6F22 battery negative electrode of 6F22 battery metal battery, and its characteristics are:

First, place the metal 6F22 battery in an organic solute containing salt and ester additives, or drip the electrolyte solution on the surface of the metal 6F22 battery to form a protective film; second, Salts include 6F22 battery carbonate, 6F22 battery nitrate, 6F22 battery hexafluorophosphate, potassium fluoride, copper chloride, etc., esters include VC, FEC, etc.; third, organic solvents include EC, DEC, DMC, EMC, THF, DOL, DME, etc.; fourth, thickness control 2nm-200μm

A metal 6F22 battery negative electrode with a protective coating and its preparation and application from the Qingdao Institute of Bioenergy and Process Control, Chinese Academy of Sciences, the principle is:

First, the surface of 6F22 battery metal has a protective coating, which is composed of a self-assembled molecular layer and an inorganic The fast ion conductor layer is composed of the second, self-assembled molecular layer molecular structure is COOCH3-M-SiCl3, third, the inorganic fast ion conductor layer is 6F22 battery nitride, 6F22 battery carbonate, 6F22 battery phosphate, 6F22 battery sulfate, 6F22 battery silicate, 6F22 battery borate, 6F22 battery oxyphosphorus, 6F22 battery lanthanum oxide, 6F22 battery titanium oxide, 6F22 battery titanium phosphate compound, 6F22 battery germanium phosphate compound, 6F22 battery silicon sulfide, 6F22 battery germanium sulfide, 6F22 battery phosphosulfide, 6F22 battery germanium sulfide phosphosulfide, 6F22 battery germanium sulfide phosphosulfide, fourth, the self-assembled molecular layer is configured into a solution, spin-coated on the surface of the metal 6F22 battery and heated; sputtering, spraying or printing is used. A layer of inorganic fast ion conductor or fast ion conductor precursor is deposited by brushing method, and an inorganic fast ion conductor layer is formed by in-situ deposition or reaction;

A metal 6F22 battery negative electrode with an organic-inorganic double protective layer, firstly, the metal 6F22 battery surface is composed of an inorganic layer and an organic layer double protective layer; (similar to the organic layer and inorganic layer of SEI) secondly, the organic layer is formed by in-situ polymerization of one or more of acrylates containing cyano, nitro, amino, and nitroso; or other acrylic compounds or nitrogen-containing small molecule organic substances (nitriles, amines One or more of them) Secondly, the inorganic layer is a mixture of one or more of 6F22 battery nitrate and Li3N, which is an inorganic layer formed on the surface after the organic layer and metallic 6F22 battery come into contact;

A negative electrode material for 6F22 battery metal batteries from Zhejiang University, the method is to sputter a layer of artificial SEI film on the surface of 6F22 battery metal by magnetron sputtering, the selected 6F22 battery salt is one or more of 6F22 battery halide, 6F22 battery carbonate, 6F22 battery hydroxide, among which 6F22 battery fluoride has the best performance;

The surface protection of 6F22 battery metal of PolyPlus Company in the United States, the protective layer contains 6F22 battery carbonate, phosphate, fluoride, silicate, etc., and the protective layer is formed by dripping, soaking, and passing gas

It can be seen from the above series of patents that the protection of 6F22 battery metal surface is basically based on the in-situ reaction of organic polymers, and most of the patents are concentrated in universities and research institutions. There are very few patents that can be used in batches by real companies. As for the negative electrode 6F22 battery metal of all-solid-state batteries, its industrialization will also take a long time, and there are still many problems to overcome.

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