TW201533960A - Silicon carbon composite electrode material and method of preparing the same - Google Patents

Abstract

The specification discloses a silicon carbon composite electrode material and method of preparing the same. The silicon carbon composite electrode material can improve efficient dispersibility for silicon-containing particles on a carbon-containing particle surface by packaging organic polymers modified films on silicon-containing particles and a surface of silicon-containing particles respectively. The silicon carbon composite electrode material can further comprise a silicon-containing conductive film coated on a silicon carbon composite electrode material surface for improving efficient adhesion of the silicon-containing particles. The method of preparing the silicon carbon composite electrode material can be implemented in aqueous solution and dry mixture. Accordingly, it can effectively avoid volatile organic compounds from causing damages on operators and environment. According to this invention, the silicon carbon composite electrode material can effectively improve capacitance, charging/discharging performance, and cycle life of a battery product using the silicon carbon composite electrode material.

Description

Carbon germanium composite electrode material and preparation method thereof

The present invention relates to a carbon substrate electrode material, and more particularly to a carbon germanium composite electrode material and a method of preparing the same.

The development of lithium-ion batteries depends to a large extent on the development and application of high-performance positive and negative materials. The current practical mesophase carbon microsphere material (MCMB) is relatively expensive to prepare. In terms of natural and artificial graphite, in order to reduce the initial irreversible capacity and improve the cycle life, it is necessary to carry out surface modification with a bituminous aromatic compound material. In the preparation process, carbonization is required at a high temperature of 1300 ° C or higher, wherein the raw material (asphalt-type aromatic hydrocarbon) Compounds) have large price fluctuations, as well as environmental pollution and high energy consumption caused by high-temperature carbonization, which are not the direction of long-term sustainable operation.

In addition, there are patents using different water-soluble polymer polyacrylic acid PAA (polyacrylic acid) or sodium carboxymethyl cellulose CMC (Carboxymethyl Cellulose Sodium), respectively, as a coating material or an adhesive in the preparation of the slurry. In comparing the single aqueous polymer with this patented technology, as described above, the uniformity of coating with a single polymer PAA or CMC and the inefficiency of reducing lithium ions are inferior. In addition, if the single PAA material is applied to the adhesive in the preparation of the slurry, the prepared slurry has poor suspension ability, and needs to be combined with other thickeners to avoid sedimentation of the active particles and affect the slurry. Uniformity, in addition The resulting pole piece is brittle and hard, which is not conducive to the subsequent winding process of the electrode sheet. The reason is that if the surface of the negative electrode material is modified, the lower molecular weight will have a better coating effect (more easily penetrate into the micropores). Conversely, if it is to be applied to an adhesive in a slurry, a higher molecular weight will result in better suspension and dispersibility.

On the other hand, in the conventional carbon substrate surface modification process, an organic solvent is often used to prepare a polymer solution to be coated. Although the effect of uniform dispersion can be obtained during the preparation process, not only in the preparation process, many organic wastes are generated, and the organic solvent used also produces volatile organic compounds (VOC) which are also prone to environmental protection. The problem is even harmful to the operator.

In the development of electrode materials, the researchers later found that only carbon substrates or surface-modified carbon substrates can have good electrical conductivity, but in terms of further improving the performance of effective capacitance, However, there is still room for improvement. Therefore, a composite material derived from a battery anode material in which a carbon substrate is mixed with a semiconductor property has also become a research object of an electrode material. The most common is a carbon-ruthenium composite electrode material composed of a carbon substrate and ruthenium. The first figure is a carbon germanium composite electrode material in the prior art. It mainly adheres to a plurality of ruthenium particles 140 on the surface of the carbon substrate 120, and it is desirable to increase the battery cycle capacity by the ruthenium particles on the surface of the carbon substrate. However, since the ruthenium particles themselves are not easily dispersed efficiently on the surface of the carbon substrate, the ruthenium particles 140 on the surface of the carbon substrate 120 often have some sputum particles 140 aggregated in some places, but in some places there is no agglomeration of the ruthenium particles. Agglomeration. In addition to the first picture, this problem can also be performed by the fourth A picture. Can be seen in the photo with the fourth B picture. On the other hand, since the connection between the ruthenium particles 140 and the carbon substrate 120 is not strong, there are often many ruthenium particles 140 that have been dispersed and adhered to the surface of the carbon substrate 120 from a carbon basis in a subsequent process. The surface of the material 120 falls off and becomes ineffectively dispersed ruthenium particles 140'. The effect that originally wanted to use this design to increase the battery capacity was greatly reduced.

In view of the above, the carbon ruthenium composite electrode material capable of increasing the effective circulating capacity of the lithium ion battery, increasing the power and cycle life of the lithium ion battery, and the preparation method thereof can be developed It is a subject that deserves the attention of the industry and can effectively enhance the competitiveness of the industry.

In view of the above-mentioned invention, in order to meet the requirements of the industry, the present invention provides a carbon germanium composite electrode material and a preparation method thereof, and the carbon germanium composite electrode material is not only simple in process, low in cost, but also has a lithium ion battery. The utility model has the advantages of effective circulating capacity and prolonging the cycle life of the battery, and more preferably, the preparation method of the carbon-cerium composite electrode material can be dispersed in an aqueous solution, thereby achieving the effects of environmental protection and effectively improving industrial competitiveness.

An object of the present invention is to provide a carbon ruthenium composite electrode material and a preparation method thereof, which are characterized in that the surface of the carbon substrate and the ruthenium-containing particles are modified by an organic polymer to enhance the relationship between the ruthenium-containing particles and the carbon substrate. Bonding and uniformity further greatly enhance the effective cycle capacity of the battery using the surface-modified carbon-germanium composite electrode material.

Another object of the present invention is to provide a carbon germanium composite electrode material and a method for preparing the same, which comprises coating a carbonaceous particle to which a cerium-containing particle has been attached by using a carbon-containing conductive layer to enhance the cerium-containing particle and the carbon-containing particle. The effective contact between the two increases the effective circulating capacity of the battery using the carbon-germanium composite electrode material as an electrode.

Another object of the present invention is to provide a carbon-germanium composite electrode material and a preparation method thereof, which are surface-modified by using an organic polymer and uniformly dispersed on the surface of the surface-modified carbonaceous particles. The organic polymer-coated cerium-containing particles are used to reduce the volume change of the carbon ruthenium composite electrode material during charge and discharge, causing structural damage and spalling, and further prolonging the use of the surface-modified carbon ruthenium composite electrode material as The cycle life of the battery of the electrode.

Another object of the present invention is to provide a carbon-cerium composite electrode material and a preparation method thereof, which are prepared by using an aqueous slurry process of a water-soluble organic polymer to prepare the carbon-germanium composite electrode material, thereby effectively reducing the operator. The goal of harming the environment with volatile organic compounds.

In accordance with the above objects, the present invention discloses a carbon germanium composite electrode material and a method of preparing the same. The carbon germanium composite electrode material comprises a plurality of carbonaceous particles, wherein a surface of each of the carbonaceous particles comprises a first modified film and a plurality of germanium containing particles, wherein a surface of each of the germanium containing particles comprises a second modified film. Wherein, at least one cerium-containing particle is attached to each of the carbon-containing particles. The first modified film and the second modified film are cross-linked with each other. The first modified film includes the first organic polymer. The first organic polymer has a first electrical property. Above An organic polymer may be a water soluble polymer. The second modified film includes a second organic polymer. The second organic polymer has a second electrical property, wherein the second electrical property is opposite to the first electrical property. The second organic polymer may be a water-soluble polymer.

In a preferred embodiment of the present specification, the first organic polymer of the first modified film of the carbon-containing particles of the carbon-cerium composite electrode material may be one selected from the group consisting of polytetra-amine salts. (poly-Quaternary ammonium salt), anion-exchange resin or polymer. In a preferred embodiment of the present specification, the second organic polymer of the second modified film containing the cerium particles of the carbon cerium composite electrode material may be one selected from the group consisting of: having a sulfonic acid group ( A polymer of sulfonic acid group, a polymer having a carboxylic acid group, a cation-exchange resin or a polymer.

In a preferred embodiment of the present specification, the first modified film of the carbon ruthenium composite electrode material may further comprise a third organic polymer. The above third organic polymer has an average molecular weight of about 2,000 to 200,000. In a preferred embodiment according to the present specification, the third organic polymer may be polyvinyl alcohol (PVA). According to the present example, the third organic polymer may help to improve the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product.

In a preferred embodiment of the present specification, the second modified film of the carbon-cerium composite electrode material may further comprise a fourth organic polymer. The fourth has The organic polymer has an average molecular weight of about 2,000 to 200,000. In a preferred embodiment according to the present specification, the fourth organic polymer may be polyvinyl alcohol (PVA). According to the present example, the fourth organic polymer may help to improve the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product.

In a preferred embodiment according to the present specification, the carbon ruthenium composite electrode material may further comprise a third modification film. The third modified film may be a surface coated with the carbon-containing particles having at least one cerium-containing particle. The third modified film may be a carbon-containing conductive film. The above-mentioned third modified film can ensure that the above-mentioned cerium-containing particles are effectively dispersed and effectively adhere to the surface of the carbon-containing particles. In other words, the third modified film can ensure that the above-mentioned cerium-containing particles are in effective contact with the surface of the carbon-containing particles.

In a preferred embodiment of the present specification, the method for preparing the carbon-cerium composite electrode material comprises the steps of separately preparing a carbon-containing particle having a first modified film and a germanium-containing particle having a second modified film, and mixing the first The step of modifying the carbonaceous particles of the film and the cerium-containing particles having the second modified film, and the step of performing a drying process to obtain a carbon ruthenium composite electrode material.

In a preferred embodiment of the present specification, in the method for preparing the carbon-ruthenium composite electrode material, the step of separately preparing the carbon-containing particles having the first modified film and the cerium-containing particles having the second modified film may be in an aqueous solution. carry out.

In a preferred embodiment of the present specification, in the method for preparing the carbon-cerium composite electrode material, the step of mixing the carbon-containing particles having the first modified film and the cerium-containing particles having the second modified film may be performed in an aqueous solution. .

In a preferred embodiment of the present invention, in the method for producing a carbon-cerium composite electrode material, the first modified film comprises a first organic polymer. The first organic polymer has a first electrical property, and the first organic polymer may be a water-soluble polymer. The second modified film includes a second organic polymer. The second organic polymer has a second electrical property, and the second electrical property is opposite to the first electrical property. The second organic polymer may be a water-soluble polymer.

In a preferred embodiment of the present invention, in the method for producing a carbon-cerium composite electrode material, the first modified film may further comprise a third organic polymer. The above third organic polymer has an average molecular weight of about 2,000 to 200,000. According to the present specification, the third organic polymer described above contributes to improving the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product.

In a preferred embodiment of the present invention, in the method for producing a carbon-cerium composite electrode material, the second modified film may further comprise a fourth organic polymer. The fourth organic polymer has an average molecular weight of about 2,000 to 200,000. According to the present specification, the fourth organic polymer described above contributes to improving the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product.

In a preferred embodiment of the present specification, the method for preparing the carbon-cerium composite electrode material may further include the steps of mixing the carbon-cerium composite electrode material and the carbon-containing mixture, and performing a heat treatment step to obtain a third modified film. Covered on the surface of the above carbon tantalum composite. The above carbon-containing mixture may be one selected from the group consisting of pitch, fructose, phenolic resin, furan resin, polyacrylonitrile resin, epoxy resin, polyester resin, polyamide resin, and melamine. Resin, etc. The third modified film may be a carbon-containing conductive film. The third modified film can ensure that the cerium-containing particles are effectively dispersed on the surface of the carbon-containing particles, and the cerium-containing particles are in effective contact with the surface of the carbon-containing particles.

120‧‧‧Carbon substrate

140‧‧‧矽 particles

140'‧‧‧Inefficiently dispersed particles

220‧‧‧Carbon particles

222‧‧‧First modified film

240‧‧‧Inorganic particles

242‧‧‧Second modified film

260‧‧‧ Third modified film

310‧‧‧Steps for preparing carbonaceous particles with a first modified film

320‧‧‧Steps for preparing cerium-containing particles with a second modified film

330‧‧‧Step of mixing carbonaceous particles with a first modified film and cerium-containing particles having a second modified film

340‧‧‧Steps for drying procedures to obtain carbon-germanium composite electrode materials

350‧‧‧Steps of mixing the above carbon-cerium composite electrode material with a carbon-containing mixture

360‧‧‧Steps for heat treatment procedures

The first figure is a schematic diagram of a conventional carbon-ruthenium composite electrode material; the second figure is a schematic diagram of a carbon-germanium composite electrode material according to the present specification; and the third figure is a method for preparing a carbon-germanium composite electrode material according to the present specification. Schematic diagram of the process; the fourth A to the fourth B are the carbon-germanium composite electrode materials in the prior art, and the fourth C to fourth F-pictures are scanning electron microscopes of the carbon-germanium composite electrode materials according to the present specification ( SEM;Scanning Electron Microscopy) photograph; and fifth graph comparison of cyclic charge and discharge capacity and cycle life of a carbon-based composite electrode material coated with a carbon-containing conductive film according to the present specification and a graphite substrate electrode material in the prior art Figure.

The invention discussed herein is a carbon germanium composite electrode material and a method for its preparation. In order to thoroughly understand the present invention, detailed process steps or constituent structures will be set forth in the following description. Obviously, the implementation of the present invention is not limited Special details familiar to those skilled in the art. On the other hand, well-known components or process steps are not described in detail to avoid unnecessarily limiting the invention. The preferred system of the present invention will be described in detail below, but the present invention may be widely applied to other systems in addition to the detailed description, and the scope of the present invention is not limited thereto, and the scope of the following patents shall prevail.

One embodiment of the invention discloses a carbon germanium composite electrode material. The second A is a schematic view of a carbon germanium composite electrode material according to the present embodiment. As shown in FIG. 2A, the carbon-cerium composite electrode material includes a plurality of carbon-containing particles 220 and a plurality of cerium-containing particles 240. A first modified film 222 is included on the surface of each of the carbon-containing particles 220. A second modification film 242 is included on the surface of each of the cerium-containing particles 240. Therein, at least one cerium-containing particle 240 is effectively attached to each of the carbon-containing particles 220. The first modification film 222 may be crosslinked to the second modification film 242. The first modified film 222 includes a first organic polymer, and the second modified film 242 includes a second organic polymer.

In a preferred embodiment according to this embodiment, the carbon-containing particles 220 may be one selected from the group consisting of: natural graphite, artificial graphite, mesophase carbon microspheres (MCMB). , soft carbon, hard carbon.

In a preferred example of the present embodiment, between the first modified film 222 and the second modified film 242, chemical cross-linking may be formed by ion bonding. For example, in a preferred embodiment of the present example, the first organic polymer may have a first electrical property, and the second organic high The molecule has a second electrical property, wherein the second electrical property is opposite to the first electrical property of the first organic polymer. For example, when the first organic polymer is positively charged, the second organic polymer is negatively charged. An ionic bond may be formed between the first organic polymer and the second organic polymer.

In a preferred embodiment, the first organic polymer may be a positively charged water-soluble organic polymer, wherein the first organic polymer is selected from one of the group consisting of polytetraamine salts (poly - Quaternary ammonium salt), anion-exchange resin or polymer. The first organic polymer may be one selected from the group consisting of: polydiallyldimethylammonium chloride (PA), dodecyltrimethylammonium (Dodecyltrimethylammonium) Bromide), cholestyramine [or oral cholesterol lowering agent] (Cholestyramine or colestyramine; Questran, Questran Light, Cholybar), poly(acrylamido-N-propyl trimethyl ammonium chloride; PolyAPTAC], poly(3-methacryloylamino-propyl trimethylammonium chloride; PolyMAPTAC), poly(allylamine hydrochloride), poly Poly(dimethylaminoethylacrylate methylchloride quat; p-DMAEA*MCQ), poly(dimethylaminoethylmethacrylate methylchloride quat); p-DMAEM* MCQ]. In a preferred example according to this embodiment, the first The organic polymer has an average molecular weight of about 10,000 to 500,000. The first organic polymer is added in an amount of about 0.5 to 5.0% by weight (solid content) of the carbonaceous particles.

The second organic polymer may be a negatively charged water-soluble organic polymer, and the second organic polymer may be one selected from the group consisting of a polymer having a sulfonic acid group and having A polymer of a carbonic acid group, a cation-exchange resin or a polymer. In a preferred embodiment according to this embodiment, the second organic polymer may be one selected from the group consisting of or a combination thereof: poly(sodium 4-styrene sulfonate) Poly(2-acrylamido-2-methyl-1-propanesulfonic acid; polyAMPS), polyacrylic acid (PAA), sodium polyacrylate Salt [Poly (sodium acrylate)]. In a preferred embodiment according to this embodiment, the second organic polymer has an average molecular weight of about 50,000 to 1,000,000. The second organic polymer is added in an amount of about 0.5 to 5.0% by weight (solid content) of the cerium-containing particles.

In a preferred embodiment of the present embodiment, the first modifying film 222 may further comprise a third organic polymer. The above third organic polymer has an average molecular weight of about 2,000 to 200,000. According to the present example, the third organic polymer described above contributes to improving the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product. The third organic polymer is added in an amount of about 0.5 to 5.0 wt.% (solid content) of the carbonaceous particles. In a preferred embodiment according to this embodiment, the third organic polymer may be one selected from the group consisting of: polyvinyl alcohol (PVA), vinyl alcohol ethylene copolymer [Poly (vinyl alcohol-co-ethylene)].

In a preferred example of the present embodiment, the second modifying film 242 may further comprise a fourth organic polymer. The fourth organic polymer has an average molecular weight of about 2,000 to 200,000. According to the present example, the fourth organic polymer described above contributes to improving the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product. The fourth organic polymer is added in an amount of about 0.5 to 5.0% by weight (solid content) of the cerium-containing particles. In a preferred embodiment according to this embodiment, the fourth organic polymer may be one selected from the group consisting of polyvinyl alcohol (PVA), vinyl alcohol ethylene copolymer [Poly (vinyl alcohol-co-ethylene)].

In a preferred example of the present embodiment, the carbon germanium composite electrode material may further include a third modification film 260, as shown in FIG. The third modification film 260 may be a surface coated with the carbonaceous particles having at least one cerium-containing particle. The composition of the third modification film 260 described above may be a carbon atom. According to the present example, the composition of the third modification film 260 may be a carbon-containing conductive film. According to the present example, the third modifying film 260 may be a result of coating a carbon-containing mixture on the surface of the carbon-containing particles having at least one cerium-containing particle and subjecting to a heat treatment process. The above carbon-containing mixture may be one selected from the group consisting of petroleum or coal pitch, fructose, phenolic resin, furan resin, polyacrylonitrile resin, epoxy resin, polyester resin, polyamide resin. And acetamide resin. The third modification 260 film ensures that the ruthenium-containing particles are effectively adhered to the surface of the carbon-containing particles, and the ruthenium-containing particles are in effective contact with the surface of the carbon-containing particles.

According to the present embodiment, the first modifying film 222 and the second modifying film 242 contribute to the dispersion of the cerium-containing particles 240 on the surface of the carbon-containing particles 220, thereby preventing the cerium-containing particles 240 from agglomerating on the surface of the carbon-containing particles 220. . Therefore, when the carbon ruthenium composite electrode material is applied to a battery, the internal structure of the carbon ruthenium composite material is collapsed due to volume expansion at the time of cyclic charge and discharge. On the other hand, the third modification film 260 contributes to effective contact between the ruthenium-containing particles 240 and the carbon-containing particles 220 to improve the conductivity of the ruthenium-containing particles 240, thereby effectively improving the battery using the carbon ruthenium composite electrode material. Capacity and cycle life.

Another embodiment of the present invention discloses a method of preparing a carbon germanium composite electrode material. The third figure is a schematic flow chart of a method for preparing a carbon-cerium composite electrode material according to the present embodiment. Referring to the third figure, the method for preparing the carbon-germanium composite electrode material comprises the steps of preparing carbonaceous particles having a first modified film and ruthenium-containing particles having a second modified film, respectively, and mixing the first modified film. Step 330 of carbon particles and cerium-containing particles having a second modified film, and a drying process to obtain a carbon ruthenium composite electrode material (step 340).

According to this embodiment, the carbon-containing particles may be selected from one or a combination of the following: natural graphite, artificial graphite, mesocarbon microbeads (MCMB), soft carbon, Hard carbon.

According to this embodiment, the chemical cross-linking may be formed by the ionic bonding method between the first modified film and the second modified film. The first modified film and the second modified film may respectively comprise a first An organic polymer and a second organic polymer. The first organic polymer may have a first electrical property, and the second organic polymer may have a second electrical property, wherein the second electrical property is opposite to a first electrical property of the first organic polymer.

In a preferred embodiment of the present invention, the first organic polymer may be a positively charged water-soluble organic polymer, wherein the first organic polymer is selected from one of the following groups: poly four Poly-Quaternary ammonium salt, anion-exchange resin or polymer. The first organic polymer may be one selected from the group consisting of: polydiallyldimethylammonium chloride (PA), dodecyltrimethylammonium (Dodecyltrimethylammonium) Bromide), cholestyramine [or oral cholesterol lowering agent] (Cholestyramine or colestyramine; Questran, Questran Light, Cholybar), poly(acrylamido-N-propyl trimethyl ammonium chloride; PolyAPTAC], poly(3-methacryloylamino-propyl trimethylammonium chloride; PolyMAPTAC), poly(allylamine hydrochloride), poly Poly(dimethylaminoethylacrylate methylchloride quat; p-DMAEA*MCQ), poly(dimethylaminoethylmethacrylate methylchloride quat); p-DMAEM* MCQ]. In a preferred example according to this embodiment, the first The organic polymer has an average molecular weight of about 10,000 to 500,000.

In a preferred example of the present embodiment, the second organic polymer may be a negatively charged water-soluble organic polymer, and the second organic polymer may be one selected from the group consisting of: having a sulfonate A polymer of a sulfonic acid group, a polymer having a carbonic acid group, a cation-exchange resin or a polymer. In a preferred embodiment according to this embodiment, the second organic polymer may be one selected from the group consisting of or a combination thereof: poly(sodium 4-styrene sulfonate) Poly(2-acrylamido-2-methyl-1-propanesulfonic acid; polyAMPS), polyacrylic acid (PAA), sodium polyacrylate Salt [Poly (sodium acrylate)]. In a preferred embodiment according to this embodiment, the second organic polymer has an average molecular weight of about 50,000 to 1,000,000.

In a preferred embodiment of the present embodiment, the step 310 of preparing the carbonaceous particles having the first modified film comprises the steps of mixing the carbonaceous particles with the first organic polymer solution, and performing a drying process, which is not shown in the figure. in. The first organic polymer solution includes the first organic polymer described above. The content of the first organic polymer is 0.5 to 5.0 wt.% (solid content) of the carbon-containing particles. The solvent of the first organic polymer solution may be water (H ₂ O). After sufficiently mixing the carbonaceous particles with the first organic polymer solution and the subsequent drying process, carbonaceous particles having the first modified film can be obtained. The drying procedure described above can be a drying method well known to those skilled in the art, such as spray drying or vacuum agitation drying. The above drying procedure is controlled to be about 80-150 °C.

In a preferred embodiment of the present invention, the step 320 of preparing the ruthenium-containing particles having the second modified film comprises the steps of mixing the ruthenium-containing particles with the second organic polymer solution, and performing a drying process, which is not shown in In the picture. The second organic polymer solution includes the second organic polymer described above. The content of the second organic polymer is 0.5 to 5.0 wt.% (solid content) of the cerium-containing particles. The solvent of the second organic polymer solution may be water (H ₂ O). After the cerium-containing particles and the second organic polymer solution are sufficiently mixed and the subsequent drying process, the cerium-containing particles having the second modified film can be obtained. The drying procedure described above can be a drying means well known to those skilled in the art, such as spray drying, or vacuum agitation drying. The above drying procedure is controlled to be about 80-150 °C.

In a preferred example of the present embodiment, the first modified film may further comprise a third organic polymer. The above third organic polymer has an average molecular weight of about 2,000 to 200,000. According to the present example, in the above step 310, the first organic polymer solution may further comprise the third organic polymer. The third organic polymer is added in an amount of about 0.5 to 5.0 wt.% (solid content) of the carbonaceous particles. The third organic polymer and the first organic polymer may form the first surface on the surface of the carbon-containing particles by the steps of mixing the carbon-containing particles with the first organic polymer solution and performing a drying process. Modify the film. According to the present example, the third organic polymer described above contributes to improving the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product. In a preferred example of the present embodiment, the third organic polymer may be one selected from the group consisting of the following Or a combination thereof: polyvinyl alcohol (PVA), polyvinyl alcohol-co-ethylene.

In a preferred embodiment of the present embodiment, the second modified film may further comprise a fourth organic polymer. The fourth organic polymer has an average molecular weight of about 2,000 to 200,000. According to the present example, in the above step 320, the second organic polymer solution may further comprise the fourth organic polymer. The fourth organic polymer is added in an amount of about 0.5 to 5.0% by weight (solid content) of the cerium-containing particles. The fourth organic polymer and the second organic polymer may form the above-mentioned first surface of the cerium-containing particles by the above-described steps of mixing the cerium-containing particles and the second organic polymer solution, and performing a drying process. Two modified films. According to the present example, the fourth organic polymer described above contributes to improving the dispersibility of the conductive material in the subsequent process, thereby further improving the charge and discharge efficiency of the final battery product. In a preferred embodiment according to this embodiment, the fourth organic polymer may be one selected from the group consisting of polyvinyl alcohol (PVA), vinyl alcohol ethylene copolymer [Poly (vinyl alcohol-co-ethylene)].

In a preferred embodiment according to this embodiment, the step 330 of mixing the carbonaceous particles of the first modified film with the cerium-containing particles having the second modified film may be carried out in a solution. Wherein, the above solution may be water (H ₂ O). The weight ratio of the carbonaceous particles having the first modified film to the cerium-containing particles having the second modified film is about 100:0.5 to 100:20. More preferably, in a preferred embodiment according to this embodiment, the weight ratio of the carbonaceous particles having the first modified film to the cerium-containing particles having the second modified film is about 100:5.

In a preferred embodiment according to this embodiment, the first drying procedure described above may be a drying method well known to those skilled in the art, such as spray drying, or vacuum agitation drying. The above drying procedure is controlled to be about 80-150 °C.

In a preferred example of the present embodiment, the method for preparing the carbon-cerium composite electrode material may further include the step 350 of mixing the carbon-cerium composite electrode material and the carbon-containing mixture, and performing heat treatment after the first drying process. Step 360 of the program. The above carbon-containing mixture may be one selected from the group consisting of petroleum or coal tar pitch, fructose, phenolic resin, furan resin, polyacrylonitrile resin, epoxy resin, polyester resin, polyamide resin, and Pyrimidine resin and the like. In the above step 350, the weight ratio of the carbon ruthenium composite electrode material to the carbonaceous mixture is about 100:0.5 to 100:20. More preferably, in a preferred embodiment according to this embodiment, the weight ratio of the carbon ruthenium composite electrode material to the carbonaceous mixture is about 100:10. In a preferred embodiment according to this embodiment, the above step 350 may be a dry mixing.

The heat treatment procedure described above may be a heating method well known to those skilled in the art, for example, a carbonization heat treatment procedure in which the temperature is set to about 500 to 1500 ° C under a nitrogen atmosphere.

After the completion of the step 360 of the above heat treatment process, a third modified film can be formed on the surface of the above carbon-cerium composite electrode material. The third modified film may be a carbon-containing conductive film. According to the present example, the above-mentioned third modified film can prevent the cerium-containing particles having the second modified film from falling off from the carbon-containing particles having the first modified film, and can effectively improve the charge and discharge performance of the carbon-cerium composite electrode material.

Since the above carbon ruthenium composite electrode material can be prepared by water The phase solution and the dry mixing method and the like complete the entire process, so the preparation method according to the embodiment can not only eliminate the waste problem generated by the organic phase solution process in the prior art, but also avoid volatile organic compounds (volatile organic compounds, VOC) is more toxic to the operator and the environment, thus achieving a more environmentally friendly effect.

On the other hand, since the electrical properties of the first organic polymer and the second organic polymer are opposite, in the preparation process according to the embodiment, the first organic polymer and the second organic polymer may be electrically connected to each other. The electrostatic action of the phase attracts the cross-linking effect of self-assembly. More preferably, stable ionic bonding can be formed between the first organic polymer and the second organic polymer. In this way, although the first organic polymer and the second organic polymer are all water-soluble, even if the aqueous phase solution is continuously used in the subsequent process, it is difficult to dissolve the first organic polymer or the second organic polymer again at room temperature. The second organic polymer. In other words, according to the design of the present specification, the cerium-containing particles having the second modified film which are effectively dispersed to the surface of the carbon-containing particles having the first modified film are effectively adhered, and are not easily detached in the subsequent process.

In a preferred embodiment according to this embodiment, when the carbonaceous particles are graphite substrates, the partial surface of the graphite substrate in the aqueous solution will be negatively charged. Therefore, if the first organic polymer is a positively charged organic polymer, the first organic polymer can be easily infiltrated into the inner nano or micron range by the surface of the graphite substrate by electrostatic action. The defect or the hole causes the first modified film formed by the first organic polymer to form a strong coating uniformity to the carbon-containing particles. More preferably, the first modified film can change the electrical properties of the surface of the carbon-containing particles, and is favorable for attracting the second organic polymer, which can help to improve between the first modified film and the second modified film. Jointability. More preferably, after the drying process described above, the surface of the second modified film may provide a relatively hydrophilic property in addition to electrical properties, and contribute to the carbon ruthenium composite electrode material in a subsequent process. Further applied to the process of aqueous slurry.

Preferred examples of the carbon-ruthenium composite electrode material and the preparation method thereof according to the present specification will be described below. However, the scope of this specification should be determined by the scope of the subsequent patent application and should not be limited to the following examples.

Example 1: A ruthenium-containing particle having a second modified film (PS/PVA) is effectively adhered to a carbon ruthenium composite electrode material having a surface of a carbonaceous particle having a first modified film (PA/PVA)

First, the first organic polymer, poly(diallyldimethylammonium chloride (PA), having a molecular weight of about 100,000; 1.4 wt.%), is uniformly dispersed in water while adding polyvinyl alcohol ( Polyvinyl alcohol; PVA, molecular weight range of about 2,000; 0.94 wt.%), prepared into a first aqueous polymer solution. To the obtained first aqueous polymer solution, 100 wt.% of a natural graphite substrate (particle size of about 15 μm; carbonaceous particles to be surface-treated) was uniformly dispersed at an appropriate rotation speed (600 rpm) for 60 minutes, and then passed through a general Dry or spray dry (95 ° C) to form carbonaceous particles with a first modified film.

Then, the second organic polymer, sodium polystyrene sulfonate [Poly (sodium 4-styrenesulfonate); PS; molecular weight range of about 70,000; 2.1 wt.%], uniformly dispersed in water, while adding polyvinyl alcohol (polyvinyl Alcohol PVA has a molecular weight in the range of about 2,000; 1.4 wt.%) to prepare a second aqueous polymer solution. Adding 100 wt.% of nano-polymer aqueous solution (particle size of about 100 nm; cerium-containing particles requiring surface treatment) to the obtained second high molecular polymer aqueous solution, uniformly dispersing at a suitable rotation speed (600 rpm) for 30 minutes, and then drying normally. Or spray drying (95 ° C) to form cerium-containing particles with a second modified film.

The carbonaceous particles (100 wt.%) having the first modified film described above were uniformly dispersed in water to prepare a solution having a concentration of 80 wt.%. To the above solution, cerium-containing particles (5 wt.%, relative to the above-mentioned carbon-containing particles having the first modified film) having the second modified film were added and uniformly stirred. After uniform stirring, general drying or spray drying (100 ° C), and then sieved to obtain a carbon-ruthenium composite electrode material.

Example 2: Carbon ruthenium composite electrode material coated with a third modified film

The carbon ruthenium composite electrode material obtained in the above Example 1 was uniformly mixed with pitch (particle diameter D _{50 of} about 1 to 6 μm; about 10 wt.% of the carbon ruthenium composite electrode material), and then subjected to a heat treatment process in a carbonization furnace. The heat treatment procedure described above has a temperature of about 1100 ° C and a temperature increase rate of about 2 ° C/min, and the heat treatment procedure is carried out under a nitrogen (N ₂ ) atmosphere. The heat treatment procedure described above took about 14 hours. After the heat treatment process is completed, the carbon ruthenium composite electrode material coated with the third modified film can be obtained by cooling, sieving, and the like.

Example 3: Carbon ruthenium composite electrode material coated with a third modified film

The carbon ruthenium composite electrode material obtained in the above Example 1 was uniformly mixed with pitch (having a particle diameter D _{50 of} about 20 to 50 μm; about 10 wt.% of the carbon ruthenium composite electrode material), and then subjected to a heat treatment process in a carbonization furnace. The heat treatment procedure described above has a temperature of about 1100 ° C and a temperature increase rate of about 2 ° C/min, and the heat treatment procedure is carried out under a nitrogen (N ₂ ) atmosphere. The heat treatment procedure described above took about 14 hours. After the heat treatment process is completed, the carbon ruthenium composite electrode material coated with the third modified film can be obtained by cooling, sieving, and the like.

Comparative Example 1: Graphite electrode material (Pristine)

This electrode material can be obtained by sieving the original graphite substrate (Pristine).

Comparative Example 2: Carbon ruthenium composite electrode material containing ruthenium particles directly adhered to a graphite substrate

After the original graphite substrate (Pristine) was sieved, the original graphite substrate (100 wt.%) was uniformly dispersed in water to prepare a solution having a concentration of 80 wt.%. To the above solution, cerium-containing particles (5 wt.%, relative to the above-mentioned original graphite substrate) were added and uniformly stirred. After uniform stirring, general drying or spray drying (100 ° C), and then sieved to obtain a carbon-ruthenium composite electrode material.

Example 4: Negative pole piece coating production

In this example, the materials used are as follows:

a. CMC: (Carboxymethyl Cellulose Sodium) sodium carboxymethyl cellulose

b.Conductive Carbon Black (Super-P)

c.SBR: (styrene-butadiene rubber) styrene butadiene rubber

First, the modified carbon ruthenium composite material (for example, the product of the above example/comparative example) is dried to remove moisture. Dissolve CMC in DI water, then add 3wt.% conductive agent Super-P, then add 93.3wt.% modified carbon ruthenium composite material, add SBR binder after thorough mixing, and obtain uniform after stirring. The active material slurry is subjected to vacuum defoaming of the above-mentioned active material slurry. Cut the copper foil of the appropriate size, wipe the copper foil with alcohol, place it on the automatic coater platform, tiling the copper foil against the platform, and pour the active paste onto the copper foil, using 100 micron. The scraper is used to uniformly apply the active material slurry to the copper foil. The coated copper foil was placed on a heating platform and dried, and then placed in a vacuum oven to evacuate, and the residual solvent was removed at a temperature of 110 °C. The copper foil from which the residual solvent was removed was placed on a roller compactor, and the copper foil was pressed at an appropriate rolling thickness. The puncher cuts into a 13mm diameter negative pole piece and an 18mm isolation film. After completion, it is placed in a glove box filled with argon (control humidity and oxygen less than 1ppm) to obtain a negative electrode piece. on The negative electrode tabs can be assembled into a battery, such as a button type battery, in a subsequent process.

Example 5: Battery Assembly Process:

Firstly, the battery top cover, bottom cover, spring piece and stainless steel current collecting piece of the button type battery assembly are cleaned with alcohol and deionized water, placed in a vacuum oven, and set to a temperature of 110 ° C to remove moisture, after the water is completely evaporated. Put it in the glove box. In the argon-filled glove box, the negative electrode tab is placed in the center of the battery bottom cover, and the electrolyte is dropped into the negative electrode tab. The separator was immersed in the electrolyte to be wetted and covered on the negative electrode tab, and it was confirmed that the negative electrode tab and the separator were maintained at the center of the bottom cover. After the lithium metal piece as the positive electrode is cut into the same current collecting piece size, the lithium metal piece is placed at the center of the bottom cover, and then the stainless steel current collecting piece is placed over the lithium metal. Place the spring piece on the center of the stainless steel current collecting piece, cover the top cover, press it with the battery special press, seal the button type battery pack, and complete the battery assembly.

4A to 4F are photographs of a scanning electron microscope (SEM; Scanning Electron Microscopy) of the carbon-germanium composite electrode materials of Comparative Example 2 , Example 1 , Example 2 , and Example 3 , respectively. Here, the fourth A diagram and the fourth B diagram are SEM photographs of the carbon-ruthenium composite electrode material obtained by directly adhering the ruthenium-containing particles to the graphite substrate at 5000 times and 10000 times, respectively, in the above Comparative Example 2 . The fourth C map and the fourth D graph are SEM photographs of the carbon-niobium composite electrode material obtained in the above Example 1 at 5000 times and 10000 times, respectively. The fourth E diagram and the fourth F diagram are SEM photographs observed at 10,000 times of the carbon-ruthenium composite electrode material coated with the carbon-containing conductive film in the above examples 2 and 3 , respectively. The white dots in the fourth to fourth F diagrams are ruthenium-containing particles. It can be seen from the comparison between the fourth A picture and the fourth C picture that the cerium-containing particles of the carbon lanthanum composite electrode material according to the present specification can exhibit better dispersibility (such as the fourth C picture), and do not generate habits. Agglomeration phenomenon of knowing skills (such as Figure A).

On the other hand, it can be found from the fourth C diagram that in the prior art, the graphite substrate without surface modification is directly adhered to the non-surface-modified cerium-containing particles, and the cerium-containing particles are effective on the surface of the graphite substrate. The amount of adhesion is not large, and the agglomeration phenomenon of the ruthenium-containing particles itself. It is well known to those skilled in the art that the carbon-ruthenium composite electrode material thus distributed cannot not only effectively increase the capacitance, but may even cause volume expansion of the graphite substrate and the ruthenium-containing particles during the cycle of charge and discharge. The internal structure of the carbonium composite electrode material collapses. However, in the carbon-germanium composite electrode material according to the present specification, referring to the SEM photographs of the fourth C to fourth F diagrams, the cerium-containing particles did not undergo significant agglomeration. More preferably, the cerium-containing particles are not only uniformly dispersed on the surface of the carbon-containing particles, but also the cerium-containing particles are more effectively attached to the surface of the carbon-containing particles. This indicates that the carbon-rhenium composite electrode material according to the present specification can effectively increase the capacitance of a battery using such a carbon-ruthenium composite electrode material because the amount of the ruthenium-containing particles effectively adhered to the surface of the carbon-containing particles is increased. More preferably, because of the effective dispersion of the ruthenium-containing particles on the surface of the carbonaceous particles, the battery using such a carbon-ruthenium composite electrode material is also less likely to cause internalization of the carbon-ruthenium composite electrode material due to excessive volume change during cyclic charge and discharge. The structure collapsed.

The fifth graph is a comparison of the cycle charge and discharge capacity and the cycle life of the above Example 2 , Example 3, and Comparative Example 1 . From the fifth figure, the above-mentioned inference about the influence of the ruthenium-containing particles on the battery capacity and the cycle life can be actually proved. As is apparent from the fifth diagram, in terms of capacitance, the carbon-cerium composite electrode material coated with the carbon-containing conductive film according to the present specification can provide a natural graphite electrode material (about 350 mAh/g) of Comparative Example 1 . High capacitance (about 450 mAh/g and about 500 mAh/g).

In terms of cycle life, as shown in the fifth graph, the graphite electrode material of Comparative Example 1 was subjected to a plurality of cycles of curves under different charge and discharge states (0.1 C and 0.2 C). It is worth noting that the carbon-germanium composite electrode material obtained according to Example 2 and Example 3 of the present specification is also subjected to multiple cycles under different charge and discharge states (0.1 C and 0.2 C), and the measured curve can also be presented. Out almost constant perfection. It was confirmed that the carbon-ruthenium composite electrode material coated with a carbon-containing conductive film according to the present specification can maintain the stability of its capacitance while being charged and discharged at different rates (0.1 C and 0.2 C), and has no carbon ruthenium composite. The problem of internal collapse of the electrode material occurs.

In summary, the present specification discloses a carbon germanium composite electrode material and a preparation method thereof. The carbon ruthenium composite electrode material can be surface-modified by carbon-containing particles and ruthenium-containing particles, respectively, to improve the dispersibility of the ruthenium-containing particles on the surface of the carbon-containing particles and to effectively adhere. According to the present specification, the carbon-cerium composite electrode material includes a plurality of carbon-containing particles and a plurality of cerium-containing particles. The surface of each of the above carbonaceous particles comprises a first modified film. Each of the surfaces of the above cerium-containing particles comprises a second modified film. At least one ruthenium-containing particle is attached to each carbon-containing particle. The first modified film includes a first organic polymer, and the second modified film includes a second organic polymer. Above first The organic polymer and the second organic polymer may be organic polymers having opposite electrical properties, respectively. According to the present specification, chemical crosslinking may be formed by the ionic bonding method between the first modified film and the second modified film. As a result, the above-mentioned cerium-containing particles attached to the carbon-containing particles will not easily fall off in the subsequent process. More preferably, the first modified film and the second modified film may further comprise a third organic polymer and a fourth organic polymer, respectively. The third organic polymer and the fourth organic polymer may enhance the internal structural stability of the carbon-cerium composite electrode material by a physical cross-linking tangle. More preferably, the carbon-cerium composite electrode material may further comprise a third modified film coated on the surface of the carbon-containing particles having at least one cerium-containing particle. The third modified film may be a carbon-containing conductive film. By the third modified film, the ruthenium-containing particles having the second modified film can be further prevented from falling off from the carbon-containing particles having the first modified film, and the capacitance and charge of the carbon-cerium composite electrode material can be effectively improved. Discharge performance. The method for preparing a carbon-cerium composite electrode material according to the present specification comprises the steps of separately preparing a carbon-containing particle having a first modified film and a cerium-containing particle having a second modified film, and mixing the carbon-containing particle having the first modified film with The step of ruthenium-containing particles of the second modified film, and a drying process to obtain a carbon-cerium composite electrode material. More preferably, the carbon ruthenium composite electrode material preparation method may further comprise the steps of mixing the carbon ruthenium composite electrode material and the carbonaceous mixture, and performing the heat treatment procedure to form a third modified film coated on the above The surface of the carbon germanium composite electrode material. The method for preparing the above carbon-cerium composite electrode material can be carried out in the manner of aqueous slurry and dry mixing. Therefore, according to the preparation method of the carbon-ruthenium composite electrode material of the present specification, the harm of VOCs can be avoided, and the method can be more effectively Improve the protection of the operator and the environment. According to the present specification, not only can the entanglement and uniformity between the cerium-containing particles and the carbon-containing particles be effectively increased, but the current carbon-based composite electrode material can be overcome, and the capacity and charge of the final battery product can be effectively improved. Discharge efficiency, and cycle life.

Compared with the prior art, the carbon-ruthenium composite electrode material proposed in the present specification and the preparation method thereof have the following progress. First, the preparation method of the carbon-ruthenium composite electrode material disclosed in the present specification is particularly suitable for the preparation process of the aqueous slurry preparation, especially in the coating stage of the negative electrode material. Second, according to the carbon germanium composite electrode material of the present specification, the charge and discharge rate of the final product can be effectively improved. Third, according to the carbon germanium composite electrode material of the present specification, the capacitance can be effectively increased. Fourth, according to the carbon germanium composite electrode material of the present specification, the effective dispersibility and effective adhesion of the cerium-containing particles on the surface of the carbon-containing particles can be effectively improved, thereby improving the material stability of the carbon-cerium composite electrode material during charging and discharging of the battery product. Sexuality is conducive to the efficiency of rapid charge and discharge. Fifthly, the carbon germanium composite electrode material disclosed in the present specification and the preparation method thereof can provide a more effective coating on the carbon substrate, and the cerium-containing particles can be effectively dispersed and effectively adhered, thereby reducing the carbon ruthenium composite electrode material. During charging and discharging, the structural damage and peeling caused by the change in the volume of the graphite material further prolongs the cycle life of the battery.

Obviously, the invention may have many modifications and differences as described in the above system. Therefore, it is to be understood that within the scope of the appended claims, the invention may be The above is only a preferred system of the present invention, and is not intended to limit the present invention. The scope of the patent application is intended to be within the scope of the following claims.

220‧‧‧Carbon particles

222‧‧‧First modified film

240‧‧‧Inorganic particles

242‧‧‧Second modified film

Claims (19)

A carbon-germanium composite electrode material comprising: a plurality of carbon-containing particles, wherein a surface of each carbon-containing particle comprises a first modified film, wherein the first modified film comprises a first organic polymer, wherein the first organic The polymer has a first electrically soluble water-soluble polymer; and a plurality of cerium-containing particles, wherein a surface of each of the carbon-containing particles comprises a second modified film, wherein each of the carbon-containing particles has at least one of the The second modified film comprises a second organic polymer, wherein the second organic polymer has a second electrically soluble water-soluble polymer, wherein the second electrical property and the first organic polymer The first electrical opposite is that an ionic bond is formed between the second polymer in the second modified film and the first polymer in the first modified film. The carbon-germanium composite electrode material according to the first aspect of the patent application, wherein the first organic polymer is a positively charged organic polymer, wherein the first organic polymer is selected from one of the group consisting of: poly four a poly-quaternary ammonium salt, an anion-exchange resin or polymer, wherein the second organic polymer is a negatively charged organic polymer, wherein the second organic polymer One selected from the group consisting of a polymer having a sulfonic acid group, a polymer having a carbonic acid group, a cation-exchange resin or a polymer. The carbon-germanium composite electrode material according to claim 1, wherein the first organic polymer is selected from one or a combination of the following groups: polydiallyldimethylammonium chloride; ), Dodecyltrimethylammonium bromide, cholestyramine [Cholesterolamine or colestyramine; Questran, Questran Light, Cholybar), polypropylene guanamine propyl trimethyl chloride Poly(acrylamido-N-propyl trimethyl ammonium chloride; PolyAPTAC, poly(3-methacryloylamino-propyl trimethylammonium chloride); PolyMAPTAC Poly(allylamine hydrochloride), poly(dimethylaminoethylacrylate methylchloride quat; p-DMAEA*MCQ), polydimethylaminomethyl methacrylate Poly(dimethylaminoethylmethacrylate methylchloride quat; p-DMAEM*MCQ), wherein the second organic polymer is selected from one or a combination of the following groups: sodium polystyrene sulfonate [poly(sodium 4) -styrene sulfonate)], poly(2-acrylamido-2-methyl-1-propanesulfonic acid; polyAMPS), polyacrylic acid (PAA) ), sodium polyacrylate [Poly (sodium acrylate)]. The carbon-germanium composite electrode material according to claim 1, wherein the first organic polymer has an average molecular weight of about 10,000 to 500,000, and the second organic polymer has an average molecular weight of about 50,000 to 1,000,000. The carbon germanium composite electrode material according to the first aspect of the invention, wherein the first modified film further comprises a third organic polymer, wherein the third organic polymer has an average molecular weight of about 2.000-200,000, wherein the second modification The film further comprises a fourth organic polymer, wherein the fourth organic polymer has an average molecular weight of about 2,000 to 200,000. The carbon-cerium composite electrode material according to claim 5, wherein the third organic polymer and the fourth organic polymer are respectively selected from one or a combination of the following groups: polyvinyl alcohol; PVA), polyvinyl alcohol-co-ethylene. The carbon-cerium composite electrode material according to the first aspect of the patent application, further comprising a third modified film, wherein the third modified film is coated on the surface of the carbon-containing particles having at least one cerium-containing particle. The carbon germanium composite electrode material according to claim 7, wherein the third modified film is a carbon-containing conductive film. A method for preparing a carbon-cerium composite electrode material, comprising: separately preparing a carbon-containing particle having a first modified film and a cerium-containing particle having a second modified film, wherein the first modified film and the second modified film may respectively comprise a first organic polymer and a second organic polymer, wherein the first organic polymer has a first electrical property, and the second organic polymer has a second electrical property, wherein the second electrical property and the second electrical property Electrolyticly opposite; mixing the carbonaceous particles having the first modified film with the cerium-containing particles having the second modified film, wherein the first modified film forms an ionic bond with the second modified film; performing a drying process To obtain a carbon germanium composite electrode material. The method for preparing a carbon-cerium composite electrode material according to claim 9, wherein the first organic polymer is a positively-charged water-soluble organic polymer, wherein the first organic polymer is selected from the group consisting of One: a poly-quaternary ammonium salt, an anion-exchange resin or a polymer, wherein the second organic polymer is a negatively-charged water-soluble organic polymer, wherein The second organic polymer is selected from one of the group consisting of a polymer having a sulfonic acid group, a polymer having a carbonic acid group, a cation exchange resin or a polymer (cation -exchange resin or polymer). a method for preparing a carbon-cerium composite electrode material according to item 9 of the patent application scope, The first organic polymer is selected from one or a combination of the following groups: polydiallyldimethylammonium chloride (PA), dodecyltrimethylammonium bromide (Dodecyltrimethylammonium) Bromide), cholestyramine [or oral cholesterol lowering agent] (Cholestyramine or colestyramine; Questran, Questran Light, Cholybar), poly(acrylamido-N-propyl trimethyl ammonium chloride; PolyAPTAC], poly(3-methacryloylamino-propyl trimethylammonium chloride; PolyMAPTAC), poly(allylamine hydrochloride), poly Poly(dimethylaminoethylacrylate methylchloride quat; p-DMAEA*MCQ), poly(dimethylaminoethylmethacrylate methylchloride quat); p-DMAEM* MCQ], wherein the second organic polymer is selected from one or a combination of the following groups: poly(sodium 4-styrene sulfonate), poly(2-propene oxime) Poly(2-acrylamido-2-methyl-1-propanesulfonic acid); polyAMPS], polyacrylic acid (PAA), poly(sodium acrylate) . The method for preparing a negative electrode structure of a carbon substrate battery having a plurality of layers of self-assembled modified film according to claim 9 wherein the first organic polymer has an average molecular weight of about 10,000 to 500,000, wherein the average of the second organic polymer The molecular weight is about 50,000-1,000,000, wherein the content of the first organic polymer is 0.5-5.0 wt.% (solid content) of the carbon-containing particles, wherein the content of the second organic polymer is 0.5- of the cerium-containing particles. 5.0 wt.% (solid content). The method for preparing a carbon-cerium composite electrode material according to claim 9 , wherein the first modified film further comprises a third organic polymer, wherein the third organic high The molecule is 0.5-5.0 wt.% (solid content) of the carbon-containing particles, wherein the third organic polymer has an average molecular weight of about 2,000-200,000, wherein the second modified film further comprises a fourth organic polymer, wherein The content of the fourth organic polymer is 0.5 to 5.0 wt.% (solid content) of the cerium-containing particles, and the fourth organic polymer has an average molecular weight of about 2,000 to 200,000. The method for preparing a carbon-cerium composite electrode material according to claim 13 , wherein the third organic polymer and the fourth organic polymer are respectively selected from one or a combination of the following groups: polyvinyl alcohol ( Polyvinyl alcohol; PVA), polyvinyl alcohol-co-ethylene. The method for preparing a carbon-cerium composite electrode material according to claim 9, wherein the carbon-containing particles having the first modified film and the cerium-containing particles having the second modified film are separately prepared, and the first modified film is mixed The carbonaceous particles and the cerium-containing particles having the second modified film are all subjected to an aqueous solution. The method for preparing a carbon-cerium composite electrode material according to claim 9 , wherein the weight ratio of the carbon-containing particles having the first modified film to the cerium-containing particles having the second modified film is about 100:0.5 to 100: 20. The method for preparing a carbon-cerium composite electrode material according to claim 9, wherein after the first drying step, the step of mixing the carbon-germanium composite electrode material and the carbon-containing mixture, and the step of performing a heat treatment process to form A third modified film is coated on the surface of the carbon germanium composite electrode material. The method for producing a carbon-cerium composite electrode material according to claim 9, wherein the third modified film is a carbon-containing conductive film. The method for preparing a carbon-cerium composite electrode material according to claim 9, wherein the carbon-containing mixture is selected from one of the group consisting of petroleum or coal pitch, fructose, phenolic resin, furan resin, Polyacrylonitrile resin, epoxy resin, polyester resin, polyamide resin and melamine resin.