TWI657068B - Magnesium-based ceramic metal graphite conductive material comprising magnesium carbide and manufacturing method thereof - Google Patents

Abstract

The invention relates to a magnesium-based ceramic metal graphite conductive material containing magnesium carbide and a preparation method thereof, the preparation method comprising the steps of: depositing a pure magnesium (Mg) or a magnesium alloy on a carbon (C) film to form a carbonization a multi-layered metal structure of magnesium (MgC); and a gel, solution or powder of magnesium monophosphate (MgPO ₄ ), magnesium sulfate (MgSO ₄ ) or magnesium nitrate (MgNO ₃ ), coated and baked in a multilayer metal Structurally, a magnesium-based ceramic metal graphite conductive material containing magnesium carbide is formed; the magnesium-based ceramic metal graphite conductive material containing magnesium carbide has good electrical conductivity and can be applied to an electrode of a battery.

Description

Magnesium-based ceramic metal graphite conductive material containing magnesium carbide and preparation method thereof

The invention relates to a magnesium-based ceramic metal graphite conductive material, in particular to a magnesium-based ceramic metal graphite conductive material prepared with magnesium carbide, which is deposited on a carbon film to deposit pure magnesium (Mg) or magnesium alloy, and is subjected to high temperature to make magnesium. Combined with carbon (C) to form magnesium carbide (MgC), with magnesium phosphate (MgPO ₄ ), magnesium sulfate (MgSO ₄ ) or magnesium nitrate (MgNO ₃ ) structure can play the role of electrode charge and discharge applications.

According to the application of secondary batteries, more and more, especially in recent years, electric steam locomotives and portable electronic products have developed rapidly, and rechargeable secondary batteries have become mainstream. At present, the electrodes of the secondary battery are classified into a powder electrode and a thin film electrode, and in order to enable the secondary battery to have the advantages of rapid charge and discharge, long life, high capacitance, high safety, etc., its manufacturing technology and material application have become related fields. Focus.

The conventional thin film electrode preparation technology has a metal interfacial layer and a uniformly distributed active film material layer, so that the charge and discharge are stable, and the capacitance is higher than that of the powder electrode. For example, the Republic of China Patent Publication No. TW I459617 " "Magnesium electrode composition", which is a patent previously approved by the applicant of the present invention, which utilizes a magnesium-based powder and a thermal evaporation process to form a magnesium film electrode having a capacitance of up to about 1500 mAh/g; Compared with the sintering procedure used for the powder electrode, the process is extremely competitive in terms of process. However, since the capacity of the vapor deposition furnace is not large, it cannot be mass-produced, so it costs more. The film electrode was fabricated in multiple times.

In order to improve the aforementioned disadvantages, the inventors have proposed a method for preparing other electrode materials, and can refer to the Republic of China Patent Publication No. TW I577074 "Manufacturing Method of Secondary Battery Electrode with Peritectic and Columnar Crystal Structure", which mainly discloses a preparation method. A method for a secondary battery electrode having a heat-induced thin film layer, wherein a mixed material of a powder material and a low-melting-point cladding material is formed into a positive electrode or a negative electrode having a heat-induced thin film layer by a sintering remelting process to simultaneously have The advantages of the thin film electrode and the powder electrode improve the capacitance and the charge and discharge efficiency, and since the heat-induced film layer has a peritectic structure and a columnar structure, the safety of the battery can be improved.

It is known from the aforementioned patents that a method for preparing an electrode using magnesium powder has been proposed. However, since the current demand for secondary batteries is extremely large, how to develop various conductive materials to serve as secondary batteries and increase their capacitance. With the charge and discharge efficiency, it is still the direction that the inventors think about in related fields.

Nowadays, the inventor is still in the light of the tireless spirit of the above-mentioned existing electrode materials in practical use, and is improved by their rich professional knowledge and years of practical experience. Based on this, the present invention has been developed.

The main object of the present invention is to provide a magnesium-based ceramic metal graphite conductive material containing magnesium carbide and a preparation method thereof, which utilizes magnesium carbide (MgC) combined with magnesium phosphate (MgPO ₄ ), magnesium sulfate (MgSO ₄ ) or magnesium nitrate (MgNO _{3 )} ), a magnesium-based ceramic metal graphite conductive material containing magnesium carbide is formed to be applied to an electrode of a battery.

In order to achieve the above-mentioned object, the present invention provides a magnesium-based ceramic-based graphite metal conductive material and a preparation method thereof, which comprise a method of depositing a pure magnesium (Mg) or a magnesium alloy on a carbon (C) film, Forming a multi-layered metal structure having magnesium carbide (MgC); and coating a gel, solution or powder of magnesium monophosphate (MgPO ₄ ), magnesium sulfate (MgSO ₄ ) or magnesium nitrate (MgNO ₃ ) The baking is baked on the multi-layer metal structure to form a magnesium-based ceramic metal graphite conductive material containing magnesium carbide.

In an embodiment of the present invention, the magnesium alloy may be selected, for example, from magnesium sodium (Mg-Na), magnesium iron (Mg-Fe), magnesium manganese (Mg-Mn), magnesium nickel (Mg-Ni), magnesium copper. (Mg-Cu), Mg-Al, Mg-Si, Mg-Ti, Mg-Li, Mg-Sn, Mg-Zn -Zn), Mg-Zr, Mg-Ca, Mg-Y, Mg-Gd, Mg-C ) or magnesium rare earth (Mg-RE).

In one embodiment of the invention, the deposition process can be, for example, one of 3D printing, evaporation, or sputtering.

In one embodiment of the present invention, if magnesium phosphate is coated, the structure of the magnesium-based ceramic-metal graphite conductive material containing magnesium carbide is sequentially magnesium phosphate/magnesium or magnesium alloy/magnesium carbide/carbon.

In one embodiment of the present invention, if magnesium sulfate is coated, the structure of the magnesium-based ceramic-metal graphite conductive material containing magnesium carbide is sequentially magnesium sulfate/magnesium or magnesium alloy/magnesium carbide/carbon.

In one embodiment of the present invention, if magnesium nitrate is coated, the structure of the magnesium-based ceramic-metal graphite conductive material containing magnesium carbide is sequentially magnesium nitrate/magnesium or magnesium alloy/magnesium carbide/carbon.

In one embodiment of the invention, the temperature at which the pure magnesium (Mg) or magnesium alloy is deposited on the carbon (C) film is 400 °C.

(1)‧‧‧Magnesium phosphate

(2) ‧‧‧Magnesium or magnesium alloy

(3)‧‧‧Magnesium carbide

(4) ‧‧‧carbon

(5) ‧ ‧ magnesium sulfate

(6)‧‧‧Magnesium nitrate

First Figure: A schematic cross-sectional view of a preferred embodiment of the present invention.

The object of the present invention and its structural and functional advantages will be explained in conjunction with the specific embodiments according to the structure shown in the following drawings, so that the reviewing committee can have a more in-depth and specific understanding of the present invention.

The invention relates to a magnesium-based ceramic-based metallic graphite conductive material containing magnesium carbide and a preparation method thereof, the preparation step comprising the first step: taking a pure magnesium (Mg) or a magnesium alloy deposited on the carbon (C) film, and depositing, the temperature About 400 ° C to form a multi-layer metal structure with magnesium carbide (MgC) selected from magnesium sodium (Mg-Na), magnesium iron (Mg-Fe), magnesium manganese (Mg-Mn), magnesium nickel (Mg-Ni), Mg-Cu, Mg-Al, Mg-Si, Mg-Ti, Mg-Li -Sn), Mg-Zn, Mg-Zr, Mg-Ca, Mg-Y, Mg-Gd, Mg-C , magnesium cobalt (Mg-Co) or magnesium rare earth (Mg-RE); and step two: a gel of magnesium monophosphate (MgPO ₄ ), magnesium sulfate (MgSO ₄ ) or magnesium nitrate (MgNO ₃ ), The solution or powder is coated and baked on the multilayer metal structure to form a magnesium-based ceramic metal graphite conductive material containing magnesium carbide. The deposition process may be, for example, one of 3D printing, evaporation or sputtering.

Referring to the first figure, if magnesium phosphate (1) is coated, the structure of the magnesium-based ceramic-metal graphite conductive material containing magnesium carbide is sequentially magnesium phosphate (1) / magnesium or magnesium alloy (2) / magnesium carbide ( 3) / carbon (4); if coated with magnesium sulfate (5), the structure of the magnesium-based ceramic-metal graphite conductive material containing magnesium carbide is sequentially magnesium sulfate (5) / magnesium or magnesium alloy (2) / carbonization Magnesium (3) / carbon (4); if coated with magnesium nitrate (6), the structure of the magnesium-based ceramic metal graphite conductive material containing magnesium carbide is sequentially magnesium nitrate (6) / magnesium or magnesium alloy (2) / Magnesium carbide (3) / carbon (4).

The present invention also provides a magnesium-based ceramic metal graphite conductive material containing magnesium carbide, which is obtained by the above-mentioned manufacturing method, and which has good electrical conductivity as a whole and can be applied to an electrode of a battery.

In addition, the scope of the invention may be further exemplified by the following specific examples, which are not intended to limit the scope of the invention.

Please continue to refer to the first figure, a pure magnesium or magnesium alloy (2) deposited on the carbon (4) film, deposition temperature of about 400 ° C, to form a multi-layer metal structure with magnesium carbide (3), magnesium carbide (3 ) can be used as a buffer layer; if it is deposited on carbon (4) film with pure magnesium, multilayer metal The structure will change from Mg/C to Mg/MgC/C; if magnesium alloy is deposited on carbon (4) film, the multilayer metal structure will change from MgX/C to MgX/MgC/C, where X represents an element other than magnesium. For the magnesium alloy, for example, magnesium sodium (Mg-Na), magnesium iron (Mg-Fe), magnesium manganese (Mg-Mn), magnesium nickel (Mg-Ni), magnesium copper (Mg-Cu), magnesium aluminum (Mg) may be used. -Al), Mg-Si, Mg-Ti, Mg-Li, Mg-Sn, Mg-Zn, Mg-Zr ), magnesium calcium (Mg-Ca), magnesium strontium (Mg-Y), magnesium strontium (Mg-Gd), magnesium carbon (Mg-C), magnesium cobalt (Mg-Co) or magnesium rare earth (Mg-RE) one. Wherein, the above deposition process can be applied to another film uniformly, for example, by using one of 3D printing, evaporation or sputtering.

Successively, a ceramic material may be taken as magnesium phosphate (1), magnesium sulfate (5) or magnesium nitrate (6), which may be in the form of a gel, a solution or a powder, and coated and baked in a multilayer metal structure ( On Mg/MgC/C or MgX/MgC/C), a magnesium-based ceramic metal graphite conductive material containing magnesium carbide (3) is formed on the magnesium layer or the magnesium alloy layer; if it is coated with magnesium phosphate (1) In the multilayer metal structure, the structure of the magnesium-based ceramic metal graphite conductive material containing magnesium carbide (3) is MgPO ₄ /Mg or MgX/MgC/C, which may be referred to as a phosphorous gold carbide structure; 5) coated on a multi-layer metal structure, the structure of the magnesium-based ceramic metal graphite conductive material containing magnesium carbide (3) is sequentially MgSO ₄ /Mg or MgX/MgC/C, which may be referred to as a sulfur-gold carbide structure; Applying magnesium sulfate (5) to a multilayer metal structure, the structure of the magnesium-based ceramic metal graphite conductive material containing magnesium carbide (3) is MgNO ₃ /Mg or MgX/MgC/C, which may be called carbon gold carbonization. Structure of matter.

The above-mentioned magnesium phosphate (1), magnesium sulfate (5) or magnesium nitrate (6) can be prepared by the following method, first preparing magnesium metal, one of pure magnesium, magnesium oxide or magnesium alloy, and then mixing the metal magnesium In an acid solution, treatment with a temperature of 25 ° C ~ 65 ° C for 1 to 12 hours, depending on the phosphate solution, sulfate solution or nitrate solution selected for the acid solution, respectively, forming magnesium phosphate (1), magnesium sulfate (5) or Magnesium nitrate (6); or the acid can be easily coated on the surface of magnesium metal, and after low temperature baking, magnesium phosphate (1), magnesium sulfate (5) or Magnesium nitrate (6).

Three kinds of magnesium-based ceramic-metal graphite conductive materials containing magnesium carbide were prepared as electrodes of secondary batteries, and electrical tests were conducted. Conductivity, electron mobility and charge and discharge test results are shown in Table 1 to Table 3. Charge and discharge tests The lithium metal is used as a positive electrode to form a half-cell, and the number of charge and discharge times is evaluated in a test environment of 0.1 C. The symbols in the table represent ●: excellent, ◎: normal, ○: poor, and the standards are as follows, conductivity: >10 ⁴ ( Excellent), 10 ⁴ -10 ³ (ordinary), <10 ³ (poor); mobility: 0.5 (excellent), 0.5-0.1 (normal), <0.1 (poor); charge and discharge: >100 times (excellent), 10-100 times (ordinary), <10 (poor).

From the data presented in Tables 1 to 3, it is known that the conductivity of the phosphorous gold carbide structure and the sulfur gold carbide structure is better than that of the nitrate metal carbide structure, but in the application of the general secondary battery, the performance of the three materials is suitable for preparation. Form the electrode.

It can be seen from the above description that the present invention has the following advantages compared with the prior art:

1. The magnesium-based ceramic-based metallic graphite conductive material of the present invention and the preparation method thereof, using metal magnesium element combined with carbon element, converting it into magnesium carbide, and then combining magnesium phosphate, magnesium sulfate or magnesium nitrate to enhance conductivity Effect, test the conductivity, move Both the rate of change and the charge and discharge have a good performance.

2. The magnesium-containing magnesium-based ceramic metal graphite conductive material of the invention and the preparation method thereof, the magnesium-based ceramic metal graphite conductive material containing the magnesium carbide prepared by the invention has good electrical conductivity and is suitable as a secondary battery. Electrode material.

In summary, the magnesium-containing magnesium-based ceramic metal graphite conductive material of the present invention and the preparation method thereof can achieve the intended use efficiency by the above disclosed embodiments, and the present invention has not been disclosed in the application. Before, Cheng has fully complied with the requirements and requirements of the Patent Law.爰Issuing an application for a patent for invention in accordance with the law, and asking for a review, and granting a patent, is truly sensible.

The illustrations and descriptions of the present invention are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; those skilled in the art, which are characterized by the scope of the present invention, Equivalent variations or modifications are considered to be within the scope of the design of the invention.

Claims (7)

A method for preparing a magnesium-based ceramic metal graphite conductive material containing magnesium carbide, the steps comprising the steps of: taking a pure magnesium (Mg) or a magnesium alloy deposited on a carbon (C) film to form a carbonized a multi-layered metal structure of magnesium (MgC); and step 2: coating a paste, a solution or a powder of magnesium monophosphate (MgPO ₄ ), magnesium sulfate (MgSO ₄ ) or magnesium nitrate (MgNO ₃ ) On the multilayer metal structure, a magnesium-based ceramic metal graphite conductive material containing magnesium carbide is formed. The method for preparing a magnesium-based ceramic-based metallic graphite conductive material according to claim 1, wherein the magnesium alloy is selected from the group consisting of magnesium sodium (Mg-Na), magnesium iron (Mg-Fe), magnesium manganese ( Mg-Mn), Mg-Ni, Mg-Cu, Mg-Al, Mg-Si, Mg-Ti, Mg- Li), Mg-Sn, Mg-Zn, Mg-Zr, Mg-Ca, Mg-Y, Mg-Gd Magnesium carbon (Mg-C), magnesium cobalt (Mg-Co) or magnesium rare earth (Mg-RE). The method for preparing a magnesium-based ceramic-based metallic graphite conductive material according to claim 1, wherein the deposition process is one of 3D printing, evaporation or sputtering. The method for preparing a magnesium-based ceramic-based metallic graphite conductive material according to claim 1, wherein the magnesium-containing magnesium-based ceramic metal graphite conductive material coated with the magnesium phosphate is sequentially structured as magnesium phosphate. , magnesium or magnesium alloy, magnesium carbide, carbon. The method for preparing a magnesium-based ceramic-based metallic graphite conductive material according to claim 1, wherein the magnesium-containing magnesium-based ceramic metal graphite conductive material coated with the magnesium sulfate is sequentially structured as magnesium sulfate. , magnesium or magnesium alloy, magnesium carbide, carbon. The method for preparing a magnesium-based ceramic-based metallic graphite conductive material according to claim 1, wherein the magnesium-containing ceramic-based metallic graphite conductive material coated with the magnesium nitrate is sequentially structured as magnesium nitrate. , magnesium or magnesium alloy, magnesium carbide, carbon. The method for preparing a magnesium-based ceramic-based metallic graphite conductive material according to claim 1, wherein the pure magnesium (Mg) or the magnesium alloy is deposited on the carbon (C) film at a temperature of 400 ° C.