TW201724625A - Electrode structure - Google Patents

Abstract

An electrode structure is provided. The cross section of the electrode structure includes a substrate layer, a first coating layer disposed on the substrate layer, a second coating layer disposed on the first coating layer, and a third coating layer disposed on the second coating layer, where when the second coating layer is one of an inorganic material and an organic material, one of the third coating layer and the first coating layer is the other of the inorganic material and the organic material.

Description

Electrode structure

The present invention relates to an electrode structure, and more particularly to an electrode structure having a coating layer of an organic material and an inorganic material.

In the prior art, the factor that the performance of the battery cannot be fully exerted is often because the contact between the cathode or the anode and the electrolyte in the electrode structure of the battery produces a side reaction after the battery is subjected to multiple cycles of charging and discharging. Forming a solid oxide layer that is detrimental to the conduction of lithium ions or other conductive ions. Or because the impedance of the cathode or the anode itself in the electrode structure is too large, the performance of the battery cannot be effectively expressed, and after the repeated charging and discharging cycles, the solid oxide layer is accompanied by a longer and thicker layer. An unfavorable electrical structure is formed, causing the overall battery capacity to decline. Therefore, as can be seen from the above, the electrode structure is related to the thickness of the solid oxide layer generated in the cycle of charging and discharging.

For the sake of his position, the applicant invented the "electrode structure" of the case in view of the lack of prior art to improve the above-mentioned deficiency.

The present invention maintains the stability of the electrode structure by improving the coating or coating layer configuration of the material in the electrode structure, and at the same time increases the material conductivity, so that after multiple charging and discharging, the present invention has One of the electrode structures can increase the capacitance of 10 to 30% compared with the primary battery.

The present invention provides an electrode structure and method for bonding a coating layer composed of an inorganic material and another coating layer composed of an organic material adjacent to the coating layer to produce a surface capable of stably protecting the electrode structure. And can simultaneously increase the conductivity of the material of the battery, thereby effectively reducing the impedance of the battery.

Through the modification technology of the cathode material in the electrode structure and the coating layer configuration technology in the electrode structure, an electrode structure having a composite material plating layer can be obtained, so that the battery having the electrode structure is more than the battery with the original material. Higher capacitance and more stable cycle life.

One aspect of the present invention provides an electrode structure having a cross section including: a substrate layer; a first coating layer on the substrate layer; and a second coating layer on the first coating layer a third coating layer on the second coating layer, wherein the second coating layer is an organic material, and the third coating layer is an inorganic material and has a first thickness range Less than 10 nm.

Another aspect of the present invention provides an electrode structure comprising: a substrate layer; and a granular structure on the substrate layer, and the granular structure comprises: a core; a first coating layer covering the a core; and a second coating layer covering the first coating layer, wherein when the first coating layer is one of an inorganic material and an organic material, the second coating layer is The inorganic material and the other of the organic materials.

A further aspect of the present invention provides an electrode structure having a cross section including: a substrate layer; a first coating layer on the substrate layer; and a second coating layer on the first coating layer a third coating layer on the second coating layer, wherein the third coating layer is one of an inorganic material and an organic material, the third coating layer and the first layer One of the coating layers is the inorganic material and the other of the organic materials.

100, 200, Cd‧‧‧ electrode structure

101, 201‧‧‧ substrate layer

102, 103, 104, 20, 30, 202, L1~L5‧‧‧ coating layer

A‧‧‧ granular structure

10‧‧‧ core

P‧‧‧Precursors

Sv1, Sv2, Sv3‧‧‧ solvent

Sn1, Sn2, Sn3, Sn4‧‧‧ solution

C1, C2, C3, C4‧‧‧ compounds

Sy, Sy1, Sy2, Sy3‧‧‧ slurry

S‧‧‧Substrate

I, I1, I2, I3‧‧‧ coating device

X0, X1, X2, X3, Y0, Y1, Y2, Y3‧‧‧ samples

The first drawing is a perspective view of a electrode structure of a first embodiment of the present invention and a cross-sectional view thereof.

The second drawing is a cross-sectional view of an electrode structure of a second embodiment of the present invention and a partial cross-sectional view thereof.

Fig. 3(A) is a flow chart showing the preparation of the electrode structure of the third embodiment of the present invention.

The third drawing (B) is a cross-sectional view showing the structure of the intermediate product of the third embodiment of the present invention.

Figure 3 (C) is a cross-sectional view showing the structure of the product of the third embodiment of the present invention.

The third diagram (D) is a side view of the electrode structure of the third embodiment of the present invention.

The fourth figure is a flow chart for preparing the electrode structure of the fourth embodiment of the present invention.

Fig. 5(A) is a view showing the results of specific capacitance and number of cycles of different electrode structures of the third embodiment of the present invention.

Fig. 5(B) is a view showing the results of the specific capacitance and the number of cycles of the different electrode structures of the third embodiment of the present invention.

Fig. 5(C) is a view showing the results of the specific capacitance and the number of cycles of the different electrode structures of the third embodiment of the present invention.

Fig. 6(A) is a view showing the results of the specific capacitance and the number of cycles of the different electrode structures of the fourth embodiment of the present invention.

Fig. 6(B) is a view showing the results of the specific capacitance and the number of cycles of the different electrode structures of the fourth embodiment of the present invention.

Fig. 6(C) is a view showing the results of specific capacitance and number of cycles of different electrode structures of the fourth embodiment of the present invention.

The present invention will be fully understood from the following description of the embodiments of the present invention, which can be practiced by those skilled in the art.

The present invention provides an electrode structure which is improved according to the configuration of the coating layer in the electrode structure and the modification of the electrode material, so that the battery having the electrode structure of the present invention has a phase compared with the primary battery. More excellent electrical performance.

The battery includes a primary battery, a secondary battery, a fuel battery, and a solar battery, and the secondary battery and the fuel battery generate electrical energy by chemical energy, and the solar battery generates energy by using light energy, wherein The secondary battery stores the generated electric energy by a chemical reaction formed by one of the electrode structures (ie, a cathode structure) and another electrode structure (ie, an anode structure), and includes a lithium battery and an aluminum battery. , sodium battery, nickel hydrogen battery, nickel cadmium battery, lead storage battery and so on. The fuel cell also includes a two-electrode structure (ie, a cathode structure and an anode structure) and an electrolyte. However, the fuel cell generates a hydrogen-containing fuel and oxygen in the air through a catalyst in the electrolyte. A chemical reaction converts into electrical energy. The solar cell includes a p-n diode and a metal electrode structure, and the battery passes through the p-n The photoelectric effect produced by the diode and the light energy to the metal electrode structure (i.e., the electrode structure of the present invention) generates electrical energy. Accordingly, the electrode structure provided by the present invention refers to the cathode structure, the anode structure or the metal electrode structure applied to the secondary battery, the fuel cell or the solar cell.

1 and 2 are respectively a perspective view of an electrode structure according to a first embodiment of the present invention, a cross-sectional view thereof, and a cross-sectional view of the electrode structure of the second embodiment and a partial cross-sectional view thereof.

As shown in the first figure, the cross-section of the electrode structure 100 of the first embodiment of the present invention includes a substrate layer 101, a first coating layer 102 on the substrate layer 101, and the first coating layer 102. a second coating layer 103, and a third coating layer 104 on the second coating layer 103, wherein the first coating layer 102, the second coating layer 103, and the third coating layer The 104 series are parallel, and when the second coating layer 103 is one of an inorganic material and an organic material, the third coating layer 104 is the inorganic material and the other of the organic materials.

The first coating layer 102 is a cathode material, and the cathode material is a lithium ion metal oxide such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide or the like.

According to an embodiment of the present invention, in order to allow a cathode structure composed of the cathode material to allow lithium ions to migrate into and out, the type of the cathode material may have one dimension (1-D) according to the material. The characteristics of the two-dimensional (2-D) and three-dimensional (3-D) spatial structures are distinguished. The cathode material is a combination of an excess of lithium and one of the materials distinguished, wherein the material (relative to the spatial structure of 1-D) includes titanium trisulfide (TiS ₃ ), niobium selenide (NbSe ₃ ), chain Sulfur, as well as sulfur compounds.

The material (relative to the 2-D spatial structure) comprises a layered dichalcogenide transition metal compound (MX ₂ ) and a layered transition metal oxide (LiM'O ₂ ), wherein M is titanium (Ti), lanthanum (Nb), tantalum (Ta), molybdenum (Mo), or tungsten (W), and M' is cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn), or chromium (Cr).

The material (relative to the 3-D spatial structure) includes a spinel structure of lithium manganate (LiMn ₂ O ₄ ), a high voltage LiMnVO ₄ , an inverse spinel structure (LiNiVO ₄ ), a vanadium series oxide, such as V ₂ O ₅ , V ₆ O ₁₃ , and LiV ₃ O ₈ , lithium iron phosphate (LiFePO ₄ ), and lithium titanate (Li ₄ Ti ₅ O ₁₂ ).

The organic material includes an unsaturated alkyl compound, an aromatic ring compound, and an aromatic heterocyclic compound. The unsaturated alkyl compound is poly(acetylene)s, PAC, and the aromatic ring compounds include poly(fluorene), polyphenylenes, polypyrenes, polyfluorene (Polypyrenes). Polyazulenes), as well as polynaphthalenes.

The aromatic heterocyclic compound includes a nitrogen-containing compound and a sulfur-containing compound, wherein the nitrogen-containing compound includes polypyrrole (PPY), polycarbazoles, polyindoles, polyazepines, and Polyaniline (PANI), and the sulfur-containing compounds include poly(thiophene)s, PT, poly(3,4-ethylenedioxythiophene, PEDOT), and polyphenylene sulfide (poly( P-phenylene sulfide), PPS).

The organic material also includes a pitch.

The inorganic material includes zirconium (Zr), aluminum (Al), tin (Sn), magnesium (Mg), cerium (Si), titanium (Ti), zinc (Zn), lithium (Li), and boron (B). Oxides such as ZrO ₂ , MgO, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZnO, SnO ₂ , Li ₂ CO ₃ , AlPO ₄ , SnO ₂ /carbon, and Li ₂ O. 2B ₂ O ₃ glass (LBO).

The first coating layer 102 is 60% to 95% by weight of the cathode material, The second coating layer 103 is 0.05% by weight to 5% by weight of the organic material, and the third coating layer 104 is 0.05% by weight to 5% by weight of the inorganic material, and the second coating layer 102 has a second thickness. The third thickness of the second coating layer 103 ranges from 1 to 100 nm, and the fourth thickness of the third coating layer 104 ranges from 0.5 to 10 nm.

According to another embodiment of the present invention, the first coating layer 102 is an anode material, and the anode material is a carbon material, such as graphite, and includes any material that can be used as an anode structure in a battery in the art. . The concentration and thickness of the first coating layer 102 and the materials, concentrations, and thicknesses of the second coating layer 103 and the third coating layer 104 have been previously described.

According to still another embodiment of the present invention, the first coating layer 102 is a metal material, and the metal material is any material in the art that can function as the metal electrode structure in the solar cell. The concentration and thickness of the first coating layer 102 and the materials, concentrations, and thicknesses of the second coating layer 103 and the third coating layer 104 have been previously described.

As shown in the second figure, the cross section of the electrode structure 200 of the second embodiment of the present invention includes a substrate layer 201, a plurality of granular structures A, and a coating layer 202 composed of the plurality of granular structures A, wherein A cross section of each of the plurality of granular structures A includes a first coating layer L1 on the substrate layer 201, and a second coating layer L2 on the first coating layer L1. And a third coating layer L3 on the second coating layer L2. If the cross section of the granular structure A is horizontally cut according to a horizontal dashed line, the cross section of each granular structure A further includes the third coating layer L3 and is the second coating layer L2. An extended fourth coating layer L4 and a fifth coating layer L5 located on the fourth coating layer L4 and extending from the first coating layer L1.

The third coating layer L3 is a core, and the first coating layer L2 and the fourth coating layer L4 are in the same layer, and is also named as a first layer 20. The second coating layer L1 and the fifth coating layer The layer L5 is also located on the same layer and is also named as a second layer 30. The first layer 20 covers the core and the second layer 30 covers the first layer 20. That is, the first layer 20, the second layer 30, and the third coating layer L3 can form a granular structure A, and when the second layer 30 is one of an inorganic material and an organic material, The first layer 20 is one of the inorganic material and the organic material.

The core is a cathode material, an anode material or a metal material, and the range of the cathode material, the anode material, the metal material, the organic material, and the inorganic material has been described above.

The material of the first layer 20 has a first ratio with the cathode material (the anode material or the metal material), and the first ratio is 0.1 wt% to 5 wt%. The material of the second layer 30 has a second ratio to the material of the first layer 20 covering the core, and the second ratio is 0.05 wt% to 1 wt%.

Regarding the modification method of the cathode material (the anode material or the metal material) itself in the electrode structure according to the present invention, please refer to the third figure (A), the third figure (B), the third figure (C) and the third method. Figure (D) is a flow chart showing the structure of the electrode structure, a cross-sectional view of the structure of the intermediate product, a cross-sectional view of the structure of the product, and a side view of the electrode structure, respectively, in accordance with a third embodiment of the present invention.

As shown in the third diagram (A), a precursor P and a first solvent Sv1 are first placed in a container for stirring to form a first solution Sn1, and then a first compound C1 is disposed in the first solution. Stirring is performed in Sn1 to form a second solution Sn2, and then the second solution Sn2 is dried to obtain a second compound C2 (i.e., an intermediate product, the cross-sectional view of the intermediate product is as shown in the third figure (B). ). When necessary, the second compound C2 is subjected to a high-temperature sintering process, and the conditions as necessary will be described later in detail.

When a third compound C3 and a second solvent Sv2 are disposed in another container When stirring to form a third solution Sn3, the second compound C2 obtained above is placed in the third solution Sn3 to be stirred to form a fourth solution Sn4, and then the fourth solution Sn4 is dried to obtain A fourth compound C4 (i.e., a product having a cross-sectional view of the product as shown in the third panel (C)).

Finally, the fourth compound C4 and a third solvent Sv3 are disposed in a slurry Sy, and the slurry Sy is coated on a substrate S by a coating device I, and the substrate S is dried to obtain An electrode structure Cd (i.e., a cathode having a cross-sectional view as shown in the third figure (D)).

The nouns described in the above methods are defined as follows, but are not limited thereto. The precursor P is a salt compound, and particularly includes zirconium (Zr), aluminum (Al), tin (Sn), magnesium (Mg), bismuth (Si), titanium (Ti), zinc (Zn), A salt compound of lithium (Li) or boron (B), and a preferred embodiment thereof means a salt compound containing zirconium (Zr) such as Zr(OC ₃ H ₇ ) ₄ .

The first solvent Sv1, the second solvent Sv1, and the third solvent Sv3 are a polar solvent, particularly a polar solvent of water, an alcohol, a ketone or an alkane, and the most preferred embodiment refers to an alcohol. A polar solvent such as ethanol or propanol. Polar solvents for alkanes include hexane. In addition, the choice of such solvents will vary depending on the characteristics of the compound to be used (e.g., C1 to C4).

The first compound C1 is of a type known in the art as a cathode material, particularly a type of cathode material as described above, wherein the preferred embodiment refers to lithium nickel manganese oxide (product type A650). Cathode material.

The second compound C2 is as shown in the third diagram (B), which is a Li compound coated with the inorganic material, which is a complex ion of the precursor P dissolved in the first solution Sn1 ( It is assumed that Zr ⁺ ) is distributed on the surface of the first compound C1 (assumed to be the cathode material, the anode material or the powder of the metal material) to form the first layer 20 (like a coated process). Compound.

At this time, in order to make the material of the first layer 20 on the third coating layer L3 (that is, the core) in the second compound C2 an inorganic material, the second compound C2 after drying is required. After high temperature sintering, the organic residue on the layer 20 is removed by high temperature sintering, wherein the sintering temperature is between 300 and 500 °C.

The third compound C3 is an organic material which is all organic materials conventionally used in the art for the cathode structure of batteries, particularly organic materials as described hereinbefore.

The fourth compound C4 is as shown in the third diagram (C), which is a Li compound coated with an organic material, which is bonded to the second compound by a plurality of ions of the organic material in the third solution Sn3. A compound of the second layer 30 (like a coated process) is formed on the surface of C2. The fourth compound C4 is composed of the third coating layer L3 (that is, the core), the first layer 20 covering the core, and the second layer 30 covering the first layer 20. A compound in the form of a plurality of particles.

The slurry Sy is obtained by dissolving 60% by weight to 95% by weight of the fourth compound C4 in the third solvent Sv3.

The substrate S is any conventional substrate used in the art for electrode structures, particularly an aluminum foil substrate.

The coating device I is any conventional device used in the art for coating, such as a coating device, a doctor blade, a spin coating device, an Atomic Layer Deposition (ALD) device, and a chemical. Chemical Vapor Deposition (CVD) device, sputtering device, photodeposition device, hydrothermal device, Dip Coating device, ion exchange (Ion-exchange) Devices, electroplating devices, and the like.

According to an embodiment of the present invention, the coating device 1 can be replaced by a coating method according to requirements, such as chemical vapor deposition (CVD), sputtering, atomic layer deposition (ALD). Method, photodeposition method, sol-gel method, hydrothermal method, simple blade coating method, spin coating method, dip coating Method, ion exchange (Ion-exchange) method, electroplating (electroplating) method, polymer polymerization method, and the like.

According to another embodiment of the present invention, when the organic material is coated, the polymer polymerization method tends to be applied, and when the inorganic material is coated, the chemical vapor deposition method, the sputtering method, and the atomic layer deposition method are preferred. And a photo-deposition method, a sol-gel method, a hydrothermal method, a simple blade coating method, a spin coating method, a dip coating method, an ion exchange method, an electroplating method, and a device of each of the methods.

The side view of the cathode structure Cd is as shown in the third diagram (D), and includes the substrate S and a coating layer coated on the substrate S, wherein the coating layer is dried by the slurry Sy The slurry Sy is obtained from the fourth compound C4 and the third solvent Sv3.

The method for drying in the above method uses any means capable of heating at a high temperature, such as a heater, an oven, a vacuum oven, a high temperature furnace, a vacuum concentrator, etc., wherein the temperature used is determined in accordance with the compound to be dried.

The precursor P has a first ratio between the first compound C1 and the first ratio is 0.1 wt% to 5 wt%. That is, when the precursor P is Zr(OC ₃ H ₇ ) ₄ , the first compound C1 is lithium nickel manganese oxide, and the first ratio between the two is 0.1 wt%, the precursor P was 0.15 g, and the first compound C1 was 2.85 g.

The third compound C3 has a second ratio between the second compound C2 and The second ratio is 0.05 wt% to 1 wt%.

Please refer to FIG. 5(A), FIG. 5(B), and FIG. 5(C), which are diagrams showing the results of the specific capacitance and the number of cycles of different electrodes according to the third embodiment of the present invention, wherein A sample X0 represents a trend line of specific capacitance and cycle number of the electrode structure with the unmodified material, and a second sample X1 represents a modified cathode material (ie, each of the original cathode materials) a specific trend of the specific capacitance and the number of cycles of the electrode structure on which the surface of the granular powder is coated; and a third sample X2 represents the modified cathode material (ie, the surface of each particle of the original cathode material) a potential line of the specific capacitance and the number of cycles of the electrode structure coated with the inorganic material; and a fourth sample X3 representing the modified cathode material (that is, in the present case, the surface of each of the original cathode materials is subjected to the powder material) The ratio of the specific capacitance and the number of cycles of the electrode structure of the two-layer coated material, the first layer 20 being an inorganic material and the second layer 30 being an organic material. The first sample X0 is an electrode structure in which the cathode material is lithium nickel manganese oxide. The second sample X1 is an electrode structure of a modified cathode material composed of the first compound C1 being a lithium nickel manganese oxide and the first layer 20 being an organic film formed of PEDOT:PSS, and the electrode structure The first ratio in the value is 0.5 wt%. The third sample X2 is an electrode structure of a modified cathode material composed of the first compound C1 being a lithium nickel manganese oxide and the first layer 20 being an inorganic film formed of Zr, and in the electrode structure The first ratio is 0.5 wt%; and the fourth sample X3 is an inorganic film formed of the first compound C1 being a lithium nickel manganese oxide, the first layer 20 being formed of Zr, and the second layer 30 being An electrode structure of a modified cathode material composed of an organic film formed of PEDOT:PSS, and the first ratio and the second ratio in the electrode structure are 0.5 wt%. In addition, the cycle of charging and discharging was performed at 25 ° C, 2.5-4.8 V, and operated at a charge and discharge rate of 0.1 C, 0.3 C, and 0.5 C.

As shown in the fifth diagram (A), the specific electric power between the sample X0 and the sample X1 (coated with the organic film) at a charge and discharge rate of 0.1 C in the first to fifth cycles is known. The difference in capacity is not significant until the ratio of charge to discharge rate is 0.5C in the 6th to 10th cycles, and the specific capacitance of the sample X1 is significantly higher than the specific capacitance of the sample X0. The contribution of the organic film composed of a polymer material. In addition, although the specific structure of the electrode structure of the sample X1 before the 11th cycle is about 190 mAh/g or more, the electrode structure itself has the disadvantage of poor stability, so that it is in the 11th-290th cycle. The performance of the specific capacitance will drop significantly.

As shown in the fifth diagram (B), it can be seen that the specific capacitance of the sample X0 is significantly higher at the charge and discharge rates of 0.1 C and 0.3 C in the first to fifth cycles and the sixth to tenth cycles, respectively. Higher than the specific capacitance of the sample X2 (coated with the inorganic film), because the impedance of the electrode material in the sample X2 causes the impedance of the electrode material to be larger than the impedance of the electrode material of the sample X0. The phenomenon. However, when the faster charge-discharge rate is 0.5C in the 11th to 70th cycles, although the specific capacitance of the sample X0 and the sample X2 both show a downward trend (about the 27th cycle, both The specific capacitance drops to about 150 mAh/g, but the specific capacitance of the sample X2 is relatively stable in the 11th to 70th cycles compared to the specific capacitance of the sample X0, even at the 70th. The same trend is also observed at -290 cycles.

As shown in the fifth diagram (C), the specific capacitance between the sample X0 and the sample X3 and the ratio thereof at the charging rates of 0.1 C and 0.3 C in the first to tenth cycles are known. There is no significant difference in the stability of the capacitance. When the charge-discharge rate of 0.5C is used in the 11th to 290th cycles, the specific capacitance of the sample X3 is found to be higher than the specific capacitance of the sample X0, and the specific energy of the sample X3 after the 27th cycle. The capacity is maintained at about 150 mAh/g, and the sample X0 is in a state of continuous decline. This result confirms that the electrode structure provided by the present invention is simultaneously improved. The specific capacitance and the effect of maintaining the stability of the specific capacitance. In addition, the retention rate of the specific capacitance of the sample X0 and the sample X3 is 38% and 72%, respectively, and it is confirmed again that the stability of the specific capacitance of the sample X3 is much higher than the The specific capacitance of the sample X03 is stable, and has an advantage of excellent electrical properties and the like at a higher charge and discharge rate.

According to the above, it is known that the first compound C1 (such as lithium nickel manganese oxide) is coated with an inorganic material on the surface of the first compound C1 to form an inorganic film, and then An organic material is coated on the inorganic film to form an organic film, thereby achieving characteristics of the modified cathode material, such that an electrode structure Cd having a coating layer formed by the modified cathode material and using the electrode structure The battery of Cd can control the thickness of the oxidized solid layer produced in the battery, so that the battery has a good specific capacity and a long-lasting cycle number.

On the contrary, the method for modifying the cathode material of the present invention may also be applied to the surface of the first compound C1 to form an organic film (that is, the first layer 20), and then coated with an inorganic material. An inorganic film (that is, the second layer 30) is formed on the organic film to thereby achieve the characteristics of the modified cathode material, so that an electrode structure Cd having the coating layer formed by the modified cathode material is obtained. And the battery using the electrode structure Cd can control the thickness of the oxidized solid layer generated in the battery, so that the battery has a good specific capacity and a long-acting cycle number.

At this time, the precursor P is a salt compound of the organic material, and the precursor P has a first ratio with the first compound C1, and the first ratio is 0.05 wt% to 5 wt%. There is a second ratio between the third compound C3 and the second compound C2, and the second ratio is 0.05 wt% to 5 wt%. In the drying process of the second compound C2, a process which does not require high-temperature sintering, such as an ALD process, must be selected to avoid the destruction of the organic film.

Similarly, when the anode material or the metal material itself is modified as described above, the anode structure or the electrode structure of the metal material after modification has similarly excellent electrical results.

Regarding the method according to the configuration of the coating layer in the electrode structure, please refer to the fourth drawing, which is a flow chart for preparing the electrode structure according to the fourth embodiment of the present invention. First, a first slurry Sy1 is applied onto a substrate S by a first coating device I1, and after drying, a first coating layer composed of the first slurry Sy1 is formed. Next, a second coating device I2 is used to apply a second slurry Sy2 on the first coating layer, and after drying, a second coating composed of the second slurry Sy2 is formed. Floor. Finally, a third slurry Sy3 is coated on the second coating layer by a third coating device I3, and after drying, a third coating composed of the third slurry Sy3 is formed. The layer simultaneously forms an electrode structure Cd (that is, a cathode structure, an anode structure or a metal electrode structure).

The coating devices I1 to I3 are any conventional devices that can be used for coating in the art, such as a coating device, a doctor blade, a spin coating device, and an Atomic Layer Deposition (ALD). Device, Chemical Vapor Deposition (CVD) device, Sputtering device, Photodeposition device, Hydrothermal device, Dip Coating device, Ion-Ion- Exchange) Apparatus, electroplating apparatus, etc., especially refers to a doctor blade and an atomic layer deposition apparatus.

According to an embodiment of the present invention, the coating devices I1 to I3 can be replaced by a coating method according to requirements, which is a chemical vapor deposition (CVD) method, a sputtering method, and an atomic layer deposition. (ALD) method, photodeposition method, sol-gel Method, hydrothermal method, simple blade coating method, spin coating method, dip coating method, ion exchange (Ion-exchange) method, electroplating (electroplating) method, polymer Polymerization method and the like.

According to another embodiment of the present invention, when the organic material is coated, the polymer polymerization method is preferred, and when the inorganic material is coated, the chemical vapor deposition method, the sputtering method, and the atomic layer are preferred. Deposition method, photodeposition method, sol-gel method, hydrothermal method, simple blade coating method, spin coating method, dip coating method, ion exchange method, electroplating method, and devices of the respective methods.

The first slurry Sy1 is composed of the first compound C1 and a solvent, wherein the concentration of the first compound C1 is 60% by weight to 95% by weight.

When the second slurry Sy2 is composed of an organic material and a solvent, the third slurry Sy3 is composed of an inorganic material and a solvent. Vice versa, when the second slurry Sy2 is composed of an inorganic material and a solvent, the third slurry Sy3 is composed of an organic material and a solvent.

Therefore, when the second slurry Sy2 is composed of an organic material and a solvent, and the third slurry Sy3 is composed of an inorganic material and a solvent, the concentration of the organic material is 0.05 wt%~ 5 wt%, and the concentration of the inorganic material is 0.05 wt% to 5 wt%. At this time, the coating device I3 used is an atomic layer depositer to facilitate coating the inorganic material on the second coating layer (ie, composed of the organic material) to an atomic level, so that The thickness of the third coating layer formed is thin enough to facilitate the passage of conductive ions, wherein the thickness needs to be less than 10 nm and greater than 0.5 nm.

Regarding the first compound C1, the inorganic material, the organic material, and the solvent The scope has been described in the foregoing.

Please refer to FIG. 6(A), FIG. 6(B), and FIG. 6(C), which are schematic diagrams showing the results of the specific capacitance and the number of cycles of different electrodes according to the fourth embodiment of the present invention, wherein A sample Y0 represents a trend line of an electrode structure having only the cathode material of the first coating layer; and a second sample Y1 represents the first coating layer and the second coating layer and the second coating The layer is a trend line of the electrode structure of an organic layer; and a third sample Y2 represents the first coating layer and the second coating layer and the second coating layer is an inorganic layer (coated by ALD technology) a trend line of the electrode structure of the cloth), and a fourth sample Y3 representing the first coating layer, the second coating layer, and the third coating layer, and the second coating layer and the third coating The layers are respectively trend lines of the electrode structure of an organic layer and an inorganic layer (coated by ALD technology).

The first sample Y0 is an electrode structure composed of a lithium nickel manganese oxide as a cathode material, and the second sample Y1 is a lithium nickel manganese oxide from the first coating layer and the second coating layer is PEDOT: an electrode structure composed of an organic layer formed by PSS, the third sample Y2 is composed of the first coating layer being a lithium nickel manganese oxide and the second coating layer being an inorganic layer formed by Zr The electrode structure, and the fourth sample Y3 is an inorganic layer formed by the first coating layer being lithium nickel manganese oxide, the second coating layer being Zr, and the third coating layer being PEDOT:PSS An electrode structure composed of the formed organic layer.

The PEDOT:PSS concentration in the second sample Y1 was 0.1 wt% (PEDOT was 0.1 wt% and PSS was 0.05 wt%), and the Zr inorganic concentration in the third sample Y2 was 0.5 wt%. Further, the inorganic layer coated by the above ALD technique has a thickness of about 1 nm. The charging and discharging cycle was performed at 25 ° C, 2.5-4.8 V, and operated at a charge and discharge rate of 0.1 C and 0.5 C.

As shown in the sixth figure (A), in the 1st to 5th cycles and the 6th to 10th cycles The specific capacitance test of the sample Y0 and the sample Y1 (the second coating layer is an organic layer) at a charge and discharge rate of 0.1 C and 0.5 C, respectively, can be found to be replaced by a faster charge. When the discharge rate is 0.5C, the specific capacitance of the two drops sharply, but the specific capacitance of the sample Y1 in the first to tenth cycles is higher than the specific capacitance of the sample X0, which is obviously due to the conductive polymer material. The contribution of the second coating layer. Further, the specific capacitance of the electrode structure of the sample Y1 was maintained at about 200 mAh/g under the sixth to fifteenth cycle.

As shown in the sixth diagram (B), it can be seen that the specific capacitance of the sample Y2 is significantly higher than the specific capacitance of the sample Y0 at a charge and discharge rate of 0.1 C in the first to tenth cycles, and The specific capacitance of the sample Y2 is less than 250 mAh/g.

As shown in the sixth diagram (C), it can be seen that the specific capacitance of the sample Y3 is significant at the charging rates of 0.1 C and 0.5 C in the 1st to 5th cycles and the 6th to 15th cycles, respectively. The ground capacitance is higher than the specific capacitance of the sample Y0, and the specific capacitance of the sample Y3 is stably maintained at or above 250 mAh/g. This result confirms that the electrode structure provided by the present invention simultaneously has an increase in specific capacitance and maintains the The effect of the stability of the specific capacitance, and the advantage of excellent electrical properties and the like at a higher charge and discharge rate.

In summary, in the cycle of multiple charging and discharging, the present invention is based on the cathode material in the electrode structure, compared to the secondary electrode, the fuel cell, or the original electrode structure in the solar cell. The electrode structure modified by the anode material or the metal electrode material or the configuration of the coating layer in the electrode structure (that is, the cathode structure, the anode structure or the metal electrode structure) has superior electrical performance. In particular, the secondary battery and the electrode structure in the fuel cell (that is, the cathode structure or the anode structure) can not only stably maintain a high specific capacitance, but also achieve a good cycle of multiple charging and discharging. performance.

Example

An electrode structure, the cross section of the electrode structure comprising: a substrate layer; a first coating layer on the substrate layer; a second coating layer on the first coating layer; a third The coating layer is located on the second coating layer, wherein the second coating layer is an organic material, and the third coating layer is an inorganic material and has a first thickness range of less than 10 nm.

2. The electrode structure of embodiment 1, wherein: the first coating layer is a cathode material, an anode material or a metal material, the cathode material is an oxide of a lithium ion metal, and the anode material Is a carbon material; the organic material includes an unsaturated alkyl compound, an aromatic ring compound, and an aromatic heterocyclic compound; and the inorganic material includes zirconium (Zr), aluminum (Al), tin (Sn), magnesium (Mg) An oxide of cerium (Si), titanium (Ti), zinc (Zn), lithium (Li), and boron (B).

3. The electrode structure according to any one of embodiments 1 to 2, wherein the unsaturated alkyl compound is poly(acetylene), PAC; the aromatic ring compound comprises poly(fluorene), poly Polyphenylenes, polypyrenes, polyazulenes, and polynaphthalenes; the aromatic heterocyclic compound includes a nitrogen-containing compound and a sulfur-containing compound, wherein the nitrogen-containing compound includes polypyrrole ( PPY), polycarbazoles, polyindoles, polyazepines, polyaniline (PANI), and the sulfur-containing compounds including poly(thiophene), PT, poly Oxyethylthiophene (poly(3,4-ethylenedioxythiophene, PEDOT), and poly(p-phenylene sulfide, PPS); and the organic material also includes pitch.

4. The electrode structure according to any one of embodiments 1 to 3, wherein: the first coating layer has a cathode material of 60 wt% to 95 wt%; and the second coating layer has a weight of 0.05 wt% to 5 wt%. The organic material; the third coating layer is 0.05% to 5% by weight of the inorganic material; the second coating layer has a second thickness ranging from 10 to 250 microns; and the second coating layer is the third The thickness ranges from 1 to 100 nm; and the fourth thickness of the third coating layer ranges from 0.5 to 10 nm.

5. An electrode structure comprising: a substrate layer; and a granular structure on the substrate layer, and the granular structure comprises: a core; a first coating layer covering the core; and a second a coating layer covering the first coating layer, wherein when the first coating layer is one of an inorganic material and an organic material, the second coating layer is the inorganic material and the organic material The other one.

6. The electrode structure of embodiment 5, wherein the first coating layer is a cathode material, an anode material or a metal material, the cathode material is an oxide of a lithium ion metal, and the anode material Is a carbon material; the organic material includes an unsaturated alkyl compound, an aromatic ring compound, and an aromatic heterocyclic compound; The inorganic material includes zirconium (Zr), aluminum (Al), tin (Sn), magnesium (Mg), cerium (Si), titanium (Ti), zinc (Zn), lithium (Li), and boron (B). Oxide.

7. The electrode structure of any of embodiments 5-6, wherein: when the first coating layer is an inorganic material and the second coating layer is an organic material: the material of the first coating layer and the a first ratio between the cathode materials, the first ratio being 0.1 wt% to 5 wt%; and a material between the material of the second coating layer and the material of the first coating layer covering the core a second ratio, the second ratio is 0.05 wt% to 1 wt%; and when the first coating layer is an organic material, the second coating layer is an inorganic material: a material of the first coating layer and Having a first ratio between the cathode materials, the first ratio is 0.05 wt% to 5 wt%; and a material between the material of the second coating layer and the material of the first coating layer covering the core The second ratio is 0.05% by weight to 5% by weight.

8. An electrode structure, the cross section of the electrode structure comprising: a substrate layer; a first coating layer on the substrate layer; a second coating layer on the first coating layer; a third a coating layer on the second coating layer, wherein when the second coating layer is one of an inorganic material and an organic material, one of the third coating layer and the first coating layer is The inorganic material and the other of the organic materials.

9. The electrode structure of embodiment 8, wherein the first coating layer, the second coating layer, and the third coating layer are parallel in the electrode structure, wherein when the second coating layer is An inorganic material and one has In one of the machine materials, the third coating layer is the other of the inorganic material and the organic material.

10. The electrode structure of any of embodiments 8-9, wherein: the third coating layer is a core, the first coating layer and the second coating layer respectively coat the core, and the cross section The method further includes: a fourth coating layer on the third coating layer and an extension of the second coating layer; and a fifth coating layer on the fourth coating layer, and An extension of the first coating layer, wherein the first coating layer, the second coating layer, and the third coating layer form a granular structure in the electrode structure, and when the second coating layer is a In the case of one of an inorganic material and an organic material, the first coating layer is one of the inorganic material and the organic material.

100,200‧‧‧electrode structure

101, 201‧‧‧ substrate layer

102, 103, 104, 20, 30, 202, L1~L5‧‧‧ coating layer

A‧‧‧ granular structure

Claims (10)

An electrode structure, the cross section of the electrode structure comprises: a substrate layer; a first coating layer on the substrate layer; a second coating layer on the first coating layer; a third coating And a layer on the second coating layer, wherein the second coating layer is an organic material, and the third coating layer is an inorganic material and has a first thickness range of less than 10 nm. The electrode structure according to claim 1, wherein the first coating layer is a cathode material, an anode material or a metal material, and the cathode material is a lithium ion metal oxide and the anode material. Is a carbon material; the organic material includes an unsaturated alkyl compound, an aromatic ring compound, and an aromatic heterocyclic compound; and the inorganic material includes zirconium (Zr), aluminum (Al), tin (Sn), magnesium (Mg) An oxide of cerium (Si), titanium (Ti), zinc (Zn), lithium (Li), and boron (B). The electrode structure according to claim 2, wherein the unsaturated alkyl compound is poly(acetylene), PAC; the aromatic ring compound comprises poly(fluorene), polycondensation Benzyl (Polyphenylenes), Polypyrenes, Polyazulenes, and Polynaphthalenes; the aromatic heterocyclic compound includes a nitrogen-containing compound and a sulfur-containing compound, wherein the nitrogen-containing compound includes polypyrrole (PPY) ), polycarbazoles, polyindoles, polyazepines, polyaniline (PANI), and the sulfur-containing compounds including polythiophenes Poly(thiophene)s, PT), poly(3,4-ethylenedioxythiophene, PEDOT), and poly(p-phenylene sulfide, PPS); and the organic material Also included is pitch. The electrode structure of claim 3, wherein: the first coating layer has 60% to 95% by weight of the cathode material; and the second coating layer has 0.05% to 5% by weight of the organic layer. a third coating layer having 0.05% to 5% by weight of the inorganic material; a second thickness of the first coating layer ranging from 10 to 250 microns; and a third thickness of the second coating layer The range is between 1 and 100 nm; and the fourth thickness of the third coating layer is between 0.5 and 10 nm. An electrode structure comprising: a substrate layer; and a granular structure on the substrate layer, and the granular structure comprises: a core; a first coating layer covering the core; and a second coating a layer covering the first coating layer, wherein when the first coating layer is one of an inorganic material and an organic material, the second coating layer is one of the inorganic material and the organic material One. The electrode structure of claim 4, wherein the first coating layer is a cathode material, an anode material or a metal material, and the cathode material is a lithium ion metal oxide and the anode material. Is a carbon material; The organic material includes an unsaturated alkyl compound, an aromatic ring compound, and an aromatic heterocyclic compound; and the inorganic material includes zirconium (Zr), aluminum (Al), tin (Sn), magnesium (Mg), cerium (Si), An oxide of titanium (Ti), zinc (Zn), lithium (Li), and boron (B). The electrode structure of claim 6, wherein when the first coating layer is an inorganic material and the second coating layer is an organic material: the material of the first coating layer and the cathode a first ratio between the materials, the first ratio being from 0.1 wt% to 5 wt%; and a second between the material of the second coating layer and the material of the first coating layer covering the core a ratio, the second ratio is 0.05 wt% to 1 wt%; and when the first coating layer is an organic material, the second coating layer is an inorganic material: the material of the first coating layer and the a first ratio between the cathode materials, the first ratio being 0.05 wt% to 5 wt%; and a material between the material of the second coating layer and the material of the first coating layer covering the core The second ratio is 0.05% by weight to 5% by weight. An electrode structure, the cross section of the electrode structure comprises: a substrate layer; a first coating layer on the substrate layer; a second coating layer on the first coating layer; a third coating a layer on the second coating layer, wherein when the second coating layer is one of an inorganic material and an organic material, the third coating layer and one of the first coating layers are the inorganic The material and the other of the organic materials. The electrode structure of claim 8, wherein the first coating layer, the second coating layer, and the third coating layer are parallel in the electrode structure, wherein the second coating layer When it is one of an inorganic material and an organic material, the third coating layer is one of the inorganic material and the organic material. The electrode structure of claim 8, wherein the third coating layer is a core, the first coating layer and the second coating layer respectively coat the core, and the cross section is further The method includes a fourth coating layer on the third coating layer and an extension of the second coating layer, and a fifth coating layer on the fourth coating layer, and is An extension of the first coating layer, wherein the first coating layer, the second coating layer, and the third coating layer form a granular structure in the electrode structure, and when the second coating layer is an inorganic In the case of one of the material and an organic material, the first coating layer is one of the inorganic material and the organic material.