CN110783556A - Composite three-dimensional composite structure film and preparation method and application thereof - Google Patents
Composite three-dimensional composite structure film and preparation method and application thereof Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
The invention provides an energy storage film with a three-dimensional composite structure and a preparation method and application thereof. The preparation method of the composite three-dimensional structure film comprises the following steps: co-sputtering the silicon target material and the conductive lithium ion carrier metal target material in an inert atmosphere to grow a three-dimensional composite structure film on the substrate. The three-dimensional composite structure film grown by the preparation method of the three-dimensional composite structure film has the characteristics of more contact interfaces and small interface resistance, and the formed interface can absorb the falling of the film formed in the point release process caused by the volume expansion of the silicon material formed in the charging process, so that the stress of periodic volume change is reduced, and the structural stability in the lithium ion embedding/extracting process is maintained. In addition, the preparation method effectively ensures that the electrochemical performance of the grown composite three-dimensional structure film is stable.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a three-dimensional composite structure film and a preparation method and application thereof.
Background
Currently, lithium ion batteries are widely used, mainly because of their excellent characteristics of high energy density, high power density, good cycle performance, environmental friendliness, and diversified structure. In the development demand of lithium ion power batteries, the negative electrode material is required to have the characteristics of high capacity, long service life, high first efficiency, rapid charge and discharge and the like. The theoretical capacity of the existing graphite cathode material is 372mAh/g, wherein the commercial graphite cathode product reaches about 350mAh/g, and basically no promotion space exists. The theoretical capacity of silicon as the lithium ion battery negative electrode material can reach about 4200mAh/g, and the silicon is rich in the earth crust and is second to oxygen, so the silicon-based lithium ion battery negative electrode material becomes a research hotspot. However, the silicon material has a huge volume effect of about 300% in the lithium storage process, which causes the active material to expand and crack, and to be pulverized and fall off from the current collector, and then to lose activity; in addition, the silicon semiconductor material has poor conductivity, and the time required for electrons to migrate from silicon to a current collector is long, so that the electrons in the silicon are difficult to migrate during large-current charging and discharging, namely, the multiplying power performance of the silicon cathode material is poor.
In the process of lithium intercalation and deintercalation of the silicon film, volume expansion is mainly carried out along the direction vertical to the film, and compared with bulk silicon, the volume effect of the silicon can be effectively inhibited. The thickness of the silicon thin film greatly affects the electrochemical performance of the electrode material, and as the thickness increases, the deintercalation process of lithium ions is inhibited, and the cycle performance is deteriorated.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a composite three-dimensional composite structure film and a preparation method thereof, which aim to solve the problem that the existing silicon film is almost used in a load mode when being used as a negative electrode material, so that the volume expansion is caused during charging and discharging, and the film falls off from a current collector.
The invention also aims to provide an electrode plate and an application of the electrode plate, so as to solve the technical problems that the existing electrode plate containing silicon has poor electrochemical properties such as poor conductivity and the like because silicon is a semiconductor material.
In order to achieve the object of the present invention, in one aspect of the present invention, a method for preparing a three-dimensional composite structure thin film is provided. The preparation method of the three-dimensional composite structure film comprises the following steps:
co-sputtering the silicon target material and the conductive lithium ion carrier metal target material in inert atmosphere to grow a three-dimensional composite structure film on the substrate.
In another aspect of the present invention, a three-dimensional composite structural film is provided. The three-dimensional composite structure film is formed by the growth of the preparation method of the three-dimensional composite structure film.
In yet another aspect of the present invention, an electrode sheet is provided. The electrode plate comprises a current collector, wherein a three-dimensional composite structure film is also combined on the surface of the current collector, and the three-dimensional composite structure film is formed by growing on the current collector according to the preparation method disclosed by the invention.
In still another aspect of the present invention, there is provided an application of the electrode sheet of the present invention. The electrode plate is applied to the preparation of lithium ion batteries or super capacitors.
Compared with the prior art, the preparation method of the three-dimensional composite structure film directly adopts the radio frequency power supply magnetron co-sputtering method to deposit and form the silicon target material and the conductive lithium ion carrier metal target material. Thus, the nanoscale conductive lithium ion carrier metal element and silicon form a three-dimensional structure, so that a larger surface area for accommodating lithium ions is formed in the three-dimensional composite structure film, and the three-dimensional composite structure film is endowed with the characteristic of small interface resistance. And after the three-dimensional composite structure film is used as a negative electrode film layer, the conductive lithium ion carrier metal contained in the three-dimensional composite structure film can increase the conductivity, effectively reduce the direct contact between the electrolyte and silicon, reduce and prevent irreversible side reactions between the electrolyte and the silicon, reduce the generation of a Solid Electrolyte Interface (SEI), absorb the volume expansion generated by the silicon during charge and discharge, reduce the stress of periodic volume change and maintain the structural stability in the lithium ion intercalation/deintercalation process. In addition, the co-sputtering method is adopted to grow and form the film layer, the conditions are easy to control, the chemical property stability of the grown three-dimensional composite structure film is effectively ensured, the three-dimensional composite structure film is endowed with good high-rate performance, good safety performance and high efficiency, and the method is suitable for industrial large-scale production.
Therefore, the three-dimensional composite structure film has small interfacial resistance, the formed three-dimensional composite structure can effectively prevent the direct contact of the electrolyte and silicon, reduce and prevent irreversible side reactions between the electrolyte and the silicon, reduce the generation of a Solid Electrolyte Interface (SEI), enhance the conductivity, absorb the volume expansion generated during the charge and discharge of the silicon, then relieve the stress of periodic volume change, and simultaneously maintain the structural stability in the lithium ion intercalation/deintercalation process.
The electrode plate of the invention is formed by directly growing a three-dimensional composite structure film on the current collector by using the preparation method of the invention. Therefore, the electrode sheet has low internal resistance, and the contained three-dimensional composite structure film can effectively prevent the direct contact of the electrolyte and silicon, reduce and prevent the irreversible side reaction between the electrolyte and the silicon, reduce the generation of a Solid Electrolyte Interface (SEI), enhance the conductivity, absorb the volume expansion generated during the charge and discharge of the silicon, then relieve the stress of the periodic volume change, and simultaneously maintain the structural stability in the lithium ion intercalation/deintercalation process.
Because the electrode plate has the advantages, the lithium ion battery containing the electrode plate has high lithium ion conduction rate, high structural stability and high capacity retention rate, the lithium ion battery has high first charge-discharge efficiency, the lithium ion battery or the super capacitor has good cycle performance, the cycle life is prolonged, and the safety performance is high. The super capacitor containing the electrode slice has small internal resistance, fast charge and discharge and excellent energy storage performance.
Drawings
FIG. 1 is a comparative graph of the charging and discharging curves at 150mA/g of lithium ion batteries of thin film electrode materials provided by the seventh embodiment of the present invention and the second comparative example;
fig. 2 is a charge-discharge curve diagram of the first, 50 th and 100 th circles of a lithium ion battery containing a three-dimensional composite structure thin-film electrode material according to a seventh embodiment of the present invention at 150 mA/g;
FIG. 3 is a comparative graph of the first charging and discharging curves at 150mA/g of a lithium ion battery containing a three-dimensional composite structure thin film electrode material provided in the eight, nine, ten, eleven and twelve embodiments of the present invention; wherein, the curve 1 is a first charge-discharge curve of the lithium ion battery obtained in the eighth embodiment, the curve 2 is a first charge-discharge curve of the three-dimensional composite structure film electrode material obtained in the ninth embodiment, the curve 3 is a first charge-discharge curve of the lithium ion battery obtained in the tenth embodiment, the curve 4 is a first charge-discharge curve 1 of the lithium ion battery obtained in the eleventh embodiment, and the curve 5 is a first charge-discharge curve of the lithium ion battery obtained in the twelfth embodiment;
FIG. 4 is a 3000mA/g cycle performance diagram of a lithium ion battery containing a three-dimensional composite structure thin-film electrode material obtained in the seventh embodiment of the invention;
FIG. 5 is a coulombic efficiency chart of 3000mA/g lithium ion battery containing the three-dimensional composite structure thin-film electrode material obtained in the seventh embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, embodiments of the present invention provide a method for preparing a three-dimensional composite structure film. The preparation method of the three-dimensional composite structure film comprises the following steps:
co-sputtering the silicon target material and the conductive lithium ion carrier metal target material in inert atmosphere to grow a three-dimensional composite structure film on the substrate.
In the co-sputtering process, the conductive lithium ion carrier metal element is used for doping silicon, so that a film layer which takes silicon as a main body and takes the conductive lithium ion carrier metal as a doping element grows on a substrate, and a larger surface area is formed in the three-dimensional composite structure film for accommodating lithium ions, so that the interface resistance of the three-dimensional composite structure film is remarkably reduced. Meanwhile, the three-dimensional structure formed by the electrolyte can effectively prevent the electrolyte from directly contacting with silicon, so that irreversible side reactions between the electrolyte and the silicon can be reduced and prevented, the generation of a Solid Electrolyte Interphase (SEI) is reduced, the conductivity is enhanced, the volume expansion generated during the charge and discharge of the silicon is absorbed, the stress of periodic volume change is reduced, and the structural stability in the lithium ion intercalation/deintercalation process is maintained. Therefore, in an embodiment, the conductive lithium ion carrier metal target material includes at least one elemental target or alloy target of gold, silver, aluminum, cobalt, manganese, molybdenum, tin and vanadium or at least one compound target of gold, silver, aluminum, cobalt, manganese, molybdenum, tin and vanadium. The compound target may be at least one of compounds such as aluminum oxide, silver oxide, cobalt oxide, and the like. In a specific embodiment, each target should be a high purity target material, such as a corresponding ceramic target material with a purity of 99.99%. The elements contained in the conductive lithium ion carrier metal target material have the characteristics of high conductivity and lithium ion passing permission, and can form a larger surface area for accommodating lithium ions, so that the internal resistance of the three-dimensional composite structure film is remarkably reduced, and the stability of electrochemical reaction is high under the action of a three-dimensional structure.
In one embodiment, the sputtering power of the co-sputtering process satisfies: the ratio of the power for sputtering the silicon target material to the power for sputtering the high-conductivity lithium ion carrier metal target material is 8: 1-1: 1. The doping content of the high-conductivity lithium ion carrier metal element in the three-dimensional composite structure film in the silicon substrate is controlled by controlling the sputtering power ratio of the two targets, namely, the internal resistance and the corresponding electrochemical performance of the three-dimensional composite structure film are optimized indirectly by optimizing the doping content of the high-conductivity lithium ion carrier metal.
In another embodiment, the temperature of the substrate is controlled to be in the range of 100 ℃ to 800 ℃ during the co-sputtering process. In an embodiment, the inert atmosphere may also be referred to as a mixed atmosphere of at least one or more of nitrogen, argon, and ammonia, and in a further embodiment, oxygen may be mixed in the inert atmosphere. Oxygen is mixed in the inert atmosphere, partial silicon is oxidized and reduced to form silicon monoxide during sputtering of the silicon, a composite film of the silicon and the silicon monoxide is formed, and the performance of the three-dimensional composite structure film formed by the conductive lithium ion carrier target material is excellent. When two or more gases are used, the volume ratio of the mixed gas can be adjusted as required. Wherein, the nitrogen, argon, oxygen and ammonia can be 99.998% pure. The spacing between the substrate and the target is preferably 30-90mm, in particular 50 mm. The quality of the grown composite three-dimensional composite structure film is ensured and improved by controlling the temperature of the matrix and the high-purity atmosphere environment, so that the electrochemical performance of the composite three-dimensional composite structure film is ensured and improved.
In addition, under the conditions of the co-sputtering process described above, the sputtering time can be controlled to control the thickness of the grown three-dimensional composite structure film, such as but not limited to 0.1-10 μm, specifically such as 1 μm.
The silicon target material in each embodiment of the preparation method can be directly used as an existing silicon ceramic target material. A single crystal silicon wafer or a pressed target of silicon powder may also be used.
In an embodiment, the substrate in each of the above embodiments is a negative electrode current collector of a chemical power source. In a particular embodiment, the substrate may be a copper foil.
Therefore, the preparation method of the three-dimensional composite structure film directly adopts the radio frequency magnetron co-sputtering method to deposit and form the silicon target material and the high-conductivity lithium ion carrier metal target material. Thus, the three-dimensional composite structure film which is deposited and grown takes silicon as a main body, and the nanometer level high-conductivity lithium ion carrier metal element as a doping element is doped in the silicon as the main body, so that a larger surface area is formed in the three-dimensional composite structure film for accommodating lithium ions, and the three-dimensional composite structure film has the characteristic of small interface resistance and can well play the high-conductivity characteristic of high-conductivity lithium ion carriers such as aluminum, silver and the like. The three-dimensional composite structure film with the characteristics can effectively prevent the direct contact of electrolyte and silicon, reduce and prevent irreversible side reactions between the electrolyte and a silicon main body, reduce the generation of a Solid Electrolyte Interphase (SEI), and simultaneously, the formed three-dimensional structure can also absorb the volume expansion generated by the silicon during charging and discharging, lighten the stress of periodic volume change, keep the structural stability in the lithium ion embedding/removing process, and meanwhile, the grown three-dimensional composite structure film has good large rate performance and good safety performance. And the preparation method adopts a co-sputtering method to grow and form the film layer, the conditions are easy to control, the chemical property of the grown three-dimensional composite structure film is effectively ensured to be stable, the efficiency is high, and the preparation method is suitable for industrial large-scale production.
Correspondingly, based on the preparation method of the three-dimensional composite structure film, the embodiment of the invention also provides the three-dimensional composite structure film. Since the three-dimensional composite structure film is produced by the above-described production method of a three-dimensional composite structure film, the three-dimensional composite structure film has the characteristics as described above: the interface resistance is small, and the conductivity is good; the characteristic three-dimensional composite structure film can effectively prevent the electrolyte from directly contacting with silicon main body elements, can reduce and prevent irreversible side reactions between the electrolyte and the silicon main body, and reduce the generation of a Solid Electrolyte Interphase (SEI), and the formed three-dimensional structure can also absorb the volume expansion generated by silicon during charging and discharging, so that the stress of periodic volume change is reduced, the structural stability in the lithium ion embedding/removing process is maintained, and meanwhile, the grown three-dimensional composite structure film has good large rate performance and good safety performance.
On the other hand, the embodiment of the invention also provides an electrode plate. The electrode plate comprises a current collector, wherein a three-dimensional composite structure film is further combined on the surface of the current collector, and the three-dimensional composite structure film is formed by growing on the current collector according to the preparation method. Among them, the current collector is preferably a negative electrode current collector due to the three-dimensional composite structure thin film grown according to the above-described preparation method. Such as copper foil, but not exclusively. The grown composite three-dimensional composite structure film may be, but is not limited to, controlled to 0.1 to 10 μm, specifically, 1 μm. Therefore, the electrode plate has small internal resistance, and the contained three-dimensional composite structure film can effectively prevent the direct contact of the electrolyte and the nanometer level high-conductivity lithium ion carrier metal elements, reduce and prevent the irreversible side reaction between the electrolyte and the silicon main body, reduce the generation of a Solid Electrolyte Interface (SEI), absorb the volume expansion generated during the charge and discharge of silicon, then relieve the stress of the periodic volume change, and simultaneously keep the structural stability in the lithium ion insertion/extraction process.
The electrode plate provided by the embodiment of the invention has the advantages, so that the electrode plate is applied to the preparation of a lithium ion battery or a super capacitor. When the electrode sheet is used in a lithium ion battery, the lithium ion battery naturally includes necessary components, such as a cell formed of a positive electrode, a negative electrode, and a separator. Wherein the negative electrode is the electrode sheet described above. The other components may be conventional components contained in conventional lithium ion batteries. Therefore, the lithium ion battery has high first charge-discharge efficiency and good cycle performance, the cycle life is prolonged, and the safety performance is high. When the electrode sheet is applied to a supercapacitor, the supercapacitor naturally includes necessary components, such as electrode sheets, which are the electrode sheets described above. Therefore, the super capacitor has small internal resistance, quick charge and discharge, excellent energy storage performance, good cycle performance, long cycle life and high safety performance.
The three-dimensional composite structure film of the embodiment of the invention, the preparation method and the application thereof, etc. are illustrated by a plurality of specific examples.
Example one
The embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
s11: using a monocrystalline silicon wafer and a commercially available aluminum ceramic target with a purity of 99.99% as a sputtering source, and coating the substrate and the sputtering source on a copper foilThe target distance is 50mm and is 1.0X 10
-2In a high purity argon atmosphere in mbar, with Si: preparing a Si-Al composite film with the thickness of 0.1 mu m by an Al-4: 1 power ratio co-sputtering method; during deposition, the substrate was maintained at 300 ℃.
Example two
The embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
s11: using monocrystalline silicon wafer with (100) crystal face and manganese ceramic target with purity of 99.99% as sputtering source, and placing the substrate and target on copper foil at a distance of 50mm and 1.0 × 10
-2In a high purity argon atmosphere in mbar, with Si: preparing a Si-Mn composite film with the thickness of 0.8 mu m by a power ratio co-sputtering method with Mn being 2: 1; during deposition, the substrate was maintained at 400 ℃.
EXAMPLE III
The embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to the method comprising the following steps:
s11: using monocrystalline silicon wafer and tin ceramic target with purity of 99.999% as sputtering source, and placing the substrate and target on copper foil at a distance of 50mm of 1.0 × 10
-2In a high purity argon atmosphere in mbar, with Si: preparing a Si-Sn composite film with the thickness of 0.6 mu m by a power ratio co-sputtering method with Sn being 6: 1; during deposition, the substrate was maintained at 300 ℃.
Example four
The embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
s11: using monocrystalline silicon wafer and purchased cobalt ceramic target with purity of 99.999% as sputtering source, and placing the substrate and target on copper foil at a distance of 50mm of 1.0 × 10
-2In a high purity argon atmosphere in mbar, with Si: preparing a Si-Co composite film with the thickness of 0.5 mu m by a Co-sputtering method with the power ratio of 8: 1; during deposition, the substrate was maintained at 600 ℃.
EXAMPLE five
The embodiment provides a three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to the method comprising the following steps:
s11: using single crystal silicon wafer and molybdenum ceramic target with purity of 99.999% as sputtering source, and placing the substrate and target on copper foil at a distance of 50mm of 1.0 × 10
-2In a high purity argon atmosphere in mbar, with Si: preparing a Si-Mo composite film with the thickness of 2 mu m by a power ratio co-sputtering method of Mo being 5: 1; during deposition, the substrate was maintained at 500 ℃.
EXAMPLE six
The embodiment one provides a complex three-dimensional composite structure film and a preparation method thereof. The three-dimensional composite structure film is prepared according to a method comprising the following steps:
s11: using monocrystalline silicon wafer and purchased vanadium ceramic target with purity of 99.999% as sputtering source, and placing the substrate and target on copper foil at a distance of 50mm of 1.0 × 10
-2In a high purity argon atmosphere in mbar, with Si: preparing a Si-V composite film with the thickness of 5 mu m by a power ratio co-sputtering method of V-4: 1; during deposition, the substrate was maintained at 700 ℃.
Comparative example 1
The first embodiment provides a silicon thin film and a preparation method thereof. The silicon thin film is prepared according to a method comprising the following steps:
s11: using single crystal silicon wafer as sputtering source, the substrate target distance is 50mm and 1.0 × 10 mm on Japanese 304 stainless steel substrate
-2In a high-purity argon atmosphere of millibar, a Si film with the thickness of 0.1 mu m is prepared by sputtering; during deposition, the substrate was maintained at 300 ℃.
Examples seven to twelve and comparative example two
The copper foil substrate containing the three-dimensional composite structure film provided in each of the first to sixth examples is used as a negative electrode, and the copper foil containing the three-dimensional composite structure film provided in the comparative example is used as a negative electrode, and the lithium ion battery is assembled by the following methods:
a button cell is assembled by using a lithium sheet as a film electrode, an electrolyte concentration of 1mol/L and a propylene microporous film as a diaphragm of the cell in a glove box filled with argon.
Each lithium ion battery was subjected to the following relevant electrochemical test conditions: the charge-discharge voltage is 0.01V-3V.
Relevant electrochemical test results for each lithium ion battery:
the first discharge specific capacity of the lithium ion battery provided in the seventh embodiment is 1210mah/g and the charge specific capacity is 1198mah/g at a rate of 150mA/g, as shown in fig. 1. In addition, the charging and discharging curves of the first turn, the 50 th turn and the 100 th turn of the lithium ion battery provided by the seventh embodiment at 150mA/g are shown in fig. 2. The cycle performance curve at 3000mA/g is shown in FIG. 4, and the coulombic efficiency curve at 3000mA/g is shown in FIG. 5.
The lithium ion battery provided in the eighth embodiment has a first discharge specific capacity of 2916mah/g and a discharge specific capacity of 3005mah/g at a rate of 150 mA/g.
In the case of the lithium ion battery provided in the ninth embodiment, the first discharge specific capacity is 3237mah/g and the discharge specific capacity is 3239mah/g at a rate of 150 mA/g.
The first discharge specific capacity of the lithium ion battery provided in the tenth embodiment is 2855mah/g and 2880mah/g at a rate of 150 mA/g.
The first discharge specific capacity of the lithium ion battery provided in the eleventh embodiment is 2718mah/g and 2774mah/g at a rate of 150 mA/g.
The first discharge specific capacity of the lithium ion battery provided in the twelfth embodiment is 3071mah/g and 3131mah/g at a rate of 150 mA/g.
When the lithium ion battery provided by the comparative example II is at the rate of 150mA/g, the first discharge specific capacity is 1637mah/g, and the discharge specific capacity is 1684mah/g, as shown in figure 1.
In addition, the first charge and discharge curve of the lithium ion battery provided in the eight to twelve examples at 150mA/g is shown in fig. 3.
The charge and discharge performance of the lithium ion batteries provided in the seventh to twelfth embodiments and the lithium ion battery provided in the second comparative example are compared, and the lithium ion batteries containing the composite three-dimensional composite structure films provided in the first to sixth embodiments are obviously superior to the single-pure-silicon negative electrode lithium ion battery. Therefore, the relevant electrochemical test results of the lithium ion batteries show that the lithium ion batteries have high first charge and discharge efficiency, good cycle performance and stable charge and discharge performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of a three-dimensional composite structure film is characterized by comprising the following steps:
co-sputtering the silicon target material and the conductive lithium ion carrier metal target material in inert atmosphere to grow a three-dimensional composite structure film on the substrate.
2. The method of claim 1, wherein: the conductive lithium ion carrier metal target comprises at least one simple substance target or alloy target of gold, silver, aluminum, cobalt, manganese, molybdenum, tin and vanadium or at least one compound target of gold, silver, aluminum, cobalt, manganese, molybdenum, tin and vanadium;
the sputtering power of the co-sputtering treatment satisfies the following conditions: the ratio of the power for sputtering the silicon target material to the power for sputtering the high-conductivity lithium ion carrier metal target material is 8: 1-1: 1.
3. The method of claim 1, wherein: in the co-sputtering treatment process, the temperature of the matrix is controlled to be 100-800 ℃;
the inert atmosphere is at least one or a mixture of nitrogen, argon and ammonia.
4. The production method according to any one of claims 1 to 3, characterized in that: the silicon target is a silicon wafer or a pressed target of silicon powder.
5. The production method according to any one of claims 1 to 3 and 5, wherein: the substrate is a chemical power supply negative current collector.
6. A three-dimensional composite structural film characterized by: the three-dimensional composite structure film is grown according to the production method described in any one of claims 1 to 5.
7. An electrode slice, includes the mass flow body, its characterized in that: a composite three-dimensional composite structure film is combined on the surface of the current collector, and the three-dimensional composite structure film is grown on the current collector according to the preparation method of any one of claims 1 to 5.
8. The electrode sheet of claim 7, wherein: the thickness of the composite three-dimensional composite structure film is 0.1-10 mu m.
9. Use of an electrode sheet according to claim 7 or 8 in a lithium ion battery or supercapacitor.
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| CN111487465A (en) * | 2020-03-25 | 2020-08-04 | 桂林电子科技大学 | Probe spacing calibration method and contact resistivity and interface resistivity testing method |
| WO2022099595A1 (en) * | 2020-11-13 | 2022-05-19 | 桂林电子科技大学 | Composite silicon monoxide thin film, preparation method therefor and use thereof |
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| CN111487465A (en) * | 2020-03-25 | 2020-08-04 | 桂林电子科技大学 | Probe spacing calibration method and contact resistivity and interface resistivity testing method |
| WO2022099595A1 (en) * | 2020-11-13 | 2022-05-19 | 桂林电子科技大学 | Composite silicon monoxide thin film, preparation method therefor and use thereof |
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