CN114141997A - Carbon-coated silicon-containing sphere and preparation method and application thereof - Google Patents

Carbon-coated silicon-containing sphere and preparation method and application thereof Download PDF

Info

Publication number
CN114141997A
CN114141997A CN202111187627.9A CN202111187627A CN114141997A CN 114141997 A CN114141997 A CN 114141997A CN 202111187627 A CN202111187627 A CN 202111187627A CN 114141997 A CN114141997 A CN 114141997A
Authority
CN
China
Prior art keywords
silicon
carbon
layer
coating layer
carbon coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111187627.9A
Other languages
Chinese (zh)
Other versions
CN114141997B (en
Inventor
张艳芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vitalink Industry Shenzhen Co ltd
Original Assignee
Vitalink Industry Shenzhen Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vitalink Industry Shenzhen Co ltd filed Critical Vitalink Industry Shenzhen Co ltd
Priority to CN202111187627.9A priority Critical patent/CN114141997B/en
Publication of CN114141997A publication Critical patent/CN114141997A/en
Application granted granted Critical
Publication of CN114141997B publication Critical patent/CN114141997B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a carbon-coated silicon-containing sphere and a preparation method and application thereof. The preparation method comprises the following steps: providing a substrate and a micro-nano texture template with a micro-nano hemispherical structure, wherein the spherical radius is R; applying transfer printing glue on a base material, transferring, and curing to prepare a first intermediate with a micro-nano-sized hemispherical structure; preparing a first carbon coating layer on the first intermediate body in a profiling deposition mode, wherein the thickness of the first carbon coating layer is S1; profiling and depositing a silicon layer on the first carbon coating layer, wherein the thickness of the silicon layer is more than or equal to (2R-S1); preparing a protective adhesive layer with a plane surface on the silicon layer by using protective adhesive; etching the protective glue layer and the silicon layer by using an etching plasma source, wherein the etching thickness of the silicon layer is 2R, and preparing a silicon-containing sphere; a second carbon coating layer is deposited on the surface of the silicon-containing spheres that is not coated with a carbon coating layer to a thickness of S2. The method is easy to operate, low in cost and applicable to mass application, the structural stability and the energy density of the silicon material can be improved, and the charging and discharging stable times of the battery can be prolonged.

Description

Carbon-coated silicon-containing sphere and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a carbon-coated silicon-containing sphere and a preparation method and application thereof.
Background
In recent years, in order to meet the requirements of rapid development of new energy automobiles, smart power grids, distributed energy storage and the like, development of lithium ion batteries with high energy density, high safety and long cycle life becomes a research hotspot in the current energy storage field. The improvement of the energy density of the battery mainly depends on the development of key electrode materials, such as the continuous improvement of the capacities of positive and negative electrode materials. The conventional lithium ion battery cathode is close to the limit, and in order to meet the energy requirement of a new generation and improve the energy density of the battery, the development of a novel lithium battery cathode technology is urgent.
The lithium storage theoretical capacity of silicon is more than 10 times of the capacity of graphite, can reach 4200mAh/g, and belongs to an electrode material with high energy density. In addition, the safety performance of silicon is superior to that of a graphite cathode material, because the voltage platform of silicon is higher than that of graphite, lithium is not easy to precipitate on the surface of silicon in the charging and discharging process, and therefore the safety of the battery is improved. Meanwhile, as one of the most abundant elements in the nature, the silicon has wide sources and low manufacturing cost.
However, the structure of the existing nano silicon powder is easy to collapse, and the cycle number and the energy density stability are influenced. How to increase the energy density of the silicon-containing material and improve the structural stability thereof, and improve the effectiveness and the effective charge and discharge times is a difficult problem which needs to be solved urgently in the field.
Disclosure of Invention
In view of the above, the present invention provides a method for increasing the energy density of a silicon-containing material and improving the structural stability thereof.
The technical scheme is as follows:
a preparation method of a carbon-coated silicon-containing sphere comprises the following steps:
providing a substrate and a micro-nano texture template with a micro-nano sized hemispherical structure surface, wherein the radius of the hemispherical structure is R;
applying a transfer glue on the substrate;
applying the micro-nano texture template on the transfer printing glue, preparing a transition glue layer through curing, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure;
preparing a first carbon coating layer by profiling deposition on the surface of the first intermediate with the micro-nano hemispherical structure by adopting a first carbon source, wherein the thickness of the first carbon coating layer is S1;
profiling and depositing a silicon layer on the first carbon coating layer by adopting a silicon source, wherein the thickness of the silicon layer is more than or equal to (2R-S1);
preparing a protective adhesive layer with a plane surface on the silicon layer by using protective adhesive;
performing plasma equivalent etching on the protective adhesive layer by using a first etching plasma source, and etching the silicon layer and the rest protective adhesive layer by using a second etching plasma source when the convex part of the silicon layer is exposed, wherein the etching thickness of the silicon layer is 2R, so as to prepare the silicon-containing sphere;
depositing a second carbon coating layer on the surface of the silicon-containing sphere not coated by the carbon coating layer by using a second carbon source, wherein the thickness of the second carbon coating layer is S2, and the first carbon coating layer and the second carbon coating layer are combined to form the carbon coating layer.
In one embodiment, the first carbon coating layer and the second carbon coating layer each independently have a thickness of 0.1nm to 300 nm.
In one embodiment, R is 0.1nm to 600nm, and the thickness of the silicon layer is 0.1nm to 1500 nm.
In one embodiment, the first carbon cladding layer and the second carbon cladding layer are each independently one or more layers.
In one embodiment, the first carbon coating layer and the second carbon coating layer are made of at least one of carbon fiber, composite fiber, graphene and carbon.
In one embodiment, the silicon source is at least one of silicon, silicon oxide and silicon-carbon mixture.
In one embodiment, the patterned deposition is chemical deposition, chemical vapor deposition, sputtering, evaporation or DLC, spray coating, or curtain coating.
In one embodiment, before the first carbon coating layer is prepared, a transition separation layer is prepared by performing profiling deposition on the surface of the first intermediate with the micro-nano-sized hemispherical structure by using a functional material, and then the first carbon coating layer is prepared by performing profiling deposition on the transition separation layer by using the first carbon source.
In one embodiment, the functional material is selected from materials with contact angles of 80-130 degrees, or water-soluble materials, or oil-soluble materials, or vibration separation materials, or thermal volatilization materials, or thermal decomposition materials, or hydrolysis materials, or oil decomposition materials.
In one embodiment, the material with the contact angle of 80-130 degrees is selected from fluorine-containing compounds; the water-soluble material is selected from organic water-soluble substances or inorganic water-soluble substances, or a mixture of the two substances; the oil-soluble material is selected from oil-soluble resins; the vibration separating material is selected from ultrasonic vibration or mechanical vibration; the thermally volatile material is selected from low boiling point material organic materials; the thermal decomposition material is selected from easily decomposed organic materials; the hydrolytic material is selected from organic water hydrolysate or inorganic water hydrolysate or a mixture of the organic water hydrolysate and the inorganic water hydrolysate; or the oleolytic material is selected from oleolytic resin material.
In one embodiment, the method for preparing the carbon-coated silicon-containing sphere further comprises the following steps:
separating the carbon-coated silicon-containing spheres from the first intermediate, and sieving the carbon-coated silicon-containing spheres.
In one embodiment, the carbon-coated silicon-containing spheres are separated from the first intermediate by at least one of water phase separation, oil phase separation, thermal separation, exfoliation, and vibratory separation.
In one embodiment, the etching operation is performed in a vacuum environment.
In one embodiment, the protective glue is water-soluble resin, oil-soluble resin, water-soluble inorganic substance or mixture.
In one embodiment, the main material of the protective adhesive comprises at least one of UV photo-initiation resin such as epoxy acrylate, amino acrylate, polyether resin, acrylic resin, unsaturated polyester, alcohol compound, cationic resin, epoxy resin, silicone resin, etc.
In one embodiment, the protective gel further comprises an initiator.
In one embodiment, the first etching plasma source and the second etching plasma source are each independently selected from at least one of an oxygen-containing plasma source, a fluorine-containing plasma source, and a chlorine-containing plasma source.
The invention also provides a carbon-coated silicon-containing sphere prepared by the preparation method of the carbon-coated silicon-containing sphere.
The invention also provides an electrode comprising the carbon-coated silicon-containing spheres as described above.
The invention also provides a battery comprising an electrode as described above.
The invention has the following beneficial effects:
the preparation method of the carbon-coated silicon-containing sphere mainly comprises the steps of preparing a transition adhesive layer containing a micro-nano structure through transfer printing and curing, then profiling and depositing the carbon coating layer, the silicon layer and the protective adhesive layer, etching the silicon layer and the protective adhesive layer, preparing the other part of the carbon coating layer and completely coating the silicon-containing sphere, and has the advantages of simplicity in operation, material saving, low cost, long acting and large-batch application. And the structural stability and energy density of the silicon material can be remarkably improved, and if the carbon-coated silicon-containing sphere provided by the invention is used for preparing a negative electrode, the charging and discharging stable times of the battery can be remarkably prolonged, and the battery performance can be improved.
Drawings
Fig. 1 is a flow chart of a method for preparing a carbon-coated silicon-containing sphere according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of elements in a process of preparing a carbon-coated silicon-containing sphere according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It should be noted that in the description of the present invention, for the terms of orientation, there are terms such as "central", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise" and the like indicating the orientation and positional relationship based on the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and should not be construed as limiting the specific scope of the present invention.
In describing positional relationships, unless otherwise specified, when an element such as a layer, film or substrate is referred to as being "on" another layer, it can be directly on the other layer or intervening layers may also be present. Further, when a layer is referred to as being "under" another layer, it can be directly under, or one or more intervening layers may also be present. It will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
In the present invention, a plurality of times means at least one time.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
Furthermore, the drawings are not 1: 1 and the relative dimensions of the various elements in the figures are drawn for illustrative purposes only to facilitate understanding of the invention and are not necessarily drawn to scale, and are not to scale.
In the invention, the micro-nano size is 0.1nm to 3000 nm.
In the invention, the micro-nano structure, the micro-nano texture and the micro-nano spherical structure have the same meaning.
In the invention, profiling deposition refers to depositing a film layer on the surface of the micro-nano texture in an undulated manner according to the shape, and the contact surface of the film layer and the micro-nano topography is similar to the micro-nano topography so as to form a coating layer similar to the micro-nano topography.
In the invention, the thickness refers to the thickness of the micro-nano texture and the deposition thickness of the coating.
In the present invention, the first intermediate refers to the whole including the base material and the transition rubber layer.
Referring to fig. 1, the preparation method of a carbon-coated silicon-containing sphere provided by the invention, the carbon-coated silicon-containing sphere comprises a silicon-containing sphere and a carbon coating layer coated on the surface of the silicon sphere, and comprises the following steps:
s10, providing a substrate and a micro-nano texture template with a micro-nano hemispherical structure surface, wherein the radius of the hemispherical structure is R;
s20, applying a transfer glue on the base material;
s30, applying the micro-nano texture template on the transfer glue, preparing a transition glue layer through curing, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure;
s40, preparing a first carbon coating layer with the thickness of S1 by copying and depositing a first carbon source on the surface of the first intermediate with the micro-nano hemispherical structure;
s50, profiling and depositing a first silicon layer on the first carbon cladding layer by adopting a silicon source, wherein the thickness of the first silicon layer is more than or equal to (2R-S1);
s60, preparing a protective adhesive layer with a plane surface on the first silicon layer by using protective adhesive;
s70, performing plasma equivalent etching on the protective glue layer by adopting a first etching plasma source, and etching the silicon layer and the rest protective glue layer by adopting a second etching plasma source when the convex part of the silicon layer is exposed, wherein the etching thickness of the silicon layer is 2R, so as to prepare the silicon-containing sphere;
s80, depositing a second carbon coating layer on the surface of the silicon-containing sphere which is not coated by the carbon coating layer by adopting a second carbon source, wherein the thickness of the second carbon coating layer is S2, and the first carbon coating layer and the second carbon coating layer are combined to form the carbon coating layer.
In one embodiment, the method for preparing the carbon-coated silicon-containing sphere further comprises the following steps:
separating the carbon-coated silicon-containing spheres from the first intermediate with the micro-nano-sized hemispherical structure, and screening the carbon-coated silicon-containing spheres.
The preparation method of the carbon-coated silicon-containing sphere is specifically described as follows:
and S10, providing a substrate and a micro-nano texture template with a micro-nano hemispherical structure surface, wherein the radius of the hemispherical structure is R.
In one embodiment, the micro-nano-sized spherical structures or hemispherical structures are distributed in an array.
In one embodiment, R is 0.1nm to 600 nm.
In one embodiment, the base material is a resinous organic material, an inorganic material, or a mixture of the resinous organic material and the inorganic material.
Further, the organic material is selected from at least one of polyethylene terephthalate, polycarbonate, polypropylene and polyethylene; the inorganic material is selected from at least one of glass, sapphire and quartz.
S20: and applying a transfer printing glue on the base material.
In one embodiment, the main material of the transfer paste includes at least one of a water-soluble resin, an oil-soluble resin, a water-soluble inorganic substance or mixture, an epoxy acrylate, an amino acrylate, a polyether resin, an acrylic resin, an unsaturated polyester, an alcohol compound, a cationic resin, an epoxy resin, a silicone resin, and other UV light-induced resins. The transfer printing glue also comprises an initiator.
S30: applying the micro-nano texture template on the transfer glue, preparing a transition glue layer through curing, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure, wherein the preparation method specifically comprises the following steps:
dispensing glue at one side of a substrate surface where a micro-nano texture area needs to be manufactured to enable transfer printing UV glue to be linear, placing a micro-nano texture template (or called micro-nano texture mould) with a micro-nano size hemispherical structure surface on the transfer printing UV glue, enabling the micro-nano texture surface to be in contact with the glue, enabling the micro-nano texture mould and the substrate surface where the micro-nano texture area needs to be manufactured to be opposite to each other, applying roller pressure on the micro-nano texture mould, rolling from one side of the dispensing glue to the opposite side, enabling a corresponding gap between the micro-nano texture surface of the mould and the substrate surface at the corresponding position to be completely filled with the transfer printing UV glue, enabling the thickness of the filling transfer printing UV glue layer to be determined by the applied pressure and the transfer printing UV glue viscosity to obtain the required thickness, and then fixing the transfer printing UV glue layer and the micro-nano texture appearance through UV curing.
The transfer printing UV glue curing working parameters comprise: the energy of the vacuum environment and the full UV waveband non-parallel light source is 100 mJ-500 mJ, the curing time is 1 s-10 s, and the total thickness of the transition adhesive layer is 1 mu m-5 mu m.
S40: a first carbon coating layer is prepared on the surface of the first intermediate (namely a transition adhesive layer) with a micro-nano hemispherical structure by adopting a first carbon source in a copying deposition mode, and the thickness of the first carbon coating layer is S1.
In one embodiment, the thickness S1 of the first carbon coating layer is 0.1 nm-300 nm.
In one embodiment, the first carbon coating layer is one or more layers.
In one embodiment, the first carbon coating layer is made of at least one of carbon fiber, composite fiber, graphene and carbon.
In one embodiment, the first carbon cladding layer is patterned by chemical liquid deposition, chemical vapor deposition, sputter deposition, evaporation coating or DLC, spray coating, or curtain coating.
It can be understood that a transition separation layer is arranged between the micro-nano structure surface (transition glue layer) of the first intermediate and the first carbon coating layer, so that the subsequent separation of the first intermediate and the carbon-coated silicon-containing spheres is facilitated. Therefore, in one embodiment, S40 includes:
s401: preparing a transition separation layer on the surface of the first intermediate with the micro-nano hemispherical structure by copying and depositing a functional material;
s402: and preparing the first carbon coating layer on the transition separation layer by profiling deposition by adopting the first carbon source.
In one embodiment, the functional material is selected from materials with contact angles of 80-130 degrees, or water-soluble materials, or oil-soluble materials, or vibration separation materials, or thermal volatilization materials, or thermal decomposition materials, or hydrolysis materials, or oil decomposition materials.
In one embodiment, the material with the contact angle of 80-130 degrees is selected from fluorine-containing compounds; the water-soluble material is selected from organic water-soluble substances or inorganic water-soluble substances, or a mixture of the two substances; the oil-soluble material is selected from oil-soluble resins; the vibration separating material is selected from ultrasonic vibration or mechanical vibration; the thermally volatile material is selected from low boiling point material organic materials; the thermal decomposition material is selected from easily decomposed organic materials; the hydrolytic material is selected from organic water hydrolysate or inorganic water hydrolysate or a mixture of the organic water hydrolysate and the inorganic water hydrolysate; or the oleolytic material is selected from oleolytic resin material.
S50, profiling and depositing a silicon layer on the first carbon coating layer by adopting a silicon source, wherein the thickness of the silicon layer is more than or equal to (2R-S1).
In one embodiment, the silicon source is at least one of silicon, silicon oxide and silicon-carbon mixture.
In one embodiment, the silicon layer has a thickness of 0.1nm to 1500 nm.
In one embodiment, the silicon layer is conformally deposited by chemical liquid deposition, chemical vapor deposition, sputter deposition, evaporation or DLC, spray coating, or curtain coating.
S60, preparing a protective glue layer with a plane surface on the silicon layer by using protective glue.
The surface of the protective adhesive layer is set to be a plane, so that plasma equivalent etching is carried out on the protective adhesive layer by adopting an etching plasma source in the subsequent process, and the etching of the hemisphere of the silicon-containing sphere is facilitated.
In one embodiment, the main material of the protective adhesive comprises at least one of water-soluble resin, oil-soluble resin, water-soluble inorganic substance or mixture, epoxy acrylate, amino acrylate, polyether resin, acrylic resin, unsaturated polyester, alcohol compound, cationic resin, epoxy resin, silicone resin and other UV light-induced resin. In addition, the protective adhesive also comprises an initiator.
The working parameters of the UV protective adhesive curing include: the vacuum environment, the full UV wave band non-parallel light source, the energy is 100 mJ-500 mJ, the curing time is 1 s-10 s, and the total thickness of the protective adhesive layer is 1 mu m-5 mu m.
S70, performing plasma equivalent etching on the protective glue layer by adopting a first etching plasma source, and etching the silicon layer and the rest protective glue layer by adopting a second etching plasma source when the convex part of the first silicon layer is exposed, wherein the etching thickness of the silicon layer is 2R, thus preparing the silicon-containing sphere.
Understandably, the silicon layer and the rest of the protective adhesive layer are etched simultaneously by adopting a second etching plasma source, and under the action of the simultaneous etching, an upper hemisphere is etched, so that the silicon sphere is prepared; the etching plasma source is a mixed plasma source capable of etching the protective glue layer and the silicon layer simultaneously, and upper hemispherical etching is realized through proportion matching.
It is understood that the first etching plasma source is a plasma source having an etching effect on the protective adhesive layer, such as at least one of an oxygen-containing plasma source, a fluorine-containing plasma source, and a chlorine-containing plasma source.
In one embodiment, the second etching plasma source comprises a plasma source having an etching effect on both silicon and the protective glue layer, such as at least two of a fluorine-containing plasma source, an oxygen-containing plasma source, a fluorine-containing plasma source, and a chlorine-containing plasma source. The specific ratio of the mixed gas sources is dependent on the type of gas source selected and the type of material being etched.
S80 depositing a second carbon coating layer on the surface of the silicon-containing sphere not coated by the carbon coating layer using a second carbon source, the first carbon coating layer and the second carbon coating layer combining to form the carbon coating layer.
In one embodiment, the thickness S2 of the second carbon coating layer is 0.1 nm-300 nm.
In one embodiment, the second carbon coating layer is one or more layers.
In one embodiment, the second carbon coating layer is made of at least one of carbon fiber, composite fiber, graphene and carbon.
S90 separating the carbon-coated silicon-containing spheres from the first intermediate and sieving the carbon-coated silicon-containing spheres. The method comprises the following steps:
s901: separating the carbon-coated silicon-containing spheres from the first intermediate.
In one embodiment, the means for separating comprises at least one of water phase separation, oil phase separation, thermal separation, peeling and vibratory separation. The combination of the methods can separate the carbon-coated silicon-containing spheres from the substrate having the micro-nano sized hemispherical structure more quickly and/or better without damaging the micro-nano sized hemispherical structure of the substrate and the structure of the carbon-coated silicon-containing spheres.
It will be appreciated that if a transitional separation layer is included between the carbon-coated silicon-containing spheres and the first intermediate, the separation may also be by aqueous phase separation, oil phase separation, thermal separation or vibrational separation. It will be appreciated that the separation of the substrate and the carbon-coated silicon-containing spheres will generally correspond to the selection of the functional material, e.g., a water-soluble material is used to prepare the water-soluble transitional separation layer, and the substrate containing the coating is subsequently placed in water, the water-soluble transitional separation layer dissolves, and the substrate and coating separate. If a material with a large contact angle is adopted, the substrate and the coating can be directly stripped.
S902: and screening the separated carbon-coated silicon-containing spheres.
In one embodiment, the carbon-coated silicon-containing spheres are collected by sieving in a vibratory or pneumatic collection environment to yield consistent size carbon-coated silicon-containing spheres.
Fig. 2 is a schematic structural diagram of each element in a process of preparing a carbon-coated silicon-containing sphere according to an embodiment of the present invention, where 101 denotes a micro-nano texture template having a micro-nano-sized hemispherical structure surface, 102 denotes a first intermediate (including a base material and a transition adhesive layer), 103 denotes a first carbon coating layer, 104 denotes a silicon layer, 105 denotes a protective adhesive layer, 106 denotes a silicon-containing sphere, 107 denotes a second carbon coating layer, and 108 denotes a carbon-coated silicon-containing sphere (an inner core is a silicon-containing sphere, and an outer shell is a carbon coating layer composed of a first carbon coating layer and a second carbon coating layer).
The invention also provides a carbon-coated silicon-containing sphere prepared by the preparation method of the carbon-coated silicon-containing sphere.
The invention also provides an electrode comprising the carbon-coated silicon-containing spheres as described above.
The invention also provides a battery comprising an electrode as described above.
The preparation method of the carbon-coated silicon-containing sphere provided by the invention has the advantages of simplicity in operation, material saving, low cost, long acting and large-scale application. And the structural stability and energy density of the silicon material can be remarkably improved, and if the carbon-coated silicon-containing sphere provided by the invention is used for preparing an electrode, the charging and discharging stable times of a battery can be remarkably prolonged, and the battery performance can be improved.
In addition, the selection of a silicon source is changed, and other carbon-coated silicon-containing materials with special micro-nano structure functions can be obtained, so that the method has a wide application prospect.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
The PET membrane with the surface provided with the concave hemispherical array micro-nano texture template with the diameter of 100nm is used as a transfer printing mold, the texture surface has an anti-sticking effect, and the PET membrane is not adhered to the transfer printing UV glue after curing.
The method comprises the steps of point-transferring UV glue lines on one side of the edge of the outer surface of a PC board substrate, placing a transfer mold PET membrane on the glue line substrate, enabling one side of the mold texture to face the UV glue, and enabling the mold texture area to correspond to the texture area needing to be manufactured on the substrate. And applying roller pressure on the outer surface of the transfer printing mold, and rolling from one side of the dispensing line to the corresponding side to completely fill the transfer printing UV glue between the texture surface of the transfer printing mold and the surface of the base material. Wherein the transfer printing UV glue material is water-soluble functional material polyethylene glycol UV curing glue.
Irradiating UV curing glue for 3s by a full-waveband UV area light source with the energy of 200mJ, curing to prepare a transition glue layer, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure, wherein the total thickness of the transition glue layer in the first intermediate is 200 nm.
By vacuum sputtering, at 3 x 10-3In a Pa vacuum state, firstly using a carbon target, sputtering with the power of 12kW, and depositing a first carbon layer with the thickness of 20nm on the surface of the micro-nano texture of the transition adhesive layer; then, a silicon target was used to deposit a silicon layer of 160nm with a sputtering power of 10 kW.
And (3) dispensing a UV protective adhesive line on one side of the edge of the outer surface of the silicon layer, placing a transfer printing plane mold glass sheet on the adhesive line substrate, wherein the UV protective adhesive is faced to one side of the mold plane, and the mold plane area corresponds to the substrate film coating area. And applying roller pressure on the outer surface of the transfer printing mold, and rolling from one side of the dispensing line to the corresponding side to completely fill the UV protective glue between the plane of the transfer printing mold and the surface of the base material. And manufacturing an outer plane UV protection adhesive layer on the surface of the silicon layer, wherein the UV protection adhesive layer is made of silicon-containing resin UV curing resin and has the thickness of 300 nm.
Irradiating the silicon-containing resin UV curing resin for 3s by a full-wave band UV surface light source with the energy of 200mJ, and curing to prepare a UV protective adhesive layer, wherein the surface of the UV protective adhesive layer is a plane.
And carrying out plasma etching on the planar UV protective glue layer and the silicon layer by adopting an oxygen-containing and fluorine-containing plasma source. The mixing ratio of the oxygen and fluorine plasma is 1: 2.3, equal amount etching plane UV protection glue film and keep original plane appearance, after thin plane UV protection glue film etches earlier and accomplishes and expose the coating film layer, mix plasma source with the difference rate etch intermediate glue film and naked silicon layer region that spills simultaneously, its etching rate ratio is about 1: 2.
and when the maximum etching depth of the silicon layer etched area is about 160nm, taking out the silicon layer, putting the silicon layer into a film coating machine, and manufacturing a second carbon layer with the thickness of 20nm on the surface of the etched silicon layer by using the same sputtering film coating condition to prepare the carbon-coated silicon-containing sphere combination. And then taking out and placing the silicon spheres in water, vibrating and separating the carbon-coated silicon spheres, and drying the silicon spheres to obtain the battery cathode material.
Example 2
The PET membrane with the surface provided with the concave hemispherical array micro-nano texture template with the diameter of 60nm is used as a transfer printing mold, the texture surface has an anti-sticking effect, and the PET membrane is not adhered to transfer printing UV glue after curing.
The method comprises the steps of point-transferring UV glue lines on one side of the edge of the outer surface of a PC board substrate, placing a transfer mold PET membrane on the glue line substrate, enabling one side of the mold texture to face the UV glue, and enabling the mold texture area to correspond to the texture area needing to be manufactured on the substrate. And applying roller pressure on the outer surface of the transfer printing mold, and rolling from one side of the dispensing line to the corresponding side to completely fill the transfer printing UV glue between the texture surface of the transfer printing mold and the surface of the base material. Wherein the transfer printing UV glue material is water-soluble functional material polyethylene glycol UV curing glue.
Irradiating UV curing glue for 2s by a full-waveband UV area light source with the energy of 100mJ, curing to prepare a transition glue layer, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure, wherein the total thickness of the transition glue layer in the first intermediate is 200 nm.
By vacuum sputtering, at 3 x 10-3In a Pa vacuum state, firstly using a carbon target, sputtering with the power of 12kW, and depositing a carbon layer with the thickness of 10nm on the surface of the micro-nano texture of the transition adhesive layer; then, a silicon target was used to deposit a silicon layer of 40nm with a sputtering power of 10 kW.
And (3) dispensing a UV protective adhesive line on one side of the edge of the outer surface of the silicon layer, placing a transfer printing plane mold glass sheet on the adhesive line substrate, wherein the UV protective adhesive is faced to one side of the mold plane, and the mold plane area corresponds to the substrate film coating area. And applying roller pressure on the outer surface of the transfer printing mold, and rolling from one side of the dispensing line to the corresponding side to completely fill the UV protective glue between the plane of the transfer printing mold and the surface of the base material. And manufacturing an outer plane UV protection adhesive layer on the surface of the silicon layer, wherein the UV protection adhesive layer is made of silicon-containing resin UV curing resin, and the thickness of the protection adhesive layer is 100 nm.
Irradiating the silicon-containing resin UV curing resin for 3s by a full-wave band UV area light source with the energy of 100mJ, and curing to prepare a UV protective adhesive layer, wherein the surface of the UV protective adhesive layer is a plane.
And carrying out plasma etching on the planar UV protective glue layer and the silicon layer by adopting an oxygen-containing and fluorine-containing plasma source. The mixing ratio of the oxygen and fluorine plasma is 1: 2.3, equal amount etching plane UV protection glue film and keep original plane appearance, after thin plane UV protection glue film etches earlier and accomplishes and expose the coating film layer, mix plasma source with the difference rate etch intermediate glue film and naked silicon layer region that spills simultaneously, its etching rate ratio is about 1: 2.
and when the maximum etching depth of the silicon layer etched area is about 40nm, taking out the silicon layer, putting the silicon layer into a film coating machine, and manufacturing a 10nm second carbon layer on the surface of the etched silicon layer under the same sputtering film coating condition to prepare the carbon-coated silicon-containing sphere combination. And then taking out and placing the silicon spheres in water, vibrating and separating the carbon-coated silicon spheres, and drying the silicon spheres to obtain the battery cathode material.
Example 3
The PET membrane with the surface provided with the concave hemispheroid array micro-nano texture template with the diameter of 80nm is used as a transfer printing mold, the texture surface has an anti-sticking effect, and the PET membrane is not adhered to transfer printing UV glue after curing.
UV glue lines are dotted on one side of the edge of the outer surface of the PC board substrate, a transfer printing mold PET membrane is placed on the glue line substrate, the transfer printing UV glue faces to one side of the mold texture, and the mold texture area corresponds to the texture area needing to be manufactured on the substrate. And applying roller pressure on the outer surface of the transfer printing mold, and rolling from one side of the dispensing line to the corresponding side to completely fill the UV glue between the texture surface of the transfer printing mold and the surface of the base material. Wherein the UV glue material is water-soluble functional material polyethylene glycol UV curing glue.
Irradiating the UV glue layer for 2s by a full-waveband UV area light source with energy of 100mJ, curing to prepare a transition glue layer, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure, wherein the total thickness of the transition glue layer in the first intermediate is 300 nm.
By vacuum sputtering, at 3 x 10-3In a Pa vacuum state, firstly using a carbon target, sputtering with the power of 12kW, and depositing a carbon layer with the thickness of 15nm on the surface of the micro-nano texture; then, a silicon target was used to deposit a silicon layer of 50nm with a sputtering power of 10 kW.
And (3) dispensing a UV adhesive line on one side of the edge of the outer surface of the silicon layer, placing a transfer printing plane mold glass sheet on the adhesive line substrate, wherein the UV protective adhesive faces one side of the mold plane, and the mold plane area corresponds to the substrate film coating area. And applying roller pressure on the outer surface of the transfer printing mold, and rolling from one side of the dispensing line to the corresponding side to completely fill the UV protective glue between the plane of the transfer printing mold and the surface of the base material. And manufacturing an outer plane UV protection adhesive layer on the surface of the silicon layer, wherein the UV protection adhesive layer is made of silicon-containing resin UV curing resin, and the thickness of the protection adhesive layer is 120 nm.
Irradiating the silicon-containing resin UV curing resin for 2s by a full-wave band UV area light source with the energy of 100mJ, and curing to prepare a protective adhesive layer, wherein the surface of the protective adhesive layer is a plane.
And carrying out plasma etching on the plane UV protective adhesive layer and the coating layer by adopting an oxygen-containing and fluorine-containing plasma source. The mixing ratio of the oxygen and fluorine plasma is 1: 2.3, equal amount etching plane UV protection glue film and keep original plane appearance, after thin plane UV protection glue film etches earlier and accomplishes and expose the coating film layer, mix plasma source with the difference rate etch intermediate glue film and naked silicon layer region that spills simultaneously, its etching rate ratio is about 1: 2.
and when the maximum etching depth of the silicon layer etched area is about 50nm, taking out the silicon layer, putting the silicon layer into a film coating machine, and manufacturing a 15nm second carbon layer on the surface of the etched silicon layer under the same sputtering film coating condition to prepare the carbon-coated silicon-containing sphere combination. And then taking out and placing the silicon spheres in water, vibrating and separating the carbon-coated silicon spheres, and drying the silicon spheres to obtain the battery cathode material.
Comparative example 1
The nano silicon powder which is not coated by carbon is sold in the market.
The carbon-coated silicon-containing spheres prepared in examples 1 to 3 and the product of comparative example 1 were added to a negative electrode material, and a battery cycle charge-discharge capacity change test was performed, with the results shown in table 1:
TABLE 1
Figure BDA0003299922900000141
Figure BDA0003299922900000151
As can be seen from table 1, the structural stability and energy density of the silicon material can be significantly improved by using the preparation method of the carbon-coated silicon-containing sphere provided by the present invention, and if the carbon-coated silicon-containing sphere provided by the present invention is used for preparing an electrode, the charging and discharging stability times of a battery can be significantly prolonged, and the battery performance can be improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the patent of the present invention shall be subject to the content of the appended claims, and the description and the attached drawings can be used for explaining the content of the claims.

Claims (15)

1. A preparation method of a carbon-coated silicon-containing sphere is characterized in that the carbon-coated silicon-containing sphere comprises a silicon-containing sphere and a carbon coating layer coated on the surface of the silicon sphere, and comprises the following steps:
providing a substrate and a micro-nano texture template with a micro-nano sized hemispherical structure surface, wherein the radius of the hemispherical structure is R;
applying a transfer glue on the substrate;
applying the micro-nano texture template on the transfer printing glue, preparing a transition glue layer through curing, removing the micro-nano texture template, and preparing a first intermediate with a micro-nano hemispherical structure;
preparing a first carbon coating layer with the thickness of S1 by copying and depositing a first carbon source on the surface of the intermediate with the micro-nano hemispherical structure;
profiling and depositing a silicon layer on the first carbon coating layer by adopting a silicon source, wherein the thickness of the silicon layer is more than or equal to (2R-S1);
preparing a protective adhesive layer with a plane surface on the silicon layer by using protective adhesive;
performing plasma equivalent etching on the protective adhesive layer by using a first etching plasma source, and etching the silicon layer and the rest protective adhesive layer by using a second etching plasma source when the convex part of the silicon layer is exposed, wherein the etching thickness of the silicon layer is 2R, so as to prepare the silicon-containing sphere;
depositing a second carbon coating layer on the surface of the silicon-containing sphere not coated by the carbon coating layer by using a second carbon source, wherein the thickness of the second carbon coating layer is S2, and the first carbon coating layer and the second carbon coating layer are combined to form the carbon coating layer.
2. The method of claim 1, wherein the thickness of the first carbon coating layer S1 and the thickness of the second carbon coating layer S2 are each independently 0.1nm to 300 nm.
3. The method of claim 1, wherein R is 0.1nm to 600nm, and the silicon layer has a thickness of 0.1nm to 1500 nm.
4. The method of claim 1, wherein the first carbon coating layer and the second carbon coating layer are each independently one or more layers; and/or
The first carbon coating layer and the second carbon coating layer are made of at least one of carbon fiber, composite fiber, graphene and carbon independently.
5. The method according to claim 1, wherein the silicon source is at least one of silicon, silicon oxide and a mixture of silicon and carbon.
6. The method of claim 1, wherein the conformal deposition is chemical liquid deposition, chemical vapor deposition, sputtering deposition, evaporation coating, DLC, spray coating, or curtain coating.
7. The method of any one of claims 1 to 6, wherein prior to preparing the first carbon coating layer, a functional material is used to prepare a transition separation layer by conformal deposition on the surface of the first intermediate, and the first carbon coating layer is prepared by conformal deposition on the transition separation layer using the first carbon source.
8. The method for preparing the carbon-coated silicon-containing sphere according to claim 7, wherein the functional material is selected from a material having a contact angle of 80 ° to 130 °, a water-soluble material, an oil-soluble material, a vibration separation material, a thermal volatilization material, a thermal decomposition material, a hydrolysis material, and an oil decomposition material.
9. The method of manufacturing a carbon-coated silicon-containing sphere according to any one of claims 1 to 6, further comprising the steps of:
separating the carbon-coated silicon-containing spheres from the first intermediate, and sieving the carbon-coated silicon-containing spheres.
10. The method of claim 9, wherein the carbon-coated silicon-containing spheres are separated from the first intermediate by at least one of water phase separation, oil phase separation, thermal separation, exfoliation, and vibratory separation.
11. The method of any one of claims 1 to 6, wherein all etching operations are performed in a vacuum environment.
12. The method of any of claims 1-6, wherein the first etching plasma source and the second etching plasma source are each independently selected from at least one of an oxygen-containing plasma source, a fluorine-containing plasma source, and a chlorine-containing plasma source; and/or
The protective adhesive comprises: at least one of epoxy acrylate, amino acrylate, polyether resin, acrylic resin, unsaturated polyester, alcohol compound, cationic resin, epoxy resin and silicone resin.
13. A carbon-coated silicon-containing sphere produced by the method for producing a carbon-coated silicon-containing sphere according to any one of claims 1 to 12.
14. An electrode comprising the carbon-coated silicon-containing sphere of claim 13.
15. A battery comprising the electrode of claim 14.
CN202111187627.9A 2021-10-12 2021-10-12 Carbon-coated silicon-containing sphere, and preparation method and application thereof Active CN114141997B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111187627.9A CN114141997B (en) 2021-10-12 2021-10-12 Carbon-coated silicon-containing sphere, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111187627.9A CN114141997B (en) 2021-10-12 2021-10-12 Carbon-coated silicon-containing sphere, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114141997A true CN114141997A (en) 2022-03-04
CN114141997B CN114141997B (en) 2023-09-29

Family

ID=80394856

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111187627.9A Active CN114141997B (en) 2021-10-12 2021-10-12 Carbon-coated silicon-containing sphere, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114141997B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012507145A (en) * 2008-10-23 2012-03-22 ラム リサーチ コーポレーション Silicon etching method and apparatus with passivation using chemical vapor deposition
WO2018032975A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of lithium-ion battery negative-electrode material effectively buffering volume change effect of silicon
CN111342010A (en) * 2020-03-02 2020-06-26 新奥石墨烯技术有限公司 Silicon-carbon composite material with double-layer carbon-coated structure and preparation method and application thereof
CN111668474A (en) * 2020-05-06 2020-09-15 深圳市德方纳米科技股份有限公司 Negative electrode material, preparation method thereof and secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012507145A (en) * 2008-10-23 2012-03-22 ラム リサーチ コーポレーション Silicon etching method and apparatus with passivation using chemical vapor deposition
WO2018032975A1 (en) * 2016-08-15 2018-02-22 福建新峰二维材料科技有限公司 Manufacturing method of lithium-ion battery negative-electrode material effectively buffering volume change effect of silicon
CN111342010A (en) * 2020-03-02 2020-06-26 新奥石墨烯技术有限公司 Silicon-carbon composite material with double-layer carbon-coated structure and preparation method and application thereof
CN111668474A (en) * 2020-05-06 2020-09-15 深圳市德方纳米科技股份有限公司 Negative electrode material, preparation method thereof and secondary battery

Also Published As

Publication number Publication date
CN114141997B (en) 2023-09-29

Similar Documents

Publication Publication Date Title
CN105308772B (en) Diaphragm for three-dimensional batteries
TW523953B (en) Pocketed electrode plate for use in lithium ion secondary battery, its manufacturing method and lithium ion secondary battery using the same
CN108847474B (en) Micro-textured negative plate for pre-supplementing lithium and preparation method thereof
KR100296741B1 (en) Battery with trench structure and fabrication method
CN106463692B (en) Manufacture the device and method of high aspect ratio structure
CN205140763U (en) Flexible current -collecting body
KR101301826B1 (en) Battery, vehicle, electronic device and battery manufacturing method
CN101059380A (en) Flexible capacitance type touch sensor production method
CN103219164A (en) Ultra-thin, self-supporting, flexible and all-solid-state super capacitor and manufacturing method thereof
CN101584065A (en) Three-dimensional batteries and methods of manufacturing the same
WO2008155885A1 (en) Nonaqueous electrolyte secondary battery and method for producing electrode for nonaqueous electrolyte secondary battery
JP2010225432A (en) Solid secondary battery, and manufacturing method of solid secondary battery
JP2011070788A (en) Method of manufacturing all-solid battery
CN105609690B (en) A kind of battery diaphragm and preparation method thereof and lithium-sulfur cell
CN108428901B (en) A kind of composite microstructure collector and preparation method thereof for lithium ion battery
CN101714669B (en) Gel polymer lithium ion battery and preparation method thereof
CN108598559A (en) a kind of flexible lithium ion battery
CN104067432B (en) The manufacture method of all-solid-state battery
KR20120032396A (en) Lithium-ion secondary battery, vehicle, electronic device and manufacturing method of lithium-ion secondary battery
KR20160041299A (en) Electrode for Secondary Battery Having Current Corrector with Improved Structural Stability
JP2011150974A (en) Electrode body, and method for manufacturing the same
WO2023000664A1 (en) On-chip solid-state supercapacitor and preparation method therefor
CN114141997A (en) Carbon-coated silicon-containing sphere and preparation method and application thereof
CN114430029A (en) Composite modified graphite material, positive electrode material of bi-ion battery, negative electrode material of bi-ion battery and bi-ion battery
KR20130140551A (en) 3-d complex electrode having multi-active material and flexible lithium rechargeable batteries comprising the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant