Hybrid carbon composite particles having surfaces with fine particles protruding therefrom

Abstract

The present invention relates to hybrid carbon composite particles having surfaces with fine particles protruding therefrom, wherein the fine particles are coated with carbon and have a portion or the entirety thereof interconnected with adjacent fine particles by the coated carbon such that the plurality of fine particles are agglomerated in a three-dimensional structure.

Description

Hybrid carbon composite particles with a protruding surface of fine particles

[0001] The present invention relates to a hybrid carbon composite particle having a surface on which fine particles protrude, and more specifically, to a hybrid carbon composite particle having a surface on which fine particles are coated and interconnected by an organic substance containing carbon so that a plurality of fine particles are aggregated into a three-dimensional structure and plate-shaped fine particles protrude on the surface.

[0002] There are various secondary batteries that can be recharged, such as lead-acid batteries and nickel-metal hydride batteries, but among them, lithium-ion batteries (LIBs) are used as batteries to power portable mobile devices such as smart phones and netbooks due to their high energy density, high output density, and operating voltage that can withstand long-term charging and discharging. They are also widely used as energy supply elements to supply energy to hybrid vehicles.

[0003] In lithium-ion batteries, the cathode active material is being varied to enhance performance. However, even if the cathode generates high energy, if the anode, which stores it, is not balanced, efficiency will inevitably decline. In particular, the anode material must be designed to effectively accept lithium ions during charging, which can reduce charging time.

[0004] Graphite has long been widely used as an anode material. Graphite has a layered structure consisting of multiple layers of carbon atoms bonded in a regular pattern. During the charging process, lithium ions move from the anode to the cathode, and the lithium ions that reach the cathode are stored between the graphite layers.

[0005] Research is currently underway to develop new materials that can replace existing graphite anode materials to improve the performance of lithium-ion batteries. Graphite's low electrical conductivity leads to long charge / discharge times, and its insufficient capacity for lithium ion binding limits its charge capacity.

[0006] Therefore, there is a need to develop a new negative electrode material that can solve or alleviate the above-mentioned problems, improve the characteristics of the negative electrode material compared to the conventional technology, increase the charging capacity and battery life of the lithium-ion battery, and shorten the charging time.

[0007] The technical problem to be solved by the present invention is to solve the problem that graphite included in the conventional negative and positive electrode active material layers in a lithium ion battery does not have high electrical conductivity, so that the charging and discharging time is long, and the capacity for combining lithium ions is not sufficient, so that the charging capacity is not high.

[0008] The present invention relates to hybrid carbon composite particles having a protruding surface of fine particles, and more specifically, to a hybrid carbon composite particle in which fine particles are coated and interconnected by an organic material containing carbon so that a plurality of fine particles are aggregated into a three-dimensional structure and the fine particles protruding on the surface have a protruding surface.

[0009] To overcome these problems, the present invention provides a hybrid carbon composite particle having a surface with protruding fine particles, wherein the fine particles are coated with carbon, and the fine particles are partially or completely interconnected with adjacent fine particles by the coated carbon, thereby forming a three-dimensional structure in which a plurality of fine particles are aggregated.

[0010] In addition, the carbon of the present invention provides a hybrid carbon composite particle having a surface on which fine particles characterized by being any one of amorphous carbon, conductive carbon, carbon nanotubes, graphite, reduced graphene, reduced graphene oxide (rGO), graphene oxide (GO), graphene or carbon powder protrude.

[0011] In addition, the hybrid carbon composite particle of the present invention provides a hybrid carbon composite particle having a protruding surface with fine particles characterized by a polygonal, spherical or spherical shape with a sunken center.

[0012] In addition, the present invention provides a hybrid carbon composite particle having a surface from which fine particles protrude, characterized in that the surface from which the fine particles protrude has a porous structure in which empty spaces exist in part or all of the fine particles.

[0013] In addition, the fine particles of the present invention are lithium-nickel-cobalt-manganese composite oxide (NCM), lithium-nickel-cobalt-aluminum composite oxide (NCA), lithium-cobalt composite oxide (LCO), lithium-nickel composite oxide (LNO), lithium manganese (LMO), lithium iron phosphate (LFP), lithium nickel-cobalt-manganese (NCM), silver (Ag), graphite, sulfur, lithium sulfur, sulfur composite, carbon sulfur complex, silicon (Si), silicon carbide (Si2C, SiC or SiC2 containing SiC) X ), silicon oxide (SiO or SiO2 containing SiO X ), silicon composite oxide (Si-Mg x SiO x), magnesium metasilicate (enstatite, MgSiO3), foresterite (foresterite, Mg2SiO4), gold (Au), platinum (Pt), palladium (Pd), aluminum (Al), zinc (Zn), silver alloy (Ag alloy), copper (Cu) having a surface coated with silver (Ag), silver (Ag) having a surface coated with copper (Cu), or carbon powder, the present invention provides hybrid carbon composite particles having a surface with protruding fine particles characterized by being composed of one or more of the following:

[0014] In addition, the carbon powder of the present invention provides a hybrid carbon composite particle having a surface from which fine particles characterized by being any one of acetylene black, Super P black, carbon black, Denka black, activated carbon, hard carbon or soft carbon protrude.

[0015] In addition, the hybrid carbon composite particle of the present invention provides a hybrid carbon composite particle having a surface from which fine particles protrude, characterized in that the fine particles are produced by a photochemical, photothermal or heat treatment process.

[0016] In addition, the present invention provides hybrid carbon composite particles having a protruding surface, characterized in that the size of the hybrid carbon composite particles is such that the largest diameter thereof is 0.1 to 100 um.

[0017] In addition, the present invention provides hybrid carbon composite particles having a protruding surface, wherein the fine particles are further characterized by having a needle-shaped or plate-shaped shape.

[0018] In addition, the plate-shaped microparticles of the present invention provide hybrid carbon composite particles having a protruding surface, characterized by an aspect ratio of 1:2 to 1:200.

[0019] In addition, the present invention provides a hybrid graphene composite particle characterized in that the hybrid carbon composite particle has a structure bonded to the surface or interior of multilayer graphene.

[0020] The hybrid carbon composite particle having a surface with protruding microparticles on some or all of the surface of the present invention is a three-dimensional spherical composite structure having a surface coated with carbon and having interconnected microparticles protruding on the surface, and can be included in an anode active material, and can significantly improve the charge / discharge speed and efficiency with a stable structure and high electrical conductivity, and can realize a lithium-ion battery having both performance and stability by maximizing the capacity to which lithium ions can be combined.

[0021] In addition, the microparticles protruding from the surface maximize the surface area, which maximizes the area in contact with the electrolyte containing lithium ions, and this allows lithium ions to move quickly into the active material, thereby improving the charge / discharge speed.

[0022] And when manufactured as a powder with a three-dimensional spherical composite structure, it can be uniformly mixed with binders and conductive agents, and the powder can be formed into a dough to manufacture electrodes for lithium-ion batteries in the form of thin films of various thicknesses.

[0023] Finally, since a porous three-dimensional structured electrode is fabricated using a needle-shaped spherical powder, a binder, and a conductive material, the electrolyte moves smoothly through the porous passages, and the area in contact with the electrolyte in the three-dimensional structure is maximized, allowing lithium ions to move quickly and efficiently to the active material, enabling rapid charging and discharging.

[0024] Figure 1 is a conceptual diagram of a plate-shaped microparticle, a spherical hybrid carbon composite particle, and a polygonal hybrid carbon composite particle of the present invention having a protruding surface.

[0025] FIG. 2a is an enlarged photograph of plate-shaped silicon microparticles and carbon-coated silicon microparticles, which are examples of hybrid carbon composite particles having a protruding surface of the present invention.

[0026] Figure 2b is an enlarged photograph of a sphere (a), a sphere with a sunken center (b), and a surface with protruding fine particles (c), which are examples of hybrid carbon composite particles having a protruding surface of the present invention.

[0027] Figure 2c is a Raman spectroscopy analysis result of a hybrid carbon composite particle having a protruding surface of fine particles according to the present invention.

[0028] Figure 2d is an EDX analysis result of the graphene-coated silicon hybrid composite particle of the present invention, which is a hybrid carbon composite particle having a protruding surface of fine particles.

[0029] FIG. 3a is a graph showing the results of current measurement according to the concentration of an electrochemical measuring substance (PAP) for each of an electrode (Hybrid Graphene complex electrode, Graphene-Ag electrode), a graphene electrode, and a metal electrode (Gold electrode) containing hybrid carbon composite particles having a protruding surface as a negative active material for an all-solid-state battery according to the present invention.

[0030] Figure 3b is a conceptual diagram of a structure in which the hybrid carbon composite particles of the present invention are bonded to the surface or interior of multilayer graphene.

[0031] Figure 4 shows the same concentration (10) for each of hybrid carbon composite particles (Hybrid Graphene), graphene, and metal (Au) having a protruding surface as a fine particle for an all-solid-state battery negative active material according to the present invention. -3 This is a graph showing the current values ​​in PAP compared to those in mM.

[0032] Figure 5 is a graph showing battery capacity according to the number of charge / discharge cycles when manufacturing a battery negative electrode material using silicon and when manufacturing a battery negative electrode material using hybrid carbon composite particles having a protruding surface of the fine particles of the present invention.

[0033] In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

[0034] Embodiments according to the concept of the present invention may be modified in various ways and take various forms. Therefore, specific embodiments are illustrated in the drawings and described in detail in this specification or application. However, this is not intended to limit embodiments according to the concept of the present invention to specific disclosed forms, and it should be understood that all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention are included.

[0035] The terminology used herein is for the purpose of describing specific embodiments only and is not intended to limit the present invention. The singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprises" or "has" indicate the presence of a described feature, number, step, operation, component, part, or combination thereof, but do not preclude the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0036] The present invention relates to a hybrid carbon composite particle having a surface from which fine particles protrude, the fine particles being partially or completely coated with carbon, the fine particles being partially or completely interconnected with adjacent fine particles by the coated carbon to form a plurality of three-dimensional structures, thereby forming a network structure interconnected with each other by carbon, so that metal or semiconductor particles can be maintained in a stable state even when charging and discharging are repeated.

[0037] The existing process of mixing graphene with metal or semiconductor particles is a simple mixing process with already produced graphene, so the organic bonding strength between the metal or semiconductor particles and graphene is lacking.

[0038] The present invention is a composite particle comprising a plurality of needle-shaped or plate-shaped metal or semiconductor microparticles partially or fully coated with carbon, interconnected by carbon, and partially or fully empty spaces between the interconnected microparticles, wherein a portion of the surface of the composite particle is in the shape of a protruding microparticle.

[0039] The hybrid carboxylic acid composite particles of the present invention can be applied to any one of a lithium ion battery, a sodium ion battery, or a magnesium ion battery.

[0040] Figure 1 is a conceptual diagram of a plate-shaped microparticle, a spherical hybrid carbon composite particle, and a polygonal hybrid carbon composite particle of the present invention having a protruding surface.

[0041] Here, the microparticles are metals or semiconductors, and their shape is characterized by a plate-like shape. In addition to flat shapes, the plate-like shape also includes rounded and curled shapes, as well as shapes that are folded or twisted in the middle. It also includes a needle-like shape with one end pointed. A plate-like microparticle is suitable when its aspect ratio is between 1:2 and 1:200.

[0042] The microparticles may be partially or fully coated with carbon, and multiple microparticles may form a composite particle structure in which the coated carbon is partially or fully interconnected, with some of the interconnected structures comprising voids. Some microparticles may be directly connected.

[0043] Here, carbon is any one of amorphous carbon, conductive carbon, carbon nanotubes, graphite, reduced graphene, reduced graphene oxide (rGO), graphene oxide (GO), or graphene.

[0044] Additionally, the carbon may be amorphous carbon, graphene or graphite.

[0045] FIG. 2a is an enlarged photograph of plate-shaped silicon microparticles and carbon-coated silicon microparticles, which are examples of hybrid carbon composite particles having a protruding surface of the present invention.

[0046] Figure 2b is an enlarged photograph of a sphere and its surface (a) and a sphere with a sunken center (b), which are examples of hybrid carbon composite particles having a protruding surface of the fine particles of the present invention.

[0047] Other polygonal or oval shapes may also be included. The enlarged image of the surface (c) of the microparticles in Fig. 2b shows the shape of the microparticles protruding, with varying degrees of protrusion, and there may also be microparticles that are relatively non-protruding.

[0048] The size of the hybrid carbon composite particles ranges from 0.1 to 100 um in the largest diameter.

[0049] Additionally, the surface from which the fine particles protrude may have a porous structure in which empty spaces exist partially or entirely between the fine particles.

[0050] The length of the plate-shaped microparticles is 1.29㎛ and 1.41㎛, and the range of 0.1 to 10㎛ is reasonable.

[0051] The hybrid carbon composite particle having a protruding surface of fine particles of the present invention is manufactured in a form in which fine particles and a carbon material are mixed.

[0052] The above carbon may be any one of amorphous carbon, conductive carbon, carbon nanotubes, graphite, reduced graphene, reduced graphene oxide (rGO), graphene oxide (GO), graphene, or carbon powder.

[0053] Here, the carbon powder may be any one of acetylene black, Super P black, carbon black, Denka black, activated carbon, hard carbon, or soft carbon.

[0054] Figure 2c shows the Raman spectroscopy analysis results of the hybrid carbon composite particles having a protruding surface, which is the microparticle of the present invention. The Si peak is clearly visible because it contains silicon, and the D, G, and 2D peaks of graphene are clearly visible, showing that it is high-quality graphene.

[0055] In addition, Fig. 2d shows the EDX analysis results of the graphene-coated silicon hybrid composite particles of the present invention's microparticles having a protruding surface, and since the silicon particles (Si or SiOx) are coated with graphene (C) and interconnected to form spherical particles, a peak composed of only three elements clearly appears.

[0056] Heat treatment, photochemical treatment, or photothermal irradiation can coat some or all of the plate-shaped microparticles with carbon, simultaneously connecting the microparticles with carbon. Unconnected areas remain as voids, leaving the plate-shaped microparticles protruding from the spherical surface.

[0057] The structure of the negative active material composed of hybrid carbon composite particles having a protruding surface and fine particles having a carbon-mixed structure has the following effects.

[0058] First, because the surfaces of metal or semiconductor microparticles are completely coated with graphene, the volume expansion that occurs when the metal or semiconductor microparticles bind to lithium ions is effectively suppressed. This resolves the problems of metal or semiconductor particle destruction and separation from the electrode caused by excessive volume expansion and shrinkage.

[0059] Second, the carbonized carbon is fixed to the surface of metal or semiconductor microparticles, acting as a scaffold that fixes the position of the microparticles. Theoretically, graphene has a tensile strength 200 times greater than steel, making it resistant to bending and flexing. Therefore, when graphene combines with metal or semiconductor microparticles to form a multilayer structure, the positions of the metal or semiconductor microparticles are fixed, acting as a scaffold that maintains a stable structure even when the metal or semiconductor changes shape due to charging and discharging.

[0060] Third, amorphous carbon, graphene, or graphite exhibit high electron mobility and current density, facilitating electron transfer with lithium ions. This facilitates smooth electron transfer with metal or semiconductor microparticles, increasing charge / discharge speeds and enhancing the charge and discharge efficiency of graphene-metal or semiconductor composite structures.

[0061] The hybrid carbon composite particles of the present invention having a protruding surface of fine particles can be used as an anode material constituting an anode active material layer, and when configured as a lithium-ion battery, it functions to absorb lithium (Li) during charging. At this time, when lithium is combined with the fine particles, the volume of the fine particles expands significantly, and when this charging and discharging process is repeated, the fine particles eventually break and lose their function as an active material. In addition, the solid electrolyte interphase (SEI) generated through the reaction between lithium ions and fine particles during the charging and discharging process severs the interconnectivity between the fine particles. In this case, since the electrical connectivity of the fine particles is reduced, the electron movement path is blocked, and the capacity of the lithium-ion battery is reduced.

[0062] At this time, the graphene constituting the hybrid carbon composite particle having the protruding surface of the above fine particles has a high electron mobility, so that electron supply is uniform and smooth, thereby playing a role in increasing the charge / discharge speed and efficiency of the all-solid-state battery, and also has a high Young's modulus, so that it can efficiently support the expansion phenomenon of the negative electrode active material due to the combination of particles such as silicon particles and lithium (Li).

[0063] In addition, because the microparticles are interconnected by graphene despite the formation of SEI, a by-product of the charge / discharge reaction, the electrical connectivity of the microparticles is maintained, thereby solving the problem of capacity reduction in lithium-ion batteries.

[0064] Meanwhile, it is preferable that the carbon constituting the hybrid carbon composite particles having the protruding surface of the above fine particles is derived from a three-dimensional porous graphene structure rather than pure graphene without defects.

[0065] Pure carbon without any general defects has excellent properties such as excellent electrical conductivity and high specific surface area, but the advantage of high specific surface area is greatly reduced due to irreversible self-aggregation.

[0066] The hybrid carbon composite particle having a protruding surface of the fine particles of the present invention is a hybrid carbon composite particle in which carbon is fixed to the surface of the fine particles through a carbonization process of amorphous carbon, graphene or graphite by heat treatment, photochemical or photothermal reaction, and the carbonized carbon has an interconnected structure, and the interconnected carbon can be configured as a single layer and / or multiple layers, and the pores between the layers can be organically connected in a three-dimensional manner to form a three-dimensional porous structure, and due to this structural feature, the self-aggregation phenomenon is reduced, so that it has a relatively larger specific surface area, and since it allows electrons and ions to diffuse more quickly, it exhibits relatively superior characteristics in electrochemical applications such as energy conversion and storage devices.

[0067] In addition, the three-dimensional porous structure organically connected on the surface and inside of the hybrid carbon composite particle having a protruding surface of fine particles has the advantage of being able to control the pore characteristics (position and size of pores, etc.) by controlling process variables during the manufacturing process.

[0068] The fine particles of the present invention are metal or semiconductor fine particles, and include lithium-nickel-cobalt-manganese composite oxide (NCM), lithium-nickel-cobalt-aluminum composite oxide (NCA), lithium-cobalt composite oxide (LCO) and lithium-nickel composite oxide (LNO), lithium manganese (LMO), lithium iron phosphate (LFP), lithium nickel-cobalt-manganese (NCM), silver (Ag), graphite, sulfur, lithium sulfur, sulfur composite, carbon sulfur complex, silicon (Si), silicon carbide (Si2C, SiC or SiC2 containing SiC) X ), silicon oxide (SiO or SiO2 containing SiO X ), silicon composite oxide (Si-Mg x SiO x ), magnesium metasilicate (enstatite, MgSiO3), foresterite (foresterite, Mg2SiO4), gold (Au), platinum (Pt), palladium (Pd), aluminum (Al), zinc (Zn), silver alloy (Ag alloy), copper (Cu) whose surface is coated with silver (Ag) and silver (Ag) whose surface is coated with copper (Cu), carbon powder, and further, the fine particles may be metal or semiconductor particles (for example, silver-coated copper particles, copper-coated silver particles, oxide-coated silicon particles, composite oxide-coated silicon particles, etc.) including core particles made of one type of material among the metals or semiconductors and a coating layer made of a different material from the core particles), but are not necessarily limited to the metal particles described above.

[0069] Here, the carbon powder is any one of acetylene black, Super P black, carbon black, Denka black, activated carbon, hard carbon or soft carbon.

[0070] Taking silver (Ag) particles as an example among the above metal particles, silver (Ag) particles dissolve in lithium (Li) and lower the energy required for lithium to crystallize, thereby allowing lithium to grow more uniformly rather than forming pores and growing unevenly, thereby ultimately contributing to improving the performance of lithium-ion batteries.

[0071] As a method for manufacturing a hybrid carbon composite particle having a protruding surface of the fine particles by complexing carbon and metal particles, a method of uniformly mixing and complexing a three-dimensional porous graphene structure and metal particles through a stirring process such as ball milling is also possible, but more preferably, a hybrid carbon composite particle having a protruding surface of the fine particles having a three-dimensional network structure in which the fine particles are manufactured as a mixture in which an organic substance and metal particles are uniformly mixed and in which interconnections between metal particles on a spherical surface and inside, interconnections between graphene sheets, and interconnections between metal particles and graphene sheets are organically formed can be manufactured.

[0072] The carbon composite particles of the present invention can also be applied to a lithium ion battery of an all-solid-state battery including a solid electrolyte layer, and the all-solid-state battery including an anode active material made of the hybrid graphene composite can be formed by including a cathode including a cathode current collector and a cathode active material layer, a solid electrolyte layer, and an anode including an anode current collector and a cathode active material layer including an anode active material made of the hybrid graphene composite.

[0073] At this time, the positive electrode active material layer may include at least one positive electrode active material selected from the group consisting of a lithium-nickel-cobalt-manganese composite oxide (NCM), a lithium-nickel-cobalt-aluminum composite oxide (NCA), a lithium-cobalt composite oxide (LCO), and a lithium-nickel composite oxide (LNO), but the composition is not necessarily limited to the positive electrode active material.

[0074] In addition, the type of the solid electrolyte constituting the solid electrolyte layer is not particularly limited, but may include a sulfide-based solid electrolyte, and may be at least one selected from the group consisting of, for example, Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-GeS2, and Li2S-SiS2-Li3PO4.

[0075] FIG. 3a is a graph showing the results of current measurement according to the concentration of an electrochemical measuring substance (PAP) for each of a hybrid carbon composite particle electrode (Hybrid Graphene complex electrode, Graphene-Ag electrode), a graphene electrode, and a metal electrode (Gold electrode) having a surface with protruding fine particles for an all-solid-state battery negative active material according to the present invention.

[0076] For each electrode, the size of the current signal increases gradually depending on the PAP concentration.

[0077] In addition, it can be seen that for the same concentration of PAP, the signal of the graphene electrode, which has the advantage of surface area and electron inflow and outflow compared to the metal electrode, is larger, and the signal of the spherical hybrid carbon composite particle electrode, which has a lower resistance compared to the graphene electrode, is measured to be larger.

[0078] Figure 3b is a conceptual diagram of a structure in which the hybrid carbon composite particles of the present invention are bonded to the surface or interior of a multilayer graphene, and can be used as a negative electrode active material.

[0079] Figure 4 shows the same concentration (10) for each of hybrid carbon composite particles (Hybrid Graphene), graphene, and metal (Au) having a protruding surface as the fine particles for the negative active material of the all-solid-state battery according to the present invention. -3 This is a graph showing the current values ​​in PAP compared to those in mM.

[0080] Referring to FIG. 4, it is a graph showing the difference in current signals measured for the same concentration of PAP for hybrid carbon composite particles (Hybrid Graphene) having a protruding surface of fine particles of an electrode for an all-solid-state battery negative active material, a metal electrode, and a graphene electrode. It can be confirmed that the size of the signal measured with the carbon-coated fine particle electrode at the same concentration is much larger than that of the comparative electrodes. Therefore, it can be seen that the current signal of the carbon-coated fine particle electrode of the present invention generates a larger signal than that of the comparative electrodes, and thus the SNR (Signal to Noise Ration) is larger than that of the comparative electrode.

[0081] Figure 5 is a graph showing the battery capacity according to the number of charge / discharge cycles when manufacturing a battery negative electrode material using silicon and when manufacturing a battery negative electrode material using hybrid carbon composite particles with protruding fine particles on the surface of the present invention. When manufacturing a battery negative electrode material using silicon, the electrical connectivity between particles decreases due to volume changes in the silicon and the formation of a solid electrolyte interphase (SEI), so that the battery capacity decreases rapidly with repeated charge / discharge cycles. On the other hand, in the case of silicon coated with graphene, the volume expansion of the silicon is suppressed by the graphene, and even when the SEI is formed, the graphene electrically interconnects the silicon, so that the capacity decrease is very small. Through this, when manufacturing a battery using the hybrid carbon composite particles with protruding fine particles on the surface of the present invention, it is possible to manufacture a battery that can significantly increase the capacity due to the silicon while also having a long lifespan.

[0082]

[0083] The present invention described above is not limited to the above-described embodiments and the attached drawings, and it will be apparent to a person skilled in the art to which the present invention pertains that various substitutions, modifications, and changes are possible within the scope that does not depart from the technical spirit of the present invention.

Claims

1. Fine particles protrude on the surface, The above fine particles are coated with carbon, The above fine particles are interconnected in part or in whole with adjacent fine particles by coated carbon. It is characterized by multiple fine particles clumped together in a three-dimensional structure. Hybrid carbon composite particles having a surface with protruding fine particles.

2. In paragraph 1, The above carbon is a hybrid carbon composite particle having a surface with protruding fine particles characterized by being any one of amorphous carbon, conductive carbon, carbon nanotubes, graphite, reduced graphene, reduced graphene oxide (rGO), graphene oxide (GO), graphene or carbon powder.

3. In paragraph 1, The above hybrid carbon composite particle is a hybrid carbon composite particle having a protruding surface of fine particles characterized by a polygonal, spherical or spherical shape with a sunken center.

4. In paragraph 1, A hybrid carbon composite particle having a surface from which the above-mentioned fine particles protrude, characterized in that the surface has a porous structure in which empty spaces exist in part or all of the fine particles.

5. In paragraph 1 The above fine particles are lithium-nickel-cobalt-manganese composite oxide (NCM), lithium-nickel-cobalt-aluminum composite oxide (NCA), lithium-cobalt composite oxide (LCO), lithium-nickel composite oxide (LNO), lithium manganese (LMO), lithium iron phosphate (LFP), lithium nickel-cobalt-manganese (NCM), silver (Ag), graphite, sulfur, lithium sulfur, sulfur composite, carbon sulfur complex, silicon (Si), silicon carbide (Si2C, SiC or SiC2 containing SiC) X ), silicon oxide (SiO or SiO2 containing SiO X ), silicon composite oxide (Si-Mg x SiO x ), magnesium metasilicate (enstatite, MgSiO3), foresterite (foresterite, Mg2SiO4), gold (Au), platinum (Pt), palladium (Pd), aluminum (Al), zinc (Zn), silver alloy (Ag alloy), copper (Cu) whose surface is coated with silver (Ag), silver (Ag) whose surface is coated with copper (Cu), or carbon powder, characterized by a hybrid carbon composite particle having a surface with protruding fine particles.

6. In paragraph 2 or paragraph 5, The above carbon powder is a hybrid carbon composite particle having a surface with protruding fine particles characterized by being any one of acetylene black, Super P black, carbon black, Denka black, activated carbon, hard carbon or soft carbon.

7. In paragraph 1, The above hybrid carbon composite particles are hybrid carbon composite particles having a protruding surface of fine particles characterized by being produced by a photochemical, photothermal or heat treatment process.

8. In paragraph 1, The above hybrid carbon composite particle is a hybrid carbon composite particle having a protruding surface with fine particles characterized by having a largest diameter of 0.1 to 100 um.

9. In paragraph 1, The above fine particles are hybrid carbon composite particles having a protruding surface, which is further characterized by the fine particles having a needle-like or plate-like shape.

10. In paragraph 9, The above plate-shaped microparticles are hybrid carbon composite particles having a protruding surface, characterized by an aspect ratio of 1:2 to 1:

200.

11. In paragraph 1, The above hybrid carbon composite particles A hybrid graphene composite particle characterized by a structure bonded to the surface or interior of a multilayer graphene.

Images