Lithium secondary battery

Abstract

The present invention provides a lithium secondary battery, characterized in that a lithium deposition guide layer is provided on the surface of a negative electrode of the lithium secondary battery, thereby transforming the mode of relatively high-speed and excessively concentrated lithium ion deposition into the mode of relatively low-speed and high-uniformity lithium atom deposition; and a high-uniformity lithium metal layer is formed between the lithium deposition guide layer and the negative electrode, thereby effectively avoiding the formation of lithium dendrites.

Description

Lithium secondary battery TECHNICAL FIELD

[0001] The present invention relates to a lithium secondary battery, in particular, a lithium secondary battery with a lithium deposition guiding layer. BACKGROUND

[0002] Metallic lithium is currently the preferred anode active material for lithium secondary batteries due to its large specific discharge capacity (3860 mAh / g), low electrode potential (-3.040 V vs. standard hydrogen electrode), and low density (0.53 g / cm3). However, one of the major problems faced by metallic lithium anodes is the formation of lithium dendrites, which is also one of the safety concerns for lithium secondary batteries.

[0003] Lithium dendrite formation is easily induced by, for example, inappropriate operating conditions such as high rate or low temperature charging, overcharging the battery to a voltage beyond the specified cutoff voltage, and inappropriate balancing of the cell with a low anode / cathode capacity ratio. In terms of ion deposition and atomic deposition, ion deposition can be considered as a high-temperature grain growth mode because it exhibits a lower number of nuclei and larger grain size, while atomic deposition can be considered as a low-temperature grain growth mode because it exhibits a higher number of nuclei and smaller grain size. Based on the similar high-temperature grain growth mode, lithium deposition formed by the ion deposition mode is easily formed into lithium dendrites due to excessive concentration and grain growth, and the lithium dendrites gradually grow with the continuous progress of charge and discharge cycles. In particular, during the dissolution process (discharge), the lithium dendrite base (the end in contact with the electrode) dissolves, and the lithium dendrite detached from the base becomes a waste or idle state, also known as dead lithium, which reduces the amount of available lithium in the lithium battery and the cycle efficiency. These detached lithium dendrites with high specific surface area have high thermodynamic instability and high activity, and reactions related thereto can cause strong exothermic reactions, resulting in unstable overall voltage, which can lead to thermal runaway under internal short circuit conditions or thermal or mechanical shock conditions. In addition, lithium dendrites can also penetrate the separator, causing internal short circuits.

[0004] Therefore, the present invention provides a lithium secondary battery with a lithium deposition guiding layer to solve the above problems. SUMMARY

[0005] The main purpose of the present invention is to provide a lithium secondary battery with a lithium deposition guiding layer on the surface of the negative electrode, which can change the lithium deposition mode from the original ion high-speed non-uniform deposition mode to the atomic diffusion mode dominated by concentration difference, and then form a lithium metal layer as an anode active material by the uniform deposition mode at a reduced speed, which can effectively solve the problem of lithium dendrites generated by the non-uniform deposition of lithium ions.

[0006] To achieve the above object, the present application provides a lithium secondary battery, which comprises a positive electrode, a negative electrode, an electrolyte for transferring lithium ions between the positive electrode and the negative electrode, and a lithium deposition guide layer with a thickness less than 100 nm, which is arranged on the surface of the negative electrode and blocks the contact between the negative electrode and the electrolyte, wherein the lithium deposition guide layer comprises a multi-axial support frame and a nanoparticle film coated on the support frame, and the nanoparticle film is formed by a plurality of nanoparticles adjacently stacked. BRIEF DESCRIPTION OF DRAWINGS

[0007] Fig. 1(a) is a schematic diagram of an embodiment of the lithium secondary battery with a lithium deposition guide layer according to the present application.

[0008] Fig. 1(b) is a schematic diagram of another embodiment of the lithium secondary battery with a lithium deposition guide layer according to the present application.

[0009] Fig. 3(a) is a schematic diagram of another embodiment of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0010] Fig. 3(b) is a partial enlarged view of Fig. 3(a).

[0011] Fig. 3(c) is a schematic diagram of an embodiment of the lithium deposition guide layer of Fig. 3(a) combined with the negative electrode.

[0012] Fig. 4(a) is a schematic diagram of another embodiment of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0013] Fig. 4(b) is a schematic diagram of another embodiment of the secondary particles of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0014] Fig. 4(c) is a schematic diagram of still another embodiment of the secondary particles of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0015] Fig. 5(a) is a schematic diagram of another embodiment of the secondary particles of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0016] Fig. 5(b) is a schematic diagram of still another embodiment of the secondary particles of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0017] Fig. 6(a) is a schematic diagram of an embodiment of the lithium deposition guide layer of the lithium secondary battery according to the present application.

[0018] Fig. 6(b) is a schematic diagram of the preparation of the lithium deposition guide layer of Fig. 6(a).

[0019] 10 lithium secondary battery 12 positive electrode 121 positive electrode current collector layer 122 positive electrode active material 14 negative electrode 141 negative electrode current collector layer 142 negative electrode active material 143 recessed portion 16 lithium deposition guide layer 161 support frame 162 nanoparticle film 163 secondary particle 164 protruding portion 165 adhesive material 166 modified layer 167 agglomerated particle 169 sub-particle 17 separation layer 18 adhesive frame layer 21 liquid metal nanopowder 22 poison agent 32 temporary substrate DETAILED DESCRIPTION

[0020] In order to enable the advantages, spirit and features of the present application to be more readily understood, specific embodiments will be described and discussed in detail below. It should be noted, however, that these embodiments are intended to be merely representative embodiments of the present application, and are not intended to limit the scope of the present application in any way. The purpose of these embodiments is merely to enable the disclosure of the present application to be more thorough and complete, and to more readily enable the present application to be understood.

[0021] The terms used in the various embodiments disclosed herein are used for the purpose of describing particular embodiments only and are not intended to limit the various embodiments disclosed herein. The use of singular terms will also include the plural unless there is a clear indication otherwise. Unless otherwise defined, all terms used in the description (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the various embodiments disclosed herein belong. The above terms (such as terms defined in general use dictionaries) will be interpreted as having the same meaning as the contextual meaning in the same technical field, and will not be interpreted as having an idealized or overly formal meaning unless clearly defined in the various embodiments disclosed herein.

[0022] In the description of the present specification, the terms "an embodiment", "one embodiment", and the like are described to mean that a specific feature, structure, material or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. The illustrative expressions of the above terms in the present specification do not necessarily refer to the same embodiment. Also, the specific features, structures, materials or characteristics described can be combined in any suitable manner in one or more embodiments.

[0023] Referring to FIG. 1(a), an embodiment of a lithium secondary battery with a lithium deposition guide layer according to the present application is shown. As shown, the lithium secondary battery 10 includes a cathode 12, an anode 14, an electrolyte (not shown), and a lithium deposition guide layer 16. The electrolyte is used to transfer lithium ions between the cathode 12 and the anode 14. The lithium deposition guide layer 16 is disposed on the surface of the anode 14 and is capable of effectively preventing the electrolyte from contacting the anode 14. The top surface of the lithium deposition guide layer 16 provides a deposition site for lithium ions in the electrolyte during charging of the lithium secondary battery 10, i.e., the top surface serves as a lithium ion deposition surface. The lithium deposition guide layer 16 includes a multi-axial support frame and a nanoparticle film coated on the support frame and filling the hollow locations of the support frame, so that the lithium deposition guide layer 16 is capable of sufficiently preventing the electrolyte from penetrating into the anode 14. The nanoparticle film is formed by a plurality of nanoparticles abutting and stacking. In addition, the distance between the top surface and the bottom surface of the lithium deposition guide layer 16 (also referred to as the thickness) is less than 100 nm, preferably less than 50 nm, and more preferably less than 20 nm. The support frame and the nanoparticle film will be described in subsequent embodiments and figures.

[0024] The material of the nanoparticle film can be selected from silicon, arsenic, bismuth, aluminum, indium, or a mixture of two or more of the above materials. The material of the support frame can be carbon and can be planar, curved into a spherical shape (spheroid), or a mixture thereof. The support frame can have a fiber shape or a mesh shape. The negative electrode 14 includes a negative electrode current collector layer 141 and a negative electrode active material layer 142 of lithium on a top surface of the negative electrode current collector layer 141 facing the positive electrode 12. The negative electrode active material layer 142 can be originally present or can be formed by deposition of lithium during charging of the lithium secondary battery 10, i.e., a so-called negative-electrode-free lithium secondary battery. The positive electrode 12 includes a positive electrode current collector layer 121 and a positive electrode active material layer 122 on a surface of the positive electrode current collector layer 121 facing the negative electrode 14. At least one inactive variable frame layer 18 can be provided between the positive electrode current collector layer 121 and the negative electrode current collector layer 141 to seal the positive electrode active material layer 122, the negative electrode active material layer 142, the electrolyte, and the lithium deposition guide layer 16 in an encapsulation member formed by the positive electrode current collector layer 121, the negative electrode current collector layer 141, and the variable frame layer 18 to prevent the positive electrode active material layer 122, the negative electrode active material layer 142, the electrolyte, and the lithium deposition guide layer 16 from being affected by the external environment. The material of the frame layer 18 can be any adhesive that can adhere to the positive electrode current collector layer 121 without the positive electrode active material layer 122 and can adhere to the negative electrode current collector layer 141 without the negative electrode active material layer 142 and can withstand the corrosion of the relevant chemical materials in the lithium secondary battery. Furthermore, the material of the frame layer 18 can be selected from thermoplastic or thermosetting plastic, such as silicone. The above examples of the electrolyte refer to any existing electrolyte type at the time of filing this application.

[0025] In addition, when the electrolyte is in a non-solid state, a separator layer 17 can be provided between the positive electrode 12 and the negative electrode 14 to prevent the positive electrode 12 and the negative electrode 14 from contacting each other while allowing the electrolyte to pass through. The separator layer 17 is located between the lithium deposition guide layer 16 and the positive electrode 12. The material of the separator layer 17 can be any of various examples that can be implemented in the prior art, but is preferably directly stacked from ion-conductive or non-ion-conductive ceramic powder without a polymer-woven substrate.

[0026] The lithium deposition guiding layer 16 has a certain thickness range, and the surface of the lithium deposition guiding layer 16 in contact with the electrolyte must be electron-conductive, or the electrons must be able to pass to the surface of the lithium deposition guiding layer 16 in contact with the electrolyte, so that the lithium ions passing in the electrolyte can obtain electrons after contacting the surface of the lithium deposition guiding layer 16, and then form atom on the surface of the lithium deposition guiding layer 16. Then, the atom diffuses into each nanoparticle in the nanoparticle film due to the concentration difference, and forms small-grained lithium deposition with polycrystal seeds similar to low-temperature type grain growth on the surface close to the negative electrode 14. Therefore, the lithium deposition guiding layer 16 of the present application can change the lithium deposition growth speed from the original ion high-speed non-uniform deposition type to the atom diffusion dominated by the concentration difference, thereby achieving the uniform deposition type with reduced speed. Moreover, the ion deposition is affected by external environmental parameters such as electric field, current, pH value, etc., while the atom deposition is mainly dominated by the concentration difference, so that the lithium deposition layer formed by the atom deposition method has relatively high and stable uniformity.

[0027] Based on the above-mentioned architecture and related materials and process description of the present application, the lithium deposition guiding layer 16 of the present application has the following several embodiments:

[0028]

Embodiment 1

[0029] Please refer to FIG. 2, which is a first structure schematic diagram of the lithium deposition guiding layer 16. As shown in the figure, the support frame 161 has a whole appearance of a sheet shape, and the nanoparticle film 162 is formed on the support frame 161 by using a chemical vapor deposition method or a physical vapor deposition method. For example, when the material of the nanoparticle film 162 is silicon, the nanoparticle film 162 is formed by depositing and stacking adjacent silicon nanoparticles on the support frame 161 by decomposing silane (SiH4) gas.

[0030] The particle size of these silicon nanoparticles is about 1 nm to 10 nm, and adjacent particles have at least a direct contact area without other materials, such as adhesives or polymers, between the adjacent particles. The material of the support frame 161 can be any material that can withstand the process steps of the chemical vapor deposition method or the physical vapor deposition method, such as the decomposition and deposition of silane materials, and can be attached to form silicon nanoparticles. The material of the support frame 161 can be carbon material, such as hard carbon, soft carbon, or carbon tube, and the detailed structure can be fibrous with short branches or net-like with overlapping and interwoven each other.

[0031] The nano-silicon particles have very small crystal grains, low length of crystal in the particles, and few crystal defects and impurities. In addition, the specific surface area is large. Therefore, after lithium ions transferred through the electrolyte obtain electrons on the surface of the lithium deposition guide layer 16 to become lithium atoms, the lithium atoms diffuse into the nano-silicon particles through the surface of the nano-silicon particles, and the lithium atoms are deposited on the surface of the negative electrode 14 at a reduced speed and uniformly driven by the concentration difference. At the same time, because the lithium deposition guide layer 16 is composed of nano-particles, the stress generated by volume expansion is easily released, so the lithium deposition guide layer 16 is not easily deformed and broken. By using the material characteristics of nano-particles, the influence of defects such as grain boundaries on diffusion can be effectively reduced, and there are enough surfaces to provide lithium ion deposition sites, and lithium atoms diffuse in the nano-silicon particles. In addition, because the material characteristics of the nano-particle film 162 are formed by adjacent particles and particles at least partially in direct contact with each other to form a thin film, the porosity is less than the viscosity of the electrolyte, so the nano-particle film 162 can effectively prevent the electrolyte from contacting the negative electrode 14. The part where the particles are in direct contact with each other provides a way for lithium atoms to diffuse between particles.

[0032] In addition, because the lithium deposition guide layer 16 only the part of the surface in contact with the electrolyte will form an SEI layer (solid-state electrolyte interface layer), and the surface area in contact with the electrolyte is relatively small compared to the total surface area of the lithium deposition guide layer 16, the generated SEI layer can be effectively reduced, and the loss of lithium can be reduced.

[0033] The above-mentioned method of forming the lithium deposition guide layer 16 on the surface of the negative electrode 14 can be directly forming the lithium deposition guide layer 16 on the surface of the negative electrode 14, or indirectly forming, for example, by forming the lithium deposition guide layer 16 through a temporary substrate, and then transferring the lithium deposition guide layer 16 to the surface of the negative electrode 14.

[0034] In the example of embodiment 1, the negative electrode 14 can also be replaced by the current collector layer of the negative electrode, that is, the lithium deposition guide layer 16 is applied to the so-called negative electrode-free lithium metal battery. In this case, the lithium deposition guide layer 16 is directly arranged on the surface of the negative electrode current collector layer 141, as shown in FIG. 1(b), to uniformly deposit lithium atoms guided through the lithium deposition guide layer 16 between the lithium deposition guide layer 16 and the negative electrode current collector layer 141.

[0035]

Embodiment 2

[0036] Referring to FIG. 1(a), FIG. 1(b), and FIG. 3(a), which illustrates another embodiment of the lithium deposition guiding layer 16 of the present application. In this embodiment, the lithium deposition guiding layer 16 is formed by tightly stacking a plurality of secondary particles 163. As shown in FIG. 3(b), each of the secondary particles 163 is formed by agglomerating a plurality of sub-particles 169 formed by a spheroid (or globular) support frame 161 and a nanoparticle film 162 attached to the support frame 161. The support frame 161 and the nanoparticle film 162 are described above and will not be repeated here.

[0037] These secondary particles 163 can be directly disposed on the surface of the negative electrode 14 in a dry manner by pressing to form the lithium deposition guiding layer 16. In this embodiment, the density of the pressing can differentiate the lithium deposition guiding layer 16 into an electrolyte permeable region and an electrolyte impermeable region. The difference between the electrolyte permeable region and the electrolyte impermeable region is that the closer to the surface of the negative electrode 14, the higher the density of the secondary particles 163 due to the pressing, and the higher pressure also reduces the degree of agglomeration, thereby forming a region that effectively blocks the penetration of the electrolyte. Furthermore, when the negative electrode 14 has a negative electrode active material layer 142 of lithium metal, because the hardness of the lithium metal is low, it will deform after being pressed, and these secondary particles 163 will be partially embedded in the negative electrode active material layer 142. In this case, the lithium metal material will serve as connective tissue to fill between the secondary particles 163.

[0038] In this example, the secondary particles are formed by secondary granulation to greatly reduce the overall surface area. For example, if the nanosilicon particles are 1-10 nm, the secondary particles 163 formed by secondary granulation are 0.6-1.2 microns. Therefore, if it is assumed that the secondary particles 163 are composed of about 100 nanosilicon particles, the total surface area of the original silicon particles is about 100-1000 m 2 / g, but the surface area of the secondary particles 163 is about 1.6-1.8 m 2 / g. Therefore, the secondary granulation method can greatly reduce the surface area, thereby reducing the formation of SEI and the loss of lithium. Furthermore, secondary granulation increases the particle size, which is beneficial for operation.

[0039] Referring to Fig. 3(c), it is a derivative of Fig. 3(a). The derivative is that the interface between the negative electrode 14 and the lithium deposition guide layer 16 is formed with a plurality of regular recesses 143, and the bottom surface of the lithium deposition guide layer 16 has a plurality of protrusions 164 corresponding to the recesses 143 after being pressed. The recesses 143 can be arc-shaped or polygonal, so as to increase the contact area between the lithium deposition guide layer 16 and the negative electrode 14 and achieve the positioning effect. Furthermore, by the structure and shape of the recesses 143, the secondary particles 163 accommodated in the recesses 143 can be pushed against each other when the volume varies, so as to achieve the effect of effectively inhibiting the volume expansion variation. The recesses 143 can be achieved by dry pressing mold design.

[0040] In addition, when the material of the nanoparticle film 162 of the lithium deposition guide layer of the above-mentioned embodiments uses a liquid metal material that can be alloyed with lithium, such as elemental or alloy materials of arsenic, bismuth, aluminum, or indium, etc., because the nanoparticles formed by the liquid metal have low hardness and can be extruded and deformed, the nanoparticle film of the liquid metal is easier to form an electrolyte barrier region on the surface of the negative electrode 14 than when silicon is used as the material of the nanoparticle film.

[0041]

Embodiment 3

[0042] This embodiment is that when the material of the nanoparticle film of the lithium deposition guide layer is silicon, the lithium deposition guide layer 16 of Embodiments 1-2 is mixed with liquid metal nanopowder 21 that can be alloyed with lithium. For example, as shown in Fig. 4(a), the lithium deposition guide layer 16 is doped with liquid metal nanopowder 21. Alternatively, as shown in Fig. 4(b), the secondary particles 163 are doped with liquid metal nanopowder 21. When silicon is used as the material of the secondary particles 163, the secondary particles 163 only transmit electrons through the support frame 161. When the liquid metal nanopowder 21 that is easy to conduct electricity and has lower hardness than silicon is added, the overall conductivity of the secondary particles 163 can be increased, and the liquid metal nanopowder 21 between the secondary particles 163 can also act as a buffer zone for the volume variation of the secondary particles 163. In addition, the liquid metal nanopowder 21 can also act as an adhesive between the secondary particles 163, as shown in Fig. 4(c).

[0043] In addition, a poisoning agent 22 can be disposed between the secondary particles 163, as shown in FIG. 5(a) and FIG. 5(b). The poisoning agent includes an iodine molecule provider that releases iodine molecules at a second predetermined temperature to initiate the formation of stable-state iodine compounds or lithium ions from the high-activity unstable state of lithium atoms when the temperature of the lithium secondary battery using the present application reaches or approaches a first default temperature, thereby deactivating the negative electrode active material of the lithium secondary battery to achieve so-called inactivation to avoid thermal runaway. The first default temperature here refers to greater than 100°C, and preferably greater than 120°C, while the second temperature is lower or higher than the first default temperature and will vary depending on the example of the iodine molecule provider. The so-called stable-state lithium compound here can be, for example, lithium iodide, lithium fluoride, lithium iodine compounds, or lithium fluoride compounds, but is not limited thereto, because as is well known, the electrochemical system of a lithium secondary battery is a complex multi-component architecture, and the reactions that occur at the first default temperature belonging to higher temperatures are also complex, so the stable-state lithium compound stated here is relative to the activity state of lithium atoms, and is not limited to the stable-state lithium compound being lithium iodide, lithium fluoride, lithium iodine compounds, or lithium fluoride compounds, or that the lithium compound is anaerobic, non-flammable, and stable below 300 degrees. The poisoning agent claimed here is as disclosed in the WO2024 / 169768 application filed by the present inventor.

[0044] [Example 4]

[0045] Referring to FIG. 6(a), another embodiment of the lithium deposition guide layer of the present application is shown. The lithium deposition guide layer 16 includes a plurality of barrel-shaped multi-axial support frames 161, a nanoparticle film 162 coated on the support frames 161, and an adhesive material 165 located between and adjacent to the multi-axial support frames 161 to bond the multi-axial support frames 161, and the adhesive material 165 can be silicone. Furthermore, to increase the bonding strength of the multi-axial support frames 161 and the adhesive material 165, the sidewall surface of the multi-axial support frames 161 can have a modified layer 166 of silicon methane.

[0046] The lithium deposition guiding layer 16 is formed by first coating a nano-particle film 162 on the surface of a multi-axial support frame 161 in a spherical or cluster shape, then forming a modified layer 166 of silicon methane on the surface of the cluster support frame 161. The modified layer 166 can be formed on the surface of the support frame 161 coated with the nano-particle film 162 by a fluidized bed process or by soaking the support frame 161 in a solvent mixed with a modified material and then drying. Then, the cluster particles 167 with the modified layer on the surface are mixed with a bonding material. Next, a film is formed on the surface of a temporary substrate 32 by coating, as shown in FIG. 6(b). Subsequently, the upper half and the bottom of the film are removed to expose the support frame 161 and the nano-particle film 162 with larger surfaces at the top and the bottom to provide more deposition sites for lithium ions and lithium atoms. The removal is performed by, for example, laser or chemical mechanical polishing (CMP). Furthermore, the modified layer and the bonding material at the bottom are removed to enable the support frame 161 and the nano-particle film 162 to directly contact the negative electrode 14 for electron transmission and lithium atom deposition.

[0047] In summary, the present application provides a lithium secondary battery with a lithium deposition guiding layer to change the lithium deposition in the lithium secondary battery from the original high-speed non-uniform lithium ion deposition pattern to a uniform deposition pattern dominated by lithium atom diffusion with reduced speed, thereby forming a lithium metal layer with high uniformity on the surface of the negative electrode and effectively avoiding the formation of lithium dendrites and the related safety problems.

Claims

1. A lithium secondary battery comprising: a positive electrode; a negative electrode; an electrolyte for transporting lithium ions between said positive electrode and said negative electrode; and a lithium deposition guide layer disposed on a surface of said negative electrode and blocking said electrolyte from contacting said negative electrode, a top surface of said lithium deposition guide layer receiving said lithium ions from said electrolyte and forming a lithium deposition layer on a bottom surface of said lithium deposition guide layer, said lithium deposition guide layer comprising: a plurality of support frames; and a nanoparticle film coated on said support frames, said nanoparticle film being formed by a plurality of nano-sized particles adjacently stacked together; wherein a distance between said top surface and said bottom surface of said lithium deposition guide layer is less than 100 nm.

2. The lithium secondary battery of claim 1, further comprising a separator layer between said positive electrode and said negative electrode to prevent said positive electrode from directly contacting said negative electrode, said separator layer allowing said electrolyte to pass through.

3. The lithium secondary battery of claim 2, wherein said separator layer is formed by a plurality of ceramic powders stacked together.

4. The lithium secondary battery of claim 1, wherein said distance between said top surface and said bottom surface of said lithium deposition guide layer is less than 50 nm.

5. The lithium secondary battery of claim 1, wherein said lithium deposition guide layer is formed by a plurality of secondary particles, each of said secondary particles being formed by a plurality of primary particles, each of said primary particles comprising a bulk of said support frames and said nanoparticle film coated on said support frames.

6. The lithium secondary battery of claim 1, wherein said lithium deposition guide layer is further doped with liquid metal nanopowder.

7. The lithium secondary battery of claim 1, wherein a top surface of said negative electrode has a plurality of recesses, a bottom surface of said lithium deposition guide layer has a plurality of protrusions corresponding to said recesses to position said lithium deposition guide layer on said surface of said negative electrode.

8. The lithium secondary battery of claim 1, wherein said lithium deposition guide layer further comprises a plurality of barrel-shaped support frames and an adhesive material between adjacent said support frames to adhere said support frames.

9. The lithium secondary battery of claim 8, wherein a sidewall of said support frame is further coated with a modification layer.

10. The lithium secondary battery of claim 1, wherein a material of said nanoparticle film is selected from silicon, arsenic, bismuth, aluminum, indium, or a mixture of two or more of the above materials.

11. The lithium secondary battery of claim 1, wherein a material of said support frame is selected from carbon materials and said support frame can be in a sheet or bulk shape.

12. The lithium secondary battery of claim 1, wherein said negative electrode comprises a negative current collector layer and a negative active material layer having a lithium metal on a surface of said negative current collector layer facing said positive electrode.

13. The lithium secondary battery of claim 12, wherein said negative active material layer is formed by deposition of said lithium secondary battery during charging.

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