Three-layer dielectric films containing coated organic composite ceramic particles.

Abstract

A three-layer dielectric film is provided that includes coated organic composite ceramic particles. [Solution] The three-layer dielectric film 30 containing coated organic composite ceramic particles according to the present invention comprises a first film layer 31, a second film layer 37, and a third film layer 33. The first film layer comprises a first polymer material 311 and a first lithium salt 312. The second film layer comprises a second polymer material 321, a second lithium salt 322, and a plurality of second composite ceramic particles 323. The third film layer comprises a third polymer material 331, a third lithium salt 333, and a plurality of third composite ceramic particles 323'. The exterior of each second composite ceramic particle and each third composite ceramic particle is covered with a corresponding dopamine layer and a PVDF (polyvinylidene difluoride) layer.

Description

[Technical Field]

[0001] The present invention relates to a dielectric film for batteries, and more particularly to a three-layer dielectric film containing coated organic composite ceramic particles. [Background technology]

[0002] A conventional solid or semi-solid battery structure consists of an anode, a cathode, and a dielectric film located between the cathode and anode. The anode is filled with an anode slurry as a binder, and a plurality of anode particles are distributed within the anode slurry. The cathode is filled with a cathode slurry as a binder, and a plurality of cathode particles are distributed within the cathode slurry. The three-layer dielectric film is used to separate and connect the anode and cathode.

[0003] When ordinary ceramic particles become wet, they tend to generate alkaline by-products, which can easily cause lithium fluorination reactions with PVDF-HFP, leading to deterioration of the entire battery slurry and the possibility of the entire battery shorting out.Dopamine is hydrophobic, so in the prior art, the outer surfaces of the ceramic particles are coated with a dopamine layer to prevent moisture from penetrating the ceramic particles, and the functional groups of dopamine are compatible with the PAN in the polymer material of the dielectric film. Summary of the Invention [Problem to be solved by the invention]

[0004] However, the dopamine layer cannot completely cover the outer surfaces of the ceramic particles, so that some of the surfaces of the ceramic particles are exposed, which may still cause deterioration of the battery slurry.

[0005] Furthermore, conventional dielectric films have a single-layer, rigid structure and a low lithium salt concentration. Therefore, when the three-layer dielectric film is bonded to a positive electrode, the layers are not tightly packed together, resulting in poor overall structural integrity. Furthermore, conventional dielectric film materials cannot fill the gaps between the two, resulting in short circuits and reduced yields. Furthermore, the lithium salt in conventional single-layer dielectric films has only one specific concentration, resulting in high conductivity at the energy level required for lithium ions, lowering ionic conductivity and reducing overall battery performance. When a single-layer dielectric film is bonded to a negative electrode, its low ionic conductivity makes the negative electrode prone to dead lithium deposition, increasing lithium crystal formation, increasing the risk of puncture, and reducing the battery's storage capacity.

[0006] Therefore, the present inventors believed that the above drawbacks could be improved, and after extensive research, they came up with the present invention, which effectively improves the above issues through rational design.

[0007] The present invention was developed through intensive research by the present inventors in consideration of the above problems, and its purpose is to provide a three-layer dielectric film containing coated organic composite ceramic particles. [Means for solving the problem]

[0008] To achieve the above objective, one embodiment of the present invention provides a three-layer dielectric film containing coated organic composite ceramic particles. The three-layer dielectric film is formed by adding a first film layer and a third film layer to both sides of a conventional single-layer dielectric film. The first and third film layers have a flexible structure, allowing them to fill the gap between the positive and negative electrodes of a lithium battery. This reduces the gap when the positive and negative electrodes are attached, improving battery performance, reducing the risk of short circuits, and increasing battery yield. Furthermore, the outer surfaces of the composite ceramic particles in the second and third film layers are coated with corresponding PVDF layers, protecting the corresponding ceramic particles within each composite ceramic particle and preventing side reactions between the first and second ceramic particles and the polymer material of each dielectric film layer.

[0009] At least the following points will become clear from the description and drawings to be described later. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic diagram illustrating a three-layer dielectric film containing coated organic composite ceramic particles according to an embodiment of the present invention. [Figure 2] 1 is an enlarged schematic view showing a dielectric film according to an embodiment of the present invention; [Figure 3] 1 is a cross-sectional view of a second composite ceramic particle according to an embodiment of the present invention. [Figure 4] 3 is a cross-sectional view of a third composite ceramic particle in accordance with an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described below with reference to the accompanying drawings, in which: FIG. 1 is a block diagram of a conventional optical fiber cable; FIG. 2 is a block diagram of a conventional optical fiber cable;

[0012] First, a specific embodiment of a three-layer dielectric film 30 containing coated organic composite ceramic particles according to the present invention will be described with reference to FIGS. 1 to 4. FIG.

[0013] The three-layer dielectric film 30 containing coated organic composite ceramic particles according to the present invention is located between the cathode 20 and anode 10 (see FIG. 2). Anode 10 is filled with a binder, anode slurry, which is distributed among multiple anode particles (e.g., SiC particles with a tin layer) within the anode slurry. The outer surfaces of the anode particles accommodate lithium ions and facilitate uniform lithium ion flow within the anode. The anode particles partially react with lithium ions, reducing the number of available lithium ions and ultimately reducing the overall battery capacity. The cathode 20 is filled with a binder, anode slurry, which is distributed among multiple cathode particles within the cathode slurry. The cathode slurry and the cathode particles react with passing lithium ions, resulting in the depletion of available lithium ions.

[0014] 1 and 2, the three-layer dielectric film 30 of the present invention is located between the negative electrode 10 and the positive electrode 20 and is used to separate and join the negative electrode 10 and the positive electrode 20. The three-layer dielectric film 30 includes a first film layer 31, a second film layer 37, and a third film layer 33, where the first film layer 31 is connected to the positive electrode 20, the third film layer 33 is connected to the negative electrode 10, and the second film layer 37 is connected between the first film layer 31 and the third film layer 33.

[0015] 2, the first film layer 31 mainly includes the following components: The configuration of each component will be described below.

[0016] <First polymer material 311> As the base material of the first film layer 31, the first polymer material 311 includes PAN (Polyacrylonitrile), PVDF-HFP (Polyvinylidene fluoride-hexafluoropropylene copolymer), and nitrile.

[0017] The nitrile group is at least two selected from ADN (Adiponitrile), GLN (Glutaronitrile), and SN (Succinonitrile). In the first polymer material 311, the weight ratio of the PVDF-HFP to the nitrile group is between 5 and 12:1, i.e., the weight ratio of the PVDF-HFP to the nitrile group is A:B, with A being 5 to 12 times B. The weight ratio of the PVDF-HFP to the PAN is between 1:0.1 and 0.25. The weight ratio of the ADN, GLN, and SN is between 1:2:5 and 20, i.e., the weight ratio of the ADN, GLN, and SN is C:2C:E, with E being 5 to 20 times C. Since the same mathematical formulas have the same mathematical meaning, their explanations will not be repeated here.

[0018] The nitriles (e.g., ADN, GLN, and SN) in the first polymer material 311 are dispersed in the PVDF-HFP as plasticizers, and the nitriles are used to disperse the entire structure of the first polymer material 311, reducing crystalline precipitation of the first polymer material, aiding in the dissociation of the lithium salt (i.e., the first lithium salt 312 described below), and making the entire first film layer 31 easier to conduct lithium ions and easier to mold.

[0019] The function of the PAN is to prevent the crystalline precipitation of the first polymer material 311, to help conduct electrons, to enhance the electron conduction performance, and to allow electrons to penetrate the first film layer 31 and enter the middle film layer.

[0020] <First lithium salt 312> The first lithium salt 312 is dispersed in the first polymer material 311 and includes a mixture of LiBOB (LiB(C2O4)2, Lithium bis(oxalate)borate), LiTFSI (LiN(CF3SO2)2, Lithium bis(trifluoromethanesulfonyl)imide), and LiFSI (F2LiNO4S2, Lithium bis(fluorosulfonyl)imide), a weight ratio of the total weight of the first lithium salt 312 to the total weight of the first polymer material 311 is in the range of 1:2 to 7, and the LiTFSI and the LiFSI are used to enhance lithium ion conductivity. The LiBOB is used to prevent the LiTFSI and the LiFSI from being corroded by water, preventing a deterioration in overall battery performance due to attack by HF (hydrofluoric acid) generated by the reaction between water and LiTFSI. The first lithium salt 312 allows a high voltage difference to be tolerated, stabilizing the first polymer material 311 even under high pressure in the positive electrode 20. The LiBOB can enhance the stability of the first polymer material 311. In the first film layer 31, the weight ratio of the "total weight of the LiTFSI and the LiFSI" to the LiBOB is 3:2. The weight ratio of the LiFSI to the LiTFSI is 2:1.

[0021] 2, the second film layer 37 mainly includes the following components: The configuration of each component will be described below.

[0022] <Second polymer material 321> The second polymer material 321, which serves as the base material for the second film layer 37, includes a mixture of PVDF-HFP (Polyvinylidene fluoride-hexafluoropropylene copolymer), HNBR (hydrogenated nitrile butadiene rubber), and SN (Succinonitrile), and the second polymer material 321 serves as the base material. The second polymer material 321 may further include PDADMA-TFSI (poly(diallyldimethylammonium)bis(trifluoromethanesulfonyl)imide). In the second polymer material 321, the weight ratio of the PVDF-HFP, HNBR, and SN is in the range of 1:0.05-0.2:0.1-0.2.

[0023] The SN in the second polymer material 321 disperses in the PVDF-HFP as a plasticizer, and its function is to disperse the entire structure of the second polymer material 321 and reduce crystalline precipitation of the second polymer material 321. The SN is used to assist the dissociation of the lithium salt in the second film layer 37 (i.e., the second lithium salt 322 described below) and increase ionic conductivity.

[0024] <Second lithium salt 322> The second lithium salt 322 is dispersed in the second polymer material 321 and includes LiFSI, LiTSFI, and LiCl (lithium chloride). In the second film layer 37, the weight ratio of the LiFSI, LiTSFI, and LiCl is 1:2:0.1. The second lithium salt 322 is used to lower the energy level and increase stability and conductivity when conducting lithium ions through the polymer material of each layer. The weight ratio of the total weight of the second lithium salt 322 to the total weight of the second polymer material 321 is in the range of 1:3 to 1:9.

[0025] A plurality of second composite ceramic particles 323 are dispersed in the second polymer material 321, and the plurality of second composite ceramic particles 323 are used to increase the ionic conductivity and the mechanical strength of the entire three-layer dielectric film 30. The weight percentage of the total weight of the second composite ceramic particles 323 in the second polymer material 321 ranges between 8% wt and 20% wt.

[0026] 3, the second composite ceramic particle 323 mainly includes the following components: The configuration of each component will be described below.

[0027] <First ceramic particles 32> The first ceramic particles 32 have high ionic conductivity for lithium ions. Therefore, when the lithium ions pass through the three-layer dielectric film 30, the first ceramic particles 32 serve to guide and disperse the lithium ions, thereby forming uniformly distributed lithium ion channels within the three-layer dielectric film 30. The particle size of the first ceramic particles 32 is less than 100 nm.

[0028] <First dopamine layer 34> The outer surfaces of the first ceramic particles 32 are coated with the first dopamine layer 34 to form first primary particles 35. The first dopamine layer 34 is composed of polydopamine molecules. The bonding method between the polydopamine molecules and the first ceramic particles 32 is well known in the art, and therefore, the description thereof will not be repeated here.

[0029] <First PVDF (polyvinylidene difluoride) layer 36> The first ceramic particles 32 having the corresponding first dopamine layers 34 and first PVDF layers 36 coat the outer surfaces of the first primary particles 35. The first ceramic particles 32 having the corresponding first dopamine layers 34 and first PVDF layers 36 form the second composite ceramic particles 323.

[0030] The thickness of the first PVDF layer 36 is in the range of 10 nm to 100 nm, the thickness of the first dopamine layer 34 is in the range of 2 nm to 15 nm, and the whole particle size of the second composite ceramic particles 323 is less than 300 nm.

[0031] The first ceramic particles 32 have a lithium ion conducting ability (ionic conductivity of 10 -5 cm 2 The oxide having lithium ion conductivity is, for example, lithium aluminum germanium phosphate (LAGP) having a NASICON (sodium (Na) super ionic conductor) structure, and the oxide having the garnet structure is, for example, lithium lanthanum zirconium oxide (Li7La3Zr2O 12 The oxide having the perovskite structure is, for example, lithium lanthanum titanium oxide (LLTO).

[0032] When the first ceramic particles 32 are made of LLZO, the LLZO material is formed from at least one selected from the group consisting of LLZO, Ga-LLZO (Ga-doped LLZO, gallium-doped lithium-lanthanum-zirconium oxide), Cu-LLZO (Cu-doped LLZO, copper-doped lithium-lanthanum-zirconium oxide), Ta-LLZO (Ta-doped LLZO, tantalum-doped lithium-lanthanum-zirconium oxide), Sr-LLZO (Sr-doped LLZO, strontium-doped lithium-lanthanum-zirconium oxide), and Al-LLZO (Al-doped LLZO, aluminum-doped lithium-lanthanum-zirconium oxide).

[0033] When the first ceramic particles 32 are made of LAGP, the LAGP is Li 1+x Al x Ge 2-x (PO4)3 or Li 1+x+y Al x Ge 2-x-y-z M y N z (PO4)3, where x is in the range of 0.1 to 0.8, y is in the range of 0 to 0.2, and z is in the range of 0 to 0.2. M is selected from Sc 3+ (Scandium ion), Y 3+ (yttrium ion), Ga 3+ (Gallium ion), In 3+ (indium ion), La 3+ (lanthanum ion) and other trivalent cations. 4+ (zirconium ion), Si 4+ (silicon ion), Sn 4+ (tin ion) and other tetravalent cations.

[0034] 2, the third film layer 33 mainly includes the following components: The configuration of each component will be described below.

[0035] <Third polymer material 331> As the base material of the third film layer 33, the third polymer material 331 includes a mixture of PEO (Poly(ethylene oxide), polyethylene oxide), PAN, and PVDF-HFP. The weight ratio of the PEO to the PVDF-HFP and PAN is in the range of 1:1 to 3, and the weight ratio of the PEO to the PVDF-HFP and PAN is in the range of 5:1 to 10:1.

[0036] The PEO has high stability at the reduction potential of the anode 10 and favorable ionic conductivity. The PAN has good electronic and ionic conductivity, so the addition of PAN further enhances the overall performance of the PEO. The PEO is a hard material, and adding PEO provides toughness to the dielectric film and prevents puncture by lithium dendrites. The PAN in the third polymer material 331 disperses in the PEO as a plasticizer.

[0037] <Additive 332> The additive 332 is selected from the group consisting of fluoroethylene carbonate (FEC), fluoroethylene carbonate (FEC), and fluoroethylene carbonate (FEC). The additive 332 is dispersed in the third polymer material 331 and is used to help the negative electrode 10 form a good artificial solid electrolyte interphase (ASEI). The weight percentage of the additive 332 in the third polymer material 331 is less than 10% by weight.

[0038] <Tertiary Lithium Salt 333> The third lithium salt 333 is dispersed in the third polymer material 331 and is LiTFSI. During the formation or charge / discharge process, fluorine (F) from the LiTFSI and lithium (Li) ions liberated within the battery are deposited on the surface of the negative electrode 10 to form LiF (lithium fluoride), which protects the negative electrode 10 and promotes the formation of the ASEI. The third lithium salt 333 is used to lower the energy level and improve conductivity when conducting lithium ions through the polymer materials of each layer. The weight ratio of the total weight of the third lithium salt 333 to the third polymer material 331 is in the range of 1:3 to 1:9.

[0039] <Multiple Third Composite Ceramic Particles 323′> The third composite ceramic particles 323′ are dispersed in the third polymer material 331 and are used to enhance ionic conductivity, so that the negative electrode 10 has good ionic conductivity, reduces dead lithium accumulation, lowers the risk of lithium crystal formation and puncture, improves mechanical performance, suppresses partial negative electrode expansion, and provides a stress source. The weight percentage of the third composite ceramic particles 323′ in the third polymer material 331 is between 5% wt and 15% wt of the total weight.

[0040] 4, each of the third composite ceramic particles 323' mainly includes the following components: The configuration of each component will be described below.

[0041] <Second ceramic particles 32'> The second ceramic particles 32' have high ionic conductivity for lithium ions. Therefore, when the lithium ions pass through the three-layer dielectric film 30, the second ceramic particles 32' serve to guide and disperse the lithium ions, enabling the formation of uniformly distributed lithium ion channels within the three-layer dielectric film 30. The particle size of the second ceramic particles 32' is less than 100 nm.

[0042] <Second dopamine layer 34'> The second dopamine layer 34' coats the outer surfaces of the second ceramic particles 32' to form second primary particles 35'. The second dopamine layer 34' is composed of polydopamine molecules. The bonding method between the polydopamine molecules and the second ceramic particles 32' is well known in the art, and the description thereof will not be repeated here.

[0043] <Second PVDF layer 36'> The second ceramic particles 32' having the corresponding second dopamine layers 34' and second PVDF layers 36' covering the outer surfaces of the second primary particles 35' form the third composite ceramic particles 323'.

[0044] The second PVDF layer 36' has a thickness ranging from 10 nm to 100 nm, the second dopamine layer 34' has a thickness ranging from 2 nm to 15 nm, and the third composite ceramic particles 323' have an overall particle size of less than 300 nm.

[0045] The material source of the second ceramic particles 32' in each of the third composite ceramic particles 323' is the same as that of the first ceramic particles 32 in the second composite ceramic particles 323. The corresponding first ceramic particles 32 in the second composite ceramic particles 323 and the corresponding second ceramic particles 32' in the third composite ceramic particles 323' may be selected from the same material or may be formed of different materials, and the exteriors of the first ceramic particles 32 and the second ceramic particles 32' have corresponding first dopamine layers 34, second dopamine layers 34', first PVDF layers 36, and second PVDF layers 36'.

[0046] The first film layer 31 does not contain ceramic particles and is a flexible material, so it has high adhesion to the positive electrode. The first polymer material 311 of the first film layer 31 is a flexible material and may be filled in the gap between the three-layer dielectric film 30 and the positive electrode 20. The lithium salt selected for the first film layer 31 can reduce the energy level difference and increase the conductivity of lithium ions.

[0047] The concentration of the first lithium salt 312 in the first film layer 31 is higher than the concentrations of the second lithium salt 322 and the third lithium salt 333, primarily for the purpose of lowering the interfacial energy level that lithium ions must cross in the polymer material of each film layer, thereby increasing conductivity.

[0048] In the present invention, the concentration of the lithium salt in each film layer gradually decreases from the first film layer 31 to the third film layer 33, i.e., the concentration of the first lithium salt 312 in the first film layer 31 is higher than the concentration of the second lithium salt 322 in the second film layer 37. The concentration of the second lithium salt 322 in the second film layer 37 is higher than the concentration of the third lithium salt 333 in the third film layer 33, so that the energy level of the lithium ions when conducting is lowered, resulting in higher conductivity.

[0049] If the concentration of each polymer material is too high, crystalline precipitation is likely to occur, preventing the polymer from effectively linking to form a film. The plasticizer in the polymer material can prevent crystalline precipitation of each polymer material. The plasticizer supports the structure of each polymer material and enhances the overall structure of the polymer material. The plasticizer is a highly polar plasticizer, and its highly polar nature can more easily dissociate each lithium salt, increasing the amount of free lithium ions and further enhancing the lithium ion conductivity. In addition, the addition of inorganic ceramic materials (i.e., first ceramic particles 32 and second ceramic particles 32') to the second film layer 37 and the third film layer 33 can improve lithium ion conductivity and mechanical properties.

[0050] The total thickness of the first film layer 31, the second film layer 37, and the third film layer 33 is in the range of 12 μm to 24 μm. The thickness of the second film layer 37 is in the range of 10 μm to 18 μm. The thicknesses of the first film layer 31 and the third film layer 33 are each in the range of 1 μm to 3 μm.

[0051] The first film layer 31 and the third film layer 33 can be used as interfacial adhesive layers to bond the first film layer 31 to the positive electrode 20 and the third film layer 33 to the negative electrode 10 .

[0052] Although the embodiment of the present invention has been described above in detail with reference to the drawings, the specific configuration is not limited to this embodiment, and design modifications and the like are also included within the scope of the present invention without departing from the gist of the present invention. [Explanation of symbols]

[0053] 10 negative electrode 20 positive electrode 30 3-layer dielectric film 31 First film layer 32 First ceramic particle 32' Second ceramic particle 33 Third film layer 34 First dopamine layer 34'Second dopamine layer 35 1st primary particle 36 1st PVDF layer 36' 2nd PVDF layer 37 Second film layer 311 First Polymer Material 312 First Lithium Salt 321 Second Polymer Material 322 Secondary Lithium Salt 323 Secondary Composite Ceramic Particles 331 Third Polymer Material 332 Additives 333 Tertiary Lithium Salt 323' Third composite ceramic particles

Claims

1. A three-layer dielectric film including coated organic composite ceramic particles, the three-layer dielectric film comprising a first film layer, a second film layer, and a third film layer, the first film layer being connected to the positive electrode, the third film layer being connected to the negative electrode, and the second film layer being connected between the first film layer and the third film layer; The first film layer is a first polymeric material for providing a substrate for the first film layer; a first lithium salt dispersed in the first polymeric material; The second film layer is a second polymer material that serves as the base material for the second film layer; a second lithium salt dispersed in the second polymeric material, the second lithium salt being used to lower the energy level and increase stability and conductivity when conducting lithium ions through the polymeric material of each layer; a plurality of second composite ceramic particles dispersed in the second polymer material to enhance ionic conductivity and mechanical strength of the entire three-layer dielectric film; Each of the second composite ceramic particles is First ceramic particles having high ionic conductivity to lithium ions; a first dopamine layer comprising polydopamine molecules coating an outer surface of the first ceramic particle to form a first primary particle; a first PVDF layer covering the outer surface of the first primary particles; The third film layer is a third polymeric material that serves as the base material for the third film layer; a third lithium salt dispersed in the third polymeric material, the third lithium salt being used to lower the energy level and improve conductivity when conducting lithium ions through the polymeric material of each layer; a plurality of third composite ceramic particles dispersed in the third polymeric material for enhancing ionic conductivity; Each of the third composite ceramic particles is second ceramic particles having high ionic conductivity to lithium ions; a second dopamine layer comprising polydopamine molecules coating an outer surface of the second ceramic particle to form a second primary particle; a second PVDF layer covering the outer surface of the second primary particles; wherein the material source of the second ceramic particles of each of the third composite ceramic particles is the same as that of the first ceramic particles of the second composite ceramic particles, the corresponding first ceramic particles in the second composite ceramic particles and the corresponding second ceramic particles in the third composite ceramic particles are formed by selecting from the same material or different materials, and the exteriors of each of the second composite ceramic particles and each of the third composite ceramic particles all have corresponding dopamine layers and PVDF layers; The first film layer does not contain ceramic particles and is a soft material, so it has high adhesion to the positive electrode; the first polymer material of the first film layer is a soft material and is filled in the gap between the three-layer dielectric film and the positive electrode; and the lithium salt selected for the first film layer can reduce an energy level difference and improve lithium ion conductivity.

2. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the first polymer material comprises PAN, PVDF-HFP, and a nitrile system, the nitrile system being used to disperse the entire structure of the first polymer material, reduce crystalline precipitation of the first polymer material, and aid in dissociation of the lithium salt, and the nitrile system is at least two selected from the group consisting of ADN, GLN, and SN.

3. 3. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 2, wherein the weight ratio of the PVDF-HFP to the nitrile-based material in the first polymer material is in the range of 5 to 12:1, the weight ratio of the PVDF-HFP to the PAN is in the range of 1:0.1 to 0.25, and the weight ratio of the ADN, the GLN, and the SN is in the range of 1:2:5 to 20.

4. 2. The three-layer dielectric film according to claim 1, wherein the weight ratio of the total weight of the first lithium salt to the total weight of the first polymer material is in the range of 1:2 to 7, the first lithium salt comprises a mixture of LiBOB, LiTFSI, and LiFSI, the LiTFSI and the LiFSI are used to improve lithium ion conductivity, and the LiBOB is used to prevent the LiTFSI and the LiFSI from being eroded by water, and in the first film layer, the weight ratio of "the total weight of the LiTFSI and the LiFSI" to the LiBOB is 3:2, and the weight ratio of the LiFSI to the LiTFSI is 2:

1.

5. the second polymeric material comprises a blend of PVDF-HFP, HNBR, and SN; The three-layer dielectric film containing coated organic composite ceramic particles according to claim 1, characterized in that the SN in the second polymer material is used as a plasticizer and is dispersed in the PVDF-HFP.

6. 6. The three-layer dielectric film containing coated organic composite ceramic particles according to claim 5, wherein in the second polymer material, the weight ratio of the PVDF-HFP, the HNBR, and the SN is in the range of 1:0.05-0.2:0.1-0.

2.

7. 2. The three-layer dielectric film including coated organic composite ceramic particles according to claim 1, wherein the second lithium salt comprises LiFSI, LiTSFI, and LiCl, and the weight ratio of the total weight of the second lithium salt to the total weight of the second polymer material is in the range of 1:3 to 1:

9.

8. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the weight percentage of the total weight of the second composite ceramic particles in the second polymer material ranges between 8% wt and 20% wt.

9. 2. The three-layer dielectric film including coated organic composite ceramic particles according to claim 1, wherein in the second composite ceramic particles and the third composite ceramic particles, the particle size of each of the first ceramic particles and the second ceramic particles is less than 100 nm, the thickness of each of the first dopamine layer and the second dopamine layer is in the range of 2 nm to 15 nm, the thickness of each of the first PVDF layer and the second PVDF layer is in the range of 10 nm to 100 nm, and the particle size of each of the second composite ceramic particles and the third composite ceramic particles is less than 300 nm.

10. Each of the first ceramic particles and the second ceramic particles has a lithium ion conducting ability (an ion conductivity of 10 -５ cm ２ 2. The three-layer dielectric film comprising the coated organic composite ceramic particles according to claim 1, wherein at least one of the oxides is selected from the group consisting of oxides having a diffusion coefficient (diffusion coefficient) of more than 1 / s, oxides having a garnet structure, and oxides having a perovskite structure.

11. 11. The three-layer dielectric film including coated organic composite ceramic particles according to claim 10, wherein the oxide having lithium ion conductivity is selected from lithium aluminum germanium phosphate (LAGP) having a NASICON (sodium (Na) super ionic conductor) structure.

12. The oxide having the garnet structure is lithium lanthanum zirconium oxide (Li ７ La ３ Zr ２ O １２ 11. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 10, wherein the oxide having a perovskite structure is selected from the group consisting of lithium lanthanum zirconium oxide (LLZO), and the oxide having a perovskite structure is selected from the group consisting of lithium lanthanum titanium oxide (LLTO).

13. 2. The three-layer dielectric film including coated organic composite ceramic particles according to claim 1, wherein when the first ceramic particles or the second ceramic particles are made of LLZO, the LLZO material is at least one selected from the group consisting of LLZO, Ga-LLZO (Ga-doped LLZO, gallium-doped lithium lanthanum zirconium oxide), Cu-LLZO (Cu-doped LLZO, copper-doped lithium lanthanum zirconium oxide), Ta-LLZO (Ta-doped LLZO, tantalum-doped lithium lanthanum zirconium oxide), Sr-LLZO (Sr-doped LLZO, strontium-doped lithium lanthanum zirconium oxide), and Al-LLZO (Al-doped LLZO, aluminum-doped lithium lanthanum zirconium oxide).

14. When the first ceramic particles or the second ceramic particles are made of LAGP, the LAGP is preferably Li １＋ｘ Al ｘ Ge ２-ｘ (P.O. ４ ) ３ , or Li １＋ｘ＋ｙ Al ｘ Ge ２-ｘ-ｙ-ｚ M ｙ N ｚ (P.O. ４ ) ３ wherein x is in the range of 0.1 to 0.8, y is in the range of 0 to 0.2, z is in the range of 0 to 0.2, M is a trivalent cation, and N is a tetravalent cation.

15. The trivalent cation is Sc ３＋ (Scandium ion), Y ３＋ (yttrium ion), Ga ３＋ (Gallium ion), In ３＋ (indium ion), La ３＋ (lanthanum ion), and the tetravalent cation is selected from Zr ４＋ (zirconium ion), Si ４＋ (silicon ion), Sn ４＋ 15. The three-layer dielectric film comprising the coated organic composite ceramic particles of claim 14, wherein the organic composite ceramic particles are selected from the group consisting of tin ions, ...

16. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the third polymer material comprises a mixture of PEO, PAN, and PVDF-HFP, and the weight ratio of the PEO to "the PVDF-HFP and PAN" ranges from 1:1 to 3, and the weight ratio of the PEO to the PVDF-HFP and PAN ranges from 5:1 to 10:

1.

17. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the third film layer further comprises an additive, which is FEC, and the additive is dispersed in the third polymer material to help the negative electrode form a good ASEI, and the weight percentage of the additive in the third polymer material is less than 10% wt.

18. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the third lithium salt is LiTFSI, which has the effect of protecting the negative electrode and promoting the formation of ASEI.

19. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the weight percentage of the total weight of the plurality of third composite ceramic particles in the third polymer material ranges between 5% wt and 15% wt.

20. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the concentration of the first lithium salt in the first film layer is higher than the concentrations of the second lithium salt and the third lithium salt in the second film layer and the third film layer.

21. 2. The three-layer dielectric film comprising coated organic composite ceramic particles according to claim 1, wherein the sum of the thicknesses of the first film layer, the second film layer, and the third film layer is in the range of 12 μm to 24 μm, the thickness of the second film layer is in the range of 10 μm to 18 μm, and the thicknesses of the first film layer and the third film layer are each in the range of 1 μm to 3 μm.

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