Negative pole piece, secondary battery and device

Abstract

The invention provides a negative pole piece, a secondary battery and a device. The negative pole piece comprises a current collector and a conductive layer arranged on the surface of the current collector, the conductive layer comprises crystalline nanometer conductive carbon and amorphous nanometer conductive carbon, the grain size of the crystalline nanometer conductive carbon and the grain size of the amorphous nanometer conductive carbon are independently selected from 1-50 nm, and the surface roughness of the conductive layer is smaller than 1.5 micrometers. The negative electrode plate provided by the invention is relatively uniform in current density distribution on the surface of the electrode in the application process, relatively low in lithium dendrite occurrence probability, and relatively excellent in coulombic efficiency and safety.

Description

Technical Field

[0001] The present invention relates to the field of manufacturing lithium metal all-solid-state batteries, and more particularly, to a negative electrode sheet, a secondary battery, and a device. Background Art

[0002] Currently, the energy density of lithium-ion batteries has reached the limit of 300 Wh / kg - 350 Wh / kg, but this still cannot meet the application requirements of high safety and high energy density in portable electronic devices, electric vehicles, and large-scale energy storage. Among the materials that can be used as the negative electrode of lithium batteries, metallic lithium has a high theoretical specific capacity and the lowest electrochemical potential (-3.04 V relative to the standard hydrogen electrode), making it the best choice for the negative electrode material of next-generation high-energy lithium batteries.

[0003] When lithium is used as the negative electrode active material, the current density distribution on the surface of the negative electrode of the lithium metal battery is uneven. Especially at high current densities, the deposited lithium will turn into dendrites, resulting in a decrease in the Coulombic efficiency of the battery cycle, a gradual decrease in the current density that can be tolerated, and an unstable cyclic SEI film, with continuous decomposition and production of SEI. Similar problems also exist in all-solid-state battery systems, such as lithium dendrite growth and low Coulombic efficiency, which can lead to safety risks in metal lithium batteries. Summary of the Invention

[0004] The present invention aims to provide a negative electrode sheet, a secondary battery, and a device to solve the problems of uneven current density distribution on the surface of the negative electrode of the existing negative electrode sheet using lithium as the negative electrode active material, resulting in lithium dendrite growth, reduced Coulombic efficiency, and inability to guarantee safety.

[0005] A first aspect of the present application provides a negative electrode sheet, which includes a current collector and a conductive layer disposed on the surface of the current collector. The conductive layer includes crystalline nano-conductive carbon and / or amorphous nano-conductive carbon. The particle sizes of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon are independently selected from 1 nm to 50 nm, and the surface roughness of the conductive layer is < 1.5 μm.

[0006] A second aspect of the present application further provides a secondary battery, which includes a positive electrode sheet, an electrolyte layer disposed on the positive electrode sheet, and the above-mentioned negative electrode sheet.

[0007] A third aspect of the present application further provides a device, which includes the above-mentioned secondary battery.

[0008] Advantageous Effects:

[0009] The nano-conductive carbon in the conductive layer can form a compound with lithium ions as a buffer layer of an ion-electron mixed conductor, which can make the interfacial current density distribution between current collectors uniform, enable lithium ions to be uniformly deposited on the current collector, ensure physical and chemical stability during the long-term cycling of the battery, and regulate the deposition and stripping of lithium ions. At the same time, the conductive carbon with a specific nano-particle size range used in this application has a large specific surface area and surface energy, and can easily adhere to the heterogeneous interface, thus being able to well improve the structural stability of the negative electrode sheet. In addition, by controlling the surface roughness of the conductive layer, the formation of lithium dendrites can be well inhibited, thereby improving the electrochemical performance of the negative electrode sheet. On this basis, the negative electrode sheet provided in this application has a relatively uniform current density distribution on the electrode surface during application, and a low probability of lithium dendrite appearance, and has excellent Coulomb efficiency and safety. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 Shows the lithium ion deposition curves of the lithium ion all-solid-state batteries prepared in Example 1 and Comparative Example 1 of the present invention;

[0011] Figure 2 Shows the charge and discharge curves of the lithium ion all-solid-state battery prepared in Example 2 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0012] For the sake of brevity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, each individually disclosed point or single numerical value itself can be used as a lower limit or an upper limit and combined with any other point or single numerical value or combined with other lower limits or upper limits to form a range not explicitly recited.

[0013] In the description herein, unless otherwise specified, "above" and "below" include the number itself.

[0014] Unless otherwise specified, the terms used in this application have the well-known meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values of the various parameters mentioned in this application can be measured by various common measurement methods in the art (for example, they can be tested according to the methods given in the embodiments of this application). It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other.

[0015] As described in the background art, when lithium is used as the negative electrode active material, due to the uneven distribution of the current density on the surface of the battery negative electrode, problems such as the growth of lithium dendrites, the reduction of Coulomb efficiency, and the inability to guarantee safety occur. To solve the above technical problems, the present application provides a negative electrode sheet, which includes a current collector and a conductive layer provided on the surface of the current collector. The conductive layer includes crystalline nano-conductive carbon and / or amorphous nano-conductive carbon. The particle sizes of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon are independently selected from 1 nm to 50 nm, and the surface roughness of the conductive layer is <1.5 μm.

[0016] The nano-conductive carbon in the conductive layer can form a compound with lithium ions as a buffer layer of an ion-electron mixed conductor, which can make the interface current density distribution between the current collectors uniform, and make the lithium ions deposit uniformly on the current collectors, so as to ensure the physical and chemical stability during the long-term cycling of the battery and regulate the deposition and stripping of lithium ions. At the same time, the conductive carbon with a specific nano-particle size range used in the present application has a large specific surface area and surface energy, and can easily adhere to the heterogeneous interface, thus being able to well improve the structural stability of the negative electrode sheet. In addition, by controlling the surface roughness of the conductive layer, the formation of lithium dendrites can be well inhibited, thereby improving the electrochemical performance of the negative electrode sheet. On this basis, the negative electrode sheet provided by the present application has a relatively uniform current density distribution on the electrode surface during application, and a relatively low probability of lithium dendrite appearance, and has excellent Coulomb efficiency and safety.

[0017] In some embodiments of the present application, the conductive layer includes crystalline nano-conductive carbon and amorphous nano-conductive carbon, and the weight ratio of the crystalline nano-conductive carbon to the amorphous nano-conductive carbon is (5-50):(50-95).

[0018] The nano-conductive carbon used in the present application includes crystalline nano-conductive carbon and amorphous nano-conductive carbon, which belong to a mixture of short-range disordered and ordered structures and have certain electrochemical activity. The transmission mechanism of surface adsorption / desorption and lithium cluster storage in the nano-pores can provide an isotropic and non-preferential orientation three-dimensional lithium transmission path. When the above negative electrode sheet is charged and discharged, the interface current density can be gradient-uniformly distributed between the negative electrode current collectors, and the lithium ions can deposit more uniformly on the negative electrode current collectors, so as to further inhibit the generation of lithium dendrites during the cycling process and improve the cycling efficiency, always maintain physical and chemical stability, and regulate the deposition and stripping of lithium ions.

[0019] The particle sizes of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon can be selected as 8nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, or a range formed by any two of the above values. To further improve the cycling efficiency of the lithium-ion battery, preferably, the particle sizes of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon are independently selected from 10nm to 50nm.

[0020] In some embodiments of the present application, the crystalline nano-conductive carbon includes at least one of ordered mesoporous carbon, hard carbon, soft carbon, bucky carbon, graphene, and graphite.

[0021] In some embodiments of the present application, the amorphous nano-conductive carbon includes but is not limited to at least one of nano-carbon powder, carbon black, acetylene black, ketjen black, furnace black, channel black, activated carbon, and rubber carbon black.

[0022] The peak height ratio of the D band to the G band of the Raman shift of the above-mentioned crystalline nano-conductive carbon and / or amorphous nano-conductive carbon is 0.12 to 0.94, and the peak area ratio is 0.8 to 3.5. When the peak height ratio of the D band to the G band of the Raman shift is too small, the improvement of the electrochemical performance of the negative electrode sheet is insufficient, and when it is too large, it is easy to affect the structural stability of the conductive layer. When the peak height ratio of the D band to the G band of the Raman shift is limited within the above range, the larger the peak height ratio of the D band to the G band of the Raman shift of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon, the greater the defects inside the conductive carbon, and the more conducive it is to the migration of lithium ions, thereby being able to better improve the electrochemical cycling performance during the application of the negative electrode sheet. The peak height ratio of the D band to the G band of the Raman shift of the crystalline nano-conductive carbon and / or amorphous nano-conductive carbon can be selected as 0.12, 0.13, 0.15, 0.18, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.78, 0.8, 0.85, 0.9, 0.94, or a range formed by any two of the above values. To further improve its cycling performance, preferably, the peak height ratio of the D band to the G band of the Raman shift of the crystalline nano-conductive carbon and / or amorphous nano-conductive carbon is 0.78 - 0.94.

[0023] To further improve the cycling efficiency of the lithium-ion battery, preferably, the surface roughness of the conductive layer is 0.2μm to 0.5μm. The surface roughness of the conductive layer can be selected as 0.2μm, 0.25μm, 0.3μm, 0.35μm, 0.4μm, 0.45μm, 0.5μm, or a range formed by any two of the above values.

[0024] The thickness of the conductive layer affects the energy density of the electrode. The greater the thickness, the lower the energy density. Preferably, in some embodiments of the present application, the thickness of the conductive layer is 0.2 μm to 5 μm. It can be selected as 0.2 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, or the range formed by any two of the above values. More preferably, it is 0.2 μm to 1 μm.

[0025] In some embodiments of the present application, the conductive layer further includes a first binder, and the first binder includes but is not limited to at least one of polyvinylidene fluoride, styrene-butadiene rubber, and polyvinyl alcohol-acrylic acid.

[0026] In some embodiments of the present application, the negative electrode does not contain negative electrode active materials such as graphite, Si, Sn, and P. Only the current collector is used as the negative electrode, while the positive electrode uses common lithium-containing materials (such as lithium iron phosphate, ternary positive electrode, lithium cobalt oxide, etc.) to form a battery system. In some embodiments of the present application, the current collector used for the negative electrode includes but is not limited to one of copper foil, nickel foil, stainless steel foil, or surface-modified copper foil, nickel foil, and stainless steel foil. Using the above types of current collectors directly for the negative electrode instead of ultra-high chemical activity metallic lithium brings great convenience and guarantee to battery assembly and safety.

[0027] In some other embodiments of the present application, the current collector is a copper-lithium composite material. Different from the traditional method of setting a negative electrode active material layer on the current collector, when using a copper-lithium composite material as the current collector, since lithium in the copper-lithium composite material serves as the negative electrode active material, there is no need to additionally set a negative electrode active material layer during the preparation process of the negative electrode. The conductive layer can be directly set on the surface of the copper-lithium strip.

[0028] In some embodiments of the present application, the above copper-lithium composite material is prepared by the following method: embedding a copper mesh into lithium metal through mechanical processing to form a copper-lithium current collector. Compared with the untreated lithium negative electrode, the three-dimensional spatial structure of the above copper-lithium current collector can accelerate the charge transfer speed and reduce the interface resistance; the larger specific surface area reduces the local current density, making the charge distribution uniform, and the lithium deposition becomes uniform, thus reducing the growth rate of lithium dendrites.

[0029] The second aspect of the present application also provides a secondary battery, which includes a positive electrode, an electrolyte layer disposed on the positive electrode, and the negative electrode provided by the present application.

[0030] In some embodiments of the present application, the positive electrode uses LiNi 0.8 Co 0.1 Mn 0.1O2 is used as the active material, VGCF (vapor-grown carbon fiber reinforcement, also known as carbon whiskers or graphite whiskers) is used as the main conductive agent, PTFE (polytetrafluoroethylene) is used as the binder, and the solid electrolyte is used as the lithium-ion conductive medium. The electrode sheet formulation ratio is LiNi 0.8 Co 0.1 Mn 0.1 O2:VGCF:PTFE:Li6PS5Cl = 85:1:0.5:12.5. The PTFE in the mixed material is fibrillated through a high-speed shearing process to form a network structure inside the coating. Using a hot roll press, the process parameters are adjusted, and the temperature is set in the range of 10 - 350 °C to press into a positive electrode coating; subsequently, the electrode film is hot-pressed and compounded on both sides of the positive aluminum current collector (double-sided coating) to obtain a positive electrode coating with a uniform electrode sheet thickness, a dense interior of the coating, and a high tap density. Generally, the tap density is achieved to be 3.5 mg / cm 3 ~3.65 mg / cm 3 , and the double-sided electrode coating thickness is controlled within 200 μm.

[0031] In some embodiments of the present application, the thickness of the electrolyte layer is 10 μm - 50 μm, the density is greater than 97%, and the electrolyte is a sulfide solid electrolyte.

[0032] In the above secondary battery, the electrolyte forming the electrolyte layer can be of the types commonly used in the art. In some embodiments of the present application, the electrolyte includes at least one of a sulfide solid electrolyte and an oxide electrolyte.

[0033] In some embodiments of the present application, the sulfide solid electrolyte includes at least one of Li6PS5Cl, Li6PS5Cl 0.5 Br 0.5 , Li 10 GeP2S 12 and Li3PS4; the electrolyte layer includes an electrolyte and a second binder, and the second binder includes at least one of SBR (styrene-butadiene rubber), NBR (nitrile rubber), HNBR (hydrogenated nitrile rubber), FNBR (fluorinated nitrile rubber), BR (cis-1,4-polybutadiene rubber), and IIR (isobutylene-isoprene rubber).

[0034] In some embodiments of the present application, the oxide electrolyte includes at least one of a perovskite-type solid electrolyte, a garnet-type solid electrolyte, a NASICON-type solid electrolyte, and an organic polymer electrolyte.

[0035] Optionally, the perovskite-type solid electrolyte includes LLTO (lithium lanthanum titanate, Li 0.33 La 0.56 TiO3), and the garnet-type solid electrolyte includes LLZO (lithium lanthanum zirconium oxide, Li7La3Zr2O12 ),The NASICON (sodium superionic conductor) type solid electrolyte includes LATP (lithium aluminum titanium phosphate, Li 1.3 Al 0.3 Ti 1.7 (PO4)3), and the organic polymer electrolyte includes polyethylene oxide (PEO) and polymers with certain structural similarities.

[0036] During the formation of the electrolyte layer, solvents such as toluene, xylene, anisole, etc., can be added alone or in combination for film-forming effect. After film formation, the above solvents are removed by volatilization.

[0037] In some embodiments of the present application, the method for preparing the negative electrode sheet includes: directly forming a conductive layer on the current collector, and the method for forming the conductive layer includes spin coating, drop coating, spray coating, pyrolysis, or solution filtration to form a film on the current collector.

[0038] According to some embodiments of the present application, the secondary battery is a lithium secondary battery. In some embodiments, the lithium secondary battery includes, but is not limited to: lithium metal secondary battery, lithium ion secondary battery, lithium metal polymer secondary battery, or lithium ion polymer secondary battery.

[0039] According to some embodiments of the present application, the secondary battery may include an outer package, and the outer package can be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc. The outer package of the secondary battery can also be a soft package, such as a pouch soft package. The material of the soft package can be plastic, such as one or several of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.

[0040] According to some embodiments of the present application, the shape of the secondary battery is not particularly limited, and it can be cylindrical, square, or any other shape.

[0041] The third aspect of the present application also provides a device, and the device includes the secondary battery provided by the present application.

[0042] In some embodiments, the above device includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, energy storage systems, etc. In order to meet the high power and high energy density requirements of the device for the secondary battery, a battery pack or a battery module can be used.

[0043] In other embodiments, the above device can be a mobile phone, a tablet computer, a laptop computer, etc. The device usually requires thinness and lightness, and a secondary battery can be used as the power source.

[0044] The following further describes the present application in detail with specific embodiments, and these embodiments should not be construed as limiting the scope claimed by the present application.

[0045] Example 1

[0046] (1) Preparation of negative electrode sheet

[0047] The specific steps are as follows: Amorphous nano-carbon powder with a particle size of 20 nm (Zhejiang Asia-America Nano Technology Co., Ltd., model AM-C1-N-01) and binder polyvinylidene fluoride (PVDF) are fully homogenized in an N-methylpyrrolidone solvent system according to a weight ratio of 95:5, and then coated on an 8-μm-thick copper current collector, dried, rolled, and a negative electrode sheet is obtained.

[0048] (2) Evaluation of electrochemical performance

[0049] Preparation of positive electrode sheet: Using LiNi 0.6 Co 0.2 Mn 0.2 O2 as the active material, nano-carbon fiber (Showa Denko, Japan, VGCF-H, diameter 75 nm) as the main conductive agent, polytetrafluoroethylene (PTFE) as the binder, and sulfide solid electrolyte as the lithium-ion conductive medium, with its material type being Li6PS5Cl. The electrode sheet formulation ratio: LiNi 0.6 Co 0.6 Mn 0.6 O2:VGCF:PTFE:Li6PS5Cl = 75:3:1:21. The PTFE in the mixed material is fibrillated by a high-speed shearing process to form a network structure inside the coating. Using a hot roll press equipment, the process parameters are adjusted to press a positive electrode coating. Subsequently, the electrode film is thermocompounded on a positive aluminum current collector to obtain a positive electrode coating with a uniform thickness, a dense interior, and a high tap density. The tap density is achieved to be 3.5 - 3.65 mg / cm 3 , and then it is punched into pieces with a diameter of 10 mm.

[0050] A all-solid-state mold battery is assembled according to the structure of negative electrode sheet / / sulfide solid electrolyte membrane / / positive electrode sheet. The sulfide solid electrolyte membrane is an electrolyte membrane prepared by homogenizing and coating Li6PS5Cl and hydrogenated nitrile rubber in a mass ratio of 99:1, with a thickness of 30 μm and a density of 99%. Under the conditions of an areal current density of 1 mA / cm 2 , areal capacity of 0.5 mAh / cm 2 , surface roughness of the conductive layer of 0.5 μm, and a high temperature of 60 °C, the voltage range is 2.5 - 4.25 V, and charge-discharge cycle tests are carried out to evaluate the electrochemical performance.

[0051] Example 2

[0052] The difference from Example 1 is that the conductive carbon is amorphous acetylene black.

[0053] Example 3

[0054] The difference from Example 1 is that the conductive carbon is amorphous furnace black.

[0055] Comparative Example 1

[0056] The negative electrode plate directly uses an 8-μm-thick copper current collector, and an assembled mock-up battery has a structure: an asymmetric battery of lithium-indium / / solid electrolyte membrane / / copper negative electrode. Under the conditions of an areal current density of 1 mA / cm 2 and an areal capacity of 0.5 mAh / cm 2 , a discharge lithium deposition test is carried out to evaluate the electrochemical performance. The evaluation method is the same as that of Example 1.

[0057] The Raman shifts of the conductive carbon materials used in the examples and comparative examples of the present invention are shown in Table 1.

[0058] Table 1

[0059]

[0060] It can be seen from the data in Table 1 that:

[0061] By evaluating the internal defect condition of the carbon material through the Raman shift D-band / G-band, in Examples 1 to 3, as the ratio of the D-band / G-band gradually increases, the more internal defects the conductive carbon has, the more beneficial it is to improve the lithium ion diffusion coefficient. Therefore, the electrochemical performance of the negative electrode plate containing the above conductive layer will also be correspondingly improved during application.

[0062] The lithium ion deposition curves in Example 1 and Comparative Example 1 of the present invention are shown in Figure 1 . From Figure 1 , it can be seen that compared with the lithium ion deposition curve of Comparative Example 1, the decline rate of the lithium ion deposition curve of Example 1 is gentler, and at the same time, the entire discharge curve is also relatively smooth. This shows that the lithium ion battery prepared in Example 1 is not prone to overvoltage and undervoltage during use, so it has better safety performance and also has a longer cycle life.

[0063] The charge-discharge performance curve of the all-solid-state battery in Example 2 of the present invention is shown in Figure 2 . It can be known from Figure 2 that after the negative electrode plate prepared in Example 2 is made into a battery, it has a relatively high first charge-discharge efficiency (about 75%).

[0064] It should be noted that the terms "first", "second", etc. in the specification and claims of this application are used to distinguish similar objects and do not necessarily have to be used to describe a specific order or sequence. It should be understood that such terms can be interchanged under appropriate circumstances so that the embodiments of this application described herein can be implemented in an order other than those described herein, for example.

[0065] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A negative electrode plate, characterized in that, The negative electrode plate includes a current collector and a conductive layer provided on the surface of the current collector. The conductive layer includes crystalline nano-conductive carbon and / or amorphous nano-conductive carbon. The particle sizes of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon are independently selected from 1 nm to 50 nm, and the surface roughness of the conductive layer is < 1.5 μm.

2. The negative electrode sheet according to claim 1, characterized in that, The negative electrode plate satisfies at least one of the following conditions: (1) The conductive layer includes the crystalline nano-conductive carbon and the amorphous nano-conductive carbon, and the weight ratio of the crystalline nano-conductive carbon to the amorphous nano-conductive carbon is (5 - 50):(50 - 95); (2) The particle sizes of the crystalline nano-conductive carbon and the amorphous nano-conductive carbon are independently selected from 10 nm to 50 nm; (3) The peak height ratio of the D band to the G band of the Raman shift of the crystalline nano-conductive carbon is 0.12 - 0.94, and the peak area ratio is 0.8 - 3.5; (4) The peak height ratio of the D band to the G band of the Raman shift of the amorphous nano-conductive carbon is 0.12 - 0.94, and the peak area ratio is 0.8 - 3.

5.

3. The negative electrode sheet according to claim 1 or 2, characterized in that, The crystalline nano-conductive carbon includes at least one of ordered mesoporous carbon, hard carbon, soft carbon, bucky carbon, graphene, and graphite; and / or The amorphous nano-conductive carbon includes at least one of nano-carbon powder, carbon black, acetylene black, Ketjen black, furnace black, channel black, activated carbon, and rubber carbon black.

4. The negative electrode sheet according to claim 1, wherein The thickness of the conductive layer is 0.2 μm to 5 μm.

5. The negative electrode sheet according to claim 4, characterized in that, The surface roughness of the conductive layer is 0.2 μm to 0.5 μm; and / or The thickness of the conductive layer is 0.2 μm to 1 μm.

6. The negative electrode sheet according to claim 1, characterized in that, The conductive layer further includes a first binder, and the first binder includes at least one of polyvinylidene fluoride, styrene-butadiene rubber, and polyvinyl alcohol-acrylic acid.

7. A secondary battery, characterized in that, The secondary battery includes a positive electrode plate, an electrolyte layer provided on the positive electrode plate, and the negative electrode plate according to any one of claims 1 to 6.

8. The secondary battery according to claim 7, characterized in that, The thickness of the electrolyte layer is 10 μm to 50 μm, the density is greater than 97%, and the electrolyte in the electrolyte layer includes at least one of sulfide solid electrolyte and oxide electrolyte.

9. The secondary battery according to claim 8, characterized in that, The electrolyte layer satisfies at least one of the following conditions: (1) When the electrolyte includes the sulfide solid electrolyte, the sulfide solid electrolyte includes at least one of Li6PS5Cl, Li6PS5Cl 0.5 Br 0.5 , Li 10 GeP2S 12 and Li3PS4; (2) When the electrolyte includes the oxide electrolyte, the oxide electrolyte includes at least one of perovskite-type solid electrolyte, garnet-type solid electrolyte, sodium superionic conductor-type solid electrolyte, and organic polymer electrolyte; (3) The electrolyte layer includes a second binder, and the second binder includes at least one of styrene-butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, fluorinated nitrile rubber, cis-butadiene rubber, and isobutene-isoprene rubber.

10. A device, characterized in that, The device includes the secondary battery according to any one of claims 7 to 9.

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