KR102601450B1 - Manufacturing method of all-solid-state lithium-ion battery - Google Patents

Abstract

The present invention relates to a method of manufacturing an all-solid lithium ion battery. Specifically, the all-solid-state lithium ion battery manufacturing method includes manufacturing a modified solid electrolyte layer by plasma treatment on a pressed solid electrolyte layer; and manufacturing a negative electrode layer on the modified solid electrolyte layer by a thermal evaporation method.

Description

Manufacturing method of all-solid-state lithium-ion battery {MANUFACTURING METHOD OF ALL-SOLID-STATE LITHIUM-ION BATTERY}

The present invention relates to a method of manufacturing an all-solid lithium ion battery.

As the various uses and application possibilities of lithium-ion batteries are presented and realized, the importance of high capacity, high output, and stability is emerging. However, since lithium-ion batteries contain flammable organic solvent electrolytes, ignition and explosion accidents frequently occur.

To replace this, all-solid lithium ion batteries are being researched. The all-solid-state lithium ion battery replaces the conventional liquid electrolyte with a solid one, so that no explosion reaction due to a decomposition reaction of the electrolyte solution occurs at all, so it can have excellent stability.

However, all-solid-state secondary batteries have a problem of lower ionic conductivity than secondary batteries using liquid electrolytes. Accordingly, in order to commercialize an all-solid-state secondary battery, the ionic conductivity of the solid electrolyte must be improved and the interface state between the electrode and the electrolyte must be optimized to prevent degradation of battery performance.

In particular, the all-solid lithium secondary battery has a problem in which a large number of voids exist due to the interface mismatch between the electrode and the solid electrolyte, resulting in a large resistance at the interface, and research to solve this problem is continuously conducted. there is.

Republic of Korea Patent Publication No. 10-2019-0079171 (2019.07.05.)

Therefore, the present invention was developed to solve the above-mentioned problems, and the purpose of the present invention is to provide an all-solid lithium ion battery that can lower the interface resistance between the solid electrolyte and the negative electrode contained in the all-solid lithium ion battery through a process alone without adding a liquid electrolyte. The purpose is to provide a method for manufacturing an ion battery.

In addition, the purpose of the present invention is to provide a method for manufacturing an all-solid lithium ion battery that has excellent flame retardancy, long-term stability, and a wide operating potential range.

The present invention relates to an all-solid-state lithium ion battery manufacturing method, comprising the steps of producing a modified solid electrolyte layer by plasma treatment on a pressed solid electrolyte layer; and manufacturing a negative electrode layer on the modified solid electrolyte layer by a thermal evaporation method.

According to one aspect of the present invention, the compressed solid electrolyte may include being compressed at a pressure of 10 to 50 MPa.

According to one aspect of the present invention, the pressed solid electrolyte may include being pressed at a temperature of 50 to 100°C.

According to one aspect of the present invention, the plasma treatment may include treatment with air plasma.

According to one aspect of the present invention, the air plasma treatment may include treatment at 1.0 X 10 ^-3 to 1.0 X 10 torr.

According to one aspect of the present invention, the total amount of air introduced into the air plasma may be 10 to 500 cc.

According to one aspect of the present invention, the air plasma treatment may be performed for 1 to 10 minutes.

According to one aspect of the present invention, the pressure of the thermal evaporation method may be 1.0 X 10 ^-7 to 1.0 X 10 ^-4 torr.

According to one aspect of the present invention, the temperature of the thermal evaporation method may be 150 to 250 °C.

According to one aspect of the present invention, the material of the anode thin film layer is Ti ₂ O ₃ , TiO, VO ₂ , V ₂ O ₃ , V ₂ O ₅ , VO, Mn ₂ O ₃ , MnO, FeO, Co ₂ O ₃ , It may include at least one selected from the group consisting of CoO, Co ₃ O ₄ , Mo ₂ O ₅ , MoO ₂ , Mo ₂ O ₃ , MoO, W ₂ O ₅ , WO ₂ , W ₂ O ₃ and NiO.

According to one aspect of the present invention, the solid electrolyte may contain a polyvinylidene fluoro-based copolymer and a lithium salt.

According to one aspect of the present invention, the solid electrolyte may further include garnet type oxide.

According to one aspect of the present invention, the solid electrolyte may include a weight ratio of the polyvinylidene fluoro-based copolymer and the garnet-type copolymer of 1:0.5 to 5.

According to one aspect of the present invention, the cathode layer may include lithium metal.

According to one aspect of the present invention, it may include further depositing copper metal on the cathode layer.

The present invention can provide an all-solid lithium ion battery manufactured by the above all-solid lithium ion battery manufacturing method.

In manufacturing an all-solid-state lithium ion battery, the present invention can further increase the interfacial adhesion between the negative electrode and the solid electrolyte without including additional liquid electrolyte through plasma treatment and thermal deposition of the negative electrode material on the solid electrolyte.

In addition, the all-solid-state lithium ion battery has excellent stability because no additional liquid electrolyte is added to the solid electrolyte, and in particular, flame retardancy is greatly improved.

In addition, the all-solid-state lithium ion battery has an excellent interface between the negative electrode and the solid electrolyte, has a low resistance value, and has the advantage of maintaining a constant charge and discharge capacity even after repeated charge and discharge.

1 is a schematic diagram of the all-solid-state lithium ion battery manufacturing process of the present invention.
Figure 2 is a graph measuring the ionic conductivity of the solid electrolytes of Examples 1 to 4.
Figure 3 is a graph measuring impedance data of Example 1, Comparative Example 1, and Comparative Example 2.
Figure 4 is a graph measuring the cycle characteristics of Example 1, Comparative Example 1, and Comparative Example 2.
Figure 5 is a photograph of a flame retardancy test of a solid electrolyte.

Hereinafter, the present invention will be described in more detail through specific examples or examples including the attached drawings. However, the following specific examples or examples are only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Additionally, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The terminology used in the description herein is merely to effectively describe specific embodiments and is not intended to limit the invention.

Additionally, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

Additionally, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

The solid electrolyte included in an all-solid-state lithium ion battery has the advantage of greater stability than when using a liquid electrolyte, but there is a problem in that the stability of the interface between the anode or cathode and the solid electrolyte is very poor. Accordingly, in the past, attempts were made to increase the interfacial stability by adding a small amount of liquid electrolyte to the solid electrolyte, but as more liquid electrolyte is included, problems such as lower stability and increased risk of fire may occur.

Accordingly, in order to solve the above problem, the present invention provides a method for manufacturing an all-solid lithium ion battery, comprising the steps of producing a modified solid electrolyte layer by plasma treatment on a pressed solid electrolyte layer; and manufacturing a negative electrode layer on the modified solid electrolyte layer by a thermal evaporation method.

The present invention has the advantage of excellent interfacial stability by reducing voids between the interface of the cathode or anode and the interface of the solid electrolyte through this process alone, without injecting additional additives, such as liquid electrolyte, into the solid electrolyte. In addition, since no additional liquid electrolyte is added, not only is flame retardancy excellent, but stability is also greatly increased.

According to one aspect of the present invention, providing an all-solid lithium ion battery includes the steps of manufacturing an anode thin film layer on a substrate by a sputtering method; manufacturing and pressing a solid electrolyte layer on the thin film layer; Producing a modified solid electrolyte layer by plasma treating the compressed solid electrolyte layer; and manufacturing a negative electrode layer on the modified solid electrolyte layer by a thermal evaporation method. A method for manufacturing an all-solid-state lithium ion battery can be provided.

The substrate is not limited, but a stainless steel substrate (SS substrate) can be used. The SS substrate has the advantage of being superior to a glass substrate in terms of mechanical strength and flexibility.

The material of the anode thin film layer on the substrate may be metal oxide, specifically Ti ₂ O ₃ , TiO, VO ₂ , V ₂ O ₃ , V ₂ O ₅ , VO, Mn ₂ O ₃ , MnO, FeO, Co ₂ O ₃ , CoO, Co ₃ O ₄ , Mo ₂ O ₅ , MoO ₂ , Mo ₂ O ₃ , MoO, W ₂ O ₅ , WO ₂ , W ₂ O ₃ and NiO. , preferably any one or two or more selected from Ti ₂ O ₃ , TiO, VO ₂ , V ₂ O ₃ , V ₂ O ₅ , VO, Mn ₂ O ₃ and MnO, and most preferably V ₂ O It may be ₅ , but is not limited thereto.

The anode thin film layer can be manufactured on the substrate by sputtering, and preferably, the anode thin film layer can be manufactured by RF-sputtering. The RF-sputtering method has the advantage of being able to effectively deposit nonconductor targets.

The metal oxide target can be deposited on the substrate by sputtering. Under the above deposition conditions, the emission power may be 30 to 100 W, preferably 40 to 90 W, and more preferably 50 to 85 W, but is not limited thereto. Additionally, in the above deposition conditions, the vacuum may be 1 to 20 mTorr, preferably 2 to 10 mTorr, and more preferably 3 to 7 Torr, but is not limited thereto.

During sputtering under the above power and vacuum conditions, the anode thin film layer can be deposited cleanly and homogeneously on the substrate.

A solid electrolyte may be applied on the positive electrode thin film layer, and the solid electrolyte may include a polymer additive and a lithium salt.

The polymer additive may be a polymer generally included in a solid electrolyte, and is preferably a polyethylene oxide (poly(ethylene oxide), PEO)-based copolymer and a poly(vinylidene fluoride, pvdf)-based copolymer. It may be a composite, more preferably poly(vinylidene fluoride-co-hexafluoropropylene, pvdf-HFP), but is not limited thereto.

In addition, the lithium salt includes lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(pentafluoroethylsulfonyl)imide ( LiBETI) may be any one or two or more selected from the group, but is not limited thereto.

As the polymer additive and the lithium salt are included in the solid electrolyte, ionic conductivity may be further improved.

The weight ratio of the polyvinylidene fluoro-based copolymer and lithium salt contained in the solid electrolyte may be 1:0.1 to 2, preferably 1:0.3 to 1.5, and more preferably 1:0.5 to 1 day. However, it is not limited to this.

According to one aspect of the present invention, the solid electrolyte may further include garnet type oxide. As the garnet-type oxide is included in the solid electrolyte, the potential window of the solid electrolyte is relatively wide and has the advantage of low water reactivity and low reactivity with metallic lithium.

The garnet-type oxide may include Li ₇ La ₃ Ta ₂ O ₁₂ (LLTaO) and Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO), but is not limited thereto. The garnet-type oxide has the advantage of being stable to lithium metal, excellent performance against air and moisture, and chemical compatibility.

According to one aspect of the present invention, the weight ratio of the polyvinylidene fluoro-based copolymer and the garnet-type oxide contained in the solid electrolyte may be 1:0.1 to 5, preferably 1:0.5 to 2, More preferably, it may be 1:0.8 to 1.2, but is not limited thereto.

The solid electrolyte that satisfies the above weight ratio has very excellent ionic conductivity. In particular, when the weight ratio is 1:0.8 to 1.2, the ionic conductivity value is confirmed to be very excellent, although the exact reason is not known.

The solid electrolyte can be dissolved in an organic solvent to prepare a solid electrolyte solution.

The organic solvent is methylpyrrolidone (N-methyl-2-pyrrolidone: NMP), dimethylformamide (DMF), dimethyl acetamide (DMA), tetrahydrofuran (THF), and dimethyl sulfide. It may be one or a mixed solution of two or more selected from dimethyl sulfoxide (DMSO) and acetone, but is not limited thereto.

A solid electrolyte layer can be manufactured by applying the solid electrolyte solution on the anode thin film layer and drying it. The drying conditions may be from 50 to 100° C., but the temperature range is not greatly limited as long as bubbles are not generated in the solid electrolyte layer.

The solid electrolyte layer may be compressed using a hot press or the like to produce a pressed solid electrolyte layer. Ion conductivity can be further increased by compressing the solid electrolyte layer.

According to one aspect of the present invention, the compressed solid electrolyte may be compressed at a pressure of 10 to 50 MPa, preferably at a pressure of 15 to 40 MPa, and more preferably at a pressure of 20 to 30 MPa. However, it is not limited to this.

Additionally, according to one aspect of the present invention, the pressed solid electrolyte may be pressed at a temperature of 50 to 120°C, preferably 60 to 100°C, and more preferably 70 to 90°C. It is not limited.

As the solid electrolyte layer is compressed under the above compression conditions, the solid electrolyte layer is not damaged and the ionic conductivity is excellent.

The thickness of the solid electrolyte may be 10 to 100 ㎛, preferably 15 to 60 ㎛, more preferably 20 to 40 ㎛, but is not limited thereto.

The compressed solid electrolyte can be surface treated with plasma. Conventional solid electrolytes have the disadvantage of having a high interfacial resistance value due to a poor interface with the cathode. Accordingly, the present invention performs plasma treatment on the surface of the solid electrolyte layer pressed when manufacturing the all-solid-state lithium ion battery, so that the interfacial resistance value is increased through interaction between the interface between the solid electrolyte layer and the cathode, although the cause is unknown. It can have a very lowering effect.

Accordingly, low interfacial resistance can be maintained without adding additional liquid electrolyte, which has the advantage of excellent stability and flame retardancy.

According to one aspect of the present invention, the plasma treatment can be performed with argon, nitrogen, oxygen, and air, but preferably, the plasma treatment can be performed with air.

Additionally, according to one aspect ^of the present invention, the air plasma treatment may be performed ^at 1.0 Can be processed at 1 X 10 ^-2 to 1 X 10 ^-1 Torr, but is not limited thereto.

In addition, according to one aspect of the present invention, the total amount of air introduced into the air plasma may be 10 to 500 cc, preferably 50 to 400 cc, and more preferably 100 to 300 cc. However, it is not limited to this.

As the total amount of air is satisfied during the plasma treatment, the surface of the solid electrolyte layer is further modified and can have lower interfacial resistance when bonded to the cathode.

In addition, according to one aspect of the present invention, the air plasma treatment may be performed for 1 to 10 minutes, preferably for 3 to 7 minutes, and more preferably for 4 to 6 minutes. It is not limited.

By performing air plasma treatment for the above-mentioned time, there is an advantage in that the solid electrolyte layer is not deteriorated and is sufficiently reformed while suppressing separation of the anode and the solid electrolyte, resulting in lower interfacial resistance when contacted with the cathode in the future. .

A cathode can be applied on the plasma-treated solid polymer layer. The cathode may be coated with lithium metal, but is not limited thereto.

According to one aspect of the present invention, the cathode can be applied on the plasma-treated solid polymer layer by thermal evaporation. As the cathode is applied on the plasma-treated solid polymer layer using a thermal deposition method, the interface resistance value between the interface of the solid electrolyte and the interface of the applied cathode can be further lowered.

According to one aspect ^of the present invention, the ^{pressure of the} thermal evaporation method may be 1.0 , but is not limited to this.

In addition, according to one aspect of the present invention, the temperature of the thermal evaporation method may be 150 to 250 ℃, preferably 170 to 230 ℃, and more preferably 190 to 220 ℃. It is not limited.

According to one aspect of the present invention, copper metal may be further deposited on the cathode layer. By further applying copper metal on the lithium metal anode using a thermal evaporation method, the lithium metal anode can be protected from redox and external moisture.

In addition, the present invention can produce an all-solid lithium ion battery using the above all-solid lithium ion battery manufacturing method.

The all-solid lithium ion battery manufactured by the above method has superior ionic conductivity than conventional all-solid lithium ion batteries, and in particular has the advantage of low interfacial resistance between the cathode and the all-solid electrolyte.

In addition, there is no need to add additional liquid electrolyte to lower the interfacial resistance, so it has the advantage of excellent flame retardancy.

The present invention will be described in more detail below based on examples and comparative examples. However, the following Examples and Comparative Examples are only one example to explain the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[measurement method]

[Measurement of ionic conductivity]

Evaluation of ionic conductivity characteristics was measured at 20 to 80°C using an impedance meter (ZIVE SP1, Wonatech, Korea). The resistance of the manufactured coin cell was measured at each temperature, and the conductivity value was calculated by dividing the thickness into resistance and area.

[Cycle measurement]

Evaluation of charge/discharge characteristics was measured at 50 ^o C using a battery charge/discharge tester (WBCS3000, Wonatech). Cycle data was obtained through a repeated process of discharging the coin cell to 2.15 V and then charging it to 3.8 V.

[Production Example 1]

PVDF-HFP (Mw = 450,000, Sigma-Aldrich) and bis(trifluoromethane) sulfonimide lithium salt (LiTFSI, Sigma-Aldrich) were dissolved in N-Methyl-2-pyrrolidone (NMP, Sigma-Aldrich) at a weight ratio of 2:1. A uniform solution was prepared by sonication.

Afterwards, LLZO (particle size ≤ 500 nm, MSE Supplies) was added to the uniform solvent at a weight ratio of LLZO to PVDF-HFP of 1:1 to prepare a solid electrolyte solution.

[Production Example 2]

Preparation Example 1 was carried out in the same manner except that the weight ratio of LLZO added to PVDF-HFP was 1:0.5 instead of 1:1 weight ratio of LLZO to PVDF-HFP.

[Production Example 3]

Preparation Example 1 was carried out in the same manner, except that the weight ratio of LLZO to PVDF-HFP was added at a weight ratio of 1:1.5 instead of a weight ratio of 1:1.

[Production Example 4]

Preparation Example 1 was performed in the same manner, except that the weight ratio of LLZO to PVDF-HFP was added at a weight ratio of 1:2 instead of a 1:1 weight ratio of LLZO to PVDF-HFP.

[Example 1]

The cathode layer was manufactured on the substrate using a V ₂ O ₅ target (3 inch, 99.99%) using the RF magnetron sputtering method. The sputtering was performed at a pressure of 5 mTorr with RF power of 80 W (1.75 W cm ^-2 ), and the operating distance between the target and the substrate was fixed at 54 mm.

The substrate was a stainless steel (SS) substrate (diameter 16 mm), and the substrate generally had Ti and Pt deposited on it.

The solid electrolyte prepared in Preparation Example 1 was applied to the cathode layer and then dried at 80° C. for 24 hours to prepare a solid electrolyte layer.

The substrate on which the solid electrolyte layer was formed was pressed at a pressure of 25 MPa at 80°C using a hot presser.

In order to improve contact with the anode and interfacial stability on the compressed solid electrolyte layer, air plasma treatment was performed with 200 cc air injected for 5 ^minutes at 5 did.

An all-solid-state lithium ion battery was manufactured by depositing a positive electrode on the modified solid electrolyte layer using a thermal evaporation method.

In the thermal evaporation method, a Li metal anode (thickness = 10 μm) and a Cu current collector (thickness = 1 μm) were sequentially deposited in the same chamber, and the pressure was maintained at 2.0 × 10 ^-6 Torr during the deposition process.

[Example 2]

Example 1 was performed in the same manner except that the solid electrolyte of Preparation Example 2 was used instead of the solid electrolyte of Preparation Example 1.

[Example 3]

Example 1 was performed in the same manner except that the solid electrolyte of Preparation Example 3 was used instead of the solid electrolyte of Preparation Example 1.

[Example 4]

Example 1 was performed in the same manner except that the solid electrolyte of Preparation Example 4 was used instead of the solid electrolyte of Preparation Example 1.

[Comparative Example 1]

Example 1 was performed in the same manner as in Example 1, except that instead of manufacturing the positive electrode by thermally depositing lithium metal on the solid electrolyte, the positive electrode was manufactured by applying lithium foil.

[Comparative Example 2]

Example 1 was performed in the same manner as in Example 1, except that lithium metal was thermally deposited on the solid electrolyte without plasma treatment.

Figure 2 below is a graph measuring ionic conductivity. Example 1, where the PVDF-HFP:LLZO content was 1:1, had the highest ionic conductivity, and Examples 3 and 4, which had a high LLZO content, had the highest ionic conductivity. It was confirmed that the ionic conductivity was lower than that of Example 1.

In addition, as shown in FIG. 3 below, when the resistance of Example 1, Comparative Example 1, and Comparative Example 2 was measured, it can be seen that Example 1 had a lower resistance value than the Comparative Examples. In the case of Comparative Example 1, it can be seen that the interfacial resistance value increased due to the generation of voids between the solid electrolyte and the lithium foil. In addition, when comparing Example 1 and Comparative Example 2, although the exact reason is unknown, it can be confirmed that the all-solid lithium ion battery in which the surface of the solid electrolyte was plasma treated and lithium metal was subsequently thermally deposited had a lower resistance. there was.

Additionally, Figure 4 below is a graph showing the charge/discharge capacity according to the number of cycles for Example 1, Comparative Example 1, and Comparative Example 2. In the case of Comparative Example 1, the charge/discharge capacity was very low from the beginning, and in the case of Comparative Example 2, it can be seen that the charge/discharge capacity decreases as the number of cycles increases. On the other hand, in the case of Example 1, it was confirmed that the charging and discharging effect was maintained even if the number of cycles increased.

Lastly, in Figure 5 below, a) is a flammability test performed after adding a liquid electrolyte (LE (1.0 M LiPF ₆ )) to a conventional solid electrolyte (Celgard 2400 separator), and b) is a flammability test performed after adding the liquid electrolyte (LE (1.0 M LiPF 6)) prepared in Example 1. This is an image testing the flame retardancy of a solid electrolyte.

It can be confirmed that the solid electrolyte of Example 1 does not burn even when ignited.

As described above, the present invention has been described with specific details, limited embodiments, and drawings, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Anyone skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (16)

In the all-solid-state lithium ion battery manufacturing method,
Manufacturing an anode thin film layer on a substrate by sputtering; Manufacturing a solid electrolyte layer on the anode thin film layer and pressing it to produce a pressed solid electrolyte layer;
Producing a modified solid electrolyte layer by plasma treating the compressed solid electrolyte layer; and
It includes manufacturing a cathode layer on the modified solid electrolyte layer by thermal evaporation,
The modified solid electrolyte is a method of manufacturing an all-solid-state lithium ion battery, wherein the modified solid electrolyte contains polyvinylidene fluoro-based copolymer, garnet type oxide, and lithium salt at a weight ratio of 1:0.5 to 5:0.1 to 2. According to clause 1,
A method of manufacturing an all-solid lithium ion battery, wherein the compressed solid electrolyte is compressed at a pressure of 10 to 50 MPa. According to clause 2,
A method of manufacturing an all-solid lithium ion battery, wherein the compressed solid electrolyte is compressed at a temperature of 50 to 100 ° C. According to clause 1,
A method of manufacturing an all-solid lithium ion battery, wherein the plasma treatment is performed with air plasma. According to clause 4,
The air plasma treatment is a method of manufacturing an all-solid lithium ion battery, wherein the air plasma treatment is performed at ^1.0 According to clause 5,
A method of manufacturing an all-solid lithium ion battery, wherein the total amount of air introduced into the air plasma is 10 to 500 cc. According to clause 6,
A method of manufacturing an all-solid lithium ion battery, wherein the air plasma treatment is performed for 1 to 10 minutes. According to clause 1,
A method of manufacturing an all ^- solid lithium ion battery, wherein the pressure of the thermal evaporation method is ^1.0 According to clause 8,
A method for manufacturing an all-solid-state lithium ion battery, wherein the temperature of the thermal evaporation method is 150 to 250 ° C. According to clause 1,
The material of the anode thin film layer is Ti ₂ O ₃ , TiO, VO ₂ , V ₂ O ₃ , V ₂ O ₅ , VO, Mn ₂ O ₃ , MnO, FeO, Co ₂ O ₃ , CoO, Co ₃ O ₄ , Mo ₂ O ₅ , MoO ₂ , Mo ₂ O ₃ , MoO, W ₂ O ₅ , WO ₂ , W ₂ O ₃ and at least one selected from the group consisting of NiO, a method of manufacturing an all-solid-state lithium ion battery. According to clause 1,
A method of manufacturing an all-solid lithium ion battery, wherein the solid electrolyte contains a polyvinylidene fluoro-based copolymer and a lithium salt. delete delete According to clause 1,
A method of manufacturing an all-solid lithium ion battery, wherein the negative electrode layer is lithium metal. According to clause 14,
A method of manufacturing an all-solid-state lithium ion battery, comprising further depositing copper metal on the cathode layer. An all-solid lithium ion battery manufactured by the all-solid lithium ion battery manufacturing method of any one of claims 1 to 11 and 14 to 15.