KR101681297B1 - All solid lithium secondary batteries and method for manufacturing the same - Google Patents

Abstract

The present invention relates to all-solid-state lithium secondary batteries containing a cathode, an anode including Ni-Co-Mn ternary system lithium metallic oxide (NMC) and a binder, and a solid electrolyte including a polymer and lithium salts between the cathode and the anode. The all-solid-state lithium secondary battery has high capacitance and high voltage characteristics without using an organic solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a solid-state lithium secondary battery,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pre-solid lithium secondary battery, and more particularly, to a pre-solid lithium secondary battery capable of exhibiting high capacity and high voltage characteristics without using an organic solvent.

Recently, fossil fuel depletion and environmental problems have been highlighted, and interest in renewable energy and electric power storage systems has increased. As a result, research on the secondary battery has been actively conducted, but it faces various technical difficulties. Lithium secondary batteries have high energy density and are expected to be applied not only to small IT devices such as mobile phones and notebook PCs but also as mid- and large-sized batteries for electric vehicles and electric power storage. Especially, The development of a lithium secondary battery having a high energy density is required. Generally, a liquid electrolyte containing an organic solvent is used as an electrolyte of a lithium secondary battery.

However, lithium secondary batteries using a liquid electrolyte containing an organic solvent have difficulty in securing the safety of batteries in terms of overcharging and thermal characteristics. In particular, in order to efficiently respond to the demands of the industry in which the development of medium-sized lithium rechargeable batteries for electric vehicles and electric power storage is required, the safety issue is one of the most important issues in addition to the high energy density of the battery. Therefore, research to replace the liquid electrolyte with solid electrolyte has been attracting attention as an alternative to secure the safety, and researches on the optimization of the microstructure of the electrode and the interface due to solidification of the electrolyte are underway.

Conventional solid electrolyte materials are classified into organic (polymer) solid electrolytes and inorganic solid electrolytes. Polymer solid electrolytes are prepared by applying lithium salts and various inorganic fillers and additives to polyethylene oxide (PEO) based polymers and have ionic conductivities of about 10 ^-5 to 10 ^-7 S / cm at room temperature, 0.5, and the dislocation window shows a marginality of about 0 to 4.5V. Therefore, in order to improve the ionic conductivity of the polymer solid electrolyte, use conditions of about 60 DEG C or more are required. However, since the conventional polymer solid electrolyte uses some organic solvent, there is a limit to solving the safety problem fundamentally. On the other hand, inorganic solid electrolytes are somewhat disadvantageous from the standpoint of flexibility, unlike organic (polymer) solid electrolytes, but are inherently nonflammable and therefore have excellent safety and have Li singlet ion conduction characteristics, Is close to 1, and it can maintain a wider potential window (0 to 5.5 V) than the polymer solid electrolyte although it depends on the type and characteristics of the material. The inorganic solid electrolyte is classified into a crystalline material and an amorphous material. The ionic conductivity of a representative inorganic solid electrolyte has an ion conductivity in a range of about 10 ^-3 to 10 ^-6 S / cm in a bulk state (single crystal). As a solid electrolyte for a solid lithium secondary battery, the ionic conductivity required for practical use is required to be about 10 ^-3 S / cm at room temperature. Currently, such values are required for a sulfide-based solid electrolyte and a peroxide-based solid electrolyte, And Nashin Kong. Studies on these oxide-based solid electrolytes have been active since 2000. The oxide-based solid electrolyte has been improved from the initial ionic conductivity of 10 ^-13 S / cm to about 10 ^-3 S / cm in recent years.

However, there is also to show certain limitations in electrochemical properties of such a material, perop Sky teugye composition _{((La, Li) TiO 3} ) and pear kongye For composition _{(LiTi 2 (PO 4) 3} ) of about 10 ^-3 to ^10- The solid electrolyte of this composition exhibits a relatively high ionic conductivity of ⁵ S / cm. However, the solid electrolyte exhibits a characteristic of 1.5-5.0 V or 2.5-5.0 V at the dislocation window, . Therefore, there is a limit to the implementation of a pre-solid lithium secondary battery aiming at high voltage characteristics. In other words, perovskite and nacicon type oxide solid electrolytes have relatively good ion conductivity and yield. However, they show limited characteristics of dislocation window. Therefore, the next generation medium to large scale electrochemical devices aiming at adoption of high energy density anode materials and low- It has a limitation in application to a solid lithium secondary battery.

Therefore, it is necessary to develop a full-solid lithium secondary battery which is stable in yield and potential window characteristics, and can exhibit high capacity and high voltage characteristics without using an organic solvent.

An object of the present invention is to provide a pre-solid lithium secondary battery which can exhibit high capacity and high voltage characteristics without using an organic solvent.

Further, the present invention provides a pre-solid lithium secondary battery having stable yield and potential window characteristics.

According to an aspect of the present invention,

cathode; A positive electrode comprising a three-component lithium metal oxide (NMC) of Ni-Co-Mn and a binder; And a solid electrolyte including a polymer and a lithium salt between the cathode and the anode.

The solid electrolyte may further include Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ).

The positive electrode may further include Li _x La _y Zr _z O ₁₂ (6? X? 9, 2? Y? 4, 1? Z? 3) (LLZ).

Wherein the polymer is selected from the group consisting of polyethylene oxide, polyethyleneglycol, polyacrylonitrile, polyvinylchloride, polymethylmethacrylate, polypropyleneoxide, polydimethylsiloxane polydimethylsiloxane, polyvinylidene fluoride, polyvinylidenecarbonate, and polyvinyl pyrrolidinone. The polyvinylidene fluoride may be at least one selected from the group consisting of polydimethylsiloxane, polyvinylidene fluoride, polydimethylsiloxane, polyvinylidene fluoride, polyvinylidenecarbonate and polyvinyl pyrrolidinone.

The polymer may be polyethylene oxide.

Wherein the lithium salt is selected from the group consisting of lithium perchlorate (LiClO ₄ ), lithium triflate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LipF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), and lithium trifluoromethanesulfonylimide may be at least one selected from _{(LiN (CF 3 SO 2)} 2).

The lithium salt may be lithium perchlorate.

The binder may be at least one selected from the group consisting of polyvinylidene fluoride, polyvinyl acetate, and polyvinyl pyrrolidone.

The binder may be polyvinylidene fluoride.

The anode may further comprise a conductive agent.

The conductive agent may include at least one selected from conductive carbon, conductive metal, and conductive polymer.

The negative electrode may include any one selected from lithium metal, silicon, tin, graphite, and coke as an active material.

The negative electrode may include lithium metal as an active material.

According to another aspect of the present invention,

Casting a slurry obtained by mixing a polymer, a lithium salt and a plasticizer, and drying the slurry to prepare a solid electrolyte film (step a); Coating a mixture of positive electrode materials comprising a three-component lithium metal oxide (NMC) of Ni-Co-Mn and a binder on a substrate to produce a positive electrode (step b); And arranging the solid electrolyte film between the anode and the cathode to produce a pre-solid lithium secondary battery (step c).

The slurry may further include Li _x La _y Zr _z O ₁₂ (6? X? 9, 2? Y? 4, 1? Z? 3) (LLZ).

The positive electrode material mixture may further include Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ).

And then pressing the anode (step b ') after step b.

The substrate may include at least one selected from aluminum and nickel.

The entire solid lithium secondary battery of the present invention has the effect of exhibiting high capacity and high voltage characteristics without using an organic solvent unlike the prior art.

In addition, it is possible to produce a pre-solid lithium secondary battery having stable yield and potential window characteristics.

1 is a schematic diagram of a pre-solid lithium secondary battery of the present invention.
2 is a flow chart of a method for manufacturing a pre-solid lithium secondary battery of the present invention.
3 is an SEM image of LLZ prepared according to Preparation Example 1. Fig.
4 shows the results of XRD after heat treatment of LLZ prepared according to Production Example 1 at 1200 ° C for 5 hours.
FIG. 5 shows the results of measurement of bulk ion conductivity and total ion conductivity at room temperature to 300 ° C. after heat treatment of LLZ prepared in Preparation Example 1 at 1200 ° C. for 5 hours.
FIG. 6 shows the results of measurement of the charge-discharge characteristics of the all-solid lithium secondary batteries produced according to Examples 1 to 6 and Comparative Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof is contemplated by one or more other features But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Hereinafter, the entire solid lithium secondary battery of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

1 is a schematic diagram of a pre-solid lithium secondary battery of the present invention.

1, the pre-solid lithium secondary battery of the present invention includes a cathode, a cathode including a three-component lithium metal oxide (NMC) of Ni-Co-Mn and a binder, and a polymer and a lithium salt between the cathode and the anode Lt; / RTI >

The solid electrolyte may further include Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ).

The positive electrode may further include Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ).

By including the LLZ in the solid electrolyte or the anode, the discharge capacity of the all-solid lithium secondary battery is increased, so that the charge / discharge characteristics of the pre-solid lithium secondary battery can be improved.

The polymer may be at least one selected from the group consisting of polyethylene oxide, polyethylene glycol, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, polypropylene oxide, polydimethylsiloxane, polyvinylidene fluoride, polyvinylidene carbonate, And may preferably be polyethylene oxide.

The lithium salt may be lithium perchlorate, lithium triflate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonylimide, or the like, preferably lithium perchlorate.

The binder may be polyvinylidene fluoride, polyvinyl acetate, polyvinyl pyrrolidone or the like, preferably polyvinylidene fluoride.

The anode may further include a conductive agent.

The conductive agent may be conductive carbon, conductive metal, conductive polymer, or the like.

The negative electrode may include any one selected from the group consisting of lithium metal, silicon, tin, graphite, and coke as an active material. Preferably, the negative electrode may include lithium metal as an active material.

2 is a flow chart of a method for manufacturing a pre-solid lithium secondary battery including LLZ in the solid electrolyte of the present invention.

Hereinafter, a method for manufacturing a pre-solid lithium secondary battery in which LLZ is contained in a solid electrolyte will be described in detail with reference to FIG.

First, a slurry obtained by mixing Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ), a polymer, a lithium salt and a plasticizer was cast and dried to obtain a solid To prepare an electrolyte film (step a).

The polymer may be at least one selected from the group consisting of polyethylene oxide, polyethylene glycol, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, polypropylene oxide, polydimethylsiloxane, polyvinylidene fluoride, polyvinylidene carbonate, And may preferably be polyethylene oxide.

The lithium salt may be lithium perchlorate, lithium triflate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonylimide, or the like, preferably lithium perchlorate.

Next, a positive electrode material mixture containing a three-component lithium metal oxide (NMC) of Ni-Co-Mn and a binder is coated on the substrate to prepare a positive electrode (step b).

The binder may be polyvinylidene fluoride, polyvinyl acetate, polyvinyl pyrrolidone or the like, preferably polyvinylidene fluoride.

And a conductive agent in the production of the anode of step b.

The conductive agent may be conductive carbon, conductive metal, conductive polymer, or the like.

The substrate may be aluminum, nickel, or the like, preferably aluminum.

The coating can be, but is not limited to, spin coating, dip coating, drop casting, doctor blade coating, spray coating, screen printing, and the like. Any coating method that does not damage the substrate may be possible.

And then pressing the anode (step b ') after step b.

Finally, the solid electrolyte film is disposed between the anode and the cathode to produce a pre-solid lithium secondary battery (step c).

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

[Preparation of Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ) powder]

LLZ Preparation Example 1

La (NO ₃ ) ₃ .2H ₂ O and ZrO (NO ₃ ) ₂ .2H ₂ O were mixed in a molar ratio of 3: 2 and then dissolved in 500 ml of distilled water to prepare an aqueous starting solution. Further, ammonia water (NH ₄ OH) of 5 normal (N) concentration was mixed with 500 ml of distilled water as a complexing agent and dissolved to form 0.6 mol of an aqueous solution. Then, sodium hydroxide (NaOH) powder was dissolved to adjust the pH of the reactor to prepare 1000 ml of 1 mole of sodium hydroxide solution. In the coprecipitation reactor, the pH is adjusted to about 11 with about 500 ml of distilled water and the prepared NaOH, and the impeller speed of the coprecipitation reactor is set to about 1000 rpm. When the coprecipitation reaction starts, the starting material is titrated at a rate of about 4 ml / min, and at the same time, the ammonia water prepared as a complexing agent is titrated at the same rate of 4 ml / min. Also, as the coprecipitation reaction proceeds, a 1 molar solution of NaOH prepared for the pH control of the reactor is automatically titrated according to the pH change of the coprecipitation reactor. Next, additional stirring was performed at a constant impeller stirring speed (1000 rpm) for 24 hours after the completion of the coprecipitation reaction. The precipitate generated in the coprecipitation reaction was washed several times with distilled water until the pH reached 7 ~ 8. The washed precipitate is dried overnight in a general drier at about 110 ° C to prepare a first precursor powder. At this time, the first precursor is in a state in which lithium is not contained, and may be expressed in a composition form such as La ₃ Zr ₂ (OH) _x . Next, the first precursor powder and lithium hydroxide powder (LiOH.H ₂ O) were mixed so that the molar ratio of Li and La was 7: 3, and uniformly mixed using a planetary ball mill to form a second precursor powder. Next, LLZ powder was prepared by heat treatment at 900 ° C for 5 hours.

[Production of solid electrolyte film]

Film Production Example 1

LLZ LLZ powder, polyethylene oxide (PEO, number average molecular weight 2 x 10 ⁵ , Aldrich), LiClO ₄ (Aldrich) and ACN (Acetonitrile) prepared according to Production Example 1 were prepared, and LLZ 30 By weight, LiClO ₄ 15 parts by weight and ACN 263 parts by weight were mixed to prepare a slurry. The prepared slurry was coated on a PET film and dried at room temperature for 24 hours to produce a solid electrolyte film with a thickness of about 200 탆.

Film Production Example 2

A solid electrolyte film was prepared in the same manner as in Film Production Example 1 except that 70 parts by weight of LLZ powder was used instead of 30 parts by weight.

Film Production Example 3

A solid electrolyte film was prepared in the same manner as in Film Production Example 1 except that 90 parts by weight of LLZ powder was used instead of 30 parts by weight.

Film Production Example 4

A solid electrolyte film was prepared in the same manner as in Film Production Example 1 except that 120 parts by weight of LLZ powder was used instead of 30 parts by weight.

Comparative Film Production Example 1

A solid electrolyte film was prepared in the same manner as in Film Production Example 1, except that the LLZ powder was not used.

[Production of anode]

Anode Production Example 1

(NMC), polyvinylidene fluoride (PVDF, 8 wt%), and supper-p (conductive agent) were prepared in the same manner as in Example 1 except that the mixing ratio of NMC: PVDF: 8: 1: 1, and stirred so as to be uniformly mixed. Thereafter, the film was coated on an Al substrate by screen printing, dried at 110 DEG C for 24 hours, pressed and dried in a vacuum atmosphere at 80 DEG C for 24 hours to prepare a positive electrode.

Anode Production Example 2

Except that a mixed weight ratio of NMC: PVDF: conductive agent: LLZ of 7: 1: 1: 1 was used in place of a mixture of NMC: PVDF: conductive agent in a weight ratio of 8: 1: A positive electrode was prepared in the same manner as in Production Example 1.

Anode Production Example 3

Except that a mixed weight ratio of NMC: PVDF: conductive agent: LLZ of 6: 1: 1: 2 was used in place of a mixture of NMC: PVDF: conductive agent in a weight ratio of 8: A positive electrode was prepared in the same manner as in Production Example 1.

[Preparation of pre-solid lithium secondary battery]

Example 1

A solid electrolyte film produced according to Film Production Example 1, a positive electrode prepared according to Positive electrode Preparation Example 1, and a lithium metal negative electrode were prepared by punching into a coin cell size. A solid electrolyte film was disposed on the lithium metal cathode, and an anode was disposed on the solid electrolyte film. Then, all solid lithium secondary batteries were prepared using a coin cell clamping apparatus.

Example 2

All solid lithium secondary batteries were prepared in the same manner as in Example 1, except that the solid electrolyte film prepared in accordance with Film Production Example 2 was used in place of the solid electrolyte film prepared in Film Production Example 1.

Example 3

All solid lithium secondary batteries were prepared in the same manner as in Example 1, except that the solid electrolyte film prepared according to Film Production Example 3 was used in place of the solid electrolyte film prepared according to Film Production Example 1.

Example 4

All solid lithium secondary batteries were prepared in the same manner as in Example 1, except that the solid electrolyte film prepared according to Film Production Example 4 was used in place of the solid electrolyte film prepared according to Film Production Example 1.

Example 5

A solid electrolyte film produced according to comparative film production example 1, a positive electrode prepared according to positive electrode preparation example 2, and a lithium metal negative electrode were prepared by punching into a coin cell size. A solid electrolyte film was disposed on the lithium metal cathode, and an anode was disposed on the solid electrolyte film. Then, all solid lithium secondary batteries were prepared using a coin cell clamping apparatus.

Example 6

All solid lithium secondary batteries were prepared in the same manner as in Example 5 except that the positive electrode prepared in accordance with Preparation Example 3 of the positive electrode was used instead of the positive electrode prepared in accordance with the positive electrode preparation example 2.

Comparative Example 1

All solid lithium secondary batteries were prepared in the same manner as in Example 5, except that the positive electrode prepared in accordance with Preparation Example 1 of the positive electrode was used in place of the positive electrode prepared according to the positive electrode preparation example 2.

The composition of the positive electrode and the composition of the solid electrolyte film are summarized in Table 1 below. In Table 1, the weight of the anode is the weight ratio of the components of the anode, the weight of the solid electrolyte film is the weight of the components of the solid electrolyte film, and the weight of the anode and the weight of the solid electrolyte film are not related to each other.

Anode (parts by weight) Solid electrolyte film (parts by weight) NMC PVDF Supper-P LLZ PEO LLZ LiClO ₄ Example 1 80 10 10 0 100 30 15 Example 2 80 10 10 0 100 70 15 Example 3 80 10 10 0 100 90 15 Example 4 80 10 10 0 100 120 15 Example 5 70 10 10 10 100 0 15 Example 6 60 10 10 20 100 0 15 Comparative Example 1 80 10 10 0 100 0 15

[Test Example]

Test Example 1: Characterization of LLZ

3 is an SEM image of LLZ prepared according to Preparation Example 1. Fig. FIG. 4 shows XRD results after heat treatment of LLZ prepared according to Preparation Example 1 at 900 ° C. for 5 hours. FIG. 5 shows bulk ion conductivity and total ion conductivity (total) measured from room temperature to 300 ° C. This is a result.

Referring to FIG. 3, it was found that the LLZ in the powder state had an average particle size of about 2-3 μm.

Referring to FIG. 4, although the LLZ contains a small amount of impurities, it mainly exhibits a cubic system structure.

Referring to FIG. 5, the bulk ion conductivity of the LLZ was found to be approximately constant at about 2.0 × 10 ^-3 S / cm from room temperature to about 200 ° C. However, it was confirmed that the ionic conductivity increased sharply at 200 ° C or higher, and the ionic conductivity increased to about 1.6 × 10 ^-2 S / cm at 300 ° C. In the case of the total ion conductivity including the grain size of the particles, it was 2.0 x 10 ^-6 S / cm at room temperature, 4.5 x 10 ^-6 S / cm at 50 ° C, 1.3 x 10 ^-3 S / cm at 200 ° C, 300 Lt; ^-2 & gt ^; S / cm.

Test Example 2: Characterization of all solid lithium secondary batteries

The charge / discharge characteristics of the all-solid lithium secondary batteries produced according to Examples 1 to 6 and Comparative Example 1 were measured and shown in FIG. The charging conditions of the pre-solid lithium secondary battery produced according to Examples 1 to 6 and Comparative Example 1 were set to 0.05CC-0.03CV. The discharging condition was 0.05CC, charging was performed at 4.2V, and discharging was performed at 2.5V. At this time, the charging and discharging atmosphere in Examples 1 to 3 was maintained at 60 ° C, the temperature of Example 4 was kept at 70 ° C, and the charging and discharging conditions of Examples 5 and 6 and Comparative Example 1 were maintained at 25 ° C .

Referring to FIG. 6, it can be seen that the entire solid lithium secondary battery of Example 1 was not maintained for more than one cycle with very irreversible behavior in one cycle of charging / discharging behavior, and the experiment was stopped due to a short circuit. On the other hand, it was confirmed that the charging / discharging cycle of the pre-solid lithium battery of Example 3 (LLZ 90 parts by weight) was normally maintained and the capacity was about 145 mAh / g. It was also confirmed that the capacity of the pre-solid lithium secondary battery of Example 4 was 130 mAh / g, and the discharge characteristics were further reduced.

In the case of the all-solid lithium secondary battery of Comparative Example 1 which does not contain LLZ at all, the charging and discharging characteristics are not well realized. The charge / discharge characteristics of the pre-solid lithium lithium secondary battery of Example 5 including LLZ in the anode reversibly changed, the discharge capacity increased to about 120 mAh / g, and the capacity increase was observed in two cycles. It was confirmed that the discharge capacity of the pre-solid lithium lithium secondary battery of Example 6 was reduced to about 90 mAh / g and the capacity decreased in two cycles.

Therefore, it was confirmed that the discharge capacity of the all-solid lithium secondary battery of Example 4 is the largest and the cycle characteristics are excellent. When the characteristics of the all-solid lithium secondary battery in which LLZ is contained in the anode or the solid electrolyte do not include LLZ at all It was found that the lithium secondary battery of the present invention had excellent characteristics as compared with the conventional solid lithium secondary battery. In addition, it was confirmed that the pre-solid lithium lithium secondary battery of the present invention exhibits excellent cell characteristics that are maintained at substantially the same level as the discharge capacity of a lithium secondary battery to which a liquid electrolyte is applied without using any organic electrolytic solution.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (18)

cathode;
A positive electrode comprising a three-component lithium metal oxide (NMC) of Ni-Co-Mn and a binder; And
And a solid electrolyte including a polymer and a lithium salt between the cathode and the anode,
Wherein the solid electrolyte further comprises LixLa _y Zr _z O ₁₂ (6? X? 9, 2? Y? 4, 1? Z? 3)
Wherein the negative electrode contains lithium metal as an active material,
Wherein the binder is polyvinylidene fluoride,
When the polymer is polyethylene oxide
All solid lithium secondary batteries. delete The method according to claim 1,
Wherein the positive electrode further comprises Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ). delete delete The method according to claim 1,
Wherein the lithium salt is selected from the group consisting of lithium perchlorate (LiClO ₄ ), lithium triflate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LipF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), and lithium trifluoromethanesulfonylimide _{(LiN (CF 3 SO 2)} 2) all-solid lithium secondary battery, characterized in that at least one member selected from. The method according to claim 6,
Wherein the lithium salt is lithium perchlorate. delete delete The method according to claim 1,
Wherein the anode further comprises a conductive agent. ≪ RTI ID = 0.0 > 11. < / RTI > 11. The method of claim 10,
Wherein the conductive agent comprises at least one selected from the group consisting of conductive carbon, conductive metal, and conductive polymer. delete delete Casting a slurry obtained by mixing a polymer, a lithium salt and a plasticizer, and drying the slurry to prepare a solid electrolyte film (step a);
Coating a mixture of positive electrode materials comprising a three-component lithium metal oxide (NMC) of Ni-Co-Mn and a binder on a substrate to produce a positive electrode (step b); And
(C) placing the solid electrolyte film between the anode and the cathode to produce a pre-solid lithium secondary battery,
Wherein the slurry further comprises Li _x La _y Zr _z O ₁₂ (6? X? 9, 2? Y? 4, 1? Z? 3)
Wherein the negative electrode contains lithium metal as an active material,
Wherein the binder is polyvinylidene fluoride,
When the polymer is polyethylene oxide
A method for manufacturing a solid lithium secondary battery. delete 15. The method of claim 14,
Wherein the positive electrode material mixture further comprises Li _x La _y Zr _z O ₁₂ (6 ≦ _x ≦ 9, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ 3) (LLZ) Gt; 15. The method of claim 14,
Further comprising the step of compressing the positive electrode after step b (step b '). 15. The method of claim 14,
Wherein the base material comprises at least one selected from aluminum and nickel.

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