KR20180066694A - Cathode composite with high power performance and all solid lithium secondary battery comprising the same - Google Patents

Abstract

The present invention relates to an anode composite material for an all solid lithium secondary battery, which comprises: an anode active material comprising a lithium-based metal oxide; activated carbons; LLZO; a conductive material; and a binder. Accordingly, the present invention can provide the all solid lithium secondary battery comprising the anode composite material having excellent lifetime properties, output properties and high output.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive electrode composite material having high output characteristics, and a full solid lithium secondary battery including the same. BACKGROUND OF THE INVENTION < RTI ID = 0.0 >

The present invention relates to a positive electrode composite material and an all solid lithium secondary battery including the same, and more particularly, to a positive electrode composite material which is excellent in output characteristics and life characteristics and can be used as a power source for a hybrid vehicle, The present invention relates to a pre-solid lithium secondary battery.

2. Description of the Related Art With the rapid development of the electronics, communication, and computer industries, the demand for lithium secondary batteries has been increasing as a power source for driving these portable electronic communication devices as camcorders, mobile phones, notebook PCs, and the like have been remarkably developed. In particular, research and development are being actively carried out in Japan, Europe, and the United States, as well as domestic applications for applications such as electric vehicles, uninterruptible power supplies, power tools and satellites as eco-friendly power sources. Furthermore, recent commercialization of lithium secondary batteries has led to a problem of increasing the capacity and safety of lithium secondary batteries.

Meanwhile, lithium cobalt oxide (LiCoO ₂ ) has been mainly used as a positive electrode material of a lithium secondary battery. Currently, lithium nickel oxide (Li (Ni-Co-Al) O ₂ ) (Li (Ni-Co-Mn) O ₂ ) are also used. In addition, spinel-type lithium manganese oxide (LiMn ₂ O ₄ ) and olivine-type lithium iron phosphate compound (LiFePO ₄ ) of low cost and high stability are also attracting attention.

However, lithium secondary batteries using lithium cobalt oxide, lithium nickel oxide, lithium composite metal oxide or the like are excellent in basic battery characteristics, but safety, particularly, thermal stability, overcharging characteristics and the like are not sufficient. In order to improve this, various safety mechanisms such as a shut-down function of a separator, an electrolyte additive and a safety circuit such as a protection circuit and a PTC have been introduced. However, It was designed under circumstances. As a result, when the filling property of the anode material is increased in order to satisfy the demand for higher capacity, the operation of various safety mechanisms tends to be insufficient and the safety is lowered.

In this way, various battery solutions are being developed to innovate the anxiety about safety, limit of increase of energy density, and high cost burden which are pointed out as limitations of lithium secondary battery in the current market. All solid lithium secondary batteries Next-generation sodium-based batteries suitable for storing large amounts of energy, and magnesium batteries utilizing abundant magnesium resources are currently attracting attention as representative next-generation batteries.

In the case of all solid lithium secondary batteries, solid electrolytes are used instead of liquid electrolytes used in conventional lithium ion batteries, which is the most important advantage in ensuring perfect safety. The solid electrolyte is a key material for overcoming limitations of use of existing liquid electrolyte due to high capacity and high voltage of lithium ion battery electrode and assuring the safety of high performance lithium ion battery.

However, since the ion conductivity of the solid electrolyte is lower than that of the liquid electrolyte, the capacity is realized at a low current density of about 0.05C, but the capacity implementation is significantly reduced as the output density is increased have.

Also, since the contact area of the ion conductive material with the active material in the electrode is small, unlike in the liquid electrolyte, the amount of the ion conductive material should be added to the electrode of the solid lithium secondary battery. However, in order to realize a high capacity of a cell, it is difficult to contain a certain amount or more of the ion conductive material in the electrode because the amount of loading of the electrode must be increased. Therefore, the general characteristics at the anode of the all-solid-state battery fabricated by the solution process are that the electron transfer and the ion transfer in the electrode are not smooth and the capacity is realized at a current density as low as about 0.05 C. However, As the cycle progresses, the performance of the cell is drastically reduced.

SUMMARY OF THE INVENTION An object of the present invention is to provide a new anode composite material having excellent output characteristics.

Another object of the present invention is to provide a pre-solid lithium secondary battery which is excellent in lifetime characteristics of a battery even at a high output by applying a positive electrode composite material.

According to an aspect of the present invention, there is provided a positive active material comprising a lithium-based metal oxide; Activated carbon; LLZO represented by the formula (1); Conductive material; And a binder; and a positive electrode composite material for a pre-solid lithium rechargeable battery.

[Chemical Formula 1]

Li _p Al _q La _y Zr _z O

In the formula (1), 5? P <9, 0? Q? 1, 2? Y? 4, 1? Z?

The lithium-based metal oxide may be at least one selected from the group consisting of lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium tin cobalt manganese oxide (LiNiCoMnO ₂ ) Manganese oxide (NCM), and lithium nickel cobalt aluminum oxide (NCA).

The lithium nickel cobalt aluminum oxide (NCA) may be represented by the following chemical formula (2).

(2)

LiNi _x Co _y Al _z O ₂

In Formula 2,

0.01? X? 2, 0.01? Y? 0.30, and 0.01? Z? 0.99.

The conductive material may be at least one selected from the group consisting of carbon black, acetylene black, ketjen black, carbon fiber, carbon nanotube, and graphene.

The binder may be selected from the group consisting of polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-hexafluoro propylene, poly But are not limited to, polyvinylidene fluoride-cotrichloroethylene, polybutyl acrylate, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone ), Polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, polypropylene oxide, polyarylate, cellulose acetate ), Cellulose acetate butyrate, Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan (which may be referred to as cellulose acetate propionate), cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, pullulan, carboxyl methyl cellulose, styrene-butadiene rubber, acrylonitrile-styrene-butadiene copolymer, and polyimide. .

The binder may be polyethylene oxide.

Also, the positive electrode composite material for a pre-solidification secondary battery includes 100 parts by weight of a positive electrode active material containing a lithium-based metal oxide; 5 to 250 parts by weight of activated carbon; 20 to 50 parts by weight of LLZO represented by the general formula (1); 5 to 50 parts by weight of a conductive material; And 5 to 50 parts by weight of a binder.

The activated carbon may be used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the cathode active material.

The activated carbon may be 40 to 50 parts by weight based on 100 parts by weight of the cathode active material.

According to another aspect of the present invention, there is provided a positive electrode comprising a positive electrode composite material according to the present invention; A solid electrolyte layer comprising a solid electrolyte; And a cathode are provided.

In addition, the negative electrode may be made of any one of soft carbon, hard carbon, artificial graphite, natural graphite, expanded graphite, carbon fiber, hard graphitizable carbon, carbon black, carbon nanotube, acetylene black, Ketjenblack, graphene, fullerene, Any carbon selected from beads; (Me) selected from among Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Ni and Fe; An alloy including at least two of the metals (Me); And at least one oxide (MeOx) of the metal (Me); And the like.

Further, the cathode may include lithium.

The solid electrolyte is Li ₃ PO ₄ . _{(Na, Li) 1+ x Ti} 2 - x Al x (PO 4) 3 (0.1≤x≤0.9), Li 1 + x Hf 2-x Al x (PO 4) 3 (0.1≤x≤0.9), Li ₃ Zr ₂ Si ₂ PO ₁₂ , Li ₅ ZrP ₃ O ₁₂ , Li ₅ TiP ₃ O ₁₂ , Li ₃ Fe ₂ P ₃ O ₁₂ , Li ₄ NbP ₃ O ₁₂ , Li _{1 + x} (M, Al, Ga) _{x (Ge 1-y Ti y} ) 2 -x (PO 4) 3 (0≤X≤0.8, 0≤Y≤1.0, M is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , or _{Yb), Li 1 + x +} y Q x Ti 2 - x Si y P 3 - y O 12 (0 <x≤0.4, 0 <y≤0.6, Q is Al or _{Ga), Li 6 BaLa 2 Ta} 2 O 12 , Li _p Al _q La _y Zr _z O (5 ≦ _p ≦ 9, 0 ≦ _q ≦ 1, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ ₃ ), Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ M ₂ O ₁₂ (M is Nb, Ta), and Li _{7 + x} A _x La _{3 - x} Zr ₂ O ₁₂ (0 <x <3, A is Zn).

The solid electrolyte may be Li _p Al _q La _y Zr _z O (5? P <9, 0? Q? 1, 2? Y? 4, 1? Z?

In addition, the solid electrolyte layer, _{LiCl, LiBr, LiI, LiClO 4} , LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li , CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium, lithium lower aliphatic carboxylate, and lithium tetraphenylborate.

The present invention can provide a new anode composite material having excellent output characteristics.

The present invention can provide a pre-solid lithium secondary battery having stable life characteristics even at a high current density.

1 is a graph showing charge / discharge characteristics of an electrode measured at 70 ° C at 0.2C according to the ratio of metal oxide (NCA) to activated carbon (AC) of a positive electrode composite material.
FIG. 2 is a graph showing discharge capacities realized at different output densities at 70 ° C according to the ratio of metal oxide (NCA) to activated carbon (AC) of the anode composite material.
3 is a graph showing lifetime characteristics of electrodes measured by repeating charging and discharging at 70 ° C at 0.5C using the positive electrode prepared in Example 1 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, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

First, the positive electrode composite material of the present invention will be described. The positive electrode composite material of the present invention includes a positive electrode active material containing a lithium-based metal oxide; Activated carbon; LLZO represented by the formula (1); Conductive material; And a binder.

Cathode active material

The positive electrode composite material of the present invention may include a lithium-based metal oxide. (LiCoO ₂ ), lithium nickel based oxide (LiNiO ₂ ), lithium manganese based oxide (LiMn ₂ O ₄ ), lithium tin cobalt manganese based oxide (LiNiCoMnO ₂ ), lithium nickel cobalt manganese (NCM) or lithium nickel cobalt aluminum oxide (NCA) may be used alone or two or more of them may be used in combination. Preferably, lithium nickel cobalt aluminum oxide (NCA) may be used.

Here, the lithium nickel cobalt aluminum oxide (NCA) may be represented by the following chemical formula (2).

(2)

LiNi _x Co _y Al _z O ₂

In Formula 2,

 0.01? X? 2, 0.01? Y? 0.30, and 0.01? Z? 0.99.

Activated carbon

The positive electrode composite material of the present invention may contain activated carbon. Active carbon is carbon black in the form of black fine powder or particles in which wood, lignite, or peat is carbonized, treated with chemicals such as zinc chloride or phosphoric acid, which is activated, and dried or activated with water vapor. The inside is porous and has a large surface area.

The amount of activated carbon is preferably 5 to 250 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the cathode active material. When the amount of activated carbon is less than 5 parts by weight based on 100 parts by weight of the cathode active material, the contribution of the activated carbon to the electrode is small and the electron conductivity of the electrode is low, The capacity of the electrode is low due to the reduction of the high-capacity active material ratio, which is not preferable.

LLZO

The positive electrode composite material of the present invention may include LLZO, which is a solid electrolyte represented by the following formula (1).

[Chemical Formula 1]

Li _p Al _q La _y Zr _z O

In the formula (1), 5? P <9, 0? Q? 1, 2? Y? 4, 1? Z?

Conductive material

The positive electrode composite material of the present invention may include a conductive material. As the conductive material, carbon black, acetylene black, ketjen black, carbon fiber, carbon nanotube, or graphene may be used alone or in combination of two or more.

bookbinder

The positive electrode composite material of the present invention may include a binder. Also, as the binder, polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-hexafluoro propylene, poly (vinylidene fluoride) But are not limited to, polyvinylidene fluoride-cotrichloroethylene, polybutyl acrylate, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone ), Polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, polypropylene oxide, polyarylate, cellulose acetate ), Cellulose acetate butyrate, But are not limited to, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, A carboxyl methyl cellulose, a styrene-butadiene rubber, an acrylonitrile-styrenebutadiene copolymer or a polyimide may be used alone or in combination of two or more kinds. And polyethylene oxide may be preferably used.

Also, the positive electrode composite material for a pre-solidification secondary battery includes 100 parts by weight of a positive electrode active material containing a lithium-based metal oxide; 5 to 250 parts by weight of activated carbon; 20 to 50 parts by weight of LLZO represented by the general formula (1); 5 to 50 parts by weight of a conductive material; And 5 to 50 parts by weight of a binder

Next, a full solid lithium secondary battery according to the present invention will be described. A positive electrode comprising the positive electrode composite material according to the present invention; A solid electrolyte layer comprising a solid electrolyte; And a cathode.

The negative electrode may be formed of at least one selected from the group consisting of soft carbon, hard carbon, artificial graphite, natural graphite, expanded graphite, carbon fiber, hard graphitizable carbon, carbon black, carbon nanotube, acetylene black, Ketjenblack, graphene, The beads may be used alone or in combination of two or more.

As the negative electrode, there may be used a single or a combination of two or more of Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, (Me) can be used as a negative electrode, and at least one oxide (MeOx) of the metal (Me) can be used as a negative electrode .

As the solid electrolyte, Li ₃ PO ₄ . _{(Na, Li) 1+ x Ti} 2 - x Al x (PO 4) 3 (0.1≤x≤0.9), Li 1 + x Hf 2-x Al x (PO 4) 3 (0.1≤x≤0.9), Li ₃ Zr ₂ Si ₂ PO ₁₂ , Li ₅ ZrP ₃ O ₁₂ , Li ₅ TiP ₃ O ₁₂ , Li ₃ Fe ₂ P ₃ O ₁₂ , Li ₄ NbP ₃ O ₁₂ , Li _{1 + x} (M, Al, Ga) _{x (Ge 1-y Ti y} ) 2 -x (PO 4) 3 (0≤X≤0.8, 0≤Y≤1.0, M is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , or _{Yb), Li 1 + x +} y Q x Ti 2 - x Si y P 3 - y O 12 (0 <x≤0.4, 0 <y≤0.6, Q is Al or _{Ga), Li 6 BaLa 2 Ta} 2 O 12 , Li _p Al _q La _y Zr _z O (5 ≦ _p ≦ 9, 0 ≦ _q ≦ 1, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ ₃ ), Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ M ₂ O ₁₂ (M is Nb, Ta), or _{Li 7 + x a x La 3} - x Zr 2 O 12 may be used (0 <x <3, a is Zn), preferably Li _p Al _q La _y Zr _z O (5? p <9, 0? q? 1, 2? _y ? 4, 1? _z ?

LiBF ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiAsF ₆ , LiSbF ₆ , LiAlCl ₄ , CH ₃ SO ₃ Li , CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium, lower aliphatic carboxylate lithium, or lithium tetraphenylborate, or a combination of two or more thereof.

 [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.

Example  One: NCA: AC = 7: 3 ( wt: wt ) &Lt; / RTI &gt; &lt; RTI ID =

The positive electrode active material, the SuperP conductive material, and the solid electrolyte binder were mixed at a mass ratio of 70:10:20, and the resulting mixture was uniformly mixed with an acetonitrile solvent in a high-speed mixer to prepare a paste, which was then coated on an aluminum foil by a doctor blade method. Here, the cathode active material was a mixture of NCA material (NCA021) and activated carbon at a weight ratio of 7: 3. The solid electrolyte binder was prepared by mixing PEO (Polyethylene Oxide, Mn 200,000) and LLZO at a weight ratio of 55:45. The anode thus prepared was dried at 50 ° C for 10 hours and compressed at room temperature to prepare a cathode having a loading density of 5 to 9 mg / cm 2.

Example  2: NCA: AC = 5: 5 ( wt: wt ) &Lt; / RTI &gt; &lt; RTI ID =

A positive electrode was prepared in the same manner as in Example 1 except that the ratio of the cathode active material was NCA: activated carbon ratio of 5: 5 (wt: wt).

Example  4: NCA: AC = 3: 7 ( wt: wt ) &Lt; / RTI &gt; &lt; RTI ID =

The cathode was prepared in the same manner as in Example 1, except that the ratio of the cathode active material to the NCA: activated carbon was 3: 7 (wt: wt).

Comparative Example  1: NCA: AC = 10: 0 ( wt: wt ) &Lt; / RTI &gt; &lt; RTI ID =

A positive electrode was prepared in the same manner as in Example 1 except that the ratio of the cathode active material was NCA: activated carbon ratio of 10: 0 (wt: wt).

Device Example  One

Lithium foil was used as the positive electrode composite material electrode and the negative electrode prepared in Example 1, and 55 wt% of PEO (polyethylene oxide) containing 45 wt% of LLZO and lithium salt of LiClO ₄ was mixed with acetonitrile ) Was used as a separator and an electrolyte. 2032 type coin cells were prepared and stored in a 70 ° C chamber for 3 hours.

Device Example  2

A positive electrode composite material was prepared in the same manner as in Example 1 except that the positive electrode composite material of Example 2 was used instead of the positive electrode composite material of Example 1.

Device Example  3

A positive electrode composite material was prepared in the same manner as in Example 1 except that the positive electrode composite material of Example 3 was used instead of the positive electrode composite material of Example 1.

Device Example  4

A positive electrode composite material was prepared in the same manner as in Example 1 except that the positive electrode composite material of Example 4 was used instead of the positive electrode composite material of Example 1.

Device comparison example  One

A positive electrode composite material was prepared in the same manner as in Example 1 except that the positive electrode composite material of Example 4 was used instead of the positive electrode composite material of Example 1.

[Test Example]

Test Example  One: Charging and discharging  Character rating

Figs. 1 to 3 show the output characteristics of all solid lithium secondary batteries manufactured according to the device embodiments 1 to 4 and the device comparative example 1. Fig. The measurement conditions were a current of 0.2 C of the theoretical capacity and measured in a chamber of 70 캜.

FIG. 1 is a graph showing charge / discharge characteristics of an electrode measured at 70 ° C. at 0.2 ° C. according to the ratio of metal oxide (NCA) to activated carbon (AC) of a positive electrode composite material. FIG. 3 is a graph showing the discharge capacities of the electrodes measured at different output densities at 70 ° C. according to the ratio of NCA to AC. FIG. 3 is a graph showing the discharge capacities of the electrodes prepared in Comparative Example 1 and Example 1, And Fig.

Referring to FIGS. 1 to 3, it was confirmed that when the metal oxide content is high at 0.2 C, which has low output characteristics at 70 ° C., the unit cell capacity is high. However, as shown in FIG. 2, when the current density was high (50 mA / cm ² or more) and the activated carbon in the cathode active material was added, the output characteristics were excellent. Especially, the ratio of metal oxide to activated carbon was 7: 3 The best output characteristics were obtained. Also, it was confirmed that when the activated carbon in the anode was added, the life characteristics were excellent.

Claims (15)

A cathode active material comprising a lithium-based metal oxide;
Activated carbon;
LLZO represented by the formula (1);
Conductive material; And
Binders;
A positive electrode composite material for a pre-solid lithium secondary battery comprising:
[Chemical Formula 1]
Li _p Al _q La _y Zr _z O
In the formula (1), 5? P <9, 0? Q? 1, 2? Y? 4, 1? Z? The method according to claim 1,
Wherein the lithium metal oxide is at least one selected from the group consisting of lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium tin cobalt manganese oxide (LiNiCoMnO ₂ ), lithium nickel cobalt manganese Wherein the cathode active material is at least one selected from the group consisting of nickel oxide, cobalt oxide, nickel oxide, cobalt oxide, cobalt oxide, and cobalt aluminum oxide. The method according to claim 1,
Wherein the lithium nickel cobalt aluminum oxide (NCA) is represented by the following chemical formula (2).
(2)
LiNi _x Co _y Al _z O ₂
In Formula 2,
0.01? X? 2, 0.01? Y? 0.30, and 0.01? Z? 0.99. The method according to claim 1,
Wherein the conductive material is at least one selected from the group consisting of carbon black, acetylene black, ketjen black, carbon fiber, carbon nanotube, and graphene. The method according to claim 1,
Wherein the binder is selected from the group consisting of polyvinylidene fluoride (PVDF), hexafluoro propylene (HFP), polyvinylidene fluoride-hexafluoro propylene, polyvinylidene fluoride- But are not limited to, polyvinylidene fluoride-cotrichloroethylene, polybutyl acrylate, polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, Polyvinylacetate, polyethylene-co-vinyl acetate, polyethylene oxide, polypropylene oxide, polyarylate, cellulose acetate, , Cellulose acetate butyrate, cellulosic It is possible to use cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, ), At least one selected from carboxyl methyl cellulose, styrene-butadiene rubber, acrylonitrile-styrene-butadiene copolymer and polyimide. It is characterized by an anode composite material for all solid lithium secondary batteries. 6. The method of claim 5,
Wherein the binder is polyethylene oxide. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
The positive electrode composite material for a full solid secondary battery according to claim 1,
100 parts by weight of a cathode active material comprising a lithium-based metal oxide;
5 to 250 parts by weight of activated carbon;
5 to 50 parts by weight of LLZO represented by the formula (1);
5 to 50 parts by weight of a conductive material; And
5 to 50 parts by weight of a binder;
A positive electrode composite material for a pre-solid lithium secondary battery comprising: 8. The method of claim 7,
Wherein the activated carbon is 5 to 50 parts by weight based on 100 parts by weight of the cathode active material. 9. The method of claim 8,
Wherein the activated carbon is 40 to 50 parts by weight based on 100 parts by weight of the cathode active material. A positive electrode comprising the positive electrode composite material according to claim 1;
A solid electrolyte layer comprising a solid electrolyte; And
Cathode
Containing pre-solid lithium secondary battery. 11. The method of claim 10,
Wherein the negative electrode is at least one selected from the group consisting of soft carbon, hard carbon, artificial graphite, natural graphite, expanded graphite, carbon fiber, hard graphitizable carbon, carbon black, carbon nanotube, acetylene black, Ketjenblack, graphene, fullerene, Carbon; (Me) selected from among Si, Sn, Li, Al, Ag, Bi, In, Ge, Pb, Pt, Ti, Zn, Mg, Cd, Ce, Cu, Co, Ni and Fe; An alloy including at least two of the metals (Me); And at least one oxide (MeOx) of the metal (Me); Wherein the total amount of the at least one selected from the group consisting of lithium, 12. The method of claim 11,
Wherein the cathode comprises lithium. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 11. The method of claim 10,
Wherein the solid electrolyte is Li ₃ PO ₄ . _{(Na, Li) 1+ x Ti} 2 - x Al x (PO 4) 3 (0.1≤x≤0.9), Li 1 + x Hf 2-x Al x (PO 4) 3 (0.1≤x≤0.9), Li ₃ Zr ₂ Si ₂ PO ₁₂ , Li ₅ ZrP ₃ O ₁₂ , Li ₅ TiP ₃ O ₁₂ , Li ₃ Fe ₂ P ₃ O ₁₂ , Li ₄ NbP ₃ O ₁₂ , Li _{1 + x} (M, Al, Ga) _{x (Ge 1-y Ti y} ) 2 -x (PO 4) 3 (0≤X≤0.8, 0≤Y≤1.0, M is Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm , or _{Yb), Li 1 + x +} y Q x Ti 2 - x Si y P 3 - y O 12 (0 <x≤0.4, 0 <y≤0.6, Q is Al or _{Ga), Li 6 BaLa 2 Ta} 2 O 12 , Li _p Al _q La _y Zr _z O (5 ≦ _p ≦ 9, 0 ≦ _q ≦ 1, 2 ≦ _y ≦ 4, 1 ≦ _z ≦ ₃ ), Li ₅ La ₃ Nb ₂ O ₁₂ , Li ₅ La ₃ M ₂ O ₁₂ (M is Nb, Ta), and Li _{7 + x} A _x La _{3 - x} Zr ₂ O ₁₂ (0 <x <3, A is Zn) Solid state lithium secondary battery. 14. The method of claim 13,
Wherein the solid electrolyte is Li _p Al _q La _y Zr _z O (5? P <9, 0? Q? 1, 2? Y? 4, 1? Z? 3). 13. The method of claim 12,
Wherein the solid electrolyte layer _{LiCl, LiBr, LiI, LiClO 4} , LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF ₃ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, chloroborane lithium, lithium lower aliphatic carboxylate, and lithium tetraphenylborate.

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