KR20160051057A - Multi Layer Ceramic Battery and Method for Preparing the Same - Google Patents

Abstract

The present invention relates to a multilayer ceramic battery in which a plurality of unit cells are stacked on each other, which is an all-solid-state secondary battery capable of obtaining high output in terms of a structure. The multilayer ceramic battery has a structure in which unit cells are stacked in a series manner, and has a stacked structure of a collector paste layer (c)/a cermet cathode layer (b)/a ceramic electrolyte layer (a)/an anode layer (B). The cermet cathode layer (b) and the ceramic electrolyte layer (a) are stacked using a tape casting method, and the anode layer (B) is formed through thermal pressing in a state of having been subjected to primary plastic forming. Accordingly, a boundary area between an electrode and an electrolyte can be maximized, and thus output is increased. Furthermore, a sheet-shaped stacked structure is manufactured using a tape casting method, and a plurality of unit cells are manufactured by cutting the sheet-shaped stacked structure, and a battery cell is manufactured using a method of stacking the unit cells, and thus a manufacturing process is continuous and processing efficiency is excellent.

Description

TECHNICAL FIELD [0001] The present invention relates to a multi-layer ceramic battery and a method for manufacturing the multi-

The present invention provides a high-multilayer ceramic battery employing a solid electrolyte and a method of manufacturing the same.

The lithium secondary battery includes a lithium ion liquid battery using a liquid electrolyte according to an electrolyte to be used, a lithium ion polymer battery (LiPB) using a gel type polymer electrolyte impregnated with an electrolyte in a polymer electrolyte, A lithium polymer battery (LPB) using a solid polymer electrolyte, and the like.

In the case of a conventional secondary battery using a liquid electrolyte, since the electrolytic solution is wetting all the regions of the anode and the cathode, the portion where the electrolyte contacts with the electrode corresponds to the front portion of the three-dimensional electrode, and the capacity increases in proportion to the loading amount of the electrode . However, in the case of a solid electrolyte secondary battery, a site at which an electrochemical reaction can occur is confined to the interface between the solid electrolyte and the electrode, so that it has a low capacity. In addition, since the lithium ion conductivity of the solid electrolyte is still low, efforts to develop a material having a high ion conductivity are continuing.

The present invention is to provide a high solid multilayer ceramic battery in which a plurality of unit cells are stacked as a whole solid secondary battery which can obtain a high output in terms of structure.

Further, the present invention is to provide a method for effectively manufacturing the high-multilayer ceramic battery.

The high multilayer ceramic battery according to one embodiment of the present invention comprises a ceramic electrolyte layer (a) including a garnet-type lithium oxide having a sintering temperature of not higher than 1,200 占 폚, and a sintered body formed on the electrolyte layer (B) comprising a lithium oxide having a sintering temperature not exceeding 1200 占 폚, a cermet-based lithium oxide having d -orbital electrons and a periodic table having a period of 4 to 6 cycles, and a cermet anode layer (A) which has undergone the sintering process and the lower part of the electrolyte layer (a) of the sintered body (A) are laminated to each other by thermocompression bonding And a unit cell formed by stacking a current collector, an anode, an electrolyte, and a cathode is connected in series.

In one example, the current collector paste layer (c) may be a single layer structure of a current collector paste for anode and cathode, or a cathode collector paste layer formed on the anode layer (b) and a cathode collector paste layer May be a laminated structure.

In one example, the unit cell located at the uppermost end of the high multilayer ceramic battery includes a positive electrode current collector paste layer (c), a cermet anode layer (b), a ceramic electrolyte layer (a), and a cathode layer (B) . ≪ / RTI >

In one example, the unit cell located at the lowermost end of the high multilayer ceramic battery may be a negative electrode current collector metal layer C on the bottom surface of the negative electrode layer B, wherein the negative electrode current collector metal layer has a mat surface The surface-treated copper foil is preferred, but is not limited thereto.

In one preferred example, the high multilayer ceramic battery of the present invention may be formed by stacking n unit cells.

The first unit cell is formed by stacking a first unit cell and a second unit cell on the other side of the ceramic electrolyte layer (a) in the sintered body (A) in which the ceramic electrolyte layer (a), the cermet anode layer (b), and the cathode collector paste layer The unit cell on which the pressed negative electrode layer B is formed may be located.

The second unit cell to the (n-1) th unit cell are formed from a sintered body (a), a cermet anode layer (b), a positive electrode collector paste layer and a negative electrode collector paste layer A), a unit cell on which the cathode layer B thermally compressed is formed on the other surface of the ceramic electrolyte layer (a) may be located.

The n-th unit cell is formed from a sintered body (A) in which a ceramic electrolyte layer (a), a cermet anode layer (b), a cathode current collector paste layer and a cathode current collector paste layer ) And a negative electrode current collector metal layer (C) are sequentially formed on the other surface of the negative electrode layer (B).

In one embodiment, the ceramic electrolyte layer (a), _{Li 7 La 3 M 2 O 12} (M = Zr, Sn), Li 6 ALa 2 M 2 O 12 (A = Mg, Ca, Sr, Ba, M = Nb _{, Ta), Li 5 La 3} M 2 O 12 (M = Nb, Ta, Sb), Li 3 Ln 3 Te 2 O 12 (Ln = Y, Pr, Nd, Sm, Lu), Li 3 + x Nd 3 (Li ₇ La ₃ Zr ₂ O ₁₂ ) based lithium oxide selected from Te _{2 - x} Sb _x O ₁₂ (x = 0.05 to 1.5), and mixtures thereof, and the cathode layer (B) May be made of a lithium metal foil.

In one example, the current collector paste may be made of a metal selected from copper, aluminum, nickel, silver, gold, and alloys thereof, but is not limited thereto.

In one example, the cermet anode layer (b) in said lithium transition metal oxide positive electrode active material is _{LiCoO 2, LiNi 0 .4 Mn 0} .4 Co 0 .2 O 2, LiNi 0 .5 Mn 0. _{5Co 0 .2 O 2, LiNi 0} .6 Mn 0 .2 Co 0 .2 O 2, LiNi 0.8 Mn 0.1 Co 0.1 O 2 , and can be mixtures thereof, but not limited to these.

The garnet type lithium oxide which is a ceramic electrolyte may be Li ₇ La ₃ M ₂ O ₁₂ (M = Zr, Sn), Li ₆ Ala ₂ M ₂ O ₁₂ (A = Mg, Ca, Sr, Ba, M = _{Ta), Li 5 La 3 M} 2 O 12 (M = Nb, Ta, Sb), Li 3 Ln 3 Te 2 O 12 (Ln = Y, Pr, Nd, Sm, Lu), Li 3 + x Nd 3 Te _{2 - x} Sb _x O ₁₂ (x = 0.05 to 1.5), and mixtures thereof.

The conductive agent may be selected from, but not limited to, nickel, silver, palladium, copper, gold, platinum, and mixtures or composites thereof.

The number of the unit cells is not particularly limited and may be adjusted according to capacity and output characteristics according to an application, and may include, for example, several hundreds to several hundreds of layers.

The present invention also provides a method of manufacturing a high multilayer ceramic battery comprising the steps of:

(i) tape casting with a paste prepared by mixing a lithium transition metal oxide, a garnet lithium oxide, a conductive agent, and a binder to form a cermet anode layer (b) having a thickness of 1 to 100 m;

(ii) a step of forming a ceramic electrolyte layer (a) having a thickness of 1 to 100 탆 by tape casting with a paste in which a ceramic electrolyte powder and a binder are mixed;

(iii) stacking the anode layer (b) on the formed electrolyte layer (a);

(iv) after the step of selecting the anode layer forming step (i), the electrolyte layer forming step (ii), and the laminating step (iii), a plurality of collector paste layers are printed on the anode layer in a thickness of 1 to 100 μm ;

(v) firing the laminated collector / anode / electrolyte laminate at 900 to 1100 占 폚;

(vi) inserting a thin cathode plate having a thickness of 1 to 100 占 퐉 between the sintered collector / anode / sintered body to obtain a unit cell in which a plurality of collectors / anodes / electrolytes / cathodes are stacked;

(vii) thermally compressing the unit cell laminate in an inert atmosphere at a temperature of 90 to 140 캜, and cutting the unit cell laminate by unit cell;

(viii) stacking the plurality of unit cells to manufacture a battery;

In one example, the step of (vi) inserting the negative electrode current collector thin plate having a mat surface with respect to the unit cell located at the lowermost layer so that the mat surface faces the negative electrode.

In one example, it is possible to further insulate the side surfaces of the coated unit cells after the thermocompression step (vii).

The high multilayer ceramic battery of the present invention is formed by forming a laminated sintered body of a garnet-type solid electrolyte and a lithium oxide-based anode, and then connecting a plurality of unit cells formed by thermocompression of a negative electrode such as lithium metal in series, The interface area can be maximized and the output can be increased. In addition, a process for producing a battery cell by a method of manufacturing a sheet-like laminate by tape casting and cutting a plurality of unit cells and stacking them is continuous and excellent in process efficiency.

1 is a schematic cross-sectional view of a unit cell according to an embodiment of the present invention.
2 is a schematic diagram of a unit cell laminated structure according to an embodiment of the present invention.
Fig. 3 is a perspective view (Fig. 3a) and a plan view (Fig. 3b) of a sintered body according to an example of the present invention.
Fig. 4 is a cross-sectional view of Li ₇ La ₃ Zr ₂ O ₁₂ The interface between the garnet (001) plane and the lithium metal surface with the BCC structure is the result of structural optimization using VASP code.
5 is a calculation result of the average local potential of the garnet electrolyte surface and the cathode surface of the lithium metal.
Fig. 6 shows the band structure of the interface using the band gap obtained by calculation of the GW of the garnet electrolyte surface and the lithium metal cathode surface.

Hereinafter, a high-multilayer ceramic battery according to embodiments of the present invention will be described in detail.

Prior to that, and unless explicitly stated throughout the present specification, the terminology is used merely to refer to a specific embodiment and is not intended to limit the present invention. And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning. Also, as used herein, the term " comprises " embodies certain features, areas, integers, steps, operations, elements and / or components, It does not exclude the existence or addition of a group.

1 is a schematic cross-sectional view of a unit cell according to an embodiment of the present invention. Referring to FIG. 1, a unit cell 10 has a cermet anode layer b on one side of a ceramic electrolyte layer a, and a cathode layer B on the other side. Here, the ceramic electrolyte layer (a) and the cermet anode layer (b) form a sintered body (A) manufactured through a tape casting step and a first sintering step, and the cathode layer (B) And is attached to the electrolyte layer (a).

The sintered body A is formed by forming the ceramic electrolyte layer (a) and the cermet anode layer (b) through a tape casting method, so that the area of the contact interface is wide and the cermet anode layer (b) The output characteristics can be improved by maximizing the interface area between the electrode and the electrolyte, and the interfacial stability between the solid electrolyte and the cathode of the lithium metal is excellent. The high multilayer ceramic battery of the present invention is a multi-layer ceramic battery (MLCB) in which the unit cells are repeatedly stacked in the form of a cathode-electrolyte-cathode-anode-electrolyte-cathode.

In the basic unit cell structure, in the case of the current collector paste layer (c), it may be a current collector paste single layer structure for use in combination of an anode and a cathode, or a cathode collector paste layer formed on the anode layer (b) Layer structure. Such a structure may be selected depending on the constituent components of the current collector paste or the position of the unit cell. The current collector paste may be made of a metal selected from, for example, copper, aluminum, nickel, silver, gold, and alloys thereof. As a specific example, aluminum may be used as the positive electrode collector and copper may be used as the negative electrode collector, as is applied to a conventional lithium secondary battery. When copper, nickel, silver, gold or the like other than aluminum is used as the current collector, it is not necessary to distinguish between the positive electrode and the negative electrode, and it is possible to use only a single current collector layer.

Next, a schematic view of a unit cell laminated structure according to an embodiment of the present invention will be described with reference to FIG.

The high multilayer ceramic battery of the present invention has a structure in which n unit cells are stacked in series and the anode collector paste layer (c) / cathode collector paste layer (c) / cermet anode layer (b) / ceramic electrolyte layer a basic unit cell structure having a stacked structure of a) / cathode layer (B) is repeated in the second unit cell to the (n-1) th unit cell.

However, in the case of the uppermost unit cell (the first unit cell) and the lowermost unit cell (the nth unit cell) of the laminate, the configuration of the electrode current collector is slightly different for serial connection. That is, the positive electrode collector paste layer (c) is formed on the exposed surface side in the case of the first unit cell and the negative electrode collector metal layer (C) is formed in the n th unit cell in the opposite direction. Here, the negative electrode current collector metal layer (C) may be a copper foil whose one surface is surface-treated with a mat surface.

The present invention also provides a method of manufacturing a high multilayer ceramic battery comprising the steps of:

(i) tape casting with a paste prepared by mixing a lithium transition metal oxide, a garnet lithium oxide, a conductive agent, and a binder to form a cermet anode layer (b) having a thickness of 1 to 100 m;

(ii) a step of forming a ceramic electrolyte layer (a) having a thickness of 1 to 100 탆 by tape casting with a paste in which a ceramic electrolyte powder and a binder are mixed;

(iii) stacking the anode layer (b) on the formed electrolyte layer (a);

(iv) after the step of selecting the anode layer forming step (i), the electrolyte layer forming step (ii), and the laminating step (iii), a plurality of collector paste layers are printed on the anode layer in a thickness of 1 to 100 μm ;

(v) firing the laminated collector / anode / electrolyte laminate at 900 to 1100 占 폚;

(vi) inserting a thin cathode plate having a thickness of 1 to 100 占 퐉 between the sintered collector / anode / sintered body to obtain a unit cell in which a plurality of collectors / anodes / electrolytes / cathodes are stacked;

(vii) thermally compressing the unit cell laminate in an inert atmosphere at a temperature of 90 to 140 캜, and cutting the unit cell laminate by unit cell;

(viii) stacking the plurality of unit cells to manufacture a battery;

The sheet-like cermet anode layer (b) and the ceramic electrolyte layer (a) forming step (ii) can be selectively formed first without any subsequent relationship. In addition, the current collector paste layer

Referring to FIG. 3, in the high multilayer ceramic battery of the present invention, the cermet anode layer (b) and the ceramic electrolyte layer (a) are formed into sheets by tape casting and laminated, followed by printing and laminating the current collector paste. At this time, the paste may be printed with a double layer of the negative electrode current collector paste layer (c) and the positive electrode current collector paste layer (c), or the collector paste layer (c) in the form of a single layer may be formed as the case may be. The current collector paste layer (c) may be printed on the sheet in a plurality corresponding to the unit cell size. Next, the multilayer body is fired to obtain a sintered body of the anode layer (b) and the electrolyte layer (a), laminated with the cathode layer (B), and thermocompression bonded to form a high multilayered solid battery structure.

Increased the voltage in the plurality of unit cells are connected in series, unlike the high multi-layered ceramic battery and multi-layer ceramic capacitor (MLCC) of the present invention, the high dielectric constant ceramic sheets such as for MLCC made by tape casting BaTiO ₃ Ni, Pd In the present invention, the anode and the electrolyte are firstly fired, and then the cathode metal plate is inserted between the plurality of fired anode-electrolyte composite sheets and laminated. Followed by thermocompression bonding.

As described above, in the case of the unit cell located at the lowermost layer, the negative electrode current collector thin plate is inserted into the lower surface of the negative electrode layer so that the negative electrode current collector is exposed. Therefore, in the step (vi), a step of inserting the negative electrode current collector thin plate having the mat surface into the lowermost unit cell so that the mat surface faces the negative electrode can be performed.

Inserting the side surfaces of the coated unit cells after the thermocompression step (vii); Can be further performed. The insulation may be performed by, for example, wrapping a side surface of the ceramic battery with an insulating pouch or tapping with an insulating material, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

[ Example  One]

The ceramic electrolyte powder is mixed with a binder and then formed into a thickness of 1 to 100 탆 by tape casting to form a ceramic electrolyte sheet.

The anode layer is prepared by mixing a cathode active material, a conductive agent, and a ceramic electrolyte powder with a binder and then molding the mixture into a thickness of 1 to 100 μm by a tape casting method.

The positive electrode collector paste is printed on the formed positive electrode to a thickness of less than 100 mu m. The current collector paste may be composed of two layers of aluminum paste for positive electrode and copper paste for negative electrode, or one layer of nickel, copper, aluminum or gold may be formed as one layer without separating the positive electrode and the negative electrode. However, aluminum is excluded because it forms an alloy with lithium metal.

The formed cermet anode sheet and the ceramic electrolyte sheet are laminated.

The laminated body of the stacked positive electrode (including current collector paste) / electrolyte is baked at 900 to 1100 占 폚.

A lithium metal foil (1 to 100 탆 thick) serving as a cathode is inserted between the laminated bodies of the fired anode / electrolyte and laminated. As shown in FIG. 2, the anode / electrolyte composite structure located on the uppermost layer is the unit cell 1, and the unit cell structures of the second to the (n-1) th layers are configured identically, The copper foil is inserted so that the mat side faces the lithium metal foil of the cathode layer.

The laminated high-multilayer ceramic battery is hot-pressed in an inert atmosphere at a temperature of 90 to 140 占 폚. The thermocompressed disk is cut with a CNC router machine or a laser.

To prevent the oxidation of the lithium metal cathode, wrap the insulation of the cut multi-layer ceramic battery with insulating pouch or tap it with insulation.

[ Experimental Example  One]

When the lithium metal is used as the cathode, the interfacial stability with the solid electrolyte is the most problematic. To this end, the interfacial properties between the garnet-based solid electrolyte and the lithium metal used in the present invention are confirmed. DFT Calculation Result Using VASP Code The garnet solid electrolyte and lithium metal interface used in the present invention are expected to be stable.

Li ₇ La ₃ Zr ₂ O ₁₂ The interface between the garnet (001) plane and the lithium metal surface having the BCC structure was made, and the structure was optimized using the VASP code. As a result, it was confirmed that the stable interface was formed as shown in FIG.

As a result of checking the band structure of the interface using the band gap obtained by the GW calculation as shown in the graph of FIG. 5, the Fermi level of the lithium metal is represented by the valence band maximum of the Garnet CBM (conduction band minimum). Therefore, in order for electrons to migrate from the Li metal to the garnet electrolyte, it is necessary to exceed the barrier of about 2.42 eV, so that the lithium metal is hardly oxidized by the electrons to the solid electrolyte. Therefore, the interface between the lithium metal cathode and the garnet solid electrolyte can be said to be stable.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (13)

And a sintering temperature of not higher than 1200 占 폚 and a sintering temperature of not higher than 1200 占 폚 and a sintering temperature of 1200 占 폚 or less formed on the electrolyte layer (a) A cermet anode layer (b) comprising a carbonaceous lithium oxide and d - orbital electrons not exceeding 4 to 6 cycles in the periodic table and a current collector paste layer (c) formed on the anode layer (b) A sintered body (A) having a laminated structure of collector / anode / electrolyte, which has undergone a sintering process; And
A negative electrode layer (B) thermally pressed on the lower part of the electrolyte layer (a) of the fired product (A);
And a unit cell comprising a laminate structure of a current collector, a positive electrode, an electrolyte, and a negative electrode is connected in series. The method according to claim 1,
The current collector paste layer (c) may be a single layer structure of current collector paste for anode and cathode or a layer structure of a cathode collector paste layer formed on the anode layer (b) and a cathode collector paste layer formed thereon Characterized by a high multilayer ceramic battery. 3. The method according to claim 1 or 2,
The unit cells located at the uppermost end of the high multilayer ceramic battery are sequentially stacked from the top in a laminated structure of the positive electrode current collector paste layer (c), the cermet anode layer (b), the ceramic electrolyte layer (a), and the cathode layer Lt; RTI ID = 0.0 > 1, < / RTI > 4. The method according to any one of claims 1 to 3,
Wherein the unit cell located at the lowermost end of the high multilayer ceramic battery has a negative electrode current collector metal layer (C) formed on a lower surface of the negative electrode layer (B). 5. The method of claim 4,
Wherein the negative electrode current collector metal layer is a copper foil surface-treated with a mat surface on one side. The method according to claim 1,
layer ceramic battery formed by laminating n unit cells,
The first unit cell is formed by stacking a first unit cell and a second unit cell on the other side of the ceramic electrolyte layer (a) in the sintered body (A) in which the ceramic electrolyte layer (a), the cermet anode layer (b), and the cathode collector paste layer A unit cell in which the cathode layer (B)
The second unit cell to the (n-1) th unit cell are formed by successively forming a ceramic electrolyte layer (a), a cermet anode layer (b), a cathode collector paste layer (c), and a cathode collector paste layer A unit cell in which a cathode layer B thermally pressed on the other surface of the ceramic electrolyte layer (a) is formed in the sintered body (A)
The n-th unit cell is formed from a sintered body (A) in which a ceramic electrolyte layer (a), a cermet anode layer (b), a cathode current collector (c) and a cathode current collector paste layer layer ceramic battery according to claim 1, wherein the unit cell is formed by successively forming the negative electrode layer (B) thermally pressed on the other surface of the negative electrode collector metal layer (C) and the negative electrode collector metal layer (C). The method according to claim 1,
The ceramic electrolyte layer (a), _{Li 7 La 3 M 2 O 12} (M = Zr, Sn), Li 6 ALa 2 M 2 O 12 (A = Mg, Ca, Sr, Ba, M = Nb, Ta), _{Li 5 La 3 M 2 O 12} (M = Nb, Ta, Sb), Li 3 Ln 3 Te 2 O 12 (Ln = Y, Pr, Nd, Sm, Lu), Li 3 + x Nd 3 Te 2 - x (Li ₇ La ₃ Zr ₂ O ₁₂ ) -based lithium oxide selected from Sb _x O ₁₂ (x = 0.05 to 1.5), and mixtures thereof,
Wherein the cathode layer (B) is made of a lithium metal foil. The method according to claim 1,
Wherein the current collector paste is made of a metal selected from copper, aluminum, nickel, silver, gold, and alloys thereof. The method according to claim 1, wherein in the cermet anode layer (b)
The lithium transition metal oxide is _{LiCoO 2, LiNi 0 .4 Mn 0} .4 Co 0 .2 O 2, LiNi 0 .5 Mn 0. And _{5Co 0 .2 O 2, LiNi 0.6} Mn 0.2 Co 0.2 O 2, LiNi 0 .8 Mn 0 .1 Co 0 .1 O 2 and a cathode active material selected from a mixture thereof,
The garnet lithium oxide _{Li 7 La 3 M 2 O 12} (M = Zr, Sn), Li 6 Ala 2 M 2 O 12 (A = Mg, Ca, Sr, Ba, M = Nb, Ta), Li 5 _{La 3 M 2 O 12 (M} = Nb, Ta, Sb), Li 3 Ln 3 Te 2 O 12 (Ln = Y, Pr, Nd, Sm, Lu), Li 3 + x Nd 3 Te 2 - x Sb x O ₁₂ (x = 0.05 to 1.5), and mixtures thereof,
Wherein the conductive agent is selected from the group consisting of nickel, silver, palladium, copper, gold, platinum, and mixtures or composites thereof. 4. The method according to any one of claims 1 to 3,
Wherein the number of the unit cells is two to twenty. (i) tape casting with a paste prepared by mixing a lithium transition metal oxide, a garnet lithium oxide, a conductive agent, and a binder to form a cermet anode layer (b) having a thickness of 1 to 100 m;
(ii) a step of forming a ceramic electrolyte layer (a) having a thickness of 1 to 100 탆 by tape casting with a paste in which a ceramic electrolyte powder and a binder are mixed;
(iii) stacking the anode layer (b) on the formed electrolyte layer (a);
(iv) after the step of selecting the anode layer forming step (i), the electrolyte layer forming step (ii), and the laminating step (iii), a plurality of collector paste layers are printed on the anode layer in a thickness of 1 to 100 μm ;
(v) firing the laminated collector / anode / electrolyte laminate at 900 to 1100 占 폚;
(vi) inserting a thin cathode plate having a thickness of 1 to 100 占 퐉 between the sintered collector / anode / sintered body to obtain a unit cell in which a plurality of collectors / anodes / electrolytes / cathodes are stacked;
(vii) thermally compressing the unit cell laminate in an inert atmosphere at a temperature of 90 to 140 캜, and cutting the unit cell laminate by unit cell;
(viii) stacking the plurality of unit cells to manufacture a battery;
Layer ceramic battery according to claim 1. 12. The method of claim 11,
The method according to claim 1, further comprising the step of inserting the negative electrode current collector thin plate having a mat surface with respect to the unit cell located at the lowest layer in the step (vi) so that the mat surface faces the negative electrode (Method for manufacturing high multilayer ceramic battery). 12. The method of claim 11,
Inserting the side surfaces of the coated unit cells after the thermocompression step (vii); The method of manufacturing a multilayer ceramic battery according to claim 1, further comprising:

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