An electrode assembly and a lithium secondary battery containing them

[Technology]

Mutual citations and related application (s)

5 This application is 2017 years 12 Mon 1 Date of Korea Patent Application No. 10-2017-0164085 call and

2018 years 11 Mon 29 Date of Korea Patent Application No. 10-2018-0151236 claims the benefit of priority based on the call, and all information disclosed in the literature of Korea that the patent application is included as part of the specification.

The present invention relates to a lithium secondary battery comprising an electrode assembly and him, 10 relates to a secondary battery comprising Lyrium more particularly to a high energy rechargeable lithium battery electrode assembly and him.

[Background Art]

As the technology developed, and the demand for multi-device increase the demand for energy rechargeable battery as there is increasing rapidly, such a secondary battery 15 has a high energy density and voltage, long cycle life, self-discharge rate is a lithium secondary battery low land is commercially available and widely used.

These Lyrium secondary battery is a lithium-containing cobalt oxide in the layered crystal structure as a positive electrode active material (Nishi (: 00 ), the layered crystal structure 111 ^ , you a spinel crystal structure 1此0 lithium-containing manganese oxide and lithium-containing nickel oxides such as ( Needle 0 to) typically 20 to use. In addition, as a negative electrode active material used is a carbonaceous substance mainly, in recent years, high-energy lithium than the carbon-based material with increased demand for secondary batteries 10 are blends of having a more times the effective dose based material, a silicon sanhwagye material has been considered.

On the other hand, to the recent trend of high-energy secondary battery Lyrium development silicone 25 it can be called the essential use of the negative electrode using the material as an anode active material. However, the cathode is applied to the silicon-based material has a problem that the charging / discharging efficiency is low because the size of the irreversible capacity.

For eliminating these problems, 11 0 The methods for producing the cell was sought that the irreversible capacity of the additive by applying a positive electrode mixture, such as. However, the first 30 you through the filling zero and is decomposed discharging the oxygen gas, the air gap is generated in place, after the first charge due to such voids, the density of the positive electrode has been lowered This causes the battery energy there are problems such that the density is lowered.

[Detailed Description of the Invention]

5 [Technical Problem]

Object of the present invention, the positive electrode by mixing the positive electrode active material, the irreversible additive for high-capacity exists on the outermost of the cathode present on both sides of the outermost of the stacked electrode assembly is intended to solve the problem in the case of using the positive electrode active material instead layer, characterized in that it comprises a non-reversible capacity of the coating material

10 to provide a Lyrium secondary battery comprising the electrode assembly and an object of him.

[Technical Solution]

According to an aspect of the invention, the two or more anode and a cathode at least one separator, an electrode assembly alternately stacked in the boundary, of the electrode assembly

15 outermost on both sides, the non-reversible materials including ritum oxide formed on each of the outermost positive electrode is located, and wherein the outermost positive electrode are, respectively, the cathode current collector, the entire surface of the positive electrode current collector a positive electrode formed on one surface of the active material layer and the positive electrode current collector comprising a coating layer and the non-reversible material coating layer is provided to the electrode body jochil, characterized in that positioned on the outermost side of the electrode assembly.

20. Here, the non-reversible material coating layer may be in addition to the irreversible lithium oxide material further comprises a catalyst and a conductive material, and a binder and the like.

The content of the catalyst the conductive material, and binder were 10 to 50% by weight, based on the total weight of the coating layer non-reversible material, 1 to 20 wt % , 1 to 20 wt % can be included as a.

25 The content may be appropriately selected to fit each role.

In this case, the lithium oxide was your 202, 11, 20, Needle 2 0 2 may be or a mixture of these.

Here, the Needle 202 , needle 20 is, the extinction doeneungeot days after the first charge of the cell including the electrode assembly.

30, the lithium oxide is particularly, 11 202, or you 2出0 2 may be in, you are more detail, the extinction 202 is the number of days.

In addition, the cathode may comprises a number of days, a silicon () based material as an anode active material.

At this time, the silicon-based material, a complex of silicon and silicon oxide;

5 may be a silicon alloy or a composite of silicon oxide and a silicon alloy.

The electrode according to another aspect of the invention the electrode assembly to the electrode assembly of the non-aqueous electrolyte and Lyrium secondary battery comprising a battery case which incorporates the electrode assembly and the non-aqueous electrolyte for impregnating the electrode assembly is described above the present invention the lithium secondary battery characterized in that the assembly 10 is provided.

And a device is provided which is characterized in that according to the present invention, including the battery module, the battery pack including the same, and such a battery pack comprising the Lyrium secondary battery of the above-mentioned present invention as a unit cell as a power source. Here, the device is an electric vehicle hybrid electric vehicles, plug _ 15 may be a hybrid electric vehicle or a power storage system.

[Brief description of drawings]

The accompanying drawings are intended to illustrate preferred embodiments of the invention, but the scope of the invention by explaining the principles of the invention and together with the description being limited to this. On the other hand, the shape of the elements in the figures contained in this specification, the size scale 20 or a ratio or the like may be exaggerated to emphasize a more clear description.

Figure 1 is a view showing a conventional electrode assembly. FIG. Figure 2 is a schematic diagram of an electrode assembly according to one embodiment of the present invention.

Figure 3 is an electrode assembly after the filling in accordance with one embodiment of the present invention 25 is a view showing schematically.

[Mode for Carrying out the invention]

That the specification and be construed as limited to the terms used in the claims general and dictionary meanings is not is the inventor can adequately define terms to describe his own invention in the best way 30 It interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle. Therefore, the configuration shown in the embodiments described herein are various equivalents, which in not intended to limit the scope of the present and only one embodiment the most preferred of the present invention invention can be made thereto according to the application time point and it should be understood that modifications iteulsu.

5

For the high-energy lithium secondary batteries developed in accordance with the needs of the art are required, the use of the negative electrode applying the silicon-based material as an anode active material, the anode current is the irreversible capacity large charge / non-reversible additive for high capacity in order to solve this problem, because the discharge efficiency is low It has been using the mixed cathode.

10 Fig. 1 is a prior art electrode assembly ( 10), a schematic view of a. Referring to the drawings, there is irreversible additive of high capacity is mixed in the positive electrode active material layer, with the first charge, while the irreversible additive of high capacity degradation that is dispersed in the positive electrode active material layer, a gap is generated in place, therefore the low density of the positive electrode active material layer, which is ultimately the energy density of the battery becomes low 15 was a problem.

Without the present invention, the mixture of non-reversible additive for a cathode active material and high capacity, the prior art described above of the anode present in the outermost of the electrode assembly, instead of the positive electrode active material layer positioned on the outermost side of the electrode assembly, by forming a non-reversible material coating the problem could be solved.

20

Figure 2 is a schematic diagram of an embodiment of the electrode assembly according to the invention, Figure 3 is a schematic view of the electrode assembly after the filling in accordance with one embodiment of the present invention.

If with reference to the drawings and more detailed description of the invention herein, 2 25 or more anode ( 110) and one or more cathode ( 120), the separator ( 130), the electrode assembly (laminated alternately to the boundary 100), as it said electrode assembly ( 100) of the outermost on both sides, the outermost positive electrode, respectively 110 and is located, wherein the outermost positive electrode ( 110) are all (each positive electrode current collector 111) , the positive electrode collector ( 111), the positive electrode active material layer formed on a surface of 112) and said positive electrode collector ( 111), non-reversible material containing lithium oxide is formed on the other surface of 30 the coating layer ( 113) include wherein the non-reversible material coating ( 113) is the electrode assembly 100), characterized in that positioned on the outermost face of the do.

Irreversible substance coating layer containing the oxide Lyrium 113), the electrode assembly 100) because is situated on the outermost surface, because it is not included in the positive electrode active material layer, it is not necessary to step for mixing the positive electrode active material and the non-reversible material.

In this case, the lithium oxide, 11 0, Needle 20, Needle 202 may be a, or a mixture thereof.

Here, the 1 [0, Needle 20 is, the extinction doeneungeot days after the first charge of the cell including the electrode assembly. This Figure 3 shows the.

The Needle 202, or your 20 irreversible material coating layer (containing the lithium oxide of 113) in the material are, the electrode assembly ( 100) is destroyed after the first charging of the lithium secondary battery comprising a. In this case, lithium oxide is decomposed into lithium ions and oxygen gas can be destroyed. Figures to indicate the phenomenon of oxide Lyrium be destroyed is only shown schematically, catalyst , additional material of the conductive material, binder and the like is of course that remains.

Also, needle 202 when using, it is iteulsu substances remain in the material, a catalyst, a conductive material, and a binder and the like.

On the other hand, the positive electrode active material of the positive electrode active material layer to the formula 1 or 2 can contain a transition metal oxide represented by Lyrium.

You; ( 1 ^ 1112-> ^ 04 - 2 (1)

Wherein

¾10， ，

Award silverware style 美 Acer said;

Is, 00, when, (: 11,%, 民 0, ·, ¾ and second transition period is at least one selected from the group consisting of the metals;!

Show的4 , 60 3 )期3 , and炯3 one or more selected from the group consisting of an anion in which p is 1 to 100;

0<5（<1 , 0< <0.02, 0 1 6116 ◦ 31 e 011 6 ), near to the grave every 311 11 01½ may sikilsu more the like).

In one specific example,

Li a tumyeom, highly dielectric solvent: can be prepared for re-salt-containing non-aqueous electrolyte was added to the tt or cyclic carbonate and a low viscosity solvent mixture of a linear carbonate of ^ Seedlings 亂 the solvent.

According to another aspect of the invention, there is provided a device comprising a battery pack including the battery module, the battery module including the rechargeable lithium battery in the unit battery, and the battery pack as the power source.

Here, concrete examples of the device, electric vehicles, hybrid electric vehicles, plug-in may be a hybrid electric vehicle, or a power storage system, and thus are not limited thereto.

It is supposed hereinafter described carried out for example in detail to illustrate the present invention in detail. However, it embodiments according to the invention in many different forms

It may be modified, the scope of the invention and are not to be construed as limited to the embodiments set forth herein. Embodiments of the invention are provided in order to make the normal than the present invention to those with knowledge clearly and fully described in the art.

5

< Example 1>

The positive electrode active material ( LiNio.4Coo.3Mno.3O2 ), a carbon black conductive material, and one bye one binder methylpyrrolidone in a weight ratio in a solvent money 90: 5: 5 were mixed in a ratio of preparing a composition for forming a positive electrode, and this thickness 20 to the entire surface of the aluminum current collector 100 _ 10 was coated with a thickness of 1 [0 and town catalyst with 1: 1, mixed in a ratio with the mixture,

Production, and this, the entire surface of the aluminum current collector 10 / after coating with a thickness L, 130 to prepare a positive electrode and dried at.

Artificial graphite of ¾0¾ as the negative electrode active material (11,163,003 011 1 (10 63 (1) and 0 to 95: 5 15 a mixture, a carbon black conductive material, and (正binder mixed at a weight ratio in a weight ratio from methyl pyrrolidone solvent of 85: 10:05 are mixed in the ratio of in to prepare a composition for forming a cathode, and this thickness of 20 on both sides of copper house 100 / was applied to a thickness, 130 ° (: a negative electrode was prepared in the dry.

A porous polyethylene separator between the prepared cathode and the anode as in the 20 degree to via 2 to prepare a positive electrode / negative electrode / positive electrode structure and the bi-cell is irreversible material layer positioned on the outermost, as the case the commercial electrode assembly It was placed inside, and injecting an electrolyte into the case to prepare a secondary battery Lyrium. The electrolyte solution is ethylene carbonate / dimethyl carbonate / ethyl methyl carbonate (防/ ¾1 (:用(: and mixed

25, volume ratio = 3/4/3 in an organic solvent consisting of a) 1.15¾1 phosphate (丄^ ¾) of lithium hex fluoroalkyl concentration was prepared by dissolving.

< Example 2>

In Example 1, a substance contained in the non-reversible material layer, needle 202 a 30 hagoneun embodiment except that first working gwadong was prepared if Lyrium the leg.

Example 1 from, the place of the composition for the positive electrode is formed to form a non-reversible material layer on the end face of the whole aluminum current collector 100 / except that applied to the panel thickness to prepare a positive electrode hagoneun Example 1 gwadong be prepared a lithium secondary battery It was.

Example 1 to 2 and Comparative Examples 1 to 2 of the lithium secondary battery prepared in 2.5 (to 4.2 in the voltage range of 0.1 (: the expression of the capacitance charge at the time when proceeding with the initial cycle of the current conditions are shown in Table 1 It is shown.

[Table]

Table 1 Referring to, when made according to the present invention we can see that the increase in capacity, which means an increase in energy density.

In particular, in the case of forming an active material layer by a non-reversible additives mixed with the positive electrode active material, there is seen that the capacity decreases and more severe.

[Industrial Applicability]

According to the invention, instead of the anode present in the outermost of the positive electrode is located on both sides of the active material layer of the outermost of the stacked electrode assembly, it includes a non-reversible material coating layer containing ritum oxide, it is possible to increase the energy density of the battery. In particular, it does not include a non-reversible additive in the positive electrode active material layer as in the prior art because of the problems, and therefore generation of the voids in the positive electrode which had occurred conventionally can be solved the phenomenon that the energy density of the battery decrease.

Reference Numerals

10, 100: electrode assembly

11, 110: positive

12, 120: cathode

13, 130: separator

111: positive electrode current collector

112: positive electrode active material layer

113: irreversible material coating

Claims

Two or more positive electrode and one negative electrode over the separator as the electrode assembly alternately stacked in the boundary

5, the electrodes and the outermost two sides of the assembly, the outermost positive electrode is located, respectively, the outermost positive electrode are, respectively, the cathode current collector, Lyrium oxide formed to the entire surface of the positive electrode current collector a positive electrode formed on one surface of the active material layer and the positive electrode current collector It includes a non-reversible material coating layer containing

The non-reversible material coating layer is positioned on the outermost side of the electrode assembly 10. The electrode assembly according to claim.

[Claim 2]

According to claim 1,

The lithium oxide you 0, 1 \ 0, you 0 electrode assembly, characterized in that or a mixture thereof,

15 [Claim 3]

3. The method of claim 2,

The 11 0, or you 0 is the electrode assembly characterized in that the extinction after the first charge of the cell including the electrode assembly.

[Claim 4]

20. The method of claim 1, wherein

The cathode electrode assembly comprises a silicon () based material as an anode active material.

[Claim 5]

Claim 4 in wherein

25, the silicon-based material, a complex of silicon and silicon oxide; An electrode assembly, characterized in that the composite and the silicon alloy or silicon oxide; silicon alloy.

[Claim 6]

An electrode assembly;

30, the non-aqueous electrolyte for impregnating the electrode assembly; and

Relates to Lyrium secondary battery comprising a battery case which incorporates the electrode assembly and the non-aqueous electrolyte,

The electrode assembly of claim 1 through claim 5 ritum secondary battery wherein the electrode assembly according to any one of items.

5. [Claim 7]

Low 1 6 comprises a ritum secondary battery of the unit cell, wherein a battery module according to claim.

[Claim 8 ]

Claim 7. The battery pack comprising the battery module according to the claims.

10 [Claim 9 ]

Claim 8 device comprising the battery pack according to a further power source.

[Claim 10 ]

Claim 9 in wherein

15 wherein the device is an electric vehicle hybrid electric vehicles, plug-in device, characterized in that the hybrid electric vehicle or a power storage system.