[Technology]
Mutual citations and related application (s)
This application claims the benefit of priority based on the Korea Patent Application No. 11 dated May 30, Korea Patent Application No. 10-2017-0163156 November 2018 and May 29, 2017 No. 10-2018-0151235, that of Korea Patent Application everything described in the literature are included as part of the specification.
The present invention relates to a lithium secondary battery positive electrode and that of the secondary battery Lyrium containing them, more particularly to a high energy rechargeable lithium battery and a lithium secondary battery positive electrode comprising them .
[Background Art]
As the technology developed, and the demand for multi-device increase the demand for energy rechargeable battery as there is increasing rapidly, with such a secondary battery, high energy density and voltage, long cycle life, self-discharge rate is low lithium secondary battery is It is commercially available and widely used.
As such a lithium secondary battery positive electrode active material, lithium-containing cobalt oxide in the layered crystal structure (Nishi 0) 0 2 ), of a layered crystal structure Needle 1 \ / 10 || 2 , the spinel crystal structure Needle 1 \此2 0 4 , etc. of the lithium-containing manganese oxide, lithium-containing nickel oxide (nise 0 2 a) is generally used. In addition, as a negative electrode active material is mainly used carbon-based material, in recent years, the mixed use of the high-energy lithium silicon-based material having a 10 times more effective dose than the carbon-based material with increased demand for secondary batteries, silicon sanhwagye material has been considered . On the other hand, the recent trend of high-order energy rechargeable lithium battery development can be called the essential use of the negative electrode using a silicon-based material as an anode active material. However, the negative electrode is a silicon-based material is applied has a lower charging / discharging efficiency due to the irreversible capacity size problem there is.

For these problems solved, needle 202 a way to apply the mixed positive electrode irreversible additive of high capacity, such as for manufacturing the battery has been sought but, via the first charge, needle 202 and is decomposed discharged oxygen gas, and and a void occurs in the seat, after the first charge due to such voids, the density of the positive electrode

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It was lowered, causing a problem such as the energy density of the battery to be lowered.

[Detailed Description of the Invention]

[SUMMARY]

The problem to be solved by the present invention is intended to solve the problem in the case of irreversible additive for high capacity using the positive electrode was mixed with a cathode active material, the active material layer is only a high-capacity non-reversible uncoated portion protrudes are formed is not coated on the cathode current collector that the lithium to the coating material characteristics including a lithium secondary battery positive electrode and to provide him as if an object leg.

[Technical Solution]

According to an aspect of the invention, the positive electrode current collector and containing a positive electrode active material layer formed by coating at least one surface of the positive electrode current collector, the positive electrode collector is Lyrium including a protruding thumb without coating the positive electrode active material layer a secondary battery, the positive electrode, the solid portion, is a coating material consisting of a non-reversible ritum oxide ritum secondary battery positive electrode characterized in that there is provided.

In this case, the material is non-reversible, and after the first charge decay doeneungeot days of Lyrium secondary battery including the ritum secondary battery positive electrode.

In addition, the non-reversible material, needle 2 0 2 , needle 2 is 0, or a mixture of these days. According to another aspect of the invention, the electrode assembly including a separator interposed between the positive electrode, a negative electrode and the positive electrode and the negative electrode; The non-aqueous electrolyte for impregnating the electrode assembly; And it relates to ritum secondary battery comprising a battery case which incorporates the non-aqueous electrolyte and the electrode assembly, the positive electrode is provided a lithium secondary battery, characterized in that ritum secondary battery positive electrode according to the present invention described above.

Here, the cathode is the number of days comprising a silicon (and others) based material as an anode active material.

At this time, the silicon-based material, a complex of silicon and silicon oxide; It is complex and the number of days in the silicon alloy or silicon oxide; silicon alloy.

And, according to the present invention, comprising the lithium secondary battery of the above-described present invention in a unit battery the battery module, the battery pack including the same, and 2019/108025 1 »(1 ^ 1 {2018/015109

The device characterized in that it comprises such a battery pack as a power source is provided. Here, the device is an electric vehicle, hybrid electric vehicles, plug-in hybrid electric vehicle system for days or power storage.

【Effects of the Invention】

According to the invention, a non-reversible material made of a lithium oxide is coated on the entire coated portion of the positive electrode current collector, it can enhance the energy density of the battery.

In particular, the positive electrode as a whole that only the irreversible solid material portion of the house is coated, it can eliminate the phenomenon in which the problems and energy density of the battery to thereby generate pores in the prior art non-reversible additive may exist in the mixed positive electrode is lowered. [Brief description of drawings]

The accompanying drawings are intended to illustrate preferred embodiments of the invention, as to explain the principles of the invention and together with the description, but the scope of the invention is not limited to this. On the other hand, the shape of the elements in the figures contained in this specification, the size, or scale, ratio, etc. may be exaggerated to emphasize a more clear description.

13 and Fig. 113 is a diagram showing a plan view and a side view of a conventional cathode in each schematic.

Fig 3 and Fig比is a view schematically showing a plan view and a side view of a cathode according to an embodiment of the present invention.

_ Figure 3 is a schematic view of the side of the positive electrode after charging in accordance with an embodiment of the present invention hyul.

[Mode for Carrying out the invention]

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

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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 due to the irreversible capacity large charging / discharging efficiency is low, a high dose in order to solve this problem, non-reversible has used the additives are mixed anode.

1 3 and 11 3 are each a diagram schematically showing a plan view and a side view of a conventional anode. Referring to the figure, there is a non-reversible additive of high capacity is mixed in the positive electrode active material layer 12 formed on the positive electrode current collector 11, through the first charge, is dispersed in the positive electrode active material layer 12, high capacity that as the irreversible degradation additive, a void is generated in place, and thus lowers the density of the positive electrode active material layer 12, and a problem that ultimately, the energy density of the battery becomes low.

According to the present invention by coating the positive electrode active material and high capacity without mixing the additive irreversible, irreversible material only solid portion of the positive electrode collector was able to solve the problems of the above-described hanjongrae technology.

Fig 3 and Fig. 21 3 is a view schematically showing a plan view and a side view of a cathode according to an embodiment of the present invention, respectively, Figure 3 is a schematic view of the side of the positive electrode after charging in accordance with an embodiment of the present invention to be.

. Reference to the drawings when more detailed description of the invention herein, includes a positive electrode collector 110 and a positive electrode coating portion 120 is coated on at least one surface formed of the positive electrode collector 110, the total of the positive electrode collector ( 110) on the anode active material layer 120 in the Lyrium secondary battery, the positive electrode 100 including a coated portion 130 protrudes without being coated, the uncoated portion 130, a non-reversible material made of a lithium oxide (140 ) it is characterized in that it is coated.

Since the non-reversible material 140 made of the Lyrium oxide does and is coated only on the coated portion 130, not included in the positive electrode active material layer 120, it is not necessary the process of mixing the positive electrode active material and the non-reversible material. In particular, the non-reversible material 140 composed of the lithium oxide, the lithium secondary battery positive electrode, since 100 is extinguished after the first charge of a lithium secondary battery comprising, the first coating layer on the second or subsequent charging uncoated portion 130 this is not present in the form. 2019/108025 1 »(1 ^ 1 {2018/015109

At this time, the non-reversible material composed of the lithium oxide (140) can be destroyed is decomposed into lithium ions and oxygen gas.

In this case, the non-reversible material, needle 202, Needle 20 has a mixture of or a number of days. These irreversible material 140 may be then in a state of being dissolved in an organic solvent is coated only on the coated portion 130, and dried. This material is non-reversible for the thickness, for example, corresponding to the positive electrode active material layer 120, it can be dried to remove the organic solvent and then coated to a thickness of 10 to 300, or 50 to 250_.

As the non-reversible material 140 is coated and dried in such thickness, even when the silicon-based material used in the negative electrode can effectively compensate for the irreversible capacity of the unbalance with all the electrodes, atda reducing the characteristics of the positive electrode decreases.

On the other hand, the positive electrode active material containing the above positive electrode active material layer can contain a Lyrium transition metal oxide represented by Formula 1 or 2 below.

Li x M y Mn 1.y O 2.z A z (1)

Wherein

And Lee and one or more elements selected from the group consisting of;

It is -1 or more than one monovalent anion and -2;

0.9 a <) (<1.2, 0 <1,0 <0.2 jj.

. —

1 \ / 1 '1 \ / and four;

! IV eunse, kk, 0, 0, / \ 1 , you 0, 1 \ ^, 0, gal, and a second transition period is at least one selected from the group consisting of the metals;

It is P0 4 , 60 3, 00 3, and 1 \ 103 one or more selected from the group consisting of an anion in which p is 1 to 100;

0<>«1 , 0 < 0.02, 0 is selected from the group consisting of 0,

1 may include more species.

In addition, the negative electrode active material further comprises a carbon-based material, and the carbon-based 2019/108025 1 »(1 ^ 1 {2018/015109

Material bar that can be included on the total weight of the negative electrode active material to not more than 99.9% by weight or more to 70% by weight, the carbon-based material is a crystalline artificial graphite, crystalline natural graphite, an amorphous hard carbon, low-crystalline soft carbon, carbon black, acetylene black, Ketjen black, super ^ graphene (be at least one selected from the group consisting of myameu Erie, and fibrous carbon, and, specifically, the crystalline synthetic graphite, and / or crystalline natural graphite days.

On the other hand, in addition to the anode active material, the carbon-based material, uigye material,

1 \細': when,己Hi, of the periodic table Group 1, Group 2, Group 3 element, a halogen; 0 <> << 1; 1 £ £ 3;
Metal composite oxides; Lyrium metal; Lyrium alloy; Silicon-based alloys; Tin-based alloys; I (10, 0 2 , 1¾0,) 0 2 , 1¾ 2 0 3 , 3 0 4 , ¾ 2 0 3 , to 2 0 4 , I, 060 ,. O, Li 2 0 3 , having two 0 4 , 0 and 5 , such as a metal oxide; conductive polymers such as polyacetylene; Needle-0-based material; titanium oxide; But it can include a lithium titanium oxide such as, but is not limited to these.

Then, the anode current collector is generally fabricated to have a thickness of 3 to 500 _ constituting the cathode. The anode current collector, so long as it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, copper, the surface of stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel to be surface-treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys. Also Similar to the cathode current collector, to form fine irregularities on the surface may enhance the bonding strength between the negative electrode active material, films, sheets, foils, nets, porous structures, foams and non-woven fabrics or the like can be used in various forms.

On the other hand, the separator is interposed between the positive electrode and the negative electrode, an insulating thin film having high ion permeability and mechanical strength is used. Pore diameter of the separator is generally from 0.01 to 10 _, and is generally from 5 to 300 weight . These separators are, for example, olefin polymers such as chemically resistant and hydrophobic polypropylene; A sheet or non-woven fabrics made of glass fiber or polyethylene, etc. are used. Solid polymer electrolyte such as

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If an electrolyte is used, the solid electrolyte may concurrently hold the separator. In addition, the non-aqueous electrolyte is non-aqueous and composed of the electrolyte and a lithium salt, a non-aqueous electrolyte is used, such as the non-aqueous organic solvent, an organic solid electrolyte, inorganic solid electrolytes, but are not limited to these.

In the non-aqueous organic solvent, for example,
methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyl a lactone, 1,2-dimethoxy ethane, tetrahydroxy Franc (打greater), 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxy methane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate the derivatives, tetrahydrofuran derivatives, aprotic organic solvent such as ether, fatigue propionic acid methyl, propionic acid ethyl can be used.

Then, the of the organic solid electrolyte, for example, polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, poly-edge presentation lysine (3011), polyester sulfide, polyvinyl alcohol, polyvinyl fluoride etc. the polymerization comprising a fluoride, O-ionic dissociation can be used.

Further, the inorganic solid electrolyte is, for example, needle 3 you I, needle 52 , needle - Needle 1 Needle 0卜1, Mannich 0 4 , 0 1_ 4 - Needle 1 Needle 0卜, knee,! Needle 4 and 0, 4 , did four Heb 0 4 - you got your 1 0卜, can be a nitride, halides, sulfates, etc. of you like you少John名use.

In addition, the Li salt is a material that is readily soluble in the non-aqueous electrolyte, for example, did not you 1, needle 00 4 , 1_浪1 = 4 , 1_恨10 is 10 , knee, knee ^ 3 30 3 , you 0 = 0, 2 , did moire, Thessaloniki, 1 \ ^ 0 \ 4, 0 ~ 1 3 30 3 1 ", (◦ 30 2 ) 2 1 \ 1 Thessaloniki, chloroborane lithium, lower aliphatic carboxylic bonsanri volume, lithium tetraphenyl borate, may be already in use include de.

In addition, the Li salt-containing non-aqueous electrolyte, charge and discharge characteristics, in order to improve flame retardancy, for example, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, ^ glyme (Erie, hex phosphate tree amide, nitrobenzene derivatives, sulfur, quinone imine dyes, 1 \ 1-substituted oxazolidinone,
imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxyethanol,

Aluminum trichloride may doelsudo etc. is added. In some cases, in order to provide a non-flammable, it is also possible to further include a halogen-containing solvent such as carbon tetrachloride, ethylene trifluoride, and also possible to further include a dioxide carbon dioxide gas to improve high temperature storage characteristics, FEC (Fluoro-Ethylene Carbonate), and the like may further sikilsu PRS (Propene sultone).

In one specific example, you PF 6 , LiCI0 4l you BF 4, LiN (S0 2 CF 3) 2 A lithium salt, such as, highly dielectric solvent of cyclic carbonate of the EC or PC with a low-viscosity solvent, DEC, DMC, or T was added to a mixture of a linear carbonate of VIC can be prepared for re-salt-containing non-aqueous electrolyte.

According to another aspect of the invention, there is provided a device for the Lyrium comprises a battery module, the battery pack including the battery module, and the battery pack including a battery if a unit cell as a 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.

Is supposed hereinafter described carried out for example in detail to illustrate the present invention in detail. However, embodiments according to the invention can be modified in many different forms and 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.

Example 1

(1) Preparation of positive electrode material mixture

The positive electrode active material ^^ 10.8000. ^^ . 1) 02 : conductive material (carbon black, trade name sheet 065, 11111031社): binder
= 80: 8: positive electrode material mixture carried out by dry mixing the blended in a weight ratio of 12, and Muller induced into the bowl, Example 1 It was prepared.

(2) Preparation of a positive electrode

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Example 1 After forming the slurry was applied to a thickness of 200_ throughout the aluminum current collector was dried 12 hours in a vacuum oven at 120 I] vacuum by the addition of organic solvent (NMP) in the positive electrode material mixture.

Thereafter, the electrode material mixture on a current collector is plain on the portion not coated, lithium peroxide山202 ) and a mixed solution (a mixed solution of 100 parts by weight total of the organic solvent (NMP)

\ Of%, 0 2 content of 80 \ How%) 200 / in a vacuum oven coating, and d with a thickness of 120 L was dried under vacuum 12 hours to give the positive electrode of Example 1. As a result, the.

(3) Preparation of the secondary battery Lyrium

A negative electrode active material mixture was mixed in a weight ratio of 85:: silicon-based active material and 0, and the artificial graphite 15, the conductive material (carbon black, trade name Sample 065, 11 1X1031社): Binder
94.2: 2:

2.5: combined in a weight ratio of 1.3, and by dry mixing, to thereby prepare a negative electrode mixture.

The negative electrode material mixture and then by adding an organic solvent (NMP) to form a slurry, coating the entire house copper phase by 150 X: the 12-hour anode and vacuum-dried in a vacuum oven to prepare.

Wherein between each of the prepared negative electrode and positive electrode, 42 V Double V 9_ thickness and porosity? /? In the separator of the material E in a battery container, and injecting the electrolyte, it was produced ritum secondary battery in the form of a pull cell 2032 (如 11 11) according to a conventional production method.

The electrolyte solution has
a volume ratio of 1: 2: 1 in a mixed solvent

It was dissolved 正 凡) solution of 1 M (1M Needle 111 EC: DMC: DEC = 1: 2: 1 to 沙 八八)) was used.

Comparative Example 1

(1) Preparation of positive electrode material mixture

The positive electrode active material of ^ (^ 1 0.8000. ^ ^ 0.1 ) 0 2: Lyrium peroxide (1成0 2 ): the conductive material (carbon black, trade name I 065, 1¾ 10社): Binder

社) = 64: 16: 8: 12 in combination with a weight ratio of, and induced by a mortar of a positive electrode material mixture by mixing a dry, Comparative Example 1 was prepared.

(Preparation of a positive electrode

Comparative Example 1 of the positive electrode after the addition of the organic solvent (NMP) to the mixture to form a slurry, the aluminum current collector is coated on a 120 ° , and dried for 12 hours in a vacuum oven at C in vacuo. The As a result, Comparative Example 1 a positive electrode was obtained.

(2) Preparation of a positive electrode and a secondary battery Lyrium

Carried out using the positive electrode of Example Comparative Example 1 instead of the anode 1, and the remainder Example

The working gwadong 1, the positive electrode of Comparative Example 1 was prepared and Lyrium whether battery.

Experimental Example 1: The initial charge-discharge characteristics of the battery evaluation I

Example 1 and for each cell of the comparative example 1, was evaluated for initial charge-discharge characteristics under the following conditions at room temperature.

Charge: 0.01C, CC/CV, 4.6V, 5% cut-off

Discharge: 0.01C, CC, 2.5 V, cut-off

The result of the evaluation, the initial charge capacity of Example 1 was confirmed to 904mAh / g, the initial charge capacity of Comparative Example 1 was identified to 254mAh / g.

Comparative Example 1 and Example 1 is a common Lyrium peroxide (Li 2 0 2 by applying a) a positive electrode, one can compensate for the irreversible capacity of the negative electrode additive.

The ritum peroxide (Li 2 0 2 ), according to scheme 1 to the theory, that is, per mol of the compound that can be irreversibly released by the ion Lyrium of 2 mol with 1 mol of oxygen.

[Reaction Formula 1] Li 2 0 2 -> 2Li + + 0 2

However, according to the initial charge capacity evaluation results, for example, in the high voltage area than 4.3V, the lithium peroxide (Li 2 0 2 in case of Comparative Example 1 apply) on the positive electrode active material and mixing (blending) state the lithium peroxide (Li 2 0 2 is the positive electrode initial charging capacity of the battery in the embodiment) was coated on a plain section in example 1 it can be further confirmed high. .

In Example 1, the lithium peroxide (Li 2 0 2 reduction decomposition reaction of a) is formed, the pores inside the holding (i.e., that affect the positive electrode active material layer The positive electrode active material layer according to yirueojim in uncoated portion not less than), the coated portion is terminated by being on the coating layer is destroyed Thus, loss electrode density of the positive electrode active material layer and 2019/108025 1 »(: 1 ^ 1 {2018/015109

Or the whole of the battery energy density may be decreased very small .

On the other hand, Comparative Example 1, the lithium peroxide (1走0 2 a) reduction decomposition reaction is so generated in the positive electrode active material layer, formation of voids in the cathode active material layer, and electrode density loss and the energy density decreases in natanalsu.

As a result, Example 1, while being being the irreversible capacity of the unbalance the electrodes effectively canceled in case of Comparative Example 1, a high initial charge capacity of the positive electrode, the less the energy density loss of the positive electrode, which will go for excellent service life characteristics.

[Description of Symbols]

10, 100: secondary battery positive electrode Lyrium

Cathode current collector: 11110

12, 120: positive electrode active material layer

13, 130: uncoated portion

140: non-reversible material

[Claims]
[Claim 1]
A positive electrode collector and the whole of the positive electrode collector includes a positive electrode active material layer is coated on at least one surface formed of, and the positive electrode current collector has a lithium secondary battery positive electrode including a solid extruded without coating the positive electrode active material layer,

A lithium secondary battery positive electrode characterized in that on the uncoated portion, a non-reversible material made of a lithium oxide is coated.

[Claim 2]

According to claim 1,

The non-reversible material for a lithium secondary battery positive electrode characterized in that the Lyrium destroyed after the first charge of the secondary battery including the secondary battery, the positive electrode Lyrium.

[Claim 3]

According to claim 1,

The non-reversible material, needle 202, Needle 20 or Lyrium secondary battery positive electrode characterized in that the mixtures thereof.

[Claim 4]

According to claim 1,

The non-reversible material Lyrium secondary battery, the positive electrode is coated with a thickness of 10 naeja 300_ on the uncoated portion.

[5.]

An electrode assembly including a separator interposed between the positive electrode, a negative electrode and the positive electrode and the negative electrode; .

The non-aqueous electrolyte for impregnating the electrode assembly; and

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

The anode of claim 1 to claim Lyrium secondary battery, characterized in that a lithium secondary battery positive electrode according to any one of the preceding 4 Compounds.

[Claim 6]

6. The method of claim 5,

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The negative electrode is a negative electrode active material, silicon (&) based material, a lithium secondary battery, comprising a step of including.

[Claim 7]

7. The method of claim 6,

The silicon-based material, a complex of silicon and silicon oxide; Silicon alloy; Or a lithium secondary battery, characterized in that the composite and the silicon alloy of silicon oxide.

[Claim 8]

In that it comprises a Lyrium secondary battery of the low unit cell 15 of a battery module according to claim.

[9.]

A battery pack comprising the battery module according to claim 8.

[10.]

Device comprising the battery pack according to claim 9, wherein the power source.

[Claim 11]
11. The method of claim 10,
The device is an electric vehicle, hybrid electric vehicles, plug-in device, it characterized in that the hybrid electric vehicle or a power storage system.