Electrode Assembly For All Solid Battery And Method For Fabricating Same
Abstract:
The present invention relates to an electrode assembly for an all-solid battery. The electrode assembly according to the present invention includes a cathode, an anode, and a solid electrolyte layer interposed between the cathode and the anode. In addition, binders located at an interface between the anode and the solid electrolyte layer and an interface between the cathode and the solid electrolyte layer, and/or at a predetermined depth from each of the interfaces are crosslinked with each other to form a three-dimensional network. That is, an electrode assembly according to the present invention, in which binders contained in an anode and a solid electrolyte layer and/or in a cathode and a solid electrolyte layer are crosslinked with each other, has improved interfacial binding capability between the anode and the solid electrolyte layer and/or between the cathode and the solid electrolyte layer and accordingly maintains a significantly high level of ion conductivity.
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Notices, Deadlines & Correspondence
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
2. SHIN, Ho-Suk
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
3. WOO, Seung-He
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
4. KANG, Sung-Joong
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
5. HAN, Hyea-Eun
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
Specification
Art
[1]
This application claims priority based on the Korea Patent Application No. 10-2017-0033363, filed on March 16, 2017. This invention is about how to improve the interface between the electrode and the electrolyte layer gyeolchakryeok ionic conductivity and excellent output characteristics is prepared and this cell.
[2]
BACKGROUND
[3]
A portable electronic device power supply is a lithium ion secondary battery has been widely used. In recent years, there is a movement to utilize a lithium ion secondary battery as an electric vehicle and industrial batteries. The structure of lithium ion secondary batteries are relatively simple and the negative electrode active material, the positive electrode hwalmul quality and is in three main components of the electrolytic solution. A negative electrode of lithium ions from the positive electrode, the battery action proceeds by the migration of the anode from the cathode. Electrolyte portion should only function lithium ion conductor. In the widely used lithium ion secondary cell in which there are used an electrolyte solution dissolving a lithium salt in an aprotic organic solvent. However, the electrolyte solution has a developing need for the all-solid battery has emerged to address these issues it is implied the usability problems due to battery leakage or gas.
[4]
Solid electrolyte as compared with the batteries using the electrolytic solution, batteries having the improved reliability, and optimize the structure, there is an advantage such as high energy density, high output density. However, the all-solid battery has a problem that the ionic conductivity decreases due to low ion conduction path due to a reduced contact surface with the electrode.
[5]
Detailed Description of the Invention
SUMMARY
[6]
An object of the present invention is to provide a method for ionic conductivity are improved all-solid battery, the electrode assembly and manufacture of this electrode layer and the electrolyte layer. Other objects and advantages of the invention will be understood by the following description. Also, the objects and advantages of the invention will be readily appreciated that this can be realized by the means or method, and combinations thereof described in the claims.
[7]
Problem solving means
[8]
The present invention relates to all-solid battery manufacturing method, and it produced through the cell for solving the technical problem. Preparing a (S10) one or more negative electrode, positive electrode and solid electrolyte layers, respectively;: the first aspect of the invention, the method to (S10) to include a step of (S60) as to the method (S20) are stacked such that the solid polymer electrolyte layer interposed between a cathode and an anode comprising: preparing a laminated structure; (S30) to form an electrode assembly and a rolling the laminated structure; (S40) a crosslinking initiator, and a step of mixing a solvent to prepare a crosslinking agent solution; (S50) step of impregnating the electrode assembly a in the solution; And (S60) by heating treatment to form the electrode assembly, a '.
[9]
Further, in the first aspect, the (S60) step is performed at a temperature range for which the cross-linking reaction in the electrode assembly, a 'start-up and progress.
[10]
Is a second aspect of the present invention, in the first aspect, the positive electrode and method of manufacturing the negative electrode comprises a to (S11) step to (S13) step, and to in (S11) step the solvent is a non-polar solvent: (S11) a step of preparing an electrode for making the slurry comprising an electrode active material, a binder resin, an inorganic solid electrolyte, and a solvent; (S12) forming a first electrode layer by coating and drying the electrode slurry for preparing the current collector surface; And (S13) forming a second electrode layer by rolling the first electrode layer.
[11]
The third aspect is the first aspect or according to the second aspect, the solid polymer, and to the electrolyte layer (S21) includes a step to (S23) step, to in (S21) phase solvent of the present invention is a non-polar solvent steps of preparing (S21) a binder resin, an inorganic solid electrolyte and a solid polymer electrolyte layer for producing a slurry comprising a solvent;: is (S22) forming a solid polymer electrolyte layer by coating the slurry on a release sheet and dried; And (S23) separating the solid polymer electrolyte layer on the release sheet.
[12]
The fourth aspect of the first to third according to any one of the aspects, wherein the solvent of (S40) step of the present invention is a non-polar solvent.
[13]
A fifth aspect of the present invention to the first to fourth process according to any one of the side surfaces, and said negative electrode, positive electrode and solid polymer electrolyte layer includes a binder resin, said binder resin comprises a rubber-based resin.
[14]
A method according to any of the sixth aspect of the first to the fifth aspect of the invention one, wherein (S40) step of cross-linking initiator is an organic peroxide (organic peroxide) based crosslinking initiator.
[15]
A seventh aspect of the present invention, in the sixth aspect, wherein the organic peroxide cross-linking initiator is di (2-ethylhexyl) peroxydicarbonate, di (4-t- butylcyclohexyl) peroxydicarbonate, di -sec- butyl hydroperoxide CD carbonate, t- butyl peroxyneodecanoate, t- hexylperoxy pivalate, t- butyl peroxypivalate, di-lauroyl peroxide, di -n- octanoyl peroxide, 1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t- butyl peroxy isobutyrate, 1,1-di (t- hexylperoxy ) is at least one member selected from the group consisting of cyclohexane.
[16]
The present invention further for the production of batteries according to the method of any one of the first to seventh aspects.
[17]
As for the present invention, an eighth aspect is the cell, the cell will form the interlayer in a continuous phase at the interface between the interface and the positive electrode and the solid polymer electrolyte layer of a binder polymer cross-linked resin is a cathode and a solid polymer electrolyte layer.
[18]
Ninth aspect of the present invention to according to the eighth aspect, wherein the binder resin comprises a rubber-based binder resins.
[19]
The method of claim wherein the 910 side aspect of the invention, the rubber-based binder resins include natural rubber, butyl-based rubbers, bromo-butyl-based rubber, chlorinated butyl-based rubber, styrene isoprene rubber, styrene-ethylene-butylene- styrene-based rubber, acrylonitrile-butadiene-styrene rubber, poly butadiene rubber, nitrile group consisting of butadiene rubber, styrene butadiene rubber, styrene-butadiene-styrene rubber (SBS), rubber EPDM (ethylene propylene diene monomer) type intended to include at least one selected from the.
[20]
Effects of the Invention
[21]
All-solid battery, the electrode assembly manufactured by the method according to the invention is maintained at a high ionic conductivity and excellent level gyeolchakryeok Accordingly, between the electrode and the electrolyte layer there is an effect in which a battery performance improvement.
[22]
Brief Description of the Drawings
[23]
The accompanying drawings in this specification will illustrate the preferred embodiment of the invention, the components which serve to better understanding of the technical idea of the present invention with the content of the above-described invention, the invention is limited to the details set forth in those figures It is not intended to be interpreted. On the other hand, the shape of the elements in the figures contained in this specification, the size, or scale, ratio and the like may be exaggerated to emphasize a more clear description.
[24]
[25]
Figure 1 is a schematic representation of an electrode assembly of the all-solid battery according to the present invention.
[26]
Figure 2 is a process flow diagram for the manufacturing method of the present invention;
[27]
Mode for the Invention
[28]
Hereinafter, it will be described in detail with respect to the present invention. Prior to be construed as limited to the description and the claims, the term or general and dictionary meanings as used should not, inventors properly define terms to describe his own invention in the best way on the basis of the principle that can be interpreted based on the meanings and concepts corresponding to technical aspects of the present invention. Accordingly, the configuration shown in the examples and figures disclosed herein are merely nothing but the embodiment most preferred embodiment of the invention, a not intended to limit the scope of the present invention, that can be made thereto according to the present application point it should be understood that various equivalents and modifications could be.
[29]
[30]
Throughout the present specification, when any and "includes" section is any component, which is not to exclude other components not specifically described against which means that it is possible to further include other components.
[31]
[32]
Further, "substantially free" herein the term "about" is used throughout, and the like when the manufacturing and material tolerances inherent in the stated meaning to be presented is used as a means close to the value at or figures aid the understanding of the present accurate or is used to prevent the use of unfair self absolute figures of the unscrupulous referred to the disclosure violations.
[33]
[34]
Throughout the present specification, "A and / or B" means a base material of "A or B or both".
[35]
[36]
The specific terms used in the following description are not restrictive of not for the purpose of convenience. Words "right," "left," "upper surface" and "if" represent the direction of the in the figures the reference is made. Of 'inward' and 'outward' words represent each specified apparatus, a direction toward the geometrical center of the system and its member or away from it. "Front", "rear", "upper", represent "lower" and related words and phrases are the positions and orientations in the figures the reference made restrictive should not. These terms include the words, words of similar meaning and its derivatives listed above.
[37]
[38]
The present invention relates to a battery produced by the method and the method for producing a lithium ion secondary battery. The lithium ion secondary battery according to the invention is for example an inorganic solid electrolyte as the electrolyte and / or the all-solid battery using a polymer electrolyte.
[39]
[40]
In one embodiment of the invention the lithium ion secondary battery includes an electrode assembly comprising a solid electrolyte layer interposed between the positive electrode, a negative electrode and the positive electrode and the negative electrode. Further, in the electrode assembly, a binding agent (binder resin) which is located at a predetermined depth from the interface and the interface and / or the interface between the positive electrode and the solid electrolyte layer of the negative electrode and the solid electrolyte layer to form a three-dimensional mesh is cross-linked to each other that will. That is, the electrode assembly according to the invention I The binder (binder resin) and / or the positive electrode and the binder of the solid electrolyte layer containing a negative electrode and a solid electrolyte layer has become cross-linked to each other a cathode and a solid electrolyte layer and / or the positive electrode and the solid electrolyte, gyeolchakryeok interface of the layer is improved adhesion between the higher the ionic conductivity is maintained at a very high level.
[41]
[42]
Figure 1 shows the schematic view showing an electrode assembly according to one embodiment of the present invention. Referring to this, the electrode assembly 100 includes a solid electrolyte layer 50 interposed between the anode 20 and the cathode 30 and the anode and the cathode.
[43]
[44]
First, a description will be given of a positive electrode and a negative electrode. The positive and negative electrodes are described collectively as an electrode in this specification. In a specific exemplary embodiment of the invention, the electrode is provided with an electrode active material layer formed on at least one surface of a collector and the current collector. The electrode active material layer comprises an electrode active material, a solid electrolyte, a binder (binder resin) and a conductive material. On the other hand, in an embodiment of the present invention, the binder may be cross-linked. In the electrode active material layer a solid electrolyte may be contained in a proportion of 5 parts by weight to 100 parts by weight compared to 100 parts by weight of the electrode active material. In addition, the binder (binder resin) is in a proportion electrode coating 100 parts by weight compared to 0.1 to 10 parts by weight, and, a conductive agent may be included in the electrode active material layer 100 ratio compared to 0.1 part by weight to 10 parts by weight.
[45]
[46]
In one embodiment, the cross-linking of the binder (binder resin) of the electrode active material layer may be formed by the injection of a crosslinking agent solution, as described below. According to one embodiment the cross-linking may be a cross-linking of the binder is formed in the interface between the electrode and the separator, such as the cross-linked so that the electrode assembly in the electrode assembly gyeolchyeo then impregnated with the crosslinking agent solution proceeds. Or depending on the target to be impregnated with the crosslinking agent solution according to one embodiment the cross-linking can be made only in the electrode.
[47]
[48]
In the present invention, the electrode active material layer is a binding agent (binder resin) cross-linked by being for this effect may be elastic or rigid, such as improved mechanical properties electrode active material expansion and / or contraction during the charge and discharge electrode active material layer of the electrode layer be suppressed or relaxation, and the interfacial adhesion between the electrode active material layer and an electrolyte layer is held can provide excellent cycle characteristics all-solid battery.
[49]
[50]
In one embodiment, the binder (binder resin) and a rubber-based binder resins. Rubber-based binder resin as described below may be dissolved in a non-polar solvent. Sulfide-based solid electrolyte components may be a physical property degradation caused such that the ionic conductivity decreases when in contact with polar solvents. The present invention uses a non-polar solvent and preclude the use of a polar solvent electrode production, with the binder component uses a rubber-based binder resin has high solubility in non-polar solvents. By selecting that in an embodiment of the present invention is dissolved in the rubber-based binder resin is more than 50% by weight, based on the approximately 25 ℃ for the solvent to be used, 70% or more, or at least 90%, or 99 wt% or more It can be used. In addition, the solvent will be lower than the polarity (polarity index) of from 0 to 3, and / or dielectric constant, comprising a non-polar solvent as described below 5. In this way it is possible to prevent a decrease in ion conductivity sulfide-based solid electrolyte of using a polar solvent by using a non-polar solvent.
[51]
[52]
In the present invention, in the case where the electrode is the anode, as a cathode active material, lithium manganese composite oxide (LiMn 2 O 4 , LiMnO 2 , etc.), lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 layer, etc.) the compound or compounds substituted with one or more transition metals; Formula Li 1 + x Mn 2 - x O 4 (where, x is from 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 Li-Mn oxide and the like; Lithium copper oxide (Li 2 CuO 2 ); LIV 3 O 8 , LiFe 3O 4 , V 2 O 5 , Cu 2 V 2 O 7 of vanadium oxide and the like; Formula LiNi 1 - x M x O 2 (where, the M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, x = 0.01 ~ 0.3 Im) Ni site type lithium nickel oxide which is represented by; Formula LiMn 2 -x M x O 2 (where, M = Co, Ni, Fe , Cr, and Zn, or Ta, x = 0.01 ~ 0.1 Im) or Li 2 Mn 3 MO 8 (where, M = Fe, Co, lithium manganese composite oxide represented by Ni, Cu or Zn); Some of the formula LiMn Li is substituted with alkaline earth metal ion 2O 4 ; Disulfide compounds; Fe 2 (MoO 4 ) 3 may include one or two or more kinds of mixture.
[53]
[54]
In the present invention, the case where the electrode is the negative electrode, the lithium metal oxide as a cathode active material, a carbon-I, such as graphitized carbon, graphite-based carbon; Li x Fe 2 O 3 (0≤x≤1), Li x WO 2 (0≤x≤1), Sn x Me 1 - x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' : Al, B, P, Si, Group 1 of the Periodic Table, Group 2, Group 3 element, a halogen; a metal composite oxide, such as 1≤z≤8); 0
Documents
Application Documents
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Name
Date
1
201917031610.pdf
2019-08-05
2
201917031610-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [05-08-2019(online)].pdf
2019-08-05
3
201917031610-STATEMENT OF UNDERTAKING (FORM 3) [05-08-2019(online)].pdf
2019-08-05
4
201917031610-PROOF OF RIGHT [05-08-2019(online)].pdf