KR101684127B1 - Spinel solid electrolyte and all solid battery using the same - Google Patents

Spinel solid electrolyte and all solid battery using the same Download PDF

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KR101684127B1
KR101684127B1 KR1020150083933A KR20150083933A KR101684127B1 KR 101684127 B1 KR101684127 B1 KR 101684127B1 KR 1020150083933 A KR1020150083933 A KR 1020150083933A KR 20150083933 A KR20150083933 A KR 20150083933A KR 101684127 B1 KR101684127 B1 KR 101684127B1
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solid electrolyte
spinel
active material
solid
present
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손삼익
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현대자동차주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y02E60/122—

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Abstract

The present invention relates to a spinel solid electrolyte and all-solid-state batteries using the same, more specifically, to a spinel solid electrolyte and all-solid-state batteries using the same, wherein a solid electrolyte is prepared by applying a compound with a spinel structure, thereby positive ions are uniformly dispersed in a crystalline structure with high symmetry to have structural stability. The all-solid-state batteries are manufactured using the solid electrolyte, thereby reducing surface anisotropy due to crystal structural similarity between a cathode or anode active material and the solid electrolyte compared with an existing solid electrolyte to reduce surface resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a spinel-based solid electrolyte and a solid-

More particularly, the present invention relates to a spinel-based solid electrolyte and a solid-state battery using the spinel-based solid electrolyte. More particularly, the present invention relates to a spinel- The spinel type solid electrolyte capable of reducing the interfacial resistance by reducing the interfacial anisotropy due to the crystal structure similarity between the positive electrode or the negative electrode active material and the solid electrolyte compared to the conventional solid electrolyte by using the same, Battery.

The lithium secondary battery, which functions as a power source for hybrid cars and electric vehicles, moves lithium ions from the anode to the cathode during charging, and lithium ions from the cathode to the anode during discharging. The electrolyte between the anode and the cathode should facilitate the transfer of lithium ions and maintain an electrically isolated state. Currently, organic compounds used as electrolytes are composed of lithium salts and organic solvents dissolving them. However, problems such as internal short-circuiting of the lithium secondary battery occur, thermal runway occurs, and the organic solvent becomes a fuel for combustion, resulting in battery explosion. Various safety devices have been devised in order to minimize such problems, but it can not be a fundamental solution unless the flammability of organic solvents is suppressed. Accordingly, attempts have been made to replace the organic electrolyte with a solid electrolyte.

Accordingly, the entire solid electrolyte using the solid electrolyte is a battery including a solid electrolyte of an inorganic material such as an oxide and a sulfide, has excellent safety, has an ion conductivity of about 10 -3 S / cm, has a large solid strength, There are advantages of good potential window and low temperature characteristics. However, the interface contact resistance between the positive electrode and the negative electrode and the solid electrolyte is large, which is disadvantageous to moisture.

Lithium ion solid electrolytes used in all solid state batteries are chemically divided into oxides and sulfides, and in terms of crystallinity of materials, they are classified into amorphous and crystalline. The oxide-based solid electrolyte can be subdivided into LiPON, NASICon, Perovskite, and Garnet.

Specifically, LiPON developed by Oak Ridge National Lab is an amorphous material, and the conductivity of lithium ion is usually 3.3 × 10 -6 S / cm. In order to improve the physical properties of the thin film battery, the activation energy can be lowered by doping nitrogen during the deposition, and the lithium ions migrate through the diffusion to the interstitial site and the vacancy.

In NASICON, there is an empty space between the atoms that make up the material, and lithium ions move through that channel. The ionic conductivity is the degree of 10- 5 S / cm when replacing the Na ion in Li-ion are known to (LISICon) the conductivity is increased by 10 times.

In a perovskite having an ABO 3 structure, an irregular arrangement of La results in a slight twist in the orthorhombic structure, resulting in a path through which lithium ions can move. This perovskite has an ionic conductivity of about 2 × 10 -5 S / cm. In addition, the perovskite material, when contacted with the lithium metal, becomes electrically conductive due to the reduction of the Ti in the structure, and the electrolyte characteristic is lost.

Garnet, which recently reported lithium ion conduction characteristics, has a composition of Li 5 La 3 Ta 2 O 12 or Li 7 La 3 Zr 2 O 12 , and there are two or four lithium excesses compared to a typical garnet formula. Initial ionic conductivity of 4 × 10 -6 S / cm was reported by Weppner et al., But recent improvement of physical properties was 5 × 10 -4 S / cm through cation exchange. So far, basic research on ion conduction mechanism has been actively conducted, and it is a material which is likely to improve physical properties by using cubic or tetragonal phase change or cation exchange.

Sulfide-based lithium-ion solid electrolytes have begun to be studied in earnest since 2000. And exhibits a very high lithium ion conductivity as compared with an oxide system. In addition, solid electrolytes exhibiting conductivity of 10 -3 S / cm or more in a large number of groups have recently been attracting much attention because they can be synthesized by a very simple manufacturing process such as mechanical milling. Recently, Kanno group of Tokyo Institute of Technology and Toyota have developed solid electrolyte of 10 -2 S / cm level which is almost similar to the conductivity of liquid electrolyte. Typically, Li 2 SP 2 S 5 system has developed a material with very high ionic conductivity of 3 ~ 5 × 10 -3 S / cm, and prototype solid-state batteries using this electrolyte are being manufactured one after another. Li 2 SP 2 S 5 The material may be amorphous and then partially crystallized to improve its physical properties. Sulfide-based materials have excellent ion transport properties, but they have the problem of generating hydrogen sulfide by reacting with moisture in the air. For commercialization, it is necessary to design the manufacturing process and to design a safety system for use.

Therefore, it is necessary to develop new solid electrolytes to reduce the interface contact resistance between the anode and the cathode and the electrolyte.

In order to solve the above problems, the present invention relates to a method for producing a solid electrolyte by applying a compound having a spinel structure so that positive ions are highly symmetric and uniformly distributed in a crystal structure to provide excellent structural safety, The inventors of the present invention have realized that the interfacial anisotropy can be reduced due to the crystal structure similarity between the positive electrode or the negative electrode active material and the solid electrolyte compared to the conventional solid electrolyte, thereby reducing the interfacial resistance.

Accordingly, an object of the present invention is to provide a spinel-based solid electrolyte excellent in structural stability of a cation.

Another object of the present invention is to provide a pre-solid battery in which the interface resistance between the active material and the solid electrolyte is reduced.

The present invention provides a spinel-based solid electrolyte comprising a spinel structure compound represented by the following formula.

[Chemical Formula]

Lix-My-Nz

Wherein M is at least one selected from the group consisting of Ga, Al, Mg and Na, and N is any one selected from the group consisting of O, Cl and S, and x is 0.1? X? 10 Y is 0.1? Y? 10, z is 1? Z? 15,

The present invention also relates to a positive electrode active material; Anode active material; And at least one of the positive electrode active material and the negative electrode active material has a spinel structure, and the positive electrode or the negative electrode active material is contained in at least one of the electrodes.

The spinel-based solid electrolyte according to the present invention is advantageous in that the cation is distributed symmetrically in the crystal structure by uniformly distributing the cation in the solid structure by applying the compound having the spinel structure and thus the structure is highly safe.

Also, by making the entire solid battery using the same, the interface anisotropy can be reduced due to the crystal structure similarity between the positive electrode or the negative electrode active material and the solid electrolyte compared to the conventional solid electrolyte, so that the interfacial resistance can be reduced.

1 is a view showing a metal compound having a spinel structure according to the present invention.
FIG. 2 is a schematic view showing a process for producing the spinel-based solid electrolyte of the present invention.
FIG. 3 is a graph showing the results of X-ray diffraction analysis of LiGa 5 O 8 pellets prepared in the examples of the present invention.
4 is a graph showing an AC impedance measurement result of the LiGa 5 O 8 pellet prepared in the embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to one embodiment.

The spinel-based solid electrolyte of the present invention includes a spinel structure compound represented by the following formula.

[Chemical Formula]

Lix-My-Nz

Wherein M is at least one selected from the group consisting of Ga, Al, Mg and Na, and N is any one selected from the group consisting of O, Cl and S, and x is 0.1? X? 10 Y is 0.1? Y? 10, z is 1? Z? 15,

According to a preferred embodiment of the present invention, the general formula of the spinel structure is AB 2 O 4 . For example, in the case of the MgAl 2 O 4 spinel structure, oxygen has a cubic density, and a unit cell has a cube in which eight cubes are gathered. There are eight chemical formulas in the unit cell. Therefore, 32 pieces of oxygen are contained in the unit cell, 16 out of 32 octahedral squares constituting the oxygen are filled with Al, and 8 out of 64 tetrahedral spaces are filled with Mg. Al octahedra share a corner and form a long chain, filling each other one by one in the floor. This layer shares the corners and stacks at 90 o . The Mg tetrahedron shares the vertex with the octahedron between octahedral layers. 1 is a view showing a metal compound having a spinel structure according to the present invention. As can be seen from FIG. 1, the octahedrons constituting the oxygen share long corners and are composed of long chains.

According to a preferred embodiment of the present invention, in the case of the spinel material comprising oxygen anion, there exists a tetrahedral site having oxygen as coordination ion and a cation having a size suitable for octahedral site. The ionic radius of this oxygen is 1.382 Å, and the suitable size for the octahedral site of the hexahedral coordination with oxygen is 0.572 ~ 1.101 Å. The size of the tetrahedral ion suitable for tetrahedral oxygen is 0.311 ~ 0.572 Å to be.

In the case of oxide-based spinel, the possible combinations of A and B cations are as follows: possible combination of 2 3 2 O 4 , 4 2 2 O 4 , 6 1 2 O 4 , (1 0.5 3 0.5 ) 3 2 O 4 Can come out. Here, 2 3 2 O 4 means that the divalent cation occupies the A site and the two trivalent cations occupy the B site. However, in order to function as a lithium ion conductor, lithium ions must be in the structure, so that the possible cation combination in the spinel oxide is preferably a combination of 6 1 2 O 4 or (1 0.5 3 0.5 ) 3 2 O 4 . Such a combination of the possible cations in the spinel oxide is possible because the number of cations can vary depending on the amount of charge of the cations. Specifically, ions having the same size as Li ions can enter the interstitial space of the spinel structure. For example, Li-Ga-O has a chemical structure of Ga 2.5 Li 0.5 O 4 . It can be expressed as a crystal chemical such as a combination of (1 0.5 3 0.5 ) 3 2 O 4 to be Ga 0 .5 Li 0 .5 Ga 2 O 4 . Also, the above combinations are possible in order to match the electric neutrality with the charge of the positive ions. For example, in the case of 6 1 2 O 4 combination, electrical neutrality can be satisfied as [(+6) + (+ 2 * 1) + (-2 * 4) = 0].

According to a preferred embodiment of the present invention, the compound having a spinel structure represented by the above formula satisfying a combination of an ion size and a valence suitable for tetrahedral and octahedral sites is Li-Ga-O, Li-Al- -Al-Mg-O, Li-Mg-Cl, Li-Mg-Na-Cl and Li-Al-S. Herein, the chloride of Li-Mg-Cl, Li-Mg-Na-Cl and the sulfide of Li-Al-S are substituted with Cl or S which is an anion of oxygen (O) The principle of matching the neutrality of the same can also be applied to the same approach which satisfies the ion size and valence combination with the same characteristics.

According to a preferred embodiment of the present invention, the spinel structure compound represented by the above formula may be LiGa 5 O 8 .

According to a preferred embodiment of the present invention, the spinel-based solid electrolyte may contain 80 to 99.9% by weight of the spinel-structured compound represented by the above formula with respect to the solid electrolyte. The metal oxide of the spinel structure as described above has high electron conductivity due to the interaction between the transition metals, and can have excellent lithium ion conductivity due to the three-dimensional distribution of the vacant tetrahedral sites. Therefore, the present invention can utilize the excellent conductivity of Li ion by applying a compound having a spinel structure including Li and no transition metal.

The whole solid battery of the present invention comprises a cathode active material; Anode active material; And at least one of the positive electrode active material and the negative electrode active material has a spinel structure, and the positive electrode or the negative electrode active material is contained in at least one of the electrodes.

According to a preferred embodiment of the present invention, the cathode active material may be any one selected from the group consisting of LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 and LiNi 0 .8 Co 0 .2 O 2 have. Specifically, LiMn 2 O 4, which is a positive electrode active material of a secondary battery, may have a spinel structure. In the spinel structure of LiMn 2 O 4 , Li has a tetrahedral site and Mn has an octahedral site. Such a structure has a property that Li ions are diffused through a tetrahedral site in a spinel structure, and a three-dimensional diffusion path is formed, so that the conductivity of Li ions is high. In addition, the octahedral Mn has the property of excellent electron conductivity due to the direct interaction between Mn and Mn by sharing the corner.

According to a preferred embodiment of the present invention, the negative electrode active material may be any one selected from the group consisting of Li 4 Ti 5 O 12 , LiTi 2 (PO 4 ) 3 and Li 0 .33 La 0 .56 TiO 3 . Specifically, Li 4 Ti 5 O 12, which is an anode active material of a secondary battery, also has a spinel structure. Like the LiMn 2 O 4 cathode active material, the spinel structure of Li 4 Ti 5 O 12 also has a three-dimensional lithium diffusion path and is excellent in Li ion conductivity and has no volume change due to structural safety of the spinel structure have.

According to a preferred embodiment of the present invention, in the case of the spinel-based electrolyte, the positive ions are highly symmetric and uniformly distributed in the crystal structure, so that the structural safety is excellent. Such physical properties can be confirmed by the positive electrode active material or the negative electrode active material having a spinel structure. The positive electrode active material LiMn 2 O 4 and the negative electrode active material Li 4 Ti 5 O 12 have excellent structural safety, '.

According to a preferred embodiment of the present invention, the entire pre-solid battery has a very large interface resistance between the active material and the solid electrolyte. The origin of the interfacial resistance is attributed to the difference in mass transfer resistance between different materials and the difference in energy band between the materials. Thus, the entire solid-state battery of the present invention is a chemically heterogeneous material by applying a positive electrode or a negative electrode having at least one spinel structure and a solid electrolyte having a spinel structure, but the interface resistance component can be attenuated due to structural similarity.

Therefore, the spinel-based solid electrolyte according to the present invention is produced by applying a compound having a spinel structure different from that of the conventional perovskite, garnet and LISICon structures, so that the positive ions are uniformly distributed in the crystal structure with high symmetry, It has an excellent safety advantage. In addition, the total anisotropy can be reduced due to the crystal structure similarity between the anode / electrolyte and the cathode / anode active material and the solid electrolyte compared to the conventional solid electrolyte by using the same, thereby reducing the interfacial resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example

0.7979 g of Li 2 CO 3 and 9.2021 g of Ga 2 O 3 were weighed and mixed by high energy ball milling for 2 hours on a 10 g basis, The pellet was molded. At this time, in consideration of Li lost in the high-temperature heat treatment, Li material was added in an amount of 10 wt%. Followed by the production of pellets final sintered for 24 hours at 850 ℃ to give the LiGa 5 O 8 Pellets of a spinel structure. 2 is a schematic view showing a process for producing the spinel-based solid electrolyte.

The following formula is a reaction formula in which a chemical reaction occurs to synthesize a solid electrolyte of LiGa 5 O 8 having a spinel phase of Li-Ga-O structure. The CO 2 generated in the following equation was efficiently exhausted by introducing oxygen at a rate of 5 liter / min through the sintering furnace.

Figure 112015057217316-pat00001

Experimental Example

The LiGa 5 O 8 < RTI ID = 0.0 > The pellets were pulverized, and the desired spinel phase was confirmed by X-ray diffraction analysis. Au electrodes were formed on both ends of the pellets for AC impedance measurement and lithium ion conductivity evaluation. Also, the lithium ion conductivity was obtained by using the AC impedance measurement result, the area and the thickness of the specimen. The results are shown in Figures 3 and 4.

[Evaluation condition]

Sample: LiGa 5 O 8 pellet, 1.2 mm thick

Relative density: 85% or more

Electroding: Au sputtering

(Thickness: 100 nm, area: 38.5 mm 2 )

Impedance Measurement conditions: 1 Hz to 1 MHz, 100 mV

FIG. 3 is a graph showing the results of X-ray diffraction analysis of the LiGa 5 O 8 pellet prepared in the above example. 3, the X axis represents the scan angle, and the Y axis represents the measurement intensity. The position of the measured diffraction peak was compared with the data of the material structure database, and it was confirmed that the pellet prepared in the above example was synthesized by spin-phase LiGa 5 O 8 through solid phase synthesis.

4 is a graph showing the results of AC impedance measurement of the LiGa 5 O 8 pellet prepared in the above embodiment. 4, the X-axis is the real part of the impedance and the Y-axis is the Cole-cole plot representing the imaginary part of the impedance. In FIG. 4, the initial cycle was fitted to confirm the resistance component, and the conductivity of lithium ion was confirmed using the thickness and area of the specimen. As a result, it was confirmed that the ion conductivity of the LiGa 5 O 8 pellet was 1.56 x 10 -6 S / cm at room temperature. From the phenomenon that the resistance component increases at a 45 ° slope, there is no electron conduction, I could.

Therefore, the spinel-based solid electrolyte produced in the above-mentioned embodiment can be produced by preparing a whole solid-state battery using a spinel-based solid electrolyte containing a compound having a spinel structure, thereby producing a positive electrode / electrolyte against a conventional solid electrolyte, a cathode or an anode active material It is confirmed that the interface resistance can be reduced by reducing the anisotropy of the interface due to the crystal structure similarity between the solid electrolyte and the solid electrolyte.

Claims (6)

A spinel-based solid electrolyte comprising LiGa 5 O 8 which is a spinel structure compound.
delete delete Cathode active material;
Anode active material; And
A spinel-based solid electrolyte of claim 1;
/ RTI >
Wherein at least one of the positive electrode active material and the negative electrode active material has a spinel structure, and the positive electrode or the negative electrode active material is contained in at least one of the electrodes.
5. The method of claim 4,
Wherein the cathode active material is any one selected from the group consisting of LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 and LiNi 0.8 Co 0.2 O 2 .
5. The method of claim 4,
Wherein the negative electrode active material is any one selected from the group consisting of Li 4 Ti 5 O 12 , LiTi 2 (PO 4 ) 3, and Li 0 .33 La 0 .56 TiO 3 .
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CN113508482A (en) * 2019-03-26 2021-10-15 松下知识产权经营株式会社 Solid electrolyte material and battery using the same

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WO2013140565A1 (en) * 2012-03-22 2013-09-26 株式会社 東芝 Electrochemical cell, method for producing electrochemical cell, battery pack, and vehicle

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* Cited by examiner, † Cited by third party
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WO2013140565A1 (en) * 2012-03-22 2013-09-26 株式会社 東芝 Electrochemical cell, method for producing electrochemical cell, battery pack, and vehicle

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CN113508482A (en) * 2019-03-26 2021-10-15 松下知识产权经营株式会社 Solid electrolyte material and battery using the same

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