KR101918112B1 - Lithium Battery and Method for preparing the same - Google Patents

Lithium Battery and Method for preparing the same Download PDF

Info

Publication number
KR101918112B1
KR101918112B1 KR1020130153192A KR20130153192A KR101918112B1 KR 101918112 B1 KR101918112 B1 KR 101918112B1 KR 1020130153192 A KR1020130153192 A KR 1020130153192A KR 20130153192 A KR20130153192 A KR 20130153192A KR 101918112 B1 KR101918112 B1 KR 101918112B1
Authority
KR
South Korea
Prior art keywords
sulfide
lithium
electrode
active layer
electrode active
Prior art date
Application number
KR1020130153192A
Other languages
Korean (ko)
Other versions
KR20140146990A (en
Inventor
이영기
김광만
강근영
신동옥
정윤석
신범룡
Original Assignee
한국전자통신연구원
울산과학기술원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to KR1020130069090 priority Critical
Priority to KR20130069090 priority
Application filed by 한국전자통신연구원, 울산과학기술원 filed Critical 한국전자통신연구원
Priority claimed from US14/264,804 external-priority patent/US9379383B2/en
Publication of KR20140146990A publication Critical patent/KR20140146990A/en
Application granted granted Critical
Publication of KR101918112B1 publication Critical patent/KR101918112B1/en

Links

Images

Abstract

A method of preparing a lithium battery according to an embodiment of the present invention includes: preparing a mixture containing lithium sulfide and metal sulfide; Subjecting the mixture to physical pressure to produce an electrode composite, wherein the electrode composite comprises lithium sulfide, lithium metal sulfide and amorphous sulfide; Preparing an electrode active layer using the electrode composite; Forming an electrode current collector on one surface of the electrode active layer; And forming an electrolyte layer on the other side of the electrode active layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a lithium battery,

The present invention relates to a lithium battery, and more particularly, to an electrode composite for a lithium battery.

As energy storage and conversion technologies become more important, interest in lithium batteries is increasing. The lithium battery may include an anode, a separator, a cathode, and electrolytes. The electrolyte serves as a medium through which ions can move between the anode and the cathode. Lithium batteries are very high in energy density compared to other batteries, and they are being actively researched and developed. Recently, lithium batteries have been applied not only to portable electronic devices such as smart phones or notebook computers, but also to electric vehicles. In the case of the middle- or large-sized lithium battery, excellent performance and stability are required due to a severe operating environment.

The lithium battery electrolyte may include an organic liquid electrolyte and an inorganic solid electrolyte. Organic liquid electrolytes dissolve lithium salts and are widely used because of their high ionic conductivity and stable electrochemical properties. However, organic liquid electrolytes suffer from many problems related to safety due to their high flammability, volatility, and leakage problems. The inorganic solid electrolytes have attracted attention due to their high capacity, low cost, and stability.

SUMMARY OF THE INVENTION The present invention is directed to a sulfide-based electrode composite having a high capacity and high ion conductivity.

Another object of the present invention is to provide a method for easily producing a high-performance sulfide-based electrode composite.

The problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention relates to a lithium battery and a manufacturing method thereof. A lithium battery manufacturing method according to the concept of the present invention includes: preparing a mixture containing lithium phosphorus sulfide and metal sulfide; Subjecting the mixture to physical pressure to produce an electrode composite, wherein the electrode composite comprises lithium sulfide, lithium metal sulfide and amorphous sulfide; Preparing an electrode active layer using the electrode composite; Forming an electrode current collector on one surface of the electrode active layer; And forming a solid electrolyte layer on the other surface of the electrode active layer.

According to one embodiment, the lithium metal sulfide and the amorphous sulfide are produced by reacting a lithium element contained in the mixture with a metal sulfide, and the reaction of the lithium element and the metal sulfide can be performed by the physical pressure have.

According to an embodiment, the lithium sulfide contained in the electrode composite may be partially left unreacted to the lithium sulfide contained in the mixture.

According to one embodiment, applying physical pressure to the mixture can be performed by a ball milling process.

According to one embodiment, the lithium sulfide comprises Li 3 PS 4 , and the metal sulfide may comprise TiS 2 .

According to one embodiment, the electrode active layer includes the lithium metal sulfide and includes first portions electrically connected to the electrode current collector; Second portions including the lithium phosphorus sulfide and connected to the solid electrolyte layer; And an amorphous sulphide provided between the first portions and the second portions.

According to one embodiment, the amorphous sulfide may comprise lithium, metal, phosphorus, and sulfur.

A method for preparing a lithium battery according to the present invention comprises: preparing a mixture comprising lithium sulfide, phosphorus sulfide, metal, and sulfur; Subjecting the mixture to physical pressure to produce an electrode composite, wherein the electrode composite comprises lithium sulfide, lithium metal sulfide and amorphous sulfide; Preparing an electrode active layer using the electrode composite; Forming an electrode current collector on one surface of the electrode active layer; And forming an electrolyte layer on the other side of the electrode active layer.

A lithium battery according to the concept of the present invention includes an electrode collector; A solid electrolyte layer disposed apart from the electrode current collector; First portions interposed between the electrode current collector and the solid electrolyte layer, the first portions including a lithium metal sulfide and electrically connected to the electrode current collector; Second portions including lithium sulfide and connected to the solid electrolyte layer; And an electrode active layer provided between the first and second portions and including an amorphous sulphide including lithium, metal, phosphorus, and sulfur.

According to one embodiment, the solid electrolyte may comprise the same materials as the second parts.

According to one embodiment, the first portions may be connected to the second portions.

According to an embodiment, the first portions may be provided dispersedly in the electrode active layer and may be connected to each other.

According to the present invention, an electrode composite for a lithium battery can be easily manufactured by a ball milling process or a heat treatment process. The electrode composite prepared according to the present invention may include lithium sulfide, lithium metal sulfide, and amorphous sulfide. As the electrode composite contains lithium sulfide, the ion conductivity at the interface between the electrode active layer and the solid electrolyte can be improved. As the electrode composite contains lithium metal sulfide, the electronic conductivity at the interface between the electrode current collector and the electrode active layer can be improved. The lithium battery manufactured using the electrode composite may exhibit excellent charge capacity and coulon efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS For a more complete understanding and assistance of the invention, reference is made to the following description, taken in conjunction with the accompanying drawings, in which:
1 is a cross-sectional view illustrating a lithium battery according to an embodiment of the present invention.
FIG. 2 is an enlarged view of the region II in FIG.
3 is a flowchart illustrating a method of manufacturing a lithium battery according to an embodiment of the present invention.
4 is a flowchart illustrating a method of manufacturing a lithium battery according to another embodiment of the present invention.
5 is a graph showing the results of X-ray diffraction analysis of Experimental Example 1-1 and Comparative Example 1-1.
6 is a graph showing the charge / discharge characteristics evaluation result of Experimental Example 2-1 in a voltage range of 1.5 V to 3.0 V. FIG.
7 is a graph showing the charge / discharge characteristics evaluation result of Experimental Example 2-1 in a voltage range of 1.0 V to 3.0 V. FIG.
8 is a graph showing the capacity according to the number of charge / discharge cycles in Experimental Example 2-1.

In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It will be apparent to those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or essential characteristics thereof. Those of ordinary skill in the art will understand that the concepts of the present invention may be practiced in any suitable environment.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used herein, the terms 'comprises' and / or 'comprising' mean that the stated element, step, operation and / or element does not imply the presence of one or more other elements, steps, operations and / Or additions.

When a film (or layer) is referred to herein as being on another film (or layer) or substrate it may be formed directly on another film (or layer) or substrate, or a third film Or layer) may be interposed.

 Although the terms first, second, third, etc. have been used in various embodiments herein to describe various regions, films (or layers), etc., it is to be understood that these regions, do. These terms are merely used to distinguish any given region or film (or layer) from another region or film (or layer). Thus, the membrane referred to as the first membrane in one embodiment may be referred to as the second membrane in another embodiment. Each embodiment described and exemplified herein also includes its complementary embodiment. Like numbers refer to like elements throughout the specification.

The terms used in the embodiments of the present invention may be construed as commonly known to those skilled in the art unless otherwise defined.

Hereinafter, a lithium battery according to the present invention will be described.

1 is a cross-sectional view illustrating a lithium battery according to an embodiment of the present invention. FIG. 2 is an enlarged view of the region II in FIG.

1, a lithium battery 1 includes a first electrode collector 100, a first electrode active layer 110, a solid electrolyte layer SE, a second electrode active layer 210, (200). One of the first and second electrodes 100 and 110 and the second electrode 110 and 210 may be an anode and the other may be a cathode.

The first electrode current collector 100 may be spaced apart from the second electrode current collector 200. The first electrode current collector 100 and the second electrode current collector 200 may include an electrically conductive material.

The solid electrolyte layer SE may be interposed between the first electrode current collector 100 and the second electrode current collector 200. The solid electrolyte layer SE may comprise a lithium ion conductive material. The solid electrolyte layer SE may include a material represented by Li a M b P c S 4 wherein M is at least one element selected from B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi Wherein the first electrode is any one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, (Li 3 .75 Ge 0 .25 P 0 .75 S 4 ) or Li 10 GeP 2 S 12 (Li 3 SiO 2 ) . ≪ / RTI > As another example, the solid electrolyte layer (SE) may comprise a lithium sulfide or sodium sulfide such as Li a P c S 4 or Na a P c S 4 . (2.0? A? 4.0, 0.8? C? 1.3)

The first electrode active layer 110 may be interposed between the first electrode collector 100 and the solid electrolyte layer SE. The first electrode active layer 110 may receive electrons from the first electrode collector 100. The first electrode active layer 110 may receive lithium ions from the solid electrolyte layer SE.

Referring to FIG. 2, the first electrode active layer 110 may have a first surface 110a and a second surface 110b opposite to each other. The solid electrolyte layer SE may be provided on the other surface 110b of the first electrode active layer 110. [ The first electrode current collector 100 may be provided on one surface 110a of the first electrode active layer 110. [ The first electrode active layer 110 may include first portions 111, second portions 112, and amorphous sulfide 113. The first electrode active layer 110 may further include a carbon material (not shown).

The first units 111 may be connected to the first electrode collector 100. The first portions 111 are dispersed in the first electrode active layer 110 and may be connected to each other. The first electrode current collector 100 can transfer electrons to the first electrode active layer 110 through the first portions 111. [ Accordingly, the electron conductivity at the interface between the first electrode collector 100 and the first electrode active layer 110 can be improved. The first portions 111 may comprise an electrically conductive material. For example, first portions 111 may comprise a lithium metal sulfide such as Li x TiS 2 or a sodium metal sulfide. The first portions 111 may store lithium ions in the first electrode active layer 110.

The second portions 112 may be connected to the solid electrolyte layer SE. The second portions 112 are dispersed in the second electrode active layer 210 and may be connected to each other. The second parts 112 may be connected to the first parts 111. [ The second portions 112 may include the same material as the second portions 112 of the solid electrolyte layer SE. For example, the second portions 112 may include a material represented by Li a M b P c S 4 as described above, where M is B, Al, Ga, In, Si, Ge, Sn , Any one of Pb, Sb, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta and W The solid electrolyte layer SE can supply lithium ions into the first electrode active layer 110 through the second portions 112. [ The lithium ions can move more smoothly at the interface between the solid electrolyte layer SE and the first electrode active layer 110 due to the second portions 112. [ The second portions 112 may serve as a lithium ion transfer path in the first electrode active layer 110. For example, the second portions 112 may comprise lithium sulfide or sodium phosphorus sulfide, such as Li 3 PS 4 .

The amorphous sulfide 113 may be filled in the first electrode active layer 110 between the first portions 111 and the second portions 112. The amorphous sulfide 113 may comprise lithium, metal, phosphorus, and sulfur. As an example, the amorphous sulfide 113 may be LiTiPS. The amorphous sulfide 113 can store lithium ions transferred from the solid electrolyte layer SE.

Referring again to FIG. 1, a second electrode active layer 210 may be interposed between the second electrode collector 200 and the solid electrolyte layer SE. The second electrode active layer 210 receives electrons from the second electrode current collector 200 and can receive lithium ions from the solid electrolyte layer SE. The second electrode active layer 210 may be the same as or similar to the first electrode active layer 110.

Hereinafter, a method of manufacturing a lithium battery according to an embodiment of the present invention will be described.

3 is a flowchart illustrating a method of manufacturing a lithium battery according to an embodiment of the present invention. Hereinafter, duplicated description will be omitted.

Referring to FIG. 3, a mixture containing a lithium element, a metal element, a phosphorus element, and a sulfur element may be prepared (S10). As an example, a lithium sulfide and a metal sulfide may be added, . The lithium phosphorus sulfide and the metal sulfide may be added in a weight ratio of 1: 10 to 3: 1. The lithium sulfide may be a material represented by Li a M b P c S 4 wherein M is at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Wherein at least one of Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta and W, 0.5, 0.5? C? 1.3). For example, the lithium phosphorus sulfide may be Li 3 PS 4 . A lithium phosphorus sulfide having an ionic conductivity of 10 < -4 > S / cm or more at room temperature (25 DEG C) may be used. The metal sulfide can be represented by Li a MS b . (Where M is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, Ga, In, Si, Ge, Sn, Pb, As, Sb and Bi, and a and b are each a real number between 0 and 8. For example, the metal sulfide may be TiS 2 . The lithium phosphorus sulfide and the metal sulfide may be in a solid state.

As another example, a mixture comprising lithium sulfide, phosphorus sulfide, metal, and sulfur may be prepared. For example, the lithium sulfide can be a Li 2 S. The phosphorus sulfide may be P 2 S 5 . The metal may be selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Mg, Si, Ge, Sn, Pb, As, Sb, and Bi, more specifically, Ti. The mixture may be in a solid state.

By applying mechanical force to the mixture, an electrode composite can be produced. (S20) For example, a ball milling process can be performed on the mixture. By the ball milling process, the metal elements (for example, titanium) and phosphorus elements contained in the mixture can be uniformly distributed. By the ball milling process, the lithium sulfide contained in the mixture can react chemically with the metal sulfide. For example, a lithium element can be inserted into TiS 2 . As another example, by applying thermal energy to the mixture, an electrode composite can be produced. For example, by heat treatment of the mixture, the lithium element contained in the mixture can be inserted into TiS 2 . As the lithium element is inserted into TiS 2 , a lithium metal sulfide (for example, Li x TiS 2 ) and an amorphous sulfide can be produced. The lithium metal sulfide may be crystalline. The amorphous sulphide may comprise lithium, metal, phosphorus, and sulfur. As an example, the amorphous sulphide may be LiTiPS. Some of the lithium sulfide contained in the mixture may remain unreacted. Accordingly, the electrode composite of the present invention may include lithium sulfide, lithium metal sulfide, and amorphous sulfide. The electrode composite according to the embodiment can be represented by Li a PM b S c X d . (Where M is at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, A, b, c, and d are each independently any one selected from the group consisting of 0, 1, 2, 3, 4, 5, It can be a real number between 6 and.)

A lithium battery may be formed using the electrode composite (S30). For example, pressure may be applied to a mold provided with the electrode composite. Accordingly, the first electrode active layer can be formed. The shape, size, and manufacturing method of the first electrode active layer may vary. As shown in FIG. 1, the first electrode collector 100 may be formed on one surface 110a of the first electrode active layer 110. FIG. The solid electrolyte layer SE may be formed on the other surface 110b of the first electrode active layer 110. [ The second electrode active layer 210 and the second electrode collector 200 may be spaced apart from the first electrode active layer 110 on the solid electrolyte layer SE. The order of forming the first electrode current collector 100, the first electrode active layer 110, the solid electrolyte layer SE, the second electrode active layer 210, and the second electrode current collector 200 is not limited to this, can do. The first electrode current collector 100, the first electrode active layer 110, the solid electrolyte layer SE, the second electrode active layer 210 and the second electrode current collector 200 are formed as described in the example of FIG. 1 May be the same or similar.

4 is a flowchart illustrating a method of manufacturing a lithium battery according to another embodiment of the present invention. Hereinafter, duplicated description will be omitted.

4, a mixture containing sodium element, metal element, phosphorus element, and sulfur element may be prepared (S11). As an example, sodium phosphorus sulfide and metal sulfide may be added to prepare a mixture . At this time, the metal sulfide can be represented by Na a MS b . (Where M is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, Ga, In, Si, Ge, Sn, Pb, As, Sb and Bi, 0? A? 8 and 0? B? 8.) The mixture may be in a solid state.

The electrode composite can be produced by applying mechanical force or heat energy to the mixture. (S20) The electrode composite according to the embodiment can be represented by Na a PM b S c X d . (Where M is at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, A, b, c, and d are each independently any one selected from the group consisting of 0, 1, 2, 3, 4, 5, 6). For example, a ball milling process may be performed on the mixture. The ball milling process can be carried out by the same or similar method as the ball milling process described above with reference to the example of FIG. As another example, by heat treatment of the mixture, an electrode composite can be produced.

A lithium battery may be formed using the electrode composite. (S30) The lithium battery may be manufactured by the same or similar method as the example of FIG.

Hereinafter, the production of the electrode composite according to the present invention and the evaluation results of the characteristics of the electrode composite will be described in more detail with reference to the experimental examples of the present invention.

Preparation of electrode composite

<Experimental Example 1>

TiS 2 and Li 3 PS 4 are added in a weight ratio of 1: 2 to prepare a mixture of 100 mg. The mixture is provided in a reactor having a volume of 25 ml. A ZrO 2 ball having a diameter of 5 mm is provided in the reactor. A ball milling process using the ZrO 2 ball is performed on the mixture in the reactor. The ball milling process is carried out at 2000 rpm for 10 minutes.

<Experimental Example 2>

Electrode composite can be produced. However, in this embodiment, TiS 2 , Li 2 S, and P 2 S 5 are mixed in a molar ratio of 1: 4.3: 2.2 to prepare a mixture of 100 mg. The mixture and a ZrO 2 ball having a diameter of 5 mm are provided in the reactor. A ball milling process using the ZrO 2 ball is performed on the mixture in the reactor. The ball milling process is carried out at 500 rpm for 10 hours.

&Lt; Comparative Example 1 &

Electrode composite can be produced. However, the ball milling process may be omitted in this embodiment. For example, a mixture of 100 mg prepared in the same manner as in Experimental Example 1 can be mixed without using ball milling.

Manufacture of Lithium Battery

<Experimental Example 2-1>

200 g of Li3PS4 is provided in a cylindrical mold having a diameter of 13 mm. A pressure of 360 MPa is applied to the cylindrical mold to produce a solid electrolyte pellet. 10 g of the electrode composite prepared in Experimental Example 1-1 was provided on the first side of the solid electrolyte pellet. A pressure of 360 MPa is applied to the cylindrical mold including the electrode composite to form a cathode on the first surface of the solid electrolyte pellet. A lithium foil is deposited on the second side of the solid electrolyte pellet. The second surface of the solid electrolyte is opposed to the first surface. A pressure of 30 MPa is applied to the lithium foil to produce an anode on the second side of the solid electrolyte pellet.

<Experimental Example 2-2>

A lithium battery was produced in the same manner as in Experimental Example 2-1. However, in this embodiment, the electrode composite prepared in Experimental Example 1-2 is used.

&Lt; Comparative Example 2-1 >

A lithium battery was produced in the same manner as in Experimental Example 2-1. However, in this embodiment, the electrode composite prepared in Experimental Example 1-2 is used.

5 is a graph showing the results of X-ray diffraction analysis of Experimental Example 1-1 and Comparative Example 1-1. a shows Experimental Example 1-1, and b shows the results of Comparative Example 1-2.

Referring to FIG. 5, Experimental Example 1-1 shows TiS 2 peak (*) with lower intensity than Comparative Example 1-1. The lithium element contained in the mixture can be inserted into the crystal of TiS 2 by a ball milling process. Accordingly, TiS 2 of the solid electrolyte of Experimental Example 1 can have a smaller crystal size than TiS 2 of the solid electrolyte of Comparative Example 1.

It can be seen that the TiS 2 peak (*) of Experimental Example 1 is located to the left of the TiS2 peak (*) of Comparative Example 1. As the mixture is subjected to a physical force, such as a ball milling process, Li 3 SP 4 contained in the mixture may react with TiS 2 . Accordingly, in the case of Experimental Example 1, pure TiS 2 and another lattice structure, for example, the lithium element can be formed with a TiS 2 trellis inserted.

A peak of Li 3 SP 4 (^) is shown in Experimental Example 1. From this, it can be seen that Li 3 SP 4 contained in the mixture remains in the electrode composite without reacting. The solid electrolyte produced according to Experimental Example 1 can be confirmed to have Li 3 SP 4 serving as an ion conduction pathway.

6 is a graph showing the charge / discharge characteristics evaluation result of Experimental Example 2-1 in a voltage range of 1.5 V to 3.0 V. FIG. 7 is a graph showing the charge / discharge characteristics evaluation result of Experimental Example 2-1 in a voltage range of 1.0 V to 3.0 V. FIG. The charging and discharging characteristics of FIGS. 6 and 7 were evaluated at a temperature of 30 degrees and a current rate of 0.1 C (current rate). The abscissa represents the capacitance and the ordinate represents the voltage. The dotted line indicates the measurement result at the time of charging, and the solid line indicates the measurement result at the time of discharging.

Referring to FIG. 6, Experimental Example 2-1 shows a charge capacity of 416 mAhg -1 in the second cycle. The charging capacity of Experimental Example 2-1 is larger than the theoretical charging capacity of TiS 2 (239 mAhg -1 ).

Referring to FIG. 7, Experimental Example 2-1 shows a charging capacity of 810 mA / g. In this case, it can be seen that as the voltage applied to Experimental Example 2-1 decreases, the charging capacity of the electrode increases.

Table 1 shows the charge-discharge capacity and coulombic efficiency of Experimental Example 2-1 and Comparative Example 2-1. Table 1 is analyzed from the charging / discharging characteristic evaluation results shown in Fig.

Capacity of the first cycle (mAhg -1 ) Coulomb efficiency (%) Discharge capacity Charging capacity Experimental Example 1 263 416 158 Comparative Example 1 237 220 93

Experimental Example 1 shows higher charge capacity and coulombic efficiency than Comparative Example 1. The theoretical discharge capacity of TiS 2 is 239 mAhg -1 . The lithium battery of Experimental Example 1 has a charging capacity larger than the theoretical discharge capacity. The electrode composite of Experimental Example 1-1 produced by ball milling may include a lithium metal sulfide (for example, Li x TiS 2 ) and an amorphous sulfide (for example, lithium sulfide which is lithium titanium). The lithium battery of Experimental Example 2-1 prepared using Experimental Example 1-1 can further improve the charging capacity and coulombic efficiency.

8 is a graph showing the capacity according to the number of charge / discharge cycles in Experimental Example 2-1.

Referring to FIG. 8, in the lithium battery of Experimental Example 2-1, the change in capacity is small as the number of charging and discharging times increases. Thus, it can be confirmed that the lithium battery of Experimental Example 2-1 exhibits excellent cycle characteristics and durability.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the present invention is not limited to the disclosed exemplary embodiments, and various changes and modifications may be made by those skilled in the art without departing from the scope and spirit of the invention. Change is possible.

Claims (12)

  1. Electrode collector;
    A solid electrolyte layer disposed apart from the electrode current collector; And
    A solid electrolyte layer interposed between the electrode current collector and the solid electrolyte layer,
    A first portion including lithium metal sulfide and electrically connected to the electrode current collector,
    Second portions comprising lithium sulfide and connected to the solid electrolyte layer, and
    And an electrode active layer provided between the first portions and the second portions, the electrode active layer including amorphous sulfide including lithium, metal, phosphorus, and sulfur.
  2. The method according to claim 1,
    Wherein the solid electrolyte comprises the same material as the second parts.
  3. The method according to claim 1,
    Wherein the first portions are connected to the second portions.
  4. The method according to claim 1,
    Wherein the first portions are dispersedly provided in the electrode active layer and are connected to each other.
  5. Preparing a mixture comprising lithium phosphorus sulfide and metal sulfide;
    Subjecting the mixture to physical pressure to produce an electrode composite, wherein the electrode composite comprises lithium sulfide, lithium metal sulfide and amorphous sulfide;
    Preparing an electrode active layer using the electrode composite;
    Forming an electrode current collector on one surface of the electrode active layer; And
    And forming a solid electrolyte layer on the other surface of the electrode active layer.
  6. 6. The method of claim 5,
    Wherein the lithium metal sulfide and the amorphous sulfide are prepared by reacting a lithium element contained in the mixture with a metal sulfide,
    Wherein the reaction of the lithium element and the metal sulfide is performed by the physical pressure.
  7. 6. The method of claim 5,
    Wherein the lithium sulfide contained in the electrode composite is provided such that a part of the lithium sulfide contained in the mixture is left unreacted.
  8. 6. The method of claim 5,
    And applying physical pressure to the mixture is performed by a ball milling process.
  9. 6. The method of claim 5,
    Wherein the lithium phosphorus sulfide comprises Li 3 PS 4 ,
    Wherein the metal sulfide comprises TiS 2 .
  10. 6. The method of claim 5,
    Wherein the electrode active layer comprises:
    First portions including the lithium metal sulfide and electrically connected to the electrode current collector;
    Second portions including the lithium phosphorus sulfide and connected to the solid electrolyte layer; And
    Wherein the amorphous sulfide is provided between the first portions and the second portions.
  11. 6. The method of claim 5,
    Wherein the amorphous sulfide includes lithium, metal, phosphorus, and sulfur.
  12. Preparing a mixture comprising lithium sulfide, phosphorus sulfide, metal, and sulfur;
    Subjecting the mixture to physical pressure to produce an electrode composite, wherein the electrode composite comprises lithium sulfide, lithium metal sulfide and amorphous sulfide;
    Preparing an electrode active layer using the electrode composite;
    Forming an electrode current collector on one surface of the electrode active layer; And
    And forming an electrolyte layer on the other surface of the electrode active layer.
KR1020130153192A 2013-06-17 2013-12-10 Lithium Battery and Method for preparing the same KR101918112B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020130069090 2013-06-17
KR20130069090 2013-06-17

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14/264,804 US9379383B2 (en) 2013-06-17 2014-04-29 Lithium battery and method of preparing the same

Publications (2)

Publication Number Publication Date
KR20140146990A KR20140146990A (en) 2014-12-29
KR101918112B1 true KR101918112B1 (en) 2018-11-15

Family

ID=52675987

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020130153192A KR101918112B1 (en) 2013-06-17 2013-12-10 Lithium Battery and Method for preparing the same

Country Status (1)

Country Link
KR (1) KR101918112B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101705267B1 (en) * 2015-04-13 2017-02-22 울산과학기술원 Solid electrolytes for all solid state rechargeable lithium battery, methods for manufacturing the same, and all solid state rechargeable lithium battery including the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011060649A (en) 2009-09-11 2011-03-24 Toyota Motor Corp Electrode active material layer, all solid battery, manufacturing method for electrode active material layer, and manufacturing method for all solid battery
US20110159365A1 (en) 2009-05-07 2011-06-30 Amprius, Inc. Template electrode structures for depositing active materials
JP2012204114A (en) 2011-03-25 2012-10-22 Idemitsu Kosan Co Ltd Slurry composition for electrode of lithium secondary battery, and battery using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110159365A1 (en) 2009-05-07 2011-06-30 Amprius, Inc. Template electrode structures for depositing active materials
JP2011060649A (en) 2009-09-11 2011-03-24 Toyota Motor Corp Electrode active material layer, all solid battery, manufacturing method for electrode active material layer, and manufacturing method for all solid battery
JP2012204114A (en) 2011-03-25 2012-10-22 Idemitsu Kosan Co Ltd Slurry composition for electrode of lithium secondary battery, and battery using the same

Also Published As

Publication number Publication date
KR20140146990A (en) 2014-12-29

Similar Documents

Publication Publication Date Title
Gao et al. Effects of liquid electrolytes on the charge–discharge performance of rechargeable lithium/sulfur batteries: electrochemical and in-situ X-ray absorption spectroscopic studies
Manthiram et al. Challenges and prospects of lithium–sulfur batteries
Qian et al. Nanosized Na4Fe (CN) 6/C Composite as a Low‐Cost and High‐Rate Cathode Material for Sodium‐Ion Batteries
Sakuda et al. Interfacial observation between LiCoO2 electrode and Li2S− P2S5 solid electrolytes of all-solid-state lithium secondary batteries using transmission electron microscopy
Kim et al. Tin phosphide as a promising anode material for Na‐ion batteries
Wang et al. An aqueous rechargeable lithium battery with good cycling performance
Li et al. V2O5 polysulfide anion barrier for long-lived Li–S batteries
Yang et al. Protected Lithium‐Metal Anodes in Batteries: From Liquid to Solid
Liu et al. A flexible quasi‐solid‐state nickel–zinc battery with high energy and power densities based on 3D electrode design
Lin et al. Phosphorous pentasulfide as a novel additive for high‐performance lithium‐sulfur batteries
Tang et al. Rational material design for ultrafast rechargeable lithium-ion batteries
Yuan et al. Powering lithium–sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts
Xie et al. Exploring Advanced Sandwiched Arrays by Vertical Graphene and N‐Doped Carbon for Enhanced Sodium Storage
Besenhard et al. Advances in battery technology: Rechargeable magnesium batteries and novel negative‐electrode materials for lithium ion batteries
Manthiram Materials challenges and opportunities of lithium ion batteries
Luo et al. A thermally conductive separator for stable Li metal anodes
Liu et al. Prelithiated silicon nanowires as an anode for lithium ion batteries
Chen et al. From a historic review to horizons beyond: lithium–sulphur batteries run on the wheels
Han et al. Electrochemical stability of Li10GeP2S12 and Li7La3Zr2O12 solid electrolytes
Cheng et al. A facile method to improve the high rate capability of Co 3 O 4 nanowire array electrodes
Zheng et al. In situ formed lithium sulfide/microporous carbon cathodes for lithium-ion batteries
Tang et al. “Nano‐pearl‐string” TiNb2O7 as anodes for rechargeable lithium batteries
Wang et al. Towards high‐safe lithium metal anodes: suppressing lithium dendrites via tuning surface energy
You et al. Subzero‐Temperature Cathode for a Sodium‐Ion Battery
Liu et al. Carbon/ZnO nanorod array electrode with significantly improved lithium storage capability

Legal Events

Date Code Title Description
N231 Notification of change of applicant
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant