JP2012074352A - Electrode material and lithium ion battery using the same - Google Patents

Electrode material and lithium ion battery using the same Download PDF

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JP2012074352A
JP2012074352A JP2011105298A JP2011105298A JP2012074352A JP 2012074352 A JP2012074352 A JP 2012074352A JP 2011105298 A JP2011105298 A JP 2011105298A JP 2011105298 A JP2011105298 A JP 2011105298A JP 2012074352 A JP2012074352 A JP 2012074352A
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solid electrolyte
sulfide
active material
electrode material
example
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JP6071171B2 (en
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Shinichi Kurokawa
Akiko Tsuji
明子 辻
黒川  真一
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Idemitsu Kosan Co Ltd
出光興産株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/54Manufacturing of lithium-ion, lead-acid or alkaline secondary batteries

Abstract

PROBLEM TO BE SOLVED: To provide an electrode material eliminating the need of being continuously contacted with a conductive assistant and a lithium ion battery using the electrode material.SOLUTION: The electrode material includes an active material being fused with one or more sulfide based solid electrolytes on a part of a surface of the active material.

Description

  The present invention relates to an electrode material, a manufacturing method thereof, an electrode sheet including the electrode material, and a lithium ion battery.

With the recent development of mobile communication and information electronic devices, the demand for high-capacity and lightweight lithium secondary batteries tends to increase. Most electrolytes exhibiting high lithium ion conductivity at room temperature are liquids, and many of the commercially available lithium ion secondary batteries use organic electrolytes.
In the lithium secondary battery using this organic electrolyte, there is a risk of leakage, ignition or explosion, and a battery with higher safety is desired. An all-solid battery using a solid electrolyte has a feature that electrolyte leakage and ignition hardly occur. However, the ionic conductivity of the solid electrolyte is generally low and it is difficult to put it to practical use.

In lithium secondary batteries using solid electrolytes, lithium ion conductive ceramics based on Li 3 N are conventionally known as solid electrolytes exhibiting high ion conductivity of 10 −3 Scm −1 at room temperature. However, since the decomposition voltage is low, a battery that operates at 3 V or more cannot be constructed.

As a sulfide-based solid electrolyte, Patent Document 1 discloses a solid electrolyte having ion conductivity of 10 −4 Scm −1 . Patent Document 2 discloses an ion conductive 10 −4 Scm −1 electrolyte synthesized from Li 2 S and P 2 S 5 .
Furthermore, Patent Document 3 is a sulfide-based crystallized glass obtained by synthesizing Li 2 S and P 2 S 5 in a ratio of 68 to 74 mol%: 26 to 32 mol%, and has an ion conductivity of 10 −3 Scm −1 units. Is realized.

It is desired to improve the performance of such all solid lithium batteries. However, an all-solid lithium battery is a contact between powders, and since the contact area is small, it does not become a high-performance battery such as a lithium battery using an electrolytic solution.
Therefore, it is necessary to improve the contact area between the solid electrolyte particles and between the solid electrolyte particles and the electrode active material particles, and to reduce their contact resistance.

Patent Document 4 discloses that the entire surface of the active material is covered with an inorganic solid electrolyte and a conductive additive as shown in FIG. However, when used for an electrode, in order to ensure the electron conductivity inside the electrode, it is necessary that the conductive assistant is continuously in contact from the surface of one active material to the surface of the other active material.
Thus, in order for the conductive additive to contact continuously, it was necessary to devise a method for mixing the active material, solid electrolyte, conductive additive, and electrode manufacturing method. Furthermore, this becomes a problem when the size of the lithium ion battery is increased.

JP-A-4-202024 JP 2002-109955 A JP 2005-228570 A JP 2003-59492 A

  An object of this invention is to obtain the electrode material which does not need to make a conductive support agent contact continuously, and the lithium ion battery using this electrode material.

According to the present invention, the following electrode materials and the like are provided.
1. An electrode material comprising an active material in which one or more sulfide-based solid electrolytes are fused to a part of the surface.
2. 2. The electrode material according to 1, wherein the sulfide-based solid electrolyte has no grain boundary.
3. 3. The electrode material according to 1 or 2, wherein a sulfide-based solid electrolyte is fused to 5% to 90% of the surface of the active material.
4). The electrode material according to any one of 1 to 3, wherein the active materials are fused to each other via the sulfide-based solid electrolyte.
5. Furthermore, the electrode material in any one of 1-4 containing sulfide type solid electrolyte particle.
6). A step of heat-treating a mixture of the active material and the sulfide-based solid electrolyte above the glass transition temperature of the sulfide-based solid electrolyte, and crushing the heat-treated mixture to melt one or more sulfide-based solid electrolytes on a part of the surface. The manufacturing method of the electrode material including the process of manufacturing the active material to wear.
The electrode material manufactured by the manufacturing method of 7.6.
The electrode sheet containing the electrode material in any one of 8.1-5 and 7.
The electrode sheet manufactured using the electrode material in any one of 9.1-5 and 7.
The lithium ion battery containing the electrode layer containing the electrode material in any one of 10.1-5 and 7, and the electrolyte layer which is a solid electrolyte.
11. A lithium ion battery comprising an electrode layer manufactured using the electrode material according to any one of 1 to 5 and 7 as a raw material, and an electrolyte layer which is a solid electrolyte.

  ADVANTAGE OF THE INVENTION According to this invention, the lithium ion battery using the electrode material which does not need to make a conductive support agent contact continuously, and this electrode material can be obtained.

It is sectional drawing which shows the electrode material of this invention. It is an enlarged view of the dotted line part of FIG. 2 is an enlarged photograph of the electrode material obtained in Example 1. 2 is an enlarged photograph of the electrode material obtained in Example 1. It is a graph which shows the result of the evaluation example 1. It is a graph which shows the result of the evaluation example 1. It is a graph which shows the result of the evaluation example 1. It is a graph which shows the result of the evaluation example 2. It is a graph which shows the result of the evaluation example 2. It is a graph which shows the result of the evaluation example 2. It is sectional drawing which shows the electrode material of patent document 4.

The electrode material of the present invention includes an active material in which one or more sulfide-based solid electrolytes are fused to a part of the surface.
An active material in which one or more sulfide-based solid electrolytes are fused to a part of the surface is appropriately referred to as “coat active material”.
Fusion means that the surface or the entire surface of the sulfide-based solid electrolyte is dissolved by heating, the space between the sulfide-based solid electrolyte and the active material is filled, and the contact area between the sulfide-based solid electrolyte and the active material increases. It means a state where intermolecular force is increased.

For example, as shown in FIGS. 1 and 2, the sulfide-based solid electrolyte and the active material are bonded so that the contact angle between the solid electrolyte and the active material forms an acute angle.
The contact angle means an angle α formed by the solid electrolyte surface with respect to a tangent line b of the active material at a point a where the solid electrolyte surface and the active material surface intersect.

A sulfide-based solid electrolyte is fused to one or more portions of the surface of the active material. Preferably, the sulfide-based solid electrolyte is fused to 5% to 90% of the surface of the active material. The active material is usually particulate but may be indefinite.
The average thickness of the sulfide solid electrolyte on the surface of the active material is preferably 0.01 μm to 5 μm.

The fused sulfide-based solid electrolytes preferably have no grain boundaries.
Furthermore, it is preferable that the active materials to which the sulfide-based solid electrolyte is fused are bonded to each other via the fused sulfide-based solid electrolyte.

  In such an electrode material, the contact between the active material and the sulfide-based solid electrolyte is improved, and the performance of the lithium ion battery can be enhanced. In addition, since the entire surface of the active material is not covered with the sulfide-based solid electrolyte, the surfaces of the active materials can be in direct contact with each other, and there is no need to continuously contact the conductive auxiliary agent. Therefore, it is not necessary to use a conductive additive, and it can be used for a large area battery or a battery containing a binder.

The electrode material of the present invention may be composed only of such a coat active material, but may further contain sulfide-based solid electrolyte particles.
Further, the sulfide solid electrolyte fused to the surface of the active material and the sulfide solid electrolyte particles may be the same or different.
In addition, in order to improve the electronic conductivity inside an electrode, you may use a conductive support agent.

The sulfide-based solid electrolyte of the present invention preferably contains Li and S.
The sulfide-based solid electrolyte preferably contains at least one element selected from the group consisting of P, B, Si, Ge, and Al, and an Li element and an S element.

When the sulfide-based solid electrolyte is produced from lithium sulfide and diphosphorus pentasulfide, the mixing molar ratio is usually 50:50 to 80:20, preferably 60:40 to 75:25, more preferably, 65: 35-75: 25. Particularly preferably, it is about Li 2 S: P 2 S 5 = 68: 32 to 74:26 (molar ratio).

The sulfide-based solid electrolyte is preferably crystallized.
When it is crystallized, the ionic conductivity becomes high, and when the electrode material of the present invention is used for a lithium ion battery, a higher performance lithium ion battery can be produced.

Here, as a crystal structure, for example, Li 7 PS 6 structure, Li 4 P 2 S 6 structure, Li 3 PS 4 structure, Li 4 SiS 4 structure, Li 2 SiS disclosed in Patent Document 2 are disclosed. 3 structures, the Li 7 P 3 S 11 structure disclosed in Patent Document 3 and International Publication No. 2007/066539 pamphlet is preferable, and the Li 7 P 3 S 11 structure is most preferable.
Here, the Li 7 P 3 S 11 structure has 2θ = 17.8 ± 0.3 deg, 18.2 ± 0.3 deg, 19.8 ± 0. 0 in X-ray diffraction (CuKα: λ = 1.54184). It has diffraction peaks at 3 deg, 21.8 ± 0.3 deg, 23.8 ± 0.3 deg, 25.9 ± 0.3 deg, 29.5 ± 0.3 deg, 30.0 ± 0.3 deg.
This is because the above-described crystal structure has higher ionic conductivity than the amorphous body.
Here, the crystallized portion of the sulfide-based solid electrolyte according to the present invention may consist of only one crystal structure or may have a plurality of crystal structures.

The active material includes a positive electrode active material used for manufacturing a positive electrode and a negative electrode active material used for manufacturing a negative electrode.
Here, the active material of the present invention is preferably one that does not deteriorate or dissolve even when heated to Tg or higher of the sulfide-based glass solid electrolyte.
In addition, since the active material that is preferably used depends on the Tg of the sulfide-based glass solid electrolyte, a preferable active material can be selected depending on the sulfide-based glass solid electrolyte to be fused.
As the positive electrode active material, a metal oxide capable of insertion / extraction of lithium ions and a material known as a positive electrode active material in the battery field can be used.
For example, in the sulfide system, titanium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), iron sulfide (FeS, FeS 2 ), copper sulfide (CuS), nickel sulfide (Ni 3 S 2 ), etc. can be used. TiS 2 is preferred. These substances can be used alone or in combination of two or more.

In the case of oxides, it preferably follows the formula (1) or (2).
LiNi x M 1-x O 2 (1)
LiNi a Co b Al 1-a -b O 2 (2)
(Wherein x is a number satisfying 0.1 <x <0.9, M is an element selected from the group consisting of Fe, Co, Mn and Al, and 0 ≦ a ≦ 1, 0 ≦ b ≦ 1)

Also, for example, bismuth oxide (Bi 2 O 3 ), bismuth leadate (Bi 2 Pb 2 O 5 ), copper oxide (CuO), vanadium oxide (V 6 O 13 ), lithium cobaltate (LiCoO 2 ), nickel acid Lithium (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), olivine-type lithium iron phosphate (LiFePO 4 ), nickel-manganese oxide (LiNi 0.5 Mn 0.5 O 2 ), nickel-aluminum - cobalt oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2), nickel - manganese - cobalt oxide (LiNi 0.33 Co 0.33 Mn 0.33 O 2) or the like can be used In particular, LiCoO 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 are suitable. These substances can be used alone or in combination of two or more.

It is also possible to use a mixture of the above sulfides and oxides. In addition to the above, niobium selenide (NbSe 3 ) can also be used.
A material whose surface is coated with an oxide, sulfide or the like can be suitably used as necessary.

As the negative electrode active material, a material capable of inserting and desorbing lithium ions, and a known negative electrode active material in the battery field can be used.
For example, carbon materials, specifically artificial graphite, graphite carbon fiber, resin-fired carbon, pyrolytic vapor-grown carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin-fired carbon, polyacene, pitch-based carbon Examples thereof include fibers, vapor-grown carbon fibers, natural graphite and non-graphitizable carbon, and artificial graphite is particularly preferable.

An alloy combined with a metal itself such as metallic lithium, metallic indium, metallic aluminum, metallic silicon, metallic tin, or another element or compound can be used as the negative electrode active material.
These negative electrode active materials can be used individually by 1 type or in combination of 2 or more types.

  The coated active material according to the present invention is obtained by heat-treating a mixture of active material particles and sulfide-based solid electrolyte particles above the glass transition temperature (Tg) of the sulfide-based solid electrolyte, and crushing the heat-treated mixture. The mixture of the active material particles and the sulfide-based solid electrolyte particles is simply mixed without using a mechanical method such as a ball mill, a fine pulverizer, or a composite particle generator.

  The particle diameters of the active material particles and solid electrolyte particles used are not particularly limited, but those having an average particle diameter of several μm to several tens of μm are preferable.

  The compounding ratio (weight ratio) of the active material and the sulfide-based solid electrolyte is preferably 50:50 to 90:20, more preferably 60:40 to 80:20. By mix | blending in this range, both an ion conduction path | route and an electron conduction path | route can be ensured.

The solid electrolyte used as a raw material is the same as that of the sulfide-based solid electrolyte except that a sulfide-based glass solid electrolyte is preferable. A blend of a sulfide-based glass solid electrolyte and a sulfide-based crystal glass solid electrolyte may be used. Further, if melting occurs at Tg, a sulfide-based glass solid electrolyte having crystallinity may be used.
Here, the sulfide-based glass solid electrolyte means an amorphous sulfide-based solid electrolyte.
Here, the sulfide-based crystal glass solid electrolyte means a sulfide-based solid electrolyte having a crystal structure.

  The temperature of the heat treatment is preferably not less than the Tg of the sulfide-based glass solid electrolyte and not more than the temperature at which the active material is not decomposed or altered.

  In addition, a preferable heating method is a method of heating at a crystallization temperature after the sulfide glass solid electrolyte is fused to the active material after heating at Tg of the sulfide glass solid electrolyte or lower and below the crystallization temperature. It is.

  Alternatively, a method of heating at a temperature equal to or higher than the crystallization temperature of the sulfide-based glass solid electrolyte (Tg of sulfide-based glass solid electrolyte) and simultaneously performing fusion and crystallization of the sulfide-based glass solid electrolyte on the active material is also preferable. .

Since the sulfide-based glass solid electrolyte is more easily fused to the active material, the former is preferable from the viewpoint of obtaining a high-performance lithium ion battery.
On the other hand, in the latter case of heating at a temperature higher than the crystallization temperature of the sulfide-based glass solid electrolyte, the heating temperature can be easily controlled.

The solid electrolyte in which at least a part of the raw material is in a glass state is crystallized by being heated. As a result, lithium ion conductivity is increased.
The surface or the whole of the sulfide-based glass solid electrolyte is melted by the heat treatment and adheres to the surface of the active material.

By increasing the temperature rising rate, the contact between the solid electrolyte softened before crystallization and the active material can be improved. Further, the process time can be shortened.
If the crystallinity of the fused solid electrolyte is small, it can be increased by subsequent heat treatment.

The heating time is, for example, 1 second to 60 minutes. The heating atmosphere is preferably an inert gas atmosphere and may be in a vacuum state.
Moreover, you may pressurize before heat processing and / or at the time of heat processing.
For example, heating is performed at 250 to 350 ° C. for 1 to 60 minutes.
Further, for example, heating may be performed at 250 ° C. or higher and 300 ° C. or lower for 1 minute or longer and 60 minutes or shorter, and then heated at 300 ° C. or higher and 350 ° C. or lower for 1 minute or longer and 30 minutes or shorter.

  The lump is crushed after the heat treatment, but it may be crushed or crushed.

  In addition, as described above, it is not necessary to use a conductive additive, but if used, the conductive additive may be mixed with the solid electrolyte and the active material from the beginning and heat-treated and pulverized, or after heat-treated and pulverized into the composite material. A conductive aid may be added. By arranging the conductive assistant directly on the active material, an electron conduction path can be efficiently formed. This is particularly effective when the active material has low electronic conductivity.

Examples of the method for producing a sulfide-based glass solid electrolyte that can be used as a raw material include a melt quenching method, a mechanical milling method (MM method), and a slurry method.
In the case of the melt quenching method, P 2 S 5 and Li 2 S mixed in a predetermined amount in a mortar and pelletized are placed in a carbon-coated quartz tube and vacuum-sealed. After reacting at a predetermined reaction temperature (usually 400 ° C. to 1000 ° C., 0.1 hour to 12 hours), a sulfide-based glass solid electrolyte is obtained by putting it in ice and quenching.

In the case of the MM method, a sulfide-based glass solid electrolyte is obtained by mixing a predetermined amount of P 2 S 5 and Li 2 S in a mortar and reacting them by a mechanical milling method. Li 2 S is preferably highly pure.

  In the MM method, various types such as a rotating ball mill, a rolling ball mill, a vibrating ball mill, and a planetary ball mill can be used. As conditions for the MM method, for example, when a planetary ball mill is used, the rotation speed may be several tens to several hundreds of revolutions / minute, and the treatment may be performed for 0.5 hours to 100 hours.

The slurry method is described in WO 2004/093099 and WO 2009/047977.
Specifically, a sulfide-based glass solid electrolyte is obtained by reacting a predetermined amount of raw materials (for example, P 2 S 5 particles and Li 2 S particles) in an organic solvent for a predetermined time.
Here, as described in JP-A-2010-140893, in order to advance the reaction, the slurry containing the raw material may be reacted while being circulated between the bead mill and the reaction vessel.

The reaction temperature is preferably 20 ° C. or higher and 80 ° C. or lower, more preferably 20 ° C. or higher and 60 ° C. or lower.
The reaction time is preferably 1 hour or longer and 16 hours or shorter, more preferably 2 hours or longer and 14 hours or shorter.

  It is preferable that the raw materials (for example, lithium sulfide and diphosphorus pentasulfide) become a solution or slurry by the addition of an organic solvent. Usually, the amount of the raw material (total amount) added to 1 liter of the organic solvent is about 0.001 kg or more and 1 kg or less. Preferably they are 0.005 kg or more and 0.5 kg or less, Most preferably, they are 0.01 kg or more and 0.3 kg or less.

The organic solvent is not particularly limited, but an aprotic organic solvent is particularly preferable.
Examples of the aprotic organic solvent include aprotic organic solvents (for example, hydrocarbon organic solvents), aprotic polar organic compounds (for example, amide compounds, lactam compounds, urea compounds, organic sulfur compounds, cyclic organic phosphorus). A compound or the like) can be suitably used as a single solvent or a mixed solvent.

As the hydrocarbon organic solvent, a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon can be used.
Examples of the saturated hydrocarbon include hexane, pentane, 2-ethylhexane, heptane, decane, and cyclohexane.
Examples of the unsaturated hydrocarbon include hexene, heptene, cyclohexene and the like.
Aromatic hydrocarbons include toluene, xylene, decalin, 1,2,3,4-tetrahydronaphthalene and the like.
Of these, toluene and xylene are particularly preferable.

The hydrocarbon solvent is preferably dehydrated in advance. Specifically, the water content is preferably 100 ppm by weight or less, and particularly preferably 30 ppm by weight or less.
In addition, you may add another solvent to a hydrocarbon type solvent as needed. Specific examples include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, alcohols such as ethanol and butanol, esters such as ethyl acetate, and halogenated hydrocarbons such as dichloromethane and chlorobenzene.

  The electrode sheet of the present invention contains the electrode material of the present invention or is produced using the electrode material of the present invention as a raw material.

  The lithium ion battery includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. In the lithium ion battery of the present invention, either one or both of the positive electrode layer and the negative electrode layer contains the electrode material of the present invention, or is manufactured using the electrode material of the present invention, and the electrolyte layer is a solid electrolyte.

  As the positive electrode layer, one used as a positive electrode active material in a lithium battery can be used, but the above electrode material is preferably used. Although what is used as a negative electrode active material in a lithium battery can be used for a negative electrode layer, it is preferable to use said electrode material.

The solid electrolyte layer is made of a solid electrolyte, and is preferably made of a sulfide glass ceramic solid electrolyte and / or a sulfide glass solid electrolyte.
The sulfide-based solid electrolyte used for the solid electrolyte layer is preferably a sulfide-based crystallized glass solid electrolyte having a crystallinity of 50% or more. A mixture of a sulfide-based crystallized glass solid electrolyte and a sulfide-based glass solid electrolyte may be used as long as the overall crystallinity is 50% or more.
When the crystallization degree of the sulfide-based solid electrolyte is less than 50%, the crystallization effect of increasing the ionic conductivity may be reduced.
The same applies to the solid electrolyte particles used in the electrode material of the present invention.

The degree of crystallinity can be measured by using an NMR spectrum apparatus. Specifically, a solid 31 P-NMR spectrum of a sulfide-based solid electrolyte was measured, and a resonance line observed at 70 to 120 ppm was used for the obtained solid 31 P-NMR spectrum by using a nonlinear least square method. The crystallinity can be measured by separating into Gaussian curves and determining the area ratio of each curve.

  A positive electrode current collector and a negative electrode current collector are preferably provided in the positive electrode layer and the negative electrode layer, respectively. As the positive electrode current collector and the negative electrode current collector, for example, a plate-like body or a foil-like body made of stainless steel, gold, platinum, copper, zinc, nickel, tin, aluminum, magnesium, indium, an alloy thereof, or the like Can be used.

Production Example 1 [Production Example of Lithium Sulfide]
(1) Production of lithium sulfide (Li 2 S) Lithium sulfide was produced according to the method of the first aspect (two-step method) of JP-A-7-330312. Specifically, N-methyl-2-pyrrolidone (NMP) 3326.4 g (33.6 mol) and lithium hydroxide 287.4 g (12 mol) were charged into a 10 liter autoclave equipped with a stirring blade, and 300 rpm, 130 The temperature was raised to ° C. After the temperature rise, hydrogen sulfide was blown into the liquid at a supply rate of 3 liters / minute for 2 hours.
Subsequently, this reaction solution was heated in a nitrogen stream (200 cc / min) to dehydrosulfide a part of the reacted hydrogen sulfide. As the temperature increased, water produced as a by-product due to the reaction between hydrogen sulfide and lithium hydroxide started to evaporate, but this water was condensed by the condenser and extracted out of the system. While water was distilled out of the system, the temperature of the reaction solution rose, but when the temperature reached 180 ° C., the temperature increase was stopped and the temperature was kept constant. After the dehydrosulfurization reaction was completed (about 80 minutes), the reaction was completed to obtain lithium sulfide.

(2) Purification of lithium sulfide After decanting NMP in the 500 mL slurry reaction solution (NMP-lithium sulfide slurry) obtained in (1) above, 100 mL of dehydrated NMP was added and stirred at 105 ° C. for about 1 hour. . NMP was decanted at that temperature. Further, 100 mL of NMP was added, stirred at 105 ° C. for about 1 hour, NMP was decanted at that temperature, and the same operation was repeated a total of 4 times. After completion of the decantation, lithium sulfide was dried at 230 ° C. (temperature higher than the boiling point of NMP) under a nitrogen stream for 3 hours under normal pressure. The impurity content in the obtained lithium sulfide was measured.

Incidentally, lithium sulfite (Li 2 SO 3), the content of each sulfur oxide lithium sulfate (Li 2 SO 4) and lithium thiosulfate (Li 2 S 2 O 3) , and N- methylamino acid lithium (LMAB) Was quantified by ion chromatography. As a result, the total content of sulfur oxides was 0.13% by mass, and LMAB was 0.07% by mass.

Production Example 2 [Production Example of Glass with Li 2 S and P 2 S 5 (Molar Ratio) = 70: 30]
Li 2 S and P 2 S 5 (manufactured by Aldrich) produced in Production Example 1 were used as starting materials. About 1 g of a mixture adjusted to a molar ratio of 70:30 and 10 alumina balls having a diameter of 10 mm were placed in a 45 mL alumina container, and nitrogen was measured using a planetary ball mill (manufactured by Fritsch: Model No. P-7). A lithium / phosphorous sulfide glass solid electrolyte as a white yellow powder was obtained by performing mechanical milling treatment for 20 hours at room temperature (25 ° C.) with a rotational speed of 370 rpm. It was 220 degreeC when the glass transition temperature of this thing was measured by DSC (differential scanning calorimetry).

Production Example 3 [Production Example of 70:30 Glass Ceramics]
The solid electrolyte glass particles obtained in Production Example 2 were sealed in a SUS tube under an Ar atmosphere in a glove box, and subjected to a heat treatment at 300 ° C. for 2 hours to obtain electrolyte glass ceramics (sulfide-based solid electrolyte: average particle size 14 .52 μm). In the X-ray diffraction measurement of the glass ceramic particles, peaks were observed at 2θ = 17.8, 18.2, 19.8, 21.8, 23.8, 25.9, 29.5, 30.0 deg. .
The ionic conductivity of the glass ceramic particles was 1.3 × 10 −3 S / cm. The ionic conductivity was calculated from the result measured by the AC impedance method.

Production Example 4 [Production Example of 67:33 Glass]
Solid electrolyte glass particles obtained in the same manner as in Production Example 2, except that 0.592 g of Li 2 S having an average particle size of about 30 μm obtained in Production Example 1 and 1.406 g of P 2 S 5 (Aldrich) were used. Got. The recovery rate at this time was 80%. As a result of X-ray diffraction measurement (CuKα: λ = 1.54184) of the obtained solid electrolyte glass particles, the peak of the raw material Li 2 S was not observed, and it was a halo pattern resulting from the solid electrolyte glass.

Production Example 5 [Production Example of 67:33 Glass Ceramics]
The solid electrolyte glass particles obtained in Production Example 4 were sealed in a SUS tube under an Ar atmosphere in a glove box, and subjected to heat treatment at 300 ° C. for 2 hours to obtain an electrolyte glass ceramic (sulfide-based solid electrolyte: average particle size 50 μm). ) The ionic conductivity of the glass ceramic particles was 0.2 × 10 −3 S / cm.

Production Example 6 [Production Example of 75:25 Glass]
Solid electrolyte glass particles in the same manner as in Production Example 2 except that 0.766 g of Li 2 S having an average particle size of about 30 μm obtained in Production Example 1 and 1.22 g of P 2 S 5 (manufactured by Aldrich) were used. (Sulfide-based solid electrolyte: average particle size 50 μm) was obtained. The recovery rate at this time was 82%. As a result of X-ray diffraction measurement (CuKα: λ = 1.54184) of the obtained solid electrolyte glass particles, the peak of the raw material Li 2 S was not observed, and it was a halo pattern resulting from the solid electrolyte glass.
The ionic conductivity of the solid electrolyte glass particles was 0.3 × 10 −3 S / cm.

Production Example 7 [Production Example of 80:20 Glass]
Solid electrolyte glass particles obtained in the same manner as in Production Example 2, except that 0.906 g of Li 2 S having an average particle size of about 30 μm obtained in Production Example 1 and 1.092 g of P 2 S 5 (Aldrich) were used. Got. The recovery rate at this time was 85%. As a result of X-ray diffraction measurement (CuKα: λ = 1.54184) of the obtained solid electrolyte glass particles, the peak of the raw material Li 2 S was not observed, and it was a halo pattern resulting from the solid electrolyte glass.

Production Example 8 [Production Example of 80:20 Glass Ceramics]
The solid electrolyte glass particles obtained in Production Example 7 were sealed in a SUS tube under an Ar atmosphere in a glove box, and subjected to a heat treatment at 280 ° C. for 2 hours to obtain an electrolyte glass ceramic (sulfide-based solid electrolyte: average particle size 50 μm). ) The ionic conductivity of the glass ceramic particles was 0.5 × 10 −3 S / cm.

Example 1
LiNi 0.8 Co 0.15 Al 0.05 O 2 as the positive electrode active material and the lithium / phosphorous sulfide glass solid electrolyte powder produced in Production Example 2 as the solid electrolyte were mixed at a weight ratio of 70:30, and the mixture was mixed. 1 g was pressure-molded at 10 MPa in a φ15.5 mold and pelletized. This was put into a predetermined metal hermetic container and heat-treated at 300 ° C. for 10 minutes. The heat-treated pellets were pulverized to obtain a positive electrode composite powder.

The fused state of the solid electrolyte to the active material is shown in FIGS. The white part in the lower left photo shows LiNi 0.8 Co 0.15 Al 0.05 O 2 Co, the part surrounded by the white line in the upper right photo shows the solid electrolyte S, and the part surrounded by the white line in the lower right photo shows the electrolyte P .
Therefore, it can be seen that the solid electrolyte is present on LiNi 0.8 Co 0.15 Al 0.05 O 2 , and it can be seen that the solid electrolyte is fused to the active material as shown in the upper left photograph. Furthermore, there was no grain boundary in the sulfide-based solid electrolyte, and the active material was fused via the sulfide-based solid electrolyte.

  Graphite powder was used as the negative electrode active material. This negative electrode active material and the crystallized glass solid electrolyte (glass ceramic electrolyte) produced in Production Example 3 were mixed at a weight ratio of 60:40, and this was used as a negative electrode active material mixture.

  45.1 mg of the glass-ceramic electrolyte produced in Production Example 3 was put into a stainless steel mold having a diameter of 9.5 mm, pressed into an electrolyte layer, and 12.9 mg of the positive electrode mixture prepared above was added. It was pressure molded again. 10.9 mg of the negative electrode active material mixture was added from the side opposite to the positive electrode mixture to form a three-layer structure, and pressure-molded to obtain a battery.

Example 2
The molar ratio of Li 2 S and P 2 S 5 of the solid electrolyte used in the positive electrode mixture for heat treatment was set to 80:20 (the lithium / phosphorous sulfide produced in Production Example 7 for the solid electrolyte used in the positive electrode mixture) A battery was fabricated in the same manner as in Example 1 except that the product was made of a solid glass solid electrolyte powder.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

Example 3
Graphite powder as the negative electrode active material and the lithium / phosphorous sulfide glass solid electrolyte powder produced in Production Example 2 as the solid electrolyte were mixed at a weight ratio of 60:40, and 1 g of the mixture was pressure-molded at 10 MPa in a φ15.5 mold. And pelletized. It put into the predetermined | prescribed metal sealed container, and heat-processed by gas chromatography at 300 degreeC for 10 minutes. This heat-treated pellet was pulverized to obtain a negative electrode mixture.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

LiNi 0.8 Co 0.15 Al 0.05 O 2 was used as the positive electrode active material. This positive electrode active material and the glass ceramic electrolyte produced in Production Example 3 were mixed at a weight ratio of 70:30, and this was used as a positive electrode active material mixture.
A battery was fabricated in the same manner as in Example 1 except for the above.

Example 4
LiCoO 2 as the positive electrode active material and the lithium / phosphorous sulfide glass solid electrolyte powder produced in Production Example 2 as the solid electrolyte were mixed at a weight ratio of 70:30, and 1 g of the mixture was pressure-molded at 10 MPa in a φ15.5 mold. And pelletized. It put into the predetermined | prescribed metal sealed container, and heat-processed at 300 degreeC for 10 minutes. The heat-treated pellets were pulverized to obtain a positive electrode composite powder.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

In foil (0.1 tmm, φ9.5) was used as the negative electrode active material. This In foil was punched with a φ9.5 punch.
45.1 mg of the glass-ceramic electrolyte produced in Production Example 3 was put into a stainless steel mold having a diameter of 9.5 mm, subjected to pressure molding, and 30 mg of the positive electrode mixture prepared as described above was further charged and pressure-molded again. A negative electrode foil was introduced from the side opposite to the positive electrode mixture to form a three-layer structure and pressure-molded to obtain a battery.

Example 5
LiTiO 3 as the negative electrode active material and the lithium / phosphorous sulfide glass solid electrolyte powder produced in Production Example 2 as the solid electrolyte were mixed at a weight ratio of 60:40, and 1 g of the mixture was pressure-molded with a mold of φ15.5 at 10 MPa. Pelletized. It put into the predetermined | prescribed metal sealed container, and heat-processed by 300 degreeC for 10 minutes with the gas chromatography. This heat-treated pellet was pulverized to obtain a negative electrode mixture.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

LiNi 0.8 Co 0.15 Al 0.05 O 2 was used as the positive electrode active material. This positive electrode active material and the glass ceramic electrolyte produced in Production Example 3 were mixed at a weight ratio of 70:30, and this was used as a positive electrode active material mixture.
45.1 mg of the glass-ceramic electrolyte produced in Production Example 3 is put into a stainless steel mold having a diameter of 9.5 mm, press-molded, and 12.9 mg of the positive electrode mixture prepared above is put into the mold, and then press-molded again. did. 24.2 mg of the negative electrode active material mixture was charged from the side opposite to the positive electrode mixture, and pressure molded as a three-layer structure to obtain a battery.

Example 6
A battery was fabricated in the same manner as in Example 1 except that the solid electrolyte used in the positive electrode mixture to be heat-treated was the lithium / phosphorous sulfide solid electrolyte produced in Production Example 4.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

Example 7
A battery was fabricated in the same manner as in Example 1 except that the lithium / phosphorous sulfide solid electrolyte produced in Production Example 6 was used as the solid electrolyte used for the positive electrode mixture to be heat-treated.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

Example 8
A battery was fabricated in the same manner as in Example 2, except that the solid electrolyte used in the electrolyte layer and the negative electrode layer was changed to the glass ceramic electrolyte produced in Production Example 8.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

Example 9
A battery was produced in the same manner as in Example 6 except that the glass ceramic electrolyte produced in Production Example 5 was used as the solid electrolyte used in the electrolyte layer and the negative electrode layer.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

Example 10
A battery was fabricated in the same manner as in Example 7 except that the glass electrolyte produced in Production Example 6 was used as the solid electrolyte used in the electrolyte layer and the negative electrode layer.
The fusion state of the solid electrolyte was confirmed in the same manner as in Example 1, and it was found that the solid electrolyte was fused to the active material.

Comparative Example 1
A battery was prepared in the same manner as in Example 1 except that the solid electrolyte used for the positive electrode mixture was the glass ceramic electrolyte produced in Production Example 3 and no heat treatment was performed.

Comparative Example 2
A battery was fabricated in the same manner as in Example 4 except that the solid electrolyte used for the positive electrode mixture was the glass ceramic electrolyte produced in Production Example 3 and no heat treatment was performed.

Comparative Example 3
A battery was produced in the same manner as in Example 5 except that the solid electrolyte used in the negative electrode mixture was the glass ceramic electrolyte produced in Production Example 3, and no heat treatment was performed.
Table 1 shows the configurations of the batteries of Examples 1 to 10 and Comparative Examples 1 to 3. In the table, LNCAO is LiNi 0.8 Co 0.15 Al 0.05 O 2 , LCO is LiCoO 2 , LTO is LiTiO 3 , g-SE is a glass solid electrolyte, and gc-SE is a glass ceramic electrolyte.

Evaluation Example 1
Battery evaluation (rate characteristics)
Evaluation of lithium batteries prepared in Examples 1, 2, 3 and Comparative Example 1 The battery was evaluated as follows. Charged to 4.2 V at 500 μA per cm 2 in the first cycle, discharged to 2.5 V at 500 μA, charged to 4.2 V at 500 μA in the second cycle, discharged to 2.5 V at 1 mA, and 500 μA in the third cycle The battery was charged to 4.2 V at 3 mA and discharged to 2.5 V at 3 mA, and charged to 4.2 V at 500 μA in the fourth cycle and discharged to 2.5 V at 10 mA. The average voltage during discharge in each cycle was plotted against the discharge current density. The result is shown in FIG. 5A.

Evaluation of Lithium Battery Prepared in Example 4 and Comparative Example 2 The battery was evaluated as follows. Charged to 3.6 V at 500 μA per cm 2 in the first cycle, discharged to 1.5 V at 500 μA, charged to 3.6 V at 500 μA in the second cycle, discharged to 1.5 V at 1 mA, and 500 μA in the third cycle The battery was charged to 3.6 V at 3 mA and discharged to 1.5 V at 3 mA, and charged to 3.6 V at 500 μA in the fourth cycle and discharged to 1.5 V at 10 mA. The average voltage during discharge in each cycle was plotted against the discharge current density. The result is shown in FIG. 5B.

Evaluation of Lithium Battery Prepared in Example 5 and Comparative Example 3 The battery was evaluated as follows. Charged to 2.6 V at 500 μA per cm 2 in the first cycle, discharged to 1.5 V at 500 μA, charged to 2.6 V at 500 μA in the second cycle, discharged to 1.5 V at 1 mA, and 500 μA in the third cycle The battery was charged up to 2.6 V and discharged at 3 mA up to 1.5 V, and the average value of the voltage during discharge in each cycle was plotted against the discharge current density. The result is shown in FIG. 5C.

  Table 2 shows the magnitude of the slope when an approximate straight line is drawn with respect to the above plot. Since this slope is a value corresponding to the internal resistance of the battery, a smaller value indicates that charging / discharging is performed efficiently.

Evaluation example 2
Battery evaluation (impedance measurement during charging)
The batteries prepared in Examples 1, 2, 3 and Comparative Example 1 were charged to 4.2 V at 500 μA per cm 2, and the batteries prepared in Example 4 and Comparative Example 2 were charged at 500 μA per cm 2 . The battery prepared in Example 5 and Comparative Example 3 was charged to 6 V, charged to 2.7 V at 500 μA per cm 2 , and the impedance of each battery after charging was measured by the AC impedance method. From the Cole-Cole plot (FIGS. 6A to 6C) obtained at this time, the resistance was obtained from the diameter of the arc derived from the battery interface resistance. The results are shown in Table 3.

Evaluation Example 3
Battery evaluation (cycle characteristics)
The batteries prepared in Examples 1, 2, 3 and Comparative Example 1 were charged to 4.2 V at 1 mA per cm 2 and discharged to 2.5 V at 1 mA. This was repeated 200 times, and the initial discharge capacity and the 200th discharge capacity were examined.
The batteries prepared in Example 4 and Comparative Example 2 were charged to 3.6 V at 1 mA per cm 2 and discharged to 1.5 V at 1 mA. This was repeated 200 times, and the initial discharge capacity and the 200th discharge capacity were examined.

The batteries prepared in Example 5 and Comparative Example 3 were charged to 2.6 V at 1 mA per cm 2 and discharged to 1.5 V at 1 mA. This was repeated 200 times, and the initial discharge capacity and the 200th discharge capacity were examined. Table 4 shows the cycle characteristics of each battery.

The batteries prepared in Examples 6 to 10 were charged to 4.2 V at 1 mA per 1 cm 2 and discharged to 2.5 V at 1 mA. This was repeated 200 times, and the initial discharge capacity and the 200th discharge capacity were examined. Table 4 shows the cycle characteristics of each battery.

  The electrode material of the present invention can be used for an electrode of a lithium ion battery. The lithium ion battery of the present invention can be used as a power source for various electrical appliances.

Claims (11)

  1.   An electrode material comprising an active material in which one or more sulfide-based solid electrolytes are fused to a part of the surface.
  2.   The electrode material according to claim 1, wherein the sulfide solid electrolyte has no grain boundary.
  3.   The electrode material according to claim 1 or 2, wherein a sulfide-based solid electrolyte is fused to 5% to 90% of the surface of the active material.
  4.   The electrode material according to claim 1, wherein the active materials are fused to each other via the sulfide-based solid electrolyte.
  5.   Furthermore, the electrode material in any one of Claims 1-4 containing sulfide type solid electrolyte particle.
  6. A step of heat-treating a mixture of the active material and the sulfide-based solid electrolyte above the glass transition temperature of the sulfide-based solid electrolyte, and crushing the heat-treated mixture to melt one or more sulfide-based solid electrolytes on a part of the surface. The manufacturing method of the electrode material including the process of manufacturing the active material to wear.
  7.   An electrode material manufactured by the manufacturing method according to claim 6.
  8.   The electrode sheet containing the electrode material in any one of Claims 1-5 and 7.
  9.   The electrode sheet manufactured using the electrode material in any one of Claims 1-5 and 7.
  10. An electrode layer comprising the electrode material according to any one of claims 1 to 5 and 7,
    An electrolyte layer that is a solid electrolyte;
    Including lithium ion battery.
  11. An electrode layer manufactured using the electrode material according to any one of claims 1 to 5 and 7 as a raw material,
    An electrolyte layer that is a solid electrolyte;
    Including lithium ion battery.
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JP2013214421A (en) * 2012-04-02 2013-10-17 National Institute Of Advanced Industrial & Technology Carbon-solid electrolyte complex and manufacturing method of the same
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JP2014053141A (en) * 2012-09-06 2014-03-20 Shinshu Univ Method for producing electrode mixture, electrode body and battery including electrode mixture produced by the producing method
JP2014192061A (en) * 2013-03-28 2014-10-06 Hitachi Zosen Corp Material for all-solid batteries, and method for manufacturing material for all-solid batteries
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