WO2017183255A1 - 固体電解質及び全固体電池 - Google Patents
固体電解質及び全固体電池 Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Definitions
- the present invention relates to a solid electrolyte and an all-solid battery.
- Patent Documents 1 and 2 describe all solid state batteries in which the solid electrolyte has a solid electrolyte made of a phosphate compound having a NaSICON structure.
- Patent Document 3 includes chemical formula Li x M1 y M2 z Zr 2-x (PO 4 ) 3 (where M1 includes at least one selected from Ti, Ge, and Zr, and M2 is: And a solid electrolyte material represented by at least one selected from Mg, Ca, Ba, Al, Cr, In, Sc, Y, and Hf.
- the main object of the present invention is to improve the ionic conductivity of the solid electrolyte layer and to improve the battery characteristics of the all solid state battery.
- the solid electrolyte according to the present invention is a solid electrolyte having a NaSICON type crystal structure.
- the general formula Li 1 + X M y (PO 4 ) 3 (part of P may be substituted with at least one selected from the group consisting of Si, B and V, Including at least one element of monovalent to tetravalent cations and represented by ⁇ 0.200 ⁇ x ⁇ 0.900, 2.001 ⁇ y ⁇ 2.200).
- the ion conduction path is constituted by Li sites. For this reason, it is considered that when the Li site is replaced by an element other than the ion conductive species, the ion conductivity is lowered.
- the solid electrolyte represented by the general formula Li 1 + X M y (PO 4 ) 3 when y is larger than 2, it is considered that (y ⁇ 2) M is located at the Li site. Therefore, when y is larger than 2, it is considered that the ionic conductivity of the solid electrolyte is lowered.
- M contains at least one element that becomes a monovalent to tetravalent cation and satisfies 2.001 ⁇ y ⁇ 2.200.
- the ionic conductivity of the solid electrolyte can be improved by setting y to 2.001 or more and 2.200 or less, compared with the case where y is 2, and has led to the present invention. That is, in the solid electrolyte according to the present invention, M contains at least one element that becomes a monovalent to tetravalent cation and satisfies 2.001 ⁇ y ⁇ 2.200. For this reason, the solid electrolyte according to the present invention has high ionic conductivity.
- M contains at least one element selected from monovalent to trivalent cations.
- M contains at least one element selected from the group consisting of Zr, Hf, Ca, Y, Na, Al, Ga, Sc, V, In, Ti, Ge, and Sn. Is preferred.
- M contains at least one element selected from the group consisting of Na, Ca, Y, Al, Ga, Sc, V, and In.
- M contains at least one element selected from the group consisting of Zr, Hf, Sn, Ti, and Ge.
- An all-solid battery according to the present invention includes a solid electrolyte including the solid electrolyte according to the present invention, a positive electrode bonded by sintering to one surface of the solid electrolyte layer, and a sintered electrode bonded to the other surface of the solid electrolyte.
- a negative electrode is a solid electrolyte including the solid electrolyte according to the present invention, a positive electrode bonded by sintering to one surface of the solid electrolyte layer, and a sintered electrode bonded to the other surface of the solid electrolyte.
- the ionic conductivity of the solid electrolyte layer can be improved, and the battery characteristics of the all-solid battery can be improved.
- FIG. 1 is a schematic cross-sectional view of an all solid state battery according to an embodiment of the present invention.
- FIG. 2 is a coll-coll plot of the solid electrolyte produced in Example 1.
- FIG. 3 is a coll-coll plot of the solid electrolyte produced in Comparative Example 1.
- FIG. 1 is a schematic cross-sectional view of an all solid state battery 1 according to the present embodiment. As shown in FIG. 1, a positive electrode 11, a negative electrode 12, and a solid electrolyte layer 13 are provided.
- the positive electrode 11 includes positive electrode active material particles.
- the positive electrode active material particles preferably used include, for example, lithium-containing phosphate compound particles having a NASICON type structure, lithium-containing phosphate compound particles having an olivine type structure, lithium-containing layered oxide particles, and lithium containing a spinel type structure. Examples thereof include oxide particles.
- Specific examples of the lithium-containing phosphoric acid compound having a NASICON structure that is preferably used include Li 3 V 2 (PO 4 ) 3 and the like.
- Specific examples of the lithium-containing phosphate compound having an olivine structure that is preferably used include LiFe (PO 4 ), LiMnPO 4 and the like.
- lithium-containing layered oxide particles preferably used include LiCoO 2 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and the like.
- Specific examples of the lithium-containing oxide having a spinel structure preferably used include LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4 . Only 1 type in these positive electrode active material particles may be used, and multiple types may be mixed and used.
- the positive electrode 11 may further contain a solid electrolyte.
- the kind of solid electrolyte contained in the positive electrode 11 is not particularly limited, it is preferable that the same kind of solid electrolyte as the solid electrolyte contained in the solid electrolyte layer 13 is included. In this case, the adhesion strength between the solid electrolyte layer 13 and the positive electrode 11 can be improved.
- the negative electrode 12 includes negative electrode active material particles.
- the negative electrode active material particles preferably used include, for example, MO X (M is at least one selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, P, and Mo. 9 ⁇ X ⁇ 2.5), graphite-lithium compound particles, lithium alloy particles, lithium-containing phosphate compound particles having NASICON type structure, lithium-containing phosphate compound particles having olivine type structure, spinel Examples thereof include lithium-containing oxide particles having a mold structure.
- Specific examples of the lithium alloy preferably used include a Li—Al alloy.
- Specific examples of the lithium-containing phosphoric acid compound having a NASICON structure that is preferably used include Li 3 V 2 (PO 4 ) 3 and the like.
- Specific examples of lithium-containing oxides having a spinel structure that are preferably used include Li 4 Ti 5 O 12 . Only 1 type in these negative electrode active material particles may be used, and multiple types may be mixed and used.
- the negative electrode 12 may further contain a solid electrolyte.
- the kind of solid electrolyte contained in the negative electrode 12 is not particularly limited, it is preferable that the same kind of solid electrolyte as the solid electrolyte contained in the solid electrolyte layer 13 is included. In this case, the adhesion strength between the solid electrolyte layer 13 and the negative electrode 12 can be improved.
- a solid electrolyte layer 13 is disposed between the positive electrode 11 and the negative electrode 12. That is, the positive electrode 11 is disposed on one side of the solid electrolyte layer 13 and the negative electrode 12 is disposed on the other side. Each of the positive electrode 11 and the negative electrode 12 is joined to the solid electrolyte layer 13 by sintering. That is, the positive electrode 11, the solid electrolyte layer 13, and the negative electrode 12 are an integral sintered body.
- the solid electrolyte layer 13 has a general formula Li 1 + X M y (PO 4 ) 3 (part of P may be substituted with at least one selected from the group consisting of Si, B, and V.
- M is 1 A NaSICON type crystal structure represented by ⁇ 0.200 ⁇ x ⁇ 0.900, 2.001 ⁇ y ⁇ 2.200) containing at least one element of a valence to tetravalent cation. Contains a solid electrolyte. For this reason, the solid electrolyte layer 13 according to the present embodiment has high ionic conductivity. Therefore, the all solid state battery 1 having the solid electrolyte layer 13 is excellent in characteristics such as output density.
- M includes an element that becomes a tetravalent cation and satisfies 2.001 ⁇ y ⁇ 2.200
- a high ion conduction phase is easily formed by M. It is thought that it is to become.
- M includes an element that becomes a monovalent to trivalent cation and satisfies 2.001 ⁇ y ⁇ 2.200
- charge compensation is further performed. This is considered to be because a decrease in the amount of Li contributing to ionic conduction can be suppressed from the viewpoint.
- preferable elements as monovalent to trivalent M include Na, Ca, Y, Al, Ga, Sc, V, and In. Among them, Na and Ca are monovalent to trivalent M. More preferably.
- tetravalent M examples include Zr, Hf, Sn, Ti, Ge, etc.
- Zr, Hf, Sn are more preferably used as tetravalent M.
- M may be composed of a single element or may be composed of a plurality of types of elements.
- M is composed of a plurality of kinds of elements, it is preferable that M contains both an element that becomes a monovalent to trivalent ion and an element that becomes a tetravalent ion.
- both an element that becomes a monovalent to trivalent ion and an element that becomes a tetravalent ion are included, higher ionic conductivity can be obtained. This is considered to be because the amount of Li contributing to ionic conduction can be increased.
- a part of P may be substituted with at least one selected from the group consisting of B, Si and V.
- at least one molar ratio ((at least one selected from the group consisting of B, Si and V) / (P)) selected from the group consisting of B, Si and V with respect to P relative to P is 0. It is preferably 0 or more and 2.0 or less, and more preferably 0.0 or more and 0.5 or less.
- 1 + x which is the stoichiometric ratio of Li can be appropriately adjusted within the range of ⁇ 0.200 ⁇ x ⁇ 0.900 in order to maintain the neutrality between the positive charge and the negative charge in the crystal.
- a more preferable range of x is ⁇ 0.160 ⁇ x ⁇ 0.500, and a further preferable range is 0.050 ⁇ x ⁇ 0.350.
- the compound represented by the general formula Li 1 + X M y (PO 4 ) 3 has twelve oxygens, but the number of oxygen contained in the compound represented by the general formula is positive and negative. From the viewpoint of maintaining neutrality with the electric charge, the stoichiometric ratio of O may not be exactly twelve.
- the compound represented by the general formula Li 1 + X M y (PO 4 ) 3 includes those containing 7 mol or more and 15 mol or less of oxygen.
- Example 1 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 2 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 3 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 4 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 5 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 6 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 7 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Example 8 Lithium carbonate (Li 2 CO 3 ), zirconium oxide (ZrO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), yttrium stabilized zirconia, etc. the raw materials, except that the condition is satisfied generally shown in Table 1 formula Li 1 + X M y (PO 4) 3 was weighed so that the composition obtained to give a powder of the solid electrolyte in the same manner as in Comparative example 1 .
- Comparative Example 2 A raw material containing lithium carbonate (Li 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), and hafnium oxide (HfO 2 ) is described below.
- a solid electrolyte powder was obtained in the same manner as in Comparative Example 1 except that the composition was weighed so that the general formula Li 1 + X M y (PO 4 ) 3 satisfying the conditions shown in Table 1 was obtained.
- Example 9 A raw material containing lithium carbonate (Li 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), and hafnium oxide (HfO 2 ) is described below.
- a solid electrolyte powder was obtained in the same manner as in Comparative Example 1 except that the composition was weighed so that the general formula Li 1 + X M y (PO 4 ) 3 satisfying the conditions shown in Table 1 was obtained.
- Example 10 Raw materials containing lithium carbonate (Li 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), calcium oxide (CaO), yttrium oxide (Y 2 O 3 ), tin dioxide (SnO 2 ) A solid electrolyte powder was obtained in the same manner as in Comparative Example 1 except that the composition was weighed so that the general formula Li 1 + X M y (PO 4 ) 3 satisfying the conditions shown in Table 1 was obtained.
- Li 2 CO 3 lithium carbonate
- NH 4 H 2 PO 4 ammonium dihydrogen phosphate
- CaO calcium oxide
- Y 2 O 3 yttrium oxide
- SnO 2 tin dioxide
- Comparative Example 4 The conditions shown in Table 1 below for raw materials containing lithium carbonate (Li 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), sodium carbonate (Na 2 CO 3 ), and zirconium oxide (ZrO 2 ) A solid electrolyte powder was obtained in the same manner as in Comparative Example 1 except that the composition was weighed so as to obtain the general formula Li 1 + X M y (PO 4 ) 3 to be satisfied.
- Li 2 CO 3 lithium carbonate
- NH 4 H 2 PO 4 ammonium dihydrogen phosphate
- Na 2 CO 3 sodium carbonate
- ZrO 2 zirconium oxide
- Example 11 The conditions shown in Table 1 below for raw materials containing lithium carbonate (Li 2 CO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), sodium carbonate (Na 2 CO 3 ), and zirconium oxide (ZrO 2 ) A solid electrolyte powder was obtained in the same manner as in Comparative Example 1 except that the composition was weighed so as to obtain the general formula Li 1 + X M y (PO 4 ) 3 to be satisfied.
- Li 2 CO 3 lithium carbonate
- NH 4 H 2 PO 4 ammonium dihydrogen phosphate
- Na 2 CO 3 sodium carbonate
- ZrO 2 zirconium oxide
- the solid electrolyte powders produced in Examples 1 to 11 and Comparative Examples 1 to 4 were XRD (X-ray diffractometer) at a scan rate of 4.0 ° / min at 25 ° C. and a measurement range of 10 ° to 60 °.
- the crystal structure was evaluated by measuring and collating with the pattern of JCPDS (Joint Committee on Powder Diffraction Standards) card. As a result, it was confirmed that the solid electrolytes produced in each of Examples 1 to 11 and Comparative Examples 1 to 4 had a NaSICON type crystal structure.
- the ionic conductivity of the produced sintered tablet was measured. Specifically, after forming a platinum (Pt) layer as a current collector layer by sputtering on both sides of the sintered tablet, the sintered tablet is dried at 100 ° C. to remove moisture, and a 2032 type coin cell is used. Sealed. The ionic conductivity was calculated by performing an AC impedance measurement on the sealed cell. The AC impedance was measured using a Solartron frequency response analyzer (FRA) under the conditions of a frequency range of 0.1 MHz to 1 MHz, an amplitude of ⁇ 10 mV, and a temperature of 25 ° C.
- FFA Solartron frequency response analyzer
- the ionic conductivity ⁇ was calculated from the following equation by obtaining the resistance of each solid electrolyte (the sum of the particle and grain boundary resistance) from a coll-coll plot obtained by AC impedance measurement.
- the resistance of the solid electrolyte was the value at the end of the right end of the arc in the colle-coll plot.
- ⁇ (t / A) ⁇ (1 / R)
- Ionic conductivity t Sample thickness A: Area of electrode R: Resistance of solid electrolyte
- FIG. 2 shows a colle-coll plot of the solid electrolyte prepared in Example 1.
- a coll-coll plot of the solid electrolyte produced in Comparative Example 1 is shown in FIG.
- the ionic conductivity of the solid electrolyte prepared in each of Examples 1 to 8 was 0.4 ⁇ 10 ⁇ 4 S / cm to 1.6 ⁇ 10 ⁇ 4 S / cm, both of which were manufactured in Comparative Example 1. The value was higher than that of the solid electrolyte.
- the ionic conductivity of the solid electrolyte produced in Example 9 was 1.0 ⁇ 10 ⁇ 4 S / cm, which was higher than that of the solid electrolyte produced in Comparative Example 2.
- the ionic conductivity of the solid electrolyte produced in Example 10 was 1.0 ⁇ 10 ⁇ 4 S / cm, which was higher than that of the solid electrolyte produced in Comparative Example 3.
- the ionic conductivity of the solid electrolyte produced in Example 11 was 1.5 ⁇ 10 ⁇ 4 S / cm, which was higher than that of the solid electrolyte produced in Comparative Example 4.
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Abstract
Description
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量した。次に、秤量した原料粉末を500mlのポリエチレン製ポリポットに封入してポット架上で150rpmの速度で、16時間回転させ、原料を混合した。次に、原料を、空気雰囲気下、500℃で1時間焼成した後に、800℃で6時間焼成し、揮発成分を除去した。次に、得られた焼成物を水、φ5mmの玉石と共に500mlのポリエチレン製ポリポットに封入してポット架上で150rpmの速度で、16時間回転して焼成物を粉砕した。その後、120℃のホットプレート上に粉砕物を配置して加熱することにより水分を除去した。得られた粉砕物を、空気雰囲気下、900℃~1200℃で20時間焼成し、下記の表1に記載の比較例1の組成を有する固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、酸化ジルコニウム(ZrO2)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、イットリウム安定化ジルコニアなどの原料を、表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、酸化ハフニウム(HfO2)を含む原料を下記の表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、酸化ハフニウム(HfO2)を含む原料を下記の表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、二酸化スズ(SnO2)を含む原料を下記の表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、リン酸二水素アンモニウム(NH4H2PO4)、酸化カルシウム(CaO)、酸化イットリウム(Y2O3)、二酸化スズ(SnO2)を含む原料を下記の表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、リン酸二水素アンモニウム(NH4H2PO4)、炭酸ナトリウム(Na2CO3)、酸化ジルコニウム(ZrO2)を含む原料を下記の表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
炭酸リチウム(Li2CO3)、リン酸二水素アンモニウム(NH4H2PO4)、炭酸ナトリウム(Na2CO3)、酸化ジルコニウム(ZrO2)を含む原料を下記の表1に示す条件を満たす一般式Li1+XMy(PO4)3が得られる組成となるように秤量したこと以外は、比較例1と同様にして固体電解質の粉末を得た。
実施例1~11、比較例1~4のそれぞれにおいて作製した固体電解質の粉末を25℃で4.0°/分のスキャン速度、測角範囲10°~60°でXRD(X線回折装置)測定し、JCPDS(Joint Committee on Powder Diffraction Standards)カードのパターンと照合することにより結晶構造を評価した。その結果、実施例1~11、比較例1~4のそれぞれにおいて作製した固体電解質は、NaSICON型の結晶構造を有していることが確認された。
実施例1~11、比較例1~4のそれぞれにおいて作製した固体電解質のイオン伝導度を以下のように測定した。
σ=(t/A)×(1/R)
σ:イオン伝導度
t:試料の厚さ
A:電極の面積
R:固体電解質の抵抗
また、実施例1において作製した固体電解質のcole-coleプロットを図2に示す。比較例1において作製した固体電解質のcole-coleプロットを図3に示す。
11 正極
12 負極
13 固体電解質層
Claims (9)
- NaSICON型の結晶構造を有する固体電解質であって、一般式Li1+XMy(PO4)3(Pの一部は、Si、B及びVからなる群から選ばれた少なくとも一種で置換されていてもよく、Mは、1価~4価の陽イオンとなる元素のうちの少なくとも一種を含み、-0.200≦x≦0.900、2.001≦y≦2.200)で表される、固体電解質。
- 前記一般式において、2.001≦y≦2.100である、請求項1に記載の固体電解質。
- 前記一般式において、2.001≦y≦2.050である、請求項2に記載の固体電解質。
- 前記Mが1価~3価の陽イオンとなる元素のうちの少なくとも一種を含む、請求項1~3のいずれか一項に記載の固体電解質。
- 前記Mが4価の陽イオンとなる元素を含む、請求項1~4のいずれか一項に記載の固体電解質。
- 前記Mが、Zr、Hf、Ca、Y、Na、Al、Ga、Sc、V、In、Ti、Ge及びSnからなる群より選ばれた少なくとも一種の元素を含む、請求項1~5のいずれか一項に記載の固体電解質。
- 前記Mが、Na、Ca、Y、Al、Ga、Sc、V及びInからなる群より選ばれた少なくとも一種の元素を含む、請求項4に記載の固体電解質。
- 前記Mが、Zr、Hf、Sn、Ti及びGeからなる群より選ばれた少なくとも一種の元素を含む、請求項5に記載の固体電解質。
- 請求項1~8のいずれか一項に記載の固体電解質を含む固体電解質層と、
前記固体電解質層の一方面に焼結によって接合されている正極と、
前記固体電解質の他方面に焼結によって接合されている負極と、
を備える、全固体電池。
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EP17785600.2A EP3447837A4 (en) | 2016-04-19 | 2017-02-03 | FIXED ELECTROLYTE AND SOLID BATTERY |
CN201780022831.0A CN109075389A (zh) | 2016-04-19 | 2017-02-03 | 固体电解质及全固体电池 |
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WO2021124849A1 (ja) * | 2019-12-17 | 2021-06-24 | Tdk株式会社 | 固体電解質及び全固体電池 |
WO2021124851A1 (ja) * | 2019-12-17 | 2021-06-24 | Tdk株式会社 | 固体電解質及び全固体電池 |
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