WO2015064351A1 - 固体電解質前駆体、その製造方法、固体電解質の製造方法、及び固体電解質-電極活物質複合体の製造方法 - Google Patents
固体電解質前駆体、その製造方法、固体電解質の製造方法、及び固体電解質-電極活物質複合体の製造方法 Download PDFInfo
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a solid electrolyte precursor, a method for producing the same, a method for producing a solid electrolyte, and a method for producing a solid electrolyte-electrode active material composite.
- All-solid-state batteries and lithium-air batteries are regarded as promising as next-generation secondary batteries, particularly for automobiles.
- development of oxide-based lithium ion conductive solid electrolytes has been carried out.
- a solid electrolyte synthesis method As a solid electrolyte synthesis method, a solid phase method and a liquid phase method centered on a sol-gel method are mainly known.
- the solid phase method for example, oxides, hydroxides, and / or salts of Group 3 element, Group 4 or Group 5 element, and lithium element are mixed in a stoichiometric ratio, and calcined. It is a synthetic method for sintering.
- sol-gel method for example, by first preparing a mixed solution (sol) of a Group 3 element, a Group 4 or Group 5 element, and a lithium element, a uniform mixed state at the atomic level of these elements Next, the mixed solution (sol) is gelled by heat concentration to form a solid state precursor (gel), and finally the gel is baked to synthesize a solid electrolyte. It is.
- a precursor (gel) containing a group 3 element, a group 4 or group 5 element, and a lithium element uniformly through a stoichiometric ratio is passed over the solid phase method. It is considered as a method capable of achieving the synthesis of a solid electrolyte at a low temperature.
- Patent Document 1 acetate is used as a La source and Li source, titanium tetraisopropoxide (TTIP) is used as a Ti source, a mixture of 2-propanol and water is used as a solvent, and a polyvinylpyrrolidone as a thickener is added.
- TTIP titanium tetraisopropoxide
- Patent Document 2 discloses a method of preparing a precursor solution in which each element is uniformly mixed using acetate as a La source, carbonate as a Li source, a lactate aqueous solution as a Ti source, and water as a solvent. ing.
- Patent Document 3 acetate is used as a La source and Li source, a lactate aqueous solution is used as a Ti source, a mixture of 2-propanol and water is used as a solvent, polyethylene oxide is added as a thickener, and each element is uniformly distributed A method for preparing a mixed precursor solution is disclosed.
- JP 2010-165527 A International Publication No. 2009/157524 JP 2003-346895 A
- the solid phase method since the uniformity of mixing of each raw material is low, firing at a high temperature of 1150 ° C. or higher is necessary to obtain a single-phase solid electrolyte. However, when firing at such a high temperature, it is difficult to achieve energy saving and low environmental load, and the lithium element is likely to volatilize.
- the solid-phase method is not necessarily an excellent method in compositing a solid electrolyte with a material having lower thermal stability than the solid electrolyte.
- it is important that the electrode phase and the solid electrolyte phase are in intimate contact with each other in the solid electrolyte-electrode active material composite.
- the electrode active material is likely to be decomposed at such a high temperature, so that the composite of the electrode phase and the solid electrolyte phase may be difficult in the solid phase method. Furthermore, in the solid phase method, the product tends to be coarse and irregular shaped, and it is difficult to combine with other materials from the viewpoint of low monodispersity in particle size.
- the dissolved state of the Group 4 or Group 5 element component is stabilized using an organic ligand, and the precursor that is a solid phase is obtained by distilling off the solvent.
- the precursor (gel) is fired at a temperature lower than the firing temperature of the solid phase method to obtain a final product.
- the mass reduction rate is high because desorption of the organic ligand occurs in the process.
- the present invention has been made in view of such conventional circumstances, and can provide a solid electrolyte by firing at a temperature lower than the firing temperature of the solid phase method, and the mass reduction rate during the firing is low. It is an object of the present invention to provide a solid electrolyte precursor, a method for producing the same, a method for producing a solid electrolyte, and a method for producing a solid electrolyte-electrode active material composite.
- a solid electrolyte precursor containing lithium element, Group 3 element oxide and / or hydroxide, and Group 4 and / or Group 5 element oxide and / or hydroxide It has been found that the above object can be achieved, and further, such a solid electrolyte precursor includes a Group 3 element oxide and / or hydroxide, a Group 4 and / or Group 5 element oxide, and / or It discovered that it could manufacture by precipitating a hydroxide simultaneously and mixing the obtained precipitate and a lithium compound, and came to complete this invention. Specifically, the present invention provides the following.
- a first aspect of the present invention is a solid electrolyte having a single-phase perovskite structure or a single-phase garnet structure containing a lithium element, a Group 3 element, and a Group 4 and / or Group 5 element, at 1000 ° C. or less.
- the second aspect of the present invention is a method for producing a solid electrolyte, including a firing step of obtaining the solid electrolyte by firing the solid electrolyte precursor at a temperature of 1000 ° C. or lower.
- a contact step in which the solid electrolyte precursor is brought into contact with an electrode active material or an electrode active material precursor that becomes an electrode active material by firing, the solid electrolyte precursor, and the electrode active material.
- a method for producing a solid electrolyte-electrode active material composite comprising a firing step of obtaining the solid electrolyte-electrode active material composite by firing the electrode active material precursor at a temperature of 1000 ° C. or lower.
- a solid electrolyte having a single-phase perovskite structure or a single-phase garnet structure containing a lithium element, a Group 3 element, and a Group 4 and / or Group 5 element is used at 1000 ° C. or less.
- This is a method for producing a solid electrolyte precursor for synthesis by firing at a temperature of 5 to prepare an aqueous solution containing a group 3 element-containing cation and a group 4 element-containing cation and / or a group 5 element-containing cation
- aqueous solution preparation step By mixing the aqueous solution preparation step, the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution, the oxide and / or hydroxide of the Group 3 element and the Group 4 and / or Group 5 element
- Solid electrolyte for obtaining solid electrolyte precursor by mixing oxide and / or hydroxide to obtain precipitate and mixing precipitate obtained in the above simultaneous precipitation treatment step and lithium compound Precursor builder Including the door, it is a manufacturing method of the solid electrolyte precursor.
- the fifth aspect of the present invention is obtained by an aqueous solution preparation step of preparing an aqueous solution containing a Group 3 element-containing cation, a Group 4 element-containing cation and / or a Group 5 element-containing cation, and the aqueous solution preparation step.
- the oxide and / or hydroxide of the Group 3 element and the oxide and / or hydroxide of the Group 4 and / or Group 5 element are precipitated.
- a simultaneous precipitation treatment step for obtaining a precipitate a solid electrolyte precursor preparation step for obtaining a solid electrolyte precursor by mixing the precipitate obtained in the simultaneous precipitation treatment step with a lithium compound, and the solid electrolyte precursor
- the sixth aspect of the present invention is obtained by an aqueous solution preparation step of preparing an aqueous solution containing a Group 3 element-containing cation, a Group 4 element-containing cation and / or a Group 5 element-containing cation, and the aqueous solution preparation step.
- the oxide and / or hydroxide of the Group 3 element and the oxide and / or hydroxide of the Group 4 and / or Group 5 element are precipitated.
- a solid electrolyte can be provided by firing at a temperature lower than the firing temperature of the solid phase method, and the solid electrolyte precursor having a low mass reduction rate at the time of firing, its production method, and production of the solid electrolyte
- a method and a method for producing a solid electrolyte-electrode active material composite can be provided.
- the solid electrolyte precursor according to the present invention includes a solid electrolyte having a single-phase perovskite structure or a single-phase garnet structure containing a lithium element, a Group 3 element, and a Group 4 and / or Group 5 element at 1000 ° C. It is for synthesis by firing at the following temperatures, comprising lithium element, Group 3 element oxide and / or hydroxide, Group 4 and / or Group 5 element oxide and / or Or a hydroxide.
- the solid electrolyte synthesized from the solid electrolyte precursor according to the present invention is an oxide-based lithium ion conductive solid electrolyte.
- a perovskite such as LLTO (Li 3x La 2 / 3-x TiO 3 ) is used.
- the solid electrolyte synthesized by low-temperature firing of the solid electrolyte precursor according to the present invention has a higher form uniformity than that of the solid electrolyte obtained by the solid phase method, for example, fine particles having a uniform particle diameter.
- a higher form uniformity than that of the solid electrolyte obtained by the solid phase method, for example, fine particles having a uniform particle diameter.
- the solid electrolyte precursor according to the present invention contains a Group 3 element and a Group 4 and / or Group 5 element in the form of an oxide and / or hydroxide, and is an organic substance (desorbed during firing). Therefore, the mass reduction rate during low-temperature firing tends to be low.
- the solid electrolytes are in contact with each other”, and when the solid electrolyte and the electrode active material are combined, “the solid electrolyte and the electrode active material are Since the “contact” is extremely important, the obtained solid electrolyte is preferably denser.
- a solid electrolyte precursor that has fewer components desorbed during low-temperature firing that is, a lower mass reduction rate during low-temperature firing
- the solid electrolyte precursor according to the present invention tends to have a low mass reduction rate during low-temperature firing
- the solid electrolyte obtained from this solid electrolyte precursor tends to have improved lithium ion conductivity, and cracks are also likely to occur. Since it is difficult to occur, the yield is likely to improve.
- each of the Group 3 element, the Group 4 element, and the Group 5 element may be used alone or in combination of two or more. You may use together.
- the Group 3 elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ac, Th, Pa, U, and U.
- Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, and Lr means at least one selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, And at least one selected from the group consisting of Gd, more preferably at least one selected from the group consisting of Y, La, and Ce, and even more preferably La.
- the Group 4 and / or Group 5 element means at least one selected from the group consisting of Ti, Zr, Hf, Rf, V, Nb, Ta, and Db. Ti, Zr, V, Nb And at least one selected from the group consisting of Ta, more preferably at least one selected from the group consisting of Ti, Zr, Nb, and Ta, and more preferably Ti or Zr. Is more preferable.
- the total content of carbon element and nitrogen element in the solid electrolyte precursor according to the present invention is preferably 10% by mass or less, more preferably 8% by mass or less, and 5% by mass or less. Is even more preferred.
- the mass reduction rate tends to be low.
- mass reduction rate (mass%) (solid electrolyte precursor
- mass reduction rate (solid electrolyte precursor
- the mass reduction rate calculated by (mass ⁇ mass of solid electrolyte) ⁇ 100 / mass of solid electrolyte precursor is preferably 40% by mass or less.
- the mass reduction rate is 40% by mass or less, the obtained solid electrolyte is likely to be denser, so that the lithium ion conductivity is likely to be further improved, and cracks are less likely to occur, and thus the yield is further improved. It's easy to do.
- the composition ratio of the lithium element, the Group 3 element, and the Group 4 and / or Group 5 element is based on the composition ratio of these elements in the target solid electrolyte. Can be appropriately selected.
- the solid electrolyte precursor according to the present invention is fired at a low temperature, so the lithium element content hardly decreases, so the composition ratio of the element in the obtained solid electrolyte approximates the composition ratio of the element in the solid electrolyte precursor. It is easy to become.
- the solid electrolyte precursor according to the present invention may be obtained by any manufacturing method, but is preferably obtained by, for example, a manufacturing method described later.
- the form of the solid electrolyte precursor according to the present invention is not particularly limited, and may be solid, a solution such as an aqueous solution, or a slurry.
- a method for producing a solid electrolyte precursor according to the present invention includes a solid electrolyte having a single-phase perovskite structure or a single-phase garnet structure, which includes a lithium element, a Group 3 element, and a Group 4 and / or Group 5 element.
- a method for producing a solid electrolyte precursor for synthesis by firing at a temperature of 1000 ° C. or less and comprises a Group 3 element-containing cation, a Group 4 element-containing cation and / or a Group 5 element-containing cation.
- a solid precipitate is obtained by mixing the oxide obtained by precipitating a Group 5 element oxide and / or hydroxide to obtain a precipitate, the precipitate obtained in the simultaneous precipitation treatment step, and a lithium compound.
- Electrolyte precursor It is intended to obtain and a solid electrolyte precursor preparation step.
- the above manufacturing method is to obtain a solid electrolyte precursor using a liquid phase synthesis method.
- the advantage of applying the liquid phase synthesis method is that the metal elements constituting the solid electrolyte precursor can be uniformly mixed at the atomic level through the mixed solution state.
- the sol-gel method is common to the above production method according to the present invention in that the liquid phase synthesis method is applied.
- the sol-gel method the dissolved state of the Group 4 or Group 5 element component is stabilized using an organic ligand, and a precursor (gel) as a solid phase is precipitated by distilling off the solvent by heating. A solid electrolyte is obtained from this precursor (gel) by low-temperature firing.
- the sol-gel method has a problem in that the mass reduction rate due to desorption of organic ligands and the like is high during the low-temperature firing process.
- raw materials used in the sol-gel method such as titanium hydroxycarboxylate used in Patent Documents 2 and 3
- Patent Documents 2 and 3 generally have a long synthesis process, so it is difficult to reduce raw material costs.
- the present inventors pay attention to the above-mentioned problem in the sol-gel method, in particular, the problem that the mass reduction rate associated with low-temperature baking is large, and there are few components (organic components such as organic ligands) that are eliminated by baking.
- a precursor containing lithium element, Group 3 element oxide and / or hydroxide, and Group 4 and / or Group 5 element oxide and / or hydroxide A method for precipitating the body from the solution was studied.
- a lithium compound, a Group 3 element-containing compound, a Group 4 element-containing compound and / or a Group 5 element-containing compound are dissolved in a solvent to obtain a solution, from which the lithium element and the Group 3
- the group 4 and / or 5 Group element oxides and / or hydroxides are likely to precipitate, whereas lithium compounds are highly soluble and difficult to precipitate as precipitates, so lithium compounds and Group 3 element oxides and / or hydroxides It is difficult to simultaneously precipitate the oxides and / or hydroxides of the Group 4 and / or Group 5 elements.
- the homogeneous mixing at the atomic level in the precursor stage is an oxide and / or hydroxide of a Group 3 element and an oxide and / or hydroxide of a Group 4 and / or Group 5 element.
- the lithium element component is later mixed into the precipitate of the Group 3 element oxide and / or hydroxide and the Group 4 and / or Group 5 element oxide and / or hydroxide. Even so, it has been found that there is no problem in obtaining a uniform solid electrolyte by low-temperature firing.
- a solid electrolyte precursor having a low mass reduction rate upon firing can be obtained. Moreover, in the said manufacturing method, it is easy to obtain and a cheaper raw material can be utilized. Furthermore, in the above production method, raw materials that are difficult to decompose can be used under more stable conditions.
- each process included in the manufacturing method of the solid electrolyte precursor based on this invention is demonstrated in detail.
- an aqueous solution containing a Group 3 element-containing cation and a Group 4 element-containing cation and / or a Group 5 element-containing cation is prepared.
- Group 3 element-containing cations include Group 3 element cations such as La 3+ .
- Group 4 element-containing cations include Group 4 element cations such as Ti 4+ and Zr 4+ .
- Group 5 element-containing cations include Group 5 element cations such as Nb 5+ and Ta 5+ .
- Each of the Group 3 element-containing cation, the Group 4 element-containing cation, and the Group 5 element-containing cation may be used alone or in combination of two or more.
- Each of the Group 3 element-containing cation, the Group 4 element-containing cation, and the Group 5 element-containing cation is water, ammonia, an oxide ion, a hydroxide ion, or a counter anion described later as a ligand.
- a complex may be formed.
- the counter anion of the Group 3 element-containing cation, the Group 4 element-containing cation, and the Group 5 element-containing cation may be, for example, chlorine such as chloride ions, in addition to oxide ions and hydroxide ions. Examples thereof include a contained anion and a nitrate anion. Said counter anion may be used independently or may use 2 or more types together.
- the aqueous solution includes, for example, a Group 3 element compound that generates a Group 3 element-containing cation by dissolution, a Group 4 element compound that generates a Group 4 element-containing cation by dissolution, and / or a Group 5 element that includes dissolution. It is prepared by dissolving a Group 5 element compound that generates a cation in water or an acidic aqueous solution.
- these Group 3 element compounds, Group 4 element compounds, and Group 5 element compounds include chlorides, oxychlorides, hydroxides, oxides, and nitrates, and are easily available. From the viewpoint of low cost, chloride or oxychloride is preferred. Moreover, nitrate is preferable from the viewpoint of easy dissolution.
- the form of the group 3 element compound, group 4 element compound, and group 5 element compound is not particularly limited, and examples thereof include solids such as powder, aqueous solutions, and the like.
- Each of the above Group 3 element compounds, Group 4 element compounds, and Group 5 element compounds may be used alone or in combination of two or more.
- the aqueous solution obtained in the aqueous solution preparation step preferably has a pH of less than 7, that is, acidic.
- the Group 3 element-containing cation exhibits high water solubility in the region from strong acidity to weak acidity, while the Group 4 element-containing cation and Group 5 element-containing cation exhibit high water solubility only in the strong acid region. Therefore, the aqueous solution prepared in the aqueous solution preparation step is preferably strongly acidic (for example, pH 3 or less) from the viewpoint of stability.
- [Simultaneous precipitation treatment process] by mixing the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution, the oxide and / or hydroxide of the Group 3 element and the Group 4 and / or Group 5 element are mixed. Oxide and / or hydroxide are precipitated to obtain a precipitate.
- the method of mixing the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution is not particularly limited, and examples thereof include a method of dropping or spraying the aqueous solution obtained in the aqueous solution preparation step onto the basic aqueous solution.
- the pH of the basic aqueous solution is preferably 8 or more from the viewpoint of the precipitation rate. It does not specifically limit as basic aqueous solution, For example, ammonia water and lithium hydroxide aqueous solution are mentioned. Ammonia water is preferred because it is easily available and inexpensive. From the viewpoint of preventing contamination to the solid electrolyte, an aqueous lithium hydroxide solution in which the alkali cation is a lithium ion, that is, a cation constituting the solid electrolyte is preferable.
- the molar equivalent of the base in the basic aqueous solution used in the simultaneous precipitation treatment step is the counter anion of the Group 3 element-containing cation, Group 4 element-containing cation, and Group 5 element-containing cation in the aqueous solution obtained in the aqueous solution preparation step ( However, it is preferably more than the molar equivalent (excluding oxide ions and hydroxide ions), and more preferably large excess (for example, about twice or more).
- the molar equivalent of the base in the basic aqueous solution is larger than the molar equivalent of the counter anion, the basicity of the mixed solution can be sufficiently maintained even after the aqueous solution obtained in the aqueous solution preparation step and the basic aqueous solution are mixed.
- the precipitate obtained in the simultaneous precipitation treatment step is appropriately separated and washed.
- the separation method is not particularly limited, and examples thereof include centrifugation, decantation, and filtration. Moreover, it does not specifically limit as a solvent used for washing
- Solid electrolyte precursor production process In the solid electrolyte precursor preparation step, the precipitate obtained in the simultaneous precipitation treatment step and the lithium compound are mixed to obtain a solid electrolyte precursor.
- the method for mixing the precipitate and the lithium compound is not particularly limited, and examples thereof include a solid phase mixing method, a liquid phase mixing method, and a gas phase mixing method (for example, vapor deposition).
- a hydrothermal treatment method after mixing (hydrothermal method) or a solvothermal method may be used as described later.
- a solid-phase mixing method or a liquid-phase mixing method is preferred because the preparation ratio can be easily controlled.
- the above lithium compounds may be used alone or in combination of two or more.
- the lithium compound is not particularly limited, and examples thereof include lithium carbonate, lithium chloride, lithium fluoride, lithium hydroxide, lithium nitrate, lithium acetate, and hydrates thereof.
- the form of the lithium compound may be a solid such as a powder or an aqueous solution, and is not particularly limited.
- a solid electrolyte is synthesized by low-temperature firing, there are few components to be decomposed and desorbed, and Group 3 element oxides and / or hydroxides and Group 4 and / or Group 5 element oxides and / or water Use lithium hydroxide or its hydrate with a melting point as low as 462 ° C.
- the diffusion of lithium element into the precipitate with the oxide is sufficiently performed at a temperature lower than the firing temperature.
- the lithium compound when fired at a temperature higher than the melting point, the lithium element may be volatilized easily.
- the melting point or decomposition temperature is as high as 600 ° C. Lithium carbonate with relatively few components may be used.
- the lithium compound may be a composite of lithium and a solid electrolyte precursor constituent element other than lithium.
- a composite oxide of lithium and a Group 4 and / or Group 5 element as a composite, while suppressing volatilization of the lithium element, by firing at a lower temperature (900 ° C. or lower), a single phase A solid electrolyte having a perovskite structure or a single-phase garnet structure can be obtained, which is preferable.
- composite oxides include lithium-titanium composite oxides (Li 2 TiO 3 , Li 4 Ti 5 O 12 , Li 2 Ti 3 O 7, etc.), lithium-zirconium composite oxides (Li 2 ZrO 3).
- the composite oxide is a particulate solid produced by a wet method or the like. Is preferred.
- a method for obtaining a solid electrolyte precursor by a liquid phase mixing method for example, a method for obtaining a slurry or solution containing a solid electrolyte precursor by dispersing or dissolving the precipitate and a lithium compound in a solvent and mixing them.
- the solvent and the dispersion medium used in the liquid phase mixing method include water.
- Examples of a method for obtaining a solid electrolyte precursor by a liquid phase mixing method include a method of performing hydrothermal treatment after mixing (hydrothermal method).
- a solid electrolyte precursor obtained by a hydrothermal method is preferable because a solid electrolyte having a single-phase perovskite structure or a single-phase garnet structure can be obtained by firing at a lower temperature (900 ° C. or lower).
- the hydrothermal method refers to a compound synthesis method or crystal growth method performed in the presence of hot water of high temperature and high pressure, and a chemical reaction that does not occur in an aqueous solution at normal temperature and pressure may proceed.
- a lithium element is added to a precipitate containing a Group 3 element oxide and / or hydroxide and a Group 4 and / or Group 5 element oxide and / or hydroxide.
- aqueous solution containing it By adding an aqueous solution containing it and performing a high-temperature and high-pressure treatment, lithium element which is water-soluble at room temperature and normal pressure can be taken into the precipitate, and the solid electrolyte precursor can be separated by separating the precipitate from the aqueous solution. can get.
- water is used as a solvent in the hydrothermal method, the same effect can be expected by a method (solvothermal method) using a solvent other than water (for example, an organic solvent).
- lithium element By making the aqueous solution strongly alkaline during the hydrothermal method, lithium element can be incorporated into the precipitate obtained in the simultaneous precipitation treatment step under milder treatment conditions.
- Lithium hydroxide may be used as a lithium source in the hydrothermal method, and an alkali component may be further added. However, the added alkaline component may be taken into the precipitate.
- Alkaline components whose cations are larger than ammonium ions, such as TMAH (tetramethylammonium hydroxide) and cesium hydroxide, are less likely to be taken into the precipitate, and are preferably lithiated by a hydrothermal method.
- Examples of the method for obtaining the solid electrolyte precursor by the solid phase mixing method include a method for obtaining the solid electrolyte precursor by mixing the precipitate and the lithium compound using a ball mill, a mortar or the like.
- the solid electrolyte precursor can be formed by at least the aqueous solution preparation step, the simultaneous precipitation treatment step, and the solid electrolyte precursor preparation step.
- the obtained solid electrolyte precursor may be once dispersed in a dispersion medium and used for spray drying, granulation, or the like.
- a compound that improves the properties of the solid electrolyte such as a sintering aid, is added between the aqueous solution preparation process and the solid electrolyte precursor preparation process or before the manufactured solid electrolyte precursor is fired. It may be added to the body or its raw materials.
- the manufacturing method of the solid electrolyte based on this invention includes the baking process which obtains a solid electrolyte by baking the solid electrolyte precursor which concerns on this invention at the temperature of 1000 degrees C or less.
- a solid electrolyte having a single-phase perovskite structure or a single-phase garnet structure containing a lithium element, a Group 3 element, and a Group 4 and / or Group 5 element can be synthesized.
- Specific examples of the solid electrolyte include those exemplified in the description of the solid electrolyte precursor.
- the firing method is not particularly limited, and for example, a known firing method such as solid phase heating firing, spray drying, or microwave firing can be applied.
- the firing temperature is usually 1000 ° C. or lower, preferably 600 to 1000 ° C.
- the method for producing a solid electrolyte-electrode active material composite according to the present invention comprises a contact step of contacting the solid electrolyte precursor according to the present invention with an electrode active material or an electrode active material precursor that becomes an electrode active material by firing. And a firing step of firing the solid electrolyte precursor and the electrode active material or the electrode active material precursor at a temperature of 1000 ° C. or less to obtain a solid electrolyte-electrode active material composite.
- the method for contacting the solid electrolyte precursor with the electrode active material or the electrode active material precursor is not particularly limited.
- Each of the solid electrolyte precursor, the electrode active material, and the electrode active material precursor may be used alone or in combination of two or more.
- the negative electrode active material for example, carbon (graphite, hard carbon, etc.) and lithiated products thereof; metals that form an alloy with lithium (magnesium, calcium, aluminum, silicon, germanium, tin, lead, Bismuth, antimony, silver, zinc, etc.) and lithium alloys thereof; transition metal monoxides such as cobalt, nickel, iron, titanium; sulfides of transition metals such as cobalt, nickel, copper; nickel, iron, cobalt, etc.
- Transition metal phosphides lithium nitride and lithium-transition metal composite nitrides; metal oxides such as TiO 2 , Nb 2 O 5 , WO 2 , MoO 2 , Li 4 Ti 5 O 12 , Li 2 Ti 3 O 7 Things.
- the negative electrode active material precursor that becomes a negative electrode active material by firing for example, a simple substance of an element constituting the negative electrode active material and its oxide, hydroxide, chloride, carbonate, Examples thereof include nitrates and complex salts having organic ligands.
- the positive electrode active material precursor that becomes a positive electrode active material by firing for example, a simple substance of elements constituting the positive electrode active material and its oxide, hydroxide, chloride, carbonate, Examples thereof include nitrates and complex salts having organic ligands.
- the firing step firing is performed in the same manner as described above for the method for producing the solid electrolyte. Thereby, a solid electrolyte-electrode active material complex can be obtained.
- the firing temperature is preferably as low as possible, and more preferably 900 ° C. or lower (eg, 600 to 900 ° C.).
- Example 1 A solution obtained by dissolving lanthanum hydroxide in hydrochloric acid was mixed with an aqueous titanium tetrachloride solution to prepare an aqueous solution having an La concentration of 0.98 mmol / g, a Ti concentration of 1.75 mmol / g, and a Cl concentration of 7.50 mmol / g.
- This aqueous solution was transparent and did not produce a precipitate when left at room temperature.
- 10 g of this aqueous solution was dropped little by little into 10 g of 28% by mass ammonia water, a precipitate was formed.
- the base amount is 164 mmol base equivalent (that is, a counter anion of a Group 3 element-containing cation, a Group 4 element-containing cation, and a Group 5 element-containing cation (excluding oxide ions and hydroxide ions). ) Is a chloride ion (75.0 mmol), and the base equivalent corresponds to 2.19 times the molar equivalent of the counter anion). After the precipitate is separated, washed with water and mechanically crushed, 0.21 g of lithium carbonate (2.8 mmol, 5.6 mmol in terms of lithium) is added, kneaded using a mortar, and dried at 200 ° C. As a result, a solid electrolyte precursor was obtained.
- base equivalent that is, a counter anion of a Group 3 element-containing cation, a Group 4 element-containing cation, and a Group 5 element-containing cation (excluding oxide ions and hydroxide ions).
- This precursor was fired at 950 ° C. for 5 hours to obtain a fired body (solid electrolyte).
- This fired body was a crystal having a single-phase perovskite structure.
- decrease rate at the time of baking was 26 mass%.
- Example 2 The precipitate obtained in the same manner as in Example 1 was separated, washed with water and mechanically disintegrated, then 1.12 mL of 5N lithium hydroxide aqueous solution (corresponding to 5.6 mmol of lithium hydroxide) was added, and water was added. The mixture was further stirred for 15 hours. After solidification by heating, the solid content was centrifuged and dried at 200 ° C. to obtain a solid electrolyte precursor. The total content of carbon and nitrogen contained in this precursor was 1.2% by mass. This precursor was fired at 950 ° C. for 5 hours to obtain a fired body (solid electrolyte). This fired body was a crystal having a single-phase perovskite structure. Moreover, the mass decreasing rate at the time of baking was 22 mass%. For the solid electrolyte precursor and the fired body (solid electrolyte), the production conditions are shown in Table 1, and the quality evaluation results are shown in Table 2.
- Example 3 The precipitate obtained in the same manner as in Example 1 was separated, washed with water and mechanically crushed, then placed in a pressure vessel and 1.12 mL of 5N lithium hydroxide aqueous solution (corresponding to 5.6 mmol of lithium hydroxide). And 30 g of 25 mass% TMAH (tetramethylammonium hydroxide) aqueous solution was added. The pressure vessel was sealed and subjected to hydrothermal treatment by heating in an oil bath set at 180 ° C. for 17 hours. After allowing to cool, the precipitate was separated, washed with water, and dried at 200 ° C. to obtain a solid electrolyte precursor. The total content of carbon and nitrogen contained in this precursor was 0.8% by mass.
- TMAH tetramethylammonium hydroxide
- This precursor was fired at 850 ° C. for 12 hours to obtain a fired body (solid electrolyte).
- This fired body was a crystal having a single-phase perovskite structure.
- decrease rate at the time of baking was 8.9 mass%.
- the production conditions are shown in Table 1, and the quality evaluation results are shown in Table 2.
- Example 4 In the hydrothermal treatment, a solid solid electrolyte was obtained in the same manner as in Example 3 except that 30 g of 1.8 mmol / g cesium hydroxide aqueous solution was used instead of 30 g of 25 mass% TMAH (tetramethylammonium hydroxide) aqueous solution. A precursor was obtained. The total content of carbon and nitrogen contained in this precursor was 1.2% by mass. This precursor was fired at 850 ° C. for 12 hours to obtain a fired body (solid electrolyte). This fired body was a crystal having a single-phase perovskite structure. Moreover, the mass reduction
- the production conditions are shown in Table 1, and the quality evaluation results are shown in Table 2.
- Example 5 Lanthanum chloride heptahydrate and zirconium oxychloride octahydrate were dissolved in cold water to prepare an aqueous solution having a La concentration of 0.83 mmol / g, a Zr concentration of 0.56 mmol / g, and a Cl concentration of 3.61 mmol / g. This aqueous solution was transparent and did not produce a precipitate upon standing. When 10 g of this aqueous solution was sprayed into 25 mL of 4N aqueous lithium hydroxide, a precipitate was formed.
- the base amount is 100 mmol base equivalent (that is, a counter anion of a Group 3 element-containing cation, a Group 4 element-containing cation, and a Group 5 element-containing cation (excluding oxide ions and hydroxide ions). ) Is a chloride ion (36.1 mmol), and the above base equivalent corresponds to 2.77 times the molar equivalent of the counter anion).
- the precipitate was separated, washed with water and dried at 200 ° C., then 0.82 g (19.6 mmol) of solid lithium hydroxide monohydrate was added, and the mixture was ground and mixed in a mortar. A solid electrolyte precursor was obtained. The total content of carbon and nitrogen contained in this precursor was 4.2% by mass.
- This precursor was fired at 700 ° C. for 9 hours to obtain a fired body (solid electrolyte).
- This fired body was a crystal having a single-phase garnet structure.
- decrease rate at the time of baking was 29 mass%.
- the production conditions are shown in Table 1, and the quality evaluation results are shown in Table 2.
- Example 6 When 10 g of an aqueous solution prepared in the same manner as in Example 5 was sprayed into 10 g of 28% by mass ammonia water, a precipitate was formed.
- the base amount is 164 mmol base equivalent (that is, a counter anion of a Group 3 element-containing cation, a Group 4 element-containing cation, and a Group 5 element-containing cation (excluding oxide ions and hydroxide ions). ) Is chloride ion (36.1 mmol), and the base equivalent is 4.54 times the molar equivalent of the counter anion).
- Example 7 (Precipitation generation) A solution obtained by dissolving lanthanum chloride heptahydrate in water is mixed with an aqueous titanium tetrachloride solution, and an aqueous solution having an La concentration of 0.98 mmol / g, a Ti concentration of 1.47 mmol / g, and a Cl concentration of 6.77 mmol / g. Prepared. This aqueous solution was transparent and did not produce a precipitate when left at room temperature. When 50 g of this aqueous solution was added dropwise to 50 g of 28% by mass ammonia water little by little, a precipitate was formed.
- the base amount is 820 mmol base equivalent (that is, a counter anion of a Group 3 element-containing cation, a Group 4 element-containing cation, and a Group 5 element-containing cation (excluding oxide ions and hydroxide ions). ) Is a chloride ion (338.5 mmol), and the above base equivalent is 2.42 times the molar equivalent of the counter anion). The precipitate was separated, washed with water and mechanically crushed.
- base equivalent that is, a counter anion of a Group 3 element-containing cation, a Group 4 element-containing cation, and a Group 5 element-containing cation (excluding oxide ions and hydroxide ions).
- This precursor was fired at 950 ° C. for 5 hours to obtain a fired body (solid electrolyte).
- This fired body was a crystal having a single-phase perovskite structure.
- decrease rate at the time of baking was 68 mass%.
- the production conditions are shown in Table 1, and the quality evaluation results are shown in Table 2.
- the solid-state solid electrolyte precursor (gel) was obtained.
- the total content of carbon and nitrogen contained in this precursor was 11.5% by mass.
- This precursor was fired at 950 ° C. for 5 hours to obtain a fired body (solid electrolyte).
- This fired body contained an impurity phase such as lanthanum oxide or lanthanum hydroxide in addition to the target garnet phase, and a single-phase garnet structure could not be obtained.
- decrease rate at the time of baking was 47 mass%.
- the production conditions are shown in Table 1, and the quality evaluation results are shown in Table 2.
- the pH of the aqueous solution for preparing the precursor was approximately 2 or lower.
- the basic aqueous solution used in the simultaneous precipitation treatment step was strongly basic, and the mixed solution was basic when the simultaneous precipitation treatment was completed (neutral to basic lanthanum hydroxide was precipitated).
- the molar equivalent of the base in the basic aqueous solution is the counter anion of the Group 3 element-containing cation, Group 4 element-containing cation, and Group 5 element-containing cation in the aqueous solution for precursor preparation (however, the oxide ion) And the molar equivalent of (except hydroxide ions).
- the amount added to the system in the simultaneous precipitation treatment step is 73.5 mmol. Since 14.0 mmol is contained in the lithium-titanium composite oxide, which is a lithium compound, the precursor contains a total of 87.5 mmol.
- the solid electrolyte precursors of the examples prepared through the simultaneous precipitation treatment step had a total content of carbon element and nitrogen element of 10% by mass or less.
- the mass reduction rate when this solid electrolyte precursor was baked was 40% by mass or less.
- the crystal structure of the obtained solid electrolyte was a single-phase perovskite structure or a single-phase garnet structure. Furthermore, no cracks were observed on the surface of the fired body obtained by molding the solid electrolyte precursor.
- the firing temperature for obtaining the solid electrolyte exceeded 1000 ° C.
- the obtained solid electrolyte contained an impurity phase, and a single-phase perovskite structure or a single-phase garnet structure was not obtained.
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Abstract
Description
固相法は、例えば、第3族元素、第4族又は第5族元素、及びリチウム元素の各々の酸化物、水酸化物、及び/又は塩類を化学量論比程度で混合し、焼成、焼結する合成法である。
本発明に係る固体電解質前駆体は、リチウム元素と、第3族元素と、第4族及び/又は第5族元素とを含む、単相ペロブスカイト構造又は単相ガーネット構造の固体電解質を、1000℃以下の温度での焼成により合成するためのものであって、リチウム元素と、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを含む。本発明に係る固体電解質前駆体から合成される固体電解質は、酸化物系リチウムイオン伝導性固体電解質であり、具体例としては、LLTO(Li3xLa2/3-xTiO3)等の、ペロブスカイト構造を有する固体電解質、LLZO(Li7La3Zr2O12)、LLZNb(Li6.75La3Zr1.75Nb0.25O12)、Li5La3M2O12(M=Nb,Ta)等の、ガーネット構造を有する固体電解質が挙げられる。
質量減少率(質量%)=(固体電解質前駆体の質量-固体電解質の質量)×100/固体電解質前駆体の質量
で計算される質量減少率が40質量%以下であることが好ましい。上記質量減少率が40質量%以下であると、得られる固体電解質は、更に緻密となりやすいため、リチウムイオン伝導性がより向上したものとなりやすく、また、クラックが更に生じにくいため、歩留まりがより向上しやすい。
本発明に係る固体電解質前駆体は、どのような製造方法で得られたものであってもよいが、例えば、後述の製造方法で得られるものであることが好ましい。また、本発明に係る固体電解質前駆体の形態は特に限定されず、固体状であっても水溶液等の溶液であってもスラリーであってもよい。
本発明に係る、固体電解質前駆体の製造方法は、リチウム元素と、第3族元素と、第4族及び/又は第5族元素とを含む、単相ペロブスカイト構造又は単相ガーネット構造の固体電解質を、1000℃以下の温度での焼成により合成するための固体電解質前駆体の製造方法であり、第3族元素含有カチオンと、第4族元素含有カチオン及び/又は第5族元素含有カチオンとを含む水溶液を調製する水溶液調製工程と、上記水溶液調製工程で得た上記水溶液と塩基性水溶液とを混合することにより、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを沈殿させて沈殿物を得る同時沈殿処理工程と、上記同時沈殿処理工程で得た上記沈殿物と、リチウム化合物とを混合して固体電解質前駆体を得る固体電解質前駆体作製工程とを含むものである。上記製造方法は、液相合成法を利用して固体電解質前駆体を得るものである。液相合成法を適用する利点は、混合溶液状態を経ることにより、固体電解質前駆体を構成する金属元素等を原子レベルで均一に混合できる点にある。
以下、本発明に係る、固体電解質前駆体の製造方法に含まれる各工程について詳細に説明する。
水溶液調製工程では、第3族元素含有カチオンと、第4族元素含有カチオン及び/又は第5族元素含有カチオンとを含む水溶液を調製する。第3族元素含有カチオンとしては、例えば、La3+等の第3族元素カチオンが挙げられる。第4族元素含有カチオンとしては、例えば、Ti4+、Zr4+等の第4族元素カチオンが挙げられる。第5族元素含有カチオンとしては、例えば、Nb5+、Ta5+等の第5族元素カチオンが挙げられる。第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの各々は、単独で用いても2種以上を併用してもよい。また、第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの各々は、水、アンモニア、酸化物イオン、水酸化物イオンや後述の対アニオン等を配位子として、錯体を形成していてもよい。
同時沈殿処理工程では、水溶液調製工程で得た水溶液と塩基性水溶液とを混合することにより、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを沈殿させて沈殿物を得る。水溶液調製工程で得た水溶液と塩基性水溶液とを混合する方法としては、特に限定されず、例えば、水溶液調製工程で得た水溶液を塩基性水溶液に滴下又は噴霧する方法が挙げられる。
固体電解質前駆体作製工程では、同時沈殿処理工程で得た沈殿物と、リチウム化合物とを混合して固体電解質前駆体を得る。上記沈殿物とリチウム化合物とを混合する方法としては、特に限定されず、例えば、固相混合法、液相混合法、気相混合法(例えば、蒸着等)が挙げられ、液相混合法により固体電解質前駆体を得る方法としては、後述するように、混合後に水熱処理を行う方法(水熱法)やソルボサーマル法であってもよい。仕込み比の制御が容易であることから、固相混合法又は液相混合法が好ましい。
本発明に係る、固体電解質の製造方法は、本発明に係る固体電解質前駆体を1000℃以下の温度で焼成することにより固体電解質を得る焼成工程を含むものである。この製造方法により、リチウム元素と、第3族元素と、第4族及び/又は第5族元素とを含む、単相ペロブスカイト構造又は単相ガーネット構造の固体電解質を合成することができる。固体電解質の具体例としては、固体電解質前駆体の説明中で例示したものが挙げられる。
本発明に係る、固体電解質-電極活物質複合体の製造方法は、本発明に係る固体電解質前駆体と、電極活物質又は焼成により電極活物質になる電極活物質前駆体とを接触させる接触工程と、上記固体電解質前駆体と上記電極活物質又は上記電極活物質前駆体とを1000℃以下の温度で焼成することにより固体電解質-電極活物質複合体を得る焼成工程とを含むものである。
接触工程において、上記固体電解質前駆体と上記電極活物質又は上記電極活物質前駆体との接触方法は、特に限定されない。例えば、粉末、溶液等の形態で、上記固体電解質前駆体と上記電極活物質又は上記電極活物質前駆体とを混合する方法や、上記固体電解質前駆体を含む成形体と上記電極活物質又は上記電極活物質前駆体を含む成形体とを面状に接触させる方法等が挙げられる。上記固体電解質前駆体、上記電極活物質、及び上記電極活物質前駆体の各々は、単独で用いても2種以上を併用してもよい。
焼成工程においては、固体電解質の製造方法について上述したのと同様にして、焼成を行う。これにより、固体電解質-電極活物質複合体を得ることができる。なお、電極活物質の分解を抑制する観点から、焼成温度は低いほど好ましく、900℃以下(例えば、600~900℃)の温度がより好ましい。
酸素循環燃焼-TCD法測定により、固体電解質前駆体中に含まれる炭素元素及び窒素元素の合計の含有量を測定した。
(2)焼成時の質量減少率
焼成前の固体電解質前駆体の質量と焼成後に得られた固体電解質の質量とを測定し、以下の式から質量減少率を算出した。
質量減少率(質量%)=(固体電解質前駆体質量-固体電解質質量)×100/固体電解質前駆体質量
(3)固体電解質の結晶構造解析
粉末X線回折測定により、固体電解質の結晶構造を同定した。
(4)クラックの有無
固体電解質前駆体を成形し、各実施例及び比較例に記載の手順で焼成を行い、13mmφ×0.5mm厚の焼成体を作製した。この焼成体の表面を目視で観察し、クラックの有無を確認した。
水酸化ランタンを塩酸に溶解させて得た溶液を四塩化チタン水溶液と混合し、La濃度0.98mmol/g、Ti濃度1.75mmol/g、Cl濃度7.50mmol/gの水溶液を調製した。この水溶液は透明であり、室温で放置しても沈殿を生成しなかった。この水溶液10gを28質量%アンモニア水10g中に少量ずつ滴下すると沈殿が生成した。なお、塩基量は164mmol塩基当量である(即ち、第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの対アニオン(但し、酸化物イオン及び水酸化物イオンを除く)は塩化物イオン(75.0mmol)であり、上記塩基当量は対アニオンのモル当量の2.19倍に相当する)。
沈殿を分離し、水で洗浄し、機械的に解砕した後、炭酸リチウム0.21g(2.8mmol、リチウム換算で5.6mmol)を加え、乳鉢を用いて混練し、200℃で乾燥させることで固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は2.2質量%であった。
この前駆体を950℃で5時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のペロブスカイト構造を有する結晶体であった。また、焼成時の質量減少率は26質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
実施例1と同様の方法で得た沈殿を分離し、水で洗浄し、機械的に解砕した後、5N水酸化リチウム水溶液1.12mL(水酸化リチウム5.6mmol相当)を加え、水を追加して15時間攪拌した。加熱濃縮してから固形分を遠心分離し、200℃で乾燥させることで固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は1.2質量%であった。
この前駆体を950℃で5時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のペロブスカイト構造を有する結晶体であった。また、焼成時の質量減少率は22質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
実施例1と同様の方法で得た沈殿を分離し、水で洗浄し、機械的に解砕した後、耐圧容器に入れ、5N水酸化リチウム水溶液1.12mL(水酸化リチウム5.6mmol相当)及び25質量%TMAH(テトラメチルアンモニウムヒドロキシド)水溶液30gを加えた。上記耐圧容器を密封し、180℃に設定したオイルバスで17時間加熱して水熱処理を行った。放冷後、沈殿を分離し、水で洗浄し、200℃で乾燥させることで固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は0.8質量%であった。
この前駆体を850℃で12時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のペロブスカイト構造を有する結晶体であった。また、焼成時の質量減少率は8.9質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
水熱処理において、25質量%TMAH(テトラメチルアンモニウムヒドロキシド)水溶液30gの代わりに1.8mmol/g水酸化セシウム水溶液30gを用いたこと以外は、実施例3と同一の方法で固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は1.2質量%であった。
この前駆体を850℃で12時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のペロブスカイト構造を有する結晶体であった。また、焼成時の質量減少率は10.5質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
塩化ランタン7水和物とオキシ塩化ジルコニウム8水和物を冷水に溶解させて、La濃度0.83mmol/g、Zr濃度0.56mmol/g、Cl濃度3.61mmol/gの水溶液を調製した。この水溶液は透明であり、放置しても沈殿を生成しなかった。この水溶液10gを4Nの水酸化リチウム水溶液25mL中に噴霧すると沈殿が生成した。なお、塩基量は100mmol塩基当量である(即ち、第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの対アニオン(但し、酸化物イオンと水酸化物イオンを除く)は塩化物イオン(36.1mmol)であり、上記塩基当量は対アニオンのモル当量の2.77倍に相当する)。
沈殿を分離し、水で洗浄し、200℃で乾燥させた後、固体の水酸化リチウム1水和物0.82g(19.6mmol)を添加し、乳鉢ですりつぶして混合することで固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は4.2質量%であった。
この前駆体を700℃で9時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のガーネット構造を有する結晶体であった。また、焼成時の質量減少率は29質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
実施例5と同様の方法で調製した水溶液10gを28質量%アンモニア水10g中に噴霧すると沈殿が生成した。なお、塩基量は164mmol塩基当量である(即ち、第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの対アニオン(但し、酸化物イオン及び水酸化物イオンを除く)は塩化物イオン(36.1mmol)であり、上記塩基当量は対アニオンのモル当量の4.54倍に相当する)。
沈殿を分離し、水で洗浄し、200℃で乾燥させた後、固体の炭酸リチウム0.72g(9.8mmol、リチウム換算で19.6mmol)を添加し、乳鉢ですりつぶして混合することで固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は4.5質量%であった。
この前駆体を950℃で5時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のガーネット構造を有する結晶体であった。また、焼成時の質量減少率は36質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
(沈殿の生成)
塩化ランタン7水和物を水に溶解させて得た溶液を四塩化チタン水溶液と混合し、La濃度0.98mmol/g、Ti濃度1.47mmol/g、Cl濃度6.77mmol/gの水溶液を調製した。この水溶液は透明であり、室温で放置しても沈殿を生成しなかった。この水溶液50gを28質量%アンモニア水50g中に少量ずつ滴下すると沈殿が生成した。なお、塩基量は820mmol塩基当量である(即ち、第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの対アニオン(但し、酸化物イオン及び水酸化物イオンを除く)は塩化物イオン(338.5mmol)であり、上記塩基当量は対アニオンのモル当量の2.42倍に相当する)。沈殿を分離し、水で洗浄し、機械的に解砕した。
(リチウム-チタン複合酸化物の生成)
Ti濃度3.5mmol/g、Cl濃度9.1mmol/gの四塩化チタン水溶液4.0gを28質量%アンモニア水5.0g中に滴下して生成した固形物を分離し、水で洗浄し、機械的に解砕した後、耐圧容器に入れ、5N水酸化リチウム水溶液5.6mL(水酸化リチウム28.0mmol相当)を加えた。上記耐圧容器を密封し、180℃に設定したオイルバスで15時間加熱して水熱処理を行い、固形分を分離することで固体状のリチウム-チタン複合酸化物を得た。
(固体電解質前駆体の作製)
上記の沈殿と上記のリチウム-チタン複合酸化物とを遊星ボールミルを用いて混練し、200℃で乾燥させることで固体状の固体電解質前駆体を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は1.2質量%であった。
(固体電解質の作製)
この前駆体を850℃で12時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のペロブスカイト構造を有する結晶体であった。また、焼成時の質量減少率は16質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
固体の、水酸化ランタン、炭酸リチウム、及び二酸化チタンをLa:Li:Ti=0.56:0.32:1のモル比で混合し、900℃、12時間の予備焼成を行った後に再び乳鉢ですりつぶして混合し、1050℃、12時間の焼成を行った。得られた焼成体は目的とするペロブスカイト相の他に、酸化ランタン、チタン酸リチウム、チタン酸ランタン等の不純物相を含んでおり、単相のペロブスカイト構造は得られなかった。この焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
固体の、水酸化ランタン、炭酸リチウム、及び二酸化ジルコニウムをLa:Li:Zr=3:7:2のモル比で混合し、900℃、12時間の予備焼成を行った後に再び乳鉢ですりつぶして混合し、1050℃、12時間の焼成を行った。得られた焼成体は目的とするガーネット相の他に、酸化ランタン、二酸化ジルコニウム、ジルコン酸リチウム等の不純物相を含んでおり、単相のガーネット構造は得られなかった。この焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
酢酸リチウムと酢酸ランタン1.5水和物とチタン含有率5質量%の乳酸チタン水溶液と水とを混合し、Li濃度0.14mmol/g、La濃度0.25mmol/g、Ti濃度0.44mmol/gの水溶液(ゾル)を調製した。この水溶液は黄色透明であり、沈殿物は観察されなかった。この水溶液10gを攪拌しながら120℃で8時間加熱濃縮し、更に、オーブンに移して200℃で乾燥させることで固体状の固体電解質前駆体(ゲル)を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は32質量%であった。
この前駆体を950℃で5時間焼成し、焼成体(固体電解質)を得た。この焼成体は単相のペロブスカイト構造を有する結晶体であった。また、焼成時の質量減少率は68質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
硝酸リチウムと硝酸ランタン6水和物とジルコニウム含有率72.5質量%のジルコニウムプロポキシド溶液(溶媒:1-プロパノール)とエタノール及びアセト酢酸エチルの混合物(モル比50:1.6)とを混合し、Li濃度1.47mmol/g、La濃度0.57mmol/g、Zr濃度0.39mmol/gの溶液(ゾル)を調製した。この溶液20gを攪拝しながら80℃で12時間加熱した後、150℃で5時間加熱濃縮を行った。更に、オーブンに移して200℃で乾燥させることで固体状の固体電解質前駆体(ゲル)を得た。この前駆体中に含まれる炭素元素及び窒素元素の合計の含有量は11.5質量%であった。
この前駆体を950℃で5時間焼成し、焼成体(固体電解質)を得た。この焼成体は目的とするガーネット相の他に、酸化ランタン、水酸化ランタン等の不純物相を含んでおり、単相のガーネット構造は得られなかった。また、焼成時の質量減少率は47質量%であった。上記固体電解質前駆体及び上記焼成体(固体電解質)について、作製条件を表1に、品質評価結果を表2に示す。
*2 同時沈殿処理工程で用いる塩基性水溶液は、強塩基性であり、同時沈殿処理が完了した時点で混合液は塩基性であった(中性~塩基性で水酸化ランタンが沈殿する)。
*3 塩基性水溶液の塩基のモル当量は、前駆体作製用の水溶液中の第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの対アニオン(但し、酸化物イオン及び水酸化物イオンを除く)のモル当量より多い。
*4 同時沈殿処理工程で系に加えた量は73.5mmolである。リチウム化合物であるリチウム-チタン複合酸化物中に14.0mmol含まれているため、前駆体には合計で87.5mmol含まれている。
Claims (14)
- リチウム元素と、第3族元素と、第4族及び/又は第5族元素とを含む、単相ペロブスカイト構造又は単相ガーネット構造の固体電解質を、1000℃以下の温度での焼成により合成するための固体電解質前駆体であって、
リチウム元素と、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを含む固体電解質前駆体。 - 前記固体電解質前駆体中の炭素元素及び窒素元素の合計の含有量が10質量%以下である請求項1に記載の固体電解質前駆体。
- 1000℃以下の温度で前記固体電解質前駆体を焼成して前記固体電解質を得るときに、下記式
質量減少率(質量%)=(固体電解質前駆体の質量-固体電解質の質量)×100/固体電解質前駆体の質量
で計算される質量減少率が40質量%以下である請求項1又は2に記載の固体電解質前駆体。 - 前記第3族元素が、イットリウム、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユーロピウム、及びガドリニウムからなる群より選ばれる少なくとも1種類の元素であり、前記第4族及び/又は第5族元素が、チタン、ジルコニウム、バナジウム、ニオブ、及びタンタルからなる群より選ばれる少なくとも1種類の元素である請求項1~3のいずれか1項に記載の固体電解質前駆体。
- 請求項1~4のいずれか1項に記載の固体電解質前駆体を1000℃以下の温度で焼成することにより固体電解質を得る焼成工程を含む、固体電解質の製造方法。
- 請求項1~4のいずれか1項に記載の固体電解質前駆体と、電極活物質又は焼成により電極活物質になる電極活物質前駆体とを接触させる接触工程と、前記固体電解質前駆体と前記電極活物質又は前記電極活物質前駆体とを1000℃以下の温度で焼成することにより固体電解質-電極活物質複合体を得る焼成工程とを含む、固体電解質-電極活物質複合体の製造方法。
- リチウム元素と、第3族元素と、第4族及び/又は第5族元素とを含む、単相ペロブスカイト構造又は単相ガーネット構造の固体電解質を、1000℃以下の温度での焼成により合成するための固体電解質前駆体の製造方法であり、
第3族元素含有カチオンと、第4族元素含有カチオン及び/又は第5族元素含有カチオンとを含む水溶液を調製する水溶液調製工程と、
前記水溶液調製工程で得た水溶液と塩基性水溶液とを混合することにより、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを沈殿させて沈殿物を得る同時沈殿処理工程と、
前記同時沈殿処理工程で得た沈殿物と、リチウム化合物とを混合して固体電解質前駆体を得る固体電解質前駆体作製工程とを含む、固体電解質前駆体の製造方法。 - 前記固体電解質前駆体中の炭素元素及び窒素元素の合計の含有量が10質量%以下である請求項7に記載の固体電解質前駆体の製造方法。
- 前記同時沈殿処理工程で用いる塩基性水溶液の塩基のモル当量が、前記水溶液調製工程で得た水溶液中の第3族元素含有カチオン、第4族元素含有カチオン、及び第5族元素含有カチオンの対アニオン(但し、酸化物イオン及び水酸化物イオンを除く)のモル当量より多い請求項7又は8に記載の固体電解質前駆体の製造方法。
- 前記水溶液調製工程で得た水溶液のpHが7未満であり、前記同時沈殿処理工程で用いる塩基性水溶液のpHが8以上である請求項7~9のいずれか1項に記載の固体電解質前駆体の製造方法。
- 前記固体電解質前駆体作製工程において、前記沈殿物と混合するリチウム化合物が、リチウムとリチウム以外の固体電解質前駆体構成元素との複合体である請求項7~10のいずれか1項に記載の固体電解質前駆体の製造方法。
- 前記固体電解質前駆体作製工程において、前記沈殿物と前記リチウム化合物と溶媒とを含む混合物を1気圧よりも高い圧力の下で加熱する請求項7~11のいずれか1項に記載の固体電解質前駆体の製造方法。
- 第3族元素含有カチオンと、第4族元素含有カチオン及び/又は第5族元素含有カチオンとを含む水溶液を調製する水溶液調製工程と、
前記水溶液調製工程で得た水溶液と塩基性水溶液とを混合することにより、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを沈殿させて沈殿物を得る同時沈殿処理工程と、
前記同時沈殿処理工程で得た沈殿物と、リチウム化合物とを混合して固体電解質前駆体を得る固体電解質前駆体作製工程と、
前記固体電解質前駆体作製工程で得た固体電解質前駆体を1000℃以下の温度で焼成することにより固体電解質を得る焼成工程とを含む、固体電解質の製造方法。 - 第3族元素含有カチオンと、第4族元素含有カチオン及び/又は第5族元素含有カチオンとを含む水溶液を調製する水溶液調製工程と、
前記水溶液調製工程で得た水溶液と塩基性水溶液とを混合することにより、第3族元素の酸化物及び/又は水酸化物と、第4族及び/又は第5族元素の酸化物及び/又は水酸化物とを沈殿させて沈殿物を得る同時沈殿処理工程と、
前記同時沈殿処理工程で得た沈殿物と、リチウム化合物とを混合して固体電解質前駆体を得る固体電解質前駆体作製工程と、
前記固体電解質前駆体作製工程で得た固体電解質前駆体と、電極活物質又は焼成により電極活物質になる電極活物質前駆体とを接触させる接触工程と、
前記固体電解質前駆体と前記電極活物質又は前記電極活物質前駆体とを1000℃以下の温度で焼成することにより固体電解質-電極活物質複合体を得る焼成工程とを含む、固体電解質-電極活物質複合体の製造方法。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019046559A (ja) * | 2017-08-30 | 2019-03-22 | Fdk株式会社 | 固体電解質の製造方法、全固体電池用電極材料の製造方法、および全固体電池の製造方法 |
JP2021514107A (ja) * | 2018-04-05 | 2021-06-03 | セブン キング エナージー カンパニー リミテッドSeven King Energy Co.,Ltd. | リチウム二次電池のためのセラミックス固体電解質の製造方法 |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101568468B1 (ko) * | 2013-07-04 | 2015-11-11 | 한국생산기술연구원 | 전고체 리튬이차전지용 고체 전해질 및 그 제조방법 |
JP6456241B2 (ja) * | 2014-05-26 | 2019-01-23 | 国立大学法人 名古屋工業大学 | リチウム含有複合酸化物粉末の製造方法 |
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US10218032B2 (en) * | 2015-03-10 | 2019-02-26 | Tdk Corporation | Li-ion conductive oxide ceramic material including garnet-type or similar crystal structure |
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US10734674B2 (en) * | 2017-08-14 | 2020-08-04 | Thinika, Llc | Solid-state thin film hybrid electrochemical cell |
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US20210119251A1 (en) * | 2018-03-27 | 2021-04-22 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Ceramic powder, sintered body and battery |
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EP4129916A4 (en) * | 2020-03-31 | 2023-09-27 | Panasonic Intellectual Property Management Co., Ltd. | HALIDES PRODUCTION PROCESS |
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CN115799618B (zh) * | 2023-01-05 | 2023-06-16 | 河北光兴半导体技术有限公司 | 氧化物固态电解质及其制备方法和应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01294528A (ja) * | 1988-05-20 | 1989-11-28 | Mitsubishi Petrochem Co Ltd | Abo↓3型ペロブスカイト型酸化物の製法 |
JPH03199123A (ja) * | 1989-12-28 | 1991-08-30 | Osaka Titanium Co Ltd | ペロブスカイト型複合酸化物粉末の製造方法 |
JP2009206094A (ja) * | 2008-01-31 | 2009-09-10 | Ohara Inc | リチウムイオン二次電池の製造方法 |
WO2012063827A1 (ja) * | 2010-11-09 | 2012-05-18 | 株式会社村田製作所 | 全固体電池用スラリー、全固体電池用グリーンシート、全固体電池、および全固体電池用スラリーの製造方法 |
JP2012184138A (ja) * | 2011-03-04 | 2012-09-27 | Seiko Epson Corp | チタン酸リチウムランタン粒子の製造方法及びチタン酸リチウムランタン粒子 |
JP2012224520A (ja) * | 2011-04-21 | 2012-11-15 | Toyota Central R&D Labs Inc | ガーネット型リチウムイオン伝導性酸化物の製造方法及びガーネット型リチウムイオン伝導性酸化物 |
JP2013256435A (ja) * | 2012-05-14 | 2013-12-26 | Toyota Central R&D Labs Inc | ガーネット型リチウムイオン伝導性酸化物の製造方法 |
JP2014172812A (ja) * | 2013-03-12 | 2014-09-22 | Japan Fine Ceramics Center | リチウムイオン伝導性酸化物の製造方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6330365A (ja) * | 1986-07-23 | 1988-02-09 | 新日本製鐵株式会社 | Plzt透光性セラミツクスの製造法 |
JPH09219215A (ja) * | 1996-02-07 | 1997-08-19 | Japan Storage Battery Co Ltd | リチウムイオン電池 |
JP2003346895A (ja) | 2002-05-30 | 2003-12-05 | Fujitsu Ltd | 固体電解質の形成方法およびリチウム電池 |
JP4615339B2 (ja) * | 2005-03-16 | 2011-01-19 | 独立行政法人科学技術振興機構 | 多孔質固体電極及びそれを用いた全固体リチウム二次電池 |
DE102007030604A1 (de) * | 2007-07-02 | 2009-01-08 | Weppner, Werner, Prof. Dr. | Ionenleiter mit Granatstruktur |
EP2207227A1 (en) * | 2007-11-06 | 2010-07-14 | Panasonic Corporation | Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery comprising the same |
JP2009157524A (ja) | 2007-12-25 | 2009-07-16 | Duaxes Corp | ウィルス検出装置 |
JP5353255B2 (ja) | 2009-01-14 | 2013-11-27 | トヨタ自動車株式会社 | 固体電解質の前駆体溶液の調製方法及び固体電解質膜の製造方法 |
JP5638232B2 (ja) * | 2009-12-02 | 2014-12-10 | 住友金属鉱山株式会社 | 非水系電解質二次電池正極活物質用ニッケルコバルトマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 |
DE102010030197A1 (de) | 2010-06-17 | 2011-12-22 | Sb Limotive Company Ltd. | Lithium-Ionen-Zelle |
JP5731278B2 (ja) * | 2011-05-24 | 2015-06-10 | 株式会社オハラ | 全固体リチウムイオン電池 |
JP2013189325A (ja) * | 2012-03-12 | 2013-09-26 | Ngk Insulators Ltd | 圧電/電歪体膜の製造方法及びその製造に用いられる粉末組成物 |
CN103113107A (zh) * | 2013-02-28 | 2013-05-22 | 中国科学院上海硅酸盐研究所 | 一种制备陶瓷固态电解质的方法 |
-
2013
- 2013-11-01 JP JP2013228422A patent/JP6393974B2/ja active Active
-
2014
- 2014-10-14 CN CN201480058884.4A patent/CN105684095A/zh active Pending
- 2014-10-14 DE DE112014004983.2T patent/DE112014004983T5/de not_active Withdrawn
- 2014-10-14 US US15/032,432 patent/US20160293947A1/en not_active Abandoned
- 2014-10-14 WO PCT/JP2014/077297 patent/WO2015064351A1/ja active Application Filing
- 2014-10-14 KR KR1020167014412A patent/KR101787425B1/ko active IP Right Grant
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01294528A (ja) * | 1988-05-20 | 1989-11-28 | Mitsubishi Petrochem Co Ltd | Abo↓3型ペロブスカイト型酸化物の製法 |
JPH03199123A (ja) * | 1989-12-28 | 1991-08-30 | Osaka Titanium Co Ltd | ペロブスカイト型複合酸化物粉末の製造方法 |
JP2009206094A (ja) * | 2008-01-31 | 2009-09-10 | Ohara Inc | リチウムイオン二次電池の製造方法 |
WO2012063827A1 (ja) * | 2010-11-09 | 2012-05-18 | 株式会社村田製作所 | 全固体電池用スラリー、全固体電池用グリーンシート、全固体電池、および全固体電池用スラリーの製造方法 |
JP2012184138A (ja) * | 2011-03-04 | 2012-09-27 | Seiko Epson Corp | チタン酸リチウムランタン粒子の製造方法及びチタン酸リチウムランタン粒子 |
JP2012224520A (ja) * | 2011-04-21 | 2012-11-15 | Toyota Central R&D Labs Inc | ガーネット型リチウムイオン伝導性酸化物の製造方法及びガーネット型リチウムイオン伝導性酸化物 |
JP2013256435A (ja) * | 2012-05-14 | 2013-12-26 | Toyota Central R&D Labs Inc | ガーネット型リチウムイオン伝導性酸化物の製造方法 |
JP2014172812A (ja) * | 2013-03-12 | 2014-09-22 | Japan Fine Ceramics Center | リチウムイオン伝導性酸化物の製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019046559A (ja) * | 2017-08-30 | 2019-03-22 | Fdk株式会社 | 固体電解質の製造方法、全固体電池用電極材料の製造方法、および全固体電池の製造方法 |
JP2021514107A (ja) * | 2018-04-05 | 2021-06-03 | セブン キング エナージー カンパニー リミテッドSeven King Energy Co.,Ltd. | リチウム二次電池のためのセラミックス固体電解質の製造方法 |
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