WO2016157751A1 - リチウムイオン伝導体、固体電解質層、電極、電池および電子機器 - Google Patents
リチウムイオン伝導体、固体電解質層、電極、電池および電子機器 Download PDFInfo
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- WO2016157751A1 WO2016157751A1 PCT/JP2016/001342 JP2016001342W WO2016157751A1 WO 2016157751 A1 WO2016157751 A1 WO 2016157751A1 JP 2016001342 W JP2016001342 W JP 2016001342W WO 2016157751 A1 WO2016157751 A1 WO 2016157751A1
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Definitions
- This technology relates to a lithium ion conductor, a solid electrolyte layer, an electrode, a battery, and an electronic device.
- oxide-based solid electrolytes used for all solid state batteries have high ion conductivity such as crystals (perovskite type, garnet type) and glass ceramics.
- crystals perovskite type, garnet type
- glass ceramics glass ceramics.
- a solid electrolyte When a solid electrolyte is used for a battery electrode, it is generally necessary to sinter the solid electrolyte by firing a composite containing an electrode active material and a solid electrolyte.
- the electrode active material and the solid electrolyte or oxygen in the atmosphere may react in the firing process of the composite. In order to suppress such a reaction, it is desired that the sintering temperature be 600 ° C. or lower.
- Patent Document 1 it is proposed to improve ion conductivity without performing high-temperature sintering by mixing and molding a garnet-type compound and a phosphate group-containing lithium conductor.
- Patent Document 2 a solid electrolyte sintered body having an ionic conductivity of 5 ⁇ 10 ⁇ 5 is obtained by sintering a mixture containing LAGP glass ceramics and amorphous Li—Al—Si—O. Has been proposed.
- Patent Document 3 it is proposed to obtain a solid electrolyte having an ionic conductivity of about 4 ⁇ 10 ⁇ 6 by sintering a raw material body containing a garnet-type compound and Li 3 BO 3 .
- the ionic conductivity is as low as about 2 ⁇ 10 ⁇ 7 even at 50 ° C.
- the sintering temperature is higher than 600 and not higher than 950 ° C.
- the solid electrolyte is a single material or when the solid electrolyte is a combination of a plurality of materials, it is possible to realize high ion conductivity at a sintering temperature of 600 ° C. or lower. Have difficulty.
- An object of the present technology is to provide a lithium ion conductor, a solid electrolyte layer, an electrode, a battery, and an electronic device that can obtain high lithium ion conductivity at a sintering temperature of 600 ° C. or lower.
- a first technique includes a first lithium ion conductor containing at least one of oxide crystals and glass ceramics, and a second temperature of 600 ° C. or lower.
- the lithium ion conductivity of the first lithium ion conductor is higher than the lithium ion conductivity of the second lithium ion conductor.
- the second technique is a solid electrolyte layer containing the lithium ion conductor.
- the third technique is an electrode containing the lithium ion conductor and an active material.
- the fourth technology is a battery that includes a positive electrode, a negative electrode, and an electrolyte, and at least one of the negative electrode, the positive electrode, and the electrolyte includes the lithium ion conductor.
- the fifth technology is an electronic device that includes the battery and receives power supply from the battery.
- high lithium ion conductivity can be obtained at a sintering temperature of 600 ° C. or lower.
- FIG. 1 is a schematic diagram for explaining the function of the lithium ion conductor according to the first embodiment of the present technology.
- FIG. 2A is a cross-sectional view illustrating a configuration example of a battery according to the second embodiment of the present technology.
- FIG. 2B is a cross-sectional view illustrating a configuration example of a battery according to a modification of the second embodiment of the present technology.
- FIG. 3 is a block diagram illustrating a configuration example of an electronic device according to the third embodiment of the present technology.
- the lithium ion conductor according to the first embodiment of the present technology is an inorganic lithium ion conductor, and is a lithium ion conductor composite material including a first lithium ion conductor and a second lithium ion conductor.
- the lithium ion conductivity of the first lithium ion conductor is higher than the lithium ion conductivity of the second lithium ion conductor.
- the lithium ion conductivity does not mean the lithium ion conductivity of the sintered powdery first and second lithium ion conductors, but the lithium ions of the first and second lithium ion conductors themselves. It means conductivity.
- the sintering temperature of the first lithium ion conductor is higher than the sintering temperature of the second lithium ion conductor.
- This lithium ion conductor is, for example, a powder.
- the form of the lithium ion conductor is not limited to powder, and may be a thin film or a block.
- the lithium ion conductor according to the first embodiment is suitable for use in an electrochemical device.
- the electrochemical device may be basically any device, and specifically, for example, various batteries using lithium or the like, capacitors, gas sensors, lithium ion filters, and the like.
- the battery is, for example, a primary battery, a secondary battery, an air battery, a fuel cell, or the like.
- the secondary battery is, for example, a lithium ion battery, and an all solid lithium ion battery can be realized by using the lithium ion conductor according to the first embodiment as a solid electrolyte.
- the lithium ion conductor according to the first embodiment can be used for both an all-solid battery and a liquid battery.
- the lithium ion conductor according to the first embodiment When the lithium ion conductor according to the first embodiment is applied to a battery, it can be used as, for example, a solid electrolyte, a binder, or a coating agent of the battery. Note that the lithium ion conductor according to the first embodiment can be used as a material having two or more functions of a solid electrolyte, a binder, and a coating agent.
- the solid electrolyte layer may be formed using the lithium ion conductor according to the first embodiment, or the lithium ion conductor according to the first embodiment may be formed as a solid electrolyte and / or a binder. You may make it contain in an electrode or an active material layer as an agent.
- a ceramic green sheet (hereinafter simply referred to as “green sheet”) or pressure as a solid electrolyte layer precursor, an electrode layer precursor or an active material layer precursor. Powder may be formed, and a sintered body as a solid electrolyte layer, an electrode, or an active material layer may be formed.
- the lithium ion conductor which concerns on 1st Embodiment as a surface coating agent in order to coat
- the reaction between the electrolytic solution and the electrode active material can be suppressed.
- positive electrode active material particles such as LCO (LiCoO 2 ) and NCM (Li [NiMnCo] O 2
- oxygen release from the positive electrode active material particles can be suppressed. it can.
- the lithium ion conductor according to the first embodiment may be used as a surface coating agent for the electrode active material particles in order to suppress the reaction between the electrode active material and the sulfur-based solid electrolyte.
- the lithium ion conductor according to the first embodiment may be used as an additive for adding to the battery separator or a coating agent for coating the surface of the battery separator. In this case, the safety of the battery can be improved.
- the first lithium ion conductor has a higher lithium ion conductivity than the second lithium ion conductor, but has a higher sintering temperature than the second lithium ion conductor.
- the sintering temperature of the first lithium ion conductor exceeds 600 ° C. and is 1100 ° C. or less, preferably 700 ° C. or more and 1100 ° C. or less.
- the first lithium ion conductor preferably contains at least one of crystal or glass ceramics. More specifically, it is preferable that the first lithium ion conductor includes at least one of an oxide crystal lithium ion conductor and an oxide glass ceramic lithium ion conductor. This is because high lithium ion conductivity can be obtained.
- the oxide crystal-based lithium ion conductor refers to a lithium ion conductor composed of oxide crystals.
- the oxide glass ceramic lithium ion conductor refers to a lithium ion conductor composed of oxide glass ceramic.
- oxide crystalline lithium ion conductor examples include perovskite oxide crystals composed of La—Li—Ti—O, garnet oxide crystals composed of Li—La—Zr—O, and the like. Can be used.
- oxide glass ceramic lithium ion conductor for example, a phosphate compound (LATP) containing lithium, aluminum and titanium as constituent elements, and a phosphate compound (LAGP) containing lithium, aluminum and germanium as constituent elements is used.
- LATP phosphate compound
- LAGP phosphate compound
- the crystal includes not only a single crystal but also a polycrystal in which a large number of crystal grains are aggregated.
- Crystal means a crystallographic single crystal or polycrystal such as a peak observed in X-ray diffraction or electron beam diffraction.
- Glass ceramics crystallized glass means crystallized glass in which amorphous and crystalline materials are mixed, such as peaks and halos observed in X-ray diffraction and electron diffraction, or X-rays It refers to crystallized glass that is crystallographically single crystal or polycrystalline, such as peaks observed in diffraction and electron beam diffraction.
- the second lithium ion conductor has a lower lithium ion conductivity than the first lithium ion conductor, but has a lower sintering temperature than the first lithium ion conductor.
- the sintering temperature of the second lithium ion conductor is 600 ° C. or lower, more preferably 300 ° C. or higher and 600 ° C. or lower, and even more preferably 300 ° C. or higher and 500 ° C. or lower. It can suppress that a lithium ion conductor and an electrode active material react in a baking process (sintering process) as the sintering temperature is 600 degrees C or less, and by-products, such as a nonconductor, are formed.
- the selection range of the kind of electrode active material is expanded, the freedom degree of battery design can be improved.
- the sintering temperature is 500 ° C. or lower, a carbon material can be used as the negative electrode active material. Therefore, the energy density of the battery can be improved.
- a carbon material can be used as the conductive agent, a favorable electron conduction path can be formed in the electrode layer or the electrode active material layer, and the conductivity of the electrode layer or the electrode active material layer can be improved.
- the sintering temperature is 300 ° C. or higher, an organic binder such as an acrylic resin contained in the electrode precursor and / or the solid electrolyte precursor can be burned out in the firing step (sintering step). .
- the second lithium ion conductor preferably contains glass. More specifically, the second lithium ion conductor is preferably an oxide glass-based lithium ion conductor.
- the oxide glass-based lithium ion conductor refers to a lithium ion conductor composed of oxide glass.
- the oxide glass-based lithium ion conductor is a glass containing one or more of Ge (germanium), Si (silicon), B (boron), and P (phosphorus), Li (lithium), and O (oxygen). It is preferable that it is glass which contains Si (silicon), B (boron), Li (lithium), and O (oxygen).
- the glass is preferably a glass containing at least one of GeO 2 , SiO 2 , B 2 O 3 and P 2 O 5 and Li 2 O, SiO 2 , B 2 O 3 , It is more preferable that the glass contains Li 2 O.
- glass means crystallographically amorphous material such as halo observed in X-ray diffraction or electron beam diffraction.
- the content of Li 2 O is 20 mol% or more and 75 mol% or less, preferably more than 25 mol% and 75 mol% or less, more preferably 30 mol% or more and 75 mol% or less, still more preferably 40 mol% or more and 75 mol% or less, particularly preferably 50 mol%. % Or more and 75 mol% or less. If oxide glass-based lithium ion conductor containing GeO 2, the content of the GeO 2 is preferably less 80 mol% exceed 0 mol%. If oxide glass-based lithium ion conductor containing SiO 2, the content of the SiO 2 is preferably at most 70 mol% exceed 0 mol%.
- oxide glass-based lithium ion conductor comprises a B 2 O 3
- the content of the B 2 O 3 is preferably not more than 60 mol% exceed 0 mol%.
- oxide glass-based lithium ion conductor comprises a P 2 O 5
- the content of the P 2 O 5 is preferably less 50 mol% exceed 0 mol%.
- the content of each oxide is the content of each oxide in oxide glass-based lithium ion conductor in, specifically, GeO 2, SiO 2, B 2 O 3 and P 2 O 5
- the ratio of the content (mol) of each oxide to the total amount (mol) of one or more of them and Li 2 O is expressed as a percentage (mol%).
- the content of each oxide can be measured using inductively coupled plasma emission spectroscopy (ICP-AES) or the like.
- the oxide glass-based lithium ion conductor may further contain an additive element as necessary.
- an additive element for example, Na (sodium), Mg (magnesium), Al (aluminum), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese) ), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Se (selenium), Rb (rubidium), S (sulfur), Y (yttrium) ), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium) ), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum),
- the lithium ion conductivity of the lithium ion conductor is preferably 5 ⁇ 10 ⁇ 7 S / cm or more. It is preferable that the average particle diameter of the first lithium ion conductor is not less than the average particle diameter of the second lithium ion conductor. This is because lithium ion conductivity can be improved. It is preferable that the volume ratio of a 1st lithium ion conductor is more than the volume ratio of a 2nd lithium ion conductor. This is because lithium ion conductivity can be improved.
- the volume ratio of the first lithium ion conductor is a percentage of the volume of the first lithium ion conductor to the total volume of the first and second lithium ion conductors.
- the volume ratio of the second lithium ion conductor is a percentage of the volume of the second lithium ion conductor to the total volume of the first and second lithium ion conductors.
- the average particle diameter of the second lithium ion conductor can be obtained, for example, by the same method as the average particle diameter of the first lithium ion conductor.
- the sum V2 of the volume v2 of 100 second lithium ion conductors is obtained by the same method as that for obtaining the volume V1 of the first lithium ion conductor.
- the volume ratio of the volume V1 [V1 / (V1 + V2)] ⁇ 100 (%)
- the volume ratio ([V2 / (V1 + V2)] ⁇ 100 (%)) of the volume V2 of the second lithium ion conductor to the total volume (V1 + V2) of the first and second lithium ion conductors is obtained.
- FIG. 1 schematically shows a lithium ion conductor in a state where the second lithium ion conductor 2 is sintered among the first and second lithium ion conductors 1 and 2.
- the first lithium ion conductor 1 has a function as a main lithium ion conduction path
- the second lithium ion conductor 2 has the first lithium ion conduction. It has a function of connecting the body 1 physically and ionically. Therefore, as described above, from the viewpoint of improving the lithium ion conductivity, the average particle diameter of the first lithium ion conductor 1 is preferably larger than the average particle diameter of the second lithium ion conductor 2. From the viewpoint of improving lithium ion conductivity, the volume ratio of the first lithium ion conductor 1 is preferably larger than the volume ratio of the second lithium ion conductor 2.
- An oxide glass-based lithium ion conductor as the second lithium ion conductor is produced as follows. First, Li 2 O is mixed as a raw material with at least one of GeO 2 , SiO 2 , B 2 O 3 and P 2 O 5 . The blending amounts of these GeO 2 , SiO 2 , B 2 O 3 , P 2 O 5 and Li 2 O are, for example, the same as the contents of these materials in the oxide glass-based lithium ion conductor described above. . In addition, you may further mix the said additional element or its oxide as a raw material as needed.
- an oxide glass-based lithium ion conductor is produced by vitrifying the raw material.
- a method for vitrifying the raw material for example, a method in which the raw material is melted to a melt and allowed to cool, a method in which the melt is pressed with a metal plate, a method in which the melt is dropped into mercury, a strip furnace, a splat quench, a roll method ( In addition to single and twin), there are mechanical milling method, sol-gel method, vapor deposition method, sputtering method, laser ablation method, PLD (pulse laser deposition) method, plasma method and the like.
- PLD pulse laser deposition
- the oxide glass lithium ion conductor is powdered.
- the powdering method include a mechanochemical method.
- a powder of an oxide glass-based lithium ion conductor is obtained.
- the target lithium ion conductor is obtained by mixing the second lithium ion conductor obtained as described above with the first lithium ion conductor.
- the lithium ion conductor powder according to the first embodiment has high lithium ion conductivity alone, but the first lithium ion conductor (eg, oxide crystal, oxide glass) having a high sintering temperature and exceeding 600 ° C. Ceramics) and a second lithium ion conductor (such as glass) having a low sintering temperature and not higher than 600 ° C., although the lithium ion conductivity is not so high.
- the first lithium ion conductor eg, oxide crystal, oxide glass
- a second lithium ion conductor such as glass
- the first lithium ion conductor is a crystal material and the second lithium ion conductor is a glass
- the gap between the hard crystal materials is filled with a small and relatively soft glass. For this reason, the clearance gap etc. in a lithium ion conductor reduce, and the tolerance with respect to an impact improves. Therefore, when an all solid state battery is produced using the lithium ion conductor according to the first embodiment, it is possible to suppress the occurrence of an internal short circuit of the battery or to improve the reliability when dropped.
- the oxide glass-based lithium ion conductor as the second lithium ion conductor contains two or more, three or more, or all four of Ge, Si, B, and P, and Li and O Good. Specifically, two or more, three or more, or all four of GeO 2 , SiO 2 , B 2 O 3 and P 2 O 5 and Li 2 O may be included.
- the lithium ion conductor is a lithium ion conductor composite material including two types of lithium ion conductors
- the lithium ion conductor includes two or more types of lithium ions.
- a lithium ion conductor composite material including an ion conductor may be used.
- the lithium ion conductor may be a lithium ion conductor composite material including one or more types of first lithium ion conductors and two or more types of second lithium ion conductors.
- a lithium ion conductor composite material including one lithium ion conductor and one or more second lithium ion conductors may be used.
- the first lithium ion conductor is an oxide-based lithium ion conductor.
- the first lithium ion conductor is a sulfur-based lithium ion conductor, or an oxide. It may include both a physical system and a sulfur based lithium ion conductor.
- a crystallized second lithium ion conductor specifically, a crystallized oxide glass lithium ion conductor may be used.
- the crystallized oxide glass-based lithium ion conductor is produced by heat-treating the oxide glass-based lithium ion conductor at a temperature equal to or higher than the crystallization temperature to promote crystallization.
- the crystallized oxide glass-based lithium ion conductor is a so-called glass ceramic.
- Table 1 shows examples of combinations of the first lithium-in conductor and the second lithium ion conductor.
- the sintering temperature of the first lithium ion conductor is higher than 600 ° C. and 1100 ° C. or lower has been described as an example, but the sintering temperature of the first lithium ion conductor is 600 ° C. or lower. There may be.
- a crystallized second lithium ion conductor that is, a crystallized oxide glass-based lithium ion conductor may be used.
- the sintered second lithium ion conductor is interposed between the crystallized oxide glass-based lithium ion conductors. By connecting the body physically and ionically, high lithium ion conductivity is obtained.
- the sintered body of the lithium ion conductor means one in which the second lithium ion conductor is sintered among the first and second lithium ion conductors included in the lithium ion conductor. .
- the battery according to the second embodiment of the present technology is a so-called bulk type all-solid battery, and includes a positive electrode 11, a negative electrode 12, and a solid electrolyte layer 13 as shown in FIG. And the negative electrode 12.
- This battery is a secondary battery obtained by repeatedly receiving and transferring Li, which is an electrode reactant, and may be a lithium ion secondary battery in which the capacity of the negative electrode is obtained by occlusion and release of lithium ions, It may be a lithium metal secondary battery in which the capacity of the negative electrode is obtained by precipitation dissolution of lithium metal.
- the positive electrode 11 is a positive electrode active material layer containing one or more positive electrode active materials and a solid electrolyte.
- the solid electrolyte may have a function as a binder.
- the positive electrode 11 may further include a conductive agent as necessary.
- the positive electrode 11 is, for example, a fired body of a green sheet (hereinafter referred to as “positive electrode green sheet”) as a positive electrode precursor.
- the positive electrode active material includes, for example, a positive electrode material capable of occluding and releasing lithium ions that are electrode reactants.
- the positive electrode material is preferably a lithium-containing compound or the like from the viewpoint of obtaining a high energy density, but is not limited thereto.
- This lithium-containing compound is, for example, a composite oxide (lithium transition metal composite oxide) containing lithium and a transition metal element as constituent elements, or a phosphate compound (lithium transition metal) containing lithium and a transition metal element as constituent elements. Phosphate compounds).
- the transition metal element is preferably one or more of Co, Ni, Mn, and Fe. This is because a higher voltage can be obtained.
- the lithium transition metal composite oxide is represented by, for example, Li x M1O 2 or Li y M2O 4 . More specifically, for example, the lithium transition metal composite oxide is LiCoO 2 , LiNiO 2 , LiVO 2 , LiCrO 2, or LiMn 2 O 4 . Further, the lithium transition metal phosphate compound is represented by, for example, Li z M3PO 4 . More specifically, for example, the lithium transition metal phosphate compound is LiFePO 4 or LiCoPO 4 .
- M1 to M3 are one kind or two or more kinds of transition metal elements, and the values of x to z are arbitrary.
- the positive electrode active material may be, for example, an oxide, disulfide, chalcogenide, or conductive polymer.
- the oxide include titanium oxide, vanadium oxide, and manganese dioxide.
- the disulfide include titanium disulfide and molybdenum sulfide.
- An example of the chalcogenide is niobium selenide.
- the conductive polymer include sulfur, polyaniline, and polythiophene.
- the positive electrode active material is a powder of positive electrode active material particles.
- the surface of the positive electrode active material particles may be coated with a coating agent.
- the coating is not limited to the entire surface of the positive electrode active material particles, and may be a part of the surface of the positive electrode active material particles.
- the coating agent is at least one of a solid electrolyte and a conductive agent, for example.
- the solid electrolyte is a sintered body of the lithium ion conductor according to the first embodiment described above.
- the solid electrolyte as the coating agent for the positive electrode active material particles may also be a sintered body of the lithium ion conductor according to the first embodiment described above.
- the conductive agent includes, for example, a carbon material, a metal, a metal oxide, a conductive polymer, or the like alone or in combination.
- a carbon material for example, graphite, carbon fiber, carbon black, carbon nanotube and the like can be used alone or in combination of two or more.
- the carbon fiber for example, vapor growth carbon fiber (VGCF) can be used.
- VGCF vapor growth carbon fiber
- carbon black acetylene black, Ketjen black, etc.
- the carbon nanotube for example, a multi-wall carbon nanotube (MWCNT) such as a single wall carbon nanotube (SWCNT) or a double wall carbon nanotube (DWCNT) can be used.
- MWCNT multi-wall carbon nanotube
- SWCNT single wall carbon nanotube
- DWCNT double wall carbon nanotube
- Ni powder can be used.
- SnO 2 can be used as the metal oxide.
- the conductive polymer for example, substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and one or two (co) polymers selected from these can be used.
- the conductive agent may be any material having conductivity, and is not limited to the above example.
- the negative electrode 12 is a negative electrode active material layer containing one type or two or more types of negative electrode active materials and a solid electrolyte.
- the solid electrolyte may have a function as a binder.
- the negative electrode 12 may further contain a conductive agent as necessary.
- the negative electrode 12 is, for example, a fired body of a green sheet (hereinafter referred to as “negative electrode green sheet”) as a negative electrode precursor.
- the negative electrode active material includes, for example, a negative electrode material capable of occluding and releasing lithium ions that are electrode reactants.
- the negative electrode material is preferably a carbon material or a metal-based material from the viewpoint of obtaining a high energy density, but is not limited thereto.
- Examples of the carbon material include graphitizable carbon, non-graphitizable carbon, graphite, mesocarbon microbeads (MCMB), and highly oriented graphite (HOPG).
- the metal-based material is a material containing, for example, a metal element or a metalloid element capable of forming an alloy with lithium as a constituent element. More specifically, the metal-based material is, for example, Si, Sn, Al, In, Mg, B, Ga, Ge, Pb, Bi, Cd (cadmium), Ag, Zn, Hf, Zr, Y, Pd ( One or two or more of a simple substance such as palladium) or Pt (platinum), an alloy, or a compound. However, the simple substance is not limited to 100% purity, and may contain a small amount of impurities.
- the metal material include Si, Sn, SiB 4 , TiSi 2 , SiC, Si 3 N 4 , SiO v (0 ⁇ v ⁇ 2), LiSiO, SnO w (0 ⁇ w ⁇ 2), SnSiO 3. , LiSnO, Mg 2 Sn and the like.
- the metal-based material may be a lithium-containing compound or lithium metal (lithium simple substance).
- the lithium-containing compound is a composite oxide (lithium transition metal composite oxide) containing lithium and a transition metal element as constituent elements. Examples of this composite oxide include Li 4 Ti 5 O 12 .
- the negative electrode active material is a powder of negative electrode active material particles.
- the surface of the negative electrode active material particles may be coated with a coating agent.
- the coating is not limited to the entire surface of the negative electrode active material particles, and may be a part of the surface of the negative electrode active material particles.
- the coating agent is at least one of a solid electrolyte and a conductive agent, for example.
- the solid electrolyte is a sintered body of the lithium ion conductor according to the first embodiment described above.
- the solid electrolyte as the coating agent for the negative electrode active material particles may also be a sintered body of the lithium ion conductor according to the first embodiment described above.
- the conductive agent is the same as the conductive agent in the positive electrode 11 described above.
- the solid electrolyte layer 13 includes the sintered body of the lithium ion conductor according to the first embodiment described above.
- the solid electrolyte layer 13 is, for example, a fired body of a green sheet (hereinafter referred to as “solid electrolyte green sheet”) as a solid electrolyte layer precursor.
- This manufacturing method includes a step of forming a positive electrode precursor, a negative electrode precursor, and a solid electrolyte layer precursor, and a step of laminating and firing these precursors.
- a case where the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor all include the lithium ion conductor according to the first embodiment will be described as an example.
- a positive electrode green sheet as a positive electrode precursor is formed as follows. First, a positive electrode active material, a lithium ion conductor (solid electrolyte) according to the first embodiment, an organic binder, and a conductive agent as necessary are mixed to form a positive electrode mixture as a raw material powder. After preparing the powder, the positive electrode mixture powder is dispersed in an organic solvent or the like to obtain a positive electrode slurry as a positive electrode green sheet forming composition. In addition, in order to improve the dispersibility of positive mix powder, dispersion
- organic binder for example, an organic binder such as an acrylic resin can be used.
- the solvent is not particularly limited as long as it can disperse the positive electrode mixture powder, but is preferably one that burns away in a temperature range lower than the firing temperature of the green sheet.
- Examples of the solvent include lower alcohols having 4 or less carbon atoms such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, t-butanol, ethylene glycol, propylene glycol (1,3-propanediol), 1, Aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ketones such as methyl ethyl ketone, dimethylethylamine Amines such as alicyclic alcohols such as terpineol can be used alone or in admixture of two or more, but the invention is not particularly limited thereto.
- Examples of the dispersion method include stirring treatment, ultrasonic dispersion treatment, bead dispersion treatment, kneading treatment, and homogenizer treatment.
- the positive electrode slurry may be filtered with a filter to remove foreign substances in the positive electrode slurry.
- vacuum deaeration may be performed on the positive electrode slurry to remove internal bubbles.
- the positive electrode slurry layer is formed by uniformly applying or printing the positive electrode slurry on the surface of the support substrate.
- a support substrate for example, a polymer resin film such as polyethylene terephthalate (PET) can be used.
- PET polyethylene terephthalate
- a coating or printing method it is preferable to use a simple and suitable method for mass production. Examples of coating methods include die coating, micro gravure coating, wire bar coating, direct gravure coating, reverse roll coating, comma coating, knife coating, spray coating, curtain coating, dipping, and spin. A coating method or the like can be used, but is not particularly limited thereto.
- a printing method for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method, and the like can be used, but the invention is not particularly limited thereto.
- coating or printing in advance on the surface of a support base material is mentioned, for example.
- the composition that imparts releasability include paints containing a binder as a main component and added with wax, fluorine, or the like, or silicone resins.
- a positive electrode green sheet is formed on the surface of the support substrate by drying the positive electrode slurry layer.
- the drying method include natural drying, blow drying with hot air, heating drying with infrared rays or far infrared rays, vacuum drying, and the like. These drying methods may be used alone or in combination of two or more.
- a negative electrode green sheet as a negative electrode precursor is formed as follows. First, a negative electrode active material, a lithium ion conductor (solid electrolyte) according to the first embodiment, an organic binder, and, if necessary, a conductive agent are mixed to form a negative electrode mixture as a raw material powder. After preparing the powder, the negative electrode mixture powder is dispersed in an organic solvent or the like to obtain a negative electrode slurry as a negative electrode green sheet forming composition. Except for using this negative electrode slurry, a negative electrode green sheet is obtained in the same manner as in the “positive electrode precursor forming step” described above.
- a solid electrolyte green sheet as a solid electrolyte layer precursor is formed as follows. First, the lithium ion conductor (solid electrolyte) according to the first embodiment and an organic binder are mixed to prepare an electrolyte mixture powder as a raw material powder. Disperse in a solvent or the like to obtain an electrolyte mixture slurry as a solid electrolyte green sheet forming composition. A solid electrolyte green sheet is obtained in the same manner as in the “positive electrode precursor forming step” except that this electrolyte mixture slurry is used.
- a battery is manufactured as follows. First, a positive electrode green sheet and a negative electrode green sheet are laminated to sandwich a solid electrolyte green sheet. Then, while heating a laminated body, a laminated body is pressed so that a pressure may be applied to the thickness direction of a laminated body at least. Thereby, the organic binder contained in each green sheet constituting the laminate is melted, and the green sheets constituting the laminate are brought into close contact with each other.
- Specific methods for pressing the laminate while heating include, for example, a hot press method, a warm isostatic press (WIP), and the like.
- the laminate is cut into a predetermined size and shape as necessary.
- the lithium ion conductor contained in each green sheet constituting the laminate is sintered and the organic binder is burned out.
- the firing temperature of the laminate is preferably not less than the sintering temperature of the second lithium ion conductor and not more than 600 ° C., more preferably not less than the sintering temperature of the second lithium ion conductor and not more than 500 ° C.
- the sintering temperature of a 2nd lithium ion conductor means the sintering temperature of the 2nd lithium ion conductor, when the lithium ion conductor contained in a laminated body is one kind.
- the 2nd lithium ion conductor contained in a laminated body is 2 or more types, it means the maximum thing among the sintering temperatures of those 2nd lithium ion conductors.
- the firing temperature of the laminate is equal to or higher than the sintering temperature of the second lithium ion conductor, the sintering of the second lithium ion conductor proceeds, so that the lithium ion conductivity of the positive electrode, the negative electrode, and the solid electrolyte layer can be improved. . Moreover, the intensity
- the reason why the firing temperature of the laminate is 600 ° C. or lower or 500 ° C. or lower is the same as the reason for setting the sintering temperature of the lithium ion conductor described in the first embodiment to 600 ° C. or lower or 500 ° C. or lower.
- the oxide glass-based lithium ion conductor is vitrified in the firing step to form an oxide glass ceramic lithium-ion conductor. Good. Thus, the target battery is obtained.
- the solid electrolyte contained in the positive electrode green sheet, the negative electrode green sheet, and the solid electrolyte green sheet is the lithium ion conductor according to the first embodiment, that is, lithium ion conduction that can be sintered at a low temperature. Is the body. Therefore, the firing temperature of the positive electrode green sheet, the negative electrode green sheet, and the solid electrolyte green sheet can be lowered. Thereby, the damage of the positive electrode active material and the negative electrode active material in the baking process of a laminated body can be suppressed, and the fall of a battery characteristic can be suppressed. In addition, the selection range of the positive electrode active material and the negative electrode active material is widened, and the degree of freedom in battery design is improved.
- a positive electrode green sheet, a negative electrode green sheet, and a solid electrolytic green sheet can be collectively fired at a low temperature to produce an all-solid battery. Therefore, the interface resistance between the positive electrode 11 and the solid electrolyte layer 13 and the interface resistance between the negative electrode 12 and the solid electrolyte layer 13 are reduced while suppressing damage to the positive electrode 11, the negative electrode 12, and the solid electrolyte layer 13 due to firing. Can do.
- the lithium ion conductor according to the first embodiment is sintered in the positive electrode 11 and the negative electrode 12, the film strength of the positive electrode 11 and the negative electrode 12 is high. Therefore, even when the layer thickness of the positive electrode 11 and the negative electrode 12 is increased, the battery performance can be maintained.
- the positive electrode 21 may include a positive electrode current collector 21A and a positive electrode active material layer 21B provided on one surface of the positive electrode current collector 21A.
- the negative electrode 22 may include a negative electrode current collector 22A and a negative electrode active material layer 22B provided on one surface of the negative electrode current collector 22A.
- the positive electrode 21 and the negative electrode 22 are laminated via the solid electrolyte layer 13 so that the positive electrode active material layer 21B and the negative electrode active material layer 22B face each other.
- symbol is attached
- the positive electrode current collector 21A includes, for example, a metal such as Al, Ni, and stainless steel.
- the shape of the positive electrode current collector 21A is, for example, a foil shape, a plate shape, or a mesh shape.
- the positive electrode active material layer 21B is the same as the positive electrode (positive electrode active material layer) 11 in the second embodiment.
- the negative electrode current collector 22A contains, for example, a metal such as Cu or stainless steel.
- the shape of the anode current collector 22A is, for example, a foil shape, a plate shape, or a mesh shape.
- the negative electrode active material layer 22B is the same as the negative electrode (negative electrode active material layer) 12 in the second embodiment.
- one of the positive electrode 21 and the negative electrode 22 may include a current collector and an active material layer, and the other may include only an active material layer.
- the present technology is not limited to this example.
- the present technology may be applied to a battery using another alkali metal such as Na or K, an alkaline earth metal such as Mg or Ca, or another metal such as Al or Ag as an electrode reactant.
- the case where the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor are green sheets has been described as an example.
- the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor are pressurized. Powder may be sufficient.
- the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor one or two layers of precursors may be green sheets, and the rest may be green compacts.
- the green compact as the positive electrode precursor is produced by pressure-molding the positive electrode mixture powder with a press or the like.
- the green compact as the negative electrode precursor is produced by pressure-molding the negative electrode mixture powder with a press or the like.
- the green compact as the solid electrolyte layer precursor is produced by pressure-molding the electrolyte mixture powder with a press or the like.
- the positive electrode mixture powder, the negative electrode mixture powder, and the electrolyte mixture powder may not contain an organic binder.
- the positive electrode precursor, the solid electrolyte layer precursor, and the negative electrode precursor are stacked and then fired.
- the positive electrode precursor, the solid electrolyte layer precursor, and the negative electrode precursor are fired.
- these fired bodies may be laminated to form a laminated body.
- the laminate may not be fired after pressing the laminate, or the laminate may be fired after pressing the laminate as necessary.
- the positive electrode precursor the solid electrolyte layer precursor, and the negative electrode precursor
- one or two layers of precursors are pre-fired to obtain a fired body (sintered body), and the remaining layers are the unfired precursors.
- the fired body and the precursor may be laminated to form a laminated body. In this case, it is preferable to fire the laminate after pressing the laminate.
- Two layers of the positive electrode precursor, the solid electrolyte layer precursor, and the negative electrode precursor may be laminated and fired in advance, and the remaining unfired layer may be laminated on this laminate to form a laminate. . In this case, it is preferable to fire the laminate after pressing the laminate.
- Two precursors of the positive electrode precursor, the solid electrolyte layer precursor and the negative electrode precursor are laminated and fired in advance, and the remaining one precursor is separately fired to obtain a fired body, which are then laminated.
- a laminate may be formed. In this case, the laminate may not be fired after pressing the laminate, or the laminate may be fired after pressing the laminate as necessary.
- the positive electrode precursor and the negative electrode precursor are respectively formed by the positive electrode green sheet and the negative electrode green sheet has been described as an example.
- at least one of the positive electrode precursor and the negative electrode precursor is as follows. May be formed. That is, the positive electrode slurry may be formed by applying or printing the positive electrode slurry on one surface of the solid electrolyte layer precursor or the solid electrolyte layer and then drying the positive electrode slurry. Moreover, after apply
- the positive electrode, the negative electrode, and the solid electrolyte layer have all been described as an example of a configuration including the sintered body of the lithium ion conductor according to the first embodiment as a solid electrolyte.
- the present technology is not limited to this configuration.
- at least one of the positive electrode, the negative electrode, and the solid electrolyte layer may include a sintered body of the lithium ion conductor according to the first embodiment as a solid electrolyte.
- one or two of the positive electrode, the negative electrode, and the solid electrolyte layer include the sintered body of the lithium ion conductor according to the first embodiment as the solid electrolyte, and the other remaining layers.
- a lithium ion conductor other than the lithium ion conductor according to the first embodiment may be included as a solid electrolyte.
- the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor are all described as an example including the lithium ion conductor according to the first embodiment.
- the technology is not limited to this configuration.
- at least one of the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor may include the lithium ion conductor according to the first embodiment.
- one or two of the positive electrode precursor, the negative electrode precursor, and the solid electrolyte layer precursor include the lithium ion conductor according to the first embodiment, and the other remaining layers are A lithium ion conductor other than the lithium ion conductor according to the first embodiment may be included.
- the lithium ion conductor other than the lithium ion conductor according to the first embodiment is not particularly limited as long as it can conduct lithium ions, and may be either an inorganic or polymer lithium ion conductor. May be.
- the inorganic lithium ion conductor include Li 2 S—P 2 S 5 , Li 2 S—SiS 2 —Li 3 PO 4 , Li 7 P 3 S 11 , Li 3.25 Ge 0.25 P 0.75 S, Li 10 Sulfides such as GeP 2 S 12 , Li 7 La 3 Zr 2 O 12 , Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 , Li 6 BaLa 2 Ta 2 O 12 , Li 1 + x Al x Ti 2-x ( Examples thereof include oxides such as PO 4 ) 3 and La 2 / 3-x Li 3x TiO 3 .
- the polymer lithium ion conductor include polyethylene oxide (PEO).
- both the positive electrode and the negative electrode are electrodes including a solid electrolyte
- at least one of the positive electrode and the negative electrode may be an electrode not including a solid electrolyte.
- the electrode not including the solid electrolyte may be produced by a vapor phase growth method such as a vapor deposition method or a sputtering method.
- the step of firing after pressing the laminated body has been described as an example, but a step of firing while pressing the laminated body may be employed.
- a stacked battery may be configured by stacking a plurality of batteries according to the second embodiment described above.
- At least one of the positive electrode, the negative electrode, and the solid electrolyte layer may include a lithium ion conductor sintered body according to the modification of the first embodiment as a solid electrolyte.
- the electronic device 400 includes an electronic circuit 401 of the electronic device body and a battery pack 300.
- the battery pack 300 is electrically connected to the electronic circuit 401 via the positive terminal 331a and the negative terminal 331b.
- the electronic device 400 has a configuration in which the battery pack 300 is detachable by a user.
- the configuration of the electronic device 400 is not limited to this, and the battery pack 300 is built in the electronic device 400 so that the user cannot remove the battery pack 300 from the electronic device 400. May be.
- the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of a charger (not shown), respectively.
- the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of the electronic circuit 401, respectively.
- Examples of the electronic device 400 include a notebook personal computer, a tablet computer, a mobile phone (for example, a smartphone), a portable information terminal (Personal Digital Assistants: PDA), an imaging device (for example, a digital still camera, a digital video camera, etc.), Audio devices (for example, portable audio players), game devices, cordless phones, electronic books, electronic dictionaries, radios, headphones, navigation systems, memory cards, pacemakers, hearing aids, lighting devices, toys, medical devices, robots, etc.
- PDA Personal Digital Assistants
- an imaging device for example, a digital still camera, a digital video camera, etc.
- Audio devices for example, portable audio players
- game devices for example, cordless phones, electronic books, electronic dictionaries, radios, headphones, navigation systems, memory cards, pacemakers, hearing aids, lighting devices, toys, medical devices, robots, etc.
- PDA Personal Digital Assistants
- an imaging device for example, a digital still camera, a digital video camera, etc.
- Audio devices for example, portable audio players
- the electronic circuit 401 includes, for example, a CPU (Central Processing Unit), a peripheral logic unit, an interface unit, a storage unit, and the like, and controls the entire electronic device 400.
- a CPU Central Processing Unit
- the battery pack 300 includes an assembled battery 301 and a charge / discharge circuit 302.
- the assembled battery 301 is configured by connecting a plurality of secondary batteries 301a in series and / or in parallel.
- the plurality of secondary batteries 301a are connected, for example, in n parallel m series (n and m are positive integers).
- FIG. 3 shows an example in which six secondary batteries 301a are connected in two parallel three series (2P3S).
- a plurality of secondary batteries 301a may constitute a stacked secondary battery.
- the secondary battery 301a the battery according to the second embodiment or its modification is used.
- the charging / discharging circuit 302 controls charging of the assembled battery 301.
- the charging / discharging circuit 302 controls the discharging of the electronic device 400.
- the secondary battery according to the second embodiment or the modification thereof is It can also be applied to devices other than electronic devices.
- electric power sources for electric vehicles including hybrid vehicles
- railway vehicles including hybrid vehicles
- golf carts electric carts
- road conditioners traffic lights, etc.
- power supplies for auxiliary use and power storage power sources for buildings and power generation facilities such as houses Or can be used to supply power to them.
- the secondary battery according to the second embodiment or its modification can also be used as a power storage device in a so-called smart grid.
- Such a power storage device can not only supply power but also store power by receiving power from another power source.
- thermal power generation, nuclear power generation, hydroelectric power generation, solar cells, wind power generation, geothermal power generation, fuel cells (including biofuel cells) and the like can be used.
- garnet-type oxide crystal powder Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 powder was prepared as an oxide crystal lithium ion conductor (first lithium ion conductor) powder having high ion conductivity.
- Li 2 O, SiO 2 , B 2 O 3, and Y 2 O 3 are mixed at a molar fraction of Li 2 O as an oxide glass-based lithium ion conductor (second lithium ion conductor) powder having a low sintering temperature.
- a glass powder containing 2 O: SiO 2 : B 2 O 3 : Y 2 O 3 70.31: 16.54: 12.41: 0.74 was prepared.
- the mixed powder was molded into a pellet shape using a powder molding machine so that the powder had a diameter of 10 mm ⁇ and a thickness of about 1 mm.
- the produced pellets were sintered at a glass powder sintering temperature of 320 ° C. for 10 minutes. Thus, a pellet-shaped solid electrolyte layer was obtained.
- the lithium ion conductivity of the solid electrolyte layers of Examples 1 to 4 and Comparative Examples 1 to 3 obtained as described above was measured as follows. First, Pt was sputtered with a size of 5 mm ⁇ on both surfaces of the sintered solid electrolyte layer. Next, AC impedance measurement (frequency: 10 +6 Hz to 10 ⁇ 1 Hz, voltage: 100 mV, 1000 mV) of the solid electrolyte layer on which the electrode was formed was performed using an impedance measuring device (manufactured by Toyo Technica), and lithium ion Conductivity was determined. The results are shown in Table 2.
- Table 2 shows configurations and evaluation results of the solid electrolyte layers in Examples 1 to 4 and Comparative Examples 1 to 3.
- the sintering temperature of the garnet-type oxide crystal (first lithium ion conductor) in Example 1 and Comparative Example 1 exceeds 600 ° C.
- the sintering temperature of the crystallized glass (first lithium ion conductor) in Examples 2 to 4 and Comparative Example 3 is 600 ° C. or lower.
- Table 1 shows the following.
- a hybrid material including crystal and glass lithium ion conductivity higher than that of a single crystal can be realized.
- a hybrid material containing crystallized glass and glass can achieve higher lithium ion conductivity than crystallized glass alone.
- a single crystal or crystallized glass has high interface resistance and low ionic conductivity.
- the present technology can also employ the following configurations.
- a first lithium ion conductor comprising at least one of oxide crystals and glass ceramics;
- a second lithium ion conductor having a sintering temperature of 600 ° C. or less, The lithium ion conductivity of the first lithium ion conductor is higher than the lithium ion conductivity of the second lithium ion conductor.
- the said 1st lithium ion conductor and the said 2nd lithium ion conductor are lithium ion conductors as described in (1) containing the oxide.
- the sintering temperature of said 1st lithium ion conductor is a lithium ion conductor as described in (1) or (2) which exceeds 600 degreeC.
- the lithium ion conductor according to any one of (1) to (3), wherein the second lithium ion conductor includes glass.
- the glass includes one or more of Ge (germanium), Si (silicon), B (boron), and P (phosphorus), Li (lithium), and O (oxygen).
- Lithium ion conductor In a state where the second lithium ion conductor is sintered, the lithium ion conductivity of the lithium ion conductor is 5 ⁇ 10 ⁇ 7 S / cm or more, according to any one of (1) to (5). Lithium ion conductor.
Abstract
Description
特許文献1においては、ガーネット型化合物とリン酸基含リチウム伝導体とを混合して成型することで、高温焼結をさせずにイオン伝導性を向上させることが提案されている。
1.第1の実施形態(リチウムイオン伝導体の例)
1.1 リチウムイオン伝導体の構成
1.2 リチウムイオン伝導体の作用
1.3 リチウムイオン伝導体の製造方法
1.4 効果
1.5 変形例
2.第2の実施形態(電池の例)
2.1 電池の構成
2.2 電池の動作
2.3 電池の製造方法
2.4 効果
2.5 変形例
3.第3の実施形態(電子機器の例)
3.1 電子機器の構成
3.2 変形例
[1.1 リチウムイオン伝導体の構成]
本技術の第1の実施形態に係るリチウムイオン伝導体は、無機系リチウムイオン伝導体であり、第1リチウムイオン伝導体と第2リチウムイオン伝導体とを含むリチウムイオン伝導体複合材料である。第1リチウムイオン伝導体のリチウムイオン伝導度は、第2リチウムイオン伝導体のリチウムイオン伝導度に比べて高い。ここで、リチウムイオン伝導度は、粉末状の第1、第2リチウムイオン伝導体を焼結したもののリチウムイオン伝導度を意味するのではなく、第1、第2リチウムイオン伝導体そのもののリチウムイオン伝導度を意味する。また、第1リチウムイオン伝導体の焼結温度は、第2リチウムイオン伝導体の焼結温度に比べて高い。このリチウムイオン伝導体は、例えば粉末である。但し、リチウムイオン伝導体の形態は粉末に限定されるものではなく、薄膜やブロックであってもよい。
第1リチウムイオン伝導体は、第2リチウムイオン伝導体に比べて高いリチウムイオン伝導度を有するが、第2リチウムイオン伝導体に比べて高い焼結温度を有している。第1リチウムイオン伝導体の焼結温度は、600℃を超え1100℃以下、好ましくは700℃以上1100℃以下である。
第2リチウムイオン伝導体は、第1リチウムイオン伝導体に比べて低いリチウムイオン伝導度を有するが、第1リチウムイオン伝導体に比べて低い焼結温度を有している。第2リチウムイオン伝導体の焼結温度は、600℃以下、より好ましくは300℃以上600℃以下、さらにより好ましくは300℃以上500℃以下である。焼結温度が600℃以下であると、焼成工程(焼結工程)においてリチウムイオン伝導体と電極活物質とが反応して、不導体などの副生成物が形成されることを抑制できる。したがって、電池特性の低下を抑制できる。また、電極活物質の種類の選択幅が広がるので、電池設計の自由度を向上できる。焼結温度が500℃以下であると、負極活物質として炭素材料を用いることが可能となる。したがって、電池のエネルギー密度を向上できる。また、導電剤として炭素材料を用いることができるので、電極層または電極活物質層に良好な電子伝導パスを形成し、電極層または電極活物質層の伝導性を向上できる。一方、焼結温度が300℃以上であると、焼成工程(焼結工程)において、電極前駆体および/または固体電解質前駆体に含まれる、アクリル樹脂などの有機結着剤を焼失させることができる。
まず、SEMを用いてリチウムイオン伝導体のSEM像を撮影する。次に、撮影したSEM像中から無作為に10個の第1リチウムイオン伝導体の粒子を選び出し、それらの粒子それぞれの最大の差し渡し長さ(SEM像で観察される面における最大の差し渡し長さ)を粒径(直径)D1として求める。次に、第1リチウムイオン伝導体の粒子が球形粒子であると仮定して、求めた粒径D1を用いて10個の第1リチウムイオン伝導体の体積v1(=π(D1)3/6)をそれぞれ求める。上述の体積v1を求める処理を10枚のSEM像について行い、得られた100(=10×10)個の第1リチウムイオン伝導体の体積v1の和V1を求める。
図1は、第1、第2リチウムイオン伝導体1、2のうち、第2リチウムイオン伝導体2が焼結された状態におけるリチウムイオン伝導体を模式的に示している。図1に示す状態にあるリチウムイオン伝導体では、第1リチウムイオン伝導体1が主要なリチウムイオン伝導パスとしての機能を有するのに対して、第2リチウムイオン伝導体2は第1リチウムイオン伝導体1を物理的に且つイオン伝導的につなぐ機能を有している。このため、上述したように、リチウムイオン伝導性の向上の観点からすると、第1リチウムイオン伝導体1の平均粒径は、第2リチウムイオン伝導体2の平均粒径よりも大きいことが好ましい。また、リチウムイオン伝導性の向上の観点からすると、第1リチウムイオン伝導体1の体積割合は、第2リチウムイオン伝導体2の体積割合よりも大きいことが好ましい。
以下、本技術の第1の実施形態に係るリチウムイオン伝導体の製造方法の一例について説明する。
第1の実施形態に係るリチウムイオン伝導体の粉末は、単独でのリチウムイオン伝導度は高いが、焼結温度が高く600℃を超える第1リチウムイオン伝導体(例えば酸化物結晶、酸化物ガラスセラミックスなど)と、リチウムイオン伝導度はそれほど高くないが、焼結温度が低く600℃以下である第2のリチウムイオン伝導体(例えばガラスなど)とを含んでいる。これにより、600℃以下でリチウムイオン伝導体を焼成すると、第2リチウムイオン伝導体が焼結して、第1リチウムイオン伝導体を物理的に且つイオン伝導的につなぐ。したがって、600℃以下の焼成温度(焼結温度)において、高いリチウムイオン伝導性が得られる。
第2リチウムイオン伝導体としての酸化物ガラス系リチウムイオン伝導体が、Ge、Si、BおよびPのうち2種以上、3種以上または4種全てと、Liと、Oとを含んでいてもよい。具体的には、GeO2、SiO2、B2O3およびP2O5のうち2種以上、3種以上または4種全てと、Li2Oとを含んでいてもよい。
第2の実施形態では、上述の第1の実施形態に係るリチウムイオン伝導体の焼結体を固体電解質として正極、負極および固体電解質層に含む電池について説明する。ここでは、リチウムイオン伝導体の焼結体とは、リチウムイオン伝導体に含まれる第1、第2リチウムイオン伝導体のうち第2リチウムイオン伝導体が焼結されているものを意味している。
本技術の第2の実施形態に係る電池は、いわゆるバルク型全固体電池であり、図2Aに示すように、正極11と負極12と固体電解質層13とを備え、固体電解質層13は正極11と負極12との間に設けられている。この電池は、電極反応物質であるLiの授受により電池容量が繰り返して得られる二次電池であり、リチウムイオンの吸蔵放出により負極の容量が得られるリチウムイオン二次電池であってもよいし、リチウム金属の析出溶解により負極の容量が得られるリチウム金属二次電池であってもよい。
正極11は、1種類または2種類以上の正極活物質と、固体電解質とを含んでいる正極活物質層である。固体電解質が、結着剤としての機能を有していてもよい。正極11は、必要に応じて導電剤をさらに含んでいてもよい。正極11は、例えば、正極前駆体としてのグリーンシート(以下「正極グリーンシート」という。)の焼成体である。
負極12は、1種類または2種類以上の負極活物質と、固体電解質とを含んでいる負極活物質層である。固体電解質が、結着剤としての機能を有していてもよい。負極12は、必要に応じて導電剤をさらに含んでいてもよい。負極12は、例えば、負極前駆体としてのグリーンシート(以下「負極グリーンシート」という。)の焼成体である。
固体電解質層13は、上述の第1の実施形態に係るリチウムイオン伝導体の焼結体を含んでいる。固体電解質層13は、例えば、固体電解質層前駆体としてのグリーンシート(以下「固体電解質グリーンシート」という。)の焼成体である。
この電池では、例えば、充電時において、正極11から放出されたリチウムイオンが固体電解質層13を介して負極12に取り込まれると共に、放電時において、負極12から放出されたリチウムイオンが固体電解質層13を介して正極11に取り込まれる。
次に、本技術の第2の実施形態に係る電池の製造方法の一例について説明する。この製造方法は、正極前駆体、負極前駆体および固体電解質層前駆体を形成する工程と、これらの前駆体を積層して焼成する工程とを備える。なお、この電池の製造方法では、正極前駆体、負極前駆体および固体電解質層前駆体がすべて、第1の実施形態に係るリチウムイオン伝導体を含んでいる場合を例として説明する。
正極前駆体としての正極グリーンシートを次のようにして形成する。まず、正極活物質と、第1の実施形態に係るリチウムイオン伝導体(固体電解質)と、有機系結着剤と、必要に応じて導電剤とを混合して、原料粉末としての正極合剤粉末を調製したのち、この正極合剤粉末を有機溶剤などに分散させて、正極グリーンシート形成用組成物としての正極スラリーを得る。なお、正極合剤粉末の分散性を向上させるため、分散を数回に分けて行ってもよい。
負極前駆体としての負極グリーンシートを次のようにして形成する。まず、負極活物質と、第1の実施形態に係るリチウムイオン伝導体(固体電解質)と、有機系結着剤と、必要に応じて導電剤とを混合して、原料粉末としての負極合剤粉末を調製したのち、この負極合剤粉末を有機溶剤などに分散させて、負極グリーンシート形成用組成物としての負極スラリーを得る。この負極スラリーを用いる以外のことは上述の「正極前駆体の形成工程」と同様にして、負極グリーンシートを得る。
固体電解質層前駆体としての固体電解質グリーンシートを次のようにして形成する。まず、第1の実施形態に係るリチウムイオン伝導体(固体電解質)と、有機系結着剤とを混合して、原料粉末としての電解質合剤粉末を調製したのち、この電解質合剤粉末を有機溶剤などに分散させて、固体電解質グリーンシート形成用組成物としての電解質合剤スラリーを得る。この電解質合剤スラリーを用いる以外のことは上述の「正極前駆体の形成工程」と同様にして、固体電解質グリーンシートを得る。
上述のようにして得られた正極グリーンシート、負極グリーンシートおよび固体電解質グリーンシートを用いて、次のようにして電池を作製する。まず、固体電解質グリーンシートを挟むように正極グリーンシートと負極グリーンシートとを積層して積層体する。その後、積層体を加熱するとともに、少なくとも積層体の厚さ方向に圧力が加わるように積層体をプレスする。これにより、積層体を構成する各グリーンシートに含まれる有機系結着剤が溶融されるとともに、積層体を構成する各グリーンシート間が密着される。積層体を加熱しながらプレスする具体的な方法としては、例えば、ホットプレス法、温間等方圧プレス(Warm Isostatic Press:WIP)などが挙げられる。
本技術の第2の実施形態では、正極グリーンシート、負極グリーンシートおよび固体電解質グリーンシートに含まれる固体電解質が、第1の実施形態に係るリチウムイオン伝導体、すなわち低温焼結可能なリチウムイオン伝導体である。したがって、正極グリーンシート、負極グリーンシートおよび固体電解質グリーンシートの焼成温度を低温にすることができる。これにより、積層体の焼成工程における正極活物質および負極活物質のダメージを抑制し、電池特性の低下を抑制できる。また、正極活物質および負極活物質の種類の選択幅が広がり、電池設計の自由度が向上する。
上述の第2の実施形態では、正極、負極がそれぞれ正極活物質層、負極活物質層のみにより構成された例について説明したが、正極および負極の構成はこれに限定されるものではない。例えば、図2Bに示すように、正極21が、正極集電体21Aと、この正極集電体21Aの一方の面に設けられた正極活物質層21Bとを備えていてもよい。また、負極22が、負極集電体22Aと、この負極集電体22Aの一方の面に設けられた負極活物質層22Bとを備えるようにしてもよい。この場合、正極活物質層21Bと負極活物質層22Bとが対向するように、正極21と負極22とが固体電解質層13を介して積層される。なお、上述の第2の実施形態と同様の箇所には同一の符号を付して説明を省略する。
第3の実施形態では、第2の実施形態またはその変形例に係る二次電池を備える電子機器について説明する。
以下、図3を参照して、本技術の第3の実施形態に係る電子機器400の構成の一例について説明する。電子機器400は、電子機器本体の電子回路401と、電池パック300とを備える。電池パック300は、正極端子331aおよび負極端子331bを介して電子回路401に対して電気的に接続されている。電子機器400は、例えば、ユーザにより電池パック300を着脱自在な構成を有している。なお、電子機器400の構成はこれに限定されるものではなく、ユーザにより電池パック300を電子機器400から取り外しできないように、電池パック300が電子機器400内に内蔵されている構成を有していてもよい。
電子回路401は、例えば、CPU(Central Processing Unit)、周辺ロジック部、インターフェース部および記憶部などを備え、電子機器400の全体を制御する。
電池パック300は、組電池301と、充放電回路302とを備える。組電池301は、複数の二次電池301aを直列および/または並列に接続して構成されている。複数の二次電池301aは、例えばn並列m直列(n、mは正の整数)に接続される。なお、図3では、6個の二次電池301aが2並列3直列(2P3S)に接続された例が示されている。複数の二次電池301aが積層型二次電池を構成していてもよい。二次電池301aとしては、第2の実施形態またはその変形例に係る電池が用いられる。
上述の第3の実施形態では、電子機器400が複数の二次電池301aにより構成される組電池301を備える場合を例として説明したが、電子機器400が、組電池301に代えて、一つの二次電池301aのみを備える構成としてもよい。
まず、高イオン伝導性を有する酸化物結晶系リチウムイオン伝導体(第1リチウムイオン伝導体)粉末として、ガーネット型酸化物結晶粉末:Li6.75La3Zr1.75Nb0.25O12粉末を準備した。また、低焼結温度を有する酸化物ガラス系リチウムイオン伝導体(第2リチウムイオン伝導体)粉末として、Li2OとSiO2とB2O3とY2O3とをモル分率でLi2O:SiO2:B2O3:Y2O3=70.31:16.54:12.41:0.74の割合で含むガラス粉末を準備した。次に、ガーネット型酸化物結晶粉末とガラス粉末とを重量比でガーネット型酸化物結晶粉末:ガラス粉末=70:30の割合で混合し、10mmφのジルコニアビーズ150gとともに、密閉容器に入れ、150rpmで5時間回転混合した。
高イオン伝導性を有する酸化物ガラスセラミックス系リチウムイオン伝導体(第1リチウムイオン伝導体)粉末として、Li2OとSiO2とB2O3とをモル分率でLi2O:SiO2:B2O3=70.83:16.67:12.5の割合で含むガラス粉末を結晶化させたものを準備した。また、結晶化ガラス粉末とガラス粉末とを重量比で結晶化ガラス粉末:ガラス粉末=50:50の割合で混合した。これ以外のことは実施例1と同様にして固体電解質層を得た。
結晶化ガラス粉末とガラス粉末とを重量比で結晶化ガラス粉末:ガラス粉末=70:30の割合で混合した。これ以外のことは実施例2と同様にして固体電解質層を得た。
結晶化ガラス粉末とガラス粉末とを重量比で結晶化ガラス粉末:ガラス粉末=80:20の割合で混合した。これ以外のことは実施例2と同様にして固体電解質層を得た。
ガーネット型酸化物結晶粉末とガラス粉末とを混合せずに、ガーネット型酸化物結晶粉末のみを用いた。これ以外のことは実施例1と同様にして固体電解質層を得た。
ガーネット型酸化物結晶粉末とガラス粉末とを混合せずに、ガラス粉末のみを用いた。これ以外のことは実施例1と同様にして固体電解質層を得た。
結晶化ガラス粉末とガラス粉末とを混合せずに、結晶化ガラス粉末のみを用いた。これ以外のことは実施例2と同様にして固体電解質層を得た。
以下のようにして、上述のようにして得られた実施例1~4、比較例1~3の固体電解質層のリチウムイオン伝導度を測定した。まず、焼結させた固体電解質層の両面に5mmφの大きさでPtをスパッタした。次に、インピーダンス測定装置(東洋テクニカ製)を用いて、電極を形成した固体電解質層の交流インピーダンス測定(周波数:10+6Hz~10-1Hz、電圧:100mV、1000mV)を行い、リチウムイオン伝導度を求めた。その結果を表2に示す。
結晶とガラスとを含むハイブリッド材料では、結晶単体よりも高いリチウムイオン伝導度を実現することができている。
また、結晶化ガラスとガラスとを含むハイブリッド材料では、結晶化ガラス単体よりも高いリチウムイオン伝導度を実現することができている。
結晶または結晶化ガラス単体では、界面抵抗が高くイオン伝導度が低い。
(1)
酸化物結晶およびガラスセラミクスのうちの少なくとも1種を含んでいる第1リチウムイオン伝導体と、
焼結温度が600℃以下である第2リチウムイオン伝導体と
を含み、
前記第1リチウムイオン伝導体のリチウムイオン伝導度は、前記第2リチウムイオン伝導体のリチウムイオン伝導度に比べて高いリチウムイオン伝導体。
(2)
前記第1リチウムイオン伝導体および前記第2リチウムイオン伝導体は、酸化物を含んでいる(1)に記載のリチウムイオン伝導体。
(3)
前記第1リチウムイオン伝導体の焼結温度は、600℃を超える(1)または(2)に記載のリチウムイオン伝導体。
(4)
前記第2リチウムイオン伝導体は、ガラスを含んでいる(1)から(3)のいずれかに記載のリチウムイオン伝導体。
(5)
前記ガラスは、Ge(ゲルマニウム)、Si(ケイ素)、B(ホウ素)およびP(リン)のうち1種以上と、Li(リチウム)と、O(酸素)とを含んでいる(4)に記載のリチウムイオン伝導体。
(6)
前記第2リチウムイオン伝導体が焼結された状態において、前記リチウムイオン伝導体のリチウムイオン伝導度は、5×10-7S/cm以上である(1)から(5)のいずれかに記載のリチウムイオン伝導体。
(7)
前記第1リチウムイオン伝導体の平均粒径が、前記第2リチウムイオン伝導体の平均粒径以上である(1)から(6)のいずれかに記載のリチウムイオン伝導体。
(8)
前記第1リチウムイオン伝導体の体積割合が、前記第2リチウムイオン伝導体の体積割合以上である(1)から(7)のいずれかに記載のリチウムイオン伝導体。
(9)
前記第2リチウムイオン伝導体の焼結温度が、300℃以上500℃以下である(1)から(8)のいずれかに記載のリチウムイオン伝導体。
(10)
(1)から(9)のいずれかに記載のリチウムイオン伝導体を含む固体電解質層。
(11)
前記第2リチウムイオン伝導体が、焼結されている(10)に記載の固体電解質層。
(12)
前記第2リチウムイオン伝導体が、前記第1リチウムイオン伝導体の間をつないでいる(10)または(11)に記載の固体電解質層。
(13)
(1)から(9)のいずれかに記載のリチウムイオン伝導体と、
活物質と
を含む電極。
(14)
前記活物質が、炭素材料を含んでいる(13)に記載の電極。
(15)
正極と、負極と、電解質層とを備え、
前記正極、前記負極および前記電解質層の少なくとも1つが、(1)から(9)のいずれかに記載のリチウムイオン伝導体を含む電池。
(16)
(15)に記載の電池を備え、
前記電池から電力の供給を受ける電子機器。
12、22 負極
13 固体電解質層
21A 正極集電体
21B 正極活物質層
22A 負極集電体
22B 負極活物質層
300 電池パック
301 組電池
301a 二次電池
302 充放電回路
400 電子機器
401 電子回路
Claims (16)
- 酸化物結晶およびガラスセラミクスのうちの少なくとも1種を含んでいる第1リチウムイオン伝導体と、
焼結温度が600℃以下である第2リチウムイオン伝導体と
を含み、
前記第1リチウムイオン伝導体のリチウムイオン伝導度は、前記第2リチウムイオン伝導体のリチウムイオン伝導度に比べて高いリチウムイオン伝導体。 - 前記第1リチウムイオン伝導体および前記第2リチウムイオン伝導体は、酸化物を含んでいる請求項1に記載のリチウムイオン伝導体。
- 前記第1リチウムイオン伝導体の焼結温度は、600℃を超える請求項1に記載のリチウムイオン伝導体。
- 前記第2リチウムイオン伝導体は、ガラスを含んでいる請求項1に記載のリチウムイオン伝導体。
- 前記ガラスは、Ge(ゲルマニウム)、Si(ケイ素)、B(ホウ素)およびP(リン)のうち1種以上と、Li(リチウム)と、O(酸素)とを含んでいる請求項4に記載のリチウムイオン伝導体。
- 前記第2リチウムイオン伝導体が焼結された状態において、前記リチウムイオン伝導体のリチウムイオン伝導度は、5×10-7S/cm以上である請求項1に記載のリチウムイオン伝導体。
- 前記第1リチウムイオン伝導体の平均粒径が、前記第2リチウムイオン伝導体の平均粒径以上である請求項1に記載のリチウムイオン伝導体。
- 前記第1リチウムイオン伝導体の体積割合が、前記第2リチウムイオン伝導体の体積割合以上である請求項1に記載のリチウムイオン伝導体。
- 前記第2リチウムイオン伝導体の焼結温度が、300℃以上500℃以下である請求項1に記載のリチウムイオン伝導体。
- 請求項1に記載のリチウムイオン伝導体を含む固体電解質層。
- 前記第2リチウムイオン伝導体が、焼結されている請求項10に記載の固体電解質層。
- 前記第2リチウムイオン伝導体が、前記第1リチウムイオン伝導体の間をつないでいる請求項10に記載の固体電解質層。
- 請求項1に記載のリチウムイオン伝導体と、
活物質と
を含む電極。 - 前記活物質が、炭素材料を含んでいる請求項13に記載の電極。
- 正極と、負極と、電解質層とを備え、
前記正極、前記負極および前記電解質層の少なくとも1つが、請求項1に記載のリチウムイオン伝導体を含む電池。 - 請求項15に記載の電池を備え、
前記電池から電力の供給を受ける電子機器。
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JPWO2018092370A1 (ja) * | 2016-11-16 | 2019-12-12 | 株式会社村田製作所 | 固体電池、電池パック、車両、蓄電システム、電動工具及び電子機器 |
WO2022201755A1 (ja) * | 2021-03-26 | 2022-09-29 | 太陽誘電株式会社 | 固体電解質、全固体電池、固体電解質の製造方法、および全固体電池の製造方法 |
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US10770751B2 (en) | 2018-05-17 | 2020-09-08 | Samsung Electronics Co., Ltd. | Solid state lithium-ion conductor |
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