WO2020022342A1 - 全固体ナトリウム電池用の固体電解質とその製造方法及び全固体ナトリウム電池 - Google Patents

全固体ナトリウム電池用の固体電解質とその製造方法及び全固体ナトリウム電池 Download PDF

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WO2020022342A1
WO2020022342A1 PCT/JP2019/028881 JP2019028881W WO2020022342A1 WO 2020022342 A1 WO2020022342 A1 WO 2020022342A1 JP 2019028881 W JP2019028881 W JP 2019028881W WO 2020022342 A1 WO2020022342 A1 WO 2020022342A1
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solid
solid electrolyte
sodium battery
state sodium
ionic conductivity
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French (fr)
Japanese (ja)
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晃敏 林
辰巳砂　昌弘
敦 作田
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University Public Corporation Osaka
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University Public Corporation Osaka
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Priority to CN201980048774.2A priority Critical patent/CN112470317B/zh
Priority to JP2020532414A priority patent/JP7270991B2/ja
Priority to US17/260,361 priority patent/US11830985B2/en
Priority to EP19839933.9A priority patent/EP3828978A4/en
Publication of WO2020022342A1 publication Critical patent/WO2020022342A1/ja
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Definitions

  • the present invention relates to a solid electrolyte for an all-solid sodium battery, a method for producing the same, and an all-solid sodium battery. More specifically, the present invention relates to a solid electrolyte having improved ionic conductivity for an all solid sodium battery, a method for producing the same, and an all solid sodium battery including the same.
  • Non-Patent Document 1 reports that Na 3 SbS 4 exhibits high ionic conductivity and additionally exhibits high atmospheric stability.
  • the inventors of the present invention have attempted to replace a part of Sb in Na 3 SbS 4 with another metal ion. As a result, a portion of the pentavalent Sb, by replacing an element other than pentavalent, by inserting a defect in the structure of the Na 3 SbS 4, a solid electrolyte exhibiting high ionic conductivity than Na 3 SbS 4
  • the present inventors have found out what can be provided, and have reached the present invention.
  • the following formula Na 3-x Sb 1-x ⁇ x S 4 (In the formula, ⁇ is selected from elements in which Na 3-x Sb 1-x ⁇ x S 4 has a higher ionic conductivity than Na 3 SbS 4 , and x is 0 ⁇ x ⁇ 1.)
  • the solid electrolyte for all solid sodium batteries represented by these is provided.
  • a method for producing a solid electrolyte which is a method for producing a solid electrolyte, wherein raw materials for producing a solid electrolyte are mixed by a mechanical milling treatment, and the resulting mixture is pressed.
  • an all-solid sodium battery including a positive electrode, a negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode, wherein the solid electrolyte layer is a layer containing the solid electrolyte.
  • the solid electrolyte which shows higher ionic conductivity, its manufacturing method, and the all-solid-state sodium battery using the same can be provided.
  • a solid electrolyte exhibiting higher ionic conductivity can be provided.
  • ⁇ is W or Mo.
  • x is 0.05 ⁇ x ⁇ 0.2.
  • the solid electrolyte is in the form of a glass ceramic.
  • the solid electrolyte includes at least a crystalline part, and the crystalline part is composed of a cubic crystal.
  • the fixed electrolyte shows a peak of an anion derived from ⁇ S 4 in the Raman spectrum.
  • Raw materials for producing a solid electrolyte are mixed by mechanical milling, and the resulting mixture is pressed.
  • the solid electrolyte is pressurized at a pressure of 300 MPa or more and heated at 250 to 300 ° C. for 0.1 hour or more.
  • FIG. 2 is a model diagram of an all solid state battery using Na 2.88 Sb 0.88 W 0.12 S 4 gc. It is a diagram showing the Na 3-x Sb 1-x W x S 4 ms of XRD patterns. It is a diagram showing a Raman spectrum of Na 3-x Sb 1-x W x S 4 ms. It is a diagram showing the Na 3-x Sb 1-x W x S 4 ms of DTA curve. Na 3-x Sb 1-x W x S 4 ms, which is a diagram showing an impedance plot of gc. Na 3-x Sb 1-x W x S 4 ms, illustrates the temperature dependence of ionic conductivity of gc.
  • FIG. 3 is a diagram illustrating a relationship between a voltage and a current in a DC polarization method. Is a diagram showing temperature dependence of ionic conductivity of Na 2.88 Sb 0.88 W 0.12 S 4 .
  • Square Akiraoyobi Na 2.88 Sb 0.88 W 0.12 S 4 to Na 3 SbS 4 has a diagram representing the architecture of a cubic having the.
  • the solid electrolyte has the following formula: Na 3-x Sb 1-x ⁇ x S 4 It is represented by In the formula, ⁇ is selected from elements in which Na 3-x Sb 1-x ⁇ x S 4 has a higher ionic conductivity than Na 3 SbS 4 . ⁇ may be composed of one type or a combination of plural types. Preferably, ⁇ is selected from elements exhibiting hexavalence.
  • the hexavalent element includes W, Mo, Cr, Mn, Ru, Re, Os, and Ir.
  • the hexavalent element is preferably selected from W and Mo, more preferably W.
  • x is 0 ⁇ x ⁇ 1.
  • x is, for example, 0.001, 0.002, 0.004, 0.006, 0.008, 0.01, 0.012, 0.015, 0.02, 0.05, 0.1,. Various values such as 2, 0.5, 0.75, 0.9, etc. can be taken.
  • the range of x changes according to the valence of ⁇ . x preferably indicates a range capable of providing a solid electrolyte having an ionic conductivity higher than that of Na 3 SbS 4 . Further, x is more preferably 0.05 ⁇ x ⁇ 0.2. ⁇ may be substituted with, for example, group 7 such as Mn, group 13 such as B, Al and Ga, group 14 such as C, Si, Ge, Sn and Pb, or group 15 such as P, As and Bi.
  • the substitution amount can be less than 50 atomic%.
  • the substitution amount is, for example, 0%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 49%, 49.9%, and the like.
  • S may be substituted with another element or molecule.
  • Other elements or molecules F, Cl, Br, I, NO 3, BH 4, PF 6, ClO 4, BH 4, CF 3 SO 3, (CF 3 SO 2) 2 N, (C 2 F 5 SO 2 ) 2 N, (FSO 2 ) 2 N and [B (C 2 O 4 ) 2 ].
  • the substitution amount can be 0 ⁇ Y ⁇ 3.
  • ⁇ may consist of one kind or a combination of plural kinds.
  • Y is 0.001, 0.002, 0.004, 0.006, 0.008, 0.01, 0.012, 0.015, 0.02, 0.05, 0.1, 0.5 , 0.75, 1.5, 2.5, 2.9, etc.
  • the range of Y changes according to its valence.
  • the solid electrolyte may be glassy or glass-ceramic.
  • glassy means a substantially non-crystalline state.
  • substantially includes the case where the solid electrolyte in the crystalline state is finely dispersed in addition to the 100% non-crystalline state.
  • the glass-ceramic state refers to a state generated by heating a glass-like solid electrolyte at a temperature equal to or higher than the glass transition point.
  • the glass-ceramic solid electrolyte may be in a state where at least a crystalline portion is dispersed in an amorphous glass component.
  • the ratio of the crystalline part is, for example, 0.001%, 0.01%, 0.1%, 1%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 97%, 99%, 99.9%, 100%, etc. Can take various values.
  • the ratio of the crystalline part may be 50% by mass or more, or may be 80% by mass or more based on the whole glass ceramics.
  • the ratio of the crystalline part can be measured by solid-state NMR.
  • the crystalline part may be composed of cubic and / or tetragonal crystals. Preferably, the crystalline part comprises cubic.
  • the glass-ceramic solid electrolyte may be one in which the glass transition point that was present in the corresponding glass-like solid electrolyte does not exist.
  • the solid electrolyte may be composed of one kind or a mixture of plural kinds.
  • the solid electrolyte may show a peak of an anion derived from ⁇ S 4 in a Raman spectrum obtained by Raman spectroscopy.
  • the solid electrolyte shows the peak of this anion in the Raman spectrum, the solid electrolyte has a crystal structure derived from ⁇ S 4 in the electrolyte, so that the ionic conductivity of the solid electrolyte can be improved.
  • the method for producing the solid electrolyte is not particularly limited as long as the raw materials can be mixed.
  • examples of the raw material include sodium salts of ⁇ in the elements Na 2 S, Sb 2 S 3 , S and ⁇ S z (z is a number determined according to the valence of ⁇ ).
  • a mechanical milling treatment is preferable from the viewpoint of mixing the components more uniformly.
  • the mechanical milling process is not particularly limited to the processing apparatus and processing conditions as long as the components can be uniformly mixed.
  • a ball mill can usually be used. A ball mill is preferable because a large mechanical energy can be obtained.
  • the planetary ball mill is preferable because the pot rotates and the base rotates around in the direction opposite to the direction of rotation, so that high impact energy can be efficiently generated.
  • the processing conditions can be appropriately set according to the processing apparatus used. For example, when using a ball mill, the higher the rotation speed and / or the longer the processing time, the more uniformly the raw materials can be mixed. Specifically, when a planetary ball mill is used, the conditions include a rotation speed of 50 to 600 rotations / minute, a processing time of 0.1 to 100 hours, and 1 to 100 kWh / kg of raw material. By the mechanical milling treatment, a glassy solid electrolyte is obtained.
  • the glass-ceramic solid electrolyte can be obtained by heating the glass-like solid electrolyte at a temperature equal to or higher than the glass transition point (for example, 100 to 400 ° C.).
  • the heating temperature can be, for example, 100 ° C, 150 ° C, 200 ° C, 250 ° C, 275 ° C, 300 ° C, 350 ° C, or 400 ° C.
  • the heating time can be from 10 minutes to 24 hours. For example, 10 minutes, 1 hour, 1.5 hours, 3 hours, 6 hours, 10 hours, 12 hours, 20 hours or 24 hours.
  • the all solid sodium battery may be a primary battery or a secondary battery. In the case of a secondary battery, the charge / discharge capacity and / or the number of cycles can be improved.
  • An all solid sodium battery can be used, for example, at -100 to 100 ° C.
  • the all-solid-state sodium battery includes a positive electrode, a negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode.
  • the solid electrolyte layer is a layer containing the solid electrolyte.
  • the solid electrolyte layer may contain other components used in the all-solid-state sodium battery in addition to the solid electrolyte.
  • binders such as metal oxides such as P, As, Ti, Fe, Zn, and Bi, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, and polyethylene are exemplified.
  • the solid electrolyte can be formed into a solid electrolyte layer by, for example, pressing to a predetermined thickness.
  • the press can be between 100 and 2000 MPa.
  • the pressure may be 100 MPa, 200 MPa, 300 MPa, 360 MPa, 500 MPa, 700 MPa, 1000 MPa, 1080 MPa, 1500 MPa, or 2000 MPa.
  • the thickness of the solid electrolyte layer can be, for example, 0.1 to 1 mm.
  • 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.75 mm, 0.8 mm, 0.9 mm or It can be 1.0 mm.
  • the positive electrode is not particularly limited.
  • the positive electrode may be composed of only a positive electrode active material, or may be a positive electrode composite optionally mixed with a binder, a conductive material, an electrolyte, and the like.
  • the positive electrode active material for example, Na 4 Ti 5 O 12 , NaCoO 2 , NaMnO 2 , NaVO 2 , NaCrO 2 , NaNiO 2 , Na 2 NiMn 3 O 8 , NaNi 1/3 Co 1/3 Mn 1/3 O 2 , S, Na 2 S, FeS, TiS 2 , NaFeO 2 , Na 3 V 2 (PO 4 ) 3 , NaMn 2 O 4 , Na 2 TiS 3 and the like.
  • the positive electrode active material may be coated with a material such as NaNbO 3 , Al 2 O 3 , NiS, or the like.
  • the binder include polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, and polyethylene.
  • the conductive material include natural graphite, artificial graphite, acetylene black, Ketjen black, Denka black, carbon black, and vapor grown carbon fiber (VGCF).
  • the electrolyte include an electrolyte that is usually used for a solid electrolyte layer. It is also possible to use the solid electrolyte according to the invention.
  • the positive electrode (positive electrode composite) can be obtained as a pellet by pressing.
  • the negative electrode is not particularly limited.
  • the negative electrode may be made of only the negative electrode active material, or may be a negative electrode composite mixed with a binder, a conductive material, an electrolyte, and the like.
  • the negative electrode active material include metals such as Na, In, Sn, and Sb, Na alloys, graphite, hard carbon, Na 4/3 Ti 5/3 O 4 , Na 3 V 2 (PO 4 ) 3 , and SnO. And the like.
  • the binder, the conductive material, and the electrolyte any of those listed in the column of the positive electrode can be used.
  • the negative electrode (negative electrode composite) can be obtained as a pellet by pressing.
  • a metal sheet (foil) made of a metal or an alloy thereof is used as the negative electrode active material, it can be used as it is.
  • the positive electrode and / or the negative electrode may be formed on a current collector such as SUS (stainless steel), aluminum, or copper.
  • the all-solid-state sodium battery can be obtained, for example, by laminating a positive electrode, a solid electrolyte layer, and a negative electrode, and pressing.
  • a metal layer selected from Au, Pt, In, Al, Sn, Si and the like may be provided between the negative electrode and the solid electrolyte layer. Further, the metal layer may be provided between the positive electrode and the solid electrolyte layer.
  • the metal layer may cover part of the negative electrode and / or the positive electrode, but preferably covers the entire surface from the viewpoint of further extending the cycle life.
  • the metal layer can be formed by a gas phase method. By being formed by a vapor phase method, it can be formed with good adhesion and densely on the surface of the solid electrolyte layer. As a result, the generation of dendrites caused by the dissolution and precipitation of Na during charge and discharge can be suppressed, and the cycle life can be extended. Further, it is preferable that the metal layer is formed such that the unevenness on the surface of the metal layer is smaller than the unevenness on the surface of the solid electrolyte layer. By forming in this manner, the adhesion between the solid electrolyte layer and the negative electrode and / or the positive electrode can be improved, and as a result, an all-solid sodium secondary battery having a long cycle life can be provided.
  • the vapor phase method examples include a vapor deposition method, a CVD method, and a sputtering method. Of these, the vapor deposition method is simple.
  • the all-solid-state sodium battery according to the present invention can have a charge / discharge capacity of 250 mAh g ⁇ 1 or more by being manufactured with the above configuration.
  • the thickness of the metal layer is not particularly limited as long as the reversibility of dissolution and precipitation of Na can be improved.
  • the thickness can be 0.01 to 10 ⁇ m.
  • the thickness of the metal layer is, for example, 0.01 ⁇ m, 0.02 ⁇ m, 0.03 ⁇ m, 0.04 ⁇ m, 0.05 ⁇ m, 0.06 ⁇ m, 0.07 ⁇ m, 0.08 ⁇ m, 0.09 ⁇ m, 0.10 ⁇ m, and 0 ⁇ m.
  • a more preferred thickness is from 0.03 to 0.1 ⁇ m.
  • Na 2 S was manufactured by Nagao Co. (purity> 99.1%)
  • Sb 2 S 3 was manufactured by Nippon Seimitsu Co. (purity> 98%)
  • S was manufactured by Aldrich Co. (purity> 99.98%)
  • WS 2 is manufactured by Sigma-Aldrich Corporation (purity 99%)
  • MoS 2 is manufactured by Sigma-Aldrich Corporation (purity unknown)
  • SnS 2 three-Tsuwa chemical Co., Ltd. purity 99.5%
  • SiS 2 Used was manufactured by Furuuchi Chemical Co. (purity 99.9%).
  • Example 1 Preparation of Na 3-x Sb 1-x W x S 4 Na 2 S, Sb 2 S 3 , S and WS 2 were each mixed with the composition shown in Table 1 below and charged into a planetary ball mill.
  • a mechanical milling treatment was performed to obtain glassy Na 3-x Sb 1-x W x S 4 (milled samples: ms).
  • the planetary ball mill used was Pulverisette P-7 manufactured by Fritsch, and the pot and the balls were made of ZrO 2 , and a mill having 250 balls of 4 mm in diameter in a 45 ml pot was used.
  • the said manufacturing method is described in Akitoshi Hayashi et al.
  • DTA Differential thermal analysis
  • XRD X-ray diffraction
  • Example 3 Preparation of Na 2.82 Sb 0.88 W 0.12 S 3.94 Cl 0.06 Na 2 S, Sb 2 S 3 , S, WS 2 , and NaCl were 46: 14.6: 33.3: 4: The mixture was mixed so as to have a molar ratio of 2, and subjected to mechanical milling treatment for 30 hours in the same manner as in Example 1 to obtain glassy Na 2.82 Sb 0.88 W 0.12 S 3.94 Cl 0.06 .
  • About 150 mg of glassy Na 2.82 Sb 0.88 W 0.12 S 3.94 Cl 0.06 was pressed in the same manner as in Example 1 at room temperature for 5 minutes (pressure 360 MPa) to obtain a thickness.
  • Na 2.82 Sb 0.88 W 0.12 S 3.94 Cl 0.06 pellets of approximately 1 mm.
  • Example 5 Creating the all-solid battery using Na 2.88 Sb 0.88 W 0.12 S 4 gc to produce the electrolyte of the all-solid-state battery using Na 2.88 Sb 0.88 W 0.12 S 4 gc.
  • the basic structure of the battery is as shown in FIG. AB-Na 2.88 Sb 0.88 W 0.12 S 4 obtained by mixing acetylene black (AB), Na 2.88 Sb 0.88 W 0.12 S 4 gc and Na 2 TiS 3 as the positive electrode composite
  • AB acetylene black
  • Na 2.88 Sb 0.88 W 0.12 S 4 gc and Na 2 TiS 3 as the positive electrode composite
  • Prepare 10 mg of -Na 2 TiS 3 prepare 80 mg of Na 2.88 Sb 0.88 W 0.12 S 4 gc as the electrolyte, and prepare 40 mg of Na-Sn as the negative electrode.
  • the positive electrode composite and the negative electrode do not directly touch each other.
  • the battery was manufactured by placing the SUS with the electrolyte interposed therebetween and placing the SUS on the SUS similarly.
  • Na 2.88 Sb 0.88 W 0.12 S 4 the one produced in Example 1 was used.
  • the charge / discharge capacity when the battery obtained was subjected to 5 cycles of charge / discharge at 25 ° C. under a current density of 0.13 mAcm 2 and a range of 0.8 to 3.2 V was measured.
  • the glass-like Na 3 + x Sb 1-x Si x S 4 was heated in the same manner as in Example 1 at a temperature between 250 ° C. and 280 ° C. for 1.5 hours, and the glass-ceramic Na 3 + x Sb 1-x Si x was heated. to obtain a S 4.
  • Example 1 Impedance plots of Na 3-x Sb 1-x W x S 4 ms and gc of Example 1 Impedance plots of ms and gc of the three W-containing pellets obtained in Example 1 are shown in FIG. (A) to (F). It can be seen that resistance separation between the grains and the grain boundaries cannot be performed, and that ms shows a resistance value larger than gc.
  • FIG. 7 shows XRD patterns of the obtained four types of gc pellets.
  • FIG. 7 shows that the crystallinity was increased by the heat treatment, and that no particularly noticeable peak shift was observed even when the substitution amount of Sb to W was increased.
  • FIG. 12 shows the temperature dependence of the ionic conductivity of the sample caused by the difference in the temperature.
  • FIG. 12 shows that the sample with the longer heating time shows higher ionic conductivity than the sample with the shorter heating time.
  • FIGS. 13A and 13B show the tetragonal structure of Na 3 SbS 4 and the cubic structure of Na 2.88 Sb 0.88 W 0.12 S 4 .
  • a cubic crystal has a structure with higher symmetry than a tetragonal crystal, and thus ions are easier to pass through the cubic crystal.
  • Na 3-x Sb 1-x W x S 4 differs from the tetragonal system in that Na ions are deficient (Na vacant site A) (for example, Na occupancy is 96%), so that ion conductivity is improved.
  • FIG. 15 shows the difference in ionic conductivity from 88 Sb 0.88 W 0.12 S 4 .
  • FIGS. 16 and 17 show the generation amount and the XRD pattern, respectively.
  • FIG. 16 shows that the amount of H 2 S generated after exposing Na 2.88 Sb 0.88 W 0.12 S 4 to the atmosphere is extremely small.
  • FIG. 17 the XRD pattern after exposure to the atmosphere was observed a pattern similar to Na 3 SbS 4 ⁇ 9H 2 O . From this, it is considered that a hydrate is formed after exposure to the atmosphere, so that the generation amount of H 2 S is extremely small.
  • FIG. 18 shows the results of the charge / discharge characteristics test of the all solid state battery.
  • FIG. 18 shows that the present battery has a high charge / discharge capacity exceeding 250 mAh g ⁇ 1 . From the above, it can be seen that Na 2.88 Sb 0.88 W 0.12 S 4 is extremely useful as a solid electrolyte for an all solid sodium battery.
  • FIGS. 19A to 19D show the difference in impedance from W 0.12 S 4 . From FIGS. 19A to 19D , it can be seen that Na 2.88 Sb 0.88 S4 has a larger resistance value than Na 2.88 Sb 0.88 W 0.12 S 4 .
  • FIG. 21 shows (A) and (B). From FIGS. 21A and 21B, it can be seen that the activation energy increases as x increases in each of the ms and gc categories. Table 9 shows the measurement results of the ionic conductivity and the activation energy of the Na 3 + x Sb 1-x Sn x S 4 sample.
  • the ionic conductivity is smaller for gc than for ms.

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WO2023095890A1 (ja) * 2021-11-26 2023-06-01 公立大学法人大阪 金属及び／又は半金属含有硫化物の製造方法、ナトリウム含有硫化物
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