WO2019009228A1 - リチウム二次電池の固体電解質及び当該固体電解質用硫化物系化合物 - Google Patents
リチウム二次電池の固体電解質及び当該固体電解質用硫化物系化合物 Download PDFInfo
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Definitions
- the present invention relates to a solid electrolyte of a lithium secondary battery and a sulfide-based compound that can be suitably used as the solid electrolyte.
- the lithium secondary battery is a secondary battery having a structure in which lithium is dissolved out as ions from the positive electrode during charging, moves to the negative electrode, and is occluded, and lithium ions return from the negative electrode to the positive electrode during discharging.
- Lithium secondary batteries have features such as high energy density and long life, so home appliances such as video cameras, portable electronic devices such as laptop computers and mobile phones, and electric tools such as power tools It is widely used as a power source for tools and the like, and has recently been applied to a large battery mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV).
- EV electric vehicle
- HEV hybrid electric vehicle
- This type of lithium secondary battery is composed of a positive electrode, a negative electrode, and an ion conductive layer sandwiched between the both electrodes, and in the ion conductive layer, a separator made of a porous film such as polyethylene or polypropylene is non-aqueous.
- a separator made of a porous film such as polyethylene or polypropylene is non-aqueous.
- electrolyte solution is generally used.
- an organic electrolyte solution using a flammable organic solvent as a solvent is used as the electrolyte, it is necessary to improve the structure and material to prevent volatilization and leakage, and at the time of a short circuit. It is also necessary to improve safety equipments to reduce the temperature rise, and structural and material improvements to prevent short circuits.
- the safety device can be simplified, and the manufacturing cost can be further improved. As well as being excellent in productivity, it also has a feature that it can be stacked in series in a cell to achieve high voltage.
- this type of solid electrolyte does not move except for Li ion, it is expected that it will lead to the improvement of safety and durability, for example, no side reaction due to migration of anion will occur.
- the solid electrolyte used in such a battery is required to have as high ion conductivity as possible, and be chemically and electrochemically stable.
- lithium halide, lithium nitride, lithium oxyacid salt or derivatives thereof Etc. are known as the material candidate.
- An ion conducting sulfide ceramic is disclosed.
- Patent Document 2 the chemical formula: Li + (12-nx) B n + X 2- (6- x) Y - x (B n + is P, As, Ge, Ga, Sb, Si, Sn, Al, in, at least one Ti, V, is selected from Nb and Ta, at least one X 2-is selected S, Se, and from Te, Y - is F, Cl, Br, I, CN, OCN, SCN and There is disclosed a lithium ion conductive material which is at least one selected from N 3 and represented by 0 ⁇ x ⁇ 2) and having a silver germanium germanide crystal structure.
- Patent Document 3 as a solid compound which can be prepared as a single layer in addition to high fluidity of lithium ion, a compound represented by the general formula (I) Li + (12-nx) B n + X 2- (6-x) Y - a lithium ⁇ germanium ore by x selected, in this formula, B n + is, P, As, Ge, Ga , Sb, Si, Sn, Al, in, Ti, V, from the group consisting of Nb and Ta X 2- is selected from the group consisting of S, Se and Te, Y - is selected from the group consisting of Cl, Br, I, F, CN, OCN, SCN, N 3 and 0 ⁇ x ⁇ 2
- the lithium silver sulphide germanium ore is disclosed.
- Patent Document 4 has a structure skeleton of Li 7 PS 6 as a new sulfide-based solid electrolyte that can significantly increase the conductivity compared to a conventional solid electrolyte, and a part of P is made of Si.
- Patent Document 5 relates to a compound having a cubic crystal structure in a space group F-43 m and represented by a composition formula: Li 7-x PS 6-x Ha x (Ha is Cl or Br),
- a sulfide-based solid electrolyte for a lithium secondary battery capable of enhancing charge-discharge efficiency and cycle characteristics by enhancing lithium ion conductivity and lowering electron conductivity
- x in the above composition formula is 0.2 to 1
- a sulfide-based solid electrolyte for a lithium secondary battery is disclosed, which is characterized in that the lightness L * value of the L * a * b * color system is 60.0 or more.
- Patent Document 6 relates to a sulfide-based solid electrolyte compound for a lithium secondary battery having a cubic Argyrodite type crystal structure, which can suppress the generation amount of hydrogen sulfide when exposed to the air, and is left in dry air.
- a sulfide-based solid electrolyte compound for a lithium secondary battery capable of maintaining high conductivity even in the case of lithium secondary battery represented by the composition formula: Li 7-x + y PS 6-x Cl x + y
- a sulfide-based solid electrolyte compound for a battery wherein x and y in the above composition formula satisfy 0.05 ⁇ y ⁇ 0.9 and ⁇ 3.0x + 1.8 ⁇ y ⁇ ⁇ 3.0x + 5.7.
- a sulfide based solid electrolyte compound for a lithium secondary battery is disclosed.
- Non-Patent Document 2 a Li 6 PS 5 Cl 1-x Br x (0 ⁇ x ⁇ 1) solid solution containing two types of halogens is prepared by a mechanochemical method and subsequent heat treatment, and its composition and ion conductivity The relationship with is reported.
- JP 2001-250580 A JP 2011-96630 A Japanese Patent Publication No. 2010-540396 JP, 2013-137889, A WO 2015/012042 WO 2016/104702
- Hirokawa, Y. et al. "Characterization of Algironite-type Li6PS5Cl1-xBrx solid electrolyte. March 2015 Electrochemical Society [2H08].
- a sulfide-based composite having a cubic crystal structure of Argyrodite generally has high crystallinity and is excellent in ion conductivity, but is characterized in that it is hard, and is crushed at the pressure of forming an electrode. Had the task of being difficult.
- the present invention relates to a sulfide-based compound having a cubic crystal structure of Argyrodite, and proposes a new sulfide-based compound having a low elastic modulus while maintaining high ionic conductivity. .
- a sulfide based compound for solid electrolyte of a secondary battery is proposed.
- Sulfide compounds proposed by the present invention has a crystal phase of cubic system Argyrodite type crystal structure, composition formula: in Li 7-x PS 6-x Cl represented by y Br z sulfide compound, Low modulus of elasticity while maintaining high ionic conductivity by defining the ratio of the molar ratio of Br to the molar ratio of Cl within a predetermined range while making the total molar ratio of Cl and Br larger than 1.0 Can be realized and the battery resistance can be reduced.
- the sulfide-based compound proposed by the present invention when forming an electrode using the above-mentioned sulfide-based compound proposed by the present invention as a solid electrolyte, when a pressing pressure is applied, the solid electrolyte can be crushed and the gaps between active material particles can be filled; Therefore, the battery resistance can be lowered because the contact point and the contact area with it can be increased. Therefore, the sulfide-based compound proposed by the present invention can be particularly suitably used as a solid electrolyte of a lithium secondary battery.
- (A) is a SEM photograph (5000 times) obtained by observing the sulfide type compound (sample) obtained in Example 4 with a scanning electron microscope (SEM), and (b) is obtained in Example 4 It is a SEM photograph (5000 times) obtained by pelletizing the sulfide type compound (sample) at a pressure of 200 MPa and observing the cross section with a scanning electron microscope.
- SEM scanning electron microscope
- (A) is a SEM photograph (5000 times) obtained by observing the sulfide type compound (sample) obtained in Comparative Example 1 with a scanning electron microscope (SEM), and (b) is obtained in Comparative Example 1 It is a SEM photograph (5000 times) obtained by pelletizing the sulfide type compound (sample) at a pressure of 200 MPa and observing the cross section with a scanning electron microscope.
- This sulfide compound has a crystal phase of cubic system Argyrodite type crystal structure, composition formula (1): a compound represented by Li 7-x PS 6-x Cl y Br z. Whether or not it has a crystal phase of cubic Argyrodite type crystal structure can be confirmed, for example, by analysis with an X-ray diffraction method (XRD, Cu ray source) as described later.
- XRD X-ray diffraction method
- x in the above composition formula (1) is preferably greater than 1.0 and not more than 1.8, and more preferably not less than 1.1 or not more than 1.7, and more preferably not less than 1.2 or not less than 1.6. It is further preferred that
- the ratio (z / y) of the molar ratio of Br to the molar ratio of Cl is preferably 0.1 to 10. If the ratio (z / y) of the molar ratio of Br to the molar ratio of Cl is 0.1 or more, it is preferable because the solid electrolyte has a low elastic modulus, and on the other hand, if the (z / y) is 10 or less It is preferable because of high ion conductivity. From this point of view, the ratio (z / y) of the molar ratio of Br to the molar ratio of Cl is preferably 0.1 to 10, and more preferably 0.2 or more or 5 or less, among them 0.3 or more or 3 or less It is further preferred that
- y indicating the molar ratio of Cl preferably satisfies 0.3 ⁇ y ⁇ 1.5. If the molar ratio y of Cl is 0.3 or more, it is preferable because the ion conductivity can be further increased compared to less than 0.3, while if it is 1.5 or less, the low elastic modulus is maintained. It is preferable because From this point of view, y in the above composition formula (1) is preferably 0.3 to 1.5, and more preferably 0.4 or more or 1.2 or less, and more preferably 0.6 or more or 1.0 or less. Is more preferred.
- z representing the molar ratio of Br preferably satisfies 0.3 ⁇ z ⁇ 1.5. If the molar ratio z of Br is 0.3 or more, the elastic modulus can be further reduced. On the other hand, if it is 1.5 or less, the ion conductivity can be maintained, which is preferable.
- the Br compound has a lower melting point than the Cl compound, the addition of the Br compound makes the compound highly reactive and facilitates the synthesis of the sulfide compound. From this point of view, z in the above composition formula (1) is preferably 0.3 to 1.5, and more preferably 0.4 or more or 1.2 or less, and more preferably 0.6 or more or 1.0 or less. Is more preferred.
- the present solid electrolyte only needs to contain the present sulfide-based compound, and may contain other materials and components. Therefore, even if the present solid electrolyte consists of a single phase composed of a crystal phase of cubic Argyrodite crystal structure, the crystal phase of cubic Argyrodite crystal structure and the crystal phase represented by LiCl Even if it is composed of a mixed phase containing either a mixed phase containing a crystal phase of cubic Argyrodite type crystal structure and a crystal phase represented by LiBr, a cubic system Argyrodite type crystal It may consist of a mixed phase containing the crystal phase of the structure, the crystal phase represented by LiCl, and the crystal phase represented by LiBr.
- a mixed phase containing a crystal phase of cubic system Argyrodite type crystal structure and a crystal phase represented by LiCl and / or LiBr a crystal phase of cubic system Argyrodite type crystal structure, LiCl and / or LiBr
- a crystal phase of cubic system Argyrodite type crystal structure, LiCl and / or LiBr in addition to the mixed phase with the crystal phase shown in, it also includes the case of containing other crystal phases.
- the present sulfide-based compound is the main material of the present solid electrolyte, and 50% by mass or more, particularly 80% by mass or more, among them 90% by mass or more (including 100% by mass) of the whole solid electrolyte.
- the present sulfide-based compound is occupied, and in particular, it is desirable to be composed of only the present sulfide-based compound.
- the present solid electrolyte may contain, in addition to the above-mentioned other materials, unavoidable impurities having an adverse effect on the effect of the present invention, such as less than 5% by mass, particularly less than about 3% by mass.
- the present solid electrolyte is preferably in the form of powder, and with respect to the particle size thereof, the average particle size (D50) of the present solid electrolyte, that is, the average particle size determined by laser diffraction scattering particle size distribution measurement (D50) Is preferably 0.1 ⁇ m to 10 ⁇ m. If D50 is 0.1 ⁇ m or more, it is preferable because the resistance increase due to the increase of the surface of the solid electrolyte particles and the mixing with the active material do not become difficult. On the other hand, if D50 is 10 ⁇ m or less, this solid electrolyte can easily enter the gaps between the active materials, and the contact point and the contact area become large, which is preferable.
- the average particle size (D50) of the present solid electrolyte is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m or more or 7 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more or 5 ⁇ m or less preferable.
- the average particle size (D50) of the present solid electrolyte is preferably 1 to 100% of the average particle size (D50) of the positive electrode active material or the average particle size (D50) of the negative electrode active material. If the average particle size (D50) of the present solid electrolyte is 1% or more of the average particle size (D50) of the positive electrode active material or the average particle size (D50) of the negative electrode active material, the active material may be filled without gaps It is preferable because it can be done. On the other hand, if it is 100% or less, the active material ratio in the electrode becomes high, which is preferable from the viewpoint of increasing the energy density of the battery.
- the average particle size (D50) of the present solid electrolyte is preferably 1 to 100% of the average particle size (D50) of the positive electrode active material or the average particle size (D50) of the negative electrode active material. % Or more and 50% or less, more preferably 5% or more or 30% or less.
- the Young's modulus of the present solid electrolyte is preferably 1 GPa to 30 GPa. If the Young's modulus of the present solid electrolyte is 1 GPa or more, it is preferable because it is hard to aggregate and easy to manufacture. On the other hand, if the Young's modulus of the present solid electrolyte is 30 GPa or less, it is preferable because the contact area can be increased by crushing at the interface with the active material. From such a viewpoint, the Young's modulus of the present solid electrolyte is preferably 1 GPa to 30 GPa, more preferably 5 GPa or more or 28 GPa or less, and particularly preferably 10 GPa or more or 25 GPa or less.
- the present sulfide compound to the present solid electrolyte are, for example, lithium sulfide (Li 2 S) powder, diphosphorus pentasulfide (P 2 S 5 ) powder, lithium chloride (LiCl) powder, lithium bromide (LiBr) It can be obtained by mixing with powder and firing.
- the pulverization and mixing may be carried out with the cation if the crystallinity of the raw material powder is reduced or amorphized, or the raw material mixed powder is homogenized, by a very strong mechanical pulverization and mixing such as mechanical alloying method.
- the bond with sulfur is broken, and a sulfur deficiency occurs at the time of firing, resulting in the development of electron conductivity. Therefore, grinding and mixing to such an extent that the crystallinity of the raw material powder can be maintained is desirable.
- the present sulfide-based compound can be synthesized by firing at a relatively low temperature because crystallization proceeds from about 200 ° C. Therefore, by firing at 350 ° C. or higher under an inert atmosphere or hydrogen sulfide gas (H 2 S) flow, it is possible to produce the present sulfide-based compound which is a sulfide having a target chemical composition with almost no sulfur deficiency. it can.
- H 2 S hydrogen sulfide gas
- the sulfur partial pressure in the vicinity of the fired sample can be increased by the sulfur gas generated by decomposition of hydrogen sulfide at the time of firing.
- Electron conductivity can be lowered. Therefore, when firing is performed in an atmosphere containing hydrogen sulfide gas, the firing temperature is preferably 350 to 650 ° C., and particularly preferably 450 ° C. or more or 600 ° C. or less, and particularly preferably 500 ° C. or less. .
- the sulfur partial pressure in the vicinity of the fired sample can not be increased at the time of firing. Electron conductivity will be high.
- the firing temperature is preferably 350 to 500 ° C., and particularly preferably 350 ° C. or more or 450 ° C. or less, and particularly preferably 400 ° C. or more or 450 ° C. or less.
- the raw material powder is small in particle diameter and highly reactive.
- the firing may be performed in an inert atmosphere.
- the raw materials are extremely unstable in the air, react with water and decompose, and generate hydrogen sulfide gas or oxidize, the raw materials are used in the glove box or the like substituted with an inert gas atmosphere, etc. Is preferably set in a furnace for firing.
- a compound containing lithium (Li) and phosphorus (P) are used.
- the compound containing sulfur, the compound containing sulfur (S), and the chlorine-containing compound and the bromine-containing compound are mixed, dried if necessary, and then in the flow of hydrogen sulfide gas (H 2 S) at 450 to 600 ° C. It is preferable to sinter at (component temperature), particularly at 450 to 500 ° C. (component temperature), and if necessary, pulverize and pulverize to classify.
- Examples of compounds containing lithium (Li) include lithium compounds such as lithium sulfide (Li 2 S), lithium oxide (Li 2 O) and lithium carbonate (Li 2 CO 3 ), and lithium metal alone. Can.
- Examples of the compound containing phosphorus (P) include phosphorus sulfide such as diphosphorus trisulfide (P 2 S 3 ), phosphorus pentasulfide (P 2 S 5 ), sodium phosphate (Na 3 PO 4 ), etc. Examples include phosphorus compounds and phosphorus simple substances.
- the said sulfur (S) the said lithium sulfide and phosphorus sulfide can be mentioned.
- the chlorine-containing compound may for example LiCl, PCl 3, PCl 5, POCl 3, P 2 Cl 4, SCl 2, S 2 Cl 2, NaCl, and the like BCl 3.
- the bromine-containing compound for example LiBr, PBr 3, POBr 3, S 2 Br 2, NaBr, and the like BBr 3.
- a combination of lithium sulfide, phosphorus sulfide, lithium chloride and lithium bromide is preferred.
- the raw materials are mixed by means of, for example, a ball mill, a bead mill, a homogenizer or the like instead of a mixing method to apply strong mechanical stress such as a planetary ball mill.
- a ball mill a bead mill
- a homogenizer a homogenizer or the like instead of a mixing method to apply strong mechanical stress such as a planetary ball mill.
- the raw materials are used in the glove box or the like substituted with an inert gas atmosphere, etc. Is preferably set in a furnace for firing.
- the present solid electrolyte can be used as a solid electrolyte layer of an all solid lithium secondary battery, a solid electrolyte to be mixed with a positive electrode-negative electrode mixture, and the like.
- an all solid lithium secondary battery can be configured by forming a positive electrode, a negative electrode, and a layer containing the above-described solid electrolyte between the positive electrode and the negative electrode.
- this solid electrolyte is excellent in water resistance and oxidation resistance, and there is little characteristic deterioration even when handled in dry air, for example, the assembly operation of all the solid lithium secondary batteries should be performed also in a dry room etc. it can.
- a slurry comprising a solid electrolyte, a binder and a solvent is dropped on a substrate, and the substrate is scraped off with a doctor blade or the like;
- the coating film can be formed by a printing method or the like, and then dried by heating to remove the solvent.
- a powder compact of a solid electrolyte powder is produced by a press or the like, it can be processed appropriately and produced.
- the positive electrode material currently used as a positive electrode active material of a lithium secondary battery can be used suitably.
- the positive electrode active material include spinel lithium transition metal oxides, lithium transition metal oxides having a layered structure, olivine, and a mixture of two or more of these.
- a negative electrode material used as a negative electrode active material of a lithium secondary battery can be appropriately used.
- the present solid electrolyte is electrochemically stable, artificial graphite, natural graphite, non-graphitizable, which is charged and discharged at a potential (about 0.1 V vs Li + / Li) comparable to lithium metal
- Carbon-based materials such as carbon (hard carbon) can be used as a negative electrode active material of a lithium secondary battery. Therefore, the energy density of the all solid lithium secondary battery can be greatly improved by using the present solid electrolyte as the electrolyte of the lithium secondary battery and using the carbon-based material as the negative electrode active material.
- a lithium secondary battery having the present solid electrolyte and a negative electrode active material containing carbon such as artificial graphite, natural graphite, non-graphitizable carbon (hard carbon) and the like can be configured.
- a silicon active material promising as a high capacity negative electrode material as a negative electrode active material of a lithium secondary battery.
- the present solid electrolyte is used as an electrolyte of a lithium ion all solid battery, the present solid electrolyte is characterized by having a low Young's modulus, that is, a low elastic modulus, and therefore, the solid electrolyte deforms following the expansion and contraction of the silicon active material. It is possible to expect the effect of improving the cycle characteristics. Therefore, for example, a lithium secondary battery having the present solid electrolyte and a silicon-based negative electrode active material can be configured.
- the present solid electrolyte, a negative electrode active material, and optionally, other materials such as a conductive auxiliary agent, a binder, and the like are mixed, and compressed and formed into a predetermined shape such as a plate shape to produce a negative electrode.
- a predetermined shape such as a plate shape to produce a negative electrode.
- the present solid electrolyte, a positive electrode active material, and other materials such as a conductive auxiliary agent and a binder as needed are mixed, compression pressed, and formed into a predetermined shape such as a plate to prepare a positive electrode. be able to.
- solid electrolyte refers to any substance to which ions such as Li + can move in a solid state.
- lithium secondary battery is intended to broadly encompass a secondary battery that performs charge and discharge by moving lithium ions between a positive electrode and a negative electrode.
- Examples 1 to 5 and Comparative Examples 1 to 3 Lithium sulfide (Li 2 S) powder, diphosphorus pentasulfide (P 2 S 5 ) powder, lithium chloride (LiCl) powder, and lithium bromide so as to have the raw material composition (mol%) shown in Table 1
- Li 2 S Lithium sulfide
- P 2 S 5 diphosphorus pentasulfide
- LiCl lithium chloride
- Li bromide lithium bromide
- Example 6 A powdery sample (a sulfide type compound) was obtained in the same manner as described above except that the flow gas was changed to argon and the firing temperature was changed to 450 ° C.
- the raw material composition is shown in Table 1.
- the non-water-soluble solvent is passed through a 60 ⁇ m filter, the solvent refractive index is 1.50, the particle permeability condition is transmitted, the particle refractive index is 1.59, the shape is non-spherical, and the measurement range is 0.
- the measurement time was set to 30 seconds, and the average value measured twice was set to D50.
- the measurement environment was an Ar atmosphere (oxygen concentration ⁇ 0.1 ppm, water concentration ⁇ 0.1 ppm), 25 ° C., and a measurement probe was a Bruker diamond probe (DNISP-HS).
- the resulting force curve uses DMT model to derive the damping Young's modulus using a force curve fit, and the Poisson's ratio is 0.3 from the relationship between the damping Young's modulus and the sample Young's modulus to derive the sample Young's modulus did.
- the positive electrode mixture powder is prepared by mixing the positive electrode active material powder, the solid electrolyte powder and the conductive additive (acetylene black) in a weight ratio of 60: 37: 3 in a mortar, and uniaxially pressing at 20 MPa to form a positive electrode mixture Pellets were obtained.
- the negative electrode mixture powder was prepared by mixing a graphite powder and a solid electrolyte powder in a mortar at a weight ratio of 64:36.
- the lower opening of a polypropylene cylinder opening diameter 10.5 mm, height 18 mm
- opened at the top and bottom was closed with a positive electrode (made of SUS), and the positive electrode material mixture pellet was placed on the positive electrode.
- a powder solid electrolyte was placed thereon, and uniaxially pressed at 180 MPa to form a positive electrode mixture and a solid electrolyte layer.
- a negative electrode made of SUS
- uniaxially molded at 550 MPa a positive electrode mixture of about 100 ⁇ m thickness
- a solid electrolyte layer of about 300 ⁇ m thickness about 20 ⁇ m thickness
- a die battery having a three-layer structure of a negative electrode mixture was produced.
- the battery was placed in an environmental tester set so that the environmental temperature for charging and discharging the battery was 25 ° C., and the battery was prepared for charging and discharging, and allowed to stand so that the battery temperature would be the environmental temperature.
- the AC resistance at 1 kHz was measured, and this value was taken as the AC resistance before charging.
- the battery was charged and discharged with 1 mA as 1C.
- constant current constant potential charging was performed at 0.1 C to 4.5 V to obtain an initial charge capacity.
- the AC resistance at 1 kHz was measured as before charging, and this value was taken as the pre-discharge resistance value.
- constant current discharge was performed to 2.5 V at 0.1 C to obtain an initial discharge capacity.
- the initial charge / discharge efficiency was obtained from the discharge capacity relative to the charge capacity.
- Example 3 is lower in cell resistance, that is, excellent in comparison with Comparative Example 1 despite the fact that the ion conductivity is low. That is, by containing Br as a halogen in a predetermined ratio to Cl, a solid electrolyte capable of exhibiting further excellent battery performance with respect to battery resistance while maintaining the ion conductivity at a practical height. It can be considered that it can provide.
- the ratio of the molar ratio of Br to the molar ratio of Cl within a predetermined range while making it larger than 0, it is possible to realize a low elastic modulus while maintaining a high ion conductivity, It has been found that the battery resistance can be reduced.
- firing is performed at 450 to 600 ° C. (product temperature) under flowing hydrogen sulfide gas (H 2 S) It has also been found that it is even more preferable to lower the elastic modulus or Young's modulus.
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Abstract
Description
そこで本発明者が研究した結果、結晶性が高く且つ、それでいて弾性率の低い固体電解質材料であれば、電極作成時にプレス圧を掛けることにより、当該固体電解質材料が潰れて活物質粒子間の隙間を埋めることができ、活物質粒子との接触点及び接触面積を高めることができるため、電池抵抗を低くすることができることを見出した。
本実施形態の一例に係る硫化物系固体電解質(「本固体電解質」と称する)は、立方晶系Argyrodite型結晶構造の結晶相を有し、組成式(1):Li7-xPS6-xClyBrz(x=y+z)で表される硫化物系化合物(「本硫化物系化合物」と称する)を含有するリチウム二次電池用固体電解質である。
本硫化物系化合物は、立方晶系Argyrodite型結晶構造の結晶相を有し、組成式(1):Li7-xPS6-xClyBrzで表される化合物である。
立方晶系Argyrodite型結晶構造の結晶相を有するか否かは、例えば後述するようにX線回折法(XRD、Cu線源)で分析することで確認することができる。
Cl及びBrの合計モル比x(=y+z)が1.0より大きく且つ1.8以下であれば、イオン伝導率をさらに高めることができるから好ましい。特にxが1.8以下であれば、異相の生成を制御することができ、イオン伝導率の低下を抑えることができる。
かかる観点から、上記組成式(1)におけるxは1.0より大きく且つ1.8以下であるのが好ましく、中でも1.1以上或いは1.7以下、その中でも1.2以上或いは1.6以下であるのがさらに好ましい。
Clのモル比に対するBrのモル比の割合(z/y)が0.1以上であれば、固体電解質が低弾性率となるから好ましく、他方、当該(z/y)が10以下であれば、高いイオン伝導率となるから好ましい。
かかる観点から、Clのモル比に対するBrのモル比の割合(z/y)は0.1~10であるのが好ましく、中でも0.2以上或いは5以下、その中でも0.3以上或いは3以下であるのがさらに好ましい。
Clのモル比yが0.3以上であれば、0.3未満と比べてイオン伝導電率をさらに高めることができるから好ましく、他方1.5以下であれば、低弾性率を維持することができるから好ましい。
かかる観点から、上記組成式(1)におけるyは0.3~1.5であるのが好ましく、中でも0.4以上或いは1.2以下、その中でも0.6以上或いは1.0以下であるのがさらに好ましい。
Brのモル比zが0.3以上であれば、さらに弾性率を低下させることができるから好ましく、他方、1.5以下であれば、イオン伝導率を維持することができるから好ましい。
また、Br化合物はCl化合物に比べて融点が低いため、Br化合物を添加すると、反応性に富むようになり、硫化物系化合物を合成し易くなる。
かかる観点から、上記組成式(1)におけるzは0.3~1.5であるのが好ましく、中でも0.4以上或いは1.2以下、その中でも0.6以上或いは1.0以下であるのがさらに好ましい。
よって、本固体電解質は、立方晶系Argyrodite型結晶構造の結晶相から構成される単一相からなるものであっても、立方晶系Argyrodite型結晶構造の結晶相とLiClで示される結晶相とを含有する混合相からなるものであっても、立方晶系Argyrodite型結晶構造の結晶相とLiBrで示される結晶相とを含有する混合相からなるものであっても、立方晶系Argyrodite型結晶構造の結晶相とLiClで示される結晶相とLiBrで示される結晶相とを含有する混合相からなるものであってもよい。
なお、立方晶系Argyrodite型結晶構造の結晶相と、LiCl及び/又はLiBrで示される結晶相とを含有する混合相としては、立方晶系Argyrodite型結晶構造の結晶相と、LiCl及び/又はLiBrで示される結晶相との混合相のほか、これら以外の結晶相を含有する場合も包含する。
但し、本固体電解質は、本硫化物系化合物が主材料であるのが好ましく、本固体電解質全体の50質量%以上、中でも80質量%以上、その中でも90質量%以上(100質量%を含む)を本硫化物系化合物が占めるのが好ましく、中でも特に本硫化物系化合物のみから構成されることが望ましい。
また、本固体電解質は、上記他の材料の他に、本発明の効果に悪影響の少ない程度、例えば5質量%未満、中でも3質量%未満程度の不可避不純物を含んでいてもよい。
本固体電解質は、粉末状の粒子であるのが好ましく、その粒径に関しては、本固体電解質の平均粒径(D50)、すなわちレーザー回折散乱式粒度分布測定法により求められる平均粒径(D50)が0.1μm~10μmであるのが好ましい。
D50が0.1μm以上であれば、固体電解質粒子の表面が増えることによる抵抗増大や、活物質との混合が困難となることがないから好ましい。他方、D50が10μm以下であれば、活物質間の隙間に本固体電解質に入りやすくなり、接触点及び接触面積が大きくなるから好ましい。
かかる観点から、本固体電解質の平均粒径(D50)は0.1μm~10μmであるのが好ましく、中でも0.3μm以上或いは7μm以下、その中でも特に0.5μm以上或いは5μm以下であるのがさらに好ましい。
本固体電解質の平均粒径(D50)が、正極活物質の平均粒径(D50)又は負極活物質の平均粒径(D50)の1%以上であれば、活物質間を隙間なく埋めることができるため好ましい。他方、100%以下であれば、電極内の活物質比率が高くなり、電池の高エネルギー密度化の観点から好ましい。
かかる観点から、本固体電解質の平均粒径(D50)は、正極活物質の平均粒径(D50)又は負極活物質の平均粒径(D50)の1~100%であるのが好ましく、中でも3%以上或いは50%以下、その中でも5%以上或いは30%以下であるのがさらに好ましい。
本固体電解質のヤング率は1GPa~30GPaであるのが好ましい。
本固体電解質のヤング率が1GPa以上であれば、凝集しにくく製造しやすいため好ましい。他方、本固体電解質のヤング率が30GPa以下であれば、活物質との界面で潰れて接触面積を増やすことができるため好ましい。
かかる観点から、本固体電解質のヤング率は1GPa~30GPaであるのが好ましく、中でも5GPa以上或いは28GPa以下、その中でも特に10GPa以上或いは25GPa以下であるのがさらに好ましい。
本固体電解質のヤング率を上記範囲に調整するには、硫化水素(H2S)ガスを流しながら450~600℃(品温)、特に450~500℃に加熱処理するのが好ましい。
硫化物系固体電解質はそもそもイオン伝導性に優れており、酸化物に比べて常温で活物質との良好な接触状態を形成し易く、界面抵抗を低くできることが知られている。中でも、本固体電解質は、イオン伝導率を維持しながら、低弾性率化を実現することができる。
次に、本硫化物系化合物ないし本固体電解質の製造方法の一例について説明する。但し、ここで説明する製造方法はあくまでも一例であり、この方法に限定するものではない。
この際、粉砕混合は、メカニカルアロイング法など、非常に強力な機械的粉砕混合により、原料粉末の結晶性を低下あるいは非晶質化、もしくは原料混合粉末を均質化させてしまうと、カチオンと硫黄との結合が切れてしまい、焼成時に硫黄欠損が生じ、電子伝導性を発現してしまう。そのため、原料粉末の結晶性を維持できる程度の粉砕混合が望ましい。
他方、不活性雰囲気下で焼成する場合は、硫化水素ガスの場合とは異なり、焼成時に焼成試料近傍の硫黄分圧を高めることができないため、高い焼成温度の場合、硫黄欠損が生成しやすく、電子伝導性が高くなってしまう。そのため、不活性雰囲気下で焼成する場合は、焼成温度は350~500℃とするのが好ましく、中でも350℃以上或いは450℃以下、その中でも400℃以上或いは450℃以下とするのが特に好ましい。
また、上記の原料は、大気中で極めて不安定で、水分と反応して分解し、硫化水素ガスを発生したり、酸化したりするため、不活性ガス雰囲気に置換したグローブボックス 中等で、原料を炉内にセットして焼成を行うのが好ましい。
前記 リン(P)を含有する化合物としては、例えば三硫化二リン(P2S3)、五硫化二リン(P2S5)等の硫化リン、リン酸ナトリウム(Na3PO4)等のリン化合物、及びリン単体等を挙げることができる。
前記硫黄(S)を含有する化合物としては、上記硫化リチウムや硫化リンを挙げることができる。
塩素含有化合物としては、例えばLiCl、PCl3、PCl5、POCl3、P2Cl4、SCl2、S2Cl2、NaCl、BCl3などを挙げることができる。
臭素含有化合物としては、例えばLiBr、PBr3、POBr3、S2Br2、NaBr、BBr3などを挙げることができる。
中でも、硫化リチウムと、硫化リンと、塩化リチウムと、臭化リチウムとの組み合わせが好ましい。
また、上記の原料は、大気中で極めて不安定で、水分と反応して分解し、硫化水素ガスを発生したり、酸化したりするため、不活性ガス雰囲気に置換したグローブボックス 中等で、原料を炉内にセットして焼成を行うのが好ましい。
本固体電解質は、全固体リチウム二次電池の固体電解質層や、正極・負極合材に混合する固体電解質等として使用できる。
例えば正極と、負極と、正極及び負極の間に上記の固体電解質を含む層とを形成することで、全固体リチウム二次電池を構成することができる。
この際、本固体電解質は、耐水性及び耐酸化性に優れており、乾燥空気中で取り扱っても特性劣化が少ないため、例えばドライルームなどでも全固体リチウム二次電池の組立作業を行うことができる。
例えば、本固体電解質は、電気化学的に安定であることから、リチウム金属に匹敵する卑な電位(約0.1V vs Li+/Li)で充放電する人造黒鉛、天然黒鉛、難黒鉛化性炭素(ハードカーボン)などの炭素系材料を、リチウム二次電池の負極活物質として使用することができる。そのため、リチウム二次電池の電解質として本固体電解質を用いると共に、負極活物質として炭素系材料を用いることで、全固体リチウム二次電池のエネルギー密度を大きく向上させることができる。よって、例えば本固体電解質と、人造黒鉛、天然黒鉛、難黒鉛化性炭素(ハードカーボン)などの炭素を含む負極活物質と、を有するリチウム二次電池を構成することができる。
また、高容量負極材料として有望なケイ素活物質を、リチウム二次電池の負極活物質として使用することも可能である。
リチウムイオン全固体電池の電解質として本固体電解質を用いると、本固体電解質はヤング率が低い、すなわち低弾性率であるという特徴を有しているため、ケイ素活物質の膨張収縮に追従して変形することが可能であり、サイクル特性を向上させる効果が期待できる。よって、例えば本固体電解質と、ケイ素系負極活物質と、を有するリチウム二次電池を構成することができる。
例えば、本固体電解質と、負極活物質と、必要に応じて導電助剤、バインダー、などのその他の材料を混合し、圧縮プレスして板状などの所定形状に成形して負極を作製することができる。
本発明において「固体電解質」とは、固体状態のままイオン、例えばLi+が移動し得る物質全般を意味する。
また、本発明において「リチウム二次電池」とは、リチウムイオンが正極と負極の間を移動することで充放電を行う二次電池を広く包含する意である。
また、「X以上」(Xは任意の数字)又は「Y以下」(Yは任意の数字)と記載した場合、「Xより大きいことが好ましい」又は「Yより小さいことが好ましい」旨の意図を包含する。
表1に示した原料組成(mol%)となるように、硫化リチウム(Li2S)粉末と、五硫化二リン(P2S5)粉末と、塩化リチウム(LiCl)粉末と、臭化リチウム(LiBr)粉末とを用い、全量で75gになるようにそれぞれを秤量し、ボールミルで6時間粉砕混合して混合粉末を調製した。この混合粉末をカーボン製の容器に充填し、これを管状電気炉にて硫化水素ガス(H2S、純度100%)を1.0L/minで流通させながら、昇降温速度200℃/hで加熱し、500℃で4時間焼成した。その後、試料を乳鉢で解砕し、目開き53μmの篩いで整粒して粉末状のサンプル(固体電解質としての硫化物系化合物)を得た。
この際、上記秤量、混合、電気炉へのセット、電気炉からの取り出し、解砕及び整粒作業は全て、十分に乾燥されたArガス(露点-60℃以下)で置換されたグローブボックス内で実施した。
流通ガスをアルゴンに変更し、焼成温度を450℃に変更した以外は、上記同様にして粉末状のサンプル(硫化物系化合物)を得た。原料組成を表1に示す。
実施例・比較例で得られたサンプル(硫化物系化合物)について、組成をICP発光分析法で測定し、組成式:Li7-xPS6-xClyBrzにおける、x、y、zおよび(z/y)の値を表1に示した。
実施例・比較例で得られた粉末状のサンプル(固体電解質)をX線回折法(XRD、Cu線源)で分析し、生成相を特定した。
実施例1~5で得たサンプルは、立方晶系Argyrodite型結晶構造の結晶相から構成される単一相であり、結晶性が高いことを確認した。
実施例・比較例で得られた粉末状のサンプル(固体電解質)について、レーザー回折粒子径分布測定装置用自動試料供給機(日機装株式会社製「Microtorac SDC」)を用い、サンプル(粉体)を非水系溶媒に投入し、流速を40%に設定し、40Wの超音波を360秒間照射した後、日機装株式会社製レーザー回折粒度分布測定機「MT3000II」を用いて粒度分布を測定し、得られた体積基準粒度分布のチャートから平均粒径(D50)を測定した。
なお、測定の際の非水溶性溶媒は60μmのフィルターを通し、溶媒屈折率を1.50、粒子透過性条件を透過、粒子屈折率1.59、形状を非球形とし、測定レンジを0.133~704.0μm、測定時間を30秒とし、2回測定した平均値をD50とした。
実施例・比較例で得た硫化物系化合物(サンプル)に対して、電極形成時のプレス圧縮を想定して200MPaの圧力を加えてペレット化し、その断面を走査型電子顕微鏡(SEM)で観察し、得られたSEM写真(5000倍)に基づき、次の基準で「〇:good」又は「×:poor」を判定した。なお、未評価のものは「-」とした。
〇:硫化物系化合物が潰れた様子が観察された。
×:硫化物系化合物が潰れた様子は観察されなかった。
実施例・比較例で得られた粉末状のサンプル(硫化物系化合物)について、原子間力顕微鏡(AFM)(Bruker製「Dimension Icon」)を用いてフォースカーブ測定を行い、得られたフォースカーブより弾性率(ヤング率)を求めた。
Ar雰囲気中のグローブボックス内でエポキシ樹脂を薄く塗ったシリコンウェハー上に試料を散布し固定させて測定試料とした。
測定条件は、Rampモード(フォースカーブ測定モード)を用い、1試料につき10粒子のフォースカーブを測定した。
既知の標準試料(ガラス:弾性率72Gpa)を用いて規定値が算出されるように測定パラメータの調整を行った後、サンプルの測定を実施した。
測定環境は、Ar雰囲気(酸素濃度<0.1ppm、水分濃度<0.1ppm)、25℃、測定プローブはBruker製ダイヤモンドプローブ(DNISP-HS)を用いた。
得られたフォースカーブは、DMTmodelを使ってフォースカーブフィットを用い、減衰ヤング率を導出し、減衰ヤング率とサンプルのヤング率の関係式よりポアソン比を0.3として、試料のヤング率を導出した。
一方、本発明の実施例で採用した上記方法によりヤング率を測定すると、粒子表面の数値を算出しているため、粒子本来の弾性率を測定することができる。
実施例・比較例で得たサンプル(硫化物系化合物)を、十分に乾燥されたArガス(露点-60℃以下)で置換されたグローブボックス内で200MPaの圧力にて一軸加圧成形し、さらに200MPaの圧力にて冷間等方圧加圧法(CIP)にて直径10mm、厚み2~5mmのペレットを作製し、更にペレット上下両面に電極としてのカーボンペーストを塗布した後、180℃で30分熱処理を行い、イオン伝導率測定用サンプルを作製した。イオン伝導率測定は、室温(25℃)にて交流インピーダンス法にて行った。
(材料)
正極活物質として、三元系層状化合物であるLiNi0.5Co0.2Mn0.3O2(NCM)粉末(D50=6.7μm)を用い、負極活物質としてグラファイト(Gr)粉末(D50=20μm)を用い、固体電電解質粉末として実施例・比較例で得たサンプル(硫化物系化合物)を用いた。
正極合材粉末は、正極活物質粉末、固体電解質粉末及び導電助剤(アセチレンブラック)を60:37:3の重量比で乳鉢混合して調整し、20MPaで1軸プレス成型して正極合材ペレットを得た。
負極合材粉末はグラファイト粉末と固体電解質粉末を重量比64:36の割合で乳鉢混合して調製した。
上下を開口したポリプロピレン製の円筒(開口径10.5mm、高さ18mm)の下側開口部を正極電極(SUS製)で閉塞し、正極電極上に正極合材ペレットを載せた。その上から粉末固体電解質を載せて、180MPaにて1軸プレスし正極合材と固体電解質層を形成した。その上から負極合材粉末を載せた後、負極電極(SUS製)で閉塞して550MPaにて1軸成形し、およそ100μm厚の正極合材、およそ300μm厚の固体電解質層、およそ20μm厚の負極合材の3層構造からなるダイス電池を作製した。
上記のように作製したダイス電池を用いて、次のように電気抵抗測定、充放電試験を実施した。
充電前に1kHzにおける交流抵抗を測定し、この値を充電前交流抵抗とした。
1mAを1Cとして電池の充放電を行った。次に、0.1Cで4.5Vまで定電流定電位充電し、初回充電容量を得た。充電前同様1kHzにおける交流抵抗を測定し、この値を放電前抵抗値とした。
次に、0.1Cで2.5Vまで定電流放電し、初回放電容量を得た。充電容量に対する放電容量から初回充放電効率を得た。
次に、0.2Cで4.5Vまで定電流定電位充電した後に、5Cで2.5Vまで定電流放電し5Cにおける放電容量を得た。0.1Cの放電容量を100%とした5Cの放電容量の割合を算出しレート特性(5C容量維持率(%))を得た。
つまり、ハロゲンとしてClに対してBrを所定の比率で含むことにより、イオン伝導率を実用可能な高さに維持しつつ、電池抵抗についてはより一層優れた電池性能を発揮することができる固体電解質を提供することができると考えることができる。
また、ハロゲンとしてClとBrを両方含有する場合において、レート特性をさらに高めるためには、その製造方法において、硫化水素ガス(H2S)流通下で450~600℃(品温)で焼成することにより、弾性率すなわちヤング率をより低下させるのがより一層好ましいことも分かった。
Claims (11)
- 立方晶系Argyrodite型結晶構造の結晶相を有し、組成式:Li7-xPS6-xClyBrzで表される硫化物系化合物であって、前記組成式におけるxはx=y+zかつ1.0<x≦1.8を満足し、Clのモル比に対するBrのモル比の割合(z/y)が0.1~10.0であることを特徴とするリチウム二次電池の固体電解質用硫化物系化合物。
- 前記組成式において、yは0.3≦y≦1.5を満足し、zは0.3≦z≦1.5を満足することを特徴とする請求項1記載の硫化物系化合物。
- 請求項1又は2に記載された硫化物系化合物を含有することを特徴とするリチウム二次電池用固体電解質。
- 立方晶系Argyrodite型結晶構造の結晶相から構成される単一相からなることを特徴とする請求項3に記載のリチウム二次電池用固体電解質。
- 平均粒径(D50)が0.1μm~10μmであることを特徴とする請求項3又は4に記載のリチウム二次電池用固体電解質。
- ヤング率が1GPa~30GPaであることを特徴とする、請求項3~5の何れかに記載の固体電解質。
- 請求項3~6の何れかに記載の固体電解質の製造方法であって、リチウム(Li)を含有する化合物と、リン(P)を含有する化合物と、硫黄(S)を含有する化合物と、塩素含有化合物及び臭素含有化合物を混合し、硫化水素ガス(H2S)流通下で450~600℃(品温)で焼成して得ることを特徴とする固体電解質の製造方法。
- 請求項3~6の何れかに記載の固体電解質と、負極活物質を含むことを特徴とするリチウム二次電池用の負極。
- 炭素又はケイ素を含む負極活物質を備えた請求項8に記載のリチウム二次電池用の負極。
- 請求項3~6の何れかに記載の固体電解質と、正極活物質を含むことを特徴とするリチウム二次電池用の正極。
- 請求項3~6の何れかに記載の固体電解質を備えたリチウム二次電池。
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- 2018-07-02 KR KR1020197037575A patent/KR102134749B1/ko active IP Right Grant
- 2018-07-02 JP JP2019527686A patent/JP6595152B2/ja active Active
- 2018-07-02 EP EP18828426.9A patent/EP3629412B1/en active Active
- 2018-07-02 CN CN201880042762.4A patent/CN110800149B/zh active Active
- 2018-07-02 US US16/628,651 patent/US11196083B2/en active Active
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2021
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Also Published As
Publication number | Publication date |
---|---|
KR102134749B1 (ko) | 2020-07-16 |
US20220029196A1 (en) | 2022-01-27 |
EP3629412A4 (en) | 2020-06-24 |
EP3629412A1 (en) | 2020-04-01 |
JPWO2019009228A1 (ja) | 2019-11-07 |
CN110800149B (zh) | 2021-04-20 |
KR20200003929A (ko) | 2020-01-10 |
CN110800149A (zh) | 2020-02-14 |
CN112331910A (zh) | 2021-02-05 |
JP6595152B2 (ja) | 2019-10-23 |
US11196083B2 (en) | 2021-12-07 |
EP3629412B1 (en) | 2022-10-19 |
US20200127325A1 (en) | 2020-04-23 |
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