WO2016031022A1 - 固体電解質及びその製造方法、全固体二次電池及びその製造方法 - Google Patents
固体電解質及びその製造方法、全固体二次電池及びその製造方法 Download PDFInfo
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- H01M2300/00—Electrolytes
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- H01M2300/0065—Solid electrolytes
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Definitions
- the present invention relates to a solid electrolyte and a manufacturing method thereof, an all-solid secondary battery and a manufacturing method thereof.
- Liquid secondary batteries that are widely used nowadays have a negative electrode active material that deteriorates with repeated cycles, resulting in a decrease in battery capacity, or an ignition of the organic electrolyte in the battery due to a battery short circuit caused by the formation of dendrites. Is concerned.
- a liquid electrolyte secondary battery is poor in reliability and safety for use in an energy harvesting device that is considered to be used for more than 10 years. Therefore, an all-solid secondary battery in which the constituent materials are all solid is drawing attention.
- the all-solid-state secondary battery has no risk of liquid leakage or ignition, and has excellent cycle characteristics.
- a solid electrolyte used for an all-solid secondary battery there is one using an oxide such as LaLiTiO.
- a solid electrolyte using an oxide such as LaLiTiO described above has an extremely large interparticle resistance (grain boundary resistance) in a powder state and low ionic conductivity between particles. For this reason, even if an all-solid secondary battery is manufactured using such a solid electrolyte, the internal resistance of the all-solid-state secondary battery is large, and sufficient output characteristics (load characteristics) cannot be obtained. Therefore, for example, sintering is performed at a high temperature of about 1000 ° C. or higher to connect the particles, thereby reducing the interparticle resistance, improving the ionic conductivity between the particles, and thus the internal resistance of the all-solid-state secondary battery. To improve the output characteristics.
- the present solid electrolyte covers the surface of the first part including lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements, and the lanthanum (La) as the constituent element. ), Lithium (Li), titanium (Ti), and oxygen (O), sulfur (S) is bonded to the oxygen deficient portion, and particles having at least a second portion that is oxidized are provided.
- the all-solid secondary battery includes a positive electrode, a negative electrode, and a solid electrolyte provided between the positive electrode and the negative electrode.
- the solid electrolyte includes lanthanum (La), lithium (Li), titanium (Ti) as constituent elements. ) And oxygen (O), and covers the surface of the first part, and includes lanthanum (La), lithium (Li), titanium (Ti) and oxygen (O) as constituent elements, and oxygen deficiency And a particle having sulfur (S) bonded to the portion and having at least a second portion having an oxidized surface.
- This method for producing a solid electrolyte is produced by reducing a solid electrolyte material that is a powder containing lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements, and resulting from the reduction treatment.
- a solid electrolyte material having an oxygen deficient portion is subjected to a sulfidation treatment, and a solid electrolyte material having a surface portion in which sulfur (S) is bonded to an oxygen deficient portion formed by the sulfidation treatment is subjected to a surface oxidation treatment, and the surface is subjected to a surface oxidation treatment.
- a solid electrolyte is produced by compacting a solid electrolyte material in which at least the surface of the portion is oxidized.
- the manufacturing method of the all-solid-state secondary battery includes a reduction treatment of a solid electrolyte material that is a powder containing lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements.
- the solid electrolyte material having an oxygen deficient portion generated by the above is subjected to sulfurization treatment, and the solid electrolyte material having a surface portion in which sulfur (S) is bonded to the oxygen deficient portion formed by the sulfurization treatment is subjected to surface oxidation treatment and surface oxidation.
- a solid electrolyte material in which at least the surface of the surface portion is oxidized by the treatment is sandwiched between the positive electrode material and the negative electrode material and compacted to produce an all-solid secondary battery.
- the all-solid-state secondary battery and its manufacturing method a solid with reduced interparticle resistance and improved ionic conductivity between particles without sintering at high temperature.
- FIG. 3A to FIG. 3D are schematic cross-sectional views for explaining a method for producing a solid electrolyte according to the present embodiment. It is a figure which shows the measurement result of TG-DTA of the solid electrolyte after the hydrogen heat processing of an Example.
- FIG. 5A is a diagram for explaining the measurement results of the impedance of the solid electrolyte before hydrogen heat treatment and the calculation of ionic conductivity of the example, and FIG. 5B is a diagram after hydrogen heat treatment of the example.
- FIG. 6A is a diagram for explaining the measurement results of the impedance of the solid electrolyte after the sulfurization treatment and the calculation of the ionic conductivity in the example
- FIG. 6B is the diagram after the surface oxidation treatment of the example.
- FIG. 7A is a diagram showing a cross-sectional TEM image of the solid electrolyte particles of the surface oxidation treatment (after surface modification) of the example
- FIG. 7B is a diagram showing the element distribution at each point.
- an all-solid lithium secondary battery will be described as an example of the all-solid secondary battery.
- the all solid lithium secondary battery is provided with a positive electrode 1, a negative electrode 2, a solid electrolyte 3 provided between the positive electrode 1 and the negative electrode 2, and sandwiching them.
- the positive electrode current collector 4 and the negative electrode current collector 5 thus obtained are provided.
- Such an all-solid lithium secondary battery is preferably mounted on, for example, an energy harvesting apparatus.
- the positive electrode 1 contains a positive electrode active material.
- the positive electrode 1 includes, for example, LiCoO 2 (oxide positive electrode active material) as the positive electrode active material.
- the positive electrode 1 is made of a material obtained by mixing LiCoO 2 and a solid electrolyte material (oxide solid electrolyte material) at a ratio of 6: 4.
- the negative electrode 2 includes a negative electrode active material.
- the negative electrode 2 contains, for example, Li 4 Ti 5 O 12 (oxide negative electrode active material) as the negative electrode active material.
- the negative electrode 2 is made of a material obtained by mixing Li 4 Ti 5 O 12 and a solid electrolyte material (oxide solid electrolyte material) at a ratio of 6: 4.
- the solid electrolyte 3 contains lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements, and sulfur (S) in an oxygen deficient part (oxygen defective part).
- the solid electrolyte 3 is also referred to as a lithium ion conductor or an oxide solid electrolyte.
- the solid electrolyte 3 is composed of a crystalline material containing lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements, and is a powdered solid electrolyte material (LaLiTiO; for example, La 0.55 Li 0.33 TiO 3 ; LLTO) is compacted.
- the solid electrolyte 3 covers the surface of the first portion 3A, the first portion (LLTO) 3A containing lanthanum (La), lithium (Li), titanium (Ti) and oxygen (O) as constituent elements.
- a particle 3X having a portion (LaLiTiOS; LLTOS) 3B is provided.
- the first portion (LLTO) 3A containing lanthanum (La), lithium (Li), titanium (Ti) and oxygen (O) as constituent elements is lanthanum (La), lithium (Li) as constituent elements.
- the second portion 3B containing lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements, and having sulfur (S) bonded to the oxygen deficient portion has lanthanum (La) as a constituent element.
- the surface portion in which sulfur (S) is bonded to the oxygen deficient portion, that is, the second portion 3B includes lanthanum (La), lithium (Li), titanium (Ti) and oxygen (O) as constituent elements, and , Part of oxygen (O) is substituted with sulfur (S). That is, the surface portion in which sulfur (S) is bonded to the oxygen deficient portion, that is, the second portion 3B is a portion in which the surface of the particle 3X of the solid electrolyte material that is powder is sulfided, that is, a portion in which the oxygen deficient portion is sulfided. It is. For this reason, the particles 3X of the solid electrolyte material that is a powder have a structure in which the surface is covered with a portion 3B in which the oxygen deficient portion is sulfided.
- the surface portion that is, the portion other than the oxidized portion 3C of the second portion 3B has a defect of trapping lithium ions.
- the portion other than the surface portion 3B, that is, the first portion 3A has an oxygen deficient portion and has electron conductivity.
- the amount of oxygen deficient portion oxygen deficient amount; oxygen deficient amount
- ⁇ 0.04 to 0.5
- the amount of oxygen deficiency ⁇ is assumed to be 0 based on the result of TG-DTA measurement (see FIG.
- the thickness of the surface portion where sulfur (S) is bonded to the oxygen deficient portion, that is, the second portion 3B is, for example, about 10 nm, as will be described in an example described later. According to such a solid electrolyte 3, resistance between particles can be lowered and ion conductivity between particles can be improved.
- the above solid electrolyte 3 can be manufactured as follows.
- a solid electrolyte that is a powder containing lanthanum (La), lithium (Li), titanium (Ti), and oxygen (O) as constituent elements.
- a material (LaLiTiO; for example, La 0.55 Li 0.33 TiO 3 ; LLTO) 30 is reduced.
- the solid electrolyte material 30A having an oxygen deficient portion is obtained.
- the solid electrolyte material 30A having an oxygen deficient portion generated by the reduction treatment is subjected to sulfurization treatment.
- the surfaces of the particles of the solid electrolyte material 30A, which is a powder are sulfided.
- the solid electrolyte material 30A has a surface portion 30B in which sulfur (S) is bonded to an oxygen deficient portion, that is, a surface portion 30B in which a part of oxygen (O) is substituted with sulfur (S). .
- the surface oxidation treatment is performed by placing the solid electrolyte material 30A in an environment where at least the surface 30C of the surface portion 30B of the solid electrolyte material 30A is oxidized by water.
- the solid electrolyte 3 is manufactured by compacting the solid electrolyte material 30A in which at least the surface 30C of the surface portion 30B is oxidized by the surface oxidation treatment.
- the part indicated by reference numeral 30A becomes the first part 3A having the oxygen deficient part of the particle 3X provided in the solid electrolyte 3
- the part indicated by reference numeral 30B is the particle 3X provided in the solid electrolyte 3 described above.
- the second portion 3B that covers the surface of the first portion 3A is formed, and the portion indicated by reference numeral 30C is the surface 3C of the second portion 3B of the particle 3X provided in the solid electrolyte 3 described above.
- the particle 3X provided in the solid electrolyte 3 covers the first part (LLTO- ⁇ ) 3A having an oxygen deficient part and the surface of the first part 3A, and the second part in which the surface 3C is oxidized ( LLTOS) 3B.
- an oxide solid electrolyte such as LLTO has an extremely large interparticle resistance (grain boundary resistance) in a powder state and low ionic conductivity between particles.
- the interparticle resistance is lowered and the ionic conductivity between the particles is improved without sintering at a high temperature.
- the solid electrolyte material (LLTO) 30 is heat-treated with, for example, hydrogen gas, so that titanium (Ti) in the crystal is reduced to 4%. Reduction from trivalent to trivalent. By such reduction of titanium (Ti), oxygen is desorbed to generate oxygen deficient portions in the crystal.
- the crystal (LLTO- ⁇ ) 30A in which titanium (Ti) is reduced to trivalent in this way to generate an oxygen defect portion exhibits electron conductivity. For this reason, it cannot be used as the solid electrolyte 3 of the all-solid lithium secondary battery.
- the reduced trivalent titanium (Ti) of the solid electrolyte material (LLTO- ⁇ ) 30A having an oxygen deficient portion is sulfurized (reoxidized) with sulfur (S).
- the original tetravalence is obtained, the electron conductivity is lost, and only the ionic conductivity is shown.
- the solid electrolyte material (LLTO- ⁇ ) 30A having the portion (LLTOS- ⁇ ) 30B in which oxygen (O) is partially substituted with sulfur (S) in this way is partially oxygen (O) sulfur (S ), A large amount of defects are contained in the portion 30B substituted with (), and these defects trap lithium ions (Li + ), so that high ion conductivity cannot be obtained.
- At least the surface 30C of the portion 30B having defects for trapping lithium ions (Li + ) and partially replacing oxygen (O) with sulfur (S).
- LTOS- ⁇ defects that trap lithium ions (Li + ) are suppressed, and lithium ions (Li + ) are surface-conducted between particles.
- the surface portion 30C has, for example, LiO or hydrate.
- lithium ions (Li + ) are surface-conducted between the particles.
- the ion conductivity of about 10 ⁇ 8 S / cm before being oxidized with water is improved to about 10 ⁇ 5 S / cm by being oxidized with water. Is done.
- the oxide has a large interparticle resistance peculiar to an oxide and has an ionic conductivity of about 10 ⁇ 8 S / cm before modification, which is 10 ⁇ 5. It is improved to about S / cm.
- an all-solid lithium secondary battery can be manufactured using the solid electrolyte 3 obtained as described above.
- the solid electrolyte material (powder here) obtained as described above is sandwiched between a positive electrode material (powder here) and a negative electrode material (here powder), and compacted, An all-solid lithium secondary battery is manufactured.
- an all-solid lithium secondary battery can be manufactured by compacting at room temperature, that is, by simply pressing and pressing each other at room temperature without performing sintering at a high temperature of, for example, about 1000 ° C. or higher. That is, by modifying the surface of the solid electrolyte material as described above, the ionic conductivity can be improved from about 10 ⁇ 8 S / cm to about 10 ⁇ 5 S / cm. For this reason, in order to reduce the resistance between particles and improve the ionic conductivity between particles, it is not necessary to perform sintering at a high temperature of, for example, about 1000 ° C. to connect the particles.
- the battery can be manufactured at room temperature, that is, the battery manufacturing temperature, which was a molding temperature of 1000 ° C. or higher, can be set to room temperature, so that the electrode material is decomposed and dissolved as in the case of sintering at high temperature. In other words, the electrode is not altered and the all-solid-state secondary battery cannot be operated. In this way, it is possible to realize a method of manufacturing an all-solid secondary battery by connecting particles at a temperature of 500 ° C. or less at which the electrode material does not decompose or dissolve.
- the interparticle resistance is reduced without performing sintering at a high temperature, and the ionic conductivity between the particles is increased.
- an improved solid electrolyte 3 can be realized, and consequently, an internal resistance can be reduced and an all-solid secondary battery with improved output characteristics can be realized.
- a solid electrolyte using an oxide such as LaLiTiO has a very large interparticle resistance (grain boundary resistance) in a powder state and a low ionic conductivity between particles.
- an all-solid secondary battery (all-solid lithium secondary battery) is manufactured using such a solid electrolyte
- the internal resistance of the all-solid secondary battery is large, and sufficient output characteristics cannot be obtained. That is, the oxide solid electrolyte has extremely large interparticle resistance in the powder state, and a sufficient current cannot be obtained from the all-solid secondary battery when it is made into a battery.
- the amount of oxygen deficiency ⁇ theoretically becomes 0.5 when the valence of all titanium (Ti) is changed from tetravalent to trivalent.
- the apparatus name Rigaku TG8120 was used, the temperature rising / falling rate was 10 ° C./min, the atmosphere was a dry Ar 100% dew point ( ⁇ 40 ° C. or lower), and the sample amount was 13.39 mg.
- Sample PAN was Pt.
- LLTO having electron conductivity and elemental sulfur (S) are mixed at a weight ratio of 10: 1, mixed in a glove box, sealed in a quartz ampule at about 10 Pa, and subjected to sulfidation at about 300 ° C. And opened in a dry Ar atmosphere.
- impedance measurement is performed using the AC impedance method, and as shown in FIG.
- the sample subjected to the sulfidation treatment was allowed to stand for about 12 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH, and surface oxidation treatment was performed to obtain a surface-modified solid electrolyte (powder). It was. After the surface oxidation treatment in this way, impedance measurement is performed using the AC impedance method, and as shown in FIG. 6B, one semicircular arc is extrapolated and the intersection at the right end with the Z-axis is set as the grain boundary resistance.
- the ionic conductivity was calculated by the formula described later, and it was about 3.1 ⁇ 10 ⁇ 5 S / cm.
- the surface oxidation treatment improved the ionic conductivity from 10 ⁇ 8 S / cm to 10 ⁇ 5 S / cm by three orders of magnitude compared to before the surface oxidation treatment.
- the impedance of the one after the sulfurization treatment and before the surface oxidation treatment is plotted with white circles, and the impedance of the one after the surface oxidation treatment is plotted with black circles.
- the white circles are plotted with a part of what is shown in FIG. 6A.
- a cross-sectional TEM (Transmission Electron Microscope) image of the solid electrolyte particles obtained by the surface oxidation treatment in this way is obtained, and EDS (Energy Dispersive Spectroscopy) measurement is performed.
- EDS Electronic Dispersive Spectroscopy
- FIG. 7A a cross-sectional TEM image as shown in FIG. 7A was obtained, and an element distribution at each point as shown in FIG. 7B was obtained. Note that each numerical value in FIG. 7B is the number of atoms of each element.
- a JEM-2100F transmission electron microscope was used to obtain the cross-sectional TEM image, and the acceleration voltage as a measurement condition was 200 kV.
- the surface portion of the solid electrolyte particles obtained by the surface oxidation treatment as described above that is, the surface portion of the solid electrolyte material (LLTO- ⁇ ) having an oxygen deficient portion.
- a portion (LLTOS) in which sulfur (S) having a thickness of about 10 nm was bonded was formed.
- the relative humidity is 0.0015% RH (Comparative Example 1), 0.025% RH (Example 1), 40% RH (Example 2), 50% RH (Example 3), 60% RH ( Example 4), 70% RH (Example 5), 80% RH (Example 6), and 90% RH (Example 7), and changing the humidity environment (humidity conditions), that is, oxidizing conditions with water (Oxidizing environment) was changed to obtain a solid electrolyte.
- humidity environment humidity conditions
- Comparative Example 1 the sample was placed in a glove box having a relative humidity of 0.0015% RH. In Example 1, the sample was placed in a dry room with a relative humidity of 0.025% RH. In Examples 2 to 7, samples were placed in a constant temperature room (general laboratory) with relative humidity of 40% RH, 50% RH, 60% RH, 70% RH, 80% RH, and 90% RH, respectively. It was.
- the ionic conductivity was measured to evaluate the ionic conductivity of the solid electrolytes of Examples 1 to 7 and Comparative Example 1 obtained as described above.
- the ionic conductivity was evaluated using the alternating current impedance method.
- the solid electrolytes of Examples 1 to 7 and Comparative Example 1 described above were each a 10 mm ⁇ jig using SKD11 as a material [here, the upper side is an electrode terminal (+), and the lower side is an electrode terminal ( ⁇ ).
- the applied voltage is 0.1 V
- the frequency response region is 1 MHz to 1 Hz
- the measurement temperature is Impedance was measured at 25 ° C. (room temperature).
- the ion conductivity was calculated using the intersection at the right end with the Z axis as the grain boundary resistance.
- the thickness of the solid electrolyte (lithium ion conductor) is t (cm)
- the area (electrode area) of the jig used for the measurement is S (cm 2 )
- the resistance value of the grain boundary resistance is R ( As ⁇ )
- the ionic conductivity ⁇ (S / cm) was calculated by the following equation.
- FIG. 8 shows ion conductivity data in each case of Examples 1 to 7 and Comparative Example 1.
- the ionic conductivity of the solid electrolyte (Comparative Example 1) obtained at a relative humidity of 0.0015% RH is 5.3 ⁇ 10 ⁇ 10 S / cm, and the relative humidity is 0.025% RH.
- the ionic conductivity of the obtained solid electrolyte (Example 1) is 1.0 ⁇ 10 ⁇ 9 S / cm, and the ionic conductivity of the obtained solid electrolyte (Example 2) at a relative humidity of 40% RH is 1.4.
- the ionic conductivity of the solid electrolyte (Example 3) obtained at ⁇ 10 ⁇ 8 S / cm and a relative humidity of 50% RH is 1.4 ⁇ 10 ⁇ 8 S / cm and obtained at a relative humidity of 60% RH.
- the ionic conductivity of the solid electrolyte (Example 4) was 7.7 ⁇ 10 ⁇ 5 S / cm, and the ionic conductivity of the solid electrolyte (Example 5) obtained at a relative humidity of 70% RH was 6.3 ⁇ .
- 10-4 is a S / cm
- the ion conductivity of the solid electrolyte obtained in a relative humidity of 90% RH (Example 7) was 9.2 ⁇ 10 -3 S / cm.
- the solid electrolyte (Comparative Example 1) obtained at a relative humidity of 0.0015% RH is hardly oxidized by water, it is a solid electrolyte that has not been subjected to surface oxidation treatment. It can be seen that the solid electrolyte is surface-oxidized.
- the solid electrolyte subjected to the surface oxidation treatment of each of Examples 1 to 7 has higher ionic conductivity than the solid electrolyte not subjected to the surface oxidation treatment of Comparative Example 1, and the ion Improved conductivity.
- the solid electrolyte surface-oxidized at a relative humidity of 60% RH to 90% RH that is, the solid electrolytes of Examples 4 to 7
- the ionic conductivity increased rapidly and the ionic conductivity improved rapidly.
- the unmodified LLTO powder that has not been subjected to all the above treatments is allowed to stand in an environment of a temperature of 25 ° C.
- the impedance was measured and the ionic conductivity was determined to be 1.2 ⁇ 10 ⁇ 8 S / cm.
- the ionic conductivity of the solid electrolytes obtained by performing all the above-mentioned treatments and leaving them for about 12 hours in an environment at a temperature of 25 ° C. and a relative humidity of 60% RH or more. was 10 ⁇ 5 to 10 ⁇ 3 , which was higher by 3 digits or more, and the ionic conductivity was drastically improved.
- the ionic conductivity of the solid electrolyte obtained by performing all the above-described treatments and standing for about 12 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH is 10 This order was -5 , and this order did not change even at a temperature of 25 ° C.
- the ionic conductivity of the solid electrolyte obtained by subjecting the LLTO powder before modification not subjected to all the above treatments to surface oxidation treatment was about 10 ⁇ 8 S / cm, whereas The solid electrolyte that has been treated and surface-oxidized at a relative humidity of 55% RH or higher has an ionic conductivity of 10 ⁇ 5 to 10 ⁇ 3 , and the ionic conductivity is rapidly increased. Improved.
- powder LiCoO 2 and powder-modified solid electrolyte material surface-modified as described above were mixed at a ratio of 6: 4 to prepare the material of the positive electrode 1 [see FIG. 9A. ].
- the material of the negative electrode 2 was prepared by mixing Li 4 Ti 5 O 12 in powder and the solid electrolyte material of the powder surface-modified as described above in a ratio of 6: 4 [FIG. 9]. (See (A)]. Then, as shown in FIGS. 9A and 9B, a powder negative electrode 2 is interposed between 10 mm ⁇ jigs (electrodes; electrode terminals) 11 provided in the electrochemical cell (compact cell) 10. The material of the solid electrolyte 3 of the surface modified as described above, and the material of the positive electrode 1 of the powder are arranged in order and pressed at a pressure of 1000 kgf, for example, room temperature compacting Thus, an all-solid lithium secondary battery was produced.
- reference numeral 12 denotes a cell (cell outer shell).
- the charge / discharge evaluation of the all-solid lithium secondary battery produced as described above was performed.
- the all solid lithium secondary battery manufactured as described above that is, the all solid lithium secondary battery including the solid electrolyte 3 whose surface is modified as described above
- the battery operation can be confirmed at room temperature, A charge / discharge curve (charge curve and discharge curve) as shown in FIG. 10 was obtained, and good load characteristics (output characteristics) were obtained.
- the evaluation conditions were as follows: voltage range: 4-0.5 V, charging / discharging current: charging 10 ⁇ A, discharging 1 ⁇ A, evaluation temperature: 60 ° C.
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Abstract
Description
現在広く利用されている液系二次電池は、サイクルを重ねると正極活物質が劣化して電池容量が低下したり、デンドライトの形成による電池短絡によって電池内の有機電解液に引火したりすることが懸念される。
そこで、構成材料をすべて固体にした全固体二次電池が注目されている。全固体二次電池は、液漏れや発火などの恐れがなく、サイクル特性も優れている。
例えば、全固体二次電池に用いられる固体電解質としては、LaLiTiOのような酸化物を用いたものがある。
そこで、例えば約1000℃以上の高温で焼結を行なって粒子同士を接続することで、粒子間抵抗を下げ、粒子間でのイオン導電率を向上させ、ひいては、全固体二次電池の内部抵抗を低減し、その出力特性を向上させることが考えられる。
そこで、高温で焼結を行なうことなく、粒子間抵抗を下げ、粒子間でのイオン導電率を向上させた固体電解質を実現し、ひいては、内部抵抗を低減し、その出力特性を向上させた全固体二次電池を実現したい。
以下、全固体二次電池として、全固体リチウム二次電池を例に挙げて説明する。
本実施形態では、全固体リチウム二次電池は、図2に示すように、正極1と、負極2と、正極1と負極2との間に設けられた固体電解質3と、これらを挟んで設けられた正極集電体4及び負極集電体5とを備える。このような全固体リチウム二次電池は、例えば環境発電装置に搭載されるのが好ましい。
負極2は、負極活物質を含む。ここでは、負極2は、負極活物質として例えばLi4Ti5O12(酸化物負極活物質)を含む。具体的には、負極2は、Li4Ti5O12と固体電解質材料(酸化物固体電解質材料)を6:4の割合で混ぜ合わせた材料によって構成される。
また、固体電解質3は、構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含む第1部分(LLTO)3Aと、第1部分3Aの表面を覆っており、構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含み、酸素欠損部に硫黄(S)が結合しており、少なくとも表面3Cが酸化されている第2部分(LaLiTiOS;LLTOS)3Bとを有する粒子3Xを備えるものとなる。
また、表面部分3B以外の部分、即ち、第1部分3Aは、酸素欠損部を有し、電子伝導性を有する。
ここで、固体電解質材料がLa0.55Li0.33TiO3-δであり、酸素(O)組成比を3-δとすると、酸素欠損部の量(酸素欠損量;酸素欠損分)δは0.04~0.5(δ=0.04~0.5)である。ここで、酸素欠損量δは、後述の実施例で説明するTG-DTA測定の結果(図4参照)に基づき、かつ、Tiのみが電荷中性を+3/+4で補償と仮定すると、0.04となる。また、酸素欠損量δは、理論上、全てのチタン(Ti)の価数が4価から3価になった場合、最大となり、0.5となる。
このような固体電解質3によれば、粒子間抵抗を下げ、粒子間でのイオン導電率を向上させることができる。
ところで、上述のような固体電解質3は、以下のようにして製造することができる。
次に、図3(C)に示すように、還元処理によって生じた酸素欠損部を有する固体電解質材料30Aを、硫化処理する。これにより、粉体である固体電解質材料30Aの粒子の表面が硫化される。つまり、固体電解質材料30Aは、酸素欠損部に硫黄(S)が結合した表面部分30B、即ち、酸素(O)の一部が硫黄(S)で置換されている表面部分30Bを有するものとなる。
ここでは、表面酸化処理は、固体電解質材料30Aの表面部分30Bの少なくとも表面30Cが水によって酸化される環境下に固体電解質材料30Aを置くことによって行なわれる。
つまり、図3(A)に示すように、例えばLLTOのような酸化物固体電解質は、粉体状態では粒子間抵抗(粒界抵抗)が極めて大きく、粒子間でのイオン導電率が低いため、固体電解質材料であるLLTO30の表面を、以下のようにして改質することで、高温で焼結を行なうことなく、粒子間抵抗を下げ、粒子間でのイオン導電率を向上させている。
しかしながら、このようにしてチタン(Ti)が3価に還元されて酸素欠陥部を生じた結晶(LLTO-δ)30Aは、電子伝導性を示す。このため、全固体リチウム二次電池の固体電解質3として使用することができない。
しかしながら、このようにして酸素(O)を一部硫黄(S)で置換した部分(LLTOS-δ)30Bを有する固体電解質材料(LLTO-δ)30Aは、酸素(O)を一部硫黄(S)で置換した部分30Bに欠陥が多量に入っており、これらの欠陥がリチウムイオン(Li+)をトラップしてしまうため、高いイオン導電性が得られない。
つまり、上述のようにして得られた固体電解質材料(ここでは粉体)を、正極材料(ここでは粉体)と負極材料(ここでは粉体)との間に挟んで圧粉成型して、全固体リチウム二次電池を製造する。
つまり、上述のようにして固体電解質材料の表面を改質することで、イオン導電率を10-8S/cm程度から10-5S/cm程度まで改善することができる。このため、粒子間抵抗を下げ、粒子間でのイオン導電率を向上させるために、例えば約1000℃以上の高温で焼結を行なって粒子同士を接続しなくても良くなる。そして、上述のようにして製造した固体電解質材料を、正極材料と負極材料との間に挟んで圧粉成型するだけで、室温で、全固体リチウム二次電池を製造することが可能となる。このように、室温で製造でき、即ち、1000℃以上の成型温度であった電池製造温度を室温とすることができるため、高温で焼結を行なう場合のように、電極材料が分解・固溶を起こし、電極が変質してしまって、全固体二次電池として動作しなくなってしまうということもない。このように、電極材料が分解・固溶しない500℃以下の温度で粒子間を接続して全固体二次電池を製造する方法を実現することができる。
これに対し、例えばLaLiTiOのような酸化物を用いた固体電解質は、粉体状態では粒子間抵抗(粒界抵抗)が極めて大きく、粒子間でのイオン導電率が低い。このため、このような固体電解質を用いて全固体二次電池(全固体リチウム二次電池)を製造しても、全固体二次電池の内部抵抗が大きく、十分な出力特性が得られない。つまり、酸化物固体電解質は、粉体状態では粒子間抵抗が極めて大きく、電池化した際に十分な電流が全固体二次電池から得られない。
[固体電解質の表面改質及び評価]
まず、豊島製作所製LLTO(La0.55Li0.33TiO3)粉体を、約800℃~約900℃の水素ガス雰囲気下で熱処理(水素熱処理;例えば約30分)し、チタン(Ti)を還元して、酸素欠損部を生じさせた。
ここで、硫化処理後に、交流インピーダンス法を用いてインピーダンス測定を行ない、図6(A)に示すように、一つの半円弧を外挿し、Z軸との右端の交点を粒界抵抗(ここでは6MΩ)とし、t=0.05cm、S=0.785cm2として、後述の式によってイオン導電率を算出したところ、約1.0×10-8S/cmであった。このように、硫化処理を行なったサンプルは、電子伝導性を失い、イオン導電性を取り戻した。
このようにして表面酸化処理した後に、交流インピーダンス法を用いてインピーダンス測定を行ない、図6(B)に示すように、一つの半円弧を外挿し、Z軸との右端の交点を粒界抵抗(ここでは2kΩ)とし、t=0.05cm、S=0.785cm2として、後述の式によってイオン導電率を算出したところ、約3.1×10-5S/cmであった。このように、表面酸化処理することで、表面酸化処理する前と比較して、イオン導電率が10-8S/cmから10-5S/cmへ三桁向上した。なお、図6(B)では、硫化処理後で表面酸化処理する前のもののインピーダンスを白丸でプロットし、表面酸化処理した後のもののインピーダンスを黒丸でプロットしている。また、図6(B)中、白丸でプロットしたものは、図6(A)に示したものの一部を拡大して示したものである。
ところで、上述の実施例とは別に、上述のようにして硫化処理を行なったサンプルを、温度25℃で、異なる相対湿度の環境下に、約12時間静置して、固体電解質(粉体)を得た。
イオン導電率の評価は、交流インピーダンス法を用いて行なった。
具体的には、上述の各実施例1~7及び比較例1の固体電解質を、材料としてSKD11を用いた10mmφの治具[ここでは上側が電極端子(+)、下側が電極端子(-)となる]を持つ電気化学セルに取り付けて、評価装置としてMetrohm Autolab社のAUTOLAB FRA(周波数応答解析装置)を用い、印加電圧を0.1Vとし、周波数応答領域を1MHz~1Hzとし、測定温度を25℃(室温)として、インピーダンスを測定した。
t(cm)/R(Ω)/S(cm2)=σ(1/Ω・cm)=σ(S/cm)
ここで、図8は、各実施例1~7及び比較例1のそれぞれの場合のイオン導電率データを示している。
また、比較のために、上述の全ての処理を行なっていない改質前のLLTO粉体を、温度25℃、相対湿度50%RHの環境下に、約12時間静置して、固体電解質(粉体)を得て、同様にインピーダンスを測定し、イオン導電率を求めたところ、1.2×10-8S/cmであった。これに対し、上述の全ての処理を行ない、温度25℃、相対湿度60%RH以上の環境下に、約12時間静置して得られた固体電解質(実施例4~7)のイオン導電率は10-5~10-3となり、三桁以上高くなり、急激にイオン導電性が向上した。また、上述の実施例のように、上述の全ての処理を行ない、温度23℃、相対湿度55%RHの環境下に、約12時間静置して得られた固体電解質のイオン導電率も10-5となり、このオーダは温度25℃でも変わらず、三桁以上高くなり、急激にイオン導電性が向上した。このように、上述の全ての処理を行なっていない改質前のLLTO粉体を表面酸化処理した固体電解質のイオン導電率が10-8S/cm程度であったのに対し、上述の全ての処理を行ない、相対湿度55%RH以上の条件下で表面酸化処理した固体電解質は、イオン導電率が10-5~10-3となり、急激にイオン導電率が高くなり、急激にイオン導電性が向上した。
[全固体リチウム二次電池の作製及び評価]
まず、粉体のLiCoO2と、上述のようにして表面改質された粉体の固体電解質材料を6:4の割合で混ぜ合わせて、正極1の材料を作製した[図9(A)参照]。
そして、図9(A)、図9(B)に示すように、電気化学セル(圧粉セル)10に備えられる10mmφの治具(電極;電極端子)11の間に、粉体の負極2の材料、上述のようにして表面改質された粉体の固体電解質3の材料、粉体の正極1の材料を順番に配置し、例えば1000kgfの圧力で加圧して、即ち、室温圧粉成型して、全固体リチウム二次電池を作製した。なお、図9(B)中、符号12はセル(セル外殻)である。
上述のようにして作製した全固体リチウム二次電池、即ち、上述のようにして表面改質された固体電解質3を備える全固体リチウム二次電池では、室温で電池動作を確認することができ、図10に示すような充放電カーブ(充電カーブ及び放電カーブ)が得られ、良好な負荷特性(出力特性)が得られた。ここで、評価条件は、電圧範囲:4-0.5V、充電放電電流:充電10μA、放電1μA、評価温度:60℃とした。
2 負極
3 固体電解質
3A 酸素欠損部を有する第1部分(LLTO-δ)
3B 酸素欠損部に硫黄(S)が結合した表面部分(第2部分;LLTOS)
3C 酸素欠損部に硫黄(S)が結合した表面部分(第2部分)の表面(第2部分の酸化されている部分)
3X 粒子
30 固体電解質材料(LLTO)
30A 酸素欠損部を有する固体電解質材料
30B 固体電解質材料の酸素欠損部に硫黄(S)が結合した表面部分
30C 固体電解質材料の酸素欠損部に硫黄(S)が結合した表面部分の表面
4 正極集電体
5 負極集電体
10 電気化学セル
11 治具(電極端子)
12 セル
Claims (10)
- 構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含む第1部分と、前記第1部分の表面を覆っており、構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含み、酸素欠損部に硫黄(S)が結合しており、少なくとも表面が酸化されている第2部分とを有する粒子を備えることを特徴とする固体電解質。
- 前記第2部分の酸化されている部分以外の部分は、リチウムイオンをトラップする欠陥を有することを特徴とする、請求項1に記載の固体電解質。
- 前記第1部分は、酸素欠損部を有し、電子伝導性を有することを特徴とする、請求項1又は2に記載の固体電解質。
- 正極と、
負極と、
前記正極と前記負極との間に設けられた固体電解質とを備え、
前記固体電解質は、構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含む第1部分と、前記第1部分の表面を覆っており、構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含み、酸素欠損部に硫黄(S)が結合しており、少なくとも表面が酸化されている第2部分とを有する粒子を備えることを特徴とする全固体二次電池。 - 前記第2部分の酸化されている部分以外の部分は、リチウムイオンをトラップする欠陥を有することを特徴とする、請求項4に記載の全固体二次電池。
- 前記第1部分は、酸素欠損部を有し、電子伝導性を有することを特徴とする、請求項4又は5に記載の全固体二次電池。
- 構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含む粉体である固体電解質材料を、還元処理し、
前記還元処理によって生じた酸素欠損部を有する前記固体電解質材料を、硫化処理し、
前記硫化処理によって形成された前記酸素欠損部に硫黄(S)が結合した表面部分を有する前記固体電解質材料を、表面酸化処理し、
前記表面酸化処理によって前記表面部分の少なくとも表面が酸化されている前記固体電解質材料を圧粉成型して固体電解質を製造することを特徴とする固体電解質の製造方法。 - 前記表面酸化処理は、前記固体電解質材料の前記表面部分の少なくとも表面が水によって酸化される環境下に前記固体電解質材料を置くことによって行なわれることを特徴とする、請求項7に記載の固体電解質の製造方法。
- 構成元素としてランタン(La)、リチウム(Li)、チタン(Ti)及び酸素(O)を含む粉体である固体電解質材料を、還元処理し、前記還元処理によって生じた酸素欠損部を有する前記固体電解質材料を、硫化処理し、前記硫化処理によって形成された前記酸素欠損部に硫黄(S)が結合した表面部分を有する前記固体電解質材料を、表面酸化処理し、前記表面酸化処理によって前記表面部分の少なくとも表面が酸化されている前記固体電解質材料を、正極材料と負極材料との間に挟んで圧粉成型して、全固体二次電池を製造することを特徴とする全固体二次電池の製造方法。
- 前記表面酸化処理は、前記固体電解質材料の前記表面部分の少なくとも表面が水によって酸化される環境下に前記固体電解質材料を置くことによって行なわれることを特徴とする、請求項9に記載の全固体二次電池の製造方法。
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EP14900776.7A EP3196892B1 (en) | 2014-08-28 | 2014-08-28 | Solid electrolyte, method for manufacturing same, all-solid-state secondary cell, and method for manufacturing same |
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CN107681189A (zh) * | 2016-08-02 | 2018-02-09 | 财团法人工业技术研究院 | 掺杂硫的氧化物固态电解质粉末及包含其之固态电池 |
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DE102018219510A1 (de) * | 2018-11-15 | 2020-05-20 | Robert Bosch Gmbh | Verfahren zur Behandlung eines Festkörperelektrolyten einer Batteriezelle |
US11611103B2 (en) | 2020-06-29 | 2023-03-21 | Samsung Electronics Co., Ltd. | Solid ion conductor compound, solid electrolyte comprising the same, electrochemical cell comprising the solid ion conductor compound, and preparation method thereof |
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JPWO2016031022A1 (ja) | 2017-06-08 |
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US10505221B2 (en) | 2019-12-10 |
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