WO2016017769A1 - リチウム含有ガーネット結晶体、その製造方法、および全固体リチウムイオン二次電池 - Google Patents
リチウム含有ガーネット結晶体、その製造方法、および全固体リチウムイオン二次電池 Download PDFInfo
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- H01M2220/00—Batteries for particular applications
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Definitions
- the present invention relates to a high-density lithium-containing garnet crystal, a manufacturing method thereof, and an all-solid-state lithium ion secondary battery using the lithium-containing garnet crystal as a solid electrolyte.
- Lithium ion secondary batteries are used in small information devices such as mobile phones and laptop computers because of their high energy density and operation at high potentials. In consideration of safety, all-solid-state lithium ion secondary batteries that do not use flammable electrolytes are being researched and developed. High ion conductivity is required for a solid electrolyte used in an all-solid lithium ion secondary battery.
- Li 7 La 3 Zr 2 O 12 having a tetragonal garnet-type crystal structure is known as a high lithium ion conductive oxide (Patent Document 1).
- the solid electrolyte In order for a solid electrolyte to achieve high ionic conductivity, it is necessary to reduce grain boundary resistance and interface resistance. For this reason, it is desirable that the solid electrolyte is a high-density dense molded body. Moreover, if the solid electrolyte is a dense molded body having a high density, it is possible to prevent a short circuit between the positive and negative electrodes during the charge / discharge process. Furthermore, since the high-density dense molded body can be thinned, if the solid electrolyte is a high-density dense molded body, the all-solid lithium ion secondary battery can be downsized. However, since Li 7 La 3 Zr 2 O 12 having a garnet-type crystal structure is difficult to sinter, it is difficult to produce a dense compact with high density (Non-patent Document 1).
- the present invention has been made in view of such circumstances, and has a high-density lithium-containing garnet crystal and a method for producing the same, and an all-solid-state lithium ion secondary battery using the lithium-containing garnet crystal as a solid electrolyte.
- the purpose is to provide.
- the inventors of the present invention thought that a high-density Li 7 La 3 Zr 2 O 12 crystal having no grain boundary can be obtained by devising a method for producing a crystal, and the above problem can be solved. Then, the polycrystalline Li 7 La 3 Zr 2 O 12 samples the melted at a high temperature cooling Li 7 La 3 Zr 2 O 12 results manufacturing method of intensive studies for the crystal, high density garnet related structure Li 7 La 3 The present invention was completed by confirming that a Zr 2 O 12 crystal can be grown and that this Li 7 La 3 Zr 2 O 12 crystal can be mechanically thinned.
- the lithium-containing garnet crystal of the present invention for example, a Li 7 La 3 Zr 2 O 12 crystal has a relative density of 99% or more, belongs to a tetragonal system, and has a garnet-related structure.
- the method for producing a Li 7 La 3 Zr 2 O 12 crystal of the present invention melts at least a part of a raw material composed of polycrystalline Li 7 La 3 Zr 2 O 12 to form a molten part, and moves the molten part A Li 7 La 3 Zr 2 O 12 crystal having a garnet-related structure, wherein the moving speed of the molten part is 8 mm / h or more, and the relative density of the Li 7 La 3 Zr 2 O 12 crystal Is 99% or more.
- the all solid lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, and a solid electrolyte, and the solid electrolyte is composed of the lithium-containing garnet crystal of the present invention.
- a high-density lithium-containing garnet crystal and an all-solid-state lithium ion secondary battery using the lithium-containing garnet crystal as a solid electrolyte can be obtained.
- the lithium-containing garnet crystal according to the embodiment of the present invention has a relative density of 99% or more, belongs to a tetragonal system, and has a garnet-related structure.
- the relative density is calculated by measuring the outer shape of the manufactured flakes, calculating the apparent volume, and dividing the apparent density calculated from the measured mass by the true density obtained from the single crystal X-ray structural analysis result. .
- the lithium-containing garnet crystal of the present embodiment is more preferable as the relative density is higher. In the lithium-containing garnet crystal of the present embodiment, it is not necessary that all crystal domains are oriented in the same direction.
- FIG. 1 is a single crystal X-ray diffraction pattern of a tetragonal Li 7 La 3 Zr 2 O 12 crystal produced in an experiment in which the orientation of crystal domains is not uniform.
- This sample is a tetragonal Li 7 La 3 Zr 2 O 12 single crystal produced by moving the melting part at 100 mm / h in the FZ method. Since the cooling rate of the melted part is too high, the crystal domain cannot be grown in a uniform direction in the sample.
- the diffraction spots become complicated, or diffraction from various domains overlap and the diffraction spots become close to a ring shape.
- the lithium-containing garnet crystal of the present embodiment include Li 7 La 3 Zr 2 O 12 crystal, tetragonal Li 7 La 3 Hf 2 O 12 crystal, or tetragonal Li 7 La 3 Sn 2 O 12 crystal. Can be mentioned.
- the Nyquist plot based on AC impedance measurement shows two resistance components, a resistance component due to grain boundaries and a resistance component due to the material itself (non-patent literature). 1).
- the Nyquist plot of the lithium-containing garnet crystal of the present embodiment does not show a resistance component due to crystal grain boundaries, but shows only the resistance component of the material itself, as shown in FIG.
- the lithium-containing garnet crystal of the present embodiment in the X-ray diffraction measurement, neutron diffraction measurement, or electron diffraction measurement using a single crystal, as shown in FIG. Appears at
- the lithium-containing garnet crystal of the present invention is excellent in lithium ion conductivity, it can be used as a solid electrolyte of an all-solid lithium ion secondary battery. That is, the all solid lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, and a solid electrolyte, and the solid electrolyte is a lithium-containing garnet crystal of the present invention, for example, a relative density of 99% or more, and a square It consists of Li 7 La 3 Zr 2 O 12 crystals belonging to the crystal system and having a garnet-related structure. Further, Li 7 La 3 Zr 2 O 12 crystal having a relative density of 100%, that is, the original Li 7 La 3 Zr 2 O 12 single crystal is particularly excellent in lithium ion conductivity.
- the method for producing a Li 7 La 3 Zr 2 O 12 crystal forms a molten part by melting at least a part of a raw material composed of polycrystalline Li 7 La 3 Zr 2 O 12 ,
- the relative density of the crystals is 99% or more.
- the Li 7 La 3 Zr 2 O 12 crystal production method of this embodiment is a method of growing Li 7 La 3 Zr 2 O 12 crystal from a raw material melt, specifically, a floating zone (FZ) method, Examples include the Czochralski (CZ) method, the Bridgeman method, and the pedestal method. An appropriate method may be selected from these methods according to the size and shape of the Li 7 La 3 Zr 2 O 12 crystal to be produced.
- FZ floating zone
- CZ Czochralski
- Bridgeman method Bridgeman method
- pedestal method An appropriate method may be selected from these methods according to the size and shape of the Li 7 La 3 Zr 2 O 12 crystal to be produced.
- Li 7 La 3 Zr 2 O 12 crystals When producing Li 7 La 3 Zr 2 O 12 crystals by the FZ method, part of the rod-shaped raw material is melted while rotating on a plane perpendicular to the longitudinal direction, and the molten part is moved in the longitudinal direction. To grow Li 7 La 3 Zr 2 O 12 crystals.
- a rod-shaped raw material composed of polycrystalline Li 7 La 3 Zr 2 O 12 is produced as follows. First, lithium compounds, lanthanum compounds, and zirconium compounds are weighed so that the molar ratio of Li: La: Zr is 7 to 8: 3: 2 in consideration of the volatilization of lithium at a high temperature.
- the lithium compound is not particularly limited as long as it contains lithium, and examples thereof include Li 2 O and Li 2 CO 3 .
- the lanthanum compound is not particularly limited as long as it contains lanthanum, and examples thereof include La 2 O 3 and La (OH) 3 .
- the zirconium compound is not particularly limited as long as it contains zirconium, and examples thereof include ZrO 2 and ZrCl 4 .
- the molar ratio of Li: La: Zr is 7 to 8: 3: 2. You may weigh so that it may become a ratio.
- each weighed compound is mixed.
- the mixing method is not particularly limited as long as these compounds can be uniformly mixed, and may be mixed by a wet method or a dry method using a mixer such as a mixer.
- the powder of polycrystalline Li 7 La 3 Zr 2 O 12 as a raw material is calcined at 900 ° C. to 1000 ° C., preferably 930 ° C. to 990 ° C. Is obtained.
- This polycrystalline Li 7 La 3 Zr 2 O 12 powder belongs to the tetragonal system.
- the obtained polycrystalline Li 7 La 3 Zr 2 O 12 powder is pulverized to reduce the particle size.
- the pulverization method is not particularly limited as long as the powder can be refined.
- the pulverization method may be wet or dry using a pulverizer such as a planetary ball mill, pot mill, or bead mill.
- a pulverizer such as a planetary ball mill, pot mill, or bead mill.
- the obtained molded body is fired at about 800 ° C. to 1300 ° C., preferably 900 ° C. to 1100 ° C., a rod-shaped polycrystalline Li 7 La 3 Zr 2 O 12 raw material is obtained.
- This rod-shaped polycrystalline Li 7 La 3 Zr 2 O 12 belongs to the tetragonal system.
- a rod-shaped polycrystalline Li 7 La 3 Zr 2 O 12 raw material belonging to the tetragonal system is melted in an infrared condensing heating furnace and then rapidly cooled to thereby form a Li 7 La 3 Zr 2 having a garnet-related structure. O 12 crystals are produced.
- the produced Li 7 La 3 Zr 2 O 12 crystal belongs to the tetragonal system.
- the bubbles are generated as lithium is volatilized, but the bubbles can be removed by increasing the rotational speed of the rod-shaped polycrystalline Li 7 La 3 Zr 2 O 12 material to 30 rpm or more.
- the rotation speed of the raw material is preferably 30 rpm or more and 60 rpm or less.
- it is preferable that the raw material is melted and the molten part is moved in a dry air atmosphere. In this way, a high-density Li 7 La 3 Zr 2 O 12 crystal having a relative density of 99% or more can be produced. Li 7 La 3 Zr 2 O 12 crystals having a relative density of 100% can also be produced.
- Li 7 La 3 Zr 2 O 12 crystal by FZ method (1) Production of polycrystalline Li 7 La 3 Zr 2 O 12 powder First, lithium carbonate Li 2 CO 3 (rare metallic, purity 99.99%) 10.1175 g as a starting material and lanthanum oxide La 2 O 3 (rare metallic) , 97.4% purity) 17.4606 g and zirconium oxide ZrO 2 (rare metallic, purity 99.99% purity) 8.7648 g were put in an agate mortar and mixed uniformly by a wet method using ethanol. The lanthanum oxide used was pre-baked at 900 ° C. in advance. Next, an alumina crucible with a lid (made by Nikkato, C5 type) was charged with 36 g of this mixture.
- this polycrystalline Li 7 La 3 Zr 2 O 12 powder was pulverized. That is, 30 g of polycrystalline Li 7 La 3 Zr 2 O 12 powder, 50 g of zirconia balls with a diameter of 5 mm, and 14 mL of ion-exchanged water were filled in a zirconia grinding vessel with a capacity of 45 mL, Using P-6), the mixture was pulverized by rotating at a revolution speed of 200 rpm for a total of 300 minutes. The pulverized polycrystalline powder was dried at 100 ° C. for 24 hours, and classified using a sieve having an opening of 250 ⁇ m.
- the obtained fired body had a rod shape with a width of 1 cm and a length of 7 cm close to a cylinder, and its mass was 26 g. From the powder X-ray diffraction pattern by a powder X-ray diffractometer (manufactured by Rigaku Corporation, Smart Lab), it was found that this fired body was polycrystalline Li 7 La 3 Zr 2 O 12 belonging to the tetragonal system.
- FIG. 2 shows the appearance of a Li 7 La 3 Zr 2 O 12 crystal (hereinafter sometimes referred to as “sample 1”) obtained at a moving speed of the installation table of 19 mm / h.
- Sample 1 was examined using a single crystal X-ray diffractometer (Rigaku Corporation, R-AXIS RAPID-II). The X-ray diffraction pattern of Sample 1 is shown in FIG. As shown in FIG. 3, a clear diffraction point could be measured.
- RAPID AUTO attached to the single crystal X-ray diffractometer and the crystal structure of the sample 1 was examined by the crystal structure analysis program Jana2006, it was found that the sample 1 belonged to a tetragonal crystal.
- Sample 1 was cut with a diamond cutter to produce four thin pieces having a thickness of 0.1 mm. And these relative densities were computed by the above-mentioned method. As a result, their relative densities were 99.0%, 99.4%, 99.7% and 100%, respectively.
- FIG. 4 shows the results of collecting the diffraction intensity data by the program RAPID AUTO attached to the single crystal X-ray diffractometer and analyzing the crystal structure of the sample 1 by the crystal structure analysis program Jana2006. Compared with the tetragonal garnet-related structure reported so far, Sample 1 is different in the arrangement of lithium ions in the crystal structure and the occupied state of lithium seats.
- the tetragonal Li 7 La 3 Zr 2 O 12 reported so far has three types of lithium ion seats (8a seat, 16f seat, 32g seat) in the crystal structure, and each seat occupancy rate is 100
- the sample 1 has four types of lithium ion seats (8a seat, 16f seat, two 32g seats, 16e seat) in the crystal structure, and the occupancy rate of each seat is 30-50% there were.
- the powder X-ray diffraction pattern of Sample 1 was similar to the pattern of Li 7 La 3 Zr 2 O 12 having a tetragonal garnet-related structure reported so far.
- sample 1 was cut to produce a cylindrical thin piece having a diameter of about 1.0 cm and a thickness of about 0.19 cm.
- a rectangular parallelepiped gold having a bottom surface of 0.18 cm on a side and a thickness of 40 nm was sputtered on both sides of the thin piece to form electrodes.
- the impedance of the sample 1 was measured by an alternating current impedance method (measuring device: Solartron, 1260) at 25 ° C. in a nitrogen atmosphere.
- the Nyquist plot at this time is shown in FIG.
- the lithium ion conductivity was calculated from the Nyquist plot shown in FIG. 6 and found to be 4.6 ⁇ 10 ⁇ 5 S / cm.
- this tungsten rod was rotated at 10 rpm in a plane perpendicular to the longitudinal direction and placed in the molten portion of Li 7 La 3 Zr 2 O 12 , and then the tungsten rod was raised at a moving speed of 10 mm / h to make Li 7 La 3 Zr 2 O 12 crystals were grown.
- the appearance of the grown Li 7 La 3 Zr 2 O 12 crystal (hereinafter sometimes referred to as “sample 2”) is shown in FIG.
- the result of having pulverized Sample 2 and performing powder X-ray diffraction measurement is shown in FIG.
- the powder X-ray diffraction pattern of Sample 2 was similar to the pattern of Li 7 La 3 Zr 2 O 12 having a tetragonal garnet-related structure reported so far.
- the lattice constants of the Li 7 La 3 Zr 2 O 12 crystal are 1.3052 nm ⁇ a ⁇ 1.31323 nm and 1.26702 nm ⁇ c ⁇ 1.3024 nm.
- the lithium-containing garnet crystal of the present invention can be used as a solid electrolyte material for an all-solid lithium ion secondary battery.
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Abstract
Description
(1)多結晶Li7La3Zr2O12粉末の作製
まず、出発原料として炭酸リチウムLi2CO3(レアメタリック製、純度99.99%)10.1175gと、酸化ランタンLa2O3(レアメタリック製、純度99.99%)17.4606gと、酸化ジルコニウムZrO2(レアメタリック製、純度99.99%)8.7648gをメノウ製乳鉢に入れて、エタノールを使用した湿式法によって均一に混合した。なお、酸化ランタンは、あらかじめ900℃で仮焼成したものを使用した。つぎに、ふた付きのアルミナるつぼ(ニッカトー製、C5型)にこの混合物36gを充填した。そして、これをボックス型電気炉(ヤマト科学製、FP100型)に入れて、950℃で5時間仮焼成して粉末を得た。つぎに、得られた粉末を、乳鉢で粉砕した後に980℃で10時間焼成することを2回行い、多結晶Li7La3Zr2O12粉末を作製した。
上記工程でふるいを通過した多結晶Li7La3Zr2O12粉末を用いて、以下の手順で棒形状の多結晶Li7La3Zr2O12を作製した。まず、ゴム製の型にこの多結晶Li7La3Zr2O12粉末26gを充填して脱気した。つぎに、この型を密閉した状態で水中に入れて、40MPaで5分間維持した。そして、水の圧力を下げた後、成形体を型から取り出した。成形体は、直径1.2cm、高さ7cmの円柱形状をしていた。つぎに、箱型電気炉(デンケン製、型番KDF009)を用いて、この成形体を1150℃で8時間焼成した。得られた焼成体は、円柱に近い幅1cm、長さ7cmの棒形状をしており、その質量は26gであった。粉末X線回折装置(リガク社製、Smart Lab)による粉末X線回折パターンによって、この焼成体は正方晶系に属する多結晶Li7La3Zr2O12であることがわかった。
まず、100kWのハロゲンランプを装備した四楕円型赤外線集光加熱炉(FZ炉)(Crystal System社製、FZ-T-10000H型)に、上記工程で得られた棒形状の多結晶Li7La3Zr2O12原料を設置して、乾燥空気雰囲気にした。つぎに、棒形状の多結晶Li7La3Zr2O12原料を長手方向と垂直な面で原料を45rpmで回転させながら、出力51.9%で加熱した。しばらくすると、多結晶Li7La3Zr2O12原料の一部が溶融して溶融部を形成した。そして、多結晶Li7La3Zr2O12原料の設置台を8mm/hと19mm/hの移動速度で下降させてLi7La3Zr2O12結晶を育成した。設置台の移動速度を19mm/hとして得られたLi7La3Zr2O12結晶(以下「試料1」ということがある)の外観を図2に示す。
まず、試料1を切断して、直径約1.0cm、厚さ約0.19cmの円柱状の薄片を作製した。つぎに、底面が一辺0.18cmの正方形で、厚さが40nmの直方体状の金を、この薄片の両面にスパッタリングして電極を形成した。そして、窒素雰囲気中25℃で、交流インピーダンス法(測定装置:Solartron、1260)によって、試料1のインピーダンスを測定した。このときのナイキストプロットを図6に示す。図6に示すナイキストプロットからリチウムイオン伝導率を算出したところ4.6×10-5S/cmであった。
(1)多結晶Li7La3Zr2O12粉末の作製
上記「FZ法によるLi7La3Zr2O12結晶の製造」での「多結晶Li7La3Zr2O12粉末の作製」と同様の手順で、ふるいを通過した多結晶Li7La3Zr2O12粉末を作製した。
まず、内径2.6cm、深さ2.8cmの円筒状のイリジウム容器に、上記工程で得られた多結晶Li7La3Zr2O12粉末38gを充填した。つぎに、高周波誘導加熱機能を備える単結晶引き上げ炉(CZ炉)(テクノサーチ社製、TCH-3)に、このイリジウム容器を設置した。そして、長さ0.8mmのタングステンロッドを引き上げ部に設置して、CZ炉内を乾燥窒素雰囲気にした。つぎに、高周波出力を少しずつ上げていき、出力76.2%でイリジウム容器を加熱し続けた。しばらくすると、イリジウム容器に充填したLi7La3Zr2O12粉末が溶融した。
Claims (15)
- 相対密度が99%以上で、正方晶系に属し、ガーネット関連型構造を有するリチウム含有ガーネット結晶体。
- 請求項1において、
Li7La3Zr2O12結晶であるリチウム含有ガーネット結晶体。 - 請求項1または2において、
前記相対密度が100%であるリチウム含有ガーネット結晶体。 - 請求項1から3のいずれかにおいて、
下記(1)および(2)の少なくとも一方を満たすリチウム含有ガーネット結晶体。
(1)交流インピーダンス測定によるナイキストプロットが、結晶粒界による抵抗成分を示さず、材料自体の抵抗成分のみを示す。
(2)単結晶を用いたX線回折測定、中性子回折測定、または電子回折測定において、回折パターンに回折スポットがリング状で現れる。 - 請求項1から4のいずれかにおいて、
格子定数が1.3052nm≦a≦1.31323nm、1.26702nm≦c≦1.3024nmであるリチウム含有ガーネット結晶体。 - 請求項5において、
Liが8a席、16f席、32g席、および16e席の4種類のイオン席に存在するリチウム含有ガーネット結晶体。 - 多結晶Li7La3Zr2O12から構成される原料の少なくとも一部を溶融して溶融部を形成し、前記溶融部を移動してガーネット関連型構造を有するLi7La3Zr2O12結晶を製造する方法であって、
前記溶融部の移動速度が8mm/h以上であり、
前記Li7La3Zr2O12結晶の相対密度が99%以上であるLi7La3Zr2O12結晶の製造方法。 - 請求項7において、
前記移動速度が8mm/h以上19mm/h以下であるLi7La3Zr2O12結晶の製造方法。 - 請求項7または8において、
棒形状の前記原料を長手方向と垂直な面で回転させながらその一部を溶融し、
前記溶融部を前記長手方向に移動するLi7La3Zr2O12結晶の製造方法。 - 請求項9において、
前記原料の回転速度が30rpm以上であるLi7La3Zr2O12結晶の製造方法。 - 請求項10において、
前記原料の回転速度が30rpm以上60rpm以下であるLi7La3Zr2O12結晶の製造方法。 - 請求項7から11のいずれかにおいて、
前記多結晶Li7La3Zr2O12および前記Li7La3Zr2O12結晶が正方晶系に属するLi7La3Zr2O12結晶の製造方法。 - 請求項7から12のいずれかにおいて、
前記Li7La3Zr2O12結晶の相対密度が100%であるLi7La3Zr2O12結晶の製造方法。 - 請求項7から13のいずれかにおいて、
前記原料の溶融および前記溶融部の移動を乾燥空気雰囲気で行うLi7La3Zr2O12結晶の製造方法。 - 正極と、負極と、固体電解質とを有する全固体リチウムイオン二次電池であって、
前記固体電解質が請求項1から6のいずれかのリチウム含有ガーネット結晶体から構成される全固体リチウムイオン二次電池。
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