JP2020158339A - Method for producing lithium metal complex oxide powder - Google Patents
Method for producing lithium metal complex oxide powder Download PDFInfo
- Publication number
- JP2020158339A JP2020158339A JP2019058988A JP2019058988A JP2020158339A JP 2020158339 A JP2020158339 A JP 2020158339A JP 2019058988 A JP2019058988 A JP 2019058988A JP 2019058988 A JP2019058988 A JP 2019058988A JP 2020158339 A JP2020158339 A JP 2020158339A
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- Prior art keywords
- lithium metal
- composite oxide
- metal composite
- lithium
- oxide powder
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 236
- 239000000843 powder Substances 0.000 title claims abstract description 131
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 150000004696 coordination complex Chemical class 0.000 title abstract 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 59
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
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- 239000010936 titanium Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001882 dioxygen Inorganic materials 0.000 claims description 11
- 150000002642 lithium compounds Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 description 39
- 239000007773 negative electrode material Substances 0.000 description 33
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウム元素、チタン元素、及び、酸素元素を含むリチウム金属複合酸化物粉末、その製造方法、並びにリチウム金属複合酸化物粉末を用いた二次電池及びその製造方法に関する。 The present invention relates to a lithium metal composite oxide powder containing a lithium element, a titanium element, and an oxygen element, a method for producing the same, and a secondary battery using the lithium metal composite oxide powder and a method for producing the same.
リチウム元素、チタン元素及び酸素元素を含むリチウム金属複合酸化物は、リチウムイオン二次電池や全固体電池、リチウムイオンキャパシタ等の二次電池用の負極活物質として使用できることが知られている。
例えば、特許文献１及び特許文献２には、スピネル型のＬｉ４Ｔｉ５Ｏ１２、ラムスデライト型のＬｉＴｉ２Ｏ４、ラムスデライト型のＬｉ２Ｔｉ３Ｏ７等のリチウム金属複合酸化物が紹介されている。また、特許文献１にはこれらのリチウム金属複合酸化物がリチウムイオン二次電池に用いられる旨が紹介され、特許文献２には、それに加えて、当該リチウム金属複合酸化物がリチウムイオンキャパシタに用いられる旨も紹介されている。
更に、特許文献１及び特許文献２には、上記のリチウム金属複合酸化物のうちラムスデライト型のものはスピネル型のものに比べて理論容量が大きい旨が紹介されている。
It is known that a lithium metal composite oxide containing a lithium element, a titanium element and an oxygen element can be used as a negative electrode active material for a secondary battery such as a lithium ion secondary battery, an all-solid-state battery or a lithium ion capacitor.
For example, Patent Document 1 and Patent Document 2 introduce lithium metal composite oxides such as spinel-type Li 4 Ti 5 O 12 , rams delite-type Li Ti 2 O 4 , and rams delite-type Li 2 Ti 3 O 7. Has been done. Further, Patent Document 1 introduces that these lithium metal composite oxides are used for lithium ion secondary batteries, and Patent Document 2 additionally uses the lithium metal composite oxides for lithium ion capacitors. It is also introduced that it will be done.
Further, Patent Document 1 and Patent Document 2 introduce that among the above-mentioned lithium metal composite oxides, the rams delight type has a larger theoretical capacity than the spinel type.
特許文献１及び特許文献２等に紹介されている従来の製造方法によると、種々のリチウム金属複合酸化物粉末を製造することが可能である。しかし乍ら、近年、二次電池の用途は拡大の一途をたどり、当該二次電池に用いられるリチウム金属複合酸化物粉末についても、従来のものとは異なる、新規なものが望まれている。
本発明は、かかる事情に鑑みてなされたものであり、新規なリチウム金属複合酸化物粉末を製造し得る、リチウム金属複合酸化物粉末の製造方法を提供することを目的とする。
According to the conventional production methods introduced in Patent Document 1 and Patent Document 2, various lithium metal composite oxide powders can be produced. However, in recent years, the applications of secondary batteries have been steadily expanding, and new lithium metal composite oxide powders used in the secondary batteries, which are different from the conventional ones, are desired.
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for producing a lithium metal composite oxide powder capable of producing a novel lithium metal composite oxide powder.
本発明のリチウム金属複合酸化物粉末の製造方法は、
リチウム元素、チタン元素、及び、酸素元素を含むリチウム金属複合酸化物源を導入流にて、プラズマ内に導入する工程を有する、平均粒子径がナノ水準であるリチウム金属複合酸化物粉末の製造方法である。
The method for producing a lithium metal composite oxide powder of the present invention is
A method for producing a lithium metal composite oxide powder having a nano-level average particle size, which comprises a step of introducing a lithium metal composite oxide source containing a lithium element, a titanium element, and an oxygen element into a plasma by an introduction flow. Is.
本発明のリチウム金属複合酸化物粉末の製造方法によると、新規なリチウム金属複合酸化物粉末を製造し得る。 According to the method for producing a lithium metal composite oxide powder of the present invention, a novel lithium metal composite oxide powder can be produced.
以下に、本発明を実施するための最良の形態を説明する。なお、特に断らない限り、本明細書に記載された数値範囲「ｘ〜ｙ」は、下限ｘ及び上限ｙをその範囲に含む。そして、これらの上限値及び下限値、並びに実施例中に列記した数値も含めてそれらを任意に組み合わせることで数値範囲を構成し得る。さらにこれらの数値範囲内から任意に選択した数値を新たな数値範囲の上限、下限の数値とすることもできる。 The best mode for carrying out the present invention will be described below. Unless otherwise specified, the numerical range "x to y" described in the present specification includes the lower limit x and the upper limit y in the range. Then, a numerical range can be constructed by arbitrarily combining these upper and lower limit values and the numerical values listed in the examples. Further, numerical values arbitrarily selected from these numerical values can be set as upper and lower limit values of a new numerical range.
（リチウム金属複合酸化物粉末）
本発明のリチウム金属複合酸化物粉末の製造方法は、リチウム元素、チタン元素、及び、酸素元素を含むリチウム金属複合酸化物源を導入流にて、プラズマ内に導入する工程を有する。また、本発明のリチウム金属複合酸化物粉末の製造方法によると平均粒子径がナノ水準であるリチウム金属複合酸化物粉末を製造できる。本明細書において「平均粒子径がナノ水準である」とは、平均粒子径が１ｎｍ以上１０００ｎｍ未満の範囲内であることを指すものとする。つまり本発明の製造方法で得られたリチウム金属複合酸化物粉末の平均粒子径は上記範囲内である。なお、本発明の製造方法により得られたリチウム金属複合酸化物粉末の平均粒子径がナノ水準であるか否かは、後述するように電子顕微鏡像によって確認できる。
以下、必要に応じて、本発明のリチウム金属複合酸化物粉末の製造方法で得られるリチウム金属複合酸化物粉末を、本発明のリチウム金属複合酸化物粉末と称する場合がある。また、本発明のリチウム金属複合酸化物粉末の製造方法を、単に、本発明の製造方法と称する場合がある。
本発明のリチウム金属複合酸化物粉末は多数の粒子からなる。各々の粒子は結晶子からなるものであっても良いし、幾つかの結晶子が複合化したものであっても良い。
(Lithium metal composite oxide powder)
The method for producing a lithium metal composite oxide powder of the present invention includes a step of introducing a lithium metal composite oxide source containing a lithium element, a titanium element, and an oxygen element into a plasma by an introduction flow. Further, according to the method for producing a lithium metal composite oxide powder of the present invention, a lithium metal composite oxide powder having a nano-level average particle size can be produced. In the present specification, "the average particle size is at the nano level" means that the average particle size is in the range of 1 nm or more and less than 1000 nm. That is, the average particle size of the lithium metal composite oxide powder obtained by the production method of the present invention is within the above range. Whether or not the average particle size of the lithium metal composite oxide powder obtained by the production method of the present invention is at the nano level can be confirmed by an electron microscope image as described later.
Hereinafter, if necessary, the lithium metal composite oxide powder obtained by the method for producing a lithium metal composite oxide powder of the present invention may be referred to as the lithium metal composite oxide powder of the present invention. In addition, the method for producing a lithium metal composite oxide powder of the present invention may be simply referred to as the method for producing a lithium metal composite oxide powder of the present invention.
The lithium metal composite oxide powder of the present invention comprises a large number of particles. Each particle may be composed of crystallites, or may be a composite of several crystallites.
以下、本発明の製造方法に沿って、本発明を説明する。 Hereinafter, the present invention will be described along with the manufacturing method of the present invention.
本発明の製造方法は、リチウム元素、チタン元素、及び、酸素元素を含むリチウム金属複合酸化物源を材料とする。したがって、本発明の製造方法で製造される本発明のリチウム金属複合酸化物粉末は、リチウム金属複合酸化物源に由来するリチウム元素、チタン元素及び酸素元素を含む、粉末状のリチウム金属複合酸化物であるといえる。 The production method of the present invention uses a lithium metal composite oxide source containing a lithium element, a titanium element, and an oxygen element as a material. Therefore, the lithium metal composite oxide powder of the present invention produced by the production method of the present invention is a powdered lithium metal composite oxide containing lithium element, titanium element and oxygen element derived from the lithium metal composite oxide source. You can say that.
リチウム元素、チタン元素及び酸素元素を含むリチウム金属複合酸化物は、スピネル型のものとラムスデライト型のものとに大別される。
スピネル型のリチウム金属複合酸化物としては、Ｌｉ４＋ｚＴｉ５Ｏ１２（但し、０≦ｚ≦３）を満足するものが例示され、このうちＬｉ４Ｔｉ５Ｏ１２が一般的である。
ラムスデライト型のリチウム金属複合酸化物としては、Ｌｉ２＋ｙＴｉ３Ｏ７（但し、０≦ｙ≦３）を満足するもの及びＬｉ１＋ｘＴｉ２Ｏ４（但し、０≦ｘ≦３）を満足するものが例示される。このうち前者としてはＬｉ２Ｔｉ３Ｏ７が一般的であり、後者としてはＬｉＴｉ２Ｏ４が一般的である。
Lithium metal composite oxides containing lithium element, titanium element and oxygen element are roughly classified into spinel type and rams delight type.
As the spinel-type lithium metal composite oxide, those satisfying Li 4 + z Ti 5 O 12 (however, 0 ≦ z ≦ 3) are exemplified, and among them, Li 4 Ti 5 O 12 is generally used.
The rams delite type lithium metal composite oxide satisfies Li 2 + y Ti 3 O 7 (however, 0 ≦ y ≦ 3) and Li 1 + x Ti 2 O 4 (however, 0 ≦ x ≦ 3). Things are illustrated. Of these, Li 2 Ti 3 O 7 is generally used as the former, and Li Ti 2 O 4 is generally used as the latter.
リチウム金属複合酸化物は、リチウム元素、チタン元素及び酸素元素を含むものであれば良く、その他の金属元素を含んでも良い。当該その他の金属元素として、第１族元素、第２族元素、遷移金属及び第１３族元素からなる群から選ばれる少なくとも１種を例示できる。好ましくは遷移金属であり、Ｃｒ又はＦｅが例示される。 The lithium metal composite oxide may contain any lithium element, titanium element and oxygen element, and may contain other metal elements. As the other metal element, at least one selected from the group consisting of Group 1 elements, Group 2 elements, transition metals and Group 13 elements can be exemplified. It is preferably a transition metal, and Cr or Fe is exemplified.
また、本発明におけるリチウム金属複合酸化物は、上記のＬｉ４＋ｚＴｉ５Ｏ１２（但し、０≦ｚ≦３）、Ｌｉ２＋ｙＴｉ３Ｏ７（但し、０≦ｙ≦３）又はＬｉ１＋ｘＴｉ２Ｏ４を基本構造とするものであるのが良く、更にその他のドープ元素を含み得る。ドープ元素としては上記のその他の金属元素が例示される。また、当該リチウム金属複合酸化物におけるＴｉの一部は他の遷移金属で置換されても良い。 The lithium metal composite oxide in the present invention includes the above-mentioned Li 4 + z Ti 5 O 12 (however, 0 ≦ z ≦ 3), Li 2 + y Ti 3 O 7 (however, 0 ≦ y ≦ 3) or Li 1 + x Ti 2. It preferably has O 4 as a basic structure, and may further contain other doping elements. Examples of the doping element include the above-mentioned other metal elements. Further, a part of Ti in the lithium metal composite oxide may be replaced with another transition metal.
本発明のリチウム金属複合酸化物粉末は、これら各種のリチウム金属複合酸化物の一種のみを含むものであっても良いし、二種以上を含むものであっても良い。場合によっては、二種以上のリチウム金属複合酸化物が複合化したものであっても良い。 The lithium metal composite oxide powder of the present invention may contain only one of these various lithium metal composite oxides, or may contain two or more of them. In some cases, it may be a composite of two or more kinds of lithium metal composite oxides.
本発明のリチウム金属複合酸化物粉末は、二次電池用の負極活物質として使用することができる。その場合、本発明のリチウム金属複合酸化物粉末のみを負極活物質として使用しても良いし、本発明のリチウム金属複合酸化物粉末にその他の負極活物質を併用しても良い。本発明のリチウム金属複合酸化物粉末に併用し得るその他の負極活物質については後述する。 The lithium metal composite oxide powder of the present invention can be used as a negative electrode active material for a secondary battery. In that case, only the lithium metal composite oxide powder of the present invention may be used as the negative electrode active material, or the lithium metal composite oxide powder of the present invention may be used in combination with other negative electrode active materials. Other negative electrode active materials that can be used in combination with the lithium metal composite oxide powder of the present invention will be described later.
本発明のリチウム金属複合酸化物粉末の製造方法は、リチウム金属複合酸化物源を導入流にて、プラズマ内に導入する工程を有する。
リチウム金属複合酸化物源は、リチウム元素、チタン元素、及び、酸素ガスとなり得る酸素元素を含みさえすれば良く、粉末状の本発明のリチウム金属複合酸化物の原料となり得る原料物質又は原料混合物であれば良い。つまり、リチウム金属複合酸化物源は、上記したリチウム金属複合酸化物と同じものであっても良いし、異なるものであっても良いし、単体であっても良いし、複数の単体の混合体であっても良い。更には、リチウム金属複合酸化物源は固体状、液体状、ガス状の何れの性状であっても良いし、これらの混合物であっても良い。
The method for producing a lithium metal composite oxide powder of the present invention includes a step of introducing a lithium metal composite oxide source into plasma by an introduction flow.
The lithium metal composite oxide source may contain a lithium element, a titanium element, and an oxygen element that can be an oxygen gas, and is a raw material or a raw material mixture that can be a raw material of the lithium metal composite oxide of the present invention in powder form. All you need is. That is, the lithium metal composite oxide source may be the same as the above-mentioned lithium metal composite oxide, may be different, may be a simple substance, or a mixture of a plurality of simple substances. It may be. Furthermore, the lithium metal composite oxide source may have any of solid, liquid, and gaseous properties, or may be a mixture thereof.
本発明の製造方法において、リチウム金属複合酸化物源は、プラズマ内に導入されるため、プラズマ内に導入し易い形状、すなわち、粉末状、液体状及び／又はガス状であるのが好ましい。 In the production method of the present invention, since the lithium metal composite oxide source is introduced into the plasma, it is preferably in a shape that can be easily introduced into the plasma, that is, in the form of powder, liquid and / or gas.
以下、必要に応じて、リチウム金属複合酸化物源に含まれるリチウム元素を有するものをＬｉ源と称し、チタン元素を有するものをＴｉ源と称し、酸素ガスとなり得る酸素元素を有するものをＯ源と称する。リチウム金属複合酸化物源の取り扱い性を考慮すると、少なくともＬｉ源及びＴｉ源は粉末状であるのが好ましい。Ｌｉ源及びＴｉ源は、各々単独で使用しても良いし、これらのうち二種以上を含む化合物の状態で使用しても良い。Ｏ源はＬｉ源及びＴｉ源の少なくとも一種とともに化合物の状態で使用しても良いし、単独でつまり酸素ガスの状態で使用しても良い。 Hereinafter, if necessary, a lithium metal composite oxide source containing a lithium element is referred to as a Li source, a titanium element-containing source is referred to as a Ti source, and a lithium metal composite oxide source containing an oxygen element that can be an oxygen gas is referred to as an O source. It is called. Considering the handleability of the lithium metal composite oxide source, at least the Li source and the Ti source are preferably in the form of powder. The Li source and the Ti source may be used alone or in the form of a compound containing two or more of them. The O source may be used in the form of a compound together with at least one of the Li source and the Ti source, or may be used alone, that is, in the state of oxygen gas.
具体的には、Ｌｉ源は、リチウム単体つまり金属リチウムであっても良いし、リチウム元素に加えてチタン元素及び酸素元素の一方又は両方を含む化合物であっても良い。更には、リチウム源を必須とし上記以外の元素を含む化合物であっても良い。 Specifically, the Li source may be lithium alone, that is, metallic lithium, or may be a compound containing one or both of titanium element and oxygen element in addition to lithium element. Furthermore, it may be a compound that requires a lithium source and contains elements other than the above.
このようなＬｉ源としては、リチウム単体、又は、Ｌｉ２ＣＯ３、ＬｉＯＨ、ＬｉＮＯ３、Ｌｉ４／３Ｔｉ５／３Ｏ４、Ｌｉ２Ｏ、Ｌｉ２Ｏ２、ＬｉＯ２に代表されるリチウム化合物を例示することができる。その他、ＬｉＢｒ、Ｌｉ２Ｃ２、ＬｉＣｌ、ＬｉＦ、ＬｉＨ、ＬｉＩ、ＬｉＮ３、Ｌｉ３Ｎ等を用いても良い。Ｌｉ源は、これらの何れかを単独で用いても良いし、これらの複数を組み合わせて用いても良い。 As such Li source, lithium simple substance, or, Li 2 CO 3, LiOH, LiNO 3, Li 4/3 Ti 5/3 O 4, Li 2 O, lithium represented by Li 2 O 2, LiO 2 Compounds can be exemplified. Other, LiBr, Li 2 C 2, LiCl, LiF, LiH, LiI, may be used LiN 3, Li 3 N and the like. As the Li source, any one of these may be used alone, or a plurality of these may be used in combination.
Ｔｉ源もまた単体であっても良いし、上記のＬｉ源とともに化合物を構成しても良いし、上記のＯ源とともに酸化物等の化合物を構成しても良いし、その他の元素とともに化合物を構成しても良い。例えばＴｉ源は、単体で使用しても良いし、酸化物、水酸化物、炭酸塩、硝酸塩、硫酸塩、酢酸塩、シュウ酸塩、ハロゲン酸塩等の金属化合物の状態で使用しても良い。 The Ti source may also be a simple substance, a compound may be formed together with the above Li source, a compound such as an oxide may be formed together with the above O source, or a compound may be formed together with other elements. It may be configured. For example, the Ti source may be used alone or in the form of a metal compound such as an oxide, a hydroxide, a carbonate, a nitrate, a sulfate, an acetate, a oxalate, or a halide. good.
具体的には、Ｔｉ源としては、チタン単体、ＴｉＯ、Ｔｉ２Ｏ３、ＴｉＯ２、Ｈ２ＴｉＯ４、Ｈ２ＴｉＯ３、Ｈ４ＴｉＯ４、ＴｉＣ、ＴｉＯＳＯ４、Ｔｉ２（ＳＯ４）３、Ｔｉ（ＳＯ４）２、ＴｉＣｌ２等を例示できる。 Specifically, the Ti source, titanium alone, TiO, Ti 2 O 3, TiO 2, H 2 TiO 4, H 2 TiO 3, H 4 TiO 4, TiC, TiOSO 4, Ti 2 (SO 4) 3 , Ti (SO 4 ) 2 , TiCl 2, etc. can be exemplified.
リチウム金属複合酸化物源におけるＬｉ源及びＴｉ源の割合は、リチウム元素及びチタン元素のモル比が、目的とするリチウム金属複合酸化物における各元素のモル比に近い値となるよう設定すれば良い。 The ratio of the Li source and the Ti source in the lithium metal composite oxide source may be set so that the molar ratio of the lithium element and the titanium element is close to the molar ratio of each element in the target lithium metal composite oxide. ..
但し、実施例の欄で詳しく述べるように、本発明の製造方法においては、リチウム金属複合酸化物源に含まれるリチウム元素とチタン元素とのモル比をＬｉ：Ｔｉ＝１：１とした場合と、Ｌｉ：Ｔｉ＝１：２とした場合とで、得られたリチウム金属複合酸化物粉末に含まれるリチウム金属複合酸化物の組成比が大きく変化した。 However, as described in detail in the column of Examples, in the production method of the present invention, the molar ratio of the lithium element and the titanium element contained in the lithium metal composite oxide source is Li: Ti = 1: 1. , Li: Ti = 1: 2, and the composition ratio of the lithium metal composite oxide contained in the obtained lithium metal composite oxide powder was significantly changed.
具体的には、Ｌｉ：Ｔｉ＝１：１とした場合には、リチウム金属複合酸化物粉末におけるスピネル型のＬｉ４Ｔｉ５Ｏ１２の含有率が非常に多くなり、Ｌｉ：Ｔｉ＝１：２とした場合には、リチウム金属複合酸化物粉末におけるラムスデライト型のＬｉ２Ｔｉ３Ｏ７の含有率が増大した。
このため、本発明の製造方法においては、目的とするリチウム金属複合酸化物に応じて、リチウム金属複合酸化物源に含まれるリチウム元素とチタン元素とのモル比を適宜適切に設定するのが良いと考えられる。
Specifically, when Li: Ti = 1: 1, the content of spinel-type Li 4 Ti 5 O 12 in the lithium metal composite oxide powder becomes very large, and Li: Ti = 1: 2 In the case of, the content of rams delight type Li 2 Ti 3 O 7 in the lithium metal composite oxide powder increased.
Therefore, in the production method of the present invention, it is preferable to appropriately set the molar ratio of the lithium element and the titanium element contained in the lithium metal composite oxide source according to the target lithium metal composite oxide. it is conceivable that.
例えば、目的とするリチウム金属複合酸化物粉末が、Ｌｉ２＋ｙＴｉ３Ｏ７（但し、０≦ｙ≦３）を満足するラムスデライト型のリチウム金属複合酸化物を多く含むものである場合には、リチウム金属複合酸化物源は、１モルのリチウム元素に対して１モルを超えるチタン元素を含むのが好ましいと考えられる。また、この場合、リチウム金属複合酸化物源におけるリチウム元素とチタン元素のモル比の好ましい範囲としては、１：１．２〜１：３、１：１．５〜１：２．５、１：１．６〜１：２．３、１：１．８〜１：２．２、１：１．９〜１：２．１の各範囲を挙げることができる。リチウム元素とチタン元素のモル比は、１：２に近い程良いと推測される。 For example, when the target lithium metal composite oxide powder contains a large amount of rams delite type lithium metal composite oxide satisfying Li 2 + y Ti 3 O 7 (however, 0 ≦ y ≦ 3), the lithium metal It is considered that the composite oxide source preferably contains more than 1 mol of titanium element with respect to 1 mol of lithium element. In this case, the preferable range of the molar ratio of the lithium element and the titanium element in the lithium metal composite oxide source is 1: 1.2 to 1: 3, 1: 1.5 to 1: 2.5, 1: 1. Each range of 1.6 to 1: 2.3, 1: 1.8 to 1: 2.2, 1: 1.9 to 1: 2.1 can be mentioned. It is presumed that the closer the molar ratio of lithium element to titanium element is to 1: 2, the better.
また、例えば、目的とするリチウム金属複合酸化物粉末が、Ｌｉ４＋ｚＴｉ５Ｏ１２（但し、０≦ｚ≦３）を満足するスピネル型のリチウム金属複合酸化物を多く含むものである場合には、リチウム金属複合酸化物源は、１モルのリチウム元素に対して２モル未満のチタン元素を含むのが好ましいと考えられる。また、この場合、リチウム金属複合酸化物源におけるリチウム元素とチタン元素のモル比の好ましい範囲としては、１：１．５〜１：０．５、１：１．３〜１：０．７、１：１．２〜１：０．８、１：１．１〜１：０．９の各範囲を挙げることができる。リチウム元素とチタン元素のモル比は、１：１に近い程良いと推測される。 Further, for example, when the target lithium metal composite oxide powder contains a large amount of spinel-type lithium metal composite oxide satisfying Li 4 + z Ti 5 O 12 (however, 0 ≦ z ≦ 3), lithium is used. It is considered that the metal composite oxide source preferably contains less than 2 mol of titanium element with respect to 1 mol of lithium element. In this case, the preferable ranges of the molar ratios of the lithium element and the titanium element in the lithium metal composite oxide source are 1: 1.5 to 1: 0.5, 1: 1.3 to 1: 0.7, and the like. Each range of 1: 1.2 to 1: 0.8 and 1: 1.1 to 1: 0.9 can be mentioned. It is presumed that the closer the molar ratio of lithium element to titanium element is, the better.
本発明の製造方法は、プラズマ発生装置を用いて実施される。プラズマは、アーク放電、多相アーク放電、高周波電磁誘導、マイクロ波加熱放電などで発生させればよい。本発明の製造方法は、熱プラズマ法によってリチウム金属複合酸化物粉末を製造する方法と捉えることができる。 The manufacturing method of the present invention is carried out using a plasma generator. Plasma may be generated by arc discharge, multi-phase arc discharge, high frequency electromagnetic induction, microwave heating discharge, or the like. The production method of the present invention can be regarded as a method for producing a lithium metal composite oxide powder by a thermal plasma method.
高周波電磁誘導式のプラズマ発生装置の場合、その周波数は、例えば０．５〜４００ＭＨｚの範囲内、好ましくは１〜８０ＭＨｚの範囲内とすればよい。プラズマ出力は、例えば３〜３００ｋＷの範囲内、好ましくは５〜１００ｋＷの範囲内とすればよい。プラズマ発生装置内の圧力は適宜設定すればよく、例えば１０ｋＰａ〜大気圧の範囲内を例示できる。プラズマ出力やプラズマ発生装置内の圧力を変動させることで、本発明のリチウム金属複合酸化物粉末の平均粒子径を変化させることができる。例えば、プラズマ出力を増加することで、本発明のリチウム金属複合酸化物粉末の平均粒子径を小さくすることができる。 In the case of a high-frequency electromagnetic induction type plasma generator, the frequency may be, for example, in the range of 0.5 to 400 MHz, preferably in the range of 1 to 80 MHz. The plasma output may be, for example, in the range of 3 to 300 kW, preferably in the range of 5 to 100 kW. The pressure in the plasma generator may be set as appropriate, and can be exemplified in the range of 10 kPa to atmospheric pressure, for example. By fluctuating the plasma output and the pressure in the plasma generator, the average particle size of the lithium metal composite oxide powder of the present invention can be changed. For example, by increasing the plasma output, the average particle size of the lithium metal composite oxide powder of the present invention can be reduced.
導入流はプラズマへ向かう気体の流動によって発生する。導入流としては、プラズマの安定性を考慮して、プラズマ下で使用し得る気体を主流とするのが好ましい。導入流を構成する気体、つまり、導入ガスとしては、ヘリウム、アルゴンなどの希ガスが好ましい。導入ガスの流量としては、２０〜１２０Ｌ／分を例示できる。 The introductory flow is generated by the flow of gas towards the plasma. As the introduction flow, it is preferable to use a gas that can be used under the plasma as the main flow in consideration of the stability of the plasma. As the gas constituting the introduction flow, that is, the introduction gas, a rare gas such as helium or argon is preferable. As the flow rate of the introduced gas, 20 to 120 L / min can be exemplified.
プラズマ発生装置の種類によるが、本発明の製造方法においては、導入ガスとして、上記したＬｉ源、Ｔｉ源及びＯ源を運搬するキャリヤーガス、キャリヤーガスとは別にコイル内に導入されるインナーガス、及び、プラズマ発生部位を不活性雰囲気下にするためのプロセスガスを採用するのが好ましい。 Although it depends on the type of plasma generator, in the production method of the present invention, as the introduction gas, the carrier gas that carries the above-mentioned Li source, Ti source and O source, and the inner gas that is introduced into the coil separately from the carrier gas, Further, it is preferable to use a process gas for creating an inert atmosphere at the plasma generation site.
キャリヤーガスの流量としては、１〜１０Ｌ／分を例示できる。インナーガスの流量としては、１〜１０Ｌ／分を例示できる。プロセスガスの流量としては、１５〜１００Ｌ／分を例示できる。 The flow rate of the carrier gas can be exemplified by 1 to 10 L / min. As the flow rate of the inner gas, 1 to 10 L / min can be exemplified. As the flow rate of the process gas, 15 to 100 L / min can be exemplified.
導入ガスは酸素ガスを含んでも良いし、含まなくても良い。導入ガスが酸素ガスを含む場合、当該酸素ガスをＯ源とみなすことができる。なお、本発明の製造方法におけるＯ源はガス状に限定されず、例えばＬｉ源及び／又はＴｉ源ともに化合物を構成していても良い。この場合には、導入ガスは酸素ガスを含まなくても良い。 The introduced gas may or may not contain oxygen gas. When the introduced gas contains oxygen gas, the oxygen gas can be regarded as an O source. The O source in the production method of the present invention is not limited to the gaseous state, and for example, both the Li source and / or the Ti source may constitute a compound. In this case, the introduced gas does not have to contain oxygen gas.
酸素ガスを含む導入ガスを用いる場合、導入ガスの酸素濃度の好ましい範囲としては、導入ガス、例えば上記したキャリヤーガス、インナーガス、及び、プロセスガス等、導入流を構成するガスの体積の総和を１００体積％としたときに、０．５〜１０体積％、２〜６体積％、３〜５体積％、及び３．５〜４．５体積％の各範囲を挙げ得る。 When an introduction gas containing an oxygen gas is used, the preferable range of the oxygen concentration of the introduction gas is the total volume of the introduction gas, for example, the above-mentioned carrier gas, inner gas, process gas, and other gases constituting the introduction flow. When it is 100% by volume, each range of 0.5 to 10% by volume, 2 to 6% by volume, 3 to 5% by volume, and 3.5 to 4.5% by volume can be mentioned.
本発明のリチウム金属複合酸化物粉末の生成機構について考察する。プラズマ内の温度は、８０００〜２００００℃程度である。プラズマ内に導入されたリチウム金属複合酸化物源は、プラズマ内で気化又は分解状態となると考えられる。そして、当該リチウム金属複合酸化物源に含まれるリチウム元素、チタン元素及び酸素元素は、プラズマ内において、各々高温のガスとして存在すると考えられる。 The mechanism for producing the lithium metal composite oxide powder of the present invention will be considered. The temperature in the plasma is about 8000 to 20000 ° C. The lithium metal composite oxide source introduced into the plasma is considered to be in a vaporized or decomposed state in the plasma. Then, it is considered that the lithium element, the titanium element and the oxygen element contained in the lithium metal composite oxide source each exist as a high-temperature gas in the plasma.
ここで、プラズマ内の上記各元素は、導入ガスとともに流動したり、自重で落下したりすることで、プラズマ外に移動する。このとき、上記各元素がおかれる雰囲気の温度は、急激に降下し、各元素を含むガスの温度もまた急激に降下する。当該温度降下に伴って、上記の各元素は気相→液相→固相の順に相転移する。
リチウム、チタン及びこれらの化合物のうち、金属チタンの核生成温度は最も高く、２４００℃程度である。このため、本発明の製造方法においては、先ず金属チタンが核生成し、次いで、当該金属チタンの結晶核にリチウムが酸化を伴いながら凝縮することで、目的物であるリチウム金属複合酸化物、例えば上記したＬｉ４Ｔｉ５Ｏ１２やＬｉ２Ｔｉ３Ｏ７が生成すると推測される。
Here, each of the above elements in the plasma moves out of the plasma by flowing with the introduced gas or falling by its own weight. At this time, the temperature of the atmosphere in which each of the above elements is placed drops sharply, and the temperature of the gas containing each element also drops sharply. As the temperature drops, each of the above elements undergoes a phase transition in the order of gas phase → liquid phase → solid phase.
Among lithium, titanium and these compounds, the nucleation temperature of metallic titanium is the highest, about 2400 ° C. Therefore, in the production method of the present invention, metallic titanium is first nucleated, and then lithium is condensed in the crystal nuclei of the metallic titanium with oxidation, so that the target lithium metal composite oxide, for example, It is presumed that the above-mentioned Li 4 Ti 5 O 12 and Li 2 Ti 3 O 7 are produced.
本発明の製造方法によると、ナノ水準のリチウム金属複合酸化物粉末が得られる。これは、主として、本発明の製造方法が熱プラズマ法を用いることに因ると考えられる。
つまり、本発明の製造方法において、リチウム金属複合酸化物の合成に用いるプラズマは非常に高温であり、また、高温の範囲もプラズマ内のみであるから、例えば電気炉等に比べて非常に狭い範囲である。このため、プラズマに導入されたリチウム金属複合酸化物源は、プラズマを通過した後に、急激に冷却されてリチウム金属複合酸化物となる。このような急激な冷却に因り、リチウム金属複合酸化物の結晶成長は抑制されるため、本発明の製造方法で得られるリチウム金属複合酸化物粉末は、平均粒子径がナノ水準という非常に微細なリチウム金属複合酸化物粒子で構成される。
プラズマ内で高温に加熱されたリチウム金属複合酸化物源を急激に冷却するためには、導入流の流量を適宜コントロールするのが合理的である。当該導入流の流量の好ましい範囲は、２０Ｌ／分以上、３０Ｌ／分以上、５０Ｌ／分以上、６０Ｌ／分以上の各範囲を例示できる。当該好ましい流量に上限はないが、強いて挙げるとすれば、２００Ｌ／分以下とするのが合理的である。
According to the production method of the present invention, a nano-level lithium metal composite oxide powder can be obtained. It is considered that this is mainly due to the fact that the production method of the present invention uses the thermal plasma method.
That is, in the production method of the present invention, the plasma used for synthesizing the lithium metal composite oxide has a very high temperature, and the high temperature range is only in the plasma, so that the range is very narrow as compared with, for example, an electric furnace. Is. Therefore, the lithium metal composite oxide source introduced into the plasma is rapidly cooled after passing through the plasma to become a lithium metal composite oxide. Since the crystal growth of the lithium metal composite oxide is suppressed due to such rapid cooling, the lithium metal composite oxide powder obtained by the production method of the present invention has a very fine average particle size of nano-level. It is composed of lithium metal composite oxide particles.
In order to rapidly cool the lithium metal composite oxide source heated to a high temperature in the plasma, it is rational to appropriately control the flow rate of the introduction flow. The preferable range of the flow rate of the introduced flow can be exemplified in each range of 20 L / min or more, 30 L / min or more, 50 L / min or more, and 60 L / min or more. There is no upper limit to the preferable flow rate, but if it is strongly mentioned, it is rational to set it to 200 L / min or less.
本発明の製造方法で得られるリチウム金属複合酸化物粉末は、多数のリチウム金属複合酸化物粒子で構成される。本発明のリチウム金属複合酸化物粉末を構成するリチウム金属複合酸化物粒子（以下、本発明の粒子という。）は、上記したように、高温状態から室温付近にまで、急激に冷却されるため、結晶成長する期間がほとんどない。そのため、本発明の粒子は、一般的な製造方法で得られるような、特定の軸が成長した針状結晶となることが妨げられている。その結果、本発明のリチウム金属複合酸化物粉末に含まれる本発明の粒子は、各軸の結晶成長速度にムラの無い形状となっている。 The lithium metal composite oxide powder obtained by the production method of the present invention is composed of a large number of lithium metal composite oxide particles. As described above, the lithium metal composite oxide particles constituting the lithium metal composite oxide powder of the present invention (hereinafter referred to as the particles of the present invention) are rapidly cooled from a high temperature state to near room temperature, so that the lithium metal composite oxide particles are rapidly cooled. There is almost no period for crystal growth. Therefore, the particles of the present invention are prevented from becoming acicular crystals having a specific axis grown, which can be obtained by a general production method. As a result, the particles of the present invention contained in the lithium metal composite oxide powder of the present invention have a shape in which the crystal growth rate of each axis is not uneven.
本発明のリチウム金属複合酸化物粉末を構成する本発明の粒子は、その結晶子径が０．１ｎｍ〜１５０ｎｍの範囲内にあるのが好ましく、１ｎｍ〜１００ｎｍの範囲にあるのがより好ましく、５０ｎｍ〜９０ｎｍの範囲にあるのがさらに好ましく、６０〜８０ｎｍの範囲にあるのがなお好ましい。本発明の粒子の結晶子径は、Ｘ線回折法で得られた回折ピークの半値幅と回折角を基にシェラーの式を用いて算出できる。なお、当該回折ピークが複数である場合には、各々の回折ピークを基に複数の結晶子径を算出し、その算術平均値を本発明の粒子の結晶子径とみなしても良い。 The particles of the present invention constituting the lithium metal composite oxide powder of the present invention preferably have a crystallite diameter in the range of 0.1 nm to 150 nm, more preferably in the range of 1 nm to 100 nm, and more preferably 50 nm. It is more preferably in the range of ~ 90 nm, and even more preferably in the range of 60-80 nm. The crystallite diameter of the particles of the present invention can be calculated using Scheller's equation based on the half width and diffraction angle of the diffraction peak obtained by the X-ray diffraction method. When there are a plurality of diffraction peaks, a plurality of crystallite diameters may be calculated based on each diffraction peak, and the arithmetic mean value thereof may be regarded as the crystallite diameter of the particles of the present invention.
本発明のリチウム金属複合酸化物粉末は、その平均粒子径がナノ水準すなわち１ｎｍ以上１０００ｎｍ未満の範囲内である。当該平均粒子径の好ましい範囲としては、１ｎｍ以上４００ｎｍ以下、１ｎｍ以上２００ｎｍ以下、１０ｎｍ以上１００ｎｍ未満、１５ｎｍ以上９０ｎｍ以下、２０ｎｍ以上８０ｎｍ以下、３０ｎｍ以上７０ｎｍ以下、４０ｎｍ以上６０ｎｍ以下の各範囲を挙げることができる。
なお、ここでの平均粒子径とは、本発明のリチウム金属複合酸化物粉末を走査型電子顕微鏡や透過型電子顕微鏡などの電子顕微鏡で観察した場合における、観察された粒子像の外接円の直径の算術平均値を意味する。例えば、四角形の粒子像が観察されたら、その外接円を作成し、該外接円の直径を測定する。そのようにして、例えば２００個の粒子につき、各外接円の直径を測定して、その算術平均値を算出する。この値が平均粒子径である。
The lithium metal composite oxide powder of the present invention has an average particle size in the nano level, that is, in the range of 1 nm or more and less than 1000 nm. Preferred ranges of the average particle size include 1 nm or more and 400 nm or less, 1 nm or more and 200 nm or less, 10 nm or more and less than 100 nm, 15 nm or more and 90 nm or less, 20 nm or more and 80 nm or less, 30 nm or more and 70 nm or less, and 40 nm or more and 60 nm or less. Can be done.
The average particle size here is the diameter of the circumscribing circle of the observed particle image when the lithium metal composite oxide powder of the present invention is observed with an electron microscope such as a scanning electron microscope or a transmission electron microscope. Means the arithmetic average value of. For example, when a quadrangular particle image is observed, the circumscribed circle is created and the diameter of the circumscribed circle is measured. In this way, for example, for 200 particles, the diameter of each circumscribed circle is measured and the arithmetic mean value is calculated. This value is the average particle size.
本発明の製造方法において、リチウム金属複合酸化物源を含むガス流の冷却速度が増加すれば、リチウム金属複合酸化物における結晶核の結晶成長が初期段階で中断されるため、より微細であり、かつ形状が均一なリチウム金属複合酸化物粒子が得られるといえる。 In the production method of the present invention, if the cooling rate of the gas stream containing the lithium metal composite oxide source is increased, the crystal growth of the crystal nuclei in the lithium metal composite oxide is interrupted at an initial stage, so that the size is finer. Moreover, it can be said that lithium metal composite oxide particles having a uniform shape can be obtained.
したがって、より微細な本発明の粒子を含む本発明のリチウム金属複合酸化物粉末を得るためには、本発明の製造方法に、導入流がプラズマ内を通過した後の通過流を当該通過流に対向する冷却ガス流で冷却する工程を設けるのが良いと言える。 Therefore, in order to obtain the lithium metal composite oxide powder of the present invention containing finer particles of the present invention, the passing flow after the introduction flow has passed through the plasma is used as the passing flow in the production method of the present invention. It can be said that it is good to provide a step of cooling with the opposing cooling gas flow.
冷却ガス流のガスとしては、ヘリウム、アルゴンなどの希ガスや、酸素、空気を例示することができ、これらを混合して用いてもよい。上記した導入流用の導入ガスと同様に、冷却ガス流用のガスとしては酸素ガスを含まないものを用いても良いし、酸素ガスを含むものを用いても良い。
冷却ガス流の温度は室温でもよいし、室温以下でもよい。冷却ガスの流量としては、導入流よりも小さい流量であればよく、例えば１〜３０Ｌ／分の範囲内を例示できる。
Examples of the cooling gas flow gas include rare gases such as helium and argon, oxygen, and air, and these may be mixed and used. Similar to the introduction gas for introduction diversion described above, the gas for cooling gas diversion may be a gas that does not contain oxygen gas or a gas that contains oxygen gas.
The temperature of the cooling gas flow may be room temperature or lower than room temperature. The flow rate of the cooling gas may be smaller than the introduced flow rate, and can be, for example, in the range of 1 to 30 L / min.
なお、微細な本発明の粒子で構成される本発明のリチウム金属複合酸化物粉末が電池の負極活物質として使用された場合、例えば、電池の反応抵抗を低減できる、高速の充放電でも十分な容量を示すことができるなどの効果が期待される。 When the lithium metal composite oxide powder of the present invention composed of fine particles of the present invention is used as the negative electrode active material of the battery, for example, high-speed charge / discharge that can reduce the reaction resistance of the battery is sufficient. It is expected to have effects such as being able to show the capacity.
本発明のリチウム金属複合酸化物粉末は、上述したように二次電池用の負極活物質として使用可能である。以下、本発明のリチウム金属複合酸化物粉末を具備する負極を本発明の負極と呼び、本発明の負極を具備する二次電池を本発明の二次電池と呼ぶ。 As described above, the lithium metal composite oxide powder of the present invention can be used as a negative electrode active material for a secondary battery. Hereinafter, the negative electrode provided with the lithium metal composite oxide powder of the present invention is referred to as the negative electrode of the present invention, and the secondary battery provided with the negative electrode of the present invention is referred to as the secondary battery of the present invention.
（二次電池）
〔負極〕
本発明の二次電池は、負極、正極、並びに、電解液又は固体電解質、及び必要に応じてセパレータを具備する。このうち負極は、集電体と、集電体の表面に形成されている負極活物質層とを有する。
(Secondary battery)
[Negative electrode]
The secondary battery of the present invention includes a negative electrode, a positive electrode, and an electrolytic solution or solid electrolyte, and if necessary, a separator. Of these, the negative electrode has a current collector and a negative electrode active material layer formed on the surface of the current collector.
負極活物質としては、既述したとおり、本発明のリチウム金属複合酸化物粉末を用いる。本発明の二次電池における負極活物質層は、本発明のリチウム金属複合酸化物粉末以外にも、他の公知の負極活物質、結着剤、導電助剤、その他の添加剤を含有し得る。 As the negative electrode active material, as described above, the lithium metal composite oxide powder of the present invention is used. The negative electrode active material layer in the secondary battery of the present invention may contain other known negative electrode active materials, binders, conductive aids, and other additives in addition to the lithium metal composite oxide powder of the present invention. ..
他の公知の負極活物質としては、電荷担体（例えば充放電に寄与するリチウムイオン）を吸蔵及び放出可能な炭素系材料、リチウムと合金化可能な元素、リチウムと合金化可能な元素を有する化合物、あるいは高分子材料などを例示することができる。 Other known negative electrode active materials include carbon-based materials capable of occluding and releasing charge carriers (for example, lithium ions contributing to charging and discharging), elements capable of alloying with lithium, and compounds having elements capable of alloying with lithium. , Or a polymer material and the like can be exemplified.
具体的には、炭素系材料としては、難黒鉛化性炭素、黒鉛、コークス類、グラファイト類、ガラス状炭素類、有機高分子化合物焼成体、炭素繊維、活性炭あるいはカーボンブラック類が例示できる。ここで、有機高分子化合物焼成体とは、フェノール類やフラン類などの高分子材料を適当な温度で焼成して炭素化したものをいう。
リチウムと合金化可能な元素としては、具体的にＮａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ、Ｔｉ、Ａｇ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉが例示でき、特に、Ｓｉ又はＳｎが好ましい。
リチウムと合金化可能な元素を有する化合物としては、具体的にＺｎＬｉＡｌ、ＡｌＳｂ、ＳｉＢ４、ＳｉＢ６、Ｍｇ２Ｓｉ、Ｍｇ２Ｓｎ、Ｎｉ２Ｓｉ、ＴｉＳｉ２、ＭｏＳｉ２、ＣｏＳｉ２、ＮｉＳｉ２、ＣａＳｉ２、ＣｒＳｉ２、Ｃｕ５Ｓｉ、ＦｅＳｉ２、ＭｎＳｉ２、ＮｂＳｉ２、ＴａＳｉ２、ＶＳｉ２、ＷＳｉ２、ＺｎＳｉ２、ＳｉＣ、Ｓｉ３Ｎ４、Ｓｉ２Ｎ２Ｏ、ＳｉＯｖ（０＜ｖ≦２）、ＳｎＯｗ（０＜ｗ≦２）、ＳｎＳｉＯ３、ＬｉＳｉＯあるいはＬｉＳｎＯを例示でき、特に、ＳｉＯｘ（０．３≦ｘ≦１．６、又は０．５≦ｘ≦１．５）が好ましい。
Specifically, examples of the carbon-based material include non-graphitizable carbon, graphite, cokes, graphites, glassy carbons, calcined organic polymer compound, carbon fibers, activated carbon, and carbon blacks. Here, the calcined organic polymer compound refers to a polymer material such as phenols and furans that is calcined at an appropriate temperature and carbonized.
Specific elements that can be alloyed with lithium include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, and Si. , Ge, Sn, Pb, Sb, Bi can be exemplified, and Si or Sn is particularly preferable.
Specific examples of the compound having an element that can be alloyed with lithium include ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , and NiSi 2 . CaSi 2, CrSi 2, Cu 5 Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 <v ≦ 2), SnO w (0 <w ≦ 2), SnSiO 3 , LiSiO or LiSnO can be exemplified, and in particular, SiO x (0.3 ≦ x ≦ 1.6 or 0.5 ≦ x ≦ 1.5). Is preferable.
本発明のリチウム金属複合酸化物粉末に対する上記した他の公知の負極活物質の量は特に問わないが、負極活物質全体に対して５０質量％以下とするのが好ましく、３０質量％以下とするのがより好ましく、２０質量％以下とするのが更に好ましく、１０質量％以下とするのが特に好ましい。
また、負極活物質層全体を１００質量％としたときの負極活物質全体の量の好ましい範囲として、３０〜１００質量％、４０〜９０質量％、５０〜８０質量％を例示できる。その他、５０〜９９質量％、６０〜９８質量％、７０〜９７質量％を例示することもできる。
The amount of the above-mentioned other known negative electrode active material with respect to the lithium metal composite oxide powder of the present invention is not particularly limited, but is preferably 50% by mass or less, preferably 30% by mass or less, based on the entire negative electrode active material. More preferably, it is more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
Further, 30 to 100% by mass, 40 to 90% by mass, and 50 to 80% by mass can be exemplified as a preferable range of the total amount of the negative electrode active material when the entire negative electrode active material layer is 100% by mass. In addition, 50 to 99% by mass, 60 to 98% by mass, and 70 to 97% by mass can be exemplified.
結着剤は、負極活物質や導電助剤を集電体の表面に繋ぎ止める役割を果たすものである。結着剤としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ素ゴム等の含フッ素樹脂、ポリプロピレン、ポリエチレン等の熱可塑性樹脂、ポリイミド、ポリアミドイミド等のイミド系樹脂、アルコキシシリル基含有樹脂、ポリ（メタ）アクリル酸等のアクリル系樹脂、スチレン−ブタジエンゴム、カルボキシメチルセルロースを例示することができる。これらの結着剤を単独で又は複数で採用すれば良い。 The binder plays a role of binding the negative electrode active material and the conductive auxiliary agent to the surface of the current collector. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, fluororesin such as fluororubber, thermoplastic resin such as polypropylene and polyethylene, imide resin such as polyimide and polyamideimide, alkoxysilyl group-containing resin, and poly ( Examples thereof include acrylic resins such as meta) acrylic acid, styrene-butadiene rubber, and carboxymethyl cellulose. These binders may be used alone or in combination of two or more.
結着剤の配合量は特に限定されないが、あえて負極活物質層における結着剤の配合量を挙げると、０．５〜１０質量％の範囲内が好ましく、１〜７質量％の範囲内がより好ましく、２〜５質量％の範囲内が特に好ましい。結着剤の配合量が少なすぎると負極活物質層の成形性が低下するおそれがある。また、結着剤の配合量が多すぎると、負極活物質層における負極活物質の量が相対的に減少するため、好ましくない。 The blending amount of the binder is not particularly limited, but the blending amount of the binder in the negative electrode active material layer is preferably in the range of 0.5 to 10% by mass, preferably in the range of 1 to 7% by mass. More preferably, it is particularly preferably in the range of 2 to 5% by mass. If the amount of the binder compounded is too small, the moldability of the negative electrode active material layer may deteriorate. Further, if the blending amount of the binder is too large, the amount of the negative electrode active material in the negative electrode active material layer is relatively reduced, which is not preferable.
導電助剤は化学的に不活性な電子高伝導体であれば良く、炭素質微粒子であるカーボンブラック、黒鉛、気相法炭素繊維（Vapor Grown Carbon Fiber）、及び各種金属粒子等が例示される。カーボンブラックとしては、アセチレンブラック、ケッチェンブラック（登録商標）、ファーネスブラック、チャンネルブラック等が例示される。これらの導電助剤を単独または二種以上組み合わせて負極活物質層に添加することができる。 The conductive auxiliary agent may be a chemically inert electron high conductor, and examples thereof include carbon black, graphite, vaporized carbon fiber (Vapor Grown Carbon Fiber), and various metal particles, which are carbonaceous fine particles. .. Examples of carbon black include acetylene black, Ketjen black (registered trademark), furnace black, and channel black. These conductive aids can be added to the negative electrode active material layer alone or in combination of two or more.
導電助剤の形状は特に制限されないが、その役割からみて、導電助剤の平均粒子径は小さいほうが好ましい。導電助剤の好ましい平均粒子径として１０μｍ以下が例示され、より好ましい平均粒子径として０．０１〜１μｍの範囲が例示される。 The shape of the conductive auxiliary agent is not particularly limited, but from the viewpoint of its role, it is preferable that the average particle size of the conductive auxiliary agent is small. A preferable average particle size of the conductive auxiliary agent is 10 μm or less, and a more preferable average particle size is in the range of 0.01 to 1 μm.
導電助剤の配合量は特に限定されないが、あえて負極活物質層における導電助剤の配合量を挙げると、０．５〜１０質量％の範囲内がよく、１〜７質量％の範囲内が好ましく、２〜５質量％の範囲内が特に好ましい。 The blending amount of the conductive auxiliary agent is not particularly limited, but the blending amount of the conductive auxiliary agent in the negative electrode active material layer is preferably in the range of 0.5 to 10% by mass, and is in the range of 1 to 7% by mass. It is preferably in the range of 2 to 5% by mass, and particularly preferably in the range of 2 to 5% by mass.
導電助剤及び結着剤以外の分散剤などの添加剤は、公知のものを採用することができる。 Known additives such as dispersants other than the conductive auxiliary agent and the binder can be adopted.
集電体は、リチウムイオン二次電池の放電又は充電の間、電極に電流を流し続けるための化学的に不活性な電子高伝導体をいう。集電体としては、銀、銅、金、アルミニウム、タングステン、コバルト、亜鉛、ニッケル、鉄、白金、錫、インジウム、チタン、ルテニウム、タンタル、クロム、モリブデンから選ばれる少なくとも一種、並びにステンレス鋼などの金属材料を例示することができる。集電体は公知の保護層で被覆されていても良い。集電体の表面を公知の方法で処理したものを集電体として用いても良い。 A current collector is a chemically inert electron high conductor that keeps current flowing through the electrodes during the discharge or charging of a lithium ion secondary battery. Collectors include at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel. Metallic materials can be exemplified. The current collector may be coated with a known protective layer. A current collector whose surface is treated by a known method may be used as the current collector.
集電体は箔、シート、フィルム、線状、棒状、メッシュなどの形態をとることができる。そのため、集電体として、例えば、銅箔、ニッケル箔、アルミニウム箔、ステンレス箔などの金属箔を好適に用いることができる。集電体が箔、シート、フィルム形態の場合は、その厚みが１μｍ〜１００μｍの範囲内であることが好ましい。 The current collector can take the form of foil, sheet, film, linear, rod, mesh or the like. Therefore, as the current collector, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, or a stainless steel foil can be preferably used. When the current collector is in the form of a foil, a sheet, or a film, the thickness is preferably in the range of 1 μm to 100 μm.
負極を製造するためには、上記のリチウム金属複合酸化物粉末を必要に応じてその他の材料及び溶剤と混合し、得られた負極活物質層用組成物を上記の集電体に塗布すれば良い。
溶剤としては、Ｎ−メチル−２−ピロリドン、メタノール、メチルイソブチルケトン、水を例示できる。溶剤の使用量は、負極活物質層用組成物がスラリー状になる程度の量であるのが好ましい。
In order to produce a negative electrode, the above lithium metal composite oxide powder is mixed with other materials and a solvent as necessary, and the obtained composition for a negative electrode active material layer is applied to the above current collector. good.
Examples of the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water. The amount of the solvent used is preferably such that the composition for the negative electrode active material layer becomes a slurry.
負極活物質層用組成物を集電体に塗布するには、ロールコート法、ダイコート法、ディップコート法、ドクターブレード法、スプレーコート法、カーテンコート法などの従来から公知の方法を用いればよい。 In order to apply the composition for the negative electrode active material layer to the current collector, conventionally known methods such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, and a curtain coating method may be used. ..
〔その他の電池構成要素〕
正極は、集電体と、集電体の表面に形成されている正極活物質層を有する。集電体については、負極の欄で説明したものを適宜適切に採用すれば良い。正極活物質層は正極活物質、並びに必要に応じて導電助剤、結着剤、添加剤等を含む。
[Other battery components]
The positive electrode has a current collector and a positive electrode active material layer formed on the surface of the current collector. As the current collector, the one described in the column of the negative electrode may be appropriately adopted. The positive electrode active material layer contains a positive electrode active material and, if necessary, a conductive auxiliary agent, a binder, an additive and the like.
正極活物質としては、層状岩塩構造の一般式：ＬｉａＮｉｂＣｏｃＭｎｄＤｅＯｆ(０．２≦ａ≦２、ｂ＋ｃ＋ｄ＋ｅ＝１、０≦ｅ＜１、ＤはＷ、Ｍｏ、Ｒｅ、Ｐｄ、Ｂａ、Ｃｒ、Ｂ、Ｓｂ、Ｓｒ、Ｐｂ、Ｇａ、Ａｌ、Ｎｂ、Ｍｇ、Ｔａ、Ｔｉ、Ｌａ、Ｚｒ、Ｃｕ、Ｃａ、Ｉｒ、Ｈｆ、Ｒｈ、Ｆｅ、Ｇｅ、Ｚｎ、Ｒｕ、Ｓｃ、Ｓｎ、Ｉｎ、Ｙ、Ｂｉ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ｐ、Ｖから選ばれる少なくとも１の元素、１．７≦ｆ≦３)で表されるリチウム複合金属酸化物、Ｌｉ２ＭｎＯ３を挙げることができる。また、正極活物質として、ＬｉＭｎ２Ｏ４等のスピネル構造の金属酸化物、スピネル構造の金属酸化物と層状化合物の混合物で構成される固溶体、ＬｉＭＰＯ４、ＬｉＭＶＯ４又はＬｉ２ＭＳｉＯ４（式中のＭはＣｏ、Ｎｉ、Ｍｎ、Ｆｅのうちの少なくとも一種から選択される）などで表されるポリアニオン系化合物を挙げることができる。さらに、正極活物質として、ＬｉＦｅＰＯ４ＦなどのＬｉＭＰＯ４Ｆ（Ｍは遷移金属）で表されるタボライト系化合物、ＬｉＦｅＢＯ３などのＬｉＭＢＯ３（Ｍは遷移金属）で表されるボレート系化合物を挙げることができる。正極活物質として用いられるいずれの金属酸化物も上記の組成式を基本組成とすればよく、基本組成に含まれる金属元素を他の金属元素で置換したものも使用可能である。また、正極活物質として、リチウムイオン等の電荷担体を含まないものを用いても良い。例えば、硫黄単体、硫黄と炭素を複合化した化合物、ＴｉＳ２などの金属硫化物、Ｖ２Ｏ５、ＭｎＯ２などの酸化物、ポリアニリン及びアントラキノン並びにこれら芳香族を化学構造に含む化合物、共役二酢酸系有機物などの共役系材料、その他公知の材料を用いることもできる。さらに、ニトロキシド、ニトロニルニトロキシド、ガルビノキシル、フェノキシルなどの安定なラジカルを有する化合物を正極活物質として採用してもよい。リチウム等の電荷担体を含まない正極活物質材料を用いる場合には、正極及び／又は負極に、公知の方法により、予め電荷担体を添加しておく必要がある。電荷担体は、イオンの状態で添加しても良いし、金属等の非イオンの状態で添加しても良い。例えば、電荷担体がリチウムである場合には、リチウム箔を正極及び／又は負極に貼り付けるなどして一体化しても良い。 As the positive electrode active material, the general formula of the layered rock salt structure: Li a Ni b Co c Mn d D e O f (0.2 ≦ a ≦ 2, b + c + d + e = 1,0 ≦ e <1, D is W, Mo, Re, Pd, Ba, Cr, B, Sb, Sr, Pb, Ga, Al, Nb, Mg, Ta, Ti, La, Zr, Cu, Ca, Ir, Hf, Rh, Fe, Ge, Zn, Ru, Li 2 MnO, a lithium composite metal oxide represented by 1.7 ≦ f ≦ 3), which is at least one element selected from Sc, Sn, In, Y, Bi, S, Si, Na, K, P, and V. 3 can be mentioned. Further, as the positive electrode active material, a metal oxide having a spinel structure such as LiMn 2 O 4 , a solid solution composed of a mixture of a metal oxide having a spinel structure and a layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (in the formula). M is selected from at least one of Co, Ni, Mn, and Fe) and the like. Furthermore, as the positive electrode active material, tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal) include borate-based compound represented by be able to. Any metal oxide used as the positive electrode active material may have the above composition formula as the basic composition, and those in which the metal element contained in the basic composition is replaced with another metal element can also be used. Further, as the positive electrode active material, a material that does not contain a charge carrier such as lithium ion may be used. For example, elemental sulfur, compounds complexed with sulfur and carbon, metal sulfides such as TiS 2, oxides such as V 2 O 5, MnO 2, polyaniline and anthraquinone and compounds containing these aromatic in chemical structure, conjugated double Conjugated materials such as acetic acid-based organic substances and other known materials can also be used. Further, a compound having a stable radical such as nitroxide, nitronyl nitroxide, galbinoxyl, and phenoxyl may be adopted as the positive electrode active material. When a positive electrode active material that does not contain a charge carrier such as lithium is used, it is necessary to add a charge carrier to the positive electrode and / or the negative electrode in advance by a known method. The charge carrier may be added in an ionic state or may be added in a nonionic state such as a metal. For example, when the charge carrier is lithium, a lithium foil may be attached to the positive electrode and / or the negative electrode to integrate them.
高容量及び耐久性などに優れる点から、正極活物質として、層状岩塩構造の一般式：ＬｉａＮｉｂＣｏｃＭｎｄＤｅＯｆ(０．２≦ａ≦２、ｂ＋ｃ＋ｄ＋ｅ＝１、０≦ｅ＜１、ＤはＷ、Ｍｏ、Ｒｅ、Ｐｄ、Ｂａ、Ｃｒ、Ｂ、Ｓｂ、Ｓｒ、Ｐｂ、Ｇａ、Ａｌ、Ｎｂ、Ｍｇ、Ｔａ、Ｔｉ、Ｌａ、Ｚｒ、Ｃｕ、Ｃａ、Ｉｒ、Ｈｆ、Ｒｈ、Ｆｅ、Ｇｅ、Ｚｎ、Ｒｕ、Ｓｃ、Ｓｎ、Ｉｎ、Ｙ、Ｂｉ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ｐ、Ｖから選ばれる少なくとも１の元素、１．７≦ｆ≦３)で表されるリチウム複合金属酸化物を採用することが好ましい。 From the viewpoint of excellent and high capacity, and durability, as the positive electrode active material, the general formula of the layered rock salt structure: Li a Ni b Co c Mn d D e O f (0.2 ≦ a ≦ 2, b + c + d + e = 1,0 ≦ e <1, D are W, Mo, Re, Pd, Ba, Cr, B, Sb, Sr, Pb, Ga, Al, Nb, Mg, Ta, Ti, La, Zr, Cu, Ca, Ir, Hf, It is represented by at least one element selected from Rh, Fe, Ge, Zn, Ru, Sc, Sn, In, Y, Bi, S, Si, Na, K, P, and V, 1.7 ≦ f ≦ 3). It is preferable to use a lithium composite metal oxide.
上記一般式において、ｂ、ｃ、ｄの値は、上記条件を満足するものであれば特に制限はないが、０＜ｂ＜１、０＜ｃ＜１、０＜ｄ＜１であるものが良く、また、ｂ、ｃ、ｄの少なくともいずれか一つが１０／１００＜ｂ＜９０／１００、１０／１００＜ｃ＜９０／１００、５／１００＜ｄ＜７０／１００の範囲であることが好ましく、２０／１００＜ｂ＜８０／１００、１２／１００＜ｃ＜７０／１００、１０／１００＜ｄ＜６０／１００の範囲であることがより好ましく、３０／１００＜ｂ＜７０／１００、１５／１００＜ｃ＜５０／１００、１２／１００＜ｄ＜５０／１００の範囲であることがさらに好ましい。 In the above general formula, the values of b, c, and d are not particularly limited as long as they satisfy the above conditions, but those having 0 <b <1, 0 <c <1, 0 <d <1 are used. It is good, and at least one of b, c, and d is in the range of 10/100 <b <90/100, 10/100 <c <90/100, 5/100 <d <70/100. More preferably, the range is 20/100 <b <80/100, 12/100 <c <70/100, 10/100 <d <60/100, 30/100 <b <70/100, It is more preferably in the range of 15/100 <c <50/100 and 12/100 <d <50/100.
ａ、ｅ、ｆについては、上記一般式で規定する範囲内の数値であればよく、好ましくは０．５≦ａ≦１．５、０≦ｅ＜０．２、１．８≦ｆ≦２．５、より好ましくは０．８≦ａ≦１．３、０≦ｅ＜０．１、１．９≦ｆ≦２．１をそれぞれ例示することができる。 The values a, e, and f may be values within the range specified by the above general formula, and preferably 0.5 ≦ a ≦ 1.5, 0 ≦ e <0.2, 1.8 ≦ f ≦ 2. 5.5, more preferably 0.8 ≦ a ≦ 1.3, 0 ≦ e <0.1, 1.9 ≦ f ≦ 2.1 can be exemplified, respectively.
高容量及び耐久性などに優れる点から、正極活物質として、スピネル構造のＬｉｘＭｎ２―ｙＡｙＯ４（Ａは、Ｃａ、Ｍｇ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ａｌ、Ｐ、Ｇａ、Ｇｅから選ばれる少なくとも１の元素、及び、Ｎｉなどの遷移金属元素から選ばれる少なくとも１種の金属元素から選択される。０＜ｘ≦２．２、０≦ｙ≦１）を例示できる。ｘの値の範囲としては、０．５≦ｘ≦１．８、０．７≦ｘ≦１．５、０．９≦ｘ≦１．２を例示でき、ｙの値の範囲としては、０≦ｙ≦０．８、０≦ｙ≦０．６を例示できる。具体的なスピネル構造の化合物として、ＬｉＭｎ２Ｏ４、ＬｉＭｎ１．５Ｎｉ０．５Ｏ４を例示できる。 As a positive electrode active material, Li x Mn 2-y Ay O 4 (A is Ca, Mg, S, Si, Na, K, Al, P, Ga) having a spinel structure from the viewpoint of high capacity and excellent durability. , At least one element selected from Ge, and at least one metal element selected from transition metal elements such as Ni. 0 <x ≦ 2.2, 0 ≦ y ≦ 1) can be exemplified. Examples of the range of the value of x include 0.5 ≦ x ≦ 1.8, 0.7 ≦ x ≦ 1.5, and 0.9 ≦ x ≦ 1.2, and the range of the value of y is 0. Examples thereof include ≦ y ≦ 0.8 and 0 ≦ y ≦ 0.6. Examples of specific spinel-structured compounds include LiMn 2 O 4 and Limn 1.5 Ni 0.5 O 4 .
具体的な正極活物質として、ＬｉＦｅＰＯ４、Ｌｉ２ＦｅＳｉＯ４、ＬｉＣｏＰＯ４、Ｌｉ２ＣｏＰＯ４、Ｌｉ２ＭｎＰＯ４、Ｌｉ２ＭｎＳｉＯ４、Ｌｉ２ＣｏＰＯ４Ｆを例示できる。他の具体的な正極活物質として、Ｌｉ２ＭｎＯ３−ＬｉＣｏＯ２を例示できる。 Specific examples of the positive electrode active material include LiFePO 4 , Li 2 FeSiO 4 , LiCoPO 4 , Li 2 CoPO 4 , Li 2 MnPO 4 , Li 2 MnSiO 4 , and Li 2 CoPO 4 F. As another specific positive electrode active material, Li 2 MnO 3- LiCoO 2 can be exemplified.
正極活物質としては、以上のものの一種以上を使用することができる。
正極に用いる導電助剤、結着剤、その他の添加剤については、負極の欄で説明したものを同様の配合割合で適宜適切に採用すれば良い。
As the positive electrode active material, one or more of the above can be used.
As for the conductive auxiliary agent, the binder, and other additives used for the positive electrode, those described in the column of the negative electrode may be appropriately and appropriately adopted in the same blending ratio.
電解液は、非水溶媒と当該非水溶媒に溶解されたリチウム塩とを含む。
非水溶媒としては、環状カーボネート、環状エステル、鎖状カーボネート、鎖状エステル、エーテル類等が使用できる。環状カーボネートとしては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネートを例示でき、環状エステルとしては、ガンマブチロラクトン、２−メチル−ガンマブチロラクトン、アセチル−ガンマブチロラクトン、ガンマバレロラクトンを例示できる。鎖状カーボネートとしては、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジプロピルカーボネート、エチルメチルカーボネートを例示でき、鎖状エステルとしては、プロピオン酸アルキルエステル、マロン酸ジアルキルエステル、酢酸アルキルエステル等を例示できる。エーテル類としては、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、１，２−ジブトキシエタンを例示できる。非水溶媒としては、上記具体的な溶媒の化学構造のうち一部又は全部の水素がフッ素に置換した化合物を採用しても良い。
電解液には、これらの非水溶媒を単独で用いてもよいし、又は、複数を併用してもよい。
The electrolytic solution contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
As the non-aqueous solvent, cyclic carbonates, cyclic esters, chain carbonates, chain esters, ethers and the like can be used. Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, and examples of the cyclic ester include gamma-butyrolactone, 2-methyl-gamma-butyrolactone, acetyl-gamma-butyrolactone, and gamma-valerolactone. Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, and ethyl methyl carbonate, and examples of the chain ester include propionic acid alkyl ester, malonic acid dialkyl ester, and acetate alkyl ester. Examples of ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane. As the non-aqueous solvent, a compound in which some or all of the chemical structure of the specific solvent is replaced with fluorine may be adopted.
These non-aqueous solvents may be used alone or in combination of two or more as the electrolytic solution.
電解質としては、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２等のリチウム塩を例示できる。
電解液としては、エチレンカーボネート、ジメチルカーボネート、プロピレンカーボネート、ジエチルカーボネートなどの非水溶媒に、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３などのリチウム塩を０．５ｍｏｌ／Ｌから１．７ｍｏｌ／Ｌ程度の濃度で溶解させた溶液を例示できる。
Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
As the electrolytic solution, 0.5 mol / L to 1.7 mol of lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , and LiCF 3 SO 3 are added to a non-aqueous solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate. An example of a solution dissolved at a concentration of about / L can be exemplified.
本発明の二次電池は、必要に応じて、セパレータを備え得る。
セパレータは、正極と負極とを隔離し、両極の接触による電流の短絡を防止しつつ、リチウムイオンを通過させるものである。セパレータとしては、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリイミド、ポリアミド、ポリアラミド（Ａｒｏｍａｔｉｃ ｐｏｌｙａｍｉｄｅ）、ポリエステル、ポリアクリロニトリル等の合成樹脂、セルロース、アミロース等の多糖類、フィブロイン、ケラチン、リグニン、スベリン等の天然高分子、セラミックスなどの電気絶縁性材料を１種若しくは複数用いた多孔体、不織布、織布などを挙げることができる。また、セパレータは多層構造としてもよい。
The secondary battery of the present invention may be provided with a separator, if necessary.
The separator separates the positive electrode and the negative electrode, and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes. As the separator, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, synthetic resin such as polyaramid (Aromatic polyamide), polyester, polyacrylonitrile, polysaccharides such as cellulose and amylose, and natural products such as fibroin, keratin, lignin and sverin. Examples thereof include porous bodies, non-woven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics. Further, the separator may have a multi-layer structure.
本発明の二次電池は、固体電解質を有する全固体電池であっても良い。固体電解質としては、有機固体電解質及び無機固体電解質の何れを用いても良い。 The secondary battery of the present invention may be an all-solid-state battery having a solid electrolyte. As the solid electrolyte, either an organic solid electrolyte or an inorganic solid electrolyte may be used.
有機固体電解質としては公知のものを用いることができる。また、有機固体電解質のポリマーは特に限定されず、例えば、ポリエーテル、ポリエステル、ポリアミン又はポリスルフィド等のポリマーを一種又は複数種有するものを使用することができる。複数種のポリマーを併用する場合、ポリマー同士の少なくとも一部は共重合体であっても良い。
無機固体電解質もまた特に限定されず、各種の酸化物、硫化物、窒化物、ハロゲン化物等、例えば、Ｌｉ２Ｓ−Ｐ２Ｓ５、Ｌｉ２Ｓ−ＳｉＳ２、Ｌｉ２Ｓ−Ｂ２Ｓ３、Ｌｉ２Ｓ−ＧｅＳ２、Ｌｉ２Ｓ−Ａｌ２Ｓ３、Ｌｉ２Ｓ−ＳｉＳ２−Ｌｉ３ＰＯ４、ＬｉＴｉ２（ＰＯ４）３、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２、Ｌｉ６．７５Ｌａ３Ｚｒ１．７５Ｎｂ０．２５Ｏ１２、（ＬａＬｉ）ＴｉＯ３、Ｌｉ１４ＺｎＧｅ４Ｏ１６、Ｌｉ４ＳｉＯ４、ＬｉＧｅＯ４、Ｌｉ３ＩｎＢｒ６、Ｌｉ３ＩｎＣｌ６、Ｌｉ２ＦｅＣｌ４等の通常のものを用い得る。
As the organic solid electrolyte, known ones can be used. The polymer of the organic solid electrolyte is not particularly limited, and for example, one having one or more polymers such as polyether, polyester, polyamine, and polysulfide can be used. When a plurality of types of polymers are used in combination, at least a part of the polymers may be a copolymer.
The inorganic solid electrolyte is also not particularly limited, and various oxides, sulfides, nitrides, halides and the like, for example, Li 2 SP 2 S 5 , Li 2 S-SiS 2 , Li 2 SB 2 S, etc. 3 , Li 2 S-GeS 2 , Li 2 S-Al 2 S 3 , Li 2 S-SiS 2 -Li 3 PO 4 , LiTi 2 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , Li 6. 75 La 3 Zr 1.75 Nb 0.25 O 12 , (LaLi) TiO 3 , Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , LiGeO 4 , Li 3 InBr 6 , Li 3 InCl 6 , Li 2 FeCl 4, etc. Ordinary ones can be used.
本発明の二次電池は、上記した負極及び正極を用い、定法によって製造すれば良い。例えば、本発明の二次電池がリチウムイオン二次電池であれば、上記した正極および負極に必要に応じてセパレータを挟装させ電極体とする。電極体は、正極、セパレータ及び負極を重ねた積層型、又は、正極、セパレータ及び負極の積層体を捲いた捲回型のいずれの型にしても良い。正極の集電体および負極の集電体から外部に通ずる正極端子および負極端子までを、集電用リード等を用いて接続した後に、電極体に電解液を加えてリチウムイオン二次電池とする。
また、本発明の二次電池は、電極に含まれる活物質の種類に適した電圧範囲で充放電可能であれば良い。
本発明の二次電池の形状は特に限定されるものでなく、円筒型、角型、コイン型、ラミネート型等、種々の形状を採用することができる。
The secondary battery of the present invention may be manufactured by a conventional method using the above-mentioned negative electrode and positive electrode. For example, if the secondary battery of the present invention is a lithium ion secondary battery, a separator is sandwiched between the positive electrode and the negative electrode as needed to form an electrode body. The electrode body may be of either a laminated type in which a positive electrode, a separator and a negative electrode are stacked, or a wound type in which a laminated body of a positive electrode, a separator and a negative electrode is wound. After connecting the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal leading to the outside using a current collector lead or the like, an electrolytic solution is added to the electrode body to form a lithium ion secondary battery. ..
Further, the secondary battery of the present invention may be charged and discharged in a voltage range suitable for the type of active material contained in the electrode.
The shape of the secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical type, a square type, a coin type, and a laminated type can be adopted.
本発明の二次電池は、車両に搭載してもよい。車両は、その動力源の全部あるいは一部にリチウムイオン二次電池による電気エネルギーを使用している車両であればよく、たとえば、電気車両、ハイブリッド車両などであるとよい。車両に二次電池を搭載する場合には、二次電池を複数直列に接続して組電池とするとよい。二次電池を搭載する機器としては、車両以外にも、パーソナルコンピュータ、携帯通信機器など、電池で駆動される各種の家電製品、オフィス機器、産業機器などが挙げられる。さらに、本発明の二次電池は、風力発電、太陽光発電、水力発電その他電力系統の蓄電装置及び電力平滑化装置、船舶等の動力及び／又は補機類の電力供給源、航空機、宇宙船等の動力及び／又は補機類の電力供給源、電気を動力源に用いない車両の補助用電源、移動式の家庭用ロボットの電源、システムバックアップ用電源、無停電電源装置の電源、電動車両用充電ステーションなどにおいて充電に必要な電力を一時蓄える蓄電装置に用いてもよい。 The secondary battery of the present invention may be mounted on a vehicle. The vehicle may be a vehicle that uses electric energy from a lithium ion secondary battery for all or part of its power source, and may be, for example, an electric vehicle or a hybrid vehicle. When a secondary battery is installed in a vehicle, a plurality of secondary batteries may be connected in series to form an assembled battery. In addition to vehicles, devices equipped with a secondary battery include various battery-powered home appliances such as personal computers and mobile communication devices, office devices, and industrial devices. Further, the secondary battery of the present invention includes wind power generation, solar power generation, hydroelectric power generation and other power system power storage devices and power smoothing devices, power sources for ships and / or auxiliary machinery, aircraft, and spacecraft. Power supply source for power and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as power source, power supply for mobile household robots, power supply for system backup, power supply for power failure-free power supply, electric vehicle It may be used as a power storage device that temporarily stores the power required for charging at a charging station or the like.
以上、本発明の実施形態を説明したが、本発明は、上記実施形態に限定されるものではない。本発明の要旨を逸脱しない範囲において、当業者が行い得る変更、改良等を施した種々の形態にて実施することができる。なお、本発明のリチウム金属複合酸化物粉末には、不純物が含まれるものもある。 Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. It can be carried out in various forms with modifications, improvements, etc. that can be made by those skilled in the art, without departing from the gist of the present invention. In addition, some of the lithium metal composite oxide powders of the present invention contain impurities.
以下に、実施例を示し、本発明をより具体的に説明する。なお、本発明は、これらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples.
（実施例１）
図１に示すプラズマ発生装置を用いて、実施例１のリチウム金属複合酸化物粉末を製造した。図１に示すプラズマ発生装置において黒塗り矢印は冷却水を表す。
(Example 1)
The lithium metal composite oxide powder of Example 1 was produced using the plasma generator shown in FIG. In the plasma generator shown in FIG. 1, the black arrow indicates the cooling water.
Ｌｉ源及びＯ源としてＬｉ２ＣＯ３を、Ｔｉ源としてＴｉ（金属Ｔｉ）を各々準備した。Ｌｉ２ＣＯ３とＴｉとを１：２のモル比で混合して混合粉体として、当該混合粉体を粉体供給器に配置した。なお、当該混合粉体におけるリチウム元素とチタン元素とのモル比、すなわち、リチウム金属複合酸化物原料におけるリチウム元素とチタン元素とのモル比は１：１であった。 Li 2 CO 3 was prepared as a Li source and an O source, and Ti (metal Ti) was prepared as a Ti source. Li 2 CO 3 and Ti were mixed at a molar ratio of 1: 2 to form a mixed powder, and the mixed powder was placed in a powder feeder. The molar ratio of lithium element to titanium element in the mixed powder, that is, the molar ratio of lithium element to titanium element in the lithium metal composite oxide raw material was 1: 1.
プラズマ発生装置内に、プロセスガスとしてアルゴンと酸素を体積比５７．５：２．５で混合した混合ガスを６０Ｌ／分で供給した。
その他、インナーガスとしてアルゴンを５Ｌ／分で供給し、キャリヤーガスとしてアルゴンを３Ｌ／分で供給した。電力供給装置から電力を供給し、周波数４ＭＨｚの磁場をコイルに印加して、出力２０ｋＷのプラズマを発生させた。なお、プラズマ発生装置内の圧力は大気圧とした。
このときのプラズマ発生装置における導入流の流量は、プロセスガスとインナーガスとキャリヤーガスとの和、すなわち、６８Ｌ／分であった。
A mixed gas in which argon and oxygen were mixed as a process gas at a volume ratio of 57.5: 2.5 was supplied into the plasma generator at 60 L / min.
In addition, argon was supplied as an inner gas at 5 L / min, and argon was supplied as a carrier gas at 3 L / min. Power was supplied from the power supply device, and a magnetic field having a frequency of 4 MHz was applied to the coil to generate plasma having an output of 20 kW. The pressure inside the plasma generator was atmospheric pressure.
The flow rate of the introduction flow in the plasma generator at this time was the sum of the process gas, the inner gas, and the carrier gas, that is, 68 L / min.
プラズマの安定後、粉体供給器を作動させ、混合粉体を３００ｍｇ／分の供給量で、キャリヤーガスとともに、プラズマ内へ導入した。プラズマ内を通過した後の通過流とともに放出された粉末を収集し、実施例１のリチウム金属複合酸化物粉末とした。 After the plasma was stabilized, the powder feeder was operated to introduce the mixed powder into the plasma together with the carrier gas at a supply amount of 300 mg / min. The powder released together with the passing flow after passing through the plasma was collected and used as the lithium metal composite oxide powder of Example 1.
なお、実施例１においては冷却ガスを使用しなかったが、既述したアルゴン等の冷却ガスを用い、導入流がプラズマ内を通過した後の通過流を当該通過流に対向する冷却ガス流で冷却する工程を実施しても良い。この場合には、粉末の冷却速度が高まり、より微細な粒子からなる粉末が得られると考えられる。 Although the cooling gas was not used in Example 1, the cooling gas such as argon described above was used, and the passing flow after the introduction flow passed through the plasma was a cooling gas flow facing the passing flow. A cooling step may be carried out. In this case, it is considered that the cooling rate of the powder is increased and a powder composed of finer particles can be obtained.
上記の実施例１のリチウム金属複合酸化物粉末を用いて、以下のとおり、実施例１の負極及びリチウムイオン二次電池を製造した。
負極活物質として実施例１のリチウム金属複合酸化物粉末５質量部、導電助剤としてアセチレンブラック４質量部、結着剤としてポリテトラフルオロエチレン１質量部を秤量して、メノウ乳鉢で混合し、粘土状に加工して負極活物質層用組成物を得た。集電体としてメッシュ状の銅を準備し、これに負極活物質層用組成物を圧着することで、実施例１の負極を得た。作業はすべてアルゴンガス置換された水分濃度１ｐｐｍ以下のグローブボックス内で行った。
Using the lithium metal composite oxide powder of Example 1 described above, the negative electrode and the lithium ion secondary battery of Example 1 were manufactured as follows.
Weigh 5 parts by mass of the lithium metal composite oxide powder of Example 1 as the negative electrode active material, 4 parts by mass of acetylene black as the conductive auxiliary agent, and 1 part by mass of polytetrafluoroethylene as the binder, and mix them in a Menou dairy pot. The composition was processed into a clay to obtain a composition for a negative electrode active material layer. A mesh-shaped copper was prepared as a current collector, and a composition for a negative electrode active material layer was pressure-bonded thereto to obtain a negative electrode of Example 1. All the work was performed in a glove box having a water concentration of 1 ppm or less, which was replaced with argon gas.
上記の手順で作製した実施例１の負極を作用極として用い、リチウムイオン二次電池（ハーフセル）を作製した。対極は金属リチウム箔とした。
作用極及び対極、並びに両極の間に介装させるセパレータ（ヘキストセラニーズ社製ガラスフィルター及びＣｅｌｇａｒｄ社製「Ｃｅｌｇａｒｄ２４００」）を配設して電極体とした。この電極体を電池ケース（ＣＲ２０３２型コイン電池用部材、宝泉株式会社製）に収容した。電池ケースに、エチレンカーボネートとジエチルカーボネートとを体積比３：７で混合した混合溶媒にＬｉＰＦ６を１Ｍの濃度で溶解した非水電解液を注入し、電池ケースを密閉して、実施例１のリチウムイオン二次電池を得た。
A lithium ion secondary battery (half cell) was prepared using the negative electrode of Example 1 prepared in the above procedure as a working electrode. The opposite electrode was a metallic lithium foil.
The working electrode and the counter electrode, and a separator (a glass filter manufactured by Hoechst Celanese and "Celgard 2400" manufactured by Celgard) intervening between the two electrodes were arranged to form an electrode body. This electrode body was housed in a battery case (CR2032 type coin battery member, manufactured by Hosen Co., Ltd.). In the battery case, a non-aqueous electrolyte solution in which LiPF 6 was dissolved at a concentration of 1 M was injected into a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 3: 7, and the battery case was sealed to seal the battery case of Example 1. A lithium ion secondary battery was obtained.
（実施例２）
Ｌｉ２ＣＯ３とＴｉとを１：４のモル比で混合して混合粉体としたこと以外は、実施例１と同様にして、実施例２のリチウム金属複合酸化物粉末、実施例２の負極及び実施例２のリチウムイオン二次電池を製造した。なお、実施例２のリチウム金属複合酸化物粉末の製造方法において、混合粉体におけるリチウム元素とチタン元素とのモル比、すなわち、リチウム金属複合酸化物原料におけるリチウム元素とチタン元素とのモル比は１：２であった。
(Example 2)
Lithium metal composite oxide powder of Example 2 and Lithium metal composite oxide powder of Example 2 in the same manner as in Example 1 except that Li 2 CO 3 and Ti were mixed at a molar ratio of 1: 4 to form a mixed powder. The negative electrode and the lithium ion secondary battery of Example 2 were manufactured. In the method for producing the lithium metal composite oxide powder of Example 2, the molar ratio of the lithium element and the titanium element in the mixed powder, that is, the molar ratio of the lithium element and the titanium element in the lithium metal composite oxide raw material is It was 1: 2.
（比較例１）
比較例１は、固相法によってリチウム金属複合酸化物粉末を製造する方法である。
比較例１では、Ｌｉ２ＣＯ３とＴｉとを１：２のモル比で秤量し、これらの粉末をボールミルに投入した。そして、ボールミルによる混合を約１００ｒｐｍで２４時間行い、混合物とした。混合物を成形した上で、アルゴンガス雰囲気下、１０００℃で１２時間加熱して焼成することで、焼成物である比較例１のリチウム金属複合酸化物粉末を得た。
当該比較例１のリチウム金属複合酸化物粉末と導電助剤としてのアセチレンブラックとを、質量比５：２となるように秤量して、ボールミルに投入した。そして、ボールミルによる混合を６００ｒｐｍで０．５時間行い、比較例１のリチウム金属複合酸化物及びアセチレンブラックを含む比較例１の混合物を得た。
(Comparative Example 1)
Comparative Example 1 is a method for producing a lithium metal composite oxide powder by a solid phase method.
In Comparative Example 1, Li 2 CO 3 and Ti were weighed at a molar ratio of 1: 2, and these powders were put into a ball mill. Then, mixing with a ball mill was carried out at about 100 rpm for 24 hours to prepare a mixture. After molding the mixture, it was heated at 1000 ° C. for 12 hours in an argon gas atmosphere and calcined to obtain a lithium metal composite oxide powder of Comparative Example 1 which was a calcined product.
The lithium metal composite oxide powder of Comparative Example 1 and acetylene black as a conductive auxiliary agent were weighed so as to have a mass ratio of 5: 2 and charged into a ball mill. Then, mixing with a ball mill was carried out at 600 rpm for 0.5 hours to obtain a mixture of Comparative Example 1 containing the lithium metal composite oxide of Comparative Example 1 and acetylene black.
上記した比較例１の混合物、アセチレンブラック、結着剤としてのポリテトラフルオロエチレンを乳鉢で混合して、粘土状の負極活物質層用組成物とした。当該負極活物質層用組成物において、比較例１のリチウム金属複合酸化物とアセチレンブラックとポリテトラフルオロエチレンとの質量比は５：４：１であった。
集電体としてメッシュ状の銅を準備し、これに負極活物質層用組成物を圧着して、比較例１の負極を得た。当該比較例１の負極を用い、実施例１と同様に、比較例１のリチウムイオン二次電池を製造した。
The above-mentioned mixture of Comparative Example 1, acetylene black, and polytetrafluoroethylene as a binder were mixed in a mortar to obtain a clay-like composition for a negative electrode active material layer. In the composition for the negative electrode active material layer, the mass ratio of the lithium metal composite oxide of Comparative Example 1, acetylene black, and polytetrafluoroethylene was 5: 4: 1.
A mesh-shaped copper was prepared as a current collector, and a composition for a negative electrode active material layer was pressure-bonded thereto to obtain a negative electrode of Comparative Example 1. Using the negative electrode of Comparative Example 1, the lithium ion secondary battery of Comparative Example 1 was manufactured in the same manner as in Example 1.
（評価試験１）
実施例１のリチウム金属複合酸化物粉末及び実施例２のリチウム金属複合酸化物粉末を、透過型電子顕微鏡（ＴＥＭ）で観察した。実施例１のリチウム金属複合酸化物粉末のＴＥＭ像を図２に示し、実施例２のリチウム金属複合酸化物粉末のＴＥＭ像を図３に示す。
(Evaluation test 1)
The lithium metal composite oxide powder of Example 1 and the lithium metal composite oxide powder of Example 2 were observed with a transmission electron microscope (TEM). The TEM image of the lithium metal composite oxide powder of Example 1 is shown in FIG. 2, and the TEM image of the lithium metal composite oxide powder of Example 2 is shown in FIG.
図２及び図３を基に、実施例１のリチウム金属複合酸化物粉末の平均粒子径及び実施例２のリチウム金属複合酸化物粉末の平均粒子径を測定した。その結果、実施例１のリチウム金属複合酸化物粉末の平均粒子径は５９ｎｍであり、実施例２のリチウム金属複合酸化物粉末の平均粒子径は５２ｎｍであることがわかった。 Based on FIGS. 2 and 3, the average particle size of the lithium metal composite oxide powder of Example 1 and the average particle size of the lithium metal composite oxide powder of Example 2 were measured. As a result, it was found that the average particle size of the lithium metal composite oxide powder of Example 1 was 59 nm, and the average particle size of the lithium metal composite oxide powder of Example 2 was 52 nm.
なお、例えば特許文献１には、スピネル型のリチウム金属複合酸化物につき、その一次粒径は０．１μｍ以上０．５μｍ以下であるのが好ましく、二次粒径は５μｍ以上５０μｍ以下であるのが好ましい旨が紹介されている。特許文献１の実施例において、スピネル型のリチウム金属複合酸化物の一次粒径は０．２〜０．４μｍ、二次粒径は１５．５〜１８μｍであり、ラムスデライト型のリチウム金属複合酸化物の二次粒径は１０．５〜１７μｍである。
また、特許文献２には、スピネル型のＬｉ４Ｔｉ５Ｏ１２とラムスデライト型のＬｉＴｉ２Ｏ４とが混晶状態にあるリチウム金属複合酸化物につき、平均一次粒子径が１〜７μｍの範囲にある旨が紹介されている。
For example, in Patent Document 1, the primary particle size of the spinel-type lithium metal composite oxide is preferably 0.1 μm or more and 0.5 μm or less, and the secondary particle size is 5 μm or more and 50 μm or less. Is introduced to the effect that is preferable. In the examples of Patent Document 1, the primary particle size of the spinel type lithium metal composite oxide is 0.2 to 0.4 μm, the secondary particle size is 15.5 to 18 μm, and the rams delite type lithium metal composite oxidation. The secondary particle size of the product is 10.5 to 17 μm.
Further, in Patent Document 2, the average primary particle diameter is in the range of 1 to 7 μm for a lithium metal composite oxide in which a spinel-type Li 4 Ti 5 O 12 and a rams delite-type Li Ti 2 O 4 are in a mixed crystal state. It is introduced that it is in.
実施例１及び実施例２のリチウム金属複合酸化物粉末の平均粒子径は、これら従来のリチウム金属複合酸化物粉末の平均粒子径に比べて、非常に小さいといい得る。これは、特許文献１や特許文献２に紹介されているような従来のリチウム金属複合酸化物粉末の製造方法と、本発明の製造方法との違いに因るものと考えられる。 It can be said that the average particle size of the lithium metal composite oxide powders of Examples 1 and 2 is very small as compared with the average particle size of these conventional lithium metal composite oxide powders. It is considered that this is due to the difference between the conventional method for producing the lithium metal composite oxide powder as introduced in Patent Document 1 and Patent Document 2 and the production method of the present invention.
つまり、実施例１や実施例２で用いた本発明の製造方法は、熱プラズマ法を用いた製造方法である。これに対して、特許文献１及び特許文献２に紹介されているリチウム金属複合酸化物粉末の製造方法は、何れも、リチウム金属複合酸化物原料の粉末を比較的低い温度で加熱してリチウム金属複合酸化物を合成する、所謂固相法を用いたものである。 That is, the production method of the present invention used in Examples 1 and 2 is a production method using the thermal plasma method. On the other hand, in each of the methods for producing a lithium metal composite oxide powder introduced in Patent Document 1 and Patent Document 2, the powder of the lithium metal composite oxide raw material is heated at a relatively low temperature to form a lithium metal. This is a method using a so-called solid phase method for synthesizing a composite oxide.
固相法によると、熱プラズマ法とは異なり、リチウム金属複合酸化物原料が気化又は分解状態となる過程はない。つまり、固相法は微細なリチウム金属複合酸化物粒子が生成する端緒となる工程を備えず、その結果、当該固相法で得られるリチウム金属複合酸化物粒子は、熱プラズマ法により得られる本発明の粒子に比べて、粗大なものにしかなり得ないと推測される。実際に、上記したように、特許文献１及び特許文献２に紹介されているリチウム金属複合酸化物粉末の平均粒子径は、実施例１及び実施例２のリチウム金属複合酸化物粉末の平均粒子径に比べて格段に大きい。 According to the solid-phase method, unlike the thermal plasma method, there is no process in which the lithium metal composite oxide raw material is vaporized or decomposed. That is, the solid phase method does not include a step that is a starting point for producing fine lithium metal composite oxide particles, and as a result, the lithium metal composite oxide particles obtained by the solid phase method are obtained by the thermal plasma method. It is presumed that it can only be made coarser than the particles of the invention. Actually, as described above, the average particle size of the lithium metal composite oxide powder introduced in Patent Document 1 and Patent Document 2 is the average particle size of the lithium metal composite oxide powder of Examples 1 and 2. It is much larger than.
この結果から、本発明の製造方法により製造された本発明のリチウム金属複合酸化物粉末が、従来のリチウム金属複合酸化物とは異なる、新規なリチウム金属複合酸化物粉末であることが裏付けられる。 From this result, it is confirmed that the lithium metal composite oxide powder of the present invention produced by the production method of the present invention is a novel lithium metal composite oxide powder different from the conventional lithium metal composite oxide.
（評価試験２）
粉末Ｘ線回折装置にて、実施例１及び実施例２のリチウム金属複合酸化物粉末を分析した。実施例１及び実施例２のリチウム金属複合酸化物粉末のＸ線回折チャートを図４に示す。
(Evaluation test 2)
The lithium metal composite oxide powders of Examples 1 and 2 were analyzed by a powder X-ray diffractometer. The X-ray diffraction charts of the lithium metal composite oxide powders of Examples 1 and 2 are shown in FIG.
図４に示すように、実施例１のリチウム金属複合酸化物粉末及び実施例２のリチウム金属複合酸化物粉末は、何れも、スピネル型のＬｉ４Ｔｉ５Ｏ１２及びラムスデライト型のＬｉ２Ｔｉ３Ｏ７を含んでいた。
また、実施例２のリチウム金属複合酸化物粉末のＸ線回折チャートには、実施例１のリチウム金属複合酸化物粉末のＸ線回折チャートに比べて、ラムスデライト型のＬｉ２Ｔｉ３Ｏ７に由来するピークが多く観察された。
更に、実施例２のリチウム金属複合酸化物粉末のＸ線回折チャートには、実施例１のリチウム金属複合酸化物粉末のＸ線回折チャートではあまりみられなかった、ルチル型のＴｉＯ２に由来するピークやアナターゼ型のＴｉＯ２に由来するピークが多く観察された。
As shown in FIG. 4, the lithium metal composite oxide powder of Example 1 and the lithium metal composite oxide powder of Example 2 are both spinel-type Li 4 Ti 5 O 12 and Rams delight-type Li 2 Ti. It contained 3 O 7 .
Further, the X-ray diffraction chart of the lithium metal composite oxide powder of Example 2 has a Rams delight type Li 2 Ti 3 O 7 as compared with the X-ray diffraction chart of the lithium metal composite oxide powder of Example 1. Many derived peaks were observed.
Further, the X-ray diffraction chart of the lithium metal composite oxide powder of Example 2 is derived from rutile-type TiO 2 , which was rarely seen in the X-ray diffraction chart of the lithium metal composite oxide powder of Example 1. Many peaks and peaks derived from anatase-type TiO 2 were observed.
当該Ｘ線回折チャートのピーク高さを基に、実施例１のリチウム金属複合酸化物粉末及び実施例２のリチウム金属複合酸化物粉末における各リチウム金属複合酸化物の比率を算出した。その結果、実施例１のリチウム金属複合酸化物粉末においては、スピネル型のＬｉ４Ｔｉ５Ｏ１２の含有率は９０％、ラムスデライト型のＬｉ２Ｔｉ３Ｏ７の含有率は５％、及び、ＴｉＯ２の含有率は５％であった。また、実施例２のリチウム金属複合酸化物粉末においては、スピネル型のＬｉ４Ｔｉ５Ｏ１２の含有率は４５％、ラムスデライト型のＬｉ２Ｔｉ３Ｏ７の含有率は４５％、及び、ＴｉＯ２の含有率は１０％であった。 Based on the peak height of the X-ray diffraction chart, the ratio of each lithium metal composite oxide in the lithium metal composite oxide powder of Example 1 and the lithium metal composite oxide powder of Example 2 was calculated. As a result, in the lithium metal composite oxide powder of Example 1, the content of spinel type Li 4 Ti 5 O 12 was 90%, the content of Rams delight type Li 2 Ti 3 O 7 was 5%, and , TiO 2 content was 5%. Further, in the lithium metal composite oxide powder of Example 2, the content of spinel type Li 4 Ti 5 O 12 was 45%, the content of Rams delight type Li 2 Ti 3 O 7 was 45%, and so on. The content of TiO 2 was 10%.
これらの結果から、熱プラズマ法を用いた本発明の製造方法によると、スピネル型のリチウム金属複合酸化物だけでなくラムスデライト型のリチウム金属複合酸化物も得られることがわかる。また、リチウム金属複合酸化物源として、リチウム元素よりも多くのチタン元素を含むものを用いることで、リチウム金属複合酸化物粉末におけるラムスデライト型のリチウム金属複合酸化物の含有率を高め得ることもわかる。 From these results, it can be seen that according to the production method of the present invention using the thermal plasma method, not only a spinel-type lithium metal composite oxide but also a rams delite-type lithium metal composite oxide can be obtained. Further, by using a lithium metal composite oxide source containing more titanium elements than the lithium element, the content of the rams delight type lithium metal composite oxide in the lithium metal composite oxide powder can be increased. Recognize.
ところで、スピネル型のリチウム金属複合酸化物とラムスデライト型のリチウム金属複合酸化物とは互いに相転移可能であると考えられる。例えば特許文献２には、スピネル型のＬｉ４Ｔｉ５Ｏ１２からラムスデライト型のＬｉＴｉ２Ｏ４に相転移する境界温度は９２５℃である旨が紹介されている。
また、ラムスデライト型のリチウム金属複合酸化物は、高温かつ上記の境界温度を下回る温度で保持されることで、ラムスデライト型からスピネル型に相転移する可能性がある。つまり、高温下でラムスデライト型に相転移したリチウム金属複合酸化物は、緩やかに冷却されると、再度ラムスデライト型からスピネル型に相転移する可能性がある。
By the way, it is considered that the spinel-type lithium metal composite oxide and the rams delite-type lithium metal composite oxide can undergo a phase transition with each other. For example, Patent Document 2 introduces that the boundary temperature at which the phase transition from the spinel-type Li 4 Ti 5 O 12 to the Rams delight-type Li Ti 2 O 4 is 925 ° C.
Further, the rams delight type lithium metal composite oxide may undergo a phase transition from the rams delight type to the spinel type by being held at a high temperature and a temperature lower than the above boundary temperature. That is, the lithium metal composite oxide that has undergone a phase transition from the rams delight type to the spinel type at high temperature may undergo a phase transition from the rams delite type to the spinel type again when slowly cooled.
これに対して本発明の製造方法では、既述したように、リチウム金属複合酸化物粉末の製造時において、プラズマ内で高温に加熱されたリチウム金属複合酸化物源が急激に冷却される。このため、ラムスデライト型からスピネル型へのリチウム金属複合酸化物の相転移は生じ難く、その分だけ、リチウム金属複合酸化物の組成をコントロールし易いと考えられる。
つまり、本発明の製造方法によると、リチウム金属複合酸化物源におけるリチウム元素とチタン元素との比を適宜適切にコントロールすることで、リチウム金属複合酸化物の組成を容易にコントロールし得ると考えられる。
On the other hand, in the production method of the present invention, as described above, the lithium metal composite oxide source heated to a high temperature in the plasma is rapidly cooled during the production of the lithium metal composite oxide powder. Therefore, it is considered that the phase transition of the lithium metal composite oxide from the rams delight type to the spinel type is unlikely to occur, and the composition of the lithium metal composite oxide can be easily controlled accordingly.
That is, according to the production method of the present invention, it is considered that the composition of the lithium metal composite oxide can be easily controlled by appropriately and appropriately controlling the ratio of the lithium element and the titanium element in the lithium metal composite oxide source. ..
具体的には、本発明の製造方法によると、実施例１のようにリチウム金属複合酸化物源におけるチタンの元素比とリチウムの元素比とを同程度にすることで、その大部分がスピネル型のリチウム金属複合酸化物で構成されるリチウム金属複合酸化物粉末を得ることができる。また、実施例２のようにリチウム金属複合酸化物源におけるチタンの元素比をリチウムの元素比よりも多くすることで、ラムスデライト型のリチウム金属複合酸化物を多く含むリチウム金属複合酸化物粉末を得ることができる。 Specifically, according to the production method of the present invention, by making the element ratio of titanium and the element ratio of lithium in the lithium metal composite oxide source about the same as in Example 1, most of them are spinel type. A lithium metal composite oxide powder composed of the above lithium metal composite oxide can be obtained. Further, by increasing the element ratio of titanium in the lithium metal composite oxide source to be higher than the element ratio of lithium as in Example 2, a lithium metal composite oxide powder containing a large amount of rams delite type lithium metal composite oxide can be obtained. Obtainable.
また、上記した評価試験１の図２及び図３に示すように、実施例１のリチウム金属複合酸化物粉末及び実施例２のリチウム金属複合酸化物粉末は、何れも、ナノ水準の球状の粒子、及び、ナノ水準であり四角形にみえる粒子を多く含む。このうち小径かつ四角形にみえる粒子は、八面体のスピネル型のリチウム金属複合酸化物粒子であると推測され、小径かつ球状の粒子は、ラムスデライト型のリチウム金属複合酸化物粒子であると推測される。 Further, as shown in FIGS. 2 and 3 of the evaluation test 1 described above, the lithium metal composite oxide powder of Example 1 and the lithium metal composite oxide powder of Example 2 are both nano-level spherical particles. , And contains many particles that are nano-level and appear to be square. Of these, the small-diameter and quadrangular particles are presumed to be octahedral spinel-type lithium metal composite oxide particles, and the small-diameter and spherical particles are presumed to be rams delite-type lithium metal composite oxide particles. To.
図２及び図３に示すように、実施例１及び実施例２の製造方法により得られるリチウム金属複合酸化物粉末は、ナノ水準であり互いに独立した非常に微細な粒子で構成されている。
ここで、特許文献１及び特許文献２に紹介されている走査型電子顕微鏡像によると、固相法で得られたリチウム金属複合酸化物粉末は、粗大なリチウム金属複合酸化物粒子が多数凝集したマイクロ水準の二次粒子で構成されていると考えられる。
したがって、実施例１及び実施例２の製造方法により得られる本発明のリチウム金属複合酸化物粉末は、その平均粒子径及び外観において、従来の固相法で得られたリチウム金属複合酸化物と大きく相違するということができる。
As shown in FIGS. 2 and 3, the lithium metal composite oxide powder obtained by the production methods of Examples 1 and 2 is composed of very fine particles at the nano level and independent of each other.
Here, according to the scanning electron microscope images introduced in Patent Document 1 and Patent Document 2, a large number of coarse lithium metal composite oxide particles are aggregated in the lithium metal composite oxide powder obtained by the solid phase method. It is considered to be composed of micro-level secondary particles.
Therefore, the lithium metal composite oxide powder of the present invention obtained by the production methods of Examples 1 and 2 is larger in average particle size and appearance than the lithium metal composite oxide obtained by the conventional solid phase method. It can be said that they are different.
（評価試験３）
実施例１のリチウムイオン二次電池及び比較例１のリチウムイオン二次電池に対し、室温で、１．０Ｖ−２．０Ｖ間の充放電を、電流値０．０５ｍＡ、０．１ｍＡ、１ｍＡ、２ｍＡ及び５ｍＡの順序で行う充放電サイクル試験を行った。また、実施例２のリチウムイオン二次電池については、上記の電圧での充放電を０．０５ｍＡで行う充放電試験を行った。評価試験３の結果を表１に示す。
なお、ここでの記述は、対極を正極、作用極を負極とみなしている。
(Evaluation test 3)
The lithium ion secondary battery of Example 1 and the lithium ion secondary battery of Comparative Example 1 were charged and discharged at room temperature between 1.0V and 2.0V at current values of 0.05mA, 0.1mA, 1mA, and so on. A charge / discharge cycle test was performed in the order of 2 mA and 5 mA. Further, the lithium ion secondary battery of Example 2 was subjected to a charge / discharge test in which charging / discharging at the above voltage was performed at 0.05 mA. The results of the evaluation test 3 are shown in Table 1.
In the description here, the counter electrode is regarded as a positive electrode and the working electrode is regarded as a negative electrode.
表１に示すように、実施例１のリチウムイオン二次電池は、比較例１のリチウムイオン二次電池に比べて大きな容量を示した。また、実施例１のリチウムイオン二次電池は、比較例１のリチウムイオン二次電池に比べて、高い電流値でも容量の低下が少なかった。
実施例１のリチウムイオン二次電池と実施例２のリチウムイオン二次電池とを比較すると、実施例２のリチウムイオン二次電池は、電流値０．０５ｍＡにおいて、実施例１のリチウムイオン二次電池と同程度に大きな容量を示した。
これらの結果は、実施例１及び実施例２のリチウムイオン二次電池では、比較例１のリチウムイオン二次電池に比べて、負極における電池反応が効率良く行われていることを意味すると考えられる。
As shown in Table 1, the lithium ion secondary battery of Example 1 showed a larger capacity than the lithium ion secondary battery of Comparative Example 1. Further, the lithium ion secondary battery of Example 1 had less decrease in capacity even at a high current value than the lithium ion secondary battery of Comparative Example 1.
Comparing the lithium ion secondary battery of Example 1 and the lithium ion secondary battery of Example 2, the lithium ion secondary battery of Example 2 has a lithium ion secondary battery of Example 1 at a current value of 0.05 mA. It showed as large a capacity as a battery.
These results are considered to mean that the lithium ion secondary batteries of Examples 1 and 2 carry out the battery reaction at the negative electrode more efficiently than the lithium ion secondary batteries of Comparative Example 1. ..
実施例１及び実施例２のリチウムイオン二次電池において電池反応が効率良く行われた理由の１つとして、実施例１及び実施例２のリチウム金属複合酸化物粒子の形状を挙げることができる。上記したように、実施例１及び実施例２のリチウム金属複合酸化物粉末は、平均粒子径がナノ水準であるために、その比表面積は非常に大きい。このようなリチウム金属複合酸化物粉末を負極活物質として用いることで、負極における電池反応の反応場が非常に大きくなり、その結果、負極における電池反応が効率良く行われたと推測される。 One of the reasons why the battery reaction was efficiently performed in the lithium ion secondary batteries of Examples 1 and 2 is the shape of the lithium metal composite oxide particles of Examples 1 and 2. As described above, the lithium metal composite oxide powders of Examples 1 and 2 have a very large specific surface area because the average particle size is at the nano level. It is presumed that by using such a lithium metal composite oxide powder as the negative electrode active material, the reaction field of the battery reaction at the negative electrode becomes very large, and as a result, the battery reaction at the negative electrode is efficiently performed.
Claims (10)
平均粒子径がナノ水準である粒子を有する、リチウム金属複合酸化物粉末。 Contains lithium element, titanium element, and oxygen element
A lithium metal composite oxide powder having particles having an average particle size of nano level.
前記リチウム金属複合酸化物粉末を用いて負極を製造する工程を含む、負極の製造方法。 A step of producing a lithium metal composite oxide powder having a nano-level average particle size by the method for producing a lithium metal composite oxide powder according to any one of claims 1 to 4, and a step of producing the lithium metal composite oxide powder.
A method for manufacturing a negative electrode, which comprises a step of manufacturing a negative electrode using the lithium metal composite oxide powder.
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