TWI651883B - Anode material for lithium ion secondary battery, method for producing the same, anode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents
Anode material for lithium ion secondary battery, method for producing the same, anode for lithium ion secondary battery, and lithium ion secondary battery Download PDFInfo
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- TWI651883B TWI651883B TW104135240A TW104135240A TWI651883B TW I651883 B TWI651883 B TW I651883B TW 104135240 A TW104135240 A TW 104135240A TW 104135240 A TW104135240 A TW 104135240A TW I651883 B TWI651883 B TW I651883B
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- lithium ion
- secondary battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 271
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 82
- 238000009826 distribution Methods 0.000 claims abstract description 73
- 239000007773 negative electrode material Substances 0.000 claims abstract description 72
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 22
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 25
- 230000001186 cumulative effect Effects 0.000 claims description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 17
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical class [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 17
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052684 Cerium Inorganic materials 0.000 description 6
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- 238000011156 evaluation Methods 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- 239000006258 conductive agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
Abstract
本發明係提供循環特性優異的鋰離子二次電池負極用負極材料以及該製造方法。 The present invention provides a negative electrode material for a lithium ion secondary battery negative electrode excellent in cycle characteristics and a method for producing the same.
本發明係一種鋰離子二次電池用負極材料之製造方法，其係準備由含有矽原子的材料所構成的基材粒子，在前述基材粒子之表面形成碳被膜而使成為被覆粒子，在前述碳被膜未形成的狀態，將對於前述基材粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為a%，對於前述被覆粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為b%時，以成為a/b≧3的方式，進行前述碳被膜之形成。 The present invention relates to a method for producing a negative electrode material for a lithium ion secondary battery, which comprises preparing a substrate particle composed of a material containing a ruthenium atom, and forming a carbon film on the surface of the substrate particle to form a coated particle. In a state in which the carbon film is not formed, the ratio of particles having a particle diameter of 1 μm or less which is measured by a laser diffraction particle size distribution measuring device to the substrate particles is set to a%, and the coated particles are thunder. When the ratio of the particles having a particle diameter of 1 μm or less in the volume-based distribution measured by the diffraction-difference particle size distribution measuring apparatus is b%, the formation of the carbon film is performed so that a/b≧3 is obtained.
Description
本發明係關於鋰離子二次電池用負極材料及其製造方法，另外，有關使用有該鋰離子二次電池用負極材料的負極以及鋰離子二次電池。 The present invention relates to a negative electrode material for a lithium ion secondary battery and a method for producing the same, and a negative electrode and a lithium ion secondary battery using the negative electrode material for a lithium ion secondary battery.
近年來，隨著攜帶型之電子機器、通訊機器等之顯著的發展，由經濟性和機器之小型化、輕量化之觀點，而強烈地期待高能量密度之二次電池。 In recent years, with the remarkable development of portable electronic devices and communication devices, secondary batteries of high energy density have been strongly expected from the viewpoints of economy and miniaturization and weight reduction of machines.
先前，作為此種之二次電池之高容量化策略，例如已知有於負極材料使用V、Si、B、Zr、Sn等之氧化物以及該複合氧化物的方法(例如，參照專利文獻1、2)、將熔融急冷的金屬氧化物作為負極材料來適用的方法(例如，參照專利文獻3)、於負極材料使用氧化矽的方法(例如，參照專利文獻4)、於負極材料使用Si2N2O以及Ge2N2O(例如，參照專利文獻5)等。 In the prior art, as a method of increasing the capacity of such a secondary battery, for example, an oxide of V, Si, B, Zr, Sn, or the like and a method of using the composite oxide are known (for example, refer to Patent Document 1). And 2) a method in which a molten and quenched metal oxide is used as a negative electrode material (for example, refer to Patent Document 3), a method in which ruthenium oxide is used for a negative electrode material (for example, refer to Patent Document 4), and Si 2 is used for a negative electrode material. N 2 O and Ge 2 N 2 O (for example, refer to Patent Document 5) and the like.
另外，作為於負極材料賦予導電性的目的，將SiO與石墨機械合金化之後進行碳化處理的方法(例 如，參照專利文獻6)、於矽粒子表面藉由化學氣相沈積法而被覆碳層的方法(例如，參照專利文獻7)、於氧化矽粒子表面藉由化學氣相沈積法而被覆碳層的方法(例如，參照專利文獻8)。 Further, as a purpose of imparting conductivity to the negative electrode material, a method of mechanically alloying SiO with graphite and then performing carbonization treatment (for example) For example, refer to Patent Document 6), a method of coating a carbon layer on a surface of a cerium particle by a chemical vapor deposition method (for example, refer to Patent Document 7), and coating a carbon layer on a surface of cerium oxide particles by chemical vapor deposition. Method (for example, refer to Patent Document 8).
然而，在上述先前之方法中，雖然充放電容量上昇，能量密度變高，但是循環性不充分、於市場之要求特性尚不充分，而且未必可滿足需求，所以期待可更進一步提高能量密度。 However, in the above-described conventional method, although the charge/discharge capacity is increased and the energy density is increased, the cycle property is insufficient, the required characteristics in the market are not sufficient, and the demand is not necessarily satisfied. Therefore, it is expected that the energy density can be further improved.
[專利文獻1]日本特開平5-174818號公報 [Patent Document 1] Japanese Patent Laid-Open No. 5-174818
[專利文獻2]日本特開平6-60867號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 6-60867
[專利文獻3]日本特開平10-294112號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 10-294112
[專利文獻4]日本專利第2997741號公報 [Patent Document 4] Japanese Patent No. 2997741
[專利文獻5]日本特開平11-102705號公報 [Patent Document 5] Japanese Patent Laid-Open No. Hei 11-102705
[專利文獻6]日本特開2000-243396號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-243396
[專利文獻7]日本特開2000-215887號公報 [Patent Document 7] Japanese Laid-Open Patent Publication No. 2000-215887
[專利文獻8]日本特開2002-42806號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2002-42806
如以上所述，於先前之負極材料尚有問題。 特別是在專利文獻4，其係將氧化矽作為鋰離子二次電池用負極材料使用，可得高容量之電極，但就本發明者們所知，其尚有在初次充放電時的不可逆容量大、循環性未達實用等級等之問題，還有改良的餘地。 As mentioned above, there are still problems with the prior negative electrode materials. In particular, in Patent Document 4, cerium oxide is used as a negative electrode material for a lithium ion secondary battery, and a high-capacity electrode can be obtained. However, as far as the inventors know, there is an irreversible capacity at the time of initial charge and discharge. There is still room for improvement, such as large and cyclical problems that do not reach the practical level.
另外，關於在負極材料賦予劑導電性的技術，亦在專利文獻6中係因為固體和固體之融接所以不形成均勻的碳被膜，有導電性不充分的問題。在專利文獻8之方法，其問題在於雖然確認循環性提高，但因細微的矽結晶析出、碳被覆之構造以及與基材之融合係不充分，而有一累積充放電之循環數，容量就徐徐下降，在一定次數後就劇烈地下降的現象，作為二次電池用尚不充分。 In addition, in the technique of the conductivity of the negative electrode material imparting agent, in Patent Document 6, since the solid and the solid are fused, a uniform carbon film is not formed, and there is a problem that conductivity is insufficient. The method of Patent Document 8 has a problem in that although the cycle property is improved, the fine crystallization of ruthenium, the structure of carbon coating, and the fusion with the substrate are insufficient, and there is a cumulative number of cycles of charge and discharge, and the capacity is gradually reduced. The phenomenon of falling and falling sharply after a certain number of times is not sufficient as a secondary battery.
本發明係鑑於有關的問題點而為者，其目的為提供循環特性優良的鋰離子二次電池負極用負極材料、以及該製造方法。另外，本發明，其目的為提供使用如該負極材料的負極以及鋰離子二次電池。 The present invention has been made in view of the problems, and an object thereof is to provide a negative electrode material for a lithium ion secondary battery negative electrode excellent in cycle characteristics, and a method for producing the same. Further, the present invention has an object of providing a negative electrode using a negative electrode material and a lithium ion secondary battery.
為了解決上述課題，本發明提供一種鋰離子二次電池用負極材料之製造方法，其係具有準備由含有矽原子的材料所構成，可吸藏以及放出鋰離子的基材粒子的步驟、與在前述基材粒子之表面形成碳被膜而設為被覆粒子的步驟的鋰離子二次電池用負極材料之製造方法，其特徵為在前述碳被膜未形成的狀態，將對於前述基材粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的 粒徑1μm以下之粒子之比例設為a%，對於前述被覆粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為b%時，以成為a/b≧3的方式，進行形成前述碳被膜的步驟。 In order to solve the above problems, the present invention provides a method for producing a negative electrode material for a lithium ion secondary battery, which comprises the steps of preparing a substrate particle which is made of a material containing a ruthenium atom and is capable of occluding and releasing lithium ions. A method for producing a negative electrode material for a lithium ion secondary battery in which a carbon film is formed on the surface of the substrate particle to form a coating film, and a laser is formed on the substrate particle in a state where the carbon film is not formed. Diffraction-based particle size distribution measuring device for volume distribution The ratio of the particles having a particle diameter of 1 μm or less is set to a%, and when the ratio of the particles having a particle diameter of 1 μm or less measured by the volume-based distribution measured by the laser diffraction particle size distribution measuring apparatus is b%, In the form of a/b≧3, the step of forming the carbon film is performed.
如此，如以成為a/b≧3的方式進行而執行碳被膜之形成的負極材料之製造方法，則在進行以碳被膜所形成的被覆之前所存在的粒徑1μm以下之粒子(也就是，粒徑較小的微粉)，其係藉由被覆而形成以碳凝集的2次粒子。在藉由負極材料製作負極時，此2次粒子埋入大粒子之間隙而對負極之電阻降低帶來貢獻。由此而有關於反覆充放電循環時之電容維持率提高。 In the method of producing a negative electrode material which is formed by the formation of the carbon film, the particles having a particle diameter of 1 μm or less which are present before the coating with the carbon film are formed (that is, The fine powder having a small particle size is formed by coating to form secondary particles agglomerated with carbon. When the negative electrode is made of a negative electrode material, the secondary particles are buried in the gap between the large particles to contribute to the reduction in the electric resistance of the negative electrode. As a result, the capacitance maintenance ratio at the time of the reverse charge/discharge cycle is improved.
在此情況，在準備前述基材粒子的步驟，作為前述基材粒子，準備前述a%為0.1%以上30%以下者為理想。 In this case, in the step of preparing the substrate particles, it is preferable that the a% is 0.1% or more and 30% or less as the substrate particles.
如此般地進行，藉由將基材粒子，設為在體積基準分布的粒徑1μm以下之粒子之比例為0.1%以上30%以下者，而變為容易形成2次粒子。 In the case where the ratio of the particles having a particle diameter of 1 μm or less in the volume-based distribution is 0.1% or more and 30% or less, the secondary particles are easily formed.
另外，在準備前述基材粒子的步驟，作為前述基材粒子，可準備矽粒子、具有矽之微粒子為分散於矽系化合物的複合構造的粒子、以一般式SiOx(0.5≦x≦1.6)所表示的氧化矽粒子、或是這些成分之混合物。 Further, in the step of preparing the substrate particles, as the substrate particles, ruthenium particles, particles having ruthenium particles as a composite structure dispersed in an oxime compound, and a general formula of SiO x (0.5 ≦ x ≦ 1.6) can be prepared. The cerium oxide particles indicated, or a mixture of these components.
本發明之負極材料之製造方法，亦可適用於上述任一之基材粒子。 The method for producing a negative electrode material of the present invention can also be applied to any of the above substrate particles.
另外，相對於前述被覆粒子之質量，將含有 於該被覆粒子的碳之質量之比例，設為0.5質量%以上40質量%以下為理想。 In addition, it will contain the mass of the coated particles. The ratio of the mass of carbon to the coated particles is preferably 0.5% by mass or more and 40% by mass or less.
藉由如此的碳被覆量，可對負極材料賦予充分的導電性，而且可提高充放電容量。 By such a carbon coating amount, sufficient conductivity can be imparted to the negative electrode material, and charge and discharge capacity can be improved.
另外，在準備前述基材粒子的步驟，作為前述基材粒子，準備前述基材粒子之在以雷射繞射法粒度分布測定裝置所測定的體積基準分布的累積50%徑(D50)為0.1μm以上30μm以下者為理想。 Further, in the step of preparing the substrate particles, the cumulative 50% diameter (D 50 ) of the volume reference distribution measured by the laser diffraction particle size distribution measuring apparatus of the substrate particles is prepared as the substrate particles. It is preferably 0.1 μm or more and 30 μm or less.
藉由使用具有如此的累積50%徑的基材粒子，在為了製作負極而塗布有負極材料時不傷及隔離膜，另外可將電極之導電性作為良好者。 By using the substrate particles having such a cumulative 50% diameter, when the negative electrode material is applied to produce the negative electrode, the separator is not damaged, and the conductivity of the electrode can be made good.
另外，將進行前述碳被膜之形成的步驟，以前述被覆粒子之雷射繞射法粒度分布測定裝置所測定的體積基準分布的累積50%徑(D50)，係成為1μm以上30μm以下的方式來進行理想。 Further, in the step of forming the carbon film, the cumulative 50% diameter (D 50 ) of the volume-based distribution measured by the laser diffraction particle size distribution measuring apparatus for the coated particles is 1 μm or more and 30 μm or less. Come to the ideal.
藉由將被覆粒子之累積50%徑設為如此的值，在為了製作負極而塗布有負極材料時不傷及隔離膜，另外可將電極之導電性作為良好者。 By setting the cumulative 50% diameter of the coated particles to such a value, when the negative electrode material is applied to produce the negative electrode, the separator is not damaged, and the conductivity of the electrode can be made good.
另外，理想為將進行前述碳被膜之形成的步驟，藉由對於前述基材粒子，在熱分解而可生成碳的有機氣體環境中以600~1200℃之溫度範圍將碳進行化學氣相沈積而執行。 Further, it is preferable that the carbon film is formed by chemical vapor deposition in a temperature range of 600 to 1200 ° C in an organic gas atmosphere in which carbon atoms can be thermally decomposed in the substrate particles. carried out.
藉由以如此的條件進行碳被覆，可進行良好的碳被膜之形成，可賦與負極材料適切的導電性。 By performing carbon coating under such conditions, a favorable carbon film can be formed, and the conductivity of the negative electrode material can be imparted.
另外，作為進行前述熱分解而可生成碳的有機物氣體之原料，由甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丁烷、丁烯、戊烷、異丁烷、己烷、苯、甲苯、二甲苯、苯乙烯、乙基苯、二苯基甲烷、萘、酚、甲酚、硝基苯、氯苯、茚、香豆酮、吡啶、蒽、菲、焦油蒸餾步驟所得到的煤氣輕油、雜酚油、蒽油以及石腦油分解焦油之中選擇1種以上使用為理想。 Further, as a raw material of the organic gas which can generate carbon by the above thermal decomposition, methane, ethane, ethylene, acetylene, propane, propylene, butane, butene, pentane, isobutane, hexane, benzene, toluene Light gas obtained by distillation steps of xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, hydrazine, coumarone, pyridine, hydrazine, phenanthrene and tar It is preferable to use one or more of the oil, creosote oil, eucalyptus oil, and naphtha decomposition tar.
作為有機物氣體之原料係可將這些成分合適地使用。 These components can be suitably used as a raw material of an organic substance gas.
另外，本發明係提供一種鋰離子二次電池用負極材料，其特徵為藉由上述任一之鋰離子二次電池用負極材料之製造方法而製造。 Moreover, the present invention provides a negative electrode material for a lithium ion secondary battery, which is produced by the method for producing a negative electrode material for a lithium ion secondary battery.
另外，本發明係提供一種鋰離子二次電池用負極材料，其係由含有矽原子的材料所構成，可吸藏以及放出鋰離子的基材粒子、與形成在該基材粒子之表面的碳被膜所構成的被覆粒子的鋰離子二次電池用負極材料，其特徵為在前述碳被膜未形成的狀態，將對於前述基材粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為a%，對於前述被覆粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為b%時，成為a/b≧3。 Further, the present invention provides a negative electrode material for a lithium ion secondary battery, which is composed of a material containing a ruthenium atom, a substrate particle capable of occluding and releasing lithium ions, and carbon formed on a surface of the substrate particle. The negative electrode material for a lithium ion secondary battery of the coated particles, which is composed of a film, is characterized in that the carbon film is not formed, and the volume of the base material is measured by a laser diffraction particle size distribution measuring device. The ratio of the particles having a particle diameter of 1 μm or less to be distributed is set to a%, and when the ratio of the particles having a particle diameter of 1 μm or less measured by the volume-based distribution measured by the laser diffraction particle size distribution measuring apparatus is b%. , become a/b≧3.
在本發明之負極材料，在進行由碳被膜所形成的被覆之前所存在的粒徑1μm以下之微粉係藉由被覆 而形成以碳凝集的2次粒子。在藉由負極材料製作負極時，此2次粒子埋入大粒子之間隙而對負極之電阻降低帶來貢獻。由此而有關於反覆充放電循環時之電容維持率提高。 In the negative electrode material of the present invention, the fine powder having a particle diameter of 1 μm or less which is present before the coating formed of the carbon film is coated The second-order particles agglomerated with carbon are formed. When the negative electrode is made of a negative electrode material, the secondary particles are buried in the gap between the large particles to contribute to the reduction in the electric resistance of the negative electrode. As a result, the capacitance maintenance ratio at the time of the reverse charge/discharge cycle is improved.
另外，本發明係提供一種鋰離子二次電池用負極，其特徵為使用上述之鋰離子二次電池用負極材料。 Further, the present invention provides a negative electrode for a lithium ion secondary battery, which is characterized by using the above negative electrode material for a lithium ion secondary battery.
另外，本發明係提供一種鋰離子二次電池，其特徵為使用上述之鋰離子二次電池用負極。 Further, the present invention provides a lithium ion secondary battery characterized by using the above negative electrode for a lithium ion secondary battery.
在使用了本發明之負極材料的鋰離子二次電池用負極，包含於負極材料的上述之2次粒子之存在為有助於負極之電阻降低。此係有關於反覆進行使用了該負極的鋰離子二次電池之充放電循環時之電容維持率提高。 In the negative electrode for a lithium ion secondary battery using the negative electrode material of the present invention, the presence of the above-described secondary particles contained in the negative electrode material contributes to a decrease in the electric resistance of the negative electrode. This is an increase in the capacity retention rate when the charge and discharge cycle of the lithium ion secondary battery using the negative electrode is repeated.
在本發明之鋰離子二次電池用負極材料，在進行由碳被膜所形成的被覆之前所存在的粒徑1μm以下之微粉，其為藉由被覆而形成以碳凝集的2次粒子。在藉由負極材料製作負極時，此2次粒子埋入大粒子之間隙而有助於負極之電阻降低。由此而有關於反覆充放電循環時之電容維持率提高。另外，因為將含有矽原子的材料作為基材粒子使用，所以本發明之負極材料係可設為高容量者。另外，該製造方法係不特別複雜而簡便，亦能夠承受工業規模之生產。 In the negative electrode material for a lithium ion secondary battery of the present invention, fine particles having a particle diameter of 1 μm or less which are present before coating with a carbon film are formed by coating to form secondary particles agglomerated with carbon. When the negative electrode is made of a negative electrode material, the secondary particles are buried in the gap between the large particles to contribute to the reduction in the electric resistance of the negative electrode. As a result, the capacitance maintenance ratio at the time of the reverse charge/discharge cycle is improved. Further, since a material containing a ruthenium atom is used as the substrate particles, the negative electrode material of the present invention can be used as a high capacity. In addition, the manufacturing method is not particularly complicated and simple, and can withstand industrial scale production.
[第1圖]在進行由實施例1~3以及比較例1的CVD的碳被覆之前之基材粒子之粒度分布圖。 [Fig. 1] A particle size distribution map of the substrate particles before the carbon coating of the CVD of Examples 1 to 3 and Comparative Example 1 was carried out.
[第2圖]在實施例1的被覆粒子之粒度分布圖。 [Fig. 2] A particle size distribution diagram of the coated particles of Example 1.
[第3圖]在實施例2的被覆粒子之粒度分布圖。 [Fig. 3] A particle size distribution diagram of the coated particles of Example 2.
[第4圖]在實施例3的被覆粒子之粒度分布圖。 [Fig. 4] A particle size distribution map of the coated particles of Example 3.
[第5圖]在實施例4的被覆粒子之粒度分布圖。 [Fig. 5] A particle size distribution map of the coated particles of Example 4.
[第6圖]在比較例1的被覆粒子之粒度分布圖。 [Fig. 6] A particle size distribution map of the coated particles of Comparative Example 1.
[第7圖]在進行由比較例2的CVD的碳被覆之前之基材粒子之粒度分布圖。 [Fig. 7] A particle size distribution map of the substrate particles before the carbon coating of the CVD of Comparative Example 2 was carried out.
[第8圖]在比較例2的被覆粒子之粒度分布圖。 [Fig. 8] A particle size distribution map of the coated particles of Comparative Example 2.
以下，關於本發明加以詳細地說明。 Hereinafter, the present invention will be described in detail.
本發明之鋰離子二次電池用負極材料，其係由含有矽原子的材料所構成，由可吸藏及放出鋰離子的基材粒子、與形成於該基材粒子之表面的碳被膜所構成的被覆粒子。另外，本發明之負極材料，其係在碳被膜之形成前後之粒子為滿足以下之條件者。在碳被膜未形成的狀態下，對於基材粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為a%。另外， 對於被覆粒子以雷射繞射法粒度分布測定裝置所測定的在體積基準分布的粒徑1μm以下之粒子之比例設為b%。此時，本發明之負極材料係滿足a/b≧3之關係者。 The negative electrode material for a lithium ion secondary battery of the present invention is composed of a material containing a ruthenium atom, and is composed of a substrate particle capable of occluding and releasing lithium ions and a carbon film formed on the surface of the substrate particle. Covered particles. Further, the negative electrode material of the present invention is a particle which satisfies the following conditions before and after the formation of the carbon film. In the state in which the carbon film was not formed, the ratio of the particles having a particle diameter of 1 μm or less measured by the laser diffraction particle size distribution measuring device to the substrate particles was set to a%. In addition, The ratio of the particles having a particle diameter of 1 μm or less in the volume-based distribution measured by the laser diffraction particle size distribution measuring apparatus for the coated particles was set to b%. At this time, the negative electrode material of the present invention satisfies the relationship of a/b≧3.
本發明者群係將基材粒子及被覆粒子各別之粒徑之分布設為特定之範圍，也就是將上述之a/b成為3以上的粒子，以作為鋰離子二次電池用負極材料(活性物質)使用，發現可得高容量而且循環特性優異的鋰離子二次電池，進而完成本發明。 In the inventors' group, the distribution of the respective particle diameters of the substrate particles and the coated particles is set to a specific range, that is, the above a/b is 3 or more particles, and is used as a negative electrode material for a lithium ion secondary battery ( When the active material was used, it was found that a lithium ion secondary battery having high capacity and excellent cycle characteristics was obtained, and the present invention was completed.
如上所述，在本發明的粒子之粒度分布之規定，其係根據使用了雷射繞射法的粒度分布測定(亦稱為雷射繞射式粒度分布測定)。作為雷射繞射法粒度分布測定裝置，其係可使用例如島津製作所公司製之SALD-3100。關於特定之粒子(粒子群、粉體)以雷射繞射法粒度分布測定裝置來測定的體積基準分布，在以下亦單獨稱為「體積基準分布」。尚，「粒徑1μm以下之粒子之比例」，一般亦有稱為「累積1μm」者。 As described above, the specification of the particle size distribution of the particles of the present invention is determined based on the particle size distribution using the laser diffraction method (also referred to as laser diffraction type particle size distribution measurement). As the laser diffraction particle size distribution measuring apparatus, for example, SALD-3100 manufactured by Shimadzu Corporation can be used. The volume reference distribution measured by a laser diffraction particle size distribution measuring apparatus for a specific particle (particle group or powder) is also referred to as a "volume reference distribution" hereinafter. In addition, "the ratio of particles having a particle diameter of 1 μm or less" is generally referred to as "accumulation of 1 μm".
本發明之鋰離子二次電池用負極材料，其係可經由以下之步驟製造。首先，準備由含有矽原子的材料所構成，可吸藏及放出鋰離子的基材粒子(步驟A)。接著，於基材粒子之表面形成碳被膜而設為被覆粒子(步驟B)。此時，上述a與b係以成為a/b≧3的方式，形成基材粒子之碳被膜。此製造方法係不特別複雜而簡便，亦能夠承受 工業規模之生產。 The negative electrode material for a lithium ion secondary battery of the present invention can be produced by the following steps. First, a substrate particle composed of a material containing germanium atoms and capable of occluding and releasing lithium ions is prepared (step A). Next, a carbon film is formed on the surface of the substrate particles to form coated particles (step B). At this time, the above a and b form a carbon film of the substrate particles so as to become a/b≧3. This manufacturing method is not particularly complicated and simple, and can withstand Industrial scale production.
在本發明中，如以上所述，在由含有矽原子的材料所構成，可吸藏及放出鋰離子的粒子(基材粒子)進行碳被覆。在本發明所使用的基材粒子(也就是，在步驟A所準備的基材粒子)，其係矽粒子、具有矽之微粒子為分散於矽系化合物的複合構造的粒子、以一般式SiOx(0.5≦x≦1.6)所表示的氧化矽粒子、或是這些成分之混合物為理想。本發明之負極材料之製造方法，亦可適用於上述任一之基材粒子。以作為基材粒子而使用上述任一者，可得到初次充放電效率更高，高容量而且循環性優異的鋰離子二次電池用負極材料。 In the present invention, as described above, particles composed of a material containing germanium atoms, and particles (substrate particles) capable of occluding and releasing lithium ions are carbon-coated. In the substrate particles used in the present invention (that is, the substrate particles prepared in the step A), the ruthenium particles and the particles having ruthenium are particles of a composite structure dispersed in the lanthanoid compound, and the general formula SiO x The cerium oxide particles represented by (0.5 ≦ x ≦ 1.6) or a mixture of these components are desirable. The method for producing a negative electrode material of the present invention can also be applied to any of the above substrate particles. When any of the above is used as the substrate particles, a negative electrode material for a lithium ion secondary battery having a higher initial charge and discharge efficiency, a high capacity, and excellent cycle properties can be obtained.
所謂在本發明的氧化矽，其係非晶質之矽氧化物之總稱，歧化前之氧化矽係以一般式SiOx(0.5≦x≦1.6)所表示。x係0.8≦x<1.3為理想，0.8≦x<1.0為較理想。此氧化矽係例如可將二氧化矽與金屬矽之混合物加熱而生成的一氧化矽氣體進行冷卻．析出而得。 The cerium oxide of the present invention is a general term for amorphous cerium oxide, and the cerium oxide before disproportionation is represented by a general formula of SiO x (0.5 ≦ x ≦ 1.6). The x-series 0.8 ≦ x < 1.3 is ideal, and 0.8 ≦ x < 1.0 is preferable. The lanthanum oxide system can be cooled, for example, by heating a cerium oxide gas formed by heating a mixture of cerium oxide and metal cerium. Precipitated.
具有矽之微粒子分散於矽系化合物的複合構造的粒子，例如可將矽之微粒子與矽系化合物混合者進行燒結的方法、或是將以一般式SiOx所表示的歧化前之氧化矽粒子，在氬等之惰性的非氧化性環境中，以400℃以上，合適上為800~1,100℃之溫度進行熱處理，進行歧化反應而得。特別是以後者之方法所得的材料，其係因為矽 之微結晶為均勻地分散所以為合適。藉由如上述的歧化反應，可將矽奈米粒子之尺寸設為1~100nm。尚，關於具有矽奈米粒子為分散於氧化矽中的構造的粒子中之氧化矽，其係二氧化矽為最佳。尚，藉由穿透電子顯微鏡而可確認矽之奈米粒子(結晶)為分散於無定形之氧化矽。 A particle having a composite structure in which fine particles of cerium are dispersed in a lanthanoid compound, for example, a method of sintering a fine particle of cerium and a lanthanoid compound, or a cerium oxide particle before disproportionation represented by a general formula SiO x In a non-oxidizing environment inert to argon or the like, heat treatment is carried out at a temperature of 400 ° C or higher and suitably 800 to 1,100 ° C to obtain a disproportionation reaction. In particular, the material obtained by the latter method is suitable because the microcrystals of cerium are uniformly dispersed. The size of the nanoparticle can be set to 1 to 100 nm by the disproportionation reaction as described above. Further, cerium oxide having cerium nanoparticles as particles dispersed in cerium oxide is preferred as cerium oxide. Further, it was confirmed by penetrating electron microscopy that the nanoparticles of yttrium (crystals) were dispersed in amorphous yttrium oxide.
作為基材粒子，氧化矽系之材料為鋰之吸藏及放出時之體積膨脹率低，為特別理想。若基材粒子本身之體積膨脹率低，則循環性成為特別良好。 As the substrate particles, the cerium oxide-based material is particularly preferable because the volume expansion ratio at the time of occlusion and release of lithium is low. When the volume expansion ratio of the substrate particles themselves is low, the cycle property is particularly excellent.
在本發明所使用的基材粒子之物性，其係藉由設為目的的被覆粒子(複合粒子)，而可適宜選定。例如在以雷射繞射法粒度分布測定裝置所測定的體積基準分布的累積50%徑(D50，亦稱為體積平均粒徑。)，可合適地使用0.1μm以上30μm以下者。此範圍之下限係0.2μm以上為較理想，0.3μm以上為更理想。上限係20μm以下為較理想，10μm以下為更理想。如累積50%徑(D50)為0.1μm以上，則可將後述的BET比表面積設為夠小者，而不會帶來BET比表面積過大所生的不良影響。另外，如累積50%徑(D50)為30μm以下，則成為容易進行在製作負極時之負極材料之塗布等。 The physical properties of the substrate particles used in the present invention can be suitably selected by using the coated particles (composite particles). For example, in the cumulative 50% diameter (D 50 , also referred to as volume average particle diameter) of the volume-based distribution measured by the laser diffraction particle size distribution measuring apparatus, 0.1 μm or more and 30 μm or less can be suitably used. The lower limit of the range is preferably 0.2 μm or more, and more preferably 0.3 μm or more. The upper limit is preferably 20 μm or less, and more preferably 10 μm or less. When the cumulative 50% diameter (D 50 ) is 0.1 μm or more, the BET specific surface area to be described later can be made small enough, and the adverse effect caused by the excessive BET specific surface area is not caused. In addition, when the cumulative 50% diameter (D 50 ) is 30 μm or less, it is easy to apply the negative electrode material during the production of the negative electrode.
在本發明所使用的基材粒子之BET比表面積，其係0.5m2/g以上100m2/g以下為理想，1m2/g以上20m2/g以下為較理想。如BET比表面積為0.5m2/g以上，則可將為了製作負極而塗布負極材料時之接著性設為充分者，可使電池特性提高。另外，如BET比表面積為 100m2/g以下，則可將由粒子表面之自然氧化所生的二氧化矽之比例變少。該結果，因為可將無助於電池反應的二氧化矽變少，所以可抑制在設為鋰離子二次電池用負極材料使用時電池容量低下。 The BET specific surface area of the substrate particles used in the present invention is preferably 0.5 m 2 /g or more and 100 m 2 /g or less, and more preferably 1 m 2 /g or more and 20 m 2 /g or less. When the BET specific surface area is 0.5 m 2 /g or more, the adhesion when the negative electrode material is applied to produce the negative electrode can be made sufficient, and the battery characteristics can be improved. Further, when the BET specific surface area is 100 m 2 /g or less, the proportion of cerium oxide produced by natural oxidation of the surface of the particles can be reduced. As a result, since the cerium oxide which does not contribute to the battery reaction can be reduced, it is possible to suppress the battery capacity from being lowered when used as a negative electrode material for a lithium ion secondary battery.
另外，在本發明所使用的基材粒子之上述「a%」係0.1%以上30%以下為理想。藉由將基材粒子，設為在體積基準分布的粒徑1μm以下之粒子之比例為0.1%以上30%以下者，而變為容易形成上述的2次粒子，有助於在負極的電阻之降低。 Further, the above "a%" of the substrate particles used in the present invention is preferably 0.1% or more and 30% or less. When the ratio of the particles having a particle diameter of 1 μm or less in the volume-based distribution is 0.1% or more and 30% or less, the above-mentioned secondary particles are easily formed, which contributes to the electric resistance of the negative electrode. reduce.
在本發明，如以上所述，在步驟B，於基材粒子之表面形成碳被膜而設為被覆粒子。此係為了於上述基材粒子賦予導電性，謀求電池特性提高。在本發明，於基材粒子之表面形成碳被膜為必需，但在進行此碳被覆，同時與石墨等之有導電性的粒子混合亦佳。作為於基材粒子之表面形成碳被膜的方法，其係藉由化學氣相沈積(CVD)而進行的方法為合適。 In the present invention, as described above, in step B, a carbon film is formed on the surface of the substrate particles to be coated particles. In order to impart conductivity to the substrate particles, the battery characteristics are improved. In the present invention, it is necessary to form a carbon film on the surface of the substrate particles, but it is also preferable to mix the particles with conductivity such as graphite while performing the carbon coating. As a method of forming a carbon film on the surface of the substrate particles, a method by chemical vapor deposition (CVD) is suitable.
作為化學氣相沈積(CVD)之方法，例如可舉出對於基材粒子，在熱分解而可生成碳的有機物氣體環境中以600~1200℃之溫度範圍將碳進行化學氣相沈積而執行的方法。 As a method of chemical vapor deposition (CVD), for example, chemical vapor deposition of carbon on a substrate particle in a temperature range of 600 to 1200 ° C in an organic gas atmosphere capable of generating carbon by thermal decomposition is used. method.
此化學氣相沈積(CVD)，其係在常壓、減壓下都可適用，作為減壓下，係可舉出50~30,000Pa之減 壓下。另外，使用於碳被膜之成形步驟的裝置，其係可使用批次式爐、旋轉窯爐、輥道窯之連續爐，以及流動層等之一般周知的裝置。特別是，可進行攪拌同時連續而進行蒸鍍的旋轉窯爐，其係有效率，可更均勻地被覆碳，可謀求電池特性之提高。 This chemical vapor deposition (CVD) is applicable under normal pressure and reduced pressure. As a reduced pressure, it can be reduced by 50 to 30,000 Pa. Press down. Further, an apparatus for forming a carbon film may be a generally known apparatus such as a batch furnace, a rotary kiln, a continuous furnace of a roller kiln, and a fluidized bed. In particular, a rotary kiln that can be continuously vaporized while being stirred can be more efficiently coated with carbon and can improve battery characteristics.
於藉由化學氣相沈積所致的碳被膜之形成，可舉出如下述般的各式各樣的有機物作為該碳源，但熱分解溫度或蒸鍍速度、或是於蒸鍍後所形成的碳被膜之特性等係有依使用的物質而有大幅差異的情況。碳源係可依照設為目的的被覆粒子之物性而適宜變更。蒸鍍速度小的物質，其係因為容易將表面之碳被膜之均勻性設為充分，所以為理想。如為反面分解為在低溫進行的物質，則因為蒸鍍時之基材粒子中之矽結晶之成長被抑制，所以可抑制放電效率或循環特性之低下。 In the formation of a carbon film by chemical vapor deposition, various organic substances such as the following may be mentioned as the carbon source, but the thermal decomposition temperature, the vapor deposition rate, or the vapor deposition may be formed. The characteristics of the carbon film, etc., may vary greatly depending on the substance to be used. The carbon source can be appropriately changed depending on the physical properties of the coated particles for the purpose. A material having a small vapor deposition rate is preferable because it is easy to make the uniformity of the carbon film on the surface sufficient. When the material is decomposed into a low temperature, the growth of the ruthenium crystal in the substrate particles during vapor deposition is suppressed, so that the discharge efficiency or the cycle characteristics can be suppressed.
作為進行熱分解而可生成碳的有機物氣體之原料，可舉出甲烷、乙烷、乙烯、乙炔、丙烷、丙烯、丁烷、丁烯、戊烷、異丁烷、己烷、苯、甲苯、二甲苯、苯乙烯、乙基苯、二苯基甲烷、萘、酚、甲酚、硝基苯、氯苯、茚、香豆酮、吡啶、蒽、菲、焦油蒸餾步驟所得到的煤氣輕油、雜酚油、蒽油以及石腦油分解焦油等。此等係可適宜地選擇單獨1種或2種以上來使用。 Examples of the raw material of the organic gas which can generate carbon by thermal decomposition include methane, ethane, ethylene, acetylene, propane, propylene, butane, butene, pentane, isobutane, hexane, benzene, and toluene. Gas light oil obtained by distillation steps of xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, hydrazine, coumarone, pyridine, hydrazine, phenanthrene and tar , creosote oil, eucalyptus oil and naphtha decomposition tar. These may be used singly or in combination of two or more.
關於碳被膜之被覆量，其係相對於被覆粒子之質量，將含有於該被覆粒子的碳之質量之比例，設為0.5質量%以上40質量%以下為理想。此比例為1.0~30質 量%為較理想。雖然亦依被被覆的粒子，但以將碳被覆量設為0.5質量%以上，可維持大致上充分的導電性，可確實地達成作為無水電解質二次電池之負極時之循環性提高。另外，如碳被覆量為40質量%以下，則可得到以碳被覆所致的賦予導電性之效果，同時可抑制因於負極材料所佔的碳的比例變多所致的充放電容量之低下。 The amount of the carbon film to be coated is preferably 0.5% by mass or more and 40% by mass or less based on the mass of the coated particles. This ratio is 1.0~30 The amount % is ideal. In addition, the amount of carbon coating is 0.5% by mass or more, and substantially sufficient conductivity can be maintained, and the cycle property as a negative electrode of a nonaqueous electrolyte secondary battery can be reliably achieved. In addition, when the carbon coating amount is 40% by mass or less, the effect of imparting conductivity by carbon coating can be obtained, and the decrease in the charge/discharge capacity due to the increase in the proportion of carbon in the negative electrode material can be suppressed. .
本發明之負極材料係如上述，粒徑之規定為滿足a/b≧3之關係者。在未形成碳被覆的狀態之基材粒子之體積基準分布的粒徑1μm以下之粒子(微粉)，其係藉由被覆而形成以碳凝集的2次粒子。在藉由負極材料製作負極時，此2次粒子埋入大粒子之間隙而有助於負極(電極)之電阻降低。由此而有關於反覆充放電循環時之電容維持率提高。 The negative electrode material of the present invention is as described above, and the particle size is defined as a relationship satisfying a/b≧3. Particles (fine powder) having a particle diameter of 1 μm or less in a volume-based distribution of the substrate particles in a state in which no carbon coating is formed are formed by coating to form secondary particles agglomerated with carbon. When the negative electrode is made of a negative electrode material, the secondary particles are buried in the gap between the large particles to contribute to a decrease in the electric resistance of the negative electrode (electrode). As a result, the capacitance maintenance ratio at the time of the reverse charge/discharge cycle is improved.
另外，碳被膜之形成，其係以被覆粒子之雷射繞射法粒度分布測定裝置所測定的體積基準分布的累積50%徑(D50)，係成為1μm以上30μm以下的方式來進行理想。由此，在為了製作負極而塗布有負極材料時不傷及隔離膜，另外可將電極之導電性設為良好。 In addition, it is preferable that the carbon film is formed so that the cumulative 50% diameter (D 50 ) of the volume-based distribution measured by the laser diffraction particle size distribution measuring apparatus of the coated particles is 1 μm or more and 30 μm or less. Therefore, when the negative electrode material is applied to produce the negative electrode, the separator is not damaged, and the conductivity of the electrode can be made good.
在本發明，為了將基材粒子設為特定之粒徑分布以及粒徑範圍，其係可藉由粉碎或分級等之處理等而適宜調整。另外，為了將形成有碳被膜的被覆粒子設為特定之粒徑分布以及粒徑範圍，其係可藉由該被覆量等而適 宜調整。碳被膜之被覆量，其係除了基材粒子之物性以外，還相依於使用於CVD的碳源氣體或熱處理溫度、熱處理時間等。進行被覆時之條件與被覆量之關係係可在實驗上容易地求出。 In the present invention, in order to set the substrate particle to a specific particle size distribution and particle size range, it can be suitably adjusted by treatment such as pulverization or classification. Further, in order to set the particle size distribution and the particle size range of the coated particles on which the carbon film is formed, it is possible to apply the coating amount or the like. Should be adjusted. The coating amount of the carbon film depends on the physical properties of the substrate particles, and also depends on the carbon source gas used for CVD, the heat treatment temperature, the heat treatment time, and the like. The relationship between the conditions at the time of coating and the amount of coating can be easily obtained experimentally.
於粒子之粉碎係可使用一般周知之裝置。例如可使用於以下所例示的裝置。首先，可例示使球、珠粒等之粉碎媒體運動，利用該運動能量所生的衝擊力或摩擦力、壓縮力而粉碎被碎物的球磨機、媒體攪拌研磨機。另外，可例示利用由輥所生的壓縮力而進行粉碎的輥磨機。另外，可例示將被碎物以高速衝撞內襯材料或是使粒子相互衝撞，藉由因該衝擊的衝擊力而進行粉碎的噴射磨機。另外，可例示利用固定設置錘、葉片、銷等的轉子之旋轉所致的衝擊力而粉碎被碎物的錘磨機、柱式粉碎機、圓盤粉碎機。另外，可例示利用剪切力的膠體研磨機。另外，可例示高壓濕式對向衝撞式分散機「Ultimaizer」。粉碎係濕式、乾式均可使用。 For the pulverization of the particles, a generally known device can be used. For example, it can be used for the device exemplified below. First, a ball mill or a media agitating mill that pulverizes a crushed medium such as a ball or a bead and pulverizes the scraped material by an impact force, a frictional force, or a compressive force generated by the kinetic energy can be exemplified. Further, a roll mill that pulverizes by a compressive force generated by a roll can be exemplified. Further, a jet mill that pulverizes the scraped material at a high speed against the lining material or causes the particles to collide with each other and is pulverized by the impact force of the impact can be exemplified. In addition, a hammer mill, a column pulverizer, and a disc pulverizer that pulverize the scraped object by an impact force by a rotation of a rotor such as a hammer, a blade, or a pin are fixed. Further, a colloid mill using shearing force can be exemplified. Further, a high pressure wet type collision type disperser "Ultimaizer" can be exemplified. The pulverizing system can be used in both wet and dry forms.
而且，為了於粉碎後整理粒度分布，可使用乾式分級、濕式分級、以及篩選分級等。乾式分級，主要是使用氣流，逐次或同時進行分散、分離(細粒子與粗粒子之分離)、捕集(固體與氣體之分離)、排出之製程。另外，為了不因粒子相互間之干涉、粒子之形狀、氣流之流動之紊亂、速度分布、靜電之影響等使分級效率下降，所以在進行分級之前進行前處理(水分、分散性、濕度等之調整)、調整所使用的氣流之水分或氧氣濃度而使用。 另外，在旋風器等之乾式而與分級機成為一體的形式中，其係成為可同時進行粉碎、分級，成為希望的粒度分布。 Moreover, in order to defragment the particle size distribution, dry classification, wet classification, and screening classification may be used. Dry grading is mainly carried out by using air flow, dispersion or separation (separation of fine particles and coarse particles), collection (separation of solid and gas), and discharge. Further, in order to prevent the classification efficiency from being lowered by the interference of the particles, the shape of the particles, the disturbance of the flow of the gas flow, the velocity distribution, and the influence of static electricity, the pretreatment (water, dispersibility, humidity, etc.) is performed before the classification. Adjust) and adjust the moisture or oxygen concentration of the airflow used. Further, in a form in which the cyclone or the like is dry and integrated with the classifier, it is possible to simultaneously pulverize and classify, and to achieve a desired particle size distribution.
本發明係可將上述被覆粒子使用於鋰離子二次電池用負極材料(活性物質)者，使用以本發明所得的鋰離子二次電池用負極材料，製作負極，可製造鋰離子二次電池。 In the present invention, the negative electrode material (active material) for a lithium ion secondary battery can be used, and a negative electrode material for a lithium ion secondary battery obtained by the present invention can be used to produce a negative electrode, thereby producing a lithium ion secondary battery.
在使用上述鋰離子二次電池用負極材料而製作負極的情況，可更添加碳或石墨等之導電劑。在此情況中亦不特別限定導電劑之種類，在所構成的電池中，如為不產生分解或變質的電子傳導性之材料即可。具體而言，可使用Al、Ti、Fe、Ni、Cu、Zn、Ag、Sn、Si等之金屬粒子或金屬纖維或天然石墨、人造石墨、各種焦炭粒子、中間相碳、氣相沉積碳纖維、瀝青系碳纖維、PAN系碳纖維、各種樹脂燒結體等之石墨。 When a negative electrode is produced using the negative electrode material for a lithium ion secondary battery, a conductive agent such as carbon or graphite may be further added. In this case, the type of the conductive agent is not particularly limited, and the battery to be formed may be a material that does not cause decomposition or deterioration of electron conductivity. Specifically, metal particles or metal fibers of Al, Ti, Fe, Ni, Cu, Zn, Ag, Sn, Si, or the like, or natural graphite, artificial graphite, various coke particles, mesophase carbon, vapor deposited carbon fiber, or the like may be used. Graphite such as pitch-based carbon fiber, PAN-based carbon fiber, and various resin sintered bodies.
作為負極(成型體)之調製方法，作為一例可舉出如下述的方法。 The method of preparing the negative electrode (molded body) is exemplified by the following method.
首先，於上述之負極材料、與按照必要而於導電劑、和聚醯亞胺樹脂等之黏合劑等之其他添加劑，混練N-甲基吡咯啶酮或水等之溶劑而設為糊狀之混合劑。將此混合劑塗布於集電體之薄片。此情況，作為集電體係銅箔、鎳箔等，通常如作為負極之集電體使用的材料，則可不特別限制厚度、表面處理而使用。尚，將混合劑成形 為薄片狀的形成方法係不特別限定，可使用一般周知之方法。 First, a solvent such as N-methylpyrrolidone or water is kneaded in the above-mentioned negative electrode material and other additives such as a conductive agent and a binder such as a polyimide resin, and the paste is formed. Mixture. This mixture was applied to a sheet of a current collector. In this case, as a material for the current collector copper foil, nickel foil, or the like, which is generally used as a current collector of the negative electrode, the thickness and surface treatment can be used without particular limitation. Still, forming the mixture The method for forming the sheet form is not particularly limited, and a generally known method can be used.
本發明之鋰離子二次電池，其係使用有上述之鋰離子二次電池用負極的鋰離子二次電池。除了負極之外，至少具有正極、與鋰離子導電性之非水電解質。本發明之鋰離子二次電池，其係在由使用有以上述被覆粒子所構成的負極材料的負極所形成之點上有特徵，此外之正極、電解質、隔離膜等之材料以及電池形狀等係可使用一般周知者，不特別限定。如上述，本發明之負極材料，其係在作為鋰離子二次電池用之負極材料使用的情況之電池特性(充放電容量以及循環特性)為良好，特別是循環耐久性優異。 The lithium ion secondary battery of the present invention is a lithium ion secondary battery using the above-described negative electrode for a lithium ion secondary battery. A non-aqueous electrolyte having at least a positive electrode and lithium ion conductivity in addition to the negative electrode. The lithium ion secondary battery of the present invention is characterized in that it is formed of a negative electrode using a negative electrode material composed of the coated particles, and a material such as a positive electrode, an electrolyte, a separator, and a battery shape. A general person can be used, and it is not particularly limited. As described above, the negative electrode material of the present invention is excellent in battery characteristics (charge and discharge capacity and cycle characteristics) when used as a negative electrode material for a lithium ion secondary battery, and is particularly excellent in cycle durability.
作為正極活性物質，可使用LiCoO2、LiNiO2、LiMn2O4、V2O5、MnO2、TiS2、MoS2等之過渡金屬之氧化物、鋰以及硫屬化合物等之一般周知者。 As the positive electrode active material, generally known ones of oxides of transition metals such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , V 2 O 5 , MnO 2 , TiS 2 , and MoS 2 , lithium, and chalcogen compounds can be used.
作為電解質，例如可使用含有六氟化磷酸鋰、過氯酸鋰等之鋰鹽的非水溶液。作為非水溶媒係可使用丙烯碳酸酯、碳酸伸乙酯、碳酸二乙酯、二甲氧基乙烷、γ-丁內酯、2-甲基四氫呋喃等之1種或組合2種以上而使用。另外，亦可使用此外之各式各樣之非水系電解質或固體電解質。 As the electrolyte, for example, a nonaqueous solution containing a lithium salt such as lithium hexafluorophosphate or lithium perchlorate can be used. As the non-aqueous solvent, one or a combination of two or more of propylene carbonate, ethyl carbonate, diethyl carbonate, dimethoxyethane, γ-butyrolactone, and 2-methyltetrahydrofuran can be used. . Further, various other nonaqueous electrolytes or solid electrolytes may be used.
以下，表示實施例及試驗例而更具體地說明本發明，但本發明係不受限於下述之實施例。 Hereinafter, the present invention will be more specifically described by showing examples and test examples, but the present invention is not limited to the examples described below.
將以顎式破碎機(前川工業所製)粒碎的SiOx(x=1.0)，將直徑10mm之氧化鋁球作為媒體而以球磨機(MAKINO製)粉碎80分鐘。將此粒子作為基材粒子(步驟A)。將此基材粒子用雷射繞射法粒度分布測定裝置(島津製作所SALD-3100)以折射率3.90-0.01i之條件測定時，在體積基準分布的D50(累積50%徑)為4.6μm、累積1μm(粒徑1μm以下之粒子之比例)為14.8%(也就是，a=14.8)。基材粒子之粒度分布圖係表示於第1圖。 An alumina ball having a diameter of 10 mm was pulverized by a ball mill (manufactured by MAKINO) for 80 minutes using SiO x (x = 1.0) crushed by a jaw crusher (manufactured by Hosei Industry Co., Ltd.) as a medium. This particle was used as a substrate particle (step A). When the substrate particles were measured by a laser diffraction particle size distribution measuring apparatus (Shimadzu Corporation SALD-3100) under the conditions of a refractive index of 3.90 to 0.01 μ, the D 50 (accumulated 50% diameter) in the volume-based distribution was 4.6 μm. The cumulative 1 μm (ratio of particles having a particle diameter of 1 μm or less) was 14.8% (that is, a=14.8). The particle size distribution map of the substrate particles is shown in Fig. 1.
將此基材粒子100g以粉體層厚度成為10mm的方式舖設於托盤上，裝入批次式加熱爐內。然後以油旋轉式真空幫浦一邊將爐內減壓，同時以200℃/hr之昇溫速度將爐內昇溫至1,000℃。然後到達1,000℃後，於爐內將甲烷以0.3L/min通氣，進行10小時之碳被覆處理(步驟B)。甲烷停止後，將爐內降溫、冷卻，得到106g之黑色粒子。 100 g of the substrate particles were placed on a tray so that the thickness of the powder layer became 10 mm, and the mixture was placed in a batch type heating furnace. Then, the inside of the furnace was decompressed with an oil rotary vacuum pump while the temperature in the furnace was raised to 1,000 ° C at a heating rate of 200 ° C / hr. Then, after reaching 1,000 ° C, methane was ventilated at 0.3 L/min in a furnace, and carbon coating treatment was carried out for 10 hours (step B). After the methane was stopped, the inside of the furnace was cooled and cooled to obtain 106 g of black particles.
所得到的黑色粒子係相對於黑色粒子的碳被覆量4.8質量%之導電性粒子。另外，將此粒子之粒度分布與上述同樣地進行測定時，在體積基準分布的D50係 5.3μm，累積1μm(粒徑1μm以下之粒子之比例)為2.6%(也就是，b=2.6)。此被覆粒子之粒度分布圖係表示於第2圖。 The obtained black particles were conductive particles having a carbon coating amount of 4.8% by mass with respect to the black particles. Further, when the particle size distribution of the particles was measured in the same manner as described above, the D 50 of the volume-based distribution was 5.3 μm, and the cumulative 1 μm (the ratio of the particles having a particle diameter of 1 μm or less) was 2.6% (that is, b = 2.6). . The particle size distribution map of the coated particles is shown in Fig. 2.
接著，用以下之方法，將所得到的被覆粒子作為負極活性物質來使用而進行電池評估。首先，將所得到的負極材料45質量%和人造石墨(平均粒徑10μm)45質量%、聚醯亞胺10質量%混合，更進一步加入N-甲基吡咯啶酮而作為漿液。將此漿液塗布於厚度12μm之銅箔，以80℃1小時乾燥後，藉由輥壓而加壓成形電極，將此電極以350℃ 1小時進行真空乾燥。之後沖裁至2cm2，作為負極。 Next, the obtained coated particles were used as a negative electrode active material by the following method to carry out battery evaluation. First, 45 mass% of the obtained negative electrode material, 45 mass% of artificial graphite (average particle diameter: 10 micrometer), 10 mass% of polyimine, and N-methyl pyrrolidone are further added as a slurry. This slurry was applied to a copper foil having a thickness of 12 μm, dried at 80 ° C for 1 hour, and then the electrode was pressed by rolling, and the electrode was vacuum dried at 350 ° C for 1 hour. Then punched to 2 cm 2 as a negative electrode.
然後，為了評估所得到的負極之充放電特性，製作於對極使用鋰箔，作為非水電解質使用將六氟化磷酸鋰於碳酸伸乙酯和碳酸二乙酯之1/1(體積比)混合液以1mole/L之濃度溶解的非水電解質溶液，於隔離膜使用厚度30μm之聚乙烯製微多孔質薄膜的評估用鋰離子二次電池。 Then, in order to evaluate the charge and discharge characteristics of the obtained negative electrode, a lithium foil was used for the counter electrode, and 1/1 (volume ratio) of lithium hexafluorophosphate to ethyl carbonate and diethyl carbonate was used as the nonaqueous electrolyte. A nonaqueous electrolyte solution in which the mixed solution was dissolved at a concentration of 1 mole/L, and a lithium ion secondary battery for evaluation of a polyethylene microporous film having a thickness of 30 μm was used as the separator.
將所製作的鋰離子二次電池，以室溫放置一晚後，使用二次電池充放電試驗裝置(NAGANO公司製)，直到測試單元之電壓到達0V以0.5mA/cm2之定電流進行充電，在到達0V之後，以單元電壓保持在0V的方式使電流減少而進行充電。然後，在電流值低於 40μA/cm2時點使充電結束。然後，放電係以0.5mA/cm2之定電流進行，在單元電壓達到1.4V的時點結束放電，求出放電容量。 After the prepared lithium ion secondary battery was allowed to stand at room temperature for one night, a secondary battery charge and discharge tester (manufactured by NAGANO Co., Ltd.) was used until the voltage of the test cell reached 0 V and charged at a constant current of 0.5 mA/cm 2 . After reaching 0V, the current is reduced and the battery is charged so that the cell voltage is maintained at 0V. Then, the charging is ended when the current value is lower than 40 μA/cm 2 . Then, the discharge was performed at a constant current of 0.5 mA/cm 2 , and the discharge was terminated when the cell voltage reached 1.4 V, and the discharge capacity was determined.
重覆以上充放電試驗，進行評估用鋰離子二次電池之50次循環後之充放電試驗。將該結果表示於表1。可確認為初次放電容量1781mAh/g、50次循環後之循環保持率94%之高容量而且以及循環性優異的鋰離子二次電池。 The above charge and discharge test was repeated, and a charge and discharge test after 50 cycles of the lithium ion secondary battery for evaluation was performed. The results are shown in Table 1. It was confirmed that the initial discharge capacity was 1781 mAh/g, the cycle retention rate after 50 cycles was 94%, and the lithium ion secondary battery excellent in cycle property was obtained.
將與實施例1相同的SiOx(x=1.0)粉碎品(基材粒子)100g，與實施例1同樣地裝入批次式加熱爐內。然後以油旋轉式真空幫浦一邊將爐內減壓，同時以200℃/hr之昇溫速度將爐內昇溫至1,100℃。然後到達1,100℃後，於爐內將甲烷以0.3L/min通氣，進行16小時之碳被覆處理。在甲烷停止後，將爐內降溫、冷卻。 100 g of the SiO x (x = 1.0) pulverized product (base material particle) similar to that of Example 1 was placed in a batch type heating furnace in the same manner as in Example 1. Then, the inside of the furnace was decompressed with an oil rotary vacuum pump while the temperature was raised to 1,100 ° C at a heating rate of 200 ° C / hr. Then, after reaching 1,100 ° C, methane was ventilated at 0.3 L/min in a furnace for 16 hours of carbon coating treatment. After the methane is stopped, the furnace is cooled and cooled.
所得到的黑色粒子係相對於黑色粒子的碳被覆量21.3質量%之導電性粒子。此粒子之粒度分布係D50為5.8μm，累積1μm(粒徑1μm以下之粒子之比例)為0.3%(也就是，b=0.3)。此被覆粒子之粒度分布圖係表示於第3圖。 The obtained black particles were conductive particles having a carbon coating amount of 21.3% by mass with respect to the black particles. This particle size D 50 of the distribution system 5.8μm, cumulative 1 m (ratio of particle diameter of 1 m or less) 0.3% (i.e., b = 0.3). The particle size distribution map of the coated particles is shown in Fig. 3.
將與實施例1相同的SiOx(x=1.0)粉碎品(基材粒 子)，在使其傾斜至1°而使窯爐內部昇溫至1000℃的旋轉窯爐，從入口側供給2kg/hr，從出口側通氣有以氮氣稀釋至16體積%的甲烷。窯爐之旋轉數係設為1rpm。由投入開始6小時後，從出口側得到被覆量3.5質量%之導電性粒子。此粒子之粒度分布係D50為5.2μm，累積1μm(粒徑1μm以下之粒子之比例)為3.7%(也就是，b=3.7)。此被覆粒子之粒度分布圖係表示於第4圖。 The SiO x (x = 1.0) pulverized product (substrate particles) which was the same as in Example 1 was heated to 1000 ° C in a kiln at a temperature of 1 °, and the inside of the kiln was supplied with 2 kg / hr from the inlet side. From the outlet side, methane was diluted with nitrogen to 16% by volume. The number of revolutions of the kiln was set to 1 rpm. Six hours after the start of the introduction, the conductive particles having a coating amount of 3.5% by mass were obtained from the outlet side. This particle size D 50 of the distribution system 5.2μm, cumulative 1 m (ratio of particle diameter of 1 m or less) of 3.7% (i.e., b = 3.7). The particle size distribution map of the coated particles is shown in Fig. 4.
將與實施例1相同的SiOx(x=1.0)粉碎品(基材粒子)，在使其傾斜至1°而使窯爐內部昇溫至1000℃的旋轉窯爐，從入口側供給2.8kg/hr，從出口側通氣有以氮氣稀釋至16體積%的甲烷。窯爐之旋轉數係設為1rpm。由投入開始6小時後，從出口側得到被覆量2.6質量%之導電性粒子。此粒子之粒度分布係D50為4.4μm，累積1μm(粒徑1μm以下之粒子之比例)為4.9%(也就是，b=4.9)。此被覆粒子之粒度分布圖係表示於第5圖。 The SiO x (x = 1.0) pulverized product (substrate particles) which was the same as in Example 1 was heated to 1000 ° C in a kiln at a temperature of 1 °, and the kiln was supplied at a rate of 2.8 kg / from the inlet side. Hr, ventilated from the outlet side with methane diluted to 16 vol% with nitrogen. The number of revolutions of the kiln was set to 1 rpm. Six hours after the start of the introduction, the conductive particles having a coating amount of 2.6% by mass were obtained from the outlet side. This particle size D 50 of the distribution system 4.4μm, cumulative 1 m (ratio of particle diameter of 1 m or less) 4.9% (i.e., b = 4.9). The particle size distribution map of the coated particles is shown in Fig. 5.
將與實施例1相同的SiOx(x=1.0)粉碎品(基材粒子)100g，同樣地裝入批次式加熱爐內。然後以油旋轉式真空幫浦一邊將爐內減壓，同時以200℃/hr之昇溫速度將爐內昇溫至1,000℃。然後到達1,000℃後，於爐內將甲烷以0.1L/min通氣，進行2小時之碳被覆處理。甲烷停 止後，將爐內降溫、冷卻，得到127g之黑色粒子。 100 g of the SiO x (x = 1.0) pulverized product (base material particle) similar to that of Example 1 was placed in a batch type heating furnace in the same manner. Then, the inside of the furnace was decompressed with an oil rotary vacuum pump while the temperature in the furnace was raised to 1,000 ° C at a heating rate of 200 ° C / hr. After reaching 1,000 ° C, methane was ventilated at 0.1 L/min in a furnace for 2 hours of carbon coating treatment. After the methane was stopped, the inside of the furnace was cooled and cooled to obtain 127 g of black particles.
所得到的黑色粒子係相對於黑色粒子的碳被覆量0.3質量%之導電性粒子。此粒子之粒度分布係D50為4.8μm，累積1μm(粒徑1μm以下之粒子之比例)為11.4%(也就是，b=11.4)。此被覆粒子之粒度分布圖係表示於第6圖。 The obtained black particles were conductive particles having a carbon coating amount of 0.3% by mass based on the black particles. This particle size D 50 of the distribution system 4.8μm, cumulative 1 m (ratio of particle diameter of 1 m or less) was 11.4% (i.e., b = 11.4). The particle size distribution map of the coated particles is shown in Fig. 6.
將與實施例1相同的SiOx(x=1.0)粉碎品，用氣流式分級機(日清工程公司製TC-15)以風量2.5Nm3/min、轉子旋轉數10,000rpm之條件進行分級。以分級機下所回收的粗粉側之粒子之D50係6.1μm，累積1μm(粒徑1μm以下之粒子之比例)為1.0%(也就是，a=1.0)。將此粉末設為在比較例2的基材粒子(進行碳被覆的對象之粒子)。此基材粒子之粒度分布圖係表示於第7圖。對於此基材粒子，與實施例1同樣地進行碳被覆處理。所得的粒子係碳被覆量4.2質量%、D50為6.2μm，累積1μm(粒徑1μm以下之粒子之比例)為0.7%(也就是，b=0.7)。此被覆粒子之粒度分布圖係表示於第8圖。 The SiO x (x=1.0) pulverized product which was the same as in Example 1 was classified by a gas flow classifier (TC-15 manufactured by Nissin Engineering Co., Ltd.) under the conditions of an air volume of 2.5 Nm 3 /min and a rotor rotation number of 10,000 rpm. The D 50 of the particles on the coarse powder side recovered under the classifier was 6.1 μm, and the cumulative 1 μm (the ratio of the particles having a particle diameter of 1 μm or less) was 1.0% (that is, a = 1.0). This powder was used as the substrate particles of Comparative Example 2 (particles to be carbon-coated). The particle size distribution map of this substrate particle is shown in Fig. 7. The carbon coating treatment was carried out in the same manner as in Example 1 on the substrate particles. The obtained particle-based carbon coating amount was 4.2% by mass, D 50 was 6.2 μm, and the cumulative 1 μm (ratio of particles having a particle diameter of 1 μm or less) was 0.7% (that is, b=0.7). The particle size distribution map of the coated particles is shown in Fig. 8.
關於以實施例2~4、比較例1、2所得到的粒子，與實施例1同樣地進行電池評估。 With respect to the particles obtained in Examples 2 to 4 and Comparative Examples 1 and 2, battery evaluation was performed in the same manner as in Example 1.
將實施例1~4、比較例1、2之粒度以及電池特性之一覽表表示於表1。 Tables 1 of the particle sizes and battery characteristics of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1.
實施例1~4之負極材料係可確認相較於比較例1、2之負極材料為明顯的電池特性優異的鋰離子二次電池。 In the negative electrode materials of Examples 1 to 4, lithium ion secondary batteries having excellent battery characteristics as compared with the negative electrode materials of Comparative Examples 1 and 2 were confirmed.
尚，本發明係不被限定於上述實施形態。上述實施形態為例示，任何具有與記載於本發明之專利申請範圍的技術上的思想和實質上同一的構成，顯現出同樣的作用效果者，均包含於本發明之技術上的範圍。 Further, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and any ones having substantially the same effects as those of the technical scope described in the patent application of the present invention are included in the technical scope of the present invention.
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