TWI528620B - Negative electrode material for lithium-ion secondary battery and method of producing the same, negative electrode for lithium-ion secondary battery using negative electrode material for lithium-ion secondary battery, and lithium-ion secondary battery - Google Patents

Negative electrode material for lithium-ion secondary battery and method of producing the same, negative electrode for lithium-ion secondary battery using negative electrode material for lithium-ion secondary battery, and lithium-ion secondary battery Download PDF

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TWI528620B
TWI528620B TW102123713A TW102123713A TWI528620B TW I528620 B TWI528620 B TW I528620B TW 102123713 A TW102123713 A TW 102123713A TW 102123713 A TW102123713 A TW 102123713A TW I528620 B TWI528620 B TW I528620B
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negative electrode
secondary battery
ion secondary
composite
lithium
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TW201407864A (en
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時田智
間所靖
江口邦彦
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杰富意化學股份有限公司
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • 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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Description

鋰離子二次電池用負極材料及其製造方法、及使用此鋰離子 二次電池用負極材料的鋰離子二次電池用負極、以及鋰離子二次電池 Anode material for lithium ion secondary battery, method for producing the same, and use of the lithium ion Negative electrode for lithium ion secondary battery of negative electrode material for secondary battery, and lithium ion secondary battery

本發明是有關於一種包含鱗片狀石墨粒子(flake graphite)、煅燒碳(baked carbon)、及可與鋰合金化的金屬粒子的鋰離子二次電池用負極材料用複合粒子(composite particle)及其製造方法、及使用此鋰離子二次電池用負極材料用複合粒子的鋰離子二次電池用負極、以及使用該負極的鋰離子二次電池。 The present invention relates to a composite particle for a negative electrode material for a lithium ion secondary battery comprising flaky graphite particles, baked carbon, and metal particles which can be alloyed with lithium and A production method, a negative electrode for a lithium ion secondary battery using the composite particles for a negative electrode material for a lithium ion secondary battery, and a lithium ion secondary battery using the negative electrode.

與其他二次電池相比，鋰離子二次電池具有高電壓、高能量密度的優異特性，故而作為電子機器的電源而得到廣泛普及。近年來，電子機器的小型化及高性能化不斷推進，對鋰離子二次電池的進一步的高能量密度化的要求越來越高。 Compared with other secondary batteries, lithium ion secondary batteries have excellent characteristics of high voltage and high energy density, and thus are widely used as power sources for electronic equipment. In recent years, miniaturization and high performance of electronic devices have been progressing, and there is an increasing demand for further high energy density of lithium ion secondary batteries.

目前，鋰離子二次電池通常為對正極使用LiCoO2、對負極使用石墨的二次電池。然而，石墨負極雖充放電的可逆性優異，但 其放電電容(discharge capacitance)已達到接近於與層間化合物(intercalation compound)LiC6相當的理論值372mAh/g的值，為了達成進一步的高能量密度化，必須開發一種放電電容大於石墨的負極材料。 At present, a lithium ion secondary battery is generally a secondary battery using LiCoO 2 for a positive electrode and graphite for a negative electrode. However, the graphite negative electrode has excellent reversibility of charge and discharge, but its discharge capacitance has reached a value close to the theoretical value of 372 mAh/g equivalent to the intercalation compound LiC 6 in order to achieve further high energy density. It is necessary to develop a negative electrode material having a discharge capacity larger than that of graphite.

金屬鋰作為負極材料而具有最高的放電電容，但於充電時鋰呈樹枝狀結晶狀地析出而使負極劣化，從而有充放電循環變短的問題。另外，亦有呈樹枝狀結晶狀地析出的鋰貫通分隔構件到達正極而發生短路的可能性。 Metal lithium has the highest discharge capacity as a negative electrode material, but lithium is precipitated in a dendritic crystal during charging to deteriorate the negative electrode, which causes a problem that the charge and discharge cycle becomes short. Further, there is a possibility that lithium which is precipitated in a dendritic crystal penetrates the separator to reach the positive electrode and is short-circuited.

因此，作為代替金屬鋰的負極材料，研究了與鋰形成合金的金屬質物(metallic materials)。該等合金負極具有雖不及金屬鋰但遠超過石墨的放電電容。然而，會因伴隨合金化的體積膨脹而產生活性物質的粉化、剝離，從而尚未獲得實用水準的循環特性。 Therefore, as a negative electrode material instead of metallic lithium, metallic materials which form an alloy with lithium have been studied. These alloy negative electrodes have a discharge capacitance that is not as good as metallic lithium but far exceeds graphite. However, powdering or peeling of the active material occurs due to volume expansion accompanying alloying, and thus practical cycle characteristics have not yet been obtained.

為了改善如上所述的合金負極的缺點，而對金屬質物、與石墨質物(graphite material)或碳質物(carbon material)的任一者或兩者的複合化進行了研究。大致可區分為：(1)於將金屬質物、石墨質物、碳質物前驅物混合後進行熱處理者(專利文獻1)；(2)使用化學氣相沈積(Chemical Vapor Deposition，CVD)法，將碳質層被覆於金屬質物上者(專利文獻2)；(3)對上述(2)併用機械合金化者(專利文獻3)等。然而現狀為：於上述(1)~(3)的任一者中，均僅於金屬質物的周圍配置石墨質物或碳質物，從而無法充分緩和充電時的金屬質物的膨脹，故而未能解決活性物質的微粉化或剝離的問題，從而未能獲得實用水準的循環特性。 In order to improve the disadvantages of the alloy negative electrode as described above, a combination of a metal substance, a graphite material or a carbon material, or both, has been studied. It can be roughly divided into: (1) heat treatment after mixing metal materials, graphite materials, and carbonaceous precursors (Patent Document 1); (2) Carbon deposition using Chemical Vapor Deposition (CVD) method The material layer is coated with a metal material (Patent Document 2); (3) The above-mentioned (2) is used in combination with a mechanical alloying (Patent Document 3). However, in any of the above (1) to (3), the graphite material or the carbonaceous material is disposed only around the metal material, and the expansion of the metal material during charging cannot be sufficiently alleviated, so that the activity cannot be solved. The problem of micronization or peeling of the substance does not result in a practical level of cycle characteristics.

於專利文獻4中，記載有一種金屬-石墨質系粒子的製 造方法，其是於平均粒徑為2~5μm、縱橫比為3以下的石墨質粒子表面，對平均粒徑為該石墨質粒子的平均粒徑的1/2以下的可與鋰合金化的金屬粒子進行機械化學處理並使該可與鋰合金化的金屬粒子附著後，以樹脂等對該機械化學處理物進行造粒(例如噴霧乾燥)，使該造粒物中含浸碳質前驅物，並於600℃以上進行熱處理，從而製造金屬-石墨質系粒子。 Patent Document 4 describes the production of a metal-graphite-based particle. a method for producing a graphite particle having an average particle diameter of 2 to 5 μm and an aspect ratio of 3 or less, and alloying with lithium having an average particle diameter of 1/2 or less of an average particle diameter of the graphite particle. After the metal particles are mechanochemically treated and adhered to the metal particles which are alloyed with lithium, the mechanochemically treated material is granulated (for example, spray-dried) with a resin or the like to impregnate the granulated product with a carbonaceous precursor. Further, heat treatment is performed at 600 ° C or higher to produce metal-graphite-based particles.

先前技術文獻 Prior technical literature

專利文獻 Patent literature

專利文獻1：日本專利特開2002-231225號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-231225

專利文獻2：日本專利特開2002-151066號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-151066

專利文獻3：日本專利特開2002-216751號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2002-216751

專利文獻4：日本專利特開2006-294476號公報 Patent Document 4: Japanese Patent Laid-Open Publication No. 2006-294476

本發明是鑒於如上所述的狀況而完成。發明了如下：藉由將負極材料設為特定的構造，從而即便作為金屬質物的例如Si反覆膨脹、收縮亦可防止循環特性的降低。本發明的目的在於提供一種負極材料，使用該負極材料作為鋰離子二次電池負極材料，可充分緩和充電時的金屬質物的膨脹，且顯示超過石墨的理論電容的較高的放電電容、與優異的初始充放電效率及循環特性。另外，本發明的目的在於提供一種使用所獲得的負極材料而成的鋰離子二次電池用負極、及使用該二次電池用負極的鋰離子二次電池。 The present invention has been made in view of the circumstances as described above. In the invention, the negative electrode material has a specific structure, and even if, for example, Si which is a metal material re-expands and contracts, it is possible to prevent a decrease in cycle characteristics. An object of the present invention is to provide a negative electrode material which can be used as a negative electrode material for a lithium ion secondary battery, which can sufficiently alleviate the expansion of the metal material during charging, and exhibits a high discharge capacity exceeding the theoretical capacitance of graphite, and is excellent. Initial charge and discharge efficiency and cycle characteristics. Moreover, an object of the present invention is to provide a negative electrode for a lithium ion secondary battery using the obtained negative electrode material, and a lithium ion secondary battery using the negative electrode for a secondary battery.

為了解決上述課題，本發明提供一種負極材料，其是包 含鱗片狀石墨粒子、及可與鋰合金化的金屬粒子的球狀或大致球狀的複合體，且上述複合體至少於內部具有空隙，上述鱗片狀石墨粒子非平行地存在於上述複合體的內部，並呈同心圓狀地配向存在於上述複合體的表面，且上述金屬粒子分散存在於該複合體粒子內。 In order to solve the above problems, the present invention provides a negative electrode material which is a package a spherical or substantially spherical composite of scaly graphite particles and metal particles that can be alloyed with lithium, and the composite has at least a void therein, and the flaky graphite particles are present in the composite in a non-parallel manner. The inside is concentrically arranged on the surface of the composite, and the metal particles are dispersed in the composite particles.

即，本發明提供以下。 That is, the present invention provides the following.

(1)一種鋰離子二次電池用負極材料，其是包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀的複合體，其特徵在於：上述複合體於內部具有空隙，且上述鱗片狀石墨粒子非平行地存在於上述複合體的內部，並呈同心圓狀地配向存在於上述複合體的表面，且上述金屬粒子分散存在於上述複合體粒子內部及/或表面。 (1) A negative electrode material for a lithium ion secondary battery, which is a spherical composite body comprising flaky graphite particles, calcined carbon, and metal particles which can be alloyed with lithium, wherein the composite body has voids therein The flaky graphite particles are present in the inside of the composite in a non-parallel manner, and are present in a concentric shape on the surface of the composite, and the metal particles are dispersed in the inside and/or the surface of the composite particles.

(2)如(1)所述之鋰離子二次電池用負極材料，其中將上述複合體設為100質量%，上述鱗片狀石墨粒子：98~60質量%、上述煅燒碳：1~20質量%、及上述金屬粒子：1~20質量%。 (2) The negative electrode material for a lithium ion secondary battery according to the above aspect, wherein the composite is 100% by mass, the flaky graphite particles are 98 to 60% by mass, and the calcined carbon is 1 to 20% by mass. %, and the above metal particles: 1 to 20% by mass.

(3)如(1)所述之鋰離子二次電池用負極材料，其中上述複合體中更包含石墨質纖維。 (3) The negative electrode material for a lithium ion secondary battery according to (1), wherein the composite further comprises a graphite fiber.

(4)如(3)所述之鋰離子二次電池用負極材料，其中將上述複合體設為100質量%，上述鱗片狀石墨粒子：97.5~55質量%、上述煅燒碳：1~20質量%、上述金屬粒子：1~20質量%、及上述石墨質纖維：0.5~5質量%。 (4) The negative electrode material for a lithium ion secondary battery according to the above aspect, wherein the composite is 100% by mass, the flaky graphite particles are 97.5 to 55 mass%, and the calcined carbon is 1 to 20 mass. %, the above metal particles: 1 to 20% by mass, and the above-mentioned graphite fibers: 0.5 to 5% by mass.

(5)如(1)至(4)中任一項所述之鋰離子二次電池用負極材料，其中上述鱗片狀石墨粒子的平均扁平度(Ly/t)為0.5~40。 (5) The negative electrode material for a lithium ion secondary battery according to any one of (1) to (4), wherein the flaky graphite particles have an average flatness (Ly/t) of 0.5 to 40.

(6)一種鋰離子二次電池用負極，其含有如上述(1)至(5) 中任一項所述之鋰離子二次電池用負極材料。 (6) A negative electrode for a lithium ion secondary battery, which contains the above (1) to (5) A negative electrode material for a lithium ion secondary battery according to any one of the preceding claims.

(7)一種鋰離子二次電池，其包含如上述(6)所述之鋰離子二次電池用負極。 (7) A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to (6) above.

(8)一種鋰離子二次電池用負極材料的製造方法，其是包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀的複合體的製造方法，其特徵在於：使上述鱗片狀石墨粒子及上述金屬粒子分散於作為碳質材料及/或碳質材料的前驅物結著劑的溶液中，進行噴霧乾燥處理後，於700℃以上、1500℃以下的溫度範圍內進行熱處理，使上述碳質材料及碳質材料的前驅物成為煅燒碳，其後不經過粉碎步驟而製成最終製品。 (8) A method for producing a negative electrode material for a lithium ion secondary battery, which is a method for producing a spherical composite comprising flaky graphite particles, calcined carbon, and metal particles capable of alloying with lithium, characterized in that The flaky graphite particles and the metal particles are dispersed in a solution of a precursor of a carbonaceous material and/or a carbonaceous material, and are spray-dried and then subjected to a temperature range of 700 ° C to 1500 ° C. The heat treatment is such that the precursor of the carbonaceous material and the carbonaceous material becomes calcined carbon, and thereafter, the final product is produced without undergoing a pulverization step.

(9)一種鋰離子二次電池用負極材料的製造方法，其是包含鱗片狀石墨粒子、煅燒碳、可與鋰合金化的金屬粒子及石墨質纖維的球狀的複合體的製造方法，其特徵在於：使上述鱗片狀石墨粒子、上述金屬粒子及石墨質纖維分散於作為碳質材料及/或碳質材料的前驅物結著劑的溶液中，進行噴霧乾燥處理後，於700℃以上、1500℃以下的溫度範圍內進行熱處理，使上述碳質材料及碳質材料的前驅物成為煅燒碳，其後不經過粉碎步驟而製成最終製品。 (9) A method for producing a negative electrode material for a lithium ion secondary battery, which is a method for producing a spherical composite comprising flaky graphite particles, calcined carbon, metal particles which can be alloyed with lithium, and graphite fibers. The flaky graphite particles, the metal particles, and the graphite fibers are dispersed in a solution of a precursor of a carbonaceous material and/or a carbonaceous material, and are spray-dried at 700 ° C or higher. The heat treatment is performed in a temperature range of 1500 ° C or lower, and the precursor of the carbonaceous material and the carbonaceous material is calcined carbon, and thereafter, the final product is produced without undergoing a pulverization step.

(10)如(8)或(9)所述之鋰離子二次電池用負極材料的製造方法，其中進而使碳質材料及/或碳質材料的前驅物附著於上述噴霧乾燥處理品，之後進行上述熱處理。 (10) The method for producing a negative electrode material for a lithium ion secondary battery according to the above aspect, wherein the precursor of the carbonaceous material and/or the carbonaceous material is further adhered to the spray-dried product, and thereafter The above heat treatment is carried out.

作為本發明的負極材料的複合體於用於鋰離子二次電池用負極材料的情況下，可充分緩和充電時的金屬質物的膨脹， 且顯示超過石墨的理論電容的較高的放電電容、與優異的初始充放電效率。 When the composite material of the negative electrode material of the present invention is used for a negative electrode material for a lithium ion secondary battery, the expansion of the metal material during charging can be sufficiently alleviated. It also shows a higher discharge capacity than the theoretical capacitance of graphite, and excellent initial charge and discharge efficiency.

1‧‧‧外裝護罩 1‧‧‧Outer cover

2‧‧‧負極混合劑 2‧‧‧Negative mixture

3‧‧‧外裝罐 3‧‧‧Outer cans

4‧‧‧對極 4‧‧‧ pole

5‧‧‧分隔構件 5‧‧‧Parts

6‧‧‧絕緣墊片 6‧‧‧Insulation gasket

7a、7b‧‧‧集電體 7a, 7b‧‧‧ collector

圖1是表示實施例1中所獲得的複合體的外觀的電子顯微鏡照片(3000倍)。 Fig. 1 is an electron micrograph (3000 magnifications) showing the appearance of the composite obtained in Example 1.

圖2是實施例1中所獲得的複合體的剖面的偏光顯微鏡照片(3000倍)。 2 is a polarizing microscope photograph (3000 times) of a cross section of the composite obtained in Example 1. FIG.

圖3是表示存在於實施例1中所獲得的複合體的外表面的利用能量分散型X射線分光法測定的Si元素的能量分散型X射線分光法(Energy Dispersive X-ray Spectroscopy，EDX)映像(mapping)(3000倍)。 3 is an Energy Dispersive X-ray Spectroscopy (EDX) image showing Si element measured by energy dispersive X-ray spectroscopy on the outer surface of the composite obtained in Example 1. (mapping) (3000 times).

圖4是用以評價本發明的負極的電池特性的評價電池的剖面圖。 4 is a cross-sectional view of an evaluation battery for evaluating the battery characteristics of the negative electrode of the present invention.

[負極材料：包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀的複合體] [Anode material: a spherical composite containing flaky graphite particles, calcined carbon, and metal particles which can be alloyed with lithium]

本發明提供一種負極材料，其是包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀或大致球狀的複合體，且上述複合體至少於內部具有空隙，上述鱗片狀石墨粒子非平行地存在於上述複合體的內部，並呈同心圓狀地配向存在於上述複合體的表面，且上述金屬粒子分散存在於該複合體粒子內部及/或表 面。於本說明書中，有時將「分散於複合粒子內部及/或表面」稱為「分散於複合粒子內」。 The present invention provides a negative electrode material which is a spherical or substantially spherical composite body including flaky graphite particles, calcined carbon, and metal particles which can be alloyed with lithium, and the composite body has voids at least inside, and the scaly shape The graphite particles are present in the inside of the composite body in a non-parallel manner, and are present in a concentric shape on the surface of the composite body, and the metal particles are dispersed in the composite particle and/or surface. In the present specification, "dispersion in the inside and/or surface of the composite particles" may be referred to as "dispersion in the composite particles".

由於複合體為於內部具有空隙的構造，故可吸收伴隨合金化的體積的膨脹，防止活性物質的粉化或剝離。另外，由於是鱗片狀石墨粒子呈同心圓狀地配向於複合體的表面的構造，故導致露出表面的是反應性相對較低的基底(basal)面，從而不會引起由邊緣(edge)面的露出導致的充放電效率或循環特性的降低。 Since the composite has a structure in which voids are formed inside, the expansion of the volume accompanying the alloying can be absorbed, and the powdering or peeling of the active material can be prevented. Further, since the flaky graphite particles are arranged concentrically to the surface of the composite body, the basal surface having a relatively low reactivity is caused to expose the surface, so that the edge surface is not caused. The exposure causes a decrease in charge and discharge efficiency or cycle characteristics.

關於複合體的形狀，更具體而言，複合體的平均縱橫比(aspect ratio)較佳為3以下，尤佳為2以下。於平均縱橫比大於3的情況下會有循環特性惡化的情況。此外，縱橫比是指複合體1粒子的長軸長相對於短軸長的比，且將藉由掃描式電子顯微鏡觀察任意100個粒子而測定到的各粒子的縱橫比的算術平均值設為平均縱橫比。 Regarding the shape of the composite, more specifically, the average aspect ratio of the composite is preferably 3 or less, and particularly preferably 2 or less. When the average aspect ratio is more than 3, the cycle characteristics may deteriorate. In addition, the aspect ratio means the ratio of the major axis length of the composite 1 particle to the minor axis length, and the arithmetic mean value of the aspect ratio of each particle measured by observing arbitrary 100 particles by a scanning electron microscope is average. aspect ratio.

複合體的平均粒徑較佳為1~50μm的範圍，進而較佳為5~30μm的範圍。於本發明中，複合體的平均粒徑是雷射繞射式粒度分佈計的累積度數以體積分佈率計成為50%的粒徑(D50)。 The average particle diameter of the composite is preferably in the range of 1 to 50 μm, and more preferably in the range of 5 to 30 μm. In the present invention, the average particle diameter of the composite is a particle diameter (D 50 ) which is 50% by volume distribution ratio of the cumulative number of laser diffraction type particle size distribution meters.

對於本發明的負極材料而言，只要為可達成上述特徵的方法，則可以任意方法製造。另外，亦可為異種的石墨材料、碳質或石墨質的纖維、非晶質硬碳(hard carbon)等碳材料、有機材料、無機材料與金屬材料的混合物、複合物。 The negative electrode material of the present invention can be produced by any method as long as it is a method capable of achieving the above characteristics. Further, it may be a heterogeneous graphite material, a carbonaceous or graphite fiber, a carbon material such as an amorphous hard carbon, an organic material, a mixture or a composite of an inorganic material and a metal material.

關於複合體內部的空隙，其形狀或存在狀態並無限定，可分散存在，亦可存在於中心附近，還可到達至複合體的表面。 Regarding the voids inside the composite, the shape or the state of existence thereof is not limited, and may be dispersed, may exist in the vicinity of the center, and may reach the surface of the composite.

尤其更理想為複合體於內部包含石墨質纖維。石墨質纖維具有不破壞複合體內部的空隙而將鱗片狀石墨粒子或金屬粒子彼此 電性連接的作用，且降低複合體的電阻而提高循環特性。 It is especially preferred that the composite contains graphite fibers inside. Graphite fibers have scaly graphite particles or metal particles that do not break the voids inside the composite The function of electrical connection reduces the resistance of the composite and improves the cycle characteristics.

另外，以水銀壓入法測定的大小0.01~100μm的空隙的容積較佳為0.05~0.4cm3/g。若空隙的容積小於0.05cm3/g，則會有循環特性的改良效果變小的情況，若超過0.4cm3/g，則會有導電性降低的情況。 Further, the volume of the void having a size of 0.01 to 100 μm measured by the mercury intrusion method is preferably 0.05 to 0.4 cm 3 /g. When the volume of the void is less than 0.05 cm 3 /g, the effect of improving the cycle characteristics may be small, and if it exceeds 0.4 cm 3 /g, the conductivity may be lowered.

該範圍的空隙可將電解液適當地保持於其內部，從而提高使用本發明的負極材料的鋰離子二次電池的急速充放電特性。 The voids in this range can appropriately maintain the electrolyte inside, thereby improving the rapid charge and discharge characteristics of the lithium ion secondary battery using the anode material of the present invention.

關於複合體表面的鱗片狀石墨粒子的存在狀態，可利用掃描式電子顯微鏡(以下亦稱為SEM(Scanning Electron Microscope))觀察進行確認。關於複合體內部的鱗片狀石墨粒子的存在狀態，可藉由對埋入樹脂中的複合體粒子進行研磨後利用SEM或偏光顯微鏡觀察剖面而確認。另外，關於複合體表面及內部的金屬粒子的存在狀態，可利用EDX(能量分散型X射線分光法)分析進行確認。 The state of existence of the flaky graphite particles on the surface of the composite can be confirmed by observation with a scanning electron microscope (hereinafter also referred to as SEM (Scanning Electron Microscope)). The state of existence of the flaky graphite particles in the composite can be confirmed by polishing the composite particles embedded in the resin and observing the cross section by SEM or a polarizing microscope. Further, the state of existence of the metal particles on the surface and inside of the composite can be confirmed by EDX (energy dispersive X-ray spectroscopy) analysis.

本發明的鋰離子二次電池用負極材料如圖1中其一例的外觀的掃描式電子顯微鏡(以下，稱為SEM)照片所示般，是包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀的複合體。另外，關於複合體內部的鱗片狀石墨粒子的存在狀態，可藉由對埋入樹脂中的複合體粒子進行研磨後利用掃描式顯微鏡(SEM)或偏光顯微鏡觀察剖面而確認。如圖2中其一例的內部的偏光顯微鏡照片所示般，於內部具有空隙，且鱗片狀石墨粒子非平行地存在於複合體的內部，於複合體的表面鱗片狀石墨粒子呈同心圓狀地配向存在。 The negative electrode material for a lithium ion secondary battery of the present invention contains flaky graphite particles, calcined carbon, and a lithium alloy as shown in a scanning electron microscope (hereinafter referred to as SEM) photograph of an example of one of the examples of the present invention. A spherical composite of metal particles. In addition, the state of existence of the flaky graphite particles in the composite can be confirmed by polishing the composite particles embedded in the resin and observing the cross section by a scanning microscope (SEM) or a polarizing microscope. As shown in the internal polarizing microscope photograph of an example of FIG. 2, the inside of the composite has a void, and the flaky graphite particles are present in the inside of the composite in a non-parallel manner, and the scaly graphite particles are concentrically formed on the surface of the composite. Orientation exists.

此處所謂複合體的表面，是指自複合體的最表面起至鱗片狀 石墨的厚度的2倍以下(大約1μm以下)的範圍。所謂內部，是指除表面以外的範圍。 The surface of the composite here means from the outermost surface of the composite to the scale A range of twice or less (about 1 μm or less) of the thickness of graphite. The term "internal" refers to a range other than the surface.

圖2是實施例1中所獲得的複合體的剖面的偏光顯微鏡照片。球狀的粒子的中央附近的黑色所表示的部分為內部的空隙。於圖2中，並非黑色的部分表示鱗片狀石墨粒子非平行地存在於複合體的內部的狀態。非平行地存在的含義是指存在於內部的鱗片狀石墨粒子的總數的90%以上為非平行。 2 is a polarizing microscope photograph of a cross section of the composite obtained in Example 1. FIG. The portion indicated by black near the center of the spherical particles is an internal void. In FIG. 2, the portion which is not black indicates a state in which scaly graphite particles are present in a non-parallel manner inside the composite. The meaning of non-parallel existence means that 90% or more of the total number of flaky graphite particles present inside is non-parallel.

圖3是將表示存在於實施例1中所獲得的複合體的外表面的利用能量分散型X射線分光法測定的Si元素的EDX(能量分散型X射線分光法)映像以與圖1相同的視野表示。於圖3中，白色的點表示Si元素的存在，藉由將圖1與圖3重疊觀察，可確認矽粒子分散存在於複合體表面。 3 is an EDX (energy dispersive X-ray spectroscopy) image showing Si element measured by energy dispersive X-ray spectroscopy, which is present on the outer surface of the composite obtained in Example 1, in the same manner as in FIG. Field of view. In Fig. 3, white dots indicate the presence of Si element, and by observing Fig. 1 and Fig. 3, it was confirmed that ruthenium particles were dispersed on the surface of the composite.

複合體中的可與鋰合金化的金屬粒子分散存在於複合體粒子中。此是意指當可與鋰合金化的金屬粒子例如為Si時，利用能量分散型X射線分光法對測定複合體粒子表面所獲得的Si的存在頻度，與對埋入樹脂中的複合體粒子進行研磨後的剖面的Si的存在頻度進行了測定的情況大致相同。於本發明的複合體中，可與鋰合金化的金屬粒子分散於複合體粒子的內部及表面。 The metal particles which are alloyed with lithium in the composite are dispersed in the composite particles. This means that when the metal particles which can be alloyed with lithium are, for example, Si, the frequency of occurrence of Si obtained by measuring the surface of the composite particles by energy dispersive X-ray spectroscopy, and the composite particles embedded in the resin The case where the frequency of Si in the cross section after polishing was measured was substantially the same. In the composite of the present invention, metal particles which are alloyed with lithium are dispersed in the interior and surface of the composite particles.

[鱗片狀石墨粒子] [Scale-like graphite particles]

本發明中所使用的鱗片狀石墨粒子只要可吸藏、釋出鋰離子即可，並無特別限定。可列舉：其一部分或全部由石墨質所形成的石墨粒子，例如天然石墨、或將焦油、瀝青類最終以1500℃以上進行熱處理而成的人造石墨。具體而言，可將對被稱為易石墨化性碳材料的石油系、煤系的焦油瀝青類進行熱處理使其聚縮合 而成的中間相煅燒體、焦炭類以1500℃以上、較理想為以2800~3300℃進行石墨化處理而獲得。 The flaky graphite particles used in the present invention are not particularly limited as long as they can absorb and release lithium ions. For example, graphite particles formed of graphite or a part thereof, such as natural graphite or artificial graphite obtained by heat-treating tar or pitch at 1500 ° C or higher, may be mentioned. Specifically, a petroleum-based or coal-based tar pitch known as an easily graphitizable carbon material may be heat-treated to be polycondensed. The obtained mesophase calcined body and coke are obtained by graphitizing at 1500 ° C or higher, preferably at 2800 to 3300 ° C.

本發明的鱗片狀石墨粒子的平均粒徑較佳為0.1μm~20μm的範圍，進而較佳為0.3μm~10μm的範圍。鱗片狀石墨粒子的平均粒徑與上述複合體的情況同樣地為D50。形狀為鱗片狀時的平均粒徑是設為換算成與該粒子同一體積的球狀粒子的平均粒徑的值。 The average particle diameter of the flaky graphite particles of the present invention is preferably in the range of 0.1 μm to 20 μm, and more preferably in the range of 0.3 μm to 10 μm. The average particle diameter of the flaky graphite particles is D 50 as in the case of the above composite. The average particle diameter when the shape is a scaly shape is a value which is an average particle diameter of spherical particles converted into the same volume as the particles.

另外，上述鱗片狀石墨粒子的平均扁平度(Ly/t)較佳為0.5以上，更佳為2~40。此處所謂平均扁平度，是指鱗片狀石墨粒子的1粒子的短軸長Ly相對於厚度t的比(Ly/t)，且以藉由掃描式電子顯微鏡觀察100個鱗片狀石墨粒子而測定到的各粒子的扁平度的簡單平均值算出。 Further, the average flatness (Ly/t) of the flaky graphite particles is preferably 0.5 or more, and more preferably 2 to 40. Here, the average flatness refers to a ratio (Ly/t) of the short axis length Ly of one particle of the flaky graphite particles to the thickness t, and is measured by observing 100 scaly graphite particles by a scanning electron microscope. A simple average of the flatness of each of the particles obtained was calculated.

另外，亦可實施液相、氣相、固相下的各種化學處理、熱處理、氧化處理、物理處理等。若上述鱗片狀石墨粒子的平均扁平度小於0.5，則有不會成為鱗片狀石墨呈同心圓狀地配向於複合體表面的構造的情況，若平均扁平度超過40，則有無法形成球狀的複合體的情況。 Further, various chemical treatments, heat treatments, oxidation treatments, physical treatments, and the like in the liquid phase, the gas phase, and the solid phase can also be carried out. When the average flatness of the flaky graphite particles is less than 0.5, the flaky graphite does not have a structure that is concentrically arranged on the surface of the composite. If the average flatness exceeds 40, the spherical shape cannot be formed. The case of a complex.

鱗片狀石墨粒子的比率相對於複合體粒子總量，較佳為98~60質量%。更佳為95~60質量%。若石墨粒子為98%以上，則會有電容提高的效果變小的情況，若小於60%，則會有循環特性的改良效果變小的情況。 The ratio of the flaky graphite particles is preferably 98 to 60% by mass based on the total amount of the composite particles. More preferably, it is 95 to 60% by mass. When the graphite particles are 98% or more, the effect of improving the capacitance may be small, and if it is less than 60%, the effect of improving the cycle characteristics may be small.

於本發明的負極材料的複合體的表面露出的是鱗片狀石墨粒子的反應性相對較低的基底面(AB面)，從而不會引起如上述般由邊緣面的露出導致的充放電效率或循環特性的降低。 The surface of the composite of the negative electrode material of the present invention is exposed on the surface of the flaky graphite particles having a relatively low reactivity (AB surface), so that the charge and discharge efficiency due to the exposure of the edge faces is not caused or Reduced cycle characteristics.

[煅燒碳] [calcined carbon]

本發明中所使用的煅燒碳是於對將上述鱗片狀石墨粒子與下述結著劑混合而成的分散液進行噴霧乾燥處理並於其後進行煅燒所獲得的複合體中與石墨粒子區別存在的碳成分，且為對作為前驅物的結著劑、溶液進行煅燒而成的煅燒碳；或者將噴霧乾燥處理品含浸於下述結著劑後進行煅燒而成的煅燒碳。可源自以下任一種前驅物，例示有焦油瀝青類及/或樹脂類。具體而言，作為焦油瀝青類，可列舉：煤焦油、焦油輕油、焦油中油、焦油重油、萘油、蒽油、煤焦油瀝青、瀝青油、中間相瀝青、氧交聯石油瀝青、重油等。作為樹脂類，例示有：聚乙烯醇、聚丙烯酸、聚氯乙烯、聚偏二氯乙烯、氯化聚氯乙烯等鹵化乙烯樹脂等熱塑性樹脂；酚樹脂、呋喃樹脂、糠醇樹脂、纖維素樹脂、聚丙烯腈、聚醯胺醯亞胺樹脂、聚醯胺樹脂等熱硬化性樹脂。藉由對該等碳質物前驅物以下述溫度進行熱處理而可獲得煅燒碳。 The calcined carbon used in the present invention is obtained by subjecting a dispersion obtained by mixing the above flaky graphite particles and a binder described below to a spray drying treatment and then calcining the graphite to distinguish it from graphite particles. The carbon component is calcined carbon obtained by calcining a binder or a solution as a precursor, or calcined carbon obtained by impregnating a spray-dried product with the following binder. It may be derived from any of the following precursors, exemplified by tar pitch and/or resin. Specifically, examples of the tar pitch include coal tar, tar light oil, tar medium oil, tar heavy oil, naphthalene oil, eucalyptus oil, coal tar pitch, asphalt oil, mesophase pitch, oxygen crosslinked petroleum pitch, heavy oil, and the like. . Examples of the resin include thermoplastic resins such as a vinyl halide resin such as polyvinyl alcohol, polyacrylic acid, polyvinyl chloride, polyvinylidene chloride, and chlorinated polyvinyl chloride; phenol resin, furan resin, decyl alcohol resin, and cellulose resin; A thermosetting resin such as polyacrylonitrile, polyamidoximine resin, or polyamide resin. Calcined carbon can be obtained by heat-treating the carbonaceous precursors at the following temperatures.

煅燒碳較佳為未進行石墨化而為非晶質。 The calcined carbon is preferably amorphous without being graphitized.

煅燒碳的製品複合體中的含量較佳為1~20質量%。更佳為1~15質量%。若煅燒碳小於1質量%，則會有循環特性的改良效果變小的情況，若為20質量%以上，則會有電容及/或初始效率降低的情況。 The content of the calcined carbon product composite is preferably from 1 to 20% by mass. More preferably, it is 1 to 15% by mass. When the calcined carbon is less than 1% by mass, the effect of improving the cycle characteristics may be small, and if it is 20% by mass or more, the capacitance and/or the initial efficiency may be lowered.

[可與鋰合金化的金屬粒子] [Metal particles that can be alloyed with lithium]

作為可與鋰合金化的金屬粒子，可列舉Al、Pb、Zn、Sn、Bi、In、Mg、Ga、Cd、Ag、Si、B、Au、Pt、Pd、Sb、Ge、Ni等金屬粒子，較佳為Si粒子、Sn粒子。另外，上述金屬粒子可為上述金屬的兩種以上的合金，亦可於合金中除上述金屬以外更含有其他 元素。上述金屬粒子的一部分亦可形成氧化物、氮化物、碳化物，尤佳為至少一部分包含氧化物。 Examples of the metal particles which can be alloyed with lithium include metal particles such as Al, Pb, Zn, Sn, Bi, In, Mg, Ga, Cd, Ag, Si, B, Au, Pt, Pd, Sb, Ge, and Ni. It is preferably Si particles or Sn particles. Further, the metal particles may be two or more alloys of the above metals, and may contain other alloys than the above metals. element. A part of the metal particles may form an oxide, a nitride or a carbide, and it is particularly preferable that at least a part of the metal particles contain an oxide.

本發明中使用的上述金屬粒子的比率相對於複合粒子總量，較佳為1質量%以上、20質量%以下，尤佳為2質量%以上、20質量%以下。於上述金屬粒子小於1質量%的情況下會有電容提高的效果變小的情況，於超過20質量%的情況下會有循環特性的改良效果變小的情況。 The ratio of the metal particles used in the present invention is preferably 1% by mass or more and 20% by mass or less, and particularly preferably 2% by mass or more and 20% by mass or less based on the total amount of the composite particles. When the metal particles are less than 1% by mass, the effect of improving the capacitance may be small, and when the amount is more than 20% by mass, the effect of improving the cycle characteristics may be small.

上述金屬粒子的平均粒徑較佳為10μm以下，更佳為5μm以下，尤佳為1μm以下。於上述金屬粒子的平均粒徑超過10μm的情況下會有循環特性的改良效果變小的情況。 The average particle diameter of the metal particles is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less. When the average particle diameter of the metal particles exceeds 10 μm, the effect of improving the cycle characteristics may be small.

上述金屬粒子的形狀並無特別限制。粒狀、球狀、板狀、鱗片狀、針狀、線狀等均可。 The shape of the above metal particles is not particularly limited. Granular, spherical, plate-like, scaly, needle-like, linear, etc.

[石墨質纖維] [graphite fiber]

石墨質纖維只要為具有導電性的纖維狀的石墨即可，並無特別限定。較佳的形狀是平均纖維徑10~1000nm、平均纖維長1~20μm，例示有奈米碳管(carbon nanotube)、奈米碳纖維(carbon nanofiber)、氣相沈積碳纖維等。 The graphite fiber is not particularly limited as long as it is a fibrous graphite having conductivity. The preferred shape is an average fiber diameter of 10 to 1000 nm and an average fiber length of 1 to 20 μm, and examples thereof include a carbon nanotube, a carbon nanofiber, and a vapor-deposited carbon fiber.

石墨質纖維的比率相對於複合粒子總量，較佳為0.5質量%以上、5質量%以下，更佳為1質量%以上、3質量%以下。於石墨質纖維小於0.5質量%的情況下會有循環特性提高的效果變小的情況，於超過5質量%的情況下會有初始充放電效率降低的情況。 The ratio of the graphite fibers is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less based on the total amount of the composite particles. When the amount of the graphite fiber is less than 0.5% by mass, the effect of improving the cycle characteristics may be small, and when it exceeds 5% by mass, the initial charge and discharge efficiency may be lowered.

[複合體的製造方法] [Manufacturing method of composite]

本發明亦提供一種包含鱗片狀石墨粒子、煅燒碳、及可與鋰合金化的金屬粒子(以下有時稱為金屬粒子)的球狀的複合體的 製造方法。煅燒碳可將上述鱗片狀石墨粒子及金屬粒子與結著劑或其溶液混合並進行噴霧乾燥，其後進行煅燒(稱為「噴霧乾燥→煅燒」製程)。或者亦可將鱗片狀石墨粒子及金屬粒子分散於結著劑或其溶液中進行噴霧乾燥，其後混合作為結著劑的碳材料前驅物或其溶液並進行煅燒而製造煅燒碳(稱為「噴霧乾燥→碳被覆→煅燒」製程)。還可將兩者組合。另外，於添加石墨質纖維的情況下，較佳為與鱗片狀石墨粒子及金屬粒子一起分散於結著劑或其溶液中並供給至噴霧乾燥。此外，亦可預先使金屬粒子與石墨質纖維附著於鱗片狀石墨粒子。本發明的複合體較佳為藉由煅燒處理後不經粉碎步驟而製成最終製品的製造方法所獲得。結著劑是碳質材料及/或碳質材料的前驅物。與作為上述煅燒碳的前驅物所例示的物質相同。只要可溶解於適當的溶劑中，則任一種結著劑均可，例示有作為上述煅燒碳的前驅物所例示的焦油瀝青類及/或樹脂類。作為結著劑的原料的添加量相對於鱗片狀石墨粒子100質量%，較佳為1~30質量%。更佳為1~15質量%。作為結著劑的溶液所使用的溶液可為水溶液、醇溶液、有機溶劑溶液等中的任一者。較佳為於水中添加了作為界面活性劑、黏度調節劑的聚乙烯醇等的溶液。 The present invention also provides a spherical composite comprising flaky graphite particles, calcined carbon, and metal particles (hereinafter sometimes referred to as metal particles) which can be alloyed with lithium. Production method. The calcined carbon may be obtained by mixing the flaky graphite particles and the metal particles with a binder or a solution thereof, followed by spray drying, followed by calcination (referred to as a "spray drying→calcination" process). Alternatively, the flaky graphite particles and the metal particles may be dispersed in a binder or a solution thereof to be spray-dried, and then a carbon material precursor or a solution thereof as a binder may be mixed and calcined to produce calcined carbon (referred to as " Spray drying → carbon coating → calcination process). You can also combine the two. Further, when a graphite fiber is added, it is preferably dispersed in a binder or a solution together with the flaky graphite particles and the metal particles and supplied to the spray drying. Further, the metal particles and the graphite fibers may be attached to the flaky graphite particles in advance. The composite of the present invention is preferably obtained by a method of producing a final product by a calcination treatment without a pulverization step. The binder is a precursor to carbonaceous materials and/or carbonaceous materials. It is the same as the substance exemplified as the precursor of the above calcined carbon. Any of the binders may be used as long as it is soluble in a suitable solvent, and tar pitches and/or resins exemplified as the precursor of the calcined carbon are exemplified. The amount of the raw material to be used as the binder is preferably from 1 to 30% by mass based on 100% by mass of the flaky graphite particles. More preferably, it is 1 to 15% by mass. The solution used as the solution of the binder may be any of an aqueous solution, an alcohol solution, an organic solvent solution, and the like. It is preferred to add a solution of polyvinyl alcohol or the like as a surfactant or a viscosity modifier to water.

噴霧乾燥處理只要是與氣流一起噴霧散布分散液，並藉由熱風使溶劑瞬時乾燥的方法，則可為任意方法，所述分散液是使鱗片狀石墨粒子與金屬粒子分散於作為結著劑的碳質材料的前驅物的溶液中或使鱗片狀石墨碳粒子分散於溶液中而成。藉由分散液的表面張力，乾燥後的粒子形成真球狀。此處將藉由煅燒前的噴霧乾燥處理所獲得的球狀粒子稱為複合體前驅物。此時，藉 由分散液的固含量比或氣流的調整而使氣泡不介存於噴霧的液滴中，藉此可形成內部亦存在鱗片狀石墨粒子的構造而並非完全的中空構造。 The spray drying treatment may be any method in which a dispersion liquid is sprayed together with a gas stream and the solvent is instantaneously dried by hot air, and the dispersion liquid is obtained by dispersing flaky graphite particles and metal particles as a binding agent. The solution of the precursor of the carbonaceous material or the flaky graphite carbon particles are dispersed in the solution. The dried particles form a true spherical shape by the surface tension of the dispersion. Here, the spherical particles obtained by the spray drying treatment before calcination are referred to as a composite precursor. At this time, borrow The bubble does not accumulate in the droplets of the spray due to the solid content ratio of the dispersion or the adjustment of the gas flow, whereby a structure in which flaky graphite particles are present inside can be formed, and a hollow structure is not completed.

例如，分散液的固含量比較佳為總量中的5~25質量%，噴霧乾燥器的入口溫度較佳為150~250℃，噴嘴空氣量較佳為20~100公升/分鐘等。 For example, the solid content of the dispersion is preferably from 5 to 25% by mass in the total amount, the inlet temperature of the spray dryer is preferably from 150 to 250 ° C, and the air volume of the nozzle is preferably from 20 to 100 liters per minute.

於未對進行噴霧乾燥的溶液添加作為結著劑的碳材料的前驅物的情況下，將進行噴霧乾燥所獲得的複合體前驅物浸漬於碳材料的前驅物的溶液中進行碳被覆。亦可將複合體前驅物與碳材料的前驅物混合而進行碳被覆。 In the case where a precursor of a carbon material as a binder is not added to the solution to be spray-dried, the composite precursor obtained by spray drying is immersed in a solution of a precursor of a carbon material to carry out carbon coating. The composite precursor may also be mixed with a precursor of a carbon material to carry out carbon coating.

於噴霧乾燥處理中，藉由原液的固含量比或氣流的調整可調整為任意的粒度，從而無需最終進行粉碎而進行粒度調整的步驟。另外，由於使用石墨粒子作為主原料，故而無需石墨化處理，僅以煅燒處理便可表現出作為鋰離子二次電池的負極材料而充分的電容。 In the spray drying treatment, the solid content ratio of the stock solution or the adjustment of the gas flow can be adjusted to an arbitrary particle size, so that the step of adjusting the particle size without final pulverization is required. Further, since graphite particles are used as the main raw material, the graphitization treatment is not required, and the capacitor which is sufficient as a negative electrode material of the lithium ion secondary battery can be expressed only by the calcination treatment.

藉由將噴霧乾燥處理品(複合體前驅物)於惰性環境中，於700℃以上、1500℃以下的溫度範圍內進行煅燒處理而可獲得複合體。較佳為900℃~1400℃。惰性環境可使用N2、Ar、He、真空環境等及該等的混合物。若煅燒溫度小於700℃或超過1500℃，則會有初始效率降低的情況。 The spray-dried product (composite precursor) is subjected to a calcination treatment in a temperature range of 700 ° C to 1500 ° C in an inert atmosphere to obtain a composite. It is preferably from 900 ° C to 1400 ° C. N 2 , Ar, He, a vacuum environment, etc., and mixtures thereof may be used in an inert environment. If the calcination temperature is less than 700 ° C or exceeds 1500 ° C, there is a case where the initial efficiency is lowered.

亦可於煅燒處理前，附著、埋設、複合異種的石墨材料、碳質或石墨質的纖維、非晶質硬碳等碳材料、有機材料、無機材料、金屬材料。亦可於煅燒處理前將噴霧乾燥處理品浸漬於碳質材料及/或碳質材料的前驅物的溶液中，而使碳質材料及/或碳質材 料的前驅物附著於噴霧乾燥品。此種方法可藉由造粒構造的強化及被覆而降低反應性(充放電損耗)。較佳的附著量(煅燒前的量)相對於鱗片狀石墨粒子100質量%，較佳為1~30質量%。更佳為1~15質量%。 Before the calcination treatment, carbon materials such as graphite materials, carbonaceous or graphite fibers, amorphous hard carbon, organic materials, inorganic materials, and metal materials may be adhered, embedded, and composited. The spray dried product may be immersed in a solution of a precursor of a carbonaceous material and/or a carbonaceous material before the calcination treatment to obtain a carbonaceous material and/or a carbonaceous material. The precursor of the material is attached to the spray dried product. This method can reduce the reactivity (charge and discharge loss) by strengthening and coating the granulation structure. The amount of adhesion (amount before calcination) is preferably from 1 to 30% by mass based on 100% by mass of the flaky graphite particles. More preferably, it is 1 to 15% by mass.

[負極] [negative electrode]

本發明的鋰離子二次電池用的負極是依據通常的負極的成形方法而製作，只要為可獲得化學性、電氣化學性穩定的負極的方法，則並無任何限制。於製作負極時，較佳為使用對本發明的負極材料添加結合劑而預先製備而成的負極混合劑。作為結合劑，較佳為對於電解質而於化學性及電氣化學性方面顯示穩定性的結合劑，例如使用有聚四氟乙烯、聚偏二氟乙烯等氟系樹脂粉末、聚乙烯、聚乙烯醇等樹脂粉末、羧基甲基纖維素等。亦可併用該等。結合劑通常以負極混合劑的總量中的1~20質量%左右的比率使用。 The negative electrode for a lithium ion secondary battery of the present invention is produced by a usual method for forming a negative electrode, and is not limited as long as it is a method for obtaining a chemically and electrochemically stable negative electrode. In the case of producing a negative electrode, a negative electrode mixture prepared in advance by adding a binder to the negative electrode material of the present invention is preferably used. As the binder, a binder which exhibits chemical and electrochemical chemistry for the electrolyte is preferably used, for example, a fluorine resin powder such as polytetrafluoroethylene or polyvinylidene fluoride, polyethylene or polyvinyl alcohol. Such as resin powder, carboxymethyl cellulose, and the like. You can also use these together. The binder is usually used in a ratio of about 1 to 20% by mass based on the total amount of the negative electrode mixture.

更具體而言，首先，藉由分級等將本發明的負極材料調整為所需的粒度，並與結合劑混合，使所得的混合物分散於溶劑中，製成膠狀而製備負極混合劑。即，使用公知的攪拌機、混合機、混練機、捏合機等，對將本發明的負極材料及結合劑與水、異丙醇、N-甲基吡咯啶酮、二甲基甲醯胺等溶劑混合所得的漿料進行攪拌混合，從而製備膠體。若將該膠體塗佈於集電材的單面或兩面並進行乾燥，則可獲得均勻且牢固地接著有負極混合劑層的負極。負極混合劑層的膜厚為10~200μm，較佳為20~100μm。 More specifically, first, the negative electrode material of the present invention is adjusted to a desired particle size by classification or the like, and mixed with a binder, and the resulting mixture is dispersed in a solvent to form a gel to prepare a negative electrode mixture. That is, a solvent such as water, isopropyl alcohol, N-methylpyrrolidone or dimethylformamide is used in the negative electrode material and the binder of the present invention by using a known agitator, a mixer, a kneader, a kneader or the like. The resulting slurry was mixed and stirred to prepare a colloid. When the colloid is applied to one surface or both surfaces of the current collector and dried, a negative electrode in which the negative electrode mixture layer is uniformly and firmly adhered can be obtained. The film thickness of the negative electrode mixture layer is 10 to 200 μm, preferably 20 to 100 μm.

另外，本發明的負極亦可將本發明的負極材料、與聚乙烯、聚乙烯醇等樹脂粉末進行乾式混合，並於模具內進行熱壓成 形而製作。 Further, in the negative electrode of the present invention, the negative electrode material of the present invention may be dry-mixed with a resin powder such as polyethylene or polyvinyl alcohol, and hot pressed in a mold. Made in shape.

若於形成負極混合劑層後進行壓製加壓等壓接，則可進一步提高負極混合劑層與集電體的接著強度。 When the negative electrode mixture layer is formed and pressure-bonded by pressurization or the like, the adhesion strength between the negative electrode mixture layer and the current collector can be further improved.

作為負極的製作中使用的集電體的形狀，並無特別限定，為箔狀、網狀、金屬擴張網(expanded metal)等網狀等。作為集電材的材質，較佳為銅、不鏽鋼、鎳等。集電體的厚度於箔狀的情況下較佳為5~20μm左右。 The shape of the current collector used for the production of the negative electrode is not particularly limited, and is a mesh shape such as a foil shape, a mesh shape, or an expanded metal. The material of the current collector is preferably copper, stainless steel, nickel or the like. When the thickness of the current collector is in the form of a foil, it is preferably about 5 to 20 μm.

此外，本發明的負極亦可於不損害本發明的目的之範圍內混合、內含、被覆或積層異種的石墨質材料、非晶質硬碳等碳質材料、有機物、金屬、金屬化合物等。 Further, the negative electrode of the present invention may be mixed, contained, coated or laminated with a heterogeneous graphite material, a carbonaceous material such as amorphous hard carbon, an organic substance, a metal, a metal compound or the like, within a range not impairing the object of the present invention.

[正極] [positive electrode]

正極是藉由將例如包含正極材料與結合劑及導電劑的正極混合劑塗佈於集電體的表面而形成。正極的材料(正極活性物質)較佳為選擇可吸藏/脫附充分量的鋰的材料。例如為含鋰過渡金屬氧化物、過渡金屬硫屬化物(chalcogenide)、釩氧化物及其鋰化合物等含鋰化合物、由通式MXMo6OS8-Y(式中，M為至少一種過渡金屬元素，X為0≦X≦4的範圍的數值，Y為0≦Y≦1的範圍的數值)所表示的謝弗萊相化合物(Chevrel compound)、活性碳、活性碳纖維等。釩氧化物是由V2O5、V6O13、V2O4、V3O8所表示。 The positive electrode is formed by applying, for example, a positive electrode mixture containing a positive electrode material and a binder and a conductive agent to the surface of the current collector. The material of the positive electrode (positive electrode active material) is preferably a material selected to be capable of occluding/desorbing a sufficient amount of lithium. For example, a lithium-containing compound such as a lithium-containing transition metal oxide, a transition metal chalcogenide, a vanadium oxide, and a lithium compound thereof, and a general formula M X Mo 6 OS 8-Y (wherein M is at least one transition) The metal element, X is a numerical value in the range of 0≦X≦4, and Y is a value of a range of 0≦Y≦1) Chevrel compound, activated carbon, activated carbon fiber, or the like. The vanadium oxide is represented by V 2 O 5 , V 6 O 13 , V 2 O 4 , and V 3 O 8 .

含鋰過渡金屬氧化物為鋰與過渡金屬的複合氧化物，亦可將鋰與兩種以上的過渡金屬固溶。複合氧化物可單獨使用，亦可組合兩種以上使用。具體而言，含鋰過渡金屬氧化物是由LiM1 1-xM2 XO2(式中，M1、M2為至少一種過渡金屬元素，X為0≦X≦1的範圍的數值)、或LiM1 1-YM2 YO4(式中，M1、M2為至少一 種過渡金屬元素，Y為0≦Y≦1的範圍的數值)所表示。 The lithium-containing transition metal oxide is a composite oxide of lithium and a transition metal, and lithium may be solid-solved with two or more transition metals. The composite oxide may be used singly or in combination of two or more. Specifically, the lithium-containing transition metal oxide is composed of LiM 1 1-x M 2 X O 2 (wherein M 1 and M 2 are at least one transition metal element, and X is a value in the range of 0≦X≦1) Or LiM 1 1-Y M 2 Y O 4 (wherein M 1 and M 2 are at least one transition metal element, and Y is a value in the range of 0 ≦ Y ≦ 1).

由M1、M2所表示的過渡金屬元素為Co、Ni、Mn、Cr、Ti、V、Fe、Zn、Al、In、Sn等，較佳為Co、Fe、Mn、Ti、Cr、V、Al等。更佳的具體例為LiCoO2、LiNiO2、LiMnO2、LiNi0.9Co0.1O2、LiNi0.5Co0.5O2等。 The transition metal element represented by M 1 and M 2 is Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn, etc., preferably Co, Fe, Mn, Ti, Cr, V. , Al, etc. More specific examples are LiCoO 2 , LiNiO 2 , LiMnO 2 , LiNi 0.9 Co 0.1 O 2 , LiNi 0.5 Co 0.5 O 2 and the like.

含鋰過渡金屬氧化物例如可藉由如下方式而獲得：以鋰、過渡金屬的氧化物、氫氧化物、鹽類等作為起始原料，將該等起始原料依據所需的金屬氧化物的組成進行混合，並於氧氣環境下以600~1000℃的溫度進行煅燒。 The lithium-containing transition metal oxide can be obtained, for example, by using lithium, a transition metal oxide, a hydroxide, a salt or the like as a starting material, and the starting materials are based on the desired metal oxide. The composition is mixed and calcined at a temperature of 600 to 1000 ° C in an oxygen atmosphere.

正極活性物質可將上述化合物單獨使用亦可併用兩種以上。例如，可於正極中添加碳酸鋰等碳鹽。另外，於形成正極時，可適當使用先前公知的導電劑或結著劑等各種添加劑。 The positive electrode active material may be used singly or in combination of two or more kinds. For example, a carbon salt such as lithium carbonate may be added to the positive electrode. Further, when forming the positive electrode, various additives such as a conventionally known conductive agent or a binder can be suitably used.

正極是將包含上述正極材料、結合劑、及用以對正極賦予導電性的導電劑的正極混合劑塗佈於集電體的兩面而形成正極混合劑層而製作。作為結合劑，可使用與負極的製作中所使用的結合劑相同的結合劑。作為導電劑，使用有石墨化物、碳黑等公知的導電劑。 The positive electrode is produced by applying a positive electrode mixture containing the above-described positive electrode material, a binder, and a conductive agent for imparting conductivity to the positive electrode to both surfaces of the current collector to form a positive electrode mixture layer. As the binder, the same binder as that used in the production of the anode can be used. As the conductive agent, a known conductive agent such as graphite or carbon black is used.

集電體的形狀並無特別限定，使用有箔狀或網狀、金屬擴張網等網狀等的集電體。集電體的材質為鋁、不鏽鋼、鎳等。其厚度較佳為10~40μm。 The shape of the current collector is not particularly limited, and a current collector such as a mesh shape such as a foil shape or a mesh shape or a metal expanded mesh is used. The material of the current collector is aluminum, stainless steel, nickel, and the like. The thickness is preferably from 10 to 40 μm.

正極亦與負極同樣地，可使正極混合劑分散於溶劑中製成膠狀，將該膠狀的正極混合劑塗佈於集電體並進行乾燥而形成正極混合劑層，亦可於形成正極混合劑層後，進而進行壓製加壓等壓接。藉此，可使正極混合劑層均勻且牢固地與集電材接著。 Similarly to the negative electrode, the positive electrode mixture can be dispersed in a solvent to form a gel, and the gel-like positive electrode mixture can be applied to a current collector and dried to form a positive electrode mixture layer, or a positive electrode can be formed. After the mixture layer is further pressed, pressure bonding or the like is performed. Thereby, the positive electrode mixture layer can be uniformly and firmly adhered to the current collector.

[非水電解質] [non-aqueous electrolyte]

作為本發明的鋰離子二次電池中所使用的非水電解質，可使用作為通常的非水電解液中所使用的電解質鹽的LiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)、LiCl、LiBr、LiCF3SO3、LiCH3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3、LiN(CF3CH2OSO2)2、LiN(CF3CF2OSO2)2、LiN(HCF2CF2CH2OSO2)2、LiN((CF3)2CHOSO2)2、LiB[{C6H3(CF3)2}]4、LiAlCl4、LiSiF6等鋰鹽。就氧化穩定性方面而言，尤佳為LiPF6、LiBF4。 As the nonaqueous electrolyte used in the lithium ion secondary battery of the present invention, LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB (C 6 H) which is an electrolyte salt used in a usual nonaqueous electrolytic solution can be used. 5 ), LiCl, LiBr, LiCF 3 SO 3 , LiCH 3 SO 3 , LiN(CF 3 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiN(CF 3 CH 2 OSO 2 ) 2 , LiN (CF 3 CF 2 OSO 2 ) 2 , LiN(HCF 2 CF 2 CH 2 OSO 2 ) 2 , LiN((CF 3 ) 2 CHOSO 2 ) 2 , LiB[{C 6 H 3 (CF 3 ) 2 }] 4 , LiAlCl 4 Lithium salt such as LiSiF 6 . In terms of oxidative stability, LiPF 6 and LiBF 4 are particularly preferred.

電解液中的電解質鹽濃度較佳為0.1~5mol/L，更佳為0.5~3.0mol/L。 The electrolyte salt concentration in the electrolyte is preferably from 0.1 to 5 mol/L, more preferably from 0.5 to 3.0 mol/L.

非水電解質可設為液狀非水電解質，亦可設為固體電解質或凝膠電解質等高分子電解質。於前者的情況下，非水電解質電池構成為所謂的鋰離子二次電池，於後者的情況下，非水電解質電池構成為高分子固體電解質、高分子凝膠電解質電池等高分子電解質電池。 The nonaqueous electrolyte may be a liquid nonaqueous electrolyte, or may be a polymer electrolyte such as a solid electrolyte or a gel electrolyte. In the case of the former, the nonaqueous electrolyte battery is a so-called lithium ion secondary battery, and in the latter case, the nonaqueous electrolyte battery is a polymer electrolyte battery such as a polymer solid electrolyte or a polymer gel electrolyte battery.

作為用以製備非水電解質液的溶劑，可使用：碳酸乙二酯、碳酸丙二酯、碳酸二甲酯、碳酸二乙酯等碳酸酯；1,1-二甲氧基乙烷或1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、四氫呋喃、2-甲基四氫呋喃、γ-丁內酯、1,3-二氧戊環、4-甲基-1,3-二氧戊環、苯甲醚、二***等醚；環丁碸、甲基環丁碸等硫醚；乙腈、氯腈、丙腈等腈；硼酸三甲酯、矽酸四甲酯、硝基甲烷、二甲基甲醯胺、N-甲基吡咯啶酮、乙酸乙酯、原甲酸三甲酯、硝基苯、苯甲醯氯、苯甲醯溴、四氫噻吩、二甲基亞碸、3-甲基-2-噁唑啶酮、乙二醇、亞硫酸二甲酯等非質子性有機溶劑等。 As a solvent for preparing the nonaqueous electrolyte solution, a carbonate such as ethylene carbonate, propylene carbonate, dimethyl carbonate or diethyl carbonate; 1,1-dimethoxyethane or 1, can be used. 2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, 1,3-dioxolane, 4-methyl-1, Ethers such as 3-dioxolane, anisole, diethyl ether; thioethers such as cyclobutyl hydrazine and methylcyclobutyl hydrazine; nitriles such as acetonitrile, chloronitrile, and propionitrile; trimethyl borate, tetramethyl citrate, Nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, trimethyl orthoformate, nitrobenzene, benzamidine chloride, benzamidine bromide, tetrahydrothiophene, dimethyl Aprotic organic solvents such as anthraquinone, 3-methyl-2-oxazolidinone, ethylene glycol, and dimethyl sulfite.

於將非水電解質設為高分子固體電解質或高分子凝膠電解質等高分子電解質的情況下，較佳為使用經塑化劑(非水電解液)凝膠化的高分子作為基質。作為構成上述基質的高分子，尤佳為使用聚環氧乙烷或其交聯物等醚系高分子化合物、聚甲基丙烯酸酯系高分子化合物、聚丙烯酸酯系高分子化合物、聚偏二氟乙烯或偏二氟乙烯-六氟丙烯共聚物等氟系高分子化合物等。 When the nonaqueous electrolyte is a polymer electrolyte such as a polymer solid electrolyte or a polymer gel electrolyte, it is preferred to use a polymer gelled with a plasticizer (nonaqueous electrolyte) as a matrix. The polymer constituting the above-mentioned matrix is preferably an ether polymer compound such as polyethylene oxide or a crosslinked product thereof, a polymethacrylate polymer compound, a polyacrylate polymer compound, or a polydisperse polymer. A fluorine-based polymer compound such as a vinyl fluoride or a vinylidene fluoride-hexafluoropropylene copolymer.

於上述高分子固體電解質或高分子凝膠電解質中調配有塑化劑，作為該塑化劑，可使用上述電解質鹽或非水溶劑。於高分子凝膠電解質的情況下，作為塑化劑的非水電解液中的電解質鹽濃度較佳為0.1~5mol/L，更佳為0.5~2.0mol/L。 A plasticizer is blended in the polymer solid electrolyte or the polymer gel electrolyte, and the electrolyte salt or the nonaqueous solvent can be used as the plasticizer. In the case of a polymer gel electrolyte, the concentration of the electrolyte salt in the nonaqueous electrolyte as the plasticizer is preferably from 0.1 to 5 mol/L, more preferably from 0.5 to 2.0 mol/L.

高分子固體電解質的製作方法並無特別限定，例如可列舉：將構成基質的高分子化合物、鋰鹽及非水溶劑(塑化劑)混合並進行加熱而使高分子化合物熔融的方法；於使高分子化合物、鋰鹽、及非水溶劑(塑化劑)溶解於有機溶劑中後使混合用有機溶劑蒸發的方法；將聚合性單體、鋰鹽及非水溶劑(塑化劑)混合，並對混合物照射紫外線、電子束或分子束等而使聚合性單體聚合，從而獲得聚合物的方法等。 The method for producing the polymer solid electrolyte is not particularly limited, and examples thereof include a method in which a polymer compound constituting a matrix, a lithium salt, and a nonaqueous solvent (plasticizer) are mixed and heated to melt the polymer compound; a method in which a polymer compound, a lithium salt, and a nonaqueous solvent (plasticizer) are dissolved in an organic solvent to evaporate the organic solvent for mixing; and a polymerizable monomer, a lithium salt, and a nonaqueous solvent (plasticizer) are mixed. A method of obtaining a polymer by irradiating a mixture with an ultraviolet ray, an electron beam or a molecular beam or the like to polymerize a polymerizable monomer.

此處，上述固體電解質中的非水溶劑(塑化劑)的比率較佳為10~90質量%，更佳為30~80質量%。若小於10質量%則導電率變低，若超過90質量%則機械強度變弱而難以成膜。 Here, the ratio of the nonaqueous solvent (plasticizer) in the solid electrolyte is preferably from 10 to 90% by mass, more preferably from 30 to 80% by mass. When it is less than 10% by mass, the electrical conductivity is low, and if it exceeds 90% by mass, the mechanical strength is weak and it is difficult to form a film.

[分隔構件] [separating member]

於本發明的鋰離子二次電池中，亦可使用分隔構件。 In the lithium ion secondary battery of the present invention, a partition member can also be used.

分隔構件的材質並無特別限定，例如可使用織布、不織布、合成樹脂製微多孔膜等。作為上述分隔構件的材質，較佳為合成 樹脂製微多孔膜，其中就厚度、膜強度、膜電阻方面而言，較佳為聚烯烴系微多孔膜。具體而言，較佳為聚乙烯及聚丙烯製微多孔膜、或將該等複合而成的微多孔膜等。 The material of the partition member is not particularly limited, and for example, a woven fabric, a non-woven fabric, a microporous film made of a synthetic resin, or the like can be used. As the material of the partition member, it is preferably synthesized The resin-made microporous film is preferably a polyolefin-based microporous film in terms of thickness, film strength, and film resistance. Specifically, a microporous film made of polyethylene or polypropylene or a microporous film obtained by combining these is preferable.

[鋰離子二次電池] [Lithium ion secondary battery]

本發明的鋰離子二次電池是藉由將上述構成的負極、正極及非水電解質例如以負極、非水電解質、正極的順序進行積層，並收納於電池的外裝材內而構成。進而，亦可於負極與正極的外側配置非水電解質。 In the lithium ion secondary battery of the present invention, the negative electrode, the positive electrode, and the nonaqueous electrolyte having the above-described configuration are laminated in the order of, for example, a negative electrode, a nonaqueous electrolyte, and a positive electrode, and are housed in an exterior material of the battery. Further, a nonaqueous electrolyte may be disposed outside the negative electrode and the positive electrode.

另外，本發明的鋰離子二次電池的構造並無特別限定，關於其形狀、形態亦無特別限定，可依據用途、搭載機器、及所要求的充放電電容等而自圓筒型、角型、硬幣型、紐扣型等中任意選擇。為了獲得安全性更高的密閉型非水電解液電池，較佳為使用具備於過量充電等異常時感知電池內壓上升並遮斷電流的元件的電池。 In addition, the structure of the lithium ion secondary battery of the present invention is not particularly limited, and the shape and shape thereof are not particularly limited, and may be from a cylindrical type or an angular type depending on the application, the mounting device, and the required charge and discharge capacitance. , coin type, button type, etc. In order to obtain a sealed non-aqueous electrolyte battery having higher safety, it is preferable to use a battery having an element that senses an increase in internal pressure of the battery and interrupts current when an abnormality such as excessive charging occurs.

於鋰離子二次電池為高分子固體電解質電池或高分子凝膠電解質電池的情況下，亦可設為封入層壓膜中的構造。 When the lithium ion secondary battery is a polymer solid electrolyte battery or a polymer gel electrolyte battery, it may be a structure that is sealed in a laminate film.

[實施例] [Examples]

繼而，藉由實施例具體說明本發明，但本發明並不限定於該等實施例。另外，於以下實施例及比較例中，如圖4所示，製作單極評價用的紐扣型二次電池並進行評價，該電池係由至少於表面的一部分附著有包含本發明的負極材料的負極混合劑2的集電體(current collector)(負極)7b與包含鋰箔的對極(正極)4所構成。實體電池可基於本發明的概念並依據公知的方法進行製作。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Further, in the following examples and comparative examples, as shown in FIG. 4, a button-type secondary battery for unipolar evaluation was prepared and evaluated, and the battery was adhered to at least a part of the surface to which the negative electrode material of the present invention was attached. The current collector (negative electrode) 7b of the negative electrode mixture 2 is composed of a counter electrode (positive electrode) 4 containing a lithium foil. The solid battery can be fabricated based on the concepts of the present invention and in accordance with well-known methods.

(實施例1) (Example 1)

[負極材料的製作] [Production of negative electrode material]

將平均粒徑5μm、平均扁平度20的鱗片狀石墨粒子、與平均粒徑0.2μm的矽粒子分散於聚丙烯酸水溶液中，並以噴霧乾燥裝置進行噴霧乾燥處理，獲得球狀的複合體前驅物。繼而，使用行星式攪拌機，對上述複合體前驅物添加煤焦油瀝青的焦油中油溶液並加以混練後，於氮氣的惰性環境中以1000℃進行煅燒處理，藉此獲得作為目標複合體的負極材料。各原材料的調配量是以作為最終製品的複合體中的各自的存在比率成為如表1所示的方式進行調整。噴霧乾燥是以表2所示的條件進行。以雷射式粒度分佈計測定到的複合體的平均粒徑為10μm。複合體的平均縱橫比於以後的實施例中全部為2以內。根據圖1所示的SEM像可知，鱗片狀石墨粒子呈同心圓狀地配向存在於表面。根據圖2所示的複合體剖面的偏光顯微鏡像可知，於內部存在空隙，另外，鱗片狀石墨粒子彼此非平行地存在於內部。另外，根據圖3所示的EDX映像可知，矽粒子分散存在。 The flaky graphite particles having an average particle diameter of 5 μm and an average flatness of 20 and the cerium particles having an average particle diameter of 0.2 μm were dispersed in a polyacrylic acid aqueous solution, and spray-dried by a spray drying device to obtain a spherical composite precursor. . Then, the oil solution of the tar of the coal tar pitch was added to the composite precursor by a planetary mixer and kneaded, and then calcined at 1000 ° C in an inert atmosphere of nitrogen to obtain a negative electrode material as a target composite. The blending amount of each raw material was adjusted as shown in Table 1 in the respective ratios in the composites as the final product. Spray drying was carried out under the conditions shown in Table 2. The average particle diameter of the composite measured by a laser particle size distribution meter was 10 μm. The average aspect ratio of the composites was all within 2 of the following examples. According to the SEM image shown in Fig. 1, the flaky graphite particles are present in a concentric shape on the surface. According to the polarizing microscope image of the cross section of the composite shown in FIG. 2, it is understood that voids are present inside, and the flaky graphite particles are present in non-parallel to each other. Further, from the EDX image shown in Fig. 3, it is understood that the ruthenium particles are dispersed.

[負極混合劑膠的製作] [Production of negative electrode mixture glue]

繼而，使用負極材料製作負極。首先，將包含上述複合體的負極材料96質量份、作為結合劑的羧基甲基纖維素2質量份、及苯乙烯-丁二烯橡膠2質量份放入水中，進行攪拌而製備負極混合劑膠。 Then, a negative electrode was used to make a negative electrode. First, 96 parts by mass of the negative electrode material containing the above composite, 2 parts by mass of carboxymethylcellulose as a binder, and 2 parts by mass of styrene-butadiene rubber are placed in water and stirred to prepare a negative electrode mixture gel. .

[作用電極(負極)的製作] [Production of the working electrode (negative electrode)]

將上述負極混合劑膠以均勻的厚度塗佈於厚度15μm的銅箔上，進而於真空中以90℃使分散介質的水蒸發而進行乾燥。繼而， 藉由手壓機對塗佈於該銅箔上的負極混合劑層進行加壓。進而，將銅箔與負極混合劑層沖裁成直徑15.5mm的圓柱狀，製作包含與銅箔密接的負極混合劑層的作用電極(負極)。負極混合劑層的密度為1.4g/cm3。 The negative electrode mixture rubber was applied to a copper foil having a thickness of 15 μm in a uniform thickness, and further, the water in the dispersion medium was evaporated at 90 ° C in a vacuum to be dried. Then, the negative electrode mixture layer coated on the copper foil was pressurized by a hand press. Further, the copper foil and the negative electrode mixture layer were punched out into a cylindrical shape having a diameter of 15.5 mm, and a working electrode (negative electrode) including a negative electrode mixture layer in close contact with the copper foil was produced. The density of the negative electrode mixture layer was 1.4 g/cm 3 .

[對極(正極)的製作] [production of the pole (positive electrode)]

繼而，使用上述負極製作單極評價用的紐扣型二次電池。對正極使用有包含鎳網的集電體、及與該集電體密接的包含鋰金屬箔的極板。 Then, a coin-type secondary battery for unipolar evaluation was produced using the above negative electrode. A current collector including a nickel mesh and an electrode plate containing a lithium metal foil in close contact with the current collector are used for the positive electrode.

[電解液、分隔構件] [electrolyte, partition member]

電解液是使LiPF6以成為1mol/L的濃度溶解於碳酸乙二酯33體積%與碳酸甲基乙酯67體積%的混合溶劑中，製備非水電解液。使所獲得的非水電解液含浸於作為分隔構件的厚度20μm的聚丙烯多孔質體中，製作含浸有電解液的分隔構件。此外，關於實體電池，可基於本發明的概念並依據公知的方法進行製作。 In the electrolytic solution, LiPF 6 was dissolved in a mixed solvent of 33% by volume of ethylene carbonate and 67% by volume of methyl ethyl carbonate at a concentration of 1 mol/L to prepare a nonaqueous electrolytic solution. The obtained non-aqueous electrolyte solution was impregnated into a polypropylene porous body having a thickness of 20 μm as a partition member to prepare a partition member impregnated with an electrolytic solution. Further, regarding the solid battery, it can be fabricated based on the concept of the present invention and according to a known method.

[評價電池的構成] [Evaluation of battery composition]

圖4中表示紐扣型二次電池作為評價電池的構成。 Fig. 4 shows a configuration of a button type secondary battery as an evaluation battery.

外裝護罩1與外裝罐3是使絕緣墊片(gasket)6介存於其周緣部將兩周緣部斂縫而進行密閉。該紐扣型二次電池是於其內部自外裝罐3的內面起依序積層有包含鎳網的集電體7a、包含鋰箔的圓筒狀的對極(正極)4、含浸有電解液的分隔構件5、及附著有負極材料的包含銅箔的集電體7b的電池系統。 In the exterior cover 1 and the outer can 3, an insulating gasket 6 is interposed in the peripheral portion thereof, and the both peripheral edges are caulked and sealed. In the button-type secondary battery, a current collector 7a including a nickel mesh, a cylindrical counter electrode (positive electrode) 4 containing a lithium foil, and an impregnation electrolysis are sequentially stacked from the inner surface of the outer can 3. A battery separator of the liquid separating member 5 and a current collector 7b containing a copper foil to which a negative electrode material is attached.

上述評價電池是以如下方式製作，即，使含浸有電解液的分隔構件5夾於包含集電體7b及負極混合劑2的作用電極(負極)、與密接於集電體7a的對極4之間並進行積層後，將集電體7b收 納於外裝護罩1內，將對極4收納於外裝罐3內，使外裝護罩1與外裝罐3合在一起，進而使絕緣墊片6介存於外裝護罩1與外裝罐3的周緣部將兩周緣部斂縫而進行密閉。 The evaluation battery is produced by sandwiching the separator member 5 impregnated with the electrolytic solution between the working electrode (negative electrode) including the current collector 7b and the negative electrode mixture 2, and the counter electrode 4 in close contact with the current collector 7a. After the layering is carried out, the current collector 7b is collected In the outer casing 1 , the counter electrode 4 is housed in the outer can 3 , and the outer cover 1 and the outer can 3 are combined, and the insulating spacer 6 is interposed in the outer cover 1 . The peripheral edge portion of the outer can 3 is crimped by both peripheral edges and sealed.

針對藉由以上方式製作而成的評價電池，於25℃的溫度下進行以下所示的充放電試驗，計算初始充放電效率、充電膨脹率及循環特性。將結果示於表1~3。 With respect to the evaluation battery fabricated by the above method, the charge and discharge test described below was carried out at a temperature of 25 ° C to calculate the initial charge and discharge efficiency, the charge expansion ratio, and the cycle characteristics. The results are shown in Tables 1 to 3.

[初始充放電效率] [Initial charge and discharge efficiency]

於進行0.9mA的定電流充電直至電路電壓達到0mV後，於電路電壓達到0mV的時間點切換成定電壓充電，進而持續充電直至電流值變成20μA。根據其間的通電量求出單位質量的充電電容(單位：mAh/g)。其後，暫停120分鐘。繼而，以0.9mA的電流值進行定電流放電直至電路電壓達到1.5V，根據其間的通電量求出單位質量的放電電容(單位：mAh/g)。藉由下述式計算初始充放電效率。 After the constant current charging of 0.9 mA is performed until the circuit voltage reaches 0 mV, the constant voltage charging is switched at the time when the circuit voltage reaches 0 mV, and charging is continued until the current value becomes 20 μA. A charging capacitor per unit mass (unit: mAh/g) is obtained from the amount of energization therebetween. Thereafter, pause for 120 minutes. Then, constant current discharge was performed at a current value of 0.9 mA until the circuit voltage reached 1.5 V, and a discharge capacitance per unit mass (unit: mAh/g) was obtained from the amount of energization therebetween. The initial charge and discharge efficiency was calculated by the following formula.

初始充放電效率(%)=(放電電容/充電電容)×100 Initial charge and discharge efficiency (%) = (discharge capacitor / charge capacitor) × 100

此外，於該試驗中，將鋰離子吸藏於負極材料中的過程設為充電，將鋰離子自負極材料脫附的過程設為放電。 Further, in this test, the process of occluding lithium ions in the negative electrode material was set as charging, and the process of desorbing lithium ions from the negative electrode material was set as discharge.

[充電膨脹率] [Charge expansion rate]

於進行0.9mA的定電流充電直至電路電壓達到0mV後，切換成定電壓充電，持續充電直至電流值變成20μA。於充電狀態下將評價電池拆開，將負極於氬氣環境下藉由碳酸乙基甲酯洗淨，並以測微計測定厚度。根據充電前後的負極的厚度與銅箔的厚度(15μm)，藉由下式計算負極活性物質的充電膨脹率。 After constant current charging of 0.9 mA is performed until the circuit voltage reaches 0 mV, it is switched to constant voltage charging, and charging is continued until the current value becomes 20 μA. The evaluation battery was disassembled in a charged state, and the negative electrode was washed with ethyl methyl carbonate under an argon atmosphere, and the thickness was measured with a micrometer. The charge expansion ratio of the negative electrode active material was calculated from the thickness of the negative electrode before and after charging and the thickness of the copper foil (15 μm) by the following formula.

充電膨脹率(%)=((充電後的負極的厚度-充電前的負極 的厚度)/(充電前的負極的厚度-銅箔的厚度))×100 Charging expansion ratio (%) = ((the thickness of the negative electrode after charging - the negative electrode before charging) Thickness) / (thickness of negative electrode before charging - thickness of copper foil)) × 100

[循環特性] [Circulation characteristics]

製作與評價單位質量的放電電容、急速充電率、急速放電率的評價電池不同的評價電池，進行如下評價。 An evaluation battery which was different from the battery for evaluating the discharge capacity, the rapid charge rate, and the rapid discharge rate of the unit mass was evaluated as follows.

於進行4.0mA的定電流充電直至電路電壓達到0mV後，切換成定電壓充電，持續充電直至電流值變成20μA後，暫停120分鐘。繼而，以4.0mA的電流值進行定電流放電直至電路電壓達到1.5V。重複20次充放電，根據所獲得的單位質量的放電電容，使用下式計算循環特性。 After constant current charging of 4.0 mA until the circuit voltage reaches 0 mV, the battery is switched to constant voltage charging, and charging is continued until the current value becomes 20 μA, and the time is suspended for 120 minutes. Then, constant current discharge was performed at a current value of 4.0 mA until the circuit voltage reached 1.5V. The charge and discharge were repeated 20 times, and the cycle characteristics were calculated using the following formula based on the obtained discharge capacitance per unit mass.

循環特性(%)=(第20循環中的放電電容/第1循環中的放電電容)×100 Cycle characteristics (%) = (discharge capacitance in the 20th cycle / discharge capacitance in the 1st cycle) × 100

(實施例2) (Example 2)

將製作複合體時的調配比設為如表1、2所示，除此以外，以與實施例1同樣的方式進行複合體的製作、負極及評價電池的製作、以及電池特性評價。 The preparation of the composite, the production of the negative electrode and the evaluation battery, and the evaluation of the battery characteristics were carried out in the same manner as in Example 1 except that the mixing ratio at the time of the production of the composite was as shown in Tables 1 and 2.

根據複合體的SEM像可知，鱗片狀石墨粒子呈同心圓狀地配向存在於表面，根據複合體剖面的偏光顯微鏡像可知，於內部存在空隙，另外，鱗片狀石墨粒子彼此非平行地存在於內部。另外，根據EDX映像亦可知，矽粒子分散存在。 According to the SEM image of the composite, the flaky graphite particles are present in a concentric shape on the surface. According to the polarizing microscope image of the cross section of the composite, voids are present inside, and the flaky graphite particles are not parallel to each other. . Further, it is also known from the EDX image that the ruthenium particles are dispersed.

(實施例3、4) (Examples 3 and 4)

以表1所示的比率將平均粒徑5μm、平均扁平度20的鱗片狀石墨粒子、平均粒徑0.2μm的矽粒子及石墨質纖維添加於聚丙烯酸水溶液中並進行混合，除此以外，以與實施例1同樣的方式進行複合體的製作、負極及評價電池的製作、以及電池特性評價。 The flaky graphite particles having an average particle diameter of 5 μm and an average flatness of 20, ruthenium particles having an average particle diameter of 0.2 μm, and graphite fibers were added to a polyacrylic acid aqueous solution and mixed at a ratio shown in Table 1 except that The production of the composite, the production of the negative electrode and the evaluation battery, and the evaluation of the battery characteristics were carried out in the same manner as in the first embodiment.

根據複合體的SEM像可知，鱗片狀石墨粒子呈同心圓狀地配向存在於表面，根據複合體剖面的偏光顯微鏡像可知，於內部存在空隙，另外，鱗片狀石墨粒子彼此非平行地存在於內部。另外，根據EDX映像亦可知，矽粒子分散存在。根據複合體的外觀及剖面的SEM像亦可知，石墨質纖維分散存在於複合體中。 According to the SEM image of the composite, the flaky graphite particles are present in a concentric shape on the surface. According to the polarizing microscope image of the cross section of the composite, voids are present inside, and the flaky graphite particles are not parallel to each other. . Further, it is also known from the EDX image that the ruthenium particles are dispersed. It is also known from the SEM image of the appearance and cross section of the composite that the graphite fibers are dispersed in the composite.

(比較例1) (Comparative Example 1)

以雙軸捏合機對平均粒徑5μm、平均扁平度20的鱗片狀石墨粒子、平均粒徑0.2μm的矽粒子、及煤焦油瀝青的焦油中油溶液進行混練。繼而，將混練品進行模具成形，並以1000℃對該成形品進行煅燒處理後，以平均粒徑成為10μm的方式進行粉碎而獲得目標負極材料。除此以外，以與實施例1同樣的方式進行負極混合劑的製備、負極及評價電池的製作、以及電池特性評價。另外，以與實施例1同樣的方式觀察複合體的表面與剖面，結果對於所獲得的複合體，可確認其雖於內部具有空隙，但鱗片狀石墨粒子無論於表面抑或內部均是非平行地存在。 The scaly graphite particles having an average particle diameter of 5 μm and an average flatness of 20, the cerium particles having an average particle diameter of 0.2 μm, and the tar oil solution of the coal tar pitch were kneaded by a twin-axis kneader. Then, the kneaded product was subjected to mold molding, and the molded product was fired at 1000 ° C, and then pulverized so that the average particle diameter became 10 μm to obtain a target negative electrode material. The preparation of the negative electrode mixture, the production of the negative electrode and the evaluation battery, and the evaluation of the battery characteristics were carried out in the same manner as in Example 1. Further, the surface and the cross section of the composite were observed in the same manner as in Example 1. As a result, it was confirmed that the obtained composite had voids therein, but the flaky graphite particles were non-parallel regardless of the surface or the inside. .

將以上評價結果示於表1~3。根據實施例1~4可知，使用有本發明的負極材料的鋰離子二次電池具有超過石墨的理論電容的較高的放電電容。另外，根據實施例2~4與比較例1的比較可知，藉由本發明的負極材料，可使初始充放電效率、充電耐膨脹率及循環特性更優異。 The above evaluation results are shown in Tables 1 to 3. According to Examples 1 to 4, the lithium ion secondary battery using the negative electrode material of the present invention has a higher discharge capacity than the theoretical capacitance of graphite. Further, according to the comparison between Examples 2 to 4 and Comparative Example 1, it is understood that the initial charge and discharge efficiency, the charge expansion expansion ratio, and the cycle characteristics can be further improved by the negative electrode material of the present invention.

[產業上的可利用性] [Industrial availability]

本發明提供一種可充分緩和充電時的金屬質物的膨脹，且顯示超過石墨的理論電容的較高的放電電容、與優異的初始充放電效率的負極材料作為鋰離子二次電池用負極材料。因此，使用本發明的負極材料的鋰離子二次電池滿足近年來對電池的高能量密度化的要求，對搭載的機器的小型化及高性能化有用。本發明的負極材料可發揮其特性而用於小型至大型的高性能鋰離子二次電池。 The present invention provides a negative electrode material which can sufficiently relax the expansion of the metal material during charging and exhibits a high discharge capacity exceeding the theoretical capacitance of graphite and excellent initial charge and discharge efficiency as a negative electrode material for a lithium ion secondary battery. Therefore, the lithium ion secondary battery using the negative electrode material of the present invention satisfies the demand for high energy density of the battery in recent years, and is useful for miniaturization and high performance of the mounted device. The negative electrode material of the present invention can be used for small to large-sized high-performance lithium ion secondary batteries by exerting its characteristics.

1‧‧‧外裝護罩 1‧‧‧Outer cover

2‧‧‧負極混合劑 2‧‧‧Negative mixture

3‧‧‧外裝罐 3‧‧‧Outer cans

4‧‧‧對極 4‧‧‧ pole

5‧‧‧分隔構件 5‧‧‧Parts

6‧‧‧絕緣墊片 6‧‧‧Insulation gasket

7a、7b‧‧‧集電體 7a, 7b‧‧‧ collector

Claims (9)

一種鋰離子二次電池用負極材料，其是包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀的複合體，其特徵在於：上述複合體於內部具有空隙，且上述鱗片狀石墨粒子非平行地存在於上述複合體的內部，並呈同心圓狀地配向存在於上述複合體的表面，且上述金屬粒子分散存在於上述複合體粒子內部及/或表面，上述鱗片狀石墨粒子的平均扁平度(Ly/t)為0.5~40，上述複合體的上述表面是指自上述複合體的最表面起至上述鱗片狀石墨粒子的厚度的2倍以下的範圍，其中大小0.01~100μm的上述空隙的容積為0.05~0.4cm3/g。 A negative electrode material for a lithium ion secondary battery, which is a spherical composite body including flaky graphite particles, calcined carbon, and metal particles which can be alloyed with lithium, wherein the composite body has a void therein and the above The flaky graphite particles are present in the inside of the composite body in a non-parallel manner, and are present in a concentric manner on the surface of the composite body, and the metal particles are dispersed in the inside and/or the surface of the composite particles, and the scaly shape The average flatness (Ly/t) of the graphite particles is 0.5 to 40, and the surface of the composite refers to a range from the outermost surface of the composite to twice the thickness of the flaky graphite particles, wherein the size is 0.01. The volume of the above-mentioned voids of ~100 μm is 0.05 to 0.4 cm 3 /g. 如申請專利範圍第1項所述之鋰離子二次電池用負極材料，其中將上述複合體設為100質量%，上述鱗片狀石墨粒子：98~60質量%、上述煅燒碳：1~20質量%、及上述金屬粒子：1~20質量%。 The negative electrode material for a lithium ion secondary battery according to claim 1, wherein the composite is 100% by mass, the flaky graphite particles are 98 to 60% by mass, and the calcined carbon is 1 to 20% by mass. %, and the above metal particles: 1 to 20% by mass. 如申請專利範圍第1項所述之鋰離子二次電池用負極材料，其中上述複合體中更包含石墨質纖維。 The negative electrode material for a lithium ion secondary battery according to claim 1, wherein the composite further comprises a graphite fiber. 如申請專利範圍第3項所述之鋰離子二次電池用負極材料，其中將上述複合體設為100質量%，上述鱗片狀石墨粒子：97.5~55質量%、上述煅燒碳：1~20質量%、上述金屬粒子：1~20質量%、及上述石墨質纖維：0.5~5質量%。 The negative electrode material for a lithium ion secondary battery according to the third aspect of the invention, wherein the composite is 100% by mass, the flaky graphite particles are 97.5 to 55 mass%, and the calcined carbon is 1 to 20 mass. %, the above metal particles: 1 to 20% by mass, and the above-mentioned graphite fibers: 0.5 to 5% by mass. 一種鋰離子二次電池用負極，其含有如申請專利範圍第1項至第4項中任一項所述之鋰離子二次電池用負極材料。 A negative electrode material for a lithium ion secondary battery according to any one of claims 1 to 4, which is a negative electrode material for a lithium ion secondary battery. 一種鋰離子二次電池，其包含如申請專利範圍第5項所述之鋰離子二次電池用負極。 A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to claim 5 of the invention. 一種鋰離子二次電池用負極材料的製造方法，其是包含鱗片狀石墨粒子、煅燒碳及可與鋰合金化的金屬粒子的球狀的複合體的製造方法，其特徵在於：使上述鱗片狀石墨粒子及上述金屬粒子分散於作為碳質材料及/或碳質材料的前驅物的結著劑的溶液中，進行噴霧乾燥處理後，於700℃以上、1500℃以下的溫度範圍內進行熱處理，使上述碳質材料及碳質材料的前驅物成為煅燒碳，其後不經過粉碎步驟而製成最終製品。 A method for producing a negative electrode material for a lithium ion secondary battery, which is a method for producing a spherical composite comprising flaky graphite particles, calcined carbon, and metal particles capable of alloying with lithium, characterized in that the scaly shape is used The graphite particles and the metal particles are dispersed in a solution of a binder which is a precursor of the carbonaceous material and/or the carbonaceous material, and are subjected to a spray drying treatment, and then heat-treated at a temperature of 700 ° C or more and 1500 ° C or less. The precursor of the carbonaceous material and the carbonaceous material is made into calcined carbon, and thereafter, the final product is produced without undergoing a pulverization step. 一種鋰離子二次電池用負極材料的製造方法，其是包含鱗片狀石墨粒子、煅燒碳、可與鋰合金化的金屬粒子及石墨質纖維的球狀的複合體的製造方法，其特徵在於：使上述鱗片狀石墨粒子、上述金屬粒子及石墨質纖維分散於作為碳質材料及/或碳質材料的前驅物的結著劑的溶液中，進行噴霧乾燥處理後，於700℃以上、1500℃以下的溫度範圍內進行熱處理，使上述碳質材料及碳質材料的前驅物成為煅燒碳，其後不經過粉碎步驟而製成最終製品。 A method for producing a negative electrode material for a lithium ion secondary battery, which is a method for producing a spherical composite comprising flaky graphite particles, calcined carbon, metal particles capable of alloying with lithium, and graphite fibers, characterized in that: Dispersing the flaky graphite particles, the metal particles, and the graphite fibers in a solution of a binder as a precursor of a carbonaceous material and/or a carbonaceous material, and performing a spray drying treatment at 700 ° C or higher and 1500 ° C The heat treatment is performed in the following temperature range so that the precursor of the carbonaceous material and the carbonaceous material becomes calcined carbon, and thereafter, the final product is produced without undergoing a pulverization step. 如申請專利範圍第7項或第8項所述之鋰離子二次電池用負極材料的製造方法，其中進而使碳質材料及/或碳質材料的前驅物附著於上述噴霧乾燥處理品，之後進行上述熱處理。 The method for producing a negative electrode material for a lithium ion secondary battery according to claim 7 or claim 8, wherein the precursor of the carbonaceous material and/or the carbonaceous material is further adhered to the spray-dried product, and thereafter The above heat treatment is carried out.
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