JP2015156358A - Method for producing graphene based composite negative electrode material, negative electrode material produced thereby, and lithium ion secondary battery - Google Patents
Method for producing graphene based composite negative electrode material, negative electrode material produced thereby, and lithium ion secondary battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 44
- 239000010439 graphite Substances 0.000 claims abstract description 44
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
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- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/13—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
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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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- 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
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Abstract
Description
本発明はリチウムイオン二次電池用負極材料の技術分野に関する。具体的には、グラフェン基複合負極材料の製造方法及び製造された負極材料とリチウムイオン二次電池に関する。 The present invention relates to the technical field of negative electrode materials for lithium ion secondary batteries. Specifically, the present invention relates to a method for producing a graphene-based composite negative electrode material, a produced negative electrode material, and a lithium ion secondary battery.
リチウムイオン二次電池はプロセスが成熟した電気化学電源体系として、すでに人間の日常生活の各方面に適用されているが、その性能が相変わらず適用中の各種の需要を満たし難い。従来、適用が最も広く、性能が最も優れたリチウムイオン二次電池用負極材料は黒鉛類材料であることが間違いなく、それがよい層状構造、安定な放電プラットフォームを有し、リチウム挿入脱離の過程に体積の変化が小さく、電圧ヒステリシス現象がない。しかしながら、他方から見れば、黒鉛類負極材料は容量の上限値を有し、突破し難く、電解液との相溶性が悪く、それによって電池の循環安定性が悪くなることを引き起こし、且つ大電流充放電性能が悪く、レート特性を高める必要がある。それゆえ、研究開発者は黒鉛をリチウムイオン二次電池用負極材料とすることに対して数十年の改質研究を行い、比較的に成功した改質方法は、例えば表面酸化又はハロゲン化を行い、表面に非晶質炭素、金属及びその酸化物、ポリマーなどを被覆し、あるいは金属又は非金属元素をドーピングし、黒鉛に特別な性能を有するその他成分を少量引き込んで複合材料を構成してもよく、以上によって黒鉛負極の総合性能を変更した。 Lithium ion secondary batteries have already been applied to various aspects of human daily life as an electrochemical power supply system with a mature process, but their performance is still difficult to meet the various demands being applied. Conventionally, the negative electrode material for lithium ion secondary batteries with the widest application and the best performance is definitely graphite material, which has good layered structure, stable discharge platform, There is little change in volume in the process and there is no voltage hysteresis phenomenon. However, when viewed from the other side, the graphite negative electrode material has an upper limit of capacity, is difficult to break through, has poor compatibility with the electrolytic solution, thereby causing poor circulation stability of the battery, and high current. Charge / discharge performance is poor, and it is necessary to improve rate characteristics. Researchers have therefore conducted decades of modification research on graphite as a negative electrode material for lithium ion secondary batteries, and relatively successful modification methods include surface oxidation or halogenation, for example. The surface is coated with amorphous carbon, metal and its oxide, polymer, etc., or doped with metal or non-metal elements, and a small amount of other components with special performance is drawn into the graphite to form a composite material. The overall performance of the graphite negative electrode was changed as described above.
グラフェンは黒鉛の単層構造であり、黒鉛を液相酸化し、加熱して膨張し、さらに機械剥離し還元して取得され、高い導電性、高い伝熱性、高い機械強度と柔軟性、高安定性などの特徴を有し、それゆえ、グラフェンと黒鉛との複合は優れた各種の性能が現れる。該複合材料はリチウムイオン二次電池用負極材料として用いられ、導電性を強め、電池パワー特性を高め、リチウム貯蔵容量を増加し、電池エネルギー密度を高め、循環安定性を強め、電池寿命を延ばすなどの特徴が現れる。しかしながら、純相グラフェン材料の生産コストが高く、且つグラフェンシートの比表面積が大きく、独立的に存在することが難しく、集塊しやく、黒鉛相に均一に分散することが難しく、それゆえ、好適なグラフェン基複合プロセスを選択し、且つ負極材料の総合性能を高めることは本分野に解決する必要がある１つの技術問題である。 Graphene is a single layer structure of graphite, which is obtained by liquid phase oxidation of graphite, heating to expand, and mechanical exfoliation and reduction. High conductivity, high heat conductivity, high mechanical strength and flexibility, high stability Therefore, the composite of graphene and graphite exhibits various excellent performances. The composite material is used as a negative electrode material for lithium ion secondary batteries, enhances conductivity, enhances battery power characteristics, increases lithium storage capacity, increases battery energy density, enhances circulation stability, and extends battery life. Features such as appear. However, the production cost of the pure phase graphene material is high and the specific surface area of the graphene sheet is large, it is difficult to exist independently, it is easy to agglomerate, it is difficult to uniformly disperse in the graphite phase, and therefore suitable Selecting a suitable graphene-based composite process and enhancing the overall performance of the negative electrode material is one technical problem that needs to be solved in this field.
中国発明特許出願ＣＮ１０２４１２３９６Ａは不連続のグラフェンで覆われたリチウムイオン二次電池の電極材料を開示し、正極材料、正極材料前躯体又は負極材料を雰囲気炉に置いて焼結し、酸素含有有機物を入れると同時に水蒸気を入れ、また惰性ガスである窒素ガス及び／又はアルゴンガスを入れ、入れる酸素含有有機物と水蒸気の体積分率がそれぞれ１〜９０％と０．１〜１５％であり、雰囲気炉の温度を５００〜１３００℃に制御し、３〜４０時間で反応し、室温まで冷却し、不連続のグラフェンで覆われたリチウムイオン二次電池電極材料を取得する。前記方法は不連続のグラフェンで覆われたリチウムイオン二次電池用負極材料を取得したにも係わらず、構造が十分に安定せず、比容量、導電率、レート特性、液吸収性能及びサイクル特性が悪く、応用における各種の需要を満たすことができない。 Chinese patent application CN102412396A discloses an electrode material of a lithium ion secondary battery covered with discontinuous graphene, and the positive electrode material, the positive electrode material precursor or the negative electrode material is placed in an atmosphere furnace to sinter the oxygen-containing organic material. Steam is added at the same time, nitrogen gas and / or argon gas is added, and the volume fraction of oxygen-containing organic substance and water vapor is 1 to 90% and 0.1 to 15%, respectively, The temperature is controlled at 500 to 1300 ° C., reacted for 3 to 40 hours, cooled to room temperature, and a lithium ion secondary battery electrode material covered with discontinuous graphene is obtained. Although the above method has obtained a negative electrode material for lithium ion secondary battery covered with discontinuous graphene, the structure is not sufficiently stable, specific capacity, conductivity, rate characteristics, liquid absorption performance and cycle characteristics It is bad and cannot meet various demands in application.
中国発明特許出願ＣＮ１０２５６９８１０Ａはグラフェン改質リチウムイオン二次電池用負極材料及びその製造方法を開示し、酸化グラフェンを水溶液又は有機溶剤に均一に分散し、黒鉛ビーズを有機溶剤に均一に分散させ、さらに２種類の分散液を均一に混合し、還元剤を加えて撹拌還流させ、次に濾過し乾燥してグラフェンと黒鉛ビーズとの複合材料の一次生成物を取得し、最後に、高温仮焼を経ってグラフェン改質リチウムイオン二次電池用負極材料を取得する。前記方法は不連続のグラフェンで覆われたリチウムイオン二次電池用負極材料を取得することができるにも係わらず、構造が十分に安定せず、比容量、導電率、レート特性、液吸収性能及びサイクル特性が悪い問題もある。 Chinese patent application CN102569810A discloses a negative electrode material for graphene-modified lithium ion secondary battery and a manufacturing method thereof, and graphene oxide is uniformly dispersed in an aqueous solution or an organic solvent, and graphite beads are uniformly dispersed in an organic solvent. Mix two types of dispersions uniformly, add a reducing agent, stir to reflux, then filter and dry to obtain the primary product of graphene and graphite bead composites, and finally high temperature calcination After that, a negative electrode material for graphene-modified lithium ion secondary battery is obtained. Although the above method can obtain a negative electrode material for lithium ion secondary batteries covered with discontinuous graphene, the structure is not sufficiently stable, specific capacity, conductivity, rate characteristics, liquid absorption performance There is also a problem that cycle characteristics are bad.
従来技術の欠点に対して、本発明はグラフェン基複合負極材料及びその製造方法とリチウムイオン二次電池を提供することを目的とし、前記方法により製造された負極材料は黒鉛と、黒鉛相に均一に分布するナノグラフェンシート層構造とを備え、二相が緊密に接触し、構造が安定で、高い比容量、高い導電率、高いレート特性、優れた液吸収性能及びサイクル特性を有する。 In contrast to the disadvantages of the prior art, the present invention aims to provide a graphene-based composite negative electrode material, a method for producing the same, and a lithium ion secondary battery, and the negative electrode material produced by the method is homogeneous in graphite and the graphite phase. The nanographene sheet layer structure distributed in the two layers, intimate contact between the two phases, stable structure, high specific capacity, high electrical conductivity, high rate characteristics, excellent liquid absorption performance and cycle characteristics.
本発明の目的を達成するために、以下の技術手段を採用する。
手段１として、本発明はグラフェン基複合負極材料の製造方法を提供し、天然黒鉛及び／又は人造黒鉛の前躯体を原料とし、一定の量の酸化黒鉛と均一に混合し、次ぎに一定の比例のバインダーを加えて高温混練し、混練材料を圧延して粉砕を行い、次に、プレスを行い、プレス製品を高温で黒鉛化し、黒鉛化する過程に酸化黒鉛は膨張、層剥離が発生してグラフェンと黒鉛の二相が緊密に接触する複合材料を形成し、最後に、粉砕してふるいにかけ、所望粒度のグラフェン基複合負極材料を取得する。
In order to achieve the object of the present invention, the following technical means are adopted.
As means 1, the present invention provides a method for producing a graphene-based composite negative electrode material, using a precursor of natural graphite and / or artificial graphite as a raw material, uniformly mixed with a certain amount of graphite oxide, and then with a certain proportion The binder is added and kneaded at high temperature, the kneaded material is rolled and pulverized, then pressed, the press product is graphitized at high temperature, and graphite oxide expands and delaminates during the graphitization process. A composite material in which two phases of graphene and graphite are in intimate contact is formed, and finally, pulverized and sieved to obtain a graphene-based composite negative electrode material having a desired particle size.
具体的には、前記方法は
黒鉛原料を酸化黒鉛と均一に混合し、混合材料を得る工程（１）、
前記混合材料にバインダーを加えて混練し、混練材料を取得する工程（２）、
前記混練材料を圧延し、圧延薄板を取得する工程（３）、
前記圧延薄板に対して粉砕処理を行い、粉体材料を取得する工程（４）、
前記粉体材料に対してプレスしてプレス製品を取得する工程（５）、
保護性雰囲気で前記プレス製品に対して黒鉛化処理を行い、グラフェン基複合負極材料を取得する工程（６）を含む。
Specifically, the method comprises the step (1) of uniformly mixing a graphite raw material with graphite oxide to obtain a mixed material,
A step of adding a binder to the mixed material and kneading to obtain a kneaded material (2);
Rolling the kneaded material to obtain a rolled sheet (3),
Crushing the rolled sheet to obtain a powder material (4),
A step of pressing the powder material to obtain a pressed product (5),
A step (6) of obtaining a graphene-based composite negative electrode material by performing graphitization on the pressed product in a protective atmosphere;
本発明の好ましい技術手段として、前記工程（１）において、黒鉛原料は天然黒鉛と人造黒鉛の前躯体のうちの１種又は少なくとも２種の組み合わせである。前記天然黒鉛は、好ましくは鱗片状黒鉛及び／又は微結晶黒鉛である。前記人造黒鉛の前躯体は、好ましくはニードルコークス未黒鉛化製品、石油コークス未黒鉛化製品及びカーボンマイクロビーズ未黒鉛化製品のうちの１種又は少なくとも２種の組み合わせである。前記組み合わせには典型で制限されない例として、鱗片状黒鉛と微結晶黒鉛の組み合わせ、鱗片状黒鉛とニードルコークス未黒鉛化製品の組み合わせ、ニードルコークス未黒鉛化製品と石油コークス未黒鉛化製品とカーボンマイクロビーズ未黒鉛化製品の組み合わせがある。 As a preferred technical means of the present invention, in the step (1), the graphite raw material is one kind or a combination of at least two kinds of precursors of natural graphite and artificial graphite. The natural graphite is preferably scaly graphite and / or microcrystalline graphite. The precursor of the artificial graphite is preferably one or a combination of at least two of needle coke non-graphitized product, petroleum coke non-graphitized product, and carbon microbead non-graphitized product. Examples of the above combinations that are typical and not limited include combinations of flaky graphite and microcrystalline graphite, combinations of flaky graphite and needle coke non-graphitized products, needle coke non-graphitized products, petroleum coke non-graphitized products, and carbon micro There are combinations of beaded non-graphitized products.
前記黒鉛原料の純度は、好ましくは９０（重量）％以上、例えば９０．００（重量）％、９０．１０（重量）％、９０．９０（重量）％、９１．１０（重量）％、９２．５０（重量）％、９２．９０（重量）％、９３．００（重量）％、９３．１０（重量）％、９４．００（重量）％、９５．００（重量）％、９５．１０（重量）％、９６．４５（重量）％、９８．８０（重量）％、９９．２０（重量）％、９９．９０（重量）％又は９９．９５（重量）％などである。 The purity of the graphite raw material is preferably 90 (wt)% or more, for example, 90.00 (wt)%, 90.10 (wt)%, 90.90 (wt)%, 91.10 (wt)%, 92 .50 (wt)%, 92.90 (wt)%, 93.00 (wt)%, 93.10 (wt)%, 94.00 (wt)%, 95.00 (wt)%, 95.10. (Wt)%, 96.45 (wt)%, 98.80 (wt)%, 99.20 (wt)%, 99.90 (wt)%, 99.95 (wt)%, or the like.
前記酸化黒鉛は、好ましくは前記混合材料の重量の０．１％〜４０.０％、例えば０．１％、５％、１０％、３０％又は４０％などである。 The graphite oxide is preferably 0.1% to 40.0% of the weight of the mixed material, such as 0.1%, 5%, 10%, 30% or 40%.
前記混合の時間は、好ましくは３〜１８０ｍｉｎ、例えば３ｍｉｎ、１０ｍｉｎ、６０ｍｉｎ、１２０ｍｉｎ又は１８０ｍｉｎなどである。 The mixing time is preferably 3 to 180 min, such as 3 min, 10 min, 60 min, 120 min, or 180 min.
前記混合に採用される設備は、好ましくはＶ型ミキサー、溝型ミキサー、バレルミキサー、円錐形二重らせんミキサー又はダブルコン・ミキサーである。 The equipment employed for the mixing is preferably a V-type mixer, a groove-type mixer, a barrel mixer, a conical double helix mixer or a double-con mixer.
本発明の好ましい技術手段として、前記工程（２）において、バインダーはピッチ、樹脂、高分子材料及びポリマーのうちの１種又は少なくとも２種の組み合わせであり、好ましくは石炭ピッチ、石油ピッチ、天然ピッチ、中間相ピッチ、樹脂、高分子材料及びポリマーのうちの１種又は少なくとも２種の組み合わせである。前記組み合わせには制限するものでない典型的な例は、石炭ピッチと天然ピッチの組み合わせ、天然ピッチと樹脂の組み合わせ、石炭ピッチと樹脂とポリマーとの組み合わせがある。 As a preferred technical means of the present invention, in the step (2), the binder is one or a combination of at least two of pitch, resin, polymer material and polymer, preferably coal pitch, petroleum pitch, natural pitch. , Intermediate phase pitch, resin, polymer material and polymer, or a combination of at least two. Typical examples that are not limited to the combination include a combination of coal pitch and natural pitch, a combination of natural pitch and resin, and a combination of coal pitch, resin, and polymer.
前記バインダーは、好ましくは前記混練材料の重量の５．０％〜４０．０％、例えば５％、１０％、２０％、３０％又は４０％などである。 The binder is preferably 5.0% to 40.0% of the weight of the kneaded material, such as 5%, 10%, 20%, 30% or 40%.
前記混練は、好ましくは５０〜２００℃の温度範囲内、例えば５０℃、１００℃、１５０℃、１７０℃又は２００℃などの温度で行う。 The kneading is preferably performed within a temperature range of 50 to 200 ° C., for example, at a temperature such as 50 ° C., 100 ° C., 150 ° C., 170 ° C., or 200 ° C.
前記混練の時間は、好ましくは１〜１０ｈ、例えば１ｈ、２ｈ、３ｈ、５ｈ又は１０ｈなどである。 The kneading time is preferably 1 to 10 h, such as 1 h, 2 h, 3 h, 5 h, or 10 h.
本発明の好ましい技術手段として、前記工程（３）に記載の圧延は二本ロールミルを採用する。 As a preferred technical means of the present invention, the rolling described in the step (3) employs a two-roll mill.
前記圧延は、好ましくは２０〜３００℃の温度範囲内、例えば２０℃、３０℃、５０℃、１００℃、１２０℃、１５０℃、２００℃、２５０℃、２８０℃又は３００℃などの温度で行う。 The rolling is preferably performed within a temperature range of 20 to 300 ° C., for example, at a temperature of 20 ° C., 30 ° C., 50 ° C., 100 ° C., 120 ° C., 150 ° C., 200 ° C., 250 ° C., 280 ° C., or 300 ° C. .
前記二本ロールミルの二本ロールの回転速度比は、好ましくは１：１．１〜１：２、例えば１：１．１、１：１．２、１：１．５、１：１．７又は１：２などであること、ローラー軸の間隔は、好ましくは０．５〜５ｍｍ、例えば０．６ｍｍ、０．８ｍｍ、１．２ｍｍ、１．８ｍｍ、２．５ｍｍ、４ｍｍ又は４．８ｍｍである。 The rotation speed ratio of the two rolls of the two-roll mill is preferably 1: 1.1 to 1: 2, for example 1: 1.1, 1: 1.2, 1: 1.5, 1: 1.7. Or 1: 2, etc., and the roller shaft spacing is preferably 0.5-5 mm, for example 0.6 mm, 0.8 mm, 1.2 mm, 1.8 mm, 2.5 mm, 4 mm or 4.8 mm. is there.
本発明の好ましい技術手段として、前記工程（４）において、粉砕処理はターボミル、渦流ジェットミル、スーパーサイクロンミル、風選粉砕機又は双ロールミルを採用する。 As a preferred technical means of the present invention, in the step (4), a turbo mill, a vortex jet mill, a super cyclone mill, a wind selective pulverizer or a twin roll mill is adopted for the pulverization treatment.
前記粉体材料の平均粒度は、好ましくは５．０〜３０．０μm、例えば５．３２μm、７．８５μm、９．５６μm、１５．８９μm、１８．２３μm又は２８．２８μmなどである。 The average particle size of the powder material is preferably 5.0 to 30.0 μm, such as 5.32 μm, 7.85 μm, 9.56 μm, 15.89 μm, 18.23 μm or 28.28 μm.
本発明の好ましい技術手段として、前記工程（５）において、プレスは単一コラム形油圧プレス、４コラム形油圧プレス、横式油圧プレス、直立式油圧プレス及びユニバーサル油圧機械を採用する。 As a preferred technical means of the present invention, in the step (5), the press employs a single column type hydraulic press, a four column type hydraulic press, a horizontal hydraulic press, an upright hydraulic press and a universal hydraulic machine.
前記プレス製品の体積密度は、好ましくは１．０〜１．８ｇ／ｃｍ３、例えば１．００６ｇ／ｃｍ３、１．３９８ｇ／ｃｍ３、１．４３６ｇ／ｃｍ３又は１．７１２ｇ／ｃｍ３などである。 The volume density of the pressed product is preferably 1.0 to 1.8 g / cm 3 , such as 1.006 g / cm 3 , 1.398 g / cm 3 , 1.436 g / cm 3, or 1.712 g / cm 3. It is.
前記プレス製品の形状は、好ましくは円筒体及び／又はブロック体である。 The shape of the pressed product is preferably a cylindrical body and / or a block body.
本発明の好ましい技術手段として、前記工程（６）において、黒鉛化処理は内部ストリング型黒鉛化炉又はアチソン型黒鉛化炉を採用する。 As a preferred technical means of the present invention, in the step (6), the graphitization treatment employs an internal string type graphitization furnace or an Atchison type graphitization furnace.
前記保護性雰囲気は、好ましくはヘリウムガス、ネオンガス、アルゴンガス及び窒素ガスのうちの１種又は少なくとも２種の組み合わせである。前記組み合わせには制限するものでない典型的な例は、ヘリウムガスとネオンガスの組み合わせ、ネオンガスとアルゴンガスの組み合わせ、アルゴンガスと窒素ガスの組み合わせ、ヘリウムガスとネオンガスとアルゴンガスの組み合わせ、ネオンガスとアルゴンガスと窒素ガスの組み合わせなどがある。 The protective atmosphere is preferably one or a combination of at least two of helium gas, neon gas, argon gas and nitrogen gas. Typical examples that are not limited to the above combinations are a combination of helium gas and neon gas, a combination of neon gas and argon gas, a combination of argon gas and nitrogen gas, a combination of helium gas, neon gas and argon gas, a neon gas and argon gas. And nitrogen gas combination.
前記黒鉛化処理は、好ましくは２７００〜３３００℃の温度範囲内、例えば２７００℃、２８００℃、３０００℃又は３３００℃などの温度で行う。
本発明の好ましい技術手段として、前記工程（６）の後に、
前記グラフェン基複合負極材料を粉砕し、ふるいにかけ、平均粒度が５．０〜３０．０μmであるグラフェン基複合負極材料を取得する工程（７）を行う。
The graphitization treatment is preferably performed within a temperature range of 2700 to 3300 ° C., for example, at a temperature such as 2700 ° C., 2800 ° C., 3000 ° C., or 3300 ° C.
As a preferred technical means of the present invention, after the step (6),
The said graphene group composite negative electrode material is grind | pulverized, it sifts, and the process (7) which acquires the graphene group composite negative electrode material whose average particle diameter is 5.0-30.0 micrometers is performed.
前記粉砕は、好ましくはターボミル、渦流ジェットミル、スーパーサイクロンミル、風選粉砕機又は双ロールミルを採用する。 The pulverization preferably employs a turbo mill, a vortex jet mill, a super cyclone mill, a wind-selective pulverizer, or a twin roll mill.
本発明による方法は従来の二相の単純な混合複合プロセスから離脱し、新たな生産フローを採用し、且つ過程を正確的に制御し、厳しい条件がなく、工業化を実現しやすい。該方法により製造したグラフェン基複合負極材料は構造が安定で、優れた総合性能を有する。 The method according to the present invention leaves the conventional two-phase simple mixed complex process, adopts a new production flow, controls the process accurately, has no severe conditions, and is easy to realize industrialization. The graphene-based composite negative electrode material produced by this method has a stable structure and excellent overall performance.
手段２として、本発明は前記製造方法により製造されるグラフェン基複合負極材料を提供し、前記グラフェン基複合負極材料がコア黒鉛とシェルグラフェンシート層を含む。 As means 2, the present invention provides a graphene-based composite negative electrode material produced by the production method, and the graphene-based composite negative electrode material includes a core graphite and a shell graphene sheet layer.
前記グラフェン基複合負極材料の平均粒度は、好ましくは５．０〜３０．０μmである。 The average particle size of the graphene-based composite negative electrode material is preferably 5.0 to 30.0 μm.
前記グラフェン基複合負極材料の純度は、好ましくは９９．９（重量）％以上である。 The purity of the graphene group composite negative electrode material is preferably 99.9% (by weight) or more.
前記グラフェン基複合負極材料の比表面積は、好ましくは３．０〜４０ｍ２／ｇである。 The specific surface area of the graphene-based composite negative electrode material is preferably 3.0 to 40 m 2 / g.
前記グラフェン基複合負極材料の粉体は、好ましくは２ｇ／ｃｍ３のプレス密度での導電率が１０３Ｓ／ｃｍのオーダー以上である。 The powder of the graphene-based composite negative electrode material preferably has a conductivity at a press density of 2 g / cm 3 is on the order of 103 S / cm or more.
前記グラフェン基複合負極材料の可逆的比容量は、好ましくは３６０ｍＡｈ／ｇ以上である。 The reversible specific capacity of the graphene-based composite negative electrode material is preferably 360 mAh / g or more.
前記グラフェン基複合負極材料の初回クーロン効率は、好ましくは９０％以上である。 The initial Coulomb efficiency of the graphene-based composite negative electrode material is preferably 90% or more.
前記グラフェン基複合負極材料は、好ましくは１．６５ｇ／ｃｍ３のプレス密度でのポールピース液吸収時間が１８０ｓ以下である。 The graphene-based composite negative electrode material preferably has a pole piece liquid absorption time of 180 s or less at a press density of 1.65 g / cm 3 .
前記グラフェン基複合負極材料のレート特性は、好ましくは１０Ｃ／１Ｃ≧９５％、２０Ｃ／１Ｃ≧９０％であり、５００サイクル後の容量保持率は、好ましくは９０％以上である。 The rate characteristics of the graphene-based composite negative electrode material are preferably 10C / 1C ≧ 95% and 20C / 1C ≧ 90%, and the capacity retention after 500 cycles is preferably 90% or more.
本発明のグラフェン基複合負極材料のナノグラフェンシート層は黒鉛相に均一に分布し、両者の接触性能がよく、黒鉛系材料の導電率を大幅に向上し、電池製造時に導電剤の添加量を減少することができ、さらに、導電剤を全く使用せずに、限られた電池空間により多くの活性物質を仕込むことができ、電池のエネルギー密度を増加する。グラフェンシート層の比表面積が大きく、強度が高く、同時に複数の黒鉛粒子表面と緊密に接触し、中断することがないため、二次元網状構造を形成して黒鉛に直接に連通し、充放電に際して、体積の膨張収縮が小さくなり、、「離島」という現象を引き起こすまでにはならず、体系インピーダンスと電池分極を減少し、導電性能を向上させ、電池のレート特性を強め、その良い柔軟性を加えて電極構造の破裂、粉化を避け、循環寿命を延ばす。グラフェン材料のリチウム貯蔵容量は単純の黒鉛より高く、両者の複合がさらに材料の比容量を高め、電池エネルギー密度の向上に貢献をもたらす。グラフェンの大きな比面積は電解液の黒鉛表面での貯蔵に有利であり、材料の液保持性能を向上させる。 The nano graphene sheet layer of the graphene-based composite negative electrode material of the present invention is uniformly distributed in the graphite phase, both have good contact performance, greatly improve the conductivity of the graphite-based material, and reduce the amount of conductive agent added during battery production In addition, more active materials can be charged into the limited battery space without using any conductive agent, increasing the energy density of the battery. The graphene sheet layer has a large specific surface area, high strength, and intimate contact with multiple graphite particle surfaces at the same time, without interruption, so it forms a two-dimensional network structure and communicates directly with graphite. , Expansion and shrinkage of the volume is reduced, not only to cause the phenomenon of "remote islands", but also to reduce system impedance and battery polarization, improve the conductive performance, strengthen the rate characteristics of the battery, the good flexibility In addition, it avoids rupture and powdering of the electrode structure and extends the circulation life. The lithium storage capacity of graphene material is higher than that of simple graphite, and the combination of both increases the specific capacity of the material and contributes to the improvement of battery energy density. The large specific area of graphene is advantageous for storing the electrolyte on the graphite surface, and improves the liquid retention performance of the material.
手段３として、本発明はリチウムイオン二次電池を提供し、前記リチウムイオン二次電池の負極材料成分が活性物質と結合添加剤を含み、そのうち、前記活性物質が本発明による製造方法により製造されるグラフェン基複合負極材料である。 As means 3, the present invention provides a lithium ion secondary battery, wherein the negative electrode material component of the lithium ion secondary battery includes an active substance and a binding additive, wherein the active substance is manufactured by the manufacturing method according to the present invention. Graphene-based composite negative electrode material.
本発明の好ましい技術手段として、活性物質としての本発明によるグラフェン基複合負極材料の導電率が高く、それゆえ、本発明のリチウムイオン二次電池の製造に導電剤の追加を省略し、よって、有限の電池空間内により多くの活性物質を置き、電池のエネルギー密度を増加する。 As a preferred technical means of the present invention, the conductivity of the graphene-based composite negative electrode material according to the present invention as an active substance is high, and therefore the addition of a conductive agent is omitted in the production of the lithium ion secondary battery of the present invention, Place more active material in a finite battery space to increase the energy density of the battery.
本発明は従来の技術と比べて、前記方法により製造されるグラフェン基複合負極材料は、構造が安定で、高い比容量、高い導電率、高いレート特性、優れた液吸収性能とサイクル特性の特性を有し、その粉体は２ｇ／ｃｍ３のタップ密度での導電率が１０３Ｓ／ｃｍのオーダー以上であり、可逆的比容量が３６０ｍＡｈ／ｇ以上であり、初回クーロン効率が９０％以上であり、ポールピースの液吸収時間が１８０ｓ以下であり、レート特性が１０Ｃ／１Ｃ≧９５％、２０Ｃ／１Ｃ≧９０％であり、５００サイクル後の容量保持率は９０％以上である。前記方法は従来の二相の単純な混合複合プロセスから離脱し、新たな生産フローを採用し、且つ過程を正確的に制御し、厳しい条件がなく、工業化を実現しやすい。 Compared with the prior art, the graphene-based composite negative electrode material produced by the above method has a stable structure, high specific capacity, high conductivity, high rate characteristics, excellent liquid absorption performance and cycle characteristics The powder has an electrical conductivity at a tap density of 2 g / cm 3 is not less than the order of 103 S / cm, a reversible specific capacity is not less than 360 mAh / g, and an initial Coulomb efficiency is not less than 90%. The liquid absorption time of the pole piece is 180 s or less, the rate characteristics are 10C / 1C ≧ 95%, 20C / 1C ≧ 90%, and the capacity retention after 500 cycles is 90% or more. The method leaves the conventional two-phase simple mixed complex process, adopts a new production flow, controls the process accurately, has no severe conditions, and is easy to realize industrialization.
以下、実施例を参照しながら本発明の実施手段を詳しく説明する。当業者は、以下の実施例が本発明の好ましい実施例に過ぎず、よりよく本発明を理解するためのものであり、従って、本発明の範囲を限定するものと見なすわけてはないことが分かる。 Hereinafter, the implementation means of the present invention will be described in detail with reference to examples. Those skilled in the art will appreciate that the following examples are only preferred embodiments of the present invention and are for better understanding of the present invention and are therefore not to be considered as limiting the scope of the present invention. I understand.
本発明の実施例と対比例の具体的な製造プロセス及びパラメーターをより明らかにするように、実施例１〜５と対比例１〜３の具体的な製造プロセス条件及びパラメーターを表１のように示している。 In order to clarify the specific manufacturing process and parameters in comparison with the embodiment of the present invention, the specific manufacturing process conditions and parameters in the comparison with Examples 1 to 5 and in comparison with 1-3 are shown in Table 1. Show.
実施例１〜５と対比例１〜３に製造されるリチウムイオン二次電池用グラフェン基複合負極材料に対して以下のような性能検出を行い、測定結果を表３に示している。 The following performance detection was performed on the graphene-based composite negative electrode material for lithium ion secondary batteries manufactured in the proportions 1 to 3 in comparison with Examples 1 to 5, and the measurement results are shown in Table 3.
（１）ミクロ状態
中国中科科儀ＫＹＫＹ−２８００Ｂ型走査電子顕微鏡を用いて本発明により製造されるグラフェン基複合負極材料の表面形態を検出する。本発明の実施例１により製造されるグラフェン基複合負極材料のＳＥＭ図は図１のように示し、ナノ構造のグラフェンが黒鉛粒子表面に均一に付着され、二相が緊密に接触し、且つ小さい粒子により結合してなる「二次粒子」が存在し、それぞれの粒子が独立に存在している。本発明による「グラフェン基複合負極材料」は性質が異なる２種の材料として定義され、コア黒鉛とシェルグラフェンシート層を含み、本発明に記載のプロセスフローにより新たな特性を有する材料をマクロ的に構成し、２種の材料が性能上で互いに補償し、協同効果を発生させ、複合材料の総合性能が元の構成材料よりも優れて異なる各種の要求を満たす。
(1) Micro state The surface morphology of the graphene-based composite negative electrode material produced according to the present invention is detected using a Chinese medical science KYKY-2800B scanning electron microscope. The SEM diagram of the graphene-based composite negative electrode material produced according to Example 1 of the present invention is as shown in FIG. 1, and the nanostructured graphene is uniformly attached to the surface of the graphite particles, the two phases are in intimate contact, and small There are “secondary particles” formed by particles, and each particle exists independently. The “graphene-based composite negative electrode material” according to the present invention is defined as two kinds of materials having different properties, and includes a core graphite and a shell graphene sheet layer, and a material having new characteristics according to the process flow described in the present invention macroscopically. The two materials compensate for each other in performance and produce a cooperative effect, the overall performance of the composite material is superior to the original constituent materials and meets different requirements.
（２）純度
中国国家標準ＧＢ２１２−９１「石炭の工業分析方法」に定められる方法を参照し、本発明による方法により製造されるリチウムイオン二次電池用グラフェン基複合負極材料の純度が９９．９％以上であることを検出した。前記「純度」は製品の中の炭素含有量の百分率として定義される
(2) Purity The purity of the graphene-based composite negative electrode material for a lithium ion secondary battery produced by the method according to the present invention is 99.9 with reference to the method defined in the Chinese National Standard GB212-91 “Coal Industrial Analysis Method”. % Was detected. Said “purity” is defined as the percentage of the carbon content in the product
（３）粒度
イギリスＭａｌｖｅｒｎ−Ｍａｓｔｅｒｓｉｚｅｒ２０００型レーザ粒度分析器を採用して本発明におけるリチウムイオン二次電池用グラフェン基複合負極材料の平均粒度が５〜３０μｍであることを検出した。
(3) Particle size A British Malvern-Mastersizer 2000 type laser particle size analyzer was employed to detect that the average particle size of the graphene-based composite negative electrode material for lithium ion secondary batteries in the present invention was 5 to 30 μm.
（４）比表面積
窒素ガス吸着のＢＥＴ法、アメリカコンタＮｏｖａ １０００ｅ比表面積／孔径分析器を採用して本発明におけるリチウムイオン二次電池用グラフェン基複合負極材料の比表面積が３．０〜４０．０ｍ２／ｇであることを検出した。
(4) Specific surface area The specific surface area of the graphene-based composite negative electrode material for a lithium ion secondary battery in the present invention is 3.0 to 40, employing a nitrogen gas adsorption BET method and an American Conta Nova 1000e specific surface area / pore size analyzer. 0 m 2 / g was detected.
（５）導電率
フォーポイントプローブ検出原理、日本三菱化学製ＭＣＰ−ＰＤ５１型粉体抵抗率検出器を用いて本発明におけるリチウムイオン二次電池用グラフェン基複合負極材料の導電率が１０３Ｓ／ｃｍオーダーであることを検出した。前記導電率の検出条件は１ｇ粉体が１０ｋＮの圧力で、直径が２ｃｍであるウエハーを形成することである。
(5) Conductivity Using a four-point probe detection principle, MCP-PD51 type powder resistivity detector manufactured by Mitsubishi Chemical Corporation, the conductivity of the graphene-based composite negative electrode material for lithium ion secondary batteries in the present invention is 10 3 S / It was detected to be in the cm order. The condition for detecting the conductivity is that a 1 g powder is formed at a pressure of 10 kN and a wafer having a diameter of 2 cm.
（６）電気化学性能検出
Ａ、本発明におけるリチウムイオン二次電池用グラフェン基複合負極材料を用いてリチウムイオン模擬電池を製造し、具体的には、以下のような工程を含む。
１．本発明方法により製造されるグラフェン基複合負極材料をリチウムイオン二次電池負極活性物質とし、カルボキシメチルセルロースＣＭＣを増粘剤とし、スチレンブタジエンゴムＳＢＲをバインダーとし、導電剤が必要とせず、電極材料を製造し、三者が質量比、活性物質：ＣＭＣ：ＳＢＲ＝９６．５：１．５：２で混合される。適量の脱イオン水を加えてペーストミキサーでペーストに均一に混合し、次に、塗布機で銅箔に塗布し、塗布の厚さが２００μmであり、乾燥した後に直径が８．４ｍｍのポールピースに打ち抜く。
(6) Electrochemical performance detection A, A lithium ion simulated battery is manufactured using the graphene group composite negative electrode material for a lithium ion secondary battery in the present invention, and specifically includes the following steps.
1. The graphene-based composite negative electrode material produced by the method of the present invention is a lithium ion secondary battery negative electrode active material, carboxymethylcellulose CMC is a thickener, styrene butadiene rubber SBR is a binder, no conductive agent is required, and an electrode material is used. The three are mixed in a mass ratio, active substance: CMC: SBR = 96.5: 1.5: 2. An appropriate amount of deionized water is added and uniformly mixed with the paste with a paste mixer, then applied to the copper foil with a coating machine, the coating thickness is 200 μm, and after drying, a pole piece having a diameter of 8.4 mm Punch out.
２．純リチウムシートを対電極とし、前記ポールピースが稼動電極であり、Ｃｅｌｇａｒｄ２４００型ＰＥ／ＰＰ／ＰＥ複合セパレーターを採用してドイツブラウングローブボックスに金型式（正極ステンレス鋼製ガスケットの直径が８．４ｍｍであり、負極銅製ガスケットの直径が１１．４ｍｍであり）模擬電池を組み立て、Ｈ２ＯとＯ２のバイアス電圧がいずれも１ｐｐｍよりも低い。電解液は１ＭＬｉＰＦ６／ＥＣ＋ＤＭＣ＋ＥＭＣの溶液を採用する。 2. A pure lithium sheet is used as a counter electrode, the pole piece is a working electrode, a Celgard 2400 PE / PP / PE composite separator is used in a German brown glove box with a mold type (positive stainless steel gasket with a diameter of 8.4 mm). Yes, the negative electrode copper gasket has a diameter of 11.4 mm). A simulated battery is assembled, and the bias voltages of H 2 O and O 2 are both lower than 1 ppm. As the electrolytic solution, a solution of 1 M LiPF 6 / EC + DMC + EMC is adopted.
Ｂ、武漢金諾Ｌａｎｄ ＣＴ ２００１Ａ充放電検出キャビネットを用いて、０．００１〜１．５Ｖの電圧範囲内で、セクション化の電流密度で模擬電池の充放電性能検出を行う。検出方法とデータの計算は以下のとおりである。
初回リチウム挿入比容量は、０．１Ｃの電流密度で０．００５Ｖまで充電し、さらに０．０２Ｃの電流密度で０．００１Ｖまで充電する電気容量／負極活性物質の質量である。
初回リチウム脱離比容量は、０．１Ｃの電流密度で１．５Ｖまで放電する電気容量／負極活性物質の質量である。
初回クーロン効率＝初回リチウム脱離比容量／初回リチウム挿入比容量＊１００％である。
B. Using a Wuhan Kinnoku Land CT 2001A charge / discharge detection cabinet, the charge / discharge performance of the simulated battery is detected at a current density of sectioning within a voltage range of 0.001 to 1.5V. The detection method and data calculation are as follows.
The initial lithium insertion specific capacity is the mass of the electric capacity / negative electrode active material charged to 0.005 V at a current density of 0.1 C and further charged to 0.001 V at a current density of 0.02 C.
The initial lithium desorption specific capacity is the mass of electric capacity / negative electrode active material that discharges to 1.5 V at a current density of 0.1 C.
Initial Coulomb efficiency = initial lithium desorption specific capacity / initial lithium insertion specific capacity * 100%.
本発明実施例１に製造されるグラフェン基複合負極材料の充放電循環回り数１〜３の充電比容量、放電比容量及び効率が表２に示す通りで、充放電曲線が図２〜図４に示す通りであり、図において充電曲線１、充電曲線２及び充電曲線３がそれぞれ第１、２及び３サイクルの充電曲線を代表し、放電曲線１、放電曲線２及び放電曲線３がそれぞれ第１、２及び３サイクルの放電曲線を代表する。 The charge specific capacity, discharge specific capacity and efficiency of the charge / discharge circulation numbers 1 to 3 of the graphene-based composite negative electrode material produced in Example 1 of the present invention are as shown in Table 2, and the charge / discharge curves are shown in FIGS. In the figure, the charging curve 1, the charging curve 2 and the charging curve 3 represent the charging curves of the first, second and third cycles, respectively, and the discharging curve 1, the discharging curve 2 and the discharging curve 3 respectively represent the first. Representative of 2 and 3 cycle discharge curves.
（７）フル電池性能評価
Ａ、本発明におけるリチウムイオン二次電池用グラフェン基複合負極材料を用いてリチウムイオンフル電池を製造し、具体的には、以下のような工程を含む。
１．本発明の方法により製造されるグラフェン基複合負極材料をリチウムイオン二次電池負極活性物質とし、導電剤が必要とせず、スチレンブタジエンゴムＳＢＲをバインダーとし、カルボキシメチルセルロースＣＭＣを増粘剤とし、電極材料を製造し、三者が質量比、活性物質：ＣＭＣ：ＳＢＲ＝９６．５：１．５：２で混合される。適量の脱イオン水を加えてペーストミキサーでペーストに均一に混合し、次に、塗布機で銅箔に塗布し、真空で乾燥した後にリチウムイオンフル電池の負極とする。
(7) Full battery performance evaluation A, A lithium ion full battery is manufactured using the graphene group composite negative electrode material for lithium ion secondary batteries in the present invention, and specifically includes the following steps.
1. The graphene-based composite negative electrode material produced by the method of the present invention is a negative electrode active material for a lithium ion secondary battery, no conductive agent is required, styrene butadiene rubber SBR is used as a binder, carboxymethyl cellulose CMC is used as a thickener, and an electrode material The three are mixed in a mass ratio, active substance: CMC: SBR = 96.5: 1.5: 2. An appropriate amount of deionized water is added and uniformly mixed with the paste with a paste mixer, then applied to the copper foil with a coating machine, dried in vacuum, and then used as the negative electrode of a lithium ion full battery.
２．コバルト酸リチウムＬｉＣｏＯ２、リチウムニッケルＬｉＮｉＯ２又はリチウムマンガン酸化物スピネルＬｉＭｎ２Ｏ４を正極材料とし、１ＭＬｉＰＦ６／ＥＣ＋ＤＭＣ＋ＥＭＣを電解液とし、Ｃｅｌｇａｒｄ２４００型ＰＥ／ＰＰ／ＰＥの複合膜をセパレーターとし、普通の１８６５０型単体電池の生産プロセスを採用してフル電池を組み立てる。 2. Lithium cobaltate LiCoO 2 , lithium nickel LiNiO 2 or lithium manganese oxide spinel LiMn 2 O 4 is used as a cathode material, 1M LiPF 6 / EC + DMC + EMC is used as an electrolyte, and a composite film of Celgard 2400 type PE / PP / PE is used as a separator. A full battery is assembled by adopting the production process of the 18650 type single battery.
Ｂ、武漢金諾Ｌａｎｄ ＣＴ ２００１Ａ充放電検出キャビネットを用いて、３〜４，２Ｖの電圧範囲内で、異なる電流密度で充放電検出を行う。性能評価と検出方法は以下の通りである。
ポールピースの液吸収性能評価について、本発明により製造されるグラフェン基複合負極材料を前記要求に従って塗布し、乾燥してポールピースを形成し、ポールピースをタップ密度１．６５ｇ／ｃｍ３までローリングした時、ドイツブラウングローブボックス内に入れ、液銃でポールピースの表面に１０μＬの電解液を滴下し、次に、計時を始め、電解液がポールピースの表面に完全に浸潤するまで、計時が終わる。３回検出して平均値を取る。
B. Charge / discharge detection is performed at a different current density within a voltage range of 3 to 4 and 2 V using a Wuhan Kinnobu Land CT 2001A charge / discharge detection cabinet. The performance evaluation and detection method are as follows.
Regarding the liquid absorption performance evaluation of the pole piece, the graphene-based composite negative electrode material produced according to the present invention was applied according to the above requirements, dried to form a pole piece, and the pole piece was rolled to a tap density of 1.65 g / cm 3 . At the time, put it in a German brown glove box, drop 10 μL of electrolyte on the surface of the pole piece with a liquid gun, then start timing, and the time measurement is completed until the electrolyte completely infiltrates the surface of the pole piece . Detect three times and take the average value.
電池レート特性の評価について、フル電池に対して０．５ｍＡｈ／ｃｍ２の電流密度で定電流充電を行い、次に、それぞれ１Ｃ、５Ｃ、１０Ｃ、１５Ｃ、２０Ｃの放電電流で放電を行い、フル電池の放電容量の変化を検出し、且つ異なる放電レートの容量保持率を計算し、
１０Ｃ／１Ｃは１０Ｃレート放電容量と１Ｃレート放電容量との比値を表し、
２０Ｃ／１Ｃは２０Ｃレート放電容量と１Ｃレート放電容量との比値を表す。
For the evaluation of the battery rate characteristics, the full battery was charged with a constant current at a current density of 0.5 mAh / cm 2 , and then discharged with a discharge current of 1 C, 5 C, 10 C, 15 C, and 20 C, respectively. Detecting changes in the discharge capacity of the battery and calculating the capacity retention of different discharge rates;
10C / 1C represents a ratio value of 10C rate discharge capacity and 1C rate discharge capacity,
20C / 1C represents a ratio value between the 20C rate discharge capacity and the 1C rate discharge capacity.
前記２つの比値は大きければ大きいほど、異なる放電レートの容量保持率が高く、１８６５０型フル電池のレート性能が良く、前記グラフェン基複合負極材料の電気化学性能が良いことを示す。 The larger the two ratio values, the higher the capacity retention rate of the different discharge rates, the better the rate performance of the 18650-type full battery, and the better the electrochemical performance of the graphene-based composite negative electrode material.
本発明実施例１に製造されるグラフェン基複合負極材料の異なるレート放電曲線と充放電循環曲線は図５と図６のように示している。 Different rate discharge curves and charge / discharge circulation curves of the graphene-based composite negative electrode material produced in Example 1 of the present invention are shown in FIGS.
実施例１〜５と対比例１〜３の物理性能と電気化学性能測定結果は、以下のことを示している。
対比例１に取得されるグラフェン基複合負極材料は、製造の過程にバインダーを添加した後に混練を行わず、直接にシートの圧延を行ったため、混合の均一性が悪くなることを引き起こし、シート圧延効果が悪くなり、材料表面被覆状態が均一ではなく、且つ粒子とグラフェンシートとの接触も悪く、それゆえ、材料の導電率が低下し、初回クーロン効率とサイクル特性がわずかに低下し、ひいては電池のレート特性の悪化を引き起こす。
The physical performance and electrochemical performance measurement results of Comparative Examples 1 to 3 in comparison with Examples 1 to 5 indicate the following.
The graphene-based composite negative electrode material obtained in contrast 1 has a problem that the mixing uniformity is deteriorated because the sheet is directly rolled without adding kneading after the binder is added in the manufacturing process. The effect becomes worse, the material surface coating state is not uniform, and the contact between the particles and the graphene sheet is also bad, so the conductivity of the material is lowered, the initial Coulomb efficiency and the cycle characteristics are slightly lowered, and the battery Cause deterioration of rate characteristics.
対比例２に取得されるグラフェン基複合負極材料は、製造の過程にシート圧延を行わないため、混練した後の粉料に対して押出作用が不足であり、粒子と粒子、及び粒子とグラフェンシートとの間の接触が不良であることを引き起こし、且つ二次粒子化の効果が悪く、結晶配列の異方性特徴が著しく、それゆえ、材料の導電率が低く、電池循環過程にポールピースの膨張が著しく、サイクル特性とレート特性が低下する。 Since the graphene-based composite negative electrode material obtained in contrast 2 does not perform sheet rolling in the manufacturing process, the extruding action is insufficient for the powder after kneading, and particles and particles, and particles and graphene sheets And the effect of secondary particle formation is poor, the anisotropic characteristics of the crystal arrangement are remarkable, and therefore the conductivity of the material is low, and Swelling is remarkable, and cycle characteristics and rate characteristics deteriorate.
対比例３に取得されるグラフェン基複合負極材料は、製造の過程にプレスを行わずに粉体の黒鉛化を直接に行うため、その坩堝のコストが増加し、且つ材料の黒鉛化の過程に「気体による孔形成」効果が悪く、気孔率が低下し、液吸収性能を低減させる。また、粒子間の伝熱効果が悪く、受熱の均一性が低下し、安定性が悪くなり、容量の発揮に影響をもたらす。 The graphene-based composite negative electrode material obtained in contrast 3 directly performs powder graphitization without pressing during the manufacturing process, which increases the cost of the crucible and increases the material graphitization process. The “pore formation by gas” effect is poor, the porosity is lowered, and the liquid absorption performance is reduced. In addition, the heat transfer effect between the particles is poor, the uniformity of heat reception is lowered, the stability is deteriorated, and the capacity is affected.
実施例１〜５に取得されるグラフェン基複合負極材料は、良い電気化学性能を有し、粉体の導電率が１０３Ｓ／ｃｍオーダーに達し、可逆的比容量が３６０ｍＡｈ／ｇ以上であり、初回クーロン効率は９０％以上であり、液吸収時間が１８０ｓ以下であり、レート特性が１０Ｃ／１Ｃ≧９５％、２０Ｃ／１Ｃ≧９０％であり、５００回りの容量保持率は９０％以上であり、ここから見れば、本発明におけるリチウムイオン二次電池用グラフェン基複合負極材料は各種の性能で優勢が明らかであり、例えば比容量が高く、レート特性が良く、液吸収性能が良く、サイクル特性が良く、安全性能がよいなどの利点を有し、未来のエネルギー貯蔵電池と動力電池の負極材料とするのが好ましい。 The graphene-based composite negative electrode materials obtained in Examples 1 to 5 have good electrochemical performance, the powder conductivity reaches the order of 10 3 S / cm, and the reversible specific capacity is 360 mAh / g or more. The initial coulombic efficiency is 90% or more, the liquid absorption time is 180 s or less, the rate characteristics are 10C / 1C ≧ 95%, 20C / 1C ≧ 90%, and the capacity retention around 500 is 90% or more. From this, the graphene-based composite negative electrode material for lithium ion secondary batteries according to the present invention clearly shows superiority in various performances, for example, high specific capacity, good rate characteristics, good liquid absorption performance, It has advantages such as good characteristics and good safety performance, and is preferably used as a negative electrode material for future energy storage batteries and power batteries.
出願人は、本発明が前記実施例により本発明の詳しい特徴及び詳しい方法を説明したが、本発明が前記詳しい特徴及び詳しい方法に限定せず、即ち、本発明が必ず前記詳しい特徴及び詳しい方法に依存して実施するという意味ではないことを声明する。当業者は、本発明に対しての如何なる改進、本発明に選択される構成の同等置換及び補助構成の添加、具体的な形態の選択などが、いずれも本発明の保護範囲と開示範囲内に属することが分かる。 The applicant has described the detailed features and detailed methods of the present invention by way of the above-described embodiments, but the present invention is not limited to the detailed features and detailed methods, ie, the present invention is not limited to the detailed features and detailed methods. It does not mean that it depends on Those skilled in the art will understand that any modifications to the present invention, equivalent replacement of the configuration selected for the present invention, addition of auxiliary configurations, selection of specific forms, etc. are all within the protection scope and disclosure scope of the present invention. You can see that it belongs.
Claims (10)
黒鉛原料を酸化黒鉛と均一に混合し、混合材料を得る工程（１）と、
前記混合材料にバインダーを加えて混練し、混練材料を取得する工程（２）と、
前記混練材料を圧延し、圧延薄板を取得する工程（３）と、
前記圧延薄板に対して粉砕処理を行い、粉体材料を取得する工程（４）と、
前記粉体材料に対してプレスしてプレス製品を取得する工程（５）と、
保護性雰囲気で前記プレス製品に対して黒鉛化処理を行い、グラフェン基複合負極材料を取得する工程（６）と、を含むグラフェン基複合負極材料の製造方法。 A method for producing a graphene-based composite negative electrode material,
A step (1) of uniformly mixing a graphite raw material with graphite oxide to obtain a mixed material;
Adding a binder to the mixed material and kneading to obtain a kneaded material (2);
Rolling the kneaded material to obtain a rolled sheet (3);
Crushing the rolled sheet to obtain a powder material (4);
A step (5) of obtaining a pressed product by pressing the powder material;
And a step (6) of obtaining a graphene-based composite negative electrode material by performing graphitization treatment on the press product in a protective atmosphere to obtain a graphene-based composite negative electrode material.
前記天然黒鉛は、好ましくは鱗片状黒鉛及び／又は微結晶黒鉛であり、
前記人造黒鉛の前躯体は、好ましくはニードルコークス未黒鉛化製品、石油コークス未黒鉛化製品及びカーボンマイクロビーズ未黒鉛化製品のうちの１種又は少なくとも２種の組み合わせであり、
前記黒鉛原料の純度は、好ましくは９０％（重量）以上であり、
前記酸化黒鉛は、好ましくは前記混合材料の重量の０．１％〜４０.０％であり、
前記混合の時間は、好ましくは３〜１８０ｍｉｎであり、
前記混合に採用される設備は、好ましくはＶ型ミキサー、溝型ミキサー、バレルミキサー、円錐形二重らせんミキサー又はダブルコン・ミキサーであることを特徴とする、請求項１に記載の製造方法。 In the step (1), the graphite raw material is one or a combination of at least two of precursors of natural graphite and artificial graphite,
The natural graphite is preferably scaly graphite and / or microcrystalline graphite,
The precursor of the artificial graphite is preferably one or a combination of at least two of needle coke ungraphitized product, petroleum coke ungraphitized product and carbon microbead ungraphitized product,
The purity of the graphite raw material is preferably 90% (weight) or more,
The graphite oxide is preferably 0.1% to 40.0% of the weight of the mixed material,
The mixing time is preferably 3 to 180 min.
The manufacturing method according to claim 1, wherein the equipment employed for the mixing is preferably a V-type mixer, a groove-type mixer, a barrel mixer, a conical double helix mixer or a double-con mixer.
前記バインダーは、好ましくは前記混練材料の重量の５．０％〜４０．０％であり、
前記混練は、好ましくは５０〜２００℃の温度範囲内にて行い、
前記混練の時間は、好ましくは１〜１０ｈであることを特徴とする、請求項１又は２に記載の製造方法。 In the step (2), the binder is one or a combination of at least two of pitch, resin, polymer material and polymer, preferably coal pitch, petroleum pitch, natural pitch, intermediate phase pitch, resin, high One or a combination of at least two of molecular materials and polymers;
The binder is preferably 5.0% to 40.0% of the weight of the kneaded material,
The kneading is preferably performed within a temperature range of 50 to 200 ° C.,
The production method according to claim 1 or 2, wherein the kneading time is preferably 1 to 10 hours.
前記圧延は、好ましくは２０〜３００℃の温度範囲内で行い、
前記二本ロールミルの二本ロールの回転速度比は、好ましくは１：１．１〜１：２であり、ローラー軸の間隔は、好ましくは０．５〜５ｍｍであることを特徴とする、請求項１〜３のいずれか一項に記載の製造方法。 In the step (3), a two-roll mill is adopted for rolling,
The rolling is preferably performed within a temperature range of 20 to 300 ° C.
The rotation speed ratio of the two rolls of the two-roll mill is preferably 1: 1.1 to 1: 2, and the interval between the roller shafts is preferably 0.5 to 5 mm. The manufacturing method as described in any one of claim | item 1 -3.
前記粉体材料の平均粒度は、好ましくは５．０〜３０．０μmであることを特徴とする、請求項１〜４のいずれか一項に記載の製造方法。 In the step (4), the pulverization process employs a turbo mill, a vortex jet mill, a super cyclone mill, a wind-selective pulverizer or a twin roll mill.
5. The method according to claim 1, wherein the powder material has an average particle size of preferably 5.0 to 30.0 μm.
前記プレス製品の体積密度は、好ましくは１．０〜１．８ｇ／ｃｍ３であり、
前記プレス製品の形状は、好ましくは円筒体及び／又はブロック体であることを特徴とする、請求項１〜５のいずれか一項に記載の製造方法。 In the step (5), the press adopts a single column type hydraulic press, a four column type hydraulic press, a horizontal hydraulic press, an upright hydraulic press and a universal hydraulic machine,
The volume density of the pressed product is preferably 1.0 to 1.8 g / cm 3 ,
The manufacturing method according to any one of claims 1 to 5, wherein the shape of the press product is preferably a cylindrical body and / or a block body.
前記保護性雰囲気は、好ましくはヘリウムガス、ネオンガス、アルゴンガス及び窒素ガスのうちの１種又は少なくとも２種の組み合わせであり、
前記黒鉛化処理は、好ましくは２７００〜３３００℃の温度範囲内で行うことを特徴とする、請求項１〜６のいずれか一項に記載の製造方法。 In the step (6), the graphitization treatment employs an internal string type graphitization furnace or an Atchison type graphitization furnace,
The protective atmosphere is preferably one or a combination of at least two of helium gas, neon gas, argon gas and nitrogen gas,
The production method according to any one of claims 1 to 6, wherein the graphitization treatment is preferably performed within a temperature range of 2700 to 3300 ° C.
前記グラフェン基複合負極材料を粉砕し、ふるいにかけ、平均粒度が５．０〜３０．０μmであるグラフェン基複合負極材料を取得する工程（７）を行い、
前記粉砕は、好ましくはターボミル、渦流ジェットミル、スーパーサイクロンミル、風選粉砕機又は双ロールミルを採用することを特徴とする、請求項１〜７のいずれか一項に記載の製造方法。 After the step (6),
Crushing and sieving the graphene-based composite negative electrode material to obtain a graphene-based composite negative electrode material having an average particle size of 5.0 to 30.0 μm (7);
The manufacturing method according to any one of claims 1 to 7, wherein the pulverization preferably uses a turbo mill, a vortex jet mill, a super cyclone mill, a wind-selective pulverizer, or a twin roll mill.
前記グラフェン基複合負極材料の平均粒度は、好ましくは５．０〜３０．０μmであり、
前記グラフェン基複合負極材料の純度が、好ましくは９９．９（重量）％以上であり、
前記グラフェン基複合負極材料の比表面積は、好ましくは３．０〜４０ｍ２／ｇであり、
前記グラフェン基複合負極材料の粉体は、好ましくは２ｇ／ｃｍ３のプレス密度での導電率が１０３Ｓ／ｃｍのオーダー以上であり、
前記グラフェン基複合負極材料の可逆的比容量は、好ましくは３６０ｍＡｈ／ｇ以上であり、
前記グラフェン基複合負極材料の初回クーロン効率は、好ましくは９０％以上であり、
前記グラフェン基複合負極材料は、好ましくは１．６５ｇ／ｃｍ３のプレス密度でのポールピース液吸収時間が１８０ｓ以下であり、
前記グラフェン基複合負極材料のレート特性は、好ましくは１０Ｃ／１Ｃ≧９５％、２０Ｃ／１Ｃ≧９０％であり、５００サイクル後の容量保持率は、好ましくは９０％以上であることを特徴とする、請求項１〜８のいずれか一項に記載の製造方法により製造されるグラフェン基複合負極材料。 The graphene-based composite negative electrode material includes a core graphite and a shell graphene sheet layer,
The average particle size of the graphene-based composite negative electrode material is preferably 5.0 to 30.0 μm,
The purity of the graphene-based composite negative electrode material is preferably 99.9% (by weight) or more,
The specific surface area of the graphene-based composite negative electrode material is preferably 3.0 to 40 m 2 / g,
The powder of the graphene-based composite negative electrode material preferably has an electrical conductivity at a press density of 2 g / cm 3 is on the order of 103 S / cm or more,
The reversible specific capacity of the graphene-based composite negative electrode material is preferably 360 mAh / g or more,
The initial Coulomb efficiency of the graphene-based composite negative electrode material is preferably 90% or more,
The graphene-based composite negative electrode material preferably has a pole piece liquid absorption time of 180 s or less at a press density of 1.65 g / cm 3 .
The rate characteristics of the graphene-based composite negative electrode material are preferably 10C / 1C ≧ 95% and 20C / 1C ≧ 90%, and the capacity retention after 500 cycles is preferably 90% or more. The graphene group composite negative electrode material manufactured by the manufacturing method as described in any one of Claims 1-8.
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103811718B (en) | 2016-08-17 |
| KR101631590B1 (en) | 2016-06-20 |
| JP5864687B2 (en) | 2016-02-17 |
| CN103811718A (en) | 2014-05-21 |
| KR20150098548A (en) | 2015-08-28 |
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