JP2015118911A - Silicon-based composite negative electrode material for lithium ion secondary batteries, manufacturing method, and battery - Google Patents
Silicon-based composite negative electrode material for lithium ion secondary batteries, manufacturing method, and battery Download PDFInfo
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- JP2015118911A JP2015118911A JP2014169853A JP2014169853A JP2015118911A JP 2015118911 A JP2015118911 A JP 2015118911A JP 2014169853 A JP2014169853 A JP 2014169853A JP 2014169853 A JP2014169853 A JP 2014169853A JP 2015118911 A JP2015118911 A JP 2015118911A
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- silicon
- graphite
- negative electrode
- ketone
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical class [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
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- XIYUIMLQTKODPS-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CC[N+]=1C=CN(C)C=1 XIYUIMLQTKODPS-UHFFFAOYSA-M 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
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- 238000004458 analytical method Methods 0.000 description 1
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- 150000001721 carbon Chemical class 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/366—Composites as layered products
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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
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/44—Alloys based on cadmium
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明はリチウムイオン二次電池技術分野に関する。具体的にはリチウムイオン二次電池用シリコン系複合負極材、製造方法及び電池に関する。 The present invention relates to the technical field of lithium ion secondary batteries. Specifically, the present invention relates to a silicon-based composite negative electrode material for a lithium ion secondary battery, a manufacturing method, and a battery.
エネルギー蓄積デバイスとしてのリチウムイオン二次電池は、作動電圧が高く、サイクル寿命が長く、メモリー効果がなく、自己放電が小さく、エコなどの利点を持つので、携帯型電子製品及び電気自動車に幅広く用いられている。従来、商品化されたリチウムイオン二次電池は、主として黒鉛類負極材を用いており、その理論比容量は３７２ｍＡｈ／ｇであるが、従来の技術で開発した黒鉛類負極材の比容量はその理論値に近いため、黒鉛類負極材の開発可能性には限界があり、現在の様々な携帯型電子機器の小型化発展及び電気自動車の高い比エネルギー・高出力密度のリチウムイオン二次電池の幅広い需要を満たすことは難しい。 Lithium ion secondary batteries as energy storage devices have high operating voltage, long cycle life, no memory effect, small self-discharge, and eco-friendly advantages, so they are widely used in portable electronic products and electric vehicles. It has been. Conventionally, commercialized lithium ion secondary batteries mainly use a graphite negative electrode material, and its theoretical specific capacity is 372 mAh / g, but the specific capacity of the graphite negative electrode material developed by the conventional technology is Because it is close to the theoretical value, there is a limit to the possibility of development of graphite negative electrode materials. The development of miniaturization of various portable electronic devices and the high specific energy and high output density of lithium-ion secondary batteries of electric vehicles It is difficult to meet a wide range of demand.
シリコン材料は、比較的高いリチウム貯蔵容量（理論比容量４２００ｍＡｈ／ｇ）を有し、しかも資源として豊富なので、新世代の高比エネルギー・高出力密度のリチウムイオン二次電池用負極材料を開発する理想的な候補材料の一つであると考えられる。しかしながら、シリコン材料は、使用過程で電池容量の減衰が比較的速いため、その実用性がある程度制限される。分析によると、シリコン材料のリチウム吸蔵放出の体積膨張収縮は比較的大きく（＞３００％）、材料の破壊や粉砕をもたらし、低い材料導電率及び比較的速い材料容量減衰を及ぼす要因であると考えられる。そのため、シリコン材料の体積膨張の抑制、材料構造の安定性の向上はシリコン材料の導電率及びサイクル安定性の向上に対して重要な意味を持つ。現在、主としてシリコンのナノ化、シリコンと金属との合金化、シリコンと活性又は不活性材料との複合によって、シリコン材料の体積膨張を改善し、そのうち、シリコンと活物質である炭素との複合は幅広い市場において将来性がある。 Since silicon materials have a relatively high lithium storage capacity (theoretical specific capacity 4200 mAh / g) and are abundant as resources, we will develop a new generation of high specific energy and high power density negative electrode materials for lithium ion secondary batteries. It is considered one of the ideal candidate materials. However, the practical use of silicon materials is limited to some extent because the battery capacity decays relatively quickly during use. Analysis shows that the volume expansion and contraction of lithium occlusion and release of silicon material is relatively large (> 300%), leading to material destruction and crushing, which is responsible for low material conductivity and relatively fast material capacity decay It is done. Therefore, suppression of the volume expansion of the silicon material and improvement of the stability of the material structure are important for improving the conductivity and cycle stability of the silicon material. At present, the volume expansion of silicon materials has been improved mainly by silicon nano-alloying, silicon-metal alloying, and silicon-active or inert material composites, of which silicon and active carbon composites Promising in a wide range of markets.
特許文献ＣＮ１０３３２６０２３Ａには、高性能リチウムイオン二次電池用シリコン炭素負極材及びその製造方法が開示され、該負極材はＳｉ−ＳｉＯｘ／Ｃ／ＤＣ複合系を含み、前記複合系は、Ｃ基体と、Ｃ基体の中に接着されるＳｉ−ＳｉＯｘ複合物と、Ｃ基体及びＳｉ−ＳｉＯｘ−Ｃの中に分布しているカーボンナノチューブと、最外層である有機熱分解炭素被覆層とを含む。該発明により製造された多孔質複合物Ｓｉ−ＳｉＯｘは、シリコン粒子が大きく、且つ、シリコン酸化物を含有することによってその初回効率を低くし、該発明はＳｉ−ＳｉＯｘがカーボンナノチューブ及び炭素基体と複合し、且つ表面に分解炭素を被覆することで製造されるが、該方法では、大粒度シリコンの体積膨張が抑制されにくいし、比較的悪いサイクル特性を招く。 Patent document CN1033326033A discloses a silicon carbon negative electrode material for a high-performance lithium ion secondary battery and a method for manufacturing the same, and the negative electrode material includes a Si-SiOx / C / DC composite system, and the composite system includes a C substrate, , Si-SiOx composite adhered in the C substrate, carbon nanotubes distributed in the C substrate and Si-SiOx-C, and the outermost organic pyrolytic carbon coating layer. The porous composite Si-SiOx produced according to the invention has large silicon particles and contains silicon oxide, thereby reducing its initial efficiency. The composite is manufactured by covering the surface with cracked carbon. However, in this method, the volume expansion of large-grain silicon is difficult to be suppressed and relatively poor cycle characteristics are caused.
特許文献ＣＮ１０３０７８０９２Ａには、リチウムイオン二次電池用シリコン炭素（Ｓｉ／Ｃ）複合負極材の製造方法が開示され、該発明はシリコン源（エッチング処理前又は処理後）と黒鉛を第２類添加剤の存在下で溶剤に分散させ、温度を制御して溶剤を完全に揮発させた後、前駆体固体を得て、そして前駆体固体に非晶質炭素被覆を行う。該発明にかかるエッチングによって製造されたナノシリコンは比表面積が大きく、黒鉛の表面に均一に分散し難いので、該方法で製造されたシリコン炭素材料は、シリコンの凝集が深刻で、シリコンの膨張を解決することができず、該材料の悪いサイクル特性を招く。 Patent document CN1030778092A discloses a method for producing a silicon carbon (Si / C) composite negative electrode material for a lithium ion secondary battery, and the invention relates to a silicon source (before or after etching treatment) and graphite as a second type additive. After the solvent is completely volatilized by controlling the temperature and the solvent is completely volatilized, a precursor solid is obtained and the precursor solid is subjected to amorphous carbon coating. Nanosilicon produced by etching according to the present invention has a large specific surface area and is difficult to disperse uniformly on the surface of graphite. Therefore, the silicon carbon material produced by this method has severe silicon agglomeration and causes silicon expansion. Which cannot be solved, leading to poor cycling properties of the material.
そのため、小粒径のシリコンを製造してシリコン粒子の分散性を向上させるとともに、シリコン粒子に緩衝体を供給し、シリコン系負極材がリチウムを吸蔵放出する時の体積膨張と収縮を緩和し、高性能シリコン系負極材を製造する。リチウムイオン二次電池へのシリコン系負極材の実用化を達成することは、本分野で解決すべき技術課題である。 Therefore, while manufacturing silicon with a small particle size and improving the dispersibility of the silicon particles, supplying a buffer to the silicon particles, the silicon negative electrode material relaxes the volume expansion and contraction when the lithium is occluded and released, Manufactures high performance silicon negative electrode materials. Achieving practical application of silicon-based negative electrode materials for lithium ion secondary batteries is a technical problem to be solved in this field.
本発明は、リチウムイオン二次電池用シリコン系複合負極材、その製造方法及び該負極材を含む電池を提供することを目的とし、前記リチウムイオン二次電池用シリコン系複合負極材はシリコン粒子の分散性が良く、プレス密度及び初回クーロン効率が高く、サイクル特性に優れる。 An object of the present invention is to provide a silicon-based composite negative electrode material for a lithium ion secondary battery, a method for producing the same, and a battery including the negative electrode material. Good dispersibility, high press density and high initial Coulomb efficiency, and excellent cycle characteristics.
本発明の目的を達成するために、下記の技術的手段を提供する。
第１の態様において、本発明はリチウムイオン二次電池用シリコン系複合負極材を提供し、これは埋込複合コア−シェル構造であり、該コアはナノシリコン粒子が中空黒鉛の内層隙間に埋め込まれてなる構造であり、該シェルは非黒鉛炭素材料である。
In order to achieve the object of the present invention, the following technical means are provided.
In a first aspect, the present invention provides a silicon-based composite negative electrode material for a lithium ion secondary battery, which has an embedded composite core-shell structure, in which nanosilicon particles are embedded in an inner layer gap of hollow graphite. The shell is a non-graphitic carbon material.
本発明に係るリチウムイオン二次電池用シリコン系複合負極材において、コアのナノシリコン粒子が中空黒鉛の内層隙間内に埋め込まれ、ナノシリコン粒子の分散性が良く、中空黒鉛は同時にナノシリコン粒子の良好な緩衝体として機能し、シリコン材料のリチウム吸蔵放出の体積膨張と収縮を効果的に抑制する。 In the silicon-based composite negative electrode material for a lithium ion secondary battery according to the present invention, the core nanosilicon particles are embedded in the inner space of the hollow graphite, and the dispersibility of the nanosilicon particles is good. It functions as a good buffer and effectively suppresses the volume expansion and contraction of the lithium occlusion / release of the silicon material.
本発明に係るリチウムイオン二次電池用シリコン系複合負極材において、前記中空黒鉛の内層隙間はスリット、又は前記スリットから派生された多角形孔であってもよい。 In the silicon-based composite negative electrode material for a lithium ion secondary battery according to the present invention, the inner layer gap of the hollow graphite may be a slit or a polygonal hole derived from the slit.
前記リチウムイオン二次電池用シリコン系複合負極材は、好ましくは、ナノシリコン１〜５０％（重量）、黒鉛３０〜９０％（重量）、及び非黒鉛炭素材料５〜４０％（重量）を含む。例えば、ナノシリコンは２％（重量）、５％（重量）、１０％（重量）、２０％（重量）又は４５％（重量）などであってもよく、黒鉛は３５％（重量）、４５％（重量）、５５％（重量）、７０％（重量）又は８５％（重量）などであってもよく、非黒鉛炭素材料は６％（重量）、１０％（重量）、２０％（重量）、３０％（重量）又は３５％（重量）などであってもよい。 The silicon-based composite negative electrode material for a lithium ion secondary battery preferably includes 1 to 50% (weight) of nanosilicon, 30 to 90% (weight) of graphite, and 5 to 40% (weight) of non-graphitic carbon material. . For example, nanosilicon may be 2% (weight), 5% (weight), 10% (weight), 20% (weight), 45% (weight), etc., and graphite is 35% (weight), 45%. % (Weight), 55% (weight), 70% (weight), 85% (weight), etc., and non-graphitic carbon material is 6% (weight), 10% (weight), 20% (weight) ), 30% (weight) or 35% (weight).
第２の態様において、本発明は第１の態様に記載のリチウムイオン二次電池用シリコン系複合負極材の製造方法を提供し、
（１）黒鉛類材料を機械的加工し、中空黒鉛を得る工程と、
（２）ナノシリコン、分散剤及び中空黒鉛を有機溶剤で混合乾燥処理し、第１前駆体を得る工程と、
（３）第１前駆体に対して機械的融合処理を行い、次に炭素源被覆処理を行い、第２前駆体を得る工程と、
（４）第２前駆体に対して等方性加圧処理を行い、塊状又は円柱状の第３前駆体を得る工程と、
（５）第３前駆体を高温焼結し、前記シリコン系複合負極材を得る工程と、を含む。
In a second aspect, the present invention provides a method for producing a silicon-based composite negative electrode material for a lithium ion secondary battery according to the first aspect,
(1) mechanically processing a graphite material to obtain hollow graphite;
(2) A step of mixing and drying nanosilicon, a dispersant and hollow graphite with an organic solvent to obtain a first precursor;
(3) performing a mechanical fusion process on the first precursor and then performing a carbon source coating process to obtain a second precursor;
(4) performing an isotropic pressure treatment on the second precursor to obtain a massive or columnar third precursor;
(5) high temperature sintering the third precursor to obtain the silicon-based composite negative electrode material.
本発明に係る方法では、黒鉛類材料を機械的加工することによって中空黒鉛を得て、前記中空黒鉛の内層は隙間を含み、その中におけるナノシリコン粒子の均一且つ良好な分散に空間を提供し、機械的融合処理工程で、ナノシリコン粒子と中空黒鉛粒子は押出力とせん断力の作用を絶えずに受けることによって、中空黒鉛の内部におけるナノシリコン粒子はさらに秩序よく配列し、さらにシリコンと黒鉛シートとの間の結合力を向上させ、等方性加圧処理工程で、第２前駆体粉末に等方性圧縮応力を加えることにより、中空黒鉛粒子の内部シートは異なる軸方向に沿って伸びるとともに、中空黒鉛シートの間に埋め込まれたナノシリコン粒子は二次分散し、また、等方性圧縮応力の作用で、軟質の有機炭素源粉末も中空黒鉛粒子の表面で拡張し、そして一部の有機炭素源粉末は中空黒鉛の内層に圧入され、黒鉛シート同士の粘着力を大幅に向上させることによって、高プレス密度の粒子を得る。 In the method according to the present invention, hollow graphite is obtained by mechanically processing a graphite material, the inner layer of the hollow graphite includes a gap, and provides a space for uniform and good dispersion of the nanosilicon particles therein. In the mechanical fusion process, nanosilicon particles and hollow graphite particles are constantly subjected to the action of pushing force and shearing force, so that the nanosilicon particles inside hollow graphite are arranged more orderly, and further, silicon and graphite sheet And by applying isotropic compressive stress to the second precursor powder in the isotropic pressure treatment process, the inner sheet of the hollow graphite particles extends along different axial directions. The nanosilicon particles embedded between the hollow graphite sheets are secondarily dispersed, and the soft organic carbon source powder expands on the surface of the hollow graphite particles by the action of isotropic compressive stress. , And a part of the organic carbon source powder is pressed into the inner layer of the hollow graphite, by greatly improve the adhesion of graphite sheet each other to obtain particles of high press density.
本発明では、前記工程（５）の後に好ましくは、工程（５）で得た複合負極材を解砕、粉砕、篩い分けして除磁し、中央粒径が５．０〜４５．０μｍ、好ましくは１０．０〜３５．０μｍ、さらに好ましくは１３．０〜２５．０μｍのシリコン系複合負極材を得る工程（６）を含む。 In the present invention, preferably, after the step (5), the composite negative electrode material obtained in the step (5) is crushed, pulverized, sieved and demagnetized, and the median particle size is 5.0 to 45.0 μm. Preferably, the method includes a step (6) of obtaining a silicon-based composite negative electrode material of 10.0 to 35.0 μm, more preferably 13.0 to 25.0 μm.
本発明では、前記工程（１）の機械的加工は、好ましくは黒鉛類材料を粉砕、除磁、篩い分けして中央粒径が５．０〜２５．０μｍの黒鉛粒子を得て、次に、機械的研磨を行って中央粒径が１．０〜１０．０μｍの中空黒鉛を得ることを含む。 In the present invention, the mechanical processing in the step (1) is preferably performed by pulverizing, demagnetizing, and sieving the graphite material to obtain graphite particles having a median particle size of 5.0 to 25.0 μm, And performing mechanical polishing to obtain hollow graphite having a median particle size of 1.0 to 10.0 μm.
前記黒鉛類材料は、好ましくは天然結晶質黒鉛、天然隠微晶質黒鉛、天然結晶脈状黒鉛、人造黒鉛及び導電性黒鉛のうちの１種又は少なくとも２種の組合せである。前記組合せとして、天然結晶質黒鉛と天然隠微晶質黒鉛の組合せ、天然結晶質黒鉛と天然結晶脈状黒鉛の組合せ、天然隠微晶質黒鉛と天然結晶脈状黒鉛の組合せ、天然結晶脈状黒鉛と人造黒鉛の組合せ、人造黒鉛と導電性黒鉛の組合せは典型例として挙げられるが、それらに限定されない。 The graphite material is preferably one or a combination of at least two of natural crystalline graphite, natural hidden crystalline graphite, natural crystalline veined graphite, artificial graphite and conductive graphite. As the above combinations, a combination of natural crystalline graphite and natural microcrystalline graphite, a combination of natural crystalline graphite and natural crystalline vein graphite, a combination of natural crystalline graphite and natural crystalline vein graphite, a natural crystalline vein A combination of graphite and artificial graphite, and a combination of artificial graphite and conductive graphite are given as typical examples, but are not limited thereto.
前記黒鉛類材料の形状は、好ましくは片状、略球状及び球状のうちの１種又は少なくとも２種の組合せである。前記黒鉛類材料の形状は特に限定されない。 The shape of the graphite material is preferably one or a combination of at least two of flaky, substantially spherical and spherical. The shape of the graphite material is not particularly limited.
前記粉砕は、好ましくはボールミル粉砕、機械的粉砕、ジェットミル粉砕、高圧微粉砕及び回転式高速粉砕のうちの１種又は少なくとも２種の組合せであり、つまり、前記のいずれかによって粉砕を行うことができる。 The pulverization is preferably one or a combination of at least two of ball mill pulverization, mechanical pulverization, jet mill pulverization, high-pressure fine pulverization, and rotary high-speed pulverization. Can do.
前記機械的研磨は、好ましくは乾式研磨又は湿式研磨であり、さらに好ましくは湿式研磨であり、前記湿式研磨は高速撹拌ミル、ボールミル、チューブミル、コロイドミル、ロッドミル及びサンドミルのいずれかを用いる。 The mechanical polishing is preferably dry polishing or wet polishing, more preferably wet polishing, and the wet polishing uses any of a high-speed stirring mill, a ball mill, a tube mill, a colloid mill, a rod mill, and a sand mill.
前記機械的研磨の媒体は、好ましくは銅、亜鉛、銀、錫、バナジウム、クロム、タングステン、銅合金、アルミニウム合金、亜鉛合金、鉄炭素合金、マグネシウム合金、リチウム合金、酸化ホウ素、酸化ケイ素、酸化ジルコニウム、アルミナ、炭酸カルシウム、酸化マグネシウム、二酸化チタン、酸化亜鉛、酸化錫、三酸化二鉄、四酸化三鉄、炭化タングステン、炭化チタン、窒化チタン、炭化ケイ素、窒化ケイ素、炭窒化チタン及び炭窒化タングステンのうちの１種又は少なくとも２種の組合せである。 The mechanical polishing medium is preferably copper, zinc, silver, tin, vanadium, chromium, tungsten, copper alloy, aluminum alloy, zinc alloy, iron carbon alloy, magnesium alloy, lithium alloy, boron oxide, silicon oxide, oxidation Zirconium, alumina, calcium carbonate, magnesium oxide, titanium dioxide, zinc oxide, tin oxide, ferric trioxide, ferric tetroxide, tungsten carbide, titanium carbide, titanium nitride, silicon carbide, silicon nitride, titanium carbonitride and carbonitride One or a combination of at least two of tungsten.
前記機械的研磨の媒体のサイズは、好ましくは０．０１〜１０ｍｍであり、さらに好ましくは０．０３〜８．０ｍｍであり、特に好ましくは０．０５〜５．０ｍｍである。 The size of the mechanical polishing medium is preferably 0.01 to 10 mm, more preferably 0.03 to 8.0 mm, and particularly preferably 0.05 to 5.0 mm.
前記湿式研磨に用いられる溶剤は、好ましくは水及び／又は有機溶剤であり、前記有機溶剤はテトラヒドロフラン、アミド、アルコール及びケトンのうちの１種又は少なくとも２種の組合せであり、さらに好ましくはテトラヒドロフラン、ジメチルアセトアミド、Ｃ１−Ｃ６アルコール及びＣ３−Ｃ８ケトンのうちの１種又は少なくとも２種の組合せであり、前記Ｃ１−Ｃ６アルコールはメタノール、エタノール、エチレングリコール、プロパノール、イソプロパノール、１，２−プロパンジオール、１，３−プロパンジオール、グリセロール、ｎ−ブタノール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ｎ−ペンタノール及び２−ヘキサノールのうちの１種又は少なくとも２種の組合せであり、前記Ｃ３−Ｃ８ケトンはアセトン、メチルエチルケトン、メチルプロピルケトン、Ｎ−メチルピロリドン、エチルプロピルケトン、メチルブチルケトン、エチルｎ−ブチルケトン、メチルアミルケトン及びメチルヘキシルケトンのうちの１種又は少なくとも２種の組合せである。 The solvent used for the wet polishing is preferably water and / or an organic solvent, and the organic solvent is one or a combination of at least two of tetrahydrofuran, amide, alcohol and ketone, more preferably tetrahydrofuran, One or a combination of at least two of dimethylacetamide, C1-C6 alcohol and C3-C8 ketone, wherein the C1-C6 alcohol is methanol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-propanediol, One or at least two of 1,3-propanediol, glycerol, n-butanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, n-pentanol and 2-hexanol A combination of species, the C The -C8 ketone is one or a combination of at least two of acetone, methyl ethyl ketone, methyl propyl ketone, N-methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone. .
機械的研磨工程で、黒鉛粒子と研磨媒体は互いに衝突し又は摩擦し、黒鉛粒子は衝撃力とせん断力の作用を絶えずに受け、そしてこの作用力が黒鉛内シート同士の接着力よりも大きくなることで、黒鉛シートをずれさせて隙間を形成し、中空黒鉛を形成する。 In the mechanical polishing process, the graphite particles and the polishing medium collide or rub against each other, the graphite particles are constantly subjected to the action of impact force and shear force, and this action force is greater than the adhesion force between the sheets in the graphite. As a result, the graphite sheet is displaced to form a gap to form hollow graphite.
本発明では前記工程（２）のナノシリコンは、好ましくはシリコン原料を機械的加工して得られる。 In the present invention, the nanosilicon in the step (2) is preferably obtained by mechanically processing a silicon raw material.
前記機械的加工は、好ましくはシリコン原料を粉砕、除磁、篩い分けして中央粒径が５．０〜４０．０μｍのシリコン粒子を得て、次に、機械的研磨を行って中央粒径が１０〜５００ｎｍのナノシリコンを得ることを含む。 The mechanical processing is preferably performed by pulverizing, demagnetizing, and sieving a silicon raw material to obtain silicon particles having a median particle size of 5.0 to 40.0 μm, and then performing mechanical polishing to obtain a median particle size. Includes obtaining nano-silicon having a thickness of 10 to 500 nm.
前記粉砕は、好ましくはボールミル粉砕、機械的粉砕、ジェットミル粉砕、高圧微粉砕及び回転式高速粉砕のうちの１種又は少なくとも２種の組合せであり、つまり、前記のいずれかによって粉砕を行うことができる。 The pulverization is preferably one or a combination of at least two of ball mill pulverization, mechanical pulverization, jet mill pulverization, high-pressure fine pulverization, and rotary high-speed pulverization. Can do.
前記機械的研磨は、好ましくは乾式研磨又は湿式研磨であり、さらに好ましくは湿式研磨である。 The mechanical polishing is preferably dry polishing or wet polishing, and more preferably wet polishing.
前記機械的研磨は、好ましくは高速撹拌ミル、ボールミル、チューブミル、コロイドミル、ロッドミル及びサンドミルのいずれかを用いる。 The mechanical polishing is preferably performed using any one of a high speed stirring mill, a ball mill, a tube mill, a colloid mill, a rod mill, and a sand mill.
前記サンドミルによる研磨の媒体は、好ましくは銅、亜鉛、銀、錫、バナジウム、クロム、タングステン、銅合金、アルミニウム合金、亜鉛合金、鉄炭素合金、マグネシウム合金、リチウム合金、酸化ホウ素、酸化ケイ素、酸化ジルコニウム、アルミナ、炭酸カルシウム、酸化マグネシウム、二酸化チタン、酸化亜鉛、酸化錫、三酸化二鉄、四酸化三鉄、炭化タングステン、炭化チタン、窒化チタン、炭化ケイ素、窒化ケイ素、炭窒化チタン及び炭窒化タングステンのうちの１種又は少なくとも２種の組合せである。 The sand mill polishing medium is preferably copper, zinc, silver, tin, vanadium, chromium, tungsten, copper alloy, aluminum alloy, zinc alloy, iron-carbon alloy, magnesium alloy, lithium alloy, boron oxide, silicon oxide, oxidation Zirconium, alumina, calcium carbonate, magnesium oxide, titanium dioxide, zinc oxide, tin oxide, ferric trioxide, ferric tetroxide, tungsten carbide, titanium carbide, titanium nitride, silicon carbide, silicon nitride, titanium carbonitride and carbonitride One or a combination of at least two of tungsten.
前記機械的研磨の媒体のサイズは、好ましくは０．０１〜１．００ｍｍであり、さらに好ましくは０．０２〜０．８０ｍｍであり、特に好ましくは０．０３〜０．５０ｍｍである。 The size of the mechanical polishing medium is preferably 0.01 to 1.00 mm, more preferably 0.02 to 0.80 mm, and particularly preferably 0.03 to 0.50 mm.
前記湿式研磨に用いられる溶剤は、好ましくは有機溶剤であり、前記有機溶剤はテトラヒドロフラン、アミド、アルコール及びケトンのうちの１種又は少なくとも２種の組合せであり、さらに好ましくはテトラヒドロフラン、ジメチルアセトアミド、Ｃ１−Ｃ６アルコール及びＣ３−Ｃ８ケトンのうちの１種又は少なくとも２種の組合せであり、前記Ｃ１−Ｃ６アルコールはメタノール、エタノール、エチレングリコール、プロパノール、イソプロパノール、１，２−プロパンジオール、１，３−プロパンジオール、グリセロール、ｎ−ブタノール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ｎ−ペンタノール及び２−ヘキサノールのうちの１種又は少なくとも２種の組合せであり、前記Ｃ３−Ｃ８ケトンはアセトン、メチルエチルケトン、メチルプロピルケトン、Ｎ−メチルピロリドン、エチルプロピルケトン、メチルブチルケトン、エチルｎ−ブチルケトン、メチルアミルケトン及びメチルヘキシルケトンのうちの１種又は少なくとも２種の組合せである。 The solvent used in the wet polishing is preferably an organic solvent, and the organic solvent is one or a combination of at least two of tetrahydrofuran, amide, alcohol and ketone, more preferably tetrahydrofuran, dimethylacetamide, C1. One or a combination of at least two of -C6 alcohol and C3-C8 ketone, wherein the C1-C6 alcohol is methanol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-propanediol, 1,3- One or a combination of at least two of propanediol, glycerol, n-butanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, n-pentanol and 2-hexanol Yes, the C3-C8 keto Acetone, methyl ethyl ketone, methyl propyl ketone, N- methylpyrrolidone, ethyl propyl ketone, is one or at least two combinations of the methyl ketone, ethyl n- butyl ketone, methyl amyl ketone and methyl hexyl ketone.
本発明では、前記工程（２）の混合乾燥処理は、好ましくはナノシリコンと分散剤を有機溶剤に添加し、０．１〜１時間超音波撹拌し、均一に分散したナノシリコン懸濁液を形成し、さらに中空黒鉛を懸濁液に添加し、回転速度６００〜３０００ｒｐｍで１〜５時間撹拌し、乾燥して第１前駆体を得ることを含む。 In the present invention, the mixing and drying treatment in the step (2) is preferably performed by adding nanosilicon and a dispersing agent to an organic solvent, ultrasonically stirring for 0.1 to 1 hour, and uniformly dispersing the nanosilicon suspension. Forming, further adding hollow graphite to the suspension, stirring at a rotational speed of 600-3000 rpm for 1-5 hours, and drying to obtain a first precursor.
前記分散剤は、好ましくはトリポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム、ピロリン酸ナトリウム、トリエチルヘキシルリン酸、ドデシル硫酸ナトリウム、メチルペンタノール、セルロース誘導体、ポリアクリルアミド、グアーガム、脂肪酸ポリエチレングリコールエステル、臭化ヘキサデシルトリメチルアンモニウム、ポリエチレングリコールｐ−イソオクチルフェニルエーテル、ポリアクリル酸、ポリビニルピロリドン、ポリオキシエチレンソルビタンモノオレアート、ｐ−エチル安息香酸及びポリエーテルイミドのうちの１種又は少なくとも２種の組合せである。 The dispersant is preferably sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, hexadecyltrimethyl bromide One or a combination of at least two of ammonium, polyethylene glycol p-isooctyl phenyl ether, polyacrylic acid, polyvinyl pyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid and polyetherimide.
前記乾燥は、好ましくは噴霧乾燥機、吸引濾過器、回転蒸発器又は冷凍乾燥機を用いる。 The drying is preferably performed using a spray dryer, a suction filter, a rotary evaporator or a freeze dryer.
前記噴霧乾燥機の入り口温度は、より好ましくは１００〜４００℃であり、さらに好ましくは１１０〜３００℃であり、特に好ましくは１２０〜２５０℃である。前記噴霧乾燥機の出口温度は、より好ましくは２０〜２５０℃であり、さらに好ましくは３５〜２００℃であり、特に好ましくは５０〜１２０℃である。前記噴霧乾燥機の圧力は、より好ましくは５〜１５０ＭＰａであり、さらに好ましくは７〜１２０ＭＰａであり、特に好ましくは１０〜１００ＭＰａである。前記噴霧乾燥機のフィード周波数は、より好ましくは２〜２００Ｈｚであり、さらに好ましくは５〜１６０Ｈｚであり、特に好ましくは１０〜１００Ｈｚである。 The inlet temperature of the spray dryer is more preferably 100 to 400 ° C, still more preferably 110 to 300 ° C, and particularly preferably 120 to 250 ° C. The outlet temperature of the spray dryer is more preferably 20 to 250 ° C, still more preferably 35 to 200 ° C, and particularly preferably 50 to 120 ° C. The pressure of the spray dryer is more preferably 5 to 150 MPa, still more preferably 7 to 120 MPa, and particularly preferably 10 to 100 MPa. The feed frequency of the spray dryer is more preferably 2 to 200 Hz, further preferably 5 to 160 Hz, and particularly preferably 10 to 100 Hz.
前記ナノシリコン、分散剤、中空黒鉛及び有機溶剤の質量比は、好ましくは（１〜５０）：（０．５〜１０）：（３０〜９０）：（９０〜８００）である。 The mass ratio of the nanosilicon, the dispersant, the hollow graphite, and the organic solvent is preferably (1-50) :( 0.5-10) :( 30-90) :( 90-800).
本発明では、前記工程（３）の機械的融合処理は、好ましくは第１前駆体を融合機に入れ、回転速度を５００〜３０００ｒｐｍ、刃物クリアランス幅を０．０１〜１ｃｍに調整し、少なくとも０．２５時間融合し、融合前駆体材料を得ることを含む。 In the present invention, the mechanical fusion treatment in the step (3) is preferably performed by putting the first precursor into the fusion machine, adjusting the rotation speed to 500 to 3000 rpm, and the blade clearance width to 0.01 to 1 cm, and at least 0. Fusing for 25 hours to obtain a fusion precursor material.
前記融合機の回転速度は、好ましくは８００〜２０００ｒｐｍ、例えば９００ｒｐｍ、１１００ｒｐｍ、１３００ｒｐｍ、１６００ｒｐｍ又は１８００ｒｐｍである。 The rotation speed of the fusion machine is preferably 800 to 2000 rpm, for example 900 rpm, 1100 rpm, 1300 rpm, 1600 rpm or 1800 rpm.
前記刃物クリアランス幅は、好ましくは０．１〜０．３ｃｍ、例えば０．１２ｃｍ、０．１５ｃｍ、０．１８ｃｍ、０．２１ｃｍ、０．２５ｃｍ又は０．２８ｃｍである。 The blade clearance width is preferably 0.1 to 0.3 cm, for example, 0.12 cm, 0.15 cm, 0.18 cm, 0.21 cm, 0.25 cm, or 0.28 cm.
前記融合時間は、好ましくは０．２５〜８．０時間、例えば０．３時間、０．５時間、１時間、３時間、５時間又は７時間であり、特に好ましくは０．５〜４．０時間である。
機械的融合処理工程で、ナノシリコン粒子と中空黒鉛粒子は押出力とせん断力の作用を絶えずに受けることによって、中空黒鉛の内部におけるナノシリコン粒子はさらに秩序よく配列し、さらにシリコンと黒鉛シートとの間の結合力を向上させることができる。
The fusion time is preferably 0.25 to 8.0 hours, such as 0.3 hours, 0.5 hours, 1 hour, 3 hours, 5 hours or 7 hours, particularly preferably 0.5 to 4. hours. 0 hours.
In the mechanical fusion treatment process, the nanosilicon particles and the hollow graphite particles are constantly subjected to the action of the pushing force and the shearing force, so that the nanosilicon particles inside the hollow graphite are arranged more orderly, and the silicon and the graphite sheet The bonding force between the two can be improved.
本発明では、前記工程（３）の炭素源被覆処理は、好ましくは融合前駆体材料と有機炭素源に対して、固相被覆又は液相被覆処理、さらに好ましくは固相被覆処理を行い、第２前駆体を得ることを含む。 In the present invention, the carbon source coating treatment in the step (3) is preferably carried out by subjecting the fusion precursor material and the organic carbon source to solid phase coating or liquid phase coating treatment, more preferably solid phase coating treatment. Obtaining two precursors.
前記固相被覆処理は、好ましくは融合前駆体材料と有機炭素源をＶＣ混合機に入れ、少なくとも０．５時間被覆処理し、第２前駆体を得ることを含む。 The solid phase coating process preferably includes placing the fusion precursor material and the organic carbon source in a VC mixer and coating process for at least 0.5 hours to obtain a second precursor.
前記有機炭素源は、好ましくは粉末状であり、中央粒径として、０．５〜２５．０μｍ、例えば１μｍ、５μｍ、１０μｍ、１５μｍ、１８μｍ又は２３μｍであり、特に好ましくは１．０〜８．０μｍである。 The organic carbon source is preferably in a powder form, and has a median particle size of 0.5 to 25.0 μm, such as 1 μm, 5 μm, 10 μm, 15 μm, 18 μm, or 23 μm, and particularly preferably 1.0 to 8. 0 μm.
前記融合前駆体材料と有機炭素源の質量比は、好ましくは１：１〜１０：１、例えば２：１、５：１、７：１又は９：１であり、特に好ましくは２：１〜６：１である。 The mass ratio of the fusion precursor material to the organic carbon source is preferably 1: 1 to 10: 1, such as 2: 1, 5: 1, 7: 1 or 9: 1, particularly preferably 2: 1. 6: 1.
前記有機炭素源は、好ましくは石炭ピッチ、石油ピッチ、メソフェースピッチ、石炭タール、石油工業重質油、重質芳香族炭化水素、エポキシ樹脂、フェノール樹脂、フルフラール樹脂、尿素樹脂、ポリビニルアルコール、ポリ塩化ビニル、ポリエチレングリコール、ポリエチレンオキシド、ポリフッ化ビニリデン、アクリル樹脂及びポリアクリロニトリルのうちの１種又は少なくとも２種の組合せである。 The organic carbon source is preferably coal pitch, petroleum pitch, mesophase pitch, coal tar, petroleum industry heavy oil, heavy aromatic hydrocarbon, epoxy resin, phenol resin, furfural resin, urea resin, polyvinyl alcohol, poly One or a combination of at least two of vinyl chloride, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, acrylic resin and polyacrylonitrile.
本発明では前記工程（４）の等方性加圧処理は、好ましくは圧力１０００〜２００００ＫＮ、加圧処理温度２０〜３００℃の条件で、第２前駆体を０．０５〜４時間加圧処理し、第３前駆体を得ることを含む。 In the present invention, the isotropic pressure treatment in the step (4) is preferably performed under pressure of 1000 to 20000 KN and a pressure treatment temperature of 20 to 300 ° C. for 0.05 to 4 hours. And obtaining a third precursor.
前記加圧処理は、好ましくは押出成形処理、冷間加圧処理、熱間加圧処理及び等方圧加圧処理のうちの１種又は少なくとも２種の組合せであり、つまり、前記のいずれかによって加圧処理を行うことができる。 The pressure treatment is preferably one or a combination of at least two of an extrusion molding process, a cold pressure process, a hot pressure process and an isotropic pressure process, that is, any one of the above Can be pressurized.
前記圧力は、好ましくは５０００〜１００００ＫＮ、例えば６０００ＫＮ、８０００ＫＮ、９０００ＫＮ又は９５００ＫＮである。 The pressure is preferably 5000 to 10000 KN, for example 6000 KN, 8000 KN, 9000 KN or 9500 KN.
前記加圧処理の温度は、好ましくは３０〜２００℃、例えば５０℃、７０℃、９０℃、１２０℃、１５０℃、１８０℃又は１９０℃である。 The temperature of the pressure treatment is preferably 30 to 200 ° C., for example, 50 ° C., 70 ° C., 90 ° C., 120 ° C., 150 ° C., 180 ° C. or 190 ° C.
前記加圧処理の時間は、好ましくは０．１〜２時間、例えば０．２時間、０．５時間、０．７、１．２時間又は１．８時間である。 The pressure treatment time is preferably 0.1 to 2 hours, for example, 0.2 hours, 0.5 hours, 0.7, 1.2 hours, or 1.8 hours.
等方性加圧処理工程で、第２前駆体粉末に等方性圧縮応力が加えられることによって、黒鉛粒子の内部シートは異なる軸方向によって伸びるとともに、黒鉛シートの間に埋め込まれたナノシリコン粒子は二次分散し、また、等方性圧縮応力の作用で、軟質の有機炭素源粉末も黒鉛粒子の表面で拡張し、そして一部の有機炭素源粉末は黒鉛の内層に圧入され、黒鉛シート同士の粘着力を大幅に向上させることによって、高プレス密度の粒子を得る。 By applying isotropic compressive stress to the second precursor powder in the isotropic pressure treatment process, the inner sheet of graphite particles extends in different axial directions, and the nanosilicon particles embedded between the graphite sheets Is dispersed by the second, and by the action of isotropic compressive stress, the soft organic carbon source powder expands on the surface of the graphite particles, and a part of the organic carbon source powder is pressed into the inner layer of the graphite, and the graphite sheet Particles with high press density are obtained by greatly improving the adhesion between them.
本発明では、前記工程（５）の高温焼結は、好ましくは保護ガス雰囲気下で行う。 In the present invention, the high-temperature sintering in the step (5) is preferably performed in a protective gas atmosphere.
前記保護ガスは、好ましくは窒素ガス、ヘリウムガス、ネオンガス、アルゴンガス、クリプトンガス、キセノンガス及び水素ガスのうちの１種又は少なくとも２種の組合せであり、特に好ましくは窒素ガス、ヘリウムガス、アルゴンガス及び水素ガスのうちの１種又は少なくとも２種の組合せである。 The protective gas is preferably nitrogen gas, helium gas, neon gas, argon gas, krypton gas, xenon gas and hydrogen gas, and particularly preferably nitrogen gas, helium gas, argon One or a combination of at least two of gas and hydrogen gas.
前記保護ガスの流量は、好ましくは０．５〜１０．０Ｌ／分であり、さらに好ましくは０．５〜５．０Ｌ／分であり、特に好ましくは１．０〜４．０Ｌ／分である。 The flow rate of the protective gas is preferably 0.5 to 10.0 L / min, more preferably 0.5 to 5.0 L / min, and particularly preferably 1.0 to 4.0 L / min. .
前記焼結時の昇温速度は、好ましくは２０．０℃／分以下であり、さらに好ましくは１．０〜１５．０℃／分であり、特に好ましくは２．０〜１０．０℃／分である。 The heating rate during the sintering is preferably 20.0 ° C./min or less, more preferably 1.0 to 15.0 ° C./min, and particularly preferably 2.0 to 10.0 ° C./min. Minutes.
前記焼結温度は、好ましくは５００〜１１５０℃であり、さらに好ましくは６００〜１０５０℃であり、特に好ましくは８００〜１０００℃である。 The sintering temperature is preferably 500 to 1150 ° C, more preferably 600 to 1050 ° C, and particularly preferably 800 to 1000 ° C.
前記焼結時間は、好ましくは少なくとも０．５時間であり、さらに好ましくは０．５〜２０．０時間であり、特に好ましくは１．０〜１０．０時間である。 The sintering time is preferably at least 0.5 hours, more preferably 0.5 to 20.0 hours, and particularly preferably 1.0 to 10.0 hours.
好ましくは、前記工程（５）において、高温焼結が終了した後、室温まで自然冷却する。 Preferably, in the step (5), after the high-temperature sintering is completed, it is naturally cooled to room temperature.
第３の態様において、本発明は第２の態様に記載の方法により製造されたリチウムイオン二次電池用シリコン系複合負極材を提供する。 In a third aspect, the present invention provides a silicon-based composite negative electrode material for a lithium ion secondary battery produced by the method described in the second aspect.
前記シリコン系複合負極材の中央粒径は、好ましくは５．０〜４５．０μｍであり、さらに好ましくは１０．０〜３５．０μｍであり、特に好ましくは１３．０〜２５．０μｍである。 The median particle size of the silicon composite negative electrode material is preferably 5.0 to 45.0 μm, more preferably 10.0 to 35.0 μm, and particularly preferably 13.0 to 25.0 μm.
前記シリコン系複合負極材の比表面積は、好ましくは１．０〜２０．０ｍ2／ｇであり、特に好ましくは２．０〜１０．０ｍ2／ｇである。 The specific surface area of the silicon-based composite negative electrode material is preferably 1.0~20.0m 2 / g, particularly preferably 2.0 to 10.0 m 2 / g.
前記シリコン系複合負極材の粉末プレス密度は、好ましくは１．０〜２．０ｇ／ｃｍ3であり、特に好ましくは１．３〜１．８ｇ／ｃｍ3である。 The powder press density of the silicon-based composite negative electrode material is preferably 1.0 to 2.0 g / cm 3 , particularly preferably 1.3 to 1.8 g / cm 3 .
前記ナノシリコン粒子の中央粒径は、好ましくは１０〜５００ｎｍであり、さらに好ましくは１０〜４００ｎｍであり、特に好ましくは１０〜３００ｎｍである。 The median particle size of the nanosilicon particles is preferably 10 to 500 nm, more preferably 10 to 400 nm, and particularly preferably 10 to 300 nm.
第４の態様において、本発明は、電池正極、電池負極及び電解液を備えるリチウムイオン二次電池を提供し、前記電池負極は負極活物質材料、導電剤、接着剤及び溶剤を含み、前記負極活物質材料は第１の態様又は第３の態様に記載のリチウムイオン二次電池用シリコン系複合負極材である。 4th aspect WHEREIN: This invention provides a lithium ion secondary battery provided with a battery positive electrode, a battery negative electrode, and electrolyte solution, The said battery negative electrode contains a negative electrode active material, a electrically conductive agent, an adhesive agent, and a solvent, The said negative electrode The active material is the silicon-based composite negative electrode material for a lithium ion secondary battery according to the first aspect or the third aspect.
前記導電剤は、好ましくは黒鉛粉末及び／又はナノ導電液である。 The conductive agent is preferably graphite powder and / or nano conductive liquid.
前記ナノ導電液は、好ましくは０．５−２０％（重量）のナノ炭素材料と分散溶剤とからなるものである。 The nano conductive liquid is preferably composed of 0.5-20% (by weight) of a nano carbon material and a dispersion solvent.
前記ナノ炭素材料は、より好ましくはグラフェン、カーボンナノチューブ、ナノ炭素繊維、フラーレン、カーボンブラック及びアセチレンブラックのうちの１種以上であり、前記グラフェンの黒鉛層の数は１−１００であり、カーボンナノチューブ及びナノ炭素繊維の直径は０．２−５００ｎｍであり、フラーレン、カーボンブラック及びアセチレンブラックの粒径は１−２００ｎｍである。 More preferably, the nanocarbon material is at least one of graphene, carbon nanotube, nanocarbon fiber, fullerene, carbon black, and acetylene black, and the number of graphite layers of the graphene is 1-100, The diameter of the nanocarbon fiber is 0.2 to 500 nm, and the particle sizes of fullerene, carbon black, and acetylene black are 1 to 200 nm.
前記分散溶剤は、より好ましくは水、メタノール、エタノール、プロパノール、イソプロパノール、アセトン、シクロヘキサノン、ジクロロメタン、クロロホルム、シクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン、アニリン、テトラヒドロフラン、ジメチルスルホキシド、Ｎ−メチルピロリドン、Ｎ−Ｎジメチルホルムアミド、Ｎ−Ｎジメチルアセトアミド、ピリジン、ピロール、１−ブチル−３−メチルイミダゾリウムテトラフルオロボラート、１−エチル−３−メチルイミダゾリウムジシアナミド、１−ブチル−３−メチルイミダゾリウムヘキサフルオロホスファート、１−ブチル−３−メチルイミダゾリウムビストリフルオロメタンスルホニルイミド、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホナート及び１−エチル−３−メチルイミダゾリウムアセテートのうちの１種又は少なくとも２種の組合せである。 The dispersion solvent is more preferably water, methanol, ethanol, propanol, isopropanol, acetone, cyclohexanone, dichloromethane, chloroform, cyclohexane, benzene, toluene, xylene, ethylbenzene, aniline, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, N- N dimethylformamide, NN dimethylacetamide, pyridine, pyrrole, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexa Fluorophosphate, 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide, 1-butyl-3-methylimidazolium trifluoromethanes Honato and 1-ethyl-3 is one or at least two combinations of methylimidazolium acetate.
前記接着剤は、好ましくはポリイミド樹脂、アクリル樹脂、ポリビニリデンジフルオライド、ポリビニルアルコール、カルボキシメチルセルロースナトリウム及びスチレンブタジエンゴムのうちの１種又は少なくとも２種の組合せである。 The adhesive is preferably one or a combination of at least two of polyimide resin, acrylic resin, polyvinylidene difluoride, polyvinyl alcohol, sodium carboxymethyl cellulose, and styrene butadiene rubber.
前記溶剤は、好ましくはＮ−メチルピロリドン、ジメチルホルムアミド、アセトン及びメチルエチルケトンのうちの１種又は少なくとも２種の組合せである。 The solvent is preferably one or a combination of at least two of N-methylpyrrolidone, dimethylformamide, acetone and methyl ethyl ketone.
本発明の有益な効果について、本発明に係るシリコン系複合負極材は、従来の技術に比べて、機械的研磨、機械的融合、等方性加圧処理及び炭素被覆技術を組み合わせることによってナノシリコン粒子を黒鉛の内層に埋め込ませることを実現し、且つ黒鉛粒子表面の均一な被覆を達成し、高性能シリコン系材料を得て、ナノシリコン粒子が緩衝基体である黒鉛粒子の内部に均一に分散し、この埋込複合コア構造はシリコン粒子の膨張を根本的に緩和し、材料の導電率を大幅に向上させ、シリコン粒子と電解液との直接接触を回避し、それにより、材料のサイクル特性（３００回サイクルの容量維持率が９０％以上である。）及び初回効率（＞９０％）を大幅に向上させ、また、本発明に係るシリコン系複合負極材は比エネルギー及びプレス密度が高く、高出力密度のリチウムイオン二次電池のニーズを満たすことができる。該負極材は製造プロセスが簡単で、原料コストが低く、エコで無公害である。 Regarding the beneficial effects of the present invention, the silicon-based composite negative electrode material according to the present invention is a nano-silicon by combining mechanical polishing, mechanical fusion, isotropic pressure treatment and carbon coating technology compared to the conventional technology. Realizing that the particles are embedded in the inner layer of graphite, achieving a uniform coating on the surface of the graphite particles, obtaining a high-performance silicon-based material, and nano-silicon particles are uniformly dispersed inside the graphite particles as the buffer substrate This embedded composite core structure fundamentally mitigates the expansion of the silicon particles, greatly improves the conductivity of the material and avoids direct contact between the silicon particles and the electrolyte, thereby enabling the cycle characteristics of the material. (The capacity retention rate of 300 cycles is 90% or more) and the initial efficiency (> 90%) is greatly improved, and the silicon composite negative electrode material according to the present invention has a specific energy and press density. Can be high, meet the needs of the lithium ion secondary battery having a high output density. The negative electrode material has a simple manufacturing process, a low raw material cost, and is eco-friendly and non-polluting.
以下、実施例を参照しながら本発明の実施形態を詳細に説明する。当業者は、以下の実施例が本発明の好ましい実施例で、本発明をさらに理解するためのものであるので、本発明の範囲を制限するものではないと理解すべきである。当業者は、本発明に対してさまざまな変更及び変化を実施してもよく、本発明の趣旨及び原則を逸脱しない範囲で実施されるすべての修正、等価置換や改良などは、本発明の保護範囲に属すべきである。 Hereinafter, embodiments of the present invention will be described in detail with reference to examples. Those skilled in the art should understand that the following examples are preferred examples of the present invention, and are not intended to limit the scope of the present invention, for further understanding of the present invention. Those skilled in the art may make various changes and modifications to the present invention, and all modifications, equivalent substitutions, improvements, etc. implemented without departing from the spirit and principle of the present invention are protected by the present invention. Should belong to a range.
実施例１
類球状の天然黒鉛を中央粒径が５．０〜１５．０μｍの黒鉛粒子に機械的粉砕し、それを４ｍｍの窒化ケイ素ビーズ及びプロパノール溶剤を含むボールミルに入れ、ボールミル粉砕して中央粒径が１．０〜１０．０μｍの中空黒鉛を得、シリコン原料をジェットミル粉砕して中央粒径が５．０〜３０．０μｍのシリコン粒子を得、次に、それを０．０１ｍｍの炭化タングステンビーズ及びメタノール溶剤を含むサンドミルに入れて研磨し、中央粒径が１０〜３００ｎｍのナノシリコン粉末を得、前記製造したナノシリコン粉末と脂肪酸ポリエチレングリコールエステルを質量比１５：０．５でメタノールに添加し、０．５時間超音波撹拌し、均一に分散したナノシリコン懸濁液を得、中空黒鉛（ナノシリコン：中空黒鉛の質量比が１５：５０である。）を懸濁液に添加し、２０００ｒｐｍの撹拌回転速度で２時間撹拌し、乾燥して第１前駆体を得、第１前駆体を融合機に入れ、１時間融合し、融合前駆体材料を得、前記製造した融合前駆体材料と中央粒径が０．８〜４．０μｍのピッチ粉末を質量比５：１でＶＣ混合機に入れ、０．５時間混合被覆処理し、第２前駆体を得、第２前駆体を冷間プレスに入れ、１００００ＫＮの等方性圧力を加え、０．５時間圧力保持し、第３前駆体を得、第３前駆体をトンネルキルンに入れ、流量が１．０Ｌ／分のアルゴンガスの保護雰囲気で、１５．０℃／分の昇温速度で１１５０．０℃まで昇温し、８時間恒温し、室温まで自然冷却し、次に、解砕、粉砕し、３２５メッシュで篩い分けして中央粒径が１０．０〜２０．０μｍのシリコン系複合負極材を得た。
Example 1
Spherical natural graphite is mechanically pulverized into graphite particles having a median particle size of 5.0 to 15.0 μm, placed in a ball mill containing 4 mm silicon nitride beads and a propanol solvent, and pulverized by ball milling. Obtain hollow graphite of 1.0 to 10.0 μm, jet mill pulverize the silicon raw material to obtain silicon particles having a median particle size of 5.0 to 30.0 μm, and then add it to 0.01 mm tungsten carbide beads And polishing in a sand mill containing methanol solvent to obtain nanosilicon powder having a median particle size of 10 to 300 nm, and adding the prepared nanosilicon powder and fatty acid polyethylene glycol ester to methanol at a mass ratio of 15: 0.5. , Ultrasonically stirred for 0.5 hours to obtain a uniformly dispersed nanosilicon suspension, and hollow graphite (mass ratio of nanosilicon: hollow graphite is 15:50) Is added to the suspension, stirred for 2 hours at a stirring rotational speed of 2000 rpm, dried to obtain the first precursor, and the first precursor is put into the fusion machine and fused for 1 hour. A material is obtained, and the manufactured fusion precursor material and pitch powder having a median particle size of 0.8 to 4.0 μm are placed in a VC mixer at a mass ratio of 5: 1, mixed and coated for 0.5 hours, Obtain a precursor, put the second precursor in a cold press, apply an isotropic pressure of 10000 KN, hold the pressure for 0.5 hours, get a third precursor, put the third precursor in a tunnel kiln, In a protective atmosphere of argon gas at a flow rate of 1.0 L / min, the temperature was raised to 1150.0 ° C. at a rate of 15.0 ° C./min, kept constant for 8 hours, naturally cooled to room temperature, Crushing, crushing, sieving with 325 mesh, silicon composite negative electrode with a median particle size of 10.0-20.0 μm It was obtained.
実施例２
片状の天然黒鉛を中央粒径が１０．０〜２５．０μｍの黒鉛粒子に機械的粉砕し、それを０．０１ｍｍの窒化ケイ素ビーズ及びエチレングリコール溶剤を含むボールミルに入れ、ボールミル粉砕して中央粒径が１．０〜１０．０μｍの中空黒鉛を得、シリコン原料を機械的粉砕して中央粒径が５．０〜４０．０μｍのシリコン粒子を得、次に、それを０．０２ｍｍの酸化ジルコニウムビーズ及びエチレングリコール溶剤を含むサンドミルに入れて研磨し、中央粒径が１０〜４００ｎｍのナノシリコン粉末を得、前記製造したナノシリコン粉末とポリエーテルイミドを質量比５０：１でエチレングリコールに添加し、１時間超音波撹拌し、均一に分散したナノシリコン懸濁液を形成し、中空黒鉛（ナノシリコン：中空黒鉛の質量比が５０：３０である。）を懸濁液に添加し、３０００ｒｐｍの撹拌回転速度で５時間撹拌し、乾燥して第１前駆体を得、第１前駆体を融合機に入れ、４時間融合し、融合前駆体材料を得、前記製造した融合前駆体材料と中央粒径が１０．０〜２５．０μｍのフェノール樹脂粉末を質量比１：１でＶＣ高速混合機に入れ、１時間混合被覆処理し、第２前駆体を得て、第２前駆体を熱間プレスに入れ、２００００ＫＮの等方性圧力を加え、温度が９０℃であり、０．０５時間圧力保持し、第３前駆体を得、第３前駆体をトンネルキルンに入れ、流量が１０．０Ｌ／分の窒素ガスの保護雰囲気で、５．０℃／分の昇温速度で１０００．０℃まで昇温し、２０時間恒温し、室温まで自然冷却し、次に、解砕、粉砕し、３２５メッシュで篩い分けして中央粒径が５．０〜１５．０μｍのシリコン系複合負極材を得た。
Example 2
The flake natural graphite is mechanically pulverized into graphite particles having a median particle size of 10.0 to 25.0 μm, and then put into a ball mill containing 0.01 mm silicon nitride beads and an ethylene glycol solvent. Hollow graphite having a particle size of 1.0-10.0 μm is obtained, silicon raw material is mechanically pulverized to obtain silicon particles having a median particle size of 5.0-40.0 μm, and then 0.02 mm Polishing by putting in a sand mill containing zirconium oxide beads and ethylene glycol solvent to obtain nanosilicon powder having a median particle size of 10 to 400 nm. The prepared nanosilicon powder and polyetherimide are converted into ethylene glycol at a mass ratio of 50: 1. Added, ultrasonically stirred for 1 hour to form a uniformly dispersed nanosilicon suspension, and hollow graphite (mass ratio of nanosilicon: hollow graphite is 50:30) Is added to the suspension, stirred for 5 hours at a stirring rotational speed of 3000 rpm, dried to obtain a first precursor, and the first precursor is put into a fusion machine, fused for 4 hours, and fused precursor. A material is obtained, and the prepared fusion precursor material and a phenol resin powder having a median particle size of 10.0 to 25.0 μm are put into a VC high-speed mixer at a mass ratio of 1: 1 and mixed and coated for 1 hour. A precursor is obtained, the second precursor is put into a hot press, an isotropic pressure of 20000 KN is applied, the temperature is 90 ° C., the pressure is maintained for 0.05 hours, and a third precursor is obtained. The precursor is put into a tunnel kiln, heated to 1000.0 ° C. at a temperature rising rate of 5.0 ° C./min in a nitrogen gas protective atmosphere with a flow rate of 10.0 L / min, and kept at a constant temperature for 20 hours. Cool naturally, then crush, pulverize, sieve through 325 mesh, median particle size is 5.0 ~ A 15.0 μm silicon composite negative electrode material was obtained.
実施例３
球状の人造黒鉛を中央粒径が５．０〜１０．０μｍの黒鉛粒子に高圧微粉砕し、それを１０ｍｍの窒化ケイ素ビーズ及びアセトン溶剤を含むボールミルに入れ、ボールミル粉砕して中央粒径が１．０〜１０．０μｍの中空黒鉛を得、シリコン原料をジェットミル粉砕して中央粒径が５．０〜２０．０μｍのシリコン粒子を得、次に、それを１ｍｍの炭化ケイ素ビーズ及びＮ−メチルピロリドン溶剤を含むサンドミルに入れて研磨し、中央粒径が５０〜５００ｎｍのナノシリコン粉末を得、前記製造したナノシリコン粉末とポリアクリル酸を質量比１：１０でエタノールに添加し、０．１時間超音波撹拌し、均一に分散したナノシリコン懸濁液を形成し、中空黒鉛（ナノシリコン：中空黒鉛の質量比が１：９０である。）を懸濁液に添加し、６００ｒｐｍの撹拌回転速度で１時間撹拌し、乾燥して第１前駆体を得て、第１前駆体を融合機に入れ、０．２５時間融合し、融合前駆体材料を得、前記製造した融合前駆体材料と中央粒径が０．５〜２５．０μｍのメソフェースピッチ粉末を質量比１０：１でＶＣ高速混合機に入れ、０．５時間混合被覆処理し、第２前駆体を得、第２前駆体を熱間プレスに入れ、１０００ＫＮの等方性圧力を加え、温度が３００℃であり、４時間圧力保持し、第３前駆体を得、第３前駆体をトンネルキルンに入れ、流量が０．５Ｌ／分の窒素ガスの保護雰囲気で、２０．０℃／分の昇温速度で１１５０．０℃まで昇温し、１５時間恒温し、室温まで自然冷却し、次に、解砕、粉砕し、３２５メッシュで篩い分けして中央粒径が２０．０〜４５．０μｍのシリコン系複合負極材を得た。
Example 3
Spherical artificial graphite is finely pulverized into graphite particles having a median particle size of 5.0 to 10.0 μm under high pressure, put into a ball mill containing 10 mm silicon nitride beads and an acetone solvent, and pulverized by ball milling to obtain a median particle size of 1. 0.0-10.0 μm hollow graphite is obtained, and the silicon raw material is jet milled to obtain silicon particles having a median particle size of 5.0-20.0 μm, which are then divided into 1 mm silicon carbide beads and N- It is put into a sand mill containing a methylpyrrolidone solvent and polished to obtain a nanosilicon powder having a median particle size of 50 to 500 nm, and the prepared nanosilicon powder and polyacrylic acid are added to ethanol at a mass ratio of 1:10. Ultrasonic agitation for 1 hour to form a uniformly dispersed nanosilicon suspension, and hollow graphite (nanosilicon: hollow graphite mass ratio is 1:90) is added to the suspension. Stir at an agitation rotational speed of rpm for 1 hour, dry to obtain the first precursor, put the first precursor into the fusion machine, fuse for 0.25 hour to obtain the fusion precursor material, the fusion produced above The precursor material and mesophase pitch powder having a median particle size of 0.5 to 25.0 μm are put into a VC high-speed mixer at a mass ratio of 10: 1 and mixed and coated for 0.5 hours to obtain a second precursor, Put the second precursor in a hot press, apply an isotropic pressure of 1000 KN, the temperature is 300 ° C., hold the pressure for 4 hours, obtain a third precursor, put the third precursor in a tunnel kiln, In a protective atmosphere of nitrogen gas at a flow rate of 0.5 L / min, the temperature is raised to 1150.0 ° C. at a rate of temperature increase of 20.0 ° C./min, kept constant for 15 hours, naturally cooled to room temperature, Crushed, ground and sieved with 325 mesh, silicon with a median particle size of 20.0-45.0 μm To obtain a composite negative electrode material.
実施例４
塊状の導電性黒鉛を中央粒径が１０．０〜１５．０μｍの黒鉛粒子にジェットミル粉砕し、それを３ｍｍの窒化ケイ素ビーズ及びエタノール溶剤を含むボールミルに入れ、ボールミル粉砕して中央粒径が１．０〜１０．０μｍの中空黒鉛を得、シリコン原料を機械的粉砕して中央粒径が５．０〜２５．０μｍのシリコン粒子を得、次に、それを０．０５ｍｍの炭窒化ケイ素ビーズ及びエタノール溶剤を含むサンドミルに入れて研磨し、中央粒径が１０〜２００ｎｍのナノシリコン粉末を得、前記製造したナノシリコン粉末とポリビニルピロリドンを質量比３０：５でエタノールに添加し、０．５時間超音波撹拌し、均一に分散したナノシリコン懸濁液を形成し、中空黒鉛（ナノシリコン：中空黒鉛の質量比が３０：６０である）を懸濁液に添加し、２０００ｒｐｍの撹拌回転速度で３時間撹拌し、乾燥して第１前駆体を得て、第１前駆体を融合機に入れ、２時間融合し、融合前駆体材料を得、前記製造した融合前駆体材料と中央粒径が１．０〜１０．０μｍのクエン酸粉末を質量比５：１でＶＣ高速混合機に入れ、１．５時間混合被覆処理し、第２前駆体を得、第２前駆体を冷間プレスに入れ、１５０００ＫＮの等方性圧力を加え、温度が３０℃であり、０．５時間圧力保持し、第３前駆体を得、第３前駆体をトンネルキルンに入れ、流量が３Ｌ／分の窒素ガスの保護雰囲気で、６．０℃／分の昇温速度で５００．０℃まで昇温し、５時間恒温し、室温まで自然冷却し、次に、解砕、粉砕し、３２５メッシュで篩い分けして中央粒径が１０．０〜２５．０μｍのシリコン系複合負極材を得た。
Example 4
The bulk conductive graphite is jet milled into graphite particles having a median particle size of 10.0 to 15.0 μm, put into a ball mill containing 3 mm silicon nitride beads and an ethanol solvent, and ball milled to obtain a median particle size. Obtain hollow graphite of 1.0 to 10.0 μm, mechanically pulverize the silicon raw material to obtain silicon particles having a median particle size of 5.0 to 25.0 μm, and then add it to 0.05 mm silicon carbonitride It is put into a sand mill containing beads and an ethanol solvent and polished to obtain a nanosilicon powder having a median particle size of 10 to 200 nm. The prepared nanosilicon powder and polyvinylpyrrolidone are added to ethanol at a mass ratio of 30: 5. Ultrasonic stirring for 5 hours to form a uniformly dispersed nanosilicon suspension and adding hollow graphite (nanosilicon: hollow graphite mass ratio is 30:60) to the suspension , Stirred for 3 hours at a stirring rotational speed of 2000 rpm, dried to obtain a first precursor, put the first precursor into a fusion machine, fused for 2 hours to obtain a fusion precursor material, and the manufactured fusion precursor The body material and citric acid powder having a median particle size of 1.0-10.0 μm were put into a VC high speed mixer at a mass ratio of 5: 1, mixed and coated for 1.5 hours to obtain a second precursor, Put the precursor in a cold press, apply an isotropic pressure of 15000 KN, the temperature is 30 ° C., hold the pressure for 0.5 hours to obtain a third precursor, put the third precursor in a tunnel kiln, In a protective atmosphere of nitrogen gas at a flow rate of 3 L / min, the temperature was raised to 500.0 ° C. at a rate of temperature increase of 6.0 ° C./min, kept constant for 5 hours, naturally cooled to room temperature, then crushed, A silicon composite negative electrode material having a median particle size of 10.0 to 25.0 μm by pulverizing and sieving with 325 mesh It was.
実施例５
鱗片状の天然黒鉛を中央粒径が５．０〜１０．０μｍの黒鉛粒子に回転式高速粉砕し、それを０．４ｍｍの酸化ジルコニウムビーズ及び水を含むボールミルに入れ、ボールミル粉砕して中央粒径が１．０〜１０．０μｍの中空黒鉛を得、シリコン原料を機械的粉砕して中央粒径が５．０〜２５．０μｍのシリコン粒子を得、次に、それを０．８ｍｍの炭窒化ケイ素ビーズ及びエタノール溶剤を含むサンドミルに入れて研磨し、中央粒径が１０〜２００ｎｍのナノシリコン粉末を得、前記製造したナノシリコン粉末と臭化ヘキサデシルトリメチルアンモニウムを質量比１０：１でエタノールに添加し、０．５時間超音波撹拌し、均一に分散したナノシリコン懸濁液を形成し、中空黒鉛（ナノシリコン：中空黒鉛の質量比が１０：６０である。）を懸濁液に添加し、２５００ｒｐｍの撹拌回転速度で２時間撹拌し、乾燥して第１前駆体を得、第１前駆体を融合機に入れ、１．５時間融合し、融合前駆体材料を得、前記製造した融合前駆体材料と中央粒径が１．０〜５．０μｍのポリビニルアルコール粉末を質量比２：１でＶＣ高速混合機に入れ、２時間混合被覆処理し、第２前駆体を得、第２前駆体を冷間プレスに入れ、９０００ＫＮの等方性圧力を加え、温度が２０℃であり、１時間圧力保持し、第３前駆体を得て、第３前駆体をトンネルキルンに入れ、流量が５Ｌ／分の窒素ガスの保護雰囲気で、１２．０℃／分の昇温速度で８００．０℃まで昇温し、５時間恒温し、室温まで自然冷却し、次に、解砕、粉砕し、３２５メッシュで篩い分けして中央粒径が１０．０〜２５．０μｍのシリコン系複合負極材を得た。
Example 5
Scale-like natural graphite is pulverized at high speed by rotation into graphite particles having a median particle size of 5.0-10.0 μm, put into a ball mill containing 0.4 mm zirconium oxide beads and water, and pulverized by ball mill. Hollow graphite having a diameter of 1.0 to 10.0 μm is obtained, and silicon raw material is mechanically pulverized to obtain silicon particles having a median particle diameter of 5.0 to 25.0 μm. Polishing by putting in a sand mill containing silicon nitride beads and ethanol solvent to obtain nanosilicon powder having a median particle diameter of 10 to 200 nm, ethanol produced at a mass ratio of 10: 1 with the prepared nanosilicon powder and hexadecyltrimethylammonium bromide And stirred with ultrasonic waves for 0.5 hour to form a uniformly dispersed nanosilicon suspension, and hollow graphite (the mass ratio of nanosilicon: hollow graphite is 10:60). Add to the turbid liquid, stir at 2500 rpm stirring speed for 2 hours, dry to obtain the first precursor, put the first precursor into the fusion machine and fuse for 1.5 hours to obtain the fusion precursor material The prepared fusion precursor material and polyvinyl alcohol powder having a median particle size of 1.0 to 5.0 μm are placed in a VC high speed mixer at a mass ratio of 2: 1 and mixed and coated for 2 hours to obtain a second precursor. The second precursor is put into a cold press, isotropic pressure of 9000 KN is applied, the temperature is 20 ° C., the pressure is kept for 1 hour, the third precursor is obtained, and the third precursor is tunnel kiln In a protective atmosphere of nitrogen gas at a flow rate of 5 L / min, the temperature is raised to 800.0 ° C. at a rate of temperature increase of 12.0 ° C./min, kept constant for 5 hours, naturally cooled to room temperature, Crushing, crushing, sieving with 325 mesh, and a median particle size of 10.0-25.0 μm To obtain a down-based composite negative electrode material.
比較例１
類球状の天然黒鉛に対して粉砕及びボールミル粉砕処理を行わない以外、実施例１とほぼ同様な方法でシリコン系負極材を製造し、実施例１と同様な方法で電池を作製した。
Comparative Example 1
A silicon-based negative electrode material was produced in substantially the same manner as in Example 1 except that the spherical natural graphite was not crushed and ball milled, and a battery was produced in the same manner as in Example 1.
比較例２
前駆IIに対して等方性の熱間加圧処理を行わない以外、実施例２とほぼ同様な方法でシリコン系負極材を製造し、実施例２と同様な方法で電池を作製した。
Comparative Example 2
A silicon-based negative electrode material was produced in substantially the same manner as in Example 2 except that the isotropic hot pressing treatment was not performed on the precursor II, and a battery was produced in the same manner as in Example 2.
下記の方法によって実施例１〜５及び比較例１〜２の負極材をテストした。
本発明に係る粉末プレス密度はＣＡＲＶＥＲ粉末プレスを用いて実際にテストされ、粉末プレス密度＝テスト用サンプルの質量／テスト用サンプルの体積、極片プレス密度＝（負極極片質量−銅箔質量）／（極片面積×極片圧密後の厚さ）である。
The negative electrode materials of Examples 1 to 5 and Comparative Examples 1 and 2 were tested by the following method.
The powder press density according to the present invention was actually tested using a CARVER powder press. Powder press density = mass of test sample / volume of test sample, pole piece press density = (negative electrode pole piece mass−copper foil mass) / (Pole piece area × Thickness after pole piece compaction).
米国Ｍｉｃｒｏｍｅｒｉｔｉｃｓ Ｉｎｓｔｒｕｍｅｎｔ社のＴｒｉｓｔａｒ３０００全自動比表面積及び空孔率分析装置を用いて材料の比表面積をテストした。 The specific surface area of the material was tested using a Tristar 3000 fully automatic specific surface area and porosity analyzer from Micromeritics Instrument, USA.
Ｍａｌｖｅｒｎレーザー粒度測定装置ＭＳ ２０００を用いて材料粒径範囲及び原料粒子の平均粒径をテストした。 The material particle size range and the average particle size of the raw material particles were tested using a Malvern laser particle size analyzer MS 2000.
Ｘ線回折装置Ｘ′Ｐｅｒｔ Ｐｒｏ，ＰＡＮａｌｙｔｉｃａlを用いて材料の構造をテストした。 The material structure was tested using an X-ray diffractometer X'Pert Pro, PANalytical.
株式会社日立製作所のＳ４８００走査型電子顕微鏡でサンプルの表面形態、粒子の大きさなどを観察した。 The surface morphology of the sample and the size of the particles were observed with an S4800 scanning electron microscope from Hitachi, Ltd.
下記の方法によって、電気化学サイクル特性をテストし、負極材、導電剤及び接着剤を質量比９４：１：５で溶剤に溶解して混合し、固形分を５０％に制御し、銅箔集電体に塗布し、真空乾燥して負極極片を得、次に、従来の成熟したプロセスにより製造される三元系正極極片、１ｍｏｌ／ＬのＬｉＰＦ6／ ＥＣ＋ＤＭＣ＋ＥＭＣ（ｖ／ｖ＝１：１：１）電解液、Ｃｅｌｇａｒd２４００セパレータ、ケースを通常の生産プロセスによって１８６５０円筒型単電池に組み立てた。円筒型電池の充放電テストは武漢金諾電子有限公司のＬＡＮＤ電池テストシステムで行われ、常温条件で、０．２Ｃの定電流で充放電し、充放電電圧を２．７５〜４．２Ｖに制限した。 The electrochemical cycle characteristics were tested by the following method, and the negative electrode material, the conductive agent and the adhesive were dissolved and mixed in a solvent at a mass ratio of 94: 1: 5, and the solid content was controlled to 50%. A negative electrode piece is obtained by applying to an electric body and vacuum-drying, and then producing a ternary positive electrode piece manufactured by a conventional mature process, 1 mol / L LiPF 6 / EC + DMC + EMC (v / v = 1: 1: 1) The electrolyte, Celgard 2400 separator, and case were assembled into 18650 cylindrical cells by a normal production process. Cylindrical battery charge / discharge test is performed by LAND battery test system of Wuhan Jinyi Electronics Co., Ltd., charge / discharge with constant current of 0.2C under normal temperature condition, and charge / discharge voltage to 2.75 ~ 4.2V Restricted.
実施例１〜５及び比較例１〜２で製造された負極材の電気化学測定結果を表１に示す。 Table 1 shows the electrochemical measurement results of the negative electrode materials produced in Examples 1 to 5 and Comparative Examples 1 and 2.
表１ 負極材の電気化学測定結果 Table 1 Electrochemical measurement results of negative electrode material
上記の表からわかるように、比較例は放電容量及び初回充放電効率が低く、初回効率が８５．５％しかなく、３００サイクル後の容量維持率が７５％と低い。これに対し、本出願に係る方法により製造されたシリコン系複合負極材は、比表面積が低く（２．０〜４．０ｍ2／ｇ）、プレス密度が高く（１．６〜１．８ｇ／ｃｍ3）、放電容量が４００ｍＡｈ／ｇを超え、初回クーロン効率が９０．０％を超え、３００サイクル容量維持率がいずれも９０％以上であった。 As can be seen from the above table, the comparative example has a low discharge capacity and initial charge / discharge efficiency, the initial efficiency is only 85.5%, and the capacity retention rate after 300 cycles is as low as 75%. In contrast, the silicon-based composite negative electrode material produced by the method according to the present application has a low specific surface area (2.0 to 4.0 m 2 / g) and a high press density (1.6 to 1.8 g / g). cm 3 ), the discharge capacity exceeded 400 mAh / g, the initial coulombic efficiency exceeded 90.0%, and the 300 cycle capacity retention rate was 90% or more.
出願人は、本発明は上記実施例によって本発明の具体的な特徴及び具体的な方法を説明したが、本発明は上記具体的な特徴及び具体的な方法に限定されるものではなく、すなわち、本発明は上記具体的な特徴及び具体的な方法によって実施されなければならないという意味ではないことを言明する。当業者は、本発明へのすべての改良、本発明の選用する成分の等価置換及び補助成分の添加、具体的な方式の選択などがいずれも本発明の保護範囲及び開示範囲に属すると理解すべきである。 The applicant has described specific features and specific methods of the present invention with the above embodiments, but the present invention is not limited to the specific features and specific methods described above. It is stated that the present invention is not meant to be implemented by the specific features and methods set forth above. Those skilled in the art will understand that all modifications to the present invention, equivalent substitution of components to be selected and addition of auxiliary components, selection of specific methods, etc. are all within the protection scope and disclosure scope of the present invention. Should.
Claims (10)
（１）黒鉛類材料を機械的加工し、中空黒鉛を得る工程と、
（２）ナノシリコン、分散剤及び中空黒鉛を有機溶剤で混合乾燥処理し、第１前駆体を得る工程と、
（３）第１前駆体に対して機械的融合処理を行い、次に炭素源被覆処理を行い、第２前駆体を得る工程と、
（４）第２前駆体に対して等方性加圧処理を行い、塊状又は円柱状の第３前駆体を得る工程と、
（５）第３前駆体を高温焼結し、前記シリコン系複合負極材を得る工程と、
を含む、方法。 A method for producing a silicon-based composite negative electrode material for a lithium ion secondary battery according to claim 1 or 2,
(1) mechanically processing a graphite material to obtain hollow graphite;
(2) A step of mixing and drying nanosilicon, a dispersant and hollow graphite with an organic solvent to obtain a first precursor;
(3) performing a mechanical fusion process on the first precursor and then performing a carbon source coating process to obtain a second precursor;
(4) performing an isotropic pressure treatment on the second precursor to obtain a massive or columnar third precursor;
(5) a step of high-temperature sintering the third precursor to obtain the silicon-based composite negative electrode material;
Including a method.
前記黒鉛類材料が、好ましくは天然結晶質黒鉛、天然隠微晶質黒鉛、天然結晶脈状黒鉛、人造黒鉛及び導電性黒鉛のうちの１種又は少なくとも２種の組合せであり、
前記黒鉛類材料の形状が、好ましくは片状、略球状及び球状のうちの１種又は少なくとも２種の組合せであり、
前記粉砕が、好ましくはボールミル粉砕、機械的粉砕、ジェットミル粉砕、高圧微粉砕及び回転式高速粉砕のうちの１種又は少なくとも２種の組合せであり、
前記機械的研磨が、好ましくは乾式研磨又は湿式研磨であり、さらに好ましくは湿式研磨であり、
前記湿式研磨が、より好ましくは高速撹拌ミル、ボールミル、チューブミル、コロイドミル、ロッドミル及びサンドミルのいずれかを用い、
前記機械的研磨の媒体が、好ましくは銅、亜鉛、銀、錫、バナジウム、クロム、タングステン、銅合金、アルミニウム合金、亜鉛合金、鉄炭素合金、マグネシウム合金、リチウム合金、酸化ホウ素、酸化ケイ素、酸化ジルコニウム、アルミナ、炭酸カルシウム、酸化マグネシウム、二酸化チタン、酸化亜鉛、酸化錫、三酸化二鉄、四酸化三鉄、炭化タングステン、炭化チタン、窒化チタン、炭化ケイ素、窒化ケイ素、炭窒化チタン及び炭窒化タングステンのうちの１種又は少なくとも２種の組合せであり、
前記機械的研磨の媒体のサイズが、好ましくは０．０１〜１０ｍｍであり、さらに好ましくは０．０３〜８．０ｍｍであり、特に好ましくは０．０５〜５．０ｍｍであり、
前記湿式研磨に用いられる溶剤が、好ましくは水及び／又は有機溶剤であり、
前記有機溶剤が、より好ましくはテトラヒドロフラン、アミド、アルコール及びケトンのうちの１種又は少なくとも２種の組合せであり、さらに好ましくはテトラヒドロフラン、ジメチルアセトアミド、Ｃ１−Ｃ６アルコール及びＣ３−Ｃ８ケトンのうちの１種又は少なくとも２種の組合せであり、前記Ｃ１−Ｃ６アルコールはメタノール、エタノール、エチレングリコール、プロパノール、イソプロパノール、１，２−プロパンジオール、１，３−プロパンジオール、グリセロール、ｎ−ブタノール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ｎ−ペンタノール及び２−ヘキサノールのうちの１種又は少なくとも２種の組合せであり、前記Ｃ３−Ｃ８ケトンはアセトン、メチルエチルケトン、メチルプロピルケトン、Ｎ−メチルピロリドン、エチルプロピルケトン、メチルブチルケトン、エチルｎ−ブチルケトン、メチルアミルケトン及びメチルヘキシルケトンのうちの１種又は少なくとも２種の組合せである
ことを特徴とする請求項３又は４に記載の方法。 The mechanical processing of the step (1) pulverizes, demagnetizes and sieves the graphite material to obtain graphite particles having a median particle size of 5.0 to 25.0 μm, and then performs mechanical polishing. Obtaining hollow graphite having a median particle size of 1.0-10.0 μm,
The graphite material is preferably one or a combination of at least two of natural crystalline graphite, natural microcrystalline graphite, natural crystalline vein graphite, artificial graphite and conductive graphite,
The shape of the graphite material is preferably one or a combination of at least two of flaky, substantially spherical and spherical,
Said grinding is preferably one or a combination of at least two of ball milling, mechanical grinding, jet milling, high pressure fine grinding and rotary high speed grinding,
The mechanical polishing is preferably dry polishing or wet polishing, more preferably wet polishing,
The wet polishing is more preferably performed using any one of a high-speed stirring mill, a ball mill, a tube mill, a colloid mill, a rod mill, and a sand mill.
The mechanical polishing medium is preferably copper, zinc, silver, tin, vanadium, chromium, tungsten, copper alloy, aluminum alloy, zinc alloy, iron-carbon alloy, magnesium alloy, lithium alloy, boron oxide, silicon oxide, oxidation Zirconium, alumina, calcium carbonate, magnesium oxide, titanium dioxide, zinc oxide, tin oxide, ferric trioxide, ferric tetroxide, tungsten carbide, titanium carbide, titanium nitride, silicon carbide, silicon nitride, titanium carbonitride and carbonitride One or a combination of at least two of tungsten;
The size of the mechanical polishing medium is preferably 0.01 to 10 mm, more preferably 0.03 to 8.0 mm, and particularly preferably 0.05 to 5.0 mm.
The solvent used for the wet polishing is preferably water and / or an organic solvent,
More preferably, the organic solvent is one or a combination of at least two of tetrahydrofuran, amide, alcohol and ketone, and more preferably one of tetrahydrofuran, dimethylacetamide, C1-C6 alcohol and C3-C8 ketone. Or a combination of at least two, and the C1-C6 alcohol is methanol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, glycerol, n-butanol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, n-pentanol, and a combination of at least two of 2-hexanol, and the C3-C8 ketone is acetone, methyl ethyl ketone, Methylp 5. A combination of one or at least two of pyrrole ketone, N-methyl pyrrolidone, ethyl propyl ketone, methyl butyl ketone, ethyl n-butyl ketone, methyl amyl ketone and methyl hexyl ketone. The method described in 1.
前記機械的加工が、好ましくはシリコン原料を粉砕、除磁、篩い分けして中央粒径が５．０〜４０．０μｍであるシリコン粒子を得、次に、機械的研磨を行って中央粒径が１０〜５００ｎｍであるナノシリコンを得ることを含み、
前記粉砕が、好ましくはボールミル粉砕、機械的粉砕、ジェットミル粉砕、高圧微粉砕及び回転式高速粉砕のうちの１種又は少なくとも２種の組合せであり、
前記機械的研磨が、好ましくは乾式研磨又は湿式研磨であり、更に好ましくは湿式研磨であり、
前記機械的研磨が、好ましくは高速撹拌ミル、ボールミル、チューブミル、コロイドミル、ロッドミル及びサンドミルのいずれかを用い、
前記サンドミルによる研磨の媒体が、好ましくは銅、亜鉛、銀、錫、バナジウム、クロム、タングステン、銅合金、アルミニウム合金、亜鉛合金、鉄炭素合金、マグネシウム合金、リチウム合金、酸化ホウ素、酸化ケイ素、酸化ジルコニウム、アルミナ、炭酸カルシウム、酸化マグネシウム、二酸化チタン、酸化亜鉛、酸化錫、三酸化二鉄、四酸化三鉄、炭化タングステン、炭化チタン、窒化チタン、炭化ケイ素、窒化ケイ素、炭窒化チタン及び炭窒化タングステンのうちの１種又は少なくとも２種の組合せであり、
前記機械的研磨の媒体のサイズが、好ましくは０．０１〜１．００ｍｍであり、さらに好ましくは０．０２〜０．８０ｍｍであり、特に好ましくは０．０３〜０．５０ｍｍであり、
前記湿式研磨に用いられる溶剤が、好ましくは有機溶剤であり、
前記有機溶剤が、より好ましくはテトラヒドロフラン、アミド、アルコール及びケトンのうちの１種又は少なくとも２種の組合せであり、さらに好ましくはテトラヒドロフラン、ジメチルアセトアミド、Ｃ１−Ｃ６アルコール及びＣ３−Ｃ８ケトンのうちの１種又は少なくとも２種の組合せであり、前記Ｃ１−Ｃ６アルコールはメタノール、エタノール、エチレングリコール、プロパノール、イソプロパノール、１，２−プロパンジオール、１，３−プロパンジオール、グリセロール、ｎ−ブタノール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ｎ−ペンタノール及び２−ヘキサノールのうちの１種又は少なくとも２種の組合せであり、前記Ｃ３−Ｃ８ケトンはアセトン、メチルエチルケトン、メチルプロピルケトン、Ｎ−メチルピロリドン、エチルプロピルケトン、メチルブチルケトン、エチルｎ−ブチルケトン、メチルアミルケトン及びメチルヘキシルケトンのうちの１種又は少なくとも２種の組合せであり、
前記工程（２）の混合乾燥処理が、好ましくはナノシリコンと分散剤を有機溶剤に添加し、０．１〜１時間超音波撹拌し、均一に分散したナノシリコン懸濁液を形成し、さらに中空黒鉛を懸濁液に添加し、回転速度６００〜３０００ｒｐｍで１〜５時間撹拌し、乾燥して第１前駆体を得ることを含み、
前記分散剤が、好ましくはトリポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム、ピロリン酸ナトリウム、リン酸トリエチルヘキシル、ドデシル硫酸ナトリウム、メチルペンタノール、セルロース誘導体、ポリアクリルアミド、グアーガム、脂肪酸ポリエチレングリコールエステル、臭化ヘキサデシルトリメチルアンモニウム、ポリエチレングリコールｐ−イソオクチルフェニルエーテル、ポリアクリル酸、ポリビニルピロリドン、ポリオキシエチレンソルビタンモノオレアート、ｐ−エチル安息香酸及びポリエーテルイミドのうちの１種又は少なくとも２種の組合せであり、
前記乾燥が、好ましくは噴霧乾燥機、吸引濾過器、回転蒸発器又は冷凍乾燥機を用い、
前記噴霧乾燥機の入り口温度が、より好ましくは１００〜４００℃であり、さらに好ましくは１１０〜３００℃であり、特に好ましくは１２０〜２５０℃である、
前記噴霧乾燥機の出口温度が、より好ましくは２０〜２５０℃であり、さらに好ましくは３５〜２００℃であり、特に好ましくは５０〜１２０℃である。
前記噴霧乾燥機の圧力が、より好ましくは５〜１５０ＭＰａであり、さらに好ましくは７〜１２０ＭＰａであり、特に好ましくは１０〜１００ＭＰａであり、
前記噴霧乾燥機のフィード周波数が、より好ましくは２〜２００Ｈｚであり、さらに好ましくは５〜１６０Ｈｚであり、特に好ましくは１０〜１００Ｈｚであり、
前記ナノシリコン、分散剤、中空黒鉛及び有機溶剤の質量比が、好ましくは（１〜５０）：（０．５〜１０）：（３０〜９０）：（９０〜８００）である
ことを特徴とする請求項３〜５のいずれか１項に記載の方法。 The nanosilicon of the step (2) is obtained by mechanically processing a silicon raw material,
The mechanical processing is preferably performed by grinding, demagnetizing, and sieving the silicon raw material to obtain silicon particles having a median particle size of 5.0 to 40.0 μm, followed by mechanical polishing. Obtaining nanosilicon that is 10 to 500 nm,
Said grinding is preferably one or a combination of at least two of ball milling, mechanical grinding, jet milling, high pressure fine grinding and rotary high speed grinding,
The mechanical polishing is preferably dry polishing or wet polishing, more preferably wet polishing,
The mechanical polishing is preferably performed using any one of a high speed stirring mill, a ball mill, a tube mill, a colloid mill, a rod mill and a sand mill.
The sand mill polishing medium is preferably copper, zinc, silver, tin, vanadium, chromium, tungsten, copper alloy, aluminum alloy, zinc alloy, iron-carbon alloy, magnesium alloy, lithium alloy, boron oxide, silicon oxide, oxidation Zirconium, alumina, calcium carbonate, magnesium oxide, titanium dioxide, zinc oxide, tin oxide, ferric trioxide, ferric tetroxide, tungsten carbide, titanium carbide, titanium nitride, silicon carbide, silicon nitride, titanium carbonitride and carbonitride One or a combination of at least two of tungsten;
The size of the mechanical polishing medium is preferably 0.01 to 1.00 mm, more preferably 0.02 to 0.80 mm, and particularly preferably 0.03 to 0.50 mm.
The solvent used for the wet polishing is preferably an organic solvent,
More preferably, the organic solvent is one or a combination of at least two of tetrahydrofuran, amide, alcohol and ketone, and more preferably one of tetrahydrofuran, dimethylacetamide, C1-C6 alcohol and C3-C8 ketone. Or a combination of at least two, and the C1-C6 alcohol is methanol, ethanol, ethylene glycol, propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, glycerol, n-butanol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, n-pentanol, and a combination of at least two of 2-hexanol, and the C3-C8 ketone is acetone, methyl ethyl ketone, Methylp Piruketon, N- methylpyrrolidone, ethyl propyl ketone, is one or at least two combinations of the methyl ketone, ethyl n- butyl ketone, methyl amyl ketone and methyl hexyl ketone,
The mixing and drying treatment in the step (2) is preferably performed by adding nanosilicon and a dispersant to an organic solvent, and ultrasonically stirring for 0.1 to 1 hour to form a uniformly dispersed nanosilicon suspension, Adding hollow graphite to the suspension, stirring at a rotational speed of 600-3000 rpm for 1-5 hours, and drying to obtain a first precursor;
The dispersant is preferably sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, hexadecyltrimethyl bromide One or a combination of at least two of ammonium, polyethylene glycol p-isooctyl phenyl ether, polyacrylic acid, polyvinyl pyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid and polyetherimide,
The drying is preferably performed using a spray dryer, a suction filter, a rotary evaporator or a freeze dryer,
The inlet temperature of the spray dryer is more preferably 100 to 400 ° C, still more preferably 110 to 300 ° C, and particularly preferably 120 to 250 ° C.
The outlet temperature of the spray dryer is more preferably 20 to 250 ° C, still more preferably 35 to 200 ° C, and particularly preferably 50 to 120 ° C.
The pressure of the spray dryer is more preferably 5 to 150 MPa, still more preferably 7 to 120 MPa, particularly preferably 10 to 100 MPa,
The feed frequency of the spray dryer is more preferably 2 to 200 Hz, further preferably 5 to 160 Hz, and particularly preferably 10 to 100 Hz.
The mass ratio of the nanosilicon, the dispersant, the hollow graphite, and the organic solvent is preferably (1-50) :( 0.5-10) :( 30-90) :( 90-800). The method according to any one of claims 3 to 5.
前記融合機の回転速度が、好ましくは８００〜２０００ｒｐｍであり、
前記刃物クリアランス幅が、好ましくは０．１〜０．３ｃｍであり、
前記融合時間が、好ましくは０．２５〜８．０時間であり、特に好ましくは０．５〜４．０時間であり、
前記工程（３）の炭素源被覆処理が、好ましくは融合前駆体材料と有機炭素源に対して、固相被覆又は液相被覆処理、さらに好ましくは固相被覆処理を行い、第２前駆体を得ることを含み、
前記固相被覆処理が、好ましくは融合前駆体材料と有機炭素源をＶＣ混合機に入れ、少なくとも０．５時間被覆処理し、第２前駆体を得ることを含み、
前記有機炭素源が、好ましくは粉末状で、中央粒径が０．５〜２５．０μｍであり、特に好ましくは１．０〜８．０μｍであり、
前記融合前駆体材料と有機炭素源の質量比が、好ましくは１：１〜１０：１であり、特に好ましくは２：１〜６：１であり、
前記有機炭素源が、好ましくは石炭ピッチ、石油ピッチ、メソフェースピッチ、石炭タール、石油工業重質油、重質芳香族炭化水素、エポキシ樹脂、フェノール樹脂、フルフラール樹脂、尿素樹脂、ポリビニルアルコール、ポリ塩化ビニル、ポリエチレングリコール、ポリエチレンオキシド、ポリフッ化ビニリデン、アクリル樹脂及びポリアクリロニトリルのうちの１種又は少なくとも２種の組合せである
ことを特徴とする請求項３〜６のいずれか１項に記載の方法。 In the mechanical fusion process of the step (3), the first precursor is put into a fusion machine, the rotational speed is adjusted to 500 to 3000 rpm, the blade clearance width is adjusted to 0.01 to 1 cm, and the fusion is performed for at least 0.25 hours. Obtaining a fusion precursor material,
The rotational speed of the fusion machine is preferably 800 to 2000 rpm,
The blade clearance width is preferably 0.1 to 0.3 cm,
The fusion time is preferably 0.25 to 8.0 hours, particularly preferably 0.5 to 4.0 hours,
In the carbon source coating treatment in the step (3), preferably, the fusion precursor material and the organic carbon source are subjected to a solid phase coating or a liquid phase coating treatment, more preferably a solid phase coating treatment. Including obtaining
The solid phase coating preferably comprises placing the fusion precursor material and the organic carbon source in a VC mixer and coating for at least 0.5 hours to obtain a second precursor;
The organic carbon source is preferably in a powder form, and the median particle size is 0.5 to 25.0 μm, particularly preferably 1.0 to 8.0 μm,
The mass ratio of the fusion precursor material to the organic carbon source is preferably 1: 1 to 10: 1, particularly preferably 2: 1 to 6: 1.
The organic carbon source is preferably coal pitch, petroleum pitch, mesophase pitch, coal tar, petroleum industry heavy oil, heavy aromatic hydrocarbon, epoxy resin, phenol resin, furfural resin, urea resin, polyvinyl alcohol, poly The method according to any one of claims 3 to 6, which is one or a combination of at least two of vinyl chloride, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, acrylic resin and polyacrylonitrile. .
前記加圧処理が、好ましくは押出成形処理、冷間加圧処理、熱間加圧処理及び等方圧加圧処理のうちの１種又は少なくとも２種の組合せであり、
前記圧力が、好ましくは５０００〜１００００ＫＮであり、
前記加圧処理の温度が、好ましくは３０〜２００℃であり、
前記加圧処理の時間が、好ましくは０．１〜２時間であり、
前記工程（５）の高温焼結が、好ましくは保護ガス雰囲気下で行われ、
前記保護ガスが、好ましくは窒素ガス、ヘリウムガス、ネオンガス、アルゴンガス、クリプトンガス、キセノンガス及び水素ガスのうちの１種又は少なくとも２種の組合せであり、特に好ましくは窒素ガス、ヘリウムガス、アルゴンガス及び水素ガスのうちの１種又は少なくとも２種の組合せであり、
前記保護ガスの流量が、好ましくは０．５〜１０．０Ｌ／分であり、さらに好ましくは０．５〜５．０Ｌ／分であり、特に好ましくは１．０〜４．０Ｌ／分であり、
前記焼結時の昇温速度が、好ましくは２０．０℃／分以下であり、さらに好ましくは１．０〜１５．０℃／分であり特に好ましくは２．０〜１０．０℃／分であり、
前記焼結温度が、好ましくは５００〜１１５０℃であり、さらに好ましくは６００〜１０５０℃であり、特に好ましくは８００〜１０００℃であり、
前記焼結時間が、好ましくは少なくとも０．５時間であり、さらに好ましくは０．５〜２０．０時間であり、特に好ましくは１．０〜１０．０時間であり、
前記工程（５）において、好ましくは高温焼結が終了した後、室温まで自然冷却する
ことを特徴とする請求項３〜７のいずれか１項に記載の方法。 The isotropic pressure treatment in the step (4) is performed by pressure-treating the second precursor for 0.05 to 4 hours under conditions of a pressure of 1000 to 20000 KN and a pressure treatment temperature of 20 to 300 ° C. Including obtaining the body,
The pressure treatment is preferably one or a combination of at least two of extrusion treatment, cold pressure treatment, hot pressure treatment and isotropic pressure treatment,
The pressure is preferably 5000 to 10,000 KN,
The temperature of the pressure treatment is preferably 30 to 200 ° C.,
The pressure treatment time is preferably 0.1 to 2 hours,
The high-temperature sintering of the step (5) is preferably performed in a protective gas atmosphere,
The protective gas is preferably nitrogen gas, helium gas, neon gas, argon gas, krypton gas, xenon gas and hydrogen gas, and particularly preferably nitrogen gas, helium gas, argon One or a combination of at least two of gas and hydrogen gas,
The flow rate of the protective gas is preferably 0.5 to 10.0 L / min, more preferably 0.5 to 5.0 L / min, and particularly preferably 1.0 to 4.0 L / min. ,
The heating rate during the sintering is preferably 20.0 ° C./min or less, more preferably 1.0-15.0 ° C./min, and particularly preferably 2.0-10.0 ° C./min. And
The sintering temperature is preferably 500 to 1150 ° C, more preferably 600 to 1050 ° C, particularly preferably 800 to 1000 ° C,
The sintering time is preferably at least 0.5 hours, more preferably 0.5 to 20.0 hours, particularly preferably 1.0 to 10.0 hours,
The method according to any one of claims 3 to 7, wherein, in the step (5), preferably, after high-temperature sintering is finished, natural cooling to room temperature is performed.
前記シリコン系複合負極材の中央粒径が、好ましくは５．０〜４５．０μｍであり、さらに好ましくは１０．０〜３５．０μｍであり、特に好ましくは１３．０〜２５．０μｍであり、
前記シリコン系複合負極材の比表面積が、好ましくは１．０〜２０．０ｍ2／ｇであり、特に好ましく２．０〜１０．０ｍ2／ｇであり、
前記シリコン系複合負極材の粉末プレス密度が、好ましくは１．０〜２．０ｇ／ｃｍ3であり、特に好ましくは１．３〜１．８ｇ／ｃｍ3であり、
前記ナノシリコン粒子の中央粒径が、好ましくは１０〜５００ｎｍであり、さらに好ましくは１０〜４００ｎｍであり、特に好ましくは１０〜３００ｎｍである
ことを特徴とするリチウムイオン二次電池用シリコン系複合負極材。 A silicon-based composite negative electrode material for a lithium ion secondary battery manufactured by the method according to any one of claims 3 to 8,
The median particle size of the silicon-based composite negative electrode material is preferably 5.0 to 45.0 μm, more preferably 10.0 to 35.0 μm, and particularly preferably 13.0 to 25.0 μm.
The specific surface area of the silicon-based composite negative electrode material is preferably 1.0~20.0m 2 / g, particularly preferably 2.0 to 10.0 m 2 / g,
The powder press density of the silicon-based composite negative electrode material is preferably 1.0 to 2.0 g / cm 3 , particularly preferably 1.3 to 1.8 g / cm 3 ,
The center particle size of the nanosilicon particles is preferably 10 to 500 nm, more preferably 10 to 400 nm, and particularly preferably 10 to 300 nm, a silicon-based composite negative electrode for a lithium ion secondary battery Wood.
前記導電剤が、好ましくは黒鉛粉末及び／又はナノ導電液であり、
前記ナノ導電液が、好ましくは０．５〜２０％（重量）のナノ炭素材料と分散溶剤とからなり、
前記ナノ炭素材料が、より好ましくはグラフェン、カーボンナノチューブ、ナノ炭素繊維、フラーレン、カーボンブラック及びアセチレンブラックのうちの１種以上であり、前記グラフェンの黒鉛層の数は１〜１００であり、カーボンナノチューブ及びナノ炭素繊維の直径は０．２〜５００ｎｍであり、フラーレン、カーボンブラック及びアセチレンブラックの粒径は１〜２００ｎｍであり、
前記分散溶剤が、より好ましくは水、メタノール、エタノール、プロパノール、イソプロパノール、アセトン、シクロヘキサノン、ジクロロメタン、クロロホルム、シクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン、アニリン、テトラヒドロフラン、ジメチルスルホキシド、Ｎ−メチルピロリドン、Ｎ−Ｎジメチルホルムアミド、Ｎ−Ｎジメチルアセトアミド、ピリジン、ピロール、１−ブチル−３−メチルイミダゾリウムテトラフルオロボラート、１−エチル−３−メチルイミダゾリウムジシアナミド、１−ブチル−３−メチルイミダゾリウムヘキサフルオロホスファート、１−ブチル−３−メチルイミダゾリウムビストリフルオロメタンスルホニルイミド、１−ブチル−３−メチルイミダゾリウムトリフルオロメタンスルホナート及び１−エチル−３−メチルイミダゾリウムアセテートのうちの１種又は少なくとも２種の組合せであり、
前記接着剤が、好ましくはポリイミド樹脂、アクリル樹脂、ポリビニリデンジフルオライド、ポリビニルアルコール、カルボキシメチルセルロースナトリウム及びスチレンブタジエンゴムのうちの１種又は少なくとも２種の組合せであり、
前記溶剤が、好ましくはＮ−メチルピロリドン、ジメチルホルムアミド、アセトン及びメチルエチルケトンのうちの１種又は少なくとも２種の組合せである、リチウムイオン二次電池。 A lithium ion secondary battery comprising a battery positive electrode, a battery negative electrode, and an electrolyte, wherein the battery negative electrode includes a negative electrode active material, a conductive agent, an adhesive, and a solvent, and the negative electrode active material is a claim 1, 2 or 9 is a silicon-based composite negative electrode material for a lithium ion secondary battery according to 9,
The conductive agent is preferably graphite powder and / or nano conductive liquid,
The nano conductive liquid preferably comprises 0.5 to 20% (by weight) of a nanocarbon material and a dispersion solvent,
More preferably, the nanocarbon material is at least one of graphene, carbon nanotube, nanocarbon fiber, fullerene, carbon black and acetylene black, and the number of graphite layers of the graphene is 1 to 100, And the diameter of the nano carbon fiber is 0.2 to 500 nm, and the particle sizes of fullerene, carbon black and acetylene black are 1 to 200 nm,
More preferably, the dispersion solvent is water, methanol, ethanol, propanol, isopropanol, acetone, cyclohexanone, dichloromethane, chloroform, cyclohexane, benzene, toluene, xylene, ethylbenzene, aniline, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, N- N dimethylformamide, NN dimethylacetamide, pyridine, pyrrole, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexa Fluorophosphate, 1-butyl-3-methylimidazolium bistrifluoromethanesulfonylimide, 1-butyl-3-methylimidazolium trifluoromethanes Is one or at least two combinations of Honato and 1-ethyl-3-methylimidazolium acetate,
The adhesive is preferably one or a combination of at least two of polyimide resin, acrylic resin, polyvinylidene difluoride, polyvinyl alcohol, sodium carboxymethylcellulose and styrene butadiene rubber,
A lithium ion secondary battery, wherein the solvent is preferably one or a combination of at least two of N-methylpyrrolidone, dimethylformamide, acetone and methyl ethyl ketone.
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Also Published As
| Publication number | Publication date |
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| CN103682287A (en) | 2014-03-26 |
| JP6113123B2 (en) | 2017-04-12 |
| KR101687288B1 (en) | 2016-12-16 |
| KR20150072319A (en) | 2015-06-29 |
| CN103682287B (en) | 2016-09-14 |
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