JP2010501970A - Silicon / carbon composite cathode material for lithium ion battery and method for producing the same - Google Patents
Silicon / carbon composite cathode material for lithium ion battery and method for producing the same Download PDFInfo
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- JP2010501970A JP2010501970A JP2009524864A JP2009524864A JP2010501970A JP 2010501970 A JP2010501970 A JP 2010501970A JP 2009524864 A JP2009524864 A JP 2009524864A JP 2009524864 A JP2009524864 A JP 2009524864A JP 2010501970 A JP2010501970 A JP 2010501970A
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- cathode material
- lithium ion
- ion battery
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 195
- 239000010406 cathode material Substances 0.000 title claims abstract description 150
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 148
- 239000010703 silicon Substances 0.000 title claims abstract description 146
- 239000002131 composite material Substances 0.000 title claims abstract description 140
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 173
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 71
- 239000010439 graphite Substances 0.000 claims abstract description 71
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- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 153
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 72
- 239000000843 powder Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 44
- 229910052786 argon Inorganic materials 0.000 claims description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 24
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
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- 239000011856 silicon-based particle Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 12
- 229930006000 Sucrose Natural products 0.000 claims description 12
- 150000002642 lithium compounds Chemical class 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 12
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- -1 polyethylene Polymers 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
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- 229910052729 chemical element Inorganic materials 0.000 claims description 6
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000004702 methyl esters Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
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- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 44
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- 238000003780 insertion Methods 0.000 abstract description 22
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
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Images
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/362—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
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
【課題】本発明は、リチウムイオン電池の珪素・炭素複合陰極材料及びその製造方法を提供し、電池の比容量を高めることである。本発明の材料は、球形または球形近似の珪素形粒子、炭素形粒子の複合材料の基本体とし、その外側に被覆層を被覆する。
【手段】珪素形粒子を破砕し、それを炭素形粒子と混合して複合粒子を製造してから、有機物の熱分解グラファイトの前駆物と混合被覆し、炭化処理をしてから、破砕する。従来の技術に比べて、本発明の複合陰極材料は、珪素形粒子と炭素形粒子からなる複合材料の基本体とし、その外側に被覆層を有する構造をもっており、その可逆的容量は450mAh/gより大きく、第一回のサイクルクーロン効率は85%より大きく、200回のサイクル容量の保持率は80%より大きい。本発明は、リチウムの挿入・脱離時に生じた炭素を含む活性物質の体積効果を著しく減軽し、活性材料におけるリチウムの拡散行為を改善して、各種類の携帯式器具、電動工具などに使われている電池陰極材料に適している。
An object of the present invention is to provide a silicon / carbon composite cathode material for a lithium ion battery and a method for producing the same, and to increase the specific capacity of the battery. The material of the present invention is a basic body of a composite material of spherical or approximate spherical silicon-type particles and carbon-type particles, and a coating layer is coated on the outside thereof.
[Means] Crush silicon-shaped particles, mix them with carbon-shaped particles to produce composite particles, mix and coat with organic pyrolytic graphite precursor, carbonize, and crush. Compared to the prior art, the composite cathode material of the present invention is a basic body of a composite material composed of silicon-type particles and carbon-type particles, and has a structure having a coating layer on the outside thereof, and its reversible capacity is 450 mAh / g. The first cycle coulombic efficiency is greater than 85%, and the retention rate of 200 cycle capacity is greater than 80%. The present invention significantly reduces the volume effect of the active substance containing carbon generated during the insertion / extraction of lithium, improves the diffusion action of lithium in the active material, and can be used for various types of portable instruments, power tools, etc. Suitable for the battery cathode material used.
Description
本発明は、電池陰極材料及びその製造方法に関する。とくに、リチウムイオン電池の珪素・炭素複合陰極材料及びその製造方法に関する。 The present invention relates to a battery cathode material and a method for producing the same. In particular, the present invention relates to a silicon / carbon composite cathode material for a lithium ion battery and a method for producing the same.
1990年日本Sony会社が最初にリチウムイオン電池を開発し、それを商品化した以降、リチウムイオン電池は迅速な発展を成し遂げてきた。現在では、リチウムイオン電池はすでに民間用及び軍事用などの広範囲に応用されてきた。科学技術の絶えざる進歩につれて、消費者の電池の性能に対する要求はより多く、より高くなる。例えば、電子製品の小型化と個性化の発展趨勢は、より小型化、より効率の高い電池を必要とする。宇宙航空の電源は、サイクル寿命、よりよい低温充放電の性能、より高い安全性を有するものを必要とする。また、電力駆動の車は容量が大きく、コストが低く、安定性と安全性能が高い電池を必要とする。リチウムイオン電池開発の成功は、まず電極材料、特に炭素陰極材料の研究の進展によるものである。数多くの炭素材料の中に、黒鉛化の炭素材料は良好な層状構造を有するため、リチウムイオンの挿入・脱離を非常に適し、形成された黒鉛・リチウムの層間化合物Li−GICが高い比容量を有しており、すでにLiC6の理論の比容量372mAh/gに接近している。そのほか、黒鉛化の炭素材料は、良い充放電の電圧基盤、比較的に低い挿入・脱離リチウム電位を有するため、リチウム電池の陽極材料としてのLiCoO2、LiNiO2及LiMn2O4などとの整合性が良好である。これにより構成された電池は、その平均電圧が高く、放電が平穏である。そのため、現段階で商品化されたリチウムイオン電池の陰極材料として、黒鉛類炭素材料が大量に採用されている。 Since 1990, Sony Japan first developed a lithium-ion battery and commercialized it, and the lithium-ion battery has made rapid progress. At present, lithium ion batteries have already been applied in a wide range of civilian and military applications. As science and technology continue to advance, consumer demands for battery performance are higher and higher. For example, the development trend of downsizing and individualization of electronic products requires batteries that are smaller and more efficient. Aerospace power supplies need to have cycle life, better low-temperature charge / discharge performance, and higher safety. Power-driven vehicles also require batteries with high capacity, low cost, and high stability and safety performance. The success of lithium-ion battery development is first due to research progress on electrode materials, especially carbon cathode materials. Among many carbon materials, graphitized carbon material has a good layered structure, so it is very suitable for lithium ion insertion / extraction, and the formed graphite / lithium intercalation compound Li-GIC has a high specific capacity. It has already approached the specific capacity of 372 mAh / g of LiC 6 theory. In addition, graphitized carbon materials have a good charging / discharging voltage base and relatively low insertion / extraction lithium potential, so LiCoO 2 , LiNiO 2 and LiMn 2 O 4 as anode materials for lithium batteries Good consistency. The battery thus configured has a high average voltage and discharge is calm. Therefore, a large amount of graphitic carbon materials has been adopted as a cathode material for lithium ion batteries that have been commercialized at this stage.
しかし、現在の黒鉛類材料は、すでに理論容量に接近している。大電流密度のもとで安全操作を実現し、初回の不可逆的容量の損失を減少して、未来市場におけるリチウムイオン電池に対する高い容量、高い充電効率の要求を満足させるために、新型リチウムイオン電池の電極材料の開発は極めて緊急性がある。いま、学界では、この種類の電極材料に関する研究は大変盛んに行なわれている。こうした陰極材料の研究において、Al、Sn、Sb、Siなどリチウムと合金を形成することのできる金属、またはそれらの合金をリチウムイオン電池の陰極材料として、つまり、Al、Sn、Sb、Siまたはそれらの合金を陰極材料とするときは、そのリチウムの可逆的貯蔵容量が黒鉛類陰極材料のそれよりはるかに超えていることを発見した。しかし、この種類の陰極材料の高い体積効果が、サイクル安定性を悪化させるので、上記を実用化するまで時間がかかる。そのため、これらのリチウムの貯蔵容量の高い材料をいかにして実用化するのかについて、リチウムイオン電池研究において、現在注目されるところである。 However, current graphite materials are already close to the theoretical capacity. New lithium-ion battery to achieve safe operation under high current density, reduce initial irreversible capacity loss, and meet the demand for high capacity and high charging efficiency for lithium-ion battery in future market The development of electrode materials is extremely urgent. Currently, research on this type of electrode material is very active in the academic world. In the study of these cathode materials, metals that can form alloys with lithium, such as Al, Sn, Sb, and Si, or alloys thereof are used as cathode materials for lithium ion batteries, that is, Al, Sn, Sb, Si, or those It was discovered that the reversible storage capacity of lithium is far greater than that of graphite cathode materials. However, since the high volume effect of this type of cathode material deteriorates cycle stability, it takes time to put the above into practical use. For this reason, attention is currently being paid to research on how to put these materials with high lithium storage capacity into practical use in lithium ion battery research.
炭素基でない材料の研究において、珪素材料が理論的にリチウムの高い貯蔵容量(たとえば、珪素単体のリチウム貯蔵容量は4200mAh/gである)とリチウムの低い挿入電位を有しており、他の金属基材料と比べて、より高い安定性をもつため、注目されている。従って、珪素基材料をリチウムイオン電池の陰極材料として成功裏に運用することができるならば、リチウムイオン電池の発展に革新的意味をもち、且つ情報業、エネルギ業の発展にも重要な影響を及ぼすことになるに違いない。しかし、金属基材料と同様、高い程度のリチウムの挿入・脱離の場合、珪素基材料は厳重な体積効果が生じる。これにより、電極のサイクル安定性が不安になり、かつ、第一回の不可逆的容量が高くなるので、リチウムイオン電池の陰極材料としての応用が制限されることになる。そのため、現在、数多くの研究者は、リチウムの貯蔵容量の高い材料の改質と改善に努力している。たとえば、日立傘下のMaxwell社がCVD製法を用いて製造した、珪素粒子と前記珪素粒子の外部に無定形の炭素粒子を被覆するという複合材料は、珪素材料の構造とその導電性能を改善して、リチウムの挿入・脱離工程における体積効果をある程度に抑えることができるので、こうした材料のサイクル性能を上げることができた。しかし、CVD製法をコントロールすることが難しく、不確定の要素が多いため、大量生産を実現させることが困難である。また、C.S.Wang氏などが、黒鉛と珪素粉末によりボール・ミルで製造した珪素/炭素の二元体の複合材料は、第一回のリチウム挿入容量を高く有している。しかし、その充放電性能の安定性が欠き、特に最初数回のサイクル容量の減衰速度が速い(J. Electrochem. Soc.,8(1998): 2751-2758)。そのほか、S.B.NG氏などが、コロゾール・ゲル製法を用いて製造した網状近似の黒鉛―珪素/Si(OCH3)4の複合材料は、相対的に安定した機械性能をもち、サイクル性能の向上に役立つ。しかし、その一方、Si-O網状構造は、リチウムの拡散を阻んで、リチウムの挿入量を減少させるため、珪素の高い容量性能を充分に発揮させることができない(J. Power Sources,94(2001): 63-67)。 In the study of non-carbon based materials, silicon materials theoretically have a high lithium storage capacity (for example, the lithium storage capacity of silicon alone is 4200 mAh / g) and a low lithium insertion potential, and other metals It is attracting attention because it has higher stability than the base material. Therefore, if silicon-based materials can be successfully used as cathode materials for lithium-ion batteries, they will have an innovative meaning in the development of lithium-ion batteries and will have an important impact on the development of the information and energy industries. It must be affected. However, as with the metal-based material, a high volume of lithium insertion / extraction causes a severe volume effect in the silicon-based material. As a result, the cycle stability of the electrode becomes uneasy and the first irreversible capacity becomes high, so that the application as a cathode material of a lithium ion battery is limited. Therefore, many researchers are currently striving to modify and improve materials with high lithium storage capacity. For example, the composite material manufactured by Hitachi's Maxwell company using the CVD method, which covers silicon particles and amorphous carbon particles outside the silicon particles, improves the structure of the silicon material and its conductive performance. Since the volume effect in the lithium insertion / extraction process can be suppressed to some extent, the cycle performance of these materials can be improved. However, it is difficult to control the CVD process and there are many uncertain factors, making it difficult to realize mass production. In addition, the silicon / carbon binary composite material produced by CSWang and others using a ball mill with graphite and silicon powder has a high lithium insertion capacity at the first time. However, the stability of its charge / discharge performance is lacking, and in particular, the decay rate of the first several cycle capacities is fast (J. Electrochem. Soc., 8 (1998): 2751-2758). In addition, SBNG, etc., produced by using the corozol-gel process, has a reticulated graphite-silicon / Si (OCH 3 ) 4 composite material that has relatively stable mechanical performance and helps improve cycle performance. . On the other hand, the Si-O network prevents the diffusion of lithium and reduces the amount of lithium inserted, so that the high capacity performance of silicon cannot be fully exhibited (J. Power Sources, 94 (2001 ): 63-67).
電気化学の反応過程における、リチウム挿入・脱離時に生じた厳重な体積効果に応対するため、本発明は、体積補償の方法により、珪素を含む複合材料を製造し、これにより、珪素の高い比容量特性を保持しながら、電極整体の体積変化を合理的な範囲内にコントロールし、サイクル安定性を増強させる。これにより、リチウムイオン電池の陰極材料のエネルギ密度を上げ、現段階で商品化されたリチウムイオン電池に常用されている炭素陰極材料よりもっと高い比容積もたせて、各種類の携帯式電気設備の電池に対する高いエネルギ密度の要求を満足させる。 In order to respond to the severe volume effect that occurs during the insertion and desorption of lithium in the electrochemical reaction process, the present invention produces a composite material containing silicon by the volume compensation method. While maintaining the capacity characteristics, the volume change of the electrode assembly is controlled within a reasonable range to enhance cycle stability. As a result, the energy density of the cathode material of the lithium ion battery is increased, and a specific volume higher than that of the carbon cathode material commonly used in the lithium ion battery that has been commercialized at this stage is provided. Satisfy the demand for high energy density.
本発明の目的は、リチウムイオン電池の珪素・炭素複合陰極材料及びその製造方法を提供する。解決すべき技術的課題は、電池の比容積を高め、かつ、優れたサイクル性能と倍率放電性能を具備させることにある。 An object of the present invention is to provide a silicon / carbon composite cathode material for a lithium ion battery and a method for producing the same. The technical problem to be solved is to increase the specific volume of the battery and to provide excellent cycle performance and magnification discharge performance.
本発明は、以下の技術案を用いる。即ち、 The present invention uses the following technical solution. That is,
本発明は、リチウムイオン電池の珪素・炭素複合陰極材料であって、前記リチウムイオン電池の複合陰極材料は、珪素形粒子と炭素形粒子の複合粒子を基本体とし、前記基本体は球状または球状近似の形をし、基本体外側に炭素被覆層を有する。 The present invention relates to a silicon / carbon composite cathode material of a lithium ion battery, wherein the composite cathode material of the lithium ion battery is based on composite particles of silicon-type particles and carbon-type particles, and the basic body is spherical or spherical. It has an approximate shape and has a carbon coating layer outside the basic body.
前記炭素被覆層は、有機物の熱分解グラファイトの被覆層である。 The carbon coating layer is a coating layer of organic pyrolytic graphite.
前記炭素被覆層には、導電炭素を含む。 The carbon coating layer contains conductive carbon.
前記炭素被覆層の表面には、リチウム化合物を含む。 The surface of the carbon coating layer contains a lithium compound.
前記被覆層の厚さは0.1〜5μmであり、陰極材料において、有機物の熱分解グラファイトはその0.5〜20wt%、導電炭素はその0.5〜5wt%の陰極材料を占める。 The coating layer has a thickness of 0.1 to 5 μm. In the cathode material, organic pyrolytic graphite occupies 0.5 to 20 wt% of the cathode material, and conductive carbon occupies 0.5 to 5 wt% of the cathode material.
前記珪素・炭素複合陰極材料の平均粒径は5〜60μmであり、比表面積は1.0〜4.0m2/gであり、ジョルト密度は0.7〜2.0g/cm3である。 The silicon / carbon composite cathode material has an average particle size of 5 to 60 μm, a specific surface area of 1.0 to 4.0 m 2 / g, and a jolt density of 0.7 to 2.0 g / cm 3 .
前記珪素形粒子は珪素単体、珪素酸化化合物SiOx、珪素を含む固体・溶体、或いは珪素を含む金属類化合物の中のいずれでもよく、その量は複合粒子基本体の1〜50wt%を占めており、そのXは0<x≦2である。 The silicon particles may be any one of silicon alone, silicon oxide compound SiOx, solid / solution containing silicon, or metal compounds containing silicon, and the amount thereof occupies 1 to 50 wt% of the composite particle base body. , X is 0 <x ≦ 2.
前記複合粒子基本体における珪素粒子の占有比例は、好ましくは、5〜30wt%である。 The occupation proportion of silicon particles in the composite particle basic body is preferably 5 to 30 wt%.
前記複合粒子基本体における珪素粒子の占有比例は、さらに好ましくは、10〜20wt%である。 The proportion of silicon particles occupied in the composite particle basic body is more preferably 10 to 20 wt%.
前記珪素を含む固体・液体、或いは珪素を含む金属類化合物は、珪素と、(1)化学元素表におけるIIA族元素中のいずれか一つあるいは二つの元素、または(2)遷移金属元素中のいずれか一つあるいは三つの元素、または(3)IIIA族元素中のいずれか一つあるいは二つの元素、または(4)珪素以外のIVA族元素中のいずれか一つあるいは二つの元素、のいずれにより構成する。 The solid / liquid containing silicon or the metal compound containing silicon includes silicon and (1) any one or two elements of group IIA elements in the chemical element table, or (2) transition metal elements. Any one or three elements, or (3) any one or two elements in group IIIA elements, or (4) any one or two elements in group IVA elements other than silicon. It consists of.
前記炭素形粒子は、天然鱗片状黒鉛、微結晶黒鉛、人造黒鉛、中間相炭素の微小球体、またはコークスの中のいずれか一つあるいは二つ以上の混合物である。 The carbon-shaped particles may be any one of natural flaky graphite, microcrystalline graphite, artificial graphite, mesophase carbon microspheres, or a mixture of two or more cokes.
前記有機物の熱分解グラファイトは、水溶性ポリエチレン、スチレンブラジェンゴム、カルボキシメチルセルローズ、或いは、有機溶剤類のポリスチレン、ポリメタクリル酸メチルエステル、ポリフッ化エチレン、ポリフッ化ビニリデン、ポリアクリロニトリル、レジトール、エポキシ樹脂、葡萄糖、蔗糖、果糖、セルラーゼ、澱粉、あるいはアスファルトなどを前駆物として、高温炭素化を経て形成された熱分解グラファイトである。 The organic pyrolysis graphite is water-soluble polyethylene, styrene bragen rubber, carboxymethyl cellulose, or organic solvents such as polystyrene, polymethacrylic acid methyl ester, polyfluorinated ethylene, polyvinylidene fluoride, polyacrylonitrile, resistol, epoxy resin. It is pyrolytic graphite formed through high-temperature carbonization using sucrose, sucrose, fructose, cellulase, starch, or asphalt as a precursor.
前記導電炭素は、アセチレンブラック、炭素ナノメーターパイプ、ナノメーター炭素の微小球体、炭素繊維、または導電カーボンブラック(Super-P)である。 The conductive carbon is acetylene black, carbon nanometer pipe, nanometer carbon microsphere, carbon fiber, or conductive carbon black (Super-P).
前記リチウム化合物は、酸化リチウム、炭酸リチウム、フッ化リチウム、塩化リチウム、硝酸リチウム、または水素化リチウムである。 The lithium compound is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate, or lithium hydride.
本発明におけるリチウムイオン電池の珪素・炭素複合陰極材料の製造方法は、以下の工程を含む。即ち、
(1)珪素形粒子を0.1〜1μmまで破砕して非常に細かい炭素形粒子を製造し、また、粒度75μmより小さく、炭素含有量95%以上の炭素原料を分別、整形及び純化処理することにより、炭素含有量99.9%以上、粒径0.1〜5μmの炭素形粒子を得る工程、
(2)珪素形粒子と炭素形粒子を混合して、複合粒子基本体を製造する工程、
(3)複合粒子基本体と、1〜25wt%の複合粒子基本体を占める有機物の熱分解グラファイトの前駆物とを混合し、或いは1〜12時間湿式法で攪拌して、その後100〜400℃のもとで気相沈積を行い、或いは被覆して、粒子を製造する工程、
(4)被覆後の粒子を炭化処理し、密封雰囲気中において450〜1500℃まで加熱し、1〜10時間温度を維持した後、室温に下げて、炭素被覆層を形成する工程、及び、
(5)前記炭素被覆層を5〜40μmまで破砕することによって、リチウムイオン電池の珪素・炭素複合陰極材料を製造する工程。
The method for producing a silicon / carbon composite cathode material for a lithium ion battery according to the present invention includes the following steps. That is,
(1) By crushing silicon-shaped particles to 0.1 to 1 μm to produce very fine carbon-shaped particles, and by separating, shaping and purifying carbon raw materials with a particle size of less than 75 μm and a carbon content of 95% or more A step of obtaining carbon-shaped particles having a carbon content of 99.9% or more and a particle size of 0.1 to 5 μm,
(2) A step of producing a composite particle basic body by mixing silicon-type particles and carbon-type particles,
(3) The composite particle base and the organic pyrolytic graphite precursor occupying 1-25 wt% of the composite particle base are mixed or stirred by a wet method for 1 to 12 hours, and then 100 to 400 ° C. Vapor phase deposition or coating to produce particles,
(4) carbonizing the coated particles, heating to 450-1500 ° C. in a sealed atmosphere, maintaining the temperature for 1-10 hours, and then lowering to room temperature to form a carbon coating layer; and
(5) A step of producing a silicon / carbon composite cathode material for a lithium ion battery by crushing the carbon coating layer to 5 to 40 μm.
前記5〜40μmまで破砕された粉末と粉末の1〜30wt%を占めるアスファルトを混合被覆した後、炭化処理を行い、密封雰囲気中において450〜1500℃まで加熱し、1〜10時間温度を維持してから、室温に下げて、それによって得た粉末と粉末の0.5〜5wt%を占める導電炭素とを混合被覆し、混合機或いは表面被覆改質機において1〜6時間混合し、かつ、超音波で1〜30分間それを分散し、5〜60μmまで破砕する。 After coating and coating the powder crushed to 5-40 μm and asphalt occupying 1-30 wt% of the powder, it is carbonized, heated to 450-1500 ° C. in a sealed atmosphere, and maintained for 1-10 hours. Then, the temperature is lowered to room temperature, and the resulting powder and conductive carbon occupying 0.5 to 5 wt% of the powder are mixed and coated in a mixer or surface coating reformer for 1 to 6 hours, and ultrasonic Disperse it for 1-30 minutes and crush to 5-60 μm.
前記5〜60μmまで破砕された複合物を、0.2〜10wt%のリチウム化合物溶液を含む溶液(このときの固体と液体の重量比は0.1〜2である)の中に1〜48時間浸漬する。 The composite crushed to 5 to 60 μm is immersed in a solution containing 0.2 to 10 wt% lithium compound solution (the weight ratio of the solid to the liquid is 0.1 to 2 at this time) for 1 to 48 hours.
前記珪素形粒子は、珪素単体、珪素酸化化合物SiOx、珪素を含む固体・溶体、或いは珪素を含む金属類化合物であって、かつ、前記珪素形粒子は複合粒子基本体の1〜50wt%を占めており、前記Xは0<x≦2であり、前記珪素を含む固体・液体、或いは珪素を含む金属類化合物は、珪素と、(1)化学元素表におけるIIA族元素中のいずれか一つあるいは二つの元素、または(2)遷移金属元素中のいずれか一つあるいは三つの元素、または(3)IIIA族元素中のいずれか一つあるいは二つの元素、または(4)珪素以外のIVA族元素中のいずれか一つあるいは二つの元素、のいずれから構成する。 The silicon-type particles are a simple substance of silicon, a silicon oxide compound SiOx, a solid / solution containing silicon, or a metal compound containing silicon, and the silicon-type particles occupy 1 to 50 wt% of the composite particle base body. X is 0 <x ≦ 2, and the solid / liquid containing silicon or the metal compound containing silicon is silicon and (1) any one of group IIA elements in the chemical element table Or two elements, or (2) any one or three elements in transition metal elements, or (3) any one or two elements in group IIIA elements, or (4) group IVA other than silicon It is composed of any one or two of the elements.
前記炭素形粒子は、天然鱗片状黒鉛、微結晶黒鉛、人工黒鉛、中間相炭素の微小球体、またはコークスの一つあるいは二つ以上の混合であって、かつ、珪素形粒子は前記複合粒子基本体の50〜99wt%を占める。 The carbon particles are natural scaly graphite, microcrystalline graphite, artificial graphite, mesophase carbon microspheres, or a mixture of two or more cokes, and the silicon particles are the composite particle base Occupies 50-99wt% of the body.
前記被覆層は、複合材料中の1〜25wt%を占める。 The coating layer occupies 1 to 25 wt% of the composite material.
前記有機物熱分解グラファイトの前駆物は、水溶性ポリエチレン、スチレンブラジェンゴム、カルボキシメチルセルローズ、あるいは、有機溶剤類のポリスチレン、ポリメタクリル酸メチルエステル、ポリフッ化エチレン、ポリフッ化ビニリデン、ポリアクリロニトリル、レジトール、エポキシ樹脂、葡萄糖、蔗糖、果糖、セルラーゼ、或いは澱粉である。 The precursor of the organic pyrolytic graphite is water-soluble polyethylene, styrene bragen rubber, carboxymethyl cellulose, or organic solvents such as polystyrene, polymethacrylic acid methyl ester, polyfluorinated ethylene, polyvinylidene fluoride, polyacrylonitrile, resistol, Epoxy resin, sucrose, sucrose, fructose, cellulase, or starch.
前記導電炭素は、アセチレンブラック、炭素ナノメーターパイプ、ナノメーター炭素の微小球体、炭素繊維、または導電カーボンブラック(Super-P)である。 The conductive carbon is acetylene black, carbon nanometer pipe, nanometer carbon microsphere, carbon fiber, or conductive carbon black (Super-P).
前記リチウム化合物は、酸化リチウム、炭酸リチウム、フッ化リチウム、塩化リチウム、硝酸リチウム、或いは水素化リチウムである。 The lithium compound is lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate, or lithium hydride.
前記珪素形粒子の球状化過程は密封雰囲気の中に行なわれており、前記密封雰囲気は、アルゴン、水素或いは窒素のいずれか一つまたは二つ以上の混合物である。 The spheroidizing process of the silicon-type particles is performed in a sealed atmosphere, and the sealed atmosphere is any one or a mixture of two or more of argon, hydrogen, and nitrogen.
前記珪素形粒子と炭素形粒子とを混合して粒子を製造するというのは、混合式粒子製造機に混合して1〜6時間粒子を製造することである。 The production of particles by mixing the silicon-type particles and the carbon-type particles is to produce the particles for 1 to 6 hours by mixing them in a mixed particle production machine.
従来の技術と比べて、本発明は、珪素形粒子と炭素形粒子との複合材料を基本体とし、球形または球形近似の形を呈し、被覆層を有するリチウム電池の珪素・炭素複合陰極材料である。本発明は、とても高い可逆的リチウム挿入・脱離の電気化学容量と優れたサイクル安定性を有する。また、本発明の陰極材料の可逆的比容量は450mAh/gより大きく、第一回のサイクルクーロン効率は85%より大きく、200回サイクルの容量維持率は80%より大きい。かつ、本発明は、リチウム挿入・脱離時における珪素を含む活性物質の体積効果を著しく減少させ、活性物質におけるリチウムの拡散状況を改善して、珪素単体と比べ、第一回の効率とサイクル安定性を上げて、陽極材料の消耗を減少させる。また、本発明は、リチウム挿入・脱離電位が中間層炭素の微小球体などといった、リチウムイオン電池に常用される陰極材料より高くて、陰極表面におけるリチウムの析出を防いで、大電流の優れた放電能力を有する。さらに、本発明は、製造工程と操作が簡単という長所があり、各種類の携帯式器具、電動器具などに使われているリチウムイオン電池の陰極材料に適する。 Compared with the prior art, the present invention is a silicon / carbon composite cathode material for a lithium battery, which is based on a composite material of silicon-type particles and carbon-type particles, has a spherical shape or a spherical approximate shape, and has a coating layer. is there. The present invention has a very high reversible lithium insertion / extraction electrochemical capacity and excellent cycle stability. Further, the reversible specific capacity of the cathode material of the present invention is greater than 450 mAh / g, the first cycle coulomb efficiency is greater than 85%, and the capacity retention rate of 200 cycles is greater than 80%. In addition, the present invention significantly reduces the volume effect of the active material containing silicon at the time of lithium insertion / extraction, improves the diffusion state of lithium in the active material, and improves the efficiency and cycle of the first time compared to silicon alone. Increase stability and reduce anode material wear. In addition, the present invention has a lithium insertion / desorption potential higher than that of a cathode material commonly used for lithium ion batteries, such as a microsphere of intermediate layer carbon, and prevents lithium deposition on the cathode surface and has an excellent large current. Has discharge capability. Furthermore, the present invention has an advantage that the manufacturing process and operation are simple, and is suitable for a cathode material of a lithium ion battery used in various types of portable devices, electric devices and the like.
以下、図面と実施例とにより、本発明のさらに詳細な説明を行う。即ち、 Hereinafter, the present invention will be described in more detail with reference to the drawings and examples. That is,
本発明のリチウムイオン電池の珪素・炭素複合陰極材料は、珪素形粒子と炭素形粒子を基本体とし、外側に複合炭素の被覆層を被覆する。基本体における珪素形粒子は、珪素単体、珪素酸化化合物SiOx(そのXは0<x≦2である)、珪素を含む固体・溶体、或いは珪素を含む金属類化合物である。前記珪素を含む固体・液体、或いは珪素を含む金属類化合物は、珪素と、(1)化学元素表におけるIIA族元素中のいずれか一つあるいは二つの元素、または(2)遷移金属元素中のいずれか一つあるいは三つの元素、または(3)IIIA族元素中のいずれか一つあるいは二つの元素、または(4)珪素以外のIVA族元素中のいずれか一つあるいは二つの元素、のいずれから構成する。珪素形粒子は前記複合粒子基本体の1〜50wt%を占める。前記基本体における炭素形粒子は、天然鱗片状黒鉛、微結晶黒鉛、人造黒鉛、中間相炭素の微小球体、またはコークスの中のいずれか一つあるいは二つ以上の混合物である。その被覆層の厚さは0.1〜5μmであり、有機物の熱分解グラファイトは陰極材料の0.5〜20wt%を占め、導電炭素は陰極材料の0.5〜5wt%を占める。被覆層中の有機物の熱分解グラファイトは、水溶性ポリエチレン、スチレンブラジェンゴム、カルボキシメチルセルローズCMC、及びポリスチレン、ポリメタクリル酸メチルエステル、ポリフッ化エチレン、ポリフッ化ビニリデン、ポリアクリロニトリルなる有機溶剤、レジトール、エポキシ樹脂、葡萄糖、蔗糖、果糖、セルラーゼ、澱粉或いはアスファルトを前駆物として、高温炭素化の過程を経て形成されたものである。被覆層中の導電炭素は、アセチレンブラック、炭素ナノメーターパイプ、ナノメーター炭素の微小球体、炭素繊維、または導電カーボンブラック(Super-P)である。陰極材料の複合粒子の表面には、酸化リチウム、炭酸リチウム、フッ化リチウム、塩化リチウム、硝酸リチウム、或いは水素化リチウムといった、リチウムを含む化合物である。 The silicon / carbon composite cathode material of the lithium ion battery of the present invention comprises silicon-type particles and carbon-type particles as a basic body, and a composite carbon coating layer is coated on the outside. The silicon particles in the basic body are silicon simple substance, silicon oxide compound SiOx (X is 0 <x ≦ 2), solid / solution containing silicon, or metal compound containing silicon. The solid / liquid containing silicon or the metal compound containing silicon includes silicon and (1) any one or two elements of group IIA elements in the chemical element table, or (2) transition metal elements. Any one or three elements, or (3) any one or two elements in group IIIA elements, or (4) any one or two elements in group IVA elements other than silicon. Consists of. Silicon-type particles occupy 1 to 50 wt% of the composite particle basic body. The carbon particles in the basic body are any one or a mixture of natural flaky graphite, microcrystalline graphite, artificial graphite, mesophase carbon microspheres, and coke. The thickness of the coating layer is 0.1 to 5 μm, pyrolytic graphite of organic matter accounts for 0.5 to 20 wt% of the cathode material, and conductive carbon accounts for 0.5 to 5 wt% of the cathode material. Pyrolytic graphite of organic matter in the coating layer is water soluble polyethylene, styrene bragen rubber, carboxymethyl cellulose CMC, and polystyrene, polymethacrylic acid methyl ester, polyfluorinated ethylene, polyvinylidene fluoride, polyacrylonitrile organic solvent, resistol, An epoxy resin, sucrose, sucrose, fructose, cellulase, starch or asphalt is used as a precursor and formed through a high-temperature carbonization process. The conductive carbon in the coating layer is acetylene black, carbon nanometer pipe, nanometer carbon microsphere, carbon fiber, or conductive carbon black (Super-P). The surface of the composite particle of the cathode material is a compound containing lithium such as lithium oxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate, or lithium hydride.
本発明のリチウムイオン電池の珪素・炭素複合陰極材料は、以下の技術的特徴を有する。即ち、その平均粒径は5〜60μmであり、比表面積は1.0〜4.0m2/gであり、ジョルト密度は0.7〜2.0g/cm3である。前記平均粒径は、Malvernレーザー粒径測定器を用いて測定したもので、比表面積は窒素置換のBET法を用いて測定したもので、ジュルト密度はQuantachrome AutoTapジュルト密度測定器により測定したものである。 The silicon / carbon composite cathode material of the lithium ion battery of the present invention has the following technical features. That is, the average particle diameter is 5 to 60 μm, the specific surface area is 1.0 to 4.0 m 2 / g, and the jolt density is 0.7 to 2.0 g / cm 3 . The average particle size was measured using a Malvern laser particle sizer, the specific surface area was measured using a nitrogen-substituted BET method, and the jurt density was measured using a Quantachrome AutoTap jurt density meter. is there.
前記材料と比例をもって、本発明のリチウムイオン電池の珪素・炭素複合陰極材料を製造する。それは、以下の工程を含む。即ち、
1、珪素形粒子を空気または酸素でない気体、たとえば、アルゴン、水素または窒素のいずれか一つまたはそれの混合気体の中に、0.1〜1μmまでに破砕し、非常に細かい珪素形粒子を製造する。
The silicon / carbon composite cathode material of the lithium ion battery of the present invention is produced in proportion to the material. It includes the following steps. That is,
1. The silicon-type particles are crushed to 0.1 to 1 μm in a gas that is not air or oxygen, for example, any one of argon, hydrogen, and nitrogen, or a mixture thereof to produce very fine silicon-type particles. .
2、粒度75μmより少なく、炭素含有量95%以上の炭素原料を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径0.1〜5μmの炭素形粒子を製造する。 2. A carbon raw material having a particle size of less than 75 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to produce carbon-shaped particles having a carbon content of 99.9% or more and a particle size of 0.1 to 5 μm.
3、前記珪素形粒子と炭素形粒子を混合式粒子製造機の中に1〜6時間混合し、複合粒子の基本体を製造する。 3. The silicon-type particles and carbon-type particles are mixed in a mixed particle manufacturing machine for 1 to 6 hours to manufacture a basic body of composite particles.
4、前記複合粒子基本体と、複合粒子基本体の1〜25wt%を占める有機物の熱分解グラファイトの前駆物とを球状化し、または湿式法で1〜12時間混合、攪拌してから、100〜400℃のもとで気相沈積または被覆して、粒子を製造する。 4. The composite particle basic body and the organic pyrolytic graphite precursor occupying 1 to 25 wt% of the composite particle basic body are spheroidized or mixed and stirred by a wet method for 1 to 12 hours. Particles are produced by vapor deposition or coating at 400 ° C.
5、前記被覆粒子を炭化処理し、密封雰囲気中において450〜1500℃に加熱し、1〜10時間温度を維持した後、室温に下げて、炭素被覆層を形成して、5〜40μmまでに破砕する。 5. Carbonize the coated particles, heat to 450-1500 ° C. in a sealed atmosphere, maintain the temperature for 1-10 hours, lower to room temperature, and form a carbon coating layer to 5-40 μm Crush.
6、前記5〜40μmまでに破砕した粉末と、前記粉末の1〜30wt%を占めるアスファルトとを混合、被覆する。 6. The powder crushed to 5-40 μm and asphalt occupying 1-30 wt% of the powder are mixed and coated.
7、前記被覆したアスファルトを炭化処理し、密封雰囲気中において450〜1500℃に加熱し、1〜10時間温度を維持した後、室温に下げて、5〜60μmに破砕する。 7. Carbonize the coated asphalt, heat to 450-1500 ° C. in a sealed atmosphere, maintain the temperature for 1-10 hours, then lower to room temperature and crush to 5-60 μm.
8、前記複合物と、粉末の0.5〜5wt%を占める導電炭素とを混合被覆し、混合式粒子製造機または表面被覆改質機械の中に1〜6時間混合して、周波数40kHz〜28kHz、仕事率50W〜3600Wの超音波のもとで1〜30分間破砕する。 8. The composite and conductive carbon occupying 0.5 to 5 wt% of the powder are mixed and coated in a mixed particle manufacturing machine or surface coating reforming machine for 1 to 6 hours, and the frequency is 40 kHz to 28 kHz. Crush for 1-30 minutes under ultrasonic power of 50W-3600W power.
9、次の工程はリチウム化合物を浸漬するものである。つまり、リチウム化合物の1〜30wt%を含む溶液(このときの固体と液体の重量比は0.1〜2である)に複合粉末を投入し、1〜48時間浸漬して、粒度を5〜60μmに調整して、リチウムイオン電池の珪素・炭素複合陰極材料を得る。 9. The next step is to immerse the lithium compound. In other words, the composite powder is put into a solution containing 1 to 30 wt% of the lithium compound (the weight ratio of the solid to the liquid is 0.1 to 2 at this time) and immersed for 1 to 48 hours to make the particle size 5 to 60 μm. The silicon-carbon composite cathode material for the lithium ion battery is obtained by adjusting.
珪素は、リチウムと結合して、Li22Si5などの金属間化合物を形成して、リチウムを可逆的に挿入・脱離することができる。珪素を使用しリチウムイオン二次電池の陰極材料にすることは、珪素の充放電の理論容量が4200mAh/g、9783mAh/cm3までに達し(このときの体積と重量の比率は2.33である)、現在使用されている黒鉛類材料をはるかに超えている。因みに、現在、黒鉛類材料の充放電の理論容量は372mAh/g、844mAh/gであって、それの体積と重量の比率は2.27である。しかし、珪素を用いて製造した陰極材料がリチウムの挿入・脱離時に、ときに300%に達するというと著しく体積変化することは、珪素陰極を簡単にひび割れ、粉末化させ、充放電サイクル過程中にその容量を急速に減衰させる。そのため、純粋な純珪素単体をリチウムイオン二次電池の陰極材料として直接的に使用することができない。 Silicon can combine with lithium to form an intermetallic compound such as Li 22 Si 5, and can reversibly insert and desorb lithium. Using silicon as the cathode material for lithium ion secondary batteries, the theoretical capacity of silicon charge and discharge reaches 4200mAh / g, up to 9793mAh / cm 3 (the ratio of volume to weight at this time is 2.33) It is far beyond the currently used graphite materials. Incidentally, at present, the theoretical capacity of charge and discharge of graphite materials is 372 mAh / g, 844 mAh / g, and the ratio of volume to weight is 2.27. However, when the cathode material manufactured using silicon reaches a volume of 300% during lithium insertion / extraction, the volume changes significantly, which can easily crack and powder the silicon cathode during the charge / discharge cycle process. The capacity is rapidly attenuated. Therefore, pure pure silicon alone cannot be directly used as a cathode material for a lithium ion secondary battery.
本発明の製品及びその製造方法の研究において、以下のことを究明した。即ち、
珪素を含む粒子が炭素材料基本体に分散するとき、或いは珪素形粒子の表面が珪素を含む固体・液体または金属間化合物に被覆されるとき、リチウムの挿入・脱離に伴う体積変化は、緩衝または制約される。これによって、電極の粉末化を防ぎ、サイクル寿命をあげることになる。また、粒径のより小さい珪素形粒子を選択することは、こうした効果をよりよく発揮させることができる。そのため、本発明は、粒子1〜40μmの珪素形粒子を密封雰囲気に0.1〜1μmまでに球状化し、非常に細かい珪素形粒子を製造して、これを複合材料の陰極活性物質として使う。それに対して、珪素形粒子の平均粒径が1μmより大きい場合、基本体の体積吸収効果が弱まるので、複合材料のサイクル性能の上げを影響することになる。逆に、珪素形粒子の平均粒径が0.1μmより小さい場合、製造工程の困難さが上げ、かつ、活性粒子の表面に酸化が生じやすく、粒子間のお互いに集結の機会を増加させるので、陰極材料の比容量にも影響することになる。因みに、珪素形粒子の粒径は、電子走査顕微鏡SEMを用いて測定することもできるし、その他の方法を用いて測定することもできる。例えば、レーザー粒度測定器により、体積粒度グラフにおける中位の半径を平均粒径とすることができる。実施例においては、イギリスMalvern Mastersizer 2000のレーザー粒度測定器を用いて、粒子の平均粒径を測定する。
In the research of the product of the present invention and the manufacturing method thereof, the following has been investigated. That is,
When silicon-containing particles are dispersed in the carbon material base, or when the surface of silicon-type particles is coated with a solid, liquid, or intermetallic compound containing silicon, volume changes associated with lithium insertion / extraction are buffered. Or be constrained. This prevents electrode powdering and increases cycle life. In addition, selecting such silicon-type particles having a smaller particle diameter can better exhibit such effects. Therefore, the present invention spheroidizes silicon particles having a particle size of 1 to 40 μm to 0.1 to 1 μm in a sealed atmosphere to produce very fine silicon particles, which are used as the cathode active material of the composite material. On the other hand, when the average particle diameter of the silicon-type particles is larger than 1 μm, the volume absorption effect of the basic body is weakened, which affects the cycle performance of the composite material. Conversely, if the average particle size of the silicon-type particles is smaller than 0.1 μm, the difficulty of the manufacturing process is increased, and the surface of the active particles is likely to be oxidized, increasing the chance of aggregation between the particles, This also affects the specific capacity of the cathode material. Incidentally, the particle size of the silicon-type particles can be measured using an electron scanning microscope SEM, or can be measured using other methods. For example, with a laser particle size measuring device, the median radius in the volume particle size graph can be made the average particle size. In the examples, the average particle size of the particles is measured using a laser particle sizer from
また、本発明の珪素・炭素複合陰極材料における珪素形粒子は、複合粒子基本体の1〜50 wt%を占める。それに対して、珪素形粒子の比例が50wt%を超える場合、基本体は、珪素の体積効果を有効に緩衝または吸収することができない。逆に、珪素形粒子の比例が1wt%より少ない場合、陰極材料の容量は、有効にあげることができない。そのため、珪素形粒子の比例は5〜30wt%であるときに適当であるが、それは10〜20wtであるときに最適である。 Further, the silicon-type particles in the silicon / carbon composite cathode material of the present invention occupy 1 to 50 wt% of the composite particle base body. On the other hand, when the proportion of the silicon-type particles exceeds 50 wt%, the basic body cannot effectively buffer or absorb the volume effect of silicon. On the contrary, when the proportion of the silicon-type particles is less than 1 wt%, the capacity of the cathode material cannot be increased effectively. Therefore, the proportion of silicon particles is appropriate when it is 5-30 wt%, but it is optimal when it is 10-20 wt%.
前記珪素形粒子は、珪素単体、珪素酸化化合物SiOx(Xは0<x≦2である)、珪素を含む固体・溶体、或いは珪素を含む金属類化合物である。前記珪素を含む固体・液体、或いは珪素を含む金属類化合物は、珪素と、(1)化学元素表におけるIIA族元素中のいずれか一つあるいは二つの元素、または(2)遷移金属元素中のいずれか一つあるいは三つの元素、または(3)IIIA族元素中のいずれか一つあるいは二つの元素、または(4)珪素以外のIVA族元素中のいずれか一つあるいは二つの元素、のいずれかから構成する。これらの元素の一部は、リチウムの可逆的活性貯蔵物質として使い、陰極材料の比容量を増大させることができる。その他の元素は、非活性元素としてリチウムの貯蔵ができなくでも、リチウムの挿入・脱離時に生じた体積効果を緩和、吸収、または複合材料の導電性を改善、サイクル安定性を改良するものとして使うことができる。リチウムの挿入・脱離容量、珪素体積効果の緩和、複合材料導電効果の改善及びその資源の多少を考慮して、これらの元素を優先的に、IIA族元素のMg、CaとBaを、遷移金属元素中のTi、Cr、Mn、Fe、Co、Ni、Cu、Mo、Ag、CeとNdを、IIIA族元素のAl、GaとInを、及びIVA族元素のGe、SnとSbを選ぶべきである。また、これらの元素の中に、Mg、Ca、Fe、Co、NiとCuをさらに優先的に選ぶべきである。 The silicon particles are silicon simple substance, silicon oxide compound SiOx (X is 0 <x ≦ 2), solid / solution containing silicon, or metal compound containing silicon. The solid / liquid containing silicon or the metal compound containing silicon includes silicon and (1) any one or two elements of group IIA elements in the chemical element table, or (2) transition metal elements. Any one or three elements, or (3) any one or two elements in group IIIA elements, or (4) any one or two elements in group IVA elements other than silicon. Consists of Some of these elements can be used as a reversible active storage material of lithium to increase the specific capacity of the cathode material. Other elements are not intended to be able to store lithium as an inactive element, but alleviate the volume effect that occurs during lithium insertion / extraction, improve absorption, improve composite conductivity, and improve cycle stability. Can be used. Considering the insertion / extraction capacity of lithium, the volumetric effect of silicon, the improvement of the conductive effect of the composite material, and some of its resources, these elements are preferentially transitioned to Mg, Ca and Ba of group IIA elements. Select Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ag, Ce and Nd in the metal elements, Group IIIA elements Al, Ga and In, and Group IVA elements Ge, Sn and Sb. Should. Among these elements, Mg, Ca, Fe, Co, Ni and Cu should be selected with higher priority.
本発明のリチウムイオン電池の珪素・炭素複合陰極材料を製造し、陰極材料の電気化学性能を改善するために、本発明は、黒鉛と珪素形粒子を混合製造、複合被覆及び表面改質処理を行なった。 In order to manufacture the silicon-carbon composite cathode material of the lithium ion battery of the present invention and improve the electrochemical performance of the cathode material, the present invention performs mixed production of graphite and silicon-type particles, composite coating and surface modification treatment. I did it.
図面1と図面2に示しているのは、走査電子顕微鏡により観測した複合材料の微視的特性である。本発明のリチウムイオン電池の珪素・炭素複合陰極材料は、珪素形粒子と炭素形粒子を複合材料の基本体とし、被覆層に複合の炭素被覆層を有し、球形または球形近似の微視な特徴を有する。また、被覆層は、一層の有機物の熱分解グラファイトと導電炭素からなる。これにより、黒鉛材料と電解液の相溶性を改善することになる。また、被覆層は、珪素形粒子の体積効果を制約し、導電性能を上げ、かつ、リチウムの挿入・脱離を可逆的にさせて、陰極材料の容量及び大電流下の放電能力を増大させる。さらに、被覆層におけるやや大きい結晶体の層間距離は、繰り返しの充放電により生じた膨張収縮量を減少させて、陰極材料構造の破壊と剥離を防ぎ、サイクル性能を改善する。 FIG. 1 and FIG. 2 show the microscopic characteristics of the composite material observed with a scanning electron microscope. The silicon-carbon composite cathode material of the lithium ion battery of the present invention has silicon-type particles and carbon-type particles as the basic body of the composite material, and has a composite carbon coating layer in the coating layer. Has characteristics. The coating layer is composed of one layer of organic pyrolytic graphite and conductive carbon. This improves the compatibility between the graphite material and the electrolyte. In addition, the coating layer restricts the volume effect of the silicon-type particles, improves the conductive performance, and reversibly inserts and detaches lithium, thereby increasing the capacity of the cathode material and the discharge capacity under a large current. . Furthermore, the slightly larger crystal interlayer distance in the coating layer reduces the amount of expansion and contraction caused by repeated charging and discharging, prevents the cathode material structure from being broken and peeled off, and improves the cycle performance.
図面3は、本発明の実施例1に基づき、製造した珪素・炭素複合陰極材料の第一回の充放電グラフ図である。これを黒鉛類材料と比べ、充放電グラフ図は、珪素の高電位を増大させた、約0.5V vs. Li/Li+のリチウム貯蔵基盤を示し、複合材料におけるリチウムの挿入・脱離容量を大幅に上げることができる。 FIG. 3 is a first charge / discharge graph of the silicon / carbon composite cathode material produced based on Example 1 of the present invention. Compared with graphite materials, the charge / discharge graph shows a lithium storage base of approximately 0.5 V vs. Li / Li + , which increased the high potential of silicon, and the lithium insertion / extraction capacity in the composite material. Can be significantly increased.
図面4は、本発明の実施例1に基づき、製造した珪素・炭素複合陰極材料のX-射線回折図XDRである。国際X-射線粉末回折委員会の標準粉末回折資料カードPDFに基づき、本発明の複合材料の回折図の炭素PDFカード番号41-1487、珪素PDFカード番号27-1402の回折数値を照らしてみると、本発明の珪素・炭素複合材料が炭素と珪素により構成されていることがわかる。 FIG. 4 is an X-ray diffraction pattern XDR of the silicon / carbon composite cathode material produced according to Example 1 of the present invention. Based on the standard powder diffraction data card PDF of the International X-ray Powder Diffraction Committee, the diffraction values of carbon PDF card number 41-1487 and silicon PDF card number 27-1402 of the diffraction diagram of the composite material of the present invention It can be seen that the silicon-carbon composite material of the present invention is composed of carbon and silicon.
前記基本体における炭素形粒子は、天然鱗片状黒鉛、微結晶黒鉛、人造黒鉛又は中間相炭素の微小球体とコークスの中のいずれか一つあるいは二つ以上の混合であり、複合粒子基本体の99〜50 wt%を占める。炭素形粒子は、リチウムの挿入能力をある程度に高めるほか、おもに、リチウムの挿入・脱離時に生じた珪素形粒子の体積効果を吸収、緩和する。前記材料は、全部軟性の炭素材料であり、良好な弾性をもち、かつ、より高いリチウムを挿入する能力をもっている。これに対して、炭素形粒子の比例が50wt%より少ない場合、珪素形粒子が有効に分散することができないため、炭素形粒子は、リチウムの挿入・脱離時に生じた活性珪素形粒子の体積効果を緩和する能力が悪いため、材料のサイクル利用に悪影響を与える。逆に、炭素形粒子の比例が99%より大きい場合には、活性珪素の比例が減少するので、材料の比容量の引き上げに影響を及ぼすことになる。 The carbon particles in the basic body are natural scaly graphite, microcrystalline graphite, artificial graphite, or a mixture of two or more of microspheres of intermediate phase carbon and coke, It occupies 99-50 wt%. In addition to increasing the lithium insertion capability to some extent, the carbon-type particles mainly absorb and mitigate the volume effect of the silicon-type particles generated during lithium insertion / extraction. The materials are all soft carbon materials, have good elasticity and have the ability to insert higher lithium. On the other hand, when the proportion of the carbon-type particles is less than 50 wt%, the silicon-type particles cannot effectively disperse, so the carbon-type particles have a volume of active silicon-type particles generated during lithium insertion / extraction. Since the ability to mitigate the effect is poor, the cycle utilization of the material is adversely affected. On the contrary, when the proportion of the carbon-type particles is larger than 99%, the proportion of the active silicon is decreased, which affects the increase in the specific capacity of the material.
前記複合炭素被覆層の厚さは0.1〜5μmであり、当該数値はMalvernレーザー粒度測定器を用いて、被覆する前後の粒子の平均粒径を基準に算出したものである。複合炭素被覆層は、有機物の熱分解グラファイト、導電炭素を有し、陰極材料の全体の1〜25wt%を占め、また、前記有機物の熱分解グラファイトは被覆層の0.5〜20wt%を占め、前記導電炭素は被覆層の0.5〜5wt%を占める。これに対して、複合炭素被覆層の厚さが0.1μmより薄く、または陰極材料における被覆層の比例が1wt%より少ない場合は、完全な被覆層を形成することができないため、陰極材料のサイクル安定性に影響を及ぼすことになる。逆に、被覆層が厚すぎる(例えば、5μmより厚い)、或いは陰極材料における被覆層の比率が25wt%より大きい場合は、陰極材料の比容量と第一回の効率に影響を及ぼすので、陰極材料の電気化学性能の引き上げに同様に不利を与える。 The composite carbon coating layer has a thickness of 0.1 to 5 μm, and the numerical value is calculated on the basis of the average particle size of the particles before and after coating using a Malvern laser particle size measuring device. The composite carbon coating layer has organic pyrolytic graphite and conductive carbon, and occupies 1 to 25 wt% of the entire cathode material, and the organic pyrolytic graphite accounts for 0.5 to 20 wt% of the coating layer, Conductive carbon accounts for 0.5 to 5 wt% of the coating layer. On the other hand, when the composite carbon coating layer is thinner than 0.1 μm or the proportion of the coating layer in the cathode material is less than 1 wt%, a complete coating layer cannot be formed. Will affect stability. Conversely, if the coating layer is too thick (for example, thicker than 5 μm) or if the ratio of the coating layer in the cathode material is greater than 25 wt%, it will affect the specific capacity of the cathode material and the efficiency at the first time. There is a similar disadvantage in raising the electrochemical performance of the material.
前記被覆層の有機物熱分解グラファイトは、水溶性ポリエチレン、スチレンブラジェンゴム、カルボキシメチルセルローズ、或いは有機溶剤類のポリスチレン、ポリメタクリル酸メチルエステル、ポリフッ化エチレン、ポリフッ化ビニリデン、ポリアクリロニトリル、レジトール、エポキシ樹脂、葡萄糖、蔗糖、果糖、セルラーゼ、澱粉、またはアスファルトなどを前駆物として、高温炭素化工程を経て形成された熱分解グラファイトである。こうした有機物は、複合粒子の基本体と混合するとき、後記の熱分解グラファイトの前駆物として、或いは、溶液体系の粘着剤、分散剤または懸垂剤として、複合粒子基本体の表面に均一的に被覆して、かつ、後記の熱分解グラファイトの過程に熱分解反応と熱重合反応が発生する。高温熱分解過程において、有機物化合物中のH、O、Nなどを含む化合物が分解され、炭素原子が絶えずに環化、芳香族化する。それによって、H、O、Nなどの原子は絶えずに減少して、炭素が絶えずに濃縮する。前記有機物は、液相炭化の過程を経て黒鉛化しやすい炭素、即ち軟性炭素を形成し、または単に固相炭化の過程を経て黒鉛化しにくい炭素、即ち硬性炭素を形成する。この種類の熱分解グラファイトはすべて非黒鉛化炭素であり、その材料にある数多くの小分子化合物が熱分解により逸脱したときに形成した微小な穴は、充放電時に生じた活性物質の体積効果をよりよく吸収または緩和することができ、かつ、熱分解グラファイトのやや大きい層間距離はリチウムイオンの挿入・脱離に役立つ。また、熱分解グラファイトの乱層構造も、溶媒化リチウムイオンの共挿入により生じた黒鉛層の剥離を防ぎ、サイクル安定性を引き上げることができる。また、被覆層にある導電炭素は、アセチレンブラック、炭素ナノメーターパイプ、ナノメーター炭素の微小球体、炭素繊維、または導電カーボンブラック(Super-P)である。 The organic pyrolytic graphite of the coating layer may be water-soluble polyethylene, styrene bragen rubber, carboxymethyl cellulose, or organic solvents such as polystyrene, polymethacrylic acid methyl ester, polyfluorinated ethylene, polyvinylidene fluoride, polyacrylonitrile, resistol, epoxy. It is a pyrolytic graphite formed through a high-temperature carbonization process using a resin, sucrose, sucrose, fructose, cellulase, starch, or asphalt as a precursor. When these organic substances are mixed with the composite particle base, they are uniformly coated on the surface of the composite particle base as a precursor of pyrolytic graphite, which will be described later, or as a solution-based adhesive, dispersant, or suspension. In addition, a thermal decomposition reaction and a thermal polymerization reaction occur in the process of pyrolytic graphite described later. In the high-temperature pyrolysis process, compounds containing H, O, N, etc. in organic compounds are decomposed, and carbon atoms are continuously cyclized and aromaticized. As a result, atoms such as H, O, and N are constantly reduced, and carbon is constantly enriched. The organic matter forms carbon that is easily graphitized through liquid-phase carbonization, that is, soft carbon, or simply forms carbon that is difficult to graphitize through solid-phase carbonization, that is, hard carbon. This type of pyrolytic graphite is all non-graphitized carbon, and the small holes formed when a large number of small molecule compounds in the material deviate due to pyrolysis are responsible for the volume effect of the active substance generated during charging and discharging. It can be absorbed or relaxed better, and the slightly larger interlayer distance of pyrolytic graphite is useful for lithium ion insertion / extraction. Moreover, the turbulent layer structure of pyrolytic graphite can prevent peeling of the graphite layer caused by co-insertion of solvated lithium ions, and can increase cycle stability. The conductive carbon in the coating layer is acetylene black, carbon nanometer pipe, nanometer carbon microsphere, carbon fiber, or conductive carbon black (Super-P).
本発明において、複合粒子基本体と有機物の熱分解グラファイトの前駆物及び導電炭素の混合被覆方法を特別に制限するわけではなく、公知の混合式粒子製造設備のいずれを用いてもよい。混合被覆は混合球状化方法、または湿式攪拌方法を使って1〜12時間処理した後、気象沈積と被覆粒子の製造を行う。気象沈積と被覆の処理温度は100〜400℃である。処理温度が100℃以下である場合に、粉末の乾燥速度が遅く、被覆効果が悪いので、粒子と粒子がお互いに粘着し、生産効率と製品質に影響を与えることになる。逆に、処理温度が400℃以上である場合には、被覆層に炭化または酸化効果が生じるので、同様に被覆効果に影響を与える。そして、前記混合材料を炭素処理し、温度450〜1500℃のもとで1〜10時間温度を維持してから、室温に下げる。また、被覆層を緻密させるため、二次被覆処理をする。二次被覆に使用する材料はアスファルトであり、被覆量は1〜30wt%である。前記炭素化処理は酸素でない気体の中に行うである。前記酸素でない気体は、例えば、窒素、アルゴン、ネオンまたは前記気体の混合物、或いは真空、還元雰囲気である。前記炭素化処理は、450〜1500℃のもとで行なって、1〜10時間温度を維持してから、室温に下げる。 In the present invention, the mixed coating method of the composite particle basic body, the organic pyrolytic graphite precursor and the conductive carbon is not particularly limited, and any known mixed particle manufacturing equipment may be used. The mixed coating is processed for 1 to 12 hours using a mixed spheroidizing method or a wet stirring method, and then weather deposition and coating particles are produced. The processing temperature of weather deposition and coating is 100 ~ 400 ℃. When the treatment temperature is 100 ° C. or lower, the drying speed of the powder is slow and the coating effect is poor, so that the particles adhere to each other and affect production efficiency and product quality. On the other hand, when the treatment temperature is 400 ° C. or higher, a carbonization or oxidation effect occurs in the coating layer, which similarly affects the coating effect. Then, the mixed material is treated with carbon, maintained at a temperature of 450 to 1500 ° C. for 1 to 10 hours, and then lowered to room temperature. In order to make the coating layer dense, a secondary coating treatment is performed. The material used for the secondary coating is asphalt, and the coating amount is 1-30 wt%. The carbonization treatment is performed in a gas that is not oxygen. The non-oxygen gas is, for example, nitrogen, argon, neon, a mixture of the gases, a vacuum, or a reducing atmosphere. The carbonization treatment is performed at 450 to 1500 ° C., the temperature is maintained for 1 to 10 hours, and the temperature is lowered to room temperature.
複合材料の表面に黒鉛でない有機物の熱分解グラファイトを被覆するので、その導電性能は下がる。そのため、陰極材料の導電性能とそのサイクル安定性を引き上げ、比容量を充分に発揮させるため、本発明は、複合材料の表面には被覆の処理、または導電炭素を混ぜ合わせる処理を行なう。前記導電炭素は陰極材料の0.5〜5wt%を占める。これに対して、導電炭素の量が0.5wt%より少ないとき、継続的な導電線路を形成することができないため、材料の導電性能は、有効に引き上げることができない。逆に、導電炭素の比例が5wt%より大きいとき、材料の比容量及びその充放電効率に不利な影響を与えることになる。そのため、導電炭素の適当な投入量は0.5〜5wt%である。 Since the surface of the composite material is coated with pyrolytic graphite of an organic material that is not graphite, its conductive performance is lowered. Therefore, in order to raise the electroconductive performance of the cathode material and its cycle stability and to fully exhibit the specific capacity, the present invention performs a coating process or a process of mixing conductive carbon on the surface of the composite material. The conductive carbon accounts for 0.5 to 5 wt% of the cathode material. On the other hand, when the amount of conductive carbon is less than 0.5 wt%, a continuous conductive line cannot be formed, so that the conductive performance of the material cannot be effectively increased. On the contrary, when the proportion of the conductive carbon is larger than 5 wt%, it adversely affects the specific capacity of the material and its charge / discharge efficiency. Therefore, an appropriate amount of conductive carbon is 0.5 to 5 wt%.
本発明において、混合被覆処理後の珪素・炭素複合材料と導電炭素の被覆方法について特別に制限するわけではなく、公知の混合設備のいずれを用いてもよい。例えば、高速攪拌機、惑星式攪拌機など混合設備を用いてもよい。また、前記混合処理時間は1〜6時間である。前記導電炭素の配布を均一にするため、超音波を用いて、前記複合材料と導電炭素の懸濁液を処理する。超音波の使用時間は1〜30分間であり、周波数は40kHz〜28kHzであり、仕事率は50W〜3600Wである。 In the present invention, the method for coating the silicon / carbon composite material and the conductive carbon after the mixed coating treatment is not particularly limited, and any known mixing equipment may be used. For example, mixing equipment such as a high-speed stirrer or a planetary stirrer may be used. The mixing treatment time is 1 to 6 hours. In order to make the distribution of the conductive carbon uniform, the suspension of the composite material and the conductive carbon is treated using ultrasonic waves. The usage time of the ultrasonic wave is 1 to 30 minutes, the frequency is 40 kHz to 28 kHz, and the work rate is 50 W to 3600 W.
リチウムイオン電池の第一回の充放電において、溶剤及び塩化電解質は、不可逆的電気化学還元分解反応が生じるので、アルキル基炭酸リチウム、アルコキシル基炭酸リチウムなどの物質を生じる。こうした物質は陰極材料の表面に沈積して、電子に対して絶縁、イオン濾過可能の固体電解質膜SEI膜を形成する。当該鈍化膜は、陰極材料の電気化学性能に強く影響している。つまり、電極の表面にある薄くて、緻密な鈍化膜は、溶媒化リチウムイオンの共挿入を阻止することができて、電池の高い第一回サイクルクーロン効率及び低いサイクル減衰を保障するものである。実際に、陰極材料における微結晶黒鉛の基面、端面の相対量、反応性の差別及び結晶体の大小、電解液の構成、還元分解の動力学上の性質などは、電極表面の鈍化膜の緻密性を決定するものである。 In the first charge / discharge of the lithium ion battery, irreversible electrochemical reduction and decomposition reactions occur in the solvent and the chloride electrolyte, and thus substances such as alkyl group lithium carbonate and alkoxyl group lithium carbonate are generated. These substances are deposited on the surface of the cathode material to form a solid electrolyte membrane SEI film that can be insulated and ion filtered from electrons. The blunt film has a strong influence on the electrochemical performance of the cathode material. In other words, the thin and dense blunt film on the surface of the electrode can prevent co-insertion of solvated lithium ions, ensuring high first cycle Coulomb efficiency and low cycle attenuation of the battery. . Actually, the base surface of microcrystalline graphite, the relative amount of the end face, the difference in reactivity and the size of the crystal, the composition of the electrolyte, the kinetic properties of the reductive decomposition, etc. It determines the denseness.
本発明においては、リチウム化合物の無機溶液または有機溶液を用いて、珪素・炭素複合陰極材料を処理し、陰極材料の表面に緻密、かつ、リチウムイオン濾過可能の固体電解質膜を形成させることによって、陰極材料の第一回の充放電効率及びサイクル安定性を引き上げる。さらに、リチウム化合物を浸漬する方法を用いて、最終的にリチウムイオン電池の珪素・炭素複合陰極材料を得る。 In the present invention, an inorganic solution or an organic solution of a lithium compound is used to treat a silicon / carbon composite cathode material to form a dense and lithium ion filterable solid electrolyte membrane on the surface of the cathode material. The first charge / discharge efficiency and cycle stability of the cathode material are increased. Further, a silicon / carbon composite cathode material for a lithium ion battery is finally obtained by using a method of immersing a lithium compound.
以上の工程で処理し得たリチウムイオン電池の珪素・炭素複合陰極材料の平均粒径は5〜60μmであり、比表面積は1.0〜4.0m2/gであり、ジョルト密度は0.7〜2.0g/cm3である。前記平均粒径はMalvernレーザー粒径測定器を用いて測定したもので、前記比表面積は窒素置換のBET法を用いて測定したもので、ジョルト密度はQuantachrome AutoTap型ジョルト密度測定器を用いて測定したものである。 The average particle size of the silicon / carbon composite cathode material of the lithium ion battery that can be processed in the above steps is 5 to 60 μm, the specific surface area is 1.0 to 4.0 m 2 / g, and the jolt density is 0.7 to 2.0 g / g. cm 3 . The average particle size was measured using a Malvern laser particle size measuring device, the specific surface area was measured using a nitrogen-substituted BET method, and the Jolt density was measured using a Quantachrome AutoTap type Jolt density measuring device. It is a thing.
実施例1(珪素・炭素のSi-G-C- Li2CO3複合陰極材料を製造する):
アルゴンの中、粒度75μmの珪素粉末を高効率のボール・ミルにより0.5μmまでに破砕して、非常に細かい珪素粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径1μmの球形黒鉛を得る。前記工程により取得した20wt%の非常に細かい珪素粉末と80wt%の球形黒鉛を複螺旋攪拌機に投入し、6時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を10wt%のレジトールに入れ、湿式法により10時間攪拌してから、300℃のもとで乾燥し、粒子を製造する。そして、前記レジトールを被覆した後の複合材料を炭素化処理し、アルゴンの中に1100℃まで温度を上げ、温度を3時間維持した後、室温に下げ、10μmまでに破砕する。前記破砕した粉末と10wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1200℃までに温度を上げ、温度を2時間維持した後、室温に下げ、20μmまでに破砕する。その後、これと0.5wt%の炭素ナノメーターパイプとともに高速攪拌器に入れ、4時間混合し、周波数28kHz、仕事率3600Wの超音波で5分間処理する。さらに、前記工程により得たものを1%のLi2CO3溶液(このときの固体と液体の重量比は0.1である)の中に1時間浸漬し、最終に珪素・炭素複合陰極材料を得る。前記複合材料の平均粒径は20.1μmであり、比表面積は3.5m2/gであり、ジョルト密度は1.3g/cm3である。
Example 1 (Production of Si-GC-Li 2 CO 3 composite cathode material of silicon and carbon):
In argon, a silicon powder having a particle size of 75 μm is crushed to 0.5 μm by a high-efficiency ball mill to obtain a very fine silicon powder. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, fractionated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 1 μm. 20 wt% of the fine silicon powder obtained by the above process and 80 wt% of spherical graphite are put into a double helix stirrer and mixed for 6 hours to produce a composite particle basic body. Next, the composite particle basic body is put into 10 wt% resistol, stirred for 10 hours by a wet method, and then dried at 300 ° C. to produce particles. The composite material coated with the resistol is carbonized, the temperature is increased to 1100 ° C. in argon, the temperature is maintained for 3 hours, then the temperature is lowered to room temperature and crushed to 10 μm. The crushed powder and 10 wt% asphalt are mixed and coated, carbonized, and the temperature is increased to 1200 ° C. in argon. After the temperature is maintained for 2 hours, the temperature is lowered to room temperature and crushed to 20 μm. Then, it is put into a high-speed stirrer together with this and 0.5 wt% carbon nanometer pipe, mixed for 4 hours, and treated for 5 minutes with an ultrasonic wave having a frequency of 28 kHz and a power of 3600 W. Further, the product obtained by the above step is immersed in a 1% Li 2 CO 3 solution (the weight ratio of the solid to the liquid is 0.1) for 1 hour, and finally a silicon / carbon composite cathode material is obtained. . The composite material has an average particle size of 20.1 μm, a specific surface area of 3.5 m 2 / g, and a jolt density of 1.3 g / cm 3 .
前記複合材料を使用して以下の方法で電極を製造する。即ち、 An electrode is manufactured by the following method using the composite material. That is,
95グラム複合陰極材料、2.5グラムスチレンブラジェンゴムSBR、1.5グラムカルボキシメチルセルローゼCMC、1グラム導電剤Super-Pを取り、適量の分散剤である蒸留水に入れて均一に混合して電極とする。そして、リチウムを対極とし、1MのLiPF6の混合溶剤EC:DMC:EMC=1:1:1とし、v/v溶液を電解液とし、ポリプロピレン微孔膜を隔膜として、模擬電池を組み立てる。複合炭素材料の可逆的比容量は、充放電電圧を0.02〜1.5ワットとし、0.5mA/cm2の電流密度で、定電流充放電実験を行い、測定する。そして、LiCoO2を陽極とし、1モルのLiPF6の混合溶剤EC:DMC:EMC=1:1:1とし、v/v溶液を電解液とし、ポリプロピレン微孔膜を隔膜として、電池を組み立てる。当該装置を用いて、4.2〜3.0ワットを限度とする充放電電圧のもとで、1Cの速度で充放電試験を行い、リチウムイオン電池の200回のサイクル容量維持率C200/C1を測定する。 Take 95g composite cathode material, 2.5g styrene bragen rubber SBR, 1.5g carboxymethylcellulose CMC, 1g conductive agent Super-P, put it in distilled water which is an appropriate amount of dispersant and mix it uniformly with the electrode To do. Then, a simulated battery is assembled using lithium as a counter electrode, a 1M LiPF 6 mixed solvent EC: DMC: EMC = 1: 1: 1, a v / v solution as an electrolyte, and a polypropylene microporous membrane as a diaphragm. The reversible specific capacity of the composite carbon material is measured by conducting a constant current charge / discharge experiment at a current density of 0.5 mA / cm 2 with a charge / discharge voltage of 0.02 to 1.5 watts. Then, a battery is assembled using LiCoO 2 as the anode, 1 mol of LiPF 6 mixed solvent EC: DMC: EMC = 1: 1: 1, the v / v solution as the electrolyte, and the polypropylene microporous membrane as the diaphragm. Using the equipment, charge / discharge test at a rate of 1C under charge / discharge voltage of 4.2-3.0 watts limit and measuring 200 cycle capacity maintenance ratio C 200 / C 1 of lithium ion battery To do.
実施例2(珪素・炭素のSi-Mg-G-C-LiOH複合陰極材料を製造する):
粒度75μmのSi-Mg粉末(その中に珪素は50wt%を占める)をアルゴンの中で高効率のボール・ミルにより0.1μmまでに破砕して、非常に細かいSi-Mg粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により得た30wt%の非常に細かいSi-Mg粉末と70wt%の球形黒鉛を混合式粒子製造機に投入し、1時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を2.5wt%のスチレンブラジェンゴムに入れ、湿式法により4時間攪拌してから、200℃のもとで乾燥し、粒子を製造する。そして、前記スチレンブラジェンゴムを被覆した後の複合材料を炭素化処理し、アルゴンの中に700℃まで温度を上げ、温度を5時間維持した後、室温に下げ、10μmまでに破砕する。前記破砕した粉末と12wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1200℃までに温度を上げ、温度を8時間維持した後、室温に下げ、15μmまでに破砕する。その後、これと1%のナノメーター炭素の微小球体とともに高速攪拌器に入れ、1時間混合し、周波数40kHz、仕事率50Wの超音波で20分間処理する。さらに、前記工程により取得したものを5%のLiOH溶液(このときの固体と液体の重量比は1である)に12時間浸漬し、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は15.4μmであり、比表面積は2.8m2/gであり、ジョルト密度は1.2g/cm3である。
Example 2 (Production of Si-Mg-GC-LiOH composite cathode material of silicon and carbon):
A very fine Si-Mg powder is obtained by crushing Si-Mg powder with a particle size of 75 μm (in which silicon accounts for 50 wt%) to 0.1 μm in argon with a high-efficiency ball mill. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 3 μm. 30 wt% very fine Si-Mg powder obtained by the above process and 70 wt% spherical graphite are put into a mixed particle production machine and mixed for 1 hour to produce a composite particle basic body. Next, the composite particle basic body is put into 2.5 wt% styrene bragen rubber, stirred for 4 hours by a wet method, and then dried at 200 ° C. to produce particles. Then, the composite material coated with the styrene bragen rubber is carbonized, the temperature is increased to 700 ° C. in argon, the temperature is maintained for 5 hours, then the temperature is lowered to room temperature, and crushed to 10 μm. The crushed powder and 12 wt% asphalt are mixed and coated, carbonized, the temperature is increased to 1200 ° C. in argon, the temperature is maintained for 8 hours, then the temperature is lowered to room temperature and crushed to 15 μm. Then, it is put in a high-speed stirrer together with this and 1% nanometer carbon microspheres, mixed for 1 hour, and treated with ultrasonic waves with a frequency of 40 kHz and a power of 50 W for 20 minutes. Further, the material obtained in the above step is immersed in a 5% LiOH solution (the weight ratio of solid to liquid at this time is 12) for 12 hours, and finally a silicon / carbon composite cathode material is obtained. The composite material has an average particle size of 15.4 μm, a specific surface area of 2.8 m 2 / g, and a Jolt density of 1.2 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、その電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例3(珪素・炭素のSi-Fe-G-C-LiF複合陰極材料を製造する):
粒度75μmのSi-Fe粉末(その中に珪素は75wt%を占める)をアルゴンの中で高効率のボール・ミルにより1μmまでに破砕して、非常に細かいSi-Fe粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径5μmの球形黒鉛を得る。前記工程により取得した2wt%の非常に細かいSi-Fe粉末と98wt%の球形黒鉛を混合式粒子製造機に投入し、6時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を1wt%のポリエチレン溶液に入れ、湿式法により10時間攪拌してから、200℃のもとで乾燥し、粒子を製造する。そして、前記ポリエチレンを被覆した後の複合材料を炭素化処理し、アルゴンの中に1500℃まで温度を上げ、温度を1時間維持した後、室温に下げ、5μmまでに破砕する。前記破砕した粉末と10wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1200℃までに温度を上げ、温度を10時間維持した後、室温に下げ、15μmまでに破砕する。その後、これと5%の炭素繊維とともに高速攪拌器に入れ、6時間混合し、周波数40kHz、仕事率50Wの超音波で30分間処理し、100℃のもとで乾燥し粒子を製造する。さらに、前記工程により取得したものを0.2%のLiF溶液(このときの固体と液体の重量比は2である)の中に48時間浸漬し、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は15.6μmであり、比表面積は1.8m2/gであり、ジョルト密度は1.0g/cm3である。
Example 3 (Manufacturing Si-Carbon Si-Fe-GC-LiF Composite Cathode Material):
A very fine Si-Fe powder is obtained by crushing Si-Fe powder with a particle size of 75 μm (in which silicon accounts for 75 wt%) to 1 μm in argon with a high-efficiency ball mill. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 5 μm. 2 wt% of very fine Si-Fe powder obtained by the above process and 98 wt% of spherical graphite are put into a mixed particle production machine and mixed for 6 hours to produce a composite particle basic body. Next, the composite particle basic body is put in a 1 wt% polyethylene solution, stirred for 10 hours by a wet method, and then dried at 200 ° C. to produce particles. Then, the composite material coated with the polyethylene is carbonized, the temperature is increased to 1500 ° C. in argon, the temperature is maintained for 1 hour, then the temperature is lowered to room temperature, and crushed to 5 μm. The crushed powder and 10 wt% asphalt are mixed and coated, carbonized, the temperature is increased to 1200 ° C. in argon, the temperature is maintained for 10 hours, then the temperature is lowered to room temperature and crushed to 15 μm. Then, it is put into a high-speed stirrer together with this and 5% carbon fiber, mixed for 6 hours, treated with ultrasonic waves having a frequency of 40 kHz and a work power of 50 W for 30 minutes, and dried at 100 ° C. to produce particles. Further, the material obtained by the above step is immersed in a 0.2% LiF solution (the weight ratio of solid to liquid at this time is 48) for 48 hours, and finally a silicon / carbon composite cathode material is obtained. The composite material has an average particle size of 15.6 μm, a specific surface area of 1.8 m 2 / g, and a jolt density of 1.0 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例4(珪素・炭素のSi-Ca-G-C-LiCl複合陰極材料を製造する):
粒度75μmのSi-Ca粉末(その中に珪素は60wt%を占める)をアルゴンの中で高効率のボール・ミルにより0.6μmまでに破砕して、非常に細かいSi-Ca粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径5μmの球形黒鉛を得る。前記工程により取得した40wt%の非常に細かいSi-Ca粉末と60wt%の球形黒鉛を円錐形混合機に投入し、4時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を10wt%のレジトールに入れ、湿式法により4時間攪拌してから、400℃のもとで乾燥し、粒子を製造する。そして、前記レジトールを被覆した後の複合材料を炭素化処理し、アルゴンの中に800℃まで温度を上げ、温度を5時間維持した後、室温に下げ、18μmまでに破砕する。前記破砕した粉末と30wt%のアスファルトとを混合被覆、炭素化処理し、アルゴンの中に1200℃までに温度を上げ、温度を1時間維持した後、室温に下げ、15μmまでに破砕する。その後、これと1%のアセチレンブラックとともに高速攪拌器に入れ、2時間混合し、周波数40kHz、仕事率50Wの超音波で20分間処理する。さらに、前記工程により取得したものを10%のLiCl溶液(このときの固体と液体の重量比は0.5である)の中に24時間浸漬し、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は24.8μmであり、比表面積は3.8m2/gであり、ジョルト密度は0.94g/cm3である。
Example 4 (Production of Si-Carbon Si-Ca-GC-LiCl Composite Cathode Material):
A very fine Si-Ca powder is obtained by crushing Si-Ca powder with a particle size of 75 μm (in which silicon accounts for 60 wt%) to 0.6 μm in argon using a high-efficiency ball mill. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 5 μm. 40 wt% of the very fine Si-Ca powder obtained by the above process and 60 wt% of spherical graphite are put into a conical mixer and mixed for 4 hours to produce a composite particle basic body. Next, the composite particle basic body is put into 10 wt% resistol, stirred for 4 hours by a wet method, and then dried at 400 ° C. to produce particles. Then, the composite material coated with the resistol is carbonized, the temperature is increased to 800 ° C. in argon, the temperature is maintained for 5 hours, the temperature is lowered to room temperature, and the mixture is crushed to 18 μm. The crushed powder and 30 wt% asphalt are mixed and coated, carbonized, the temperature is increased to 1200 ° C. in argon, the temperature is maintained for 1 hour, then the temperature is lowered to room temperature and crushed to 15 μm. Then, it is put in a high-speed stirrer together with this and 1% acetylene black, mixed for 2 hours, and treated with ultrasonic waves having a frequency of 40 kHz and a work power of 50 W for 20 minutes. Further, the material obtained in the above step is immersed in a 10% LiCl solution (the weight ratio of solid to liquid at this time is 0.5) for 24 hours, and finally a silicon / carbon composite cathode material is obtained. The composite material has an average particle size of 24.8 μm, a specific surface area of 3.8 m 2 / g, and a Jolt density of 0.94 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例5(珪素・炭素のSiO-G-C-Li2O複合陰極材料を製造する):
粒度75μmのSiO粉末をアルゴンの中で高効率のボール・ミルにより0.8μmまでに破砕して、非常に細かいSiO粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により取得した15wt%の非常に細かいSiO粉末と85wt%の球形黒鉛を複螺旋攪拌機に投入し、5時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を2.5wt%のポリスチレンに入れ、湿式法により4時間攪拌してから、250℃のもとで乾燥し、粒子を製造する。そして、前記ポリスチレンを被覆した後の複合材料を炭素化処理し、アルゴンの中に1300℃まで温度を上げ、温度を2時間維持した後、室温に下げ、5μmまでに破砕する。前記破砕した粉末と8wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1100℃までに温度を上げ、温度を10時間維持した後、室温に下げ、5μmまでに破砕する。その後、これと5%のLi2O溶液(このときの固体と液体の重量比は1である)の中に48時間浸漬し、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は5.8μmであり、比表面積は3.8m2/gであり、ジョルト密度は0.96g/cm3である。
Example 5 (Production of silicon-carbon SiO—GC—Li 2 O composite cathode material):
A very fine SiO powder is obtained by crushing a SiO powder having a particle size of 75 μm to 0.8 μm with a high-efficiency ball mill in argon. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 3 μm. The 15 wt% very fine SiO powder and 85 wt% spherical graphite obtained by the above process are put into a double helix stirrer and mixed for 5 hours to produce a composite particle basic body. Next, the composite particle basic body is put into 2.5 wt% polystyrene, stirred for 4 hours by a wet method, and then dried at 250 ° C. to produce particles. Then, the composite material coated with polystyrene is carbonized, and the temperature is increased to 1300 ° C. in argon. After maintaining the temperature for 2 hours, the temperature is lowered to room temperature and crushed to 5 μm. The crushed powder and 8 wt% asphalt are mixed and coated, carbonized, the temperature is increased to 1100 ° C. in argon, the temperature is maintained for 10 hours, then the temperature is lowered to room temperature and crushed to 5 μm. Thereafter, this and 5% Li 2 O solution (weight ratio of solid and liquid in this case has 1) was immersed for 48 hours in to obtain a silicon-carbon composite cathode material in the final. The composite material has an average particle size of 5.8 μm, a specific surface area of 3.8 m 2 / g, and a Jolt density of 0.96 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例6(珪素・炭素のSi-G-C- LiNO3複合陰極材料を製造する):
粒度75μmのSi-Ni粉末(その中に珪素は40wt%を占める)をアルゴンの中で高効率のボール・ミルにより0.6μmまでに破砕して、非常に細かいSi-Ni粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により取得した50wt%の非常に細かいSi-Ni粉末と50wt%の球形黒鉛を複螺旋混合機に投入し、6時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を2.5wt%のスチレンブラジェンゴムに入れ、湿式法により4時間攪拌し、200℃のもとで乾燥し、粒子を製造する。そして、前記スチレンブラジェンゴムを被覆した後の複合材料を炭素化処理し、アルゴンの中に700℃まで温度を上げ、温度を5時間維持した後、室温に下げ、10μmまでに破砕する。前記破砕した粉末と12wt%のアスファルトとを混合被覆、炭素化処理し、アルゴンの中に1200℃までに温度を上げ、温度を10時間維持した後、室温に下げ、5μmまでに破砕する。その後、これと1%の導電カーボンブラックSuper-Pを高速攪拌器に入れ、2時間混合し、周波数35kHz、仕事率2500Wの超音波で15分間処理する。さらに、前記工程により取得したものを10%のLiNO3溶液(このときの固体と液体の重量比は2である)の中に36時間浸漬し、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は5.2μmであり、比表面積は4.0m2/gであり、ジョルト密度は2.0g/cm3である。
Example 6 (Production of Si-GC-LiNO 3 composite cathode material of silicon and carbon):
A very fine Si-Ni powder is obtained by crushing Si-Ni powder with a particle size of 75 µm (in which silicon accounts for 40 wt%) to 0.6 µm in argon with a high-efficiency ball mill. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 3 μm. 50 wt% very fine Si-Ni powder and 50 wt% spherical graphite obtained by the above process are put into a double helix mixer and mixed for 6 hours to produce a composite particle basic body. Next, the composite particle basic body is put into 2.5 wt% styrene bragen rubber, stirred for 4 hours by a wet method, and dried at 200 ° C. to produce particles. Then, the composite material coated with the styrene bragen rubber is carbonized, the temperature is increased to 700 ° C. in argon, the temperature is maintained for 5 hours, then the temperature is lowered to room temperature, and crushed to 10 μm. The crushed powder and 12 wt% asphalt are mixed and coated, carbonized, the temperature is increased to 1200 ° C. in argon, the temperature is maintained for 10 hours, then the temperature is lowered to room temperature and crushed to 5 μm. Thereafter, this and 1% of conductive carbon black Super-P are put into a high-speed stirrer, mixed for 2 hours, and treated with ultrasonic waves having a frequency of 35 kHz and a power of 2500 W for 15 minutes. Further, the material obtained in the above step is immersed in a 10% LiNO 3 solution (the weight ratio of solid to liquid at this time is 2) for 36 hours, and finally a silicon / carbon composite cathode material is obtained. The composite material has an average particle size of 5.2 μm, a specific surface area of 4.0 m 2 / g, and a Jolt density of 2.0 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例7(珪素・炭素のSi O2-G-C複合陰極材料を製造する):
粒度75μmのSiO2粉末を空気の中で高効率のボール・ミルにより0.8μmまでに破砕して、非常に細かいSiO2粉末を得る。粒度70μm、炭素含有量95%以上の人工の黒鉛を破砕、鈍化処理し、炭素含有量99.9%以上、粒径3μmの黒鉛微小粉末を得る。前記工程により取得した10wt%の非常に細かいSiO2粉末と90wt%の球形黒鉛を複螺旋攪拌機に投入し、5時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を25wt%のレジトールに入れ、湿式法により4時間攪拌し、250℃のもとで乾燥し、粒子を製造する。そして、レジトールを被覆した後の複合材料を炭素化処理し、水素を含む還元雰囲気の中に1300℃まで温度を上げ、温度を2時間維持した後、室温に下げ、40μmまでに破砕する。前記破砕した粉末と5wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1100℃までに温度を上げ、温度を10時間維持した後、室温に下げ、60μmまでに破砕して、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は60.4μmであり、比表面積は2.8m2/gであり、ジョルト密度は0.98g/cm3である。
Example 7 (Production of Si—carbon Si 2 O 2 -GC composite cathode material):
A very fine SiO 2 powder is obtained by crushing a SiO 2 powder having a particle size of 75 μm to 0.8 μm in air using a high-efficiency ball mill. Artificial graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed and blunted to obtain a graphite fine powder having a carbon content of 99.9% and a particle size of 3 μm. 10 wt% very fine SiO 2 powder and 90 wt% spherical graphite obtained by the above process are put into a double helix stirrer and mixed for 5 hours to produce a composite particle basic body. Next, the composite particle basic body is put in 25 wt% resistol, stirred for 4 hours by a wet method, and dried at 250 ° C. to produce particles. The composite material coated with resistol is carbonized, and the temperature is raised to 1300 ° C. in a reducing atmosphere containing hydrogen. After maintaining the temperature for 2 hours, the temperature is lowered to room temperature and crushed to 40 μm. Mixed and coated with the crushed powder and 5 wt% asphalt, carbonized, raised to 1100 ° C. in argon, maintained for 10 hours, then lowered to room temperature, crushed to 60 μm, and finally Obtain a silicon / carbon composite cathode material. The composite material has an average particle size of 60.4 μm, a specific surface area of 2.8 m 2 / g, and a Jolt density of 0.98 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例8(珪素・炭素のSi-G-C複合陰極材料を製造する):
粒度75μmの珪素粉末をアルゴンの中で高効率のボール・ミルにより0.5μmまでに破砕して、非常に細かい珪素粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により取得した5wt%の非常に細かい珪素粉末と95wt%の球形黒鉛を複螺旋攪拌機に投入し、5時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を2.5wt%のスチレンブラジェンゴムSBR、1.5%のカルボキシメチルセルローゼCMCに混合し、湿式法により1時間球状化してから、250℃のもとで乾燥し、粒子を製造する。そして、前記被覆をした後の複合材料を炭素化処理し、アルゴンの中に450℃まで温度を上げ、温度を10時間維持した後、室温に下げ、15μmまでに破砕する。前記破砕した粉末と1wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1100℃までに温度を上げ、温度を10時間維持した後、室温に下げ、17μmまでに破砕して、最終に珪素・炭素複合陰極材料を取得する。前記複合材料の平均粒径は17.2μmであり、比表面積は3.3m2/gであり、ジョルト密度は1.05g/cm3である。
Example 8 (Production of Si / GC Si-GC composite cathode material):
A silicon powder having a particle size of 75 μm is crushed to 0.5 μm by a high-efficiency ball mill in argon to obtain a very fine silicon powder. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 3 μm. 5 wt% very fine silicon powder and 95 wt% spherical graphite obtained by the above process are put into a double helix stirrer and mixed for 5 hours to produce a composite particle basic body. Next, the composite particle basic body is mixed with 2.5 wt% styrene bragen rubber SBR, 1.5% carboxymethylcellulose CMC, spheroidized by a wet method for 1 hour, and then dried at 250 ° C., Producing particles. The composite material after the coating is carbonized, and the temperature is increased to 450 ° C. in argon. After the temperature is maintained for 10 hours, the temperature is decreased to room temperature and crushed to 15 μm. Mixed and coated with the crushed powder and 1 wt% asphalt, carbonized, raised the temperature to 1100 ° C in argon, maintained the temperature for 10 hours, then lowered to room temperature, crushed to 17 μm, and finally Obtain a silicon / carbon composite cathode material. The composite material has an average particle size of 17.2 μm, a specific surface area of 3.3 m 2 / g, and a Jolt density of 1.05 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例9(珪素・炭素のSi-G-C複合陰極材料を製造する):
粒度75μmの珪素粉末をアルゴンの中で高効率のボール・ミルにより0.5μmまでに破砕して、非常に細かい珪素粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により取得した1wt%の非常に細かい珪素粉末と99wt%の球形黒鉛を複螺旋攪拌機に投入し、5時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を2.5wt%のスチレンブラジェンゴムSBR、1.5%のカルボキシメチルセルローゼCMCに混合し、湿式法により12時間球状化し、周波数28kHz、仕事率3600Wの超音波で5分間処理し、250℃のもとで乾燥し、粒子を製造する。そして、前記被覆をした後の複合材料を炭素化処理し、アルゴンの中に450℃まで温度を上げ、温度を10時間維持した後、室温に下げ、15μmまでに破砕する。前記破砕した粉末と6wt%のアスファルトと混合被覆、炭素化処理し、アルゴンの中に1100℃までに温度を上げ、温度を10時間維持した後、室温に下げ、17μmまでに破砕して、最終に珪素・炭素複合陰極材料を取得する。前記処理を経て得た材料の平均粒径は17.5μmであり、比表面積は3.2m2/gであり、ジョルト密度は1.03g/cm3である。
Example 9 (Production of Si-GC composite cathode material of silicon and carbon):
A silicon powder having a particle size of 75 μm is crushed to 0.5 μm by a high-efficiency ball mill in argon to obtain a very fine silicon powder. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 3 μm. 1 wt% of very fine silicon powder and 99 wt% of spherical graphite obtained by the above process are put into a double helix stirrer and mixed for 5 hours to produce a composite particle basic body. Next, the composite particle basic body was mixed with 2.5 wt% styrene bragen rubber SBR and 1.5% carboxymethyl cellulose CMC, and spheroidized by a wet method for 12 hours, and ultrasonically with a frequency of 28 kHz and a power of 3600 W. Treat for minutes and dry at 250 ° C. to produce particles. The composite material after the coating is carbonized, and the temperature is increased to 450 ° C. in argon. After the temperature is maintained for 10 hours, the temperature is decreased to room temperature and crushed to 15 μm. Mixed and coated with the crushed powder and 6 wt% asphalt, carbonized, raised to 1100 ° C in argon, maintained temperature for 10 hours, then lowered to room temperature, crushed to 17 μm, and finally Obtain a silicon / carbon composite cathode material. The average particle size of the material obtained through the above treatment is 17.5 μm, the specific surface area is 3.2 m 2 / g, and the jolt density is 1.03 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例10(珪素・炭素のSi-Sn-Cu-G-C複合陰極材料を製造する):
粒度75μmのSi-Sn-Cu粉末(このこきSi:Sn:Cuの重量比は65:30:5である)をアルゴンの中で高効率のボール・ミルにより0.5μmまでに破砕して、非常に細かい珪素合金粉末を得る。粒度70μm、炭素含有量95%以上の天然黒鉛を破砕、分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により取得した40wt%の非常に細かい珪素合金粉末と60wt%の球形黒鉛を複螺旋攪拌機に投入し、5時間混合し、複合粒子基本体を製造する。次に、前記複合粒子基本体を2.5wt%のスチレンブラジェンゴムSBR、1.5%のカルボキシメチルセルローゼCMCに混合し、湿式法により12時間球状化し、周波数28kHz、仕事率3600Wの超音波で5分間処理してから、250℃のもとで乾燥し、粒子を製造する。そして、前記被覆をした後の複合材料を炭素化処理し、アルゴンの中に450℃まで温度を上げ、温度を10時間維持した後、室温に下げ、15μmまでに破砕する。その後、これと6wt%のアスファルトとを混合被覆、炭素化処理し、アルゴンの中に1100℃まで温度を上げ、10時間温度を維持した後、室温に下げ、17.5μmまでに破砕して、最終に珪素・炭素複合陰極材料を取得する。前記処理を経て得た材料の平均粒径は17.5μmであり、比表面積は2.1m2/gであり、ジョルト密度は1.23g/cm3である。
Example 10 (Production of Si-Sn-Cu-GC composite cathode material of silicon and carbon):
Si-Sn-Cu powder with a particle size of 75μm (the weight ratio of this Si: Sn: Cu is 65: 30: 5) is crushed to 0.5μm by argon ball with high efficiency in argon To obtain fine silicon alloy powder. Natural graphite having a particle size of 70 μm and a carbon content of 95% or more is crushed, separated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% and a particle size of 3 μm. The very fine silicon alloy powder of 40 wt% and 60 wt% of spherical graphite obtained by the above process are put into a double helix stirrer and mixed for 5 hours to produce a composite particle basic body. Next, the composite particle basic body was mixed with 2.5 wt% styrene bragen rubber SBR and 1.5% carboxymethyl cellulose CMC, and spheroidized by a wet method for 12 hours, and ultrasonically with a frequency of 28 kHz and a power of 3600 W. Treat for a minute and then dry at 250 ° C. to produce particles. The composite material after the coating is carbonized, and the temperature is increased to 450 ° C. in argon. After the temperature is maintained for 10 hours, the temperature is decreased to room temperature and crushed to 15 μm. Then, this and 6 wt% asphalt were mixed and coated, carbonized, raised to 1100 ° C in argon, maintained for 10 hours, lowered to room temperature, crushed to 17.5 μm, and finally Obtain a silicon / carbon composite cathode material. The average particle size of the material obtained through the above treatment is 17.5 μm, the specific surface area is 2.1 m 2 / g, and the jolt density is 1.23 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
実施例11(珪素・炭素のSi-Ni-Co-Ag-G-C複合陰極材料を製造する):
粒度75μmのSi-Ni-Mg-Ag粉末(このときのSi:Ni:Co:Agの重量比は55:30:10: 5である)をアルゴン中、高効率のボール・ミルにより0.5μmまでに破砕して、非常に細かい珪素合金粉末を得る。さらに、粒度70μm、炭素含有量95%以上の天然黒鉛粉末を分別、整形及び鈍化処理し、炭素含有量99.9%以上、粒径3μmの球形黒鉛を得る。前記工程により取得した非常に細かい40wt%の珪素合金粉末と60wt%の球形黒鉛を複螺旋攪拌機の中に5時間混合し、複合粒子の基本体を製造する。そして、前記複合粒子と2.5wt%のスチレンブラジェンゴムSBR、1.5%のカルボキシメチルセルローゼCMCを混合し、12時間湿式法で球状化し、さらに周波数28kHz、仕事率3600Wの超音波で5分間を処理し、250℃のもとで乾燥し、粒子を製造する。そして、被覆した後の複合材料を炭化処理し、アルゴンの中に450℃までに加熱し、10時間を保温してから、室温に下げ、15μmまでに破砕する。さらに、破砕した粉末と6wt%のアスファルトを混合、被覆及び炭化処理して、アルゴンの中に1100℃に加熱し、10時間温度を維持してから、室温に下げ、17μmまでに破砕する。これにより、最終に珪素・炭素の複合陰極材料を得る。こうした複合材料の平均粒径は17.5μmであり、比表面積は1.9m2/gであり、ジョルト密度は1.41g/cm3である。
Example 11 (Production of Si-Ni-Co-Ag-GC composite cathode material of silicon and carbon):
Si-Ni-Mg-Ag powder with a particle size of 75μm (Si: Ni: Co: Ag weight ratio at this time is 55: 30: 10: 5) up to 0.5μm in argon with high-efficiency ball mill To obtain a very fine silicon alloy powder. Further, natural graphite powder having a particle size of 70 μm and a carbon content of 95% or more is fractionated, shaped and blunted to obtain spherical graphite having a carbon content of 99.9% or more and a particle size of 3 μm. A very fine 40 wt% silicon alloy powder obtained by the above process and 60 wt% spherical graphite are mixed in a double helix stirrer for 5 hours to produce a basic body of composite particles. Then, the composite particles, 2.5 wt% styrene bragen rubber SBR, 1.5% carboxymethylcellulose CMC are mixed, spheroidized by a wet method for 12 hours, and further 5 minutes with ultrasonic waves with a frequency of 28 kHz and a power of 3600 W. Treat and dry at 250 ° C. to produce particles. The coated composite material is carbonized, heated to 450 ° C. in argon, kept warm for 10 hours, lowered to room temperature, and crushed to 15 μm. Furthermore, the crushed powder and 6 wt% asphalt are mixed, coated and carbonized, heated to 1100 ° C. in argon, maintained at temperature for 10 hours, lowered to room temperature, and crushed to 17 μm. Thus, a silicon / carbon composite cathode material is finally obtained. These composite materials have an average particle size of 17.5 μm, a specific surface area of 1.9 m 2 / g, and a Jolt density of 1.41 g / cm 3 .
前記取得した陰極材料により実施例1と同様な方法で電極を製造して、それの電気化学性能を測定する。 An electrode is produced from the obtained cathode material in the same manner as in Example 1, and its electrochemical performance is measured.
比較例:D50=16μmの天然球形黒鉛を処理せず直接に陰極材料に使用して、実施例1と同様な方法により電極と電池を製造して、それの電気化学性能を測定する。 Comparative Example: Using natural spherical graphite with D 50 = 16 μm directly as a cathode material, an electrode and a battery are produced in the same manner as in Example 1, and their electrochemical performance is measured.
前記実施例と比較例に基づき、測定した陰極材料の電気化学性能は、表1に羅列する。 The electrochemical performances of the cathode materials measured based on the examples and comparative examples are listed in Table 1.
前記実施例から、本発明に基づいて製造した黒鉛の陰極材料の可逆的比容量が450mAh/gより大きく、200回サイクルの容量保持率が80%より大きいであることがわかる。 From the above examples, it can be seen that the reversible specific capacity of the graphite cathode material produced according to the present invention is greater than 450 mAh / g, and the capacity retention of 200 cycles is greater than 80%.
本発明のリチウムイオン電池の珪素・炭素複合陰極材料は、携帯電話、ノードパソコン、ビデオカメラなどの携帯式電気器具、工具用のリチウムイオン電池の陰極材料として広範において使用することができる。本発明は、各種類の電気使用領域に適用し、電池の比容量を著しく引き上げ、電気用電源の軽量化という要求を満足させることができる。
Claims (25)
(1)珪素形粒子を0.1〜1μmまで破砕して非常に細かい炭素形粒子を製造し、また、粒度75μmより小さく、炭素含有量95%以上の炭素原料を分別、整形及び純化処理することにより、炭素含有量99.9%以上、粒径0.1〜5μmの炭素形粒子を得る工程、
(2)珪素形粒子と炭素形粒子を混合して、複合粒子基本体を製造する工程、
(3)複合粒子基本体と、複合粒子基本体の1〜25wt%を占める有機物の熱分解グラファイトの前駆物とを混合し、或いは1〜12時間湿式法で攪拌して、その後100〜400℃のもとで気相沈積を行い、或いは被覆して粒子を製造する工程、
(4)被覆後の粒子を炭化処理し、密封雰囲気中において450〜1500℃まで加熱し、1〜10時間温度を維持した後、室温に下げて、炭素被覆層を形成する工程、及び、
(5)前記炭素被覆層を5〜40μmまで破砕することによって、リチウムイオン電池の珪素・炭素複合陰極材料を製造する工程、
ということを特徴とするリチウムイオン電池の珪素・炭素複合陰極材料の製造方法。 The present invention is a method for producing a silicon / carbon composite cathode material for a lithium ion battery, which includes the following steps. That is,
(1) By crushing silicon-shaped particles to 0.1 to 1 μm to produce very fine carbon-shaped particles, and by separating, shaping and purifying carbon raw materials with a particle size of less than 75 μm and a carbon content of 95% or more A step of obtaining carbon-shaped particles having a carbon content of 99.9% or more and a particle size of 0.1 to 5 μm,
(2) A step of producing a composite particle basic body by mixing silicon-type particles and carbon-type particles,
(3) A composite particle base and an organic pyrolytic graphite precursor occupying 1 to 25 wt% of the composite particle base are mixed or stirred by a wet method for 1 to 12 hours, and then 100 to 400 ° C. Vapor phase deposition or coating to produce particles under
(4) carbonizing the coated particles, heating to 450-1500 ° C. in a sealed atmosphere, maintaining the temperature for 1-10 hours, and then lowering to room temperature to form a carbon coating layer; and
(5) A step of producing a silicon / carbon composite cathode material for a lithium ion battery by crushing the carbon coating layer to 5 to 40 μm.
A method for producing a silicon / carbon composite cathode material for a lithium ion battery.
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