JP6683107B2 - Silicon material manufacturing method - Google Patents
Silicon material manufacturing method Download PDFInfo
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- JP6683107B2 JP6683107B2 JP2016221058A JP2016221058A JP6683107B2 JP 6683107 B2 JP6683107 B2 JP 6683107B2 JP 2016221058 A JP2016221058 A JP 2016221058A JP 2016221058 A JP2016221058 A JP 2016221058A JP 6683107 B2 JP6683107 B2 JP 6683107B2
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- Japan
- Prior art keywords
- silicon material
- halogen
- carbon
- space
- containing polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002210 silicon-based material Substances 0.000 title claims description 160
- 238000004519 manufacturing process Methods 0.000 title claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 109
- 229910052799 carbon Inorganic materials 0.000 claims description 104
- 238000010438 heat treatment Methods 0.000 claims description 79
- 229910052736 halogen Inorganic materials 0.000 claims description 72
- 150000002367 halogens Chemical class 0.000 claims description 70
- 229910004706 CaSi2 Inorganic materials 0.000 claims description 56
- 229920000642 polymer Polymers 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 34
- 239000000919 ceramic Substances 0.000 claims description 28
- 238000000354 decomposition reaction Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000001257 hydrogen Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005192 partition Methods 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000002904 solvent Substances 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 24
- 229910001416 lithium ion Inorganic materials 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 239000000126 substance Substances 0.000 description 23
- 229910052710 silicon Inorganic materials 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 239000010703 silicon Substances 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- -1 calcium halide Chemical class 0.000 description 20
- 239000002245 particle Substances 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 239000007773 negative electrode material Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000011149 active material Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 229920000915 polyvinyl chloride Polymers 0.000 description 15
- 239000004800 polyvinyl chloride Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 8
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- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 7
- 150000003377 silicon compounds Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000003738 black carbon Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000003981 vehicle Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
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- 239000002253 acid Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- 239000012298 atmosphere Substances 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
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- 229910052731 fluorine Inorganic materials 0.000 description 4
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- 239000012535 impurity Substances 0.000 description 4
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- 238000005580 one pot reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
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- 239000011347 resin Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
Description
本発明は、シリコン材料の製造方法に関するものである。 The present invention relates to a method for manufacturing a silicon material.
シリコン材料は半導体、太陽電池、二次電池などの構成要素として用いられることが知られており、それゆえに、シリコン材料に関する研究が活発に行われている。 It is known that a silicon material is used as a constituent element of a semiconductor, a solar cell, a secondary battery, etc. Therefore, research on the silicon material is actively conducted.
例えば、特許文献１には、熱ＣＶＤにより酸化珪素を炭素で被覆したシリコン複合体が記載されており、当該シリコン複合体を負極活物質として具備するリチウムイオン二次電池が記載されている。 For example, Patent Document 1 describes a silicon composite in which silicon oxide is coated with carbon by thermal CVD, and describes a lithium ion secondary battery including the silicon composite as a negative electrode active material.
また、本発明者らは、特許文献２にて、ＣａＳｉ２と酸とを反応させてＣａを除去したポリシランを主成分とする層状シリコン化合物を合成し、当該層状シリコン化合物を３００℃以上で加熱して水素を離脱させたシリコン材料を製造したこと、及び、当該シリコン材料を活物質として具備するリチウムイオン二次電池を報告している。 In addition, the inventors of the present invention synthesize a layered silicon compound containing Ca as a main component, which is obtained by reacting CaSi 2 with an acid in Patent Document 2, and heat the layered silicon compound at 300 ° C. or higher. It has been reported that a hydrogen-desorbed silicon material was produced and a lithium-ion secondary battery equipped with the silicon material as an active material.
さらに、本発明者らは、特許文献３にて、ＣａＳｉ２と酸とを反応させてＣａを除去したポリシランを主成分とする層状シリコン化合物を合成し、当該層状シリコン化合物を３００℃以上で加熱して水素を離脱させたシリコン材料を製造し、さらに、当該シリコン材料を炭素で被覆した炭素−シリコン複合体を製造したこと、及び、当該複合体を活物質として具備するリチウムイオン二次電池を報告している。 Further, the inventors of the present invention synthesize a layered silicon compound containing Ca as a main component, which is obtained by reacting CaSi 2 with an acid in Patent Document 3, and heat the layered silicon compound at 300 ° C. or higher. To produce a hydrogen-desorbed silicon material, and further to produce a carbon-silicon composite in which the silicon material is coated with carbon, and a lithium ion secondary battery comprising the composite as an active material. Reporting.
そして、本発明者らは、特許文献４にて、ＣａＳｉ２と含ハロゲンポリマーを用いた炭素被覆シリコン材料のｏｎｅ−ｐｏｔ合成方法を報告している。 Then, the present inventors have reported in Patent Document 4 a one-pot synthesis method of a carbon-coated silicon material using CaSi 2 and a halogen-containing polymer.
特許文献４で具体的に開示されたＣａＳｉ２と含ハロゲンポリマーを用いた炭素被覆シリコン材料のｏｎｅ−ｐｏｔ合成方法は、ＣａＳｉ２と含ハロゲンポリマーを接触状態として反応を進行させる方法（実施例１）と、ＣａＳｉ２と含ハロゲンポリマーを非接触状態として反応を進行させる方法（実施例２）であった。そして、特許文献４の評価例３で評価しているとおり、ＣａＳｉ２と含ハロゲンポリマーを非接触状態として反応を進行させる方法は、局所的な発熱を抑制できるため、反応をコントロールしやすいといえる。 The one-pot synthesis method of a carbon-coated silicon material using CaSi 2 and a halogen-containing polymer specifically disclosed in Patent Document 4 is a method of advancing the reaction by bringing CaSi 2 and the halogen-containing polymer into contact with each other (Example 1 ) And CaSi 2 and the halogen-containing polymer in a non-contact state to proceed the reaction (Example 2). Then, as evaluated in Evaluation Example 3 of Patent Document 4, the method of advancing the reaction with CaSi 2 and the halogen-containing polymer in a non-contact state can suppress local heat generation, and thus can be said to be easy to control the reaction. .
本発明者が、ＣａＳｉ２と含ハロゲンポリマーを非接触状態として反応を進行させる方法についての検討を進めたところ、収率の点で改善の余地があることを知見した。 The present inventor has conducted a study on a method of advancing the reaction with CaSi 2 and a halogen-containing polymer in a non-contact state, and has found that there is room for improvement in terms of yield.
本発明は、かかる事情に鑑みて為されたものであり、優れた収率でシリコン材料を製造できる製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and an object thereof is to provide a manufacturing method capable of manufacturing a silicon material with an excellent yield.
本発明者は、特許文献４の製造方法について熟慮した。ＣａＳｉ２と含ハロゲンポリマーを用いた炭素被覆シリコン材料のｏｎｅ−ｐｏｔ合成方法においては、初めに、含ハロゲンポリマーが加熱により分解されて、分解ガスを発生し、当該分解ガスとＣａＳｉ２とが接触することで、反応が開始される。ここで、特許文献４の実施例２で開示された方法においては、含ハロゲンポリマーの分解によって生じる分解ガスの流路が定まっていないため、分解ガスとＣａＳｉ２との接触が必ずしも十分ではなかったと考えられる。そこで、本発明者は、含ハロゲンポリマーの分解によって生じる分解ガスの流路上に、ＣａＳｉ２を配置することを指向した。 The present inventor has carefully considered the manufacturing method of Patent Document 4. In the one-pot synthesis method of a carbon-coated silicon material using CaSi 2 and a halogen-containing polymer, first, the halogen-containing polymer is decomposed by heating to generate a decomposed gas, and the decomposed gas and CaSi 2 are brought into contact with each other. By doing so, the reaction is started. Here, in the method disclosed in Example 2 of Patent Document 4, since the flow path of the decomposition gas generated by the decomposition of the halogen-containing polymer is not fixed, the contact between the decomposition gas and CaSi 2 was not always sufficient. Conceivable. Therefore, the inventor of the present invention directed to disposing CaSi 2 on the flow path of the decomposition gas generated by the decomposition of the halogen-containing polymer.
また、特許文献４で具体的に開示されたのは、ＣａＳｉ２と含ハロゲンポリマーを用いた炭素被覆シリコン材料のｏｎｅ−ｐｏｔ合成方法であったが、加熱温度を適切に管理することで、炭素被覆シリコン材料と、炭素被覆されていないシリコン材料とを作り分けることができることを本発明者は実証した。そして、本発明者は本発明を完成させた。 Further, what was specifically disclosed in Patent Document 4 was a one-pot synthesis method of a carbon-coated silicon material using CaSi 2 and a halogen-containing polymer, but by appropriately controlling the heating temperature, carbon The present inventor has demonstrated that a coated silicon material and a carbon material not coated with carbon can be produced separately. Then, the present inventor has completed the present invention.
すなわち、本発明のシリコン材料の製造方法は、
ＣａＳｉ２及び含ハロゲンポリマーの共存下、前記含ハロゲンポリマーの分解ガス発生温度以上かつ炭化温度未満の温度で加熱する第一加熱工程を含み、
前記含ハロゲンポリマーを配置する第一空間と、前記ＣａＳｉ２を配置する第二空間と、前記第一空間と前記第二空間とを区画し、前記分解ガスが通過可能な貫通孔を具備するセラミックス部と、を備え、かつ、前記第一空間の前記含ハロゲンポリマーから発生する分解ガスの流路に、前記第二空間が設けられている加熱炉を用いることを特徴とする。
That is, the manufacturing method of the silicon material of the present invention,
In the coexistence of CaSi 2 and a halogen-containing polymer, a first heating step of heating at a temperature above the decomposition gas generation temperature of the halogen-containing polymer and below the carbonization temperature is included.
Ceramics having a first space for arranging the halogen-containing polymer, a second space for arranging the CaSi 2 , and a through hole that partitions the first space and the second space and through which the decomposition gas can pass. And a heating furnace in which the second space is provided in the flow path of the decomposition gas generated from the halogen-containing polymer in the first space.
本発明のシリコン材料の製造方法においては、特定の加熱炉を用いることで、シリコン材料の収率が向上する。 In the method for producing a silicon material of the present invention, the yield of the silicon material is improved by using the specific heating furnace.
以下に、本発明を実施するための最良の形態を説明する。なお、特に断らない限り、本明細書に記載された数値範囲「ｘ〜ｙ」は、下限ｘおよび上限ｙをその範囲に含む。そして、これらの上限値および下限値、ならびに実施例中に列記した数値も含めてそれらを任意に組み合わせることで新たな数値範囲を構成し得る。更に、上記の何れかの数値範囲内から任意に選択した数値を新たな数値範囲の上限、下限の数値とすることができる。 The best mode for carrying out the present invention will be described below. In addition, unless otherwise specified, the numerical range “x to y” described in the present specification includes the lower limit x and the upper limit y in the range. A new numerical range can be constructed by arbitrarily combining these upper limit values and lower limit values and the numerical values listed in the examples. Further, numerical values arbitrarily selected from the above numerical range can be set as upper and lower numerical values of the new numerical range.
本発明のシリコン材料の製造方法（以下、本発明のシリコン材料の製造方法で製造されるシリコン材料を「本発明のシリコン材料」ということがある。）は、ＣａＳｉ２及び含ハロゲンポリマーの共存下、前記含ハロゲンポリマーの分解ガス発生温度以上かつ炭化温度未満の温度で加熱する第一加熱工程を含み、前記含ハロゲンポリマーを配置する第一空間と、前記ＣａＳｉ２を配置する第二空間と、前記第一空間と前記第二空間とを区画し、前記分解ガスが通過可能な貫通孔を具備するセラミックス部と、を備え、かつ、前記第一空間の前記含ハロゲンポリマーから発生する分解ガスの流路に、前記第二空間が設けられている加熱炉を用いることを特徴とする。 The method for producing a silicon material of the present invention (hereinafter, the silicon material produced by the method for producing a silicon material of the present invention may be referred to as “silicon material of the present invention”) is in the presence of CaSi 2 and a halogen-containing polymer. A first space in which the halogen-containing polymer is arranged, and a second space in which the CaSi 2 is arranged, including a first heating step of heating at a temperature not lower than a decomposition gas generation temperature of the halogen-containing polymer and lower than a carbonization temperature. A ceramic part that divides the first space and the second space and has a through hole through which the decomposition gas can pass, and a decomposition gas generated from the halogen-containing polymer in the first space. A heating furnace in which the second space is provided is used for the flow path.
含ハロゲンポリマーとしてポリ塩化ビニルを採用した場合の第一加熱工程の反応機構を以下に説明する。 The reaction mechanism of the first heating step when polyvinyl chloride is used as the halogen-containing polymer will be described below.
加熱により、まず、ポリ塩化ビニルが分解し、塩化水素を放出する。
−(ＣＨ２ＣＨＣｌ)ｎ− → ｎＨＣｌ ＋ −(ＣＨ＝ＣＨ)ｎ−
By heating, first, polyvinyl chloride is decomposed and hydrogen chloride is released.
- (CH 2 CHCl) n- → nHCl + - (CH = CH) n-
次に、ＣａＳｉ２が上記放出された塩化水素と作用し、Ｓｉ６Ｈ６で表される層状シリコン化合物となる。
３ＣａＳｉ２ ＋ ６ＨＣｌ → Ｓｉ６Ｈ６ ＋ ３ＣａＣｌ２
Next, CaSi 2 acts on the released hydrogen chloride to form a layered silicon compound represented by Si 6 H 6 .
3CaSi 2 + 6HCl → Si 6 H 6 + 3CaCl 2
そして、加熱条件下であるので、Ｓｉ６Ｈ６の水素が離脱して、シリコンが得られる。
Ｓｉ６Ｈ６ → ６Ｓｉ ＋ ３Ｈ２↑
Then, since it is under heating conditions, hydrogen of Si 6 H 6 is released and silicon is obtained.
Si 6 H 6 → 6Si + 3H 2 ↑
また、本発明のシリコン材料の製造方法における第一加熱工程の後に、含ハロゲンポリマーの炭化温度以上の温度で加熱する第二加熱工程を行うことで、炭素被覆シリコン材料を製造することができる。
すなわち、本発明の炭素被覆シリコン材料の製造方法（以下、特別な限定を付す場合を除いて、本発明の炭素被覆シリコン材料の製造方法で製造される炭素被覆シリコン材料を「本発明の炭素被覆シリコン材料」ということがある。）は、本発明のシリコン材料の製造方法における第一加熱工程の後に、前記含ハロゲンポリマーの炭化温度以上の温度で加熱する第二加熱工程を含むことを特徴とする。以下、本発明のシリコン材料の製造方法と、本発明の炭素被覆シリコン材料の製造方法とを総合して、「本発明の製造方法」ということがある。
第一加熱工程の反応機構に引き続く、第二加熱工程の反応機構は以下のとおりである。
Further, the carbon-coated silicon material can be manufactured by performing the second heating step of heating at a temperature equal to or higher than the carbonization temperature of the halogen-containing polymer after the first heating step in the method for manufacturing a silicon material of the present invention.
That is, the method for producing a carbon-coated silicon material of the present invention (hereinafter, unless otherwise specified, the carbon-coated silicon material produced by the method for producing a carbon-coated silicon material of the present invention is referred to as "carbon-coated silicon material of the present invention". "May be referred to as" silicon material ".) Includes a second heating step of heating at a temperature equal to or higher than the carbonization temperature of the halogen-containing polymer after the first heating step in the method for producing a silicon material of the present invention. To do. Hereinafter, the production method of the silicon material of the present invention and the production method of the carbon-coated silicon material of the present invention may be collectively referred to as the “production method of the present invention”.
The reaction mechanism of the second heating step following the reaction mechanism of the first heating step is as follows.
ポリ塩化ビニルの分解物である（ＣＨ＝ＣＨ）ｎはその炭化温度以上の加熱条件において炭化する。その際にシリコンと（ＣＨ＝ＣＨ）ｎの炭化物が共存するため、シリコンと炭素が一体化した炭素被覆シリコン材料が得られる。
Ｓｉ ＋ （ＣＨ＝ＣＨ）ｎ → 炭素被覆Ｓｉ ＋ ｎＨ２↑
(CH = CH) n, which is a decomposition product of polyvinyl chloride, is carbonized under heating conditions above its carbonization temperature. At that time, since silicon and carbide of (CH = CH) n coexist, a carbon-coated silicon material in which silicon and carbon are integrated can be obtained.
Si + (CH = CH) n → carbon coating Si + nH 2 ↑
以下、詳細に本発明の製造方法について説明する。
ＣａＳｉ２は、一般にＣａ層とＳｉ層が積層した構造である。ＣａＳｉ２は、公知の製造方法で合成してもよく、市販されているものを採用してもよい。本発明の製造方法に用いるＣａＳｉ２は、あらかじめ粉砕しておくことが好ましい。好ましいＣａＳｉ２の平均粒子径として、０．１〜５０μｍの範囲内を例示でき、より好ましくは０．３〜２０μｍの範囲内、さらに好ましくは０．５〜１０μｍの範囲内、特に好ましくは１〜５μｍの範囲内を例示できる。なお、本明細書における平均粒子径とは、一般的なレーザー回折式粒度分布測定装置で測定した場合のＤ５０を意味する。
Hereinafter, the manufacturing method of the present invention will be described in detail.
CaSi 2 generally has a structure in which a Ca layer and a Si layer are laminated. CaSi 2 may be synthesized by a known production method, or may be commercially available. CaSi 2 used in the production method of the present invention is preferably pulverized in advance. The preferable average particle diameter of CaSi 2 is, for example, in the range of 0.1 to 50 μm, more preferably in the range of 0.3 to 20 μm, further preferably in the range of 0.5 to 10 μm, and particularly preferably 1 to An example is within the range of 5 μm. In addition, the average particle diameter in this specification means D50 when measured by a general laser diffraction type particle size distribution measuring device.
ＣａＳｉ２をあらかじめ粉砕しておくことで、表面積の大きなＣａＳｉ２に対して、第一加熱工程及び必要に応じて第二加熱工程を行うことができるので、所望の反応が円滑に進行することを期待できる。また、本発明の製造方法においては、ＣａＳｉ２の形状を概ね保持した状態で本発明のシリコン材料又は炭素被覆シリコン材料が製造されるので、本発明のシリコン材料自体又は炭素被覆シリコン材料自体を粉砕する必要が無くなる。さらに、ＣａＳｉ２をあらかじめ粉砕しておくことで、本発明のシリコン材料又は炭素被覆シリコン材料の粒子のアスペクト比は大きくなる。ここで、アスペクト比とは、本発明のシリコン材料又は炭素被覆シリコン材料の粒子を観察した際の、短径／長径の値である。長径とは、本発明のシリコン材料又は炭素被覆シリコン材料の粒子の最長径を意味し、短径とは、最長径に直交する径のうち、最も長い径を意味する。なお、本発明のシリコン材料又は炭素被覆シリコン材料は、後述するように、複数枚の板状シリコン体が厚さ方向に積層されてなる構造を有するため、塊状の本発明のシリコン材料又は炭素被覆シリコン材料を粉砕すると、積層構造における層の結合部が破壊されて、アスペクト比の小さな偏平状態の粒子が製造される。 By crushing CaSi 2 in advance, it is possible to perform the first heating step and, if necessary, the second heating step on CaSi 2 having a large surface area, so that the desired reaction proceeds smoothly. Can be expected. Further, in the production method of the present invention, the silicon material or the carbon-coated silicon material of the present invention is produced in a state in which the shape of CaSi 2 is generally maintained, and therefore the silicon material of the present invention or the carbon-coated silicon material itself is crushed. There is no need to do it. Further, by crushing CaSi 2 in advance, the aspect ratio of the particles of the silicon material or carbon-coated silicon material of the present invention becomes large. Here, the aspect ratio is a value of minor axis / major axis when particles of the silicon material or carbon-coated silicon material of the present invention are observed. The long diameter means the longest diameter of the particles of the silicon material or the carbon-coated silicon material of the present invention, and the short diameter means the longest diameter of the diameters orthogonal to the longest diameter. The silicon material or carbon-coated silicon material of the present invention has a structure in which a plurality of plate-shaped silicon bodies are stacked in the thickness direction, as described later, and therefore, the silicon material or carbon-coated silicon material of the present invention in a lump form. When the silicon material is crushed, the bonded portions of the layers in the laminated structure are broken, and flat particles having a small aspect ratio are produced.
本発明のシリコン材料又は炭素被覆シリコン材料の粒子におけるアスペクト比ｒは、０．８≦ｒ≦１が好ましい。アスペクト比が１に近づくほど、本発明のシリコン材料又は炭素被覆シリコン材料の流動性などの粉体特性が改善するので、製造工程における本発明のシリコン材料又は炭素被覆シリコン材料の取り扱いが簡便になるし、また、本発明のシリコン材料又は炭素被覆シリコン材料を蓄電装置の負極活物質として用いた時に、好適な充放電を期待できる。 The aspect ratio r in the particles of the silicon material or carbon-coated silicon material of the present invention is preferably 0.8 ≦ r ≦ 1. As the aspect ratio approaches 1, the powder characteristics such as the fluidity of the silicon material or the carbon-coated silicon material of the present invention are improved, so that the handling of the silicon material or the carbon-coated silicon material of the present invention in the manufacturing process becomes easier. In addition, when the silicon material or carbon-coated silicon material of the present invention is used as a negative electrode active material of a power storage device, suitable charge / discharge can be expected.
含ハロゲンポリマーは、ハロゲンを化学構造に含むポリマーであればよい。その理由は、次のとおりである。本発明のシリコン材料の製造方法の加熱条件下であれば、含ハロゲンポリマーからは、ハロゲン化水素酸及び／又はハロゲン分子が離脱する。そして、ハロゲン化水素酸又はハロゲン分子を構成するマイナスチャージされたハロゲンが、ＣａＳｉ２のＣａと反応する。すなわち、含ハロゲンポリマーであれば、マイナスチャージされたハロゲンの供給源となり、所望の反応が進行する。なお、ＣａＳｉ２がハロゲン化水素酸と反応した場合にはＳｉ６Ｈ６とハロゲン化カルシウムが生成し、ＣａＳｉ２がハロゲン分子と反応した場合にはハロゲン化シリコンとハロゲン化カルシウムが生成すると考えられる。 The halogen-containing polymer may be a polymer containing halogen in its chemical structure. The reason is as follows. Under the heating condition of the method for producing a silicon material of the present invention, hydrohalic acid and / or halogen molecules are released from the halogen-containing polymer. Then, the hydrohalic acid or the negatively charged halogen constituting the halogen molecule reacts with Ca of CaSi 2 . That is, if it is a halogen-containing polymer, it becomes a source of negatively charged halogen, and the desired reaction proceeds. It is considered that when CaSi 2 reacts with hydrohalic acid, Si 6 H 6 and calcium halide are produced, and when CaSi 2 reacts with halogen molecules, silicon halide and calcium halide are produced. .
含ハロゲンポリマーとしては、一般式（１）のモノマーユニットを有するものを挙げることができる。
一般式（１）
Examples of the halogen-containing polymer include those having a monomer unit of the general formula (1).
General formula (1)
炭化水素には、飽和炭化水素、不飽和炭化水素がある。飽和炭化水素には、鎖状飽和炭化水素と環状飽和炭化水素がある。不飽和炭化水素には、鎖状不飽和炭化水素と環状不飽和炭化水素がある。 Hydrocarbons include saturated hydrocarbons and unsaturated hydrocarbons. The saturated hydrocarbon includes chain saturated hydrocarbon and cyclic saturated hydrocarbon. The unsaturated hydrocarbons include chain unsaturated hydrocarbons and cyclic unsaturated hydrocarbons.
Ｒ１の化学構造のうち、モノマーユニットの主鎖となる化学構造（重合反応に関与する炭素を含む化学構造）は、鎖状飽和炭化水素、環状飽和炭化水素、鎖状不飽和炭化水素、環状不飽和炭化水素のいずれでもよい。モノマーユニットの主鎖となる化学構造として、具体的にＣＨ、ＣＨ２−ＣＨ、ＣＨ＝ＣＨ、シクロヘキサン環、ベンゼン環などを挙げることができる。 Among the chemical structures of R 1, the chemical structure serving as the main chain of the monomer unit (chemical structure containing carbon involved in the polymerization reaction) is chain saturated hydrocarbon, cyclic saturated hydrocarbon, chain unsaturated hydrocarbon, cyclic Any of unsaturated hydrocarbons may be used. Specific examples of the chemical structure serving as the main chain of the monomer unit include CH, CH 2 —CH, CH═CH, a cyclohexane ring, and a benzene ring.
Ｒ１の化学構造のうち、モノマーユニットの主鎖に結合する化学構造（以下、副鎖ということがある。）は、水素、鎖状飽和炭化水素、環状飽和炭化水素、鎖状不飽和炭化水素、環状不飽和炭化水素のいずれでもよい。また、各炭化水素の水素は、他の元素や他の炭化水素で置換されていても良い。 Among the chemical structures of R 1, the chemical structure bonded to the main chain of the monomer unit (hereinafter sometimes referred to as a sub-chain) is hydrogen, chain saturated hydrocarbon, cyclic saturated hydrocarbon, chain unsaturated hydrocarbon. Any of cyclic unsaturated hydrocarbons may be used. Further, the hydrogen of each hydrocarbon may be replaced with another element or another hydrocarbon.
Ｘはフッ素、塩素、臭素、ヨウ素のいずれかである。ｎが２以上の場合、各Ｘは同一の種類でもよいし、他の種類でもよい。Ｘはモノマーユニットの主鎖となる炭素に直接結合していてもよいし、副鎖の炭素に結合していてもよい。ｎの上限数はＲ１の化学構造により定まる。 X is any one of fluorine, chlorine, bromine and iodine. When n is 2 or more, each X may be of the same type or of another type. X may be directly bonded to the carbon as the main chain of the monomer unit or may be bonded to the carbon of the sub chain. The upper limit number of n is determined by the chemical structure of R 1 .
含ハロゲンポリマーは、単一の種類の一般式（１）のモノマーユニットのみで構成されるものであってもよいし、複数の種類の一般式（１）のモノマーユニットで構成されるものであってもよい。また、含ハロゲンポリマーは、一般式（１）のモノマーユニットと、他の化学構造のモノマーユニットとで構成されていてもよい。 The halogen-containing polymer may be composed of only a single type of the monomer unit of the general formula (1) or may be composed of a plurality of types of the monomer unit of the general formula (1). May be. Further, the halogen-containing polymer may be composed of the monomer unit represented by the general formula (1) and a monomer unit having another chemical structure.
ここで、ハロゲンの質量％が多い含ハロゲンポリマーを採用すれば、より効率的に所望の反応が進行すると考えられるため、含ハロゲンポリマーは一般式（１）のモノマーユニットのみで構成されるのが好ましい。 Here, if a halogen-containing polymer containing a large amount of halogen in mass% is adopted, it is considered that the desired reaction proceeds more efficiently. Therefore, the halogen-containing polymer is composed of only the monomer unit of the general formula (1). preferable.
含ハロゲンポリマーの分子量は、数平均分子量で１０００〜１００万の範囲内が好ましく、１０００〜５０万の範囲内がより好ましく、３０００〜１０万の範囲内がさらに好ましい。含ハロゲンポリマーを重合度で表現すると、５〜１０万の範囲内が好ましく、１０〜５万の範囲内がより好ましく、１００〜１万の範囲内がさらに好ましい。 The number average molecular weight of the halogen-containing polymer is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 1,000 to 500,000, and even more preferably in the range of 3,000 to 100,000. When the halogen-containing polymer is expressed by the degree of polymerization, it is preferably within the range of 50,000 to 100,000, more preferably within the range of 100 to 50,000, and even more preferably within the range of 100 to 10,000.
一般式（１）のモノマーユニットのうち、好適なものを以下の一般式（２）で示す。
一般式（２）
Among the monomer units of the general formula (1), suitable ones are represented by the following general formula (2).
General formula (2)
炭化水素及びハロゲンについての説明は、上述のとおりである。一般式（２）において好ましい炭化水素として、炭素数１〜６のアルキル基、ビニル基、フェニル基を挙げることができる。 The description about the hydrocarbon and the halogen is as described above. Preferred hydrocarbons in the general formula (2) include alkyl groups having 1 to 6 carbon atoms, vinyl groups and phenyl groups.
上述のとおり、含ハロゲンポリマーはハロゲンの質量％が多いものが好ましいと考えられるため、一般式（２）のモノマーユニットのＲ２、Ｒ３、Ｒ４はそれぞれ独立に水素又はハロゲンが好ましい。 As described above, it is considered preferable that the halogen-containing polymer has a large amount of halogen by mass%. Therefore, R 2 , R 3 and R 4 of the monomer unit of the general formula (2) are preferably hydrogen or halogen independently.
特に好適な含ハロゲンポリマーとしては、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリ塩化ビニリデン、ポリ塩化ビニルを挙げることができる。 Particularly suitable halogen-containing polymers include polyvinylidene fluoride, polyvinyl fluoride, polyvinylidene chloride and polyvinyl chloride.
ＣａＳｉ２及び含ハロゲンポリマーの使用量は、使用するＣａＳｉ２のＣａに対し、ハロゲンのモル比が２以上となる量の含ハロゲンポリマーを使用することが好ましい。 As for the usage amounts of CaSi 2 and the halogen-containing polymer, it is preferable to use the halogen-containing polymer in such an amount that the molar ratio of halogen is 2 or more with respect to Ca of CaSi 2 .
本発明のシリコン材料の製造方法における第一加熱工程の加熱温度は、含ハロゲンポリマーの分解ガス発生温度以上かつ炭化温度未満の温度である。ここで、例えば、含ハロゲンポリマーの一態様であるポリ塩化ビニルは、１００℃付近から脱塩化水素反応を開始する場合があることや、通常の条件下であれば、概ね２１０〜３００℃で脱塩化水素反応を開始することが知られており、また、一般に有機化合物は４００℃付近から炭化する。よって、第一加熱工程の加熱温度としては、１００〜４００℃の範囲を例示でき、そして、２１０〜３８０℃の範囲が好ましく、２３０〜３６０℃の範囲がより好ましく、２５０〜３５０℃の範囲がさらに好ましいといえる。 The heating temperature in the first heating step in the method for producing a silicon material of the present invention is a temperature not lower than the decomposition gas generation temperature of the halogen-containing polymer and lower than the carbonization temperature. Here, for example, polyvinyl chloride, which is one embodiment of a halogen-containing polymer, may start a dehydrochlorination reaction from around 100 ° C, and under normal conditions, dehydrochlorination is generally performed at 210 to 300 ° C. It is known to initiate the hydrogen chloride reaction, and generally, organic compounds carbonize at around 400 ° C. Therefore, as the heating temperature of the first heating step, a range of 100 to 400 ° C can be exemplified, and a range of 210 to 380 ° C is preferable, a range of 230 to 360 ° C is more preferable, and a range of 250 to 350 ° C is preferable. It is even more preferable.
本発明の炭素被覆シリコン材料の製造方法における第二加熱工程の加熱温度は、含ハロゲンポリマーの炭化温度以上の温度である。上述したように、一般に有機化合物は４００℃付近から炭化する。ここで、第二加熱工程の加熱温度が高ければ高いほど、導電性の高い炭化物の被膜が得られる。他方、第二加熱工程の加熱温度が高すぎると、炭化ケイ素などの副生物の発生が懸念される。また、原料のＣａＳｉ２におけるＳｉ層に由来すると考えられるシリコン材料の構造は、シリコン材料を蓄電装置の負極活物質として用いた時に、非常に有利となると考えられる。そして、シリコンの融点は１４１４℃である。以上の観点から、第二加熱工程の加熱温度としては、４００〜１４００℃の範囲内が好ましく、５００〜１１００℃の範囲内がより好ましく、６００〜１０００℃の範囲内がさらに好ましく、７００〜９５０℃の範囲内が特に好ましく、８００〜９００℃の範囲内が最も好ましい。 The heating temperature in the second heating step in the method for producing a carbon-coated silicon material of the present invention is a temperature equal to or higher than the carbonization temperature of the halogen-containing polymer. As described above, organic compounds generally carbonize at around 400 ° C. Here, the higher the heating temperature in the second heating step, the higher the conductivity of the carbide coating film obtained. On the other hand, if the heating temperature in the second heating step is too high, there is a concern that by-products such as silicon carbide will be generated. Further, the structure of the silicon material, which is considered to be derived from the Si layer in the raw material CaSi 2, is considered to be very advantageous when the silicon material is used as the negative electrode active material of the power storage device. The melting point of silicon is 1414 ° C. From the above viewpoints, the heating temperature in the second heating step is preferably in the range of 400 to 1400 ° C, more preferably in the range of 500 to 1100 ° C, further preferably in the range of 600 to 1000 ° C, and 700 to 950. The range of 0 ° C is particularly preferable, and the range of 800 to 900 ° C is most preferable.
第一加熱工程及び第二加熱工程の加熱温度により、シリコン材料又は炭素被覆シリコン材料に含まれるアモルファスシリコン及びシリコン結晶子の割合、並びに、シリコン結晶子の大きさを調製することもでき、さらには、製造されるシリコン材料又は炭素被覆シリコン材料に含まれる、アモルファスシリコン及びシリコン結晶子を含むナノ水準の厚みの層の形状や大きさを調製することもできる。 By the heating temperature of the first heating step and the second heating step, the proportion of amorphous silicon and silicon crystallite contained in the silicon material or the carbon-coated silicon material, and the size of the silicon crystallite can be adjusted, and further It is also possible to adjust the shape and size of a nano-level layer containing amorphous silicon and silicon crystallites, which is contained in the produced silicon material or carbon-coated silicon material.
上記シリコン結晶子のサイズは、０．５ｎｍ〜３００ｎｍの範囲内が好ましく、１ｎｍ〜１００ｎｍの範囲内がより好ましく、１ｎｍ〜５０ｎｍの範囲内がさらに好ましく、１ｎｍ〜１０ｎｍの範囲内が特に好ましい。なお、シリコン結晶子のサイズは、シリコン材料又は炭素被覆シリコン材料に対してＸ線回折測定（ＸＲＤ測定）を行い、得られたＸＲＤチャートのＳｉ（１１１）面の回折ピークの半値幅を用いたシェラーの式から算出される。 The size of the silicon crystallites is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, still more preferably in the range of 1 nm to 50 nm, and particularly preferably in the range of 1 nm to 10 nm. As the size of the silicon crystallite, an X-ray diffraction measurement (XRD measurement) was performed on the silicon material or the carbon-coated silicon material, and the half width of the diffraction peak of the Si (111) plane of the obtained XRD chart was used. Calculated from Scherrer's formula.
本発明の製造方法により、複数枚の板状シリコン体が厚さ方向に積層されてなる構造を有するシリコン材料又は炭素被覆シリコン材料を得ることができる。この構造は、走査型電子顕微鏡などによる観察で確認できる。本発明のシリコン材料又は炭素被覆シリコン材料を、リチウムイオン二次電池の活物質として使用することを考慮すると、リチウムイオンの効率的な挿入及び脱離反応のためには、板状シリコン体は厚さが１０ｎｍ〜１００ｎｍの範囲内のものが好ましく、２０ｎｍ〜５０ｎｍの範囲内のものがより好ましい。また、板状シリコン体の長手方向の長さは、０．１μｍ〜５０μｍの範囲内のものが好ましい。また、板状シリコン体は、（長手方向の長さ）／（厚さ）が２〜１０００の範囲内であるのが好ましい。 By the manufacturing method of the present invention, a silicon material or a carbon-coated silicon material having a structure in which a plurality of plate-shaped silicon bodies are laminated in the thickness direction can be obtained. This structure can be confirmed by observation with a scanning electron microscope or the like. Considering that the silicon material or carbon-coated silicon material of the present invention is used as an active material of a lithium ion secondary battery, the plate-shaped silicon body has a large thickness for efficient insertion and desorption reaction of lithium ions. Is preferably in the range of 10 nm to 100 nm, more preferably in the range of 20 nm to 50 nm. The length of the plate-shaped silicon body in the longitudinal direction is preferably within the range of 0.1 μm to 50 μm. Further, the plate-like silicon body preferably has a ratio of (length in the longitudinal direction) / (thickness) of 2 to 1000.
本発明の製造方法は、アルゴン、ヘリウム、窒素ガスなどの不活性ガス雰囲気下で行うのが好ましい。 The production method of the present invention is preferably performed in an atmosphere of an inert gas such as argon, helium or nitrogen gas.
次に、加熱炉について説明する。加熱炉は、含ハロゲンポリマーを配置する第一空間と、ＣａＳｉ２を配置する第二空間と、第一空間と第二空間とを区画し、前記分解ガスが通過可能な貫通孔を具備するセラミックス部と、を備え、かつ、第一空間の含ハロゲンポリマーから発生する分解ガスの流路に、第二空間が設けられている。加熱炉のこの構造に因り、含ハロゲンポリマーから発生する分解ガスが、無駄なく、ＣａＳｉ２に接触できるため、所望の反応が好適に進行する。 Next, the heating furnace will be described. The heating furnace divides the first space in which the halogen-containing polymer is arranged, the second space in which CaSi 2 is arranged, the first space and the second space, and has a through hole through which the decomposition gas can pass. And a second space is provided in the flow path of the decomposition gas generated from the halogen-containing polymer in the first space. Due to this structure of the heating furnace, the decomposition gas generated from the halogen-containing polymer can contact CaSi 2 without waste, so that the desired reaction suitably proceeds.
具体的な加熱炉としては、高周波誘導加熱炉、電気炉、アーク炉、ガス炉を例示できる。 Specific examples of the heating furnace include a high frequency induction heating furnace, an electric furnace, an arc furnace, and a gas furnace.
加熱炉における第一空間及び第二空間は、加熱炉内部にセラミックス部を配置して形成してもよい。また、第一空間を備える第一室と、第二空間を備える第二室と、セラミックス部とを備えた反応室を加熱炉内に設置してもよい。 The first space and the second space in the heating furnace may be formed by arranging a ceramic portion inside the heating furnace. Moreover, you may install the 1st chamber provided with the 1st space, the 2nd chamber provided with the 2nd space, and the reaction chamber provided with the ceramic part in a heating furnace.
反応室の材料としては、モリブデン、タングステン、タンタル若しくはニオブ等の高融点金属、又は、アルミナ、ジルコニア、窒化珪素、窒化アルミニウム、炭化珪素、コージライト、ムライト、ステアタイト、カルシア、マグネシア、サイアロン、石英、バイコール等のセラミックスがよい。 As a material for the reaction chamber, a refractory metal such as molybdenum, tungsten, tantalum or niobium, or alumina, zirconia, silicon nitride, aluminum nitride, silicon carbide, cordierite, mullite, steatite, calcia, magnesia, sialon, quartz. Ceramics such as Vycor are preferable.
反応室は、密閉可能であってもよいし、通気部が設けられていてもよく、また、内部圧に応じて開閉する弁を具備していてもよい。第一加熱工程及び第二加熱工程を実施する際には、反応室における第一空間は、セラミックス部以外の通気部や開閉弁が存在しない構造となるのが好ましい。他方、反応室における第二空間は、セラミックス部以外の通気部や開閉弁が存在する構造が好ましい。 The reaction chamber may be hermetically sealed, may be provided with a vent, and may be equipped with a valve that opens and closes according to the internal pressure. When the first heating step and the second heating step are performed, it is preferable that the first space in the reaction chamber has a structure in which there are no vents or on-off valves other than the ceramics part. On the other hand, the second space in the reaction chamber preferably has a structure in which a ventilation part other than the ceramic part and an on-off valve are present.
セラミックス部は、第一空間と第二空間とを区画することで、含ハロゲンポリマーとＣａＳｉ２との直接接触を抑制し、かつ、具備する貫通孔が、第一空間の含ハロゲンポリマーから発生する分解ガスの通路となり、分解ガスを第二空間に案内する。セラミックス部の開気孔率としては、３０〜８０％の範囲内、３５〜７５％の範囲内を例示できる。なお、開気孔率は、ＪＩＳ Ｒ １６３４、ＪＩＳ Ｒ ２２０５、ＪＩＳ Ａ １５０９−３などで規定する方法で測定できる。 The ceramic part divides the first space and the second space to suppress direct contact between the halogen-containing polymer and CaSi 2 , and the through holes provided therein are generated from the halogen-containing polymer in the first space. It becomes a passage for the decomposition gas and guides the decomposition gas to the second space. The open porosity of the ceramic portion can be exemplified within the range of 30 to 80% and within the range of 35 to 75%. The open porosity can be measured by a method specified in JIS R 1634, JIS R 2205, JIS A 1509-3 or the like.
セラミックス部の材料としては、アルミナ、ジルコニア、窒化珪素、窒化アルミニウム、炭化珪素、コージライト、ムライト、ステアタイト、カルシア、マグネシア、サイアロン、石英、バイコールを例示できる。 Examples of the material of the ceramic part include alumina, zirconia, silicon nitride, aluminum nitride, silicon carbide, cordierite, mullite, steatite, calcia, magnesia, sialon, quartz and Vycor.
第一空間、第二空間及びセラミックス部の配置は、下部に第一空間、上部に第二空間、そして、第一空間と第二空間の仕切りとして、セラミックス部が配置されるのが好ましい。この配置であれば、第一空間で発生した分解ガスが上昇するのに伴い、自然にセラミックス部の貫通孔を通過して、第二空間に到達し、第二空間のＣａＳｉ２と接触することができる。なお、当然ではあるが、この配置であれば、貫通孔の孔径は、ＣａＳｉ２の粒子径よりも小さい方が好ましい。 As for the arrangement of the first space, the second space, and the ceramics portion, it is preferable that the first space is arranged in the lower part, the second space is arranged in the upper part, and the ceramics part is arranged as a partition between the first space and the second space. With this arrangement, as the decomposed gas generated in the first space rises, it naturally passes through the through holes of the ceramic part, reaches the second space, and contacts CaSi 2 in the second space. You can In addition, as a matter of course, in this arrangement, the hole diameter of the through hole is preferably smaller than the particle diameter of CaSi 2 .
本発明の製造方法により得られたシリコン材料又は炭素被覆シリコン材料は、粉砕や分級を経て、一定の粒度分布の粒子としてもよい。一般的なレーザー回折式粒度分布測定装置で測定した場合における、シリコン材料又は炭素被覆シリコン材料の好ましい粒度分布としては、平均粒子径（Ｄ５０）が１〜３０μｍの範囲内であることを例示でき、より好ましくは平均粒子径（Ｄ５０）が１〜１０μｍの範囲内であることを例示できる。 The silicon material or carbon-coated silicon material obtained by the manufacturing method of the present invention may be pulverized or classified to form particles having a certain particle size distribution. As a preferred particle size distribution of the silicon material or the carbon-coated silicon material when measured with a general laser diffraction particle size distribution measuring device, it can be exemplified that the average particle diameter (D50) is in the range of 1 to 30 μm, More preferably, it can be illustrated that the average particle diameter (D50) is in the range of 1 to 10 μm.
本発明の製造方法により得られたシリコン材料又は炭素被覆シリコン材料は、比誘電率５以上の溶媒で洗浄する洗浄工程に供されるのが好ましい。洗浄工程は、シリコン材料又は炭素被覆シリコン材料に付着している不要な成分を、比誘電率５以上の溶媒（以下、「洗浄溶媒」ということがある。）で洗浄することにより除去する工程である。同工程は、主に、ハロゲン化カルシウムなどの洗浄溶媒に溶解し得る塩を除去することを目的としている。例えば、含ハロゲンポリマーとしてポリ塩化ビニルを用いた場合、シリコン材料又は炭素被覆シリコン材料には、ＣａＣｌ２が残存していると推定される。そこで、洗浄溶媒でシリコン材料又は炭素被覆シリコン材料を洗浄することにより、ＣａＣｌ２を含む不要な成分を洗浄溶媒に溶解させて除去できる。洗浄工程は、洗浄溶媒中にシリコン材料又は炭素被覆シリコン材料を浸漬させる方法でもよいし、シリコン材料又は炭素被覆シリコン材料に対して洗浄溶媒を浴びせる方法でもよい。 The silicon material or carbon-coated silicon material obtained by the manufacturing method of the present invention is preferably subjected to a cleaning step of cleaning with a solvent having a relative dielectric constant of 5 or more. The cleaning step is a step of removing unnecessary components adhering to the silicon material or the carbon-coated silicon material by cleaning with a solvent having a relative dielectric constant of 5 or more (hereinafter, also referred to as “cleaning solvent”). is there. This step is mainly intended to remove salts that can be dissolved in a washing solvent such as calcium halide. For example, when polyvinyl chloride is used as the halogen-containing polymer, it is estimated that CaCl 2 remains in the silicon material or the carbon-coated silicon material. Therefore, by cleaning the silicon material or the carbon-coated silicon material with a cleaning solvent, unnecessary components including CaCl 2 can be dissolved and removed in the cleaning solvent. The cleaning step may be a method of immersing the silicon material or the carbon-coated silicon material in the cleaning solvent, or a method of exposing the silicon material or the carbon-coated silicon material to the cleaning solvent.
洗浄溶媒としては、塩の溶解しやすさの点から、比誘電率がより高いものが好ましく、比誘電率が１０以上や１５以上の溶媒をより好ましいものとして提示できる。洗浄溶媒の比誘電率の範囲としては、５〜９０の範囲内が好ましく、１０〜９０の範囲内がより好ましく、１５〜９０の範囲内がさらに好ましい。また、洗浄溶媒としては、単独の溶媒を用いても良いし、複数の溶媒の混合溶媒を用いても良い。 As the washing solvent, a solvent having a higher relative dielectric constant is preferable, and a solvent having a relative permittivity of 10 or more or 15 or more can be presented as a more preferable solvent from the viewpoint of easily dissolving the salt. The range of the relative permittivity of the washing solvent is preferably in the range of 5 to 90, more preferably in the range of 10 to 90, still more preferably in the range of 15 to 90. Moreover, as the washing solvent, a single solvent may be used, or a mixed solvent of a plurality of solvents may be used.
洗浄溶媒の具体例としては、水、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、エチレングリコール、グリセリン、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、アセトニトリル、エチレンカーボネート、プロピレンカーボネート、ベンジルアルコール、フェノール、ピリジン、テトラヒドロフラン、アセトン、酢酸エチル、ジクロロメタンを挙げることができる。これらの具体的な溶媒の化学構造のうち一部又は全部の水素がフッ素に置換したものを洗浄溶媒として採用しても良い。洗浄溶媒としての水は、蒸留水、逆浸透膜透過水、脱イオン水のいずれかが好ましい。 Specific examples of the washing solvent include water, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, ethylene glycol, glycerin, N-methyl-2-pyrrolidone. , N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, ethylene carbonate, propylene carbonate, benzyl alcohol, phenol, pyridine, tetrahydrofuran, acetone, ethyl acetate, dichloromethane. Of these specific chemical structures of the solvent, some or all of the hydrogen may be replaced with fluorine, and the cleaning solvent may be adopted. The water as a washing solvent is preferably distilled water, reverse osmosis membrane permeation water, or deionized water.
参考までに、各種の溶媒の比誘電率を表１に示す。 For reference, Table 1 shows the relative dielectric constants of various solvents.
洗浄溶媒としては、水、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、アセトンが特に好ましい。 As the washing solvent, water, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol and acetone are particularly preferable.
洗浄溶媒として複数の溶媒の混合溶媒を用いる場合には、水１００容量部に対し、その他の溶媒を好ましくは１〜１００容量部、より好ましくは２〜５０容量部、さらに好ましくは５〜３０容量部の割合で混合した混合溶媒を採用するとよい。洗浄溶媒として混合溶媒を用いることで、シリコン材料又は炭素被覆シリコン材料の洗浄溶媒に対する分散性や親和性が向上する場合があり、その結果、不要成分が洗浄溶媒に好適に溶出する。 When a mixed solvent of a plurality of solvents is used as the washing solvent, the other solvent is preferably 1 to 100 parts by volume, more preferably 2 to 50 parts by volume, further preferably 5 to 30 parts by volume with respect to 100 parts by volume of water. It is advisable to employ a mixed solvent mixed in a ratio of parts. By using the mixed solvent as the cleaning solvent, the dispersibility or affinity of the silicon material or the carbon-coated silicon material with respect to the cleaning solvent may be improved, and as a result, unnecessary components are preferably eluted in the cleaning solvent.
洗浄工程の後には、濾過及び乾燥にてシリコン材料又は炭素被覆シリコン材料から洗浄溶媒を除去することが好ましい。 After the washing step, it is preferable to remove the washing solvent from the silicon material or the carbon-coated silicon material by filtration and drying.
洗浄工程は複数回繰り返してもよい。その際には、洗浄溶媒を変更しても良い。例えば、初回の洗浄工程の洗浄溶媒として比誘電率の著しく高い水を選択し、次回の洗浄溶媒として水と相溶し、かつ沸点の低いエタノールやアセトンを用いることによって、水を効率的に除去できるとともに、容易に洗浄溶媒の残存を防ぐことができる。 The washing step may be repeated multiple times. In that case, the washing solvent may be changed. For example, by selecting water with a significantly high relative permittivity as the cleaning solvent in the first cleaning step, and using ethanol or acetone that is compatible with water and has a low boiling point as the next cleaning solvent, water can be efficiently removed. At the same time, the washing solvent can be easily prevented from remaining.
洗浄工程の後の乾燥工程は減圧環境下で行うことが好ましく、洗浄溶媒の沸点以上の温度で行うことが更に好ましい。温度としては８０℃〜１１０℃が好ましい。 The drying step after the washing step is preferably performed in a reduced pressure environment, and more preferably at a temperature equal to or higher than the boiling point of the washing solvent. The temperature is preferably 80 ° C to 110 ° C.
本発明のシリコン材料又は炭素被覆シリコン材料は、上述のとおり、本発明の製造方法を経て製造される。ここで、本発明の製造方法で得られたシリコン材料又は炭素被覆シリコン材料に対して、上述した第二加熱工程とは別工程として、炭素で被覆する炭素被覆工程を行ってもよい。また、後述するように、炭素被覆工程の前に、第二加熱工程後の炭素被覆シリコン材料の少なくとも一部の炭素を除去する炭素除去工程を行ってもよい。 The silicon material or carbon-coated silicon material of the present invention is manufactured by the manufacturing method of the present invention as described above. Here, the silicon coating or carbon-coated silicon material obtained by the manufacturing method of the present invention may be subjected to a carbon coating step of coating with carbon as a step different from the second heating step described above. Further, as described later, a carbon removing step of removing at least a part of carbon of the carbon-coated silicon material after the second heating step may be performed before the carbon coating step.
炭素被覆工程としては、従来の公知技術を適用すればよい。例えば、材料を非酸化性雰囲気下にて有機物ガスと接触させて加熱し、有機物ガスを炭素化する、いわゆる熱ＣＶＤ法を適用すればよい。 As the carbon coating step, a conventionally known technique may be applied. For example, a so-called thermal CVD method in which a material is brought into contact with an organic gas to be heated in a non-oxidizing atmosphere to carbonize the organic gas may be applied.
有機物ガスとしては、有機物が気化したガス、有機物が昇華したガスあるいは有機物の蒸気を用いることができる。また有機物ガスを発生する有機物としては、非酸化性雰囲気下での加熱によって熱分解して炭化し得るものが用いられ、例えば、メタン、エタン、プロパン、ブタン、イソブタン、ペンタン、ヘキサンなどの飽和脂肪族炭化水素、エチレン、プロピレン、アセチレンなどの不飽和脂肪族炭化水素、メタノール、エタノール、プロパノール、ブタノールなどのアルコール類、ベンゼン、トルエン、キシレン、スチレン、エチルベンゼン、ジフェニルメタン、ナフタレン、フェノール、クレゾール、安息香酸、サリチル酸、ニトロベンゼン、クロルベンゼン、インデン、クマロン、ピリジン、アントラセン、フェナントレンなどの芳香族炭化水素、酢酸エチル、酢酸ブチル、酢酸アミルなどのエステル類、脂肪酸類などから選択される一種又は混合物が挙げられる。有機物としては、プロパン等の飽和脂肪族炭化水素が好ましい。 As the organic substance gas, a gas in which the organic substance is vaporized, a gas in which the organic substance is sublimated, or a vapor of the organic substance can be used. As the organic substance that generates an organic gas, one that can be thermally decomposed and carbonized by heating in a non-oxidizing atmosphere is used, for example, saturated fats such as methane, ethane, propane, butane, isobutane, pentane, and hexane. Group hydrocarbons, unsaturated aliphatic hydrocarbons such as ethylene, propylene and acetylene, alcohols such as methanol, ethanol, propanol and butanol, benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, benzoic acid , One or a mixture selected from aromatic hydrocarbons such as salicylic acid, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, anthracene, and phenanthrene; esters such as ethyl acetate, butyl acetate and amyl acetate; and fatty acids. Thing, and the like. As the organic substance, saturated aliphatic hydrocarbon such as propane is preferable.
炭素被覆工程における処理温度は、有機物の種類によって異なるが、有機物ガスが熱分解する温度より５０℃以上高い温度とするのがよい。しかし、温度が高すぎる場合や有機物ガス濃度が高すぎる場合は、いわゆるススが発生するので、ススが発生しない条件を選択するのがよい。形成される炭素層の厚さは、有機物の量と処理時間によって制御することができる。 The treatment temperature in the carbon coating step varies depending on the type of the organic substance, but it is preferably a temperature higher than the temperature at which the organic substance gas is thermally decomposed by 50 ° C. or more. However, if the temperature is too high or the organic gas concentration is too high, so-called soot is generated, so it is preferable to select a condition in which soot is not generated. The thickness of the formed carbon layer can be controlled by the amount of organic substances and the treatment time.
炭素被覆工程は、材料を流動状態にして行うことが望ましい。このようにすることで、材料の全表面を有機物ガスと接触させることができ、均一な炭素層を形成することができる。材料を流動状態にするには、流動床を用いるなど各種方法があるが、材料を撹拌しながら有機物ガスと接触させるのが好ましい。例えば、内部に邪魔板をもつ回転炉を用いれば、邪魔板に留まった材料が回転炉の回転に伴って所定高さから落下することで撹拌され、その際に有機物ガスと接触して炭素層が形成されるので、全体に均一な炭素層を形成することができる。第一加熱工程及び第二加熱工程についても同様に、可能であれば、材料を流動状態にして実施するのが望ましい。 The carbon coating step is preferably performed with the material in a fluid state. By doing so, the entire surface of the material can be brought into contact with the organic substance gas, and a uniform carbon layer can be formed. There are various methods for bringing the material into a fluid state, such as using a fluidized bed, but it is preferable to bring the material into contact with an organic gas while stirring. For example, if a rotary furnace with a baffle inside is used, the material remaining on the baffle drops from a predetermined height as the rotary furnace rotates and is agitated. Thus, a uniform carbon layer can be formed over the entire surface. Similarly for the first heating step and the second heating step, it is desirable to carry out the material in a fluidized state if possible.
第二加熱工程及び炭素被覆工程を行って得られた本発明の炭素被覆シリコン材料は、２種類の方法で炭素被覆を為された状態となる。このような本発明の炭素被覆シリコン材料は、１種類の炭素被覆方法では不十分であった被覆状態を他の炭素被覆方法で補完された状態となる。そのため、かかる本発明の炭素被覆シリコン材料を負極活物質として具備する二次電池は、電池特性が好適化すると考えられる。 The carbon-coated silicon material of the present invention obtained by performing the second heating step and the carbon coating step is in a state where carbon coating is performed by two kinds of methods. Such a carbon-coated silicon material of the present invention becomes a state in which the coating state which was insufficient by one type of carbon coating method is complemented by another carbon coating method. Therefore, it is considered that the secondary battery including such a carbon-coated silicon material of the present invention as the negative electrode active material has favorable battery characteristics.
炭素除去工程としては、酸素存在下で第二加熱工程後の炭素被覆シリコン材料を加熱して、炭素を二酸化炭素又は一酸化炭素として除去すればよい。炭素除去工程においては、炭素被覆シリコン材料の一部又は全部の炭素を除去することができる。加熱温度としては、３５０〜６５０℃を例示できる。 In the carbon removal step, the carbon-coated silicon material after the second heating step may be heated in the presence of oxygen to remove carbon as carbon dioxide or carbon monoxide. In the carbon removal step, part or all of the carbon in the carbon-coated silicon material can be removed. The heating temperature may be 350 to 650 ° C.
炭素除去工程においては、炭素被覆シリコン材料中に含まれていた不純物も同時に除去されることが期待できる。そのため、炭素除去工程を経た後に、炭素被覆工程に供されて製造された本発明の炭素被覆シリコン材料は、より好適な材料であると推察される。 In the carbon removal step, it can be expected that impurities contained in the carbon-coated silicon material will be removed at the same time. Therefore, it is surmised that the carbon-coated silicon material of the present invention produced by being subjected to the carbon coating step after the carbon removal step is a more preferable material.
本発明の炭素被覆シリコン材料は、炭素と珪素を必須の構成要素とする。本発明の炭素被覆シリコン材料を１００とした場合に、炭素は１〜３０質量％の範囲内で含まれるのが好ましく、３〜２０質量％の範囲内で含まれるのがより好ましく、５〜１５質量％の範囲内で含まれるのがさらに好ましい。本発明の炭素被覆シリコン材料を１００とした場合に、珪素は５０〜９９質量％の範囲内で含まれるのが好ましく、６０〜９７質量％の範囲内で含まれるのがより好ましく、６５〜９５質量％の範囲内で含まれるのがさらに好ましい。 The carbon-coated silicon material of the present invention contains carbon and silicon as essential components. When the carbon-coated silicon material of the present invention is set to 100, carbon is preferably contained in the range of 1 to 30% by mass, more preferably 3 to 20% by mass, and 5 to 15% by mass. More preferably, it is contained within the range of mass%. When the carbon-coated silicon material of the present invention is set to 100, silicon is preferably contained in the range of 50 to 99% by mass, more preferably 60 to 97% by mass, and more preferably 65 to 95. More preferably, it is contained within the range of mass%.
本発明のシリコン材料又は炭素被覆シリコン材料は、Ｃａやハロゲンなどの原料由来の不純物や、不可避の不純物を含有する場合がある。そのような不純物の存在量（質量％）として、以下の範囲を例示できる。
Ｃａ：０〜５質量％、０〜３質量％、０〜２質量％、０．１〜３質量％、０．５〜２質量％
ハロゲン：０〜１０質量％、０．００１〜６質量％
The silicon material or carbon-coated silicon material of the present invention may contain impurities derived from raw materials such as Ca and halogen, and inevitable impurities. The following range can be illustrated as the amount of such impurities (mass%).
Ca: 0-5% by mass, 0-3% by mass, 0-2% by mass, 0.1-3% by mass, 0.5-2% by mass
Halogen: 0-10% by mass, 0.001-6% by mass
本発明のシリコン材料又は炭素被覆シリコン材料は、内部に空洞を有するものが好ましい。本発明のシリコン材料又は炭素被覆シリコン材料をリチウムイオン二次電池の活物質として用いた場合、当該空洞は、リチウムイオンの挿入及び脱離反応が生じる際の、シリコン材料又は炭素被覆シリコン材料の膨張及び収縮を緩衝する役割を果たすと推定される。 The silicon material or carbon-coated silicon material of the present invention preferably has a cavity inside. When the silicon material or the carbon-coated silicon material of the present invention is used as an active material of a lithium ion secondary battery, the cavity has an expansion of the silicon material or the carbon-coated silicon material when insertion and desorption reactions of lithium ions occur. And is believed to play a role in buffering contractions.
本発明の製造方法で得られるシリコン材料又は炭素被覆シリコン材料は、リチウムイオン二次電池などの二次電池の負極活物質として使用することができる。以下、二次電池の代表としてリチウムイオン二次電池を例にして説明する。本発明のリチウムイオン二次電池は、本発明のシリコン材料又は炭素被覆シリコン材料を負極活物質として具備する。具体的には、本発明のリチウムイオン二次電池は、正極、本発明のシリコン材料又は炭素被覆シリコン材料を負極活物質として具備する負極、電解液及びセパレータを具備する。 The silicon material or carbon-coated silicon material obtained by the manufacturing method of the present invention can be used as a negative electrode active material of a secondary battery such as a lithium ion secondary battery. Hereinafter, a lithium-ion secondary battery will be described as an example of a typical secondary battery. The lithium ion secondary battery of the present invention comprises the silicon material or carbon-coated silicon material of the present invention as a negative electrode active material. Specifically, the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode including the silicon material or the carbon-coated silicon material of the present invention as a negative electrode active material, an electrolytic solution, and a separator.
正極は、集電体と、集電体の表面に結着させた正極活物質層を有する。 The positive electrode has a current collector and a positive electrode active material layer bonded to the surface of the current collector.
集電体は、リチウムイオン二次電池の放電又は充電の間、電極に電流を流し続けるための化学的に不活性な電子伝導体をいう。集電体としては、銀、銅、金、アルミニウム、タングステン、コバルト、亜鉛、ニッケル、鉄、白金、錫、インジウム、チタン、ルテニウム、タンタル、クロム、モリブデンから選ばれる少なくとも一種、並びにステンレス鋼などの金属材料を例示することができる。集電体は公知の保護層で被覆されていても良い。集電体の表面を公知の方法で処理したものを集電体として用いても良い。 The current collector refers to a chemically inactive electron conductor for keeping current flowing through the electrodes during discharging or charging of the lithium ion secondary battery. As the current collector, at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, stainless steel, etc. A metal material can be illustrated. The current collector may be covered with a known protective layer. You may use what collected the surface of the collector by a well-known method as a collector.
集電体は箔、シート、フィルム、線状、棒状、メッシュなどの形態をとることができる。そのため、集電体として、例えば、銅箔、ニッケル箔、アルミニウム箔、ステンレス箔などの金属箔を好適に用いることができる。集電体が箔、シート、フィルム形態の場合は、その厚みが１μｍ〜１００μｍの範囲内であることが好ましい。 The current collector can be in the form of foil, sheet, film, wire, rod, mesh or the like. Therefore, as the current collector, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, or a stainless steel foil can be preferably used. When the current collector is in the form of foil, sheet or film, the thickness thereof is preferably in the range of 1 μm to 100 μm.
正極活物質層は正極活物質、並びに必要に応じて導電助剤及び／又は結着剤を含む。 The positive electrode active material layer contains a positive electrode active material and, if necessary, a conductive auxiliary agent and / or a binder.
正極活物質としては、層状化合物のＬｉａＮｉｂＣｏｃＭｎｄＤｅＯｆ(０．２≦ａ≦２、ｂ＋ｃ＋ｄ＋ｅ＝１、０≦ｅ＜１、ＤはＬｉ、Ｆｅ、Ｃｒ、Ｃｕ、Ｚｎ、Ｃａ、Ｍｇ、Ｓ、Ｓｉ、Ｎａ、Ｋ、Ａｌ、Ｚｒ、Ｔｉ、Ｐ、Ｇａ、Ｇｅ、Ｖ、Ｍｏ、Ｎｂ、Ｗ、Ｌａから選ばれる少なくとも１の元素、１．７≦ｆ≦３)、Ｌｉ２ＭｎＯ３を挙げることができる。また、正極活物質として、ＬｉＭｎ２Ｏ４等のスピネル、及びスピネルと層状化合物の混合物で構成される固溶体、ＬｉＭＰＯ４、ＬｉＭＶＯ４又はＬｉ２ＭＳｉＯ４（式中のＭはＣｏ、Ｎｉ、Ｍｎ、Ｆｅのうちの少なくとも一種から選択される）などで表されるポリアニオン系化合物を挙げることができる。さらに、正極活物質として、ＬｉＦｅＰＯ４ＦなどのＬｉＭＰＯ４Ｆ（Ｍは遷移金属）で表されるタボライト系化合物、ＬｉＦｅＢＯ３などのＬｉＭＢＯ３（Ｍは遷移金属）で表されるボレート系化合物を挙げることができる。正極活物質として用いられるいずれの金属酸化物も上記の各組成式を基本組成とすればよく、基本組成に含まれる金属元素を他の金属元素で置換したものも正極活物質として使用可能である。また、正極活物質として、充放電に寄与するリチウムイオンを含まない正極活物質材料、たとえば、硫黄単体（Ｓ）、硫黄と炭素を複合化した化合物、ＴｉＳ２などの金属硫化物、Ｖ２Ｏ５、ＭｎＯ２などの酸化物、ポリアニリン及びアントラキノン並びにこれら芳香族を化学構造に含む化合物、共役二酢酸系有機物などの共役系材料、その他公知の材料を用いることもできる。さらに、ニトロキシド、ニトロニルニトロキシド、ガルビノキシル、フェノキシルなどの安定なラジカルを有する化合物を正極活物質として採用してもよい。リチウムを含まない正極活物質材料を用いる場合には、正極及び／又は負極に、公知の方法により、予めイオンを添加させておく必要がある。ここで、当該イオンを添加するためには、金属または当該イオンを含む化合物を用いればよい。 As the positive electrode active material, a layered compound Li a Ni b Co c Mn d D e O f (0.2 ≦ a ≦ 2, b + c + d + e = 1,0 ≦ e <1, D is Li, Fe, Cr, Cu, At least one element selected from Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, and La, and 1.7 ≦ f ≦ 3. ) And Li 2 MnO 3 can be mentioned. Further, as a positive electrode active material, a solid solution composed of spinel such as LiMn 2 O 4 and a mixture of spinel and a layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (M in the formula is Co, Ni, Mn, And a polyanionic compound represented by the formula (1) selected from at least one of Fe). Furthermore, as the positive electrode active material, tavorite compound (the M a transition metal) LiMPO 4 F, such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal) include borate-based compound represented by be able to. Any metal oxide used as the positive electrode active material may have each of the above composition formulas as a basic composition, and a metal element contained in the basic composition replaced with another metal element can also be used as the positive electrode active material. . In addition, as the positive electrode active material, a positive electrode active material material that does not contain lithium ions that contribute to charge and discharge, for example, sulfur simple substance (S), a compound of sulfur and carbon, a metal sulfide such as TiS 2 , V 2 O 5 , oxides such as MnO 2 , polyaniline and anthraquinone, compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetic acid organic compounds, and other known materials can also be used. Further, a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, or phenoxyl may be adopted as the positive electrode active material. When using a positive electrode active material containing no lithium, it is necessary to add ions to the positive electrode and / or the negative electrode in advance by a known method. Here, in order to add the ion, a metal or a compound containing the ion may be used.
導電助剤は、電極の導電性を高めるために添加される。そのため、導電助剤は、電極の導電性が不足する場合に任意に加えればよく、電極の導電性が十分に優れている場合には加えなくても良い。導電助剤としては化学的に不活性な電子高伝導体であれば良く、炭素質微粒子であるカーボンブラック、黒鉛、気相法炭素繊維（Vapor Grown Carbon Fiber）、及び各種金属粒子等が例示される。カーボンブラックとしては、アセチレンブラック、ケッチェンブラック（登録商標）、ファーネスブラック、チャンネルブラック等が例示される。これらの導電助剤を単独または二種以上組み合わせて活物質層に添加することができる。 The conduction aid is added to enhance the conductivity of the electrode. Therefore, the conductive additive may be optionally added when the conductivity of the electrode is insufficient, and may not be added when the conductivity of the electrode is sufficiently excellent. The electrically conductive auxiliary may be a chemically inert electronic high conductor, and carbon black which is carbonaceous fine particles, graphite, vapor grown carbon fiber (Vapor Grown Carbon Fiber), and various metal particles are exemplified. It Examples of carbon black include acetylene black, Ketjen black (registered trademark), furnace black, channel black and the like. These conductive aids can be added to the active material layer either individually or in combination of two or more.
活物質層中の導電助剤の配合割合は、質量比で、活物質：導電助剤＝１：０．００５〜１：０．５であるのが好ましく、１：０．０１〜１：０．２であるのがより好ましく、１：０．０３〜１：０．１であるのがさらに好ましい。導電助剤が少なすぎると効率のよい導電パスを形成できず、また、導電助剤が多すぎると活物質層の成形性が悪くなるとともに電極のエネルギー密度が低くなるためである。 The mixing ratio of the conductive auxiliary agent in the active material layer is preferably active material: conductive auxiliary agent = 1: 0.005 to 1: 0.5 by mass ratio, and 1: 0.01 to 1: 0. 0.2 is more preferable, and 1: 0.03 to 1: 0.1 is still more preferable. This is because if the amount of the conductive additive is too small, an efficient conductive path cannot be formed, and if the amount of the conductive additive is too large, the moldability of the active material layer deteriorates and the energy density of the electrode decreases.
結着剤は、活物質や導電助剤を集電体の表面に繋ぎ止め、電極中の導電ネットワークを維持する役割を果たすものである。結着剤としては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ素ゴム等の含フッ素樹脂、ポリプロピレン、ポリエチレン等の熱可塑性樹脂、ポリイミド、ポリアミドイミド等のイミド系樹脂、アルコキシシリル基含有樹脂、ポリ（メタ）アクリル酸等のアクリル系樹脂、スチレン−ブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロースを例示することができる。これらの結着剤を単独で又は複数で採用すれば良い。 The binder holds the active material and the conductive auxiliary agent on the surface of the current collector and plays a role of maintaining the conductive network in the electrode. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, fluorine-containing resins such as fluororubber, thermoplastic resins such as polypropylene and polyethylene, polyimide, imide-based resins such as polyamide-imide, alkoxysilyl group-containing resins, and poly ( Examples include acrylic resins such as (meth) acrylic acid, styrene-butadiene rubber (SBR), and carboxymethyl cellulose. These binders may be used alone or in combination.
活物質層中の結着剤の配合割合は、質量比で、活物質：結着剤＝１：０．００１〜１：０．３であるのが好ましく、１：０．００５〜１：０．２であるのがより好ましく、１：０．０１〜１：０．１５であるのがさらに好ましい。結着剤が少なすぎると電極の成形性が低下し、また、結着剤が多すぎると電極のエネルギー密度が低くなるためである。 The compounding ratio of the binder in the active material layer is, by mass ratio, preferably active material: binder = 1: 0.001 to 1: 0.3, and 1: 0.005 to 1: 0. 0.2 is more preferable, and 1: 0.01 to 1: 0.15 is even more preferable. This is because if the amount of the binder is too small, the moldability of the electrode is lowered, and if the amount of the binder is too large, the energy density of the electrode is lowered.
負極は、集電体と、集電体の表面に結着させた負極活物質層を有する。集電体については、正極で説明したものを適宜適切に採用すれば良い。負極活物質層は負極活物質、並びに必要に応じて導電助剤及び／又は結着剤を含む。 The negative electrode has a current collector and a negative electrode active material layer bonded to the surface of the current collector. As the current collector, the one described for the positive electrode may be appropriately adopted. The negative electrode active material layer contains a negative electrode active material and, if necessary, a conductive auxiliary agent and / or a binder.
負極活物質としては、本発明のシリコン材料又は炭素被覆シリコン材料を含むものであればよく、本発明のシリコン材料又は炭素被覆シリコン材料のみを採用してもよいし、本発明のシリコン材料又は炭素被覆シリコン材料と公知の負極活物質を併用してもよい。 As the negative electrode active material, any material containing the silicon material or carbon-coated silicon material of the present invention may be used, only the silicon material or carbon-coated silicon material of the present invention may be adopted, or the silicon material or carbon of the present invention. You may use together a coating silicon material and a well-known negative electrode active material.
負極に用いる導電助剤及び結着剤については、正極で説明したものを同様の配合割合で適宜適切に採用すれば良い。 Regarding the conductive auxiliary agent and the binder used for the negative electrode, those described for the positive electrode may be appropriately adopted in the same mixing ratio.
集電体の表面に活物質層を形成させるには、ロールコート法、ダイコート法、ディップコート法、ドクターブレード法、スプレーコート法、カーテンコート法などの従来から公知の方法を用いて、集電体の表面に活物質を塗布すればよい。具体的には、活物質、溶剤、並びに必要に応じて結着剤及び／又は導電助剤を混合し、スラリーを調製する。上記溶剤としては、Ｎ−メチル−２−ピロリドン、メタノール、メチルイソブチルケトン、水を例示できる。該スラリーを集電体の表面に塗布後、乾燥する。電極密度を高めるべく、乾燥後のものを圧縮しても良い。 To form an active material layer on the surface of the current collector, a conventionally known method such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method or a curtain coating method is used. The active material may be applied to the surface of the body. Specifically, an active material, a solvent, and, if necessary, a binder and / or a conductive auxiliary agent are mixed to prepare a slurry. Examples of the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water. The slurry is applied to the surface of the current collector and then dried. The dried product may be compressed to increase the electrode density.
電解液は、非水溶媒と非水溶媒に溶解した電解質とを含んでいる。 The electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
非水溶媒としては、環状エステル類、鎖状エステル類、エーテル類等が使用できる。環状エステル類としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、フッ素化エチレンカーボネート、ガンマブチロラクトン、ビニレンカーボネート、２−メチル−ガンマブチロラクトン、アセチル−ガンマブチロラクトン、ガンマバレロラクトンを例示できる。鎖状エステル類としては、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジプロピルカーボネート、エチルメチルカーボネート、プロピオン酸アルキルエステル、マロン酸ジアルキルエステル、酢酸アルキルエステル等を例示できる。エーテル類としては、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，４−ジオキサン、１，２−ジメトキシエタン、１，２−ジエトキシエタン、１，２−ジブトキシエタンを例示できる。非水溶媒としては、上記具体的な溶媒の化学構造のうち一部又は全部の水素がフッ素に置換した化合物を採用しても良い。 As the non-aqueous solvent, cyclic esters, chain esters, ethers and the like can be used. Examples of cyclic esters include ethylene carbonate, propylene carbonate, butylene carbonate, fluorinated ethylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone. Examples of chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethylmethyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, acetic acid alkyl ester, and the like. Examples of ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane. As the non-aqueous solvent, a compound in which part or all of hydrogen in the chemical structure of the above specific solvent is replaced by fluorine may be adopted.
電解質としては、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２等のリチウム塩を例示できる。 Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
電解液としては、エチレンカーボネート、ジメチルカーボネート、プロピレンカーボネート、ジエチルカーボネートなどの非水溶媒に、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３などのリチウム塩を０．５ｍｏｌ／Ｌから１．７ｍｏｌ／Ｌ程度の濃度で溶解させた溶液を例示できる。 As the electrolytic solution, a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 or the like is added to a non-aqueous solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate or diethyl carbonate from 0.5 mol / L to 1.7 mol. An example is a solution dissolved at a concentration of about / L.
セパレータは、正極と負極とを隔離し、両極の接触による短絡を防止しつつ、リチウムイオンを通過させるものである。セパレータとしては、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ポリイミド、ポリアミド、ポリアラミド（Ａｒｏｍａｔｉｃ ｐｏｌｙａｍｉｄｅ）、ポリエステル、ポリアクリロニトリル等の合成樹脂、セルロース、アミロース等の多糖類、フィブロイン、ケラチン、リグニン、スベリン等の天然高分子、セラミックスなどの電気絶縁性材料を１種若しくは複数用いた多孔体、不織布、織布などを挙げることができる。また、セパレータは多層構造としてもよい。 The separator separates the positive electrode from the negative electrode, prevents short-circuiting due to contact between both electrodes, and allows lithium ions to pass through. As the separator, polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polyamide), polyester, synthetic resin such as polyacrylonitrile, polysaccharides such as cellulose and amylose, fibroin, keratin, lignin, natural substances such as suberin Examples include porous bodies, non-woven fabrics, woven fabrics and the like, which use one or more electrically insulating materials such as polymers and ceramics. Further, the separator may have a multi-layer structure.
次に、リチウムイオン二次電池の製造方法について説明する。 Next, a method for manufacturing a lithium ion secondary battery will be described.
正極および負極に必要に応じてセパレータを挟装させ電極体とする。電極体は、正極、セパレータ及び負極を重ねた積層型、又は、正極、セパレータ及び負極の積層体を捲いた捲回型のいずれの型にしても良い。正極の集電体および負極の集電体から、外部に通ずる正極端子および負極端子までを、集電用リード等を用いて接続した後に、電極体に電解液を加えてリチウムイオン二次電池とするとよい。また、本発明のリチウムイオン二次電池は、電極に含まれる活物質の種類に適した電圧範囲で充放電を実行されればよい。 A separator is sandwiched between the positive electrode and the negative electrode as required to form an electrode body. The electrode body may be a laminated type in which a positive electrode, a separator and a negative electrode are stacked, or a wound type in which a laminated body of a positive electrode, a separator and a negative electrode is wound. After connecting from the current collector of the positive electrode and the current collector of the negative electrode to the positive electrode terminal and the negative electrode terminal that communicate with the outside using a current-collecting lead, etc., an electrolytic solution is added to the electrode body to form a lithium ion secondary battery. Good to do. Further, the lithium-ion secondary battery of the present invention may be charged and discharged in a voltage range suitable for the type of active material contained in the electrode.
本発明のリチウムイオン二次電池の形状は特に限定されるものでなく、円筒型、角型、コイン型、ラミネート型等、種々の形状を採用することができる。 The shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminated shape can be adopted.
本発明のリチウムイオン二次電池は、車両に搭載してもよい。車両は、その動力源の全部あるいは一部にリチウムイオン二次電池による電気エネルギーを使用している車両であればよく、たとえば、電気車両、ハイブリッド車両などであるとよい。車両にリチウムイオン二次電池を搭載する場合には、リチウムイオン二次電池を複数直列に接続して組電池とするとよい。リチウムイオン二次電池を搭載する機器としては、車両以外にも、パーソナルコンピュータ、携帯通信機器など、電池で駆動される各種の家電製品、オフィス機器、産業機器などが挙げられる。さらに、本発明のリチウムイオン二次電池は、風力発電、太陽光発電、水力発電その他電力系統の蓄電装置及び電力平滑化装置、船舶等の動力及び／又は補機類の電力供給源、航空機、宇宙船等の動力及び／又は補機類の電力供給源、電気を動力源に用いない車両の補助用電源、移動式の家庭用ロボットの電源、システムバックアップ用電源、無停電電源装置の電源、電動車両用充電ステーションなどにおいて充電に必要な電力を一時蓄える蓄電装置に用いてもよい。 The lithium ion secondary battery of the present invention may be mounted on a vehicle. The vehicle may be any vehicle that uses electric energy from the lithium-ion secondary battery for all or part of its power source, and may be, for example, an electric vehicle or a hybrid vehicle. When a lithium ion secondary battery is mounted on a vehicle, it is preferable to connect a plurality of lithium ion secondary batteries in series to form an assembled battery. In addition to vehicles, examples of devices equipped with lithium-ion secondary batteries include personal computers, mobile communication devices, and other battery-driven home appliances, office devices, industrial devices, and the like. Furthermore, the lithium-ion secondary battery of the present invention is used for wind power generation, solar power generation, hydroelectric power generation, power storage devices and power smoothing devices for other power systems, power sources for ships and / or power sources for auxiliaries, aircraft, Power supply for spacecraft and / or auxiliary machinery, auxiliary power supply for vehicles that do not use electricity as a power supply, mobile home robot power supply, system backup power supply, uninterruptible power supply power supply, It may be used in a power storage device that temporarily stores electric power required for charging in an electric vehicle charging station or the like.
以上、本発明の実施形態を説明したが、本発明は、上記実施形態に限定されるものではない。本発明の要旨を逸脱しない範囲において、当業者が行い得る変更、改良等を施した種々の形態にて実施することができる。 Although the embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. Without departing from the scope of the present invention, various modifications and improvements can be made by those skilled in the art.
以下に、実施例および比較例などを示し、本発明をより具体的に説明する。なお、本発明は、これらの実施例によって限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to these examples.
（実施例１）
図１のように、反応室１が配置された加熱炉１０を用いて、実施例１の炭素被覆シリコン材料を製造した。反応室１はセラミックス製の匣鉢であり、加熱炉１０は電気炉である。
具体的には、反応室１の底に、１．６ｇのポリ塩化ビニル２（重合度１１００）を配置した。ポリ塩化ビニル２に触れないように、ポリ塩化ビニル２の上部に、貫通孔８を具備し、開気孔率４０％である板状のセラミックス部３を配置した。セラミックス部３上に、１ｇのＣａＳｉ２粉末４を配置した。そして、ＣａＳｉ２粉末４に触れないように、ＣａＳｉ２粉末４の上部に、セラミックス製の蓋５を配置した。なお、反応室１の上端と蓋５の間には隙間が存在する。反応室１において、セラミックス部３の貫通孔８は、第一空間６と第二空間７を連絡する通路となる。
以上のとおり蓋５をした反応室１を、加熱炉１０内に配置した。その結果、加熱炉１０は、含ハロゲンポリマーであるポリ塩化ビニル２を配置する第一空間６と、ＣａＳｉ２粉末４を配置する第二空間７と、第一空間６と第二空間７とを区画し、ポリ塩化ビニル２の分解ガスが通過可能な貫通孔８を具備するセラミックス部３と、を備えることになる。
(Example 1)
As shown in FIG. 1, the carbon-coated silicon material of Example 1 was manufactured using the heating furnace 10 in which the reaction chamber 1 was arranged. The reaction chamber 1 is a ceramic bowl and the heating furnace 10 is an electric furnace.
Specifically, 1.6 g of polyvinyl chloride 2 (degree of polymerization: 1100) was placed on the bottom of the reaction chamber 1. In order not to touch the polyvinyl chloride 2, a plate-shaped ceramic portion 3 having a through hole 8 and an open porosity of 40% was arranged above the polyvinyl chloride 2. 1 g of CaSi 2 powder 4 was placed on the ceramic part 3. Then, not to touch the CaSi 2 powder 4, the top of CaSi 2 powder 4 was placed the lid 5 made of ceramic. A gap exists between the upper end of the reaction chamber 1 and the lid 5. In the reaction chamber 1, the through hole 8 of the ceramic portion 3 serves as a passage that connects the first space 6 and the second space 7.
The reaction chamber 1 with the lid 5 as described above was placed in the heating furnace 10. As a result, the heating furnace 10 has a first space 6 in which the polyvinyl chloride 2 which is a halogen-containing polymer is arranged, a second space 7 in which the CaSi 2 powder 4 is arranged, a first space 6 and a second space 7. And a ceramic portion 3 having a through hole 8 through which the decomposition gas of the polyvinyl chloride 2 can pass.
アルゴン雰囲気下、電気炉を速度５℃／分で９００℃まで昇温し、そして、９００℃のまま１時間維持した。この加熱条件は、第一加熱工程及び第二加熱工程に該当する。反応生成物を水で洗浄した後に、アセトンで洗浄し、次いで減圧乾燥して、黒色の実施例１の炭素被覆シリコン材料を得た。 Under an argon atmosphere, the electric furnace was heated to 900 ° C. at a rate of 5 ° C./min and maintained at 900 ° C. for 1 hour. This heating condition corresponds to the first heating step and the second heating step. The reaction product was washed with water, then with acetone, and then dried under reduced pressure to obtain a black carbon-coated silicon material of Example 1.
（実施例２）
２４ｇのポリ塩化ビニル及び１５ｇのＣａＳｉ２粉末を用いた以外は、実施例１と同様の方法で、黒色の実施例２の炭素被覆シリコン材料を得た。
(Example 2)
A black carbon-coated silicon material of Example 2 was obtained in the same manner as in Example 1, except that 24 g of polyvinyl chloride and 15 g of CaSi 2 powder were used.
（比較例１）
図１の加熱炉１０に替えて、図２の加熱炉２０を用いた以外は、実施例１と同様の方法で、黒色の比較例１の炭素被覆シリコン材料を得た。
具体的には、１ｇのＣａＳｉ２粉末４をアルミナ製の第１坩堝１１に入れ、さらに、第１坩堝１１をこれよりも大きなアルミナ製の第２坩堝１２内に配置した。１．６ｇのポリ塩化ビニル２（重合度１１００）をアルミナ製の第２坩堝１２に入れ、第２坩堝１２に蓋１３をした。蓋１３をした第２坩堝１２を電気炉である加熱炉２０内に配置した。なお、第２坩堝１２と蓋１３の間には隙間が存在する。
以下、実施例１と同様の方法で、黒色の比較例１の炭素被覆シリコン材料を得た。
(Comparative Example 1)
A black carbon-coated silicon material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the heating furnace 20 of FIG. 2 was used instead of the heating furnace 10 of FIG. 1.
Specifically, 1 g of CaSi 2 powder 4 was put in the first crucible 11 made of alumina, and the first crucible 11 was placed in a larger second crucible 12 made of alumina. 1.6 g of polyvinyl chloride 2 (degree of polymerization: 1100) was put into the second crucible 12 made of alumina, and the second crucible 12 was covered with a lid 13. The second crucible 12 with the lid 13 was placed in the heating furnace 20 which was an electric furnace. There is a gap between the second crucible 12 and the lid 13.
Hereinafter, in the same manner as in Example 1, a black carbon-coated silicon material of Comparative Example 1 was obtained.
（比較例２）
２４ｇのポリ塩化ビニル及び１５ｇのＣａＳｉ２粉末を用いた以外は、比較例１と同様の方法で、黒色の比較例２の炭素被覆シリコン材料を得た。
(Comparative example 2)
A black carbon-coated silicon material of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that 24 g of polyvinyl chloride and 15 g of CaSi 2 powder were used.
（評価例１）
実施例１、実施例２、比較例１、比較例２の炭素被覆シリコン材料につき、粉末Ｘ線回折装置にて、Ｘ線回折測定を行った。いずれの炭素被覆シリコン材料のＸ線回折チャートにおいても、Ｓｉに由来するピークが確認でき、また、原料のＣａＳｉ２に由来するピークは著しく小さくなっていた。また、それぞれの炭素被覆シリコン材料につき、蛍光X線分析を実施した。得られたSiの定量結果から、Si換算した収率の結果を表２に示す。
(Evaluation example 1)
The carbon-coated silicon materials of Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were subjected to X-ray diffraction measurement with a powder X-ray diffractometer. In the X-ray diffraction charts of all the carbon-coated silicon materials, the peak derived from Si was confirmed, and the peak derived from CaSi 2 as the raw material was extremely small. In addition, fluorescent X-ray analysis was performed for each carbon-coated silicon material. Table 2 shows the results of Si-converted yields based on the obtained Si quantitative results.
ＣａＳｉ２の仕込み量が１ｇ又は１５ｇのいずれの場合であっても、加熱炉１０を用いた実施例の収率の方が優れている。本発明の製造方法が収率に優れた方法であることが裏付けられた。 Regardless of whether the charged amount of CaSi 2 is 1 g or 15 g, the yield of the example using the heating furnace 10 is superior. It was proved that the production method of the present invention is a method with excellent yield.
（実施例３）
開気孔率４０％の板状のセラミックス部に替えて、開気孔率７１％の板状のセラミックス部を用いた以外は、実施例１と同様の方法で、黒色の実施例３の炭素被覆シリコン材料を得た。
(Example 3)
Black carbon-coated silicon of Example 3 was prepared in the same manner as in Example 1 except that a plate-shaped ceramic portion having an open porosity of 40% was used in place of the plate-shaped ceramic portion having an open porosity of 40%. Got the material.
（比較例３）
開気孔率４０％の板状のセラミックス部に替えて、開気孔率０％の板状のセラミックス部を用いた以外は、実施例１と同様の方法で、比較例３の炭素被覆シリコン材料を得た。
(Comparative Example 3)
The carbon-coated silicon material of Comparative Example 3 was prepared in the same manner as in Example 1 except that a plate-shaped ceramic part having an open porosity of 0% was used in place of the plate-shaped ceramic part having an open porosity of 40%. Obtained.
（評価例２）
実施例１、実施例３、比較例３の炭素被覆シリコン材料につき、粉末Ｘ線回折装置にて、Ｘ線回折測定を行った。実施例１及び実施例３の炭素被覆シリコン材料のＸ線回折チャートにおいては、原料のＣａＳｉ２に由来するピークがほとんど観察されず、Ｓｉに由来するピークが確認されたものの、比較例３の炭素被覆シリコン材料のＸ線回折チャートにおいては、原料のＣａＳｉ２に由来するピークが明確に観察された。この結果から、一定程度の開気孔率のセラミックス部を採用することが好ましいといえる。
(Evaluation example 2)
The carbon-coated silicon materials of Example 1, Example 3 and Comparative Example 3 were subjected to X-ray diffraction measurement with a powder X-ray diffractometer. In the X-ray diffraction charts of the carbon-coated silicon materials of Example 1 and Example 3, almost no peaks derived from the raw material CaSi 2 were observed, and peaks derived from Si were confirmed, but the carbon of Comparative Example 3 was confirmed. In the X-ray diffraction chart of the coated silicon material, a peak derived from the raw material CaSi 2 was clearly observed. From this result, it can be said that it is preferable to adopt a ceramic portion having a certain degree of open porosity.
（実施例４）
ジェットミルを用いて、ＣａＳｉ２を粉砕し、平均粒子径が２．１８μｍのＣａＳｉ２粉末を製造した。２ｇの上記ＣａＳｉ２粉末と３．６ｇのポリ塩化ビニル（重合度１１００）とを、実施例１と同様の方法で反応室に配置した。
アルゴン雰囲気下、電気炉を速度５℃／分で３００℃まで昇温し、そして、３００℃のまま３０分間維持した。この加熱条件は、第一加熱工程に該当する。反応生成物を水で洗浄し、次いで減圧乾燥して、実施例４のシリコン材料を得た。
(Example 4)
CaSi 2 was pulverized using a jet mill to produce CaSi 2 powder having an average particle diameter of 2.18 μm. 2 g of the above CaSi 2 powder and 3.6 g of polyvinyl chloride (polymerization degree 1100) were placed in the reaction chamber in the same manner as in Example 1.
Under an argon atmosphere, the electric furnace was heated to 300 ° C. at a rate of 5 ° C./minute and maintained at 300 ° C. for 30 minutes. This heating condition corresponds to the first heating step. The reaction product was washed with water and then dried under reduced pressure to obtain the silicon material of Example 4.
負極活物質として実施例４のシリコン材料４５質量部、負極活物質として天然黒鉛４０質量部、導電助剤としてアセチレンブラック５質量部、バインダーとしてポリアミドイミド１０質量部、溶剤としてＮ−メチル−２−ピロリドンを混合し、スラリーを調製した。上記スラリーを、集電体としての厚さ約２０μｍの電解銅箔の表面にドクターブレードを用いて塗布し、乾燥して、銅箔上に負極活物質層を形成した。その後、ロールプレス機により、集電体と負極活物質層を強固に密着接合させた。これを２００℃で２時間真空乾燥して、実施例４の負極を製造した。 45 parts by mass of the silicon material of Example 4 as a negative electrode active material, 40 parts by mass of natural graphite as a negative electrode active material, 5 parts by mass of acetylene black as a conductive additive, 10 parts by mass of polyamideimide as a binder, and N-methyl-2- as a solvent. Pyrrolidone was mixed to prepare a slurry. The slurry was applied onto the surface of an electrolytic copper foil having a thickness of about 20 μm as a current collector using a doctor blade and dried to form a negative electrode active material layer on the copper foil. Then, the current collector and the negative electrode active material layer were firmly adhered and joined by a roll press. This was vacuum dried at 200 ° C. for 2 hours to manufacture the negative electrode of Example 4.
（比較例４）
ジェットミルでの粉砕を行っていないＣａＳｉ２を用いて、以下のとおり、比較例４のシリコン材料及び負極を製造した。
氷浴中の濃塩酸に、アルゴン雰囲気下、ＣａＳｉ２を加えて撹拌した。反応液からの発泡が完了したのを確認した後に反応液を室温まで昇温し、得られた反応液を濾過し、残渣を蒸留水で洗浄した後、エタノールで洗浄し、真空乾燥して層状シリコン化合物を得た。層状シリコン化合物をアルゴンガス雰囲気下にて速度５℃／分で９００℃まで昇温加熱し、９００℃で１時間保持する熱処理を行い、シリコン材料を得た。ジェットミルを用いて、シリコン材料を粉砕し、平均粒子径が３μｍである比較例４のシリコン材料を製造した。
実施例４のシリコン材料に替えて、比較例４のシリコン材料を用いた以外は、実施例４と同様の方法で、比較例４の負極を製造した。
(Comparative example 4)
The silicon material and the negative electrode of Comparative Example 4 were manufactured as follows using CaSi 2 which was not crushed by the jet mill.
CaSi 2 was added to concentrated hydrochloric acid in an ice bath under an argon atmosphere and stirred. After confirming that the foaming from the reaction solution was completed, the reaction solution was heated to room temperature, the obtained reaction solution was filtered, the residue was washed with distilled water, then with ethanol, and vacuum dried to form a layered layer. A silicon compound was obtained. The layered silicon compound was heated to 900 ° C. at a rate of 5 ° C./min in an argon gas atmosphere and heat-treated at 900 ° C. for 1 hour to obtain a silicon material. The silicon material was crushed using a jet mill to produce a silicon material of Comparative Example 4 having an average particle diameter of 3 μm.
A negative electrode of Comparative Example 4 was manufactured in the same manner as in Example 4 except that the silicon material of Comparative Example 4 was used instead of the silicon material of Example 4.
（評価例３）
実施例４のシリコン材料及び比較例４のシリコン材料につき、画像解析粒度分布計（商品名：ＩＦ−２００ｎａｎｏ、ジャスコインターナショナル株式会社）に供して、粒子の画像分析を行い、アスペクト比の平均値を算出した。実施例４のシリコン材料のアスペクト比の平均値は０．８４２であり、比較例４のシリコン材料のアスペクト比の平均値は０．７５８であった。実施例４のシリコン材料の方が球に近い形状であるといえる。
(Evaluation example 3)
The silicon material of Example 4 and the silicon material of Comparative Example 4 were subjected to an image analysis particle size distribution meter (trade name: IF-200nano, Jusco International Co., Ltd.) to perform image analysis of the particles, and obtain the average value of the aspect ratio. It was calculated. The average aspect ratio of the silicon material of Example 4 was 0.842, and the average aspect ratio of the silicon material of Comparative Example 4 was 0.758. It can be said that the silicon material of Example 4 has a shape closer to a sphere.
（評価例４）
実施例４の負極及び比較例４の負極の断面を走査型電子顕微鏡（ＳＥＭ）で観察した。実施例４の負極の断面のＳＥＭ像を図３に示し、その拡大ＳＥＭ像を図４に示す。また、比較例４の負極の断面のＳＥＭ像を図５に示す。図３〜図５の淡色の箇所が、シリコン材料である。図３〜図５のＳＥＭ像からも、実施例４のシリコン材料の方が球に近い形状であることがわかる。
(Evaluation example 4)
The cross sections of the negative electrode of Example 4 and the negative electrode of Comparative Example 4 were observed with a scanning electron microscope (SEM). The SEM image of the cross section of the negative electrode of Example 4 is shown in FIG. 3, and its enlarged SEM image is shown in FIG. Further, an SEM image of the cross section of the negative electrode of Comparative Example 4 is shown in FIG. The light-colored portions in FIGS. 3 to 5 are silicon materials. From the SEM images of FIGS. 3 to 5, it can be seen that the silicon material of Example 4 has a shape closer to a sphere.
Claims (7)
前記含ハロゲンポリマーを配置する第一空間と、前記ＣａＳｉ２を配置する第二空間と、前記第一空間と前記第二空間とを区画し、前記分解ガスが通過可能な貫通孔を具備するセラミックス部と、を備え、かつ、前記第一空間の前記含ハロゲンポリマーから発生する分解ガスの流路に、前記第二空間が設けられており、前記第一空間には前記セラミックス部以外の通気部が存在しない加熱炉を用いることを特徴とするシリコン材料の製造方法。 In the coexistence of CaSi 2 and a halogen-containing polymer, a first heating step of heating at a temperature above the decomposition gas generation temperature of the halogen-containing polymer and below the carbonization temperature is included.
Ceramics having a first space for arranging the halogen-containing polymer, a second space for arranging the CaSi 2 , and a through hole that partitions the first space and the second space and through which the decomposition gas can pass. And a second space is provided in the flow path of the decomposition gas generated from the halogen-containing polymer in the first space, and the second space is provided in the first space, and the ventilation part other than the ceramic part is provided in the first space. A method for producing a silicon material, characterized by using a heating furnace which does not exist .
一般式（１）
General formula (1)
４のいずれかに記載のシリコン材料の製造方法。
一般式（２）
5. The method for producing a silicon material according to any one of 4 above.
General formula (2)
前記含ハロゲンポリマーの炭化温度以上の温度で加熱する第二加熱工程を含む、炭素被覆シリコン材料の製造方法。
After the first heating step in the manufacturing method according to any one of claims 1 to 6,
A method for producing a carbon-coated silicon material, comprising a second heating step of heating at a temperature equal to or higher than the carbonization temperature of the halogen-containing polymer.
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