JP6957603B2 - 二次電池用負極活物質及びその製造方法 - Google Patents
二次電池用負極活物質及びその製造方法 Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims description 31
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- 238000009826 distribution Methods 0.000 claims description 42
- 239000005540 silicon based primary particle Substances 0.000 claims description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
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- 238000000034 method Methods 0.000 claims description 20
- 239000011863 silicon-based powder Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/04—Processes of manufacture in general
-
- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
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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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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Description
以下、特定の実施形態に関してより詳細に本発明を説明するが、本発明はこれらの実施形態に限定されない。
平均直径約5μmの市販のポリシリコン粉末(2kg)を100%エタノールの酸化性溶媒(10kg)に分散させて分散混合物を調製した。表1に示す条件下の応力エネルギーに制御したビーズミル粉砕プロセスを実施し、実施例及び比較例のシリコン系一次粒子を作製して、当該作製した粒子の球形度及び粒度分布を後述の表2に示す。分析したシリコン系一次粒子の純度は99%以上であった。上記の調製方法は例示的なものであり、シリコン粒子は他の研磨プロセスによって、又はバルクシリコン材料(例えば、シリコンロッド及びウェハ)における導線放電爆発法(exploding wire method)を行うことによって調製することができる。
表1及び2を参照すると、実施例1〜3に示すように、約9m/s〜18m/sの範囲の応力エネルギー下でシリコン粉末を湿式粉砕すると、球形度が0.5〜0.9の範囲内であり、かつ、D10が50以上であり、かつD90が150以下の値の範囲である粒度分布幅が1未満であることがわかる。一方、比較例1、2では、粒度分布が比較的広範囲にわたって広がり、粒度分布幅が1を超えることが分かる。応力エネルギーが大きすぎると処理時間は短くなるが、粒度分布幅が1を超えるように粒度を制御することができず、一方、比較例2では、応力エネルギーを小さくすると、かなりの粉砕時間の後でさえも、所望の粒度分布が得られないことがわかる。
12 負極
13 正極
14 セパレータ
15 電池容器
16 封入部材
Claims (15)
- 二次電池用負極活物質であって、
前記負極活物質は、シリコン粒子のコアと、前記コア上に形成された酸化シリコン層とを有するシリコン系一次粒子を含み、前記シリコン系一次粒子の粒度分布が、D10≧50nmであり、かつD90≦150nmであり、前記シリコン系一次粒子の前記粒度分布幅である(D90−D10)/D50は、1以下であり、
上記式中、D10、D50及びD90はそれぞれ、総体積100%の累積粒度分布曲線における体積10%、体積50%及び体積90%に対応する粒子の大きさである、二次電池用負極活物質。 - 前記シリコン系一次粒子の球形度が0.5〜0.9の範囲である、請求項1に記載の二次電池用負極活物質。
- 前記シリコン粒子のコア及び前記酸化シリコン層の総重量に対する前記シリコン系一次粒子中の酸素含有量が、9重量%〜20重量%、又は10重量%〜17重量%の範囲に限定される、請求項1に記載の二次電池用負極活物質。
- 前記シリコン粒子のコアは、結晶度が低い、又は非晶質である、請求項1又は3に記載の二次電池用負極活物質。
- 前記シリコン系一次粒子の純度が99%以上である、請求項1に記載の二次電池用負極活物質。
- 前記シリコン系一次粒子の粒度分布幅が、0.9以下である、請求項1に記載の二次電池用負極活物質。
- 前記シリコン系一次粒子のメジアン粒子径D50は、80nm〜100nmである、請求項1に記載の二次電池用負極活物質。
- 前記シリコン系一次粒子の粒子径D100は、250nm未満であり、またD100は、累積粒度分布曲線の体積100%に対応する粒子の大きさである、請求項1に記載の二次電池用負極活物質。
- 二次電池用負極活物質の調製方法であって、
シリコン粉末を準備する工程と、
前記シリコン粉末を酸化性溶媒中に分散させた分散混合物を準備する工程と、
機械的応力エネルギーを前記分散混合物の前記シリコン粉末に一遍に加えて、粒度分布がD10≧50nmであり、かつD90≦150nmであり、更に前記粒度分布幅である(D90−D10)/D50が、1以下である、微細粒化されたシリコン粒子を形成し、前記酸化性溶媒を用いて前記微細粒化されたシリコン粒子上に化学酸化物層を形成する工程と、
前記微細粒化されたシリコン粒子を含む生成物を乾燥してシリコン系一次粒子を得る工程と、を有し、
上記式中、D10、D50及びD90はそれぞれ、総体積100%の累積粒度分布曲線における体積10%、体積50%及び体積90%に対応する粒子の大きさである、調製方法。 - 前記酸化性溶媒は、水、脱イオン水、アルコール溶媒、又はそれらの2種以上の混合物を含む、請求項9に記載の方法。
- 前記アルコール溶媒は、エチルアルコール、メチルアルコール、グリセリン、プロピレングリコール、イソプロピルアルコール、イソブチルアルコール、ポリビニルアルコール、シクロヘキサノール、オクチルアルコール、デカノール、ヘキサデカノール、エチレングリコール、1,2オクタンジオール、1,2ドデカンジオール、及び1,2−ヘキサデカンジオール、又はそれらの混合物からなる群から選択される、任意の溶媒を含む、請求項10に記載の方法。
- 前記機械的応力エネルギーの適用は、酸化性溶媒と共に研磨粒子の組成物を用いるミル粉砕プロセスによって達成される、請求項9に記載の方法。
- 前記微細粒化されたシリコン粒子のメジアン粒子径D50は、80nm〜100nmである、請求項9に記載の方法。
- 前記微細粒化されたシリコン粒子の粒子径D100は、250nm未満であり、またD100は、累積粒度分布曲線の体積100%に対応する粒子の大きさである、請求項9に記載の方法。
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