JPWO2015152114A1 - 黒鉛系活物質材料、負極及びリチウムイオン二次電池 - Google Patents
黒鉛系活物質材料、負極及びリチウムイオン二次電池 Download PDFInfo
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- JPWO2015152114A1 JPWO2015152114A1 JP2016511860A JP2016511860A JPWO2015152114A1 JP WO2015152114 A1 JPWO2015152114 A1 JP WO2015152114A1 JP 2016511860 A JP2016511860 A JP 2016511860A JP 2016511860 A JP2016511860 A JP 2016511860A JP WO2015152114 A1 JPWO2015152114 A1 JP WO2015152114A1
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- Prior art keywords
- graphite
- composite particles
- active material
- mass
- negative electrode
- Prior art date
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Links
- 239000002391 graphite-based active material Substances 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 31
- 239000011246 composite particle Substances 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 46
- 239000007771 core particle Substances 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 42
- 239000010439 graphite Substances 0.000 claims description 42
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- 238000007906 compression Methods 0.000 claims description 19
- 239000011149 active material Substances 0.000 claims description 15
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 12
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 9
- 239000007770 graphite material Substances 0.000 claims description 7
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 description 58
- 239000011248 coating agent Substances 0.000 description 34
- 238000000576 coating method Methods 0.000 description 34
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- 239000000463 material Substances 0.000 description 19
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- 239000011888 foil Substances 0.000 description 9
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- 239000002184 metal Substances 0.000 description 7
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- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 229910052715 tantalum Inorganic materials 0.000 description 2
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- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910015724 LiNi0.85Co0.15O2 Inorganic materials 0.000 description 1
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- 229920003049 isoprene rubber Polymers 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
Description
第2の複合粒子に占める第2の非黒鉛系炭素材料の質量比率B(被覆量B)が、5質量%以上で且つ第1の複合粒子に占める第1の非黒鉛系炭素材料の質量比率A(被覆量A)より大きく、
第1の複合粒子と第2の複合粒子の合計に対する第2の複合粒子の含有比率が1質量%以上である、黒鉛系活物質材料が提供される。
本実施形態による活物質材料に含まれる第1及び第2の複合粒子の核材(第1及び第2の黒鉛コア粒子)としては、通常の天然黒鉛や人造黒鉛を用いることができる。X線回折法による(002)面の面間隔d002が好ましくは0.3354〜0.340nmの範囲、より好ましくは0.3354〜0.338nmの範囲にある黒鉛材料を用いることができる。これらの中でも、コスト等の観点から天然黒鉛(d002=0.3354)が好ましい。第1及び第2の黒鉛コア粒子は、互いに異なる材料からなるものであってもよいし、同じ材料からなるものであってもよい。
上述の核材(黒鉛コア粒子)の表面を非黒鉛系炭素材料で被覆することにより、その被覆量に従って、得られた複合粒子の硬度を高くすることができる。また、活物質材料と電解液との副反応を抑制でき、充放電効率が向上し、反応容量を増大することができる。
被覆量A(第1の複合粒子に占める非黒鉛系炭素材料の質量比率)は、0.1質量%以上が好ましく、0.2質量%以上がより好ましく、0.5質量%以上がさらに好ましい。被覆量Aが少なすぎると、黒鉛の活性な端部で電解液が分解しやすくなりガスが発生したり、サイクル寿命が低下したりする虞がある。
被覆量B(第2の複合粒子に占める非黒鉛系炭素材料の質量比率)は、被覆量Aより多く、5質量%以上が好ましく、7質量%以上がより好ましく、10質量%より大きいことがさらに好ましく、20質量%以上が特に好ましく、30質量%以上に設定できる。被覆量Bが少なすぎると、所望のサイクル特性改善効果が小さくなる虞がある。
第1及び2の複合粒子を含む黒鉛系活物質材料の平均粒径は、充放電効率や入出力特性等の観点から、2〜40μmの範囲内にあることが好ましく、5〜30μmの範囲内にあることがより好ましい。ここで、平均粒径は、レーザー回折散乱法による粒度分布(体積基準)における積算値50%での粒径(メジアン径:D50)を意味する。
第1及び第2の複合粒子は、次の条件を満たすものが好ましい。
電極密度D=A/(電極の厚さ−集電体の厚さ)
このようにして得られたプレス後の電極密度Dが圧縮密度に相当する。
第1の複合粒子と第2の複合粒子の合計に対する第2の複合粒子の含有比率は、1質量%以上が好ましく、3質量%以上がより好ましく、5質量%以上がさらに好ましい。第2の複合粒子の含有比率が少なすぎると、サイクル特性の改善効果が小さくなる虞がある。
以上に説明した第1及び第2の複合粒子を公知の混合方法で混合することによって、本実施形態による黒鉛系活物質材料を製造することができる。この黒鉛系活物質材料には、必要に応じて、所望の効果を損なわない範囲で他の活物質材料を混合してもよい。黒鉛系活物質材料全体に対する第1及び第2の複合粒子の含有量は90質量%以上が好ましく、95質量%以上がより好ましい。本実施形態による黒鉛系活物質材料は第1及び第2の複合粒子のみで構成できる。
本発明の実施形態によるリチウムイオン二次電池用負極は、例えば、負極集電体上に、上記の黒鉛系活物質材料と結着剤を含む負極活物質層を形成することで得ることができる。
本発明の実施形態によるリチウムイオン二次電池は、上記負極と正極と電解質を含む。
天然黒鉛と有機物を所定の質量比率で混合し、通常の方法に従って焼成を行って、黒鉛粒子が非晶質炭素で被覆された複合黒鉛粒子A及びBをそれぞれ調製した。
負極活物質として複合黒鉛粒子Aのみを用いた以外は実施例1と同様にしてリチウムイオン二次電池を作製した。
2 負極活物質層
3 正極集電体
4 負極集電体
5 セパレータ
6 ラミネート外装体
7 ラミネート外装体
8 負極タブ
9 正極タブ
Claims (13)
- 第1の黒鉛コア粒子とその表面を被覆する第1の非黒鉛系炭素材料からなる第1の複合粒子、及び第2の黒鉛コア粒子とその表面を被覆する第2の非黒鉛系炭素材料からなる第2の複合粒子を含み、
第2の複合粒子に占める第2の非黒鉛系炭素材料の質量比率Bが、5質量%以上で且つ第1の複合粒子に占める第1の非黒鉛系炭素材料の質量比率Aより大きく、
第1の複合粒子と第2の複合粒子の合計に対する第2の複合粒子の含有比率が1質量%以上である、黒鉛系活物質材料。 - 第1の複合粒子と第2の複合粒子の合計に対する第2の複合粒子の含有比率が3質量%以上である、請求項1記載の黒鉛系活物質材料。
- 第1の複合粒子と第2の複合粒子の合計に対する第2の複合粒子の含有比率が30質量%以下である、請求項1又は2記載の黒鉛系活物質材料。
- 第2の複合粒子に占める第2の非黒鉛系炭素材料の質量比率Bが10質量%より大きい、請求項1から3のいずれか一項に記載の黒鉛系活物質材料。
- 第2の複合粒子に占める第2の非黒鉛系炭素材料の質量比率Bが50質量%未満である、請求項1から4のいずれか一項に記載の黒鉛系活物質材料。
- 第1の複合粒子に占める第1の非黒鉛系炭素材料の質量比率Aが、0.1質量%以上5質量%未満の範囲にある、請求項1から5のいずれか一項に記載の黒鉛系活物質材料。
- 第1の複合粒子に占める第1の非黒鉛系炭素材料の質量比率Aが、0.1質量%以上4質量%以下の範囲にある、請求項1から5のいずれか一項に記載の黒鉛系活物質材料。
- 第2の複合粒子の圧縮密度を1.5g/cm3にするのに必要な線圧Bが、第1の複合粒子の圧縮密度を1.5g/cm3にするのに必要な線圧Aより大きい、請求項1から7のいずれか一項に記載の黒鉛系活物質材料。
- 第1の複合粒子の圧縮密度を1.5g/cm3にするのに必要な線圧Aが、10kgf/cm(98N/cm)以上50kgf/cm(490N/cm)未満の範囲にあり、
第2の複合粒子の圧縮密度を1.5g/cm3にするのに必要な線圧Bが、50kgf/cm(490N/cm)以上180kgf/cm(1765N/cm)以下の範囲にある、請求項1から8のいずれか一項に記載の黒鉛系活物質材料。 - 第1の黒鉛コア粒子および第2の黒鉛コア粒子がそれぞれ天然黒鉛からなる、請求項1から9のいずれか一項に記載の黒鉛系活物質材料。
- 第1の非黒鉛系炭素材料および第2の非黒鉛系炭素材料がそれぞれ非晶質炭素からなる、請求項1から10のいずれか一項に記載の黒鉛系活物質材料。
- 請求項1から11のいずれか一項に記載の黒鉛系活物質材料を含む、リチウムイオン二次電池用負極。
- リチウムイオンを吸蔵放出できる正極と、請求項12に記載の負極と、非水電解液を含むリチウムイオン二次電池。
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