JP2012221716A - 二次電池用の正極活物質およびその作製方法、ならびに二次電池 - Google Patents
二次電池用の正極活物質およびその作製方法、ならびに二次電池 Download PDFInfo
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- JP2012221716A JP2012221716A JP2011085944A JP2011085944A JP2012221716A JP 2012221716 A JP2012221716 A JP 2012221716A JP 2011085944 A JP2011085944 A JP 2011085944A JP 2011085944 A JP2011085944 A JP 2011085944A JP 2012221716 A JP2012221716 A JP 2012221716A
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- Prior art keywords
- positive electrode
- active material
- electrode active
- lithium
- secondary battery
- 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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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 123
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000013078 crystal Substances 0.000 claims abstract description 49
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000011164 primary particle Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000011800 void material Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 56
- 239000008151 electrolyte solution Substances 0.000 abstract description 16
- 238000003756 stirring Methods 0.000 abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 18
- 239000011149 active material Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 8
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
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- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
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- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 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
- 239000000835 fiber Substances 0.000 description 2
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- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
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- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
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- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- LEAMSPPOALICQN-UHFFFAOYSA-H iron(2+);diphosphate;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEAMSPPOALICQN-UHFFFAOYSA-H 0.000 description 1
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- 239000011244 liquid electrolyte Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- PDOXCFPUGNQQSW-UHFFFAOYSA-N methyl 2-methylpropyl carbonate Chemical compound COC(=O)OCC(C)C PDOXCFPUGNQQSW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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Abstract
【解決手段】正極活物質に用いるリン酸鉄リチウム結晶の一次粒子として、内部空隙を有する結晶を用いる。内部空隙を有する結晶を用いることで、結晶の比表面積が大きくなり、正極活物質と電解液との接触面積を大きくすることができる。内部空隙を有する結晶は、前駆体を含む懸濁液を、酸素を含む雰囲気中で攪拌したのち、水熱法により合成することで得られる。
【選択図】図7
Description
本実施の形態では、本発明の一態様である正極活物質とその作製方法について、図1および図2を用いて説明する。
まず、本発明の一態様である正極活物質について説明する。図1(A)および(B)に本発明の一態様である正極活物質100の模式図を示す。正極活物質100は、リン酸鉄リチウムの結晶であり、内部に空隙を有し、該空隙が開口している一次粒子である。
次に、正極活物質100の作製方法について説明する。
本実施の形態では、実施の形態1に記載の正極活物質100を用いた正極およびリチウムイオン二次電池について説明する。正極の概要を図3(A)に、リチウムイオン二次電池の概要を図3(B)に示す。
まず、リチウムイオン二次電池の正極について、図3(A)を用いて説明する。図3(A)に示す正極202は、正極集電体200と正極活物質層201を含む。
次に、上記の正極202を有するリチウムイオン二次電池について、図3(B)を用いて説明する。図3(B)に示すリチウムイオン二次電池は、正極202、負極207、及びセパレータ210を外部と隔絶する筐体220の中に設置し、筐体220中に電解液211が充填されている。また、正極202及び負極207との間にセパレータ210を有する。
本実施の形態では、実施の形態2に記載のリチウムイオン二次電池の応用形態について説明する。
まず、本発明の一態様である正極活物質の作製方法について説明する。
上記の作製方法によって得られた正極活物質100のXRD解析(X線結晶構造解析)を行った。図5にその結果を示す。横軸は回折角(2θ)、縦軸は回折強度である。図5の結果から、正極活物質100はオリビン型構造のリン酸鉄リチウムの結晶であること示された。
上記の作製方法によって得られた正極活物質100の透過型電子顕微鏡による観察を行った。図6にその結果を示す。観察には、H−9000NAR(日立ハイテクノロジーズ製)を用い、加速電圧200kV、総合倍率205,000倍(倍率精度±10%)で行った。正極活物質100のうち、結晶の欠陥もしくは結晶方位の変化に起因すると考えられる濃淡の変化は一部に限られ、ほとんどの部分は同一の結晶方位を有していた。図6の結果から、正極活物質100のほとんどの部分は単結晶のリン酸鉄リチウムであることが示された。
上記の作製方法によって得られた、正極活物質100の走査型電子顕微鏡観察を行った。図7乃至図9にその走査型電子顕微鏡写真を示す。観察は、加速電圧10kV、倍率は図7(A)は10,000倍、図7(B)は図7(A)含まれる視野で、30,000倍、図8(A)は10,000倍、図8(B)は図8(A)含まれる視野で、30,000倍、図9(A)は上記と異なる視野で、30,000倍、図9(B)は上記と異なる視野で、30,000倍で行った。図7乃至図9のように、正極活物質の粒子の多くは平板状の結晶であった。また平板状の結晶の一部に開口を有し、開口から内部の空隙を観察できる粒子が多数あった。また開口の多くは、結晶の側面に形成されていた。
また、上記の作製方法によって得られた、正極活物質100の比表面積を測定した。測定には自動比表面積・細孔分布測定装置(トライスターII3020(島津製作所社製))を用いた。自動比表面積・細孔分布測定装置とは、試料粒子の表面に吸着占有面積のわかったガス分子を吸着させ、ガス分子の吸着量から試料の比表面積を求める測定装置である。測定の結果、正極活物質100の比表面積は4.2m2/gであった。
実施例1の正極活物質の作製方法と同様に前駆体を含む懸濁液を調製した。その後、前駆体を含む懸濁液を、フッ素樹脂内筒を有する水熱合成用反応容器に入れてから、30分間空気でバブリングを行った。後の工程は実施例1の正極活物質の作製方法と同様に行った。
<正極活物質の形状>
上記の作製方法によって得られた、正極活物質100の走査型電子顕微鏡観察を行った。図10にその走査型電子顕微鏡写真を示す。実施例1の図7よりも壁が薄く、孔また凹部が大きな結晶が多数観察された。また、平板状の結晶の一部に開口を有し、開口から内部の空隙を観察できる粒子があった。また開口の多くは、結晶の側面に形成されていた。
比較例の正極活物質150として、一次粒子径が0.94μmであり、図2のような内部空隙をもたない球状のリン酸鉄リチウムの結晶の表面積を計算した。計算の結果、正極活物質150の比表面積は1.82m2/gであった。
150 正極活物質
200 正極集電体
201 正極活物質層
202 正極
205 負極集電体
206 負極活物質層
207 負極
210 セパレータ
211 電解液
220 筐体
221 電極
222 電極
300 電気自動車
301 リチウムイオン二次電池
302 制御回路
303 コンピュータ
304 駆動装置
310 建築機械
311 リチウムイオン二次電池
312 内燃機関
313 内燃機関モーター
314 インバータ
315 電気モーター
320 無停電電源装置
321 リチウムイオン二次電池
322 充電回路
323 インバータ
324 リレー
330 無停電電源装置
331 充電回路
332 整流回路
333 リチウムイオン二次電池
334 インバータ
Claims (4)
- 外形が直方体で、内部に空隙を有し、前記空隙の開口を前記直方体の側面に有するリン酸鉄リチウムの結晶を、一次粒子として含む、二次電池用の正極活物質。
- 前記直方体のそれぞれの辺は20nm以上5μm以下である、請求項1に記載の二次電池用の正極活物質。
- 請求項1または請求項2に記載の正極活物質を含む正極、前記正極に対応して設けられた負極、および電解質を有する二次電池。
- リン酸鉄リチウムを含む正極活物質の製造方法であって、
前記リン酸鉄リチウムの前駆体を含む懸濁液を、酸素を含む雰囲気中で攪拌したのち、加熱および加圧を行う工程を含む、二次電池用正極活物質の作製方法。
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