JP5314258B2 - Olivine-type lithium iron phosphate compound and method for producing the same, and positive electrode active material and non-aqueous electrolyte battery using olivine-type lithium iron phosphate compound - Google Patents
Olivine-type lithium iron phosphate compound and method for producing the same, and positive electrode active material and non-aqueous electrolyte battery using olivine-type lithium iron phosphate compound Download PDFInfo
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- JP5314258B2 JP5314258B2 JP2007196177A JP2007196177A JP5314258B2 JP 5314258 B2 JP5314258 B2 JP 5314258B2 JP 2007196177 A JP2007196177 A JP 2007196177A JP 2007196177 A JP2007196177 A JP 2007196177A JP 5314258 B2 JP5314258 B2 JP 5314258B2
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- Prior art keywords
- olivine
- iron phosphate
- type lithium
- positive electrode
- lithium iron
- 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 description 52
- -1 lithium iron phosphate compound Chemical class 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 156
- 239000002245 particle Substances 0.000 claims description 143
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 65
- 239000002184 metal Substances 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 53
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 51
- 238000002441 X-ray diffraction Methods 0.000 claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 239000010450 olivine Substances 0.000 claims description 32
- 229910052609 olivine Inorganic materials 0.000 claims description 32
- 238000006467 substitution reaction Methods 0.000 claims description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 239000013078 crystal Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 49
- 239000000203 mixture Substances 0.000 description 30
- 238000004458 analytical method Methods 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000000725 suspension Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000010419 fine particle Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
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- 238000007254 oxidation reaction Methods 0.000 description 14
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- 235000001727 glucose Nutrition 0.000 description 11
- 239000008103 glucose Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 238000004438 BET method Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
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- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 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 2
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- 239000011245 gel electrolyte Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 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
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- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
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- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Description
本発明は、低コストで安全性が高く、さらに高速充放電にも優れた電池特性を有する正極活物質となるオリビン型の正極活物質およびその製造方法と、これを含む正極を有する非水電解質電池に関する。 The present invention relates to an olivine-type positive electrode active material that is a low-cost, high-safety, and excellent battery property for high-speed charge / discharge, a method for producing the same, and a non-aqueous electrolyte having a positive electrode including the same It relates to batteries.
現在、リチウム二次電池は携帯電話、ビデオカメラやノートパソコン等の電子機器の電源として、広く普及している。また、環境保全問題やエネルギー問題から、電気自動車や夜間電力用の安価で安全性の高い大型リチウム二次電池の開発も進められている。 Currently, lithium secondary batteries are widely used as power sources for electronic devices such as mobile phones, video cameras, and notebook computers. In addition, due to environmental conservation problems and energy problems, development of large-sized lithium secondary batteries that are inexpensive and highly safe for electric vehicles and nighttime electric power is being promoted.
従来、リチウム二次電池の正極活物質には層状岩塩型のLiCoO2が主に用いられてきた。LiCoO2は充放電サイクル特性において優れているが、原料であるコバルトの資源量は少なく、コストも高価である。そのため、代替の正極活物質として、層状岩塩型のLiNiO2やスピネル型LiMn2O4が研究されてきたが、LiNiO2は充電状態の安全性に問題があり、LiMn2O4は高温域における化学的安定性に問題がある。小型電池用としては、これらの元素を組み合わせた新規正極材が提案されてきているが、コスト、安全性の面でさらに要求レベルの高くなる大型電池用正極活物質として、新たな代替材料が望まれてきた。 Conventionally, a layered rock salt type LiCoO 2 has been mainly used as a positive electrode active material of a lithium secondary battery. LiCoO 2 is excellent in charge / discharge cycle characteristics, but the resource amount of cobalt as a raw material is small, and the cost is also expensive. Therefore, layered rock salt type LiNiO 2 and spinel type LiMn 2 O 4 have been studied as alternative positive electrode active materials, but LiNiO 2 has a problem in the safety of the charged state, and LiMn 2 O 4 is in a high temperature range. There is a problem with chemical stability. New cathode materials combining these elements have been proposed for small batteries, but new alternative materials are expected as positive electrode active materials for large batteries, which are more demanding in terms of cost and safety. It has been rare.
オリビン型の正極活物質であるLiFePO4は、コスト、安全性、信頼性に優れた材料として近年開発が活発になってきている。このオリビン型LiFePO4は、極めて高い安全性と安定性を有し、かつ、低コストであるため、注目されているが、実用化への問題点として電子伝導性の低さがある。これを改善するため方法として、主には反応表面積を増やすための微粒子化、導電性を付与するためのカーボンコートなどは周知である(例えば、非特許文献1)。微粒子化では特にナノサイズの均一な粒子によって、電池特性の改善が図られることが報告されている(非特許文献2,3)。また、カーボンの添加に関しては、各種カーボン材料について非常に多くの報告がある(例えば、特許文献3や非特許文献4)。 In recent years, LiFePO 4 , which is an olivine-type positive electrode active material, has been actively developed as a material excellent in cost, safety, and reliability. This olivine-type LiFePO 4 has been attracting attention because it has extremely high safety and stability and is low in cost, but has a problem of low electronic conductivity as a problem for practical use. As methods for improving this, mainly fine particle formation for increasing the reaction surface area, carbon coating for imparting conductivity, and the like are well known (for example, Non-Patent Document 1). It has been reported that battery characteristics can be improved particularly by nano-sized uniform particles in micronization (Non-patent Documents 2 and 3). In addition, regarding the addition of carbon, there are numerous reports on various carbon materials (for example, Patent Document 3 and Non-Patent Document 4).
また、異種金属置換の特許は数多く提案されているが、効果を明示した金属はMnやMg等特定の金属に限られ、また、置換量が多くないと効果を示さない(例えば、特許文献4〜6)。また、非特許文献8に述べられているように微量の置換で、導電性の改善効果を示す金属はあるが、低レートにおいても容量は低く、ハイレートでの容量は未知である。 Further, many patents for different metal substitution have been proposed, but metals that clearly show the effect are limited to specific metals such as Mn and Mg, and the effect is not exhibited unless the substitution amount is large (for example, Patent Document 4). ~ 6). Further, as described in Non-Patent Document 8, there is a metal that shows an effect of improving conductivity by a small amount of substitution, but the capacity is low even at a low rate, and the capacity at a high rate is unknown.
また、オリビン型リン酸鉄リチウムの製造方法としては、従来、シュウ酸鉄や酢酸鉄を出発原料とした固相法(特許文献1、非特許文献5)が一般的であった。近年では、リン酸鉄を原料とした固相法(特許文献2)や、より微細な粒子を得るためのゾルゲル法や、水熱法(非特許文献6、7)などが報告されている。しかしながら、いずれの方法も、原料が高価であったり、二価の鉄の酸化を防ぐ設備が必要であったり、均一で結晶性の良い目的物を得ることが困難であった。また、置換元素をドープさせる方法についても、ゾルゲル法や水熱法に置換元素を添加すると結晶形の制御が難しく、また、一般的な固相法で置換元素を混合すると均一な相が得られないなどの問題があった。そのため、いずれの方法によっても、均一な微細置換金属含有粒子を安価な原料と単純な製造設備で、工業的に製造することは難しく、実用的な電池特性を有するオリビン型リン酸鉄リチウムを低コストで実現できる製造方法が必要とされている。 Further, as a method for producing olivine type lithium iron phosphate, a solid phase method using iron oxalate or iron acetate as a starting material (Patent Document 1, Non-Patent Document 5) has been generally used. In recent years, a solid-phase method using iron phosphate as a raw material (Patent Document 2), a sol-gel method for obtaining finer particles, a hydrothermal method (Non-Patent Documents 6 and 7), and the like have been reported. However, in any of the methods, the raw materials are expensive, facilities for preventing the oxidation of divalent iron are necessary, and it is difficult to obtain a target product having uniform and good crystallinity. As for the method of doping the substitution element, it is difficult to control the crystal form if the substitution element is added to the sol-gel method or the hydrothermal method, and a uniform phase can be obtained by mixing the substitution element by a general solid phase method. There was no problem. Therefore, in any method, it is difficult to industrially produce uniform finely substituted metal-containing particles with inexpensive raw materials and simple production equipment, and olivine type lithium iron phosphate having practical battery characteristics is reduced. There is a need for a manufacturing method that can be realized at low cost.
本発明は、コスト、安全性、信頼性に優れ、高容量でかつ、高速充放電も可能な非電解質電池の製造を可能にする正極活物質及びその製造方法、並びにこれを用いた非水電解質電池を提供することを目的とする。 The present invention relates to a positive electrode active material that is excellent in cost, safety, reliability, high capacity, and capable of producing a non-electrolyte battery capable of high-speed charge / discharge, a method for producing the same, and a non-aqueous electrolyte using the same. An object is to provide a battery.
上記のような優れた特性を有する正極活物質を製造するために、本発明者らは鋭意検討した結果、本発明を完成するに至った。
すなわち、本発明は以下のものを提供する。
In order to produce a positive electrode active material having such excellent characteristics as described above, the present inventors diligently studied, and as a result, completed the present invention.
That is, the present invention provides the following.
[1] 平均粒子径が500nm以下であり、下記一般式:
LixFeyTipMqPO4
(式中、0<x<2、0<y<1.5であり、p/y=0.001〜0.2、q/p=0〜10であり、MはCo、Ni、Mn、Zn、Cu、Mg、及びAlからなる群から選ばれる少なくとも1種の金属である)
で表されるオリビン型リン酸鉄リチウム化合物。
[1] The average particle size is 500 nm or less, and the following general formula:
Li x Fe y Ti p M q PO 4
(Wherein 0 <x <2, 0 <y <1.5, p / y = 0.001 to 0.2, q / p = 0 to 10, M is Co, Ni, Mn, (At least one metal selected from the group consisting of Zn, Cu, Mg, and Al)
An olivine type lithium iron phosphate compound represented by:
[2] 平均粒子径が500nm以下であり、粒度分布の変動係数が0.5以下であり、BET値が10〜50m2/gであり、111面の結晶面に対応するX線回折ピークの半価幅からScherrerの式に従って求めた結晶子径(D111)が20.0〜80.0nmであることを特徴とする[1]のオリビン型リン酸鉄リチウム化合物。 [2] The average particle diameter is 500 nm or less, the variation coefficient of the particle size distribution is 0.5 or less, the BET value is 10 to 50 m 2 / g, and the X-ray diffraction peak corresponding to the crystal plane of 111 planes The olivine-type lithium iron phosphate compound according to [1], wherein the crystallite diameter (D 111 ) determined from the half-value width according to Scherrer's formula is 20.0 to 80.0 nm.
[3] 炭素含有量が0.1〜10%である[1]のオリビン型リン酸鉄リチウム化合物。
[4] 平均粒子径が500nm以下の置換金属含有酸化鉄粒子を含む鉄源、リチウム源及びリン源を混合し、焼成することを特徴とする[1]のオリビン型リン酸鉄リチウム化合物の製造方法。
[3] The olivine-type lithium iron phosphate compound according to [1], which has a carbon content of 0.1 to 10%.
[4] Production of olivine-type lithium iron phosphate compound according to [1], wherein an iron source containing substituted metal-containing iron oxide particles having an average particle diameter of 500 nm or less, a lithium source, and a phosphorus source are mixed and calcined. Method.
[5] 鉄源が置換金属をドープした酸化鉄粒子及び/又は置換金属で湿式表面処理した酸化鉄粒子を含む、[4]の方法。
[6] 置換金属が、Ti、Co、Ni、Mn、Zn、Cu、Mg及びAlからなる群から選ばれる少なくとも1種の金属元素である、[4]の方法。
[5] The method according to [4], wherein the iron source includes iron oxide particles doped with a substitution metal and / or iron oxide particles wet-treated with a substitution metal.
[6] The method according to [4], wherein the substitution metal is at least one metal element selected from the group consisting of Ti, Co, Ni, Mn, Zn, Cu, Mg, and Al.
[7] 酸化鉄粒子が、鉄塩とアルカリとを反応させて得られたものである、[4]の方法。
[8] 酸化鉄粒子がマグネタイトである、[4]の方法。
[7] The method according to [4], wherein the iron oxide particles are obtained by reacting an iron salt and an alkali.
[8] The method of [4], wherein the iron oxide particles are magnetite.
[9] アルカリが水酸化アルカリ及び/又は炭酸アルカリである、[4]の方法。
[10] 平均粒子径が500nm以下の置換金属含有酸化鉄粒子を含む鉄源、リチウム源及びリン源と炭素または/および炭素前駆体を混合し、焼成することを特徴とする[4]の方法。
[9] The method according to [4], wherein the alkali is an alkali hydroxide and / or an alkali carbonate.
[10] The method according to [4], wherein an iron source, a lithium source, and a phosphorus source, and carbon or / and a carbon precursor containing substituted metal-containing iron oxide particles having an average particle diameter of 500 nm or less are mixed and calcined. .
[11] 焼成を不活性ガス雰囲気または還元雰囲気で行う、[4]〜[10]の何れかの方法。
[12] 焼成をN2雰囲気で行う、[11]の方法。
[11] The method according to any one of [4] to [10], wherein the firing is performed in an inert gas atmosphere or a reducing atmosphere.
[12] The method according to [11], wherein the firing is performed in an N 2 atmosphere.
[13] [1]〜[3]のオリビン型リン酸鉄リチウム化合物または[4]〜[12]の何れかの方法により得られたオリビン型リン酸鉄リチウム化合物を含む正極活物質。
[14] [13]の正極活物質を含む正極を有する非水電解質電池。
[13] A positive electrode active material comprising the olivine type lithium iron phosphate compound of [1] to [3] or the olivine type lithium iron phosphate compound obtained by any of the methods of [4] to [12].
[14] A nonaqueous electrolyte battery having a positive electrode including the positive electrode active material according to [13].
[15] 鉄塩とTi及び、Co、Ni、Mn、Zn、Cu、Mg及びAlからなる群から選ばれる少なくとも1種の金属の塩をアルカリと反応させるか、又はこの反応混合物を酸素含有雰囲気下で30〜90℃の温度に加熱することにより得られる金属化合物。 [15] At least one metal salt selected from the group consisting of iron salt, Ti, and Co, Ni, Mn, Zn, Cu, Mg, and Al is reacted with an alkali, or the reaction mixture is subjected to an oxygen-containing atmosphere. A metal compound obtained by heating to a temperature of 30-90 ° C.
[16] 酸化鉄粒子の表面にTi及び、Co、Ni、Mn、Zn、Cu、Mg及びAlからなる群から選ばれる少なくとも1種の金属の塩を付着させることにより得られる金属化合物。 [16] A metal compound obtained by attaching Ti and at least one metal salt selected from the group consisting of Co, Ni, Mn, Zn, Cu, Mg, and Al to the surface of the iron oxide particles.
[17] [15]又は[16]の金属化合物をオリビン型リン酸鉄リチウム化合物の製造に使用する方法。 [17] A method of using the metal compound of [15] or [16] for producing an olivine type lithium iron phosphate compound.
[オリビン型リン酸鉄リチウム化合物]
本発明のオリビン型リン酸鉄リチウム化合物は、平均粒子径が500nm以下であり、下記一般式:
LixFeyTipMqPO4
(式中、0<x<2、0<y<1.5であり、p/y=0.001〜0.2、q/p=0〜10であり、MはCo、Ni、Mn、Zn、Cu、Mg、及びAlからなる群から選ばれる少なくとも1種の金属である)
で表されるオリビン型リン酸鉄リチウム化合物である。
[Olivine-type lithium iron phosphate compound]
The olivine-type lithium iron phosphate compound of the present invention has an average particle size of 500 nm or less, and has the following general formula:
Li x Fe y Ti p M q PO 4
(Wherein 0 <x <2, 0 <y <1.5, p / y = 0.001 to 0.2, q / p = 0 to 10, M is Co, Ni, Mn, (At least one metal selected from the group consisting of Zn, Cu, Mg, and Al)
It is the olivine type lithium iron phosphate compound represented by these.
本発明は、高容量でかつ、高速充放電も可能なオリビン型リン酸鉄リチウム化合物を提供することであり、そのため、Feの一部を少なくともTiで置換し、平均粒子径500nm以下の粒子を提案する。Tiの置換より導電性を向上させるとともに、微細粒子とすることで高容量と高レート特性を可能とした。 The present invention is to provide an olivine-type lithium iron phosphate compound having a high capacity and capable of high-speed charging / discharging. Therefore, at least part of Fe is substituted with Ti, and particles having an average particle diameter of 500 nm or less are obtained. suggest. The conductivity is improved by substitution of Ti, and high capacity and high rate characteristics are made possible by using fine particles.
置換量は、p/y=0.001〜0.2、q/p=0〜10の範囲の中で任意に設定することが可能であるが、好ましくは、p/y=0.01〜0.1、特に0.01〜0.05、好ましくはq/p=0〜5である。一方、Feのモル比yは0<y<1.5の範囲の中で任意に設定することが可能であるが、通常、0.8<y<1.2である。置換金属はTiを使用することが必須であり、さらに、Co、Ni、Mn、Zn、Cu、Mg、及びAlからなる群から選ばれる少なくとも1種の金属である。 The substitution amount can be arbitrarily set within the range of p / y = 0.001 to 0.2 and q / p = 0 to 10, but preferably p / y = 0.01 to 0.1, in particular 0.01 to 0.05, preferably q / p = 0 to 5. On the other hand, the molar ratio y of Fe can be arbitrarily set within the range of 0 <y <1.5, but usually 0.8 <y <1.2. The substitution metal must use Ti, and is at least one metal selected from the group consisting of Co, Ni, Mn, Zn, Cu, Mg, and Al.
置換金属TiとMの組み合わせは、特に限定されないが、Ti単独でも十分な効果があるが、Ti−Co、Ti−Mn、Ti−Mg等の組み合わせによってもより特性の向上を図ることが可能である。また、Ti−(Co+Ni)、Ti−(Mg+Al)等のように、Tiと複数種のMとを組み合わせることもできる。 The combination of the substitutional metals Ti and M is not particularly limited, but Ti alone has a sufficient effect, but it is possible to further improve the characteristics by combining Ti-Co, Ti-Mn, Ti-Mg, and the like. is there. Further, Ti and a plurality of types of M can be combined, such as Ti— (Co + Ni), Ti— (Mg + Al).
Tiは、良好な焼結防止効果が奏され、粒子の微細化をより一層促進することができるが、更に金属元素Mと組み合わせて上記オリビン型リン酸鉄リチウム化合物のFeを置換することにより、その化合物の結晶性を向上させ、Feのレドックス(酸化還元反応)を容易にさせることも可能である。 Ti has a good anti-sintering effect and can further promote the refinement of particles, but further, by substituting Fe of the olivine-type lithium iron phosphate compound in combination with the metal element M, It is also possible to improve the crystallinity of the compound and facilitate Fe redox (oxidation-reduction reaction).
高容量と高レート特性を同時に満たすためには、オリビン型リン酸鉄リチウム化合物の粒子径は500nm以下であることが必要であり、好ましくは10〜200nmである。 In order to satisfy both high capacity and high rate characteristics at the same time, the particle size of the olivine-type lithium iron phosphate compound needs to be 500 nm or less, preferably 10 to 200 nm.
また、BET値は10〜50m2/gであることが好ましく、更に好ましくは10〜30m2/gであり、D111は20.0〜80.0nmであることが好ましく、更に好ましくは30.0〜50.0nmであり、粒度分布の変動係数が0.5以下であることが好ましく、更に好ましくは0.4以下である。 It is preferable that BET value is 10 to 50 m 2 / g, more preferably from 10 to 30 m 2 / g, preferably D 111 is 20.0~80.0Nm, more preferably 30. It is preferably 0 to 50.0 nm, and the coefficient of variation of the particle size distribution is preferably 0.5 or less, and more preferably 0.4 or less.
また、本発明のオリビン型リン酸鉄リチウム化合物は、その粒子表面に種々の物質、例えば、導電性物質等が存在してもよい。典型的な導電性物質は炭素である。 The olivine-type lithium iron phosphate compound of the present invention may have various substances such as conductive substances on the particle surface. A typical conductive material is carbon.
[オリビン型リン酸鉄リチウム化合物の製造方法]
本発明によれば、鉄源、リチウム源及びリン源を混合し、焼成することを特徴とするオリビン型リン酸鉄リチウム化合物の製造方法が提供される。この方法において、鉄源が、置換元素を含有した酸化鉄粒子を含むことが重要である。
[Method for producing olivine-type lithium iron phosphate compound]
ADVANTAGE OF THE INVENTION According to this invention, an iron source, a lithium source, and a phosphorus source are mixed and baked, The manufacturing method of the olivine type lithium iron phosphate compound characterized by the above-mentioned is provided. In this method, it is important that the iron source contains iron oxide particles containing a substitution element.
酸化鉄粒子は微細で、粒度分布を正確に制御して調製することができる。本発明者らはこの点に着目し、鉄源として置換元素を含有した酸化鉄粒子を含ませることにより、極めて微細な粒子で、かつ、粒度分布が制御されたオリビン型リン酸鉄リチウム化合物を得、この微細でかつ粒度分布の良好なオリビン型リン酸鉄リチウム化合物を含む正極活物質を用いることにより、優れた性能の非水電解質電池を製造することに成功した。 The iron oxide particles are fine and can be prepared with precisely controlled particle size distribution. The present inventors pay attention to this point, and by including iron oxide particles containing a substitution element as an iron source, an olivine-type lithium iron phosphate compound having a very fine particle and a controlled particle size distribution is obtained. As a result, the present inventors succeeded in producing a non-aqueous electrolyte battery having excellent performance by using a positive electrode active material containing an olivine type lithium iron phosphate compound having a fine particle size distribution and a good particle size distribution.
(鉄源)
本発明で使用する鉄源は、酸化鉄粒子を含む。酸化鉄粒子は、好ましくは500nm以下の平均粒径を有し、より好ましくは300nm以下、特に3〜100nmの平均粒径を有する。5nm程度の平均粒径の酸化鉄粒子からは、5〜50nm程度のオリビン型リン酸鉄リチウム化合物が、300nm程度の平均粒径の酸化鉄粒子からは、100〜500nm程度のオリビン型リン酸鉄リチウム化合物が、得られる。酸化鉄粒子はまた、0.50以下の粒子径の変動係数[=(標準偏差/平均粒子径)]を有することが好ましく、10〜150m2/gのBET比表面積値を有することが好ましい。
(Iron source)
The iron source used in the present invention includes iron oxide particles. The iron oxide particles preferably have an average particle size of 500 nm or less, more preferably 300 nm or less, particularly 3 to 100 nm. From the iron oxide particles having an average particle diameter of about 5 nm, the olivine-type lithium iron phosphate compound having an average particle diameter of about 5 to 50 nm is used. From the iron oxide particles having an average particle diameter of about 300 nm, the olivine-type iron phosphate having about 100 to 500 nm is prepared. A lithium compound is obtained. The iron oxide particles also preferably have a coefficient of variation [= (standard deviation / average particle diameter)] of a particle diameter of 0.50 or less, and preferably have a BET specific surface area value of 10 to 150 m 2 / g.
酸化鉄としては、一酸化鉄(FeO)、マグネタイトなどの四酸化三鉄(Fe3O4)、ヘマタイトなどの三酸化二鉄(Fe2O3)などが挙げられる。これらの中でも、特に、四酸化三鉄(Fe3O4)が好ましい。四酸化三鉄(Fe3O4)は、湿式法によって、比較的安価な材料と設備により、微細な粒子として且つ粒度分布を正確に制御して調製することができるので、本発明のオリビン型リン酸鉄リチウムを製造するために有用である。また、三酸化二鉄(Fe2O3)等と比較して、酸素含有率が低いため、還元しやすく、焼成時の焼結を防いだ粒子を得ることができる。この他に、微細なFe2O3などからも、微細な粒子が得られるので、本発明のオリビン型リン酸鉄リチウムを製造するために使用できる。 Examples of the iron oxide include iron monoxide (FeO), triiron tetroxide (Fe 3 O 4 ) such as magnetite, and diiron trioxide (Fe 2 O 3 ) such as hematite. Among these, triiron tetroxide (Fe 3 O 4 ) is particularly preferable. Since triiron tetroxide (Fe 3 O 4 ) can be prepared by a wet method, with relatively inexpensive materials and equipment, as fine particles and with a precisely controlled particle size distribution, the olivine type of the present invention Useful for producing lithium iron phosphate. In comparison with such diiron trioxide (Fe 2 O 3), the oxygen content is low, reducing easily, can be obtained to prevent it particles sintered during firing. In addition, since fine particles can be obtained from fine Fe 2 O 3 or the like, it can be used to produce the olivine-type lithium iron phosphate of the present invention.
例えば、酸化鉄は、鉄塩とアルカリとを反応させて、例えば、鉄塩とアルカリ水溶液、特に、水酸化アルカリ及び/又は炭酸アルカリ、とを混合して水酸化鉄を生成し、この水酸化鉄を含む反応物を酸素含有雰囲気下(例えば大気圧下)で30〜90℃の温度に加熱(酸化合成)することにより得られるFe3O4などが好ましい。 For example, iron oxide is produced by reacting an iron salt with an alkali and mixing, for example, an iron salt and an aqueous alkali solution, particularly an alkali hydroxide and / or an alkali carbonate, to produce iron hydroxide. Fe 3 O 4 obtained by heating (oxidation synthesis) a reaction product containing iron to a temperature of 30 to 90 ° C. in an oxygen-containing atmosphere (for example, atmospheric pressure) is preferable.
鉄塩としては、硫酸鉄、酢酸鉄、塩化鉄などが挙げられる。
水酸化アルカリとしては、水酸化ナトリウム、水酸化カリウム、アンモニア水などが挙げられる。炭酸アルカリとしては、炭酸ナトリウム、炭酸カリウム、炭酸アンモニウムなどが挙げられる。アルカリとしてアルカリ金属を用いても、中和反応の副生成物として生じるアルカリ金属分のほとんどは水洗により、除去が可能であるが、アルカリ金属の混入を極めて低くするためにはアンモニウム塩を用いることが適当である。また、水酸化アルカリだけでも微細粒子は得られるが、更に細かい粒子を得るには、炭酸アルカリと混合して用いることが有効である。微細な単相の酸化鉄粒子を得るためには、中和率0.8〜3.0(ここで、中和率は、中和前の酸源のモル当量に対する中和に使用したアルカリ源のモル当量の比である。例えば、MnSO4の10モルにNaOHの20モルを使用した場合、中和率は20/(10×2)=1.0となる。)、温度30〜90℃の範囲で上記の酸化合成を行うことが適当である。
Examples of iron salts include iron sulfate, iron acetate, and iron chloride.
Examples of the alkali hydroxide include sodium hydroxide, potassium hydroxide, and aqueous ammonia. Examples of the alkali carbonate include sodium carbonate, potassium carbonate, and ammonium carbonate. Even if an alkali metal is used as the alkali, most of the alkali metal produced as a by-product of the neutralization reaction can be removed by washing with water, but an ammonium salt should be used to extremely reduce the alkali metal contamination. Is appropriate. In addition, fine particles can be obtained only with alkali hydroxide, but it is effective to use them mixed with alkali carbonate in order to obtain finer particles. In order to obtain fine single-phase iron oxide particles, a neutralization rate of 0.8 to 3.0 (where the neutralization rate is the alkali source used for neutralization relative to the molar equivalent of the acid source before neutralization) For example, when 20 mol of NaOH is used for 10 mol of MnSO 4 , the neutralization rate is 20 / (10 × 2) = 1.0.) Temperature 30 to 90 ° C. It is appropriate to carry out the above oxidation synthesis within the range of
鉄源は、鉄以外の金属を置換金属として含む。置換金属としては前述したものが挙げられる。
鉄源への置換金属の導入は、例えば、酸化鉄粒子として置換金属をドープした酸化鉄粒子(ドープ法)及び/又は置換金属を湿式で表面処理した酸化鉄粒子(湿式表面処理法)を使用することにより達成できる。
The iron source contains a metal other than iron as a replacement metal. Examples of the substitution metal include those described above.
The introduction of the substitution metal into the iron source uses, for example, iron oxide particles doped with a substitution metal (doping method) and / or iron oxide particles obtained by wet-treating the substitution metal (wet surface treatment method) as iron oxide particles. This can be achieved.
ドープ法(固溶法)は、上述した酸化合成により酸化鉄粒子を調製する工程において、鉄塩および置換金属の塩と、アルカリ、特に水酸化アルカリ及び/又は炭酸アルカリを加熱下で反応させて、置換金属含有酸化物を得るか、または、鉄塩とともに置換金属の塩をアルカリ、特に水酸化アルカリ及び/又は炭酸アルカリとを反応させて水酸化物を得、その水酸化物含有混合物を30〜90℃の温度に加熱して、この混合物に酸素含有ガスを吹き込んで、金属酸化物を製造する方法である。この場合、ドープ方法としては、始めから置換金属塩の溶液を鉄塩溶液に混合して用いることも可能であるが、ドープ量の多い場合は酸化途中から置換金属溶液を少量ずつ一定時間で滴下していく傾斜ドープ方法も有効である。この方法によって、得られた原料を用いることにより、均一で、微細な置換オリビン型リン酸鉄リチウム粒子を得ることが可能となる。 The dope method (solid solution method) is a step of reacting an iron salt and a substituted metal salt with an alkali, particularly an alkali hydroxide and / or an alkali carbonate under heating in the step of preparing iron oxide particles by the above-described oxidation synthesis. The substituted metal-containing oxide is obtained, or the salt of the substituted metal is reacted with an alkali, particularly an alkali hydroxide and / or an alkali carbonate, together with an iron salt to obtain a hydroxide, and the hydroxide-containing mixture is obtained as 30 It is a method for producing a metal oxide by heating to a temperature of ˜90 ° C. and blowing an oxygen-containing gas into this mixture. In this case, as a doping method, it is possible to mix the solution of the substituted metal salt with the iron salt solution from the beginning. An inclined doping method is also effective. By using the obtained raw material by this method, uniform and fine substituted olivine type lithium iron phosphate particles can be obtained.
湿式表面処理法は、上述した酸化合成により得られる酸化鉄粒子を含む液に置換金属の塩の溶液を混合することにより、酸化鉄粒子表面に置換金属の塩を付着させる方法である。表面処理方法としては、酸化終了後の酸化鉄粒子の懸濁液を攪拌しながら、置換金属溶液を一定速度で添加する。添加速度は限定しないが、0.5〜3時間程度が好ましい。ここで、懸濁液のpHは5以上であることが好ましい。また、単独では、粒子表面に付着しにくい元素の場合、複数の金属元素を混合して添加することも有効である。例えば、FeとTi、CoとTiは混合して、添加することにより酸化粒子表面に均一に付着することが発明者らによって確認されている。 The wet surface treatment method is a method in which a substitution metal salt is attached to the surface of iron oxide particles by mixing a solution of the substitution metal salt with a liquid containing iron oxide particles obtained by the above-described oxidation synthesis. As the surface treatment method, the substitution metal solution is added at a constant rate while stirring the suspension of iron oxide particles after completion of oxidation. The rate of addition is not limited, but is preferably about 0.5 to 3 hours. Here, the pH of the suspension is preferably 5 or more. In addition, in the case of an element that does not easily adhere to the particle surface alone, it is also effective to add a plurality of metal elements in a mixture. For example, the inventors have confirmed that Fe and Ti and Co and Ti are mixed and added to uniformly adhere to the surface of the oxidized particles.
上記方法で使用する金属塩は、硫酸塩、塩酸塩、または酢酸塩などの有機酸塩等が挙げられる。得られる正極活物質中に不純物を残留させないという観点から、酢酸塩等の有機酸塩、硫酸塩等を用いることが好ましい。 Examples of the metal salt used in the above method include sulfates, hydrochlorides, or organic acid salts such as acetates. From the viewpoint of preventing impurities from remaining in the obtained positive electrode active material, it is preferable to use an organic acid salt such as acetate, a sulfate, or the like.
いずれの方法によっても、置換金属を鉄源とリン源、リチウム源との混合時に一緒に混合する方法と比較して、非常に反応性が良く、容易に性能の良い、均一で、微細な置換オリビン型リン酸鉄リチウム粒子を得ることが可能である。 Either method is very reactive, easy to perform, uniform and fine substitution compared to the method in which the substitution metal is mixed together when mixing the iron source with the phosphorus source and the lithium source. It is possible to obtain olivine type lithium iron phosphate particles.
(リチウム源及びリン源)
上記の鉄源に、リチウム源及びリン源を混合して、焼成して、オリビン型リン酸鉄リチウムを得る。
(Lithium source and phosphorus source)
A lithium source and a phosphorus source are mixed with the above iron source and fired to obtain olivine type lithium iron phosphate.
リチウム源としては、炭酸リチウム、水酸化リチウム、リン酸リチウム等、リン源としては、リン酸、リン酸二水素アンモニウム、リン酸水素二アンモニウム、リン酸二水素リチウム、リン酸リチウム等が挙げられる。 Examples of the lithium source include lithium carbonate, lithium hydroxide, and lithium phosphate. Examples of the phosphorus source include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, and lithium phosphate. .
(混合工程)
混合方法は特に限定されず、湿式混合でも乾式混合でも良く、装置としては、遊星ボールミル、ジェットミル、マグネチックスターラー等を用いることが適当である。
(Mixing process)
The mixing method is not particularly limited, and may be wet mixing or dry mixing. As an apparatus, it is appropriate to use a planetary ball mill, a jet mill, a magnetic stirrer, or the like.
(焼成工程)
焼成工程は、原料の混合物に熱エネルギーを供給することにより、その混合物を熱力学的に安定なオリビン型リン酸鉄リチウム化合物に転化させ、不純物を気化させ除去し、本発明の正極活物質の微細粒子を生成する工程である。
(Baking process)
In the firing step, by supplying thermal energy to the mixture of raw materials, the mixture is converted into a thermodynamically stable olivine-type lithium iron phosphate compound, and impurities are vaporized and removed. This is a process for producing fine particles.
焼成は、不活性ガス雰囲気もしくは還元性雰囲気下で行われる。不活性ガスとしては、窒素、ヘリウム、ネオン、アルゴン等が挙げられる。還元性雰囲気としては、水素、低級アルコール、例えば、メタノール、エタノール等の還元性化合物、還元性化合物と不活性ガスとの混合物等が挙げられる。還元性化合物と不活性ガスとの混合物を使用する場合、還元性化合物と不活性ガスとの混合比(体積比)は、特に制限を受けない。 Firing is performed in an inert gas atmosphere or a reducing atmosphere. Examples of the inert gas include nitrogen, helium, neon, and argon. Examples of the reducing atmosphere include hydrogen, lower alcohols, for example, reducing compounds such as methanol and ethanol, mixtures of reducing compounds and inert gases, and the like. When a mixture of a reducing compound and an inert gas is used, the mixing ratio (volume ratio) of the reducing compound and the inert gas is not particularly limited.
焼成温度は、400〜800℃が好ましい。1段階の焼成でも十分な結晶性を得ることは可能である。また、仮焼成工程と本焼成工程の二段階の焼成工程を行うことによって、より結晶性を上げることも可能である。仮焼成は、通常、200〜400℃の温度で行い、本焼成は、通常、400〜800℃の温度で行い、好ましくは500〜800℃、より好ましくは500〜750℃の温度で行う。 The firing temperature is preferably 400 to 800 ° C. It is possible to obtain sufficient crystallinity even by one-step firing. In addition, the crystallinity can be further improved by performing a two-stage firing process including a temporary firing process and a main firing process. The pre-baking is usually performed at a temperature of 200 to 400 ° C., and the main baking is usually performed at a temperature of 400 to 800 ° C., preferably 500 to 800 ° C., more preferably 500 to 750 ° C.
さらに、焼成前に、種々の導電性物質(例えば、炭素)またはその前駆体を混合し、不活性ガス雰囲気もしくは還元性雰囲気下で焼成することにより、オリビン型リン酸鉄リチウム粒子表面にそのような導電性物質を存在させた非常に微細な正極活物質を得ることができる。特に、炭素源を混合した場合、還元性ガスを使わずに、例えば、窒素ガスだけで、単相のオリビン型リン酸鉄リチウムを得ることができる。 Further, before firing, various conductive materials (for example, carbon) or precursors thereof are mixed and fired in an inert gas atmosphere or a reducing atmosphere, so that the surface of the olivine type lithium iron phosphate particles is so treated. It is possible to obtain a very fine positive electrode active material in which a conductive material is present. In particular, when a carbon source is mixed, single-phase olivine-type lithium iron phosphate can be obtained by using, for example, nitrogen gas alone without using a reducing gas.
導電性物質としては、炭素等が挙げられる。特に炭素が入手の容易さ、取り扱い易さの点で有利である。
炭素源の添加量は限定されないが、焼成後に残留する炭素分が正極として過剰にならない範囲であることは言うまでもなく、好ましくは、正極活物質の重量を基準として20重量%以下、特に1〜20重量%の範囲で添加することが望ましく、更に好ましくは、1〜10重量%である。
Examples of the conductive substance include carbon. In particular, carbon is advantageous in terms of easy availability and handling.
The amount of carbon source added is not limited, but it goes without saying that the carbon content remaining after firing does not become excessive as the positive electrode, preferably 20% by weight or less, particularly 1 to 20%, based on the weight of the positive electrode active material. It is desirable to add in the range of wt%, more preferably 1 to 10 wt%.
炭素源は、炭素粒子及び焼成により導電性炭素に変化する炭素前駆体の少なくとも一方を含む。炭素源として炭素前駆体を使用すると、粒子表面を炭素で平坦に被覆でき、比較的低い表面積を有する正極活物質を製造することができる。 The carbon source includes at least one of carbon particles and a carbon precursor that changes into conductive carbon by firing. When a carbon precursor is used as the carbon source, the particle surface can be coated flat with carbon, and a positive electrode active material having a relatively low surface area can be produced.
炭素粒子としては、公知のものを制限無く使用でき、例えば、アセチレンブラックなどのカーボンブラック;フラーレン;カーボンナノチューブ等が挙げられる。
炭素前駆体としては、例えば、ポリビニルアルコール、ポリオレフィン類、ポリアクリロニトリル、セルロース、デンプン、グルコース、グラニュー糖などの糖類等及び天然の有機高分子化合物(特に、水溶性のもの);アクリロニトリル、ジビニルベンゼン、ビニルアセテート等の重合性単量体(特に、炭素−炭素二重結合を有する不飽和有機化合物)等が挙げられる。
Known carbon particles can be used without limitation, and examples thereof include carbon black such as acetylene black; fullerene; carbon nanotubes and the like.
Examples of the carbon precursor include saccharides such as polyvinyl alcohol, polyolefins, polyacrylonitrile, cellulose, starch, glucose and granulated sugar, and natural organic polymer compounds (particularly water-soluble compounds); acrylonitrile, divinylbenzene, Examples thereof include polymerizable monomers such as vinyl acetate (particularly unsaturated organic compounds having a carbon-carbon double bond).
炭素源は、焼成工程のどの段階で原料に加えてもよく、例えば、仮焼成の前に加えてもよく、仮焼成後本焼成の前に加えてもよく、仮焼成の前と本焼成の前と両段階で加えてもよい。また、炭素源を加えることにより、不活性ガスのみで焼成してもオリビン単相を得ることも可能となる。 The carbon source may be added to the raw material at any stage of the baking process, for example, may be added before the preliminary baking, or may be added after the preliminary baking and before the main baking. It may be added before and at both stages. Further, by adding a carbon source, it is possible to obtain an olivine single phase even when firing with only an inert gas.
[正極活物質]
本発明の正極活物質は、オリビン型リン酸鉄リチウムを主成分として含むことが必要であるが、オリビン型リン酸鉄リチウム以外の他の成分として、炭素などの導電性物質などを含ませることができる。他の成分の配合割合は、正極活物質の30%以下とすることが必要である。
[Positive electrode active material]
The positive electrode active material of the present invention needs to contain olivine-type lithium iron phosphate as a main component, but as a component other than olivine-type lithium iron phosphate, it should contain a conductive material such as carbon. Can do. The blending ratio of other components needs to be 30% or less of the positive electrode active material.
正極活物質の平均粒径は、好ましくは500nm以下であり、より好ましくは10〜200nmである。導電性の低いオリビン型正極活物質の場合、その平均粒径が大きすぎると十分な容量が得られない。正極活物質また、粒径の変動係数が0.50以下、特に0.40以下を有することが好ましく、10〜50m2/gのBET比表面積値を有することが好ましい。 The average particle diameter of the positive electrode active material is preferably 500 nm or less, more preferably 10 to 200 nm. In the case of an olivine-type positive electrode active material with low conductivity, if the average particle size is too large, sufficient capacity cannot be obtained. The positive electrode active material preferably has a coefficient of variation in particle size of 0.50 or less, particularly 0.40 or less, and preferably has a BET specific surface area value of 10 to 50 m 2 / g.
[非水電解質電池]
(電池の構造)
本発明の正極活物質を用いた非水電解質電池の一例を添付図面を用いて説明する。
図28は電池の概略を示す断面図である。この図において非水電解質電池1は、大まかに言って電池の外部負極として機能する負極部材2と、電池の外部正極として機能する正極部材3と、両部材間に負極集電体4、負極活物質層5、セパレータ8、正極活物質層7及び正極集電体6をこの順番で有してなる。負極部材2はほぼ円筒形をしており、その内部に負極集電体4及び負極活物質5を収容できるように構成されている。一方、正極部材3もほぼ円筒形をしており、その内部に正極集電体6及び正極活物質層7を収容できるように構成されている。正極部材3及びセパレータ8の半径方向の寸法は負極部材2のものよりもやや大きめに設定されており、負極部材2の周端部とセパレータ8及び正極部材3の周端部とが重なり合うようになっている。電池内部の空間は非水電解質9が充填され、負極部材2、セパレータ8及び正極部材3の周端部の重なり合う部分には封止材10が施されて、電池内部が気密状態に保たれている。
[Nonaqueous electrolyte battery]
(Battery structure)
An example of a nonaqueous electrolyte battery using the positive electrode active material of the present invention will be described with reference to the accompanying drawings.
FIG. 28 is a cross-sectional view schematically showing the battery. In this figure, a non-aqueous electrolyte battery 1 generally includes a negative electrode member 2 that functions as an external negative electrode of the battery, a positive electrode member 3 that functions as an external positive electrode of the battery, a negative electrode current collector 4, a negative electrode active material between the two members. The material layer 5, the separator 8, the positive electrode active material layer 7, and the positive electrode current collector 6 are provided in this order. The negative electrode member 2 has a substantially cylindrical shape, and is configured to accommodate the negative electrode current collector 4 and the negative electrode active material 5 therein. On the other hand, the positive electrode member 3 also has a substantially cylindrical shape, and is configured to accommodate the positive electrode current collector 6 and the positive electrode active material layer 7 therein. The dimensions of the positive electrode member 3 and the separator 8 in the radial direction are set slightly larger than those of the negative electrode member 2 so that the peripheral end portions of the negative electrode member 2 and the peripheral end portions of the separator 8 and the positive electrode member 3 overlap each other. It has become. The space inside the battery is filled with a non-aqueous electrolyte 9, and a sealing material 10 is applied to the overlapping portions of the peripheral ends of the negative electrode member 2, the separator 8, and the positive electrode member 3 to keep the inside of the battery airtight. Yes.
負極は、負極部材2を外部負極として、それに接する負極集電体4、及び負極集電体上の負極活物質層5が形成されてなる。負極集電体としては、例えばニッケル箔、銅箔等が用いられる。負極活物質層としては、リチウムをドープ/脱ドープ可能なものを用い、具体的には、金属リチウム、リチウム合金、リチウムがドープされた導電性高分子、層状化合物(炭素材料や金属酸化物等)等を用いる。負極活物質層に含有される結着材としては、この種の非水電解質電池の負極活物質層の結着材として通常用いられている公知の樹脂材料等を用いることができる。特に、金属リチウム箔は負極活物質としてのみならず負極集電体としても用いることができるので、負極に金属リチウム箔を使用することにより電池構造を簡易なものとすることができる。 The negative electrode comprises a negative electrode member 2 as an external negative electrode, and a negative electrode current collector 4 in contact therewith and a negative electrode active material layer 5 on the negative electrode current collector. As the negative electrode current collector, for example, nickel foil, copper foil or the like is used. As the negative electrode active material layer, a layer capable of doping / de-doping lithium is used. Specifically, metallic lithium, lithium alloy, conductive polymer doped with lithium, layered compound (carbon material, metal oxide, etc. ) Etc. As the binder contained in the negative electrode active material layer, a known resin material or the like that is usually used as a binder for the negative electrode active material layer of this type of non-aqueous electrolyte battery can be used. In particular, since the metal lithium foil can be used not only as the negative electrode active material but also as the negative electrode current collector, the battery structure can be simplified by using the metal lithium foil for the negative electrode.
正極は、正極部材3を外部正極として、それに接する正極集電体6、及び正極集電体上の正極活物質層7が形成されてなる。正極活物質として、上述した本発明の正極活物質を使用する。正極集電体としては、例えばアルミニウム箔等が用いられる。正極活物質層に含有される結着材としては、ポリフッ化ビニリデン(PVDF)、ポリテトラフルオロエチレン(PTFE)等のこの種の非水電解質電池の正極活物質層の結着材として通常用いられている公知の樹脂材料等を用いることができる。正極活物質層には、導電性を向上させるために導電材を配合することができる。この導電材としては、例えば、グラファイト、アセチレンブラック等が挙げられる。 The positive electrode comprises a positive electrode member 3 as an external positive electrode, and a positive electrode current collector 6 in contact therewith, and a positive electrode active material layer 7 on the positive electrode current collector. The positive electrode active material of the present invention described above is used as the positive electrode active material. For example, an aluminum foil or the like is used as the positive electrode current collector. As the binder contained in the positive electrode active material layer, it is usually used as a binder for the positive electrode active material layer of this type of non-aqueous electrolyte battery such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and the like. A known resin material or the like can be used. A conductive material can be blended in the positive electrode active material layer in order to improve conductivity. Examples of the conductive material include graphite and acetylene black.
セパレータ8は、正極と負極とを離間させるものであり、この種の非水電解質電池のセパレータとして通常用いられている公知の材料を用いることができ、例えば、ポリプロピレン等の高分子フィルム、ポリエチレンカーボネート多孔質膜等が用いられる。また、リチウムイオン伝導度とエネルギー密度との関係から、セパレータの厚みはできるだけ薄いことが望ましい。具体的には、セパレータの厚みは例えば50μm以下が好ましい。 The separator 8 separates the positive electrode and the negative electrode, and a known material that is usually used as a separator for this type of non-aqueous electrolyte battery can be used. For example, a polymer film such as polypropylene, polyethylene carbonate, etc. A porous membrane or the like is used. In addition, it is desirable that the thickness of the separator is as thin as possible from the relationship between lithium ion conductivity and energy density. Specifically, the thickness of the separator is preferably 50 μm or less, for example.
封止材10としては、この種の非水電解質電池の正極活物質層の封止材として通常用いられている公知の樹脂材料等を用いることができる。
非水電解質としては、液体電解質のみならず、固体電解質、溶媒を含有するゲル状電解質など種々の形態のものが使用できる。液体電解質としては、非プロトン性非水溶媒に電解質を溶解させた溶液を用いる。非水溶媒としては、例えば、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、ビニレンカーボネート等の環状カーボネート類、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート等の鎖状カーボネート類、γ−ブチルラクトン、スルホラン、1,2−ジメトキシエタン、1,2−ジエトキシエタン、2−メチルテトラヒドロフラン、3−メチル1,3−ジオキソラン、プロピオン酸メチル、酪酸メチル等を挙げることができる。特に、電圧安定性の点からは、エチレンカーボネート、プロピレンカーボネート、ビニレンカーボネート等の環状カーボネート類、ジメチルカーボネート、ジエチルカーボネート、ジプロピルカーボネート等の鎖状カーボネート類を使用することが好ましい。また、このような非水溶媒は、1種類を単独で用いてもよいし、2種類以上を混合して用いてもよい。電解質としては、例えば、LiPF6、LiClO4、LiAsF6、LiBF4、LiCF3SO3、LiN(CF3SO2)2等のリチウム塩を使用することができる。これらのリチウム塩の中でも、LiPF6、LiBF4を使用することが好ましい。また、固体電解質としては、窒化リチウム、ヨウ化リチウム等の無機固体電解質;ポリ(エチレンオキサイド)、ポリ(メタクリレート)、ポリ(アクリレート)等の有機高分子電解質等が挙げられる。更に、ゲル状電解質を形成するための材料としては、上記液体電解質を吸収してゲル化できる材料であれば特に制限無く使用することができ、例えば、ポリ(ビニリデンフルオライド)、ビニリデンフルオライド/ヘキサフルオロプロピレン共重合体などの含フッ素重合体が挙げられる。
As the sealing material 10, a known resin material or the like that is normally used as a sealing material for the positive electrode active material layer of this type of non-aqueous electrolyte battery can be used.
As the non-aqueous electrolyte, not only a liquid electrolyte but also various forms such as a solid electrolyte and a gel electrolyte containing a solvent can be used. As the liquid electrolyte, a solution in which an electrolyte is dissolved in an aprotic nonaqueous solvent is used. Examples of the non-aqueous solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate, and dipropyl carbonate, γ-butyllactone, sulfolane, 1, Examples include 2-dimethoxyethane, 1,2-diethoxyethane, 2-methyltetrahydrofuran, 3-methyl-1,3-dioxolane, methyl propionate, and methyl butyrate. In particular, from the viewpoint of voltage stability, it is preferable to use cyclic carbonates such as ethylene carbonate, propylene carbonate, and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate, and dipropyl carbonate. Moreover, such a non-aqueous solvent may be used individually by 1 type, and may be used in mixture of 2 or more types. As the electrolyte, for example, lithium salts such as LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 can be used. Among these lithium salts, it is preferable to use LiPF 6 or LiBF 4 . Examples of the solid electrolyte include inorganic solid electrolytes such as lithium nitride and lithium iodide; organic polymer electrolytes such as poly (ethylene oxide), poly (methacrylate), and poly (acrylate). Furthermore, the material for forming the gel electrolyte can be used without particular limitation as long as it is a material capable of gelling by absorbing the liquid electrolyte. For example, poly (vinylidene fluoride), vinylidene fluoride / Examples thereof include fluorine-containing polymers such as hexafluoropropylene copolymers.
(電池の製造方法)
本発明の正極活物質を使用した非水電解質電池は、例えば、以下のように製造される。
まず、負極の製造方法から説明する。負極活物質と結着材とを溶媒中に分散させてスラリーを調製する。得られたスラリーを集電体上に均一に塗布、乾燥して負極活物質層を形成する。得られた負極集電体及び負極活物質層からなる積層体を負極部材内に負極集電体と負極部材内面が接するように収容して負極が形成される。また、前述したように負極活物質及び負極活物質として金属リチウム箔をそのまま用いることもできる。
(Battery manufacturing method)
The nonaqueous electrolyte battery using the positive electrode active material of the present invention is manufactured as follows, for example.
First, the negative electrode manufacturing method will be described. A negative electrode active material and a binder are dispersed in a solvent to prepare a slurry. The obtained slurry is uniformly applied on a current collector and dried to form a negative electrode active material layer. The obtained laminate including the negative electrode current collector and the negative electrode active material layer is accommodated in the negative electrode member so that the negative electrode current collector and the inner surface of the negative electrode member are in contact with each other to form a negative electrode. Further, as described above, the metal lithium foil can be used as it is as the negative electrode active material and the negative electrode active material.
次に正極の製造方法を説明する。本発明の正極活物質、導電材及び結着材を溶媒中に分散させてスラリーを調製する。スラリーを集電体上に均一に塗布、乾燥して正極活物質層を形成する。得られた正極集電体及び正極活物質層からなる積層体を正極部材内に正極集電体と正極部材内面が接するように収容して正極が形成される。 Next, the manufacturing method of a positive electrode is demonstrated. A positive electrode active material, a conductive material, and a binder of the present invention are dispersed in a solvent to prepare a slurry. The slurry is uniformly applied on the current collector and dried to form a positive electrode active material layer. The obtained laminate of the positive electrode current collector and the positive electrode active material layer is accommodated in the positive electrode member so that the positive electrode current collector and the inner surface of the positive electrode member are in contact with each other, thereby forming a positive electrode.
非水電解質は、液状のものを採用する場合は、電解質塩を非水溶媒中に溶解することにより調製される。
上述のようにして製造された負極及び正極を、負極活物質層と正極活物質層との間にセパレータが介在するように重ね合わせ、非水電解質を充填し、封止材により電池内部を密封することにより、非水電解質電池が完成する。
When a nonaqueous electrolyte is used, it is prepared by dissolving an electrolyte salt in a nonaqueous solvent.
The negative electrode and the positive electrode manufactured as described above are overlapped so that a separator is interposed between the negative electrode active material layer and the positive electrode active material layer, filled with a nonaqueous electrolyte, and the inside of the battery is sealed with a sealing material. By doing so, a non-aqueous electrolyte battery is completed.
本発明の非水電解質電池は、その形状については特に限定されることはなく、円筒型、角型、コイン型、ボタン型等の形状とすることができ、また、薄型、大型等の種々の大きさにすることができる。また、本発明は、一次電池についても二次電池についても適用可能である。 The shape of the nonaqueous electrolyte battery of the present invention is not particularly limited, and can be a cylindrical shape, a square shape, a coin shape, a button shape, or the like, and various types such as a thin shape and a large size are available. Can be sized. The present invention can be applied to both a primary battery and a secondary battery.
[実施例]
以下、本発明を実施例に基づき詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、以下の例において、酸化鉄、正極活物質及び非水電解質電池の分析は次の方法により行った。
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
In the following examples, analysis of iron oxide, positive electrode active material, and nonaqueous electrolyte battery was performed by the following method.
(X線回折)
X線回折測定は、CoKα Rigaku RINT 2200V((株)リガク社製)を用いて行った。なお、本明細書においてD111は111面の結晶面に対応する回折ピークの半価幅から下記Scherrerの式:
L=Kλ/(βcosθ)
(式中、Lは結晶子径、Kは定数(=0.9)、λはX線波長、βは半価幅、θは反射角である。)
に従って求めた結晶子径である。
(X-ray diffraction)
X-ray diffraction measurement was performed using CoKα Rigaku RINT 2200V (manufactured by Rigaku Corporation). In this specification, D 111 is the following Scherrer formula from the half-value width of the diffraction peak corresponding to the crystal plane of the 111 plane:
L = Kλ / (βcosθ)
(In the formula, L is a crystallite diameter, K is a constant (= 0.9), λ is an X-ray wavelength, β is a half-value width, and θ is a reflection angle.)
The crystallite diameter determined according to
(比表面積)
比表面積測定は、BET法に従って、全自動表面積測定装置 マルチソーブ12(湯浅アイオニックス(株)社製)を用いて行った。
(Specific surface area)
The specific surface area measurement was performed using a fully automatic surface area measuring device Multisorb 12 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.
(金属組成分析)
金属組成分析は、ICP発光分光分析(ICP発光分光分析装置SPS1500VR Seiko Instruments Inc.製)で測定し、Feに対するmol比で算出した。
(Metal composition analysis)
The metal composition analysis was measured by ICP emission spectroscopic analysis (ICP emission spectroscopic analyzer SPS1500VR Seiko Instruments Inc.) and calculated by the molar ratio with respect to Fe.
(炭素量)
炭素量測定は、CARBON ANALYZER(HORIBA EMIA−221V)を用いて行った。
(Carbon content)
The carbon content was measured using CARBON ANALYZER (HORIBA EMIA-221V).
(粒子径)
粒子径について、TEM(透過型電子顕微鏡 H−7600 日立製)又はSEM(走査型電子顕微鏡 DS130 (株)トプコン電子ビームサービス社製)で観察される200個の粒子を無作為に選び、各粒子の粒子径を測定し、それら測定値の平均値および標準偏差を算出し、この平均値を粒子径とした。なお、粒子径の変動係数は、このようにして求めた標準偏差を平均粒子径で除した値である。
(Particle size)
For the particle size, 200 particles observed randomly with TEM (transmission electron microscope H-7600 manufactured by Hitachi) or SEM (scanning electron microscope DS130 manufactured by Topcon Electron Beam Service Co., Ltd.) were randomly selected. The average particle size and standard deviation of the measured values were calculated, and this average value was taken as the particle size. The variation coefficient of the particle diameter is a value obtained by dividing the standard deviation thus obtained by the average particle diameter.
(1)Tiドープ酸化鉄の製造
60Lの反応容器にNaOHを55.2 molを含む水溶液40Lを仕込み、窒素ガスを通気して置換し、80℃に保持した。ここに、窒素通気、攪拌しながら、6molのFeSO4と 6molのFe2(SO4)3およびTi(SO4)2 0.36molを含む水溶液20Lを添加して、80℃で3時間混合した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子Tiドープ酸化鉄を得た。
(1) Manufacture of Ti-doped iron oxide 40 L of an aqueous solution containing 55.2 mol of NaOH was charged into a 60 L reaction vessel, and the gas was replaced with nitrogen gas, and kept at 80 ° C. To this, 20 L of an aqueous solution containing 6 mol of FeSO 4 , 6 mol of Fe 2 (SO 4 ) 3 and 0.36 mol of Ti (SO 4 ) 2 was added while stirring with nitrogen, and mixed at 80 ° C. for 3 hours. . The obtained suspension was filtered, washed and dried to obtain fine particle Ti-doped iron oxide.
得られた試料の比表面積測定はBET法で測定した。得られた試料のBET値は87.9m2/gであった。
得られた試料のTEM写真を図1に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は10nmであった。
得られた粒子のX線回折測定をおこなった。図2に得られた粒子のX線回折図を示す。X線回折図よりマグネタイト単相であることが確認された。
The specific surface area of the obtained sample was measured by the BET method. The BET value of the obtained sample was 87.9 m 2 / g.
A TEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The average particle size of the obtained sample was 10 nm.
X-ray diffraction measurement was performed on the obtained particles. FIG. 2 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be a magnetite single phase.
(2)LiFe0.98Ti0.02PO4の製造方法
上記で(1)で得られた酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られたTiドープ酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.079mol、(NH4)2HPO4 0.153molおよびグルコース4gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、12時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で6時間焼成し、正極活物質LiFe0.98Ti0.02PO4を得た。得られた試料のBET値は17.5m2/gであった。得られた試料のSEM写真を図3に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は57nm、変動係数は0.27であった。
(2) Method for producing LiFe 0.98 Ti 0.02 PO 4 Using the iron oxide obtained in (1) above as a raw material, olivine-type lithium iron phosphate was synthesized. Ti-doped iron oxide obtained in (1) 0.05 mol (0.15 mol as a metal content), Li 2 CO 3 0.079 mol, (NH 4 ) 2 HPO 4 0.153 mol and glucose 4 g in an 80 mL planetary ball mill container Then, 20 mL of pure water was further added and mixed at 250 rpm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.98 Ti 0.02 PO 4 . The BET value of the obtained sample was 17.5 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 57 nm and a variation coefficient of 0.27.
得られた粒子のX線回折測定をおこなった。図4に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 4 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
(3)コインセルの作製
(2)で得られた正極活物質を使って、リチウム二次電池を作製した。得られた試料と結着材としてポリテトラフルオロエチレン、導電材としてアセチレンブラックを用い、正極活物質:導電材:結着材=70:25(全C量として、即ち、予め処理してあるカーボン(グルコース由来)の量にアセチレンブラックを足した量として):5の重量比で混合し、メノウ乳鉢で混錬した後、コルクボーラーを用いて直径1.0cmのディスク状に型抜きし、これを正極ペレットとして使用した。
(3) Production of coin cell Using the positive electrode active material obtained in (2), a lithium secondary battery was produced. Using the obtained sample, polytetrafluoroethylene as the binder, and acetylene black as the conductive material, positive electrode active material: conductive material: binder = 70: 25 (total carbon content, ie, pre-treated carbon (As the amount of acetylene black added to the amount of glucose) Was used as a positive electrode pellet.
上記正極ペレットを用いてコインセルを作製した。正極ペレットの対極として、直径1.5mm、厚さ0.15mmのリチウム箔を用いた。セパレータとしては、直径22mm、厚さ0.02mmの多孔質ポリエチレンシートを用いた。非水電解質溶液としては、エチレンカーボネート(EC)とジメチルカーボネート(DMC)との体積比1:1の混合溶媒に、約1モル/リットルの濃度でLiPF6を溶解させたものを使用した。これらの構成要素をステンレス製の正極容器及び負極蓋に組み込んで、ガスケットで密封して、厚さ2mm、直径32mm(2032型)の図5に示すコイン型測定用セルを作製した。なお、一連の電池組み立て作業はアルゴン精製装置を備えた露点−90℃以下のドライボックス内で行った。 A coin cell was produced using the positive electrode pellet. As the counter electrode of the positive electrode pellet, a lithium foil having a diameter of 1.5 mm and a thickness of 0.15 mm was used. As the separator, a porous polyethylene sheet having a diameter of 22 mm and a thickness of 0.02 mm was used. As the nonaqueous electrolyte solution, a solution obtained by dissolving LiPF 6 at a concentration of about 1 mol / liter in a mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1 was used. These components were incorporated into a stainless steel positive electrode container and a negative electrode lid and sealed with a gasket to produce a coin-type measurement cell shown in FIG. 5 having a thickness of 2 mm and a diameter of 32 mm (2032 type). In addition, a series of battery assembly operations were performed in a dry box having a dew point of −90 ° C. or less equipped with an argon purification device.
このようにして得られた簡易リチウム二次電池について充放電試験を行った。充放電試験は25℃において、電位範囲:2000〜4500mV、レート:0.2、1、5C、C.C−C.Vで行った。レート0.2Cにおける初期充放電特性を図6に示す(図中、「Chg」は充電、「Dis」は放電を表す。)。また、各レートの初期充放電容量を表2に示す。 A charge / discharge test was conducted on the simple lithium secondary battery thus obtained. The charge / discharge test was conducted at 25 ° C. with a potential range of 2000 to 4500 mV, a rate of 0.2, 1, 5C, and C.I. CC. V performed. The initial charge / discharge characteristics at a rate of 0.2 C are shown in FIG. 6 (in the figure, “Chg” represents charge and “Dis” represents discharge). Table 2 shows the initial charge / discharge capacity at each rate.
(1)TiおよびMnドープ酸化鉄の製造
60Lの反応容器にNaOHを24 mol、Na2CO3を 12 molを含む水溶液40Lを仕込み、窒素ガスを通気して置換し、60℃に保持した。ここに、窒素通気、攪拌しながら、FeSO4 18mol、Fe2(SO4)3 0.9mol、Ti(SO4)2 0.40molおよびMnSO4 0.40molを含む水溶液20Lを添加して、水酸化鉄粒子を含有する懸濁液とし、60℃で60分間混合した。次に、60℃のまま、空気を10L/minで通気させ、2時間、酸化反応を行った。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。試料の比表面積測定はBET法で測定した。得られた試料のBET値は29.5m2/gであった。得られた試料のTEM写真を図7に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は65nmであった。
(1) Manufacture of Ti and Mn doped iron oxide A 60 L reaction vessel was charged with 40 L of an aqueous solution containing 24 mol of NaOH and 12 mol of Na 2 CO 3 , nitrogen gas was passed through and replaced, and the temperature was maintained at 60 ° C. To this, 20 L of an aqueous solution containing 18 mol of FeSO 4, 0.9 mol of Fe 2 (SO 4 ) 3, 0.40 mol of Ti (SO 4 ) 2 and 0.40 mol of MnSO 4 was added while stirring with nitrogen. A suspension containing iron oxide particles was prepared and mixed at 60 ° C. for 60 minutes. Next, the air was aerated at 10 L / min while maintaining the temperature at 60 ° C., and an oxidation reaction was performed for 2 hours. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide. The specific surface area of the sample was measured by the BET method. The BET value of the obtained sample was 29.5 m 2 / g. A TEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The average particle size of the obtained sample was 65 nm.
(2)LiFe0.96Ti0.02Mn0.02PO4の製造方法
上記で(1)で得られた酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られたTi、Mnドープ酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.080mol、(NH4)2HPO4 0.15 molおよびグルコース5gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、24時間混合した。150℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で12時間焼成し、正極活物質LiFe0.96Ti0.02Mn0.02PO4を得た。得られた試料のBET値は21.5m2/gであった。得られた試料のSEM写真を図8に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は62nm、変動係数は0.39であった。
(2) Production method of LiFe 0.96 Ti 0.02 Mn 0.02 PO 4 Using the iron oxide obtained in (1) above as a raw material, olivine-type lithium iron phosphate was synthesized. Ti and Mn doped iron oxide obtained in (1) 0.05 mol (0.15 mol as metal content), Li 2 CO 3 0.080 mol, (NH 4 ) 2 HPO 4 0.15 mol and glucose 5 g in 80 mL planetary Into a ball mill container, 20 mL of pure water was further added and mixed at 250 rpm for 24 hours. After drying at 150 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 12 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.96 Ti 0.02 Mn 0.02 PO 4 . The BET value of the obtained sample was 21.5 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The average particle diameter of the obtained sample was 62 nm, and the coefficient of variation was 0.39.
得られた粒子のX線回折測定をおこなった。図9に得られた粒子のX線回折図を示す。
X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 9 shows an X-ray diffraction pattern of the obtained particles.
From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)Ti表面処理酸化鉄の製造
60Lの反応容器にNaOHを52.8 molを含む水溶液40Lを仕込み、窒素ガスを通気して置換し、80℃に保持した。ここに、窒素通気、攪拌しながら、6molのFeSO4と 6molのFe2(SO4)3を含む水溶液20Lを添加して、80℃で3時間混合した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。試料の比表面積測定はBET法で測定した。得られた試料のBET値は74.2m2/gであった。
(1) Manufacture of Ti surface-treated iron oxide 40 L of an aqueous solution containing 52.8 mol of NaOH was charged into a 60 L reaction vessel, and the gas was replaced with nitrogen gas, and kept at 80 ° C. To this, 20 L of an aqueous solution containing 6 mol of FeSO 4 and 6 mol of Fe 2 (SO 4 ) 3 was added with nitrogen aeration and stirring, and mixed at 80 ° C. for 3 hours. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide. The specific surface area of the sample was measured by the BET method. The BET value of the obtained sample was 74.2 m 2 / g.
得られた酸化後の懸濁液を均一になるよう混合して、その6L(Feとして、1.8mol)を15Lの反応容器に仕込んだ。室温で、混合しながら、Ti(SO4)2 0.018molを溶解した水溶液1Lを1時間かけて滴下した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。得られた試料のTEM写真を図10に示す。 The obtained suspension after oxidation was mixed uniformly, and 6 L (1.8 mol as Fe) was charged into a 15 L reaction vessel. While mixing at room temperature, 1 L of an aqueous solution in which 0.018 mol of Ti (SO 4 ) 2 was dissolved was added dropwise over 1 hour. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide. A TEM photograph of the obtained sample is shown in FIG.
(2)LiFe0.99Ti0.01PO4の製造方法
上記で(1)で得られた表面処理酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.079mol、(NH4)2HPO4 0.162molおよびグルコース4gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、12時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で12時間焼成し、正極活物質LiFe0.99Ti0.01PO4を得た。得られた試料のBET値は15.3m2/gであった。得られた試料のSEM写真を図11に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は76nm、変動係数は0.35であった。
(2) Method for producing LiFe 0.99 Ti 0.01 PO 4 Olivine-type lithium iron phosphate was synthesized from the surface-treated iron oxide obtained in (1) above. (1) obtained in iron oxide 0.05 mol (0.15 mol as the metal component), Li 2 CO 3 0.079mol, (NH 4) 2 placed HPO 4 0.162 mol and glucose 4g in 80mL planetary ball mill, Further, 20 mL of pure water was added and mixed at 250 rpm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 12 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.99 Ti 0.01 PO 4 . The obtained sample had a BET value of 15.3 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The average particle diameter of the obtained sample was 76 nm, and the coefficient of variation was 0.35.
得られた粒子のX線回折測定を行った。図12に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 12 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)Ti、Co表面処理酸化鉄の製造
60Lの反応容器にNaOHを23 mol、Na2CO3を 11 molを含む水溶液40Lを仕込み、窒素ガスを通気して置換し、60℃に保持した。ここに、窒素通気、攪拌しながら、18molのFeSO4と 0.9molのFe2(SO4)3を含む水溶液20Lを添加して、水酸化鉄粒子を含有する懸濁液とし、60℃で60分間混合した。次に、60℃のまま、空気を10L/minで通気させ、2時間、酸化反応を行った。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。試料の比表面積測定はBET法で測定した。得られた試料のBET値は27.4m2/gであった。
(1) Manufacture of Ti and Co surface-treated iron oxide A 60 L reaction vessel was charged with 40 L of an aqueous solution containing 23 mol of NaOH and 11 mol of Na 2 CO 3 , replaced with nitrogen gas, and maintained at 60 ° C. . To this, 20 L of an aqueous solution containing 18 mol of FeSO 4 and 0.9 mol of Fe 2 (SO 4 ) 3 was added with nitrogen aeration and stirring to obtain a suspension containing iron hydroxide particles at 60 ° C. Mix for 60 minutes. Next, the air was aerated at 10 L / min while maintaining the temperature at 60 ° C., and an oxidation reaction was performed for 2 hours. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide. The specific surface area of the sample was measured by the BET method. The BET value of the obtained sample was 27.4 m 2 / g.
得られた酸化後の懸濁液を均一になるよう混合して、その6L(Feとして、1.8mol)を15Lの反応容器に仕込み、Na2CO3 0.54molを溶解した水溶液1Lを加え、混合した。室温で、混合しながら、Ti(SO4)2 0.036molおよびCoSO4・7H2O 0.018molを溶解した水溶液1Lを1時間かけて滴下した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。 The obtained suspension after oxidation was mixed uniformly, 6 L (1.8 mol as Fe) was charged into a 15 L reaction vessel, and 1 L of an aqueous solution in which 0.54 mol of Na 2 CO 3 was dissolved was added. , Mixed. While mixing at room temperature, 1 L of an aqueous solution in which 0.036 mol of Ti (SO 4 ) 2 and 0.018 mol of CoSO 4 .7H 2 O were dissolved was added dropwise over 1 hour. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide.
(2)LiFe0.97Ti0.02Co0.01PO4の製造方法
上記で(1)で得られた表面処理酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.079mol、(NH4)2HPO4 0.15 molおよびグルコース6gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、24時間混合した。150℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、700℃で4時間焼成し、正極活物質LiFe0.97Ti0.02Co0.01PO4を得た。得られた試料のBET値は13.5m2/gであった。得られた試料のSEM写真を図13に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は101nm、変動係数は0.39であった。
(2) LiFe 0.97 Ti at 0.02 Co 0.01 PO 4 of the method for manufacturing the surface-treated iron oxide obtained in (1) was synthesized olivine type lithium iron phosphate as a raw material. Into an 80 mL planetary ball mill container, 0.05 mol of iron oxide obtained in (1) (0.15 mol as a metal content), 0.079 mol of Li 2 CO 3 , 0.15 mol of (NH 4 ) 2 HPO 4 and 6 g of glucose are placed. Further, 20 mL of pure water was added and mixed at 250 rpm for 24 hours. After drying at 150 ° C., the mixture was pulverized in an agate mortar and fired at 700 ° C. for 4 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.97 Ti 0.02 Co 0.01 PO 4 . The BET value of the obtained sample was 13.5 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 101 nm and a coefficient of variation of 0.39.
得られた粒子のX線回折測定をおこなった。図14に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 14 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)Ti、Mn表面処理酸化鉄の製造
実施例3と同様にして、得られた酸化後の懸濁液を均一になるよう混合して、その6L(Feとして、1.8mol)を15Lの反応容器に仕込み、Na2CO3 0.54molを溶解した水溶液1Lを加え、混合した。室温で、混合しながら、Ti(SO4)2 0.018molおよびMnSO4 0.036molを溶解した水溶液1Lを1時間かけて滴下した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。
(1) Production of Ti and Mn surface-treated iron oxide In the same manner as in Example 3, the obtained suspension after oxidation was mixed uniformly, and 6 L (1.8 mol as Fe) was mixed with 15 L. 1 L of an aqueous solution in which 0.54 mol of Na 2 CO 3 was dissolved was added and mixed. While mixing at room temperature, 1 L of an aqueous solution in which 0.018 mol of Ti (SO 4 ) 2 and 0.036 mol of MnSO 4 were dissolved was added dropwise over 1 hour. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide.
(2)LiFe0.97Ti0.01Mn0.02PO4の製造方法
上記で(1)で得られた表面処理酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた表面処理後の酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.079mol、(NH4)2HPO4 0.153 molおよびグルコース4gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、6時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で6時間焼成し、正極活物質LiFe0.99Ti0.01PO4を得た。得られた試料のBET値は17.4m2/gであった。得られた試料のSEM写真を図15に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は65nm、変動係数は 0.34であった。
(2) LiFe 0.97 Ti at 0.01 Mn 0.02 PO 4 of the method for manufacturing the surface-treated iron oxide obtained in (1) was synthesized olivine type lithium iron phosphate as a raw material. The surface-treated iron oxide 0.05 mol (0.15 mol as a metal content) obtained in (1), Li 2 CO 3 0.079 mol, (NH 4 ) 2 HPO 4 0.153 mol and glucose 4 g in 80 mL planetary Into a ball mill container, 20 mL of pure water was further added and mixed at 250 rpm for 6 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.99 Ti 0.01 PO 4 . The obtained sample had a BET value of 17.4 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 65 nm and a coefficient of variation of 0.34.
得られた粒子のX線回折測定をおこなった。図16に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 16 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)Ti表面処理酸化鉄の製造
実施例3と同様にして、得られた酸化後の懸濁液を均一になるよう混合して、その6L(Feとして、1.8mol)を15Lの反応容器に仕込み、Na2CO3 0.54molを溶解した水溶液1Lを加え、混合した。室温で、混合しながら、Ti(SO4)2 0.178molを溶解した水溶液1Lを1時間かけて滴下した。得られた懸濁液をろ過、洗浄、乾燥して、表面処理酸化鉄を得た。
(1) Production of Ti surface-treated iron oxide In the same manner as in Example 3, the obtained suspension after oxidation was mixed uniformly, and 6 L (1.8 mol as Fe) was reacted in 15 L. The container was charged and 1 L of an aqueous solution in which 0.54 mol of Na 2 CO 3 was dissolved was added and mixed. While mixing at room temperature, 1 L of an aqueous solution in which 0.178 mol of Ti (SO 4 ) 2 was dissolved was added dropwise over 1 hour. The obtained suspension was filtered, washed and dried to obtain surface-treated iron oxide.
(2)LiFe0.91Ti0.09PO4の製造方法
上記で(1)で得られた表面処理酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.079mol、(NH4)2HPO4 0.158molおよびグルコース5gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、24時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、750℃で3時間焼成し、正極活物質LiFe0.91Ti0.09PO4を得た。得られた試料のBET値は22.9m2/gであった。得られた試料のSEM写真を図17に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は64nm、変動係数は0.39であった。
(2) Method for producing LiFe 0.91 Ti 0.09 PO 4 Using the surface-treated iron oxide obtained in (1) above as a raw material, olivine-type lithium iron phosphate was synthesized. Put the iron oxide 0.05 mol (0.15 mol as a metal content) obtained in (1), Li 2 CO 3 0.079 mol, (NH 4 ) 2 HPO 4 0.158 mol and glucose 5 g in an 80 mL planetary ball mill container, Further, 20 mL of pure water was added and mixed at 250 rpm for 24 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 750 ° C. for 3 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.91 Ti 0.09 PO 4 . The BET value of the obtained sample was 22.9 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 64 nm and a coefficient of variation of 0.39.
得られた粒子のX線回折測定をおこなった。図18に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 18 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)Ti、Mn表面処理酸化鉄の製造
実施例3と同様にして、得られた酸化後の懸濁液を均一になるよう混合して、その6L(Feとして、1.8mol)を15Lの反応容器に仕込み、Na2CO3 0.54molを溶解した水溶液1Lを加え、混合した。室温で、混合しながら、Ti(SO4)2 0.0095molおよびMnSO4 0.095molを溶解した水溶液1Lを1時間かけて滴下した。得られた懸濁液をろ過、洗浄、乾燥して、表面処理酸化鉄を得た。
(1) Production of Ti and Mn surface-treated iron oxide In the same manner as in Example 3, the obtained suspension after oxidation was mixed uniformly, and 6 L (1.8 mol as Fe) was mixed with 15 L. 1 L of an aqueous solution in which 0.54 mol of Na 2 CO 3 was dissolved was added and mixed. While mixing at room temperature, 1 L of an aqueous solution in which 0.0095 mol of Ti (SO 4 ) 2 and 0.095 mol of MnSO 4 were dissolved was added dropwise over 1 hour. The obtained suspension was filtered, washed and dried to obtain surface-treated iron oxide.
(2)LiFe0.945Ti0.005Mn0.05PO4の製造方法
上記で(1)で得られた表面処理酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた酸化鉄 0.05mol(金属分として0.15mol)、Li2CO3 0.079mol、(NH4)2HPO4 0.153 molおよびグルコース4gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、12時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で6時間焼成し、正極活物質LiFe0.945Ti0.005Mn0.05PO4を得た。得られた試料のBET値は18.3m2/gであった。得られた試料のSEM写真を図19に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は94nm、変動係数は0.38であった。
(2) LiFe 0.945 in Ti 0.005 Mn 0.05 PO 4 of the method for manufacturing the surface-treated iron oxide obtained in (1) was synthesized olivine type lithium iron phosphate as a raw material. Into an 80 mL planetary ball mill container, 0.05 mol of iron oxide obtained in (1) (0.15 mol as a metal content), 0.079 mol of Li 2 CO 3 , 0.153 mol of (NH 4 ) 2 HPO 4 and 4 g of glucose are placed. Further, 20 mL of pure water was added and mixed at 250 rpm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.945 Ti 0.005 Mn 0.05 PO 4 . The BET value of the obtained sample was 18.3 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 94 nm and a coefficient of variation of 0.38.
得られた粒子のX線回折測定をおこなった。図20に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 20 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)酸化鉄の製造
60Lの反応容器にNaOHを52.8 molを含む水溶液40Lを仕込み、窒素ガスを通気して置換し、80℃に保持した。ここに、窒素通気、攪拌しながら、6molのFeSO4と 6molのFe2(SO4)3を含む水溶液20Lを添加して、80℃で3時間混合した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子マグネタイト(Fe3O4)を得た。試料の比表面積測定はBET法で測定した。得られた試料のBET値は74.2m2/gであった。得られた試料のTEM写真を図21に示す。
(1) Production of iron oxide 40 L of an aqueous solution containing 52.8 mol of NaOH was charged into a 60 L reaction vessel, and nitrogen gas was passed through to replace it, and the temperature was maintained at 80 ° C. To this, 20 L of an aqueous solution containing 6 mol of FeSO 4 and 6 mol of Fe 2 (SO 4 ) 3 was added with nitrogen aeration and stirring, and mixed at 80 ° C. for 3 hours. The obtained suspension was filtered, washed and dried to obtain fine particle magnetite (Fe 3 O 4 ). The specific surface area of the sample was measured by the BET method. The BET value of the obtained sample was 74.2 m 2 / g. A TEM photograph of the obtained sample is shown in FIG.
(2)LiFePO4の製造方法
上記で(1)で得られた酸化鉄(Fe3O4)を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた酸化鉄 0.05mol、Li2CO3 0.079mol、(NH4)2HPO4 0.15 molおよびグルコース4gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、12時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で6時間焼成し、正極活物質LiFePO4を得た。得られた試料のBET値は12.5m2/gであった。得られた試料のSEM写真を図22に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は80nm、変動係数は0.32であった。
(2) LiFePO 4 in the manufacturing method described above: (1) iron oxide obtained in (Fe 3 O 4) was synthesized olivine type lithium iron phosphate as a raw material. Add 0.05 mol of iron oxide obtained in (1), 0.079 mol of Li 2 CO 3 , 0.15 mol of (NH 4 ) 2 HPO 4 and 4 g of glucose into an 80 mL planetary ball mill container, and then add 20 mL of pure water. And mixed at 250 rpm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material LiFePO 4 . The BET value of the obtained sample was 12.5 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 80 nm and a coefficient of variation of 0.32.
得られた粒子のX線回折測定をおこなった。図23に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 23 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)LiFe0.95Ti0.05PO4の製造方法
シュウ酸鉄0.1mol、チタンイソプロポキサイト0.0053mol、リン酸水素二アンモニウム0.107molおよび炭酸リチウム0.056molを80mL遊星ボールミル容器に入れ、更に純水 30mLを添加して、250r.p.m.で、12時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で6時間焼成し、正極活物質LiFe0.95Ti0.05PO4を得た。得られた試料のBET値は6.6m2/gであった。得られた試料のSEM写真を図24に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は125nm、変動係数は0.61であった。
(1) Production method of LiFe 0.95 Ti 0.05 PO 4 80 mL planetary ball mill container containing 0.1 mol of iron oxalate, 0.0053 mol of titanium isopropoxysite, 0.107 mol of hydrogen diammonium phosphate and 0.056 mol of lithium carbonate In addition, 30 mL of pure water was added and mixed at 250 rpm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and baked at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.95 Ti 0.05 PO 4 . The obtained sample had a BET value of 6.6 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 125 nm and a coefficient of variation of 0.61.
得られた粒子のX線回折測定をおこなった。図25に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 25 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
(1)Ti表面処理酸化鉄の製造
実施例3と同様にして、得られた酸化後の懸濁液を均一になるよう混合して、その6L(Feとして、1.8mol)を15Lの反応容器に仕込み、Na2CO3 0.54molを溶解した水溶液1Lを加え、混合した。室温で、混合しながら、Ti(SO4)2 0.45molを溶解した水溶液1Lを1時間かけて滴下した。得られた懸濁液をろ過、洗浄、乾燥して、微粒子酸化鉄を得た。
(1) Production of Ti surface-treated iron oxide In the same manner as in Example 3, the obtained suspension after oxidation was mixed uniformly, and 6 L (1.8 mol as Fe) was reacted in 15 L. The container was charged and 1 L of an aqueous solution in which 0.54 mol of Na 2 CO 3 was dissolved was added and mixed. While mixing at room temperature, 1 L of an aqueous solution in which 0.45 mol of Ti (SO 4 ) 2 was dissolved was added dropwise over 1 hour. The obtained suspension was filtered, washed and dried to obtain fine-particle iron oxide.
(2)LiFe0.8Ti0.2PO4の製造方法
上記で(1)で得られた酸化鉄を原料にオリビン型リン酸鉄リチウムを合成した。(1)で得られた酸化鉄 0.05mol、Li2CO3 0.079mol、(NH4)2HPO4 0.15 molおよびグルコース4gを80mL遊星ボールミル容器に入れ、更に純水 20mLを添加して、250r.p.m.で、12時間混合した。120℃で乾燥後、メノウ乳鉢で粉砕し、N2雰囲気下、650℃で6時間焼成し、正極活物質LiFe0.8Ti0.2PO4を得た。得られた試料のBET値は20.9m2/gであった。得られた試料のSEM写真を図26に示す。粒子径はTEM写真から200個の粒子を無作為に測定し、平均値で算出した。得られた試料の平均粒子径は62nm、変動係数は0.48であった。
(2) In LiFe 0.8 Ti 0.2 PO 4 of the method for manufacturing the iron oxide obtained in (1) was synthesized olivine type lithium iron phosphate as a raw material. Add 0.05 mol of iron oxide obtained in (1), 0.079 mol of Li 2 CO 3 , 0.15 mol of (NH 4 ) 2 HPO 4 and 4 g of glucose into an 80 mL planetary ball mill container, and then add 20 mL of pure water. And mixed at 250 rpm for 12 hours. After drying at 120 ° C., the mixture was pulverized in an agate mortar and fired at 650 ° C. for 6 hours in an N 2 atmosphere to obtain a positive electrode active material LiFe 0.8 Ti 0.2 PO 4 . The BET value of the obtained sample was 20.9 m 2 / g. An SEM photograph of the obtained sample is shown in FIG. The particle diameter was calculated from an average value obtained by randomly measuring 200 particles from a TEM photograph. The obtained sample had an average particle size of 62 nm and a coefficient of variation of 0.48.
得られた粒子のX線回折測定をおこなった。図27に得られた粒子のX線回折図を示す。X線回折図よりオリビン型リン酸鉄リチウム単相であることが確認された。
ICP分析による組成分析結果、BET値、D111および炭素量を表1に示す。
X-ray diffraction measurement was performed on the obtained particles. FIG. 27 shows an X-ray diffraction pattern of the obtained particles. From the X-ray diffraction pattern, it was confirmed to be an olivine type lithium iron phosphate single phase.
Table 1 shows the composition analysis result, BET value, D111, and carbon content by ICP analysis.
実施例1と同様にして、コインセルを組み立て、充放電試験を行った。初期充放電容量を表2に示す。 In the same manner as in Example 1, a coin cell was assembled and a charge / discharge test was performed. Table 2 shows the initial charge / discharge capacity.
本発明の正極活物質を利用した非水電解質電池としては、例えば、金属リチウム電池、リチウムイオン電池、リチウムポリマー電池等のリチウム二次電池が挙げられる。 Examples of the nonaqueous electrolyte battery using the positive electrode active material of the present invention include lithium secondary batteries such as metal lithium batteries, lithium ion batteries, and lithium polymer batteries.
Claims (15)
LixFeyTipMqPO4
(式中、0<x<2、0<y<1.5であり、p/y=0.001〜0.2、q/p=0〜10であり、MはCo、Ni、Mn、Zn、Cu、Mg、及びAlからなる群から選ばれる少なくとも1種の金属である)
で表されるオリビン型リン酸鉄リチウム化合物であって、
粒度分布の変動係数が0.5以下であり、BET値が10〜50m2/gであり、111面の結晶面に対応するX線回折ピークの半価幅からScherrerの式に従って求めた結晶子径(D111)が20.0〜80.0nmであることを特徴とするオリビン型リン酸鉄リチウム化合物。 The average particle size is 500 nm or less, and the following general formula:
Li x Fe y Ti p M q PO 4
(Wherein 0 <x <2, 0 <y <1.5, p / y = 0.001 to 0.2, q / p = 0 to 10, M is Co, Ni, Mn, (At least one metal selected from the group consisting of Zn, Cu, Mg, and Al)
An olivine-type lithium iron phosphate compound represented by:
Variation coefficient of particle size distribution is 0.5 or less, BET value is 10 to 50 m 2 / g, was determined from the half value width of the X-ray diffraction peak corresponding to the crystal plane 111 plane according to Scherrer's formula crystals olivine type lithium iron phosphate compounds child diameter (D 111) is characterized in that it is a 20.0~80.0Nm.
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