KR101401836B1 - SYNTHESIS OF CRYSTALLINE NANOMETRIC LiFeMPO4 - Google Patents
SYNTHESIS OF CRYSTALLINE NANOMETRIC LiFeMPO4 Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 229910010574 LiFeMPO4 Inorganic materials 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 35
- 229910011570 LiFe 1-x Inorganic materials 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000002482 conductive additive Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910011993 LiFe0.5Co0.5PO4 Inorganic materials 0.000 description 5
- 229910011990 LiFe0.5Mn0.5PO4 Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920000914 Metallic fiber Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AGRIQBHIKABLPJ-UHFFFAOYSA-N 1-Pyrrolidinecarboxaldehyde Chemical compound O=CN1CCCC1 AGRIQBHIKABLPJ-UHFFFAOYSA-N 0.000 description 1
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910011980 LiFe0.4Mn0.6PO4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZSBXGIUJOOQZMP-JLNYLFASSA-N Matrine Chemical compound C1CC[C@H]2CN3C(=O)CCC[C@@H]3[C@@H]3[C@H]2N1CCC3 ZSBXGIUJOOQZMP-JLNYLFASSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910001465 mixed metal phosphate Inorganic materials 0.000 description 1
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/377—Phosphates of heavy metals of manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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Abstract
본 발명은 리튬 이차 배터리, 보다 구체적으로 비-수성 전기화학적 셀에서 Li+/Li에 대해 2.8 V보다 더 큰 전위에서 작동하는 양극 물질에 관한 것으로, 특히 입자 크기가 작고 입자 크기 분포가 좁은 결정성 나노매트릭 올리빈-타입 LiFe1-xMxPO4 (여기서, M은 Co 및/또는 Mn이고, 0<x<1)분말에 관한 것이다.The present invention relates to a lithium secondary battery, and more particularly to a cathode material that operates at a potential greater than 2.8 V for Li + / Li in a non-aqueous electrochemical cell, and more particularly to a cathode material that has a small particle size and narrow particle size distribution The present invention relates to a nano-matrix olivine-type LiFe 1-x M x PO 4 wherein M is Co and / or Mn and 0 <x <1.
직접적인 침전 공정은 하기 단계를 포함하며, 극히 미세한 입자 크기는 둘 다 좁은 분포의 Mn에 있어서는 약 80 nm 및 Co에 있어서는 약 275 nm에서 수득되고, 미세 입자 크기로 인해 탁월하게 높은 드레인 특성을 가지는 반면에 전도성 첨가제의 필요성은 최소화되며, 좁은 크기 분포로 인해 전극 제조 공정이 용이해지고, 배터리 내에 균일한 전류 분포가 얻어지는 것을 특징으로 한다:The direct precipitation process involves the following steps, with extremely fine grain sizes both obtained at about 80 nm for Mn in the narrow distribution and about 275 nm for Co and have exceptionally high drain properties due to their fine particle size The need for a conductive additive is minimized, a narrow size distribution facilitates the electrode manufacturing process, and a uniform current distribution within the battery is obtained:
- 전구물질 성분으로서 Li(I), Fe(II), P(V), 및 Co(II)와 Mn(II) 중 어느 하나 또는 둘 다, 및 쌍극성 비양성자성 첨가제(dipolar aprotic additive)를 함유하는 pH 6 내지 pH 10의 수계 혼합물을 제조하는 단계; 및- one or both of Li (I) , Fe (II) , P (V) and Co (II) and Mn (II) as precursor components and dipolar aprotic additive Lt; RTI ID = 0.0 > 6 < / RTI > to 10; And
- 상기 수계 혼합물을 대기압에서 이의 끓는점 이하의 온도로 가열하여 결정성 LiFe1-xMxPO4 분말을 침전시키는 단계.- heating said aqueous mixture to a temperature below its boiling point at atmospheric pressure to precipitate crystalline LiFe 1-x M x PO 4 powder.
Description
본 발명은 Li 배터리에 양극 물질로서 사용하기 위한 입자 크기가 작고 입자 크기 분포가 좁은 결정성 나노메트릭 LiFe1-xMxPO4(LFMP) 분말에 관한 것이다. 본 발명은 또한 결정성 나노메트릭 분말을 대기압과 저온에서 침전시키는 바람직한 제조 방법에 관한 것이다.The present invention relates to a crystalline nanometric LiFe 1-x M x PO 4 (LFMP) powder having a small particle size and a narrow particle size distribution for use as an anode material in a Li battery. The present invention also relates to a preferred process for the precipitation of crystalline nanometric powder at atmospheric pressure and low temperature.
Padhi 등[JES, 144 (1997), 1188]의 최초의 연구 이후, 포스포-올리빈(phospho-olivines) LiMPO4(여기서 M = Fe, Ni, Co, Mn,...)은 Li 배터리용 캐소드 물질로서 사용할 수 있는 잠재적인 후보물질로 생각되어 왔다. 이러한 모든 등구조 조성물(isostructural compositions) 중에서 LiFePO4가 가장 많이 연구되었으며, 현재 가역 용량(reversible capacity), 레이트 특성(rate property) 및 사이클 수명(cycle life)에 관한 매우 높은 성능으로 인해 이의 상업화도 현재 실현되어 있다(국제 출원 번호 WO2004/001881 A2).Since the first study of Padhi et al. [JES, 144 (1997), 1188], phospho-olivines LiMPO 4 where M = Fe, Ni, Co, Mn, Has been considered as a potential candidate material that can be used as a cathode material. Of all such isostructural compositions, LiFePO 4 has been studied extensively and due to its very high performance in terms of reversible capacity, rate property and cycle life, (International Application No. WO2004 / 001881 A2).
Li에 대한 산환환원 전위 값이 각각 4.8 V 및 4.1 V로 높기 때문에 LiCoPO4[Amine 등, ESSL, 3, (2000), 178] 및 LiMnPO4[Okada 등, J. Power Sources, 97-98 (2001) 430]는 특히 주목받고 있으며, 그 이유는 LiFePO4와 비교해서 이들이 제공하는 에너지 밀도가 더 높기 때문이다[3.5V vs. Li, Chen 등, JES, 149 (2002) A1184].LiCoPO 4 [Amine et al., ESSL, 3, (2000), 178] and LiMnPO 4 [Okada et al., J. Power Sources, 97-98 (2001), since the oxirane reduction potentials for Li are as high as 4.8 V and 4.1 V, respectively ) 430 is of particular interest because of their higher energy density compared to LiFePO 4 [3.5V vs. Li, Chen et al., JES, 149 (2002) A1184].
그러나 이러한 포스포-올리빈 물질은 전자 및 이온 전도성이 불량[Delacourt 등, JES, 152 (2005) A913]하여 이러한 화합물의 미세구조를 최적화시키는 단계가 필수적이다. Striebel 등[JES, 152, (2005), A664]은 매트릭스 전도성이 전도성 코팅재에 의해서 개선된다고 해도 배터리 개발자는 1차 입자 크기가 50 내지 100 nm인 이제까지 존재하지 않았던 화합물을 선호할 것이며, 대체로 더 나은 파워 효율성을 수득하기 위해서 입자 크기 분포를 최소화시키는 시도를 해야 할 것이라는 사실을 주장한다.However, these phospho-olivine materials require a step to optimize the microstructure of these compounds by poor electron and ionic conductivity [Delacourt et al., JES, 152 (2005) A913]. Although the matrix conductivity is improved by a conductive coating, Stryebel et al. [JES, 152, (2005), A664] would prefer a compound that had never existed with a primary particle size of 50-100 nm, It is claimed that an attempt should be made to minimize the particle size distribution in order to obtain power efficiency.
혼합 금속 포스페이트, 예컨대 LiFe1-xMnxPO4 물질 상의 가장 유망한 결과는, C가 소결 억제제로서 활성을 갖는 C/LiFe0.4Mn0.6P04 복합물에서 수득된다. 이러한 접근 방법으로 100 내지 200 nm 범위의 입자들을 갖는 혼합된 C/LiFeMnPO4 복합물이 생성된다[Mi 등, Mater. Sci. Eng., 129 (2006) 8]. 200 내지 300 nm의 작은 입자를 갖는 순수한 LiCoPO4 상에서도, Lloris 등[ESSL, 5 (2002) A234]에 의해서 유사한 결과가 수득되었다. 이제까지 LiFe1-xCoxPO4 물질에 대해 공개된 결과는 없었다.The most promising results on mixed metal phosphates such as LiFe 1-x Mn x PO 4 material are obtained in a C / LiFe 0.4 Mn 0.6 PO 4 composite where C is active as a sintering inhibitor. This approach produces mixed C / LiFeMnPO 4 composites with particles in the 100 to 200 nm range [Mi et al., Mater. Sci. Eng., 129 (2006) 8]. Similar results were obtained by Lloris et al. [ESSL, 5 (2002) A234] on pure LiCoPO 4 with small particles of 200-300 nm. There have been no published results for the LiFe 1-x Co x PO 4 material.
전극에서 균질한 전류 분포를 확보하여 더 나은 배터리 성능, 특히 파워 효율성을 높이고, 긴 사이클 수명을 얻기 위해서는, 작은 입자 크기에 더하여 입자 크기 분포를 감소시키는데 중점을 두어야 한다. 따라서 본 발명은 입자 크기가 작고 입자 크기 분포가 좁은 결정성 LFMP 분말을 제공하는 것이 목적이다.In order to obtain a homogeneous current distribution at the electrode to achieve better battery performance, especially power efficiency, and longer cycle life, it is important to focus on reducing particle size distribution in addition to small particle size. Accordingly, it is an object of the present invention to provide a crystalline LFMP powder having a small particle size and a narrow particle size distribution.
이를 위해, 상기에서 언급된 물질을 본질적으로 개선시킨 금속 포스페이트 분말을 수득하는 방법을 개시한다.To this end, a method of obtaining a metal phosphate powder essentially improved the above-mentioned materials is disclosed.
결정성 LiFe1-xMxPO4(여기서 M은 Co 및 Mn 중 어느 하나 또는 둘 다이며, 0<x<l, 바람직하게는 0.4<x<0.95임) 분말의 본 발명의 합성 방법은 하기 단계를 포함한다:The synthesis method of the present invention of crystalline LiFe 1-x M x PO 4 (wherein M is either or both Co and Mn and 0 <x <1, preferably 0.4 <x <0.95) Step:
- 전구물질 성분으로서 Li(I), Fe(II), P(v), 및 Co(II) 와 Mn(II) 중 어느 하나 또는 둘 다, 및 쌍극성 비양성자성 첨가제(dipolar aprotic additive)를 함유하며, pH가 6 내지 10인 수계 혼합물을 제공하는 단계; 및- one or both of Li (I) , Fe (II) , P (v) and Co (II) and Mn (II) as precursor components and dipolar aprotic additive Providing an aqueous mixture having a pH of from 6 to 10; And
- 상기 수계 혼합물을 대기압에서 이의 끓는점 이하의 온도로 가열하여 결정성 LiFe1-xMxPO4 분말을 침전시키는 단계. 수득된 분말을 비-산화 조건하에서 가열함으로써 후 처리(post-treatment)를 실행할 수 있다.- heating said aqueous mixture to a temperature below its boiling point at atmospheric pressure to precipitate crystalline LiFe 1-x M x PO 4 powder. The post-treatment can be carried out by heating the obtained powder under non-oxidizing conditions.
그러나 Li3PO4의 침전(precipitation)을 피하기 위해서 pH는 6 내지 8이 바람직하다. 첨가제는 킬레이팅 또는 착물화 성향(complexation propensity)이 없는 쌍극성 비양성자성 화합물이 바람직하다. 수계 혼합물의 가열 온도는 60 ℃ 이상이 바람직하다.However, the pH is preferably 6 to 8 in order to avoid the precipitation of Li 3 PO 4 . The additive is preferably a bipolar non-protic compound that is free of chelating or complexation propensity. The heating temperature of the aqueous mixture is preferably 60 DEG C or higher.
결정성 LiFe1-xMxPO4 분말의 제조 또는 후 열-처리(thermal post-treatment)는 1개 이상의 추가 성분, 특히 탄소 함유 물질 또는 전자 전도성 물질, 또는 전자 전도성 물질의 전구물질의 존재하에 실행하는 것이 유리하다.The preparation or the thermal post-treatment of the crystalline LiFe 1-x M x PO 4 powder is carried out in the presence of one or more additional components, in particular a carbon-containing substance or an electron-conducting substance, or a precursor of an electron- It is advantageous to execute.
LiOH로서 Li(I)의 일부 또는 전부를 도입시키는 것이 유용하다. 유사하게 P(v)의 일부 또는 전부는 H3PO4로서 도입시킬 수 있다. 수계 혼합물의 pH는 H3PO4에 대한 LiOH의 비율을 조정함으로써 수득할 수 있다.It is useful to introduce some or all of Li (I) as LiOH. Similarly, some or all of P (v) may be introduced as H 3 PO 4 . The pH of the aqueous mixture can be obtained by adjusting the ratio of LiOH to the H 3 PO 4.
대기하 끓는점이 100 내지 150 ℃, 바람직하게는 100 내지 120 ℃인 수계 혼합물을 사용하는 것이 권장된다. 디메틸설폭사이드(DMSO)를 쌍극성 비양성자성 첨가물로서 사용하는 것이 바람직하다. 수계 혼합물은 DMSO를 5 내지 50 몰%, 바람직하게는 10 내지 30 몰% 함유하는 것이 유리하다. DMSO 농도가 낮으면 조대 입자 크기 분포가 되며; 농도가 높으면 물의 유용성이 제한되어 장비 부피를 증가시켜야 한다.It is recommended to use an aqueous mixture having an atmospheric boiling point of 100 to 150 캜, preferably 100 to 120 캜. It is preferred to use dimethyl sulfoxide (DMSO) as a bipolar aprotic additive. It is advantageous that the aqueous mixture contains 5 to 50 mol%, preferably 10 to 30 mol% of DMSO. A low DMSO concentration results in a coarse particle size distribution; If the concentration is high, the utility of the water is limited and the equipment volume should be increased.
LiFe1-xMxPO4의 후 처리 단계는 675 ℃ 이하, 바람직하게는 300 ℃ 이상의 온도에서 실행하는 것이 유리하다. 침전된 LiFe1-xMxPO4의 결정도를 높이기 위해서는 하한을 선택하고; LiFe1-xMxPO4가 망간 포스파이드로 분해되는 것을 피하기 위해 상한을 선택한다.The post-treatment step of LiFe 1-x M x PO 4 is advantageously carried out at a temperature of 675 ° C or less, preferably 300 ° C or more. Select the lower limit to increase the crystallinity of the precipitated LiFe 1-x M x PO 4 ; The upper limit is selected to avoid the decomposition of LiFe 1-x M x PO 4 into manganese phosphide.
전자 전도성 물질은 탄소, 특히 전도성 탄소 또는 탄소 섬유일 수 있다. 대안적으로 전자 전도성 물질의 전구물질을 사용할 수 있으며, 특히 폴리머 또는 당-타입 거대분자(sugar-type macromolecule)를 사용할 수 있다.The electronically conductive material can be carbon, especially conductive carbon or carbon fiber. Alternatively, precursors of the electron-conducting material can be used, in particular polymers or sugar-type macromolecules.
본 발명은 또한 평균 입자 크기(d50)가 100 nm 미만, 바람직하게는 30 nm 초과인 입자 크기 분포를 가지며, 배터리에서 전극 물질로서 사용하기 위한 결정성 LiFe1-xMnxPO4 분말(o<x<1, 바람직하게는 0.4<x<0.95)에 관한 것이다. 최대 입자 크기는 500 nm 이하인 것이 바람직하다. 입자 크기 분포는 단봉형(mono-modal)인 것이 바람직하며, (d90-d10)/d50의 비율은 1.5 미만, 바람직하게는 1.3 미만인 것이 유리하다.The present invention also relates to a crystalline LiFe 1-x Mn x PO 4 powder (o < 0 & gt ;) for use as an electrode material in a battery having a particle size distribution with an average particle size (d50) of less than 100 nm, preferably greater than 30 nm, x < 1, preferably 0.4 < x < 0.95). The maximum particle size is preferably 500 nm or less. The particle size distribution is preferably mono-modal, and it is advantageous that the ratio of (d90-d10) / d50 is less than 1.5, preferably less than 1.3.
본 발명의 또 다른 실시양태는 10 중량% 이하의 전도성 첨가물 및 상기에서 규정한 결정성 LiMnPO4 분말을 함유하는 복합 분말에 관한 것이다. 추가의 실시양태는 상기 복합 분말을 사용하여 제조할 수 있는 전극 믹스에 관한 것이다. 전도성 탄소, 탄소 섬유, 유기 탄소 함유 물질의 분해에 의해서 수득되는 비정형 탄소, 전자 전도성 폴리머, 금속성 분말 및 금속성 섬유가 전도성 첨가제로서 특히 적당하다.Another embodiment of the present invention relates to a composite powder containing not more than 10% by weight of a conductive additive and a crystalline LiMnPO 4 powder as defined above. A further embodiment relates to an electrode mix which can be prepared using said composite powder. Conductive carbon, carbon fibers, amorphous carbons, electronic conductive polymers, metallic powders and metallic fibers obtained by decomposition of organic carbon-containing materials are particularly suitable as conductive additives.
본 발명의 또 다른 실시양태는 전도성 탄소-함유 첨가물과 하기 분말을 혼합함으로써, 리튬 삽입-타입 전극을 제조하기 위한 복합 분말의 용도에 관한 것이다.Another embodiment of the present invention relates to the use of a composite powder for preparing a lithium insertion-type electrode by mixing the following powder with a conductive carbon-containing additive.
본 발명은 또한 평균 입자 크기(d50)가 300 nm 미만, 바람직하게는 30 nm 초과인 입자 크기 분포를 가지는, 배터리에서 전극 물질로서 사용하는 결정성 LiFe1-xCoxPO4(여기서 0<x<1, 바람직하게는 0.4<x<0.95임) 분말에 관한 것이다. 최대 입자 크기는 900 nm 이하인 것이 바람직하다. 입자 크기 분포는 단봉형인 것이 바람직하며, (d90-d10)/d50의 비율은 1.5 미만, 바람직하게는 1.1 미만인 것이 유리하다.The present invention also relates to crystalline LiFe 1-x Co x PO 4 , wherein 0 < x < = x <≪ 1, preferably 0.4 < x < 0.95). The maximum particle size is preferably 900 nm or less. It is advantageous that the particle size distribution is of the single-pole type, and the ratio of (d90-d10) / d50 is advantageously less than 1.5, preferably less than 1.1.
본 발명의 또 다른 실시양태에서 10 중량% 이하의 전도성 첨가물 및 상기에서 규정한 결정성 LiFe1-xCoxPO4 분말을 함유하는 복합 분말에 관한 것이다. 추가의 실시양태는 상기 복합 분말을 사용하여 제조할 수 있는 전극 믹스에 관한 것이다. 전도성 탄소, 탄소 섬유, 유기 탄소 함유 물질의 분해에 의해서 수득되는 비정형 탄소, 전자 전도성 폴리머, 금속성 분말 및 금속성 섬유가 전도성 첨가제로서 특히 적당하다.In another embodiment of the present invention, the present invention relates to a composite powder containing not more than 10% by weight of a conductive additive and a crystalline LiFe 1-x Co x PO 4 powder as defined above. A further embodiment relates to an electrode mix which can be prepared using said composite powder. Conductive carbon, carbon fibers, amorphous carbons, electronic conductive polymers, metallic powders and metallic fibers obtained by decomposition of organic carbon-containing materials are particularly suitable as conductive additives.
본 발명의 또 다른 실시양태는 전도성 탄소-함유 첨가물과 하기 분말을 혼합함으로써, 리튬 삽입-타입 전극을 제조하기 위한 복합 분말의 용도에 관한 것이다.Another embodiment of the present invention relates to the use of a composite powder for preparing a lithium insertion-type electrode by mixing the following powder with a conductive carbon-containing additive.
종래 기술과 비교해서, 상기 생성물은 리튬 배터리에 잠재적인 캐소드 물질로서 고려될 수 있도록 하는 모든 잇점이 있으며, 하기와 같다:Compared to the prior art, the product has all the advantages of being able to be considered as a potential cathode material for a lithium battery, as follows:
- 저온에서 결정성 LFMP의 직접적인 침전으로 소결 공정과 연관되는 그레인(grain)의 성장을 방지한다. 나노메트릭 입자 크기가 수득된다. 이는 입자 내 Li 이온의 이동으로 인해 속도 제한(kinetic limitation)을 감소시킴으로써, 배터리의 신속한 충전/방전 거동을 강화시킨다.- Direct precipitation of crystalline LFMP at low temperature prevents grain growth associated with the sintering process. A nanometric particle size is obtained. This enhances the rapid charging / discharging behavior of the battery by reducing the kinetic limitation due to migration of Li ions in the particles.
- 입자 크기 분포가 좁아서, 배터리 내에 균질한 전류 분포가 얻어진다. 이는 특히 충전/방전율이 높을 때 중요하며, 이 경우 미세 입자가 조대 입자 보다 더 많이 고갈되며, 이러한 현상이 결국 입자를 열화시키고, 사용시에 베터리 용량을 페이딩(fading)시킨다. 추가로 상기는 전극의 제조를 촉진시킨다.- The particle size distribution is narrow, resulting in a homogeneous current distribution in the battery. This is especially important when the charge / discharge rate is high, in which case the fine particles are depleted more than the coarse particles, which eventually degrade the particles and fade the battery capacity during use. In addition, this facilitates the production of electrodes.
수계 혼합물의 대기하 끓는점은 100 내지 150 ℃, 바람직하게는 100 내지 120 ℃가 타당하다. 침전물 핵생성 속도(precipitate nucleation kinetics)를 증가시켜 LiMnPO4 나노메트릭 입자의 크기를 감소시키는 보조-용매(co-solvent)로서, 수혼화성 첨가제(water-miscible additive)를 사용한다. 물과 혼합하는 것에 더하여 유용한 보조-용매는 비양성자성이여야 하며, 즉 수소 이온의 방출에 의해서 수반되는 해리 작용이 거의 없거나 또는 최소한으로만 나타나야 한다. 에틸렌 글리콜과 같은 킬레이팅 특성 또는 착물화를 나타내는 보조-용매는, LiMnPO4의 침전 속도가 감소하여 더 큰 입자 크기가 유도되므로 적당하지 않다. 적당한 쌍극성 비양성자성 용매는 디옥산, 테트라히드로푸란, N-(C1-C18-알킬)피롤리돈, 에틸렌 글리콜 디메틸 에테르, 지방족 C1-C6-카르복실산의 C1-C4-알킬에스테르, C1-C6-디알킬 에테르, 지방족 C1-C4-카르복실산의 N,N-디-(C1-C4-알킬)아미드, 설포란, l,3-디-(C1-C8-알킬)-2-이미다졸리디논, N-(C1-C8-알킬)카프로락탐, N,N,N',N'-테트라-(C1-C8-알킬)우레아, 1,3-디-(C1-C8-알킬)-3,4,5,6-테트라히드로-2(1H)-피리미돈, N,N,N',N'-테트라-(C1-C8-알킬)설파미드, 4-포밀모르폴린, 1-포밀피페리딘 또는 1-포밀피롤리딘, N-(C1-C18-알킬)피롤리돈, N-메틸피롤리돈(NMP), N-옥틸피롤리돈, N-도데실피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세타미드 또는 헥사메틸포스포라미드이다. 다른 대안, 예컨대 테트라알킬 우레아도 또한 가능하다. 상기에서 언급한 쌍극성 비양성자성 용매 혼합물도 또한 사용할 수 있다. 바람직한 실시양태에서 디메틸설폭사이드(DMSO)를 용매로서 사용한다.The atmospheric boiling point of the aqueous mixture is 100 to 150 캜, preferably 100 to 120 캜. A water-miscible additive is used as a co-solvent to reduce the size of the LiMnPO 4 nanometric particles by increasing the precipitation nucleation kinetics. In addition to mixing with water, useful auxiliary-solvents must be non-protic, i.e. they should exhibit little or at least no dissociation action associated with the release of hydrogen ions. Co-solvents that exhibit chelating properties or complexation, such as ethylene glycol, are not suitable because the precipitation rate of LiMnPO 4 is reduced and larger particle sizes are induced. Suitable dipolar aprotic solvents include dioxane, tetrahydrofuran, N- (C 1 -C 18 - alkyl) pyrrolidone, ethylene glycol dimethyl ether, an aliphatic C 1 -C 6 - carboxylic acid of the C 1 -C 4-alkyl esters, C 1 -C 6 - dialkyl ether, an aliphatic C 1 -C 4 - carboxylic acid N, N- di - (C 1 -C 4 - alkyl) amide, sulfolane, l, 3- di - (C 1 -C 8 - alkyl) -2-imidazolidinone, N- (C 1 -C 8 - alkyl) caprolactam, N, N, N ', N'- tetra - (C 1 -C N, N ', N', N'-tetramethyl- 8 -alkyl) urea, 1,3-di- (C 1 -C 8 -alkyl) -3,4,5,6-tetrahydro- - tetra- (C 1 -C 8 -alkyl) sulfamides, 4-formyl morpholine, 1-promipiperidine or 1-formylpyrrolidine, N- (C 1 -C 18 -alkyl) N-methylpyrrolidone (NMP), N-octylpyrrolidone, N-dodecylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide or hexamethylphosphoramide. Other alternatives, such as tetraalkylureas, are also possible. The above-mentioned dipolar aprotic solvent mixture can also be used. In a preferred embodiment, dimethylsulfoxide (DMSO) is used as the solvent.
본 발명을 설명하는 도면은 하기와 같이 요약하였다:The drawings illustrating the invention are summarized as follows:
도 1: 18 시간의 반응 시간 후 LiFe0.5Mn0.5PO4 침전물의 XRDFigure 1: XRD of a LiFe 0.5 Mn 0.5 PO 4 precipitate after a reaction time of 18 hours
도 2: LiFe0.5Mn0.5PO4의 SEM 사진2: SEM photograph of LiFe 0.5 Mn 0.5 PO 4
도 3: LiFe0.5Mn0.5PO4의 체적 입자 크기 분포와 누적 분포(% 대 nm)Figure 3: Volumetric particle size distribution and cumulative distribution (% vs nm) of LiFe 0.5 Mn 0.5 PO 4
도 4: 18 시간의 반응 시간 후 LiFe0.5Co0.5PO4 침전물의 XRDFigure 4: XRD of LiFe 0.5 Co 0.5 PO 4 precipitate after a reaction time of 18 hours
도 5: LiFe0.5Co0.5PO4의 SEM 사진5: SEM picture of LiFe 0.5 Co 0.5 PO 4
도 6: LiFe0.5Co0.5PO4의 체적 입자 크기 분포와 누적 분포(% 대 nm)Figure 6: Volumetric particle size distribution and cumulative distribution (% vs nm) of LiFe 0.5 Co 0.5 PO 4
본 발명은 하기 실시예에 추가로 설명하였다.The present invention has been further described in the following examples.
실시예 1: LiFe0.5Mn0.5PO4의 합성 Example 1 : Synthesis of LiFe 0.5 Mn 0.5 PO 4
첫번째 단계에서, H3PO4 중의 0.1 M P(V), FeSO4·7H2O 중의 0.05 M Fe(II) 및 MnNO3·4H2O 중의 0.05 M Mn(II)의 등몰 용액에 DMSO를 첨가하고, 이를 교반하면서 H2O에 용해시킨다. DMSO의 양은 각각 약 80 몰% 및 20 몰%에 상응하는 50 부피%의 물과 50 부피%의 DMSO의 전체 조성(global composition)이 되도록 조정한다.In the first step, DMSO was added to a solution of 0.1 MP (V) in H 3 PO 4 , 0.05 M Fe (II) in FeSO 4 · 7H 2 O and 0.05 M Mn (II) in MnNO 3 · 4H 2 O , And dissolved in H 2 O with stirring. The amount of DMSO is adjusted to give a global composition of 50 vol% water and 50 vol% DMSO, corresponding to about 80 mole% and 20 mole%, respectively.
두번째 단계에서, 0.3 M LiOH．H2O 수용액을 25 ℃에서 상기 용액에 첨가한다; 이에 의해 pH가 6.5 내지 7.5로 올라간다. 최종 Li:Fe:Mn:P의 비율은 3:0.5:0.5:1에 근접한다.In the second step, an aqueous solution of 0.3 M LiOH.H 2 O is added to the solution at 25 ° C; Thereby raising the pH to 6.5 to 7.5. The ratio of the final Li: Fe: Mn: P is close to 3: 0.5: 0.5: 1.
세번째 단계에서, 용액의 온도를 용매의 끓는점(108 내지 110 ℃) 이하까지 올린다. 18 시간 후에 수득된 침전물을 여과하고 물로 철저하게 세척한다. 상기로 수득되는 순수한 결정성 LiFe0.5Mn0.5PO4를 도 1에 나타냈다.In the third step, the temperature of the solution is raised to below the boiling point of the solvent (108-110 ° C). The precipitate obtained after 18 hours is filtered and thoroughly washed with water. The pure crystalline LiFe 0.5 Mn 0.5 PO 4 obtained above is shown in Fig.
정확한 셀 파라메터(refined cell parameter)는 a=10.390 Å, b=6.043 Å 및 c=4.721 Å이며, 셀 부피는 296.4 Å3이다. 이것은 고용체(solid solution)의 경우 혼합 생성물의 셀 부피는 최종 생성물들의 셀 부피 값의 사이에 있어야 한다는 베가드의 법칙(Vegard's law)에서 규정하고 있는 것과 잘 맞는다(순수한 LiFePO4에 있어서는 291 Å3, 순수한 LiMnPO4에 있어서는 302 Å3). The exact cell parameters are a = 10.390 Å, b = 6.043 Å and c = 4.721 Å, and the cell volume is 296.4 Å 3 . This is in line with Vegard's law stating that the cell volume of the mixed product should be between the cell volume values of the final products in the case of a solid solution (291 Å 3 for pure LiFePO 4 , 302 Å 3 for pure LiMnPO 4 ).
도 2의 사진은 50-100 nm 범위의 단분산의 작은 결정 입자를 나타낸다. 생성물의 체적 입자 크기 분포는 이미지 분석을 사용하여 측정하였다. 도 3에서 나타낸 것과 같이 d50 값은 약 80 nm인 반면에 (d90-d10)/d50으로 정의된 상대적인 스판(relative span)은 약 1.2이다(d10=45 nm, d90=145 nm).The photograph of Fig. 2 shows monodisperse small crystal grains in the range of 50-100 nm. The volume particle size distribution of the product was measured using image analysis. As shown in FIG. 3, the relative span defined by (d90-d10) / d50 is about 1.2 (d10 = 45 nm, d90 = 145 nm) while the d50 value is about 80 nm.
실시예 2: LiFe0.5Co0.5PO4의 합성 Example 2 : Synthesis of LiFe 0.5 Co 0.5 PO 4
첫번째 단계에서, H3PO4 중의 0.1 M P(V), CoNO3·6H2O 중의 0.05 M Co(II) 및 MnSO4·H2O 중의 0.05 M Mn(II)의 등몰 용액에 DMSO를 첨가하고, 이를 교반하면서 H2O에 용해시킨다. DMSO의 양은 약 50 부피%의 물과 50 부피%의 DMSO의 전체 조성이 되도록 조정한다.In the first step, DMSO was added to a solution of 0.1 MP (V) in H 3 PO 4 , 0.05 M Co (II) in CoNO 3 .6H 2 O and 0.05 M Mn (II) in MnSO 4 .H 2 O , And dissolved in H 2 O with stirring. The amount of DMSO is adjusted to give a total composition of about 50% by volume of water and 50% by volume of DMSO.
두번째 단계에서, 0.3 M LiOH．H2O 수용액을 25 ℃에서 상기 용액에 첨가한다; 이에 의해 pH가 6.5 내지 7.5로 올라간다. 따라서 최종 Li:Fe:Co:P의 비율은 3:0.5:0.5:1에 근접한다.In the second step, an aqueous solution of 0.3 M LiOH.H 2 O is added to the solution at 25 ° C; Thereby raising the pH to 6.5 to 7.5. Therefore, the ratio of the final Li: Fe: Co: P is close to 3: 0.5: 0.5: 1.
세번째 단계에서, 용액의 온도를 용매의 끓는점(108 내지 110 ℃) 이하까지 올린다. 18 시간 후에 수득된 침전물을 여과하고 물로 철저하게 세척한다. 상기로 수득되는 순수한 결정성 LiFe0.5Co0.5PO4를 도 4에 나타냈다.In the third step, the temperature of the solution is raised to below the boiling point of the solvent (108-110 ° C). The precipitate obtained after 18 hours is filtered and thoroughly washed with water. The pure crystalline LiFe 0.5 Co 0.5 PO 4 obtained above is shown in FIG.
정확한 셀 파라메터는 a=10.292 Å, b=5.947 Å 및 c=4.712 Å이며, 셀 부피는 288.4 Å3이다. 이것은 고용체의 경우 혼합 생성물들의 셀 부피는 최종 생성물의 셀 부피 값 사이에 있어야 한다는 베가드의 법칙에서 규정하고 있는 것과 잘 맞는다(순수한 LiFePO4에 있어서는 291 Å3, 순수한 LiCoPO4에 있어서는 284 Å3). The exact cell parameters are a = 10.292 Å, b = 5.947 Å and c = 4.712 Å, and the cell volume is 288.4 Å 3 . This is in line with Veggard's law (291 Å 3 for pure LiFePO 4 and 284 Å 3 for pure LiCoPO 4) , assuming that the cell volume of the mixed products is between the cell volume values of the final product in solid solution case .
도 5의 사진은 200-300 nm 범위의 단분산의 작은 결정 입자를 나타낸다. 생성물의 용적 측정의 입자 크기 분포는 이미지 분석을 사용하여 측정하였다. 도 6에서 나타낸 것과 같이, d50 값은 약 275 nm인 반면에 (d90-d10)/d50으로 정의된 상대적인 스판은 약 1.0이다(d10=170 nm, d90=450 nm).The photograph of FIG. 5 shows monodisperse small crystal grains in the range of 200-300 nm. The particle size distribution of the volumetric measurement of the product was determined using image analysis. As shown in FIG. 6, the d50 value is about 275 nm, while the relative span, defined as (d90-d10) / d50, is about 1.0 (d10 = 170 nm, d90 = 450 nm).
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