CN104755429B - 氧化铁纳米粒子的制备方法 - Google Patents
氧化铁纳米粒子的制备方法 Download PDFInfo
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- CN104755429B CN104755429B CN201480002846.7A CN201480002846A CN104755429B CN 104755429 B CN104755429 B CN 104755429B CN 201480002846 A CN201480002846 A CN 201480002846A CN 104755429 B CN104755429 B CN 104755429B
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 47
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RHWANVADWAMYAY-UHFFFAOYSA-N ethene ethyl hydrogen carbonate Chemical compound C=C.C(C)OC(O)=O RHWANVADWAMYAY-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract
本发明涉及氧化铁纳米粒子的制备方法、通过上述方法来制备的氧化铁纳米粒子及包含上述氧化铁纳米粒子的负极材料。
Description
技术领域
本发明涉及氧化铁纳米粒子的制备方法。更具体地,本发明涉及氧化铁纳米粒子的制备方法、通过上述方法制备的氧化铁纳米粒子及包含该氧化铁纳米粒子的负极材料。
背景技术
目前,随着化石燃料的枯竭和环境破坏等问题的出现,很多研究人员正全身地投入到可以代替化石燃料的能源的开发。作为这种代替能源的一部分,进行着对能够适用于多种领域的二次电池的多种研究。
二次电池的领域并不仅限于现有的便携式系统(portable system),而且还向汽车用电池、蓄电用电池等方面扩大。
二次电池分为正极(cathode)、负极(anode)、电解液及隔膜等,其中,对电池影响最大的部分实际上是引起电化学反应的正极和负极。
上述负极主要使用在稳定性、寿命、价格等方面具有竞争力的石墨材料。但随着市场需要可适用于电动汽车和能量储存用电池等的高容量电池,兴起了用于开发高理论容量的新型负极物质的研究。
根据这种要求,作为高流量负极活性物质,目前的金属氧化物,其中尤其是氧化铁(Ⅲ)(Fe2O3:1007mAh/g)因具有高理论容量的优点而作为负极物质备受瞩目。
只是,在粒子的大小大的情况下(>1μm),上述金属氧化物具有在充放电过程中容量减少及循环效率下降的缺点,因此,通过多种化学合成将金属氧化铁粒子制成纳米大小的研究正在持续着。
作为上述氧化铁纳米粒子的合成方法,具有向氢氧化亚铁(Fe(O H)2)水溶液照射超声波的方法,所述氢氧化亚铁(Fe(OH)2)水溶液通过向铁盐水溶液添加氢氧化钠来制备。
然而,以往的氧化铁纳米粒子的合成方法不仅需要维持苛刻的合成环境(非活性气氛),而且使用高价的高纯度原料物质,但因照射超声波来得到的物质不均匀,且结晶性也不良,因而其应用范围狭窄,超声波照射时间也需要花费很长时间,因此具有无法批量生产的问题。
进而,通过现有方法制备的氧化铁(Ⅲ)纳米粒子由于很难制成微细且均匀的离子大小,因此,在充放电过程中通过体积的膨胀、收缩反应而在电极的内部产生龟裂,从而导致容量损失大,循环效率急剧下降。
对此,急需开发既能解决以往氧化铁纳米粒子的制备方法的复杂的工序及长时间的制备时间等问题,又能均匀地控制粉末的粒子大小及形态,且在数次的充放电过程中,容量损失也小的纳米粒子的制备方法。
发明内容
要解决的技术问题
本发明提供可通过简单的工序条件来进行批量生产,且在数次充放电过程中,容量损失也小的氧化铁纳米粒子的制备方法。
并且,本发明提供通过上述方法制备的氧化铁纳米粒子和包含上述氧化铁纳米粒子的负极材料。
并且,本发明提供由上述负极材料组成的电化学元件用负极及具有上述负极的电化学元件。
解决技术问题的手段
本发明提供氧化铁(Ⅲ)纳米粒子的制备方法,包括:制备氯化铁(FeCl3)水溶液的步骤;制备氢氧化钠(NaOH)水溶液的步骤;混合上述两种溶液的步骤;搅拌通过上述混合来制备的混合水溶液,同时添加硫酸钠(Na2SO4)水溶液的步骤;以及使添加有上述硫酸钠水溶液的混合水溶液在对流式电烤箱中发生反应的步骤。
发明的效果
通过本发明的氧化铁(Ⅲ)纳米粒子的制备方法,可通过经济又简单的制备工序来控制粉末的粒子大小及粒度分布,且可以制成在数次的充放电过程中,容量损失也小的氧化铁纳米粒子。并且,由此可以制备出容量及稳定性优秀的负极及包含上述负极的电化学元件。
附图说明
图1及图2为通过本发明的氧化铁Ⅲ纳米粒子的制备方法来制备的氧化铁纳米粒子的电子显微镜(SEM)照片。
图3为对在实施例1及比较例1中制备的二次电池的容量进行测定的比较图表。
具体实施方式
以下,详细说明本发明。
本发明提供氧化铁纳米粒子的制备方法,包括:制备氯化铁水溶液的步骤;制备氢氧化钠水溶液的步骤;混合上述两种溶液的步骤;搅拌通过上述混合来制备的混合水溶液,并添加硫酸钠水溶液的步骤;以及使添加有上述硫酸钠水溶液的混合水溶液在对流式电烤箱中发生反应的步骤。
具体地,在本发明的氧化铁Ⅲ纳米粒子的制备方法中,上述氯化铁水溶液的浓度可以为2M至3M,上述氢氧化钠水溶液的浓度可以为5M至6M。并且,上述硫酸钠的浓度可以为0.5M至1M,具体地可以为0.6M。
此时,在上述氯化铁水溶液的浓度为2M以下或3M以上的情况下,可能合成粒子大小为1μm以上的金属氧化物。并且,在上述氢氧化钠水溶液的浓度为6M以上的情况下,由于所合成的水溶液的pH值增加而存在无法合成金属氧化物的问题。并且,在上述硫酸钠水溶液的浓度为1M以上的情况下,存在无法制备均匀形态的金属氧化物的问题。此时,可使用磷酸钠(Na2PO4)水溶液来代替上述硫酸钠水溶液。
在本发明的氧化铁纳米粒子的制备方法中,上述氯化铁水溶液:氢氧化钠水溶液:硫酸钠水溶液的体积比可以按10:9:x(此时,x为0<x<1)的比率混合。
此时,在上述氯化铁水溶液:氢氧化钠水溶液的体积比超出上述范围的情况下,存在无法制备金属氧化物的问题。并且,在上述硫酸钠水溶液的体积比超过1的情况下,起到能够改变金属氧化物形状的因子的作用,从而有可能制备非常小的粒子大小。
并且,上述反应步骤可在100至105℃的温度下,具体地,在102℃的温度下,在常压条件下执行90至150小时,具体地,执行约90至100小时。
并且,本发明的氧化铁Ⅲ纳米粒子的制备方法还包括对结束上述反应后得到的固体生成物进行冷却之后,进行清洗及干燥的步骤。此时,上述清洗步骤利用水和乙醇来依次进行清洗。
并且,本发明可通过本发明的氧化铁纳米粒子的制备方法来得到粒子大小及粒子形态被均匀地控制的的氧化铁纳米粒子。
具体地,所得到的上述氧化铁纳米粒子的粒子大小(直径)可以为500nm至1μm。若氧化铁纳米粒子的粒子大小小于500nm而更为微细化,或者氧化铁纳米粒子的粒子大小大于1μm的情况下,具有在充放电过程中,容量保存率及循环效率急剧下降的缺点。
并且,上述氧化铁纳米粒子的粒子形态可以为大致圆形形态的椭圆形。
如上所述,本发明仅通过上述简单的制备工序也能制备粒子大小和粒子形态得到控制的氧化铁纳米粒子,并可利用上述氧化铁纳米粒子来制备在数次的充放电过程中,容量损失小的二次电池。
即,在普通的氧化铁纳米粒子的情况下,虽然具有因体积的膨胀而在充放电过程中容量减小,且发生电极的剥离等诸多问题,但在本发明中,由非常小(数nm大小)的氧化铁形成1μm以下的椭圆形粒子形态,此时,粒子内微小空间执行对各个数nm大小的金属氧化物的体积膨胀进行缓冲(buffer)的作用(参照图1)。因此,可改善在以往的充放电过程中发生的容量减少,引起电极剥离等的问题。
并且,本发明可提供包含上述氧化铁纳米粒子的负极材料。
此时,上述负极材料除了包含上述氧化铁纳米粒子之外,还可以选择性包含导电材料、粘合剂或填充剂。
以负极材料的总重量为基准,添加40至65重量百分比的上述氧化铁纳米粒子。在上述氧化铁纳米粒子的含量为40重量百分比以下的情况下,存在无法体现高容量的缺点,在氧化铁纳米粒子的含量为65重量百分比以上的情况下,由于在初始的两次循环中发生电极剥离等的缺点而存在无法体现循环稳定性的问题。
并且,通常以包含正极活性物质的混合物的整体重量为基准,添加1至30重量百分比的上述导电材料。这种导电材料只要不会对电池引起化学变化且具有导电性的,就不受特殊限制,例如,能够使用天然石墨或人工石墨等石墨;炭黑、乙炔黑、科琴黑、槽法炭黑、炉法炭黑、灯黑及热黑等炭黑;碳纤维或金属纤维等导电性纤维;碳纳米管等导电性管;氟化碳、铝、镍粉末等金属粉末;氧化锌、钛酸钾等导电性晶须;氧化钛等导电性金属氧化物;聚苯撑衍生物等导电性材料。
并且,上述粘合剂作为有助于针对活性物质和导电材料等的相结合和与集电体的相结合的成分,通常以包含正极活性物质的混合物整体重量为基准,添加1至30重量分的上述粘合剂。作为这种粘合剂,可具有例如聚偏氟乙烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、三元乙丙橡胶(EPDM)、磺化三元乙丙橡胶、丁苯橡胶、氟橡胶及多种共聚物等。
上述填充剂作为用于抑制膨胀的成分而被选择性使用,只要不会对上述电池引起化学变化,就不受特殊限制,例如,使用聚乙烯、聚丙烯等烯烃类聚合剂;玻璃纤维、碳纤维等的纤维状物质。
并且,本发明可提供上述负极材料涂敷于集电体上的电化学元件用负极。
例如,上述负极可通过将本发明的负极材料溶解于溶剂来制备浆料,并将上述浆料涂敷于负极集电体上后,通过干燥及压延来制备。
上述负极集电体只要不会对电池引起化学变化,且具有高导电性的,就不受特殊限制,例如,可使用由不锈钢、镍、铜、钛及它们的合金中的至少一种组成的等,且厚度通常为3μm至500μm。
并且,本发明可提供由包含上述负极材料的负极、正极、隔膜及非水电解液构成的电化学元件。
上述电化学元件可以为锂二次电池。
此时,可通过通常的方法来制备上述电化学元件。
实施例
以下,为了具体说明本发明而举出实施例及比较例来进行详细说明。但本发明的实施例可变形为多种不同的形态,本发明的范围并不局限于以下所述的实施例。本发明的实施例是为了使本发明所属技术领域的普通技术人员更加完整地理解本发明而提供。
实施例1
1-1.氧化铁纳米粒子的制备
将2M的氯化铁水溶液、6M的氢氧化钠水溶液及0.6M的硫酸钠水溶液以10:9:1的体积比放入反应器后,利用叶轮(impeller)来均匀地混合了水溶液。在102℃的对流式电烘箱中放入上述混合溶液后,反应96小时并得到固体生成物。
冷却上述固体生成物之后,利用水和乙醇依次进行了清洗。之后,在真空干燥器中对生成物进行干燥来得到了氧化铁纳米粒子(粒子大小:500nm)(参照图2)。
1-2.电池的制备
以65:10:25的重量比混合上述制备的氧化铁纳米粒子、导电剂(s uper-p)及粘合剂(KF1100)来制成浆料,并在铜集电体涂敷上述浆料后,在120℃的真空烘箱中干燥了12小时以上。
反电极使用了锂金属,且使用了1M的LiPF6/碳酸乙烯乙酯(EC):碳酸甲乙酯(EMC)(体积比1:1)作为电解质来制备了硬币型半电池。
实施例2
以40:30:30的重量比混合在上述实施例1-1中制备的氧化铁纳米粒子、导电剂(super-p)及粘合剂(KF1100)来制成浆料,并在铜集电体涂敷上述浆料后,在120℃的真空烘箱中干燥了12小时以上。
反电极则使用了锂金属,且使用了1M的LiPF6/碳酸乙烯酯:碳酸甲乙酯(体积比1:1)作为电解质来制备了硬币型半电池。
比较例1
以60:10:25重量比(g)混合以一般的方法制备的50nm的氧化铁纳米粒子导电剂(super-p)及粘合剂(KF1100)来制备了浆料,且向铜集电体涂敷上述浆料后在120℃的真空烘箱中干燥了12小时以上。
反电极则利用了锂金属,且电解质使用了1M的LiPF6/碳酸乙烯酯:碳酸甲乙酯(体积比1:1)来制备了硬币型半电池。
实验1
以如下方式执行了在上述实施例1、实施例2及比较例1中制备的二次电池的性能评价。在2.0至0.005V(vs.Li/Li+)充放电区域中对电池执行了10次充放电,此时的电流密度为0.1C。在以下表1中示出了这些初始充放电效率的结果。并且,以图3的图表示出了利用实施例2的电池的充放电结果。
表1
如上表1所示,在实施例1及实施例2中制备的电池的情况下,在第十次(10th)循环后的容量保存率也可维持在90%以上,相反,在利用50nm微细氧化铁纳米粒子的制备的比较例1的电池的情况下,可以确认在第十次循环后容量保存率急剧退化。
Claims (4)
1.一种氧化铁纳米粒子的制备方法,其特征在于,包括:
制备氯化铁水溶液的步骤;
制备氢氧化钠水溶液的步骤;
混合上述两种溶液的步骤;
搅拌通过上述混合来制备的混合水溶液,同时添加硫酸钠水溶液的步骤;以及
使添加有所述硫酸钠水溶液的混合水溶液在对流式电烤箱中发生反应的步骤,
其中所述氯化铁水溶液的浓度为2M至3M,所述氢氧化钠水溶液的浓度为5M至6M,所述硫酸钠水溶液的浓度为0.5M至1M,
其中所述氯化铁水溶液:氢氧化钠水溶液:硫酸钠水溶液的体积比为10:9:x,其中,x为0<x<1,以及
其中所述反应步骤在100至105℃下,在常压条件下执行90至150小时。
2.根据权利要求1所述的氧化铁纳米粒子的制备方法,其特征在于,还包括对结束反应后得到的固体生成物进行冷却、清洗及干燥的步骤。
3.根据权利要求1所述的氧化铁纳米粒子的制备方法,其特征在于,所述氧化铁纳米粒子的粒子大小为500nm至1μm。
4.根据权利要求1所述的氧化铁纳米粒子的制备方法,其特征在于,所述氧化铁纳米粒子为椭圆形粒子形态。
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JP5083866B2 (ja) * | 2007-02-20 | 2012-11-28 | 独立行政法人産業技術総合研究所 | リチウム電池用活物質およびその製造方法、並びに該活物質を用いたリチウム電池 |
JP5144108B2 (ja) * | 2007-04-12 | 2013-02-13 | トヨタ自動車株式会社 | 電極材料の製造方法、電極材料および電池 |
KR100974083B1 (ko) * | 2007-09-18 | 2010-08-04 | 전북대학교산학협력단 | Pvla가 코팅된 초상자성 산화철 나노입자, 이의제조방법 및 이를 포함하는 간질환 진단용 조영제 |
KR101129559B1 (ko) * | 2009-05-18 | 2012-03-29 | 고려대학교 산학협력단 | 크기와 형태가 제어된 헤마타이트의 제조방법 |
WO2011058981A1 (ja) | 2009-11-16 | 2011-05-19 | 国立大学法人群馬大学 | リチウム二次電池用負極及びその製造方法 |
CN102259933A (zh) * | 2011-05-09 | 2011-11-30 | 中国矿业大学 | 一种米粒状α-三氧化二铁的制备方法和应用 |
CN103043726B (zh) * | 2012-12-03 | 2015-01-14 | 云南云天化股份有限公司 | 椭球形粒径可控α-Fe2O3纳米颗粒的制备方法 |
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BR112015009488A2 (pt) | 2017-07-04 |
CN104755429A (zh) | 2015-07-01 |
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US20140220444A1 (en) | 2014-08-07 |
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JP6003008B2 (ja) | 2016-10-05 |
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EP2891629B1 (en) | 2017-12-20 |
BR112015009488B1 (pt) | 2021-11-16 |
BR112015009488B8 (pt) | 2023-03-21 |
EP2891629A4 (en) | 2015-11-11 |
KR101560441B1 (ko) | 2015-10-14 |
US9755231B2 (en) | 2017-09-05 |
EP2891629A1 (en) | 2015-07-08 |
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