CN101540394B - Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material - Google Patents
Method for preparing lithium ferrosilicon silicate of lithium-ion battery cathode material Download PDFInfo
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 239000010406 cathode material Substances 0.000 title claims abstract description 14
- ZBTSNCKGZHSCKH-UHFFFAOYSA-N lithium;silanidylidyneiron Chemical compound [Li+].[Fe]#[Si-] ZBTSNCKGZHSCKH-UHFFFAOYSA-N 0.000 title claims 2
- 238000000034 method Methods 0.000 title abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 230000002441 reversible effect Effects 0.000 claims description 12
- 229940062993 ferrous oxalate Drugs 0.000 claims description 10
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims 6
- 238000000498 ball milling Methods 0.000 claims 6
- 239000007789 gas Substances 0.000 claims 6
- 238000000227 grinding Methods 0.000 claims 6
- 238000009413 insulation Methods 0.000 claims 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 5
- 159000000002 lithium salts Chemical class 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- -1 polyparaphenylene Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- RKLROMDZXDQSDF-UHFFFAOYSA-N 1-phenylphenanthrene Chemical compound C1=CC=CC=C1C1=CC=CC2=C1C=CC1=CC=CC=C21 RKLROMDZXDQSDF-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- LJZJHELAFLRVSU-UHFFFAOYSA-N anthracene;phenanthrene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21.C1=CC=C2C3=CC=CC=C3C=CC2=C1 LJZJHELAFLRVSU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920005546 furfural resin Polymers 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种锂离子电池正极材料硅酸亚铁锂的制备方法，该方法将一定比例的锂盐、亚铁盐和二氧化硅混合物粉末充分研磨后，在惰性气氛下煅烧，得到硅酸亚铁锂锂离子电池正极材料。本专利的硅酸亚铁锂材料制备工艺简单、安全，成本低廉。该工艺得到的硅酸亚铁锂材料具有成本低、电化学性能好、环境友好等优点。采用该方法制备的硅酸亚铁锂正极材料在锂离子电池领域具有广泛的应用前景。The invention discloses a preparation method of lithium ferrous silicate, a cathode material of a lithium ion battery. In the method, a certain proportion of lithium salt, ferrous salt and silicon dioxide mixture powder is fully ground, and then calcined in an inert atmosphere to obtain silicon Lithium ferrous acid lithium ion battery cathode material. The preparation process of the lithium ferrous silicate material of the patent is simple, safe and low in cost. The lithium ferrous silicate material obtained by the process has the advantages of low cost, good electrochemical performance, and environmental friendliness. The lithium ferrous silicate cathode material prepared by the method has broad application prospects in the field of lithium ion batteries.
Description
技术领域technical field
本发明涉及锂离子电池技术领域，尤其设计一种新型锂离子电池正极材料——硅酸亚铁锂的制备方法。The invention relates to the technical field of lithium ion batteries, and in particular designs a method for preparing a novel positive electrode material of lithium ion batteries—lithium ferrous silicate.
背景技术Background technique
锂离子电池自上世纪九十年代问世以来，由于其高能密度、高功率、良好的循环性能而广泛应用于各类便携式电子产品领域。随着全球经济的发展，能源问题已经相当突出，因此混合动力汽车和电动汽车的研发已经成为全世界的焦点，而其中的关键技术就是锂离子电池技术。Since the advent of lithium-ion batteries in the 1990s, they have been widely used in various portable electronic products due to their high energy density, high power, and good cycle performance. With the development of the global economy, energy issues have become quite prominent, so the research and development of hybrid electric vehicles and electric vehicles has become the focus of the world, and the key technology is lithium-ion battery technology.
正极材料是决定锂离子电池性能的关键材料之一，目前商用的正极材料以LiCoO2为主，但是由于LiCoO2中钴的资源短缺，价格昂贵，具有毒性，对环境有一定污染，因此不能适应大型动力电池的要求。LiMn2O4虽然成本低廉，但循环性能差，安全性也较差。1997年开始，许多研究小组报道了LiMPO4(M＝Fe，Mn，Co，Ni)锂离子电池正极材料，发现这是一类很有前途的正极材料。然而，LiFePO4材料的电子电导率与振实密度很难同时提高，难以满足新一代大容量锂二次电池的需要。2005年，瑞典乌普萨拉大学的Nyte′n博士首次合成出Li2FeSiO4锂离子电池正极材料，得到较为理想的电化学性能。Li2FeSiO4属正交晶系，空间群Pmn21，晶格常数为a＝6.2661(5)，b＝5.3295(5)，c＝5.0148(4)与Li3PO4的低温结构相似。在Li2FeSiO4晶体中，Li、Si、Fe都与O形成四面体结构。由于硅酸盐具有原料易得及成本低廉等诱人的特点，Li2FeSiO4被认为是极具发展潜力的新型锂离子电池正极材料。The cathode material is one of the key materials that determine the performance of lithium-ion batteries. At present, the commercial cathode material is mainly LiCoO 2 , but due to the shortage of cobalt in LiCoO 2 , it is expensive, toxic, and pollutes the environment, so it cannot be adapted Requirements for large power batteries. Although LiMn 2 O 4 is low in cost, it has poor cycle performance and poor safety. Since 1997, many research groups have reported LiMPO 4 (M=Fe, Mn, Co, Ni) cathode materials for lithium ion batteries, and found that this is a promising cathode material. However, it is difficult to increase the electronic conductivity and tap density of LiFePO 4 materials at the same time, and it is difficult to meet the needs of a new generation of high-capacity lithium secondary batteries. In 2005, Dr. Nyte'n of Uppsala University in Sweden synthesized Li 2 FeSiO 4 lithium-ion battery cathode material for the first time, and obtained relatively ideal electrochemical performance. Li 2 FeSiO 4 belongs to orthorhombic crystal system, space group Pmn2 1 , lattice constants are a=6.2661(5), b=5.3295(5), c=5.0148(4) Similar to the low-temperature structure of Li 3 PO 4 . In Li 2 FeSiO 4 crystal, Li, Si, Fe all form tetrahedral structure with O. Due to the attractive characteristics of silicates such as easy availability of raw materials and low cost, Li 2 FeSiO 4 is considered to be a new cathode material for lithium-ion batteries with great development potential.
发明内容Contents of the invention
本发明的目的在于，提供一种新型锂离子电池正极活性材料硅酸亚铁锂的制备方法，该方法制备的硅酸亚铁锂结构稳定，与电解液相容性好，有良好的电化学性能。且操作简便、易于控制、成本低廉。The object of the present invention is to provide a method for preparing a novel lithium-ion battery cathode active material, lithium ferrous silicate. The lithium ferrous silicate prepared by the method has a stable structure, good compatibility with the electrolyte, and good electrochemical properties. performance. Moreover, the operation is simple, easy to control, and the cost is low.
为了实现上述任务，本发明采取如下的技术解决方案：In order to realize above-mentioned task, the present invention takes following technical solution:
一种锂离子电池正极材料硅酸亚铁锂的制备方法，其特征在于，包括下列步骤：A preparation method of lithium ferrous silicate, a positive electrode material for lithium ion batteries, is characterized in that it comprises the following steps:
1)按比例将原料锂盐、亚铁盐、二氧化硅和添加剂混合，其中Li∶Fe∶Si的摩尔比为(1.9-2.1)∶(0.95-1.05)∶1，添加剂的加入量为混合物总质量的1～30％；1) Mix the raw materials lithium salt, ferrous salt, silicon dioxide and additives in proportion, wherein the molar ratio of Li:Fe:Si is (1.9-2.1):(0.95-1.05):1, and the amount of additives added is the mixture 1-30% of the total mass;
2)将均匀混合的物料放入热处理设备中，在流速为100～5000ml/min的惰性气流保护中加热处理，升温速率为1℃/min～20℃/min，待热处理温度升至300℃～450℃时，保持，在该温度下加热1～30小时，然后继续升温，在700℃～900℃的范围内，热处理10小时～48小时，然后缓慢降至室温，得到硅酸亚铁锂材料。2) Put the uniformly mixed materials into the heat treatment equipment, heat treatment in the protection of inert gas flow with a flow rate of 100-5000ml/min, the heating rate is 1°C/min-20°C/min, and the temperature to be heat-treated is raised to 300°C- Keep at 450°C, heat at this temperature for 1 to 30 hours, then continue to heat up, heat treatment in the range of 700°C to 900°C for 10 hours to 48 hours, and then slowly lower to room temperature to obtain lithium ferrous silicate material .
由于本发明中在硅酸亚铁锂的合成过程中采用了添加剂，这些添加剂通过混合均匀分散到材料颗粒之间，添加剂主要起到两个作用：一是抑制硅酸亚铁锂单个颗粒的生长，减小单个颗粒的粒径。二是添加剂热解以后形成的热解炭可以包覆于颗粒表面或存在于颗粒之间，从而有效地改善颗粒之间的导电性能。所以在合成过程中加入添加剂可以得到粒径小、导电性能好、电化学性能优良的硅酸亚铁锂材料。Due to the additives used in the synthesis process of lithium ferrous silicate in the present invention, these additives are uniformly dispersed between the material particles by mixing, and the additives mainly play two roles: one is to inhibit the growth of a single particle of lithium ferrous silicate , reducing the particle size of individual particles. The second is that the pyrolytic carbon formed after the pyrolysis of the additive can be coated on the surface of the particles or exist between the particles, thereby effectively improving the electrical conductivity between the particles. Therefore, adding additives during the synthesis process can obtain lithium ferrous silicate materials with small particle size, good electrical conductivity and excellent electrochemical performance.
本发明的锂离子电池正极材料硅酸亚铁锂的制备方法，具有以下优点：The preparation method of lithium iron battery cathode material lithium ferrous silicate of the present invention has the following advantages:
1、原材料来源广泛，无污染，成本低；1. Wide source of raw materials, no pollution, low cost;
2、材料的制备工艺简单、安全性高；2. The preparation process of the material is simple and safe;
3、所制备的硅酸亚铁锂具有优良的微观结构；3. The prepared lithium ferrous silicate has excellent microstructure;
4、所制备的硅酸亚铁锂结构稳定，与电解液相容性好，有良好的电化学性能。4. The prepared lithium ferrous silicate has a stable structure, good compatibility with electrolyte, and good electrochemical performance.
5、本发明所涉及的正极材料可广泛应用于各类锂离子电池中，包括各类移动电子产品和电动交通工具。5. The cathode material involved in the present invention can be widely used in various lithium ion batteries, including various mobile electronic products and electric vehicles.
附图说明Description of drawings
图1是发明人给出的实施例1所制备的硅酸亚铁锂样品的X-射线衍射花样，采用日本Rigaku公司D/MAX-2400型X射线衍射仪，Cu Kα靶为辐射源，电压为46kV，电流为100mA，步长为0.02，扫描速度为10(°)/min，扫描范围(2θ)为3°～90°。Fig. 1 is the X-ray diffraction pattern of the lithium ferrous silicate sample prepared by the embodiment 1 provided by the inventor, adopts the D/MAX-2400 type X-ray diffractometer of Japan Rigaku Company, Cu K α target is radiation source, voltage The current is 46kV, the current is 100mA, the step size is 0.02, the scanning speed is 10(°)/min, and the scanning range (2θ) is 3°～90°.
图2是发明人给出的实施例1所制备的硅酸亚铁锂样品的扫描电镜图片，利用日本电子公司JSM-6700F型场发射扫描电子显微镜(FESEM)拍摄。Fig. 2 is a scanning electron microscope picture of the lithium ferrous silicate sample prepared by the inventor in Example 1, which was taken by a JSM-6700F field emission scanning electron microscope (FESEM) of Japan Electronics Corporation.
图3是按实施例1所制备的硅酸亚铁锂正极材料的首次充放电曲线图。Fig. 3 is the first charge and discharge curve of the lithium ferrous silicate positive electrode material prepared according to Example 1.
图4是按实施例1所制备的硅酸亚铁锂正极材料的循环寿命曲线图。4 is a graph showing the cycle life of the lithium ferrous silicate cathode material prepared in Example 1.
图5是按实施例2所制备的硅酸亚铁锂正极材料的首次充放电曲线图。Fig. 5 is the first charge and discharge curve of the lithium ferrous silicate positive electrode material prepared according to Example 2.
图6是按实施例3所制备的硅酸亚铁锂正极材料的首次充放电曲线图。Fig. 6 is the first charge and discharge curve of the lithium ferrous silicate positive electrode material prepared according to Example 3.
下面结合附图和发明人给出的实施例对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings and the embodiments given by the inventor.
具体实施方式Detailed ways
本发明涉及锂离子电池正极材料硅酸亚铁锂的制备方法，其步骤如下：The present invention relates to the preparation method of lithium ferrous silicate, the anode material of lithium ion battery, and its steps are as follows:
1、将锂盐、亚铁盐、二氧化硅和添加剂按比例混合(混合过程可以在常规的混合设备中进行，如斜式磨、锥形混合机、三维混合机中混合1～24小时；也可用湿化学方法，如溶胶-凝胶法、喷雾干燥法进行混合)，其中，Li∶Fe∶Si的摩尔比为(1.9-2.1)∶(0.95-1.05)∶1添加剂的加入量为混合物总质量的1～30％；1. Mix lithium salt, ferrous salt, silicon dioxide and additives in proportion (the mixing process can be carried out in conventional mixing equipment, such as inclined mill, cone mixer, three-dimensional mixer for 1 to 24 hours; Wet chemical method can also be used, such as sol-gel method, spray drying method to mix), wherein, the molar ratio of Li: Fe: Si is (1.9-2.1): (0.95-1.05): 1 The addition of additive is the mixture 1-30% of the total mass;
上述添加剂可以是炭黑、石墨或热解后可分解为导电性碳类物质的有机化合物；The above-mentioned additives can be carbon black, graphite or organic compounds that can be decomposed into conductive carbon substances after pyrolysis;
2、将均匀混合的原材料放入热处理设备中(任何能在气氛保护下均匀加热反应混合物的热处理设备均可使用，如管式气氛炉、旋转气氛炉或气氛保护隧道炉、箱式炉等)，在流速为100～5000ml/min的惰性气体保护中加热处理，升温速率为1～20℃/min，待热处理温度升至300～450℃时，保持温度不变，在该温度下加热1～30小时，然后继续升温，在700～900℃的范围内，热处理10～48小时，然后缓慢降至室温，便可得到硅酸亚铁锂材料。2. Put the uniformly mixed raw materials into the heat treatment equipment (any heat treatment equipment that can uniformly heat the reaction mixture under the protection of atmosphere can be used, such as tube atmosphere furnace, rotary atmosphere furnace or atmosphere protection tunnel furnace, box furnace, etc.) , heat treatment in an inert gas protection flow rate of 100-5000ml/min, the heating rate is 1-20°C/min, when the heat treatment temperature rises to 300-450°C, keep the temperature constant, and heat at this temperature for 1-20°C 30 hours, then continue to heat up, heat treatment in the range of 700-900° C. for 10-48 hours, and then slowly lower to room temperature, the lithium ferrous silicate material can be obtained.
其中，制备上述正极活性材料的锂盐、亚铁盐均无特殊限制，可以采用市售产品或本领域公知的产品，如锂盐可以选择硅酸锂、碳酸锂、氢氧化锂、草酸锂、醋酸锂、氯化锂、硝酸锂、磷酸锂等其中任一种，或者上述混合物等可。亚铁盐可以选择草酸亚铁、醋酸亚铁、氯化亚铁、磷酸亚铁等其中任一种，或者上述混合物等可。Wherein, the lithium salt and ferrous salt for preparing the above-mentioned positive electrode active material are not particularly limited, and commercially available products or products known in the art can be used, such as lithium salt can be selected from lithium silicate, lithium carbonate, lithium hydroxide, lithium oxalate, Any one of lithium acetate, lithium chloride, lithium nitrate, lithium phosphate, etc., or a mixture of the above may be used. The ferrous salt can be selected from any one of ferrous oxalate, ferrous acetate, ferrous chloride, ferrous phosphate, etc., or a mixture of the above.
添加剂可以选自炭黑、石墨、蔗糖、柠檬酸、葡萄糖、聚乙烯醇、可溶性淀粉、酚醛树脂、糠醛树脂、聚对苯、苯萘二元共聚物、苯蒽二元共聚物、苯菲二元共聚物、苯萘三元共聚物、苯萘蒽三元共聚物等的一种或几种混合物。Additives can be selected from carbon black, graphite, sucrose, citric acid, glucose, polyvinyl alcohol, soluble starch, phenolic resin, furfural resin, polyparaphenylene, benzonaphthalene binary copolymer, benzoanthracene binary copolymer, phenylphenanthrene One or more mixtures of copolymers, benzonaphthalene terpolymers, benzonaphthalene anthracene terpolymers, etc.
所述惰性气体如氮气、氩气或其混合气体。The inert gas is nitrogen, argon or a mixture thereof.
为了更清楚地说明本发明，发明人给出以下的实施例，需要说明的是，这些实施例是一些较优的例子，本发明不限于这些实施例。In order to illustrate the present invention more clearly, the inventor provides the following examples. It should be noted that these examples are some preferred examples, and the present invention is not limited to these examples.
实施例1：Example 1:
将2.7g硅酸锂、5.4g草酸亚铁、2g蔗糖在乙醇介质下混合球磨24小时，使用设备为行星球磨机，自传转速为200r/min。将充分混合研磨的混合粉末在60℃真空干燥24小时，然后以10MPa的压力压片，在1L/min的氩气气氛保护下，以10℃/min的速率升至400℃，在该温度下保温2小时，然后以10℃/min的速率升至800℃，在该温度下保温10h，然后冷却至室温既得到硅酸亚铁锂样品。2.7g of lithium silicate, 5.4g of ferrous oxalate, and 2g of sucrose were mixed and ball-milled in ethanol for 24 hours. The equipment used was a planetary ball mill with an autopropagation speed of 200r/min. The well-mixed and ground mixed powder was vacuum-dried at 60°C for 24 hours, then pressed into tablets at a pressure of 10 MPa, and raised to 400°C at a rate of 10°C/min under the protection of an argon atmosphere of 1 L/min. Keep it warm for 2 hours, then raise it to 800°C at a rate of 10°C/min, keep it at this temperature for 10h, and then cool it down to room temperature to obtain a lithium ferrous silicate sample.
图1为所得硅酸亚铁锂的XRD图谱，图中大部分的衍射峰都可以与硅酸亚铁锂的特征峰相对应，同时也存在少量的杂质。图2为所得硅酸亚铁锂的扫描电镜照片，合成材料的颗粒度在0.5-3μm之间，近球形形貌，分布较均匀。Figure 1 is the XRD spectrum of the obtained lithium ferrous silicate, most of the diffraction peaks in the figure can correspond to the characteristic peaks of lithium ferrous silicate, and there are also a small amount of impurities. Fig. 2 is a scanning electron microscope photo of the obtained lithium ferrous silicate. The particle size of the synthesized material is between 0.5-3 μm, the shape is nearly spherical, and the distribution is relatively uniform.
实施例1所得样品按下述方法进行电化学性能测试：将硅酸亚铁锂试样粉末、导电炭黑和PVDF(聚偏二氟乙烯)按质量比80∶10∶10的比例混合，加入适量有机溶剂NMP(N-甲基吡咯烷酮)，充分搅拌成均匀糊状物后涂于铝箔上，在真空干燥箱中120℃干燥12h。取直径为16mm的小片为正极，金属锂片为负极，Celgard2400微孔聚丙烯膜为隔膜，以溶于体积比为1∶1的EC(碳酸乙烯酯)/DMC(1，2-二甲基碳酸酯)的1mol·L-1LiPF6为电解液，在充满氩气的手套箱中装配成CR2032型扣式电池。将扣式电池置于CT2001A型电池测试***上测试其电化学性能。充放电倍率为C/10，电压范围为1.5V-4.8V。图3为该材料首次充放电曲线，由图可见，所合成的材料的充电容量达到242mAh/g，可逆容量为137mAh/g，图4给出该材料的10次循环曲线图，可见该材料的循环性能良好。The sample obtained in Example 1 was tested for electrochemical performance according to the following method: the lithium ferrous silicate sample powder, conductive carbon black and PVDF (polyvinylidene fluoride) were mixed in a mass ratio of 80:10:10, and added Appropriate amount of organic solvent NMP (N-methylpyrrolidone), fully stirred into a uniform paste, coated on aluminum foil, and dried in a vacuum oven at 120°C for 12 hours. Take a small piece with a diameter of 16mm as the positive electrode, a lithium metal sheet as the negative electrode, and a Celgard2400 microporous polypropylene membrane as the diaphragm, and dissolve it in EC (ethylene carbonate)/DMC (1,2-dimethyl Carbonate) 1mol L -1 LiPF 6 as the electrolyte, assembled into a CR2032 button cell in a glove box filled with argon. The button cell was placed on a CT2001A battery test system to test its electrochemical performance. The charge and discharge rate is C/10, and the voltage range is 1.5V-4.8V. Figure 3 is the first charge and discharge curve of the material. It can be seen from the figure that the charge capacity of the synthesized material reaches 242mAh/g, and the reversible capacity is 137mAh/g. Good cycle performance.
实施例2：Example 2:
将2.85g碳酸锂、2.3g二氧化硅、5.4g草酸亚铁以及2g蔗糖在乙醇介质下混合球磨24小时，使用设备为行星球磨机，自传转速为250r/min。将充分混合研磨的混合粉末在60℃真空干燥24小时，然后以10MPa的压力压片，在2L/min的氩气气氛保护下，以10℃/min的速率升至400℃，在该温度下保温2小时，然后以20℃/min的速率升至850℃，在该温度下保温15h，然后冷却至室温既得到硅酸亚铁锂样品。按照实施例1的方法测试其电化学性能，如图5所示，其首循环可逆容量为142mAh/g。2.85g of lithium carbonate, 2.3g of silicon dioxide, 5.4g of ferrous oxalate and 2g of sucrose were mixed and ball milled in ethanol medium for 24 hours. The equipment used was a planetary ball mill with an autopropagation speed of 250r/min. The well-mixed and ground mixed powder was vacuum-dried at 60°C for 24 hours, then pressed into tablets at a pressure of 10MPa, and raised to 400°C at a rate of 10°C/min under the protection of an argon atmosphere of 2L/min. Keep it warm for 2 hours, then raise it to 850°C at a rate of 20°C/min, keep it at this temperature for 15h, and then cool it down to room temperature to obtain a lithium ferrous silicate sample. Its electrochemical performance was tested according to the method of Example 1, as shown in Figure 5, its first-cycle reversible capacity was 142mAh/g.
实施例3：Example 3:
将1.85g氢氧化锂、2.3g二氧化硅、5.4g草酸亚铁以及1.5g柠檬酸在乙醇介质下混合球磨24小时，使用设备为行星球磨机，自传转速为250r/min。将充分混合研磨的混合粉末在60℃真空干燥24小时，然后以10MPa的压力压片，在1.5L/min的氩气气氛保护下，以5℃/min的速率升至400℃，在该温度下保温1小时，然后以10℃/min的速率升至750℃，在该温度下保温15h，然后冷却至室温既得到硅酸亚铁锂样品。按照实施例1的方法测试其电化学性能，如图6所示，其首循环可逆容量为118mAh/g。1.85g of lithium hydroxide, 2.3g of silicon dioxide, 5.4g of ferrous oxalate and 1.5g of citric acid were mixed and ball milled in ethanol medium for 24 hours. The equipment used was a planetary ball mill with an autopropagation speed of 250r/min. The well-mixed and ground mixed powder was vacuum-dried at 60°C for 24 hours, then pressed into tablets at a pressure of 10 MPa, and raised to 400°C at a rate of 5°C/min under the protection of an argon atmosphere of 1.5 L/min. Keep it warm for 1 hour, then raise it to 750°C at a rate of 10°C/min, keep it at this temperature for 15h, and then cool it to room temperature to obtain a lithium ferrous silicate sample. Its electrochemical performance was tested according to the method of Example 1, as shown in Figure 6, its first cycle reversible capacity was 118mAh/g.
实施例4：Example 4:
本实施例与实施例1所不同的是，仅将添加剂改为0.5g导电炭黑，其余同实施例1，所得正极材料的首循环可逆容量为138mAh/g。The difference between this example and Example 1 is that only the additive is changed to 0.5 g of conductive carbon black, and the rest is the same as that of Example 1. The first-cycle reversible capacity of the obtained positive electrode material is 138 mAh/g.
实施例5：Example 5:
本实施例与实施例2所不同的是，仅将添加剂改为1g柠檬酸，其余同实施例2，所得正极材料的首循环可逆容量为125mAh/g。The difference between this example and Example 2 is that only the additive is changed to 1 g of citric acid, and the rest is the same as that of Example 2. The first-cycle reversible capacity of the obtained positive electrode material is 125mAh/g.
实施例6：Embodiment 6:
本实施例与实施例3所不同的是，仅将添加剂改为1.8g可溶性淀粉，其余同实施例3，所得正极材料的首循环可逆容量为128mAh/g。The difference between this example and Example 3 is that only the additive is changed to 1.8 g of soluble starch, and the rest is the same as that of Example 3. The first-cycle reversible capacity of the obtained positive electrode material is 128 mAh/g.
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| CN101734675B (en) * | 2009-11-24 | 2012-06-27 | 福建师范大学 | Preparation method of Li2FeSiO4 cathode material used for controlling Fe3P |
| CN101920971B (en) * | 2010-06-28 | 2011-11-16 | 宁波大学 | Preparation method of silicate positive electrode material for lithium ion battery |
| CA2803990A1 (en) * | 2010-06-30 | 2012-01-05 | Hoganas Ab (Publ) | Lithium iron silicate cathode material and its production |
| CN101944594B (en) * | 2010-09-14 | 2013-01-09 | 耿世达 | Lithium ferrous silicate anode material for high-performance lithium ion battery and preparation method thereof |
| CN101982410B (en) * | 2010-10-15 | 2012-06-06 | 福建师范大学 | Preparation method of rare earth compound doped lithium ferrous silicate cathode material |
| EP2487746A3 (en) * | 2011-02-14 | 2014-04-16 | Basf Se | Electrode materials and method for their production |
| CN102315438A (en) * | 2011-05-23 | 2012-01-11 | 江苏正彤电子科技有限公司 | A porous C/Li2MSiO4/C (M=Fe, mn, co) composite anode material and its preparation method |
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| CN102509776B (en) * | 2011-10-19 | 2014-01-29 | 兰州理工大学 | Method for preparing doped lithium ferrous silicate positive electrode material from microsilica powder |
| CN102664262A (en) * | 2012-05-18 | 2012-09-12 | 哈尔滨工业大学 | Method for preparing lithium ferrous silicate or carbon ferrous silicate cathode material for lithium ion battery |
| CN102709561A (en) * | 2012-06-19 | 2012-10-03 | 中国科学院福建物质结构研究所 | Preparation method of carbon nano-Li2FeSiO4 composite cathode material |
| CN102969503B (en) * | 2012-12-04 | 2015-08-12 | 奇瑞汽车股份有限公司 | Composite material of composition silicate and carbon and preparation method thereof, lithium ion battery containing this material |
| CN104362318B (en) * | 2014-11-10 | 2016-10-05 | 湖南文理学院 | A kind of method of the lithium ferrosilicon silicate/carbon composite cathode material preparing micropore spherical structure |
| CN108807988B (en) * | 2018-07-25 | 2021-04-20 | 四川理工学院 | Preparation method of spherical lithium ferrous silicate cathode material for lithium ion battery |
| CN109638274B (en) * | 2018-12-14 | 2022-03-11 | 廊坊绿色工业技术服务中心 | Molybdenum-ytterbium co-doped sodium iron silicate composite electrode material and preparation method thereof |
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| CN111647863B (en) * | 2020-07-02 | 2022-03-25 | 河北大学 | Li2FexSiO4Preparation method and application of positive electrode film |
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