CN108461716A - 钛酸锂复合材料及其制备方法和用途 - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 86
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 15
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 238000005253 cladding Methods 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- -1 modified lithium titanate Chemical class 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims abstract description 4
- 229910002985 Li4+xTi5O12 Inorganic materials 0.000 claims abstract description 3
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 4
- 206010016766 flatulence Diseases 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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Abstract
本发明公开了一种钛酸锂复合材料及其制备方法和用途,具有以钛酸锂颗粒或改性钛酸锂颗粒为核,以硅化合物为壳的核‑壳结构,其中,所述钛酸锂的分子通式为Li4+xTi5O12,‑1≤x≤1,所述硅化合物的分子通式为SiOy,0≤y≤2。所述制备方法为液相包覆法或气相包覆法。所述钛酸锂复合材料可用于电极材料或电容器器件中。本发明的有益效果在于:本发明所述的钛酸锂复合材料制备工艺简单,操作简便,成本低廉,环境友好,适合于工业化大规模生产。
Description
技术领域
本发明属于材料、电池和电容器技术领域,涉及一种钛酸锂复合材料及其制备方法。
背景技术
随着社会对能源和环境问题的逐步重视,人们对可充电的二次电池(即蓄电池)的研究和开发也给予越来越多的关注。锂离子电池自上世纪90年代初商业化以来,因具有能量密度高、体积小等优势已成为人们日常生活不可缺少的一部分,在小型储能设备领域取得了巨大的商业成功。然而电动汽车等新兴市场以及技术的发展对锂离子电池的综合性能提出了更高的要求。理想的锂离子电池应满足以下要求:高能量密度、大功率密度、高安全性、低成本以及长寿命。
作为锂离子电池理想的新型负极材料,钛酸锂Li4Ti5O12材料相对于锂电极的电位为1.55V,理论比容量为175mA h/g,实验比容量为~160mA h/g。在Li+嵌入或脱出过程中,晶型基本不发生变化,体积变化小于1%,这能够避免充放电过程中由于晶胞体积变化而导致的结构破坏,从而提高电极的循环性能和使用寿命,表现出超长的循环寿命和高安全性。然而其自身电导率较低,导致倍率性能较差;此外,在实际使用过程中还存在胀气现象。针对倍率问题,目前可以通过离子掺杂、表面修饰如碳包覆、材料纳米化等手段来进行改善,并取得了较好的效果。但针对使用过程中的胀气问题,目前研究普遍认为由于材料颗粒表面Ti活性位点催化分解与之接触的电解液分解产生气体有关,从而导致电池发生严重的胀气、高温循环性能和储存性能明显下降,制约了其在动力及储能领域中的大规模商业化应用。
针对上述问题,专利《钛酸锂电池及其电解液》专利号:CN102280661A公布了一种钛酸锂电池及其电解液,采用特殊添加剂在颗粒表面形成保护膜来抑制钛酸锂电池的产气,间接隔离电解液与钛酸锂颗粒表面的接触。然而该方法在钛酸锂表面形成的钝化膜往往不能连续有效的包覆钛酸锂颗粒,无法将钛酸锂颗粒表面与电解液完全隔离,而且在形成SEI膜时会导致电解液损失,进而增加电池内阻。
专利《钛酸锂复合材料及其制备方法、电化学电池》专利号:CN105633355A公布了一种钛酸锂复合材料,包括钛酸锂和包覆在钛酸锂表面的磷酸锆,采用磷酸锆包覆层将钛酸锂颗粒与电解液隔离,避免直接接触,可以改善钛酸锂电池高温胀气的问题。然而通过上述方法在颗粒表面形成的包覆层不够均匀,包覆层厚度不可控制,无法保证颗粒表面形成均匀连续的磷酸锆保护层,使该方法大规模工业化应用的难度较高。
发明内容
针对现有技术的不足,本发明的目的在于提出一种钛酸锂复合材料及其制备方法及其应用,以解决其组成的电池产气问题,提高锂离子电池的高温存储与循环性能,满足钛酸锂电池的实际应用。
本发明是通过以下技术方案实现的:
一种钛酸锂复合材料,具有以钛酸锂颗粒或改性钛酸锂颗粒为核,以硅化合物为壳的核-壳结构,其中,所述钛酸锂的分子通式为Li4+xTi5O12,-1≤x≤1,所述硅化合物的分子通式为SiOy,0≤y≤2。
作为优选方案,所述钛酸锂的晶型为尖晶石型。
作为优选方案,所述改性钛酸锂为掺杂有金属元素的钛酸锂。
作为优选方案,所述金属元素包括Nb、Mg、Al、Zr、V、Zn、La、N、Cr、Fe、Co、Ni、Cu、Ag、Mo中的一种或几种。
作为优选方案,所述硅化合物为SiO或SiO2。
作为优选方案,所述SiO和SiO2均为晶态、无定型态或非晶态。
作为优选方案,所述硅化合物的含量为0.1~10w.t.%。
作为优选方案,所述硅化合物的厚度为0.5~50nm。
一种如前述的钛酸锂复合材料的制备方法,其包括液相包覆法或气相包覆法,其中,所述液相包覆法是将钛酸锂本体与液体硅源均匀混合,在一定条件下均匀沉积而获得本体表面均匀连续包覆层的方法;所述气相包覆法是将钛酸锂本体置于反应炉中,在设定温度和气体氛围下,将气相硅源带入反应炉中,从而在钛酸锂表面形成硅化合物包覆层。
本发明的原理在于:所述的钛酸锂复合材料,即硅源在钛酸锂本体表面通过化学反应或物理沉积形成的核壳结构,从而直接隔绝电解液与钛酸锂本体表面的接触,抑制电解液分解产气的副反应发生。
一种如前述的钛酸锂复合材料在电极材料以及电容器器件中的用途。
本发明的有益效果在于:
1、本发明中,由于在钛酸锂颗粒表面形成了均匀连续的包覆层,能够有效将钛酸锂颗粒与电解液实现隔离,避免了钛酸锂与电解液的直接接触,可抑制电解液在钛酸锂表面分解的副反应,进而抑制产气,能较好的解决其化成终封后的产气问题,提高钛酸锂电池的高温循环、存储性能;
2、氧化硅SiOx包覆层为化学、电化学惰性保护层,在电池工作时不影响电池的现有性能;
3、本发明所述的钛酸锂复合材料制备工艺简单,操作简便,成本低廉,环境友好,适合于工业化大规模生产。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为本发明实施例1中得到的二氧化硅包覆钛酸锂复合材料的透射电镜对比图;
图2为本发明实施例1中得到的二氧化硅包覆钛酸锂复合材料的充放电曲线。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
将钛酸锂本体材料加入到三颈圆底烧瓶中,分别加入无水乙醇、去离子水(70毫升)以及氨水(4毫升),超声分散5分钟。然后,加入3毫升正硅酸乙酯,室温搅拌10小时,过滤,去离子水和乙醇各清洗三次后,即制得核壳结构的复合材料。通过调节钛酸锂本体颗粒尺寸、正硅酸乙酯和氨水的用量,可以得到包覆层厚度可调节的SiO2包覆钛酸锂复合材料。
包覆前后的钛酸锂材料的TEM照片分别如图1a和1b所示。结果表明,经上述方法得到的钛酸锂复合材料具有均匀连续的表面包覆层,包覆层厚度约为15nm。
实施例2
将钛酸锂本体材料加入到三颈圆底烧瓶中,分别加入无水乙醇、去离子水(70毫升)以及氨水(4毫升),超声分散5分钟。然后,加入6毫升正硅酸乙酯,室温搅拌10小时,过滤,去离子水和乙醇各清洗三次后,即制得核壳结构的非晶态SiO2包覆复合材料。
实施例3
将钛酸锂本体材料加入到三颈圆底烧瓶中,分别加入无水乙醇、去离子水(70毫升)以及氨水(4毫升),超声分散5分钟。然后,加入3毫升正硅酸乙酯,室温搅拌5小时,过滤,去离子水和乙醇各清洗三次后,即制得核壳结构的非晶态SiO2包覆复合材料。
实施例4
将实施例1中得到的SiO2包覆钛酸锂复合材料置于管式炉或马弗炉中在200~600℃煅烧1~10小时,以提高SiO2包覆层和钛酸锂的结晶性,同时去除挥发性有机物,即可得到高结晶性的复合材料。
实施例5
以钛酸锂材料为本体,置于管式炉中。以SiCl4为硅源,氧气作为气源,控制气体流量,将SiCl4蒸汽带入到管式炉中,期间管式炉程序升温至反应温度,保持10~600分钟。待冷却后,经研磨,即得到晶体SiO2包覆的钛酸锂复合材料。
实施例6
以钛酸锂材料为本体,置于管式炉中。以SiO为硅源,氩气作为气源,控制气体流量,将SiO高温蒸汽带入到管式炉中,期间管式炉程序升温至反应温度,保持10~600分钟。待冷却后,经研磨,即得到SiO包覆的钛酸锂复合材料。
实施例7
将Zn、N掺杂的钛酸锂改性材料加入到三颈圆底烧瓶中,分别加入无水乙醇、去离子水(70毫升)以及氨水(4毫升),超声分散5分钟。然后,加入3毫升正硅酸乙酯,室温搅拌10小时,过滤,去离子水和乙醇各清洗三次后,即制得核壳结构的非晶态SiO2包覆掺杂钛酸锂复合材料。
实施例8
实施例1得到的钛酸锂复合材料、炭黑导电剂、聚偏二氟乙烯(PVDF)粘结剂按质量比90:5:5均匀混合,用N-甲基吡咯烷酮(NMP)制成均一浆料后均匀涂敷在铝箔集流体上,然后烘干、辊压、分条、干燥等工艺制作成极片。将金属锂片负极、隔膜、上述极片组装成扣式电池,注入含1mol/L的LiPF6碳酸二甲酯(DMC)、碳酸乙烯酯(EC)(体积比3:7)的电解液封装后即组装为扣式半电池。电化学测试结果如图2所示,本发明得到的钛酸锂复合材料在~1.55V具有典型的充放电特征平台和较高的可逆容量。
实施例9
分别以实施例1~7中得到的钛酸锂复合材料进行如下实验:
将钛酸锂复合材料作为活性物质,与炭黑导电剂、聚偏二氟乙烯(PVDF)粘结剂按质量比90:6:4均匀混合,用N-甲基吡咯烷酮(NMP)制成均一浆料后均匀涂敷在铝箔集流体上,然后经烘干、辊压、分条、干燥等工艺制作成负极片。将三元材料(NCM-111)、导电剂、聚偏二氟乙烯(PVDF)粘结剂按质量比92:4:4均匀混合,用N-甲基吡咯烷酮(NMP)制成均一浆料后均匀涂敷在铝箔集流体上,然后经烘干、辊压、分条、干燥等工艺制作成正极片。将正极片、隔膜、负极片叠成电芯,经极耳焊接、电芯干燥、注入含1mol/L的LiPF6碳酸二甲酯(DMC)、碳酸乙烯酯(EC)(体积比1:1)的电解液、铝塑膜塑封后即组装为三元材料(NCM-523)/钛酸锂锂二次电池。电化学测试结果如表1所示,采用SiOx包覆钛酸锂复合材料组成的电池胀气现象得到明显抑制,进而高温存储性能和高温循环性能都得到了显著改善,达到了本发明的预期效果。
表1实施例1-7电池性能测试结果
综上所述,仅为本发明的较佳实施例而已,并非用来限定本发明实施的范围,凡依本发明权利要求范围所述的形状、构造、特征及精神所为的均等变化与修饰,均应包括于本发明的权利要求范围内。
Claims (10)
1.一种钛酸锂复合材料,其特征在于,具有以钛酸锂颗粒或改性钛酸锂颗粒为核,以硅化合物为壳的核-壳结构,其中,所述钛酸锂的分子通式为Li4+xTi5O12,-1≤x≤1,所述硅化合物的分子通式为SiOy,0≤y≤2。
2.如权利要求1所述的钛酸锂复合材料,其特征在于,所述钛酸锂的晶型为尖晶石型。
3.如权利要求1所述的钛酸锂复合材料,其特征在于,所述改性钛酸锂为掺杂有金属元素的钛酸锂。
4.如权利要求3所述的钛酸锂复合材料,其特征在于,所述金属元素包括Nb、Mg、Al、Zr、V、Zn、La、N、Cr、Fe、Co、Ni、Cu、Ag、Mo中的一种或几种。
5.如权利要求1所述的钛酸锂复合材料,其特征在于,所述硅化合物为SiO或SiO2。
6.如权利要求5所述的钛酸锂复合材料,其特征在于,所述SiO和SiO2均为晶态、无定型态或非晶态。
7.如权利要求1所述的钛酸锂复合材料,其特征在于,所述硅化合物的含量为0.1~10w.t.%。
8.如权利要求1所述的钛酸锂复合材料,其特征在于,所述硅化合物的厚度为0.5~50nm。
9.一种如权利要求1所述的钛酸锂复合材料的制备方法,其特征在于,包括液相包覆法或气相包覆法,其中,所述液相包覆法是将钛酸锂本体与液体硅源均匀混合,在一定条件下均匀沉积而获得本体表面均匀连续包覆层的方法;所述气相包覆法是将钛酸锂本体置于反应炉中,在设定温度和气体氛围下,将气相硅源带入反应炉中,从而在钛酸锂表面形成硅化合物包覆层。
10.一种如权利要求1所述的钛酸锂复合材料在电极材料以及电容器器件中的用途。
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