CN104518210B - 一种复合钛酸锂材料的制备方法 - Google Patents
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 title claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007822 coupling agent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- -1 zirconium ester Chemical class 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PEQYWQJRQVAUAZ-UHFFFAOYSA-L [Cr](=O)(=O)(Cl)Cl.C(C(=C)C)(=O)O Chemical compound [Cr](=O)(=O)(Cl)Cl.C(C(=C)C)(=O)O PEQYWQJRQVAUAZ-UHFFFAOYSA-L 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 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
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
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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
- 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
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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
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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
- H01M4/485—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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Abstract
本发明公开了一种复合钛酸锂材料的制备方法,具体的讲是公开了一种含锆掺杂和碳包覆的锂离子电池负极材料钛酸锂的制备方法。通过改性添加剂的作用达到一次完成掺杂和包覆的双重效果,方法简单易于工业化生产。所制得的产品具有良好的电化学性能。
Description
技术领域
本发明属锂离子电池负极材料技术领域,具体涉及锂离子二次电池负极材料钛酸锂的制备方法,特别是一种金属元素掺杂和碳包覆的锂离子电池负极材料钛酸锂的制备方法。
背景技术
锂离子电池具有高能量密度、高工作电压、无记忆效应等优点,有望成为电动汽车的主要动力来源之一。由于石墨对锂电位仅为0.2V左右,容易导致锂在其表面的析出,造成安全性问题。而钛酸锂具有充放电过程中骨架结构几乎不发生变化的“零应变”特性,嵌锂电位高(1.55V vs.Li/Li+)而不易引起金属锂析出,库仑效率高,锂离子扩散系数(为2×10-8cm2/s)比碳负极高一个数量级等优良特性,具备了下一代锂离子蓄电池必需的充电次数更高、充电过程更快、更安全的特性。因此,钛酸锂在电动车、储能领域有着广泛的应用前景,具有巨大的潜在经济效益。
但Li4Ti5O12材料的可逆比容量较小(约170mAh/g),无法满足高能锂离子电池在负极比容量方面的要求。另外Li4Ti5O12的固有电导率低(~10-9S/cm),只能在低电流下工作才能发挥出材料的性能优势,在大电流下放电容量损失较大。所以提高Li4Ti5O12的导电率是Li4Ti5O12材料商业化应用的关键。
围绕提高钛酸锂材料的导电率,目前国内外进行了大量的研究,主要是一次颗粒纳米化、碳包覆、离子掺杂等。其中,一次颗粒纳米化最为重要。因此常采用纳米二氧化钛或有机钛化合物为钛源,其次是掺杂和包覆。通常采取的掺杂方式是在过渡金属Ti位或O位掺杂金属阳离子或1价阴离子,包括Li+、Mg2+、Al3+、Ga3+、Zn2+、Co3+、Ta5+、Cr3+、、Ni3+、Zr4+、Mn3+、F-等,但是金属离子掺杂降低了放电容量。而通常采用的包覆剂为导电碳,碳源主要包括:糖类、石墨、聚合物、炭黑、活性炭、碳纳米管、碳纤维等。
目前公知的掺杂包覆钛酸锂材料制备方法主要有;CN102122710A公开了一种Zr掺杂钛酸锂电极材料制备方法,该方法是由含锂化合物、锐钛矿二氧化钛以及Zr的化合物为原料,通过固相合成方法制备得到;又如CN10194455 90A公开了一种碳包覆钛酸锂的制备方法,该方法通过长链型脂肪羧酸与钛酸锂表面配位,在非氧化性气体的保护下形成均匀的碳包覆层。但这些相关技术都没有一次性达到既掺杂又包覆的效果,且这些方法虽然改善了循环寿命、倍率特性等,但同时降低了放电容量和首次充放电效率等。
因此需要一种简单的,可一次性达到掺杂包覆目的的方法来制备钛酸锂材料。
发明内容
本发明旨在提高钛酸锂材料的电子导电率和大电流下的倍率性能,并且易于制备、成本低廉、环保无污染,适用于工业化生产的一种掺杂包覆改性钛酸锂的制备方法。
本发明解决其技术问题所采用的技术方案包括以下步骤:一种钴酸锂材料的制备方法主要包括以下步骤,
充分混合无机锂盐、二氧化钛、掺杂改性剂和分散剂,高能球磨机球磨分散0.5~20h,得均匀混合的前驱体浆料;
将上述浆料在50~120℃的真空烘箱中烘干,研磨破碎得均匀分散的前驱体细粉;
惰性气氛保护下煅烧上述细粉,破碎过筛得最终复合钛酸锂材料。
上述制备方法中,步骤1中所述的无机锂盐可以是碳酸锂、氢氧化锂或硝酸锂等中的一种或几种。
上述制备方法中,步骤1中所述二氧化钛可以是锐钛或金红石晶型中的一种或二种的混合物。
上述制备方法中,步骤1中所述的掺杂改性剂为偶联剂,具体可以是铝酸锆偶联剂、锆酸酯偶联剂或铬络合物偶联剂等。
上述制备方法中,步骤1中所述的分散剂可以是乙醇、丙醇、异丙醇和丙酮等有机溶剂中一种或其中几种的混合物。
上述制备方法中,步骤1所制得的混合前驱体浆料中掺杂金属元素/Ti/Li的摩尔比范围是:0~0.1:1:0.8~0.89。
上述制备方法中,步骤1所制得的混合前驱体浆料的固含量为10wt%~60wt%。
上述制备方法中,步骤3中所述的惰性气氛可以是氮气、氦气、氩气中的一种或其中几种混合0~15%的氢气。
上述制备方法中,步骤3中所述的煅烧可以是一次或两次煅烧;当所述煅烧为一次烧结时,温度范围为400~950℃,烧结时间为2~40h;当所述煅烧为二次烧结时,烧结过程为:(1)400~700℃热处理1~20h,自然冷却至室温;(2)700~950℃热处理2~40h,自然冷却至室温。
本发明公布了使用偶联剂对钛酸锂进行了改性,在纳米二氧化钛与碳酸锂等原料混合物中加入偶联剂,利用偶联剂中含有的有机与无机官能团与原料表面官能团的相互作用,容易实现纳米原材料组份间的均匀混合与分散,由此制备的钛酸锂材料表面与体相分别形成均匀的碳包覆层和均匀分布的金属元素掺杂,起到了掺杂和包覆的双重作用,可以实现金属元素均匀掺杂和碳均匀包覆,所制得的产品一致性好,具有良好的电化学性能。该方法工艺流程简单,成本低廉、产率高,且易于工业化生产。
附图说明
图1为实施例1中所制得的复合钛酸锂材料的扫描电镜图。
具体实施例
实施例1
将2mol碳酸锂、4.9mol锐钛二氧化钛和0.1mol的四正丙基锆酸酯(锆酸酯偶联剂)分散于乙醇中,固体和有机溶剂的比例为1:1.5,在行星式球磨机上研磨分散5小时制得钛酸锂前驱体混合物,在真空烘箱里100℃下烘干,研磨破碎得均匀分散的前驱体细粉,所得分散粉体放入坩埚中,置于氮气气氛保护高温炉中,升温至700℃,保温12小时后,自然冷却至常温,取出,经粉碎、筛分后得到复合钛酸锂材料Li4Zr0.1Ti4.9O12/Cy(0≤y≤0.05)。
实施例2
将4.2mol硝酸锂、5mol金红石二氧化钛和0.05mol的甲基丙烯酸氯化铬(铬络合物偶联剂)分散于乙醇中,固体和有机溶剂的比例为1:2,在行星式球磨机上研磨分散10小时制得钛酸锂前驱体混合物,在120℃下烘干,研磨破碎得均匀分散的前驱体细粉,所得分散粉体放入坩埚中,置于氮气混合10%氢气气氛保护高温炉中,升温至950℃,保温10小时后,自然冷却至常温,取出,经粉碎、筛分后得到复合钛酸锂材料Li4Cr0.05Ti4.95O12/Cy(0≤y≤0.05)。
实施例3
将4mol氢氧化锂、5mol锐钛二氧化钛和0.1mol的甲基丙烯氧官能基铝酸锆(铝锆酸酯偶联剂)分散于丙酮中,固体和有机溶剂的比例为1:1.7,在行星式球磨机上研磨分散10小时制得钛酸锂前驱体混合物,在真空烘箱中100℃下烘干,研磨破碎得均匀分散的前驱体细粉,所得分散粉体放入坩埚中,置于氮气气氛保护高温炉中,升温至600℃,保温5小时后,自然冷却至常温,取出,经粉碎、筛分后,再升温至900℃,保温10小时,自然冷却至常温,取出,经粉碎、筛分后得到复合钛酸锂材料Li4M0.1Ti4.9O12/Cy(M=Al、Zr;0≤y≤0.05)。
Claims (8)
1.一种复合钛酸锂材料的制备方法,充分混合无机锂盐、二氧化钛、掺杂改性剂和分散剂,高能球磨机球磨分散0.5~20h,得均匀混合的前驱体浆料;将浆料在50~120℃的真空烘箱中烘干,研磨破碎得均匀分散的前驱体细粉;惰性气氛保护下煅烧上述细粉,破碎过筛,最终得复合钛酸锂材料,
其中,所述掺杂改性剂为偶联剂,所述偶联剂选自铝酸锆偶联剂、锆酸酯偶联剂或铬络合物偶联剂。
2.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述的无机锂盐是碳酸锂、氢氧化锂或硝酸锂中的一种或其中几种的混合物。
3.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述的二氧化钛为锐钛或金红石晶型中的一种或二种的混合物。
4.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述前驱体浆料中掺杂金属元素/Ti/Li的摩尔比范围是:0~0.1:1:0.8~0.89。
5.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述分散剂为乙醇、丙醇、异丙醇和丙酮中一种或其中几种的混合物。
6.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述前驱体浆料的固含量为10wt%~60wt%。
7.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述惰性气氛是氮气、氦气、氩气中的一种或其中几种混合0~15%的氢气。
8.根据权利要求1所述的复合钛酸锂材料的制备方法,其特征在于,所述的煅烧温度为400~950℃,煅烧时间为2~40h。
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