CN114804883B - 一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法 - Google Patents
一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 239000010405 anode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 71
- 238000005530 etching Methods 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000012429 reaction media Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 98
- 239000000919 ceramic Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- -1 titanium hydride Chemical compound 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000009694 cold isostatic pressing Methods 0.000 claims description 2
- 238000000280 densification Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000004694 iodide salts Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
- 239000002002 slurry Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000006258 conductive agent Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 238000007790 scraping Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及锂离子电池领域，具体为一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法。以熔盐作为反应介质，在较低温度下合成出小晶粒尺寸的Ti2AlC粉体；采用盐酸、氟化锂作为刻蚀液刻蚀该粉体，制备纳米/亚微米Ti2CTx迈科烯。将其与导电剂、粘结剂与分散剂均匀混合成浆料后，刮涂于集流体并进行真空干燥，制备出锂离子电池负极。电化学性能测试结果表明，该电极材料具有良好的倍率性能与循环寿命。
Description
技术领域
本发明涉及锂离子电池领域，具体为一种基于Ti2CTx迈科烯(MXene)的高倍率锂离子电池负极材料制备方法。
背景技术
目前，生活生产中最常用的电化学储能器件主要可以分为两大类，一类为锂离子电池，另一类为超级电容器。前者一般通过锂离子向电极材料晶格内部嵌入/脱出实现电能与化学能的相互转化，优点是容量较高，缺点是倍率性能一般较差。后者则一般通过静电吸附(双电层电容器)或表面的氧化还原反应(赝电容)储存能量，优点是倍率性能好，但是容量普遍偏低。近年来，一类新型的电化学储能材料被开发出来，其特点为材料一般为原子级厚度的二维薄片组成，片层内一般含有可变价的金属元素，片层之间的距离较大，方便离子在层间扩散，这类材料兼具较高的容量与良好的倍率性能，被称为插层赝电容[1]。二维材料迈科烯(MXene)，作为MAX相陶瓷的衍生物，就是一类重要插层赝电容材料。MAX相陶瓷是一类三元层状碳氮化合物的统称，其化学通式可以表达为Mn+1AXn(n＝1、2、3)，其中M指早期过渡族金属元素，A主要指第三、四主族元素，X指碳和/或氮元素[2]。目前已制备出来的MAX相已经超过七十种[3]，Ti2AlC就是其中典型的一员[4]。由于MX之间结合力较强，MA之间结合力较弱，MAX相在含氟的酸性溶液会被选择性刻蚀掉结合力较弱的A原子层得到MX片层，同时表面形成-O、-F、-OH等官能团，以Tx表示。作为插层赝电容材料，迈科烯适用于无机、有机多种体系[5]。无机电解液体系中，迈科烯在酸性电解液表现出了超高的比电容，其体积比电容超过了目前商业化产品中体积比容量最高的氧化钌[6]。有机电解液中，迈科烯在锂离子电池中同样表现出较好的性能[7]，但是其倍率性能仍有提升的空间[8]。另一方面，MAX相合成温度一般高达1500℃左右，高的合成温度增加了MAX相的制备难度，进而影响了迈科烯的研究与产业化进程。
参考文献：
[1]Wang Y,Song Y,Xia Y.Electrochemical capacitors:mechanism,materials,systems,characterization and applications[J].Chemical SocietyReviews,2016,45(21):5925-5950.
[2]Barsoum M W.The MN+1AXN phases:A new class of solids:Thermodynamically stable nanolaminates[J].Progress in solid state chemistry,2000,28(1-4):201-281.
[3]Barsoum M W.MAX phases:properties of machinable ternary carbidesand nitrides[M].John Wiley&Sons,2013.
[4]Wang X H,Zhou Y C.Layered machinable and electrically conductiveTi2AlC and Ti3AlC2 ceramics:a review[J].Journal of Materials Science&Technology,2010,26(5):385-416.
[5]Anasori B,Lukatskaya M R,Gogotsi Y.2D metal carbides and nitrides(MXenes)for energy storage[J].Nature Reviews Materials,2017,2(2):1-17.
[6]Ghidiu M,Lukatskaya M R,Zhao M Q,et al.Conductive two-dimensionaltitanium carbide‘clay’with high volumetric capacitance[J].Nature,2014,516(7529):78-81.
[7]Tang X,Guo X,Wu W,et al.2D Metal Carbides and Nitrides(MXenes)asHigh-Performance Electrode Materials for Lithium-BasedBatteries[J].AdvancedEnergy Materials,2018,8(33):1801897.
[8]Naguib M,Come J,DyatkinB,et al.MXene:a promising transition metalcarbide anode for lithium-ion batteries[J].Electrochemistry Communications,2012,16(1):61-64.
发明内容
本发明的目的是提供一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，在熔盐介质下合成小晶粒尺寸的Ti2AlC MAX相陶瓷粉体，制备出具有高倍率性能纳米/亚微米Ti2CTx迈科烯。
本发明的技术方案：
一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，包括如下步骤：
(1)将反应介质盐与氢化钛、铝粉和纳米碳黑三种反应物进行球磨均匀混合后烘干；
(2)对混合后烘干的粉体进行冷压成型、冷等静压致密化后，在惰性气氛下进行热处理合成小晶粒尺寸的Ti2AlC MAX相陶瓷粉体；
(3)用去离子水将热处理后Ti2AlC MAX相陶瓷粉体中的盐溶解去除，利用抽滤或离心的方法将Ti2AlC粉体分离并进行烘干；
(4)使用盐酸、氟化锂刻蚀液对Ti2AlC粉体进行刻蚀，刻蚀完成后进行分离，得到目标产物：纳米/亚微米Ti2CTx迈科烯。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(1)中，使用的盐为碱金属或碱土金属的氯化物、溴化物、碘化物盐中的一种或两种以上。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(1)中，氢化钛粉的粒度为100nm～50μm，铝粉的粒度为100nm～50μm，纳米碳黑的粒度为10nm～500nm，盐的粒度为1μm～500μm。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(1)中，反应物TiH2:Al:C摩尔比范围为(2:0.8:0.5)～(2:1.5:1.5)，盐与反应物的质量之比为(1:10)～(10:1)，球磨时间1h～100h，烘干温度为50℃～200℃。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(2)中，冷等静压的压力在50MPa～500MPa范围内，合成温度在700℃～1400℃范围内，保温时间在1min～100h范围内，Ti2AlC MAX相陶瓷粉体的晶粒尺寸为10nm～1μm。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(3)中，Ti2AlC粉体的烘干温度为50℃～200℃。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(4)中，Ti2AlC粉体与氟化锂的质量比为(10:1)～(1:10)，Ti2AlC粉体与盐酸的摩尔比为(1:1)～(1:20)；其中，盐酸的浓度为0.1mol L-1～12mol L-1，刻蚀温度为25℃～80℃，时间为1h～100h。
所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，步骤(4)中，将刻蚀产物与刻蚀液通过真空抽滤或离心方式分离，并用去离子水清洗数次直到pH在6以上，分离得到的Ti2CTx迈科烯通过真空干燥得到Ti2CTx迈科烯粉体。
本发明的设计思想：
本发明提出以熔盐为反应介质，在较低温度下合成小晶粒尺寸的Ti2AlC MAX相陶瓷粉体，并以此为前躯体，通过盐酸、氟化锂刻蚀液选择性刻蚀掉Ti2AlC MAX相陶瓷粉体中铝原子层，得到具有高倍率性能锂离子电池负极材料——纳米/亚微米级Ti2CTx迈科烯。一方面，减小Ti2CTx的晶粒尺寸提升了其比表面积，表面吸附贡献容量将得到提升。另一方面减小晶粒尺寸缩短了锂离子扩散路径同样对实现高倍率性能有益，所以制备出的纳米/亚微米Ti2CTx迈科烯作为锂离子电池负极材料展现出极佳的倍率性能。
本发明的优点及有益效果是：
1、本发明以熔盐为反应介质，利用金属在熔盐中具有一定溶解度的特点，使反应活性明显提高，降低了Ti2AlC MAX相陶瓷粉体合成温度，此方法将Ti2AlC的合成温度降低到1000℃，实现了高质量、小晶粒尺寸Ti2AlC MAX相陶瓷粉体低温制备。
2、本发明刻蚀熔盐中制备的小晶粒尺寸Ti2AlC MAX相陶瓷粉体，得到纳米/亚微米Ti2CTx迈科烯展现出极佳的倍率性能，在10A g-1的高电流密度下质量比容量仍能达到约155mAh g-1，在高倍率储能器件中具有良好的应用前景。
附图说明
图1为1000℃下保温1h熔盐中合成Ti2AlC MAX相陶瓷粉体XRD图谱。图中，横坐标2θ代表衍射角(degree)，纵坐标Intensity代表相对强度(arb.units)。
图2为1000℃下保温1h熔盐中合成Ti2AlC MAX相陶瓷粉体形貌。
图3为刻蚀Ti2AlC MAX相陶瓷粉体后得到纳米/亚微米Ti2CTx迈科烯XRD图谱。图中，横坐标2θ代表衍射角(degree)，纵坐标Intensity代表相对强度(arb units)。
图4为刻蚀Ti2AlC MAX相陶瓷粉体后得到纳米/亚微米Ti2CTx迈科烯形貌。
图5为纳米/亚微米Ti2CTx迈科烯的倍率性能。图中，横坐标Cycle number代表循环次数，左侧纵坐标Capacity代表质量比容量(mAhg-1)，右侧纵坐标Coulombic efficiency代表库仑效率(％)，Discharge capacity代表放电质量比容量，Charge capacity代表充电质量比容量。
图6为纳米/亚微米Ti2CTx迈科烯的循环稳定性。图中，横坐标Cycle number代表循环次数，左侧纵坐标Discharge capacity代表放电质量比容量(mAh g-1)，右侧纵坐标Coulombic efficiency代表库仑效率(％)。
具体实施方式
在具体实施过程中，基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法如下：
(1)制备高倍率性能纳米/亚微米Ti2CTx迈科烯，首先需要制备出Ti2AlC MAX相陶瓷粉体，以熔盐为反应介质合成小晶粒尺寸的Ti2AlC MAX相陶瓷粉体。
(2)对合成出来的小晶粒尺寸的Ti2AlC MAX相陶瓷粉体进行刻蚀并表征。
(3)对刻蚀产物，即纳米/亚微米Ti2CTx迈科烯进行电化学性能表征。
本发明以熔盐作为反应介质，在较低温度下合成出小晶粒尺寸的Ti2AlC粉体；采用盐酸、氟化锂作为刻蚀液刻蚀该粉体，制备纳米/亚微米Ti2CTx迈科烯。将其与导电剂、粘结剂与分散剂均匀混合成浆料后，刮涂于集流体并进行真空干燥，制备出锂离子电池负极。电化学性能测试结果表明，该电极材料具有良好的倍率性能与循环寿命。
下面，通过实施例进一步证实本发明的可行性。
实施例1
本实施例中，以氢化钛粉、铝粉、纳米碳黑为反应物，原子比设置为TiH2:Al:C＝2:1.05:0.8。选取摩尔比为1:1的氯化钠、氯化钾共晶盐，反应物与盐的质量比为1:4进行混料。以酒精作为介质球磨10h后60℃下烘干。氢化钛粉的平均粒度为2μm，铝粉的平均粒度为1μm，纳米碳黑的平均粒度为60nm，氯化钠、氯化钾的平均粒度为30μm。
烘干后，将混合物冷压成型后进行冷等静压密实，压强为300MPa，再在管式炉中氩气气氛下进行合成。采用去离子水将热处理后Ti2AlC MAX相陶瓷粉体中的盐溶解去除，利用抽滤的方法将Ti2AlC粉体分离并进行烘干，烘干温度为60℃。
如图1所示，当合成温度为1000℃保温1h，产物为较纯的Ti2AlC MAX相；如图2所示，扫描电子显微镜下观察，Ti2AlC MAX相粉体为亚微米级颗粒。
使用盐酸、氟化锂刻蚀液，对如上制备的Ti2AlC粉体进行刻蚀。将0.5g的Ti2AlC粉体加入到0.34g的氟化锂与5mL摩尔浓度6M盐酸组成的刻蚀液中进行刻蚀，刻蚀温度为35℃，时间为36h。将刻蚀产物与刻蚀液通过真空抽滤方式分离，并用去离子水清洗数次直到pH为6，分离得到的Ti2CTx迈科烯通过真空干燥得到Ti2CTx迈科烯粉体。
如图3所示，刻蚀后样品的XRD衍射图谱中可以看出，对应Ti2AlC MAX相粉体的衍射峰大部分消失，而(002)衍射峰向小角度偏移，表明刻蚀已经完成，制备出Ti2CTx迈科烯。如图4所示，扫描电子显微镜下观察，刻蚀后，原先存在于Ti2AlC MAX相粉体中的晶界被溶解，得到纳米/亚微米Ti2CTx迈科烯粉体。
如图5所示，基于纳米/亚微米Ti2CTx迈科烯制备的电极在10A g-1电流密度下，质量比容量仍能达到约155mAhg-1，展现出极佳的倍率性能。
如图6所示，循环稳定性测试表明，Ti2CTx电极展现出极佳的循环稳定性，在5A g-1电流密度下循环一千圈质量比容量仍高于130mAhg-1。
实施例2
本实施例中，以氢化钛粉、铝粉、纳米碳黑为反应物，原子比设置为TiH2:Al:C＝2:1.05:0.8。选取摩尔比为1:1的氯化钠、氯化钾共晶盐，反应物与盐的质量比为1:4进行混料。以酒精作为介质球磨10h后60℃下烘干。氢化钛粉的平均粒度为2μm，铝粉的平均粒度为1μm，纳米碳黑的平均粒度为60nm，氯化钠、氯化钾的平均粒度为30μm。
烘干后，将混合物冷压成型后进行冷等静压密实，压强为300MPa，再在管式炉中氩气气氛下进行合成。当合成温度为1000℃保温5h，产物为较纯的Ti2AlC MAX相，扫描电子显微镜下观察，Ti2AlC MAX相粉体为亚微米级颗粒。
采用去离子水将热处理后Ti2AlC MAX相陶瓷粉体中的盐溶解去除，利用离心的方法将Ti2AlC粉体分离并进行烘干，烘干温度为60℃。
使用盐酸、氟化锂刻蚀液，对如上制备的Ti2AlC粉体进行刻蚀。将1g的Ti2AlC粉体加入到0.67g的氟化锂与10mL摩尔浓度6M盐酸组成的刻蚀液中进行刻蚀，刻蚀温度为35℃，时间为24h。将刻蚀产物与刻蚀液通过真空抽滤方式分离，并用去离子水清洗数次直到pH为6，分离得到的Ti2CTx迈科烯通过真空干燥得到Ti2CTx迈科烯粉体。
刻蚀后，对应Ti2AlC MAX相粉体的衍射峰大部分消失，而(002)衍射峰向小角度偏移，表明刻蚀已经完成，制备出Ti2CTx迈科烯。刻蚀后，原先存在于Ti2AlC MAX相粉体中的晶界被溶解，得到纳米/亚微米Ti2CTx迈科烯粉体。
实施例3
本实施例中，以氢化钛粉、铝粉、纳米碳黑为反应物，原子比设置为TiH2:Al:C＝2:1.05:0.8。选取溴化钾作为反应介质盐，反应物与盐的质量比为1:1进行混料。以酒精作为介质球磨5h后50℃下烘干。氢化钛粉的平均粒度为5μm，铝粉的平均粒度为3μm，纳米碳黑的平均粒度为40nm，溴化钾的平均粒度为200μm。
烘干后，将混合物冷压成型后进行冷等静压密实，压强为200MPa，再在管式炉中氩气气氛下进行合成。当合成温度为1150℃保温1h，产物为较纯的Ti2AlC MAX相，扫描电子显微镜下观察，Ti2AlC MAX相粉体为亚微米级颗粒。
采用去离子水将热处理后Ti2AlC MAX相陶瓷粉体中的盐溶解去除，利用抽滤的方法将Ti2AlC粉体分离并进行烘干，烘干温度为80℃。
使用盐酸、氟化锂刻蚀液，对如上制备的Ti2AlC粉体进行刻蚀。将1g的Ti2AlC粉体加入到1g的氟化锂与10mL摩尔浓度9M盐酸组成的刻蚀液中进行刻蚀，刻蚀温度为30℃，时间为48h。将刻蚀产物与刻蚀液通过真空抽滤方式分离，并用去离子水清洗数次直到pH为7，分离得到的Ti2CTx迈科烯通过真空干燥得到Ti2CTx迈科烯粉体。
刻蚀后，对应Ti2AlC MAX相粉体的衍射峰大部分消失，而(002)衍射峰向小角度偏移，表明刻蚀已经完成，制备出Ti2CTx迈科烯。刻蚀后，原先存在于Ti2AlC MAX相粉体中的晶界被溶解，得到纳米/亚微米Ti2CTx迈科烯粉体。
实例结果表明，本发明提出基于熔盐法合成Ti2AlC，显著降低了Ti2AlC的合成温度。进一步的，通过刻蚀制备纳米/亚微米Ti2CTx迈科烯作为锂离子电池负极材料展现出极佳的倍率性能，在高倍率电化学储能器件领域的应用中，具有重要的意义和优异的应用前景。
Claims (5)
1.一种基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，其特征在于，包括如下步骤：
(1)将反应介质盐与氢化钛、铝粉和纳米碳黑三种反应物进行球磨均匀混合后烘干；
(2)对混合后烘干的粉体进行冷压成型、冷等静压致密化后，在惰性气氛下进行热处理合成小晶粒尺寸的Ti2AlC MAX相陶瓷粉体；
(3)用去离子水将热处理后Ti2AlC MAX相陶瓷粉体中的盐溶解去除，利用抽滤或离心的方法将Ti2AlC粉体分离并进行烘干；
(4)使用盐酸、氟化锂刻蚀液对Ti2AlC粉体进行刻蚀，刻蚀完成后进行分离，得到目标产物：纳米/亚微米Ti2CTx迈科烯；
步骤(1)中，氢化钛粉的粒度为100nm～50μm，铝粉的粒度为100nm～50μm，纳米碳黑的粒度为10nm～500nm，盐的粒度为1μm～500μm；
步骤(1)中，反应物TiH2:Al:C摩尔比范围为(2:0.8:0.5)～(2:1.5:1.5)，盐与反应物的质量之比为(1:10)～(10:1)，球磨时间1h～100h，烘干温度为50℃～200℃；
步骤(2)中，冷等静压的压力在50MPa～500MPa范围内，合成温度在700℃～1150℃范围内，保温时间在1min～100h范围内，Ti2AlC MAX相陶瓷粉体的晶粒尺寸为10nm～1μm。
2.按照权利要求1所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，其特征在于，步骤(1)中，使用的盐为碱金属或碱土金属的氯化物、溴化物、碘化物盐中的一种或两种以上。
3.按照权利要求1所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，其特征在于，步骤(3)中，Ti2AlC粉体的烘干温度为50℃～200℃。
4.按照权利要求1所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，其特征在于，步骤(4)中，Ti2AlC粉体与氟化锂的质量比为(10:1)～(1:10)，Ti2AlC粉体与盐酸的摩尔比为(1:1)～(1:20)；其中，盐酸的浓度为0.1mol L-1～12mol L-1，刻蚀温度为25℃～80℃，时间为1h～100h。
5.按照权利要求1所述的基于Ti2CTx迈科烯的高倍率锂离子电池负极材料制备方法，其特征在于，步骤(4)中，将刻蚀产物与刻蚀液通过真空抽滤或离心方式分离，并用去离子水清洗数次直到pH在6以上，分离得到的Ti2CTx迈科烯通过真空干燥得到Ti2CTx迈科烯粉体。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220180A (zh) * | 2016-07-08 | 2016-12-14 | 中国科学院上海硅酸盐研究所 | 一种二维晶体MXene纳米材料的制备方法 |
| CN108922793A (zh) * | 2018-07-24 | 2018-11-30 | 启东创潞新材料有限公司 | 一种二维层状Ti2CTx柔性纸的制备方法 |
| CN110739429A (zh) * | 2019-10-29 | 2020-01-31 | 肇庆市华师大光电产业研究院 | 一种锂硫电池功能性隔层的制备方法 |
| WO2020042948A1 (zh) * | 2018-08-31 | 2020-03-05 | 中国科学院金属研究所 | 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020136865A1 (ja) * | 2018-12-28 | 2020-07-02 | 株式会社アドマテックス | ＭＸｅｎｅ粒子材料、それらの粒子材料の製造方法、及び、二次電池 |
-
2021
- 2021-01-27 CN CN202110111917.9A patent/CN114804883B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220180A (zh) * | 2016-07-08 | 2016-12-14 | 中国科学院上海硅酸盐研究所 | 一种二维晶体MXene纳米材料的制备方法 |
| CN108922793A (zh) * | 2018-07-24 | 2018-11-30 | 启东创潞新材料有限公司 | 一种二维层状Ti2CTx柔性纸的制备方法 |
| WO2020042948A1 (zh) * | 2018-08-31 | 2020-03-05 | 中国科学院金属研究所 | 球磨制备具有片层结构的纳米max相陶瓷粉体或料浆并调控粉体氧含量的方法 |
| CN110739429A (zh) * | 2019-10-29 | 2020-01-31 | 肇庆市华师大光电产业研究院 | 一种锂硫电池功能性隔层的制备方法 |
Non-Patent Citations (4)
| Title |
|---|
| "High-capacitance Ti3C2Tx MXene obtained by etching submicron Ti3AlC2 grains grown in molten salt;Cong Cui，;《Chemical Communication》;20180725;第58卷;第8132-8135页 * |
| 2维层状Ti2CTx电极材料的制备和电化学性能研究;李银银;《江西师范大学学报》;20201130;第44卷(第6期);第573-579页 * |
| Molten salt synthesis of MAX phases in the Ti-Al-C sys;T. Galvin;《Journal of the European Ceramic Society》;20180625;第38卷;第4585-4589页 * |
| 二维碳化物Ti_2C在超级电容器中的电化学性能研究;王冰心等;《现代技术陶瓷》;20170215(第01期);全文 * |
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