技术领域technical field
本发明涉及一种锂离子电池负极材料的制备方法，具体涉及一种Ce掺杂Li4Ti5O12锂离子电池纳米负极材料的制备方法。The invention relates to a preparation method of a lithium ion battery negative electrode material, in particular to a preparation methodof a Ce- dopedLi4Ti5O12 lithium ion battery nanometer negative electrode material.
背景技术Background technique
钛酸锂是一种最近几年才开始兴起的锂离子电池的负极材料，它具有尖晶石型的晶体结构，在作为电极材料时，随着充放电过程的进行钛酸锂的晶体结构基本上不发生变化，形变率小于1％，被称为“零应变”材料，因此它可以具有良好的循环性能。但是它也存在着一定的缺陷，比如材料本身的电子电导率很低，大约为10-9S/cm，接近于绝缘体材料，而且它的嵌锂电位相对较高，约为1.5V，这使得电池的输出电压偏低。如果对钛酸锂进行一定方法的改性提高它的导电率，再加上钛资源的含量十分丰富并且对环境的不利影响很小，它很有可能取代目前广泛使用的碳负极材料而成为新一代的锂离子电池负极材料。Lithium titanate is a negative electrode material for lithium-ion batteries that has only begun to emerge in recent years. It has a spinel crystal structure. When used as an electrode material, the crystal structure of lithium titanate is basically There is no change in the material, and the deformation rate is less than 1%, which is called "zero strain" material, so it can have good cycle performance. But it also has certain defects, such as the electronic conductivity of the material itself is very low, about 10-9 S/cm, close to the insulator material, and its lithium intercalation potential is relatively high, about 1.5V, which makes The output voltage of the battery is low. If lithium titanate is modified in a certain way to improve its conductivity, coupled with the rich content of titanium resources and little adverse impact on the environment, it is likely to replace the widely used carbon negative electrode material and become a new A new generation of lithium-ion battery anode materials.
离子掺杂提高Li4Ti5O12的电导率主要是靠电荷补偿来完成的。在掺杂过程中，通过加入高价的阳离子如Mg2+、Zn2+、Al3+等替换低价的Li+，造成电荷过剩，此时为了保持晶体的电中性，Ti4+将会发生向Ti3+的转变，Ti3+含量越多，Li4Ti5O12的导电性越好。Ion doping improves the conductivity of Li4 Ti5 O12 mainly by charge compensation. During the doping process, the low-priced Li+ is replaced by adding high-valent cations such as Mg2+ , Zn2+ , Al3+ , etc., resulting in excess charge. At this time, in order to maintain the electrical neutrality of the crystal, Ti4+ will A transformation to Ti3+ occurs, and the more Ti3+ content, the better the conductivity of Li4 Ti5 O12 .
由于颗粒形貌对样品的电化学性能也可能会造成一定的影响，颗粒越小、比表面积越大，则材料与电解液的接触越好，Li+的迁移距离也会变短，这样更有利于锂离子电池负极材料倍率性能的提升。另外，一维纳米材料如纳米棒、纳米管、纳米线等这些特殊的结构在电化学性能等方面会产生一些新颖的特点。Since the particle morphology may also have a certain impact on the electrochemical performance of the sample, the smaller the particle and the larger the specific surface area, the better the contact between the material and the electrolyte, and the shorter the migration distance of Li+ , which is more It is beneficial to the improvement of the rate performance of the negative electrode material of the lithium ion battery. In addition, one-dimensional nanomaterials such as nanorods, nanotubes, nanowires and other special structures will produce some novel characteristics in terms of electrochemical performance.
过渡金属由于具有未充满的价层d轨道，基于十八电子规则，性质与其他元素有明显差别，故制备Ce掺杂Li4Ti5O12锂离子电池纳米材料具有很大的研究应用价值。Transition metals have unfilled valence layer d orbitals, based on the eighteen-electron rule, and their properties are significantly different from other elements. Therefore, the preparation of Ce-doped Li4 Ti5 O12 lithium-ion battery nanomaterials has great research and application value.
目前所报道的通过掺杂制备锂离子电池负极材料的方法主要为高温固相法[F.X.Wu,Z.X.Wang,X.H.Li,L.Wu,X.J.Wang,X.P.Zhang,et al.Preparationand characterization of spinel Li4Ti5O12 anode material from industrial titanyl sulfatesolution[J].J.Alloys Compd.,2011,509:596-601.]、溶胶凝胶法[Y.K.Sun,D.J.Jung,Y.S.Lee,K.S.Nahm,Synthesis and electrochemical characterization of spinelLi[Li(1-x)/3CrxTi(5-2x)/3]O4 anode materials[J].J.Power Sources 2004,125(2):242-245.]，其中高温固相法锻烧时间久、能耗大、效率低、目标材料的均匀性较差、制备的目标产物电化学性能较差、配方控制困难等；溶胶-凝胶法制备方法简单，反应条件温和，但容易出现沉淀，得不到凝胶，从而很难得到产品。The currently reported methods for preparing lithium-ion battery anode materials by doping are mainly high-temperature solid-phase methods [FXWu, ZXWang, XHLi, L.Wu, XJWang, XPZhang, et al.Preparation and characterization of spine Li4 Ti5 O12 anode material from industrial titanium sulfatesolution[J].J.Alloys Compd.,2011,509:596-601.], sol-gel method[YKSun,DJJung,YSLee,KSNahm,Synthesis and electrochemical characterization of spineLi[Li(1-x )/3 Crx Ti(5-2x)/3 ]O4 anode materials[J].J.Power Sources 2004,125(2):242-245.], in which the high-temperature solid-state method has a long calcination time and can High consumption, low efficiency, poor uniformity of the target material, poor electrochemical properties of the prepared target product, difficulty in formula control, etc.; the sol-gel method is simple to prepare, and the reaction conditions are mild, but it is prone to precipitation and cannot be obtained. gel, making it difficult to get the product.
发明内容Contents of the invention
为克服现有技术中的问题，本发明的目的是提供一种Ce掺杂Li4Ti5O12锂离子电池负极材料的制备方法，该方法具有制备成本低、操作简单、制备周期短的特点，所制备的Ce掺杂Li4Ti5O12锂离子电池纳米负极材料纯度高、结晶性强、形貌均匀。In order to overcome the problems in the prior art, the purpose of the present invention is to provide a kind of Ce-doped Li4 Ti5 O12 the preparation method of lithium-ion battery anode material, this method has the characteristics of low preparation cost, simple operation, short preparation cycle , the prepared Ce-doped Li4 Ti5 O12 lithium-ion battery nano-anode material has high purity, strong crystallinity and uniform morphology.
为实现上述目的，本发明采用如下的技术方案：To achieve the above object, the present invention adopts the following technical solutions:
1)将锂源溶于去离子水中，配制成锂离子浓度为0.5～0.9mol/L的溶液A，将Ce(NO3)4溶于去离子水中，配制成浓度为0.1～0.2mol/L的溶液B，将TiCl4溶于去离子水中，配制成浓度为0.2～0.5mol/L溶液C，并调节溶液C的pH值为1～3；1) Dissolve the lithium source in deionized water to prepare a solution A with a lithium ion concentration of 0.5-0.9 mol/L, and dissolve Ce(NO3 )4 in deionized water to prepare a solution A with a concentration of 0.1-0.2 mol/L solution B, dissolving TiCl4 in deionized water, and preparing solution C with a concentration of 0.2-0.5mol/L, and adjusting the pH value of solution C to 1-3;
2)将溶液A、溶液B、调节pH值后的溶液C按照Li、Ce、Ti元素摩尔比nLi:nCe:nTi＝(4～6):(0.05～0.1):(5～7.5)的比例混合均匀，得到混合溶液D；2) Solution A, solution B, and solution C after adjusting the pH value are according to Li, Ce, Ti element molar ratio nLi :nCe :nTi =(4～6):(0.05～0.1):(5～7.5 ) is mixed evenly to obtain a mixed solution D;
3)将混合溶液D采用水热电沉积法反应后过滤，得到滤饼，将滤饼干燥得到Ce掺杂Li4Ti5O12锂离子电池负极材料；其中，水热电沉积法反应的具体条件为：反应温度为80～120℃，正负两极电压为800～1000V，脉冲占空比为50％～60％。3) The mixed solution D is filtered by the hydrothermal electrodeposition method to obtain a filter cake, and the filter cake is dried to obtain a Ce-doped Li4 Ti5 O12 lithium ion battery negative electrode material; wherein, the specific conditions of the hydrothermal electrodeposition reaction are : The reaction temperature is 80-120°C, the positive and negative pole voltages are 800-1000V, and the pulse duty ratio is 50%-60%.
所述步骤1)中锂源为LiOH·H2O、Li2CO3、LiNO3或LiOH。The lithium source in the step 1) is LiOH·H2 O, Li2 CO3 , LiNO3 or LiOH.
所述步骤1)中溶液C的pH值是采用0.5-2mol/L的盐酸进行调节的。The pH value of the solution C in the step 1) is adjusted with 0.5-2mol/L hydrochloric acid.
所述步骤2)中混合均匀的具体条件是于40～60℃下搅拌1～3h。The specific condition for uniform mixing in the step 2) is to stir at 40-60° C. for 1-3 hours.
所述步骤3)中将混合溶液D转移至水热电沉积反应釜中，然后进行水热电沉积法反应，其中，反应釜的体积填充比为50％～60％。In the step 3), the mixed solution D is transferred to a hydrothermal electrodeposition reactor, and then the hydrothermal electrodeposition reaction is performed, wherein the volume filling ratio of the reactor is 50% to 60%.
所述步骤3)中将滤饼干燥前，先采用去离子水将滤饼洗涤2～3次，再采用无水乙醇洗涤2～3次。Before drying the filter cake in the step 3), the filter cake is washed 2 to 3 times with deionized water, and then washed 2 to 3 times with absolute ethanol.
所述步骤3)中干燥的温度为80～100℃，干燥的时间为1～3h。The drying temperature in the step 3) is 80-100° C., and the drying time is 1-3 hours.
所述步骤3)中反应时间为1～3小时。The reaction time in the step 3) is 1 to 3 hours.
与现有技术相比，本发明具有的有益的效果：本发明通过先制备含锂离子水溶液、Ce(NO3)4水溶液以及TiCl4水溶液，然后，调节TiCl4水溶液pH值后将三种水溶液混合，通过水热电沉积法的方式制得Ce掺杂Li4Ti5O12锂离子电池负极材料，由于本发明中水热条件下的特殊物理化学环境可以加快溶液中的传质速度，所以制备温度低且制备的纳米材料不需要后期的晶化热处理，一定程度上能够避免在后期热处理过程中可能导致的卷曲、晶粒粗化等缺陷；本发明采用电沉积方法制备纳米材料，操作简单，原材料的利用率高，而且能够获得具有较大比表面积的纳微米材料，这有利于电池负极材料电化学性能的提升。本发明将水热法与电沉积方法结合，利用水热电沉积技术在较低的温度下合成Ce掺杂Li4Ti5O12锂离子电池纳米负极材料，纯度高、结晶性强、形貌均匀，同时该方法制备成本低、操作简单、制备周期短。Compared with the prior art, the present invention has beneficial effects: the present invention prepares lithium-ion-containing aqueous solution, Ce(NO3 )4 aqueous solution and TiCl4 aqueous solution first, and then adjusts the pH value of TiCl4 aqueous solution to prepare the three aqueous solutions Mixing, the Ce-doped Li4 Ti5 O12 lithium ion battery negative electrode material is obtained by the hydrothermal electrodeposition method, because the special physical and chemical environment under the hydrothermal condition in the present invention can accelerate the mass transfer rate in the solution, so the preparation The temperature is low and the prepared nanomaterials do not require later crystallization heat treatment, which can avoid defects such as curling and grain coarsening that may be caused in the later heat treatment process to a certain extent; the present invention uses the electrodeposition method to prepare nanomaterials, and the operation is simple. The utilization rate of raw materials is high, and nano-micron materials with large specific surface area can be obtained, which is conducive to the improvement of electrochemical performance of battery negative electrode materials. The present invention combines the hydrothermal method with the electrodeposition method, and uses the hydrothermal electrodeposition technology to synthesize Ce-doped Li4 Ti5 O12 lithium-ion battery nano-negative electrode materials at a relatively low temperature, with high purity, strong crystallinity, and uniform appearance , and at the same time, the method has low preparation cost, simple operation and short preparation period.
由于本发明水热电沉积法中采用电弧放电加热，所以能够使温度瞬时达到反应温度，从而缩短了反应时间，此外由于水热电沉积法中采用水热进行加热，所以具有加热均匀，能够控制最终产品的形貌，进而提高电化学性能。本发明提供的制备方法具有成本低、操作简单、制备周期短的优点。本发明制备的Ce掺杂Li4Ti5O12锂离子电池负极材料为纳米片状结构所组成的花球状粉体，纯度高、结晶性强、形貌均匀，具有优异的充放电性能，在0.1C低倍率下，其首次放电容量可达到300mAh/g，在10C的高倍率下，其首次放电容量可达到180mAh/g。Because arc discharge heating is used in the hydrothermal electrodeposition method of the present invention, the temperature can reach the reaction temperature instantaneously, thereby shortening the reaction time. In addition, since the hydrothermal electrodeposition method is heated by water heat, it has uniform heating and can control the final product. morphology, thereby improving the electrochemical performance. The preparation method provided by the invention has the advantages of low cost, simple operation and short preparation cycle. The Ce-doped Li4 Ti5 O12 lithium-ion battery negative electrode material prepared by the present invention is a spherical powder composed of a nano-sheet structure, which has high purity, strong crystallinity, uniform appearance, and excellent charge-discharge performance. At a low rate of 0.1C, its initial discharge capacity can reach 300mAh/g, and at a high rate of 10C, its initial discharge capacity can reach 180mAh/g.
附图说明Description of drawings
图1是本发明实施例1所制备Ce掺杂Li4Ti5O12锂离子电池纳米材料的SEM图。Fig. 1 is a SEM image of the Ce-doped Li4 Ti5 O12 lithium ion battery nanomaterial prepared in Example 1 of the present invention.
具体实施例specific embodiment
下面结合附图通过具体实施例对本发明进行详细说明。The present invention will be described in detail below through specific embodiments in conjunction with the accompanying drawings.
实施例1Example 1
1)将LiOH·H2O溶于去离子水中，配制成锂离子浓度为0.5mol/L的溶液A，将Ce(NO3)4溶于去离子水中，配制成浓度为0.1mol/L的溶液B，将TiCl4溶于去离子水中，配制成浓度为0.2mol/L溶液C，然后用1mol/L盐酸调节溶液C的pH值为1。1) Dissolve LiOH·H2 O in deionized water to prepare a solution A with a lithium ion concentration of 0.5 mol/L, and dissolve Ce(NO3 )4 in deionized water to prepare a solution A with a concentration of 0.1 mol/L For solution B, dissolve TiCl4 in deionized water to prepare solution C with a concentration of 0.2 mol/L, and then adjust the pH value of solution C to 1 with 1 mol/L hydrochloric acid.
2)将溶液A、溶液B、调节pH值后的溶液C三种溶液按照Li、Ce、Ti元素摩尔比nLi:nCe:nTi＝4:0.05:5的比例混合后，在40℃下磁力搅拌1h，形成均匀稳定的混合溶液D。2) After mixing the three solutions of solution A, solution B, and solution C after adjusting the pH value according to the molar ratio of Li, Ce, and Ti elements nLi : nCe : nTi = 4:0.05:5, at 40 ° C Under magnetic stirring for 1 h, a uniform and stable mixed solution D was formed.
3)将混合溶液D放入水热电沉积反应釜中，密封反应釜，控制体积填充比为50％，反应温度控制在80℃，正负两极电压为800V，脉冲占空比为50％，采用电弧放电水热反应1h。3) Put the mixed solution D into the hydrothermal electrodeposition reaction kettle, seal the reaction kettle, control the volume filling ratio to 50%, control the reaction temperature at 80°C, the positive and negative pole voltages are 800V, and the pulse duty ratio is 50%. Arc discharge hydrothermal reaction for 1h.
4)待反应釜自然冷却直室温后，经过滤得到滤饼，将滤饼先采用去离子水洗涤2次，再用无水乙醇洗涤2次得到粉体，然后以在80℃下干燥1h，得到Ce掺杂Li4Ti5O12锂离子电池负极材料。4) After the reaction kettle was naturally cooled down to room temperature, the filter cake was obtained by filtration. The filter cake was washed twice with deionized water and then twice with absolute ethanol to obtain a powder, and then dried at 80°C for 1 hour. The Ce-doped Li4 Ti5 O12 lithium ion battery negative electrode material is obtained.
图1为实施例1制得的Ce掺杂Li4Ti5O12锂离子电池负极材料的SEM图，从图1中可以看出掺杂后的样品表面是由纳米片自组成的花状结构，纳米片的厚度大约为几个纳米。Figure 1 is the SEM image of the Ce-doped Li4 Ti5 O12 lithium-ion battery negative electrode material prepared in Example 1. It can be seen from Figure 1 that the surface of the doped sample is a flower-like structure composed of nanosheets , the thickness of the nanosheets is on the order of several nanometers.
实施例2Example 2
1)将Li2CO3溶于去离子水中，配制成锂离子浓度为0.7mol/L的溶液A，将Ce(NO3)4溶于去离子水中，配制成浓度为0.15mol/L的溶液B，将TiCl4溶于去离子水中，配制成浓度为0.35mol/L溶液C，同时用0.5mol/L盐酸调节溶液C的pH值为2。1) Dissolve Li2 CO3 in deionized water to prepare a solution A with a lithium ion concentration of 0.7mol/L, and dissolve Ce(NO3 )4 in deionized water to prepare a solution with a concentration of 0.15mol/L B. Dissolve TiCl4 in deionized water to prepare solution C with a concentration of 0.35 mol/L, and adjust the pH value of solution C to 2 with 0.5 mol/L hydrochloric acid.
2)将溶液A、溶液B、调节pH值后的溶液C三种溶液按照Li、Ce、Ti元素摩尔nLi:nCe:nTi＝5:0.1:6的比例混合后，在50℃下磁力搅拌3h，形成均匀稳定的混合溶液D。2) After mixing the three solutions of solution A, solution B, and solution C after adjusting the pH value according to the ratio of Li, Ce, and Ti element moles nLi :nCe :nTi =5:0.1:6, at 50°C Stir magnetically for 3 h to form a uniform and stable mixed solution D.
3)将混合溶液D放入水热电沉积反应釜中，密封反应釜，控制体积填充比为55％，反应温度控制在100℃，正负两极电压为900V，脉冲占空比为55％，采用电弧放电水热反应2h。3) Put the mixed solution D into the hydrothermal electrodeposition reaction kettle, seal the reaction kettle, control the volume filling ratio to 55%, the reaction temperature to 100°C, the positive and negative pole voltages to 900V, and the pulse duty ratio to 55%. Arc discharge hydrothermal reaction for 2h.
4)待反应釜自然冷却至室温后，经过滤得到滤饼，将滤饼先采用去离子水洗涤3次，再用无水乙醇洗涤3次得到粉体，然后在90℃下干燥2h，得到Ce掺杂Li4Ti5O12锂离子电池负极材料。4) After the reaction kettle was naturally cooled to room temperature, the filter cake was obtained by filtration, and the filter cake was washed 3 times with deionized water, and then washed 3 times with absolute ethanol to obtain a powder, and then dried at 90°C for 2 hours to obtain Ce-doped Li4 Ti5 O12 lithium-ion battery anode material.
实施例3Example 3
1)将LiNO3溶于去离子水中，配制成锂离子浓度为0.9mol/L的溶液A，将Ce(NO3)4溶于去离子水中，配制成浓度为0.2mol/L的溶液B，将TiCl4溶于去离子水中，配制成浓度为0.5mol/L溶液C，同时用2mol/L盐酸调节溶液C的pH值为3。1) Dissolve LiNO3 in deionized water to prepare a solution A with a lithium ion concentration of 0.9 mol/L, and dissolve Ce(NO3 )4 in deionized water to prepare a solution B with a concentration of 0.2 mol/L, Dissolve TiCl4 in deionized water to prepare solution C with a concentration of 0.5 mol/L, and adjust the pH of solution C to 3 with 2 mol/L hydrochloric acid.
2)将溶液A、溶液B、调节pH值后的溶液C三种溶液按照Li、Ce、Ti元素摩尔nLi:nCe:nTi＝6:0.05:7.5的比例混合后，在60℃下磁力搅拌3h，形成均匀稳定的混合溶液D。2) After mixing the three solutions of solution A, solution B, and solution C after adjusting the pH value according to the ratio of Li, Ce, and Ti element moles nLi :nCe :nTi =6:0.05:7.5, at 60°C Stir magnetically for 3 h to form a uniform and stable mixed solution D.
3)将混合溶液D放入水热电沉积反应釜中，密封反应釜，控制体积填充比为60％，反应温度控制在120℃，正负两极电压为1000V，脉冲占空比为60％，采用电弧放电水热反应3h。3) Put the mixed solution D into the hydrothermal electrodeposition reaction kettle, seal the reaction kettle, control the volume filling ratio to 60%, the reaction temperature to 120°C, the positive and negative pole voltages to 1000V, and the pulse duty ratio to 60%. Arc discharge hydrothermal reaction for 3h.
4)待反应釜自然冷却至室温后，经过滤得到滤饼，将滤饼先采用去离子水洗涤3次，再用无水乙醇洗涤3次得到粉体，然后在100℃下干燥3h，得到Ce掺杂Li4Ti5O12锂离子电池负极材料。4) After the reaction kettle was naturally cooled to room temperature, the filter cake was obtained by filtration, and the filter cake was washed with deionized water for 3 times, and then washed with absolute ethanol for 3 times to obtain a powder, and then dried at 100°C for 3 hours to obtain Ce-doped Li4 Ti5 O12 lithium-ion battery anode material.
实施例4Example 4
1)将LiOH溶于去离子水中，配制成锂离子浓度为0.6mol/L的溶液A，将Ce(NO3)4溶于去离子水中，配制成浓度为0.2mol/L的溶液B，将TiCl4溶于去离子水中，配制成浓度为0.4mol/L溶液C，并采用1.5mol/L的盐酸调节溶液C的pH值为2.5；1) Dissolve LiOH in deionized water to prepare a solution A with a lithium ion concentration of 0.6mol/L, and dissolve Ce(NO3 )4 in deionized water to prepare a solution B with a concentration of 0.2mol/L. TiCl4 was dissolved in deionized water to prepare solution C with a concentration of 0.4 mol/L, and the pH value of solution C was adjusted to 2.5 with 1.5 mol/L hydrochloric acid;
2)将溶液A、溶液B、调节pH值后的溶液C按照Li、Ce、Ti元素摩尔比nLi:nCe:nTi＝4.5:0.06:6.5的比例混合，并于55℃下搅拌1h，得到混合溶液D；2) Mix solution A, solution B, and solution C after pH adjustment according to the molar ratio of Li, Ce, and Ti elements nLi : nCe : nTi = 4.5:0.06:6.5, and stir at 55 ° C for 1 h , to obtain a mixed solution D;
3)将混合溶液D转移至水热电沉积反应釜中，且反应釜的体积填充比为52％，然后采用水热电沉积法反应3h后过滤，得到滤饼，将滤饼先采用去离子水将滤饼洗涤2次，再采用无水乙醇洗涤3次，然后在85℃下干燥3h，得到Ce掺杂Li4Ti5O12锂离子电池负极材料；其中，水热电沉积法反应的具体条件为：反应温度为90℃，正负两极电压为960V，脉冲占空比为53％。3) Transfer the mixed solution D to a hydrothermal electrodeposition reaction kettle, and the volume filling ratio of the reaction kettle is 52%, and then use the hydrothermal electrodeposition method to react for 3 hours and then filter to obtain a filter cake, which is firstly deionized with deionized water The filter cake was washed twice, then washed three times with absolute ethanol, and then dried at 85°C for 3 hours to obtain the Ce-doped Li4 Ti5 O12 lithium-ion battery negative electrode material; the specific conditions for the reaction of the hydrothermal electrodeposition method were: : The reaction temperature is 90°C, the positive and negative pole voltages are 960V, and the pulse duty ratio is 53%.
实施例5Example 5
1)将LiOH·H2O溶于去离子水中，配制成锂离子浓度为0.8mol/L的溶液A，将Ce(NO3)4溶于去离子水中，配制成浓度为0.1mol/L的溶液B，将TiCl4溶于去离子水中，配制成浓度为0.3mol/L溶液C，并采用2mol/L的盐酸调节溶液C的pH值为1.5；1) Dissolve LiOH·H2 O in deionized water to prepare a solution A with a lithium ion concentration of 0.8 mol/L, and dissolve Ce(NO3 )4 in deionized water to prepare a solution A with a concentration of 0.1 mol/L For solution B, dissolveTiCl4 in deionized water to prepare solution C with a concentration of 0.3mol/L, and adjust the pH value of solution C to 1.5 with 2mol/L hydrochloric acid;
2)将溶液A、溶液B、调节pH值后的溶液C按照Li、Ce、Ti元素摩尔比nLi:nCe:nTi＝5.5:0.08:5.5的比例混合，并于45℃下搅拌2h，得到混合溶液D；2) Mix solution A, solution B, and solution C after pH adjustment according to the molar ratio of Li, Ce, and Ti elements nLi :nCe :nTi =5.5:0.08:5.5, and stir at 45°C for 2h , to obtain a mixed solution D;
3)将混合溶液D转移至水热电沉积反应釜中，且反应釜的体积填充比为58％，然后采用水热电沉积法反应1.5h后过滤，得到滤饼，将滤饼先采用去离子水将滤饼洗涤3次，再采用无水乙醇洗涤2次，然后在95℃下干燥1h，得到Ce掺杂Li4Ti5O12锂离子电池负极材料；其中，水热电沉积法反应的具体条件为：反应温度为105℃，正负两极电压为850V，脉冲占空比为56％。3) Transfer the mixed solution D to a hydrothermal electrodeposition reaction kettle, and the volume filling ratio of the reaction kettle is 58%, and then use the hydrothermal electrodeposition method to react for 1.5h and then filter to obtain a filter cake, which is firstly filled with deionized water The filter cake was washed 3 times, then washed 2 times with absolute ethanol, and then dried at 95°C for 1 hour to obtain the Ce-doped Li4 Ti5 O12 lithium-ion battery negative electrode material; among them, the specific conditions of the hydrothermal electrodeposition reaction It is: the reaction temperature is 105°C, the positive and negative pole voltages are 850V, and the pulse duty cycle is 56%.
本发明制备Ce掺杂花球片状Li4Ti5O12锂离子电池纳米负极材料的方法，具有制备成本低、操作简单、制备周期短的特点，所制备的Ce掺杂花球片状Li4Ti5O12锂离子电池纳米负极材料纯度高、结晶性强、形貌均匀。The method for preparing Ce-doped curd flake-shaped Li4 Ti5 O12 lithium-ion battery nano-negative electrode material of the present invention has the characteristics of low preparation cost, simple operation and short preparation cycle, and the prepared Ce-doped curd flake Li4 Ti5 O12 lithium-ion battery nano anode material has high purity, strong crystallinity and uniform morphology.
本发明制备的Ce掺杂Li4Ti5O12锂离子电池负极材料为纳米片状结构所组成的花球状粉体，其充放电性能优异，在0.1C低倍率下，其首次放电容量可达到300mAh/g，在10C的高倍率下，其首次放电容量可达到180mAh/g。The Ce-doped Li4 Ti5 O12 lithium-ion battery anode material prepared by the present invention is a spherical powder composed of a nano-sheet structure, and its charge and discharge performance is excellent. At a low rate of 0.1C, its initial discharge capacity can reach 300mAh/g, at a high rate of 10C, its initial discharge capacity can reach 180mAh/g.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510141708.3ACN104868111A (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of Ce-doped Li4Ti5O12 lithium-ion battery negative electrode material |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510141708.3ACN104868111A (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of Ce-doped Li4Ti5O12 lithium-ion battery negative electrode material |
| Publication Number | Publication Date |
|---|---|
| CN104868111Atrue CN104868111A (en) | 2015-08-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510141708.3APendingCN104868111A (en) | 2015-03-27 | 2015-03-27 | A kind of preparation method of Ce-doped Li4Ti5O12 lithium-ion battery negative electrode material |
| Country | Link |
|---|---|
| CN (1) | CN104868111A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109449433A (en)* | 2018-10-31 | 2019-03-08 | 桑顿新能源科技有限公司 | A kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1766175A (en)* | 2005-09-29 | 2006-05-03 | 陕西科技大学 | A method and device for preparing coating or thin film by ultrasonic hydrothermal electrodeposition |
| CN101478038A (en)* | 2008-12-29 | 2009-07-08 | 浙江大学 | Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process |
| CN103024261A (en)* | 2011-09-20 | 2013-04-03 | 佳能株式会社 | Image capturing apparatus and control method thereof |
| CN103107323A (en)* | 2012-12-27 | 2013-05-15 | 东莞上海大学纳米技术研究院 | Lithium titanate, a lithium-ion secondary battery negative electrode material modified by cerium doping, and preparation method thereof |
| CN104370303A (en)* | 2014-11-27 | 2015-02-25 | 陕西科技大学 | Preparing method of lithium titanate with good rate performance |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1766175A (en)* | 2005-09-29 | 2006-05-03 | 陕西科技大学 | A method and device for preparing coating or thin film by ultrasonic hydrothermal electrodeposition |
| CN101478038A (en)* | 2008-12-29 | 2009-07-08 | 浙江大学 | Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process |
| CN103024261A (en)* | 2011-09-20 | 2013-04-03 | 佳能株式会社 | Image capturing apparatus and control method thereof |
| CN103107323A (en)* | 2012-12-27 | 2013-05-15 | 东莞上海大学纳米技术研究院 | Lithium titanate, a lithium-ion secondary battery negative electrode material modified by cerium doping, and preparation method thereof |
| CN104370303A (en)* | 2014-11-27 | 2015-02-25 | 陕西科技大学 | Preparing method of lithium titanate with good rate performance |
| Title |
|---|
| XUELIANG LI,ET AL: ""Controllable solvo-hydrothermal electrodeposition of lithium vanadate uniform carnation-like nanostructure and their electrochemical performance"", 《J SOLID STATE ELECTROCHEM》* |
| ZHENWEI ZHANG,ET AL: ""Hydrothermal synthesis of Zn-doped Li4Ti5O12 with improved high rate properties for lithium ion batteries"", 《CERAMICS INTERNATIONAL》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109449433A (en)* | 2018-10-31 | 2019-03-08 | 桑顿新能源科技有限公司 | A kind of preparation method of rear-earth-doped metatitanic acid lithium ultrathin nanometer piece negative electrode material |
| Publication | Publication Date | Title |
|---|---|---|
| CN102569780B (en) | Method for preparing lithium ion battery cathode material with layered structure | |
| CN105161679B (en) | Lithium-rich anode material and its preparation method and application | |
| CN104393277B (en) | Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material | |
| CN103227321B (en) | Preparation method of MnOx/Fe2O3 nanocomposite material for lithium ion battery negative electrode | |
| CN101635348B (en) | Tantalum-containing lithium ion battery cathode material lithium titanate preparation method | |
| CN106564967A (en) | Lithium-rich manganese-based cathode material precursor, cathode material and preparation method thereof | |
| CN105185977B (en) | A kind of preparation method of lithium ion battery negative material | |
| CN104466158A (en) | Lithium-rich positive electrode material and preparation method thereof | |
| CN104466160A (en) | Preparation method of lithium enriched ternary system nanometer material | |
| CN104733726B (en) | Prepare cobalt acid manganese hollow microspheres and method | |
| CN105810934A (en) | Method capable of improving stability of crystal domain structure of lithium-rich layered oxide material | |
| CN106159254A (en) | Nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor preparation method | |
| CN105428633A (en) | Method for preparing titanium niobate mesoporous microspheres | |
| Li et al. | Spray pyrolysis synthesis of nickel-rich layered cathodes LiNi1− 2xCoxMnxO2 (x= 0.075, 0.05, 0.025) for lithium-ion batteries | |
| CN109390564B (en) | Ternary metal oxide based on zinc ion doping, preparation method and application thereof | |
| CN112225261B (en) | Lithium-rich manganese-based positive electrode material carbonate precursor and preparation method and application thereof | |
| CN103395828A (en) | Preparation method of porous hollow micro-cube blocky tin dioxide | |
| CN104600285A (en) | Method for preparing spherical lithium nickel manganese oxide positive pole material | |
| CN107256964A (en) | A kind of preparation method of the bar-shaped nickel ion doped of high-voltage lithium-battery cathode material | |
| CN103606675A (en) | Preparation method of metallic-ion-doped lithium-nickel-cobalt-oxygen positive pole material | |
| CN104253265A (en) | Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof | |
| CN108083348A (en) | A kind of ternary anode material precursor of core-shell structure | |
| CN111106343A (en) | Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof | |
| CN116375110A (en) | A lithium-rich manganese-based positive electrode material and its preparation method and application | |
| CN104716318A (en) | Preparation method of spherical nickel-cobalt-manganese precursor |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20150826 | |
| RJ01 | Rejection of invention patent application after publication |