CN116062735A - Hard carbon prepared by non-sintering dehydration carbonization method and application thereof - Google Patents
Hard carbon prepared by non-sintering dehydration carbonization method and application thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于储能新材料技术领域,具体为一种非烧结脱水碳化方法制备硬碳及其应用。The invention belongs to the technical field of new energy storage materials, in particular to a non-sintering dehydration carbonization method for preparing hard carbon and its application.
背景技术Background technique
碳具有丰富的同素异形体,如金刚石、石墨、非晶碳、碳纳米管、石墨烯和碳炔等。由于其优异的性能和广泛的应用,一直是研究的热点。因此,探索具有不同碳原子空间排列的新型碳同素异形体非常重要,这将带来新的性质、功能和应用。例如,石墨是商用锂离子电池(LIB)最常用的阳极材料,对钠离子电池(SIB)几乎没有电化学活性,因为Na+离子嵌入石墨层间间距(0.335nm)在热力学上是不利的。Carbon has abundant allotropes, such as diamond, graphite, amorphous carbon, carbon nanotubes, graphene, and carbyne, etc. Due to its excellent properties and wide range of applications, it has always been a research hotspot. Therefore, it is very important to explore new carbon allotropes with different carbon atom spatial arrangements, which will bring new properties, functions and applications. For example, graphite, the most commonly used anode material for commercial lithium-ion batteries (LIBs), has little electrochemical activity for sodium-ion batteries (SIBs), because the intercalation of Na + ions into the graphite interlayer space (0.335 nm) is thermodynamically unfavorable.
硬碳通常被认为是不可石墨化的碳或无序碳,其中具有指纹层堆叠的随机定向的小尺寸伪石墨,通过非晶碳区域中sp3杂化碳原子的强交联而固定,即使在高于3000℃的温度下,也不能形成真实的图形结构。它在堆叠的石墨烯层之间具有大于0.37nm的大层间距,这有利于Na+离子的嵌入/脱嵌,显示的有利容量是SIB最有前途的阳极材料之一。Hard carbons are generally considered as non-graphitizable carbons or disordered carbons, in which randomly oriented small-sized pseudographites with stacks of fingerprint layers are fixed by strong cross-linking of sp hybridized carbon atoms in the amorphous carbon domains, even At temperatures higher than 3000 °C, no real graphic structure can be formed. It has a large interlayer spacing greater than 0.37 nm between stacked graphene layers, which is beneficial for the intercalation/deintercalation of Na + ions, and the displayed favorable capacity is one of the most promising anode materials for SIBs.
发明内容Contents of the invention
有鉴于此,本发明的目的在于提供非烧结脱水碳化方法,通过该方法得到了一种硬碳材料。在该方法中,原材料成本低廉,制备方法简单易行,作为电极材料能够提供优异的性能,具有广阔的应用前景。In view of this, the object of the present invention is to provide a non-sintering dehydration carbonization method, by which a hard carbon material is obtained. In this method, the cost of raw materials is low, the preparation method is simple and feasible, and it can provide excellent performance as an electrode material, and has broad application prospects.
为了实现以上发明目的,本发明的具体技术方案为:In order to realize above object of the invention, concrete technical scheme of the present invention is:
一种非烧结脱水碳化方法,采用该方法制备得到了硬碳材料,该方法包括以下步骤:A non-sintering dehydration carbonization method, adopting the method to prepare a hard carbon material, the method comprises the following steps:
1)将大量有机物溶解在少量去离子水中直至成为过饱和溶液;1) Dissolving a large amount of organic matter in a small amount of deionized water until it becomes a supersaturated solution;
2)向步骤(1)所得的产物中滴加强氧化剂,得到硬碳产物;2) drop a strong oxidizing agent into the product obtained in step (1) to obtain a hard carbon product;
3)将步骤(2)所得的产物在用去离子水离心清洗并烘干,得到硬碳材料。3) The product obtained in step (2) is centrifugally washed with deionized water and dried to obtain a hard carbon material.
作为本申请中一种较好的实施方式,步骤1)中所述的有机物为蔗糖、葡萄糖、海藻糖、己酮糖或淀粉中的任意一种。As a preferred embodiment of the present application, the organic matter described in step 1) is any one of sucrose, glucose, trehalose, ketohexose or starch.
作为本申请中一种较好的实施方式,有机物与去离子水的比例关系为0.5g:1mL~4g:1mL。As a preferred embodiment in this application, the ratio of organic matter to deionized water is 0.5g: 1mL to 4g: 1mL.
作为本申请中一种较好的实施方式,所述步骤2)中的强氧化剂为硫酸。As a preferred embodiment of the present application, the strong oxidizing agent in step 2) is sulfuric acid.
作为本申请中一种较好的实施方式,强氧化剂与步骤(1)中所得产物的比例关系为0.1mL:1g-1mL:1g;更优选为1mL:1g。As a preferred embodiment of the present application, the ratio between the strong oxidizing agent and the product obtained in step (1) is 0.1 mL: 1 g-1 mL: 1 g; more preferably 1 mL: 1 g.
作为本申请中一种较好的实施方式,步骤3)中所述的离心的转速为3000~12000rmp,时间为3~10分钟,烘干的温度为60~120℃。As a preferred embodiment of the present application, the speed of the centrifugation described in step 3) is 3000-12000 rpm, the time is 3-10 minutes, and the drying temperature is 60-120°C.
本申请的另外一个发明目的是保护一种采用以上任一技术方案或技术方案任意组合得到的硬碳材料。Another object of the invention of the present application is to protect a hard carbon material obtained by adopting any of the above technical solutions or any combination of technical solutions.
本发明还提供了采用上述方法制备得到的硬碳材料的应用,该硬碳材料可作为钠离子电池负极材料。比如用于制备钠离子电池硬碳负极。在100mA/g的活化过程首效为75.6%比容量为263mAh/g。在1A/g的电流密度下,比容量为165mAh/g,说明材料具有优异的电化学性能。The present invention also provides the application of the hard carbon material prepared by the above method, and the hard carbon material can be used as the negative electrode material of the sodium ion battery. For example, it is used to prepare hard carbon negative electrodes for sodium-ion batteries. In the activation process of 100mA/g, the first effect is 75.6%, and the specific capacity is 263mAh/g. At a current density of 1A/g, the specific capacity is 165mAh/g, indicating that the material has excellent electrochemical performance.
与现有技术相比,本发明的有益效果为:Compared with prior art, the beneficial effect of the present invention is:
(一)本方法中利用高浓度过饱和溶液,随后利用强氧化与水作用产生高温将有机物碳化,得到硬碳材料。这种方法制备的硬碳材料具有丰富的缺陷,可以增强材料的电化学性能。(1) In this method, a high-concentration supersaturated solution is used, followed by strong oxidation and water to generate high temperature to carbonize the organic matter to obtain a hard carbon material. The hard carbon materials prepared by this method have abundant defects, which can enhance the electrochemical performance of the materials.
(二)该方法制备的硬碳材料,由于具备丰富的闭孔结构,较多的缺陷具有良好的物理和化学性能,独特的孔结构和优越的导电性,从而可较好的应用锂离子电池、钠离子电池、锂/钠硫电池,锂/钠硒电池,水系电池,空气电池,传感器、环境净化、能源、催化等重要领域。(2) The hard carbon material prepared by this method has good physical and chemical properties due to its rich closed-cell structure, more defects, unique pore structure and superior conductivity, so it can be better applied to lithium-ion batteries , Na-ion batteries, lithium/sodium-sulfur batteries, lithium/sodium-selenium batteries, water-based batteries, air batteries, sensors, environmental purification, energy, catalysis and other important fields.
附图说明:Description of drawings:
图1为实施例1所得的硬碳材料1#的SEM图。Fig. 1 is the SEM picture of the
图2为实施例1所得的硬碳材料1#的TEM图。Fig. 2 is the TEM picture of
图3为实施例1、2、3、4、5所得的硬碳材料1#、2#、3#、4#、5#的XPS图。Fig. 3 is the XPS figure of the
图4为实施例1、2、3、4、5所得的硬碳材料1#、2#、3#、4#、5#的XRD图。Fig. 4 is the XRD pattern of
图5为实施例1所得到的硬碳材料1#的Raman图。Fig. 5 is the Raman graph of
图6为实施例1得到的硬碳材料1#的首圈充放电曲线。FIG. 6 is the first cycle charge and discharge curve of the
图7为实施例1所得到的硬碳材料1#在1A g-1的电流密度下的循环曲线。Fig. 7 is the cycle curve of
图8为实施例1所得到的硬碳材料1#在1A/g的电流密度下不同圈数的充放电曲线。Fig. 8 is the charge and discharge curves of the
图9为实施例1所得到的硬碳材料1#在0.1mV/s扫速下的CV曲线。FIG. 9 is the CV curve of
具体实施方式Detailed ways
为了使本发明的内容更加便于理解,下面将结合附图和具体实施方式对本发明中所述的工艺做进一步的阐述。但不应将此理解为本发明上述主题的范围仅限于下述实施例。In order to make the content of the present invention easier to understand, the process described in the present invention will be further described below in conjunction with the drawings and specific embodiments. However, it should not be construed that the scope of the above-mentioned subject matter of the present invention is limited to the following examples.
在以下实施例中,所描述的惰性气氛均为氩气气氛。本申请中所采用的药剂均为市售产品。In the following examples, the described inert atmosphere is an argon atmosphere. The medicaments adopted in this application are all commercially available products.
实施例1:Example 1:
一种非烧结脱水碳化方法,按如下步骤:A non-sintering dehydration carbonization method, as follows:
(1)将20g蔗糖溶解在20mL去离子水中,形成高浓度过饱和溶液;(1) Dissolve 20g of sucrose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2)向所得的产物中滴加20mL硫酸(12M),得到硬碳产物;(2) 20mL sulfuric acid (12M) is added dropwise in the product of gained, obtains hard carbon product;
(3)将所得的产物在用去离子水并于12000rmp离心5分钟,并重复4次。随后将材料转移至鼓风干燥箱内70℃直至烘干,得到硬碳材料1#。(3) The obtained product was centrifuged at 12000 rpm for 5 minutes with deionized water, and repeated 4 times. Then the material was transferred to a blast drying oven at 70°C until it was dried to obtain
采用与实施例1相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸的体积分别替换为10mL,30mL,40mL、50mL或100mL。具体性能数据如表1:The hard carbon material was prepared using the same steps as in Example 1, except that the volume of sulfuric acid was replaced by 10 mL, 30 mL, 40 mL, 50 mL or 100 mL. The specific performance data are shown in Table 1:
表1:Table 1:
采用与实施例1相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸分别替换为盐酸或硝酸。但是未能发生反应。The preparation of the hard carbon material was carried out in the same manner as in Example 1, the only difference being that sulfuric acid was replaced by hydrochloric acid or nitric acid. But failed to react.
实施例2:Example 2:
一种非烧结脱水碳化方法,按如下步骤:A non-sintering dehydration carbonization method, as follows:
(1)将20g葡萄糖溶解在20mL去离子水中,形成高浓度过饱和溶液;(1) Dissolve 20g of glucose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2)向所得的产物中滴加20mL硫酸(12M),得到硬碳产物;(2) 20mL sulfuric acid (12M) is added dropwise in the product of gained, obtains hard carbon product;
(3)将所得的产物在用去离子水并于12000rmp离心5分钟,并重复4次。随后将材料转移至鼓风干燥箱内70℃直至烘干,得到硬碳材料2#。(3) The obtained product was centrifuged at 12000 rpm for 5 minutes with deionized water, and repeated 4 times. Then the material was transferred to a blast drying oven at 70°C until it was dried to obtain hard carbon material 2#.
采用与实施例2相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸的体积分别替换为10mL,30mL,40mL、50mL或100mL。具体性能数据如表2:The hard carbon material was prepared using the same steps as in Example 2, except that the volume of sulfuric acid was replaced by 10 mL, 30 mL, 40 mL, 50 mL or 100 mL. The specific performance data are shown in Table 2:
表2:Table 2:
采用与实施例2相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸分别替换为盐酸或硝酸。但是未能发生反应。The preparation of the hard carbon material was carried out in the same method steps as in Example 2, the only difference being that the sulfuric acid was replaced by hydrochloric acid or nitric acid respectively. But failed to react.
实施例3:Example 3:
一种非烧结脱水碳化方法,按如下步骤:A non-sintering dehydration carbonization method, as follows:
(1)将20g海藻糖溶解在20mL去离子水中,形成高浓度过饱和溶液;(1) Dissolve 20g trehalose in 20mL deionized water to form a high-concentration supersaturated solution;
(2)向所得的产物中滴加20mL硫酸(12M),得到硬碳产物;(2) 20mL sulfuric acid (12M) is added dropwise in the product of gained, obtains hard carbon product;
(3)将所得的产物在用去离子水并于12000rmp离心5分钟,并重复4次。随后将材料转移至鼓风干燥箱内70℃直至烘干,得到硬碳材料3#。(3) The obtained product was centrifuged at 12000 rpm for 5 minutes with deionized water, and repeated 4 times. Then the material was transferred to a blast drying oven at 70°C until it was dried to obtain hard carbon material 3#.
采用与实施例3相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸的体积分别替换为10mL,30mL,40mL、50mL或100mL。具体性能数据如表3:The hard carbon material was prepared using the same steps as in Example 3, except that the volume of sulfuric acid was replaced by 10 mL, 30 mL, 40 mL, 50 mL or 100 mL. The specific performance data are shown in Table 3:
表3table 3
采用与实施例3相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸分别替换为盐酸或硝酸。但是未能发生反应。The preparation of the hard carbon material was carried out in the same method steps as in Example 3, the only difference being that sulfuric acid was replaced by hydrochloric acid or nitric acid respectively. But failed to react.
实施例4:Example 4:
一种非烧结脱水碳化方法,按如下步骤:A non-sintering dehydration carbonization method, as follows:
(1)将20g己酮糖溶解在20mL去离子水中,形成高浓度过饱和溶液;(1) Dissolve 20g of ketohexose in 20mL of deionized water to form a high-concentration supersaturated solution;
(2)将所得的产物中滴加20mL硫酸(12M),得到硬碳产物;(2) Add 20 mL of sulfuric acid (12M) dropwise to the resulting product to obtain a hard carbon product;
(3)将所得的产物在用去离子水并于12000rmp离心5分钟,并重复4次。随后将材料转移至鼓风干燥箱内70℃直至烘干,得到硬碳材料4#。(3) The obtained product was centrifuged at 12000 rpm for 5 minutes with deionized water, and repeated 4 times. Then the material was transferred to a blast drying oven at 70°C until it was dried to obtain hard carbon material 4#.
采用与实施例4相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸的体积分别替换为10mL,30mL,40mL、50mL或100mL。具体性能数据如表4:The hard carbon material was prepared using the same steps as in Example 4, except that the volume of sulfuric acid was replaced by 10 mL, 30 mL, 40 mL, 50 mL or 100 mL. The specific performance data are shown in Table 4:
表4:Table 4:
采用与实施例4相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸分别替换为盐酸或硝酸。但是未能发生反应。The preparation of the hard carbon material was carried out in the same method steps as in Example 4, the only difference being that sulfuric acid was replaced by hydrochloric acid or nitric acid respectively. But failed to react.
实施例5:Example 5:
一种非烧结脱水碳化方法,按如下步骤:A non-sintering dehydration carbonization method, as follows:
(1)将20g淀粉分散在20mL去离子水中,形成高浓度过饱和溶液;(1) Disperse 20g of starch in 20mL of deionized water to form a high-concentration supersaturated solution;
(2)将所得的产物中滴加20mL硫酸(12M),得到硬碳产物;(2) Add 20 mL of sulfuric acid (12M) dropwise to the resulting product to obtain a hard carbon product;
(3)将所得的产物在用去离子水并于12000rmp离心5分钟,并重复4次。随后将材料转移至鼓风干燥箱内70℃直至烘干,得到硬碳材料5#。(3) The obtained product was centrifuged at 12000 rpm for 5 minutes with deionized water, and repeated 4 times. Then the material was transferred to a blast drying oven at 70°C until it was dried to obtain hard carbon material 5#.
采用与实施例5相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸的体积分别替换为10mL,30mL,40mL、50mL或100mL。具体性能数据如表5:The hard carbon material was prepared using the same steps as in Example 5, except that the volume of sulfuric acid was replaced by 10 mL, 30 mL, 40 mL, 50 mL or 100 mL. The specific performance data are shown in Table 5:
表5:table 5:
采用与实施例5相同的方法步骤进行硬碳材料的制备,区别仅在于将硫酸分别替换为盐酸或硝酸。但是未能发生反应。The preparation of the hard carbon material was carried out using the same method steps as in Example 5, the only difference being that sulfuric acid was replaced by hydrochloric acid or nitric acid. But failed to react.
对比例1:Comparative example 1:
固相法制备硬碳材料的方法,按如下步骤制备:The method for preparing hard carbon material by solid phase method is prepared according to the following steps:
将蔗糖在惰性气氛1300℃热解3小时,升温速率为3℃每分,得到硬碳材料。The sucrose was pyrolyzed in an inert atmosphere at 1300°C for 3 hours with a heating rate of 3°C per minute to obtain a hard carbon material.
采用与对比例1相同的方法步骤进行硬碳材料的制备,区别仅在于将热解温度替换为900,1100,1500或1700℃。具体性能数据如表6The preparation of the hard carbon material was carried out using the same method steps as in Comparative Example 1, the only difference being that the pyrolysis temperature was replaced by 900, 1100, 1500 or 1700°C. Specific performance data are shown in Table 6
表6:Table 6:
对比例2:Comparative example 2:
固相法制备硬碳材料的方法,按如下步骤制备:The method for preparing hard carbon material by solid phase method is prepared according to the following steps:
将葡萄糖糖在惰性气氛1300℃热解3小时,升温速率为3℃每分,得到硬碳材料。Glucose was pyrolyzed at 1300° C. for 3 hours in an inert atmosphere with a heating rate of 3° C. per minute to obtain a hard carbon material.
采用与对比例2相同的方法步骤进行硬碳材料的制备,区别仅在于将热解温度分别替换为900,1100,1500或1700℃。具体性能数据如表7:The preparation of the hard carbon material was carried out using the same method steps as in Comparative Example 2, the only difference being that the pyrolysis temperature was replaced by 900, 1100, 1500 or 1700° C. respectively. The specific performance data are shown in Table 7:
表7:Table 7:
对比例3:Comparative example 3:
固相法制备硬碳材料的方法,按如下步骤制备:The method for preparing hard carbon material by solid phase method is prepared according to the following steps:
将海藻糖在惰性气氛1300℃热解3小时,升温速率为3℃每分,得到硬碳材料。The trehalose was pyrolyzed in an inert atmosphere at 1300°C for 3 hours with a heating rate of 3°C per minute to obtain a hard carbon material.
采用与对比例3相同的方法步骤进行硬碳材料的制备,区别仅在于将热解温度替换为900,1100,1500或1700℃。具体性能数据如表8:The preparation of the hard carbon material was carried out using the same method steps as in Comparative Example 3, the only difference being that the pyrolysis temperature was replaced by 900, 1100, 1500 or 1700°C. The specific performance data are shown in Table 8:
表8:Table 8:
对比例4:Comparative example 4:
固相法制备硬碳材料的方法,按如下步骤制备:The method for preparing hard carbon material by solid phase method is prepared according to the following steps:
将己酮糖在惰性气氛1300℃热解3小时,升温速率为3℃每分,得到硬碳材料。The ketohexose was pyrolyzed in an inert atmosphere at 1300°C for 3 hours with a heating rate of 3°C per minute to obtain a hard carbon material.
采用与对比例4相同的方法步骤进行硬碳材料的制备,区别仅在于将热解温度替换为900,1100,1500或1700℃。具体性能数据如表9:The preparation of the hard carbon material was carried out using the same method steps as in Comparative Example 4, the only difference being that the pyrolysis temperature was replaced by 900, 1100, 1500 or 1700°C. The specific performance data are shown in Table 9:
表9:Table 9:
对比例5:Comparative example 5:
固相法制备硬碳材料的方法,按如下步骤制备:The method for preparing hard carbon material by solid phase method is prepared according to the following steps:
将淀粉在惰性气氛1300℃热解3小时,升温速率为3℃每分,得到硬碳材料。The starch was pyrolyzed in an inert atmosphere at 1300°C for 3 hours, and the heating rate was 3°C per minute to obtain a hard carbon material.
采用与对比例5相同的方法步骤进行硬碳材料的制备,区别仅在于将热解温度替换为900,1100,1500或1700℃。具体性能数据如表10:The preparation of the hard carbon material was carried out using the same method steps as in Comparative Example 5, the only difference being that the pyrolysis temperature was replaced by 900, 1100, 1500 or 1700°C. The specific performance data are shown in Table 10:
表10:Table 10:
实验:experiment:
将实施例1、2、3、4、5中制备的硬碳材料1#、2#、3#、4#、5#和对比例1、2、3、4、5制备的材料分别制成钠离子电池负极并进行相关性能测试。
分别取硬碳材料1#、2#、3#、4#、5#和对比例1、2、3、4、5制得的材料与PVDF粘结剂按质量比90:10混合,再加入适量的NMP,在玛瑙研钵中研磨至糊状,涂敷在铝集流体上。涂覆质量大约为2.5mg的电极活性物质。然后将电极于120℃真空干燥12小时,从而得到钠离子电池负极。并以金属钠为正极,电解液为NaPF6 in EC+DMC(vol%:1:1),电压范围为0.01-3V。充放电测试仪为Land CT2001A。具体结果见表11。Take
表11硬碳材料1#、2#、3#、4#、5#和对比例1、2、3、4、5中的材料的电化学性能对比表格:Table 11
图1为实施例1所得的硬碳材料1#不同拍摄倍率下的SEM图,其中a为2000倍;b为10000倍。由低倍扫描电镜图可以看出材料呈现块状且表面粗糙,并伴随着空洞的出现,这是由于硫酸刻蚀的结果。Fig. 1 is the SEM image of the
图2为实施例1所得的硬碳材料1#不同拍摄倍率下的TEM图,其中a的比例尺为20nm;b为1nm。由透射电镜图可以看出,存才丰富的微孔和介孔。同时可以观察到杂乱无序的硬碳的晶格间隙。Fig. 2 is the TEM image of the
图3为硬碳材料1#、2#、3#、4#、5#的XPS图。观察到材料中只含有C和O两种元素的存在。Figure 3 is the XPS diagram of
图4为硬碳材料1#、2#、3#、4#、5#的XRD图。在20度左右的宽包衍射峰可以看出,所得到的材料为硬碳材料,并且没有检测到其他杂峰的存在。Figure 4 is the XRD patterns of
图5为实施例1所得到的硬碳材料1#的Raman图。在1350和1580处清晰的看到属于碳材料的D峰和G峰。Fig. 5 is the Raman graph of
图6为实施例1得到的硬碳材料1#的首圈充放电曲线。由图可知,在100mA/g电流密度下,在0.1V左右开始出现平台并给予较高的容量。FIG. 6 is the first cycle charge and discharge curve of the
图7为实施例1所得到的硬碳材料1#在1A g-1的电流密度下的循环曲线。由图可知,在100mA/g的活化过程中材料首效为75.6%比容量为263mAh/g。在1A/g的电流密度下,容量为165mAh/g,说明材料具有良好的电化学性能。Fig. 7 is the cycle curve of
图8为实施例1所得到的硬碳材料1#在1A/g的电流密度下不同圈数的充放电曲线。由图可知,该材料具有较好的循环稳定性。Fig. 8 is the charge and discharge curves of the
图9为实施例1所得到的硬碳材料1#在0.1mV/s扫速下的CV曲线。由图可知,第一圈与第二圈基本重合,侧面验证材料具有优秀的循环稳定性。FIG. 9 is the CV curve of
最后说明的是,以上优选实施例仅用以说明本发明的技术方案而非限制,尽管通过上述优选实施例已经对本发明进行了详细的描述,但本领域技术人员应当理解,可以在形式上和细节上对其作出各种各样的改变,而不偏离本发明权利要求书所限定的范围。Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that it can be described in terms of form and Various changes may be made in the details without departing from the scope of the invention defined by the claims.
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