CN107403927A - A kind of preparation method of Mg doped titanic acids lithium titanate cathode material - Google Patents
A kind of preparation method of Mg doped titanic acids lithium titanate cathode material Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 title 1
- 150000007513 acids Chemical class 0.000 title 1
- 239000010406 cathode material Substances 0.000 title 1
- 239000007773 negative electrode material Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- -1 wherein Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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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- 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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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
本发明公开了一种Mg掺杂钛酸锂负极材料的制备方法，具有如下步骤：按照Li4‑xMgxTi5O12原子比分别称取原料，锂源过量6％，并同分散剂一起放入球磨罐中，其中，Mg来自Mg化合物，x＝0.1‑0.3；将球磨罐装入球磨机，以400～600的转速，球磨1～6h；将球磨后的液体置于干燥箱中，120℃干燥12h；将干燥好的粉末集于玛瑙研钵中，研磨均匀，得到钛酸锂前驱体；将钛酸锂前驱体置于管式炉中，在600～900℃，空气气氛下，热处理4～8h后得到Mg掺杂钛酸锂负极材料。通过本发明，Mg掺杂钛酸锂负极材料在100mAhg‑1时其首次放电比容量可达到193.6mAhg‑1。 The invention discloses a preparation method of Mg - doped lithium titanate negative electrode material. Put them together into a ball mill jar, wherein, Mg comes from the Mg compound, x=0.1-0.3; put the ball mill jar into the ball mill, and mill at a speed of 400-600 for 1-6 hours; put the milled liquid in a dry box, Dry at 120°C for 12 hours; put the dried powder in an agate mortar and grind evenly to obtain a lithium titanate precursor; place the lithium titanate precursor in a tube furnace at 600-900°C in an air atmosphere, The Mg-doped lithium titanate negative electrode material is obtained after heat treatment for 4-8 hours. According to the present invention, the first discharge specific capacity of the Mg-doped lithium titanate negative electrode material can reach 193.6mAhg- 1 at 100mAhg -1 .
Description
技术领域technical field
本发明涉及负极材料的制备领域，具体地说是一种Mg掺杂钛酸锂负极材料的制备方法。The invention relates to the field of preparation of negative electrode materials, in particular to a preparation method of Mg-doped lithium titanate negative electrode materials.
背景技术Background technique
目前，锂离子电池已经被广泛应用于各种电器设备，并且商业化的锂离子电池的负极材料以碳材料为主，但是碳材料由于在放电过程中容易产生锂枝晶，导致电池短路，安全性差以及循环性能低等劣势。因此寻找一种安全性高、循环性好，结构稳定的负极材料。尖晶石型的Li4Ti5O12作为锂离子电池负极材料，由于其充放电过程中小于0.2％的体积变化，并且在此过程中结构几乎持不变，被称为“零应变”材料。与碳材料对比，好的循环性能和稳定的放电平台是其显著优点。因此，被认为是很有前景的一种锂离子电池负极材料。但钛酸锂材料存在导电性差，储锂容量低的问题。因此采用方法简便、且成本低的固相法制备高储锂容量的Li4Ti5O12材料仍然是目前研究的难点。At present, lithium-ion batteries have been widely used in various electrical equipment, and the negative electrode materials of commercial lithium-ion batteries are mainly carbon materials, but carbon materials are prone to generate lithium dendrites during the discharge process, resulting in short-circuit of the battery, which is safe. Poor performance and low cycle performance. Therefore, a negative electrode material with high safety, good cycle performance and stable structure is sought. Spinel-type Li 4 Ti 5 O 12 is used as the negative electrode material of lithium-ion batteries. Because of its volume change of less than 0.2% during charge and discharge, and its structure remains almost unchanged during the process, it is called "zero strain" material . Compared with carbon materials, good cycle performance and stable discharge platform are its significant advantages. Therefore, it is considered to be a promising anode material for lithium-ion batteries. However, the lithium titanate material has the problems of poor conductivity and low lithium storage capacity. Therefore, the preparation of Li 4 Ti 5 O 12 materials with high lithium storage capacity by a simple and low-cost solid-state method is still a difficult point in current research.
发明内容Contents of the invention
根据上述提出的技术问题，而提供一种Mg掺杂钛酸锂负极材料的制备方法。本发明采用的技术手段如下：According to the technical problem raised above, a method for preparing a Mg-doped lithium titanate negative electrode material is provided. The technical means adopted in the present invention are as follows:
一种Mg掺杂钛酸锂负极材料的制备方法，其特征在于具有如下步骤：A preparation method of Mg-doped lithium titanate negative electrode material is characterized in that it has the following steps:
S1、按照Li4-xMgxTi5O12原子比分别称取原料，锂源过量6％，并同分散剂(分散剂没过球磨球即可)一起放入球磨罐中，其中，Mg来自Mg化合物，x＝0.1-0.3；S1. Weigh the raw materials respectively according to the atomic ratio of Li 4-x Mg x Ti 5 O 12 , with an excess of 6% of the lithium source, and put them into the ball mill jar together with the dispersant (the dispersant should not pass through the ball milling ball), wherein, Mg From Mg compound, x=0.1-0.3;
S2、将球磨罐装入球磨机，以400～600的转速，球磨1～6h；S2. Put the ball mill jar into the ball mill, and mill for 1-6 hours at a speed of 400-600;
S3、将球磨后的液体置于干燥箱中，120℃干燥12h；将干燥好的粉末集于玛瑙研钵中，研磨均匀，得到钛酸锂前驱体；S3. Put the ball-milled liquid in a drying oven and dry at 120° C. for 12 hours; put the dried powder in an agate mortar and grind it evenly to obtain a lithium titanate precursor;
S4、将钛酸锂前驱体置于管式炉中，在600～900℃，空气气氛下，热处理4～8h后得到Mg掺杂钛酸锂负极材料。S4. The lithium titanate precursor is placed in a tube furnace, and heat-treated at 600-900° C. for 4-8 hours in an air atmosphere to obtain a Mg-doped lithium titanate negative electrode material.
所述分散剂为乙醇。The dispersant is ethanol.
所述Mg化合物为Mg(CH3COO)2·4H2O，MgO或Mg(OH)2。The Mg compound is Mg(CH3COO) 2 ·4H 2 O, MgO or Mg(OH) 2 .
通过本发明，Mg掺杂钛酸锂负极材料在100mAhg-1(即0.57C)时其首次放电比容量可达到193.6mAhg-1(Mg化合物为Mg(OH)2，x＝0.2，球磨转速400，球磨3h，800℃下热处理8h)，比未掺杂的钛酸锂负极材料的145.3mAhg-1的初始容量提高了33.2％，同时Mg掺杂钛酸锂负极材料经过100次循环，容量保持在190.5mAhg-1，容量保持率为98.4％。在10C倍率下仍然具有很好的电压平台，比容量保持在125.2mAhg-1。Through the present invention, the first discharge specific capacity of the Mg-doped lithium titanate negative electrode material can reach 193.6mAhg -1 at 100mAhg -1 (ie 0.57C) (the Mg compound is Mg(OH) 2 , x=0.2, and the ball milling speed is 400 , ball milling for 3h, heat treatment at 800°C for 8h), the initial capacity of 145.3mAhg -1 of the undoped lithium titanate negative electrode material was increased by 33.2%, and the Mg-doped lithium titanate negative electrode material was maintained after 100 cycles. At 190.5mAhg -1 , the capacity retention was 98.4%. It still has a good voltage platform at 10C rate, and the specific capacity remains at 125.2mAhg -1 .
本发明中Mg离子的加入，能够有效的抑制钛酸锂颗粒的生长；较小的尺寸将使晶粒与电解质更充分的接触，从而提高电极的电化学性能。The addition of Mg ions in the present invention can effectively inhibit the growth of lithium titanate particles; the smaller size will make the crystal particles more fully contact with the electrolyte, thereby improving the electrochemical performance of the electrode.
基于上述理由本发明可在负极材料的制备等领域广泛推广。Based on the above reasons, the present invention can be widely promoted in the fields of preparation of negative electrode materials and the like.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图做以简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained according to these drawings on the premise of not paying creative efforts.
图1是本发明的具体实施方式中XRD测试图(a为Mg掺杂钛酸锂负极材料，b未掺杂钛酸锂负极材料)。Fig. 1 is an XRD test pattern in a specific embodiment of the present invention (a is Mg-doped lithium titanate negative electrode material, b is undoped lithium titanate negative electrode material).
图2是本发明的具体实施方式中未掺杂钛酸锂负极材料的不同倍率下电压电容曲线。Fig. 2 is a voltage-capacitance curve of the undoped lithium titanate negative electrode material at different rates in a specific embodiment of the present invention.
图3是本发明的具体实施方式中Mg掺杂钛酸锂负极材料的不同倍率下电压电容曲线。Fig. 3 is a voltage-capacitance curve at different rates of the Mg-doped lithium titanate negative electrode material in a specific embodiment of the present invention.
图4是本发明的具体实施方式中循环稳定性曲线(a为Mg掺杂钛酸锂负极材料，b未掺杂钛酸锂负极材料)。Fig. 4 is a cycle stability curve in a specific embodiment of the present invention (a is Mg-doped lithium titanate negative electrode material, b is undoped lithium titanate negative electrode material).
图5是本发明的具体实施方式中倍率性能曲线(a为Mg掺杂钛酸锂负极材料，b未掺杂钛酸锂负极材料)。Fig. 5 is a rate performance curve in a specific embodiment of the present invention (a is Mg-doped lithium titanate negative electrode material, b is undoped lithium titanate negative electrode material).
具体实施方式detailed description
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
一种Mg掺杂钛酸锂负极材料的制备方法，其特征在于具有如下步骤：A preparation method of Mg-doped lithium titanate negative electrode material is characterized in that it has the following steps:
S1、按照Li4-xMgxTi5O12原子比分别称取原料，锂源过量6％，并同分散剂(一起放入球磨罐中，其中，Mg来自Mg化合物，x＝0.1-0.3；S1. Weigh the raw materials respectively according to the atomic ratio of Li 4-x Mg x Ti 5 O 12 , the excess of lithium source is 6%, and put them into the ball mill jar together with the dispersant (wherein, Mg comes from Mg compound, x=0.1-0.3 ;
S2、将球磨罐装入球磨机，以400～600的转速，球磨1～6h；S2. Put the ball mill jar into the ball mill, and mill for 1-6 hours at a speed of 400-600;
S3、将球磨后的液体置于干燥箱中，120℃干燥12h；将干燥好的粉末集于玛瑙研钵中，研磨均匀，得到钛酸锂前驱体；S3. Put the ball-milled liquid in a drying oven and dry at 120° C. for 12 hours; put the dried powder in an agate mortar and grind it evenly to obtain a lithium titanate precursor;
S4、将钛酸锂前驱体置于管式炉中，在600～900℃，空气气氛下，热处理4～8h后得到Mg掺杂钛酸锂负极材料。S4. The lithium titanate precursor is placed in a tube furnace, and heat-treated at 600-900° C. for 4-8 hours in an air atmosphere to obtain a Mg-doped lithium titanate negative electrode material.
所述分散剂为乙醇。The dispersant is ethanol.
所述Mg化合物为Mg(CH3COO)2·4H2O，MgO或Mg(OH)2。The Mg compound is Mg(CH3COO) 2 ·4H 2 O, MgO or Mg(OH) 2 .
本实施例中，Mg掺杂钛酸锂负极材料的工艺参数为Mg化合物为Mg(OH)2，x＝0.2，球磨转速400，球磨3h，800℃下热处理8h；In this embodiment, the process parameters of the Mg-doped lithium titanate negative electrode material are that the Mg compound is Mg(OH) 2 , x=0.2, the ball milling speed is 400, the ball milling is 3 hours, and the heat treatment is 8 hours at 800° C.;
本实施例中，未掺杂钛酸锂负极材料的工艺参数为球磨转速400，球磨3h，800℃下热处理8h。In this embodiment, the process parameters of the undoped lithium titanate negative electrode material are ball milling speed of 400, ball milling for 3 hours, and heat treatment at 800° C. for 8 hours.
图1是本发明的具体实施方式中XRD测试图(a为Mg掺杂钛酸锂负极材料，b未掺杂钛酸锂负极材料)，从图中可以看出，掺杂Mg并没有改变Li4Ti5O12的结构。Fig. 1 is XRD test pattern in the specific embodiment of the present invention (a is Mg-doped lithium titanate negative electrode material, b is undoped lithium titanate negative electrode material), as can be seen from the figure, doping Mg does not change Li 4 Ti 5 O 12 structure.
图2是本发明的具体实施方式中未掺杂钛酸锂负极材料的不同倍率下电压电容曲线，从图中可以看出，样品都显示了平稳的充放电平台(1.5-1.6V VS Li/Li+)，对应于Li4Ti5O12中Ti4+/Ti3+的氧化还原反应的过程。从图中可以明显观察到样品的充放电平台间差值都随放电倍率的递增而增加。未掺杂样品在10C已经不具有良好的电压平台。Fig. 2 is the voltage-capacitance curve under the different rates of undoped lithium titanate negative electrode material in the specific embodiment of the present invention, as can be seen from the figure, the sample has all shown stable charge-discharge platform (1.5-1.6V VS Li/ Li + ), corresponding to the redox reaction process of Ti 4+ /Ti 3+ in Li 4 Ti 5 O 12 . It can be clearly observed from the figure that the difference between the charge and discharge platforms of the samples increases with the increase of the discharge rate. Undoped samples already do not have a good voltage plateau at 10C.
图3是本发明的具体实施方式中Mg掺杂钛酸锂负极材料的不同倍率下电压电容曲线，从图中可以看出，样品都显示了平稳的充放电平台(1.5-1.6V VS Li/Li+)，对应于Li4Ti5O12中Ti4+/Ti3+的氧化还原反应的过程。从图中可以明显观察到样品的充放电平台间差值都随放电倍率的递增而增加。但掺杂后的Li3.8Mg0.2Ti5O12在0.57C，充放电平台电压差为0.06V，即使在10C，充放电平台电压差为0.1V，明显低于未掺杂样品，说明掺杂后材料的电极极化程度得到了大幅度下降，表明Mg2+掺杂可以提高电极反应动力学。掺杂后的样品在10C仍然具有良好的电压平台。Fig. 3 is the voltage-capacitance curve under the different ratios of Mg-doped lithium titanate negative electrode material in the specific embodiment of the present invention, as can be seen from the figure, the sample has all shown stable charge-discharge platform (1.5-1.6V VS Li/ Li + ), corresponding to the redox reaction process of Ti 4+ /Ti 3+ in Li 4 Ti 5 O 12 . It can be clearly observed from the figure that the difference between the charge and discharge platforms of the samples increases with the increase of the discharge rate. However, the doped Li 3.8 Mg 0.2 Ti 5 O 12 has a charge-discharge platform voltage difference of 0.06V at 0.57C, and even at 10C, the charge-discharge platform voltage difference is 0.1V, which is significantly lower than that of the undoped sample, indicating that the doped The degree of electrode polarization of the latter material has been greatly reduced, indicating that Mg 2+ doping can improve the electrode reaction kinetics. The doped sample still has a good voltage plateau at 10C.
图4是本发明的具体实施方式中循环稳定性曲线(a为Mg掺杂钛酸锂负极材料，b未掺杂钛酸锂负极材料)，从图中可以看出，适量Mg2+的掺杂没有破坏其本身结构，保留了其尖晶石结构的良好性能，并且有足够多的Ti4+转变为Ti3+，改善了其本身电子导电性差的缺点，得到的Li3.8Mg0.2Ti5O12具有最高的首次放电比容量，达到193.6m Ahg-1，比未掺杂Li4Ti5O12的首次放电比容量145.3m Ahg-1高出33.2％。Fig. 4 is the cycle stability curve in the embodiment of the present invention (a is Mg-doped lithium titanate negative electrode material, b is undoped lithium titanate negative electrode material), as can be seen from the figure, the doping of an appropriate amount of Mg 2+ The impurity does not destroy its own structure, retains the good performance of its spinel structure, and has enough Ti 4+ to transform into Ti 3+ , which improves its own shortcomings of poor electronic conductivity, and the obtained Li 3.8 Mg 0.2 Ti 5 O 12 has the highest initial discharge specific capacity of 193.6m Ahg -1 , which is 33.2% higher than that of undoped Li 4 Ti 5 O 12 (145.3m Ahg -1 ).
图5是本发明的具体实施方式中倍率性能曲线(a为Mg掺杂钛酸锂负极材料，b未掺杂钛酸锂负极材料)，从图中可以看出，随着放电倍率的增加，未掺杂Li4Ti5O12样品的容量快速降低，而掺杂样品拥有更好的容量保持率。即使在10C倍率，其仍拥有125.1mAhg-1的放电比容量，相当于初始0.57C倍率下放电比容量的64.6％。而未掺杂Li4Ti5O12在10C时放电容量只有47.6mAhg-1。当倍率再次回到0.57C时，仍然可以保持190.8mAhg-1的放电比容量，说明Li3.8Mg0.2Ti5O12具有良好的可逆性和稳定性。Mg2+的掺杂使Ti4+转化为Ti3+，增加了电子浓度，这就增加了Li4Ti5O12的导电性，增强了Li+的扩散。Figure 5 is a rate performance curve in a specific embodiment of the present invention (a is Mg-doped lithium titanate negative electrode material, b is undoped lithium titanate negative electrode material), as can be seen from the figure, with the increase of discharge rate, The capacity of the undoped Li 4 Ti 5 O 12 sample decreases rapidly, while the doped sample has better capacity retention. Even at 10C rate, it still has a specific discharge capacity of 125.1mAhg-1, which is equivalent to 64.6% of the discharge specific capacity at the initial 0.57C rate. The discharge capacity of undoped Li 4 Ti 5 O 12 is only 47.6mAhg-1 at 10C. When the rate returns to 0.57C again, the specific discharge capacity of 190.8mAhg-1 can still be maintained, indicating that Li 3.8 Mg 0.2 Ti 5 O 12 has good reversibility and stability. The doping of Mg 2+ converts Ti4+ into Ti3+ and increases the electron concentration, which increases the conductivity of Li 4 Ti 5 O 12 and enhances the diffusion of Li+.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.
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