CN103682418B - Lithium-ion battery with excellent comprehensive performance and preparation method thereof - Google Patents
Lithium-ion battery with excellent comprehensive performance and preparation method thereof Download PDFInfo
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- CN103682418B CN103682418B CN201310737676.4A CN201310737676A CN103682418B CN 103682418 B CN103682418 B CN 103682418B CN 201310737676 A CN201310737676 A CN 201310737676A CN 103682418 B CN103682418 B CN 103682418B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- 239000007773 negative electrode material Substances 0.000 claims description 33
- 239000002033 PVDF binder Substances 0.000 claims description 26
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 26
- 239000002174 Styrene-butadiene Substances 0.000 claims description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 22
- 239000006258 conductive agent Substances 0.000 claims description 21
- 229910021385 hard carbon Inorganic materials 0.000 claims description 20
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 11
- 229920000126 latex Polymers 0.000 claims description 11
- 239000011115 styrene butadiene Substances 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 3
- 238000012858 packaging process Methods 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 2
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 239000011149 active material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000003475 lamination Methods 0.000 abstract description 5
- 238000004804 winding Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 229910021382 natural graphite Inorganic materials 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种综合性能优异的锂离子电池及其制备方法，本发明将正、负极片包含一种或多种不同电极，包括活性物质不同，同时根据极片的活性物质对导电剂或粘结剂的规格、种类、成分进行搭配，同时调整电极的涂覆量，使本发明提供的锂离子电池综合了各种电极的材料、配方及制作工艺等的优势，综合性能优异、可满足用户对电池的多方面性能需求；另外通过本发明提供的叠层或卷绕方式能够将多种不同的极片组合成为极组，其制备方法简单，工艺可操作性强，适用于大规模的生产应用。
The invention discloses a lithium-ion battery with excellent comprehensive performance and a preparation method thereof. In the invention, the positive and negative electrodes include one or more different electrodes, including different active materials. The specifications, types, and components of the binder are matched, and the coating amount of the electrode is adjusted at the same time, so that the lithium-ion battery provided by the invention combines the advantages of various electrode materials, formulas, and manufacturing processes, and has excellent comprehensive performance. The user has various performance requirements for the battery; in addition, through the lamination or winding method provided by the present invention, a variety of different pole pieces can be combined into an pole group. The preparation method is simple, the process is highly operable, and it is suitable for large-scale production application.
Description
技术领域technical field
本发明涉及技术领域，特别是涉及一种综合性能优异的锂离子电池及其制备方法。The invention relates to the technical field, in particular to a lithium-ion battery with excellent comprehensive performance and a preparation method thereof.
背景技术Background technique
锂离子电池具有能量密度高、质量轻、安全性能好等其他储能电池不可比拟的优势，已经成功应用于各种电子产品、通讯设备、自动化仪器仪表和各种电动工具中，在电动自行车、电动汽车上也得到了广泛的应用，对于航天、航空、野战等军事领域也极具诱惑力。Lithium-ion batteries have the incomparable advantages of other energy storage batteries, such as high energy density, light weight, and good safety performance. Electric vehicles have also been widely used, and are also very attractive for military fields such as aerospace, aviation, and field operations.
锂离子电池的性能受电极材料、配方和制作工艺的影响极大，例如目前最成熟的钴酸锂正极材料，其不同的形貌、粒径、掺杂元素种类和掺杂量决定了电池不同的性能特征，包括充电范围、能量密度、倍率性能、安全性能等。同样，负极材料的差异对电池性能的影响也非常显著。例如由于采用不同原材料和制备工艺得到的碳负极，又分为人造石墨、天然石墨改性材料、中间相碳微球、硬碳、软碳等等，制得的电池产品也性能各异。The performance of lithium-ion batteries is greatly affected by electrode materials, formulations, and manufacturing processes. For example, the most mature lithium cobalt oxide cathode material currently has different shapes, particle sizes, types of doping elements, and doping amounts that determine different batteries. Performance characteristics, including charging range, energy density, rate performance, safety performance, etc. Similarly, the difference in anode materials has a significant impact on battery performance. For example, due to the use of different raw materials and preparation processes, carbon negative electrodes are divided into artificial graphite, natural graphite modified materials, mesocarbon microspheres, hard carbon, soft carbon, etc., and the performance of the battery products is also different.
由此，目前很难获得一款综合性能优异的电池。即便是在已成熟应用的领域，锂离子电池性能也还是略显不足，无法体现出绝对的优势以取代其他电池体系；而在一些特殊应用领域目前技术的锂离子电池则根本无法胜任。Therefore, it is difficult to obtain a battery with excellent comprehensive performance at present. Even in the field of mature application, the performance of lithium-ion battery is still slightly insufficient, unable to show absolute advantages to replace other battery systems; and in some special application fields, the current technology of lithium-ion battery is simply not competent.
因此，目前迫切需要寻找一种方法，可以综合各种电极材料、体系的优势，。研发出一种综合性能优异的锂离子电池。Therefore, there is an urgent need to find a method that can integrate the advantages of various electrode materials and systems. A lithium-ion battery with excellent comprehensive performance has been developed.
发明内容Contents of the invention
本发明的目的是针对现有技术中存在的技术缺陷，而提供一种综合性能优异的锂离子电池及其制备方法。The object of the present invention is to provide a lithium-ion battery with excellent comprehensive performance and a preparation method thereof for the technical defects existing in the prior art.
为实现本发明的目的所采用的技术方案是：一种综合性能优异的锂离子电池，其特征在于包括由正极片和负极片组成的极组、隔膜、非水电解液、极耳和外壳；所述正极片包括正极活性物质、导电剂、粘结剂和集流体；所述负极片包括负极活性物质、导电剂、粘结剂和集流体；所述负极片分为由两种不同的负极活性物质制成的负极片A和负极片B；所述正极片与所述负极片A依次叠层或卷绕组成为极组单元A，所述正极片与所述负极片B依次叠层或卷绕组成为极组单元B；所述极组由所述极组单元A与所述极组单元B并联叠加组成。The technical solution adopted for realizing the purpose of the present invention is: a lithium-ion battery with excellent comprehensive performance, characterized in that it includes a pole group composed of a positive electrode sheet and a negative electrode sheet, a separator, a non-aqueous electrolyte, a tab and a casing; The positive electrode sheet includes a positive electrode active material, a conductive agent, a binder, and a current collector; the negative electrode sheet includes a negative electrode active material, a conductive agent, a binder, and a current collector; the negative electrode sheet is divided into two types of different negative electrodes. Negative electrode sheet A and negative electrode sheet B made of active materials; the positive electrode sheet and the negative electrode sheet A are sequentially laminated or wound to form an electrode group unit A, and the positive electrode sheet and the negative electrode sheet B are sequentially laminated or wound The winding group constitutes a pole group unit B; the pole group is composed of the pole group unit A and the pole group unit B superimposed in parallel.
优选的，所述负极片与所述正极片的容量比为1～1.2：1，其目的为了同时达到对电池容量、尺寸、电性能、安全性能等多方面的指标要求，以正极限制容量，负极过量为设计原则。Preferably, the capacity ratio of the negative electrode sheet to the positive electrode sheet is 1 to 1.2:1, the purpose of which is to simultaneously meet various index requirements for battery capacity, size, electrical performance, safety performance, etc., and limit the capacity with the positive electrode. Negative excess is the design principle.
所述负极活性物质为人造石墨、天然石墨、硬碳、钛酸锂、金属硅、氧化硅的一种或多种的混合物。The negative electrode active material is a mixture of one or more of artificial graphite, natural graphite, hard carbon, lithium titanate, metal silicon, and silicon oxide.
优选的，所述负极片A的负极活性物质为质量比为87：8的人造石墨和金属硅的混合物Preferably, the negative electrode active material of the negative electrode sheet A is a mixture of artificial graphite and metal silicon with a mass ratio of 87:8
优选的，所述负极片B的负极活性物质为硬碳。Preferably, the negative electrode active material of the negative electrode sheet B is hard carbon.
上述一种综合性能优异的锂离子电池的制备方法，其特征在于包括以下步骤：The above-mentioned preparation method of a lithium-ion battery with excellent comprehensive performance is characterized in that it comprises the following steps:
（1）制作正极片；(1) Making the positive electrode sheet;
（2）使用两种不同的负极活性物质分别制作成负极片A和负极片B；(2) Using two different negative electrode active materials to make negative electrode sheet A and negative electrode sheet B respectively;
（3）将正极片与负极片A依次叠层或卷绕组成为极组单元A；将正极片与负极片B依次叠层或卷绕组成为极组单元B；(3) The positive electrode sheet and the negative electrode sheet A are sequentially stacked or wound to form the electrode group unit A; the positive electrode sheet and the negative electrode sheet B are sequentially stacked or wound to form the electrode group unit B;
（4）将步骤（3）制成的极组单元A和极组单元B并联叠加成为极组；(4) The pole group unit A and the pole group unit B made in step (3) are superimposed in parallel to form a pole group;
（5）将步骤（4）制成的极组进行极耳焊接，并置于电池外壳中，按常规封装工艺封装，液入电解液后封口，从而制成锂离子电池。(5) Weld the electrode group produced in step (4) with the tabs, place it in the battery casing, package it according to the conventional packaging process, and seal it after the liquid is poured into the electrolyte, so as to make a lithium-ion battery.
所述步骤（2）中的负极活性物质为人造石墨、天然石墨、硬碳、钛酸锂、金属硅、氧化硅的一种或多种的混合物。The negative electrode active material in the step (2) is a mixture of one or more of artificial graphite, natural graphite, hard carbon, lithium titanate, metal silicon, and silicon oxide.
优选的，所述步骤（2）中的负极片A包括负极活性物质、导电剂、粘结剂和集流体；所述负极片A的负极活性物质为质量比为87：8的人造石墨和金属硅的混合物，所述导电剂为导电碳黑，所述粘结剂为重量比为1：2的羧甲基纤维素（CMC）和丁苯胶乳（SBR）；所述人造石墨、金属硅、导电碳黑、羧甲基纤维素（CMC）和丁苯胶乳（SBR）的重量比为87：8：2：1：2；所述集流体为10um厚的铜箔。Preferably, the negative electrode sheet A in the step (2) includes a negative electrode active material, a conductive agent, a binder and a current collector; the negative electrode active material of the negative electrode sheet A is artificial graphite and metal with a mass ratio of 87:8 Silicon mixture, the conductive agent is conductive carbon black, the binder is carboxymethyl cellulose (CMC) and styrene-butadiene latex (SBR) with a weight ratio of 1:2; the artificial graphite, metal silicon, The weight ratio of conductive carbon black, carboxymethyl cellulose (CMC) and styrene-butadiene latex (SBR) is 87:8:2:1:2; the current collector is 10um thick copper foil.
所述步骤（2）中的负极片B包括负极活性物质、导电剂、粘结剂和集流体；所述负极片B的负极活性物质为硬碳；所述粘接剂为聚偏氟乙烯（PVDF），硬碳与聚偏氟乙烯（PVDF）的重量比为97：3；所述集流体为10um厚的铜箔。The negative electrode sheet B in the step (2) includes a negative electrode active material, a conductive agent, a binder and a current collector; the negative electrode active material of the negative electrode sheet B is hard carbon; the binder is polyvinylidene fluoride ( PVDF), the weight ratio of hard carbon to polyvinylidene fluoride (PVDF) is 97:3; the current collector is 10um thick copper foil.
与现有技术相比，本发明的有益效果是：将正、负极片包含一种或多种不同电极，包括活性物质不同，同时根据极片的活性物质对导电剂或粘结剂的规格、种类、成分进行搭配，同时调整电极的涂覆量，使本发明提供的锂离子电池综合了各种电极的材料、配方及制作工艺等的优势，综合性能优异、可满足用户对电池的多方面性能需求；另外通过本发明提供的叠层或卷绕方式能够将多种不同的极片组合成为极组，其制备方法简单，工艺可操作性强，适用于大规模的生产应用。Compared with the prior art, the beneficial effect of the present invention is that the positive and negative electrodes include one or more different electrodes, including different active materials, and at the same time, according to the specifications of the active material of the electrode sheet to the conductive agent or binder, The types and components are matched, and the coating amount of the electrode is adjusted at the same time, so that the lithium-ion battery provided by the present invention combines the advantages of various electrode materials, formulas, and manufacturing processes. Performance requirements; In addition, a variety of different pole pieces can be combined into a pole group through the lamination or winding method provided by the present invention. The preparation method is simple, the process is highly operable, and it is suitable for large-scale production applications.
附图说明Description of drawings
图1是本发明实施例提供的一种锂离子电池的制作过程示意图；Fig. 1 is a schematic diagram of the manufacturing process of a lithium-ion battery provided by an embodiment of the present invention;
图2为1#、2#、3#电池进行20安培（简称A）恒流放电曲线；Figure 2 is the 20 ampere (referred to as A) constant current discharge curve for 1#, 2#, 3# batteries;
图3为1#、2#、3#电池在-30℃条件下搁置4小时后，再采用以下放电制式进行放电：22.5A恒流放电30秒，再以4A恒流放电直至电压降低至2.0V得到的曲线。Figure 3 shows that 1#, 2#, and 3# batteries were left at -30°C for 4 hours, and then discharged using the following discharge system: 22.5A constant current discharge for 30 seconds, and then 4A constant current discharge until the voltage dropped to 2.0 The curve obtained by V.
具体实施方式detailed description
以下结合具体实施例对本发明作进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention will be described in further detail below in conjunction with specific examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
本发明所涉一种综合性能优异的锂离子电池，包括由正极片和负极片组成的极组、隔膜、非水电解液、极耳和外壳。The invention relates to a lithium-ion battery with excellent comprehensive performance, comprising an electrode group composed of a positive electrode sheet and a negative electrode sheet, a separator, a non-aqueous electrolyte, a tab and a casing.
所述正极片包括正极活性物质、导电剂、粘结剂和集流体；所述正极活性物质包括钴酸锂、锰酸锂、磷酸铁锂、镍酸锂、钴镍锰三元材料等可用作锂离子电池正极活性物质的材料，以及其中两种或多种材料的混合体系。The positive electrode sheet includes a positive electrode active material, a conductive agent, a binder, and a current collector; the positive electrode active material includes lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickelate, and cobalt-nickel-manganese ternary materials, etc. It can be used as a material for the positive electrode active material of lithium-ion batteries, and a mixed system of two or more materials.
所述负极片包括负极活性物质、导电剂、粘结剂和集流体；所述负极活性物质为人造石墨、天然石墨、硬碳、钛酸锂、金属硅、氧化硅的一种或多种的混合物。所述负极片分为由两种不同的负极活性物质制成的负极片A和负极片B；所述正极片与所述负极片A依次叠层或卷绕组成为极组单元A，所述正极片与所述负极片B依次叠层或卷绕组成为极组单元B；所述极组由所述极组单元A与所述极组单元B并联叠加组成。The negative electrode sheet includes a negative electrode active material, a conductive agent, a binder, and a current collector; the negative electrode active material is one or more of artificial graphite, natural graphite, hard carbon, lithium titanate, metal silicon, and silicon oxide. mixture. The negative electrode sheet is divided into negative electrode sheet A and negative electrode sheet B made of two different negative electrode active materials; the positive electrode sheet and the negative electrode sheet A are sequentially stacked or wound to form an electrode group unit A, and the positive electrode The sheet and the negative electrode sheet B are sequentially stacked or wound to form an electrode group unit B; the electrode group is composed of the electrode group unit A and the electrode group unit B stacked in parallel.
上述叠层操作是指将不同体系的正极片或负极片进行区分编号，叠层时根据设计要求叠加相应数量的正极和负极，以达到预设的电池的容量，其尺寸及性能满足客户要求。The above stacking operation refers to distinguishing and numbering the positive and negative electrodes of different systems, and stacking the corresponding number of positive and negative electrodes according to the design requirements during lamination to achieve the preset battery capacity, and its size and performance meet customer requirements.
上述卷绕操作是将设计匹配的正、负极片用隔膜分隔开，卷绕成一个极组单元；将不同体系卷绕而成的极组单元采用焊接或铆接等方法并联形成一个最终的极组。The above-mentioned winding operation is to separate the matched positive and negative electrode sheets with a separator and wind them into an electrode group unit; the electrode group units wound by different systems are connected in parallel by welding or riveting to form a final electrode unit. Group.
优选的，所述负极片A的负极活性物质为质量比为87：8的人造石墨和金属硅的混合物，两者的特点均为高比容量。Preferably, the negative electrode active material of the negative electrode sheet A is a mixture of artificial graphite and metal silicon with a mass ratio of 87:8, both of which are characterized by high specific capacity.
优选的，所述负极片B的负极活性物质为硬碳，其特点为硬碳具有优异的大倍率放电性能和低温性能。Preferably, the negative electrode active material of the negative electrode sheet B is hard carbon, which is characterized in that hard carbon has excellent high-rate discharge performance and low-temperature performance.
所述粘结剂包括聚偏氟乙烯（PVDF）和丁苯胶乳（SBR）、聚氧化乙烯（PEO）等等可用于锂离子电池电极粘结剂的材料。The binder includes polyvinylidene fluoride (PVDF), styrene-butadiene latex (SBR), polyethylene oxide (PEO), and other materials that can be used for lithium-ion battery electrode binders.
所述外壳包括铝壳、钢壳和铝塑封装膜。The shell includes an aluminum shell, a steel shell and an aluminum-plastic packaging film.
所述电解液包括液态、凝胶态电解质和全固态电解质。The electrolyte includes liquid electrolyte, gel electrolyte and all-solid electrolyte.
从整体上来说，所述负极片与所述正极片的容量比为1～1.2：1，其目的为了同时达到对电池容量、尺寸、电性能、安全性能等多方面的指标要求，以正极限制容量，负极过量为设计原则。On the whole, the capacity ratio of the negative electrode sheet to the positive electrode sheet is 1-1.2:1. Capacity, negative electrode excess is the design principle.
上述一种综合性能优异的锂离子电池的制备方法，包括以下步骤：The above-mentioned preparation method of a lithium-ion battery with excellent comprehensive performance comprises the following steps:
（1）制作正极片；(1) Making the positive electrode sheet;
1）将正极活性物质与导电剂充分混合，加入溶剂，如N-甲基吡咯烷酮（NMP）；加入粘结剂，如聚偏氟乙烯（PVDF），将其充分搅拌得到正极浆料；1) Fully mix the positive electrode active material with the conductive agent, add a solvent, such as N-methylpyrrolidone (NMP); add a binder, such as polyvinylidene fluoride (PVDF), and stir it thoroughly to obtain the positive electrode slurry;
2）采用涂布机按一定涂覆量（面密度）涂覆得到正极片；2) Use a coating machine to apply a certain amount of coating (area density) to obtain the positive electrode sheet;
3）采用碾压机将正极片碾压到一定厚度或压实密度；3) Use a rolling machine to roll the positive electrode sheet to a certain thickness or compaction density;
4）将碾压后极片剪切、冲切、裁切成规定尺寸的小片；4) Cutting, punching and cutting the rolled pole pieces into small pieces of specified size;
（2）使用两种不同的负极活性物质分别制作成负极片A和负极片B，负极片的制作方法为：(2) Use two different negative electrode active materials to make negative electrode sheet A and negative electrode sheet B respectively. The method of making the negative electrode sheet is as follows:
1）将负极活性物质与导电剂充分混合，加入溶剂，如N-甲基吡咯烷酮（NMP）或水，加入粘结剂，如聚偏氟乙烯（PVDF）或丁苯胶乳（SBR），将其充分搅拌得到负极浆料；1) Fully mix the negative electrode active material with the conductive agent, add a solvent, such as N-methylpyrrolidone (NMP) or water, add a binder, such as polyvinylidene fluoride (PVDF) or styrene-butadiene latex (SBR), and put it Thoroughly stir to obtain negative electrode slurry;
2）采用涂布机按一定涂覆量（面密度）涂覆得到负极片；2) Use a coating machine to apply a certain amount of coating (area density) to obtain the negative electrode sheet;
3）采用碾压机将负极片碾压到一定厚度或压实密度；3) Use a rolling machine to roll the negative electrode sheet to a certain thickness or compaction density;
4）将碾压后极片剪切、冲切、裁切成规定尺寸的小片。4) Cutting, punching and cutting the pole piece after rolling into small pieces of specified size.
（3）将正极片与负极片A依次叠层或卷绕组成为极组单元A；将正极片与负极片B依次叠层或卷绕组成为极组单元B；(3) The positive electrode sheet and the negative electrode sheet A are sequentially stacked or wound to form the electrode group unit A; the positive electrode sheet and the negative electrode sheet B are sequentially stacked or wound to form the electrode group unit B;
1）叠层操作是指将不同体系的正极片或负极片进行区分编号，叠层时根据设计要求叠加相应数量的正极和负极，以达到预设的电池的容量，其尺寸及性能满足客户要求；1) Lamination operation refers to distinguishing and numbering the positive or negative electrodes of different systems, and stacking the corresponding number of positive and negative electrodes according to the design requirements during lamination to achieve the preset battery capacity, and its size and performance meet customer requirements ;
2）卷绕操作是将设计匹配的正、负极片用隔膜分隔开，卷绕成一个极组单元；2) The winding operation is to separate the matched positive and negative electrode sheets with a diaphragm and wind them into an electrode group unit;
（4）将步骤（3）制成的极组单元A和极组单元B并联叠加成为极组；(4) The pole group unit A and the pole group unit B made in step (3) are superimposed in parallel to form a pole group;
（5将步骤（4）制成的极组进行极耳焊接，并置于电池外壳中，按常规封装工艺封装，液入电解液后封口，从而制成锂离子电池。(5) Weld the electrode group produced in step (4) with tabs, place it in the battery casing, package it according to the conventional packaging process, and seal it after the liquid is poured into the electrolyte, so as to make a lithium-ion battery.
所述步骤（2）中的负极活性物质为人造石墨、天然石墨、硬碳、钛酸锂、金属硅、氧化硅的一种或多种的混合物。The negative electrode active material in the step (2) is a mixture of one or more of artificial graphite, natural graphite, hard carbon, lithium titanate, metal silicon, and silicon oxide.
优选的，所述步骤（2）中的负极片A包括负极活性物质、导电剂、粘结剂和集流体；所述负极片A的负极活性物质为质量比为87：8的人造石墨和金属硅的混合物，所述导电剂为导电碳黑，所述粘结剂为重量比为1：2的羧甲基纤维素（CMC）和丁苯胶乳（SBR）；所述人造石墨、金属硅、导电碳黑、羧甲基纤维素（CMC）和丁苯胶乳（SBR）的重量比为87：8：2：1：2；所述集流体为10um厚的铜箔。Preferably, the negative electrode sheet A in the step (2) includes a negative electrode active material, a conductive agent, a binder and a current collector; the negative electrode active material of the negative electrode sheet A is artificial graphite and metal with a mass ratio of 87:8 Silicon mixture, the conductive agent is conductive carbon black, the binder is carboxymethyl cellulose (CMC) and styrene-butadiene latex (SBR) with a weight ratio of 1:2; the artificial graphite, metal silicon, The weight ratio of conductive carbon black, carboxymethyl cellulose (CMC) and styrene-butadiene latex (SBR) is 87:8:2:1:2; the current collector is 10um thick copper foil.
所述步骤（2）中的负极片B包括负极活性物质、导电剂、粘结剂和集流体；所述负极活性物质为硬碳；所述粘接剂为聚偏氟乙烯（PVDF），硬碳与聚偏氟乙烯（PVDF）的重量比为97：3；所述集流体为10um厚的铜箔。The negative electrode sheet B in the step (2) includes a negative electrode active material, a conductive agent, a binder and a current collector; the negative electrode active material is hard carbon; the binder is polyvinylidene fluoride (PVDF), hard The weight ratio of carbon to polyvinylidene fluoride (PVDF) is 97:3; the current collector is 10um thick copper foil.
如图1所示为本发明提供的一种锂离子电池的制作过程，为了便于说明，仅示出了与本发明实施例有关的部分。图1中采用叠片式极组结构为例进行说明，其外型为方型，外壳采用铝塑膜进行软包装，包含正极片1和两种不同体系的负极片2-A、2-B，将负极片2-A用隔膜3-A包裹，负极片2-B用隔膜3-B包裹；按设计要求将相应层数正极片1和负极片2-A依次叠层得到极组单元A，按设计要求将相应层数正极片1和负极片2-B依次叠层得到极组单元B，将极组单元A和B并联叠加在一起得到极组4；负极耳箔5、正极耳箔6分别与含热熔胶负极耳7、含热熔胶正极耳8焊接在一起，将焊接极耳7、8的极组4放置于外包装壳9中，经过封装、注液、化成等工序加工得到锂离子电池10。As shown in FIG. 1 , a manufacturing process of a lithium-ion battery provided by the present invention is shown. For convenience of description, only the parts related to the embodiment of the present invention are shown. In Figure 1, the laminated pole group structure is used as an example for illustration. Its appearance is square, and the outer shell is soft-packed with aluminum-plastic film, including positive electrode sheet 1 and negative electrode sheets 2-A and 2-B of two different systems. Wrap the negative electrode sheet 2-A with a separator 3-A, and wrap the negative electrode sheet 2-B with a separator 3-B; according to the design requirements, stack the corresponding layers of the positive electrode sheet 1 and the negative electrode sheet 2-A in order to obtain the electrode group unit A, According to the design requirements, the corresponding layers of positive electrode sheet 1 and negative electrode sheet 2-B are sequentially laminated to obtain the electrode group unit B, and the electrode group units A and B are superimposed in parallel to obtain the electrode group 4; negative electrode ear foil 5, positive electrode ear foil 6 Weld them with the negative tab 7 containing hot melt adhesive and the positive tab 8 containing hot melt adhesive respectively, place the pole group 4 with the welded tabs 7 and 8 in the outer packaging shell 9, and process through packaging, liquid injection, chemical formation and other processes Lithium ion battery 10 was obtained.
下面通过具体的实施例来说明本发明的技术方案的优越性。The superiority of the technical solution of the present invention is illustrated below through specific examples.
实施例：Example:
一种综合性能优异的锂离子电池，采用可4.35V高电压充电的钴酸锂材料为正极，正极配方为钴酸锂：导电碳黑：聚偏氟乙烯（PVDF）=95：2：3（重量比），采用15um厚铝箔作为集流体，电极涂覆量为39mg/cm2，碾压密度为4.0cm/cm3，极片剪切尺寸为60mm宽*120mm长，极耳箔尺寸为：12mm宽*12mm长。对正极片进行真空烘干，烘干参数为100℃，12h。A lithium-ion battery with excellent comprehensive performance, using lithium cobalt oxide material that can be charged at a high voltage of 4.35V as the positive electrode, and the positive electrode formula is lithium cobalt oxide: conductive carbon black: polyvinylidene fluoride (PVDF) = 95: 2: 3 ( weight ratio), 15um thick aluminum foil is used as the current collector, the coating amount of the electrode is 39mg/cm 2 , the rolling density is 4.0cm/cm 3 , the cut size of the pole piece is 60mm wide * 120mm long, and the size of the tab foil is: 12mm wide * 12mm long. Vacuum drying is performed on the positive electrode sheet, and the drying parameter is 100° C. for 12 hours.
负极采用高比容量的人造石墨和金属硅混合作为活性材料制作电极A，电极配方为C：Si：导电碳黑：羧甲基纤维素（CMC）：丁苯胶乳（SBR）=87：8：2：1：2（重量比），采用10um厚铜箔作为集流体，电极涂覆量为7.5mg/cm2，碾压密度为1.7cm/cm3，极片剪切尺寸为62mm宽*122mm长，极耳箔尺寸为：12mm宽*12mm长。对负极片进行真空烘干，烘干参数为130℃，12h。The negative electrode uses artificial graphite with high specific capacity and metal silicon as the active material to make electrode A. The electrode formula is C: Si: conductive carbon black: carboxymethyl cellulose (CMC): styrene-butadiene latex (SBR) = 87: 8: 2:1:2 (weight ratio), 10um thick copper foil is used as the current collector, the electrode coating amount is 7.5mg/cm 2 , the rolling density is 1.7cm/cm 3 , and the shear size of the pole piece is 62mm wide*122mm Long, the size of the ear foil is: 12mm wide * 12mm long. Vacuum drying is performed on the negative electrode sheet, and the drying parameter is 130° C. for 12 hours.
采用硬碳为活性材料制作电极B，电极配方为硬碳：聚偏氟乙烯（PVDF）=97：3（重量比），采用10um厚铜箔作为集流体，电极涂覆量为7mg/cm2，碾压密度为1.0cm/cm3，极片剪切尺寸为62mm宽*122mm长，极耳箔尺寸为：12mm宽*12mm长。对负极片进行真空烘干，烘干参数为130℃，12h。Electrode B is made of hard carbon as the active material, the electrode formula is hard carbon: polyvinylidene fluoride (PVDF) = 97:3 (weight ratio), 10um thick copper foil is used as the current collector, and the coating amount of the electrode is 7mg/cm 2 , the rolling density is 1.0cm/cm 3 , the cutting size of the pole piece is 62mm wide * 122mm long, and the tab foil size is: 12mm wide * 12mm long. Vacuum drying is performed on the negative electrode sheet, and the drying parameter is 130° C. for 12 hours.
将PP隔膜裁切成130mm宽*128mm长片状，沿130mm方向对折后将负极片居中封入隔膜袋中。将10片正极片与11片负极片A交叉居中叠加，得到极组1#；将10片正极片与11片负极片B交叉居中叠加，得到极组2#。将5片负极片A与5片正极片交叉居中叠加，再将5片正极片与6片负极片B交叉居中叠加，得到极组3#。Cut the PP separator into a 130mm wide*128mm long sheet, fold it in half along the 130mm direction, and seal the negative electrode in the center of the separator bag. Superimpose 10 positive electrode sheets and 11 negative electrode sheets A in the center to obtain electrode group 1#; cross and superimpose 10 positive electrode sheets and 11 negative electrode sheets B in the center to obtain electrode group 2#. 5 pieces of negative electrode sheet A and 5 pieces of positive electrode sheet are crossed and superimposed in the middle, and then 5 pieces of positive electrode sheet and 6 pieces of negative electrode sheet B are crossed and superimposed to obtain the electrode group 3#.
采用110um厚的铝塑膜分别对制得的1#、2#、3#极组进行封装，真空烘干后注入同一种电解液，电解配方为六氟磷酸锂（LiPF6）：碳酸乙烯酯（EC）：碳酸甲乙酯（EMC）：丙酸乙酯(EP)：氟代碳酸乙烯酯(FEC)：亚硫酸丙烯酯(PS)：乙腈（AN）=16:30:25:21:5:2:1，注液量为8～8.5g，对电池分别进行真空一次封口，然后再采用0.4安培（简称A）电流充电至4.35V，4.35V恒压充电至电流降低至0.2安培（简称A）时停止充电，静置24小时后，对电池进行真空除气封口。在常温条件下搁置7天后，剔除不良品后，再对1#、2#、3#良品电池分别进行以下测试项目：The prepared 1#, 2#, and 3# electrode groups were respectively packaged with 110um thick aluminum-plastic film, and the same electrolyte was injected after vacuum drying. The electrolytic formula was lithium hexafluorophosphate (LiPF6): ethylene carbonate (EC): Ethyl methyl carbonate (EMC): ethyl propionate (EP): fluoroethylene carbonate (FEC): propylene sulfite (PS): acetonitrile (AN)=16:30:25:21:5:2: 1. The liquid injection volume is 8-8.5g, and the batteries are vacuum-sealed once respectively, and then charged to 4.35V with a current of 0.4 amps (referred to as A), and charged at a constant voltage of 4.35V until the current drops to 0.2 amps (referred to as A). Stop charging, and after standing for 24 hours, carry out vacuum degassing and sealing to the battery. After laying it aside for 7 days at room temperature, after removing the defective products, the following test items are carried out on the 1#, 2#, and 3# good-quality batteries:
（1）以2A充电至4.35V，4.35V恒压充电至电流降低至0.2A时停止充电，以2A放电得到电池容量；(1) Charge at 2A to 4.35V, charge at constant voltage at 4.35V until the current drops to 0.2A, stop charging, and discharge at 2A to obtain the battery capacity;
（2）采用精度为0.01g的电子天平进行电池称重；(2) Use an electronic balance with an accuracy of 0.01g to weigh the battery;
（3）采用以下制式对电池进行放电：20A恒流放电直至电压降低至2.0V；(3) Discharge the battery using the following formula: 20A constant current discharge until the voltage drops to 2.0V;
（4）将电池在-30℃条件下搁置4小时后，再采用以下放电制式进行放电：22.5A恒流放电30秒，再以4A恒流放电直至电压降低至2.0V。(4) After leaving the battery at -30°C for 4 hours, discharge it using the following discharge method: 22.5A constant current discharge for 30 seconds, and then 4A constant current discharge until the voltage drops to 2.0V.
表1为1#、2#、3#电池的容量、重量及比能量对比数据；Table 1 is the capacity, weight and specific energy comparison data of 1#, 2# and 3# batteries;
表1Table 1
表2为1#、2#、3#电池进行20A恒流放电对比数据；Table 2 is the comparison data of 1#, 2#, and 3# batteries for 20A constant current discharge;
表2Table 2
表3为1#、2#、3#电池在-30℃条件下搁置4小时后，再采用以下放电制式进行放电：22.5A恒流放电30秒，再以4A恒流放电直至电压降低至2.0V得到的对比数据。Table 3 shows that 1#, 2#, and 3# batteries were left for 4 hours at -30°C, and then discharged using the following discharge system: 22.5A constant current discharge for 30 seconds, and then 4A constant current discharge until the voltage dropped to 2.0 The comparative data obtained by V.
表3table 3
图2为1#、2#、3#电池进行5C恒流放电曲线；Figure 2 shows the 5C constant current discharge curves for 1#, 2#, and 3# batteries;
图3为1#、2#、3#电池在-30℃条件下搁置4小时后，再采用以下放电制式进行放电：22.5A恒流放电30秒，再以4A恒流放电直至电压降低至2.0V得到的曲线。Figure 3 shows that 1#, 2#, and 3# batteries were left at -30°C for 4 hours, and then discharged using the following discharge system: 22.5A constant current discharge for 30 seconds, and then 4A constant current discharge until the voltage dropped to 2.0 The curve obtained by V.
通过以上测试结果可以看出，本发明实施例制备的锂离子电池3#同时采用了高比能量的人造石墨水性体系负极片和功率性能、低温性能优异的硬碳油性体系负极片，相比单纯采用人造石墨和硬碳制得的电池1#和2#，其综合了两种负极材料体系的优势，不仅获得了硬碳材料体系的大倍率性能，且能量密度大大提高，加上低温和功率性能优异的电解液，电池的20安培（约5C倍率）放电性能和低温大倍率脉冲性能都得到了显著的提高。It can be seen from the above test results that lithium-ion battery 3# prepared in the embodiment of the present invention adopts the artificial graphite water-based system negative electrode sheet with high specific energy and the hard carbon oil-based system negative electrode sheet with excellent power performance and low temperature performance. Batteries 1# and 2# made of artificial graphite and hard carbon combine the advantages of the two anode material systems, not only obtain the large rate performance of the hard carbon material system, but also greatly improve the energy density, coupled with low temperature and power The electrolyte with excellent performance, the battery's 20 ampere (about 5C rate) discharge performance and low temperature large rate pulse performance have been significantly improved.
以上所述仅是本发明的优选实施方式，应当指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvements and Retouching should also be regarded as the protection scope of the present invention.
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