WO2019000861A1 - Lithium-ion battery positive electrode and preparation method therefor and method for preparing lithium-ion battery - Google Patents
Lithium-ion battery positive electrode and preparation method therefor and method for preparing lithium-ion battery Download PDFInfo
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Definitions
- a positive electrode of a lithium ion battery comprising a positive electrode material, PVDF, a conductive agent and STOBA, wherein the mass fraction of the positive electrode material, PVDF, conductive agent and STOBA are 95-98, 0.5-0.9, 0.8-1.2 and 0.2-0.5, respectively
- the positive electrode material is at least one of lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum.
- Step 2 mixing step 1 to weigh the good material to obtain a mixed powder
- Step 1 Weigh each raw material of the positive electrode of the lithium ion battery, and pass the weighed raw materials through a 100 mesh sieve for use;
Abstract
Disclosed are a lithium-ion battery positive electrode and a preparation method therefor, and a method for preparing a lithium-ion battery, the lithium-ion battery positive electrode comprising a positive electrode material, PVDF, a conductive agent and STOBA, wherein the parts by mass of the positive electrode material, the PVDF, the conductive agent and the STOBA are respectively 95-98 parts, 0.5-0.9 part, 0.8-1.2 parts and 0.2-0.5 part; the positive electrode material is at least one of lithium nickel cobalt manganate, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum ternary materials. A lithium-ion battery prepared by using the positive electrode has the advantages of a good high temperature cycle performance, a low internal resistance and a low self-discharge, and same solves the technical problems of a poor cycle life and a high internal resistance of lithium-ion batteries in high temperature environments in the prior art.
Description
本发明涉及一种化学电源技术领域，尤其涉及一种锂离子电池正极及其制备方法及锂离子电池制备方法。The invention relates to the technical field of chemical power sources, in particular to a cathode of a lithium ion battery, a preparation method thereof and a preparation method of the lithium ion battery.
随着动力市场和储能市场在人们生活中的使用范围越来越广，在使用过程中，人们对电池的性能要求也越来越严格。现有的电池性能存在有如热效应差、高温充电性能差等的缺点，同时还存在特高温度条件下，电池循环寿命低、内阻高、自放电大的缺点，这些缺点严重影响了人们的使用。目前市场上锂离子电池，一方面，正极使用镍钴锰酸锂或磷酸铁锂或钴酸锂材料等正极材料中的一种或多种，使用该配方制造的电池在高温下电池循环差，内阻偏大，另一方面，由普通工艺生产的电池电子导热网络比较单一，在高温度下循环寿命低，所以改变锂离子电池配方成分，提高电池在高温环境下的循环寿命、降低内阻是很有必要的。As the power market and the energy storage market become more and more widely used in people's lives, the performance requirements of the battery are becoming more and more strict during use. The existing battery performance has the disadvantages of poor thermal effect and poor high-temperature charging performance. At the same time, there are disadvantages of low cycle life, high internal resistance and large self-discharge under extremely high temperature conditions, which seriously affect people's use. . On the one hand, lithium-ion batteries on the market, on the one hand, one or more kinds of positive electrode materials such as lithium nickel cobalt manganese oxide or lithium iron phosphate or lithium cobalt oxide materials, and batteries manufactured using the formula have poor battery cycling at high temperatures. On the other hand, the electronic heat conduction network of the battery produced by the common process is relatively simple, and the cycle life is low at high temperatures, so the composition of the lithium ion battery is changed, the cycle life of the battery in a high temperature environment is improved, and the internal resistance is lowered. It is very necessary.
发明内容Summary of the invention
本发明提供了锂离子电池正极及其制备方法及锂离子电池制备方法，其克服了背景技术中锂离子电池正极及其制备方法所存在的不足。The invention provides a positive electrode of a lithium ion battery, a preparation method thereof and a preparation method of the lithium ion battery, which overcome the deficiencies of the positive electrode of the lithium ion battery and the preparation method thereof in the background art.
本发明解决其技术问题的所采用的技术方案之一是：One of the technical solutions adopted by the present invention to solve its technical problems is:
一种锂离子电池正极，包含正极材料、PVDF、导电剂和STOBA，所述正极材料、PVDF、导电剂和STOBA的质量份数分别为95～98、0.5～0.9、0.8～1.2和0.2～0.5；所述正极材料为镍钴锰酸锂、磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种。A positive electrode of a lithium ion battery, comprising a positive electrode material, PVDF, a conductive agent and STOBA, wherein the mass fraction of the positive electrode material, PVDF, conductive agent and STOBA are 95-98, 0.5-0.9, 0.8-1.2 and 0.2-0.5, respectively The positive electrode material is at least one of lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum.
一实施例之中：所述导电剂选用super P，CNT，KS-6中的至少一种。In one embodiment, the conductive agent is at least one selected from the group consisting of super P, CNT, and KS-6.
一实施例之中：所述STOBA为高分歧寡聚物。In one embodiment: the STOBA is a high divergence oligomer.
本发明解决其技术问题的所采用的技术方案之二是：The second technical solution adopted by the present invention to solve the technical problems thereof is:
一种锂离子电池正极制备方法，包括：A method for preparing a positive electrode of a lithium ion battery, comprising:
步骤1：称取95～98质量份数的正极材料、0.5～0.9质量份数的PVDF、0.8～1.2质量份数的导电剂和0.2～0.5质量份数的STOBA；所述正极材料为镍钴锰酸锂、磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种；
Step 1: Weigh 95 to 98 parts by mass of the positive electrode material, 0.5 to 0.9 parts by mass of PVDF, 0.8 to 1.2 parts by mass of the conductive agent, and 0.2 to 0.5 parts by mass of STOBA; the positive electrode material is nickel cobalt At least one of lithium manganate, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum;
步骤2：混合步骤1称取好的材料至均匀以制得混合粉末；Step 2: mixing step 1 to weigh the good material to obtain a mixed powder;
步骤3：将步骤2制得的混合粉末加入真空搅拌机中，再加入NMP液体，并搅拌以制得正极浆料；Step 3: adding the mixed powder prepared in the step 2 to a vacuum mixer, adding a NMP liquid, and stirring to prepare a positive electrode slurry;
步骤4：将步骤3制得的正极浆料涂到正极基体上，接着滚压涂有正极浆料的正极基体，再接着对滚压后的涂有正极浆料的正极基体进行切片分条，然后在其上焊接极耳制成正极片。Step 4: The positive electrode slurry prepared in the step 3 is applied onto the positive electrode substrate, and then the positive electrode substrate coated with the positive electrode slurry is rolled, and then the rolled positive electrode substrate coated with the positive electrode slurry is sliced and sliced. A tab is then soldered thereon to form a positive electrode tab.
一实施例之中：所述步骤2中混合时间5min～15min；所述步骤3中搅拌时间2h～3h。In one embodiment, the mixing time in the step 2 is 5 min to 15 min; and the stirring time in the step 3 is 2 h to 3 h.
本发明解决其技术问题的所采用的技术方案之三是：The third technical solution adopted by the present invention to solve the technical problems thereof is:
一种锂离子电池制备方法，包括：A method for preparing a lithium ion battery, comprising:
步骤1：称取95～98质量份数的正极材料、0.5～0.9质量份数的PVDF、0.8～1.2质量份数的导电剂和0.2～0.5质量份数的STOBA；所述正极材料为镍钴锰酸锂、磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种；Step 1: Weigh 95 to 98 parts by mass of the positive electrode material, 0.5 to 0.9 parts by mass of PVDF, 0.8 to 1.2 parts by mass of the conductive agent, and 0.2 to 0.5 parts by mass of STOBA; the positive electrode material is nickel cobalt At least one of lithium manganate, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum;
步骤2：混合步骤1称取好的材料至均匀以制得混合粉末；Step 2: mixing step 1 to weigh the good material to obtain a mixed powder;
步骤3：将步骤2制得的混合粉末加入真空搅拌机中，再加入NMP液体，并搅拌以制得正极浆料；Step 3: adding the mixed powder prepared in the step 2 to a vacuum mixer, adding a NMP liquid, and stirring to prepare a positive electrode slurry;
步骤4：将步骤3制得的正极浆料涂到正极基体上，接着滚压涂有正极浆料的正极基体，再接着对滚压后的涂有正极浆料的正极基体进行切片分条，然后在其上焊接极耳制成正极片；Step 4: The positive electrode slurry prepared in the step 3 is applied onto the positive electrode substrate, and then the positive electrode substrate coated with the positive electrode slurry is rolled, and then the rolled positive electrode substrate coated with the positive electrode slurry is sliced and sliced. Then soldering the tabs thereon to form a positive electrode sheet;
步骤5：称取负极片所需的负极石墨、导电剂、粘结剂配成负极浆料，将负极浆料涂在负极基体上；Step 5: weigh the negative electrode graphite, the conductive agent, and the binder required for the negative electrode sheet to form a negative electrode slurry, and apply the negative electrode slurry to the negative electrode substrate;
步骤6：将步骤5喷涂有负极浆料的负极基体烘干并滚压、切片分条，再在其上焊接极耳制成负极片；Step 6: drying the negative electrode substrate sprayed with the negative electrode slurry in step 5, rolling, slicing and slicing, and then welding the tabs thereon to prepare a negative electrode sheet;
步骤7：步骤4制得的正极片和步骤6制得的负极片利用隔膜隔离，用自动卷绕机卷绕正极片、隔膜和负极片的整体，再将卷绕的整体装入钢壳，再对其进行滚槽，接着点焊电池盖帽及加注电解液，然后检测，制得锂离子电池。Step 7: The positive electrode sheet prepared in the step 4 and the negative electrode sheet prepared in the step 6 are separated by a separator, and the whole of the positive electrode sheet, the separator and the negative electrode sheet are wound by an automatic winding machine, and the wound whole is placed in the steel shell. Then, the groove is grooved, and then the battery cap is spot-welded and the electrolyte is filled, and then detected to obtain a lithium ion battery.
一实施例之中：所述步骤2中混合时间5min～15min；所述步骤3中搅拌时间2h～3h。In one embodiment, the mixing time in the step 2 is 5 min to 15 min; and the stirring time in the step 3 is 2 h to 3 h.
本技术方案与背景技术相比，它具有如下优点：Compared with the background art, the technical solution has the following advantages:
采用该配方制得的锂离子电池具有高温循环性能好、内阻低、自放电低的优
点，解决了现有技术中的锂离子电池在高温环境下循环寿命差，内阻高的技术问题。本发明提供的包含有上述正极配方的锂离子电池制备方法，工序简单，所制得的锂离子电池高温循环性能好。The lithium ion battery prepared by the formula has excellent high temperature cycle performance, low internal resistance and low self-discharge.
The invention solves the technical problem that the lithium ion battery in the prior art has poor cycle life and high internal resistance in a high temperature environment. The method for preparing a lithium ion battery comprising the above positive electrode formula provided by the invention has a simple process, and the obtained lithium ion battery has high temperature cycle performance.
下面结合附图和实施例对本发明作进一步说明。The invention will now be further described with reference to the accompanying drawings and embodiments.
图1是本发明一种锂离子电池的制备方法所制得的MX18650-29P 2750mAh锂离子电池与普通2750mAh锂离子电池在高温55℃循环时的曲线对比效果图；1 is a graph showing a comparison effect of a MX18650-29P 2750 mAh lithium ion battery prepared by a method for preparing a lithium ion battery of the present invention and a conventional 2750 mAh lithium ion battery at a high temperature of 55 ° C;
图2是本发明一种锂离子电池的制备方法所制得的MX18650-29P 2750mAh锂离子电池与普通2750Ah锂离子电池内阻对比图。2 is a comparison diagram of internal resistance of a MX18650-29P 2750 mAh lithium ion battery prepared by a method for preparing a lithium ion battery according to the present invention and a conventional 2750 Ah lithium ion battery.
一种锂离子电池正极，由镍钴锰酸锂、PVDF、导电剂和STOBA组成，所述镍钴锰酸锂、PVDF、导电剂和STOBA的质量份数分别为95～98、0.5～0.9、0.8～1.2和0.2～0.5。所述PVDF选用聚偏氟乙烯，所述STOBA选用高分歧寡聚物，所述导电剂选用super P，CNT，KS-6中的至少一种。采用该配方制得的锂离子电池具有高温循环性能好、内阻低、自放电低的优点。该正极配方可应用于以下但不限于：圆柱形锂离子电池、方形锂离子电池、软包锂离子电池等各种装配类型的锂离子电池。The positive electrode of a lithium ion battery is composed of lithium nickel cobalt manganese oxide, PVDF, a conductive agent and STOBA, and the mass fraction of the lithium nickel cobalt manganate, PVDF, conductive agent and STOBA are 95-98, 0.5-0.9, respectively. 0.8 to 1.2 and 0.2 to 0.5. The PVDF is selected from polyvinylidene fluoride, and the STOBA is selected from a high-dividing oligomer, and the conductive agent is at least one selected from the group consisting of super P, CNT and KS-6. The lithium ion battery prepared by the formula has the advantages of high temperature cycle performance, low internal resistance and low self-discharge. The positive electrode formulation can be applied to the following, but not limited to, lithium ion batteries of various assembly types such as a cylindrical lithium ion battery, a square lithium ion battery, and a soft lithium ion battery.
一种锂离子电池正极的制备方法，包括：A method for preparing a positive electrode of a lithium ion battery, comprising:
步骤1：称取锂离子电池正极的各原料，并将称取的各原料过100目筛后备用；Step 1: Weigh each raw material of the positive electrode of the lithium ion battery, and pass the weighed raw materials through a 100 mesh sieve for use;
步骤2：将步骤1筛后的各原料投入V型混合机混合至均匀以制得混合粉末，其中：混合时间5min～15min，混合至保证肉眼看不见STOBA和PVDF组分；Step 2: The raw materials sieved in step 1 are put into a V-type mixer and mixed until uniform to prepare a mixed powder, wherein: mixing time is 5 min to 15 min, and mixing is performed to ensure that the STOBA and PVDF components are invisible to the naked eye;
步骤3：将步骤2制得的混合粉末加入真空搅拌机中，再加入NMP液体，启动公转开关和自转开关进行搅拌以制得正极浆料，其中：搅拌时间2h～3h，所述的NMP液体为N–甲基吡咯烷酮；Step 3: adding the mixed powder prepared in the step 2 to a vacuum mixer, adding a NMP liquid, starting a revolution switch and a rotation switch to stir to obtain a positive electrode slurry, wherein: the stirring time is 2 h to 3 h, and the NMP liquid is N-methylpyrrolidone;
步骤4：将步骤3制得的正极浆料喷涂到正极用的正极基体(所述正极基体如集流体或铝箔)上，接着滚压喷涂正极浆料的正极基体，对滚压后的喷涂正极浆料的正极基体进行切片分条，再在其上焊接极耳以制成正极片。本发明的包含有上述正极配方的锂离子电池正极的制备方法，工序简单，所制得的锂离子电池高温循环性能好。Step 4: spraying the positive electrode slurry prepared in the step 3 onto the positive electrode substrate for the positive electrode (the positive electrode substrate such as a current collector or an aluminum foil), and then rolling the positive electrode substrate of the positive electrode slurry, and spraying the positive electrode after rolling The positive electrode substrate of the slurry was sliced and stripped, and the tabs were welded thereon to form a positive electrode sheet. The preparation method of the positive electrode for a lithium ion battery comprising the above positive electrode formula of the invention has a simple process, and the obtained lithium ion battery has high temperature cycle performance.
一种锂离子电池的制备方法，包括：
A method for preparing a lithium ion battery, comprising:
步骤1：称取锂离子电池正极的各原料，并将称取的各原料过100目筛后备用；Step 1: Weigh each raw material of the positive electrode of the lithium ion battery, and pass the weighed raw materials through a 100 mesh sieve for use;
步骤2：将步骤1筛后的各原料投入V型混合机混合至均匀以制得混合粉末，其中：混合时间5min～15min，混合至保证肉眼看不见STOBA和PVDF组分；Step 2: The raw materials sieved in step 1 are put into a V-type mixer and mixed until uniform to prepare a mixed powder, wherein: mixing time is 5 min to 15 min, and mixing is performed to ensure that the STOBA and PVDF components are invisible to the naked eye;
步骤3：将步骤2制得的混合粉末加入真空搅拌机中，再加入NMP液体，启动公转开关和自转开关进行搅拌以制得正极浆料，其中：搅拌时间2h～3h；Step 3: The mixed powder prepared in the step 2 is added to a vacuum mixer, and then the NMP liquid is added, and the revolution switch and the autorotation switch are started to stir to obtain a positive electrode slurry, wherein: the stirring time is 2 h to 3 h;
步骤4：将步骤3制得的正极浆料喷涂到正极用的正极基体(所述正极基体如集流体或铝箔)上，接着滚压喷涂正极浆料的正极基体，对滚压后的喷涂正极浆料的正极基体进行切片分条，再在其上焊接极耳以制成正极片；Step 4: spraying the positive electrode slurry prepared in the step 3 onto the positive electrode substrate for the positive electrode (the positive electrode substrate such as a current collector or an aluminum foil), and then rolling the positive electrode substrate of the positive electrode slurry, and spraying the positive electrode after rolling The positive electrode substrate of the slurry is sliced and stripped, and the tab is welded thereon to form a positive electrode sheet;
步骤5：称取负极片所需的负极石墨、导电剂和粘结剂配成负极浆料，将负极浆料喷涂在负极的负极基体上(负极基体如选用集流体或铜箔)；Step 5: Weigh the negative electrode graphite, the conductive agent and the binder required for the negative electrode sheet into a negative electrode slurry, and spray the negative electrode slurry on the negative electrode substrate of the negative electrode (such as a current collector or a copper foil for the negative electrode substrate);
步骤6：将步骤5喷涂有负极浆料的负极基体烘干并滚压，滚压后进行切片分条，再在其上焊接极耳以制成负极片；Step 6: drying and pressing the negative electrode substrate sprayed with the negative electrode slurry in step 5, rolling and then slicing and stripping, and then welding the tabs thereon to prepare a negative electrode sheet;
步骤7：步骤4制得的正极片和步骤6制得的负极片利用隔膜隔离，用自动卷绕机卷绕正极片、隔膜和负极片的整体，再将卷绕的整体装入钢壳，再对其进行滚槽，接着点焊电池盖帽及加注电解液，然后检测，最终制得圆柱形锂离子电池。本发明的包含有上述正极配方的锂离子电池的制备方法，工序简单，所制得的锂离子电池高温循环性能好。Step 7: The positive electrode sheet prepared in the step 4 and the negative electrode sheet prepared in the step 6 are separated by a separator, and the whole of the positive electrode sheet, the separator and the negative electrode sheet are wound by an automatic winding machine, and the wound whole is placed in the steel shell. Then, it is grooved, and then the battery cap is spot-welded and the electrolyte is filled, and then tested, and finally a cylindrical lithium ion battery is obtained. The preparation method of the lithium ion battery comprising the above positive electrode formula of the invention has a simple process, and the obtained lithium ion battery has high temperature cycle performance.
如图1所示，按照上述配方制得的正极和普通的正极进行对比，测试两种正极的锂离子电池分别在高温55℃相同的测试条件下(以0.2C放电至2.5V，0.5C充电至4.2V恒压，截止电流0.05C)进行循环测试的效果对比，由图1得知：普通正极的锂离子电池循环寿命500次≥85.90％，本发明的正极的锂离子电池循环寿命500次≥94.24％，所以采用本发明正极的锂离子电池在高温(55℃)条件下循环性能明显高于普通锂离子电池的循环性能。As shown in Fig. 1, the positive electrode prepared according to the above formula is compared with a common positive electrode, and the lithium ion batteries of the two positive electrodes are tested under the same test conditions at a high temperature of 55 ° C (discharge at 0.2 C to 2.5 V, 0.5 C charge). To 4.2V constant voltage, off-current 0.05C) The effect of cycle test is compared. It can be seen from Fig. 1 that the cycle life of lithium ion battery of ordinary positive electrode is 500 times ≥85.90%, and the cycle life of lithium ion battery of positive electrode of the invention is 500 times. ≥94.24%, so the cycle performance of the lithium ion battery using the positive electrode of the invention at high temperature (55 ° C) is significantly higher than that of the ordinary lithium ion battery.
如图2所示，将普通锂离子电池和本发明的锂离子电池在循环过程中的内阻上升做对比，由图2得知：本发明的锂离子电池内阻上升幅度小于普通锂离子电池内阻的上升幅度。而电池内阻大，会产生大量焦耳热引起电池温度升高，导致电池放电工作电压降低，放电时间缩短，对电池性能、寿命等造成严重影响。As shown in FIG. 2, comparing the internal resistance of the ordinary lithium ion battery and the lithium ion battery of the present invention during the cycle, it is known from FIG. 2 that the internal resistance of the lithium ion battery of the present invention rises less than that of the ordinary lithium ion battery. The increase in internal resistance. The internal resistance of the battery is large, which will cause a large amount of Joule heat to cause the battery temperature to rise, resulting in a decrease in the discharge voltage of the battery, a shortened discharge time, and a serious impact on battery performance and life.
实施例一 Embodiment 1
按照质量百分比分别称取正极的如下组分：97.5％的镍钴锰酸锂，0.9％的PVDF，1.2％的导电剂，0.4％的STOBA，以上组分的质量百分比总和是100％，并
将称取正极材料过100目筛后备用，将上述物料加入V型混合机内混合5min，后加入到真空搅拌机中再加入NMP胶液，搅拌时间2.5h，将搅拌好的正极浆料喷涂到正极基体上，辊压、分条，焊接极耳成正极片；称取负极片所需的负极石墨、导电剂、粘结剂配成负极浆料，将负极浆料喷涂在负极基体上；制备好的正极片、制备好的负极片、隔膜用自动卷绕机隔膜进行卷绕、装入钢壳，再进行滚槽、点焊电池盖帽、加注电解液、化成检测，最终制得锂离子电池。The following components of the positive electrode were weighed according to the mass percentage: 97.5% lithium nickel cobalt manganese oxide, 0.9% PVDF, 1.2% conductive agent, 0.4% STOBA, and the total mass percentage of the above components was 100%, and
The positive electrode material is weighed through a 100 mesh sieve and then used. The above materials are added to a V-type mixer for 5 minutes, and then added to a vacuum mixer and then NMP glue is added. The stirring time is 2.5 hours, and the stirred positive electrode slurry is sprayed to On the positive electrode substrate, rolling, slitting, welding the tab into a positive electrode sheet; weighing the negative electrode graphite, the conductive agent and the binder required for the negative electrode sheet into a negative electrode slurry, and spraying the negative electrode slurry on the negative electrode substrate; A good positive electrode sheet, a prepared negative electrode sheet, and a separator are wound by an automatic winding machine diaphragm, and are placed in a steel shell, and then subjected to rolling grooves, spot welding battery caps, filling of an electrolyte, and formation detection, thereby finally producing lithium ions. battery.
实施例二 Embodiment 2
按照质量百分比分别称取正极的如下组分：98％的镍钴锰酸锂，0.8％的PVDF，0.9％的导电剂，0.3％的STOBA，以上组分的质量百分比总和是100％，并将称取正极材料过100目筛后备用，将上述物料加入V型混合机内混合5min，后加入到真空搅拌机中再加入胶液，搅拌时间2h，将搅拌好的正极浆料喷涂到正极基体上，辊压、分条，焊接极耳成正极片；称取负极片所需的负极石墨、导电剂、粘结剂配成负极浆料，将负极浆料喷涂在负极基体上；制备好的正极片、制备好的负极片、隔膜用自动卷绕机隔膜进行卷绕、装入钢壳，再进行滚槽、点焊电池盖帽、加注电解液、化成检测，最终制得锂离子电池。The following components of the positive electrode were weighed according to the mass percentage: 98% lithium nickel cobalt manganese oxide, 0.8% PVDF, 0.9% conductive agent, 0.3% STOBA, and the total mass percentage of the above components was 100%, and Weigh the positive electrode material through a 100 mesh sieve and set aside. Add the above materials to the V-type mixer for 5 minutes, then add to the vacuum mixer and add the glue. Stir the time for 2 hours, spray the stirred positive electrode slurry onto the positive electrode substrate. Rolling, slitting, welding the tab into a positive electrode sheet; weighing the negative electrode graphite, conductive agent and binder required for the negative electrode sheet into a negative electrode slurry, spraying the negative electrode slurry on the negative electrode substrate; preparing the positive electrode The sheet, the prepared negative electrode sheet, and the separator are wound by an automatic winder diaphragm, and are placed in a steel shell, and then rolled, spot welded, sealed, filled with an electrolyte, and chemically detected, and finally a lithium ion battery is obtained.
实施例三 Embodiment 3
按照质量百分比分别称取正极的如下组分：98.5％的镍钴锰酸锂，0.4％的PVDF，0.8％的导电剂，0.3％的STOBA，以上组分的质量百分比总和是100％，并将称取正极材料过100目筛后备用，将上述物料加入V型混合机内混合5min，后加入到真空搅拌机中再加入胶液，搅拌时间2.5h，将搅拌好的正极浆料喷涂到正极基体上，辊压、分条，焊接极耳成正极片；称取负极片所需的负极石墨、导电剂、粘结剂配成负极浆料，将负极浆料喷涂在负极基体上；制备好的正极片、制备好的负极片、隔膜用自动卷绕机隔膜进行卷绕、装入钢壳，再进行滚槽、点焊电池盖帽、加注电解液、化成检测，最终制得锂离子电池。The following components of the positive electrode were weighed according to the mass percentage: 98.5% lithium nickel cobalt manganese oxide, 0.4% PVDF, 0.8% conductive agent, 0.3% STOBA, and the total mass percentage of the above components was 100%, and After weighing the positive electrode material through a 100 mesh sieve, the above materials are added to a V-type mixer for 5 minutes, and then added to a vacuum mixer and then added with a glue solution. The stirring time is 2.5 hours, and the stirred positive electrode slurry is sprayed onto the positive electrode substrate. Upper, rolling, slitting, welding the tab into a positive electrode sheet; weighing the negative electrode graphite, conductive agent, and binder required for the negative electrode sheet into a negative electrode slurry, and spraying the negative electrode slurry on the negative electrode substrate; The positive electrode sheet, the prepared negative electrode sheet, and the separator are wound by an automatic winder diaphragm, and are placed in a steel shell, and then rolled, spot welded, sealed, filled with an electrolyte, and chemically detected to obtain a lithium ion battery.
实施例四Embodiment 4
按照质量百分比分别称取正极的如下组分：98％的镍钴锰酸锂，0.9％的PVDF，0.9％的导电剂，0.4％的STOBA，以上组分的质量百分比总和是100％，并将称取正极材料过100目筛后备用，将上述物料加入V型混合机内混合5min，后加入到真空搅拌机中再加入胶液，搅拌时间2.5h，将搅拌好的正极浆料喷涂到正极基体上，辊压、分条，焊接极耳成正极片；称取负极片所需的负极石墨、导电剂、粘
结剂配成负极浆料，将负极浆料喷涂在负极基体上；制备好的正极片、制备好的负极片、隔膜用自动卷绕机隔膜进行卷绕、装入钢壳，再进行滚槽、点焊电池盖帽、加注电解液、化成检测，最终制得锂离子电池。The following components of the positive electrode were weighed according to the mass percentage: 98% lithium nickel cobalt manganese oxide, 0.9% PVDF, 0.9% conductive agent, 0.4% STOBA, and the total mass percentage of the above components was 100%, and After weighing the positive electrode material through a 100 mesh sieve, the above materials are added to a V-type mixer for 5 minutes, and then added to a vacuum mixer and then added with a glue solution. The stirring time is 2.5 hours, and the stirred positive electrode slurry is sprayed onto the positive electrode substrate. On the top, rolling, slitting, welding the ear into a positive electrode; weighing the negative graphite required for the negative electrode, conductive agent, sticky
The agent is formulated into a negative electrode slurry, and the negative electrode slurry is sprayed on the negative electrode substrate; the prepared positive electrode sheet, the prepared negative electrode sheet, and the separator are wound by an automatic winder diaphragm, loaded into a steel shell, and then rolled into a groove. The spot welding battery cap, the filling electrolyte, the formation test, and finally the lithium ion battery.
正极材料可以选用镍钴锰酸锂，还可以选用磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种。As the positive electrode material, lithium nickel cobalt manganese oxide may be used, and at least one of lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum may be used.
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。The above is only the preferred embodiment of the present invention, and thus the scope of the present invention is not limited thereto, that is, equivalent changes and modifications made in accordance with the scope of the invention and the contents of the specification should still be covered by the present invention. Within the scope.
本发明一种锂离子电池正极及其制备方法及锂离子电池制备方法，其锂离子电池正极，包含正极材料、PVDF、导电剂和STOBA，该锂离子电池具有高温循环性能好、内阻低、自放电低的优点，解决了现有技术中的锂离子电池在高温环境下循环寿命差，内阻高的技术问题。
The invention provides a positive electrode of a lithium ion battery, a preparation method thereof and a preparation method of the lithium ion battery, wherein the positive electrode of the lithium ion battery comprises a positive electrode material, a PVDF, a conductive agent and a STOBA, and the lithium ion battery has high temperature cycle performance and low internal resistance. The advantage of low self-discharge solves the technical problem that the lithium ion battery in the prior art has poor cycle life and high internal resistance in a high temperature environment.
Claims (9)
- 一种锂离子电池正极，其特征在于：包含正极材料、PVDF、导电剂和STOBA，所述正极材料、PVDF、导电剂和STOBA的质量份数分别为95～98.5、0.4～0.9、0.8～1.2和0.2～0.5；所述正极材料为镍钴锰酸锂、磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种。A positive electrode of a lithium ion battery, comprising: a positive electrode material, PVDF, a conductive agent and STOBA, wherein the mass fraction of the positive electrode material, PVDF, conductive agent and STOBA are 95-98.5, 0.4-0.9, 0.8-1.2, respectively And 0.2 to 0.5; the positive electrode material is at least one of lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum.
- 权利要求1所述的一种锂离子电池正极，其特征在于：所述导电剂选用super P，CNT，KS-6中的至少一种。A positive electrode for a lithium ion battery according to claim 1, wherein said conductive agent is at least one selected from the group consisting of super P, CNT, and KS-6.
- 权利要求1所述的一种锂离子电池正极，其特征在于：所述STOBA为高分歧寡聚物。A positive electrode for a lithium ion battery according to claim 1, wherein said STOBA is a high-dividing oligomer.
- 一种锂离子电池正极制备方法，其特征在于：包括：A method for preparing a positive electrode of a lithium ion battery, comprising:步骤1：称取95～98质量份数的正极材料、0.5～0.9质量份数的PVDF、0.8～1.2质量份数的导电剂和0.2～0.5质量份数的STOBA；所述正极材料为镍钴锰酸锂、磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种；Step 1: Weigh 95 to 98 parts by mass of the positive electrode material, 0.5 to 0.9 parts by mass of PVDF, 0.8 to 1.2 parts by mass of the conductive agent, and 0.2 to 0.5 parts by mass of STOBA; the positive electrode material is nickel cobalt At least one of lithium manganate, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum;步骤2：混合步骤1称取好的材料至均匀以制得混合粉末；Step 2: mixing step 1 to weigh the good material to obtain a mixed powder;步骤3：将步骤2制得的混合粉末加入真空搅拌机中，再加入NMP液体，并搅拌以制得正极浆料；Step 3: adding the mixed powder prepared in the step 2 to a vacuum mixer, adding a NMP liquid, and stirring to prepare a positive electrode slurry;步骤4：将步骤3制得的正极浆料涂到正极基体上，接着滚压涂有正极浆料的正极基体，再接着对滚压后的涂有正极浆料的正极基体进行切片分条，然后在其上焊接极耳制成正极片。Step 4: The positive electrode slurry prepared in the step 3 is applied onto the positive electrode substrate, and then the positive electrode substrate coated with the positive electrode slurry is rolled, and then the rolled positive electrode substrate coated with the positive electrode slurry is sliced and sliced. A tab is then soldered thereon to form a positive electrode tab.
- 根据权利要求4所述的一种锂离子电池正极制备方法，其特征在于：所述步骤2中混合时间5min～15min；所述步骤3中搅拌时间2h～3h。The method for preparing a positive electrode of a lithium ion battery according to claim 4, wherein the mixing time in the step 2 is 5 min to 15 min; and the stirring time in the step 3 is 2 h to 3 h.
- 根据权利要求4所述的一种锂离子电池正极制备方法，其特征在于：所述导电剂选用super P，CNT，KS-6中的至少一种。The method for preparing a positive electrode of a lithium ion battery according to claim 4, wherein the conductive agent is at least one selected from the group consisting of super P, CNT, and KS-6.
- 一种锂离子电池制备方法，其特征在于：包括：A method for preparing a lithium ion battery, comprising:步骤1：称取95～98质量份数的正极材料、0.5～0.9质量份数的PVDF、0.8～1.2质量份数的导电剂和0.2～0.5质量份数的STOBA；所述正极材料为镍钴锰酸锂、磷酸铁锂、锰酸锂、磷酸钒锂、镍钴铝中的至少一种；Step 1: Weigh 95 to 98 parts by mass of the positive electrode material, 0.5 to 0.9 parts by mass of PVDF, 0.8 to 1.2 parts by mass of the conductive agent, and 0.2 to 0.5 parts by mass of STOBA; the positive electrode material is nickel cobalt At least one of lithium manganate, lithium iron phosphate, lithium manganate, lithium vanadium phosphate, and nickel cobalt aluminum;步骤2：混合步骤1称取好的材料至均匀以制得混合粉末；Step 2: mixing step 1 to weigh the good material to obtain a mixed powder;步骤3：将步骤2制得的混合粉末加入真空搅拌机中，再加入NMP液体，并 搅拌以制得正极浆料；Step 3: Add the mixed powder prepared in step 2 to a vacuum mixer, and then add NMP liquid, and Stirring to prepare a positive electrode slurry;步骤4：将步骤3制得的正极浆料涂到正极基体上，接着滚压涂有正极浆料的正极基体，再接着对滚压后的涂有正极浆料的正极基体进行切片分条，然后在其上焊接极耳制成正极片；Step 4: The positive electrode slurry prepared in the step 3 is applied onto the positive electrode substrate, and then the positive electrode substrate coated with the positive electrode slurry is rolled, and then the rolled positive electrode substrate coated with the positive electrode slurry is sliced and sliced. Then soldering the tabs thereon to form a positive electrode sheet;步骤5：称取负极片所需的负极石墨、导电剂、粘结剂配成负极浆料，将负极浆料涂在负极基体上；Step 5: weigh the negative electrode graphite, the conductive agent, and the binder required for the negative electrode sheet to form a negative electrode slurry, and apply the negative electrode slurry to the negative electrode substrate;步骤6：将步骤5喷涂有负极浆料的负极基体烘干并滚压、切片分条，再在其上焊接极耳制成负极片；Step 6: drying the negative electrode substrate sprayed with the negative electrode slurry in step 5, rolling, slicing and slicing, and then welding the tabs thereon to prepare a negative electrode sheet;步骤7：步骤4制得的正极片和步骤6制得的负极片利用隔膜隔离，用自动卷绕机卷绕正极片、隔膜和负极片的整体，再将卷绕的整体装入钢壳，再对其进行滚槽，接着点焊电池盖帽及加注电解液，然后检测，制得锂离子电池。Step 7: The positive electrode sheet prepared in the step 4 and the negative electrode sheet prepared in the step 6 are separated by a separator, and the whole of the positive electrode sheet, the separator and the negative electrode sheet are wound by an automatic winding machine, and the wound whole is placed in the steel shell. Then, the groove is grooved, and then the battery cap is spot-welded and the electrolyte is filled, and then detected to obtain a lithium ion battery.
- 根据权利要求7所述的一种锂离子电池制备方法，其特征在于：所述步骤2中混合时间5min～15min；所述步骤3中搅拌时间2h～3h。The method for preparing a lithium ion battery according to claim 7, wherein the mixing time in the step 2 is 5 min to 15 min; and the stirring time in the step 3 is 2 h to 3 h.
- 根据权利要求7所述的一种锂离子电池制备方法，其特征在于：所述导电剂选用super P，CNT，KS-6中的至少一种。 The method for preparing a lithium ion battery according to claim 7, wherein the conductive agent is at least one selected from the group consisting of super P, CNT, and KS-6.
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| CN106299485A (en) * | 2016-10-19 | 2017-01-04 | 江苏海四达电源股份有限公司 | High specific energy lithium-ion-power cell and preparation method thereof |
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- 2017-12-19 WO PCT/CN2017/117156 patent/WO2019000861A1/en active Application Filing
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| TW200828658A (en) * | 2006-12-29 | 2008-07-01 | Ind Tech Res Inst | A battery electrode paste composition containing modified maleimides |
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