CN109786854B - A kind of fast charging lithium ion battery and preparation method thereof - Google Patents
A kind of fast charging lithium ion battery and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract 9
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract 9
- 238000002360 preparation method Methods 0.000 title claims abstract 5
- 239000011248 coating agent Substances 0.000 claims abstract 10
- 238000000576 coating method Methods 0.000 claims abstract 10
- 239000004020 conductor Substances 0.000 claims abstract 9
- 239000002002 slurry Substances 0.000 claims abstract 6
- 239000000203 mixture Substances 0.000 claims abstract 4
- 239000003792 electrolyte Substances 0.000 claims abstract 3
- 239000002905 metal composite material Substances 0.000 claims abstract 3
- 238000002156 mixing Methods 0.000 claims abstract 2
- 239000011265 semifinished product Substances 0.000 claims abstract 2
- 238000003466 welding Methods 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 9
- 229910052799 carbon Inorganic materials 0.000 claims 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 3
- 239000002041 carbon nanotube Substances 0.000 claims 3
- 239000003575 carbonaceous material Substances 0.000 claims 3
- 239000002270 dispersing agent Substances 0.000 claims 3
- 239000007773 negative electrode material Substances 0.000 claims 3
- 239000007774 positive electrode material Substances 0.000 claims 3
- 239000000565 sealant Substances 0.000 claims 3
- 239000006229 carbon black Substances 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 2
- 229910021389 graphene Inorganic materials 0.000 claims 2
- 238000002347 injection Methods 0.000 claims 2
- 239000007924 injection Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 229920000058 polyacrylate Polymers 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229920002125 Sokalan® Polymers 0.000 claims 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical group [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000007772 electrode material Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 1
- 239000004005 microsphere Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 229910021384 soft carbon Inorganic materials 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
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- 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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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
Description
技术领域technical field
本发明涉及一种锂离子电池,特别涉及一种快充锂离子电池及其制备方法。The invention relates to a lithium ion battery, in particular to a fast charge lithium ion battery and a preparation method thereof.
背景技术Background technique
锂离子电池是一种二次电池,它主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中,Li+在两个电极之间往返嵌入和脱嵌:充电时,Li+从正极脱嵌,经过电解质嵌入负极,负极处于富锂状态;放电时则相反。A lithium-ion battery is a secondary battery that mainly relies on the movement of lithium ions between the positive and negative electrodes to work. During the charging and discharging process, Li + intercalates and deintercalates back and forth between the two electrodes: during charging, Li+ is deintercalated from the positive electrode, intercalated into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; during discharge, the opposite is true.
传统锂离子电池的优点是能量密度高,但是为了提高续航里程,用电器设计的电池容量比较高时就会面临充电时间长的问题。充电是电池重复使用的重要步骤,锂离子电池的充电过程分为两个阶段:恒流快充阶段和恒压电流递减阶段。恒流快充阶段,电池电压逐步升高到电池的标准电压,随后在控制芯片下转入恒压阶段,电压不再升高以确保不会过充,电流则随着电池电量的上升逐步减弱到设定的值,而最终完成充电。The advantage of traditional lithium-ion batteries is high energy density, but in order to improve the cruising range, when the battery capacity of the electrical appliance is relatively high, it will face the problem of long charging time. Charging is an important step for battery reuse. The charging process of lithium-ion batteries is divided into two stages: constant current fast charging stage and constant voltage current decreasing stage. In the constant current fast charging stage, the battery voltage gradually increases to the standard voltage of the battery, and then switches to the constant voltage stage under the control chip, the voltage does not increase to ensure that it will not be overcharged, and the current gradually decreases as the battery power increases. to the set value, and finally complete the charging.
一般而言,目前高容量的锂离子电池充电时间达2~5小时,甚至更高,用户体验好感度下降。所以说,如何制备一种可以实现快充的锂离子电池成为了行内工作者关注的热点问题。Generally speaking, the charging time of current high-capacity lithium-ion batteries is 2 to 5 hours, or even higher, and the user experience is less favorable. Therefore, how to prepare a lithium-ion battery that can achieve fast charging has become a hot issue for industry workers.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术存在的问题,本发明的目的在于提供一种快充锂离子电池及其制备方法。In order to overcome the problems existing in the prior art, the purpose of the present invention is to provide a fast-charging lithium-ion battery and a preparation method thereof.
本发明所采取的技术方案是:The technical scheme adopted by the present invention is:
一种快充锂离子电池的制备方法,包括以下步骤:A preparation method of a fast-charging lithium-ion battery, comprising the following steps:
1)将正极活性物质和负极活性物质分别进行碳包覆处理,得到正极导电材料和负极导电材料;1) carbon coating treatment is performed on the positive electrode active material and the negative electrode active material, respectively, to obtain a positive electrode conductive material and a negative electrode conductive material;
2)将石墨烯、超导电炭黑、碳纳米管、分散剂和溶剂混合,得到导电浆液;2) mixing graphene, superconducting carbon black, carbon nanotubes, dispersant and solvent to obtain conductive slurry;
3)将导电浆液与正极导电材料混合,所得的正极涂料涂覆在正极基材上,得到正极片;将导电浆液与负极导电材料混合,所得的负极涂料涂覆在负极基材上,得到负极片;正极片和负极片的涂层边缘分别预留空白;3) mixing the conductive slurry with the positive electrode conductive material, and the obtained positive electrode coating is coated on the positive electrode substrate to obtain a positive electrode sheet; the conductive slurry is mixed with the negative electrode conductive material, and the obtained negative electrode coating is coated on the negative electrode substrate to obtain a negative electrode sheet; the coating edges of the positive sheet and the negative sheet are left blank respectively;
4)分别切割正极片和负极片的预留空白,形成电极连接片;4) Cut the reserved blanks of the positive electrode sheet and the negative electrode sheet respectively to form the electrode connecting sheet;
5)将切割后的正极片、负极片和隔膜卷成方形电芯,电极连接片分别在垂直于电极长度方向叠层式引出;5) Roll the cut positive electrode sheet, negative electrode sheet and separator into a square cell, and the electrode connecting sheets are respectively drawn out in a stacked manner perpendicular to the length of the electrode;
6)分别将正电极和负电极引出的连接片与带密封胶的金属复合片焊接;6) Weld the connecting piece drawn from the positive electrode and the negative electrode to the metal composite piece with sealant;
7)裁切焊接后多余的连接片;7) Cut the excess connecting piece after welding;
8)将连接片以垂直于电芯横截面的方向弯折成型;8) Bend the connecting piece in a direction perpendicular to the cross section of the cell;
9)对电芯外露的连接片贴胶保护,得到电芯半成品;9) Protect the exposed connecting piece of the cell with glue to obtain the semi-finished product of the cell;
10)将电芯半成品进行顶侧封边,并预留注液侧边;10) Seal the top side of the semi-finished battery cell, and reserve the liquid injection side;
11)将封边后的电芯进行烘烤,然后注入电解液,分容,得到快充锂离子电池。11) Bake the edge-sealed battery cells, then inject electrolyte, and divide the capacity to obtain a fast-charging lithium-ion battery.
优选的,这种快充锂离子电池的制备方法步骤1)中,碳包覆处理的方法具体是:将正极活性物质或者负极活性物质分别浸泡到碳材料的分散液中,通过混合浸渍包覆处理,获得表面包覆的正极或负极复合电极材料,再通过喷雾干燥造粒,得到正极或负极导电材料。Preferably, in step 1) of the preparation method of the fast-charging lithium ion battery, the carbon coating treatment method is specifically: soaking the positive electrode active material or the negative electrode active material in the dispersion liquid of the carbon material respectively, and coating by mixing and dipping. treatment to obtain a positive electrode or a negative electrode composite electrode material coated on the surface, and then spray drying and granulation to obtain a positive electrode or a negative electrode conductive material.
优选的,这种快充锂离子电池的制备方法步骤1)中,活性物质(正极或负极)与碳包覆所用的碳材料质量比为1:(0.05~0.3)。Preferably, in step 1) of the preparation method of the fast-charging lithium ion battery, the mass ratio of the active material (positive electrode or negative electrode) to the carbon material used for carbon coating is 1:(0.05-0.3).
优选的,这种快充锂离子电池的制备方法步骤1)中,正极活性物质为钴酸锂(LCO)、锰酸锂(LMO)、磷酸铁锂(LFP)、镍钴锰酸锂(NCM)中的至少一种。Preferably, in step 1) of the preparation method of the fast-charging lithium-ion battery, the positive active material is lithium cobalt oxide (LCO), lithium manganate (LMO), lithium iron phosphate (LFP), nickel cobalt lithium manganate (NCM) ) at least one of them.
优选的,这种快充锂离子电池的制备方法步骤1)中,负极活性物质为两亲性炭材料(ACM)、中间相碳微球(MCMB)中的至少一种;进一步优选的,负极活性物质为中间相碳微球。Preferably, in step 1) of the preparation method of the fast-charging lithium ion battery, the negative electrode active material is at least one of amphiphilic carbon material (ACM) and mesocarbon microspheres (MCMB); further preferably, the negative electrode The active material is mesocarbon microspheres.
优选的,这种快充锂离子电池的制备方法步骤1)中,碳材料在分散液中的质量浓度为1%~10%。Preferably, in step 1) of the preparation method of the fast-charging lithium ion battery, the mass concentration of the carbon material in the dispersion liquid is 1% to 10%.
优选的,这种快充锂离子电池的制备方法步骤1)中,碳材料为碳纳米管、碳纤维、碳球、软碳中的至少一种。Preferably, in step 1) of the preparation method of the fast-charging lithium ion battery, the carbon material is at least one of carbon nanotubes, carbon fibers, carbon balls, and soft carbon.
优选的,这种快充锂离子电池的制备方法步骤1)中,碳材料的分散液可为碳材料的醇溶液、酮溶液或酰胺溶液。Preferably, in step 1) of the preparation method of the fast-charging lithium ion battery, the dispersion liquid of the carbon material may be an alcohol solution, a ketone solution or an amide solution of the carbon material.
优选的,这种快充锂离子电池的制备方法步骤2)中,石墨烯、超导电炭黑、碳纳米管、分散剂和溶剂的质量比为(0.5~1):(0.5~2):(0.5~1):(0.5~1):100。Preferably, in step 2) of the preparation method of the fast-charging lithium ion battery, the mass ratio of graphene, superconducting carbon black, carbon nanotubes, dispersant and solvent is (0.5-1): (0.5-2): (0.5 to 1): (0.5 to 1): 100.
优选的,这种快充锂离子电池的制备方法步骤2)中,分散剂为聚乙烯吡咯烷酮、聚乙二醇、聚丙烯酸、聚丙烯酸酯中的至少一种。Preferably, in step 2) of the preparation method of the fast-charging lithium ion battery, the dispersant is at least one of polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid, and polyacrylate.
优选的,这种快充锂离子电池的制备方法步骤2)中,溶剂为N-甲基吡咯烷酮(NMP)、碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)中的至少一种。Preferably, in step 2) of the preparation method of the fast-charging lithium ion battery, the solvent is N-methylpyrrolidone (NMP), propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC) , at least one of diethyl carbonate (DEC) and ethyl methyl carbonate (EMC).
优选的,这种快充锂离子电池的制备方法步骤3)中,导电浆液的用量分别占正极导电材料或负极导电材料的总质量3%~20%。Preferably, in step 3) of the preparation method of the fast-charging lithium ion battery, the amount of the conductive slurry used accounts for 3% to 20% of the total mass of the positive electrode conductive material or the negative electrode conductive material, respectively.
优选的,这种快充锂离子电池的制备方法步骤3)中,在正极基材或负极基材上预涂覆导电层后,再涂覆正极涂料或负极涂料;导电层的厚度为0.5μm~3μm,导电层为石墨烯、超导电炭黑、碳纳米管、科琴黑、碳纤维、碳微球中的至少两种组成的复合物。Preferably, in step 3) of the preparation method of the fast-charging lithium ion battery, after pre-coating a conductive layer on the positive electrode substrate or the negative electrode substrate, the positive electrode coating or the negative electrode coating is applied; the thickness of the conductive layer is 0.5 μm ~3 μm, and the conductive layer is a composite composed of at least two of graphene, superconducting carbon black, carbon nanotubes, Ketjen black, carbon fiber, and carbon microspheres.
优选的,这种快充锂离子电池的制备方法步骤3)中,正极基材厚度为10μm~30μm,正极基材的材质优选为铝。Preferably, in step 3) of the preparation method of the fast-charging lithium ion battery, the thickness of the positive electrode substrate is 10 μm˜30 μm, and the material of the positive electrode substrate is preferably aluminum.
优选的,这种快充锂离子电池的制备方法步骤3)中,负极基材厚度为5μm~20μm,负极基材的材质优选为铜。Preferably, in step 3) of the preparation method of the fast-charging lithium ion battery, the thickness of the negative electrode substrate is 5 μm˜20 μm, and the material of the negative electrode substrate is preferably copper.
优选的,这种快充锂离子电池的制备方法步骤3)中,正极片或负极片的涂层厚度分别为70μm~150μm,涂层边缘预留长度为10mm~30mm空白。Preferably, in step 3) of the preparation method of the fast-charging lithium ion battery, the coating thickness of the positive electrode sheet or the negative electrode sheet is respectively 70 μm~150 μm, and the reserved length of the coating edge is 10 mm~30 mm blank.
优选的,这种快充锂离子电池的制备方法步骤4)中,电极连接片的长度为10mm~15mm。Preferably, in step 4) of the preparation method of the fast-charging lithium ion battery, the length of the electrode connecting sheet is 10 mm˜15 mm.
优选的,这种快充锂离子电池的制备方法步骤5)中,隔膜为孔隙率是45%~65%,透气率≤200s的聚乙烯隔膜。Preferably, in step 5) of the preparation method of the fast-charging lithium ion battery, the separator is a polyethylene separator with a porosity of 45% to 65% and an air permeability of ≤200s.
优选的,这种快充锂离子电池的制备方法步骤6)中,带密封胶的金属复合片为带聚丙烯酸酯密封胶的铜铝复合片。Preferably, in step 6) of the preparation method of the fast-charging lithium ion battery, the metal composite sheet with sealant is a copper-aluminum composite sheet with polyacrylate sealant.
优选的,这种快充锂离子电池的制备方法步骤11)中,烘烤的温度为70℃~100℃。Preferably, in step 11) of the preparation method of the fast-charging lithium ion battery, the baking temperature is 70°C to 100°C.
优选的,这种快充锂离子电池的制备方法步骤11)中,电解液的注入量为4g/Ah~6g/Ah;电解液为常规的电解液,如六氟磷酸锂电解液。Preferably, in step 11) of the preparation method of the fast-charging lithium ion battery, the injection amount of the electrolyte is 4g/Ah~6g/Ah; the electrolyte is a conventional electrolyte, such as lithium hexafluorophosphate electrolyte.
一种快充锂离子电池,是由上述的制备方法制得。A fast-charging lithium-ion battery is prepared by the above-mentioned preparation method.
本发明的有益效果是:The beneficial effects of the present invention are:
本发明公开了一种可超快充电的锂离子电池,能够将充电时间缩短在15分钟以内,6分钟即可充电达电池总电量的90%以上。The invention discloses an ultra-fast rechargeable lithium ion battery, which can shorten the charging time within 15 minutes, and can charge more than 90% of the total battery power in 6 minutes.
与现有技术相比,本发明具有以下的优点:Compared with the prior art, the present invention has the following advantages:
1、所用正极材料预先经过碳纳米包覆掺杂在其颗粒表面形成优良导电层;2、所用负极材料预先经过软碳包覆技术在其颗粒表面形成优良导电层;3、所用导电剂为石墨烯、超导电炭黑与CNT等按照一定比例组合后添加到电极片中,使用前需与特定的分散剂与溶剂混合分散;4、所用隔膜在特制隔离膜,其孔隙率为45%~65%,透气率≤200s;5、电芯结构:极耳为全极耳结构,由电极片留白边组成;6、本发明可快充软包锂离子电池在10C充电时间6min,达到恒流比≥90%的总充电容量。1. The positive electrode material used is pre-coated and doped with carbon nano-particles to form an excellent conductive layer on the surface of the particles; 2. The negative electrode material used is pre-coated with soft carbon to form an excellent conductive layer on the surface of the particles; 3. The conductive agent used is graphite Alkene, superconducting carbon black and CNT are combined in a certain proportion and added to the electrode sheet. Before use, it needs to be mixed with a specific dispersant and solvent to disperse; 4. The separator used is a special separator with a porosity of 45% to 65%. %, the air permeability is less than or equal to 200s; 5. The structure of the battery cell: the tab is a full tab structure, which is composed of the white edge of the electrode sheet; than ≥90% of the total charge capacity.
附图说明Description of drawings
图1是成型电芯的示意图;Fig. 1 is the schematic diagram of forming electric core;
图2是连接片与铜铝复合片焊接的制备步骤示意图;Fig. 2 is a schematic diagram of the preparation steps for welding the connecting sheet and the copper-aluminum composite sheet;
图3是连接片裁切的制备步骤示意图;Fig. 3 is a schematic diagram of the preparation steps of the cutting of the connecting piece;
图4是连接片弯折成型的制备步骤示意图;Figure 4 is a schematic diagram of the preparation steps of the bending and forming of the connecting piece;
图5是外露金属片贴保护的制备步骤示意图;Figure 5 is a schematic diagram of the preparation steps for the protection of exposed metal sheet stickers;
图6是实施例1的电池在50A/9C充电电压-时间-温度曲线图;Fig. 6 is the charging voltage-time-temperature curve diagram of the battery of Example 1 at 50A/9C;
图7是实施例1的电池在50A/9C充电容量-电压曲线图。7 is a graph of the charging capacity-voltage curve of the battery of Example 1 at 50A/9C.
具体实施方式Detailed ways
附图1是本发明快充锂离子电池的成型电芯示意图。本发明的电芯其极耳为全极耳结构,连接片是有双头极耳引出。FIG. 1 is a schematic diagram of a formed cell of the fast-charging lithium-ion battery of the present invention. In the electric core of the present invention, the pole lugs are of a full lug structure, and the connecting piece is led out by double-headed lugs.
附图2~5是制备本发明快充锂离子电池某步骤的示意图,其中图2对应上述制备方法的步骤6),图3对应上述制备方法的步骤7),图4对应上述制备方法的步骤8),图5对应上述制备方法的步骤9)。2 to 5 are schematic diagrams of a certain step of preparing the fast-charging lithium-ion battery of the present invention, wherein FIG. 2 corresponds to step 6) of the above-mentioned preparation method, FIG. 3 corresponds to step 7) of the above-mentioned preparation method, and FIG. 4 corresponds to the step of the above-mentioned preparation method 8), Figure 5 corresponds to step 9) of the above preparation method.
以下结合附图1~5,通过具体的实施例对本发明的内容作进一步详细的说明。实施例中所用的原料/装置如无特殊说明,均可从常规商业途径得到。The content of the present invention will be described in further detail below with reference to the accompanying drawings 1 to 5 through specific embodiments. The raw materials/devices used in the examples can be obtained from conventional commercial channels unless otherwise specified.
实施例1Example 1
一种快充锂离子电池的制备方法,包括以下步骤:A preparation method of a fast-charging lithium-ion battery, comprising the following steps:
1)将NCM523正极材料与含有5wt%碳纳米管的DMF分散液混合均匀,NCM523正极材料与碳纳米管的质量比为1:0.1,将所得混合物进行喷雾干燥造粒,分级,得到正极导电材料;将中间相碳微球与含有2wt%软碳的乙醇分散液混合均匀,中间相碳微球与软碳的质量比为1:0.05,将所得混合物进行喷雾干燥造粒,分级,得到负极导电材料。1) Mix the NCM523 positive electrode material and the DMF dispersion liquid containing 5wt% carbon nanotubes evenly, the mass ratio of the NCM523 positive electrode material and the carbon nanotubes is 1:0.1, and the obtained mixture is spray-dried and granulated, and graded to obtain a positive electrode conductive material ; Mix the mesocarbon microspheres with the ethanol dispersion liquid containing 2wt% soft carbon, and the mass ratio of the mesocarbon microspheres to the soft carbon is 1:0.05, and the obtained mixture is spray-dried and granulated, and graded to obtain a negative electrode conductive Material.
2)将石墨烯、超导电炭黑、碳纳米管、聚乙烯吡咯烷酮和N-甲基吡咯烷酮溶剂按质量比0.8:2:1:0.8:100混合,得到导电浆液。2) Mix graphene, superconducting carbon black, carbon nanotubes, polyvinylpyrrolidone and N-methylpyrrolidone solvent in a mass ratio of 0.8:2:1:0.8:100 to obtain a conductive slurry.
3)将导电浆液与正极导电材料按质量比15:100混合,经高速分散混合均匀,所得的正极涂料涂覆在12~20μm基材上,经过干燥得到正极片,正极涂层的厚度为100μm;其中所用基材主体材质为铝箔并预先在其表面涂覆1~2μm厚度的导电层,导电层为石墨烯与碳纳米管复合物,其质量比为1:3;将导电浆液与负极导电材料按质量比6:100混合,经高速分散混合均匀,所得的负极涂料涂覆在6~10μm基材上,得到负极片,负极涂层的厚度为85μm;其中所用基材主体材质为铜箔并预先在其表面涂覆1~2μm厚度的导电层,导电层为超导电炭黑与碳纳米管复合物,其质量比为1:0.5;正极片和负极片的涂层边缘分别预留25mm长度的空白。3) Mix the conductive slurry and the positive electrode conductive material in a mass ratio of 15:100, and uniformly disperse and mix at a high speed. The obtained positive electrode coating is coated on a 12-20 μm substrate, and dried to obtain a positive electrode sheet. The thickness of the positive electrode coating is 100 μm The main material of the base material used is aluminum foil and a conductive layer with a thickness of 1 to 2 μm is pre-coated on its surface, and the conductive layer is a composite of graphene and carbon nanotubes, and its mass ratio is 1:3; the conductive slurry and the negative electrode are conductive The materials are mixed at a mass ratio of 6:100, and are uniformly dispersed and mixed at a high speed. The obtained negative electrode coating is coated on a 6-10 μm substrate to obtain a negative electrode sheet. The thickness of the negative electrode coating is 85 μm; the main material of the substrate used is copper foil. A conductive layer with a thickness of 1 to 2 μm is pre-coated on its surface. The conductive layer is a composite of superconducting carbon black and carbon nanotubes, and its mass ratio is 1:0.5; length of whitespace.
4)分别用激光切割正极片和负极片的预留空白,形成长度15mm的电极连接片。4) Use a laser to cut the reserved blanks of the positive electrode sheet and the negative electrode sheet respectively to form an electrode connecting sheet with a length of 15 mm.
5)将切割后的正极片、负极片和隔膜卷成方形电芯,电极连接片分别在垂直于电极长度方向叠层式引出;所用的隔膜为孔隙率是53%,透气率为150s的高透气性聚乙烯隔膜。5) Roll the cut positive electrode sheet, negative electrode sheet and separator into a square cell, and the electrode connecting sheets are respectively drawn out in a laminated manner perpendicular to the length of the electrode; the separator used is a high porosity of 53% and an air permeability of 150s Breathable polyethylene diaphragm.
6)分别将正电极和负电极引出的连接片与带聚丙烯酸酯密封胶的铜铝复合片超声焊接到一起,此制备步骤可参见图2。6) Ultrasonic welding the connecting sheets drawn from the positive electrode and the negative electrode and the copper-aluminum composite sheet with polyacrylate sealant respectively, the preparation steps can be seen in FIG. 2 .
7)裁切焊接后多余的连接片,此制备步骤可参见图3。7) Cut the excess connection piece after welding, the preparation step can be seen in Figure 3.
8)将连接片以垂直于电芯横截面的方向弯折成型,此制备步骤可参见图4。8) Bend and shape the connecting sheet in a direction perpendicular to the cross section of the cell. See Figure 4 for this preparation step.
9)对电芯外露的连接片贴胶保护,得到电芯半成品,此制备步骤可参见图5;贴胶所用的为耐腐性的聚丙烯酸酯胶。9) Protect the exposed connecting piece of the cell with glue to obtain the semi-finished product of the cell. This preparation step can be seen in Figure 5; the glue used is a corrosion-resistant polyacrylate glue.
10)将电芯半成品装入铝塑膜盒子进行顶侧封边,并预留一个侧边作为注液用。10) Put the semi-finished battery cell into the aluminum-plastic film box for edge sealing on the top side, and reserve a side edge for liquid injection.
11)将封边后的电芯进行烘烤,烘烤的温度为80℃,然后注入5Ah/g电解液,分容,得到快充锂离子电池。11) Bake the edge-sealed cells at a temperature of 80° C., and then inject 5Ah/g electrolyte to divide the capacity to obtain a fast-charging lithium-ion battery.
实施例2Example 2
一种快充锂离子电池的制备方法,包括以下步骤:A preparation method of a fast-charging lithium-ion battery, comprising the following steps:
1)将磷酸铁锂正极材料与含有5wt%碳纳米管的乙醇分散液混合均匀,磷酸铁锂正极材料与碳纳米管的质量比为1:0.12,将所得混合物进行喷雾干燥造粒,分级,得到正极导电材料;将中间相碳微球与含有3wt%软碳的乙醇分散液混合均匀,中间相碳微球与软碳的质量比为1:0.15,将所得混合物进行喷雾干燥造粒,分级,得到负极导电材料。1) uniformly mix the lithium iron phosphate positive electrode material with the ethanol dispersion liquid containing 5wt% carbon nanotubes, the mass ratio of the lithium iron phosphate positive electrode material to the carbon nanotubes is 1:0.12, and the obtained mixture is spray-dried and granulated, and classified, A positive electrode conductive material is obtained; the mesocarbon microspheres are uniformly mixed with an ethanol dispersion containing 3 wt % soft carbon, the mass ratio of the mesocarbon microspheres to the soft carbon is 1:0.15, the obtained mixture is spray-dried and granulated, and classified , to obtain a negative electrode conductive material.
2)将石墨烯、超导电炭黑、碳纳米管、聚乙烯吡咯烷酮和N-甲基吡咯烷酮溶剂按质量比0.8:2:0.8:0.5:100混合,得到导电浆液。2) Mix graphene, superconducting carbon black, carbon nanotubes, polyvinylpyrrolidone and N-methylpyrrolidone solvent in a mass ratio of 0.8:2:0.8:0.5:100 to obtain a conductive slurry.
3)将导电浆液与正极导电材料按质量比20:100混合,经高速分散混合均匀,所得的正极涂料涂覆在12~20μm基材上,经过干燥得到正极片,正极涂层的厚度为100μm;其中所用基材主体材质为铝箔并预先在其表面涂覆1~2μm厚度的导电层,导电层为石墨烯与碳纳米管复合物,其质量比为1:3;将导电浆液与负极导电材料按质量比7:100混合,经高速分散混合均匀,所得的负极涂料涂覆在6~10μm基材上,得到负极片,负极涂层的厚度为85μm;其中所用基材主体材质为铜箔并预先在其表面涂覆1~2μm厚度的导电层,导电层为超导电炭黑与碳纳米管复合物,其质量比为1:0.5;正极片和负极片的涂层边缘分别预留20mm长度的空白。3) Mix the conductive slurry and the positive electrode conductive material in a mass ratio of 20:100, and uniformly disperse and mix at a high speed. The obtained positive electrode coating is coated on a 12-20 μm substrate, and dried to obtain a positive electrode sheet. The thickness of the positive electrode coating is 100 μm The main material of the base material used is aluminum foil and a conductive layer with a thickness of 1 to 2 μm is pre-coated on its surface, and the conductive layer is a composite of graphene and carbon nanotubes, and its mass ratio is 1:3; the conductive slurry and the negative electrode are conductive The materials are mixed at a mass ratio of 7:100, and are uniformly dispersed and mixed at a high speed. The obtained negative electrode coating is coated on a 6-10 μm substrate to obtain a negative electrode sheet. The thickness of the negative electrode coating is 85 μm; the main material of the substrate is copper foil. A conductive layer with a thickness of 1-2 μm is pre-coated on its surface. The conductive layer is a composite of superconducting carbon black and carbon nanotubes, and its mass ratio is 1:0.5; length of whitespace.
4)分别用激光切割正极片和负极片的预留空白,形成长度10mm的电极连接片。4) Use a laser to cut the reserved blanks of the positive electrode sheet and the negative electrode sheet respectively to form an electrode connecting sheet with a length of 10 mm.
5)将切割后的正极片、负极片和隔膜卷成方形电芯,电极连接片分别在垂直于电极长度方向叠层式引出;所用的隔膜为孔隙率是55%,透气率为180s的高透气性聚乙烯隔膜。5) Roll the cut positive electrode sheet, negative electrode sheet and separator into a square cell, and the electrode connecting sheets are respectively drawn out in a laminated manner perpendicular to the length of the electrode; the separator used has a porosity of 55% and a high air permeability of 180s. Breathable polyethylene diaphragm.
6)分别将正电极和负电极引出的连接片与带聚丙烯酸酯密封胶的铜铝复合片超声焊接到一起,此制备步骤可参见图2。6) Ultrasonic welding the connecting sheets drawn from the positive electrode and the negative electrode and the copper-aluminum composite sheet with polyacrylate sealant respectively, the preparation steps can be seen in FIG. 2 .
7)裁切焊接后多余的连接片,此制备步骤可参见图3。7) Cut the excess connection piece after welding, the preparation step can be seen in Figure 3.
8)将连接片以垂直于电芯横截面的方向弯折成型,此制备步骤可参见图4。8) Bend and shape the connecting sheet in a direction perpendicular to the cross section of the cell. See Figure 4 for this preparation step.
9)对电芯外露的连接片贴胶保护,得到电芯半成品,此制备步骤可参见图5;贴胶所用的为耐腐性的聚丙烯酸酯胶。9) Protect the exposed connecting piece of the cell with glue to obtain the semi-finished product of the cell. This preparation step can be seen in Figure 5; the glue used is a corrosion-resistant polyacrylate glue.
10)将电芯半成品装入铝塑膜盒子进行顶侧封边,并预留一个侧边作为注液用。10) Put the semi-finished battery cell into the aluminum-plastic film box for edge sealing on the top side, and reserve a side edge for liquid injection.
11)将封边后的电芯进行烘烤,烘烤的温度为90℃,然后注入5Ah/g电解液,分容,得到快充锂离子电池。11) Bake the edge-sealed cell at a temperature of 90° C., then inject 5Ah/g electrolyte, and divide the capacity to obtain a fast-charging lithium-ion battery.
实施例3Example 3
一种快充锂离子电池的制备方法,包括以下步骤:A preparation method of a fast-charging lithium-ion battery, comprising the following steps:
1)将锰酸锂与钴酸锂正极材料与含有5wt%碳纳米管的DMF分散液混合均匀,锰酸锂正极材料与碳纳米管的质量比为1:0.12,钴酸锂正极材料与碳纳米管的质量比为1:0.12,将所得混合物进行喷雾干燥造粒,分级,得到正极导电材料;将中间相碳微球与含有4.5wt%软碳的乙醇分散液混合均匀,中间相碳微球与软碳的质量比为1:0.1,将所得混合物进行喷雾干燥造粒,分级,得到负极导电材料。1) Mix the lithium manganate and lithium cobalt oxide cathode materials with a DMF dispersion containing 5 wt % carbon nanotubes evenly, the mass ratio of lithium manganate cathode material and carbon nanotubes is 1:0.12, and the lithium cobalt oxide cathode material and carbon nanotubes are mixed uniformly. The mass ratio of the nanotubes is 1:0.12, and the obtained mixture is spray-dried and granulated, and graded to obtain a positive electrode conductive material; the mesocarbon microspheres are uniformly mixed with an ethanol dispersion containing 4.5 wt % soft carbon, and the mesocarbon microspheres are mixed uniformly. The mass ratio of the ball to the soft carbon is 1:0.1, and the obtained mixture is spray-dried and granulated, and classified to obtain a negative electrode conductive material.
2)将石墨烯、超导电炭黑、碳纳米管、聚乙烯吡咯烷酮和N-甲基吡咯烷酮溶剂按质量比0.5:1:1:0.5:100混合,得到导电浆液。2) Mix graphene, superconducting carbon black, carbon nanotubes, polyvinylpyrrolidone and N-methylpyrrolidone solvent in a mass ratio of 0.5:1:1:0.5:100 to obtain a conductive slurry.
3)将导电浆液与正极导电材料按质量比20:100混合,经高速分散混合均匀,所得的正极涂料涂覆在12~20μm基材上,经过干燥得到正极片,正极涂层的厚度为110μm;其中所用基材主体材质为铝箔并预先在其表面涂覆1~2μm厚度的导电层,导电层为石墨烯与碳纳米管复合物,其质量比为1:3;将导电浆液与负极导电材料按质量比7:100混合,经高速分散混合均匀,所得的负极涂料涂覆在6~10μm基材上,得到负极片,负极涂层的厚度为80μm;其中所用基材主体材质为铜箔并预先在其表面涂覆1~2μm厚度的导电层,导电层为超导电炭黑与碳纳米管复合物,其质量比为1:0.5;正极片和负极片的涂层边缘分别预留20mm长度的空白。3) Mix the conductive slurry and the positive electrode conductive material in a mass ratio of 20:100, and uniformly disperse and mix at a high speed. The obtained positive electrode coating is coated on a 12-20 μm substrate, and dried to obtain a positive electrode sheet. The thickness of the positive electrode coating is 110 μm ; The main material of the base material used is aluminum foil and a conductive layer with a thickness of 1 to 2 μm is pre-coated on its surface, and the conductive layer is a composite of graphene and carbon nanotubes, and its mass ratio is 1:3; The conductive slurry and the negative electrode are conductive The materials are mixed at a mass ratio of 7:100, and are uniformly dispersed and mixed at a high speed. The obtained negative electrode coating is coated on a 6-10 μm substrate to obtain a negative electrode sheet. The thickness of the negative electrode coating is 80 μm; the main material of the substrate used is copper foil. A conductive layer with a thickness of 1-2 μm is pre-coated on its surface. The conductive layer is a composite of superconducting carbon black and carbon nanotubes, and its mass ratio is 1:0.5; length of whitespace.
4)分别用激光切割正极片和负极片的预留空白,形成长度10mm的电极连接片。4) Use a laser to cut the reserved blanks of the positive electrode sheet and the negative electrode sheet respectively to form an electrode connecting sheet with a length of 10 mm.
5)将切割后的正极片、负极片和隔膜卷成方形电芯,电极连接片分别在垂直于电极长度方向叠层式引出;所用的隔膜为孔隙率是55%,透气率为180s的高透气性聚乙烯隔膜。5) Roll the cut positive electrode sheet, negative electrode sheet and separator into a square cell, and the electrode connecting sheets are respectively drawn out in a laminated manner perpendicular to the length of the electrode; the separator used is a high porosity of 55% and an air permeability of 180s Breathable polyethylene diaphragm.
6)分别将正电极和负电极引出的连接片与带聚丙烯酸酯密封胶的铜铝复合片超声焊接到一起,此制备步骤可参见图2。6) Ultrasonic welding the connecting sheets drawn from the positive electrode and the negative electrode and the copper-aluminum composite sheet with polyacrylate sealant respectively, the preparation steps can be seen in FIG. 2 .
7)裁切焊接后多余的连接片,此制备步骤可参见图3。7) Cut the excess connection piece after welding, the preparation step can be seen in Figure 3.
8)将连接片以垂直于电芯横截面的方向弯折成型,此制备步骤可参见图4。8) Bend and shape the connecting sheet in a direction perpendicular to the cross section of the cell. See Figure 4 for this preparation step.
9)对电芯外露的连接片贴胶保护,得到电芯半成品,此制备步骤可参见图5;贴胶所用的为耐腐性的聚丙烯酸酯胶。9) Protect the exposed connecting piece of the cell with glue to obtain a semi-finished product of the cell. This preparation step can be seen in Figure 5; the glue used is a corrosion-resistant polyacrylate glue.
10)将电芯半成品装入铝塑膜盒子进行顶侧封边,并预留一个侧边作为注液用。10) Put the semi-finished battery cell into the aluminum-plastic film box for edge sealing on the top side, and reserve a side edge for liquid injection.
11)将封边后的电芯进行烘烤,烘烤的温度为90℃,然后注入5Ah/g电解液,分容,得到快充锂离子电池。11) Bake the edge-sealed battery cells at a temperature of 90° C., then inject 5Ah/g electrolyte, and divide the capacity to obtain a fast-charging lithium-ion battery.
通过实施例制备得到的快充锂离子电池成品电芯可见附图1。The finished cell of the fast-charging lithium-ion battery prepared by the embodiment can be seen in FIG. 1 .
性能测试Performance Testing
电池容量和内阻:实施例1~3所制得的电池在常温下的容量和内阻测试结果见表1。Battery capacity and internal resistance: Table 1 shows the capacity and internal resistance test results of the batteries prepared in Examples 1 to 3 at room temperature.
表1实施例1-3的电池容量和内阻Table 1 Battery capacity and internal resistance of Examples 1-3
高低温倍率放电测试:将实施例1的电池进行高低温倍率放电测试,以1C电流恒流恒压充满电,然后在不同的温度下用不同倍率电流去放电,放电容量及保持率情况见表2。High and low temperature rate discharge test: carry out the high and low temperature rate discharge test of the battery of Example 1, fully charge with 1C current, constant current and constant voltage, and then discharge with different rate currents at different temperatures. The discharge capacity and retention rate are shown in the table. 2.
表2实施例1电池高低温倍率放电测试结果Table 2 Example 1 battery high and low temperature rate discharge test results
室温充电性能:附图6是实施例1的电池在50A/9C充电电压-时间-温度曲线图。从图6可以看出,在50A恒流充电条件下仅用5分45秒就可以把电池的电压升到4.20V,且整个充电过程电池表面温度低于45℃。附图7是实施例1的电池在50A/9C充电容量-电压曲线图。结合图7在4.20V的充电容量比率可知,当充电电压达到4.20V时,电池的充电比率>90%。Room temperature charging performance: FIG. 6 is a graph showing the charging voltage-time-temperature curve of the battery of Example 1 at 50A/9C. It can be seen from Figure 6 that the voltage of the battery can be raised to 4.20V in only 5 minutes and 45 seconds under the condition of 50A constant current charging, and the battery surface temperature is lower than 45°C during the whole charging process. FIG. 7 is a graph showing the charging capacity-voltage curve of the battery of Example 1 at 50A/9C. Combining with the charging capacity ratio at 4.20V in Figure 7, it can be known that when the charging voltage reaches 4.20V, the charging ratio of the battery is >90%.
不同温度下的充电倍率:先将实施例1的电池以1C电流放空电,分别在不同温度下搁置12h后以不同倍率进行恒流充电,测试其充电性能。结果如表3所示。Charging rate at different temperatures: First, the battery of Example 1 was discharged at a current of 1C, and then left at different temperatures for 12 hours, respectively, and then charged with constant current at different rates to test its charging performance. The results are shown in Table 3.
表3实施例1电池不同温度下的充电性能Table 3 Charging performance of the battery of Example 1 at different temperatures
循环性能:将实施例1、2和3的电池在1C下进行循环充放电测试,在循环测试300次后,实施例1、2和3的电池循环保持率分别为93.6%、92.7%和93.1%,循环性能良好。Cycle performance: The batteries of Examples 1, 2 and 3 were subjected to a cyclic charge-discharge test at 1C. After 300 cycles of the cycle test, the cycle retention rates of the batteries of Examples 1, 2 and 3 were 93.6%, 92.7% and 93.1, respectively. %, good cycle performance.
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