CN102104140A - Power battery electrode and manufacturing method thereof - Google Patents

Power battery electrode and manufacturing method thereof Download PDF

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CN102104140A
CN102104140A CN2010106113429A CN201010611342A CN102104140A CN 102104140 A CN102104140 A CN 102104140A CN 2010106113429 A CN2010106113429 A CN 2010106113429A CN 201010611342 A CN201010611342 A CN 201010611342A CN 102104140 A CN102104140 A CN 102104140A
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electrode
lithium
material
manufacturing method
battery electrode
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CN2010106113429A
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夏圣安
李新宏
杨万光
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常州华科新能源科技有限公司
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/54Manufacturing of lithium-ion, lead-acid or alkaline secondary batteries

Abstract

The invention relates to the technical field of rechargeable lithium ion batteries, in particular to a high-performance power battery electrode and a manufacturing method thereof. The manufacturing method is suitable for manufacturing pole pieces of a positive electrode and a negative electrode of a rechargeable lithium ion battery. The manufacturing method comprises the following steps of: coating a conductive layer without lithium storage activity on a metal foil by a water-based process first and then coating a material with the lithium storage activity on the metal foil by using an oil-system formula to obtain a power battery electrode after drying and rolling the conductive layer. The electrode manufacturing method utilizes the advantages of high acting force and low internal resistance of the water-based process and metal, utilizes the characteristics of stable process and long cycle life of the oil-system formula, reduces the using amount of a bonding agent, can greatly improve the high-rate performance and the cycle life of the battery, and is an ideal power battery electrode manufacturing method.

Description

动力电池电极及其制备方法 Its battery electrode preparation

技术领域 FIELD

[0001] 本发明属于二次锂离子电池领域,涉及电化学、材料化学领域,尤其涉及一种动力电池电极及其制备方法。 [0001] The present invention belongs to the field of secondary lithium ion batteries, relates to electrochemical, chemical materials, and in particular relates to a power battery electrode preparation method thereof.

技术背景 technical background

[0002] 能源危机及环境恶化问题近年来日趋严重,引起了全球性的关注。 [0002] energy crisis and worsening environmental degradation in recent years, attracted global attention. 按目前世界石油消耗速度看,全球石油储藏量大约60年就会消耗殆尽。 At the current rate of world oil consumption, the global oil reserves will be exhausted in about 60. 此外世界石油消耗速度还在逐年增加中。 Furthermore world oil consumption rate is also gradually increasing. 目前全球汽车保有量在不断上升,整个行业约消耗石油总开采量的45%。 The current global car ownership is rising, the industry consumes about 45% of the total amount of oil exploitation. 传统汽车对石油的依赖也是全球气候变暖的最根本原因。 Traditional car dependence on oil is the most fundamental cause of global warming. 降低汽车行业对石油的依赖已经成为人类解决能源危机最快速、最环保和成本最低的方式。 Reduce the auto industry's dependence on oil has become a human to solve the energy crisis the fastest, lowest cost and most environmentally friendly way.

[0003] 电动汽车能够充分利用由多种来源产生的电能、以及用电低谷的“富裕”电能充电,可以有效地缓解能源危机,保护环境。 [0003] electric car can take advantage of the power generated by a variety of sources, as well as "rich" energy charge of electricity trough, can effectively alleviate the energy crisis and protect the environment. 锂离子动力电池可以在大量领域内使用电能取代石油能源,节约了大量宝贵的石油资源,同时电能是一种清洁能源,可以缓解使用石油能源带来的严重的环境污染。 Lithium-ion battery may be used in the field of large electric power energy to replace oil, saves a lot of valuable petroleum resources, while energy is a clean energy, can be used to alleviate severe environmental pollution caused by oil energy. 新型锂离子二次电池的研发是电动汽车发展的关键,并且电池技术依然是制约纯电动汽车产业化的瓶颈,在车载电池比功率、比能量、循环次数、耗费的充电时间长短等关键指标方面均存在着瓶颈。 The new lithium-ion secondary battery research and development is the key to development of electric vehicles and battery technology is still the bottleneck restricting the industrialization of pure electric vehicles, on-board battery power than the specific energy, the number of cycles, the length of time spent charging and other key indicators there are bottlenecks. 目前欧、美、日及我国都积极开展了将锂离子电池应用与电动汽车的研究,并取得良好的效果。 Currently in Europe, America, Japan and China are actively engaged in the research and application of lithium-ion battery electric vehicles, and achieved good results. 因此,大量发展锂离子动力电池具有重要的社会经济意义。 Therefore, a large number of lithium-ion battery development has important social and economic significance.

[0004] 近年来为了提高锂二次电池的能量和功率密度,人们在电极活性材料制作方面做了很多工作,如新材料的合成、元素掺杂、包覆、纳米化等等,成果显著,大大提高的电极活性材料的综合性能。 [0004] In recent years, lithium secondary batteries in order to improve the energy and power density, the electrode active material it has done a lot of work, such as the synthesis of new materials, doping elements, coating, nano etc., remarkable results, overall performance electrode active material is greatly improved. 但是电池的性能不仅取决于原材料的性能,还和制作工艺有很大的关系。 However, battery performance depends not only on the performance of raw materials, production process and also have a great relationship. 多年来电极的制作工艺都没有太大的进展:一种是以NMP为溶剂,以PVDF或PTFE为粘结剂的油系工艺,该工艺最为成熟,产品性能稳定、循环性好,但内阻大,对生产环境要求高,处理不当还会有污染;另一种是以水为溶剂,以高分子溶液或乳液为粘结剂的工艺,该工艺得成本低、无污染,产品内阻小、高倍率性能好,但循环寿命和稳定性不如油系,有待于进一步完善;还有一种以导电高分子为粘结剂的工艺,生产条件极为苛刻,还处于研究阶段。 Over the years the production process of the electrode are not much progress: one is NMP as the solvent, PVDF, or PTFE binder is an oil-based process, the process is the most mature, stable product performance, recycling is good, but the internal resistance large, high requirements on the production environment, there will be contamination of improper handling; the other is a water as the solvent, the polymer solution or emulsion of the binder for the process, the process to be low cost, non-polluting products internal resistance , high rate performance is good, but the cycle life and less stable than oil-based, to be further improved; there is a conductive polymer as the binder in the process, the production of extremely harsh conditions, still in the research stage.

发明内容 SUMMARY

[0005] 本发明的目的就是为了克服现有技术中的不足之处,提出了一种倍率性能好、循环寿命长的动力电池电极及其制造方法。 [0005] The object of the present invention is to overcome the shortcomings of the prior art, proposes a rate of good performance, long cycle life of the battery electrode and its manufacturing method.

[0006] 一种动力电池电极,它包括金属箔片,在金属箔片上涂有一层导电剂,经烘干、辊压后,再涂上储锂活性材料,导电层厚度为0. 01-30 μ m。 [0006] A battery electrode comprising a metal foil, the metal foil coated with a conductive agent, after drying, rolling, and then coated with the active material reservoir lithium, a conductive layer having a thickness of 0. 01-30 μ m.

[0007] 所述金属箔片为铝箔和铜箔。 The [0007] the metal foil is an aluminum foil and a copper foil.

[0008] 所述导电剂为导电炭黑、导电石墨和导电碳纳米管或者对前述三种材料任选两种以上材料进行元素掺杂、表面包覆、改性所得的复合材料。 [0008] The resulting composite modifying the conductive agent is a conductive carbon black, graphite and conductive carbon nanotube electrically conductive material or, optionally, two or more of the aforementioned three elements doped materials, surface coating. [0009] 所述储锂活性材料为钴酸锂LiCoO2、镍酸锂LiNi02、LiMePO4, Li2MeSiO4、磷酸钒锂Li3V2 (PO4) 3、Lii^eBOp 富锂正极材料bLi2Mn03 · (l_b) LiMO2、钛酸锂Li4Ti5012、H2Ti12O25、二氧化钼MoO2、石墨、MCMB、金属锡、锡基复合材料、单质硅和硅合金或者对上述材料进行元素掺杂、表面包覆、改性所得到的复合材料中的任意一种或多种,其中Me为Fe、Mn、C0、m,其中, O 彡b < 1,LiMO2 为LiCoxNiyMnzO2, x+y+z = 1 或锰酸锂LiMn2O4 或Li4Mn5O9 或Li4Mn5O120 [0009] The active material is a lithium storage lithium cobaltate LiCoO2, lithium nickelate LiNi02, LiMePO4, Li2MeSiO4, lithium vanadium phosphate Li3V2 (PO4) 3, Lii ^ eBOp lithium rich cathode material bLi2Mn03 · (l_b) LiMO2, lithium titanate Li4Ti5012, H2Ti12O25, MoO2 molybdenum dioxide, graphite, the MCMB, metallic tin, tin-based composite, elemental silicon or silicon alloy and the above-described doping element material, surface coating, a composite material of any modification of the obtained or more, wherein Me is Fe, Mn, C0, m, wherein, San O b <1, LiMO2 is LiCoxNiyMnzO2, x + y + z = 1 or lithium manganate LiMn2O4 or Li4Mn5O9 or Li4Mn5O120

[0010] 动力电池电极的制备方法,其具体制作过程为: Preparation of [0010] power battery electrode, the specific production process of:

[0011] a、将导电层材料和去离子水在球磨机中球磨1-5小时,再加入占固体质量比的0. 1-10%水性粘结剂乳液或溶液球磨0. 1-1小时得到第一浆料; [0011] a, conductive material and a layer of deionized water milling in a ball mill for 1-5 hours, then added accounted for 0.5% 1-10 binder emulsion or an aqueous solution of 0.5 mass ratio of solid milling 1-1 hours to give The first slurry;

[0012] b、将第一浆料除气泡后涂布在金属箔片上,经干燥、辊压后形成电极坯材; [0012] b, the slurry is first coated on the air bubble removing the metal foil, dried, rolled to form the electrode blank;

[0013] C、将占固体质量比0. 1-10%的油性粘结剂用有机溶剂配成溶液,再把占固体质量比0. 1-40%的导电剂和储锂活性材料分散在该溶液中得到第二浆料; [0013] C, the solid mass ratio of 0.5 to account for 1-10% of an oily binder solution was formulated with an organic solvent, then accounting for 1-40% of solid mass ratio of 0.5 and a conductive agent is dispersed in the active material reservoir lithium the second slurry obtained in the solution;

[0014] d、将第二浆料除气泡后将浆料涂布在b步骤中的电极坯材上,形成电极片,将涂覆后的极片干燥。 [0014] d, in addition to the second slurry after the slurry is applied to the bubble electrode blanks in step b, the electrode sheet is formed, the electrode sheet after coating and drying.

[0015] 所述水性粘结剂为聚氧化乙烯、聚丙烯腈、聚甲基丙烯酸酯、羧甲基纤维素钠、 氯丁橡胶、丁腈橡胶、丁苯橡胶、氯磺化聚乙烯橡胶、苯乙烯-丁二烯-苯乙烯橡胶、丙烯腈-丁二烯-苯乙烯橡胶、阿拉伯胶和天然橡胶或者上述材料的衍生物中的一种或多种。 [0015] The aqueous binder is a polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, sodium carboxymethyl cellulose, chloroprene rubber, nitrile rubber, styrene-butadiene rubber, chlorosulfonated polyethylene rubber, styrene - butadiene - styrene rubber, acrylonitrile - butadiene - styrene rubber, natural rubber, gum arabic and derivatives of the above materials, or of one or more.

[0016] 所述的有机溶剂是指以N-甲基吡咯烷酮、二甲基酰胺和二甲基乙酰胺或者上述材料的衍生物中的一种或多种;所述油性粘结剂为偏聚四氟乙烯、聚四氟乙烯和聚合类树脂或者上述材料的衍生物中的一种或多种。 [0016] The organic solvent refers to N- methylpyrrolidone, dimethylformamide and derivatives dimethylacetamide or above materials one or more; The oily binder is Segregation tetrafluoroethylene, polytetrafluoroethylene or a derivative thereof and a polymeric resin material in the above-described one or more.

[0017] 本发明的技术效果体现在: [0017] Technical effects of the present invention are embodied in:

[0018] 1、双层涂覆工艺,既利用了水系工艺与金属作用力强、内阻小的优势,又利用了油系配方工艺稳定、循环寿命长的特点,还减少了粘结剂的使用量,提高了电池的高倍率性能和循环寿命。 [0018] 1, a double coating process, both the use of technology and strong aqueous metal effect, the advantages of a small internal resistance, and the use of oil-based formulation process stability, long cycle life characteristics, but also reduces the adhesive the amount of improved high rate and cycle life performance of the battery.

[0019] 2、导电层的使用延长了电池的循环寿命。 [0019] 2, using the conductive layer is extended the cycle life of the battery. 因为铝箔在空气和电解液中都比较容易在表面形成氧化物膜,铜箔在使用过程中也容易腐蚀生成一层绝缘薄膜,致使电池内阻增大,循环过程中放电效率降低,使用导电层涂覆后可以大大减少隔绝空气和电解液与集流体的接触;另外,电池在长时间循环过程中因为发热、电解液的腐蚀、锂离子的迁移等原因, 粘结剂会粉化,金属箔会腐蚀,导致活性物质层与集流体脱落,电池内阻急剧上升而报废, 使用导电层涂覆后,由于导电层没有储锂活性材料,这一过程也会大大延缓。 Because the foil are relatively easy to form an oxide film on the surface in air and the electrolytic solution, a copper foil during use can be easily generated etching an insulating film, resulting in increased battery internal resistance, lowering of the discharge efficiency of the cycle process, using the conductive layer after coating can significantly reduce the exclusion of air in contact with the current collector and the electrolyte; in addition, the battery for a long time because of the heating cycle, corrosive electrolyte migration of lithium ions and the like, the adhesive will powder, a metal foil will corrode, resulting in the active material layer and the current collector to fall off, a sharp rise in the internal resistance of the battery scrapped after use coated with a conductive layer, the conductive layer is not active lithium storage material, the process will be greatly delayed.

附图说明 BRIEF DESCRIPTION

[0020] 图1为对比例la、对比例lb.和实施例1.在5C下的循环曲线具体实施方式 [0020] FIG. 1 is a Comparative Example la, lb. Comparative Example 1 and curve cycle at specific embodiments 5C

[0021] 下面通过实施例对本发明进行具体描述,有必要在此指出的是以下实施例只能用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术熟练人员根据上述本发明的内容做出一些非本质的改进和调整仍属本发明的保护范围。 [0021] Next, by the present invention will be specifically described embodiments, it is necessary to point out that the following examples are only for the present invention is further illustrated not to be construed as limiting the scope of the invention, the skilled in the art in accordance SUMMARY of the present invention still make some non-essential scope of the invention modifications and adjustments.

[0022] 对比例la. [0022] la of proportion.

[0023] 先将偏聚四氟乙烯(下称:PVDF)用N-甲基吡咯烷酮(下称:NMP)配成7%的溶液(占最终固形物含量的5% ),然后加入导电剂(占最终固形物含量的5% ),采用高速剪切分散3小时,再加入磷酸铁锂(占最终固形物含量的90%),采用高速剪切分散3小时, 抽真空搅拌1小时后,将浆料均勻的涂布在铝箔上,采用110°C的大量热风循环烤干极片。 [0023] The first partial polytetrafluoroethylene (hereinafter: PVDF) with N- methylpyrrolidone (hereinafter referred to: NMP) was formulated 7% (5% final solid content), followed by addition of a conductive agent ( after a final 5% solids content), high-speed shearing dispersing for 3 hours, lithium iron phosphate was added (90% final solid content), high-speed shearing dispersing for 3 hours and the vacuum pump was stirred for 1 hour, the slurry was applied uniformly on an aluminum foil using a 110 ° C hot air circulation to dry large pole pieces. 将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/EC-DMC(l : 1)溶液为电解液组装扣式电池,并在4. 2〜2. 5V的电压范围,0. IC到20C的电流密度下进行等倍率充放电实验和5C循环实验, 结果在表1.和表2.中给出。 The pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC ( l:.. 1) as the electrolyte assembled coin cell, and the voltage range of 4. 2~2 5V, 0 IC to be 20C at a current density charge-discharge rate and the like, and 5C cycle test experiments, the results in table 1 . and given in table 2..

[0024] 表1.不同制作方式的电极片放电比容量结果对比表 [0024] Table 1. Different production methods of electrode sheet discharge capacity results Comparison Table

[0025] [0025]

Figure CN102104140AD00051

[0026] 对比例lb. [0026] Comparative Example lb.

[0027] 先将聚氧化乙烯配成2%的水溶液(占最终固形物含量的1. 5% ),然后加入导电剂(占最终固形物含量的5% ),采用高速剪切分散3小时,再加入磷酸铁锂(占最终固形物含量的90% ),采用高速剪切分散3小时,最后加入经过稀释的氯丁橡胶乳液(占最终固形物含量的3. 5% ),抽真空搅拌1小时后,将浆料均勻的涂布在铝箔上,采用80°C的大量热风循环烤干极片。 [0027] First polyoxyethylene dubbed a 2% aqueous solution (representing 1.5% of the final solids content), followed by addition of a conductive agent (5% final solid content), high-speed shearing dispersing for 3 hours lithium iron phosphate was added (90% final solid content), using high shear dispersed for 3 hours, and finally adding the diluted emulsion of chloroprene rubber (accounting for 3.5% of the final solids content), vacuum stirring 1 after hours, the slurry was coated uniformly on an aluminum foil, to 80 ° C using a circulating hot air to dry a large number of pole pieces. 将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/EC-DMC(l : 1)溶液为电解液组装扣式电池,并在4. 2〜2. 5V的电压范围,0. IC到20C的电流密度下进行等倍率充放电实验和5C循环实验,结果在表1.和表2.中给出。 The pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC ( l:.. 1) as the electrolyte assembled coin cell, and the voltage range of 4. 2~2 5V, 0 IC to be 20C at a current density charge-discharge rate and the like, and 5C cycle test experiments, the results in table 1 . and given in table 2..

[0028] 实施例1. [0028] Example 1.

[0029] 先将乙炔黑和去离子水在球磨机中球磨3小时,再加入聚氧化乙烯(占总固含量的)和氯丁橡胶乳液(占总固含量的2% )球磨0. 5小时,将浆料除气泡后涂布在铝箔片上,经烘干、辊压后备用,导电层厚度为15 μ m;将PVDF用NMP配成7%的溶液(占最终固形物含量的5% ),然后加入导电剂(占最终固形物含量的5% ),采用高速剪切分散3小时,再加入磷酸铁锂(占最终固形物含量的90% ),采用高速剪切分散3小时,抽真空搅拌1小时后,将浆料均勻的涂布在前述铝箔上,采用110°C的大量热风循环烤干极片。 [0029] First, acetylene black, and deionized water were ball milled in a ball mill for 3 hours, was added polyoxyethylene (total solids) and chloroprene rubber latex (2% of total solids) milled 0.5 hours, after addition the slurry was coated on aluminum foil bubbles, after drying, the standby roll, the conductive layer having a thickness of 15 μ m; the NMP 7% PVDF with a solution formulated (5% final solid content), a conductive agent was then added (final 5% solid content), high-speed shearing dispersing for 3 hours, lithium iron phosphate was added (90% final solid content), high-speed shearing dispersing for 3 hours and vacuum was stirred after 1 hour, the slurry was uniformly coated on the aluminum foil using a 110 ° C hot air circulation to dry large pole pieces. 将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/EC-DMC(l : 1)溶液为电解液组装扣式电池,并在4. 2〜 2. 5V的电压范围,0. IC到20C的电流密度下进行等倍率充放电实验和5C循环实验,结果在表1.和表2.中给出。 The pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC ( l:. 1) as the electrolyte assembled coin cell, and the voltage range of 4. 2~ 2. 5V, 0 IC to be 20C at a current density charge-discharge rate and the like, and 5C cycle test experiments, the results in table 1 . and given in table 2..

[0030] 为了对比起见,对比例la.、对比例lb.和实施例1.中所用磷酸铁锂材料、导电剂及活性物质含量是完全相同的。 [0030] For comparison purposes, comparative La., Lb. Comparative Example 1 as the lithium iron phosphate material, a conductive agent and the active substance content is identical. 从表1.中可以看到,在0. IC电流密度下三种极片的放电比容量非常接近,从IC开始,倍率越大,对比例la.的比容量下降越快,在5C电流密度下放电比容量为64mAh/g,20C电流密度下基本就没有容量了。 Can be seen from Table 1, under a current density of 0. The IC chip discharge specific capacity of the three kinds of electrodes is very close to, the IC starts, the greater the ratio, the specific capacity of Comparative Example la. The faster the decrease in current density 5C the discharge capacity of 64mAh / g, the current density at 20C of substantially no capacity. 而对比例lb.与实施例1.则降得比较慢,远高于对比例la.,显示出较强的的大电流充放电能力。 Lb. and Comparative Example 1 is reduced relatively slowly, much higher than the comparative La., Shows a strong high current charge and discharge capability. 从表2.中可以看到,5C 循环100次后实施例lb.衰减1. 42%,而实施例la.和实施例1.基本无衰减。 As can be seen in Table 2, after 100 cycles Example 5C attenuation lb. 1.42%, whereas Example la embodiments. Example 1 and substantially without attenuation embodiment. 综上所述, 实施例1.得到的电极片的综合性能最佳,显示出突出的循环性能和大倍率充放电能力。 In summary, the overall performance of the electrode sheet obtained in Example 1. The best, showing outstanding cycle performance and high rate discharge capability.

[0031] 实施例2 [0031] Example 2

[0032] 先将超导导电炭黑和去离子水在球磨机中球磨4小时,再加入羧甲基纤维素钠(占总固含量的0. 5% )和氯磺化聚乙烯橡胶乳液(占总固含量的2. 5% )球磨1小时,将浆料除气泡后涂布在铜箔片上,经烘干、辊压后备用,导电层厚度为10 μ m ;将聚四氟乙烯(下称:PTFE)用二甲基酰胺配成6%的溶液(占最终固形物含量的4% ),然后加入导电剂(占最终固形物含量的6,采用高速剪切分散3小时,再加入二氧化钼MoO2 (占最终固形物含量的90% ),采用高速剪切分散2. 5小时,抽真空搅拌0. 5小时后,将浆料均勻的涂布在前述铜箔上,采用100°C的大量热风循环烤干极片。将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/ EC-DMC(1 : 1)溶液为电解液组装扣式电池,并在3. 0〜0. 2V的电压范围,0. IC到20 [0032] The first superconducting conductive carbon black, and deionized water milling in a ball mill for 4 hours, was added sodium carboxymethylcellulose (0.5% total solids) and chlorosulfonated polyethylene rubber latex (% of 2.5% total solids) ball milled for 1 hour after the addition the slurry was coated on copper foil bubbles, after drying, the standby roll, the conductive layer having a thickness of 10 μ m; polytetrafluoroethylene (lower He said: PTFE) 6% was formulated with dimethylformamide (final 4% solids content), followed by addition of a conductive agent (solid content of the final 6, using high shear dispersed for 3 hours, then adding diethyl after molybdenum MoO2 (90% final solid content), high-speed shearing dispersing 2.5 hours, the vacuum pump was stirred for 0.5 hours, the slurry was uniformly coated on the copper foil, using 100 ° C a circulating hot air to dry a large number of pole pieces. the pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC (1: 1) solution as the electrolyte assembled coin cell, and the voltage range 3. 0~0 2V, 0 IC 20. C的电流密度下进行等倍率充放电实验,该电极在0. IC电流密度下充放电比容量为626mAh/g, 在5C电流密度下放电比容量为213mAh/g,20C电流密度下放电比容量仍可达到92mAh/g ; 5C循环100次基本衰减2. 7%,显示出突出的循环性能和大倍率充放电能力。 C conducted at a current density of other rate discharge test, the electrodes at a current density of 0. IC discharge capacity was 626mAh / g, the discharge capacity was 213mAh / g at a current density 5C discharge capacity at a current density of 20C You can reach 92mAh / g; 5C 100 cycles substantially attenuating 2.7%, exhibited outstanding cycling performance and high rate discharge capability.

[0033] 实施例3 [0033] Example 3

[0034] 先将导电炭黑和去离子水在球磨机中球磨2小时,再加入聚丙烯腈(占总固含量的1. 5% )和丁腈橡胶乳液(占总固含量的2. 5% )球磨1小时,将浆料除气泡后涂布在铜箔片上,经烘干、辊压后备用,导电层厚度为20 μ m;将PVDF用二甲基乙酰胺配成5%的溶液(占最终固形物含量的4% ),然后加入导电剂(占最终固形物含量的2% ),采用高速剪切分散2. 5小时,再加入天然石墨(占最终固形物含量的94% ),采用高速剪切分散3小时, 抽真空搅拌0.5小时后,将浆料均勻的涂布在前述铜箔上,采用90°C的大量热风循环烤干极片。 [0034] The first electrically conductive carbon black, and deionized water were ball milled in a ball mill for 2 hours, then added polyacrylonitrile (total solids content of 1.5%) and nitrile rubber latex (total solid content of 2.5% ) ball milled for 1 hour after the addition the slurry was coated on copper foil bubbles, after drying, the standby roll, the conductive layer having a thickness of 20 μ m; the PVDF dimethylacetamide formulated with a 5% solution of ( 4% final solid content), followed by addition of a conductive agent (2% final solid content), high-speed shearing dispersing 2.5 hours, natural graphite was added (94% final solid content), using high shear dispersed for 3 hours, vacuum was stirred for 0.5 hours, the slurry was uniformly coated on the copper foil of 90 ° C using a circulating hot air to dry a large number of pole pieces. 将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/EC-DMC(l : 1)溶液为电解液组装扣式电池, 并在2. 0〜0. 005V的电压范围,0. IC到20C的电流密度下进行等倍率充放电实验,该电极在0. IC电流密度下充放电比容量为319mAh/g,在5C电流密度下放电比容量为123mAh/g, 20C电流密度下放电比容量仍可达到43mAh/g ;5C循环100次基本无衰减,显示出突出的循环性能和大倍率充放电能力。 The pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC ( l:.. 1) as the electrolyte assembled coin cell, and the voltage range 2. 0~0 005V, 0 IC to be 20C at a current density rate discharge test and the like, of the electrode current density at 0. IC the charge-discharge capacity of 319mAh / g, at 5C discharge capacity of current densities than 123mAh / g, the discharge capacity at 20C can reach current densities than 43mAh / g; 5C 100 cycles substantially without attenuation, showing outstanding cycle properties and high rate charge-discharge capability.

[0035] 实施例4 [0035] Example 4

[0036] 先将碳黑和去离子水在球磨机中球磨5小时,再加入聚甲基丙烯酸酯(占总固含量的)和丙烯腈-丁二烯-苯乙烯橡胶乳液(占总固含量的1. 5% )球磨0. 5小时,将浆料除气泡后涂布在铝箔片上,经烘干、辊压后备用,导电层厚度为25 μ m ;将PTFE用NMP 配成5%的溶液(占最终固形物含量的2.5% ),然后加入导电剂(占最终固形物含量的4% ),采用高速剪切分散3小时,再加入0. 5Li2Mn03 · 0. 5LiCo0.44Ni0.25Mn0.3102(占最终固形物含量93. 5% ),采用高速剪切分散2小时,抽真空搅拌1小时后,将浆料均勻的涂布在前述铝箔上,采用130°C的大量热风循环烤干极片。 [0036] The first carbon black, and deionized water were ball milled in a ball mill for 5 hours and then added polymethacrylate (total solids) and acrylonitrile - butadiene - styrene rubber latex (total solid content of 1.5%) 0.5 hours milling, the slurry after the addition of bubbles was coated on aluminum foil, after drying, the standby roll, the conductive layer having a thickness of 25 μ m; the PTFE with a 5% solution of NMP dubbed (2.5% of final solids content), followed by addition of a conductive agent (4% final solid content), high-speed shearing dispersing for 3 hours, was added 0. 5Li2Mn03 · 0. 5LiCo0.44Ni0.25Mn0.3102 ( of the final solids content of 93.5 percent), dispersed for 2 hours using a high shear, vacuum after stirring for 1 hour, the slurry was uniformly coated on the aluminum foil using a 130 ° C hot air circulation to dry large pole pieces . 将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/ EC-DMC(1 : 1)溶液为电解液组装扣式电池,并在4. 6〜2. OV的电压范围,0. IC到20C的电流密度下进行等倍率充放电实验,该电极在0. IC电流密度下充放电比容量为^OmAh/g, 在5C电流密度下放电比容量为135mAh/g,20C电流密度下放电比容量仍可达到^mAh/g ; 5C循环100次无衰减1. 03%,显示出突出的循环性能和大倍率充放电能力。 The pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC ( 1: 1) solution as the electrolyte assemble button batteries, and 4. 6~2 OV voltage range, 0 IC 20C at a current density to be rate discharge test and the like, of the electrode current density at 0. IC the charge-discharge capacity of ^ OmAh / g, the discharge capacity was 135mAh / g at a current density of 5C, 20C discharge capacity at the current density can reach ^ mAh / g; 5C unattenuated 100 cycles 1.03%, exhibited outstanding cycling performance and high rate discharge capability.

[0037] 实施例5 [0037] Example 5

[0038] 先将碳纳米管(CNTs)和去离子水在球磨机中球磨2小时,再加入羧甲基纤维素钠(占总固含量的)和苯乙烯-丁二烯-苯乙烯橡胶(占最终固形物含量2. 5% )球磨0. 5 小时,将浆料除气泡后涂布在铜箔片上,经烘干、辊压后备用,导电层厚度为13μπι ^fPTFE 用NMP配成6%的溶液(占最终固形物含量的4%),然后加入导电剂(占最终固形物含量的4% ),采用高速剪切分散3. 5小时,再加入钛酸锂Li4Ti5O12 (占最终固形物含量92% ), 采用高速剪切分散3小时,抽真空搅拌0. 5小时后,将浆料均勻的涂布在前述铜箔上,采用120°C的大量热风循环烤干极片。 [0038] The first carbon nanotube (of CNTs) and deionized water were milled in a ball mill for 2 hours, was added sodium carboxymethylcellulose (total solids) and styrene - butadiene - styrene rubber (% of the final solids content 2.5%) 0.5 hours milling, the slurry after the addition of bubbles was coated on copper foil, after drying, the standby roll, the thickness of the conductive layer 13μπι ^ fPTFE paired with NMP 6% solution (4% final solid content), followed by addition of a conductive agent (4% final solid content), high-speed shearing dispersing 3.5 hours, the lithium titanate of Li4Ti5O12 was added (solids content of the final 92%), dispersed for 3 hours using high-speed shearing, vacuum was stirred 0.5 hours, the slurry was uniformly coated on the copper foil to 120 ° C using a circulating hot air to dry a large number of pole pieces. 将烘干后的极片进行辊压,再经真空干燥后直接以该极片为工作电极,以聚丙烯微孔膜为隔膜,金属锂片为负极,以lmol/L LiPF6/EC-DMC(l : 1)溶液为电解液组装扣式电池,并在2. 5〜0. 2V的电压范围,0. IC到20C的电流密度下进行等倍率充放电实验,该电极在0. IC电流密度下充放电比容量为174mAh/g,在5C电流密度下放电比容量为141mAh/g,20C电流密度下放电比容量仍可达到82mAh/g ;5C循环100次无衰减,显示出突出的循环性能和大倍率充放电能力。 The pole pieces after drying was rolled, and then dried under vacuum directly after the pole piece as a working electrode, a polypropylene microporous membrane as a separator, a negative electrode as metal lithium sheet to lmol / L LiPF6 / EC-DMC ( l:.. 1) as the electrolyte assembled coin cell, and the voltage range 2. 5~0 2V, 0 IC to be 20C at a current density rate discharge test and the like, of the electrode current density at 0. IC the charge-discharge capacity of 174mAh / g, at 5C discharge capacity of current densities than 141mAh / g, the discharge capacity at 20C can reach current densities than 82mAh / g; 5C 100 cycles without attenuation, showing outstanding cycling performance and high rate charge-discharge capability.

Claims (7)

1. 一种动力电池电极,其特征在于:它包括金属箔片,在金属箔片上涂有一层导电剂, 经烘干、辊压后,再涂上储锂活性材料,导电层厚度为0. 01-30 μ m。 A battery electrode, which is characterized in that: it comprises a metal foil, the metal foil coated with a conductive agent, after drying, rolling, and then coated with the active material reservoir lithium, a conductive layer having a thickness of 0. 01-30 μ m.
2.根据权利要求1所述动力电池电极,其特征在于,所述金属箔片为铝箔和铜箔。 2. The battery electrode according to claim 1, characterized in that the metal foil is an aluminum foil and a copper foil.
3.根据权利要求1所述动力电池电极,其特征在于,所述导电剂为导电炭黑、导电石墨和导电碳纳米管或者对前述三种材料任选两种以上材料进行元素掺杂、表面包覆、改性所得的复合材料。 3. The battery electrode according to claim 1, characterized in that said conductive agent is a conductive carbon black, graphite and conductive carbon nanotube electrically conductive material or, optionally, two or more of the aforementioned three elements doped materials, surface coated, modified resulting composite material.
4.根据权利要求1所述动力电池电极,其特征在于,所述储锂活性材料为钴酸锂LiCoO2、镍酸锂LiNi02、LiMePO4, Li2MeSi04、磷酸钒锂Li3V2 (PO4) 3、Lii^eBO3、富锂正极材料bLi2Mn03 · (l_b)LiM02、钛酸锂Li4Ti5012、H2Ti12O25、二氧化钼MoO2、石墨、MCMB、金属锡、锡基复合材料、单质硅和硅合金或者对上述材料进行元素掺杂、表面包覆、改性所得到的复合材料中的任意一种或多种,其中Me为Fe、Mn、Co、Ni,其中,O彡b < LLiMO2为LiCoxNiyMnzO2, x+y+z = 1 或锰酸锂LiMn2O4 或Li4Mn5O9 或Li4Mn5O1215 4. The battery electrode of claim 1, wherein said active material is a lithium storage lithium cobaltate LiCoO2, lithium nickelate LiNi02, LiMePO4, Li2MeSi04, lithium vanadium phosphate Li3V2 (PO4) 3, Lii ^ eBO3, lithium rich cathode material bLi2Mn03 · (l_b) LiM02, lithium titanate Li4Ti5012, H2Ti12O25, MoO2 molybdenum dioxide, graphite, the MCMB, metallic tin, tin-based composite material, and elemental silicon or a silicon alloy material of the above-described doping elements, surface coated, composite material obtained by modification of any one or more, wherein Me is Fe, Mn, Co, Ni, wherein, San O b <LLiMO2 is LiCoxNiyMnzO2, x + y + z = 1 or manganate or LiMn2O4 lithium or Li4Mn5O9 Li4Mn5O1215
5. 一种如权利要求1所述的动力电池电极的制备方法,其具体制作过程为:a、将导电剂和去离子水在球磨机中球磨1-5小时,再加入占固体质量比的0. 1-10%水性粘结剂乳液或溶液球磨0. 1-1小时得到第一浆料;b、将第一浆料除气泡后涂布在金属箔片上,经干燥、辊压后形成电极坯材;C、将占固体质量比0. 1-10%的油性粘结剂用有机溶剂配成溶液,再把占固体质量比0. 1-40%的导电剂和储锂活性材料分散在该溶液中得到第二浆料;d、将第二浆料除气泡后将浆料涂布在b步骤中的电极坯材上,形成电极片,将涂覆后的极片干燥。 5. A method of preparing an electrode of the battery as claimed in claim 1, which is a production process specifically: a, a conductive agent, and deionized water were ball milled in a ball mill for 1-5 hours, then was added solid mass ratio accounted 0 1-10% binder emulsion or an aqueous solution of 0. 1-1 hours to obtain a first milled slurry; B, except after the first slurry coated bubbles on the metal foil, dried, rolled to form a rear electrode blanks; C, the solid mass ratio of 0.5 to account for 1-10% of an oily binder solution was formulated with an organic solvent, then accounting for 1-40% of solid mass ratio of 0.5 and a conductive agent is dispersed in the active material reservoir lithium the second slurry obtained solution; D, except the second slurry after the slurry is applied electrode raw material gas bubbles in step b, the electrode sheet is formed, the electrode sheet after coating and drying.
6.根据权利要求5所述动力电池电极的制备方法,其特征在于,所述水性粘结剂为聚氧化乙烯、聚丙烯腈、聚甲基丙烯酸酯、羧甲基纤维素钠、氯丁橡胶、丁腈橡胶、丁苯橡胶、氯磺化聚乙烯橡胶、苯乙烯-丁二烯-苯乙烯橡胶、丙烯腈-丁二烯-苯乙烯橡胶、阿拉伯胶和天然橡胶或者上述材料的衍生物中的一种或多种。 6. The method of preparing the power battery electrode according to claim, wherein the aqueous binder is a polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, sodium carboxymethyl cellulose, chloroprene rubber , nitrile rubber, styrene-butadiene rubber, chlorosulfonated polyethylene rubber, styrene - butadiene - styrene rubber, acrylonitrile - butadiene - styrene rubber, natural rubber, gum arabic and derivatives of the above material, or one or more.
7.根据权利要求5所动力电池电极的制备方法,其特征在于,所述的有机溶剂是指以N-甲基吡咯烷酮、二甲基酰胺和二甲基乙酰胺或者上述材料的衍生物中的一种或多种;所述油性粘结剂为偏聚四氟乙烯、聚四氟乙烯和聚合类树脂或者上述材料的衍生物中的一种或多种。 7.5 battery electrode production method according to claim, wherein said organic solvent refers to derivatives of N- methylpyrrolidone, dimethylformamide and dimethylacetamide or a material in the above one or more; the oily binder is polytetrafluoroethylene vinylidene, polytetrafluoroethylene, and derivatives of the above-described polymeric resin material, or of one or more.
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CN102315426A (en) * 2011-08-31 2012-01-11 李学智 Oil-water system composite flaking technology of polymer battery
CN102412388A (en) * 2011-11-03 2012-04-11 湖南丰源业翔晶科新能源股份有限公司 Pole piece used for ternary material lithium ion battery anode and its coating method
CN102437369A (en) * 2011-12-20 2012-05-02 中国东方电气集团有限公司 Lithium ion battery
CN102768901A (en) * 2012-08-06 2012-11-07 张宝生 Long-life capacitance battery
CN102827541A (en) * 2011-11-28 2012-12-19 中航锂电(洛阳)有限公司 Coating, aqueous flexible anode piece prepared through adopting it, and lithium ion battery
CN103022420A (en) * 2011-09-27 2013-04-03 力神迈尔斯动力电池系统有限公司 Slurry homogenizing method for positive electrode of lithium-ion power battery
CN103074007A (en) * 2012-12-27 2013-05-01 上海交通大学 Water-based adhesive used in silicon anode of lithium ion battery and preparation method of silicon anode
CN103855401A (en) * 2012-12-06 2014-06-11 上海比亚迪有限公司 Lithium ion battery positive pole piece as well as preparation method and lithium ion battery comprising pole piece
CN103928657A (en) * 2014-04-30 2014-07-16 泉州劲鑫电子有限公司 High-power lithium ion battery pole piece and preparation process thereof
CN104332602A (en) * 2014-10-11 2015-02-04 柳州豪祥特科技有限公司 Preparation method of doped modified lithium manganate positive electrode material
CN105870403A (en) * 2016-05-16 2016-08-17 张升亮 Lithium-ion battery cathode sheet, preparation method thereof as well as super capacitor composite battery comprising lithium-ion battery cathode sheet
CN106560947A (en) * 2016-09-05 2017-04-12 深圳市优特利电源有限公司 High-comprehensive-performance positive electrode of lithium iron phosphate battery and preparation method thereof, and lithium ion battery
US9786916B2 (en) 2012-04-18 2017-10-10 Lg Chem, Ltd. Electrode and secondary battery including the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1126536A2 (en) * 2000-02-16 2001-08-22 Itochu Corporation Multi-layer electrode structure, and method of manufacturing same
WO2003038846A1 (en) * 2001-11-01 2003-05-08 Maxwell Technologies, Inc. Electrochemical double layer capacitor having carbon powder electrodes
CN101911345A (en) * 2008-01-11 2010-12-08 丰田自动车株式会社 Electrode and method for manufacturing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1126536A2 (en) * 2000-02-16 2001-08-22 Itochu Corporation Multi-layer electrode structure, and method of manufacturing same
WO2003038846A1 (en) * 2001-11-01 2003-05-08 Maxwell Technologies, Inc. Electrochemical double layer capacitor having carbon powder electrodes
CN101911345A (en) * 2008-01-11 2010-12-08 丰田自动车株式会社 Electrode and method for manufacturing the same

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102315426A (en) * 2011-08-31 2012-01-11 李学智 Oil-water system composite flaking technology of polymer battery
CN102315426B (en) 2011-08-31 2014-04-30 李学智 Oil-water system composite flaking technology of polymer battery
CN103022420B (en) * 2011-09-27 2015-06-10 力神迈尔斯动力电池系统有限公司 Slurry homogenizing method for positive electrode of lithium-ion power battery
CN103022420A (en) * 2011-09-27 2013-04-03 力神迈尔斯动力电池系统有限公司 Slurry homogenizing method for positive electrode of lithium-ion power battery
CN102412388A (en) * 2011-11-03 2012-04-11 湖南丰源业翔晶科新能源股份有限公司 Pole piece used for ternary material lithium ion battery anode and its coating method
CN102827541A (en) * 2011-11-28 2012-12-19 中航锂电(洛阳)有限公司 Coating, aqueous flexible anode piece prepared through adopting it, and lithium ion battery
CN102437369A (en) * 2011-12-20 2012-05-02 中国东方电气集团有限公司 Lithium ion battery
CN102437369B (en) 2011-12-20 2014-07-02 中国东方电气集团有限公司 Lithium ion battery
US9786916B2 (en) 2012-04-18 2017-10-10 Lg Chem, Ltd. Electrode and secondary battery including the same
CN102768901A (en) * 2012-08-06 2012-11-07 张宝生 Long-life capacitance battery
CN103855401A (en) * 2012-12-06 2014-06-11 上海比亚迪有限公司 Lithium ion battery positive pole piece as well as preparation method and lithium ion battery comprising pole piece
CN103074007A (en) * 2012-12-27 2013-05-01 上海交通大学 Water-based adhesive used in silicon anode of lithium ion battery and preparation method of silicon anode
CN103074007B (en) * 2012-12-27 2015-08-26 上海交通大学 The method of preparing a lithium ion battery aqueous adhesive silicon anode and cathode of silicon
CN103928657A (en) * 2014-04-30 2014-07-16 泉州劲鑫电子有限公司 High-power lithium ion battery pole piece and preparation process thereof
CN104332602A (en) * 2014-10-11 2015-02-04 柳州豪祥特科技有限公司 Preparation method of doped modified lithium manganate positive electrode material
CN105870403A (en) * 2016-05-16 2016-08-17 张升亮 Lithium-ion battery cathode sheet, preparation method thereof as well as super capacitor composite battery comprising lithium-ion battery cathode sheet
CN106560947A (en) * 2016-09-05 2017-04-12 深圳市优特利电源有限公司 High-comprehensive-performance positive electrode of lithium iron phosphate battery and preparation method thereof, and lithium ion battery

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