WO2017000742A1 - 一种降低锂离子电池三元正极材料pH值的简便方法 - Google Patents

一种降低锂离子电池三元正极材料pH值的简便方法 Download PDF

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WO2017000742A1
WO2017000742A1 PCT/CN2016/084414 CN2016084414W WO2017000742A1 WO 2017000742 A1 WO2017000742 A1 WO 2017000742A1 CN 2016084414 W CN2016084414 W CN 2016084414W WO 2017000742 A1 WO2017000742 A1 WO 2017000742A1
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positive electrode
ascorbic acid
lithium ion
electrode material
reducing
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French (fr)
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陈晓
李廷峰
吕金钊
赵成龙
王瑛
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山东玉皇新能源科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the invention relates to the field of electrochemistry, in particular to a simple method for reducing the pH value of a ternary cathode material of a lithium ion battery.
  • Betray proposes to wash the lithium ion battery cathode material by using a mixed solution of an organic acid (preferably a carboxylic acid) and an alcohol (preferably a C 1-6 alcohol), which can effectively lower the pH of the positive electrode material and improve the material.
  • an organic acid preferably a carboxylic acid
  • an alcohol preferably a C 1-6 alcohol
  • the present invention provides a simple method for reducing the pH value of the positive electrode material while reducing the number of washings and reducing the pH value of the ternary positive electrode material of the lithium ion battery.
  • a simple method for reducing the pH value of a ternary cathode material of a lithium ion battery is as follows:
  • step 1) ascorbic acid is dissolved in an organic solvent by stirring, ultrasonic wave or the like to form a uniform solution.
  • the purpose of dissolving ascorbic acid in an organic solvent to form a uniform solution is to prevent the local concentration of ascorbic acid in the reaction system from being too high, which affects the treatment effect.
  • the organic solvent in the step 1) is at least one of ethanol, methanol, and ethyl acetate.
  • the concentration of the ascorbic acid is 0.001 to 0.015 times the concentration of the lithium ion positive electrode material suspension.
  • concentration of ascorbic acid is lower than the above range, lithium hydroxide and lithium carbonate on the surface of the positive electrode material are not sufficiently involved in the reaction, and when the concentration of ascorbic acid is higher than the above range, the cost is increased on the one hand, and may be caused on the other hand. Destruction of the structure of the positive electrode material;
  • the reaction temperature in the step 2) is 20 to 40 ° C, and the reaction time is 3 to 6 hours.
  • the lithium ion positive electrode material has a molecular formula of LiNi 1-xy Co x M y O 2 , 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, and M is one of the metal elements Mn and Al.
  • step 3 solid-liquid separation is achieved by centrifugation.
  • step 3 the solid is washed with methanol or ethanol.
  • step 3 the drying is carried out in two steps, first drying at 75-85 ° C for 6-8 h, and then drying in a vacuum drying oven at 120 ° C for 10-12 h.
  • the concentration of ascorbic acid is 0.001-0.015 times the concentration of the suspension of the lithium ion positive electrode material, and the amount of ascorbic acid used is small, which can reduce the processing cost.
  • a small amount of unreacted ascorbic acid molecules may participate in the formation of the SEI film during the activation of the battery, thereby reducing the washing operation of the positive electrode material obtained after the surface treatment.
  • the discharge rate performance can be improved, and the discharge capacity of the first week of the battery and the charge and discharge efficiency of the first week are improved.
  • Figure 2 is an XRD chart of the solid obtained in Example 1 and Comparative Example of the present invention.
  • Figure 3 is a graph showing the rate discharge curves of Examples 1 to 5 and Comparative Examples of the present invention.
  • the ratio of ascorbic acid concentration A to lithium ion cathode material suspension concentration B is 0.0106, and the surface treatment of LiNi 0.5 Co 0.2 Mn 0.3 O 2 material is carried out for 4 hours at 20 °C:
  • the ratio of ascorbic acid concentration A to lithium ion positive electrode material suspension concentration B is 0.0052, and the surface treatment of LiNi 0.5 Co 0.2 Mn 0.3 O 2 material is carried out at 20 ° C for 4 h:
  • a surface-treated LiNi 0.5 Co 0.2 Mn 0.3 O 2 material was obtained in the same manner as in Example 1 except that the ascorbic acid mass was adjusted to 0.026 g.
  • the ratio of ascorbic acid concentration A to lithium ion cathode material suspension concentration B is 0.0106, and the surface treatment of LiNi 0.5 Co 0.2 Mn 0.3 O 2 material is carried out at 40 ° C for 4 h:
  • a surface-treated LiNi 0.5 Co 0.2 Mn 0.3 O 2 material was obtained in the same manner as in Example 1 except that the reaction temperature was adjusted to 40 °C.
  • the ratio of ascorbic acid concentration A to lithium ion cathode material suspension concentration B is 0.0106, and the surface treatment of LiNi 0.5 Co 0.2 Mn 0.3 O 2 material is carried out at 20 ° C for 6 h:
  • a surface-treated LiNi 0.5 Co 0.2 Mn 0.3 O 2 material was obtained in the same manner as in Example 1 except that the reaction time was adjusted to 6 h.
  • the ratio of ascorbic acid concentration A to lithium ion positive electrode material suspension concentration B is 0.0070, and the surface treatment of LiNi 0.5 Co 0.2 Mn 0.3 O 2 material is carried out at 20 ° C for 4 h:
  • a surface-treated LiNi 0.5 Co 0.2 Mn 0.3 O 2 material was obtained in the same manner as in Example 2 except that the ascorbic acid mass was adjusted to 0.035 g.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 material without surface treatment LiNi 0.5 Co 0.2 Mn 0.3 O 2 material without surface treatment.
  • pH test 1 g of the positive electrode material was weighed into 10 mL of deionized water, and the pH was tested after stirring for 1 hour.
  • the positive electrode slurry was formulated using NMP so that the weight ratio (wt%) of the positive electrode material: SP:PVDF was 94.5:3:2.5.
  • the positive electrode slurry was uniformly coated on an aluminum foil and dried at 120 ° C for 4 hours to evaporate the solvent NMP.
  • the roller was pressed to a compaction density of 3.0 to 3.3 g/cm 3 by a roll press, and further punched into a positive electrode sheet having a diameter of 12 mm by a punching machine.
  • the positive electrode sheets were assembled with the Li sheets into a 2032 type button battery.
  • Button battery activation charging at 230 °C to 4.3V at 25 °C, then charging at 4.3V constant voltage until the current is less than 0.05C, after standing for 5min, discharging to 3V at 0.2C rate is a charge and discharge cycle. The battery activation process is completed after three charge and discharge cycles.
  • Charging and discharging test Under the condition of 25 °C, the battery is charged at a rate of 0.5C in a voltage range of 3V to 4.3V with respect to Li metal, and then charged at a constant voltage of 4.3V until the current is less than 0.05C, after standing for 5 minutes. The battery was discharged at a rate of 0.5 C to complete a charge and discharge cycle to obtain a discharge capacity of 0.5 C. For the 1 C, 2 C, 3 C, and 5 C discharge capacities, the charge was charged at a rate of 1 C, and was obtained by discharging at a rate of 1 C, 2 C, 3 C, and 5 C, respectively. Before performing the charge and discharge test, the battery must first complete the activation process.
  • Cyclic performance retention rate The activation process of the buckle battery was completed at 25 ° C, and then charged and discharged 50 times at 1 C rate, and the 1 C cycle performance of the buckle battery was characterized by the ratio of the 50th 1 C discharge capacity to the first 1 C discharge capacity.
  • Example 1 is an SEM image of the treated positive electrode material obtained in Example 1, and it can be seen from the figure that the ascorbic acid ethanol system is passed through The surface morphology of the NCM523 cathode material was not destroyed after surface treatment.
  • Examples 1 to 5 are discharge rate diagram of Examples 1 to 5 and a comparative example. It can be seen from the figure that the NCM523 cathode material surface-treated by the ascorbic acid ethanol system has improved rate discharge performance, which can be explained as the surface of the cathode material after surface treatment with ascorbic acid.
  • the decrease in the content of basic substances such as Li 2 CO 3 and LiOH enhances the electrical conductivity.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明公开了一种降低锂离子电池三元正极材料pH值的简便方法，属于电化学领域。本发明采用抗坏血酸的有机溶液体系降低锂电池正极材料pH值。该方法的特征之一在于，抗坏血酸和锂离子正极材料悬浊液浓度的关系满足0.001B≤A≤0.015B，式中A为抗坏血酸浓度，单位为g/L；B为正极材料浓度，单位为g/L；同时抗坏血酸浓度A应进一步满足关系式A≤0.8s(s为抗坏血酸在相应有机溶剂中的溶解度s，单位为g/100g)。该方法的特征之二在于，经抗坏血酸改性的锂离子正极材料在离心分离后所需洗涤次数少。本发明工艺简单，成本低廉，可以通过调整VC浓度得到具有改善的放电倍率性能的正极材料。

Description

一种降低锂离子电池三元正极材料pH值的简便方法 技术领域
本发明涉及电化学领域，特别涉及一种降低锂离子电池三元正极材料pH值的简便方法。
背景技术
三元材料，尤其是高镍三元材料在制备过程中常因Li源过量等原因引起产物pH值偏高，造成正极材料的电化学性能及加工性能的恶化。针对这一问题，松下在专利“CN102047473A”中提出采用含有卤化氢，含氟锂盐以及碳酸亚丙酯等非质子性溶剂组成的洗净剂来洗净锂离子电池用正极，同时在正极活性物质的表面附着卤化锂。贝特瑞在专利“CN103337614A”中提出采用有机酸(优选羧酸)与醇(优选C1-6醇)混合溶液洗涤锂离子电池正极材料，该方法能有效降低正极材料的pH值并提高材料的加工性能，但是离心后所得改性正极材料需用醇进行多次洗涤(优选3～5次)，造成了正极材料的额外损耗。
发明内容
为了弥补以上不足，本发明提供了一种可有效降低正极材料pH值同时可减少洗涤次数且成本低的降低锂离子电池三元正极材料pH值的简便方法。
本发明的技术方案为：
一种降低锂离子电池三元正极材料pH值的简便方法，步骤如下：
1)将抗坏血酸溶于有机溶剂，形成均一溶液；其中有机溶剂为沸点≤100℃的醇或酯，抗坏血酸的浓度≤0.8s，其中，s为抗坏血酸在相应有机溶剂中的溶解度；
2)向所述均一溶液中加入锂离子正极材料，形成悬浊液，在10-60℃下持续搅拌反应2-10h；3)固液分离，洗涤所得固体1-2次，干燥。
其中步骤1)中通过搅拌、超声波等方式将抗坏血酸溶于有机溶剂形成均一溶液。抗坏血酸溶解于有机溶剂形成均一溶液的目的在于防止反应体系中抗坏血酸局部浓度过高，影响处理效果。
作为优选，步骤1)中的有机溶剂为乙醇、甲醇、乙酸乙酯中的至少一种。
作为优选，步骤2)中，抗坏血酸的浓度为锂离子正极材料悬浊液浓度的0.001-0.015倍。当抗坏血酸的浓度低于上述范围时，正极材料表面氢氧化锂及碳酸锂未充分参与反应，而当抗坏血酸的浓度高于上述范围时，一方面会造成成本的升高，另一方面可能会引起正极材料结构的破坏；
作为优选，步骤2)中的反应温度为20-40℃，反应时间为3-6h。
优选的，所述锂离子正极材料的分子式为LiNi1-x-yCoxMyO2，0＜x≤0.5，0＜y≤0.5，M为金属元素Mn，Al中的一种。
优选的，步骤3)中，通过离心实现固液分离。
优选的，步骤3)中，使用甲醇、乙醇对固体进行洗涤。
优选的，步骤3)中，所述干燥分两步完成，首先在75-85℃下干燥6-8h，然后在真空干燥箱120℃干燥10-12h。
本发明的有益效果为：
1)选用抗坏血酸对正极材料进行表面处理时，抗坏血酸的浓度为锂离子正极材料悬浊液浓度的0.001-0.015倍，抗坏血酸使用量少，可降低处理成本。
2)少量未反应的抗坏血酸分子可参与电池活化过程中SEI膜的形成，因而可减少经表面处理后所得正极材料的洗涤操作。
3)经处理后的正极材料作为锂电池正极时，可改善放电倍率性能，电池首周放电容量以及首周充放电效率均有提高。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
附图1为本发明实施例1所得固体的SEM图。
附图2为本发明实施例1及对比例所得固体的XRD图。
附图3本发明实施例1～5及对比例的倍率放电曲线图。
具体实施方式
实施例1
抗坏血酸浓度A与锂离子正极材料悬浊液浓度B比值为0.0106，20℃条件下反应4h对LiNi0.5Co0.2Mn0.3O2材料进行表面处理：
1)称取0.053g抗坏血酸通过搅拌溶解于500ml乙醇中，形成均一稳定溶液；
2)加入5g LiNi0.5Co0.2Mn0.3O2材料，20℃下搅拌条件反应4h；
3)离心该悬浊液以实现固液分离，离心所得样品用乙醇洗涤2次；
4)样品在80℃干燥8h，继而在真空条件下120℃干燥12h即得经表面处理的LiNi0.5Co0.2Mn0.3O2材料。
实施例2
抗坏血酸浓度A与锂离子正极材料悬浊液浓度B比值为0.0052，20℃条件下反应4h对LiNi0.5Co0.2Mn0.3O2材料进行表面处理：
除了将抗坏血酸质量调整为0.026g之外，以与实施例1相同的方式获得经表面处理的LiNi0.5Co0.2Mn0.3O2材料。
实施例3
抗坏血酸浓度A与锂离子正极材料悬浊液浓度B比值为0.0106，40℃条件下反应4h对LiNi0.5Co0.2Mn0.3O2材料进行表面处理：
除了将反应温度调整为40℃之外，以与实施例1相同的方式获得经表面处理的LiNi0.5Co0.2Mn0.3O2材料。
实施例4
抗坏血酸浓度A与锂离子正极材料悬浊液浓度B比值为0.0106，20℃条件下反应6h对LiNi0.5Co0.2Mn0.3O2材料进行表面处理：
除了将反应时间调整为6h之外，以与实施例1相同的方式获得经表面处理的LiNi0.5Co0.2Mn0.3O2材料。
实施例5
抗坏血酸浓度A与锂离子正极材料悬浊液浓度B比值为0.0070，20℃条件下反应4h对LiNi0.5Co0.2Mn0.3O2材料进行表面处理：
除了将抗坏血酸质量调整为0.035g之外，以与实施例2相同的方式获得经表面处理的LiNi0.5Co0.2Mn0.3O2材料。
对比例
未经表面处理的LiNi0.5Co0.2Mn0.3O2材料。
pH值测试：称取1g正极材料加入10mL去离子水中，搅拌1h后测试pH值。
对实施例1～5及对比例所述正极材料采用以下方法组装成扣式电池：
利用NMP配制正极浆料，使得正极材料：SP：PVDF的重量比(wt％)为94.5:3:2.5。将正极浆料均匀涂覆在铝箔上，在120℃条件下干燥4h以蒸发溶剂NMP。采用辊压机将其辊压至压实密度3.0～3.3g/cm3，采用冲片机进一步将其冲裁为直径12mm的正极片。在手套箱中正极片与Li片一起组装成2032型扣式电池。
对实施例1～5及对比例制备的2032型扣式电池采用以下方法进行性能测试：
扣式电池活化：在25℃条件下以0.2C倍率充电至4.3V，再以4.3V恒压充电至电流小于0.05C，静置5min后以0.2C倍率放电至3V即为一个充放电循环，三次充放电循环后完成扣电池活化过程。
充放电测试：在25℃条件下，以相对于Li金属3V～4.3V电压区间内，以0.5C倍率对扣电池进行充电，再以4.3V恒压充电至电流小于0.05C，静置5min后以0.5C倍率放电，完成一个充放电循环，获得0.5C放电容量；对于1C，2C，3C，5C放电容量的测定则以1C倍率充电，分别采用1C，2C，3C，5C倍率放电而得。进行充放电测试前，扣电池需首先完成活化过程。
循环性能保持率：在25℃条件下完成扣电池的活化过程，随后以1C倍率充放电50次，以第50次1C放电容量与首次1C放电容量的比值来表征扣电池的1C循环性能。
对上述实施例1～5以及对比例进行pH测试以及扣电性能测试，测试结果如下表：
Figure PCTCN2016084414-appb-000001
如上表所示，经过抗坏血酸有机溶液体系表面处理的实施例1～5与未经抗坏血酸处理的对比例相比较，pH值均有不同幅度降低，这表明抗坏血酸有机溶剂体系可与三元材料表面Li2CO3、LiOH等碱性物质发生反应。实施例1～5中pH的降低幅度与抗坏血酸浓度、反应时间及反应温度有关。与对比例相比，实施例1～5中材料的首周放电容量以及首周充放电效率均有提高。
图1为实施例1所得经处理正极材料的SEM图，由图可知，经过抗坏血酸乙醇体系 表面处理后NCM523正极材料的表面形貌未遭破坏。
由图2实施例1与对比例的XRD图进一步可知，经过抗坏血酸乙醇体系表面处理的NCM523正极材料与未进行表面处理的原材料相比，其特征峰未发生变化，这表明抗坏血酸乙醇溶剂体系表面处理NCM523材料未对其结构造成破坏。
图3为实施例1～5与对比例的放电倍率图，由图可知，经过抗坏血酸乙醇体系表面处理的NCM523正极材料具有改善的倍率放电性能，这可以解释为经抗坏血酸表面处理后，正极材料表面Li2CO3、LiOH等碱性物质含量的降低提高了其导电性。

Claims (8)

  1. 一种降低锂离子电池三元正极材料pH值的简便方法，其特征在于，步骤如下：
    1)将抗坏血酸溶于有机溶剂，形成均一溶液；其中有机溶剂为沸点≤100℃的醇或酯，抗坏血酸的浓度≤0.8s，其中，s为抗坏血酸在相应有机溶剂中的溶解度；
    2)向所述均一溶液中加入锂离子正极材料，形成悬浊液，在10-60℃下持续搅拌反应2-10h；
    3)固液分离，洗涤所得固体1-2次，干燥。
  2. 如权利要求1所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：步骤1)中的有机溶剂为乙醇、甲醇、乙酸乙酯中的至少一种。
  3. 如权利要求1所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：步骤2)中，抗坏血酸的浓度为锂离子正极材料悬浊液浓度的0.001-0.015倍。
  4. 如权利要求1所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：步骤2)中的反应温度为20-40℃，反应时间为3-6h。
  5. 如权利要求1-4任一项所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：所述锂离子正极材料的分子式为LiNi1-x-yCoxMyO2，0＜x≤0.5，0＜y≤0.5，M为金属元素Mn，Al中的一种。
  6. 如权利要求1所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：步骤3)中，通过离心实现固液分离。
  7. 如权利要求1所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：步骤3)中，使用甲醇、乙醇对固体进行洗涤。
  8. 如权利要求1所述降低锂离子电池三元正极材料pH值的简便方法，其特征在于：步骤3)中，所述干燥分两步完成，首先在75-85℃下干燥6-8h，然后在真空干燥箱120℃干燥10-12h。
PCT/CN2016/084414 2015-06-29 2016-06-01 一种降低锂离子电池三元正极材料pH值的简便方法 WO2017000742A1 (zh)

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