CN114792793A - A sodium-ion battery additive and high-power sodium-ion battery - Google Patents

A sodium-ion battery additive and high-power sodium-ion battery Download PDF

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CN114792793A
CN114792793A CN202110098328.1A CN202110098328A CN114792793A CN 114792793 A CN114792793 A CN 114792793A CN 202110098328 A CN202110098328 A CN 202110098328A CN 114792793 A CN114792793 A CN 114792793A
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胡勇胜
周权
陆雅翔
陈立泉
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
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    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
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Abstract

本发明涉及一种钠离子电池添加剂和高功率钠离子电池。所述添加剂为β‑氧化铝,所述β‑氧化铝的化学式为M2O·xAl2O3,其中M为元素周期表中IA族元素或IB族元素中的一种或几种,x=5‑11;所述添加剂用作钠离子电池正极材料和/或钠离子电池负极材料的添加剂。

Figure 202110098328

The present invention relates to a sodium-ion battery additive and a high-power sodium-ion battery. The additive is β-alumina, and the chemical formula of the β-alumina is M 2 O xAl 2 O 3 , wherein M is one or more of the elements of group IA or group IB in the periodic table of elements , x=5-11; the additive is used as an additive for the positive electrode material of sodium ion battery and/or the negative electrode material of sodium ion battery.

Figure 202110098328

Description

一种钠离子电池添加剂和高功率钠离子电池A sodium-ion battery additive and high-power sodium-ion battery

技术领域technical field

本发明涉及材料技术领域,尤其涉及一种钠离子电池添加剂和高功率钠离子电池。The invention relates to the technical field of materials, in particular to a sodium-ion battery additive and a high-power sodium-ion battery.

背景技术Background technique

在高功率应用工况下(10C,分钟级响应时间),单一锂离子电池系统在实际工况下的循环使用寿命会大幅度降低,通常采用功率型和能量型电芯的搭配使用,来提升使用寿命,应用成本较高。Under high-power application conditions (10C, minute-level response time), the cycle life of a single lithium-ion battery system under actual conditions will be greatly reduced. Usually, the combination of power type and energy type cells is used to improve Service life, high application cost.

目前,高功率应用工况多数仍然沿用铅酸蓄电池,但铅酸蓄电池的使用寿命也只有2-3年,且业内在铅酸蓄电池回收及处理方面仍然缺乏有效的方法来杜绝对环境的污染。At present, most of the high-power application conditions still use lead-acid batteries, but the service life of lead-acid batteries is only 2-3 years, and the industry still lacks effective methods in the recycling and treatment of lead-acid batteries to eliminate environmental pollution.

钠离子电池拥有原料资源丰富、成本低廉、环境友好、能量转换效率高、循环寿命长、功率特性强和安全性好等诸多独特优势,可广泛应用于包括各类储能,包括5G通讯基站、数据中心、应急后备电源、家庭储能和电网储能等。但目前现有的钠离子电池还不能够满足大倍率充放电性能的要求,尤其是不低于10C的高功率应用工况的应用。Sodium-ion batteries have many unique advantages, such as abundant raw material resources, low cost, environmental friendliness, high energy conversion efficiency, long cycle life, strong power characteristics and good safety, and can be widely used in various types of energy storage, including 5G communication base stations, Data center, emergency backup power supply, home energy storage and grid energy storage, etc. However, the current existing sodium-ion batteries cannot meet the requirements of high-rate charge-discharge performance, especially the application of high-power application conditions not lower than 10C.

发明内容SUMMARY OF THE INVENTION

本发明实施例针对现有高功率工况下电池存在的寿命短、安全隐患大的问题,提供了一种钠离子电池添加剂和高功率钠离子电池,具有高功率、高安全可靠的性能。The embodiments of the present invention provide a sodium-ion battery additive and a high-power sodium-ion battery, which have high power, high safety and reliable performance, in view of the problems of short service life and great safety hazard of the battery under the existing high-power working condition.

第一方面,本发明实施例提供了一种钠离子电池添加剂,所述添加剂为β-氧化铝,所述β-氧化铝的化学式为M2O·xAl2O3,其中M为元素周期表中IA族元素或IB族元素中的一种或几种,x=5-11;In a first aspect, an embodiment of the present invention provides a sodium-ion battery additive, the additive is β-alumina, and the chemical formula of the β-alumina is M 2 O·xAl 2 O 3 , where M is the periodic table of elements One or more of IA group elements or IB group elements, x=5-11;

所述添加剂用作钠离子电池正极材料和/或钠离子电池负极材料的添加剂。The additive is used as an additive for the positive electrode material of sodium ion battery and/or the negative electrode material of sodium ion battery.

优选的,所述IA族元素包括:Li、Na、K、Rb中的任一种;IB族包括Ag。Preferably, the IA group elements include: any one of Li, Na, K, and Rb; the IB group includes Ag.

优选的,所述添加剂在所述钠离子电池正极材料中的质量比为0.1%-30%;所述添加剂在所述钠离子电池负极材料中的质量比为1%-30%。Preferably, the mass ratio of the additive in the positive electrode material of the sodium ion battery is 0.1%-30%; the mass ratio of the additive in the negative electrode material of the sodium ion battery is 1%-30%.

优选的,钠离子电池中的钠离子在β-氧化铝的M-O平面内迁移。Preferably, the sodium ions in the sodium-ion battery migrate in the M-O plane of β-alumina.

第二方面,本发明实施例提供了一种高功率钠离子电池,包括:正极、负极、隔膜和电解液;In a second aspect, an embodiment of the present invention provides a high-power sodium-ion battery, including: a positive electrode, a negative electrode, a diaphragm, and an electrolyte;

其中所述正极包括:正极材料、正极粘结剂、正极导电剂、正极添加剂和正极集流体;所述负极包括:负极材料、负极粘结剂、负极导电剂、负极添加剂和负极集流体;The positive electrode comprises: positive electrode material, positive electrode binder, positive electrode conductive agent, positive electrode additive and positive electrode current collector; the negative electrode comprises: negative electrode material, negative electrode binder, negative electrode conductive agent, negative electrode additive and negative electrode current collector;

所述正极添加剂和/或负极添加剂包括上述第一方面所述的钠离子电池添加剂。The positive electrode additive and/or the negative electrode additive includes the sodium ion battery additive described in the first aspect above.

所述正极中,正极材料所占质量比为60%-99%,正极粘结剂所占质量比为0.1%-20%,正极导电剂所占质量比为0.1%-20%,正极添加剂所占质量比为0.1%-30%;正极单面面密度5.0-30.0mg/cm2;所述正极集流体为厚度为4-30μm的铝箔;In the positive electrode, the mass ratio of the positive electrode material is 60%-99%, the mass ratio of the positive electrode binder is 0.1%-20%, the mass ratio of the positive electrode conductive agent is 0.1%-20%, and the total mass ratio of the positive electrode additive is 0.1%-20%. The mass ratio is 0.1%-30%; the single-sided density of the positive electrode is 5.0-30.0 mg/cm 2 ; the positive electrode current collector is an aluminum foil with a thickness of 4-30 μm;

所述正极材料包括:氧化物正极材料、聚阴离子类正极材料、普鲁士蓝类正极材料、有机类材料和转化正极材料中的任一种;The positive electrode material includes: any one of oxide positive electrode material, polyanion positive electrode material, Prussian blue positive electrode material, organic material and conversion positive electrode material;

其中,所述氧化物正极材料的结构通式为NaxM1O2,M1为过渡金属元素中的一种或者多种;Wherein, the general structural formula of the oxide cathode material is Na x M1O 2 , and M1 is one or more transition metal elements;

所述聚阴离子类正极材料的结构通式为NaxM2y(XaOb)zZw,其中,M2为Ti、V、Cr、Mn、Fe、Co、Ni、Ca、Mg、Al、Nb等中的一种或几种;X为Si、S、P、As、B、Mo、W、Ge中的一种或几种;Z为F或OH;The general structural formula of the polyanion cathode material is Na x M2 y (X a O b ) z Z w , wherein M2 is Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al, One or more of Nb, etc.; X is one or more of Si, S, P, As, B, Mo, W, Ge; Z is F or OH;

所述普鲁士蓝类正极材料的结构通式为AxMa[Mb(CN)6](1-y)·y·nH2O,其中0≤x≤2,0<y<1,A为碱金属离子,Ma、Mb分别为Mn、Fe中的一种。The general structural formula of the Prussian blue cathode material is A x M a [M b (CN) 6 ] (1-y)·y ·nH 2 O, wherein 0≤x≤2, 0<y<1, A is an alkali metal ion, and Ma and Mb are one of Mn and Fe, respectively.

优选的,所述负极中,负极材料所占质量比为60%-99%,负极粘结剂所占质量比为0.1%-20%,负极导电剂所占质量比为0.1%-20%,负极添加剂所占质量比为1%-30%;负极单面密度3.0-20.0mg/cm2;所述负极集流体为厚度为4-30μm的铝箔或铜箔;Preferably, in the negative electrode, the negative electrode material accounts for 60%-99% by mass, the negative electrode binder accounts for 0.1%-20% by mass, and the negative electrode conductive agent accounts for 0.1%-20% by mass, The mass ratio of the negative electrode additive is 1%-30%; the single-sided density of the negative electrode is 3.0-20.0 mg/cm 2 ; the negative electrode current collector is aluminum foil or copper foil with a thickness of 4-30 μm;

所述负极材料包括:软碳、硬碳、复合型的无定形碳材料或钛酸锂中的任一种。The negative electrode material includes any one of soft carbon, hard carbon, composite amorphous carbon material or lithium titanate.

优选的,所述隔膜包括:聚丙烯、聚乙烯、芳纶、聚酰亚胺或无纺布隔膜,或以上述材料为基材的陶瓷涂敷隔膜,或为涂胶隔膜;所述隔膜的厚度为5-50μm。Preferably, the diaphragm includes: polypropylene, polyethylene, aramid, polyimide or non-woven diaphragm, or a ceramic-coated diaphragm based on the above materials, or a glue-coated diaphragm; Thickness is 5-50μm.

优选的,所述电解液为电解质钠盐和非水溶剂的混合溶液;Preferably, the electrolyte is a mixed solution of electrolyte sodium salt and non-aqueous solvent;

所述电解质钠盐包括六氟磷酸钠(NaPF6)、高氯酸钠、四氟硼酸钠、六氟砷酸钠、氯铝酸钠中的一种或几种;The electrolyte sodium salt includes one or more of sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate, and sodium chloroaluminate;

所述非水溶剂为链状酸酯和环状酸酯的混合溶液,其中链状酸酯具体包括碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其它含氟、含硫或含不饱和键的链状有机酯类中的至少一种;环状酸酯具体包括:碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、磺内酯以及其它含氟、含硫或含不饱和键的环状有机酯类中的至少一种;The non-aqueous solvent is a mixed solution of a chain ester and a cyclic ester, wherein the chain ester specifically includes dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), At least one of methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other fluorine-containing, sulfur-containing or unsaturated bond-containing chain organic esters; cyclic esters specifically include: ethylene carbonate ( At least one of EC), propylene carbonate (PC), vinylene carbonate (VC), sultone and other fluorine-containing, sulfur-containing or unsaturated bond-containing cyclic organic esters;

所述电解液的钠盐浓度为0.2-2.0mol/L。The sodium salt concentration of the electrolyte is 0.2-2.0 mol/L.

优选的,所述高功率钠离子电池为圆柱钠离子电池,方形钠离子电池或软包电池。Preferably, the high-power sodium ion battery is a cylindrical sodium ion battery, a square sodium ion battery or a soft pack battery.

本发明提供的钠离子电池添加剂用作钠离子电池的正极添加剂和/或负极添加剂,有效降低内阻,提高钠离子迁移性能,能够满足5C-10C倍率充放电,其中10C/10C充放条件下,放电时间>3min;在1C/5C充放循环寿命>1000周,容量保持率>80%;本发明首次实现了圆柱钠离子电池的大倍率充放电性能,尤其是大倍率充电性能,可满足不低于10C的充电。The sodium ion battery additive provided by the invention is used as the positive electrode additive and/or negative electrode additive of the sodium ion battery, effectively reduces the internal resistance, improves the sodium ion migration performance, and can satisfy the charge and discharge rate of 5C-10C. , discharge time > 3min; charge-discharge cycle life > 1000 cycles at 1C/5C, capacity retention > 80%; the invention realizes the high-rate charge-discharge performance of cylindrical sodium-ion batteries for the first time, especially the high-rate charge performance, which can meet the Not less than 10C charging.

附图说明Description of drawings

下面通过附图和实施例,对本发明实施例的技术方案做进一步详细描述。The technical solutions of the embodiments of the present invention will be described in further detail below through the accompanying drawings and embodiments.

图1是本发明实施例2提供的钠离子电池在0.2C-10C的倍率性能测试曲线;Fig. 1 is the rate performance test curve of the sodium ion battery provided in the embodiment of the present invention 2 at 0.2C-10C;

图2是本发明对比例1提供的钠离子电池在0.2C-10C的倍率性能测试曲线;Fig. 2 is the rate performance test curve of the sodium ion battery provided by comparative example 1 of the present invention at 0.2C-10C;

图3是本发明实施例2提供的钠离子电池在不同充放条件下的快速充放倍率性能测试曲线;Fig. 3 is the fast charge-discharge rate performance test curve of the sodium-ion battery provided by the embodiment of the present invention 2 under different charge-discharge conditions;

图4是本发明对比例1提供的钠离子电池在不同充放条件下的快速充放倍率性能测试曲线。FIG. 4 is a test curve of the fast charge-discharge rate performance of the sodium-ion battery provided in Comparative Example 1 of the present invention under different charge-discharge conditions.

具体实施方式Detailed ways

下面通过附图和具体的实施例,对本发明进行进一步的说明,但应当理解为这些实施例仅仅是用于更详细说明之用,而不应理解为用以任何形式限制本发明,即并不意于限制本发明的保护范围。The present invention will be further described below through the accompanying drawings and specific embodiments, but it should be understood that these embodiments are only used for more detailed description, and should not be construed as limiting the present invention in any form, that is, it is not intended to to limit the protection scope of the present invention.

本发明提出了一种钠离子电池添加剂,用于钠离子电池正极材料和/或钠离子电池负极材料的添加剂。该添加剂为β-氧化铝,β-氧化铝的化学式为M2O·xAl2O3,其中M为元素周期表中IA族元素或IB族元素中的一种或几种,x为正整数;IA族元素包括:Li、Na、K或Rb等的一种或几种;IB族包括Ag等。The present invention provides a sodium ion battery additive, which is used as an additive for the positive electrode material of the sodium ion battery and/or the negative electrode material of the sodium ion battery. The additive is β-alumina, and the chemical formula of β-alumina is M 2 O·xAl 2 O 3 , wherein M is one or more of the elements of group IA or group IB in the periodic table, and x is Positive integer; IA group elements include: one or more of Li, Na, K or Rb, etc.; IB group includes Ag and the like.

以Na-β-氧化铝为例,化学式为Na2O·Al2O3,其晶体结构特点是:钠离子仅处于含等量钠离子和氧离子的疏松平面中(Na-O层),两个Na-O层面相距11.23埃,夹在Na-O层平面中间的是四层氧原子;按立方最密堆积排列,适量的铝离子占据其中的八面体位置和四面体位置,由这样的四个密堆积氧层和铝离子构成的密堆积基块,基块在Na-O层上下互为镜面反映。Taking Na-β-alumina as an example, the chemical formula is Na 2 O·Al 2 O 3 , and its crystal structure is characterized by the fact that sodium ions are only in the loose plane (Na-O layer) containing equal amounts of sodium ions and oxygen ions, The two Na-O planes are 11.23 Angstroms apart, and four layers of oxygen atoms are sandwiched between the Na-O planes; according to the cubic closest packing arrangement, an appropriate amount of aluminum ions occupy the octahedral and tetrahedral positions. The close-packed base block composed of four close-packed oxygen layers and aluminum ions, the base blocks mirror each other on the top and bottom of the Na-O layer.

由于上述的Na-β-氧化铝的结构特征,Na-O层内是氧离子和钠离子的松散结构,Na-O之间的距离是2.87埃,而正常的Na2O中的Na-O的距离是2.4埃,因此钠离子可以在Na-O层平面内二维空间扩散。Due to the above-mentioned structural characteristics of Na-β-alumina, the Na-O layer is a loose structure of oxygen ions and sodium ions, and the distance between Na-O is 2.87 angstroms, while the Na-O in normal Na 2 O The distance is 2.4 Angstroms, so Na ions can diffuse in two-dimensional space within the plane of the Na-O layer.

钠离子在Na-O面的扩散机理可认为是钠离子占据了离子间的填隙位置,由填隙位置到正常位置之间的离子跃迁而起到扩散作用。因此通过有效增强钠离子在β-氧化铝的M-O平面内迁移,从而降低内阻,提高钠离子迁移性能。The diffusion mechanism of sodium ions on the Na-O surface can be considered that sodium ions occupy the interstitial positions between ions, and the diffusion effect is played by the ion transition between the interstitial positions and the normal positions. Therefore, by effectively enhancing the migration of sodium ions in the M-O plane of β-alumina, the internal resistance is reduced and the sodium ion migration performance is improved.

将该添加剂应用于高功率钠离子电池中。高功率钠离子电池包括:正极、负极、隔膜和电解液。The additive was applied in high-power sodium-ion batteries. High-power sodium-ion batteries include: positive electrode, negative electrode, separator, and electrolyte.

其中正极包括:正极材料、正极粘结剂、正极导电剂、正极添加剂和正极集流体;负极包括:负极材料、负极粘结剂、负极导电剂、负极添加剂和负极集流体;正极添加剂和/或负极添加剂包括上述钠离子电池添加剂。The positive electrode comprises: positive electrode material, positive electrode binder, positive electrode conductive agent, positive electrode additive and positive electrode current collector; negative electrode comprises: negative electrode material, negative electrode binder, negative electrode conductive agent, negative electrode additive and negative electrode current collector; positive electrode additive and/or The negative electrode additive includes the above-mentioned sodium ion battery additive.

正极中,正极材料所占质量比为60%-99%,正极粘结剂所占质量比为0.1%-20%,正极导电剂所占质量比为0.1%-20%,正极添加剂所占质量比为0.1%-30%;正极单面面密度5.0-30.0mg/cm2;正极集流体为厚度为4-30μm的铝箔;In the positive electrode, the mass ratio of the positive electrode material is 60%-99%, the mass ratio of the positive electrode binder is 0.1%-20%, the mass ratio of the positive electrode conductive agent is 0.1%-20%, and the mass ratio of the positive electrode additive is 0.1%-20%. The ratio is 0.1%-30%; the single-sided density of the positive electrode is 5.0-30.0 mg/cm 2 ; the positive electrode current collector is an aluminum foil with a thickness of 4-30 μm;

正极材料包括:氧化物正极材料、聚阴离子类正极材料、普鲁士蓝类正极材料、有机类材料和转化正极材料中的任一种;The positive electrode material includes: any one of oxide positive electrode material, polyanion positive electrode material, Prussian blue positive electrode material, organic material and conversion positive electrode material;

其中,氧化物正极材料的结构通式为NaxM1O2,M1为过渡金属元素中的一种或者多种,例如铁锰铜基正极材料或镍铁锰基正极材料;聚阴离子类正极材料的结构通式为NaxM2y(XaOb)zZw,其中,M2为Ti、V、Cr、Mn、Fe、Co、Ni、Ca、Mg、Al、Nb等中的一种或几种;X为Si、S、P、As、B、Mo、W、Ge中的一种或几种;Z为F或OH;普鲁士蓝类正极材料的结构通式为AxMa[Mb(CN)6](1-y)·y·nH2O,其中0≤x≤2,0<y<1,A为碱金属离子,Ma、Mb分别为Mn、Fe中的一种。Wherein, the general structural formula of the oxide cathode material is Na x M1O 2 , and M1 is one or more transition metal elements, such as iron-manganese-copper-based cathode materials or nickel-iron-manganese-based cathode materials; polyanion cathode materials The general structural formula is Na x M2 y (X a O b ) z Z w , wherein M2 is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al, Nb, etc. X is one or more of Si, S, P, As, B, Mo, W, Ge; Z is F or OH; the general structural formula of Prussian blue cathode material is A x M a [M b (CN) 6 ] (1-y)·y ·nH 2 O, wherein 0≤x≤2, 0<y<1, A is an alkali metal ion, M a and M b are one of Mn and Fe, respectively .

负极中,负极材料所占质量比为60%-99%,负极粘结剂所占质量比为0.1%-20%,负极导电剂所占质量比为0.1%-20%,负极添加剂所占质量比为1%-30%;负极单面密度3.0-20.0mg/cm2;负极集流体为厚度为4-30μm的铝箔或铜箔;负极材料包括:软碳、硬碳、复合型的无定形碳材料或钛酸锂中的任一种。In the negative electrode, the mass ratio of the negative electrode material is 60%-99%, the mass ratio of the negative electrode binder is 0.1%-20%, the mass ratio of the negative electrode conductive agent is 0.1%-20%, and the mass ratio of the negative electrode additive is 0.1%-20%. The ratio is 1%-30%; the single-sided density of the negative electrode is 3.0-20.0 mg/cm 2 ; the negative electrode current collector is aluminum foil or copper foil with a thickness of 4-30 μm; the negative electrode material includes: soft carbon, hard carbon, composite amorphous Either carbon material or lithium titanate.

隔膜包括:聚丙烯、聚乙烯、芳纶、聚酰亚胺或无纺布隔膜,或以上述材料为基材的陶瓷涂敷隔膜,或为涂胶隔膜;隔膜的厚度为5-50μm。The separator includes: polypropylene, polyethylene, aramid, polyimide or non-woven separator, or a ceramic-coated separator based on the above materials, or a rubber-coated separator; the thickness of the separator is 5-50 μm.

电解液为电解质钠盐和非水溶剂的混合溶液;电解质钠盐包括六氟磷酸钠(NaPF6)、高氯酸钠、四氟硼酸钠、六氟砷酸钠、氯铝酸钠中的一种或几种;非水溶剂为链状酸酯和环状酸酯的混合溶液,其中链状酸酯具体包括碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、碳酸二丙酯(DPC)以及其它含氟、含硫或含不饱和键的链状有机酯类中的至少一种;环状酸酯具体包括:碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸亚乙烯酯(VC)、磺内酯以及其它含氟、含硫或含不饱和键的环状有机酯类中的至少一种;电解液的钠盐浓度为0.2-2.0mol/L。The electrolyte is a mixed solution of an electrolyte sodium salt and a non-aqueous solvent; the electrolyte sodium salt includes one of sodium hexafluorophosphate (NaPF 6 ), sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate, and sodium chloroaluminate. One or more; the non-aqueous solvent is a mixed solution of a chain ester and a cyclic ester, wherein the chain ester specifically includes dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate ( EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and at least one of other fluorine-containing, sulfur-containing or unsaturated bond-containing chain organic esters; cyclic esters specifically include: carbonic acid At least one of vinyl ester (EC), propylene carbonate (PC), vinylene carbonate (VC), sultone and other fluorine-containing, sulfur-containing or unsaturated bond-containing cyclic organic esters; electrolyte The concentration of sodium salt is 0.2-2.0mol/L.

本发明的高功率钠离子电池可以为圆柱钠离子电池,方形钠离子电池或软包电池。The high-power sodium ion battery of the present invention can be a cylindrical sodium ion battery, a square sodium ion battery or a soft pack battery.

为更好的理解本发明提供的技术方案,下述以几个具体实例分别进行进一步说明。In order to better understand the technical solutions provided by the present invention, several specific examples are used for further description below.

实施例1Example 1

正极极片的制备:向行星搅拌缸中加入100wt%的溶剂N-甲基吡咯烷酮(NMP)和5wt%的黏结剂聚偏氟乙烯(PVDF)粉末,按公转30r/min、分散3000r/min速度搅拌2小时,再加入5wt%的导电剂炭黑(SP),按公转30r/min、分散3000r/min的速度搅拌1小时,再加入5wt%的Na-β-氧化铝,按公转30r/min、分散3000r/min的速度搅拌1小时,再加入85wt%的正极活性物质O3-Na[Cu0.22Fe0.3Mn0.48]O2,按公转30r/min、分散3000r/min搅拌3小时,再经脱泡,过200目筛完成钠离子电池正极浆料的制备;Preparation of positive pole piece: add 100wt% solvent N-methylpyrrolidone (NMP) and 5wt% binder polyvinylidene fluoride (PVDF) powder into the planetary stirring cylinder, rotate at a speed of 30r/min and disperse at a speed of 3000r/min Stir for 2 hours, then add 5wt% of conductive agent carbon black (SP), stir for 1 hour at the speed of revolution 30r/min, dispersion 3000r/min, then add 5wt% Na-β-alumina, press revolution 30r/min , stirring at a speed of 3000r/min for 1 hour of dispersion, then adding 85wt% of the positive active material O3-Na[Cu 0.22 Fe 0.3 Mn 0.48 ]O 2 , stirring for 3 hours at 30 r/min revolution and 3000 r/min dispersion, and then removing Bubble and pass through a 200-mesh sieve to complete the preparation of the positive electrode slurry for sodium-ion batteries;

将上述制备完成的正极浆料,采用挤压的方式均匀涂布在15μm厚的铝箔上,经烘干、辊压分切制备成正极极片。The positive electrode slurry prepared above was evenly coated on an aluminum foil with a thickness of 15 μm by means of extrusion, and was dried, rolled and cut to prepare a positive electrode pole piece.

负极极片的制备:向行星搅拌缸中加入100wt%的去离子水和5wt%的黏结剂聚偏氟乙烯(PVDF)粉末,按公转30r/min、分散3000r/min速度搅拌2小时,再加入5wt%的SP,按公转30r/min、分散3000r/min的速度搅拌1小时,再加入5wt%的Na-β-氧化铝,按公转30r/min、分散3000r/min的速度搅拌1小时,再加入85wt%的负极活性物质无烟煤硬碳材料,按公转30r/min、分散3000r/min搅拌3小时,再经脱泡,过200目筛完成钠离子电池负极浆料的制备;Preparation of negative pole piece: add 100wt% deionized water and 5wt% binder polyvinylidene fluoride (PVDF) powder into the planetary stirring cylinder, stir for 2 hours at the speed of revolution 30r/min and disperse 3000r/min, and then add 5wt% SP, stir for 1 hour at the speed of revolution 30r/min, disperse 3000r/min, then add 5wt% Na-β-alumina, stir for 1 hour at the speed of revolution 30r/min, disperse 3000r/min, and then Add 85wt% negative electrode active material anthracite hard carbon material, stir for 3 hours at 30 r/min revolution and 3000 r/min dispersion, then defoaming and sieving through 200 mesh sieve to complete the preparation of sodium ion battery negative electrode slurry;

将上述制备完成的负极浆料,采用挤压的方式均匀涂布在15μm厚的铝箔上,经烘干、辊压分切制备成正极极片。The negative electrode slurry prepared above was evenly coated on an aluminum foil with a thickness of 15 μm by means of extrusion, and was dried, rolled and cut to prepare a positive electrode pole piece.

将所得正、负极片经制片、卷绕使用12um+4um氧化铝陶瓷涂敷的PE隔膜、装配、烘烤,注液按照12g/只,六氟磷酸钠浓度为1mol/L,溶剂为碳酸乙烯酯(EC):碳酸二乙酯(DEC):碳酸丙烯酯(PC)=1:1:1的电解液,在注液后经化成、老化、分容等工艺,制备完成26650电芯,编号A1。The obtained positive and negative electrode sheets are filmed, wound with a PE diaphragm coated with 12um+4um alumina ceramics, assembled and baked, and the liquid injection is 12g/piece, the concentration of sodium hexafluorophosphate is 1mol/L, and the solvent is carbonic acid. Ethylene ester (EC): diethyl carbonate (DEC): propylene carbonate (PC) = 1:1:1 electrolyte, after injection, the 26650 cells are prepared through the processes of chemical formation, aging, and volume separation. Number A1.

实施例2Example 2

采用于实施例1相同的方法制备26650电芯,与实施例1区别在于,正、负极材料中,Na-β-氧化铝所占比例是10wt%,正、负极活性物质所占比例均是80wt%,编号A2。The 26650 cell was prepared by the same method as in Example 1. The difference from Example 1 is that in the positive and negative electrode materials, the proportion of Na-β-alumina is 10wt%, and the proportion of positive and negative active materials is both 80wt% %, number A2.

实施例3Example 3

采用于实施例1相同的方法制备26650电芯,与实施例1区别在于,正、负极材料中,Na-β-氧化铝所占比例是15wt%,正、负极活性物质所占比例均是75wt%,编号A3。The 26650 cell was prepared by the same method as in Example 1. The difference from Example 1 is that in the positive and negative electrode materials, the proportion of Na-β-alumina is 15wt%, and the proportion of positive and negative electrode active materials is both 75wt% %, number A3.

实施例4Example 4

采用于实施例1相同的方法制备26650电芯,与实施例1区别在于,正、负极材料中,Na-β-氧化铝所占比例是20wt%,正、负极活性物质所占比例均是70wt%,编号A4。The 26650 cell was prepared by the same method as in Example 1. The difference from Example 1 is that in the positive and negative electrode materials, the proportion of Na-β-alumina is 20wt%, and the proportion of the positive and negative active materials is both 70wt% %, number A4.

实施例5Example 5

采用于实施例1相同的方法制备26650电芯,与实施例1区别在于,正、负极材料中,Na-β-氧化铝所占比例是25wt%,正、负极活性物质所占比例均是65wt%,编号A5。The 26650 cell was prepared by the same method as in Example 1. The difference from Example 1 is that in the positive and negative electrode materials, the proportion of Na-β-alumina is 25wt%, and the proportion of the positive and negative active materials is both 65wt% %, number A5.

实施例6Example 6

采用于实施例1相同的方法制备26650电芯,与实施例1区别在于,正、负极材料中,Na-β-氧化铝所占比例是30wt%,正、负极活性物质所占比例均是60wt%,编号A6。The 26650 cell was prepared by the same method as in Example 1. The difference from Example 1 is that in the positive and negative electrode materials, the proportion of Na-β-alumina is 30wt%, and the proportion of positive and negative active materials is both 60wt% %, number A6.

对比例1Comparative Example 1

采用于实施例1相同的方法制备26650电芯,与实施例1区别的是正负极浆料中不添加Na-β-氧化铝,正负极活性物质的比例是90%,编号B1。26650 cells were prepared by the same method as in Example 1. The difference from Example 1 was that Na-β-alumina was not added to the positive and negative electrode slurry, and the ratio of positive and negative electrode active materials was 90%, number B1.

把装配所得电池采用恒流-恒压充电模式及恒流放电模式进行电化学性能测试,充放电的截止电压范围为1.5-4V。温度为室温25℃,测试的充放电电流为0.2C、1C、3C、5C、8C、10C。测试结果见表1。The assembled battery was tested for electrochemical performance using constant current-constant voltage charging mode and constant current discharging mode, and the cut-off voltage range of charge and discharge was 1.5-4V. The temperature is room temperature 25°C, and the test charge and discharge currents are 0.2C, 1C, 3C, 5C, 8C, and 10C. The test results are shown in Table 1.

Figure BDA0002914764580000091
Figure BDA0002914764580000091

表1Table 1

由表1数据可知,实施例所得A1-A6,0.2C/10C放电容量保持率都大于对比例所得的B1,说明本发明对于电芯倍率性能具有明显的提升作用,It can be seen from the data in Table 1 that the discharge capacity retention rates of A1-A6 and 0.2C/10C obtained in the examples are all greater than those of B1 obtained in the comparative example, indicating that the present invention has an obvious effect of improving the rate performance of the cells.

由表1数据中实施例2和对比例1可知,Na-β-氧化铝重量比例为10%,倍率性能明显提高It can be seen from Example 2 and Comparative Example 1 in the data in Table 1 that the weight ratio of Na-β-alumina is 10%, and the rate performance is significantly improved

图1为本发明实施例2提供的钠离子电池在0.2C-10C的倍率性能测试曲线;图2为对比例1提供的钠离子电池在0.2C-10C的倍率性能测试曲线;通过对比可以看出,实施例2中的10C放电容量明显大于对比例1中的容量,提升比例5.1%。Fig. 1 is the rate performance test curve of the sodium ion battery provided by Example 2 of the present invention at 0.2C-10C; Fig. 2 is the rate performance test curve of the sodium ion battery provided by Comparative Example 1 at 0.2C-10C; It can be seen that the 10C discharge capacity in Example 2 is significantly larger than that in Comparative Example 1, and the improvement ratio is 5.1%.

图3为本发明实施例2提供的钠离子电池在不同充放条件下的快速充放倍率性能测试曲线;图4为对比例1提供的钠离子电池在不同充放条件下的快速充放倍率性能测试曲线,通过对比可以看出,高倍率充放电时,实施例2各项测试领先于对比例1,倍率越大,差距越明显,尤其是10C/10C倍率充放时,对比例2的放电保持率相比于对比例1由12.5%,提高至50%;明显改善了大电流充电能力。Fig. 3 is the fast charge-discharge rate performance test curve of the sodium-ion battery provided by Example 2 of the present invention under different charge-discharge conditions; Fig. 4 is the fast-charge-discharge rate performance of the sodium-ion battery provided by Comparative Example 1 under different charge-discharge conditions From the comparison of the performance test curve, it can be seen that when charging and discharging at a high rate, the tests of Example 2 are ahead of those of Comparative Example 1. The greater the rate, the more obvious the gap is. Compared with the comparative example 1, the discharge retention rate is increased from 12.5% to 50%; the high-current charging capability is obviously improved.

本发明提供的钠离子电池添加剂用作钠离子电池的正极添加剂和/或负极添加剂,有效降低内阻,提高钠离子迁移性能,能够满足5C-10C倍率充放电,其中10C/10C充放条件下,放电时间>3min;在1C/5C充放循环寿命>1000周,容量保持率>80%;本发明首次实现了圆柱钠离子电池的大倍率充放电性能,尤其是大倍率充电性能,可满足不低于10C的充电。The sodium ion battery additive provided by the invention is used as the positive electrode additive and/or negative electrode additive of the sodium ion battery, effectively reduces the internal resistance, improves the sodium ion migration performance, and can satisfy the charge and discharge rate of 5C-10C. , discharge time > 3min; charge-discharge cycle life > 1000 cycles at 1C/5C, capacity retention > 80%; the invention realizes the high-rate charge-discharge performance of cylindrical sodium-ion batteries for the first time, especially the high-rate charge performance, which can meet the Not less than 10C charging.

以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The specific embodiments described above further describe the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. The sodium-ion battery additive is characterized in that the additive is beta-alumina, and the chemical formula of the beta-alumina is M 2 O·xAl 2 O 3 Wherein M is I in the periodic table A Group elements or I B One or more of group elements, wherein x is 5-11;
the additive is used as an additive of a positive electrode material and/or a negative electrode material of a sodium-ion battery.
2. The sodium ion battery additive of claim 1, wherein I is A The group elements include: any one of Li, Na, K and Rb; i is B The group includes Ag.
3. The sodium-ion battery additive according to claim 1, wherein the mass ratio of the additive in the positive electrode material of the sodium-ion battery is 0.1-30%; the mass ratio of the additive in the negative electrode material of the sodium-ion battery is 1-30%.
4. The sodium ion battery additive according to claim 1, wherein sodium ions in the sodium ion battery migrate within the M-O plane of the beta alumina.
5. A high power sodium ion battery, comprising: a positive electrode, a negative electrode, a separator and an electrolyte;
wherein the positive electrode includes: the cathode comprises a cathode material, a cathode binder, a cathode conductive agent, a cathode additive and a cathode current collector; the negative electrode includes: the cathode comprises a cathode material, a cathode binder, a cathode conductive agent, a cathode additive and a cathode current collector;
the positive electrode additive and/or negative electrode additive comprises the sodium ion battery additive of claim 1.
6. The high-power sodium-ion battery according to claim 5, wherein in the positive electrode, the positive electrode material accounts for 60-99% by mass, the positive electrode binder accounts for 0.1-20% by mass, the positive electrode conductive agent accounts for 0.1-20% by mass, and the positive electrode additive accounts for 0.1-30% by mass; the single-sided surface density of the positive electrode is 5.0-30.0mg/cm 2 (ii) a The positive current collector is an aluminum foil with the thickness of 4-30 mu m;
the positive electrode material includes: any one of an oxide positive electrode material, a polyanion positive electrode material, a prussian blue positive electrode material, an organic material and a conversion positive electrode material;
wherein the structural general formula of the oxide cathode material is Na x M1O 2 M1 is one or more of transition metal elements;
the structural general formula of the polyanion cathode material is Na x M2 y (X a O b ) z Z w Wherein M2 is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al, Nb, etc.; x is one or more of Si, S, P, As, B, Mo, W and Ge; z is F or OH;
the structural general formula of the Prussian blue type anode material is A x M a [M b (CN) 6 ] (1-y)·y ·nH 2 O, wherein x is more than or equal to 0 and less than or equal to 2 and 0<y<1, A is an alkali metal ion, M a 、M b Respectively one of Mn and Fe.
7. The high-power sodium-ion battery according to claim 5, wherein in the negative electrode, the negative electrode material accounts for 60-99% by mass, the negative electrode binder accounts for 0.1-20% by mass, the negative electrode conductive agent accounts for 0.1-20% by mass, and the negative electrode additive accounts for 1-30% by mass; the single-sided density of the negative electrode is 3.0-20.0mg/cm 2 (ii) a The negative current collector is an aluminum foil or a copper foil with the thickness of 4-30 mu m;
the anode material includes: any one of soft carbon, hard carbon, a composite amorphous carbon material, or lithium titanate.
8. The high power sodium ion battery of claim 5, wherein the separator comprises: polypropylene, polyethylene, aramid fiber, polyimide or non-woven fabric diaphragm, or ceramic coating diaphragm using the above materials as base materials, or gluing diaphragm; the thickness of the diaphragm is 5-50 μm.
9. The high power sodium ion battery of claim 5, wherein the electrolyte is a mixed solution of electrolyte sodium salt and non-aqueous solvent;
the sodium salt of the electrolyte comprises sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluoroarsenate and sodium chloroaluminate;
the non-aqueous solvent is a mixed solution of chain ester and cyclic ester, wherein the chain ester specifically comprises at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC) and other chain organic esters containing fluorine, sulfur or unsaturated bonds; the cyclic acid ester specifically includes: at least one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Vinylene Carbonate (VC), sultone and other cyclic organic esters containing fluorine, sulfur or unsaturated bonds;
the sodium salt concentration of the electrolyte is 0.2-2.0 mol/L.
10. The high power sodium ion battery of claim 5, wherein the high power sodium ion battery is a cylindrical sodium ion battery, a prismatic sodium ion battery, or a pouch battery.
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