CN116093417A - Sodium ion battery and energy storage device - Google Patents
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Abstract
Translated fromChineseDescription
Translated fromChinese技术领域technical field
本发明属钠离子电池技术领域，具体涉及一种钠离子电池和储能设备。The invention belongs to the technical field of sodium ion batteries, and in particular relates to a sodium ion battery and energy storage equipment.
背景技术Background technique
近年来，与锂离子电池相似的钠离子电池由于其低成本、电解液中较好的离子传导性以及接近于锂的低标准氧化还原电位，引起了学术和行业界极大的关注度。但由于钠离子电池首圈形成SEI膜会有不可逆的钠消耗，以及循环过程中副反应会持续消耗电化学活性钠离子，极大地影响了钠离子电池的长使用寿命。In recent years, Na-ion batteries, which are similar to Li-ion batteries, have attracted great academic and industry attention due to their low cost, better ionic conductivity in the electrolyte, and low standard redox potential close to Li. However, due to the irreversible sodium consumption in the formation of the SEI film in the first cycle of the sodium-ion battery, and the continuous consumption of electrochemically active sodium ions in the side reaction during the cycle, the long service life of the sodium-ion battery is greatly affected.
为了解决上述技术问题，现有技术中大多采用在正极片中添加补钠添加剂，例如专利CN 113113681A提供了一种复合补钠添加剂的制备和应用，该发明的补钠添加剂中含有金属氧化物碳催化剂与钠盐，该金属氧化物碳催化剂为金属氧化物与碳基底的复合物。该补钠添加剂中的钠盐在钠离子电池首圈充电时即完全分解并释放出钠离子和二氧化碳气体，分解产生的二氧化碳在化成阶段即可除去，而分解产生的钠离子则可以有效解决由钠离子不可逆消耗引起的电池能量密度低、循环稳定性差的问题。In order to solve the above-mentioned technical problems, most of the prior art uses adding sodium supplement additives in the positive electrode sheet, for example, patent CN 113113681A provides a preparation and application of a composite sodium supplement additive, the sodium supplement additive of the invention contains metal oxide carbon Catalyst and sodium salt, the metal oxide carbon catalyst is a compound of metal oxide and carbon substrate. The sodium salt in the sodium supplement additive is completely decomposed and releases sodium ions and carbon dioxide gas when the sodium-ion battery is charged for the first cycle. The problems of low battery energy density and poor cycle stability caused by the irreversible consumption of sodium ions.
但是上述技术方案具有如下缺点：第一，补钠添加剂在首圈充电即完全分解，因此其只能在首圈充电时提供电化学活性钠离子，后续循环过程中不会持续释放电化学活性钠离子，不利于构筑长寿命钠离子电池。第二，该补钠添加剂在释放钠离子的同时也会分解产生气体，如果气体压力过大会导致电池胀气，甚至发生爆炸，具有一定的安全隐患。第三，钠离子电池负极材料表面形成的SEI膜是由含钠的有机物和无机物构成的，这种含钠的SEI膜的力学性能以及导离子性要差于锂电负极表面形成的含锂的SEI膜，因此，不宜构筑长使用寿命钠离子电池。However, the above technical solution has the following disadvantages: First, the sodium supplement additive is completely decomposed during the first cycle of charging, so it can only provide electrochemically active sodium ions during the first cycle of charging, and will not continuously release electrochemically active sodium during subsequent cycles ions, which is not conducive to the construction of long-life sodium-ion batteries. Second, the sodium supplement additive will also decompose and generate gas while releasing sodium ions. If the gas pressure is too high, it will cause the battery to inflate or even explode, which poses a certain safety hazard. Third, the SEI film formed on the surface of the negative electrode material of a sodium ion battery is composed of sodium-containing organic and inorganic substances. SEI film, therefore, is not suitable for constructing long-life Na-ion batteries.
发明内容Contents of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的目的在于提出一种钠离子电池和储能设备。本发明的钠离子电池中含有的锂元素提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，确保了电池体系中电化学活性碱性离子的充足，确保了电解液具有较高的离子电导率，提升了电池的循环稳定性以及使用寿命。The present invention aims to solve one of the technical problems in the related art at least to a certain extent. For this reason, the object of the present invention is to propose a kind of sodium ion battery and energy storage device. The lithium element contained in the sodium ion battery of the present invention improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transport capacity of the battery system, ensures sufficient electrochemically active alkaline ions in the battery system, and ensures that the electrolyte has Higher ionic conductivity improves the cycle stability and service life of the battery.
在本发明的一个方面，本发明提出了一种钠离子电池。根据本发明的实施例，所述钠离子电池包括：In one aspect of the invention, the invention provides a sodium ion battery. According to an embodiment of the present invention, the sodium ion battery includes:
正极集流体；Positive current collector;
正极层，所述正极层形成在所述正极集流体上，所述正极层包括钠元素和锂元素，基于所述正极层的总质量，所述钠元素的含量为10-20wt％，所述锂元素的含量为0.1-1.5wt％；a positive electrode layer, the positive electrode layer is formed on the positive electrode current collector, the positive electrode layer includes sodium element and lithium element, based on the total mass of the positive electrode layer, the content of the sodium element is 10-20wt%, the The content of lithium element is 0.1-1.5wt%;
所述钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环预设圈数后，所述正极层中的钠元素的含量为10-20wt％，所述正极层中的锂元素的含量为0.01-0.6wt％，所述预设圈数大于或等于1且小于或等于6000。After the sodium ion battery is cycled for a preset number of cycles under the condition of a cycle current density of 1C and a charging voltage of 2.0V-4.0V, the content of sodium element in the positive electrode layer is 10-20wt%, and the positive electrode layer The content of lithium element in the layer is 0.01-0.6wt%, and the preset number of turns is greater than or equal to 1 and less than or equal to 6000.
根据本发明实施例的钠离子电池，该钠离子电池中含有的锂元素提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，确保了电池体系中电化学活性碱性离子的充足，确保了电解液具有较高的离子电导率，由此提升了钠离子电池的循环稳定性以及使用寿命，提升了钠离子电池的能量密度以及首圈放电比容量，降低了钠离子电池的放电阻抗。According to the sodium ion battery of the embodiment of the present invention, the lithium element contained in the sodium ion battery improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transport capacity of the battery system, ensuring the electrochemically active alkaline ions in the battery system Sufficiency ensures that the electrolyte has a high ionic conductivity, thereby improving the cycle stability and service life of the sodium-ion battery, improving the energy density and the first-cycle discharge specific capacity of the sodium-ion battery, and reducing the battery life of the sodium-ion battery. discharge impedance.
另外，根据本发明上述实施例的钠离子电池还可以具有如下附加的技术特征：In addition, the sodium ion battery according to the above-mentioned embodiments of the present invention may also have the following additional technical features:
在本发明的一些实施例中，所述钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环第一预设圈数后，所述锂元素的含量为第一值；所述钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环第二预设圈数后，所述锂元素的含量为第二值；在所述第一预设圈数小于所述第二预设圈数的条件下，所述第一值大于所述第二值。In some embodiments of the present invention, after the sodium ion battery is cycled for a first preset number of cycles under the conditions of a cycle current density of 1C and a charging voltage of 2.0V-4.0V, the content of the lithium element is the second One value; after the sodium ion battery is cycled for a second preset number of cycles under the condition of a cycle current density of 1C and a charging voltage of 2.0V-4.0V, the content of the lithium element is a second value; Under the condition that the first preset number of turns is smaller than the second preset number of turns, the first value is greater than the second value.
在本发明的一些实施例中，在所述第一预设圈数大于或者等于500的条件下，所述第一值和所述第二值的差值的绝对值小于0.5wt％。In some embodiments of the present invention, under the condition that the first preset number of turns is greater than or equal to 500, the absolute value of the difference between the first value and the second value is less than 0.5 wt%.
在本发明的一些实施例中，所述正极层包括正极活性材料、富锂添加剂、导电剂和粘结剂，所述正极活性材料包括所述钠元素，所述富锂添加剂包括所述锂元素。In some embodiments of the present invention, the positive electrode layer includes a positive electrode active material, a lithium-rich additive, a conductive agent and a binder, the positive electrode active material includes the sodium element, and the lithium-rich additive includes the lithium element .
在本发明的一些实施例中，基于所述正极层的总质量，所述富锂添加剂的含量为1wt％-5wt％。In some embodiments of the present invention, based on the total mass of the positive electrode layer, the content of the lithium-rich additive is 1wt%-5wt%.
在本发明的一些实施例中，所述正极活性材料、所述富锂添加剂、所述导电剂和所述粘结剂的质量比为(90-97):(1-5):(0.1-2):(0.5-3)。In some embodiments of the present invention, the mass ratio of the positive electrode active material, the lithium-rich additive, the conductive agent and the binder is (90-97):(1-5):(0.1- 2): (0.5-3).
在本发明的一些实施例中，所述富锂添加剂包括无机锂盐。In some embodiments of the present invention, the lithium-rich additive includes an inorganic lithium salt.
在本发明的一些实施例中，所述无机锂盐包括Li2NiO2、Li6CoO4、Li2CuO2、Li2NixCuyO2、Li2MoO3、Li2O/M1、Li2S/M2和LiF/M3中的至少一种，其中，x+y＝1，且x大于0，y大于0，M1为Co、Fe、Ni或Mn，M2为Co或Fe，M3为Co或Fe。In some embodiments of the present invention, the inorganic lithium salts include Li2 NiO2 , Li6 CoO4 , Li2 CuO2 , Li2 Nix Cuy O2 , Li2 MoO3 , Li2 O/M1 , Li2 S/M2 and LiF/M3 at least one, wherein, x+y=1, and x is greater than 0, y is greater than 0, M1 is Co, Fe, Ni or Mn, M2 is Co Or Fe,M3 is Co or Fe.
在本发明的一些实施例中，所述正极活性材料包括Na0.95Ni0.159Mn0.317Cu0.158Mg0.158Ti0.208O2、Na3V2(PO4)3、Na4V2(PO4)3、Na2Fe2(SO4)3、Na2.5Fe1.75(SO4)3、Na3.32Fe2.34(P2O7)2、Na4Fe3(PO4)2P2O7、Na4Mn3(PO4)2P2O7、Na4Ni3(PO4)2P2O7、NaNi1/3Fe1/3Mn1/3O2、Na0.85Ni0.4Mn0.4Fe0.2O2、Na0.85Ni0.3Mn0.4Fe0.3O2和Na0.95Ni0.159Mn0.317Cu0.316Ti0.208O2中的至少一种。In some embodiments of the present invention, the positive electrode active material includes Na0.95 Ni0.159 Mn0.317 Cu0.158 Mg 0.158 Ti0.208 O2 , Na3V 2( PO4 )3 , Na4 V2 (PO4 )3 , Na2 Fe2 (SO4 )3 , Na2.5 Fe1.75 (SO4 )3 , Na3.32 Fe2.34 (P2 O7 )2 , Na4 Fe3 (PO4 )2 P2 O7 , Na4 Mn3 (PO4 )2 P2 O7 , Na4 Ni3 (PO4 )2 P2 O7 , NaNi1/3 Fe1/3 Mn1/3 O2 , Na0.85 Ni0.4 Mn0.4 Fe0.2 O2 , Na0.85 Ni0.3 Mn0.4 Fe0.3 O2 and at least one of Na0.95 Ni0.159 Mn0.317 Cu0.316 Ti0.208 O2 .
在本发明的一些实施例中，所述导电剂包括Super p炭黑、乙炔黑、科琴黑、石墨烯和导电碳管中的至少一种。In some embodiments of the present invention, the conductive agent includes at least one of Super p carbon black, acetylene black, Ketjen black, graphene and conductive carbon tubes.
在本发明的一些实施例中，所述粘结剂包括PVDF、PTFE和NBR中的至少一种。In some embodiments of the present invention, the binder includes at least one of PVDF, PTFE and NBR.
在本发明的再一个方面，本发明提出了一种储能设备。根据本发明的实施例，所述储能设备具有如上所述的钠离子电池。由此，所述储能设备具有所述钠离子电池的所有优点，在此不再赘述。In yet another aspect of the present invention, the present invention provides an energy storage device. According to an embodiment of the present invention, the energy storage device has a sodium-ion battery as described above. Therefore, the energy storage device has all the advantages of the sodium ion battery, which will not be repeated here.
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。Additional aspects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
具体实施方式Detailed ways
下面详细描述本发明的实施例，所述实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below, and the embodiments are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.
在本发明的一个方面，本发明提出了一种钠离子电池。根据本发明的实施例，钠离子电池包括：正极集流体；正极层，所述正极层形成在所述正极集流体上，所述正极层包括包括钠元素和锂元素，基于所述正极层的总质量，所述钠元素的含量为10-20wt％，所述锂元素的含量为0.1-1.5wt％；所述钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环预设圈数后，所述正极层中的钠元素的含量为10-20wt％，所述正极层中的锂元素的含量为0.01-0.6wt％，所述预设圈数大于或等于1且小于或等于6000。由此，该钠离子电池中含有的富锂添加剂提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，确保了电池体系中电化学活性碱性离子的充足，确保了电解液具有较高的离子电导率，提升了电池的循环稳定性以及使用寿命，提升了钠离子电池的能量密度以及首圈放电比容量，降低了钠离子电池的放电阻抗。In one aspect of the invention, the invention provides a sodium ion battery. According to an embodiment of the present invention, the sodium ion battery includes: a positive electrode collector; a positive electrode layer, the positive electrode layer is formed on the positive electrode collector, the positive electrode layer includes sodium and lithium elements, based on the positive electrode layer The total mass, the content of the sodium element is 10-20wt%, the content of the lithium element is 0.1-1.5wt%; the sodium ion battery has a cycle current density of 1C and a charging voltage of 2.0V-4.0V After circulating the preset number of turns under the condition, the content of sodium element in the positive electrode layer is 10-20wt%, the content of lithium element in the positive electrode layer is 0.01-0.6wt%, and the preset number of turns is greater than or Equal to 1 and less than or equal to 6000. As a result, the lithium-rich additive contained in the sodium-ion battery improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transport capacity of the battery system, ensuring sufficient electrochemically active alkaline ions in the battery system and ensuring electrolysis. The liquid has a high ionic conductivity, which improves the cycle stability and service life of the battery, improves the energy density and first-cycle discharge specific capacity of the sodium-ion battery, and reduces the discharge impedance of the sodium-ion battery.
下面对本发明提出的钠离子电池能够实现上述有益效果的原理进行详细说明：The principle that the sodium ion battery proposed by the present invention can realize the above-mentioned beneficial effects is described in detail below:
本发明实施例的钠离子电池中含有富锂添加剂，该富锂添加剂在电化学反应过程中，会从其表面到内部逐步释放电化学活性锂离子，使得该富锂添加剂在首圈充电过程中会释放一部分锂离子，该部分锂离子可以通过电解液传输到负极材料表面参与SEI膜的形成，使形成的SEI膜同时含有钠和锂的有机和/或无机混合物，从而提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，提升了电池的循环稳定性。同时，该富锂添加剂在首圈充电过程中提供的电化学活性锂离子，减少了正极材料中电化学活性钠离子的消耗，进而提升钠离子电池的能量密度。另外，该富锂添加剂会在后续的循环过程中缓慢地逐步释放锂离子，该锂离子有利于不断补充电池体系中消耗的活性钠，确保了电池体系中电化学活性碱性离子的充足，以及确保了电解液具有较高的离子电导率，由此进一步提升了电池的循环稳定性以及使用寿命。The sodium-ion battery of the embodiment of the present invention contains a lithium-rich additive, and the lithium-rich additive will gradually release electrochemically active lithium ions from its surface to the inside during the electrochemical reaction, so that the lithium-rich additive can be charged during the first cycle. A part of lithium ions will be released, which can be transported to the surface of the negative electrode material through the electrolyte to participate in the formation of the SEI film, so that the formed SEI film contains an organic and/or inorganic mixture of sodium and lithium, thereby improving the SEI of the surface of the negative electrode material The structural stability of the membrane and the sodium ion transport capacity of the battery system improve the cycle stability of the battery. At the same time, the electrochemically active lithium ions provided by the lithium-rich additive during the first cycle of charging reduce the consumption of electrochemically active sodium ions in the positive electrode material, thereby increasing the energy density of the sodium-ion battery. In addition, the lithium-rich additive will slowly and gradually release lithium ions during the subsequent cycle, which is conducive to continuously supplementing the active sodium consumed in the battery system, ensuring sufficient electrochemically active alkaline ions in the battery system, and It ensures that the electrolyte has a high ion conductivity, thereby further improving the cycle stability and service life of the battery.
需要说明的是，现有技术中采用的补钠添加剂，负极材料表面形成的SEI膜仅由含钠的有机物和无机物构成，该SEI膜中不含锂，这种仅含钠的SEI膜的力学性能以及导离子性显著差于本申请的同时含有钠和锂的有机和/或无机混合物的SEI膜，因此，不宜构筑长使用寿命钠离子电池。且，现有技术中采用的补钠添加剂，在首圈充电即完全分解，因此其只能在首圈充电时提供电化学活性钠离子，后续循环过程中不会持续释放电化学活性钠离子，不利于构筑长寿命钠离子电池，而本发明采用的富锂添加剂会在后续的循环过程中缓慢地逐步释放锂离子。由此，本发明有效解决了现有技术中采用补钠添加剂存在的问题。It should be noted that for the sodium supplement additives used in the prior art, the SEI film formed on the surface of the negative electrode material is only composed of sodium-containing organic and inorganic substances, and the SEI film does not contain lithium. The SEI film containing only sodium The mechanical properties and ion conductivity are significantly worse than the SEI film of the present application containing an organic and/or inorganic mixture of sodium and lithium. Therefore, it is not suitable to construct a long-life sodium-ion battery. Moreover, the sodium supplement additive used in the prior art is completely decomposed during the first cycle of charging, so it can only provide electrochemically active sodium ions during the first cycle of charging, and will not continuously release electrochemically active sodium ions during subsequent cycles. It is not conducive to the construction of long-life sodium-ion batteries, and the lithium-rich additives used in the present invention will gradually release lithium ions slowly and gradually during subsequent cycles. Therefore, the present invention effectively solves the problems existing in the use of sodium supplement additives in the prior art.
本发明的钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环的具体过程如下：The sodium-ion battery of the present invention is 1C in circulation current density, and the specific process of circulation under the condition of charging voltage is 2.0V-4.0V is as follows:
在电池首圈充电过程中，钠离子会从正极活性材料晶体结构中脱出，在此过程中，由于富锂添加剂的氧化还原电势与钠离子工作电位部分重合，因此，在活性钠离子从正极材料中脱出的同时，会有部分锂离子从富锂添加剂中脱出，与钠离子一起在电解液中通过隔膜迁移到负极，参与负极的成膜反应，在此过程中，大部分锂离子参与成膜反应被消耗，大部分钠离子则储存到了负极材料的可逆活性位点处。放电时，钠离子可以可逆的从负极脱出，经过电解液隔膜嵌入正极材料，即钠离子可逆的在正负极之间嵌入脱出。During the first charge of the battery, sodium ions will be released from the crystal structure of the positive electrode active material. At the same time, some lithium ions will be extracted from the lithium-rich additive, and together with the sodium ions, they will migrate to the negative electrode through the diaphragm in the electrolyte and participate in the film-forming reaction of the negative electrode. During this process, most of the lithium ions participate in the film-forming process The reaction is consumed, and most of the sodium ions are stored in the reversible active sites of the negative electrode material. During discharge, sodium ions can be reversibly extracted from the negative electrode, and embedded in the positive electrode material through the electrolyte diaphragm, that is, sodium ions can be reversibly inserted and extracted between the positive and negative electrodes.
需要说明的是，本发明的钠离子电池在其他预设条件下的循环过程与其在循环电流密度为1C且充电电压为2.0V-4.0V的预设条件下的循环过程相同。It should be noted that the cycle process of the sodium ion battery of the present invention under other preset conditions is the same as that under the preset conditions of cycle current density of 1C and charging voltage of 2.0V-4.0V.
由于SEI膜首圈消耗的锂离子和钠离子最多，因此，在后续的循环过程中由于副反应减少，消耗的锂离子也逐步减少。具体来说，所述钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环第一预设圈数后，所述锂元素的含量为第一值；所述钠离子电池在循环电流密度为1C，且充电电压为2.0V-4.0V的条件下循环第二预设圈数后，所述锂元素的含量为第二值；在所述第一预设圈数小于所述第二预设圈数的条件下，所述第一值大于所述第二值。进一步地，在所述第一预设圈数大于或者等于500的条件下，所述第一值和所述第二值的差值的绝对值小于0.5wt％。Since the first cycle of the SEI film consumes the most lithium ions and sodium ions, the consumption of lithium ions gradually decreases during subsequent cycles due to the reduction of side reactions. Specifically, after the sodium-ion battery is cycled for a first preset number of cycles under the conditions of a cycle current density of 1C and a charging voltage of 2.0V-4.0V, the content of the lithium element is a first value; After the sodium-ion battery is cycled for the second preset number of cycles under the condition that the cycle current density is 1C and the charging voltage is 2.0V-4.0V, the content of the lithium element is the second value; in the first preset cycle Under the condition that the number of turns is less than the second preset number of turns, the first value is greater than the second value. Further, under the condition that the first preset number of turns is greater than or equal to 500, the absolute value of the difference between the first value and the second value is less than 0.5 wt%.
具体地，正极层包括正极活性材料、富锂添加剂、导电剂和粘结剂，正极活性材料包括钠元素，富锂添加剂包括锂元素。Specifically, the positive electrode layer includes a positive electrode active material, a lithium-rich additive, a conductive agent and a binder, the positive electrode active material includes sodium element, and the lithium-rich additive includes lithium element.
根据本发明的又一个具体实施例，基于正极层的总质量，富锂添加剂的含量为1wt％-5wt％，由此，将富锂添加剂的含量限定在上述范围内，进一步提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，进一步确保了电池体系中电化学活性碱性离子的充足，进一步确保了电解液具有较高的离子电导率，进一步提升了电池的循环稳定性以及使用寿命。具体来说，如果富锂添加剂的含量过低，会导致形成的负极SEI膜主要成分为含钠无机、有机物质，致密性低，导致SEI膜的机械力学强度低，从而导致钠离子电池的循环性能差。如果富锂添加剂的含量过高，会导致非电化学活性物质含量增加，导致电池体系中的电化学活性钠离子相对降低，从而导致电池的能量密度降低。According to another specific embodiment of the present invention, based on the total mass of the positive electrode layer, the content of the lithium-rich additive is 1wt%-5wt%, thus, limiting the content of the lithium-rich additive within the above range further improves the surface of the negative electrode material. The structural stability of the SEI film and the sodium ion transport capacity of the battery system further ensure the sufficient electrochemically active alkaline ions in the battery system, further ensure that the electrolyte has a high ion conductivity, and further improve the cycle stability of the battery performance and service life. Specifically, if the content of lithium-rich additives is too low, the main components of the formed negative electrode SEI film are sodium-containing inorganic and organic substances, and the density is low, resulting in low mechanical strength of the SEI film, which leads to the cycle of sodium-ion batteries. Poor performance. If the content of lithium-rich additives is too high, the content of non-electrochemically active substances will increase, resulting in a relative decrease in the electrochemically active sodium ions in the battery system, resulting in a decrease in the energy density of the battery.
根据本发明的再一个具体实施例，正极活性材料、富锂添加剂、导电剂和粘结剂的质量比为(90-97):(1-5):(0.1-2):(0.5-3)，由此，将上述正极活性材料、富锂添加剂、导电剂和粘结剂的质量比限定在上述范围内，既可以确保负极表面形成的SEI膜致密度高，机械力学强度高，从而使电池体系的钠离子传输能力强，提升电池的循环稳定性，又可以确保不影响电池体系中电化学活性物质的含量，最大化地提升了电池的能量密度、循环稳定性以及使用寿命。According to another specific embodiment of the present invention, the mass ratio of positive electrode active material, lithium-rich additive, conductive agent and binder is (90-97):(1-5):(0.1-2):(0.5-3 ), thus, the mass ratio of the above-mentioned positive electrode active material, lithium-rich additive, conductive agent and binder is limited within the above-mentioned range, which can ensure that the SEI film formed on the surface of the negative electrode has high density and high mechanical strength, so that The sodium ion transport capacity of the battery system is strong, which improves the cycle stability of the battery and ensures that the content of electrochemically active substances in the battery system is not affected, maximizing the energy density, cycle stability and service life of the battery.
根据本发明的又一个具体实施例，上述富锂添加剂包括无机锂盐，该无机锂盐在首圈充电过程中会释放一部分锂离子，该部分锂离子可以通过电解液传输到负极材料表面参与SEI膜的形成，使形成的SEI膜同时含有钠和锂的有机和/或无机混合物，从而提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，提升了电池的循环稳定性；同时，该富锂添加剂会在后续的循环过程中缓慢地逐步释放锂离子，有利于不断补充电池体系中消耗的活性钠，确保了电池体系中电化学活性碱性离子的充足。另外，该无机锂盐在提供电化学活性锂的过程中不会产生气体，因此避免了电池胀气带来的安全隐患。According to another specific embodiment of the present invention, the above-mentioned lithium-rich additive includes an inorganic lithium salt, which will release a part of lithium ions during the first cycle of charging, and this part of lithium ions can be transported to the surface of the negative electrode material through the electrolyte to participate in SEI. The formation of the film makes the formed SEI film contain organic and/or inorganic mixtures of sodium and lithium, thereby improving the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transport capacity of the battery system, improving the cycle stability of the battery ; At the same time, the lithium-rich additive will slowly and gradually release lithium ions in the subsequent cycle process, which is conducive to continuously supplementing the active sodium consumed in the battery system and ensuring sufficient electrochemically active alkaline ions in the battery system. In addition, the inorganic lithium salt does not generate gas during the process of providing electrochemically active lithium, thus avoiding the safety hazard caused by battery gas.
在本发明的实施例中，上述无机锂盐的具体种类并不受特别限定，优选地，无机锂盐包括Li2NiO2、Li6CoO4、Li2CuO2、Li2NixCuyO2、Li2MoO3、Li2O/M1、Li2S/M2和LiF/M3中的至少一种，其中，x+y＝1，且x大于0，y大于0，M1为Co、Fe、Ni或Mn，M2为Co或Fe，M3为Co或Fe，以上种类的无机锂盐不仅具有上述无机锂盐的所有优点，具体地，该富锂添加剂在首圈充电过程中会释放一部分锂离子，参与SEI膜的形成，同时该富锂添加剂会在后续的循环过程中缓慢地逐步释放锂离子，确保了电池体系中电化学活性碱性离子的充足。而且，上述种类的无机锂盐对空气中含有的水分敏感度较低，避免了无机锂盐在电池的制备过程中因空气中的水分而变质，且有利于电池的制备过程能在正常的空气氛围中进行，不需要对空气进行除湿处理。In the embodiment of the present invention, the specific type of the above-mentioned inorganic lithium salt is not particularly limited, preferably, the inorganic lithium salt includes Li2 NiO2 , Li6 CoO4 , Li2 CuO2 , Li2 Nix Cuy O2. At least one of Li2 MoO3 , Li2 O/M1 , Li2 S/M2 and LiF/M3 , wherein x+y=1, and x is greater than 0, y is greater than 0, and M1 is Co, Fe, Ni or Mn,M2 is Co or Fe, andM3 is Co or Fe. The above types of inorganic lithium salts not only have all the advantages of the above-mentioned inorganic lithium salts, specifically, the lithium-rich additive is charged in the first cycle During the process, a part of lithium ions will be released to participate in the formation of the SEI film. At the same time, the lithium-rich additive will slowly and gradually release lithium ions during the subsequent cycle, ensuring sufficient electrochemically active alkaline ions in the battery system. Moreover, the above-mentioned types of inorganic lithium salts are less sensitive to the moisture contained in the air, which avoids the deterioration of the inorganic lithium salts due to moisture in the air during the preparation of the battery, and is conducive to the preparation of the battery. In the atmosphere, there is no need to dehumidify the air.
需要解释的是，上述Li2O/M1指的是Li2O和金属M1的复合材料，Li2O和金属M1的摩尔比为2：3或者1：1。Li2S/M2指的是Li2S和金属M2的复合材料，Li2S和金属M2的摩尔比为2：3或者1：1。LiF/M3指的是LiF和金属M3的复合材料，LiF和金属M3的摩尔比为2：1。It should be explained that the aforementioned Li2 O/M1 refers to a composite material of Li2 O and metal M1 , and the molar ratio of Li2 O and metal M1 is 2:3 or 1:1. Li2 S/M2 refers to a composite material of Li2 S and metal M2 , and the molar ratio of Li2 S and metal M2 is 2:3 or 1:1. LiF/M3 refers to the composite material of LiF and metalM3 , and the molar ratio of LiF and metalM3 is 2:1.
在本发明的实施例中，上述正极活性材料为能嵌入脱出钠离子的材料，其具体种类并不受特别限定，作为一些具体示例，正极活性材料包括Na0.95Ni0.159Mn0.317Cu0.158Mg0.158Ti0.208O2、Na3V2(PO4)3、Na4V2(PO4)3、Na2Fe2(SO4)3、Na2.5Fe1.75(SO4)3、Na3.32Fe2.34(P2O7)2、Na4Fe3(PO4)2P2O7、Na4Mn3(PO4)2P2O7、Na4Ni3(PO4)2P2O7、NaNi1/3Fe1/3Mn1/3O2、Na0.85Ni0.4Mn0.4Fe0.2O2、Na0.85Ni0.3Mn0.4Fe0.3O2和Na0.95Ni0.159Mn0.317Cu0.316Ti0.208O2中的至少一种。In an embodiment of the present invention, the positive electrode active material is a material capable of intercalating and extracting sodium ions, and its specific type is not particularly limited. As some specific examples, the positive electrode active material includes Na0.95 Ni0.159 Mn0.317 Cu0.158 Mg0.158 Ti0.208 O2 , Na3 V2 (PO4 )3 , Na4 V2 (PO4 )3 , Na2 Fe2 (SO4 )3 , Na2.5 Fe1.75 (SO4 )3 , Na3.32 Fe2.34 (P2 O7 )2 , Na4 Fe3 (PO4 )2 P2 O7 , Na4 Mn3 (PO4 )2 P2 O7 , Na4 Ni3 (PO4 )2 P2 O7 , NaNi1 At least one of/3 Fe1/3 Mn1/3 O2 , Na0.85 Ni0.4 Mn0.4 Fe0.2 O2 , Na0.85 Ni0.3 Mn0.4 Fe0.3 O2 and Na0.95 Ni0.159 Mn0.317 Cu0.316 Ti0.208 O2 A sort of.
在本发明的实施例中，导电剂的具体种类并不受特别限制，本领域人员可根据实际情况随意选择，作为一些具体示例，导电剂包括Super p炭黑、乙炔黑、科琴黑、石墨烯和导电碳管中的至少一种。In the embodiments of the present invention, the specific type of conductive agent is not particularly limited, and those skilled in the art can choose at will according to the actual situation. As some specific examples, the conductive agent includes Super p carbon black, acetylene black, Ketjen black, graphite At least one of ene and conductive carbon tubes.
在本发明的实施例中，粘结剂的具体种类并不受特别限制，本领域人员可根据实际情况随意选择，作为一些具体示例，粘结剂包括PVDF、PTFE和NBR中的至少一种。In the embodiment of the present invention, the specific type of the binder is not particularly limited, and those skilled in the art can choose at will according to the actual situation. As some specific examples, the binder includes at least one of PVDF, PTFE and NBR.
具体地，钠离子电池包括以上实施例所述的正极片、负极片和和隔膜，隔膜设置在正极片和负极片之间。隔膜包括PP隔膜、PE隔膜、单面陶瓷隔膜、双面陶瓷隔膜、无纺布隔膜、玻璃纤维隔膜中的至少一种。Specifically, the sodium ion battery includes the positive electrode sheet, the negative electrode sheet and the separator described in the above embodiments, and the separator is arranged between the positive electrode sheet and the negative electrode sheet. The diaphragm includes at least one of PP diaphragm, PE diaphragm, single-sided ceramic diaphragm, double-sided ceramic diaphragm, non-woven fabric diaphragm, and glass fiber diaphragm.
负极片包括负极集流体和形成在负极集流体上的负极活性材料层，负极活性材料层包括负极活性材料、导电剂和粘结剂。负极活性材料可以采用碳基负极材料(例如硬碳、软碳、软硬复合碳)、金属氧化物负极材料(例如氧化钛、钛酸钠等)、合金基负极材料(例如锡合金)等。负极片的制备方法包括：按照不同比例将负极活性材料、导电剂和粘结剂混合均匀，加入去离子水搅拌均匀，然后涂布到集流体上，烘干，最后根据电池外壳的不同，切成特定形状的负极片备用。The negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector. The negative electrode active material layer includes a negative electrode active material, a conductive agent and a binder. The negative electrode active material can be carbon-based negative electrode materials (such as hard carbon, soft carbon, soft-hard composite carbon), metal oxide negative electrode materials (such as titanium oxide, sodium titanate, etc.), alloy-based negative electrode materials (such as tin alloy) and the like. The preparation method of the negative electrode sheet includes: uniformly mixing the negative electrode active material, the conductive agent and the binder according to different proportions, adding deionized water and stirring evenly, then coating on the current collector, drying, and finally cutting according to the difference of the battery shell. A negative electrode sheet of a specific shape is prepared for use.
钠离子电池中填充有传输钠离子的电解液，电解液包括电解质(例如六氟磷酸钠)和溶剂(例如碳酸酯类、醚类以及混合酯类醚类等)。The sodium ion battery is filled with an electrolyte solution for transporting sodium ions, and the electrolyte solution includes electrolytes (such as sodium hexafluorophosphate) and solvents (such as carbonates, ethers, mixed ester ethers, etc.).
以下对上述钠离子电池的制备方法进行详细描述：The preparation method of above-mentioned sodium ion battery is described in detail below:
首先是制备正极片的方法，包括：The first is the method of preparing the positive electrode sheet, including:
S100：将正极活性材料、富锂添加剂、导电剂、粘结剂和有机溶剂混合S100: Mix positive electrode active material, lithium-rich additive, conductive agent, binder and organic solvent
在该步骤中，按照比例将正极活性材料、富锂添加剂、导电剂、粘结剂和有机溶剂混合，形成正极浆料。在本发明的实施例中，正极浆料的固含量和粘度并不受特别限定，作为一些具体示例，正极浆料的固含量可以为60％-80％，正极浆料的粘度可以为5000-8000cp。有机溶剂的具体种类也不受特别限定，例如可以选择NMP(N-甲基吡咯烷酮)、DMF(二甲基甲酰胺)以及DMSO中的至少一种。In this step, the positive electrode active material, the lithium-rich additive, the conductive agent, the binder and the organic solvent are mixed in proportion to form the positive electrode slurry. In the embodiments of the present invention, the solid content and viscosity of the positive electrode slurry are not particularly limited. As some specific examples, the solid content of the positive electrode slurry can be 60%-80%, and the viscosity of the positive electrode slurry can be 5000- 8000cp. The specific type of organic solvent is not particularly limited, for example, at least one of NMP (N-methylpyrrolidone), DMF (dimethylformamide) and DMSO can be selected.
S200：将正极浆料形成在正极集流体上，干燥S200: forming the positive electrode slurry on the positive electrode current collector, drying
在该步骤中，将正极浆料涂布到正极集流体上，干燥(例如真空烘干)，以便在正极集流体上形成正极层，最终得到正极片。最后根据电池外壳的不同，切成特定形状的正极片备用。In this step, the positive electrode slurry is coated on the positive electrode current collector, and dried (such as vacuum drying), so as to form a positive electrode layer on the positive electrode current collector, and finally obtain a positive electrode sheet. Finally, according to the difference of the battery case, the positive electrode sheet is cut into a specific shape for later use.
根据本发明实施例的制备上述正极片的方法，采用常规制备正极片的方法将富锂添加剂添加到正极片的正极层中，该制备过程简单易实施，制备工艺成熟。且该方法制备得到的正极片中的富锂添加剂在电化学反应过程中，会从其表面到内部逐步释放电化学活性锂离子，使得该富锂添加剂在首圈充电过程中会释放一部分锂离子，该部分锂离子可以通过电解液传输到负极材料表面参与SEI膜的形成，使形成的SEI膜同时含有钠和锂的有机和/或无机混合物，从而提升了负极材料表面SEI膜的结构稳定性以及电池体系的钠离子传输能力，提升了电池的循环稳定性。同时，该富锂添加剂在首圈充电过程中提供的电化学活性锂离子，减少了正极材料中电化学活性钠离子的消耗，进而提升钠离子电池的能量密度。另外，该富锂添加剂会在后续的循环过程中缓慢地逐步释放锂离子，该锂离子有利于不断补充电池体系中消耗的活性钠，确保了电池体系中电化学活性碱性离子的充足，以及确保了电解液具有较高的离子电导率，由此进一步提升了电池的循环稳定性以及使用寿命。According to the method for preparing the above-mentioned positive electrode sheet in the embodiment of the present invention, a lithium-rich additive is added to the positive electrode layer of the positive electrode sheet by using a conventional method for preparing the positive electrode sheet. The preparation process is simple and easy to implement, and the preparation process is mature. Moreover, the lithium-rich additive in the positive electrode sheet prepared by this method will gradually release electrochemically active lithium ions from its surface to the inside during the electrochemical reaction, so that the lithium-rich additive will release a part of lithium ions during the first cycle of charging. , this part of lithium ions can be transported to the surface of the negative electrode material through the electrolyte to participate in the formation of the SEI film, so that the formed SEI film contains an organic and/or inorganic mixture of sodium and lithium, thereby improving the structural stability of the SEI film on the surface of the negative electrode material And the sodium ion transport capacity of the battery system improves the cycle stability of the battery. At the same time, the electrochemically active lithium ions provided by the lithium-rich additive during the first cycle of charging reduce the consumption of electrochemically active sodium ions in the positive electrode material, thereby increasing the energy density of the sodium-ion battery. In addition, the lithium-rich additive will slowly and gradually release lithium ions during the subsequent cycle, which is conducive to continuously supplementing the active sodium consumed in the battery system, ensuring sufficient electrochemically active alkaline ions in the battery system, and It ensures that the electrolyte has a high ion conductivity, thereby further improving the cycle stability and service life of the battery.
负极片的制备方法与正极片的相似，在此不再赘述。The preparation method of the negative electrode sheet is similar to that of the positive electrode sheet, and will not be repeated here.
组装钠离子电池的方法包括：将正极片、隔膜和负极片按照layer-by-layer卷绕或者叠片的方式组装，并按照相应的注液系数注入电解液，然后将电芯放入壳体中密封。The method of assembling the sodium-ion battery includes: assembling the positive electrode sheet, separator, and negative electrode sheet in a layer-by-layer winding or stacking manner, injecting the electrolyte according to the corresponding injection coefficient, and then putting the cell into the casing medium seal.
在本发明的第二个方面，本发明提出了一种储能设备。根据本发明的实施例，所述储能设备具有如上所述的钠离子电池。由此，所述储能设备具有所述钠离子电池的所有优点，在此不再赘述。In a second aspect of the invention, the invention proposes an energy storage device. According to an embodiment of the present invention, the energy storage device has a sodium-ion battery as described above. Therefore, the energy storage device has all the advantages of the sodium ion battery, which will not be repeated here.
具体地，该储能设备可以包括用于电力系统的发电侧的电力储能装置、用于电力系统的配电侧的电力储能装置(例如电化学储能装置)和用于电力系统的用户侧的电力储能装置中的至少之一。Specifically, the energy storage device may include an electric energy storage device for the power generation side of the power system, an electric energy storage device (such as an electrochemical energy storage device) for the power distribution side of the power system, and a power system user At least one of the electrical energy storage devices on the side.
下面详细描述本发明的实施例，需要说明的是下面描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。另外，如果没有明确说明，在下面的实施例中所采用的所有试剂均为市场上可以购得的，或者可以按照本文或已知的方法合成的，对于没有列出的反应条件，也均为本领域技术人员容易获得的。Embodiments of the present invention are described in detail below, and it should be noted that the embodiments described below are exemplary, and are only used to explain the present invention, and should not be construed as limiting the present invention. In addition, if not clearly stated, all reagents used in the following examples are commercially available, or can be synthesized according to this article or known methods, and for the reaction conditions not listed, they are all readily available to those skilled in the art.
实施例1Example 1
正极片的制备：将NaNi1/3Fe1/3Mn1/3O2、Li2NiO2、乙炔黑和PVDF按照质量比为93：4：2：1的比例加入到NMP溶剂中搅拌均匀，然后涂布到铝箔集流体上，100℃真空烘干，在铝箔集流体上形成正极层，分切成带极耳的6cm*8cm的正极片备用。计算可以得到，基于正极层的总质量，钠元素的含量为19.18％，锂元素的含量为0.53％。Preparation of the positive electrode sheet: NaNi1/3 Fe1/3 Mn1/3 O2 , Li2 NiO2 , acetylene black and PVDF were added to the NMP solvent according to the mass ratio of 93:4:2:1 and stirred evenly , and then coated on the aluminum foil current collector, vacuum-dried at 100°C to form a positive electrode layer on the aluminum foil current collector, and cut into 6cm*8cm positive electrode pieces with tabs for future use. It can be obtained from calculation that, based on the total mass of the positive electrode layer, the content of sodium element is 19.18%, and the content of lithium element is 0.53%.
负极片的制备：将硬碳材料、super P以及CMC/SBR/PAA按照质量比为97：1：2的比例加入到去离子水中搅拌均匀，然后涂布到铜箔集流体上，100℃烘干，分切成带极耳的7cm*9cm的负极片备用。Preparation of negative electrode sheet: Add hard carbon material, super P and CMC/SBR/PAA into deionized water with a mass ratio of 97:1:2 and stir evenly, then coat it on the copper foil current collector, and bake at 100°C Dry, cut into 7cm*9cm negative electrode sheets with tabs for later use.
电池组装：将正极片-隔膜-负极片按照layer by layer的形式叠片，烘烤至水分含量低于300ppm，注入电解液，并用铝塑膜密封，制备得到钠离子电池。Battery assembly: Laminate the positive electrode sheet-diaphragm-negative electrode sheet in the form of layer by layer, bake until the moisture content is lower than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium-ion battery.
实施例2Example 2
正极片的制备：将Na4Fe3(PO4)2P2O7、Li2CuO2、乙炔黑和PVDF按照质量比94：3：2：1的比例加入到NMP溶剂中搅拌均匀，然后涂布到铝箔集流体上，100℃真空烘干，分切成带极耳的6cm*8cm的极片备用。Preparation of the positive electrode sheet: Na4 Fe3 (PO4 )2 P2 O7 , Li2 CuO2 , acetylene black and PVDF were added to the NMP solvent at a mass ratio of 94:3:2:1 and stirred evenly, then Coated on the aluminum foil current collector, dried in vacuum at 100°C, cut into 6cm*8cm pole pieces with lugs for later use.
负极片的制备：将硬碳材料、super P以及CMC/SBR/PAA按照质量比为97：1：2的比例加入到去离子水中搅拌均匀，然后涂布到铜箔集流体上，100℃烘干，分切成带极耳的7cm*9cm的极片备用。Preparation of negative electrode sheet: Add hard carbon material, super P and CMC/SBR/PAA into deionized water with a mass ratio of 97:1:2 and stir evenly, then coat it on the copper foil current collector, and bake at 100°C Dry, cut into 7cm*9cm pole pieces with tabs for later use.
电池组装：将正极片-隔膜-负极片按照layer by layer的形式叠片，烘烤至水分含量低于300ppm，注入电解液，并用铝塑膜密封，制备得到钠离子电池。Battery assembly: Laminate the positive electrode sheet-diaphragm-negative electrode sheet in the form of layer by layer, bake until the moisture content is lower than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium-ion battery.
实施例3Example 3
正极片的制备：将Na3V2(PO4)3、3Li2O/2Fe、乙炔黑和PVDF按照质量比93：4：2：1的比例加入到NMP溶剂中搅拌均匀，然后涂布到铝箔集流体上，100℃真空烘干，分切成带极耳的6cm*8cm的极片备用。Preparation of the positive electrode sheet: Na3 V2 (PO4 )3 , 3Li2 O/2Fe, acetylene black and PVDF were added to the NMP solvent according to the mass ratio of 93:4:2:1 and stirred evenly, and then coated on On the aluminum foil current collector, vacuum-dry at 100°C, cut into 6cm*8cm pole pieces with tabs for later use.
负极片的制备：将硬碳材料、super P以及CMC/SBR/PAA按照质量比为97：1：2的比例加入到去离子水中搅拌均匀，然后涂布到铜箔集流体上，100℃烘干，分切成带极耳的7cm*9cm的极片备用。Preparation of negative electrode sheet: Add hard carbon material, super P and CMC/SBR/PAA into deionized water with a mass ratio of 97:1:2 and stir evenly, then coat it on the copper foil current collector, and bake at 100°C Dry, cut into 7cm*9cm pole pieces with tabs for later use.
电池组装：将正极片-隔膜-负极片按照layer by layer的形式叠片，烘烤至水分含量低于300ppm，注入电解液，并用铝塑膜密封，制备得到钠离子电池。Battery assembly: Laminate the positive electrode sheet-diaphragm-negative electrode sheet in the form of layer by layer, bake until the moisture content is lower than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium-ion battery.
实施例4Example 4
将NaNi1/3Fe1/3Mn1/3O2、Li2NiO2、乙炔黑和PVDF的质量比设置为96：1：2：1，其他内容均与实施例1相同。The mass ratio of NaNi1/3 Fe1/3 Mn1/3 O2 , Li2 NiO2 , acetylene black and PVDF was set to 96:1:2:1, and other contents were the same as in Example 1.
实施例5Example 5
将NaNi1/3Fe1/3Mn1/3O2、Li2NiO2、乙炔黑和PVDF的质量比设置为95：2：2：1，其他内容均与实施例1相同。The mass ratio of NaNi1/3 Fe1/3 Mn1/3 O2 , Li2 NiO2 , acetylene black and PVDF was set to 95:2:2:1, and the other contents were the same as in Example 1.
实施例6Example 6
将NaNi1/3Fe1/3Mn1/3O2、Li2NiO2、乙炔黑和PVDF的质量比设置为92：5：2：1，其他内容均与实施例1相同。The mass ratio of NaNi1/3 Fe1/3 Mn1/3 O2 , Li2 NiO2 , acetylene black and PVDF was set to 92:5:2:1, and other contents were the same as in Example 1.
实施例7Example 7
将实施例1中Li2NiO2替换为Li6CoO4，其他内容均与实施例1相同。In Example 1, Li2 NiO2 was replaced by Li6 CoO4 , and other contents were the same as in Example 1.
实施例8Example 8
将实施例1中Li2NiO2替换为Li2MoO3，其他内容均与实施例1相同。In Example 1, Li2 NiO2 was replaced by Li2 MoO3 , and other contents were the same as in Example 1.
实施例9Example 9
将实施例1中Li2NiO2替换为Li2Ni0.5Cu0.5O2，其他内容均与实施例1相同。In Example 1, Li2 NiO2 was replaced by Li2 Ni0.5 Cu0.5 O2 , and other contents were the same as in Example 1.
实施例10Example 10
将实施例1中Li2NiO2替换为3Li2S/2Ni，其他内容均与实施例1相同。Li2 NiO2 in Example 1 was replaced by 3Li2 S/2Ni, and other contents were the same as in Example 1.
实施例11Example 11
将实施例1中Li2NiO2替换为2LiF/Fe，其他内容均与实施例1相同。In Example 1, Li2 NiO2 was replaced by 2LiF/Fe, and other contents were the same as in Example 1.
对比例1Comparative example 1
正极片的制备：将NaNi1/3Fe1/3Mn1/3O2、乙炔黑和PVDF按照质量比为97：2：1的比例加入到NMP溶剂中搅拌均匀，然后涂布到铝箔集流体上，100℃真空烘干，分切成带极耳的6cm*8cm的极片备用。Preparation of the positive electrode sheet: NaNi1/3 Fe1/3 Mn1/3 O2 , acetylene black and PVDF were added to the NMP solvent with a mass ratio of 97:2:1 and stirred evenly, and then coated on the aluminum foil set On the fluid, vacuum-dry at 100°C, cut into 6cm*8cm pole pieces with lugs for later use.
负极片的制备：将硬碳材料、super P以及CMC/SBR/PAA按照质量比为97：1：2的比例加入到去离子水中搅拌均匀，然后涂布到铜箔集流体上，100℃烘干，分切成带极耳的7cm*9cm的负极片备用。Preparation of negative electrode sheet: Add hard carbon material, super P and CMC/SBR/PAA into deionized water with a mass ratio of 97:1:2 and stir evenly, then coat it on the copper foil current collector, and bake at 100°C Dry, cut into 7cm*9cm negative electrode sheets with tabs for later use.
电池组装：将正极片-隔膜-负极片按照layer by layer的形式叠片，烘烤至水分含量低于300ppm，注入电解液，并用铝塑膜密封，制备得到钠离子电池。Battery assembly: Laminate the positive electrode sheet-diaphragm-negative electrode sheet in the form of layer by layer, bake until the moisture content is lower than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium-ion battery.
对比例2Comparative example 2
正极片的制备：将Na4Fe3(PO4)2P2O7、乙炔黑和PVDF按照质量比97：2：1的比例加入到NMP溶剂中搅拌均匀，然后涂布到铝箔集流体上，100℃真空烘干，分切成带极耳的6cm*8cm的极片备用。Preparation of the positive electrode sheet: Na4 Fe3 (PO4 )2 P2 O7 , acetylene black and PVDF were added to the NMP solvent according to the mass ratio of 97:2:1 and stirred evenly, and then coated on the aluminum foil current collector , vacuum-dried at 100°C, cut into 6cm*8cm pole pieces with lugs for later use.
负极片的制备：将硬碳材料、super P以及CMC/SBR/PAA按照质量比为97：1：2的比例加入到去离子水中搅拌均匀，然后涂布到铜箔集流体上，100℃烘干，分切成带极耳的7cm*9cm的极片备用。Preparation of negative electrode sheet: Add hard carbon material, super P and CMC/SBR/PAA into deionized water with a mass ratio of 97:1:2 and stir evenly, then coat it on the copper foil current collector, and bake at 100°C Dry, cut into 7cm*9cm pole pieces with tabs for later use.
电池组装：将正极片-隔膜-负极片按照layer by layer的形式叠片，烘烤至水分含量低于300ppm，注入电解液，并用铝塑膜密封，制备得到钠离子电池。Battery assembly: Laminate the positive electrode sheet-diaphragm-negative electrode sheet in the form of layer by layer, bake until the moisture content is lower than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium-ion battery.
对比例3Comparative example 3
正极片的制备：将Na3V2(PO4)3、乙炔黑和PVDF按照质量比97：2：1的比例加入到NMP溶剂中搅拌均匀，然后涂布到铝箔集流体上，100℃真空烘干，分切成带极耳的6cm*8cm的极片备用。Preparation of positive electrode sheet: Na3 V2 (PO4 )3 , acetylene black and PVDF were added to NMP solvent according to the mass ratio of 97:2:1 and stirred evenly, then coated on the aluminum foil current collector, vacuum at 100°C Dry and cut into 6cm*8cm pole pieces with lugs for later use.
负极片的制备：将硬碳材料、super P以及CMC/SBR/PAA按照质量比为97：1：2的比例加入到去离子水中搅拌均匀，然后涂布到铜箔集流体上，100℃烘干，分切成带极耳的7cm*9cm的极片备用。Preparation of negative electrode sheet: Add hard carbon material, super P and CMC/SBR/PAA into deionized water with a mass ratio of 97:1:2 and stir evenly, then coat it on the copper foil current collector, and bake at 100°C Dry, cut into 7cm*9cm pole pieces with tabs for later use.
电池组装：将正极片-隔膜-负极片按照layer by layer的形式叠片，烘烤至水分含量低于300ppm，注入电解液，并用铝塑膜密封，制备得到钠离子电池。Battery assembly: Laminate the positive electrode sheet-diaphragm-negative electrode sheet in the form of layer by layer, bake until the moisture content is lower than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium-ion battery.
分别计算实施例1-11形成的正极层在循环前的钠元素和锂元素的含量，结果如表1所示，采用电感耦合等离子发射光谱仪(ICP)分别测试实施例1-11形成的正极层在循环1圈、100圈、500圈、1000圈、3000圈和6000圈后的钠元素和锂元素的含量，结果如表1所示。Calculate respectively the content of sodium element and lithium element in the positive electrode layer formed in Examples 1-11 before cycling, and the results are shown in Table 1. The positive electrode layer formed in Examples 1-11 is tested respectively by using an inductively coupled plasma emission spectrometer (ICP) The contents of sodium and lithium elements after 1 cycle, 100 cycles, 500 cycles, 1000 cycles, 3000 cycles and 6000 cycles are shown in Table 1.
表1Table 1
从表1中可以看出，在首圈循环中钠离子的损失比较少，锂离子的损失比较多，说明首圈充电过程中大部分的锂离子参与了负极SEI膜的形成，减少了活性钠离子的损耗，从而可以提升电池的能量密度。同时，随着循环圈数的增加，锂离子逐步补偿钠离子的消耗，提升了电池的循环稳定性，从而有利于构筑高使用寿命钠离子电池。It can be seen from Table 1 that the loss of sodium ions in the first cycle is relatively small, and the loss of lithium ions is relatively large, indicating that most of the lithium ions participate in the formation of the negative electrode SEI film during the first cycle of charging, reducing the active sodium The loss of ions can increase the energy density of the battery. At the same time, as the number of cycles increases, lithium ions gradually compensate for the consumption of sodium ions, improving the cycle stability of the battery, which is conducive to the construction of a high-life-span sodium-ion battery.
分别对实施例1-11以及对比例1-3的首圈放电比容量、首圈放电阻抗、1000圈保持率和1000圈放电阻抗进行测试，测试结果如表2所示。The first-cycle discharge specific capacity, first-cycle discharge impedance, 1000-cycle retention rate and 1000-cycle discharge impedance of Examples 1-11 and Comparative Examples 1-3 were tested respectively, and the test results are shown in Table 2.
表2Table 2
从表2中可以看出，与未添加富锂添加剂的对比例1-3相比，添加富锂添加剂的实施例1-11的首圈放电比容量和1000圈循环保持率得到明显提升，且实施例1-11的首圈放电阻抗和1000圈放电阻抗得到明显降低。It can be seen from Table 2 that compared with Comparative Examples 1-3 without adding lithium-rich additives, the first-cycle discharge specific capacity and 1000-cycle cycle retention rate of Examples 1-11 with lithium-rich additives were significantly improved, and The discharge impedance of the first cycle and the discharge impedance of 1000 cycles of Examples 1-11 are significantly reduced.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.
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