Electrolyte additive, electrolyte and battery

Abstract

Electrolyte additive comprising a first additive, a second additive and a third additive, wherein the first additive comprises a compound represented by formula 1: where: R1 is selected from a C atom or an O atom; R2 is selected from or R3 is selected from methylene, or R4 is selected from or and at least one of R2, R3 and R4 contains a sulfur atom; wherein the second additive comprises at least one of a compound represented by formula 2 and one of a compound represented by formula 3: formula 2, formula 3, where X comprises a phosphorus atom or a phosphorus atom; and where the third additive comprises a compound represented by formula 4: RN=C=O Formula 4, where R comprises at least one of alkyl, O=C=N-substituted alkyl, cycloalkyl, O=C=N-substituted cycloalkyl, aryl or O=C=N-substituted aryl.

Description

PRIORITY INFORMATION

[0001] This application claims the priority and benefits of Chinese patent application No. 202410720189.5, filed with the Chinese Patent Office on June 5, 2024, the entire contents of which are incorporated into this document by reference. AREA

[0002] The present disclosure relates to the technical field of batteries and in particular to an electrolyte additive, an electrolyte and a battery. BACKGROUND

[0003] In recent years, secondary batteries have seen widespread use in portable electronics, electric vehicles, and energy storage. However, increasingly demanding market requirements for performance can accelerate electrolyte reactions on the surface of electrode materials, leading to electrolyte degradation and gas generation. This gas can cause the battery to swell and bulge, potentially leading to cracking and electrolyte leakage, which poses significant safety risks. Furthermore, prior art electrolytes exhibit problems such as slow ion dynamics, slow ion solvation and desolvation processes, and reduced ion deintercalation rates.These problems can lead to increased concentration polarization and internal impedance of the battery, as well as a reduced lifespan. SUMMARY

[0004] The present disclosure aims to solve at least one of the technical problems in the prior art.

[0005] In a first aspect, the present disclosure provides an electrolyte additive. The electrolyte additive comprises a first additive, a second additive, and a third additive. The first additive comprises a compound represented by Formula 1: Formula 1, wherein: R1 is selected from a carbon atom or an oxygen atom; R2 is selected from, or R3 is selected from, methylene; or R4 is selected from, and at least one of R2, R3, and R4 contains a sulfur atom. The second additive comprises at least one of a compound represented by Formula 2 and one of a compound represented by Formula 3: Formula 2, Formula 3, wherein X comprises a phosphorus atom or a borosilicate atom. The third additive comprises a compound represented by formula 4: RN=C=O Formula 4, where R comprises at least one of alkyl, O=C=N-substituted alkyl, cycloalkyl, O=C=N-substituted cycloalkyl, aryl or O=C=N-substituted aryl.In this way, a stable, low-impedance interface film can be formed on an electrode surface, thereby reducing the battery's impedance and gas generation. This improves the battery's cycle performance.

[0006] According to some embodiments of the present disclosure, R comprises at least one of alkyl having 1 to 10 carbon atoms, O=C=N-substituted alkyl having 1 to 10 carbon atoms, cycloalkyl having 1 to 10 carbon atoms, O=C=N-substituted cycloalkyl having 1 to 10 carbon atoms, aryl having 6 to 10 carbon atoms or O=C=N-substituted aryl having 6 to 10 carbon atoms.

[0007] According to some embodiments of the present disclosure, the mass ratio of the first additive, the second additive, and the third additive in the electrolyte additive is 1:(0.01 to 10):(0.01 to 10). In this way, a stable, low-impedance interface film can be formed on the electrode surface, thereby reducing gas generation in the battery and removing water or acid produced by a reaction in the electrolyte. Thus, the structural stability of an electrode can be improved.

[0008] According to some embodiments of the present disclosure, the first additive comprises at least one of Formula 1-1, Formula 1-2 or Formula 1-3.

[0009] According to some embodiments of the present disclosure, the second additive comprises at least one of formula 3-1, formula 2-1 or formula 2-2. In this way, a stable and highly conductive interface film can be formed on the electrode surface, thereby improving the electrode's ability to transfer charges and reducing the battery's impedance.

[0010] According to some embodiments of the present disclosure, the third additive comprises at least one of formula 4-1, formula 4-2, formula 4-3, formula 4-4, or formula 4-5. In this way, while removing water and preventing acid formation, the third additive described above can polymerize on the electrode surface to form long polymer chains, thereby creating the stable, low-impedance interface film. Thus, the internal resistance of the battery can be reduced.

[0011] According to some embodiments of the present disclosure, the electrolyte additive further comprises a fourth additive. The fourth additive comprises at least one of vinylene carbonate, fluoroethylene carbonate, ethylene sulfate, 1,3-propanesultone, or polystyrene. Thus, the fourth additive acts synergistically with the first, second, and third additives to degrade prior to an early stage of battery formation through a carbon chain ring opening reaction, thereby forming an interface film. In this way, the stability of the interface film and the wettability of the electrolyte can be improved. Consequently, the cycle performance of the battery is enhanced.

[0012] According to some embodiments of the present disclosure, the mass ratio of the first additive, the second additive, the third additive and the fourth additive in the electrolyte additive is 1:(0.01 to 10):(0.01 to 10):(0.005 to 100).

[0013] In a second aspect, the present revelation provides an electrolyte. The electrolyte comprises the electrolyte additive provided in the first aspect of the present revelation.

[0014] According to some embodiments of the present disclosure, the mass fraction of the first additive is in the range of 0.1% to 5% based on the total mass of the electrolyte. This forms a low-impedance interface film on the electrode surface, thereby reducing the internal resistance of the battery. This also reduces the contact between the electrolyte solvent and the electrode, the likelihood of electrolyte solvent degradation, and suppresses gas generation from the battery.

[0015] According to some embodiments of the present disclosure, the mass fraction of the second additive is in the range of 0.1% to 5% based on the total mass of the electrolyte. In this way, the low-impedance interface film is formed on the electrode surface, thereby reducing the internal resistance of the battery.

[0016] According to some embodiments of the present disclosure, the mass fraction of the third additive is in the range of 0.1% to 5% based on the total mass of the electrolyte. In this way, while removing water and preventing acid formation, a stable, low-impedance interface film is formed and the internal resistance of the battery is reduced.

[0017] According to some embodiments of the present disclosure, the electrolyte further comprises a fourth additive. Based on the total mass of the electrolyte, the mass fraction of the fourth additive is in the range of 0.5% to 5%. In this way, the fourth additive acts synergistically with the first, second, and third additives to degrade itself prior to the early stages of battery formation through a carbon chain ring opening reaction, thereby forming the interface film. This improves the stability of the interface film and the wettability of the electrolyte. Consequently, the cycle performance of the battery is improved.

[0018] According to some embodiments of the present disclosure, the electrolyte further comprises an electrolyte salt. Based on the total mass of the electrolyte, the mass fraction of the electrolyte salt is in the range of 12% to 18%.

[0019] In a third aspect, the present disclosure provides a battery. The battery comprises the electrolyte additive provided in the first aspect of the present disclosure, or the electrolyte provided in the second aspect of the present disclosure.

[0020] According to some embodiments of the present disclosure, the battery comprises a positive electrode plate and a negative electrode plate. The battery is a lithium-ion battery, wherein a positive active material of the positive electrode plate is one or more LiFePO4 ions. 1-x' M' x' PO4, LiMn 2-y' M y' O4 or LiNi x Co y Mn z M 1-x-y-zO2 comprises, wherein: M' comprises one or more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti; M comprises one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti; and 0≤x' <1, 0≤y'≤1, 0≤y≤1, 0≤x≤1, 0≤z≤1 and x + y + z≤1; and / or the battery is a sodium-ion battery, wherein a positive active material of the positive electrode plate Na c P d (W a O b )Z e comprising, where: P comprises a transition metal element; W comprises at least one of phosphorus, sulfur, silicon or tungsten; Z comprises an F atom; and 0≤c≤10, 0≤d≤5, 0≤a≤10, 0 <b≤10 und 0≤e≤5; und / oder ein negatives Aktivmaterial der negativen Elektrodenplatte mindestens eines von weichem Kohlenstoff, hartem Kohlenstoff, einem Material auf Silizium-Basis oder einem Material auf Zinn-Basis umfasst. DETAILED DESCRIPTION OF THE EXECUTION FORMS

[0021] Embodiments of the present disclosure are described in detail below. The embodiments described below are exemplary and are intended only to illustrate the present disclosure and are not to be construed as limiting the present disclosure. The techniques or conditions not specifically mentioned are those described in the literature in the field or according to the product specification. The reagents or instruments used without mention of the manufacturers are all conventional products that can be obtained commercially.

[0022] In a first aspect, the present revelation provides an electrolyte additive. The electrolyte additive comprises a first additive, a second additive, and a third additive.

[0023] The first additive comprises a compound represented by formula 1: Formula 1, where: R1 is selected from C atom or O atom; R2 is selected from or R3 is selected from methylene, or R4 is selected from or and at least one of R2, R3 and R4 contains a sulfur atom.

[0024] The second additive comprises at least one of a compound represented by formula 2 and one of a compound represented by formula 3, where X comprises a P atom or a B atom.

[0025] The third additive comprises a compound represented by formula 4: RN=C=O Formula 4, where R comprises at least one of alkyl, O=C=N-substituted alkyl, cycloalkyl, O=C=N-substituted cycloalkyl, aryl or O=C=N-substituted aryl.

[0026] In this way, a stable, low-impedance interface film can be formed on an electrode surface, thereby improving the transport rate of active metal ions, reducing the impedance of a battery, reducing battery gas generation, and improving the battery's rate performance.

[0027] The principle by which the present disclosure can achieve the advantageous effects described above is described in detail below.

[0028] The electrolyte additive provided in the present disclosure comprises the first, second, and third additives. Due to the ring structure of ethylene carbonate (EC) and ethylene sulfate (DTD), the first additive exhibits a higher HOMO energy than a carbonate solvent and a lower LUMO energy. Therefore, the first additive can undergo a redox polymerization reaction at both the positive and negative electrodes in front of the solvent to form the interface film on the electrode surface (CEI film on the positive electrode and SEI film on the negative electrode). The interface film formed exhibits good ionic conductivity, which can increase the transport rate of the active metal ions and reduce the internal resistance of the battery.Furthermore, the interface film formed on the electrode surface can also reduce the likelihood of contact between the electrolyte and the electrodes (i.e., the positive and negative electrodes), thereby reducing the risk of catalytic electrolyte degradation and gas generation. Meanwhile, the second additive is introduced to prevent the interface film from continuously thickening during charging and discharging, which would impair the transport of the active metal ions. The first additive and the products obtained from the degradation of the second additive together form an interface film on the electrode surface containing the trimethylsiloxyalkyl compound (Me3-Si-OR).As a result, the interface film formed has more pores and better conductivity, which can increase the transport rate of the active metal ions and thus reduce the battery's internal resistance. Meanwhile, the interface film can also prevent the formation of long-chain substances by reducing the adhesion of organic material from the electrolyte to the electrode surface and mitigate the effect of steric hindrance caused by excessively long carbon chains on the transport of the active metal ions, further reducing the battery's SEI internal resistance. However, the second additive contains a leaving group (acid or alcohol residue) that reacts with trace water or acid in the electrolyte to produce acid, affecting the electrolyte's stability. This is where the third additive comes in.The isocyanate in the third additive can react with water, alcohol, and acid to remove water and prevent acid degradation, and furthermore, to prevent the hydrolysis of lithium salts and battery gas generation. In addition, it can polymerize on the electrode surface to form substances with polyamide groups, which are involved in the formation of the interface film, thereby improving the stability of the interface film and reducing impedance. This improves the battery's cycle life. The combined use of the second and third additives can also prevent an excessively high water removal reaction rate, ensuring stable battery operation.

[0029] According to some embodiments of the present disclosure, R comprises at least one of alkyl having 1 to 10 carbon atoms, O=C=N-substituted alkyl having 1 to 10 carbon atoms, cycloalkyl having 1 to 10 carbon atoms, O=C=N-substituted cycloalkyl having 1 to 10 carbon atoms, aryl having 6 to 10 carbon atoms or O=C=N-substituted aryl having 6 to 10 carbon atoms.

[0030] According to some embodiments of the present disclosure, the first additive comprises at least one of formula 1-1, formula 1-2, or formula 1-3. Therefore, the first additive described above can be subjected to the redox polymerization reaction at the positive and negative electrodes prior to the solvent to form the interface film on the electrode surface (CEI film on the positive electrode and SEI film on the negative electrode). The interface film formed exhibits good ionic conductivity, which can increase the transport rate of the active metal ions and reduce the internal resistance of the battery. Furthermore, the interface film formed on the electrode surface can also increase the probability of contact between the electrolyte and the electrodes (i.e.,the positive electrode and the negative electrode) reduce the risk of catalytic degradation of the electrolyte and gas generation.

[0031] According to some embodiments of the present disclosure, the second additive comprises at least one of formula 3-1, formula 2-1, and formula 2-2. In this way, the products obtained by the degradation of the second additive described above can participate in the formation of the low-impedance interface film on the electrode surface. The products obtained by the degradation and the first additive together form the interface film on the electrode surface. The interface film formed contains the trimethylsilyloxyalkyl compounds (Me3-Si-OR). Consequently, the interface film formed has more pores and better conductivity, which can increase the transport rate of the active metal ions and thus reduce the internal resistance of the battery.Meanwhile, the interface film can also prevent the formation of long-chain substances by reducing the adhesion of organic material from the electrolyte to the electrode surface and mitigate the effect of steric hindrance caused by excessively long carbon chains on the transport of active metal ions, thereby further improving the internal resistance of the battery.

[0032] According to some embodiments of the present disclosure, the third additive comprises at least one of formula 4-1, formula 4-2, formula 4-3, formula 4-4, or formula 4-5. Therefore, the third additive described above can remove water or acid from the electrolyte and reduce the effect of water or acid on the electrode structure. Furthermore, the third additive can also generate long polymer chains on the electrode surface to participate in the formation of the interface film, thereby improving the stability of the interface film and reducing its impedance. Consequently, the internal resistance of the battery is reduced, and the battery's rate performance and cycle life are improved.

[0033] According to some embodiments of the present disclosure, the mass ratio of the first additive, the second additive, and the third additive in the electrolyte additive is 1:(0.01 to 10):(0.01 to 10), for example, 1:0.05:0.05, 1:1:1, 1:1:5, 1:1:10, 1:5:1, 1:10:1, etc., or can lie within a range consisting of any of the numerical values ​​described above. Therefore, by controlling the mass ratio of the first additive, the second additive, and the third additive within the range described above, the first additive, the second additive, and the third additive can exert their synergistic effects more effectively and form the stable, low-impedance interface film on the electrode surface.In this way, the transport rate of the active metal ions is improved, the internal resistance of the battery is reduced, and the gas production of the battery is reduced, thereby improving the rate performance and cycle performance of the battery.

[0034] According to some embodiments of the present disclosure, the electrolyte additive further comprises a fourth additive. The fourth additive comprises at least one of vinylene carbonate, fluoroethylene carbonate (FEC), ethylene sulfate, 1,3-propanesultone, or polystyrene (PS). Thus, the fourth additive acts synergistically with the first, second, and third additives to degrade prior to an early stage of battery formation, and the degradation products can participate in the formation of the interface film, thereby improving the conductivity and stability of the interface film and enhancing the cycle performance of the battery.

[0035] According to some embodiments of the present disclosure, the mass ratio of the first additive, the second additive, the third additive and the fourth additive in the electrolyte additive is 1:(0.01 to 10):(0.01 to 10):(0.005 to 100).

[0036] In a second aspect, the present disclosure provides an electrolyte. The electrolyte comprises the electrolyte additive provided in the first aspect of the present disclosure. Therefore, the electrolyte possesses all the properties and advantages of the aforementioned electrolyte additive, which are not described in detail in this document. In general, the electrolyte exhibits at least the advantages of reducing the internal resistance of the battery and reducing the gas production of the battery.

[0037] According to some embodiments of the present disclosure, the mass fraction of the first additive, based on a total mass of the electrolyte, can be in the range of 0.1% to 5%, for example, 0.1%, 1%, 2%, 3%, 4%, or 5%, etc., or can be in a range consisting of any of the numerical values ​​described above. Therefore, by controlling the content of the first additive within the range described above, the first additive can form a film on the electrode surface in front of the solvent. The interface film formed by the products obtained from the degradation of the first additive exhibits good ionic conductivity, which can increase the transport rate of the active metal ions, thereby reducing the internal resistance of the battery.Furthermore, the interface film formed on the electrode surface can also reduce the probability of contact between the electrolyte and the electrodes (the positive and negative electrodes), thereby reducing the risk of catalytic degradation of the electrolyte and gas generation. According to some specific embodiments of the present disclosure, the mass fraction of the first additive can be in the range of 0.1% to 0.5% based on the total mass of the electrolyte.

[0038] According to some embodiments of the present disclosure, the mass fraction of the second additive, based on the total mass of the electrolyte, can be in the range of 0.1% to 5%, for example, 0.1%, 1%, 2%, 3%, 4%, or 5%, etc., or can be in a range consisting of any of the numerical values ​​described above. Therefore, by controlling the content of the second additive within the range described above, the interface film formed on the electrode surface exhibits more pores and improved conductivity. As a result, the transport rate of the active metal ions is increased, and the internal resistance of the battery is reduced. According to some specific embodiments of the present disclosure, the mass fraction of the second additive can be in the range of 0.1% to 0.5% based on the total mass of the electrolyte.

[0039] According to some embodiments of the present disclosure, the mass fraction of the third additive, based on the total mass of the electrolyte, is in the range of 0.1% to 5%, for example, 0.1%, 1%, 2%, 3%, 4%, or 5%, etc., or can be in a range consisting of any of the numerical values ​​described above. Therefore, by controlling the content of the third additive within the range described above, water or acid can be removed from the electrolyte, and its effect on the electrode structure can be reduced. Furthermore, long polymer chains can be generated on the electrode surface to participate in the formation of the interface film, thereby improving the stability of the interface film, reducing the impedance of the interface film, thus reducing the internal resistance of the battery, and improving the rate power and cycle power of the battery.According to some specific embodiments of the present disclosure, the mass fraction of the third additive can be in the range of 0.1% to 0.5% based on the total mass of the electrolyte.

[0040] According to some embodiments of the present disclosure, the electrolyte further comprises a fourth additive. Based on the total mass of the electrolyte, the mass fraction of the fourth additive is in the range of 0.5% to 5%, for example, 0.5%, 1%, 2%, 3%, 4%, or 5%, etc., or may be in a range consisting of any of the numerical values ​​described above. Thus, the fourth additive acts synergistically with the first, second, and third additives and degrades in advance to participate in the formation of the interface film in the early stages of battery formation. In this way, the conductivity and stability of the interface film are improved, thereby enhancing the cycle performance of the battery.

[0041] According to some embodiments of the present disclosure, the electrolyte further comprises an electrolyte salt. Based on the total mass of the electrolyte, the mass fraction of the electrolyte salt is in the range of 12% to 18%, for example, 12%, 13%, 14%, 15%, 16%, 17%, or 18%, etc., or may be in a range consisting of any of the numerical values ​​described above. For this reason, the electrolyte can exhibit both high ionic conductivity and low cost.

[0042] For example, if the battery is a lithium-ion battery, the electrolyte salt may contain at least one of lithium hexafluorophosphate or lithium bis(fluorosulfonyl)imide.

[0043] For example, if the battery is a sodium-ion battery, the electrolyte salt may contain at least one of sodium hexafluorophosphate or sodium bis(fluorosulfonyl)imide.

[0044] According to some embodiments of the present disclosure, the electrolyte further comprises a solvent. The solvent comprises at least one carbonate compound with 3 to 6 carbon atoms, a carboxylate compound with 3 to 8 carbon atoms, a sulfone compound, or an ether compound. The solvent in the electrolyte serves as an important carrier for the transport of ions and can exhibit high ionic conductivity after dissolution of the electrolyte salt. In this way, the battery's service life, charge and discharge rates, high-temperature performance, low-temperature performance, and energy density can be improved by selecting the solvent described above.

[0045] According to some embodiments of the present disclosure, the carbonate compound with 3 to 6 carbon atoms comprises at least one of ethylene carbonate (EC), propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate (EMC), diethyl carbonate, dipropyl carbonate, methyl propyl carbonate or ethyl propyl carbonate.

[0046] According to some embodiments of the present disclosure, the carboxylate compound with 3 to 8 carbon atoms comprises at least one of γ-butyrolactone, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, ethyl butyrate, propyl acetate or propyl propionate.

[0047] According to some embodiments of the present disclosure, the sulfone compound comprises sulfolane.

[0048] According to some embodiments of the present disclosure, the ether compound comprises at least one of triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.

[0049] In a third aspect, the present disclosure provides a battery. The battery includes the electrolyte provided in the second aspect of the present disclosure. Therefore, the electrolyte exhibits all the properties and advantages of the aforementioned electrolyte, which are not described in detail in this document. In general, the battery exhibits at least the advantages of low internal resistance and low gas generation.

[0050] According to some specific embodiments of the present disclosure, the battery can be a lithium-ion battery or a sodium-ion battery.

[0051] According to some specific embodiments of the present disclosure, if the battery is the lithium-ion battery, a positive active material may be one or more LiFePO4. 1-x' M' x' PO4, LiMn 2-y' M y' O4 or LiNi x Co y Mnz M 1-x-y-z O2 include, where: M' includes one or more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti; M includes one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti; and 0≤x'<1, 0≤y'≤1, 0≤y≤1, 0≤x≤1, 0≤z≤1 and x + y + z≤1.

[0052] According to some specific embodiments of the present disclosure, if the battery is the lithium-ion battery, the positive active material may further comprise one or more sulfide, selenide or halide.

[0053] For example, the positive active material can be one or more of LiCoO2, LiFePO4, LiFe 0,8 Mn 0,2 PO4, LiMn2O4, LiNi 0,5 Co 0,2 Mn 0,3 O2, LiNi 0,6 Co 0,2 Mn 0,2 O2, LiNi 0,8 Co 0,1 Mn 0,1 O2, LiNi 0,5 Co 0,2 Mn 0,2 Al 0,1 O2 or LiNi 0,5 Co 0,2 Al 0,3 O2 included.

[0054] According to some embodiments of the present disclosure, if the battery is the sodium-ion battery, the positive active material comprises Na c P a (W a O b )Z e , where: P comprises a transition metal element; W comprises at least one of phosphorus, sulfur, silicon or tungsten; z comprises an F atom; and 0≤c≤10, 0≤d≤5, 0≤a≤10, 0 <b≤10 und 0≤e≤5.

[0055] For example, the positive active material includes at least one of NaFePO4, Na2FeP2O7, Na4Fe3(PO4)2P2O7, Na3V2(PO4)3 or Na2Fe(SO4)2.

[0056] According to some embodiments of the present disclosure, if the battery is the sodium-ion battery, the positive active material comprises at least one of a transition metal oxide, a transition metal sulfide, a phosphorus-based material, a titanate material or a Prussian blue material.

[0057] A typical battery consists of a positive electrode plate, a negative electrode plate, an electrolyte, and a separator. During the charging and discharging process, active ions are alternately intercalated and deintercalated between the positive and negative electrode plates. The electrolyte between the positive and negative electrode plates conducts ions. The separator is positioned between the positive and negative electrode plates, primarily to prevent short circuits between them while allowing ions to pass through.

[0058] In some embodiments of the present disclosure, a positive-electrode current collector may include a metal foil or a composite positive-electrode current collector. For example, the metal foil may be an aluminum foil. The composite positive-electrode current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. For example, the composite negative-electrode current collector may be formed by depositing a metal material (aluminum, aluminum alloys, nickel, nickel alloys, etc.) onto a polymer material substrate (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and other substrates).

[0059] In some embodiments of the present disclosure, a layer of positive active material may optionally further comprise a conductive agent. For example, the conductive agent may comprise at least one of superconducting carbon, acetylene carbon black, carbon black, Ketjen carbon black, carbon dots, carbon nanotubes, graphite, or carbon nanofibers.

[0060] In some embodiments of the present disclosure, the layer of positive active material may optionally further comprise a binder. For example, the binder may comprise at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, or fluorine-containing acrylate resin.

[0061] In some embodiments of the present disclosure, the positive electrode plate can be produced by the following method: Components for producing the positive electrode plate, such as the positive active material, the conductive agent, and the binder, are dispersed in a solvent (such as N-methylpyrrolidone) to form a slurry of the positive electrode; and the slurry of the positive electrode is applied to the current collector with the positive electrode, and after drying, cold pressing, and other processes, the positive electrode plate can be obtained.

[0062] The negative electrode plate comprises a current collector with a negative electrode and a layer of negative active material arranged on at least one surface of the current collector with the negative electrode. The layer of negative active material comprises a negative active material.

[0063] In some embodiments of the present disclosure, the current collector with negative electrode can be a metal foil or a composite current collector. For example, an aluminum or copper foil can be used as the metal foil. The composite current collector can comprise a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. The composite current collector can be formed by depositing a metal material (aluminum, copper, copper alloy, nickel, nickel alloy, etc.) onto the polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.).

[0064] In some embodiments of the present disclosure, the negative active material for a battery known in the related prior art can be used as the negative active material. For example, the negative active material can comprise at least one of the following materials: soft carbon, hard carbon, silicon-based materials, tin-based materials, etc., wherein the soft carbon comprises graphite. The silicon-based material can comprise at least one of elemental silicon, silicon oxide, silicon-carbon composite, silicon-nitrogen composite, or silicon alloy. The tin-based material can comprise at least one of elemental tin, tin oxide, or tin alloys.

[0065] In some embodiments of the present disclosure, the layer of negative active material may optionally further comprise a binder. The binder may comprise at least one of styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), or carboxymethyl chitosan (CMCS).

[0066] In some embodiments of the present disclosure, the layer of negative active material may optionally further comprise a conductive agent. The conductive agent may comprise at least one of superconducting carbon, acetylene carbon black, carbon black, Ketjen carbon black, carbon dots, carbon nanotubes, graphite, or carbon nanofibers.

[0067] In some embodiments of the present disclosure, the layer of negative active material may optionally further include other additives, such as a thickening agent (e.g. sodium carboxymethylcellulose (CMC-Na)).

[0068] In some embodiments of the present disclosure, the negative electrode plate can be produced by the following method: Components for producing the negative electrode plate, such as the negative active material, the conductive agent, the binder, and any other components, are dispersed in a solvent (such as deionized water) to form a slurry of the negative electrode; and the slurry of the negative electrode is applied to the current collector with the negative electrode, and after drying, cold pressing, and other processes, the negative electrode plate can be obtained.

[0069] The type of separator is not particularly restricted in the present disclosure and any known porous separator with good chemical and mechanical stability can be selected.

[0070] In some embodiments of the present disclosure, the separator material can comprise one or more of polyolefin, aromatic polyamide, polytetrafluoroethylene, and polyethersulfone. Furthermore, the separator comprises one or both of polyethylene and polypropylene. Additionally, the separator can be obtained by stacking a plurality of material layers. For example, the separator comprises a polypropylene layer, a polyethylene layer, and another polypropylene layer stacked on top of each other.

[0071] In some embodiments of the present disclosure, the separator has a thickness in the range of 9 µm to 12 µm, for example 9 µm, 10 µm, 11 µm, 12 µm, etc.

[0072] Embodiments of the present disclosure are described in detail below. The embodiments described below are exemplary and are intended only to illustrate the present disclosure; they are not to be construed as limiting the present disclosure. Techniques or conditions not specifically mentioned are to be understood as corresponding to those described in the literature in the field or as specified in the product specification. Reagents or instruments used without mention of manufacturers are all conventional products that can be obtained commercially. Example 1

[0073] 1. Preparation of an electrolyte: EC and EMC were mixed in a mass ratio of 3:7, and the electrolyte salt, the first additive, the second additive, the third additive, and the fourth additive were added and mixed uniformly to obtain an electrolyte. The types and amounts of the first, second, third, and fourth additives are illustrated in Table 1. The electrolyte salts were LiPF6 and LiFSI. Based on a total mass of solvent, the mass fraction of LiPF6 was 10% and the mass fraction of LiFSI was 2%.

[0074] 2. Production of a positive electrode plate: A positive electrode material LiFePO4, a conductive agent SuperP (conductive carbon black), carbon nanotubes, and an adhesive polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 94.5:2.5:0.5:2.5 and stirred under vacuum until the mixture exhibited a specific viscosity and uniform fluidity; the slurry was uniformly applied to the front and back of the aluminum foil, dried at 85 °C, cold-pressed, cut to size, divided into pieces, subdivided into strips, and dried under vacuum at 85 °C for 10 hours; after welding tabs, a positive electrode plate with an areal density of 33 mg / cm² was produced. 2 manufactured.

[0075] 3. Production of a negative electrode plate: A negative electrode material made of hard carbon, the conductive agent SuperP (conductive carbon black), a thickening agent sodium carboxymethylcellulose (CMC-Na), and an adhesive styrene-butadiene rubber emulsion (SBR) were thoroughly mixed to a uniform slurry in a mass ratio of 95:1.5:2.0:1.5. After application to both sides of the aluminum foil, the slurry was dried at 85 °C and then cold-pressed, cut to size, sliced ​​into pieces, and divided into strips. Finally, the slurry was dried under vacuum conditions at 85 °C for 12 hours. After welding tabs, a negative electrode plate with an areal density of 14.2 mg / cm² was produced. 2 manufactured.

[0076] 4. Separator: A 9 µm thick porous polyethylene polymer film was used as a substrate and a 2 µm adhesive coating was applied to both sides of the substrate.

[0077] 5. Manufacturing the Lithium-Ion Battery: The positive electrode plate, separator, and negative electrode plate were stacked and then processed using a winding process to create a raw cell with a theoretical capacity of 1,000 mAh. The raw cell was then placed in an aluminum foil and baked under vacuum at 75 °C for 10 hours before the electrolyte was injected. After vacuum packaging, resting, training, aging, and capacity classification, the lithium-ion battery was manufactured.

[0078] The lithium-ion batteries in Example 2 to Example 35 and Comparative Example 1 to Comparative Example 10 were manufactured using essentially the same process as Example 1, with the respective differences listed in Table 1.

[0079] The battery from Example 27 was produced using essentially the same process as Example 19, except that the positive active material was Na4Fe3(PO4)2(P2O7) (abbreviated as NFPP) and that the electrolyte salts in the electrolyte were NaPF6 and NaFSI.

[0080] In example 35, the positive active material is Li(NiCoMn)O2. [Table 1] First additive Second additive Third additive Fourth additive type Salary(%) type Salary(%) type Salary(%) type Salary(%) type Salary(%) Comparative example 1 / / / / / / PS 2 FEC 1 Comparative example 2 Formula 1-1 0,5 / / / / PS 2 FEC 1 Comparative example 3 / / Formula 3-1 0,5 / / PS 2 FEC 1 Comparative example 4 / / / / Formula 4-1 0,5 PS 2 FEC 1 Comparative example 5 Formula 1-1 0,5 Formula 3-1 0,5 / / PS 2 FEC 1 Comparative example 6 Formula 1-1 0,5 / / Formula 4-1 0,5 PS 2 FEC 1 Comparative example 7 / / Formula 3-1 0,5 Formula 4-1 0,5 PS 2 FEC 1 Example 1 Formula 1-1 0,1 Formula 3-1 0,1 Formula 4-1 0,1 / / / / Example 2 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 3 Formula 1-1 0,07 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 4 Formula 1-1 0,1 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 5 Formula 1-1 3 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 6 Formula 1-1 5 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 7 Formula 1-1 6 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 8 Formula 1-1 0,5 Formula 3-1 0,07 Formula 4-1 0,5 / / / / Example 9 Formula 1-1 0,5 Formula 3-1 0,1 Formula 4-1 0,5 / / / / Example 10 Formula 1-1 0,5 Formula 3-1 3 Formula 4-1 0,5 / / / / Example 11 Formula 1-1 0,5 Formula 3-1 5 Formula 4-1 0,5 / / / / Example 12 Formula 1-1 0,5 Formula 3-1 6 Formula 4-1 0,5 / / / / Example 13 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,07 / / / / Example 14 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,1 / / / / Example 15 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 3 / / / / Example 16 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 5 / / / / Example 17 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 6 / / / / Example 18 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 PS 0,25 FEC 0,25 Example 19 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 PS 2 FEC 1 Example 20 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 PS 3 FEC 2 Example 21 Formula 1-1 0,5 Formula 2-1 0,5 Formula 4-1 0,5 / / / / Example 22 Formula 1-1 0,5 Formula 3-2 0,5 Formula 4-1 0,5 / / / / Example 23 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-3 0,5 / / / / Example 24 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-4 0,5 / / / / Example 25 Formula 1-2 0,5 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 26 Formula 1-3 0,5 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 27 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 PS 2 FEC 1 Example 28 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 / / FEC 1 Example 29 Formula 1-1 0,5 Formula 2-2 0,5 Formula 4-1 0,5 / / / / Example 30 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-2 0,5 / / / / Example 31 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-5 0,5 / / / / Example 32 Formula 1-1 + Formula 1-2 0,5 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Example 33 Formula 1-1 0,5 Formula 3-1 + Formula 2-1 0,5 Formula 4-1 0,5 / / / / Example 34 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 + Formula 4-3 0,5 / / / / Example 35 Formula 1-1 0,5 Formula 3-1 0,5 Formula 4-1 0,5 / / / / Comparative example 8 Formula 1-1 0,5 / / / / / / / / Comparative example 9 / / Formula 3-1 0,5 / / / / / / Comparative example 10 / / / / Formula 4-1 0,5 / / / / Performance test 1. Capacity retention rate of the cycle at 25 °C

[0081] At 25 °C, a battery underwent 400 cycles for a capacity retention rate test. A sodium-ion battery was left to rest for 4 hours at an ambient temperature of 25 °C and then subjected to 400 charge-discharge cycles at a current of 1.0 C with a voltage window ranging from 1.5 V to 3.6 V. The discharge capacity of the first cycle was designated C1, and the discharge capacity of the 400th cycle was designated C. 400 The capacity retention rate after 400 cycles at 25 °C was defined as η1=C 400 / C1*100 % is designated. 2. Test of the thickness swelling rate after storage at 60 °C for 20 days

[0082] A battery was stored at 60 °C for 20 days before testing its thickness swelling rate. Before storage, the battery thickness was measured using a flat thickness gauge and designated d0. After 20 days of storage, the battery thickness was measured while still hot and designated d1. The swelling rate of the battery after 20 days of high-temperature storage at 60 °C was defined as η2 = (d1 - d0) / d0 * 100%. 3. Testing the capacity retention rate after storage at 60 °C for 20 days

[0083] At an ambient temperature of 25 °C, a battery was charged to 3.6 V at a constant current and voltage of 1.0 C and then discharged to 1.5 V at a constant current of 1.0 C. The discharge capacity was denoted as C0. The battery was then exposed to ambient temperature at 60 °C for 20 days and subsequently discharged to 1.5 V at a constant current of 1.0 C. The capacity retention rate during high-temperature storage was denoted as η3 = (C1 / C0)*100%. 4. Testing the DC resistance (DCR) of the battery

[0084] DCR test prior to storage: At an ambient temperature of 25 °C, a battery was charged to 3.6 V at a constant current of 1.0 C and then held at a constant voltage of 3.6 V until a cutoff current of 0.05 C was reached. The battery was then left to rest for 30 min, followed by discharge at 1.0 C for 30 min (set to 50% SOC), with a final voltage designated V1. After resting for 1 h, the battery was discharged at 2.0 C for 10 s, with a final voltage designated V2. The DCR prior to storage was designated DCR1 = (V1-V2) / (2.0 C-1.0 C). DCR test after storage at 60 °C for 20 days: At an ambient temperature of 25 °C, a stored battery was charged to 3.6 V at a constant current of 1.0 C and then held at a constant voltage of 3.6 V until the cutoff current reached 0.05 C.The battery was then left to rest for 30 minutes, followed by discharge at 1.0 C for 30 minutes (set to 50% SOC), with a final voltage designated V3. After resting for 1 hour, the battery was discharged at 2.0 C for 10 seconds, and a final voltage designated V4. The DCR after storage was defined as DCR2 = (V3 - V4) / (2.0 C - 1.0 C). The DCR growth rate was defined as η4 = (DCR2 - DCR1) / DCR1 * 100%.

[0085] Test results for the batteries from examples 1 to 35 and comparison examples 1 to 10 are shown in Table 2. [Table 2] Capacity retention rate after 400 cycles η1 Storage at 60 °C for 20 days Thickness swelling rateη2 Capacity retention rate η3 DCR growth rate η4 Comparative example 1 85,70 % 9,00 % 78,80 % 12,50 % Comparative example 2 86,85 % 8,78 % 79,76 % 11,54 % Comparative example 3 87,24 % 8,49 % 80,15 % 10,35 % Comparative example 4 87,66 % 7,95 % 81,71 % 12,64 % Comparative example 5 87,82 % 7,89 % 80,64 % 10,98 % Comparative example 6 86,21 % 7,77 % 81,92 % 10,05 % Comparative example 7 87,95 % 7,98 % 80,44 % 10,17 % Example 1 90,45 % 6,82 % 88,33 % 8,44 % Example 2 92,58 % 6,34 % 90,15 % 7,74 % Example 3 89,25 % 6,95 % 85,56 % 9,62 % Example 4 92,18 % 6,66 % 88,38 % 7,85 % Example 5 91,36 % 6,82 % 87,55 % 8,43 % Example 6 89,09 % 6,93 % 86,65 % 8,84 % Example 7 88,37 % 7,00 % 86,40 % 9,80 % Example 8 88,98 % 6,80 % 85,20 % 8,70 % Example 9 91,45 % 6,58 % 88,10 % 7,79 % Example 10 90,77 % 6,88 % 87,71 % 7,88 % Example 11 90,69 % 6,96 % 87,36 % 7,93 % Example 12 89,68 % 7,14 % 85,73 % 8,64 % Example 13 89,64 % 6,75 % 87,45 % 9,27 % Example 14 91,52 % 6,51 % 90,01 % 7,22 % Example 15 90,17 % 6,85 % 90,05 % 7,90 % Example 16 90,76 % 6,94 % 89,10 % 9,22 % Example 17 88,43 % 6,95 % 87,38 % 9,44 % Example 18 93,21 % 6,20 % 92,38 % 6,89 % Example 19 94,54 % 5,92 % 92,88 % 6,61 % Example 20 93,92 % 6,21 % 92,39 % 6,92 % Example 21 91,17 % 6,69 % 89,42 % 7,34 % Example 22 91,29 % 6,52 % 89,71 % 7,28 % Example 23 91,32 % 6,66 % 89,30 % 7,29 % Example 24 91,29 % 6,79 % 89,25 % 7,45 % Example 25 91,86 % 6,62 % 90,02 % 7,88 % Example 26 92,12 % 6,60 % 90,10 % 7,79 % Example 27 93,99 % 6,02 % 92,58 % 6,68 % Example 28 94,51 % 5,99 % 92,78 % 6,69 % Example 29 94,50 % 6,00 % 92,77 % 6,71 % Example 30 91,30 % 6,69 % 89,28 % 7,33 % Example 31 91,31 % 6,67 % 89,29 % 7,30 % Example 32 92,55 % 6,36 % 90,13 % 7,76 % Example 33 92,56 % 6,35 % 90,15 % 7,75 % Example 34 92,54 % 6,38 % 90,11 % 7,78 % Example 35 92,33 % 6,55 % 90,08 % 7,85 % Comparative example 8 89,28 % 7,58 % 85,00 % 9,90 % Comparative example 9 89,25 % 7,60 % 84,98 % 9,95 % Comparative example 10 89,12 % 7,68 % 84,95 % 9,98 %

[0086] Conclusion: As can be seen from the comparison of Example 1 to Example 35 with Comparative Example 1 to Comparative Example 10, the simultaneous addition of the first, second, and third additives to the electrolyte can improve the capacity retention rate of the battery cycle of the present disclosure and can reduce the thickness swelling rate and the internal resistance of the battery. These results indicate that the electrolyte containing the first, second, and third additives can improve the rate performance and the cycle performance of the battery.

[0087] As can be seen from Examples 1 to 7, adjusting the concentration of the first additive can improve the ionic conductivity of the interface film formed, reduce the probability of contact between the electrode and the electrolyte, and reduce the risk of catalytic degradation of the electrolyte and gas generation. In this way, the battery's capacity retention rate can be improved, the battery's thickness swelling rate can be reduced, and the battery's internal resistance can be lowered.

[0088] As can be seen from Example 1, Example 2 and Example 8 to Example 12, by adjusting the content of the second additive, the present disclosure can form an interface film with more pores and better conductivity at the electrode surface, thereby reducing the internal resistance of the battery and improving the capacity retention rate of the battery cycle.

[0089] As can be seen from Example 1, Example 2, and Example 13 through Example 17, adjusting the concentration of the third additive allows the present disclosure to improve the stability of the interface film while reducing its impedance. This improves the rate performance and cycle performance of the battery.

[0090] As can be seen from Example 18 to Example 20, according to the present disclosure, the first additive, the second additive, the third additive and the fourth additive are added to the electrolyte simultaneously, which can further improve the rate performance and cycle performance of the battery.

[0091] As can be seen from Example 32 to Example 34, the electrolyte can contain two types of the first additive, two types of the second additive, and two types of the third additive, which can also improve the rate performance and cycle performance of the battery.

[0092] Although embodiments have been shown and described above, it is understood that the above embodiments are merely exemplary and cannot be interpreted as limiting the present disclosure. A person skilled in the art may make various changes, modifications, substitutions, and variations to the embodiments without deviating from the scope of the present disclosure. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] CN 202410720189.5

[0001]

Claims

[1] Electrolyte additive comprising a first additive, a second additive and a third additive, wherein the first additive comprises a compound represented by formula 1: where: R1 is selected from a C atom or an O atom; R2 is selected from or R3 is selected from methylene, or R4 is selected from or and at least one of R2, R3 and R4 contains a sulfur atom; wherein the second additive comprises at least one of a compound represented by formula 2 and a compound represented by formula 3: Formula 2, Formula 3, where X comprises a phosphorus atom or a phosphorus atom; and where the third additive comprises a compound represented by formula 4: RN=C=O Formula 4, where R comprises at least one of alkyl, O=C=N-substituted alkyl, cycloalkyl, O=C=N-substituted cycloalkyl, aryl or O=C=N-substituted aryl. [2] Electrolyte additive according to claim 1, wherein R comprises at least one of alkyl having 1 to 10 carbon atoms, O=C=N-substituted alkyl having 1 to 10 carbon atoms, cycloalkyl having 1 to 10 carbon atoms, O=C=N-substituted cycloalkyl having 1 to 10 carbon atoms, aryl having 6 to 10 carbon atoms or O=C=N-substituted aryl having 6 to 10 carbon atoms. [3] Electrolyte additive according to claim 1 or 2, wherein the mass ratio of the first additive, the second additive and the third additive in the electrolyte additive is 1:(0.01 to 10):(0.01 to 10). [4] Electrolyte additive according to claim 3, wherein the first additive comprises at least one of Formula 1-1, Formula 1-2 or Formula 1-3. [5] Electrolyte additive according to claim 3, wherein the second additive comprises at least one of formula 3-1, formula 2-1 or formula 2-2. [6] Electrolyte additive according to claim 3, wherein the third additive comprises at least one of Formula 4-1, Formula 4-2, Formula 4-3, Formula 4-4 or Formula 4-5. [7] Electrolyte additive according to claim 3, further comprising a fourth additive, wherein the fourth additive comprises at least one of vinylene carbonate, fluoroethylene carbonate, ethylene sulfate, 1,3-propanesultone or polystyrene. [8] Electrolyte additive according to claim 7, wherein the mass ratio of the first additive, the second additive, the third additive and the fourth additive in the electrolyte additive is 1:(0.01 to 10):(0.01 to 10):(0.005 to 100). [9] Electrolyte comprising the electrolyte additive according to any one of claims 1 to 8. [10] Electrolyte according to claim 9, wherein based on a total mass of the electrolyte: a mass fraction of the first additive is in the range of 0.1% to 5%; and / or The mass fraction of the second additive is in the range of 0.1% to 5%. [11] Electrolyte according to claim 9, wherein, based on a total mass of the electrolyte, a mass fraction of the third additive is in the range of 0.1% to 5%. [12] Electrolyte according to claim 9, further comprising a fourth additive, wherein, based on a total mass of the electrolyte, a mass fraction of the fourth additive is in the range of 0.5% to 5%. [13] Electrolyte according to claim 9, further comprising an electrolyte salt, wherein, based on a total mass of the electrolyte, a mass fraction of the electrolyte salt is in the range of 12% to 18%. [14] Battery comprising the electrolyte additive according to any one of claims 1 to 8 or the electrolyte according to any one of claims 9 to 13. [15] Battery according to claim 14, comprising a positive electrode plate and a negative electrode plate, wherein: The battery is a lithium-ion battery, wherein a positive active material of the positive electrode plate is one or more LiFePO4 ions. 1-x' M' x' PO4, LiMn 2-y' My'O4 or LiNi x Co y Mn z M 1-x-y-z O2 comprises, where: M' comprises one or more of Mn, Mg, Co, Ni, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti; M comprises one or more of Fe, Co, Ni, Mn, Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V or Ti; and 0≤x' <1, 0≤y'≤1, 0≤y≤1, 0≤x≤1, 0≤z≤1 and x + y + z≤1; and / or The battery is a sodium-ion battery, with a positive active material of the positive electrode plate Na c P a (W a O b )Z e comprising, where: P comprises a transition metal element; W comprises at least one of phosphorus, sulfur, silicon or tungsten; z comprises an F atom; and 0≤c≤10, 0≤d≤5, 0≤a≤10, 0 <b≤10 und 0≤e≤5; odera negative active material of the negative electrode plate comprises at least one of soft carbon, hard carbon, a silicon-based material or a tin-based material.< / b≤10>