WO2024120067A1

WO2024120067A1 - High-initial-efficiency quick-charging sodium-ion battery and application

Info

Publication number: WO2024120067A1
Application number: PCT/CN2023/128254
Authority: WO
Inventors: 刘中波; 杨泰源; 刘杨; 敖小虎; 郑仲天
Original assignee: 深圳新宙邦科技股份有限公司
Priority date: 2022-12-07
Filing date: 2023-10-31
Publication date: 2024-06-13
Also published as: CN115911558A; CN115911558B

Abstract

A high-initial-efficiency quick-charging sodium-ion battery and an application. The high-initial-efficiency quick-charging sodium-ion battery comprises an electrolytic solution, a negative electrode, and a positive electrode; the electrolytic solution comprises a solvent, an electrolyte salt, a first additive, and a second additive; the first additive is sodium trifluoromethanesulfonate, and the second additive is a chalcogenide compound; the content of the first additive in the electrolytic solution is a wt%, and the content of the second additive in the electrolytic solution is b wt%; the negative electrode comprises a negative electrode material, and the compacted density of the negative electrode material is c g/cm3, c having the following relation with a and b: 0.2≤(a+b)/4c≤2.5.

Description

A high initial efficiency fast-charging sodium ion battery and its application

Technical Field

The present application relates to the field of energy storage technology, and in particular to a high initial efficiency fast-charging sodium ion battery and its application.

Background technique

Sodium ion batteries have similar principles and structures to lithium ion batteries. Compared with lithium batteries, sodium ion batteries have wide resources, low costs and small fluctuations, and have wide temperature range and high safety performance, which gives them alternative potential. With the continuous advancement of sodium ion battery technology, sodium ion batteries will occupy an important position in the energy system, especially in the field of energy storage, and have broad growth space. Therefore, the development of high-performance, low-cost sodium ion batteries is the decisive factor in determining whether they can be industrialized. At present, sodium trifluoromethanesulfonate (CF ₃ NaO ₃ S) is usually used as the main salt of the electrolyte, but the inventors have found in experiments that sodium trifluoromethanesulfonate as the main salt affects the formation quality of the SEI film and increases the difficulty of desolvation of sodium ions due to its excessive content, which will deteriorate the battery performance.

Summary of the invention

In view of this, one object of the present application is to provide a high initial efficiency fast-charging sodium ion battery, using sodium trifluoromethanesulfonate as the first additive to the electrolyte, and a sulfur compound as the second additive to the electrolyte, while controlling the content of the first additive, the content of the second additive and the compaction density of the negative electrode material and limiting the relationship between them, so that the sodium ion battery can have higher initial charge and discharge efficiency, better rate performance and cycle performance.

Another object of the present application is to provide an application of a high initial efficiency fast-charging sodium ion battery.

To achieve the above-mentioned object, an embodiment of the first aspect of the present application provides a high initial efficiency fast-charging sodium ion battery, comprising an electrolyte, a negative electrode and a positive electrode;

The electrolyte comprises a solvent, an electrolyte salt, a first additive and a second additive, wherein the first additive is sodium trifluoromethanesulfonate, the second additive is a sulfur compound, the content of the first additive in the electrolyte is a wt%, and the content of the second additive in the electrolyte is b wt%,

The negative electrode includes a negative electrode material, the compaction density of the negative electrode material is c g/cm ³ , and c has the following relationship with a and b:
0.2≤(a+b)/4c≤2.5;

Among them: a is 0.1-4, b is 1-4, and c is 0.8-1.2.

In some embodiments of the present application, the c, a and b have the following relationship: 0.5≤(a+b)/4c≤1.

In some embodiments of the present application, a is 0.5-2.

In some embodiments of the present application, b is 2-3.

In some embodiments of the present application, c is 0.9-1.

In some embodiments of the present application, the sulfur-based compound is one or more of compounds 1-9:

In some embodiments of the present application, the negative electrode material includes a negative electrode active material, and the negative electrode active material is hard carbon and/or soft carbon.

In some embodiments of the present application, the electrolyte further includes an auxiliary additive, the content of the auxiliary additive in the electrolyte is 1-5wt%, and the auxiliary additive is a fluorinated carbonate.

In some embodiments of the present application, the solvent is a non-aqueous organic solvent; the non-aqueous organic solvent includes one or more of an ether solvent, a nitrile solvent, a carbonate solvent, and a carboxylate solvent.

In some embodiments of the present application, the electrolyte salt includes one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium dioxalatoborate, sodium difluorooxalatoborate, sodium hexafluoroarsenate, sodium trifluoroacetate, sodium tetraphenylborate, sodium bis(fluorosulfonyl)imide, and sodium bis(trifluoromethylsulfonyl)imide.

In some embodiments of the present application, the positive electrode includes a positive electrode active material, and the positive electrode active material includes one or more of a sodium-containing layered oxide, a sodium-containing polyanion compound, and a sodium-containing Prussian blue compound.

In some embodiments of the present application, the sodium-containing layered oxide is Na _i MO ₂ , wherein 0＜i≤1, and M is selected from one or more of V, Cr, Mn, Fe, Co, Ni, and Cu.

In some embodiments of the present application, the sodium-containing polyanion compound is Na ₃ V ₂ (PO ₄ ) ₂ F ₃ .

In some embodiments of the present application, the sodium-containing Prussian blue compound is Na _r Mn[Fe(CN) ₆ ] _1-m ·□ _m ·nH ₂ O, wherein 0≤r≤2, 0≤m≤1, 0≤n≤20, and □ is a [Fe(CN) ₆ ] vacancy.

To achieve the above-mentioned purpose, the embodiments of the second aspect of the present application relate to the application of the high initial efficiency fast-charging sodium ion battery of the embodiments of the present application in the field of energy storage and the field of new energy electric vehicles.

The high initial efficiency fast-charging sodium ion battery of the embodiment of the present application can bring the following beneficial effects: sodium trifluoromethanesulfonate is used as the first additive to the electrolyte, a sulfur-based compound is used as the second additive to the electrolyte, and the content of the first additive, the content of the second additive and the compaction density of the negative electrode material are controlled at the same time and the relationship between them is defined, which can make the sodium ion battery have higher initial charge and discharge efficiency, better rate performance and cycle performance.

Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and/or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

FIG. 1 is a cycle capacity retention curve of Example 1 and Comparative Example 1 at 25° C.

FIG. 2 is a cycle capacity retention curve of Example 1 and Comparative Example 1 at 45° C.

Detailed ways

The embodiments of the present application are described in detail below. The embodiments are exemplary and intended to be used to explain the present application, but should not be construed as limiting the present application.

Throughout the application, the disclosure of numerical ranges includes disclosure of all values within the entire range and further subdivided ranges, including endpoints and subranges given within those ranges.

In the application, the raw materials, equipment, etc. involved, unless otherwise specified, are all raw materials and equipment that can be made through commercial channels or known methods; the methods involved, unless otherwise specified, are all conventional methods.

The inventive concept of this application is: Sodium trifluoromethanesulfonate participates in film formation at the negative electrode as an electrolyte additive, which can isolate the electrolyte from the negative electrode, thereby reducing the decomposition of the electrolyte. After participating in the film formation, it can also improve the conduction of the SEI film to ions, increase the diffusion rate of sodium ions, and reduce the impedance of the SEI film, thereby improving the first effect and cycle performance of the battery. When used in combination with sulfur compounds that are also electrolyte additives, it can participate in the negative electrode SEI film formation earlier than other components of the electrolyte, forming a stable positive and negative electrode interface, reducing the decomposition of the electrolyte, and thus improving the cycle performance of the battery. At the same time, the content of sodium trifluoromethanesulfonate in the electrolyte, the content of sulfur compounds in the electrolyte, and the compaction density of the negative electrode material are controlled; the compaction density of the negative electrode material is within a certain range, and it has been found through multiple tests that it can make the particles fully contact without blocking the ion movement channel, which is beneficial to sodium trifluoromethanesulfonate participating in the film formation of the SEI film on the surface of the negative electrode material, ensuring that the electrons have good conductivity and rapid ion movement during large current discharge, reducing discharge polarization, improving capacity density, and improving the battery rate and cycle performance. When the content of sodium trifluoromethanesulfonate in the electrolyte, the content of the sulfur compound in the electrolyte and the compaction density of the negative electrode material meet a certain relationship (see formula ① at the end of the text), the purpose of simultaneously improving the initial charge and discharge efficiency, rate performance and cycle performance of the sodium ion battery can be achieved.

It should be noted that in the present application, sodium trifluoromethanesulfonate and sulfur compounds are positioned as additives for the electrolyte. Compared with the solvent and the electrolyte salt, their respective contents will be less, at least the content of sodium trifluoromethanesulfonate is less than when it is used as an electrolyte salt under normal circumstances.

The high first-effect fast-charging sodium-ion battery of the embodiment of the present application comprises an electrolyte, a negative electrode and a positive electrode; the electrolyte comprises a solvent, an electrolyte salt, a first additive and a second additive, the first additive is sodium trifluoromethanesulfonate, the second additive is a sulfur compound, the content of the first additive in the electrolyte is a wt%, the content of the second additive in the electrolyte is b wt%, and the negative electrode comprises The compacted density of the negative electrode material is c g/cm ³ , and c, a and b have the following relationship:
0.2≤(a+b)/4c≤2.5 Formula ①;

Among them: a is 0.1-4, b is 1-4, and c is 0.8-1.2.

The high first-efficiency fast-charging sodium-ion battery of the embodiment of the present application uses sodium trifluoromethanesulfonate as the first additive to the electrolyte and a sulfur-based compound as the second additive to the electrolyte. The content of the first additive, the content of the second additive and the compaction density of the negative electrode material are controlled and the relationship between them is defined (see formula ①), which can make the sodium-ion battery have higher first-time charge and discharge efficiency, better rate performance and cycle performance.

In the present application, when the value of (a+b)/4c is greater than 2.5, the viscosity of the electrolyte increases, the electrolyte is excessively consumed to participate in film formation, and the first efficiency is low; when it is less than 0.2, sodium trifluoromethanesulfonate cannot effectively participate in film formation, the electrolyte conductivity is too low, and the cycle performance is poor. In some embodiments of the present application, among the compaction density c of the negative electrode material, the content a wt% of the first additive in the electrolyte, and the content b wt% of the second additive in the electrolyte, the relationship between c and a and b includes but is not limited to the following relationship: 0.5≤(a+b)/4c≤1. As a non-limiting example, the value of (a+b)/4c includes but is not limited to 0.5, 0.6, 0.7, 0.8, 0.9 or 1.

In the present application, the content of the first additive in the electrolyte is greater than 4wt% (that is, a is greater than 4), the first additive excessively participates in film formation, affects the conduction of ions by the SEI film, and reduces the diffusion rate of sodium ions; the content of the first additive in the electrolyte is less than 0.1wt% (that is, a is less than 0.1), the first additive cannot effectively participate in film formation, the electrolyte conductivity is low, and the cycle performance is deteriorated. In some embodiments of the present application, the value of a is between 0.5-2, the value of b is between 2-3, and the value of c is between 0.9-1. As a non-limiting example, the value of a includes but is not limited to 0.5, 0.8, 1.1, 1.4, 1.7 and 2, the value of b includes but is not limited to 2, 2.2, 2.4, 2.6, 2.8 or 3, and the value of c includes but is not limited to 0.9, 0.92, 0.94, 0.96, 0.98 or 1.

In the present application, the content of the second additive in the electrolyte is greater than 4wt% (that is, b is greater than 4), which will increase the internal resistance and reduce the rate and low temperature performance of the sodium ion battery; the content of the second additive in the electrolyte is less than 1wt% (that is, b is less than 1), the second additive cannot effectively participate in film formation, the electrolyte conductivity is low, and the cycle performance is deteriorated. In some embodiments of the present application, the value of b is between 2-3. As a non-limiting example, the value of b includes but is not limited to 2, 2.2, 2.4, 2.6, 2.8 or 3, etc.

In the present application, the compaction density of the negative electrode material is greater than 1.2g/cm ³ (that is, c is greater than 1.2), the distance between particles is reduced, the ion movement channel is reduced or blocked, which is not conducive to the rapid movement of a large number of ions, deteriorates the battery rate performance, and reduces the discharge capacity; the compaction density of the negative electrode material is less than 0.8g/cm ³ (that is, c is less than 0.8), the distance between particles is too large, the contact probability and contact area between particles are reduced, the conductivity is reduced, the large current discharge is affected, the discharge polarization is increased, and the battery rate and cycle performance are deteriorated. In some embodiments of the present application, the value of c is between 0.9-1. As a non-limiting example, the value of c includes but is not limited to 0.9, 0.92, 0.94, 0.96, 0.98 or 1, etc.

As a non-limiting example, sulfur compounds include but are not limited to compound 2 (DTD) and compound 3 (RPS). When compound 2 (DTD) and compound 3 (RPS) are used as the second additive, the mass ratio of compound 2 (DTD) and compound 3 (RPS) is (0.8-1.2): (0.8-1.2). When the mass ratio of compound 2 (DTD) and compound 3 (RPS) is within the above range, it can participate in the negative electrode SEI film formation earlier than other components of the electrolyte, form a stable positive and negative electrode interface, reduce electrolyte decomposition, and thus improve the cycle performance of the battery; if it exceeds the above range, it will increase the internal resistance and reduce the battery's rate and low temperature performance.

In some embodiments of the present application, in order to improve the cycle performance of the battery, the electrolyte further includes auxiliary additives, and the auxiliary additives include but are not limited to fluorocarbonates. In some embodiments of the present application, fluorocarbonates include but are not limited to one or both of fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC). In some embodiments of the present application, the content of the auxiliary additive in the electrolyte is 1-5wt%. As a non-limiting example, the content of the auxiliary additive in the electrolyte includes but is not limited to 1wt%, 2wt%, 3wt%, 4wt% or 5wt%, etc. The content of the auxiliary additive in the electrolyte is within the above range, and a soft and thin SEI film can be formed, which can better withstand the material volume changes caused by sodium in the process of extraction and embedding, thereby improving the cycle life of the battery.

In some embodiments, the solvent is a non-aqueous organic solvent, and the non-aqueous organic solvent includes one or more of an ether solvent, a nitrile solvent, a carbonate solvent, and a carboxylate solvent.

In some embodiments, the ether solvent includes a cyclic ether or a chain ether, preferably a chain ether with 3-10 carbon atoms and a cyclic ether with 3-6 carbon atoms. The cyclic ether may be, but is not limited to, one or more of 1,3-dioxolane (DOL), 1,4-dioxolane (DX), crown ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH3-THF), and 2-trifluoromethyltetrahydrofuran (2-CF3-THF); the chain ether may be, but is not limited to, dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether. Since the chain ether has a high solvation ability with sodium ions and can improve ion dissociation, dimethoxymethane, diethoxymethane, and ethoxymethoxymethane, which have low viscosity and can impart high ionic conductivity, are particularly preferred. The ether compound can be used alone or in any combination and ratio. There is no special restriction on the amount of ether compound added, as long as it does not significantly damage the effect of the high initial efficiency fast charging sodium ion battery of the present application. The range is arbitrary, and the volume ratio is usually 1% or more, preferably 2% or more, and more preferably 3% or more in the non-aqueous solvent volume ratio of 100%. In addition, the volume ratio is usually 30% or less, preferably 25% or less, and more preferably 20% or less. When two or more ether compounds are used in combination, the total amount of the ether compounds can satisfy the above range. When the amount of ether compounds added is within the above preferred range, it is easy to ensure the improvement effect of ion conductivity brought about by the increase in sodium ion dissociation degree and the decrease in viscosity of the chain ether. In addition, when the negative electrode active material is a carbon-based material, the phenomenon of co-embedding of chain ethers and sodium ions can be suppressed, so that the input-output characteristics and charge-discharge rate characteristics can reach an appropriate range.

In some embodiments, the nitrile solvent may specifically be, but is not limited to, one or more of acetonitrile, glutaronitrile, and malononitrile.

In some embodiments, the carbonate solvent includes a cyclic carbonate or a chain carbonate, and the cyclic carbonate may be, but is not limited to, one or more of ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (GBL), and butylene carbonate (BC); the chain carbonate may be, but is not limited to, one or more of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and dipropyl carbonate (DPC). There is no special restriction on the content of the cyclic carbonate, and it is arbitrary within the range that does not significantly damage the effect of the sodium ion battery of the present application, but when one is used alone, the lower limit of its content is usually 3% or more by volume, preferably 5% or more by volume, relative to the total amount of solvent in the non-aqueous electrolyte. By setting this range, the conductivity can be reduced due to the reduction in the dielectric constant of the non-aqueous electrolyte, and it is easy to make the large current discharge characteristics, stability relative to the negative electrode, and cycle characteristics of the non-aqueous electrolyte battery reach a good range. In addition, the upper limit is usually less than 90% by volume, preferably less than 85% by volume, and more preferably less than 80% by volume. By setting this range, the oxidation/reduction tolerance of the nonaqueous electrolyte can be improved, thereby helping to improve the stability during high temperature storage. The content of the linear carbonate is not particularly limited, and relative to the total amount of solvent of the nonaqueous electrolyte, it is usually more than 15% by volume, preferably more than 20% by volume, and more preferably more than 25% by volume. In addition, usually the volume ratio is less than 90%, preferably less than 85% by volume, and more preferably less than 80% by volume. By making the content of the linear carbonate in the above-mentioned range, it is easy to make the viscosity of the nonaqueous electrolyte reach an appropriate range, suppress the reduction of ionic conductivity, and then help to make the output characteristics of the nonaqueous electrolyte battery reach a good range. When two or more linear carbonates are used in combination, the total amount of the linear carbonate is made to meet the above-mentioned range.

In certain embodiments, it is also possible to preferably use chain carbonates with fluorine atoms (hereinafter referred to as "fluorinated chain carbonates"). The number of fluorine atoms possessed by the fluorinated chain carbonate is not particularly limited as long as it is more than 1, but is generally less than 6, preferably less than 4. When the fluorinated chain carbonate has a plurality of fluorine atoms, these fluorine atoms can be bonded to the same carbon or to different carbons. As the fluorinated chain carbonate, fluorinated dimethyl carbonate derivatives, fluorinated ethyl methyl carbonate derivatives, fluorinated diethyl carbonate derivatives, etc. can be listed.

Carboxylate solvents include cyclic carboxylate and/or chain carbonate. Examples of cyclic carboxylate include one or more of γ-butyrolactone, γ-valerolactone, and δ-valerolactone. Examples of chain carbonate include one or more of methyl acetate (MA), ethyl acetate (EA), propyl acetate (EP), butyl acetate, propyl propionate (PP), and butyl propionate.

In some embodiments, the sulfone solvent includes a cyclic sulfone and a chain sulfone. Preferably, in the case of a cyclic sulfone, the carbon number is usually 3-6, preferably 3-5, and in the case of a chain sulfone, the carbon number is usually 2-6, preferably 2-6. 2-5. There is no particular restriction on the amount of sulfone solvent added, and it is arbitrary within the range that does not significantly damage the effect of the sodium ion battery of the present application. Relative to the total amount of solvent in the non-aqueous electrolyte, the volume ratio is usually 0.3% or more, preferably 0.5% or more, and more preferably 1% or more. In addition, the volume ratio is usually 40% or less, preferably 35% or less, and more preferably 30% or less. When two or more sulfone solvents are used in combination, the total amount of sulfone solvents can be made to meet the above range. When the amount of sulfone solvent added is within the above range, a non-aqueous electrolyte with excellent high-temperature storage stability tends to be obtained.

In a preferred embodiment, the non-aqueous organic solvent is a mixture of cyclic carbonate and linear carbonate.

In some embodiments of the present application, the electrolyte salt in the electrolyte includes one or more of sodium perchlorate (NaClO ₄ ), sodium tetrafluoroborate (NaBF ₄ ), sodium hexafluorophosphate (NaPF ₆ ), sodium dioxalatoborate (NaBOB), sodium difluorooxalatoborate (NaODFB), NaAsF ₆ (sodium hexafluoroarsenate), sodium trifluoroacetate (CF ₃ COONa), sodium tetraphenylborate (NaB(C ₆ H ₅ ) ₄ ), sodium bis(fluorosulfonyl)imide (Na[(FSO ₂ ) ₂ N]), and sodium bis(trifluoromethylsulfonyl)imide (Na[(CF ₃ SO ₂ ) ₂ N]). In the above solvent, sodium ions formed by the dissociation of the electrolyte salt are deintercalated and intercalated between the positive electrode and the negative electrode to complete the charge and discharge cycle. The concentration of the electrolyte salt directly affects the transfer speed of the sodium ions, and the transfer speed of the sodium ions affects the potential change of the negative electrode. During the rapid charging process of sodium ion batteries, it is necessary to increase the movement speed of sodium ions as much as possible to prevent the negative electrode potential from dropping too fast, resulting in the formation of sodium dendrites, which brings safety hazards to sodium ion batteries, and at the same time prevent the cycle capacity of sodium ion batteries from decaying too quickly. When the content of electrolyte salt is too low, the embedding and extraction efficiency of sodium ions between the positive and negative electrodes will be reduced, and the demand for fast charging of the battery cannot be met; when the content of electrolyte salt is too high, the viscosity of the non-aqueous electrolyte will increase, which is also not conducive to the improvement of the embedding and extraction efficiency of alkali metal ions, and increases the internal resistance of the battery. As a non-limiting example, the content of electrolyte salt in the electrolyte may include, but is not limited to, 8-15wt%.

In some embodiments of the present application, the negative electrode includes a negative electrode material and a negative electrode current collector, and the negative electrode material is disposed on at least one surface of the negative electrode current collector. The negative electrode current collector may include, but is not limited to, one or more of aluminum foil, copper foil, etc. The negative electrode material includes a negative electrode active material, and may also include one or more of a negative electrode binder, a negative electrode conductor, and a negative electrode solvent. Among them: the negative electrode active material may include, but is not limited to, one or both of hard carbon and soft carbon. Using one or both of hard carbon and soft carbon can improve the cycle performance and increase the cycle life. The negative electrode binder may include, but is not limited to, polyvinylidene fluoride (PVDF), copolymers of vinylidene fluoride, polytetrafluoroethylene, copolymers of vinylidene fluoride-hexafluoropropylene, copolymers of tetrafluoroethylene-hexafluoropropylene, copolymers of tetrafluoroethylene-perfluoroalkyl vinyl ether, copolymers of ethylene-tetrafluoroethylene, copolymers of vinylidene fluoride-tetrafluoroethylene, copolymers of vinylidene fluoride-trifluoroethylene, copolymers of vinylidene fluoride-trichloroethylene, copolymers of vinylidene fluoride-fluoroethylene, copolymers of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene, thermoplastic polyimide, thermoplastic resins such as polyethylene and polypropylene, acrylic resins, styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC). The negative electrode conductive agent may include, but is not limited to, one or more of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide. The negative electrode solvent may include, but is not limited to, one or more of pure water and N-methyl-2-pyrrolidone (NMP). The preparation method of the negative electrode is: after mixing the components of the negative electrode material, coating them on the negative electrode current collector, removing the negative electrode solvent, and obtaining the negative electrode. The thickness of the negative electrode includes but is not limited to between 120-150 μm.

In some embodiments of the present application, the positive electrode includes a positive electrode material and a positive electrode current collector, wherein the positive electrode material is disposed on the positive electrode current collector. on at least one surface. The compacted density of the positive electrode material may include, but is not limited to, 3.5 g/cm ³ . The positive electrode current collector may include, but is not limited to, one or more of aluminum foil, carbon-coated aluminum foil, and the like. The positive electrode material may include a positive electrode active material, and in some cases may also include one or more of a positive electrode binder, a positive electrode conductor, and a positive electrode solvent. In some embodiments, the positive electrode active material may include, but is not limited to, one or more of a sodium-containing layered oxide, a sodium-containing polyanion compound, and a sodium-containing Prussian blue compound. Wherein, the sodium-containing layered oxide is Na _i MO ₂ , wherein 0＜i≤1, M is selected from one or more of V, Cr, Mn, Fe, Co, Ni, and Cu; the sodium-containing polyanion compound is Na ₃ V ₂ (PO ₄ ) ₂ F ₃ ; the sodium-containing Prussian blue compound is Na _r Mn[Fe(CN) ₆ ] _1-m ·□ _m ·nH ₂ O, wherein 0≤r≤2, 0≤m≤1, 0≤n≤20, and □ is a [Fe(CN) ₆ ] hole. The positive electrode binder and the positive electrode conductor may be the same as the aforementioned negative electrode binder and negative electrode conductor, respectively, and will not be repeated here. The positive electrode solvent may include but is not limited to one or more of N-methyl-2-pyrrolidone (NMP) and pure water. The preparation method of the positive electrode is: after mixing the components of the positive electrode material, coating them on the positive electrode current collector, removing the positive electrode solvent, and obtaining the positive electrode. The thickness of the positive electrode includes but is not limited to between 120-150μm.

In some embodiments of the present application, the sodium ion battery further comprises a diaphragm, which is located between the positive electrode and the negative electrode. The diaphragm may be an existing conventional diaphragm, which may be a ceramic diaphragm, a polymer diaphragm, a non-woven fabric, an inorganic-organic composite diaphragm, etc., including but not limited to single-layer PP (polypropylene), single-layer PE (polyethylene), double-layer PP/PE, double-layer PP/PP and triple-layer PP/PE/PP diaphragms.

The high initial efficiency fast-charging sodium ion battery of the present application can be widely used in the field of energy storage and new energy electric vehicles.

Certain features of the present technology are further illustrated in the following non-limiting examples.

1. Examples and Comparative Examples

Example 1

The high first-effect fast-charging sodium-ion battery of this embodiment comprises a positive electrode, a negative electrode, a three-layer separator and an electrolyte, wherein: the thickness of the positive electrode is 135 μm, the positive electrode comprises a positive electrode current collector and a positive electrode material layer formed on the upper surface and the lower surface of the positive electrode current collector, the positive electrode current collector is an aluminum foil, the positive electrode material layer comprises a positive electrode active material, a positive electrode conductive agent, a positive electrode binder, and a positive electrode solvent, the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is 93:4:3, and the positive electrode active material is NaNi _0.7 Co _0.15 Mn _0.15 O ₂ The positive electrode conductive agent is conductive carbon black Super-P, the positive electrode binder is polyvinylidene fluoride (PVDF), and the positive electrode solvent is N-methyl-2-pyrrolidone (NMP); the thickness of the negative electrode is 135μm, the negative electrode includes a negative electrode collector and a negative electrode material layer formed on the upper surface and the lower surface of the negative electrode collector, the negative electrode collector is copper foil, the compaction density of the negative electrode material layer is 0.9g/ ^cm3 , the negative electrode material layer includes a negative electrode active material, a negative electrode conductive agent, a negative electrode binder, and a negative electrode solvent. The mass ratio of the negative electrode active material, the negative electrode conductive agent, and the negative electrode binder is 94:1:5, and the negative electrode active material has a specific surface area of ^5m2. /g of hard carbon, the negative electrode conductive agent is conductive carbon black Super-P, the negative electrode binder is styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC), the mass ratio of styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) is 1:1, the negative electrode solvent is deionized water; the separator is a polypropylene film (PP), and the separator thickness is 20μm. The electrolyte includes a solvent, an electrolyte salt, a first additive, a second additive, and an auxiliary additive. The solvent is a mixture of ethylene carbonate (EC), propylene carbonate (PC), and ethyl methyl carbonate (EMC) in a mass ratio of 2:1:7. The electrolyte salt is NaPF ₆ , and the concentration of the electrolyte salt is 0.9mol/L. The first additive is sodium trifluoromethanesulfonate (CF ₃ NaO ₃ S), and the content of the first additive in the electrolyte is 1wt%. The second additive is a mixture of compound 2 (DTD) and compound 3 (RPS) in a mass ratio of 1:1. The second additive is The content of the additive in the electrolyte is 2wt%; the auxiliary additive is fluoroethylene carbonate (FEC), and the content of the auxiliary additive in the electrolyte is 3wt% of the electrolyte.

The method for preparing a high initial efficiency fast-charging sodium ion battery of this embodiment comprises the following steps:

(1) Preparation of electrolyte: Solvents EC, PC, and EMC were mixed in a mass ratio of 2:1:7, 0.9 M NaPF ₆ was added as an electrolyte salt, 1 wt % CF ₃ NaO ₃ S was added as a first additive, and RPS and DTD in a mass ratio of 1:1 were added as a second additive, and mixed evenly to obtain an electrolyte.

(2) Preparation of positive electrode: The positive electrode active material NaNi _0.7 Co _0.15 Mn _0.15 O ₂ , the positive electrode conductive agent conductive carbon black Super-P and the positive electrode binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 93:4:3, and then dispersed in N-methyl-2-pyrrolidone (NMP) to obtain positive electrode slurry; the obtained positive electrode slurry was evenly coated on both sides of aluminum foil, and after drying, rolling and vacuum drying, aluminum lead wires were welded with an ultrasonic welder to obtain a positive electrode plate.

(3) Preparation of negative electrode: hard carbon with a specific surface area of 5 m2/g of negative electrode active material, conductive carbon black Super-P as a negative electrode conductive agent, styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) as negative electrode binders were mixed in a mass ratio of 94 ^:1:2.5:2.5 , and then dispersed in deionized water to obtain negative electrode slurry; the negative electrode slurry was coated on both sides of a copper foil, dried, rolled and vacuum dried, and a nickel lead wire was welded on with an ultrasonic welder to obtain a negative electrode plate.

(4) Preparation of sodium ion secondary battery: A three-layer separator with a thickness of 20 μm was placed between the positive electrode plate and the negative electrode plate prepared above, and then the sandwich structure consisting of the positive electrode plate, the negative electrode plate and the separator was wound, and then the wound body was flattened and placed in an aluminum foil packaging bag, and vacuum-baked at 75°C for 48 hours to obtain a battery cell to be injected with liquid. In a glove box with a dew point controlled below -40°C, the electrolyte prepared above was injected into the battery cell, vacuum-sealed, and left to stand for 24 hours.

Example 2-32 is basically the same as Example 1, except that some parameter designs are different.

Comparative Examples 1-7 are substantially the same as Example 1, except that some parameters are designed differently.

Some parameter designs of Examples 2-32 and Comparative Examples 1-7 are shown in Table 1.

Table 1 Partial parameter design of embodiments and comparative examples

2. Performance Test

1. Test methods

1) Initial effectiveness test

At room temperature, charge at 0.2C to 3.9V, then drop the constant voltage charging current to 0.02C to test the initial capacity C ₀ of the sodium ion battery, and then discharge at 0.2C constant current to 1.5V to obtain the discharge capacity C ₁ of the sodium ion battery. Calculate the first efficiency according to formula ②:
First effect = C ₁ /C ₀ × 100% Formula ②.

2) 25℃ normal temperature cycle test

The sodium ion battery was placed at 25°C, charged at a constant current of 0.7C to 3.9V, then charged at a constant voltage of 3.9V, with a cut-off current of 0.05C, and then discharged at a constant current of 1C to 1.5V. This cycle was repeated for 200 cycles. The capacity retention rate for 200 cycles was calculated according to formula ③:
200-cycle capacity retention rate = 200th-cycle discharge capacity / average value of 1st-3rd-cycle discharge capacity × 100% Formula ③.

3) 45℃ high temperature cycle test

The sodium ion battery was placed under high temperature conditions of 45°C, charged to 3.9V at a constant current of 0.7C, then the constant voltage charging current was reduced to 0.02C, and then discharged to 1.5V at a constant current of 1C. This cycle was repeated for 200 cycles. The 200-week capacity retention rate was calculated according to formula ④:
200-cycle capacity retention rate = 200th-cycle discharge capacity / 1st-cycle discharge capacity × 100% Formula ④.

4) 3C rate discharge capacity ratio

The ratio of the capacity released by a sodium-ion battery at 3C rate from 3.95-1.5V to the capacity released by a sodium-ion battery at 0.2C rate during the activation stage.

5) 25℃ electrolyte conductivity test

The prepared electrolytes in the embodiments and comparative examples were tested with a conductivity meter at 25°C.

2. Test results

According to the above performance testing method, the performance of the sodium ion batteries in Examples 1-32 and Comparative Examples 1-7 were tested. The test results are shown in Table 2, Table 3, Table 4 and Table 5, Figures 1 and 2.

Table 2 Performance test results of sodium ion batteries in Examples 1-14 and Comparative Examples 1-7

It can be seen from Table 2 that the sodium ion batteries of the embodiments of the present application generally have better electrochemical performance than the sodium ion batteries of the comparative examples because they meet the limitations of the present application on the first additive, the second additive and the negative electrode compaction density.

in:

Compared with comparative example 1, after using the first additive within the content range of the present application, CF ₃ NaO ₃ S participates in film formation at the negative electrode, which can isolate the electrolyte from contacting the negative electrode, thereby reducing the decomposition of the electrolyte, improving the conduction of the SEI film to ions, and increasing the diffusion rate of sodium ions, thereby improving the first efficiency and cycle performance of the sodium ion battery (this can also be verified from Figures 1 and 2).

Compared with Comparative Examples 2 and 3, when the amount of the first additive used in Example 1 is too small (the content is lower than the lower limit of the content of the first additive in the present application), CF ₃ NaO ₃ S cannot effectively participate in film formation, the electrolyte conductivity is low, and the battery performance cannot be effectively improved; when the amount of the first additive used is too large (the content is higher than the upper limit of the content of the first additive in the present application), the reaction with the electrolyte is increased, CF ₃ NaO ₃ S excessively participates in film formation, and the performance of the SEI film is seriously deteriorated, thereby significantly reducing the first efficiency and cycle performance of the lithium ion battery.

Compared with Comparative Examples 4 and 5, when a small amount of the second additive (the content is lower than the lower limit of the second additive content of the present application) is used in Example 1, less additives are involved in film formation, the electrolyte conductivity is low, and the battery performance cannot be significantly improved; and when a large amount of the second additive (the content is higher than the upper limit of the second additive content of the present application) is used, too much additive is involved in film formation. The membrane increases the reaction with the electrolyte, seriously deteriorates the performance of the SEI membrane, and causes a significant decrease in the initial efficiency and cycle performance of the battery.

Compared with Comparative Examples 6 and 7, when the compaction density of the negative electrode material in Example 1 is too small (the compaction density is less than the lower limit of the compaction density of the negative electrode material of the present application), the distance between the particles is too large, the contact probability and contact area between the particles are reduced, and the conductivity is reduced, which affects the large current discharge, increases the discharge polarization, and deteriorates the battery rate and cycle performance; when the compaction density of the negative electrode material is too large (the compaction density is greater than the lower limit of the compaction density of the negative electrode material of the present application), the distance between the particles is reduced, the ion movement channel is reduced or blocked, which is not conducive to the rapid movement of a large number of ions, deteriorates the battery rate performance, and reduces the discharge capacity.

Table 3 Performance test results of sodium ion batteries in Example 1 and Examples 15-25

As can be seen from Table 3, when the second additive is a sulfur compound of the present application, these sulfur compounds, whether used alone or in combination, can achieve the purpose of improving the performance of the sodium ion battery by ensuring that their content is within the content range of the second additive of the present application and conforms to the limited relationship between the first additive, the second additive, and the negative electrode compaction density. Among them, when the second additive is a mixture of multiple sulfur compounds of the present application, the improvement of the performance of the sodium ion battery is more obvious than when a single sulfur compound is used.

Table 4 Performance test results of sodium ion batteries in Example 1 and Examples 26-28

It can be seen from Table 4 that when the limitations of the present application on the first additive, the second additive and the negative electrode compaction density are met, the negative electrode active material, whether it is soft carbon or a mixture of soft carbon and hard carbon, can achieve the purpose of improving the performance of the sodium ion battery.

Table 5 Performance test results of sodium ion batteries in Example 1 and Examples 29-32

It can be seen from Table 5 that when the limitations of the present application on the first additive, the second additive and the negative electrode compaction density are met, and the first additive and the second additive are used in the same amount and the negative electrode compaction density is the same, compared with the case where no auxiliary additive is added, adding auxiliary additives to the electrolyte can significantly improve the performance of the sodium ion battery, and when the auxiliary additive is a mixture of multiple auxiliary additives of the present application, the improvement in the performance of the sodium ion battery is more obvious.

In summary, the high first-efficiency fast-charge sodium-ion battery of the present application uses sodium trifluoromethanesulfonate as the first additive to the electrolyte and a sulfur-based compound as the second additive to the electrolyte, and controls the content of the first additive, the content of the second additive, and the compaction density of the negative electrode material and defines the relationship between them (see formula ①), which can make the sodium-ion battery have a higher first charge and discharge efficiency, better rate performance, and better cycle performance. If the content of the first additive, the content of the second additive, and the compaction density of the negative electrode material are not within their respective value ranges in the present application, and the three of them do not conform to the relationship defined in the present application, they will have the effect of deteriorating the battery performance.

In the present application, the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in the field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

A high initial efficiency fast-charging sodium ion battery, comprising an electrolyte, a negative electrode and a positive electrode;

The electrolyte comprises a solvent, an electrolyte salt, a first additive and a second additive, wherein the first additive is sodium trifluoromethanesulfonate, the second additive is a sulfur compound, the content of the first additive in the electrolyte is a wt%, and the content of the second additive in the electrolyte is b wt%,

The negative electrode includes a negative electrode material, the compaction density of the negative electrode material is c g/cm 3 , and c has the following relationship with a and b:
0.2≤(a+b)/4c≤2.5;

Among them: a is 0.1-4, b is 1-4, and c is 0.8-1.2.
The high initial efficiency fast-charging sodium ion battery according to claim 1, wherein the c is related to the a and the b as follows: 0.5≤(a+b)/4c≤1.
The high initial efficiency fast-charging sodium ion battery according to claim 1 or 2, wherein a is 0.5-2;

And/or, b is 2-3;

And/or, c is 0.9-1.
The high initial efficiency fast-charging sodium ion battery according to any one of claims 1 to 3, wherein the sulfur-based compound is one or more of compounds 1-9:
A high initial efficiency fast-charging sodium ion battery according to any one of claims 1 to 4, wherein the negative electrode material comprises a negative electrode active material, and the negative electrode active material is hard carbon and/or soft carbon.
A high initial efficiency fast-charging sodium ion battery according to any one of claims 1 to 5, wherein the electrolyte further comprises an auxiliary additive, the content of the auxiliary additive in the electrolyte is 1-5wt%, and the auxiliary additive is a fluorocarbonate.
The high initial efficiency fast-charging sodium ion battery according to any one of claims 1 to 6, wherein the solvent is a non-aqueous Organic solvent; the non-aqueous organic solvent includes one or more of ether solvents, nitrile solvents, carbonate solvents and carboxylate solvents;

And/or, the electrolyte salt includes one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium bisoxalatoborate, sodium difluorooxalatoborate, sodium hexafluoroarsenate, sodium trifluoroacetate, sodium tetraphenylborate, sodium bis(fluorosulfonyl)imide, and sodium bis(trifluoromethylsulfonyl)imide.
A high first-efficiency fast-charging sodium ion battery according to any one of claims 1 to 7, wherein the positive electrode comprises a positive electrode active material, and the positive electrode active material comprises one or more of a sodium-containing layered oxide, a sodium-containing polyanion compound, and a sodium-containing Prussian blue compound.
The high initial efficiency fast-charging sodium ion battery according to claim 8, wherein the sodium-containing layered oxide is Na i MO 2 , wherein 0＜i≤1, and M is selected from one or more of V, Cr, Mn, Fe, Co, Ni, and Cu;

and/or, the sodium-containing polyanion compound is Na 3 V 2 (PO 4 ) 2 F 3 ;

And/or, the sodium-containing Prussian blue compound is Na r Mn[Fe(CN) 6 ] 1-m ·□ m ·nH 2 O, wherein 0≤r≤2, 0≤m≤1, 0≤n≤20, and □ is a [Fe(CN) 6 ] hole.
Application of the high initial efficiency fast-charging sodium ion battery as described in any one of claims 1 to 9 in the field of energy storage and new energy electric vehicles.