WO2024125486A1 - Batterie au sodium-ion et dispositif de stockage d'énergie - Google Patents

Batterie au sodium-ion et dispositif de stockage d'énergie Download PDF

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WO2024125486A1
WO2024125486A1 PCT/CN2023/138047 CN2023138047W WO2024125486A1 WO 2024125486 A1 WO2024125486 A1 WO 2024125486A1 CN 2023138047 W CN2023138047 W CN 2023138047W WO 2024125486 A1 WO2024125486 A1 WO 2024125486A1
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positive electrode
lithium
ion battery
sodium
sodium ion
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PCT/CN2023/138047
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English (en)
Chinese (zh)
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刘枭枭
易梓琦
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厦门海辰储能科技股份有限公司
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Publication of WO2024125486A1 publication Critical patent/WO2024125486A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention belongs to the technical field of sodium ion batteries, and in particular relates to a sodium ion battery and an energy storage device.
  • sodium-ion batteries which are similar to lithium-ion batteries, have attracted great attention from academia and industry due to their low cost, good ion conductivity in the electrolyte, and low standard redox potential close to that of lithium.
  • patent CN 113113681 A provides a preparation and application of a composite sodium supplement additive.
  • the sodium supplement additive of the invention contains a metal oxide carbon catalyst and a sodium salt.
  • the metal oxide carbon catalyst is a composite of a metal oxide and a carbon substrate.
  • the sodium salt in the sodium supplement additive is completely decomposed and releases sodium ions and carbon dioxide gas during the first cycle of charging of the sodium ion battery.
  • the carbon dioxide produced by the decomposition can be removed in the formation stage, and the sodium ions produced by the decomposition can effectively solve the problems of low battery energy density and poor cycle stability caused by irreversible consumption of sodium ions.
  • the sodium supplement additive is completely decomposed during the first cycle of charging, so it can only provide electrochemically active sodium ions during the first cycle of charging, and will not continuously release electrochemically active sodium ions during subsequent cycles, which is not conducive to the construction of a long-life sodium ion battery.
  • the sodium supplement additive will also decompose and produce gas while releasing sodium ions. If the gas pressure is too high, it will cause the battery to swell or even explode, which poses certain safety hazards.
  • the SEI film formed on the surface of the negative electrode material of the sodium ion battery is composed of sodium-containing organic and inorganic substances. The mechanical properties and ion conductivity of this sodium-containing SEI film are worse than those of the lithium-containing SEI film formed on the surface of the lithium battery negative electrode. Therefore, it is not suitable for the construction of a long-life sodium ion battery.
  • the present disclosure aims to solve at least one of the technical problems in the related art to a certain extent.
  • the purpose of the present disclosure is to provide a sodium ion battery and an energy storage device.
  • the lithium element contained in the sodium ion battery of the present disclosure improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transmission capacity of the battery system, ensures the sufficiency of electrochemically active alkaline ions in the battery system, ensures that the electrolyte has a high ionic conductivity, improves the cycle stability of the battery and Service life.
  • the present disclosure provides a sodium ion battery.
  • the sodium ion battery comprises:
  • a positive electrode layer the positive electrode layer is formed on the positive electrode current collector, the positive electrode layer comprises sodium and lithium, based on the total mass of the positive electrode layer, the content of the sodium element is 10-20wt%, and the content of the lithium element is 0.1-1.5wt%;
  • the content of sodium in the positive electrode layer is 10-20wt%
  • the content of lithium in the positive electrode layer is 0.01-0.6wt%
  • the preset number of cycles is greater than or equal to 1 and less than or equal to 6000.
  • the lithium element contained in the sodium ion battery improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transmission capacity of the battery system, ensures the sufficiency of electrochemically active alkaline ions in the battery system, and ensures that the electrolyte has a high ionic conductivity, thereby improving the cycle stability and service life of the sodium ion battery, improving the energy density and first-cycle discharge specific capacity of the sodium ion battery, and reducing the discharge impedance of the sodium ion battery.
  • the sodium ion battery according to the above embodiment of the present disclosure may also have the following additional technical features:
  • the content of the lithium element is a first value
  • the content of the lithium element is a second value
  • the content of the lithium element is a second value
  • the absolute value of the difference between the first value and the second value is less than 0.5 wt %.
  • the positive electrode layer includes a positive electrode active material, a lithium-rich additive, a conductive agent, and a binder, the positive electrode active material includes the sodium element, and the lithium-rich additive includes the lithium element.
  • the mass ratio of the positive electrode active material, the lithium-rich additive, the conductive agent and the binder is (90-97):(1-5):(0.1-2):(0.5-3).
  • the lithium-rich additive includes an inorganic lithium salt.
  • the conductive agent includes at least one of Super p carbon black, acetylene black, Ketjen black, graphene and conductive carbon tubes.
  • the binder includes at least one of PVDF, PTFE and NBR.
  • the present disclosure provides an energy storage device.
  • the energy storage device has a sodium ion battery as described above. Therefore, the energy storage device has all the advantages of the sodium ion battery, which will not be repeated here.
  • the present disclosure proposes a sodium ion battery.
  • the sodium ion battery includes: a positive electrode current collector; a positive electrode layer, the positive electrode layer is formed on the positive electrode current collector, the positive electrode layer includes sodium and lithium elements, based on the total mass of the positive electrode layer, the content of the sodium element is 10-20wt%, and the content of the lithium element is 0.1-1.5wt%; after the sodium ion battery is cycled for a preset number of times under the conditions of a cycle current density of 1C and a charging voltage of 2.0V-4.0V, the content of the sodium element in the positive electrode layer is 10-20wt%, and the content of the lithium element in the positive electrode layer is 0.01-0.6wt%, and the preset number of cycles is greater than or equal to 1 and less than or equal to 6000.
  • the lithium-rich additive contained in the sodium ion battery improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transmission capacity of the battery system, ensures the sufficiency of electrochemically active alkaline ions in the battery system, ensures that the electrolyte has a high ionic conductivity, improves the cycle stability and service life of the battery, improves the energy density and first-cycle discharge capacity of the sodium ion battery, and reduces the discharge impedance of the sodium ion battery.
  • the sodium ion battery of the disclosed embodiment contains a lithium-rich additive, which gradually releases electrochemically active lithium ions from its surface to its interior during the electrochemical reaction, so that the lithium-rich additive releases a portion of lithium ions during the first cycle of charging.
  • the portion of lithium ions can be transferred to the surface of the negative electrode material through the electrolyte to participate in the formation of the SEI film, so that the formed SEI film contains an organic and/or inorganic mixture of sodium and lithium at the same time, thereby improving the SEI film on the surface of the negative electrode material.
  • the structural stability and sodium ion transmission capacity of the battery system improve the cycle stability of the battery.
  • the electrochemically active lithium ions provided by the lithium-rich additive during the first cycle of charging reduce the consumption of electrochemically active sodium ions in the positive electrode material, thereby improving the energy density of the sodium ion battery.
  • the lithium-rich additive will slowly and gradually release lithium ions during subsequent cycles.
  • the lithium ions are conducive to continuously replenishing the active sodium consumed in the battery system, ensuring the sufficiency of electrochemically active alkaline ions in the battery system and ensuring that the electrolyte has a high ionic conductivity, thereby further improving the cycle stability and service life of the battery.
  • the sodium-supplementing additives used in the prior art form an SEI film on the surface of the negative electrode material that is composed only of organic and inorganic substances containing sodium, and the SEI film does not contain lithium.
  • the mechanical properties and ion conductivity of this SEI film containing only sodium are significantly worse than those of the SEI film of an organic and/or inorganic mixture containing sodium and lithium in the present application. Therefore, it is not suitable for constructing a long-life sodium-ion battery.
  • the sodium-supplementing additives used in the prior art are completely decomposed during the first cycle of charging, so they can only provide electrochemically active sodium ions during the first cycle of charging, and will not continuously release electrochemically active sodium ions during subsequent cycles, which is not conducive to the construction of a long-life sodium-ion battery.
  • the lithium-rich additives used in the present disclosure will slowly and gradually release lithium ions during subsequent cycles. Therefore, the present disclosure effectively solves the problems existing in the use of sodium-supplementing additives in the prior art.
  • sodium ions will be released from the crystal structure of the positive electrode active material.
  • the redox potential of the lithium-rich additive partially overlaps with the working potential of the sodium ions, at the same time as the active sodium ions are released from the positive electrode material, some lithium ions will be released from the lithium-rich additive and migrate to the negative electrode through the diaphragm in the electrolyte together with the sodium ions to participate in the film-forming reaction of the negative electrode.
  • most of the lithium ions are consumed in the film-forming reaction, and most of the sodium ions are stored in the reversible active sites of the negative electrode material.
  • sodium ions can be reversibly released from the negative electrode and embedded in the positive electrode material through the electrolyte diaphragm, that is, sodium ions can be reversibly embedded and released between the positive and negative electrodes.
  • cycle process of the sodium ion battery disclosed in the present invention under other preset conditions is the same as the cycle process under the preset conditions of a cycle current density of 1C and a charging voltage of 2.0V-4.0V.
  • the SEI film consumes the most lithium ions and sodium ions in the first cycle, the consumed lithium ions gradually decrease in the subsequent cycles due to the reduction of side reactions.
  • the content of the lithium element is a first value
  • the sodium ion battery cycles for the second preset number of times under the conditions of a cycle current density of 1C and a charging voltage of 2.0V-4.0V the content of the lithium element is a second value
  • the first preset number of times is less than the second preset number of times
  • the first value is greater than the second value.
  • the absolute value of the difference between the first value and the second value is less than 0.5wt%.
  • the positive electrode layer includes a positive electrode active material, a lithium-rich additive, a conductive agent and a binder.
  • the positive electrode active material includes a sodium element
  • the lithium-rich additive includes a lithium element.
  • the content of the lithium-rich additive is 1wt%-5wt%.
  • the content of the lithium-rich additive is limited to the above range, which further improves the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transmission capacity of the battery system, further ensures the sufficiency of electrochemically active alkaline ions in the battery system, further ensures that the electrolyte has a high ionic conductivity, and further improves the cycle stability and service life of the battery.
  • the main component of the negative electrode SEI film formed will be sodium-containing inorganic and organic substances, with low density, resulting in low mechanical strength of the SEI film, thereby resulting in poor cycle performance of the sodium ion battery. If the content of the lithium-rich additive is too high, it will lead to an increase in the content of non-electrochemically active substances, resulting in a relative decrease in the electrochemically active sodium ions in the battery system, thereby resulting in a decrease in the energy density of the battery.
  • the mass ratio of the positive electrode active material, the lithium-rich additive, the conductive agent and the binder is (90-97):(1-5):(0.1-2):(0.5-3). Therefore, by limiting the mass ratio of the positive electrode active material, the lithium-rich additive, the conductive agent and the binder within the above range, it can ensure that the SEI film formed on the surface of the negative electrode has high density and high mechanical strength, thereby enhancing the sodium ion transmission capacity of the battery system and improving the cycle stability of the battery; it can also ensure that the content of electrochemically active substances in the battery system is not affected, thereby maximizing the energy density, cycle stability and service life of the battery.
  • the above-mentioned lithium-rich additive includes an inorganic lithium salt, which releases a portion of lithium ions during the first cycle of charging.
  • the portion of lithium ions can be transferred to the surface of the negative electrode material through the electrolyte to participate in the formation of the SEI film, so that the formed SEI film contains an organic and/or inorganic mixture of sodium and lithium at the same time, thereby improving the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transmission capacity of the battery system, and improving the cycle stability of the battery; at the same time, the lithium-rich additive will slowly and gradually release lithium ions during the subsequent cycles, which is conducive to continuously replenishing the active sodium consumed in the battery system, ensuring the sufficiency of electrochemically active alkaline ions in the battery system.
  • the inorganic lithium salt does not generate gas in the process of providing electrochemically active lithium, thereby avoiding the safety hazards caused by battery flatulence.
  • the specific types of the above-mentioned inorganic lithium salts are not particularly limited.
  • the above types of inorganic lithium salts not only have all the advantages of the above-mentioned inorganic lithium salts, but specifically, the lithium-rich additive will release a part of lithium ions during the first cycle of charging to participate in the formation of SEI film. At the same time, the lithium-rich additive will slowly and gradually release lithium ions in the subsequent cycles, ensuring the sufficiency of electrochemically active alkaline ions in the battery system. Moreover, the above-mentioned types of inorganic lithium salts are less sensitive to moisture in the air, which prevents the inorganic lithium salts from deteriorating due to moisture in the air during the battery preparation process, and is conducive to the battery preparation process being carried out in a normal air atmosphere without the need for dehumidification of the air.
  • Li 2 O/M 1 refers to a composite material of Li 2 O and metal M 1 , and the molar ratio of Li 2 O to metal M 1 is 2:3 or 1:1.
  • Li 2 S/M 2 refers to a composite material of Li 2 S and metal M 2 , and the molar ratio of Li 2 S to metal M 2 is 2:3 or 1:1. The molar ratio is 2:3 or 1:1.
  • LiF/ M3 refers to a composite material of LiF and metal M3 , and the molar ratio of LiF to metal M3 is 2:1.
  • the specific type of the conductive agent is not particularly limited, and those skilled in the art can freely select it according to actual conditions.
  • the conductive agent includes at least one of Super p carbon black, acetylene black, Ketjen black, graphene and conductive carbon tubes.
  • the specific type of the binder is not particularly limited, and those skilled in the art can select it at will according to actual conditions.
  • the binder includes at least one of PVDF, PTFE and NBR.
  • the sodium ion battery comprises the positive electrode sheet, the negative electrode sheet and the separator described in the above embodiment, and the separator is arranged between the positive electrode sheet and the negative electrode sheet.
  • the separator comprises at least one of a PP separator, a PE separator, a single-sided ceramic separator, a double-sided ceramic separator, a non-woven fabric separator and a glass fiber separator.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material, a conductive agent and a binder.
  • the negative electrode active material can be a carbon-based negative electrode material (such as hard carbon, soft carbon, soft and hard composite carbon), a metal oxide negative electrode material (such as titanium oxide, sodium titanate, etc.), an alloy-based negative electrode material (such as tin alloy), etc.
  • the preparation method of the negative electrode sheet includes: mixing the negative electrode active material, the conductive agent and the binder in different proportions, adding deionized water and stirring evenly, then coating it on the current collector, drying it, and finally cutting it into a specific shape of negative electrode sheets according to the different battery shells for use.
  • Sodium ion batteries are filled with an electrolyte that transports sodium ions.
  • the electrolyte includes an electrolyte (such as sodium hexafluorophosphate) and a solvent (such as carbonates, ethers, and mixed esters and ethers, etc.).
  • the first is a method for preparing a positive electrode sheet, comprising:
  • the positive electrode active material, the lithium-rich additive, the conductive agent, the binder and the organic solvent are mixed in proportion to form a positive electrode slurry.
  • the solid content and viscosity of the positive electrode slurry are not particularly limited.
  • the solid content of the positive electrode slurry can be 60%-80%, and the viscosity of the positive electrode slurry can be 5000-8000cp.
  • the specific type of organic solvent is also not particularly limited. For example, at least one of NMP (N-methylpyrrolidone), DMF (dimethylformamide) and DMSO can be selected.
  • the positive electrode slurry is coated on the positive electrode current collector and dried (e.g., vacuum drying) to form a positive electrode layer on the positive electrode current collector to finally obtain a positive electrode sheet.
  • the positive electrode sheet is cut into a specific shape according to the different battery shells for later use.
  • the lithium-rich additive is added to the positive electrode layer of the positive electrode sheet by the conventional method for preparing the positive electrode sheet.
  • the preparation process is simple and easy to implement, and the preparation process is mature.
  • the lithium-rich additive in the positive electrode sheet prepared by this method will gradually release electrochemically active lithium ions from its surface to the inside during the electrochemical reaction, so that the lithium-rich additive will release a part of lithium ions during the first cycle of charging.
  • This part of lithium ions can be transferred to the surface of the negative electrode material through the electrolyte to participate in the formation of the SEI film, so that the formed SEI film contains an organic and/or inorganic mixture of sodium and lithium at the same time, thereby improving the structural stability of the SEI film on the surface of the negative electrode material and the sodium ion transmission capacity of the battery system, and improving the cycle stability of the battery.
  • the electrochemically active lithium ions provided by the lithium-rich additive during the first cycle of charging reduce the consumption of electrochemically active sodium ions in the positive electrode material, thereby improving the energy density of the sodium ion battery.
  • the lithium-rich additive will slowly and gradually release lithium ions during subsequent cycles, which are beneficial for continuously replenishing the active sodium consumed in the battery system, ensuring sufficient electrochemically active alkaline ions in the battery system and ensuring that the electrolyte has a high ionic conductivity, thereby further improving the battery's cycle stability and service life.
  • the preparation method of the negative electrode sheet is similar to that of the positive electrode sheet and will not be repeated here.
  • the method for assembling a sodium ion battery includes: assembling a positive electrode sheet, a separator and a negative electrode sheet in a layer-by-layer winding or lamination manner, injecting an electrolyte according to a corresponding injection coefficient, and then placing the battery cell in a shell and sealing it.
  • the present disclosure proposes an energy storage device.
  • the energy storage device has a sodium ion battery as described above. Therefore, the energy storage device has all the advantages of the sodium ion battery, which will not be repeated here.
  • the energy storage device may include at least one of an electric energy storage device for the power generation side of the power system, an electric energy storage device (such as an electrochemical energy storage device) for the distribution side of the power system, and an electric energy storage device for the user side of the power system.
  • an electric energy storage device such as an electrochemical energy storage device
  • an electric energy storage device for the user side of the power system.
  • positive electrode sheet NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , Li 2 NiO 2 , acetylene black and PVDF were added to NMP solvent in a mass ratio of 93:4:2:1 and stirred evenly. Then, the mixture was coated on the aluminum foil current collector and dried under vacuum at 100°C to form a positive electrode layer on the aluminum foil current collector. The positive electrode sheets were cut into 6cm*8cm positive electrode sheets with tabs for later use. The total mass of the electrode layer has a sodium content of 19.18% and a lithium content of 0.53%.
  • Preparation of negative electrode sheets Add hard carbon material, super P and CMC/SBR/PAA in a mass ratio of 97:1:2 into deionized water and stir evenly, then apply it on the copper foil current collector, dry it at 100°C, and cut it into 7cm*9cm negative electrode sheets with tabs for use.
  • Battery assembly stack the positive electrode sheet, separator and negative electrode sheet in a layer by layer manner, bake until the moisture content is less than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium ion battery.
  • Preparation of positive electrode Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 , Li 2 CuO 2 , acetylene black and PVDF were added into NMP solvent in a mass ratio of 94:3:2:1 and stirred evenly, then coated on an aluminum foil current collector, dried at 100°C in vacuum, and cut into 6cm*8cm electrodes with tabs for later use.
  • Preparation of negative electrode sheet Add hard carbon material, super P and CMC/SBR/PAA in a mass ratio of 97:1:2 into deionized water and stir evenly, then apply it on the copper foil current collector, dry it at 100°C, and cut it into 7cm*9cm electrode sheets with pole ears for use.
  • Battery assembly stack the positive electrode sheet, separator and negative electrode sheet in a layer by layer manner, bake until the moisture content is less than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium ion battery.
  • Preparation of positive electrode Na 3 V 2 (PO 4 ) 3 , 3Li 2 O/2Fe, acetylene black and PVDF were added into NMP solvent in a mass ratio of 93:4:2:1 and stirred evenly, then coated on an aluminum foil current collector, dried at 100°C in vacuum, and cut into 6cm*8cm electrodes with tabs for later use.
  • Preparation of negative electrode sheet Add hard carbon material, super P and CMC/SBR/PAA in a mass ratio of 97:1:2 into deionized water and stir evenly, then apply it on the copper foil current collector, dry it at 100°C, and cut it into 7cm*9cm electrode sheets with pole ears for use.
  • Battery assembly stack the positive electrode sheet, separator and negative electrode sheet in a layer by layer manner, bake until the moisture content is less than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium ion battery.
  • the mass ratio of NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , Li 2 NiO 2 , acetylene black and PVDF was set to 92:5:2:1. The contents are the same as those in Example 1.
  • Example 1 The Li 2 NiO 2 in Example 1 is replaced by Li 6 CoO 4 , and the other contents are the same as those in Example 1.
  • Example 1 The Li 2 NiO 2 in Example 1 is replaced by Li 2 MoO 3 , and the other contents are the same as those in Example 1.
  • Example 1 The Li 2 NiO 2 in Example 1 is replaced by Li 2 Ni 0.5 Cu 0.5 O 2 .
  • the other contents are the same as those in Example 1.
  • Example 1 The Li 2 NiO 2 in Example 1 is replaced by 3Li 2 S/2Ni, and the other contents are the same as those in Example 1.
  • Example 1 The Li 2 NiO 2 in Example 1 is replaced by 2LiF/Fe, and the other contents are the same as those in Example 1.
  • Preparation of positive electrode NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , acetylene black and PVDF were added into NMP solvent in a mass ratio of 97:2:1 and stirred evenly, then coated on aluminum foil current collector, dried under vacuum at 100°C, and cut into 6cm*8cm electrode sheets with tabs for later use.
  • Preparation of negative electrode sheets Add hard carbon material, super P and CMC/SBR/PAA in a mass ratio of 97:1:2 into deionized water and stir evenly, then apply it on the copper foil current collector, dry it at 100°C, and cut it into 7cm*9cm negative electrode sheets with tabs for use.
  • Battery assembly stack the positive electrode sheet, separator and negative electrode sheet in a layer by layer manner, bake until the moisture content is less than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium ion battery.
  • Preparation of positive electrode Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 , acetylene black and PVDF were added into NMP solvent in a mass ratio of 97:2:1 and stirred evenly, then coated on aluminum foil current collector, dried under vacuum at 100°C, and cut into 6cm*8cm electrode sheets with tabs for later use.
  • Preparation of negative electrode sheet Add hard carbon material, super P and CMC/SBR/PAA in a mass ratio of 97:1:2 into deionized water and stir evenly, then apply it on the copper foil current collector, dry it at 100°C, and cut it into 7cm*9cm electrode sheets with pole ears for use.
  • Battery assembly stack the positive electrode sheet, separator and negative electrode sheet in a layer by layer manner, bake until the moisture content is less than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium ion battery.
  • Preparation of positive electrode sheet Na 3 V 2 (PO 4 ) 3 , acetylene black and PVDF were added into NMP solvent in a mass ratio of 97:2:1 and stirred evenly, then coated on aluminum foil current collector, dried under vacuum at 100°C, and cut into sheets with tabs. 6cm*8cm pole pieces are available for backup.
  • Preparation of negative electrode sheet Add hard carbon material, super P and CMC/SBR/PAA in a mass ratio of 97:1:2 into deionized water and stir evenly, then apply it on the copper foil current collector, dry it at 100°C, and cut it into 7cm*9cm electrode sheets with pole ears for use.
  • Battery assembly stack the positive electrode sheet, separator and negative electrode sheet in a layer by layer manner, bake until the moisture content is less than 300ppm, inject electrolyte, and seal with aluminum-plastic film to prepare a sodium ion battery.
  • the sodium and lithium contents of the positive electrode layers formed in Examples 1-11 before cycling were calculated, and the results are shown in Table 1.
  • the sodium and lithium contents of the positive electrode layers formed in Examples 1-11 after cycling for 1, 100, 500, 1000, 3000 and 6000 cycles were tested by inductively coupled plasma emission spectrometry (ICP). The results are shown in Table 1.
  • the loss of sodium ions in the first cycle is relatively small, while the loss of lithium ions is relatively large, indicating that most of the lithium ions participate in the formation of the negative electrode SEI film during the first cycle of charging, reducing the loss of active sodium ions. This can improve the energy density of the battery.
  • lithium ions gradually compensate for the consumption of sodium ions, improving the cycle stability of the battery, which is conducive to building a sodium ion battery with a long service life.

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Abstract

L'invention concerne une batterie au sodium-ion et un dispositif de stockage d'énergie. La batterie au sodium-ion comprend : un collecteur de courant d'électrode positive ; et une couche d'électrode positive, qui comprend du sodium et du lithium. Sur la base de la masse totale de la couche d'électrode positive, la teneur en sodium est de 10 à 20% en poids, et la teneur en lithium est de 0,1 à 1,5% en poids ; et après que la batterie au sodium-ion a subi un cycle, un nombre prédéfini de cycles dans des conditions prédéfinies, la teneur en sodium dans la couche d'électrode positive est de 10 à 20% en poids, et la teneur en lithium dans la couche d'électrode positive est de 0,01 à 0,6% en poids, le nombre prédéfini de cycles étant supérieur ou égal à 1 et inférieur ou égal à 6000.
PCT/CN2023/138047 2022-12-12 2023-12-12 Batterie au sodium-ion et dispositif de stockage d'énergie WO2024125486A1 (fr)

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