WO2023015408A1 - Flame-retardant electrolyte for sodium-ion batteries and sodium-ion secondary battery - Google Patents

Flame-retardant electrolyte for sodium-ion batteries and sodium-ion secondary battery Download PDF

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WO2023015408A1
WO2023015408A1 PCT/CN2021/111495 CN2021111495W WO2023015408A1 WO 2023015408 A1 WO2023015408 A1 WO 2023015408A1 CN 2021111495 W CN2021111495 W CN 2021111495W WO 2023015408 A1 WO2023015408 A1 WO 2023015408A1
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sodium
solvent
flame
carbonate
retardant
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PCT/CN2021/111495
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French (fr)
Chinese (zh)
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胡勇胜
周琳
陈立泉
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中国科学院物理研究所
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Publication of WO2023015408A1 publication Critical patent/WO2023015408A1/en

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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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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 invention belongs to the technical field of battery materials. Specifically, the present invention relates to a flame-retardant electrolyte solution for a sodium ion battery and a sodium ion secondary battery.
  • Na-ion batteries are considered to be a beneficial supplement to lithium-ion batteries due to their advantages of abundant resources, wide distribution and low cost, and are one of the ideal devices for large-scale energy storage.
  • the research and development of sodium-ion battery technology has received extensive attention from various research groups around the world.
  • sodium-ion batteries have always been the primary concern of people. Since the electrolyte used in the sodium-ion battery is a flammable carbonate and/or ether solvent system, the sodium-ion battery may catch fire, burn or explode under conditions such as overcharge, short circuit or heat, which may lead to safety accidents .
  • CN108736010A discloses the use of pure phosphoric acid ester as the electrolyte of sodium ion batteries, and the use of phosphate compounds as negative electrode materials.
  • the disadvantage of this patent application is that the electrolyte it discloses is not compatible with carbon negative electrodes.
  • CN110518287A discloses the use of phosphoric acid ester and fluoroether in a volume ratio of 1:1-2:1 as a flame retardant solvent, and sodium perchlorate as a sodium salt.
  • the disadvantage of this patent application is that, due to the low content of phosphate ester as a flame retardant (accounting for about 33.3%-66.6% by volume of the solvent), although the battery of this patent application is non-flammable, it still cannot pass the puncture test.
  • fluoroether solvent has a high vapor pressure and a low boiling point, which is not conducive to the packaging of the battery.
  • fluoroethers have anesthetic effects, such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (Cas: 16627-68-2) commonly used in the industry has Strong acute anesthetic ability.
  • the volatile gas and residual liquid of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether should be controlled to prevent the volatile gas and residual liquid from affecting the unnecessary injury to personnel.
  • fluoroethers have a low dielectric constant and hardly dissociate sodium salts, resulting in low conductivity of the electrolyte with fluoroethers as the main solvent and poor rate performance of the battery.
  • using sodium perchlorate as the sodium salt has certain potential safety hazards. Sodium perchlorate is a strong oxidizing product and an explosive product, and its use is controlled.
  • CN108028429A discloses the use of electrolytes containing high concentrations of alkali metal salts.
  • the amount of the solvent is 4 mol or less with respect to 1 mol of the alkali metal salt.
  • the anion of the alkali metal salt is selected from one or more of fluorosulfonyl, trifluoromethanesulfonyl and perfluoroethanesulfonyl.
  • the shortcoming of this patent application is, on the one hand, its disclosed salt is all organic salt, and its price is higher. Furthermore, in this patent application, the cost of the salt is about ten times that of the solvent. Electrolyte with high salt concentration results in higher price of the whole electrolyte.
  • Electrolyte with high salt concentration will increase the viscosity of the electrolyte and decrease the conductivity. Therefore, under low temperature or high current charge and discharge conditions, the battery performance is very poor.
  • the patent application only gives the performance of metal sodium and hard carbon negative electrode, but does not give the performance of hard carbon negative electrode and layered oxide full battery.
  • flame-retardant electrolytes with high salt concentrations are not safe (see, Hou J, Lu L, Wang L, et al. Thermal runaway of lithium-ion batteries employing LiN(SO 2 F) 2 -based concentrated electrolytes[ J]. Nature communications, 2020, 11(1):1-11).
  • the prior art discloses electrolytes comprising NaBOB (sodium bisoxalatoborate) as the sodium salt (see Mogensen R, Colbin S, Menon A S, et al. Sodium bis(oxalato) borate in trimethyl phosphate: a fire-extinguishing , fluorine-free, and low-cost electrolyte for full-cell sodium-ion batteries[J].ACS Applied Energy Materials,2020,3(5):4974-4982; and Mogensen R, Buckel A, Colbin S, et al .A Wide-Temperature-Range,Low-Cost,Fluorine-Free Battery Electrolyte Based On Sodium Bis(Oxalate)Borate[J].Chemistry of Materials,2021,33(4):1130-1139).
  • NaBOB sodium bisoxalatoborate
  • the salt Since the salt is easily reduced, its impedance is relatively large.
  • the coulombic efficiency of the battery is low for the first cycle, and the coulombic efficiency during the cycle is less than or equal to 99.85%. This means that there are obvious side reactions in the battery, resulting in poor cycle stability of the battery.
  • the purpose of the present invention is to provide a low-cost, high-safety flame-retardant electrolyte that is compatible with carbon negative electrodes and has excellent electrochemical properties such as cycle performance.
  • the present invention provides a kind of flame-retardant electrolytic solution for sodium-ion batteries, which comprises the following components:
  • the basic electrolyte includes a solvent and a sodium salt; the solvent includes a main solvent and an optional secondary solvent; the sodium salt includes a main sodium salt and an optional second sodium salt; the main solvent is a phosphorus-containing flame retardant Solvent, the secondary solvent is selected from at least one of carbonate solvents, carboxylate solvents and non-fluorinated ether ether solvents, the main sodium salt is sodium hexafluorophosphate and sodium tetrafluoroborate, the secondary The sodium salt is selected from one or more of sodium bistrifluoromethanesulfonimide, sodium bisfluorosulfonimide, sodium bistrifluoromethanesulfonate, sodium trifluoromethanesulfonate and sodium perchlorate ;
  • the molar ratio of the phosphorus-containing flame retardant solvent to the sodium salt is 4.2-17:1, preferably 5-10:1, more preferably 7-9:1; the mass fraction of the main sodium salt in the sodium salt is 70%-100%;
  • the volume fraction of the main solvent in the solvent is 80%-100%, more preferably 100%;
  • the mass fraction of the functional additive in the electrolyte is greater than 0 and less than or equal to 5%, preferably 1%-3%.
  • the phosphoric acid ester or phosphonic acid ester is selected from triphenyl phosphate (TPP), trimethyl phosphate (TMP), triethyl phosphate One or more of (TEP), dimethyl methylphosphonate (DMMP) and bis(2,2,2-trifluoroethyl)methylphosphate (TFMP).
  • the molar ratio of sodium hexafluorophosphate and sodium tetrafluoroborate is 1:50-50:1, more preferably 1:11- 11:1.
  • the carbonate solvent is a cyclic carbonate solvent and/or a chain carbonate solvent.
  • the cyclic carbonate is ethylene carbonate and/or propylene carbonate.
  • the chain carbonate is a carbonate synthesized from a straight-chain or branched fatty monoalcohol with a carbon number of 3-8 and carbonic acid.
  • the chain carbonate is selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate and methyl ethyl carbonate one or more of.
  • the carboxylate solvent is a cyclic carboxylate solvent and/or a chain carboxylate solvent.
  • the cyclic carboxylic acid ester is ⁇ -butyrolactone
  • the chain carbonate is a chain with 3-8 carbon atoms.
  • Carboxylate is a chain with 3-8 carbon atoms.
  • the chain carboxylate is selected from methyl acetate, ethyl acetate, propyl acetate, propyl propionate and ethyl propionate one or more of them.
  • the ethers of non-fluorinated ethers are selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, di One of methoxymethane, 1,2-dimethoxyethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether or several.
  • the functional additive is selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, 1,3-propane sultone (PS ), 1,4-butane sultone, propenyl-1,3-sultone (PST), cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, vinyl sulfate, dimethyl sulfite , one or more of one or more of diethyl sulfite and succinonitrile.
  • PS 1,3-propane sultone
  • PST propenyl-1,3-sultone
  • cyclohexylbenzene tert-butylbenzene
  • tert-amylbenzene vinyl sulfate
  • dimethyl sulfite one or more of one or more of diethyl sulfite and succinonitrile.
  • the present invention provides a sodium-ion secondary battery, which includes a positive electrode material, a negative electrode material and the flame-retardant electrolyte solution for a sodium-ion battery of the present invention.
  • the positive electrode material is layered metal oxide, polyanion positive electrode material or Prussian blue material, and the negative electrode material is carbon material.
  • the positive electrode material is a layered metal oxide
  • the negative electrode material is hard carbon
  • the inventors of the present application have unexpectedly found that when the sodium salt is sodium hexafluorophosphate and sodium tetrafluoroborate and optionally a small amount of hyposodium salt as claimed in the present invention, and when the solvent is the main solvent claimed in the present invention
  • the type and amount of the secondary solvent are used, only using a lower concentration of sodium salt instead of a higher concentration of sodium salt can achieve low cost, high safety, and electrochemical performance compatible with carbon negative electrodes such as cycling Electrolyte with excellent performance.
  • the sodium ion secondary battery of the invention has high safety performance and excellent electrochemical performance such as cycle performance.
  • the average coulombic efficiency of the sodium ion secondary battery of the present invention is greater than 99.9% in the cycle process at room temperature. Under conditions such as battery abuse or accidental injury (eg, puncture), the sodium ion secondary battery of the present invention can reduce or avoid the risk of fire.
  • the electrolyte of the present invention realizes the compatibility of the flame retardant electrolyte and the carbon negative electrode.
  • the industrial utilization value of the sodium ion secondary battery of the present invention is extremely high.
  • the electrolyte solution of the invention has low cost, high safety, and is compatible with carbon negative electrodes.
  • Fig. 1 is the charge-discharge curve diagram of the first two laps of the battery of Example 1 at room temperature;
  • Fig. 2 is the comparison chart of the cycle performance of the batteries of Example 1 and Comparative Example 1 at room temperature;
  • Fig. 3 is the coulombic efficiency comparison diagram of the batteries of Example 1 and Comparative Example 1 during the cycle at room temperature;
  • Fig. 4 is a comparison chart of the Coulombic efficiency of the batteries of Example 1 and Comparative Example 1 during cycling at high temperature;
  • Fig. 5 is the charge-discharge curve diagram of the first two cycles of the battery of Example 2 at room temperature
  • Fig. 6 is the charge-discharge curve diagram of the first two cycles of the battery of Example 3 at room temperature
  • Fig. 7 is the charge-discharge curve diagram of the first two laps of the battery of Example 14 at room temperature
  • Fig. 8 is the charge-discharge curve diagram of the first two cycles of the battery of Example 17 at room temperature
  • Fig. 9 is the charge-discharge curve diagram of the first two cycles of the battery of Example 19 at room temperature
  • Fig. 10 is the charge-discharge curve diagram of the first two cycles of the battery of Example 23 at room temperature
  • Fig. 11 is the charge and discharge curves of the first two cycles of the battery of Example 27 at room temperature.
  • O3-Na[Cu 1/9 Ni 2/9 Fe 1/3 Mn 1/3 ]O 2 is the positive electrode active material
  • acetylene black is the conductive agent
  • polytetrafluoroethylene is the binder
  • the mass ratio is 90: The ratio of 6:4 is mixed well.
  • N-methylpyrrolidone was added and slurried. Spread the slurry on aluminum foil. At 120°C, vacuum dry overnight. After rolling, the positive electrode sheet can be obtained.
  • Hard carbon is used as the negative electrode active material
  • acetylene black is used as the conductive agent
  • polytetrafluoroethylene is used as the binder, and they are mixed uniformly at a mass ratio of 90:5:5.
  • N-methylpyrrolidone was added and slurried. The slurry was coated on an aluminum foil and dried under vacuum overnight at 120°C. After rolling, the negative electrode sheet can be obtained.
  • Electrolyte configuration In a glove box filled with argon, weigh the main sodium salt and the optional secondary sodium salt according to the data in Table 1, respectively. Then, a certain volume of solvent is added. After sufficient stirring, the prepared electrolyte solution was obtained. Note that most salts dissolve completely. Part of the sodium salt was not completely dissolved in the comparative example. When part of the sodium salt was not completely dissolved in the comparative example, the upper layer saturated solution was used as the electrolyte.
  • TMP Trimethyl phosphate
  • TEP Triethyl phosphate
  • DEC Diethyl carbonate
  • EC Ethylene carbonate
  • EP Propyl acetate
  • DEGDME Diethylene glycol dimethyl ether
  • HFE 1,1,2 ,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether
  • VC vinylene carbonate
  • PS 1,3-propane sultone
  • PC propylene carbonate
  • FEC fluorine ethylene carbonate
  • DTD ethylene sulfate
  • VEC ethylene carbonate.
  • Fig. 1 is the first charge and discharge curve of the battery of Example 1 at room temperature.
  • Fig. 1, Fig. 5-Fig. 11 show the electrolyte solution based on the present invention, in the full battery, the discharge specific capacity is greater than 120mAh/g (based on the positive electrode), and the first coulombic efficiency is higher (about 85%).
  • FIG. 2 is a comparison chart of the cycle performance of the batteries of Example 1 and Comparative Example 1 at room temperature.
  • Fig. 2 shows that the first discharge specific capacity of the battery of Example 1 is 129mAh/g, the first coulombic efficiency reaches 84.7%, and the capacity retention rate after 180 cycles is 92.7%.
  • the battery of Comparative Example 1 has a capacity retention rate of 71.7% after 150 cycles.
  • Fig. 3 is a graph comparing Coulombic efficiencies of the batteries of Example 1 and Comparative Example 1 during cycling at room temperature.
  • the average coulombic efficiency of the conventional electrolyte of Comparative Example 1 from the fourth cycle was 99.75%.
  • the average Coulombic efficiency of the flame-retardant electrolyte of Example 1 from the fourth cycle is 99.995%.
  • the cycle Coulombic efficiency of the battery of Comparative Example 1 is lower than that of the battery of Example 1, and the cycle Coulombic efficiency of the battery of Comparative Example 1 is lower. This shows that the flame retardant electrolyte of Example 1 has less side reactions.
  • the flame-retardant electrolyte used in Examples 1-29 and the electrolytes of Comparative Example 1 and Comparative Example 2 were injected into cylindrical cells (with a capacity of 2.5 Ah).
  • the battery was cycled for 2 laps, and the acupuncture experiment was carried out in a fully charged state.
  • the batteries of Examples 1-29 did not smoke, catch fire, or explode.
  • thick smoke came out, posing a safety hazard.
  • Examples 1-13 show the performance of electrolytes with different molar ratios of NaBF 4 and NaPF 6 .
  • the battery has a very high capacity retention rate (84.4%-95%) after 100 cycles, and when the molar ratio of NaBF 4 to NaPF 6 is 11 From :1 to 1:11, the battery has a higher capacity retention rate (88.6%-95%) after 100 cycles.
  • Comparative example 3 shows that the electrolyte solution using only NaPF 6 salt has poor cycle stability, and the 100-cycle capacity retention rate is only 35%.
  • Comparative example 4 shows that only adopts the electrolyte of NaBF 4 salt (this electrolyte will have a small amount of NaBF 4 separate out, therefore, get supernatant liquid as electrolyte), battery cycle stability is very poor, and 100 laps capacity retention rate is only 60%.
  • Comparative Example 5 shows that when the molar ratio of NaBF 4 to NaPF 6 is 1:59, the capacity retention rate of the battery after 100 cycles is only 65%.
  • Comparative Example 6 shows that when the molar ratio of NaBF 4 to NaPF 6 is 54.6:1, the capacity retention rate of the battery after 100 cycles is only 66%.
  • Examples 14-18 show that when a suitable mixed sodium salt is used, the pure flame retardant TEP is used as a solvent, and the battery is cycled 100 times, and the capacity retention rate of the battery is still greater than 85%.
  • Examples 19-24 show that when other solvents are carbonates (such as EC, DEC), carboxylates (such as EP), and non-fluorinated ethers (DEGDME), the battery cycle performance is stable and the capacity retention rate is high.
  • carbonates such as EC, DEC
  • carboxylates such as EP
  • DEGDME non-fluorinated ethers
  • Comparative Example 9 shows that when other solvents are selected from fluoroethers, such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, when the volume fraction of the total solvent is 10% , The battery cycle is 100 cycles, and the capacity retention rate is only 74%. The performance of the battery of Comparative Example 9 was poor. Without wishing to be bound by theory, the reason for the poorer performance of Comparative Example 9 may be that the fluoroether can also act as a film-forming additive, and when the fluoroether was used in combination with NaPF6 and NaBF4 , a stable interfacial film could not be formed.
  • fluoroethers such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether
  • Examples 25-27 show that when NaPF 6 and NaBF 4 are used as the main sodium salts and other small amounts of sodium salts, such as NaFSI, NaClO 4 , and NaCF 3 SO 3 , the battery still maintains good cycle stability.
  • Comparative examples 6-8 show that when other salt combinations are selected, such as NaPF 6 +NaClO 4 or NaBF 4 +NaClO 4 , the cycle stability of the battery is poor. This fully proves the superiority of NaPF 6 and NaBF 4 as main sodium salts.
  • Examples 28-29 show that when NaPF 6 and NaBF 4 are used as the main sodium salt, even if the concentration of the sodium salt is low, the battery still maintains good cycle stability.
  • Examples 30-35 show that when NaPF 6 and NaBF 4 are used as the main sodium salt, and additives commonly used in this field (such as VC, FEC, VEC, DTD, PS) are selected, the battery still maintains good cycle stability.
  • additives commonly used in this field such as VC, FEC, VEC, DTD, PS
  • FIG. 4 is a comparison chart of Coulombic efficiencies of the batteries of Example 1 and Comparative Example 1 during cycling at high temperature.
  • the electrolyte in Example 1 was cycled 100 times at a high temperature of 60° C., the capacity retention rate of the battery was 84%, and the average Coulombic efficiency was 99.87%.
  • the electrolyte in Comparative Example 1 was cycled 100 times at a high temperature of 60° C., the capacity retention rate of the battery was 75%, and the average Coulombic efficiency was 98.79%. It can be seen that the electrolyte solution of the present invention has good high temperature performance.

Abstract

The present invention provides a flame-retardant electrolyte for sodium-ion batteries, comprising the following components: a basic electrolyte and a functional additive, wherein the basic electrolyte comprises a solvent and a sodium salt; the solvent comprises a primary solvent and an optional secondary solvent; the sodium salt comprises a primary sodium salt and an optional secondary sodium salt; the primary solvent is a phosphorus-containing flame-retardant solvent, the secondary solvent is selected from at least one of carbonate solvents, carboxylate solvents and ether solvents other than fluoroethers; the molar ratio of the phosphorus-containing flame-retardant solvent to the sodium salt is 4.2-17 : 1; the mass fraction of the primary sodium salt in the sodium salt is 70-100％; the volume fraction of the primary solvent in the solvent is 80-100％; and the mass fraction of the functional additive in the electrolyte is greater than 0 and less than or equal to 5%. The present invention further provides a sodium-ion secondary battery comprising a positive electrode material, a negative electrode material, and the flame-retardant electrolyte for sodium-ion batteries of the present invention. The electrolyte of the present invention has a low cost and a high safety, and is compatible with a carbon negative electrode.

Description

钠离子电池用阻燃性电解液和钠离子二次电池Flame-retardant electrolyte solution for sodium-ion battery and sodium-ion secondary battery 技术领域technical field
本发明属于电池材料技术领域。具体地，本发明涉及一种钠离子电池用阻燃性电解液和钠离子二次电池。The invention belongs to the technical field of battery materials. Specifically, the present invention relates to a flame-retardant electrolyte solution for a sodium ion battery and a sodium ion secondary battery.
背景技术Background technique
高性能二次电池作为最高效与最便捷的能量储存与转换器件对建立清洁的能源体系和实现规模化储能至关重要。钠离子电池以其资源丰富、分布广泛和成本低廉等优势被认为是锂离子电池的有益补充，是应用于大规模储能领域的理想器件之一。近年来，对钠离子电池技术的研发得到世界各研究组的广泛关注。As the most efficient and convenient energy storage and conversion device, high-performance secondary batteries are crucial to establishing a clean energy system and realizing large-scale energy storage. Na-ion batteries are considered to be a beneficial supplement to lithium-ion batteries due to their advantages of abundant resources, wide distribution and low cost, and are one of the ideal devices for large-scale energy storage. In recent years, the research and development of sodium-ion battery technology has received extensive attention from various research groups around the world.
然而，钠离子电池存在的安全性隐患一直是人们关心的首要问题。由于钠离子电池使用的电解液为易燃的碳酸酯和/或醚类的溶剂体系，当在过充、短路或受热等条件下，钠离子电池可能发生起火、燃烧或爆炸，进而引发安全事故。However, the potential safety hazards of sodium-ion batteries have always been the primary concern of people. Since the electrolyte used in the sodium-ion battery is a flammable carbonate and/or ether solvent system, the sodium-ion battery may catch fire, burn or explode under conditions such as overcharge, short circuit or heat, which may lead to safety accidents .
CN108736010A公开了采用纯磷酸酯作为钠离子电池的电解液，以及采用磷酸盐化合物作为负极材料。该专利申请的缺点在于，其公开的电解液不能与碳负极兼容。CN108736010A discloses the use of pure phosphoric acid ester as the electrolyte of sodium ion batteries, and the use of phosphate compounds as negative electrode materials. The disadvantage of this patent application is that the electrolyte it discloses is not compatible with carbon negative electrodes.
CN110518287A公开了采用磷酸酯和氟代醚以体积比为1:1-2:1的比例作为阻燃溶剂，以及采用高氯酸钠作为钠盐。该专利申请存在的缺点在于，由于作为阻燃剂的磷酸酯的含量较低(约占溶剂的33.3％-66.6体积％)，导致该专利申请的电池虽然不可燃，但是依然不能通过穿刺测试。将大量的氟代醚作为溶剂，一方面，会导致电解液的成本升高；另一方面，通常氟代醚溶剂的蒸汽压较高，沸点低，不利于电池的封装。此外，氟代醚具有麻醉作用，例如行业中常用的1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚(Cas:16627-68-2)具有很强的急性麻醉能力。在生产过程中，要对1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚的挥发气体和残留液进行管控，以防止挥发气体和残留液对人员造成不必要的伤害。此外，氟代醚介电常数低，几乎不解离钠盐，导致以氟代醚为主溶剂的电解液电导率较低，电池的倍率性能较差。此外，将高氯酸钠作为钠盐，存在一定的安全隐患。高氯酸钠是强氧 化性产品，也是易制爆产品，使用时受到管控。CN110518287A discloses the use of phosphoric acid ester and fluoroether in a volume ratio of 1:1-2:1 as a flame retardant solvent, and sodium perchlorate as a sodium salt. The disadvantage of this patent application is that, due to the low content of phosphate ester as a flame retardant (accounting for about 33.3%-66.6% by volume of the solvent), although the battery of this patent application is non-flammable, it still cannot pass the puncture test. Using a large amount of fluoroether as a solvent, on the one hand, will lead to an increase in the cost of the electrolyte; on the other hand, usually the fluoroether solvent has a high vapor pressure and a low boiling point, which is not conducive to the packaging of the battery. In addition, fluoroethers have anesthetic effects, such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (Cas: 16627-68-2) commonly used in the industry has Strong acute anesthetic ability. In the production process, the volatile gas and residual liquid of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether should be controlled to prevent the volatile gas and residual liquid from affecting the unnecessary injury to personnel. In addition, fluoroethers have a low dielectric constant and hardly dissociate sodium salts, resulting in low conductivity of the electrolyte with fluoroethers as the main solvent and poor rate performance of the battery. In addition, using sodium perchlorate as the sodium salt has certain potential safety hazards. Sodium perchlorate is a strong oxidizing product and an explosive product, and its use is controlled.
CN108028429A公开了采用包含高浓度的碱金属盐的电解液。在该电解液中，相对于1mol碱金属盐，溶剂量为4mol以下。在该专利申请中，碱金属盐的阴离子选自氟磺酰基、三氟甲磺酰基和全氟乙磺酰基中的一种或几种。该专利申请的缺点在于，一方面，其公开的盐均为有机盐，其价格较高。此外，在该专利申请中，盐的成本约为溶剂的十倍。高盐浓度电解液造成整个电解液价格较高。高盐浓度电解液会使电解液的黏度升高，电导率下降。因此，在低温或者大电流充放电条件下，电池性能很差。此外，该专利申请只给出了金属钠与硬碳负极的性能，并没有给出硬碳负极和层状氧化物这种全电池的性能。另一方面，高盐浓度的阻燃电解液并不安全(参见，Hou J,Lu L,Wang L,et al.Thermal runaway of lithium-ion batteries employing LiN(SO 2F) 2-based concentrated electrolytes[J].Nature communications,2020,11(1):1-11)。 CN108028429A discloses the use of electrolytes containing high concentrations of alkali metal salts. In this electrolytic solution, the amount of the solvent is 4 mol or less with respect to 1 mol of the alkali metal salt. In this patent application, the anion of the alkali metal salt is selected from one or more of fluorosulfonyl, trifluoromethanesulfonyl and perfluoroethanesulfonyl. The shortcoming of this patent application is, on the one hand, its disclosed salt is all organic salt, and its price is higher. Furthermore, in this patent application, the cost of the salt is about ten times that of the solvent. Electrolyte with high salt concentration results in higher price of the whole electrolyte. Electrolyte with high salt concentration will increase the viscosity of the electrolyte and decrease the conductivity. Therefore, under low temperature or high current charge and discharge conditions, the battery performance is very poor. In addition, the patent application only gives the performance of metal sodium and hard carbon negative electrode, but does not give the performance of hard carbon negative electrode and layered oxide full battery. On the other hand, flame-retardant electrolytes with high salt concentrations are not safe (see, Hou J, Lu L, Wang L, et al. Thermal runaway of lithium-ion batteries employing LiN(SO 2 F) 2 -based concentrated electrolytes[ J]. Nature communications, 2020, 11(1):1-11).
现有技术公开了包含NaBOB(双乙二酸硼酸钠)作为钠盐的电解液(参见Mogensen R,Colbin S,Menon A S,et al.Sodium bis(oxalato)borate in trimethyl phosphate:a fire-extinguishing,fluorine-free,and low-cost electrolyte for full-cell sodium-ion batteries[J].ACS Applied Energy Materials,2020,3(5):4974-4982；以及Mogensen R,Buckel A,Colbin S,et al.A Wide-Temperature-Range,Low-Cost,Fluorine-Free Battery Electrolyte Based On Sodium Bis(Oxalate)Borate[J].Chemistry of Materials,2021,33(4):1130-1139)。由于该盐易还原，导致其阻抗较大。该电池首次循环库仑效率低，且循环过程中库仑效率小于等于99.85％。这意味着在该电池中存在明显的副反应，导致该电池循环稳定性较差。The prior art discloses electrolytes comprising NaBOB (sodium bisoxalatoborate) as the sodium salt (see Mogensen R, Colbin S, Menon A S, et al. Sodium bis(oxalato) borate in trimethyl phosphate: a fire-extinguishing , fluorine-free, and low-cost electrolyte for full-cell sodium-ion batteries[J].ACS Applied Energy Materials,2020,3(5):4974-4982; and Mogensen R, Buckel A, Colbin S, et al .A Wide-Temperature-Range,Low-Cost,Fluorine-Free Battery Electrolyte Based On Sodium Bis(Oxalate)Borate[J].Chemistry of Materials,2021,33(4):1130-1139). Since the salt is easily reduced, its impedance is relatively large. The coulombic efficiency of the battery is low for the first cycle, and the coulombic efficiency during the cycle is less than or equal to 99.85%. This means that there are obvious side reactions in the battery, resulting in poor cycle stability of the battery.
目前急需一种成本低、安全性高，且能够与碳负极兼容的电化学性能如循环性能优异的电解液。At present, there is an urgent need for an electrolyte solution with low cost, high safety, and compatible with carbon negative electrodes, such as electrochemical performance such as excellent cycle performance.
发明内容Contents of the invention
本发明的目的在于提供一种成本低、安全性高，且能够与碳负极兼容的电化学性能如循环性能优异的阻燃电解液。The purpose of the present invention is to provide a low-cost, high-safety flame-retardant electrolyte that is compatible with carbon negative electrodes and has excellent electrochemical properties such as cycle performance.
本发明的上述目的是通过以下技术方案实现的。The above object of the present invention is achieved through the following technical solutions.
第一方面，本发明提供一种钠离子电池用阻燃性电解液，其包括以下组分：In the first aspect, the present invention provides a kind of flame-retardant electrolytic solution for sodium-ion batteries, which comprises the following components:
基础电解液和功能添加剂；其中，Basic electrolyte and functional additives; among them,
所述基础电解液包含溶剂和钠盐；所述溶剂包含主溶剂和任选的次溶剂；所述钠盐包含主钠盐和任选的次钠盐；所述主溶剂为含磷阻燃性溶剂，所述次溶剂选自碳酸酯溶剂、羧酸酯溶剂和非氟代醚的醚类溶剂中的至少一种，所述主钠盐为六氟磷酸钠和四氟硼酸钠，所述次钠盐选自双三氟甲基磺酰亚胺钠、双氟磺酰亚胺钠、双三氟甲烷磺酸钠、三氟甲基磺酸钠和高氯酸钠中的一种或几种；The basic electrolyte includes a solvent and a sodium salt; the solvent includes a main solvent and an optional secondary solvent; the sodium salt includes a main sodium salt and an optional second sodium salt; the main solvent is a phosphorus-containing flame retardant Solvent, the secondary solvent is selected from at least one of carbonate solvents, carboxylate solvents and non-fluorinated ether ether solvents, the main sodium salt is sodium hexafluorophosphate and sodium tetrafluoroborate, the secondary The sodium salt is selected from one or more of sodium bistrifluoromethanesulfonimide, sodium bisfluorosulfonimide, sodium bistrifluoromethanesulfonate, sodium trifluoromethanesulfonate and sodium perchlorate ;
所述含磷阻燃性溶剂与钠盐的摩尔比为4.2-17:1，优选为5-10:1，更优选为7-9:1；所述主钠盐占钠盐的质量分数为70％-100％；The molar ratio of the phosphorus-containing flame retardant solvent to the sodium salt is 4.2-17:1, preferably 5-10:1, more preferably 7-9:1; the mass fraction of the main sodium salt in the sodium salt is 70%-100%;
所述主溶剂占所述溶剂的体积分数为80％-100％，更优选为100％；The volume fraction of the main solvent in the solvent is 80%-100%, more preferably 100%;
所述功能添加剂占所述电解液的质量分数为大于0且小于等于5％，优选为1％-3％。The mass fraction of the functional additive in the electrolyte is greater than 0 and less than or equal to 5%, preferably 1%-3%.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述含磷阻燃性溶剂为化学式为(RO) 3P＝O的磷酸酯或化学式为R(RO 2)P＝O的膦酸酯，其中R为苯基或碳链长度为1-6的低碳数烷基或卤代烷基。 Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the phosphorus-containing flame-retardant solvent is a phosphate ester with a chemical formula of (RO) 3 P=O or a chemical formula of R(RO 2 )P Phosphonate of =O, wherein R is phenyl or a lower alkyl or haloalkyl group with a carbon chain length of 1-6.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述磷酸酯或膦酸酯选自磷酸三苯酯(TPP)、磷酸三甲酯(TMP)、磷酸三乙酯(TEP)、甲基膦酸二甲酯(DMMP)和双(2,2,2-三氟乙基)甲基磷酸酯(TFMP)中的一种或几种。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the phosphoric acid ester or phosphonic acid ester is selected from triphenyl phosphate (TPP), trimethyl phosphate (TMP), triethyl phosphate One or more of (TEP), dimethyl methylphosphonate (DMMP) and bis(2,2,2-trifluoroethyl)methylphosphate (TFMP).
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述六氟磷酸钠和四氟硼酸钠的摩尔比为1:50-50:1，更优选为1:11-11:1。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the molar ratio of sodium hexafluorophosphate and sodium tetrafluoroborate is 1:50-50:1, more preferably 1:11- 11:1.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述碳酸酯溶剂为环状碳酸酯溶剂和/或链状碳酸酯溶剂。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the carbonate solvent is a cyclic carbonate solvent and/or a chain carbonate solvent.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述环状碳酸酯为碳酸乙烯酯和/或碳酸丙烯酯。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the cyclic carbonate is ethylene carbonate and/or propylene carbonate.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述链状碳酸酯为碳数为3-8的直链或支链脂肪单醇与碳酸合成的碳酸酯。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the chain carbonate is a carbonate synthesized from a straight-chain or branched fatty monoalcohol with a carbon number of 3-8 and carbonic acid.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述链状碳酸酯选自碳酸二甲酯、碳酸二乙酯、碳酸二丙酯和碳酸甲基乙基酯中的一种或几种。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the chain carbonate is selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate and methyl ethyl carbonate one or more of.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述羧酸酯溶剂为环状羧酸酯溶剂和/或链状羧酸酯溶剂。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the carboxylate solvent is a cyclic carboxylate solvent and/or a chain carboxylate solvent.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述环状羧酸酯为γ-丁内酯，所述链状碳酸酯为碳数为3-8的链状羧酸酯。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the cyclic carboxylic acid ester is γ-butyrolactone, and the chain carbonate is a chain with 3-8 carbon atoms. Carboxylate.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述链状羧酸酯选自乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸丙酯和丙酸乙酯中的一种或几种。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the chain carboxylate is selected from methyl acetate, ethyl acetate, propyl acetate, propyl propionate and ethyl propionate one or more of them.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述非氟代醚的醚类选自四氢呋喃、2-甲基四氢呋喃、1,3-二氧环戊烷、二甲氧基甲烷、1,2-二甲氧基乙烷、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚和四乙二醇二甲醚中的一种或几种。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the ethers of non-fluorinated ethers are selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, di One of methoxymethane, 1,2-dimethoxyethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether or several.
优选地，在本发明所述的钠离子电池用阻燃性电解液中，所述功能添加剂选自、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、1,3-丙磺酸内酯(PS)、1,4-丁磺酸内酯、丙烯基-1,3-磺酸内酯(PST)、环己基苯、叔丁基苯、叔戊基苯、硫酸乙烯酯、亚硫酸二甲酯、亚硫酸二乙酯和丁二腈中的一种或几种中的一种或几种。Preferably, in the flame-retardant electrolyte solution for sodium-ion batteries of the present invention, the functional additive is selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, 1,3-propane sultone (PS ), 1,4-butane sultone, propenyl-1,3-sultone (PST), cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, vinyl sulfate, dimethyl sulfite , one or more of one or more of diethyl sulfite and succinonitrile.
第二方面，本发明提供一种钠离子二次电池，其包括正极材料、负极材料和本发明的钠离子电池用阻燃性电解液。In a second aspect, the present invention provides a sodium-ion secondary battery, which includes a positive electrode material, a negative electrode material and the flame-retardant electrolyte solution for a sodium-ion battery of the present invention.
优选地，在本发明所述的钠离子二次电池中，所述正极材料为层状金属氧化物、聚阴离子类正极材料或普鲁士蓝类材料，所述负极材料为碳类材料。Preferably, in the sodium ion secondary battery of the present invention, the positive electrode material is layered metal oxide, polyanion positive electrode material or Prussian blue material, and the negative electrode material is carbon material.
优选地，在本发明所述的钠离子二次电池中，所述正极材料为层状金属氧化物，所述负极材料为硬碳。Preferably, in the sodium ion secondary battery of the present invention, the positive electrode material is a layered metal oxide, and the negative electrode material is hard carbon.
本申请的发明人出乎意料的发现，当钠盐为本发明要求保护的六氟磷酸钠和四氟硼酸钠以及任选地少量的次钠盐，并且当溶剂为本发明要求保护的主溶剂和次溶剂的种类和用量时，仅仅采用较低浓度的钠盐而不需要采用更高浓度的钠盐，就可以实现成本低、安全性高，且能够与碳负极兼容的电化学性能如循环性能优异的电解液。The inventors of the present application have unexpectedly found that when the sodium salt is sodium hexafluorophosphate and sodium tetrafluoroborate and optionally a small amount of hyposodium salt as claimed in the present invention, and when the solvent is the main solvent claimed in the present invention When the type and amount of the secondary solvent are used, only using a lower concentration of sodium salt instead of a higher concentration of sodium salt can achieve low cost, high safety, and electrochemical performance compatible with carbon negative electrodes such as cycling Electrolyte with excellent performance.
本发明具有如下有益效果：The present invention has following beneficial effects:
本发明的钠离子二次电池安全性能高、电化学性能如循环性能优异。本发明的钠离子二次电池在室温循环过程中的平均库仑效率大于99.9％。在电池滥用或意外伤害(如，穿刺)等状况下，本发明的钠离子二次电池能降低或者避免着火的风险。The sodium ion secondary battery of the invention has high safety performance and excellent electrochemical performance such as cycle performance. The average coulombic efficiency of the sodium ion secondary battery of the present invention is greater than 99.9% in the cycle process at room temperature. Under conditions such as battery abuse or accidental injury (eg, puncture), the sodium ion secondary battery of the present invention can reduce or avoid the risk of fire.
在常规浓度的钠盐下，本发明的电解液实现了阻燃电解液与碳负极的 兼容性。本发明的钠离子二次电池的工业利用价值极高。Under the normal concentration of sodium salt, the electrolyte of the present invention realizes the compatibility of the flame retardant electrolyte and the carbon negative electrode. The industrial utilization value of the sodium ion secondary battery of the present invention is extremely high.
本发明的电解液成本低、安全性高，且能够与碳负极兼容。The electrolyte solution of the invention has low cost, high safety, and is compatible with carbon negative electrodes.
附图的简要说明Brief description of the drawings
以下，结合附图来详细说明本发明的实施方案，其中：Below, describe embodiment of the present invention in detail in conjunction with accompanying drawing, wherein:
图1是实施例1的电池在室温下的前两圈的充放电曲线图；Fig. 1 is the charge-discharge curve diagram of the first two laps of the battery of Example 1 at room temperature;
图2是实施例1和对比例1的电池在室温下的循环性能对比图；Fig. 2 is the comparison chart of the cycle performance of the batteries of Example 1 and Comparative Example 1 at room temperature;
图3是实施例1和对比例1的电池在室温下的循环过程中的库仑效率对比图；Fig. 3 is the coulombic efficiency comparison diagram of the batteries of Example 1 and Comparative Example 1 during the cycle at room temperature;
图4是实施例1和对比例1的电池在高温下的循环过程中的库仑效率对比图；Fig. 4 is a comparison chart of the Coulombic efficiency of the batteries of Example 1 and Comparative Example 1 during cycling at high temperature;
图5是实施例2的电池在室温下的前两圈的充放电曲线图；Fig. 5 is the charge-discharge curve diagram of the first two cycles of the battery of Example 2 at room temperature;
图6是实施例3的电池在室温下的前两圈的充放电曲线图；Fig. 6 is the charge-discharge curve diagram of the first two cycles of the battery of Example 3 at room temperature;
图7是实施例14的电池在室温下的前两圈的充放电曲线图；Fig. 7 is the charge-discharge curve diagram of the first two laps of the battery of Example 14 at room temperature;
图8是实施例17的电池在室温下的前两圈的充放电曲线图；Fig. 8 is the charge-discharge curve diagram of the first two cycles of the battery of Example 17 at room temperature;
图9是实施例19的电池在室温下的前两圈的充放电曲线图；Fig. 9 is the charge-discharge curve diagram of the first two cycles of the battery of Example 19 at room temperature;
图10是实施例23的电池在室温下的前两圈的充放电曲线图；Fig. 10 is the charge-discharge curve diagram of the first two cycles of the battery of Example 23 at room temperature;
图11是实施例27的电池在室温下的前两圈的充放电曲线图。Fig. 11 is the charge and discharge curves of the first two cycles of the battery of Example 27 at room temperature.
实施发明的最佳方式The best way to practice the invention
下面结合具体实施方式对本发明进行进一步的详细描述，给出的实施例仅为了阐明本发明，而不是为了限制本发明的范围。The present invention will be further described in detail below in conjunction with specific embodiments, and the given examples are only for clarifying the present invention, not for limiting the scope of the present invention.
O3-Na[Cu 1/9Ni 2/9Fe 1/3Mn 1/3]O 2为正极活性物质，乙炔黑为导电剂，聚四氟乙烯为粘结剂，并按质量比为90:6:4的比例混合均匀。然后，加入N-甲基吡咯烷酮并调成浆料。将浆料涂覆于铝箔上。于120℃下，真空干燥过夜。滚压后即可得到正极极片。以硬碳为负极活性物质，乙炔黑为导电剂，聚四氟乙烯为粘结剂，并按质量比为90:5:5的比例混合均匀。然后，加入N-甲基吡咯烷酮并调成浆料。将浆料涂覆于铝箔上，于120℃下，真空干燥过夜。滚压后即可得到负极极片。 O3-Na[Cu 1/9 Ni 2/9 Fe 1/3 Mn 1/3 ]O 2 is the positive electrode active material, acetylene black is the conductive agent, and polytetrafluoroethylene is the binder, and the mass ratio is 90: The ratio of 6:4 is mixed well. Then, N-methylpyrrolidone was added and slurried. Spread the slurry on aluminum foil. At 120°C, vacuum dry overnight. After rolling, the positive electrode sheet can be obtained. Hard carbon is used as the negative electrode active material, acetylene black is used as the conductive agent, and polytetrafluoroethylene is used as the binder, and they are mixed uniformly at a mass ratio of 90:5:5. Then, N-methylpyrrolidone was added and slurried. The slurry was coated on an aluminum foil and dried under vacuum overnight at 120°C. After rolling, the negative electrode sheet can be obtained.
电解液的配置：在充满氩气的手套箱中，分别按照表1的数据称取主钠盐和任选的次钠盐。然后，加入一定体积的溶剂。搅拌充分后，得到所制备的电解液。注意，绝大部分盐能够完全溶解。对比例中部分钠盐未完 全溶解。当对比例中部分钠盐未完全溶解时，取上层饱和溶液作为电解液。Electrolyte configuration: In a glove box filled with argon, weigh the main sodium salt and the optional secondary sodium salt according to the data in Table 1, respectively. Then, a certain volume of solvent is added. After sufficient stirring, the prepared electrolyte solution was obtained. Note that most salts dissolve completely. Part of the sodium salt was not completely dissolved in the comparative example. When part of the sodium salt was not completely dissolved in the comparative example, the upper layer saturated solution was used as the electrolyte.
表1中的英文缩写分别为：The English abbreviations in Table 1 are:
TMP：磷酸三甲酯；TEP：磷酸三乙酯；DEC：碳酸二乙酯；EC：碳酸乙烯酯；EP：乙酸丙酯；DEGDME：二乙二醇二甲醚；HFE：1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚；VC：碳酸亚乙烯酯；PS：1,3-丙磺酸内酯；PC：碳酸丙烯酯；FEC：氟代碳酸乙烯酯；DTD：硫酸亚乙酯；VEC：碳酸乙烯亚乙酯。TMP: Trimethyl phosphate; TEP: Triethyl phosphate; DEC: Diethyl carbonate; EC: Ethylene carbonate; EP: Propyl acetate; DEGDME: Diethylene glycol dimethyl ether; HFE: 1,1,2 ,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether; VC: vinylene carbonate; PS: 1,3-propane sultone; PC: propylene carbonate; FEC: fluorine ethylene carbonate; DTD: ethylene sulfate; VEC: ethylene carbonate.
表1Table 1
Figure PCTCN2021111495-appb-000001
Figure PCTCN2021111495-appb-000001
Figure PCTCN2021111495-appb-000002
Figure PCTCN2021111495-appb-000002
Figure PCTCN2021111495-appb-000003
Figure PCTCN2021111495-appb-000003
图1是实施例1的电池在室温下的首次充放电曲线。图1示出了在硬碳/O3-Na[Cu 1/9Ni 2/9Fe 1/3Mn 1/3]O 2全电池中，0.1C倍率(1C＝100mA/g)下的首次充放电曲线。图1、图5-图11示出了基于本发明的电解液，在全电池中，放电比容量大于120mAh/g(基于正极)，首次库仑效率较高(约85％)。 Fig. 1 is the first charge and discharge curve of the battery of Example 1 at room temperature. Figure 1 shows the first charge at 0.1C rate (1C = 100mA/g) in a hard carbon/O3-Na[Cu1 / 9Ni2/ 9Fe1/ 3Mn1/3 ] O2 full cell discharge curve. Fig. 1, Fig. 5-Fig. 11 show the electrolyte solution based on the present invention, in the full battery, the discharge specific capacity is greater than 120mAh/g (based on the positive electrode), and the first coulombic efficiency is higher (about 85%).
图2是实施例1和对比例1的电池在室温下的循环性能对比图。图2示出了实施例1的电池的首次放电比容量为129mAh/g，首次库仑效率达84.7％且循环180次容量保持率为92.7％。对比例1的电池循环150次容量保持率为71.7％。FIG. 2 is a comparison chart of the cycle performance of the batteries of Example 1 and Comparative Example 1 at room temperature. Fig. 2 shows that the first discharge specific capacity of the battery of Example 1 is 129mAh/g, the first coulombic efficiency reaches 84.7%, and the capacity retention rate after 180 cycles is 92.7%. The battery of Comparative Example 1 has a capacity retention rate of 71.7% after 150 cycles.
图3是实施例1和对比例1的电池在室温下的循环过程中的库仑效率对比图。对比例1的常规电解液从第四圈开始的平均库伦效率为99.75％。与之相比，实施例1的阻燃电解液从第四圈开始的平均库仑效率为99.995％。对比例1的电池的循环库仑效率与实施例1的电池的循环库仑效率相比，对比例1的电池的循环库仑效率较低。这表明实施例1的阻燃电解液存在较少的副反应。Fig. 3 is a graph comparing Coulombic efficiencies of the batteries of Example 1 and Comparative Example 1 during cycling at room temperature. The average coulombic efficiency of the conventional electrolyte of Comparative Example 1 from the fourth cycle was 99.75%. In comparison, the average Coulombic efficiency of the flame-retardant electrolyte of Example 1 from the fourth cycle is 99.995%. The cycle Coulombic efficiency of the battery of Comparative Example 1 is lower than that of the battery of Example 1, and the cycle Coulombic efficiency of the battery of Comparative Example 1 is lower. This shows that the flame retardant electrolyte of Example 1 has less side reactions.
将实施例1-29采用的阻燃电解液与对比例1、对比例2的电解液，注入圆柱型电芯(容量为2.5Ah)。电芯循环2圈，在满电的状态下，实施针刺实验。刺入过程中，实施例1-29电池不冒烟，不起火，不爆炸。对比例1及对比例2的电池刺入过程中，冒出浓烟，存在安全隐患。此对比说明较高含量的阻燃剂(占溶剂的体积分数在80％以上)，电池安全性能较高，较低含量(占溶剂的体积分数小于等于68％)电池安全性能较差。实际电解液中含量大于30％的阻燃剂，可使电解也不燃烧(Wang X,Yasukawa E,Kasuya S.Nonflammable trimethyl phosphate solvent-containing electrolytes for lithium-ion batteries:I.Fundamental properties[J].Journal of The Electrochemical Society,2001,148(10):A1058)。实际电解液不燃烧，并不代表电池不会发生热失控。The flame-retardant electrolyte used in Examples 1-29 and the electrolytes of Comparative Example 1 and Comparative Example 2 were injected into cylindrical cells (with a capacity of 2.5 Ah). The battery was cycled for 2 laps, and the acupuncture experiment was carried out in a fully charged state. During the piercing process, the batteries of Examples 1-29 did not smoke, catch fire, or explode. During the piercing process of the batteries of Comparative Example 1 and Comparative Example 2, thick smoke came out, posing a safety hazard. This comparison shows that a higher content of flame retardant (accounting for more than 80% of the volume fraction of the solvent) has higher battery safety performance, and a lower content (accounting for less than or equal to 68% of the volume fraction of the solvent) of the battery has poor safety performance. A flame retardant with a content greater than 30% in the actual electrolyte can prevent electrolysis from burning (Wang X, Yasukawa E, Kasuya S. Nonflammable trimethyl phosphate solvent-containing electrolytes for lithium-ion batteries: I. Fundamental properties[J]. Journal of The Electrochemical Society, 2001, 148(10):A1058). The fact that the actual electrolyte does not burn does not mean that the battery will not experience thermal runaway.
实施例1-13显示了不同摩尔比例的NaBF 4和NaPF 6的电解液的性能。当NaBF 4与NaPF 6的摩尔比在50:1至1:50时，电池循环100圈后具有非常高的容量保持率(84.4％-95％)，当NaBF 4与NaPF 6的摩尔比在11:1至1:11时，电池循环100圈后具有更高的容量保持率(88.6％-95％)。 Examples 1-13 show the performance of electrolytes with different molar ratios of NaBF 4 and NaPF 6 . When the molar ratio of NaBF 4 to NaPF 6 is 50:1 to 1:50, the battery has a very high capacity retention rate (84.4%-95%) after 100 cycles, and when the molar ratio of NaBF 4 to NaPF 6 is 11 From :1 to 1:11, the battery has a higher capacity retention rate (88.6%-95%) after 100 cycles.
对比例3显示单纯采用NaPF 6盐的电解液，电池循环稳定性很差，并且100圈容量保持率仅为35％。 Comparative example 3 shows that the electrolyte solution using only NaPF 6 salt has poor cycle stability, and the 100-cycle capacity retention rate is only 35%.
对比例4显示单纯采用NaBF 4盐的电解液(该电解液会有少量的NaBF 4析出，因此，取上层清液作为电解液)，电池循环稳定性很差，并 且100圈容量保持率仅为60％。 Comparative example 4 shows that only adopts the electrolyte of NaBF 4 salt (this electrolyte will have a small amount of NaBF 4 separate out, therefore, get supernatant liquid as electrolyte), battery cycle stability is very poor, and 100 laps capacity retention rate is only 60%.
对比例5显示当NaBF 4与NaPF 6的摩尔比为1:59时，电池循环100圈容量保持率仅为65％。 Comparative Example 5 shows that when the molar ratio of NaBF 4 to NaPF 6 is 1:59, the capacity retention rate of the battery after 100 cycles is only 65%.
对比例6显示当NaBF 4与NaPF 6的摩尔比为54.6:1时，电池循环100圈容量保持率仅为66％。 Comparative Example 6 shows that when the molar ratio of NaBF 4 to NaPF 6 is 54.6:1, the capacity retention rate of the battery after 100 cycles is only 66%.
实施例14-18显示，当采用合适的混合钠盐时，以纯阻燃剂TEP为溶剂，电池循环100次，电池的容量保持率也依然大于85％。Examples 14-18 show that when a suitable mixed sodium salt is used, the pure flame retardant TEP is used as a solvent, and the battery is cycled 100 times, and the capacity retention rate of the battery is still greater than 85%.
实施例19-24显示，当其他溶剂为碳酸酯(如EC、DEC)、羧酸酯(如EP)、非氟代醚类(DEGDME)时，电池循环性能稳定并且容量保持率较高。Examples 19-24 show that when other solvents are carbonates (such as EC, DEC), carboxylates (such as EP), and non-fluorinated ethers (DEGDME), the battery cycle performance is stable and the capacity retention rate is high.
对比例9显示，当其他溶剂选用氟代醚，例如1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚占总溶剂的体积分数为10％时，电池循环100周，容量保持率仅为74％。对比例9的电池性能较差。不希望受理论束缚，对比例9性能较差的原因可能是氟代醚也可以作为一种成膜添加剂，当氟代醚与NaPF 6和NaBF 4组合使用时，并不能形成稳定的界面膜。 Comparative Example 9 shows that when other solvents are selected from fluoroethers, such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, when the volume fraction of the total solvent is 10% , The battery cycle is 100 cycles, and the capacity retention rate is only 74%. The performance of the battery of Comparative Example 9 was poor. Without wishing to be bound by theory, the reason for the poorer performance of Comparative Example 9 may be that the fluoroether can also act as a film-forming additive, and when the fluoroether was used in combination with NaPF6 and NaBF4 , a stable interfacial film could not be formed.
实施例25-27显示，当采用NaPF 6和NaBF 4为主钠盐，搭配其他少量的钠盐，例如NaFSI、NaClO 4、NaCF 3SO 3时，电池依然保持了很好的循环稳定性。 Examples 25-27 show that when NaPF 6 and NaBF 4 are used as the main sodium salts and other small amounts of sodium salts, such as NaFSI, NaClO 4 , and NaCF 3 SO 3 , the battery still maintains good cycle stability.
对比例6-8显示，当选择其他的盐搭配，例如NaPF 6+NaClO 4或者NaBF 4+NaClO 4时，电池循环稳定性较差。这充分证明了，以NaPF 6和NaBF 4为主钠盐的优越性。 Comparative examples 6-8 show that when other salt combinations are selected, such as NaPF 6 +NaClO 4 or NaBF 4 +NaClO 4 , the cycle stability of the battery is poor. This fully proves the superiority of NaPF 6 and NaBF 4 as main sodium salts.
实施例28-29显示，当采用NaPF 6和NaBF 4作为主钠盐时，即使钠盐的浓度较低，电池依然保持很好的循环稳定性。 Examples 28-29 show that when NaPF 6 and NaBF 4 are used as the main sodium salt, even if the concentration of the sodium salt is low, the battery still maintains good cycle stability.
实施例30-35显示，当采用NaPF 6和NaBF 4作为主钠盐时，选择本领域内常用的添加剂(如VC、FEC、VEC、DTD、PS)，电池依然保持很好的循环稳定性。 Examples 30-35 show that when NaPF 6 and NaBF 4 are used as the main sodium salt, and additives commonly used in this field (such as VC, FEC, VEC, DTD, PS) are selected, the battery still maintains good cycle stability.
图4是实施例1和对比例1的电池在高温下的循环过程中的库仑效率对比图。将实施例1中的电解液在60℃的高温下循环100次，电池的容量保持率为84％，平均库仑效率为99.87％。将对比例1中的电解液在60℃的高温下循环100次，电池的容量保持率为75％，平均库仑效率为98.79％。可以看出，本发明的电解液具有很好的高温性能。FIG. 4 is a comparison chart of Coulombic efficiencies of the batteries of Example 1 and Comparative Example 1 during cycling at high temperature. The electrolyte in Example 1 was cycled 100 times at a high temperature of 60° C., the capacity retention rate of the battery was 84%, and the average Coulombic efficiency was 99.87%. The electrolyte in Comparative Example 1 was cycled 100 times at a high temperature of 60° C., the capacity retention rate of the battery was 75%, and the average Coulombic efficiency was 98.79%. It can be seen that the electrolyte solution of the present invention has good high temperature performance.

Claims (10)

  1. 一种钠离子电池用阻燃性电解液，其包括以下组分：A kind of flame-retardant electrolytic solution for sodium ion battery, it comprises following components:
    基础电解液和功能添加剂；其中，Basic electrolyte and functional additives; among them,
    所述基础电解液包含溶剂和钠盐；所述溶剂包含主溶剂和任选的次溶剂；所述钠盐包含主钠盐和任选的次钠盐；所述主溶剂为含磷阻燃性溶剂，所述次溶剂选自碳酸酯溶剂、羧酸酯溶剂和非氟代醚的醚类溶剂中的至少一种，所述主钠盐为六氟磷酸钠和四氟硼酸钠，所述次钠盐选自双三氟甲基磺酰亚胺钠、双氟磺酰亚胺钠、双三氟甲烷磺酸钠、三氟甲基磺酸钠和高氯酸钠中的一种或几种；The basic electrolyte includes a solvent and a sodium salt; the solvent includes a main solvent and an optional secondary solvent; the sodium salt includes a main sodium salt and an optional second sodium salt; the main solvent is a phosphorus-containing flame retardant Solvent, the secondary solvent is selected from at least one of carbonate solvents, carboxylate solvents and non-fluorinated ether ether solvents, the main sodium salt is sodium hexafluorophosphate and sodium tetrafluoroborate, the secondary The sodium salt is selected from one or more of sodium bistrifluoromethanesulfonimide, sodium bisfluorosulfonimide, sodium bistrifluoromethanesulfonate, sodium trifluoromethanesulfonate and sodium perchlorate ;
    所述含磷阻燃性溶剂与钠盐的摩尔比4.2-17:1；所述主钠盐占钠盐的质量分数为70％-100％；The molar ratio of the phosphorus-containing flame-retardant solvent to the sodium salt is 4.2-17:1; the mass fraction of the main sodium salt in the sodium salt is 70%-100%;
    所述主溶剂占所述溶剂的体积分数为80％-100％；The volume fraction of the main solvent in the solvent is 80%-100%;
    所述功能添加剂占所述电解液的质量分数为大于0且小于等于5％。The mass fraction of the functional additive in the electrolyte is greater than 0 and less than or equal to 5%.
  2. 根据权利要求1所述的钠离子电池用阻燃性电解液，其中，所述含磷阻燃性溶剂为化学式为(RO) 3P＝O的磷酸酯或化学式为R(RO 2)P＝O的膦酸酯，其中R为苯基或碳链长度为1-6的低碳数烷基或卤代烷基。 The flame-retardant electrolyte solution for sodium-ion batteries according to claim 1, wherein the phosphorus-containing flame-retardant solvent is a phosphoric acid ester with a chemical formula of (RO) 3 P=O or a chemical formula of R(RO 2 )P= A phosphonate of O, wherein R is phenyl or a lower alkyl or haloalkyl group with a carbon chain length of 1-6.
  3. 根据权利要求1所述的钠离子电池用阻燃性电解液，其中，所述磷酸酯或膦酸酯选自磷酸三苯酯、磷酸三甲酯、磷酸三乙酯、磷酸三丙酯、磷酸三丁酯、甲基膦酸二甲酯和双(2,2,2-三氟乙基)甲基磷酸酯中的一种或几种。The flame-retardant electrolyte solution for sodium-ion batteries according to claim 1, wherein, the phosphoric acid ester or phosphonic acid ester is selected from triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, phosphoric acid One or more of tributyl ester, dimethyl methyl phosphonate and bis(2,2,2-trifluoroethyl) methyl phosphate.
  4. 根据权利要求1所述的钠离子电池用阻燃性电解液，其中，所述六氟磷酸钠和四氟硼酸钠的摩尔比为1:50-50:1，优选为1:11-11:1。Flame-retardant electrolytic solution for sodium ion battery according to claim 1, wherein, the mol ratio of described sodium hexafluorophosphate and sodium tetrafluoroborate is 1:50-50:1, preferably 1:11-11: 1.
  5. 根据权利要求1所述的钠离子电池用阻燃性电解液，其中，所述碳酸酯溶剂为环状碳酸酯溶剂和/或链状碳酸酯溶剂；The flame-retardant electrolytic solution for sodium-ion batteries according to claim 1, wherein the carbonate solvent is a cyclic carbonate solvent and/or a chain carbonate solvent;
    优选地，所述环状碳酸酯为碳酸乙烯酯和/或碳酸丙烯酯；Preferably, the cyclic carbonate is ethylene carbonate and/or propylene carbonate;
    优选地，所述链状碳酸酯为碳数为3-8的直链或支链脂肪单醇与碳酸合成的碳酸酯；Preferably, the chain carbonate is a carbonate synthesized from a straight-chain or branched fatty monoalcohol and carbonic acid with a carbon number of 3-8;
    优选地，所述链状碳酸酯选自碳酸二甲酯、碳酸二乙酯、碳酸二丙酯和碳酸甲基乙基酯中的一种或几种。Preferably, the chain carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate, dipropyl carbonate and methyl ethyl carbonate.
  6. 根据权利要求1所述的钠离子电池用阻燃性电解液，其中，所述羧酸酯溶剂为环状羧酸酯溶剂和/或链状羧酸酯溶剂。The flame-retardant electrolyte solution for sodium-ion batteries according to claim 1, wherein the carboxylate solvent is a cyclic carboxylate solvent and/or a chain carboxylate solvent.
  7. 根据权利要求6所述的钠离子电池用阻燃性电解液，其中，所述环 状羧酸酯为γ-丁内酯，所述链状碳酸酯为碳数为3-8的链状羧酸酯；The flame-retardant electrolyte solution for sodium-ion batteries according to claim 6, wherein the cyclic carboxylic acid ester is gamma-butyrolactone, and the chain carbonic acid ester is a chain carboxylate with a carbon number of 3-8. acid ester;
    优选地，所述链状羧酸酯选自乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸丙酯和丙酸乙酯中的一种或几种。Preferably, the chain carboxylate is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, propyl propionate and ethyl propionate.
  8. 根据权利要求1所述的钠离子电池用阻燃性电解液，其中，所述非氟代醚的醚类选自四氢呋喃、2-甲基四氢呋喃、1,3-二氧环戊烷、二甲氧基甲烷、1,2-二甲氧基乙烷、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚和四乙二醇二甲醚中的一种或几种；The flame-retardant electrolyte solution for sodium-ion batteries according to claim 1, wherein the ethers of said non-fluorinated ethers are selected from tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, dimethyl One of oxymethane, 1,2-dimethoxyethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether or Several;
    优选地，所述功能添加剂选自碳酸乙烯亚乙酯、氟代碳酸乙烯酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、丙烯基-1,3-磺酸内酯、环己基苯、叔丁基苯、叔戊基苯、硫酸乙烯酯、亚硫酸二甲酯、亚硫酸二乙酯和丁二腈中的一种或几种。Preferably, the functional additive is selected from ethylene carbonate, fluoroethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, propenyl-1,3-sulfonic acid One or more of lactone, cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, vinyl sulfate, dimethyl sulfite, diethyl sulfite and succinonitrile.
  9. 一种钠离子二次电池，其包括正极材料、负极材料和权利要求1-8中任一项所述的钠离子电池用阻燃性电解液。A sodium-ion secondary battery, comprising a positive electrode material, a negative electrode material and the flame-retardant electrolyte for a sodium-ion battery according to any one of claims 1-8.
  10. 根据权利要求9所述的钠离子二次电池，其中，所述正极材料为层状金属氧化物、聚阴离子类正极材料或普鲁士蓝类材料，所述负极材料为碳类材料；The sodium ion secondary battery according to claim 9, wherein the positive electrode material is a layered metal oxide, a polyanionic positive electrode material or a Prussian blue material, and the negative electrode material is a carbon material;
    优选地，所述正极材料为层状金属氧化物，所述负极材料为硬碳。Preferably, the positive electrode material is layered metal oxide, and the negative electrode material is hard carbon.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115954551A (en) * 2023-03-10 2023-04-11 四川易纳能新能源科技有限公司 Sodium ion battery electrolyte, preparation method thereof and sodium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105655631A (en) * 2016-03-30 2016-06-08 武汉大学 Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery
CN105789683A (en) * 2016-03-22 2016-07-20 山东大学 Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor
US20180358654A1 (en) * 2015-11-30 2018-12-13 Deakin University Sodium-ion electrolyte composition
CN113140723A (en) * 2021-03-02 2021-07-20 复旦大学 Wide-temperature-range sodium ion battery based on metal bismuth cathode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180358654A1 (en) * 2015-11-30 2018-12-13 Deakin University Sodium-ion electrolyte composition
CN105789683A (en) * 2016-03-22 2016-07-20 山东大学 Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor
CN105655631A (en) * 2016-03-30 2016-06-08 武汉大学 Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery
CN113140723A (en) * 2021-03-02 2021-07-20 复旦大学 Wide-temperature-range sodium ion battery based on metal bismuth cathode

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115954551A (en) * 2023-03-10 2023-04-11 四川易纳能新能源科技有限公司 Sodium ion battery electrolyte, preparation method thereof and sodium ion battery
CN115954551B (en) * 2023-03-10 2023-05-23 四川易纳能新能源科技有限公司 Sodium ion battery electrolyte, preparation method thereof and sodium ion battery

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