WO2023221113A1 - 电解质、二次电池、电池模块、电池包和用电装置 - Google Patents

电解质、二次电池、电池模块、电池包和用电装置 Download PDF

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WO2023221113A1
WO2023221113A1 PCT/CN2022/094196 CN2022094196W WO2023221113A1 WO 2023221113 A1 WO2023221113 A1 WO 2023221113A1 CN 2022094196 W CN2022094196 W CN 2022094196W WO 2023221113 A1 WO2023221113 A1 WO 2023221113A1
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orthocarbonate
lithium
electrolyte
battery
oxide
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PCT/CN2022/094196
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English (en)
French (fr)
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王瀚森
刘成勇
黄圣源
胡波兵
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宁德时代新能源科技股份有限公司
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Priority to CN202280056212.4A priority Critical patent/CN117941117A/zh
Priority to PCT/CN2022/094196 priority patent/WO2023221113A1/zh
Publication of WO2023221113A1 publication Critical patent/WO2023221113A1/zh

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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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 application relates to the field of batteries, specifically to an electrolyte, a secondary battery, a battery module, a battery pack and an electrical device.
  • Secondary batteries have the characteristics of high capacity and long life, so they are widely used in electronic equipment, such as mobile phones, laptop computers, battery cars, electric cars, electric airplanes, electric ships, electric toy cars, electric toy ships, electric toy airplanes and electric tools etc. As secondary batteries have made great progress, higher requirements have been placed on the performance of secondary batteries. In order to improve the performance of secondary batteries, materials such as electrolytes in secondary batteries are usually optimized and improved. As a transport medium for metal ions in secondary batteries, electrolytes have a non-negligible impact on the performance of secondary batteries.
  • This application was made in view of the above-mentioned problems, and its purpose is to provide an electrolyte, a secondary battery, a battery module, a battery pack, and a power consumption device.
  • a first aspect of the present application provides an electrolyte for a secondary battery.
  • the electrolyte includes a crystal-plastic composite.
  • the crystal-plastic composite includes orthocarbonate and lithium salt.
  • the orthocarbonate includes the compound represented by Formula I. one or more,
  • R1 to R4 each independently represents an alkyl group or a haloalkyl group.
  • orthocarbonate and lithium salt form a crystal-plastic composite, which can improve the ionic conductivity of the electrolyte.
  • the wetting performance between the electrolyte and the positive electrode piece and/or the negative electrode piece is better, and due to its relatively high oxidation stability, it can match the high-voltage positive electrode piece, thereby improving Cycling performance of secondary batteries. Since the solid electrolyte is not prone to combustion, the safety performance of the secondary battery can be ensured.
  • alkyl is C1-C10 alkyl.
  • the mutual solubility of this type of orthocarbonate and lithium salt is relatively better, which is conducive to the formation of a crystal-plastic composite.
  • the haloalkyl group is C1-C10 haloalkyl.
  • the mutual solubility of this type of orthocarbonate and lithium salt is relatively better, which is conducive to the formation of a crystal-plastic composite.
  • haloalkyl is fluoroalkyl. Due to the strong electron-attracting effect of the fluorine group, the oxidation of the electrolyte can be further inhibited and its electrochemical window can be improved.
  • the orthocarbonate includes tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetrapropyl orthocarbonate, tetrabutyl orthocarbonate, tetrapentyl orthocarbonate, tetrahexyl orthocarbonate, and tetraheptyl orthocarbonate.
  • the orthocarbonate includes tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetrapropyl orthocarbonate, tetrabutyl orthocarbonate, tetrapentyl orthocarbonate, tetrahexyl orthocarbonate, and tetraheptyl orthocarbonate.
  • the lithium salt includes one or more of a sulfonimide lithium salt, a borate lithium salt, lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, and lithium triflate.
  • the lithium salt in the embodiment of the present application is not only easy to form a plastic composite with orthocarbonate, but the lithium salt can also form a solid electrolyte interface (Solid Electrolyte Interphase, SEI) film on the negative electrode sheet of the secondary battery, so that it can Protect the negative electrode piece to ensure the structural stability of the negative electrode piece and reduce the risk of side reactions between the negative electrode piece and the electrolyte.
  • Solid Electrolyte Interphase, SEI Solid Electrolyte Interphase
  • the lithium sulfonimide salt includes one or more of lithium bisfluorosulfonimide, lithium bisfluoromethanesulfonimide, and lithium bispentafluoroethylsulfonimide; Further optionally, the sulfonyl imide lithium salt includes lithium bisfluorosulfonyl imide and/or lithium bisfluoromethanesulfonimide; further optionally, the sulfonyl imide lithium salt includes bisfluorosulfonyl lithium salt. Lithium imide.
  • the lithium borate salt includes one or more of lithium tetrafluoroborate, lithium dioxaloborate, and lithium difluoroxaloborate.
  • the molar amount x of orthocarbonate and the molar amount y of lithium salt satisfy: 0.5 ⁇ x:y ⁇ 3; optionally, 1 ⁇ x:y ⁇ 2.
  • the participation degree of orthocarbonate around lithium ions can be reduced, and the risk of orthocarbonate decomposition can be reduced, thereby further improving the performance of the electrolyte. Oxidative stability.
  • the molar percentage of orthocarbonate is 30% to 80%; optionally, 50% to 70%, based on the total mass of orthocarbonate and lithium salt.
  • the mixing ability of orthocarbonate and lithium salt is relatively good, making it easier to form a crystal-plastic compound.
  • the molar percentage of lithium salt is 20% to 70%; optionally, 30% to 50%.
  • the molar percentage of lithium salt meets the above range, it can further reduce the participation of orthocarbonate around lithium ions and reduce the risk of orthocarbonate decomposition; it can also participate in the formation of the SEI film to further improve the protective performance of the negative electrode piece.
  • the electrolyte further includes an inorganic ceramic-based filler; optionally, the inorganic ceramic-based filler is selected from the group consisting of inorganic ceramic-based inert fillers and/or inorganic ceramic-based lithium ion conductor fillers.
  • the inorganic ceramic inert filler in the embodiment of the present application is combined with the crystal plastic composite to form an electrolyte.
  • the inorganic ceramic inert filler can improve the overall mechanical strength of the electrolyte, and can promote the formation of metal ions in the crystal plastic composite and the inorganic ceramic inert compound.
  • the interface between the fillers carries out transmission, thereby improving the cycle performance of the secondary battery.
  • the inorganic ceramic lithium ion conductor filler in the embodiment of the present application is combined with the plastic crystal composite to form an electrolyte.
  • the inorganic ceramic lithium ion conductor filler can improve the overall mechanical strength of the electrolyte and can improve the overall ion conductivity of the electrolyte, thereby improving the secondary Battery cycle performance.
  • the inorganic ceramic-based inert filler is selected from the group consisting of aluminum oxide, silicon oxide, titanium oxide, zinc oxide, magnesium oxide, iron oxide, copper oxide, calcium oxide, chromium oxide, manganese oxide, cobalt oxide, and nickel oxide. one or more.
  • the inorganic ceramic lithium ion conductor filler is selected from one or more of oxide lithium ion conductor fillers, sulfide lithium ion conductor fillers, and halide lithium ion conductor fillers.
  • a second aspect of the application also provides a secondary battery, including the electrolyte according to any embodiment of the first aspect of the application.
  • the secondary battery further includes a negative electrode sheet, and the negative electrode sheet includes lithium element.
  • a third aspect of the present application also provides a battery module, including the secondary battery according to the embodiment of the second aspect of the present application.
  • a fourth aspect of the application also provides a battery pack, including the battery module according to the embodiment of the third aspect of the application.
  • a fifth aspect of the present application also provides an electrical device, including a secondary battery as in the second embodiment of the present application, a battery module as in the third embodiment of the present application, or a battery as in the fourth embodiment of the present application. Bag.
  • FIG. 1 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 1 .
  • FIG. 3 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 4 .
  • Figure 6 is a schematic diagram of an electrical device according to an embodiment of the present application.
  • Figure 7 is the DSC curve of the crystal molding compound of Example 1 of the present application.
  • Figure 8 is a trend chart of the ionic conductivity change with temperature changes of the plastic crystal composite in Example 1 of the present application;
  • Figure 9 is a trend chart of the ionic conductivity change with temperature changes of the crystal plastic composite in Example 2 of the present application.
  • Figure 10 is a scanning voltammetry curve of a button battery composed of the plastic crystal composite in Example 1 of the present application;
  • Figure 11 is a cycle curve diagram of a button battery composed of a plastic crystal composite material in Example 1 of the present application;
  • Figure 12 is a first-cycle cycle curve diagram of a secondary battery composed of the crystal plastic composite in Example 1 of the present application.
  • Secondary battery 11. Outer packaging; 111. Top cover assembly; 112. Housing; 12. Electrode assembly; 10. Battery module; 20. Battery pack; 21. Upper box; 22. Lower box; 30 , electrical equipment.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • a method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) can be added to the method in any order.
  • the method may include steps (a), (b) and (c), and may also include step (a). , (c) and (b), and may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • alkyl encompasses both straight and branched chain alkyl groups.
  • the alkyl group may be C1-C50 alkyl, C1-C40 alkyl, C1-C30 alkyl, C1-C20 alkyl, C1-C12 alkyl, C1-C10 alkyl, C1-C6 alkyl, C1- C4 alkyl.
  • alkyl includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, isopentyl, neopentyl base, tert-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl and decyl, etc. Additionally, alkyl groups may be optionally substituted.
  • halogenated alkyl refers to an alkyl group in which hydrogen atoms are partially or entirely replaced by halogen atoms.
  • halogen atom refers to fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.
  • C1-C10 alkyl is expressly contemplated to separately disclose C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C1-C10, C1-C9, C1-C8, C1- C7, C1 ⁇ C6, C1 ⁇ C5, C1 ⁇ C4, C1 ⁇ C3, C1 ⁇ C2, C2 ⁇ C10, C2 ⁇ C9, C2 ⁇ C8, C2 ⁇ C7, C2 ⁇ C6, C2 ⁇ C5, C2 ⁇ C4, C2 ⁇ C3, C3 ⁇ C10, C3 ⁇ C9, C3 ⁇ C8, C3 ⁇ C7, C3 ⁇ C6, C3 ⁇ C5, C3 ⁇ C4, C4 ⁇ C10, C4 ⁇ C9, C4 ⁇ C8, C4 ⁇ C7, C4 ⁇ C6, C4 ⁇ C5, C5 ⁇ C
  • the substituents may be independently selected from halogen atoms.
  • solid electrolytes are used as the electrolytes of secondary batteries.
  • the solid electrolytes cannot provide a smooth migration channel for metal ions, so that the metal ions cannot smoothly move between the positive electrode and the negative electrode. Movement between sheets, resulting in poor ion conductivity of the solid electrolyte.
  • the inventor improved the composition of the electrolyte from the perspective of improving the ionic conductivity of the electrolyte, and proposed an electrolyte suitable for secondary batteries.
  • the present application will be described in detail.
  • inventions of the present application provide an electrolyte.
  • the electrolyte includes a crystal-plastic composite.
  • the crystal-plastic composite includes orthocarbonate and lithium salt.
  • the orthocarbonate includes one or more of the compounds represented by Formula I. kind,
  • R1 to R4 each independently represents an alkyl group or a haloalkyl group.
  • Orthocarbonate has solvent properties and can be mixed with lithium salt to form a crystal-plastic compound, which can improve the ion conductivity.
  • the reason for the increased ion conductivity may be that the performance of the crystal-plastic compound is between that of the crystalline state It has the characteristics of ordered position and disordered orientation between the liquid state and the plastic crystal composite. The above characteristics cause the existence of spatial defects in the plastic crystal composite, and metal ions can conduct in the spatial defects, thereby improving the ion transmission efficiency.
  • the molecules of the crystal-plastic composite have a degree of rotational freedom, which is beneficial to reducing the energy barrier for metal ion transitions and promotes the crystal-plastic composite to have a high ion conductivity at room temperature.
  • the crystal-plastic composite has a relatively low rotation barrier and can easily slide between molecules, thereby making the crystal-plastic composite plastic and further improving the ion transmission efficiency of the electrolyte.
  • plasticity can ensure that when the electrolyte is used in secondary batteries, it can better infiltrate the positive electrode piece and/or negative electrode piece, and form good interface infiltration and contact with the positive electrode piece and/or negative electrode piece, thereby improving the Capacity release capability.
  • a relatively high temperature can be set so that the crystal plastic compound melts and is in a liquid state, the electrolyte appears in a liquid state, and the electrolyte in a liquid state is injected into the secondary battery.
  • the electrolyte gradually infiltrates the positive electrode piece and/or the negative electrode piece.
  • the temperature can be lowered to convert the liquid plastic crystal compound into Plasticizes the crystalline state, causing the electrolyte to behave in a solid state.
  • the oxidation stability of the electrolyte in the embodiment of the present application is relatively high, which can reach 5V, so that when the electrolyte is used in a secondary battery, it can match the high-voltage positive electrode plate, thereby increasing the energy density of the secondary battery.
  • the electrolyte in the embodiment of the present application is solid, when the electrolyte is used in a secondary battery, it is not easy to have side reactions with the negative electrode plate, thereby ensuring the cycle life of the secondary battery; and the solid electrolyte is not easy to burn and has high safety performance .
  • the orthocarbonate and the lithium salt form a crystal-plastic composite, which can improve the ion conductivity of the electrolyte.
  • the wetting performance between the electrolyte and the positive electrode piece and/or the negative electrode piece is better, and due to its relatively high oxidation stability, it can match the high-voltage positive electrode piece, thereby improving Cycling performance of secondary batteries. Since the solid electrolyte is not prone to combustion, the safety performance of the secondary battery can be ensured.
  • R1 to R4 each independently represents an alkyl group, and the alkyl group may be a C1-C10 alkyl group.
  • the type of alkyl group is not specifically limited and can be selected according to actual needs.
  • chain alkyl group and cyclic alkyl group can be used.
  • Chain alkyl group also includes straight chain alkyl and branched chain alkyl.
  • the cyclic alkyl group may or may not contain a substituent.
  • the C1-C10 alkyl group can be selected from methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , one of neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl and decyl.
  • a C1-C10 haloalkyl group is formed, and the number of substitutions of the halogen atoms and their substitution positions are not the same.
  • the number of substitutions of halogen atoms may be 1, 2, 3 or 4.
  • the types of halogen atoms may be the same or completely different, or the selected halogen atoms may be partially the same type.
  • the haloalkyl group is a C1-C10 haloalkyl group
  • the mutual solubility between this type of orthocarbonate and the lithium salt is relatively better, which is conducive to the formation of a crystal-plastic composite.
  • the halogen atom is selected from one or both of F and Cl; for example, the haloalkyl group can be a fluoroalkyl group. Due to the strong electron-attracting effect of the fluorine group, the oxidation of the electrolyte can be further inhibited and its electrochemical window can be improved.
  • orthocarbonates include tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetrapropyl orthocarbonate, tetrabutyl orthocarbonate, tetrapentyl orthocarbonate, tetrahexyl orthocarbonate, and tetraheptyl orthocarbonate.
  • orthocarbonates include tetramethyl orthocarbonate, tetraethyl orthocarbonate, tetrapropyl orthocarbonate, tetrabutyl orthocarbonate, tetrapentyl orthocarbonate, tetrahexyl orthocarbonate, and tetraheptyl orthocarbonate.
  • ester tetraoctyl orthocarbonate, tetranonyl orthocarbonate, and tetradecyl orthocarbonate. This type of orthocarbonate and lithium salt are more likely to form crystal plastic complexes.
  • the lithium salt includes one or more of a sulfonimide lithium salt, a borate lithium salt, lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, and lithium triflate.
  • the above-mentioned lithium salt is not only easy to form a crystal-plastic complex with orthocarbonate, but the lithium salt can also form a Solid Electrolyte Interphase (SEI) film on the negative electrode of the secondary battery, thereby protecting the negative electrode.
  • SEI Solid Electrolyte Interphase
  • the sulfonimide lithium salt includes one or more of lithium bisfluorosulfonimide, lithium bisfluoromethanesulfonimide, and lithium bispentafluoroethylsulfonimide.
  • the sulfonimide lithium salt includes lithium bisfluorosulfonimide and/or lithium bisfluoromethanesulfonimide.
  • the sulfonimide lithium salt includes lithium bisfluorosulfonimide.
  • the lithium borate salt includes one or more of lithium tetrafluoroborate, lithium dioxaloborate, and lithium difluoroxaloborate.
  • the molar amount x of orthocarbonate and the molar amount y of lithium salt satisfy: 0.5 ⁇ x:y ⁇ 3.
  • the molar amount of orthocarbonate and lithium salt satisfies 0.5 ⁇ x:y ⁇ 3, optionally, 1 ⁇ x:y ⁇ 2.
  • the ratio x:y of the molar amounts of orthocarbonate and lithium salt is 0.5, 0.6, 0.8, 0.9, 1, 1.2, 1.5, 1.6, 1.8, 2, 2.2, 2.5, 2.6, 2.8, 2.9 or 2 , or it can be a combination range of any two of the above values.
  • the molar percentage of orthocarbonate is 30% to 80% based on the total mass of orthocarbonate and lithium salt.
  • the mixing ability of orthocarbonate and lithium salt is relatively good, making it easier to form a crystal-plastic compound.
  • the molar percentage of orthocarbonate is 30% to 80%, optionally, 50% to 70%.
  • the mole percentage of orthocarbonate is 30%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, or may be The range of combinations of any two of the above values.
  • the molar percentage of lithium salt is 20% to 70%; optionally, 30% to 50%.
  • the molar percentage of lithium salt meets the above range, it can further reduce the participation of orthocarbonate around lithium ions and reduce the risk of orthocarbonate decomposition; it can also participate in the formation of the SEI film to further improve the protective performance of the negative electrode piece.
  • the molar percentage of lithium salt is 20% to 70%, optionally, 30% to 50%.
  • the molar percentage of lithium salt is 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%, or can be any two of the above The range of combinations of values.
  • the electrolyte further includes inorganic ceramic fillers.
  • Inorganic ceramic fillers have many defects, which are conducive to the transmission of metal ions, thereby further improving the ion transmission efficiency of the electrolyte; and improving the mechanical strength of the electrolyte.
  • the inorganic ceramic-based filler is selected from inorganic ceramic-based inert fillers and/or inorganic ceramic-based lithium ion conductor fillers.
  • the inorganic ceramic inert filler is combined with the plastic crystal composite to form an electrolyte.
  • the inorganic ceramic inert filler can improve the overall mechanical strength of the electrolyte and promote the transmission of metal ions at the interface between the plastic crystal composite and the inorganic ceramic inert filler. Thereby improving the cycle performance of the secondary battery.
  • the inorganic ceramic lithium ion conductor filler is combined with the plastic crystal composite to form an electrolyte.
  • the inorganic ceramic lithium ion conductor filler can improve the overall mechanical strength of the electrolyte and improve the overall ion conductivity of the electrolyte, thereby improving the cycle performance of the secondary battery.
  • the inorganic ceramic inert filler is selected from one of alumina, silicon oxide, titanium oxide, zinc oxide, magnesium oxide, iron oxide, copper oxide, calcium oxide, chromium oxide, manganese oxide, cobalt oxide and nickel oxide or more.
  • the inorganic ceramic lithium ion conductor filler is selected from one or more of oxide lithium ion conductor fillers, sulfide lithium ion conductor fillers, and halide lithium ion conductor fillers.
  • the oxide-based lithium ion conductor filler is selected from at least one selected from lithium lanthanum zirconium oxide (LLZO), lithium lanthanum titanium oxide (LLTO), and lithium aluminum germanium phosphate (LATP).
  • the sulfide-based lithium ion conductor filler is at least one of lithium phosphorus sulfur (LiPS), lithium germanium phosphorus sulfur (LiGPS), lithium phosphorus sulfur chloride (LiPSCl), and lithium germanium phosphorus sulfur chloride (LiGPSCl).
  • the halide lithium ion conductor filler is at least one of lithium indium chloride (LiInCl), lithium iridium chloride (LiYCl), lithium indium bromide (LiInBr) and lithium iridium bromide (LiYBr).
  • this application proposes a secondary battery.
  • the secondary battery includes the electrolyte according to any embodiment of the first aspect of the present application.
  • the orthocarbonate and lithium salt in the electrolyte can form a plastic crystal composite, thereby improving the ion conductivity of the electrolyte.
  • the electrolyte has good wetting performance with the positive electrode piece and/or the negative electrode piece, and due to its relatively high oxidation stability, it can match the high-voltage positive electrode piece, thereby improving the cycle performance of the secondary battery. Since the solid electrolyte is not prone to combustion, the safety performance of the secondary battery can be ensured.
  • the transmission efficiency of metal ions is high, and side reactions are less likely to occur.
  • the charge and discharge current density of the secondary battery when the charge and discharge current density of the secondary battery is 0.05mA/cm2 ⁇ 0.5mA/cm2, the current density is relatively high, which can shorten the charge and discharge time of the secondary battery; and the electrolyte can provide matching ion transport capabilities, thereby improving its cycling performance.
  • the secondary battery in the embodiment of the present application also includes a negative electrode plate, a positive electrode plate and a separator.
  • the isolation film is disposed between the positive electrode piece and the negative electrode piece to separate the positive electrode piece and the negative electrode piece.
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode film layer includes a negative electrode active material.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative active material may be a negative active material known in the art for batteries.
  • the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, metallic lithium, lithium alloys, sodium alloys, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the negative electrode piece includes lithium element.
  • lithium ions as active ions, can migrate stably between the positive electrode piece and the negative electrode piece, thereby ensuring the electrochemical performance of the secondary battery.
  • the plastic crystal compound in the electrolyte has low reactivity towards the above-mentioned negative electrode piece, which can reduce the risk of side reactions between the electrolyte and the negative electrode piece, thereby reducing the risk of lithium dendrites on the negative electrode piece; and the electrolyte is relatively high in When injected into the secondary battery at a temperature that matches the isolation film, the electrolyte appears in a solid state, which can further reduce the risk of lithium dendrites puncturing the isolation film, thereby blocking the occurrence of internal short circuits to a certain extent and improving the performance of the secondary battery. Safety performance.
  • Lithium element can be used as anode active material in the form of metal element or alloy.
  • the alloy may also include one or more of tin, zinc, aluminum, magnesium, silver, gold, gallium, indium and foil; further optionally, the alloy may also include one or more of boron, carbon and silicon. kind or variety. This type of alloy not only ensures electrical conductivity, but also improves the stability between the negative electrode piece and the electrolyte.
  • the negative electrode film layer optionally further includes a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethyl At least one of acrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative electrode film layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • auxiliaries such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent such as deionized water
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode film layer includes a positive electrode active material.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode film layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (can also be abbreviated to NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (can also be abbreviated to NCM 622 ), LiNi At least one of 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as Li Li
  • the olivine structure contains Examples of lithium phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), lithium manganese phosphate and carbon. At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • composites of lithium iron phosphate and carbon such as LiMnPO 4
  • LiMnPO 4 lithium manganese phosphate and carbon.
  • At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon At least one of composite materials, lithium iron manganese phosphate, and composite materials of lithium iron manganese phosphate and carbon.
  • the positive electrode film layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene tripolymer. At least one of a meta-copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluorine-containing acrylate resin.
  • the positive electrode film layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
  • the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N -methylpyrrolidone
  • a separator film is further included in the secondary battery.
  • isolation membrane There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer casing of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, etc.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • This application has no particular limitation on the shape of the secondary battery, which can be cylindrical, square or any other shape.
  • FIGS. 1 and 2 illustrate a square-structured secondary battery 1 as an example.
  • the secondary battery 1 includes an outer packaging 11 .
  • the outer package 11 includes a top cover assembly 111 and a housing 112 .
  • the positive electrode piece, the negative electrode piece and the isolation film constitute the electrode assembly 12 and are accommodated in the casing 112.
  • the casing 112 also contains an electrolyte.
  • the positive or negative pole piece contains the tabs.
  • metal ions are inserted and detached back and forth between the positive electrode piece and the negative electrode piece.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows active ions to pass through.
  • the secondary battery 1 may be a wound or laminated battery, such as a lithium-ion battery or a sodium-ion battery, but is not limited thereto.
  • the housing 112 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose to form a receiving cavity.
  • the housing 112 has an opening communicating with the accommodation cavity, and the top cover assembly 111 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 12 through a winding process or a lamination process.
  • the electrode assembly 12 is packaged in the containing cavity.
  • the electrolyte impregnates the electrode assembly 12 .
  • the number of electrode assemblies 12 contained in the secondary battery 1 can be one or more, and those skilled in the art can select according to specific actual needs.
  • the secondary battery 1 may be assembled into a battery.
  • the battery may be a battery module or a battery included.
  • the number of secondary batteries 1 contained in the battery module may be one or more, and those skilled in the art can select the specific number according to the application and capacity of the battery module.
  • FIG. 3 is a battery module 10 as an example.
  • a plurality of secondary batteries 1 may be arranged in sequence along the length direction of the battery module 10 .
  • the plurality of secondary batteries 1 can be fixed by fasteners.
  • the battery module 10 may further include a housing having an accommodation space in which a plurality of secondary batteries 1 are accommodated.
  • the above-mentioned battery modules 10 can also be assembled into a battery pack.
  • the number of battery modules 10 contained in the battery pack can be one or more. The specific number can be selected by those skilled in the art according to the application and capacity of the battery pack.
  • the battery pack can also be directly composed of multiple secondary batteries 1 .
  • the battery pack 20 may include a battery box and a plurality of battery modules 10 disposed in the battery box.
  • the battery box includes an upper box 21 and a lower box 22 .
  • the upper box 21 can be covered with the lower box 22 and form a closed space for accommodating the battery module 10 .
  • Multiple battery modules 10 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • FIG. 6 shows an electrical device 30 as an example.
  • the electric device 30 is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or the like.
  • a battery pack or battery module may be used.
  • the device may be a mobile phone, a tablet, a laptop, etc.
  • the device is usually required to be thin and light, and a secondary battery can be used as a power source.
  • An aluminum foil with a thickness of 8 ⁇ m was used as the positive electrode current collector.
  • NMP N-methylpyrrolidone
  • a 50 ⁇ m metal lithium foil is used as the negative electrode piece.
  • the positive electrode piece, isolation film (PP/PE/PP composite film), and negative electrode piece are stacked in sequence, wrapped in aluminum plastic film to form a stacked battery core, and 0.3g of the above electrolyte is injected into the battery at 60°C.
  • the aluminum plastic film is vacuum hot-pressed and sealed, left to stand at 60°C for at least 6 hours, cooled to 30°C, and left to stand at 30°C for at least 6 hours until the electrolyte solidifies, and then undergoes hot and cold pressing, formation, etc. process to obtain a secondary battery.
  • Examples 2 to 7 use different orthocarbonates.
  • Examples 8 to 10 use different lithium salts.
  • Examples 11 to 12 add inorganic ceramic fillers to the electrolyte.
  • Example 1 The difference from Example 1 is that the molar percentages of the lithium salts in Examples 13 to 20 are different.
  • Embodiment 21 uses different negative electrode pieces.
  • Comparative Example 2 uses a different lithium salt, which does not form a crystal-plastic complex with orthocarbonate.
  • Table 1 shows each substance and related parameters of the Examples and Comparative Examples.
  • LiFSI represents lithium bisfluorosulfonyl imide
  • LiBF 4 represents lithium tetrafluoroborate
  • LiPF 6 lithium hexafluorophosphate
  • CF 3 SO 3 Li lithium trifluoromethanesulfonate
  • LiBOB lithium dioxalatoborate
  • Al 2 O 3 represents Aluminum trioxide
  • LLZO stands for lithium lanthanum zirconium oxygen.
  • DSC Differential scanning calorimetry
  • the STA449F3 test electrolyte produced by NETZSCH Instrument Manufacturing Co., Ltd. in Germany was used to conduct a heating experiment on the homogeneous mixture of lithium salt and orthocarbonate starting from room temperature.
  • the heating rate was 2°C/min until the end of 100°C.
  • the temperature rise process was recorded. Heat release and absorption data are used to analyze the phase transformation temperature of the material and whether the transformation heat is within the range of the plastic crystal material.
  • Two stainless steel sheets SUS are used as blocking electrodes and placed on both sides of a ring-shaped polyimide film with a known thickness and a hole punched in the middle to form a button battery. At 60°C, the electrolyte was melted and added to the pores of the cyclic polyimide film, and the volume between the stainless steel sheets SUS was filled.
  • a 50 ⁇ m metal lithium foil is used as the negative electrode, the aluminum foil is used as the positive electrode, and the polyethylene porous film is used as the isolation membrane.
  • the melted electrolyte is injected into the isolation membrane to form a button battery.
  • the formed button battery was left to stand for 3 hours at 40°C, and then a swept voltammetry curve (LSV) test was performed: the voltage range was the open circuit voltage -6V, the voltage sweep rate was set to 1mV/s, and the corrosion current was recorded, but The voltage when the corrosion current density reaches 10 ⁇ A/ cm is recorded as the oxidation stability threshold, which is used to evaluate its oxidation stability. The higher the threshold, the better the oxidation stability.
  • a 50 ⁇ m metal lithium foil is used as the negative electrode, the aluminum foil is used as the positive electrode, and the polyethylene porous film is used as the isolation membrane.
  • the melted electrolyte is injected into the isolation membrane to form a button battery.
  • the formed button battery was allowed to stand for 3 hours at 40°C, and then the button battery was charged and discharged using current densities from low to high to obtain a voltage curve. Specifically, the button battery was cycled 5 times at current densities of 0.1mA/cm 2 , 0.2mA/cm 2 and 0.4mA/cm 2 respectively, and at a capacity density of 0.25mAh/cm 2 .
  • the test conditions are under normal temperature conditions.
  • the produced secondary battery is charged at a rate of 0.05C and discharged at a rate of 0.05C.
  • a full charge and discharge cycle test is performed until the capacity of the secondary battery decays to 80% of the initial capacity. The test is stopped. Record the number of laps.
  • Example 1 Example 8 to Example 10, different lithium salts Y and tetraethyl orthocarbonate are used to form crystal-plastic composites.
  • the crystal-plastic composites have high ion conductivity and relatively high oxidation stability. sex.
  • Examples 11 and 12 add inorganic fillers on the basis of Example 1. Such fillers can improve the mechanical properties of the electrolyte and ensure the cycle performance of the secondary battery.
  • Example 1 Example 13 to Example 20, orthocarbonate and lithium salt adopt different molar ratios. By regulating the molar ratio, the properties of the formed crystal plastic composite can be adjusted. Especially when 0.5 ⁇ x:y ⁇ 3, orthocarbonate and lithium salt are more likely to form a plastic crystal structure at room temperature.
  • Example 1 uses metallic lithium as the negative electrode sheet, which can ensure the cycle performance of the secondary battery, thus confirming that the electrolyte of Example 1 can maintain the stability of the negative electrode sheet and reduce the occurrence of lithium dendrites. risk.
  • Figure 7 shows the DSC curve of the crystal molding compound of Example 1. It can be seen from Figure 7 that the crystal molding compound has an obvious endothermic peak at about 57°C, which means that the phase from solid to liquid occurs at this temperature. change process. The calculated entropy change of this process is 17.96J/(mol ⁇ K), which is less than the critical value 20J/(mol ⁇ K). This shows that the material has a plastic crystal structure from room temperature to 57°C. In Figure 7, T represents temperature.
  • Figure 8 shows a change trend diagram of the ionic conductivity of the crystal plastic composite of Example 1 as the temperature changes.
  • Figure 9 shows a change trend diagram of the ionic conductivity of the crystal plastic composite of Example 2 as the temperature changes. From Figure 8 and 9, it can be seen that the ion conductivity of the button battery composed of the plastic crystal composite of Example 1 is different at different temperatures, and within a certain temperature range, the ion conductivity increases with the increase of temperature. .
  • ⁇ represents the ionic conductivity
  • T represents the temperature.
  • Figure 10 shows the scanning voltammetry curve of the button battery composed of the plastic crystal composite of Example 1. It can be seen from Figure 10 that the button battery composed of the plastic crystal composite of Example 1 has a high potential against metallic lithium. When reaching 5V, the oxidation corrosion current is still less than 25 ⁇ A/cm 2 , which shows that the solid-state plastic crystal electrolyte has excellent oxidation stability.
  • Figure 11 shows the cycle curve of a button battery composed of the crystal plastic composite of Example 1. It can be seen from Figure 11 that at 40°C, the button battery composed of the crystal plastic composite of Example 1 has a 0.1mA /cm 2 , 0.2mA/cm 2 current density, the battery can cycle stably, at 0.4mA/cm 2 current density, the battery will produce more obvious polarization, and as the deposition capacity increases, the overpotential becomes more obvious of rise.
  • Figure 12 shows the first cycle cycle curve of the secondary battery composed of the plastic crystal composite of Example 1. It can be seen from Figure 12 that the secondary battery can cycle stably and can release more than 95% of the rated capacity. , and the Coulombic efficiency of the first cycle is relatively consistent with the authorized Coulombic efficiency of the ternary cathode in the liquid system.
  • Q represents capacity and U represents voltage.
  • the embodiments of the present application can improve the ionic conductivity and oxidation stability of the plastic crystal composite by regulating the plastic crystal structure in the crystal plastic composite, thereby improving the cycle performance of the secondary battery.

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Abstract

本申请实施例提供了一种电解质、二次电池、电池模块、电池包和用电装置。该电解质包括塑晶复合物，塑晶复合物包括原碳酸酯和锂盐，原碳酸酯包括式I所示的化合物中的一种或多种，式(I)中，R1至R4各自独立地表示烷基或卤代烷基。本申请实施例通过原碳酸酯和锂盐形成塑晶复合物，能够提高电解质的导离子率，从而提高二次电池的循环性能。由于固态的电解质不容易发生燃烧，从而能够保证二次电池的安全性能。

Description

电解质、二次电池、电池模块、电池包和用电装置 技术领域
本申请涉及电池领域，具体涉及一种电解质、二次电池、电池模块、电池包和用电装置。
背景技术
二次电池具有容量高、寿命长等特性，因此广泛应用于电子设备，例如手机、笔记本电脑、电瓶车、电动汽车、电动飞机、电动轮船、电动玩具汽车、电动玩具轮船、电动玩具飞机和电动工具等等。由于二次电池取得了极大的进展，因此对二次电池的性能提出了更高的要求。为了提高二次电池的性能，通常对二次电池内的材料例如电解质进行优化改善。电解质作为二次电池中金属离子的传输介质，对二次电池的性能具有不可忽略的影响。
然而，目前改进后的电解质在应用于二次电池时，二次电池的循环性能和安全性能仍有待提高。
发明内容
本申请是鉴于上述课题而进行的，其目的在于，提供一种电解质、二次电池、电池模块、电池包和用电装置。
本申请的第一方面提供了一种用于二次电池的电解质，该电解质包括塑晶复合物，塑晶复合物包括原碳酸酯和锂盐，原碳酸酯包括式I所示的化合物中的一种或多种，
Figure PCTCN2022094196-appb-000001
式I中，R1至R4各自独立地表示烷基或卤代烷基。
由此，本申请实施例通过原碳酸酯和锂盐形成塑晶复合物，能够提高电解质的导离子率。将电解质应用于二次电池时，电解质与正极极片和/或负极极片之间的浸润性能较好，并由于具有相对较高的氧化稳定性，能够与高压正极极片相匹配，从而提高二次电池的循环性能。由于固态的电解质不容易发生燃烧，从而能够保证二次电池的安全性能。
在任意实施方式中，烷基为C1-C10烷基。该类原碳酸酯与锂盐的互溶性能相对更好，有利于二者形成塑晶复合物。
在任意实施方式中，卤代烷基为C1-C10卤代烷基。该类原碳酸酯与锂盐的互溶性能相对更好，有利于二者形成塑晶复合物。
在任意实施方式中，卤代烷基为氟代烷基。由于氟基团的强吸电子作用，可以进一步抑制电解质被氧化，提高其电化学窗口。
在任意实施方式中，原碳酸酯包括原碳酸四甲酯、原碳酸四乙酯、原碳酸四丙酯、原碳酸四丁酯、原碳酸四戊酯、原碳酸四己酯、原碳酸四庚酯、原碳酸四辛酯、原碳酸四壬酯、原碳酸四癸酯、氟代原碳酸四甲酯、氟代原碳酸四乙酯、氟代原碳酸四丙酯、氟代原碳酸四丁酯、氟代原碳酸四戊酯、氟代原碳酸四己酯、氟代原碳酸四庚酯、氟代原碳酸四辛酯、氟代原碳酸四壬酯、氟代原碳酸四癸酯、四三氟甲氧基甲烷、四-(2,2,2-三氟乙氧基)-甲烷、四-(3,3,3-三氟丙氧基)-甲烷、原碳酸甲基三乙酯、原碳酸二甲二乙酯、原碳酸乙基三甲酯、原碳酸甲基三丙酯、原碳酸二甲二丙酯、原碳酸丙基三甲酯、原碳酸乙基三丙酯、原碳酸二乙二丙酯、原碳酸丙基三乙酯、原碳酸甲基三丁酯、原碳酸二甲二丁酯和原碳酸丁基三甲酯中的一种或多种。该类原碳酸酯与锂盐的混合能力更强，其形成的塑晶复合物由塑晶状态转变到液态的相变转化熵较低，更容易形成塑晶复合物。
在任意实施方式中，原碳酸酯包括原碳酸四甲酯、原碳酸四乙酯、原碳酸四丙酯、原碳酸四丁酯、原碳酸四戊酯、原碳酸四己酯、原碳酸四庚酯、原碳酸四辛酯、原碳酸四壬酯和原碳酸四癸酯中的一种或多种。该类原碳酸酯和锂盐更容易形成塑晶复合物。
在任意实施方式中，锂盐包括磺酰亚胺类锂盐、硼酸类锂盐、六氟磷酸锂、高氯酸锂、六氟砷酸锂和三氟甲基磺酸锂中的一种或多种。
由此，本申请实施例的锂盐不仅易与和原碳酸酯形成塑晶复合物，锂盐还能够在二次电池的负极极片上形成固体电解质界面(Solid Electrolyte Interphase，SEI)膜，从而能够对负极极片进行防护，保证负极极片的结构稳定性，且降低负极极片和电解质之间发生副反应的风险。
在任意实施方式中，磺酰亚胺类锂盐包括双氟磺酰亚胺锂、双氟甲基磺酰亚胺锂和双五氟乙基磺酰亚胺锂中的一种或多种；进一步可选地，磺酰亚胺类锂盐包括双氟磺酰亚胺锂和/或双氟甲基磺酰亚胺锂；进一步可选地，磺酰亚胺类锂盐包括双氟磺酰亚胺锂。
在任意实施方式中，硼酸类锂盐包括四氟硼酸锂、二草酸硼酸锂和二氟草酸硼 酸锂中的一种或多种。
在任意实施方式中，原碳酸酯的摩尔量x和锂盐的摩尔量y满足：0.5≤x:y≤3；可选地，1≤x:y≤2。
由此，本申请实施例的原碳酸酯和锂盐的摩尔量满足上述范围时，能够降低锂离子周围的原碳酸酯的参与度，能够降低原碳酸酯分解的风险，从而能够进一步提高电解质的氧化稳定性。
在任意实施方式中，基于原碳酸酯和锂盐的总质量计，原碳酸酯的摩尔百分数为30％～80％；可选地，50％～70％。原碳酸酯的摩尔百分数满足上述范围时，原碳酸酯和锂盐的混合能力相对较好，从而更易于形成塑晶化合物。
在任意实施方式中，基于原碳酸酯和锂盐的总质量计，锂盐的摩尔百分数为20％～70％；可选地，30％～50％。锂盐的摩尔百分数满足上述范围时，能够进一步降低锂离子周围的原碳酸酯的参与度，能够降低原碳酸酯分解的风险；并且可以参与SEI膜的形成，进一步提高对负极极片的防护性能。
在任意实施方式中，电解质还包括无机陶瓷类填料；可选地，无机陶瓷类填料选自无机陶瓷类惰性填料和/或无机陶瓷类锂离子导体填料。
由此，本申请实施例的无机陶瓷类惰性填料与塑晶复合物复合形成电解质，无机陶瓷类惰性填料能够提高电解质整体的机械强度，并能够促进金属离子在塑晶复合物和无机陶瓷类惰性填料之间的界面进行传输，从而提高二次电池的循环性能。
本申请实施例的无机陶瓷类锂离子导体填料与塑晶复合物复合形成电解质，无机陶瓷类锂离子导体填料能够提高电解质整体的机械强度，并能够提高电解质整体的导离子率，从而提高二次电池的循环性能。
在任意实施方式中，无机陶瓷类惰性填料选自氧化铝、氧化硅、氧化钛、氧化锌、氧化镁、氧化铁、氧化铜、氧化钙、氧化铬、氧化锰、氧化钴和氧化镍中的一种或多种。
在任意实施方式中，无机陶瓷类锂离子导体填料选自氧化物类锂离子导体填料、硫化物类锂离子导体填料和卤化物类锂离子导体填料中的一种或多种。
本申请的第二方面还提供了一种二次电池，包括本申请第一方面任一实施例的电解质。
在任意实施方式中，二次电池还包括负极极片，负极极片包括锂元素。
本申请的第三方面还提供了一种电池模块，包括如本申请第二方面实施例的二次电池。
本申请的第四方面还提供了一种电池包，包括如本申请第三方面实施例的电池模块。
本申请第五方面还提供了一种用电装置，包括如本申请第二方面实施例的二次电池、如本申请第三方面实施例的电池模块或如本申请第四方面实施例的电池包。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1是本申请一实施方式的二次电池的示意图。
图2是图1所示的本申请一实施方式的二次电池的分解图。
图3是本申请一实施方式的电池模块的示意图。
图4是本申请一实施方式的电池包的示意图。
图5是图4所示的本申请一实施方式的电池包的分解图。
图6是本申请一实施方式的用电装置的示意图；
图7是本申请实施例1的塑晶复合物的DSC曲线；
图8是本申请实施例1的塑晶复合物随温度变化的导离子率变化趋势图；
图9是本申请实施例2的塑晶复合物随温度变化的导离子率变化趋势图；
图10是本申请实施例1的塑晶复合物组成的纽扣电池的扫描伏安曲线图；
图11是本申请实施例1的塑晶复合物质组成的纽扣电池的循环曲线图；
图12是本申请实施例1的塑晶复合物组成的二次电池的首圈循环曲线图。
附图标记说明如下：
1、二次电池；11、外包装；111、顶盖组件；112、壳体；12、电极组件；10、电池模块；20、电池包；21、上箱体；22、下箱体；30、用电装置。
具体实施方式
以下，详细说明具体公开了本申请的二次电池、电池模块、电池包和用电装置的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，方法包括步骤(a)和(b)，表示方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到方法，例如，方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
术语“烷基”涵盖直链和支链烷基。例如，烷基可为C1-C50烷基、C1-C40烷基、C1-C30烷基、C1-C20烷基、C1-C12烷基、C1-C10烷基、C1-C6烷基、C1-C4烷基。在一些实施例中，烷基包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、环丁基、戊基、异戊基、新戊基、叔戊基、环戊基、己基、环己基、庚基、环庚基、辛基、环辛基、壬基和癸基等。另外，烷基可以是任选地被取代的。术语“卤代烷基”是指烷基中，氢原子部分或全部被卤素原子所取代，术语“卤素原子”是指氟原子、氯原子、溴原子、碘原子等。
在本说明书的各处，化合物的取代基以组或范围公开。明确地预期这种描述包括这些组和范围的成员的每一个单独的子组合。例如，明确地预期术语“C1～C10烷基”单独地公开C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C1～C10、C1～C9、C1～C8、C1～C7、C1～C6、C1～C5、C1～C4、C1～C3、C1～C2、C2～C10、C2～C9、C2～C8、C2～C7、C2～C6、C2～C5、C2～C4、C2～C3、C3～C10、C3～C9、C3～C8、C3～C7、C3～C6、C3～C5、C3～C4、C4～C10、C4～C9、C4～C8、C4～C7、C4～C6、C4～C5、C5～C10、C5～C9、C5～C8、C5～C7、C5～C6、C6～C10、C6～C9、C6～C8、C6～C7、C7～C10、C7～C9、C7～C8、C8～C10和C8～C9烷基。
当上述基团经取代时，取代基可独立地选自卤素原子。
相关技术中采用固态电解质作为二次电池的电解质，二次电池在充放电过程中，固态电解质不能很好地为金属离子提供顺畅的迁移通道，从而使得金属离子不能顺利在正极极片和负极极片之间运动，由此导致固态电解质导离子率较差。
鉴于此，发明人从提高电解质的导离子率的角度出发，对电解质的组成进行改进，提出了一种适用于二次电池的电解质，接下来对本申请进行详细说明。
电解质
第一方面，本申请实施例提供了一种电解质，该电解质包括塑晶复合物，塑晶复合物包括原碳酸酯和锂盐，原碳酸酯包括式I所示的化合物中的一种或多种，
Figure PCTCN2022094196-appb-000002
式I中，R1至R4各自独立地表示烷基或卤代烷基。
原碳酸酯具有溶剂性能，能够和锂盐混合形成塑晶复合物，能够提高导离子率，虽然原因并不明确，但提高导离子率的原因可能在于，塑晶复合物的性能介于结晶态和液态之间，具有位置有序、取向无序的特性，上述特性使得塑晶复合物存在空间缺陷，而金属离子可以在空间缺陷中进行传导，从而能够提高离子传输效率。
塑晶复合物的分子具有旋转自由度，有利于降低金属离子跃迁的能垒，促进塑晶复合物在室温下就具有较高的导离子率。塑晶复合物具有相对较低的旋转势垒，容易实现分子间的滑动，从而使得塑晶复合物具有塑性，并能够进一步提高电解质的离子传输效率。此外，塑性可以保证电解质应用于二次电池时，能够较好的浸润正极极片和/或负极极片，并与正极极片和/或负极极片形成良好的界面浸润与接触，从而能够提高容量释放能力。
示例性地，将包含塑晶复合物的电解质应用于二次电池时，可以设置相对较高的温度以使塑晶复合物熔融并处于液态，电解质表现为液态，将处于液态的电解质注入二次电池中，电解质逐步浸润于正极极片和/或负极极片上，待电解质与正极极片和/或负极极片形成良好的界面浸润后，可以降低温度以使处于液态的塑晶复合物转变为塑晶态，从而使得电解质表现为固态。
此外，本申请实施例的电解质的氧化稳定性相对较高，可以达到5V，从而使得电解质应用于二次电池时，能够与高压正极极片相匹配，进而提高二次电池的能量密度。
鉴于本申请实施例的电解质为固态，电解质应用于二次电池时，不容易与负极极片发生副反应，从而能够保证二次电池的循环寿命；并且固态电解质不容易发生燃烧，安全性能较高。
根据本申请实施例的电解质，通过原碳酸酯和锂盐形成塑晶复合物，能够提高电解质的导离子率。将电解质应用于二次电池时，电解质与正极极片和/或负极极片之间的浸润性能较好，并由于具有相对较高的氧化稳定性，能够与高压正极极片相匹 配，从而提高二次电池的循环性能。由于固态的电解质不容易发生燃烧，从而能够保证二次电池的安全性能。
在一些实施例中，R1至R4各自独立地表示烷基，且烷基可以为C1-C10烷基。当R1至R4各自独立地表示C1-C10烷基时，烷基的种类并不受到具体的限制，可以根据实际需求进行选择，例如链状烷基和环状烷基均可，链状烷基又包括直链烷基和支链烷基。另外，环状烷基上可以有取代基，也可以不含有取代基。C1～C10的烷基可以选自甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、环戊基、正己基、异己基、环己基、庚基、环庚基、辛基、环辛基、壬基和癸基中的一种。
该类原碳酸酯与锂盐的互溶性能相对更好，有利于二者形成塑晶复合物。
在一些实施例中，当上述C1～C10的烷基被卤素原子中的一种或几种部分取代或全部取代时，形成C1～C10的卤代烷基，卤素原子的取代个数及其取代位置并没有特别的限制，可根据实际需求进行选择。例如，卤素原子的取代个数可为1个、2个、3个或4个。当卤素原子的取代个数为2个以上时，卤素原子的种类可以相同，也可以完全不同，又或者是所选取的卤素原子的种类部分相同。
卤代烷基为C1-C10卤代烷基时，该类原碳酸酯与锂盐的互溶性能相对更好，有利于二者形成塑晶复合物。
在一些实施例中，卤素原子选自F、Cl中的一种或两种；示例性地，卤代烷基可以为氟代烷基。由于氟基团的强吸电子作用，可以进一步抑制电解质被氧化，提高其电化学窗口。
在一些实施例中，原碳酸酯包括原碳酸四甲酯、原碳酸四乙酯、原碳酸四丙酯、原碳酸四丁酯、原碳酸四戊酯、原碳酸四己酯、原碳酸四庚酯、原碳酸四辛酯、原碳酸四壬酯、原碳酸四癸酯、氟代原碳酸四甲酯、氟代原碳酸四乙酯、氟代原碳酸四丙酯、氟代原碳酸四丁酯、氟代原碳酸四戊酯、氟代原碳酸四己酯、氟代原碳酸四庚酯、氟代原碳酸四辛酯、氟代原碳酸四壬酯、氟代原碳酸四癸酯、四三氟甲氧基甲烷、四-(2,2,2-三氟乙氧基)-甲烷和四-(3,3,3-三氟丙氧基)-甲烷中的一种或多种。
该类原碳酸酯与锂盐的混合能力更强，其形成的塑晶复合物由塑晶状态转变到液态的相变转化熵较低，更容易形成塑晶复合物。
在一些实施例中，原碳酸酯包括原碳酸四甲酯、原碳酸四乙酯、原碳酸四丙酯、原碳酸四丁酯、原碳酸四戊酯、原碳酸四己酯、原碳酸四庚酯、原碳酸四辛酯、原碳酸四壬酯、原碳酸四癸酯中的一种或多种。该类原碳酸酯和锂盐更容易形成塑晶复合物。
在一些实施例中，锂盐包括磺酰亚胺类锂盐、硼酸类锂盐、六氟磷酸锂、高氯酸锂、六氟砷酸锂和三氟甲基磺酸锂中的一种或多种。
上述锂盐不仅易与和原碳酸酯形成塑晶复合物，锂盐还能够在二次电池的负极极片上形成固体电解质界面(Solid Electrolyte Interphase，SEI)膜，从而能够对负极极片进行防护，保证负极极片的结构稳定性，且降低负极极片和电解质之间发生副反应 的风险。
在一些实施例中，磺酰亚胺类锂盐包括双氟磺酰亚胺锂、双氟甲基磺酰亚胺锂和双五氟乙基磺酰亚胺锂中的一种或多种。可选地，磺酰亚胺类锂盐包括双氟磺酰亚胺锂和/或双氟甲基磺酰亚胺锂。进一步可选地，磺酰亚胺类锂盐包括双氟磺酰亚胺锂。
在一些实施例中，硼酸类锂盐包括四氟硼酸锂、二草酸硼酸锂和二氟草酸硼酸锂中的一种或多种。
在一些实施例中，原碳酸酯的摩尔量x和锂盐的摩尔量y满足：0.5≤x:y≤3。
原碳酸酯和锂盐的摩尔量满足上述范围时，能够降低锂离子周围的原碳酸酯的参与度，能够降低原碳酸酯分解的风险，从而能够进一步提高电解质的氧化稳定性。原碳酸酯和锂盐的摩尔量满足0.5≤x:y≤3，可选地，1≤x:y≤2。示例性地，原碳酸酯和锂盐的摩尔量的比值x：y为0.5、0.6、0.8、0.9、1、1.2、1.5、1.6、1.8、2、2.2、2.5、2.6、2.8、2.9或2，或者可以是上述任意两个数值的组合范围。
在一些实施例中，基于原碳酸酯和锂盐的总质量计，原碳酸酯的摩尔百分数为30％～80％。
原碳酸酯的摩尔百分数满足上述范围时，原碳酸酯和锂盐的混合能力相对较好，从而更易于形成塑晶化合物。原碳酸酯的摩尔百分数为30％～80％，可选地，50％～70％。示例性地，原碳酸酯的摩尔百分数为30％、35％、38％、40％、45％、50％、55％、60％、65％、70％、75％或80％，或者可以是上述任意两个数值的组合范围。
在一些实施例中，基于原碳酸酯和锂盐的总质量计，锂盐的摩尔百分数为20％～70％；可选地，30％～50％。
锂盐的摩尔百分数满足上述范围时，能够进一步降低锂离子周围的原碳酸酯的参与度，能够降低原碳酸酯分解的风险；并且可以参与SEI膜的形成，进一步提高对负极极片的防护性能。锂盐的摩尔百分数为20％～70％，可选地，30％～50％。示例性地，锂盐的摩尔百分数为20％、25％、30％、35％、40％、45％、50％、55％、60％、65％或70％，或者可以是上述任意两个数值的组合范围。
在一些实施例中，电解质还包括无机陶瓷类填料。无机陶瓷类填料存在较多的缺陷，有利于金属离子的传输，从而能够进一步提高电解质的离子传输效率；并且可以提高电解质的机械强度。
可选地，无机陶瓷类填料选自无机陶瓷类惰性填料和/或无机陶瓷类锂离子导体填料。
无机陶瓷类惰性填料与塑晶复合物复合形成电解质，无机陶瓷类惰性填料能够提高电解质整体的机械强度，并能够促进金属离子在塑晶复合物和无机陶瓷类惰性填料之间的界面进行传输，从而提高二次电池的循环性能。
无机陶瓷类锂离子导体填料与塑晶复合物复合形成电解质，无机陶瓷类锂离子导体填料能够提高电解质整体的机械强度，并能够提高电解质整体的导离子率，从而 提高二次电池的循环性能。
示例性地，无机陶瓷类惰性填料选自氧化铝、氧化硅、氧化钛、氧化锌、氧化镁、氧化铁、氧化铜、氧化钙、氧化铬、氧化锰、氧化钴和氧化镍中的一种或多种。
示例性地，无机陶瓷类锂离子导体填料选自氧化物类锂离子导体填料、硫化物类锂离子导体填料和卤化物类锂离子导体填料中的一种或多种。例如，氧化物类锂离子导体填料选自锂镧锆氧(LLZO)、锂镧钛氧(LLTO)和磷酸锗铝锂(LATP)中的至少一种。硫化物类锂离子导体填料为锂磷硫(LiPS)、锂锗磷硫(LiGPS)、锂磷硫氯(LiPSCl)和锂锗磷硫氯(LiGPSCl)中的至少一种。卤化物类锂离子导体填料为锂铟氯(LiInCl)、锂铱氯(LiYCl)、锂铟溴(LiInBr)和锂铱溴(LiYBr)中的至少一种。
二次电池
第二方面，本申请提出了一种二次电池。该二次电池包括本申请第一方面任一实施例的电解质。
根据本申请实施例的二次电池，电解质中的原碳酸酯和锂盐能够形成塑晶复合物，从而提高电解质的导离子率。电解质与正极极片和/或负极极片之间的浸润性能较好，并由于具有相对较高的氧化稳定性，能够与高压正极极片相匹配，从而提高二次电池的循环性能。由于固态的电解质不容易发生燃烧，从而能够保证二次电池的安全性能。
在一些实施例中，于10℃～80℃下，尤其在40℃～50℃下，二次电池在循环充放电时，金属离子的传输效率较高，且不容易发生副反应。
在一些实施例中，二次电池的充放电电流密度为0.05mA/cm2～0.5mA/cm2时，电流密度相对较高，可以缩短二次电池的充放电时间；并且则电解质能够提供相匹配的离子传输能力，从而提高其循环性能。
本申请实施例的二次电池还包括负极极片、正极极片和隔离膜。隔离膜设置于正极极片和负极极片之间，以隔开正极极片和负极极片。
[负极极片]
负极极片包括负极集流体以及设置在负极集流体至少一个表面上的负极膜层，负极膜层包括负极活性材料。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极膜层设置在负极集流体相对的两个表面中的任意一者或两者上。
在一些实施例中，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施例中，负极活性材料可采用本领域公知的用于电池的负极活性材 料。作为示例，负极活性材料可包括以下材料中的至少一种：人造石墨、天然石墨、软炭、硬炭、硅基材料、锡基材料、钛酸锂、金属锂、锂合金和钠合金等。硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅氮复合物以及硅合金中的至少一种。锡基材料可选自单质锡、锡氧化合物以及锡合金中的至少一种。但本申请并不限定于这些材料，还可以使用其他可被用作电池负极活性材料的传统材料。这些负极活性材料可以仅单独使用一种，也可以将两种以上组合使用。
可选地，负极极片包括锂元素。在二次电池充放电过程中，锂离子作为活性离子，能够在正极极片和负极极片之间稳定迁移，从而保证二次电池的电化学性能。电解质中的塑晶复合物对上述负极极片的反应活性较低，从而能够降低电解质和负极极片发生副反应的风险，进而降低负极极片上发生锂枝晶的风险；并且电解质在相对较高的温度下注入二次电池中与隔离膜相匹配，电解质表现为固态，能够进一步降低锂枝晶刺破隔离膜的风险，从而能够在一定程度上阻断内短路的发生，提高二次电池的安全性能。
锂元素可以以金属单质或合金的形式作为负极活性材料。可选地，合金还可以包括锡、锌、铝、镁、银、金、镓、铟和箔中的一种干活多种；进一步可选地，合金还包括硼、碳和硅中的一种或多种。该类合金不仅可以保证导电性，还可以提高负极极片和电解质之间的稳定性。
在一些实施例中，负极膜层还可选地包括粘结剂。粘结剂可选自丁苯橡胶(SBR)、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、聚丙烯酰胺(PAM)、聚乙烯醇(PVA)、海藻酸钠(SA)、聚甲基丙烯酸(PMAA)及羧甲基壳聚糖(CMCS)中的至少一种。
在一些实施例中，负极膜层还可选地包括导电剂。导电剂可选自超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施例中，负极膜层还可选地包括其他助剂，例如增稠剂(如羧甲基纤维素钠(CMC-Na))等。
在一些实施例中，可以通过以下方式制备负极极片：将上述用于制备负极极片的组分，例如负极活性材料、导电剂、粘结剂和任意其他组分分散于溶剂(例如去离子水)中，形成负极浆料；将负极浆料涂覆在负极集流体上，经烘干、冷压等工序后，即可得到负极极片。
[正极极片]
正极极片包括正极集流体以及设置在正极集流体至少一个表面的正极膜层，正极膜层包括正极活性材料。
作为示例，正极集流体具有在其自身厚度方向相对的两个表面，正极膜层设置在正极集流体相对的两个表面的其中任意一者或两者上。
在一些实施例中，正极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可采用铝箔。复合集流体可包括高分子材料基层和形成于高分子材料基层至少一个表面上的金属层。复合集流体可通过将金属材料(铝、铝合金、镍、镍合金、 钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而形成。
在一些实施例中，正极活性材料可采用本领域公知的用于电池的正极活性材料。作为示例，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO 2)、锂镍氧化物(如LiNiO 2)、锂锰氧化物(如LiMnO 2、LiMn 2O 4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi 1/3Co 1/3Mn 1/3O 2(也可以简称为NCM 333)、LiNi 0.5Co 0.2Mn 0.3O 2(也可以简称为NCM 523)、LiNi 0.5Co 0.25Mn 0.25O 2(也可以简称为NCM 211)、LiNi 0.6Co 0.2Mn 0.2O 2(也可以简称为NCM 622)、LiNi 0.8Co 0.1Mn 0.1O 2(也可以简称为NCM 811)、锂镍钴铝氧化物(如LiNi 0.85Co 0.15Al 0.05O 2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO 4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO 4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一些实施例中，正极膜层还可选地包括粘结剂。作为示例，粘结剂可以包括聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、偏氟乙烯-四氟乙烯-丙烯三元共聚物、偏氟乙烯-六氟丙烯-四氟乙烯三元共聚物、四氟乙烯-六氟丙烯共聚物及含氟丙烯酸酯树脂中的至少一种。
在一些实施例中，正极膜层还可选地包括导电剂。作为示例，导电剂可以包括超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、石墨烯及碳纳米纤维中的至少一种。
在一些实施例中，可以通过以下方式制备正极极片：将上述用于制备正极极片的组分，例如正极活性材料、导电剂、粘结剂和任意其他的组分分散于溶剂(例如N-甲基吡咯烷酮)中，形成正极浆料；将正极浆料涂覆在正极集流体上，经烘干、冷压等工序后，即可得到正极极片。
[隔离膜]
在一些实施例中，二次电池中还包括隔离膜。本申请对隔离膜的种类没有特别的限制，可以选用任意公知的具有良好的化学稳定性和机械稳定性的多孔结构隔离膜。
在一些实施例中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一些实施例中，正极极片、负极极片和隔离膜可通过卷绕工艺或叠片工艺制 成电极组件。
在一些实施例中，二次电池可包括外包装。该外包装可用于封装上述电极组件及电解质。
在一些实施例中，二次电池的外包可以是硬壳，例如硬塑料壳、铝壳、钢壳等。二次电池的外包装也可以是软包，例如袋式软包。软包的材质可以是塑料，作为塑料，可列举出聚丙烯、聚对苯二甲酸丁二醇酯以及聚丁二酸丁二醇酯等。本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。例如，图1和图2是作为一个示例的方形结构的二次电池1。
在一些实施例中，二次电池1包括外包装11。外包装11包括顶盖组件111和壳体112。正极极片、负极极片和隔离膜构成电极组件12容纳于壳体112内，壳体112内还容纳有电解质。正极极片或负极极片包含极耳。在二次电池1充放电过程中，金属离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使活性离子通过。具体地，该二次电池1可以为卷绕式或叠片式的电池，如锂离子电池、钠离子电池，但并不局限于此。
可选地，壳体112可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体112具有与容纳腔连通的开口，顶盖组件111能够盖设于开口，以封闭容纳腔。正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电极组件12。电极组件12封装于容纳腔内。电解质浸润于电极组件12中。二次电池1所含电极组件12的数量可以为一个或多个，本领域技术人员可根据具体实际需求进行选择。
在一些实施例中，二次电池1可以组装成电池。电池可以为电池模块或电池包括。例如，电池模块所含二次电池1的数量可以为一个或多个，具体数量本领域技术人员可根据电池模块的应用和容量进行选择。
图3是作为一个示例的电池模块10。参照图3，在电池模块10中，多个二次电池1可以是沿电池模块10的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池1进行固定。可选地，电池模块10还可以包括具有容纳空间的外壳，多个二次电池1容纳于该容纳空间。
在一些实施例中，上述电池模块10还可以组装成电池包，电池包所含电池模块10的数量可以为一个或多个，具体数量本领域技术人员可根据电池包的应用和容量进行选择。当然，电池包也可以由多个二次电池1直接组成。
图4和图5是作为一个示例的电池包20。参照图4和图5，在电池包20中可以包括电池箱和设置于电池箱中的多个电池模块10。电池箱包括上箱体21和下箱体22，上箱体21能够盖设于下箱体22，并形成用于容纳电池模块10的封闭空间。多个电池模块10可以按照任意的方式排布于电池箱中。
另外，本申请还提供一种用电装置，用电装置包括本申请提供的二次电池、电池模块、或电池包中的至少一种。所述二次电池、电池模块、或电池包可以用作所述用电装置的电源，也可以用作所述用电装置的能量存储单元。所述用电装置可以包括 移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等，但不限于此。作为所述用电装置，可以根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的用电装置30。该用电装置30为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该用电装置30对二次电池的高功率和高能量密度的需求，可以采用电池包或电池模块。作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
实施例
以下，说明本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
1、正极极片的制备
采用厚度为8μm的铝箔作为正极集流体。将正极活性材料镍钴锰酸锂(NMC)、导电剂乙炔黑、粘结剂聚偏二氟乙烯(PVDF)按98:1:1的重量比在适量的N-甲基吡咯烷酮(NMP)溶剂中充分搅拌混合，使其形成均匀的正极浆料；将正极浆料涂覆于正极集流体的表面上，经烘干等工序后，得到正极极片。
2、负极极片的制备
采用50μm的金属锂箔作为负极极片。
3、电解质的制备
取双氟磺酰亚胺锂盐Y，加入原碳酸四乙酯溶剂X，于60℃下搅拌直至形成无色透明溶液。冷却至室温静置2小时，溶液凝固，其中，双氟磺酰亚胺锂盐Y的摩尔量为1g/mol，原碳酸四乙酯溶剂X的摩尔量为1.5g/mol。
4、二次电池的制备
将正极极片、隔离膜(PP/PE/PP复合薄膜)、负极极片依次层叠设置，包裹于铝塑膜中组成叠片式电芯，于60℃下将上述电解液0.3g注入到电芯中，将铝塑膜进行真空热压封装，于60℃下静置至少6小时候，降温至30℃，并于30℃下静置至少6小时至电解质固化，之后经过热冷压、化成等工序，得到二次电池。
实施例2至实施例7
与实施例1不同的是，实施例2至实施例7采用不同的原碳酸酯。
实施例8至实施例10
与实施例1不同的是，实施例8至实施例10采用不同的锂盐。
实施例11至实施例12
与实施例1不同的是，实施例11至实施例12于电解质中增加了无机陶瓷类填料。
实施例13至实施例20
与实施例1不同的是，实施例13至实施例20的锂盐的摩尔百分量不同。
实施例21
与实施例1不同的是，实施例21采用不同的负极极片。
对比例1
与实施例1不同的是，对比例1中未添加锂盐。
对比例2
与实施例1不同的是，对比例2采用不同的锂盐，该锂盐不会与原碳酸酯形成塑晶复合物。
表1示出了实施例和对比例的各物质和相关参数。
Figure PCTCN2022094196-appb-000003
表1中，LiFSI表示双氟磺酰亚胺锂，LiBF 4表示四氟硼酸锂，LiPF 6六氟磷酸 锂，CF 3SO 3Li三氟甲基磺酸锂，LiBOB二草酸硼酸锂；Al 2O 3表示三氧化二铝；LLZO表示锂镧锆氧。
测试部分
1、电解质的状态检测
采用差示量热扫描法(differential scanning calorimetry，DSC)测定电解质中塑晶复合物的相变点与相变转化热。
采用德国耐驰仪器制造有限公司生产的STA449F3测试电解质，从室温开始，对锂盐与原碳酸酯的均相混合物进行升温实验，升温速度为2℃/min，直至100℃截止，记录升温过程中热量的释放与吸收数据，用以分析材料的相变转化温度以及转变热是否在塑晶材料区间范围内。
2、电解质的导离子率的测定
以两片不锈钢片SUS为阻塞电极，将其置于一片厚度已知且中间打孔的环状聚酰亚胺薄膜两侧，组成纽扣电池。于60℃下，将电解质融化后添加到环状聚酰亚胺薄膜的孔中，并填满不锈钢片SUS之间的体积。
对组成的纽扣电池进行不同温度下的阻抗测试，从结果中读取x轴截距为体相离子传输电阻R，再通过聚酰亚胺薄膜的厚度t及其中孔面积S，可以通过公式：σ＝t/RS计算出以上电解质在不同温度下对锂离子的导离子率。
3、电解质的氧化稳定性的测定
使用50μm的金属锂箔作为负极，铝箔为正极，聚乙烯多孔膜为隔离膜，将融化的电解质注入隔离膜中，组成纽扣电池。于40℃下，将形成的纽扣电池静置3小时，之后进行扫描伏安曲线(LSV)测试：电压区间为开路电压-6V，电压扫速设定为1mV/s，并记录腐蚀电流，但腐蚀电流密度达到10μA/cm 2时的电压记录为氧化稳定性阈值，用来评估其氧化稳定性，该阈值越高，则氧化稳定性越好。
4、二次电池的循环性能
4.1电压曲线图的测定
使用50μm的金属锂箔作为负极，铝箔为正极，聚乙烯多孔膜为隔离膜，将融化的电解质注入隔离膜中，组成纽扣电池。于40℃下，将形成的纽扣电池静置3小时，之后使用从低到高的电流密度对该纽扣电池进行充放电循环，得到电压曲线图。具体地，该纽扣电池分别在0.1mA/cm 2、0.2mA/cm 2和0.4mA/cm 2的电流密度下，0.25mAh/cm 2的容量密度下分别循环5圈。
4.2循环寿命
测试条件为常温条件下，将所制作的二次电池以0.05C倍率充电、以0.05C倍率放电，进行满充满放循环测试，直至二次电池的容量衰减至初始容量的80％，停止测试，记录循环圈数。
测试结果
本申请的电解质在改善二次电池的循环性能的作用如表2所示，
Figure PCTCN2022094196-appb-000004
Figure PCTCN2022094196-appb-000005
由表2可知，实施例1至实施例7采用不同的原碳酸酯，该类原碳酸酯均可以与锂盐Y在室温下形成塑晶复合物。且在原碳酸酯中的烷基链的加长，塑晶复合物的导离子率下降，二次电池的循环性能呈下降趋势，但是塑晶复合物的氧化稳定性上升。尤其原碳酸酯中的R1至R4各自独立地表示C1至C10的烷基时，塑晶复合物能够兼顾导离子率和氧化稳定性。当原碳酸酯中的烷基链被氟取代后，能够稳定电解质的氧化稳定性。
实施例1、实施例8至实施例10，采用不同的锂盐Y与原碳酸酯四乙酯形成塑晶复合物，塑晶复合物的导离子率较高，且具有相对较高的氧化稳定性。
实施例11和实施例12，在实施例1的基础上增加了无机填料，该类填料能够提高电解质的机械性能，且能够保证二次电池的循环性能。
实施例1、实施例13至实施例20，原碳酸酯和锂盐采用不同的摩尔比，通过对摩尔比的调控，可以调节所形成的塑晶复合物的性能。尤其是在0.5≤x:y≤3时，原碳酸酯和锂盐在室温下更容易形成塑晶结构。
相较于实施例21，实施例1采用金属锂作为负极极片，可以保证二次电池的循环性能，从而证实实施例1的电解质能够维持负极极片的稳定性并能够降低发生锂枝晶的风险。
图7示出了实施例1的塑晶复合物的DSC曲线，由图7可以看出，塑晶复合物 在约57℃左右存在明显吸热峰，意味着该温度发生由固态到液态的相变过程。经计算该过程的熵变为17.96J/(mol·K)，小于临界值20J/(mol·K)。这说明该材料从室温至57℃之间具有塑晶结构。在图7中，T表示温度。
图8示出了实施例1的塑晶复合物随温度变化的导离子率变化趋势图，图9示出了实施例2的塑晶复合物随温度变化的导离子率变化趋势图，由图8和图9可以看出，由实施例1的塑晶复合物组成的纽扣电池在不同温度下的导离子率不同，且在一定的温度范围内，导离子率随温度的升高而升高。在图8和图9中，λ表示导离子率，T表示温度。
图10示出了实施例1的塑晶复合物组成的纽扣电池的扫描伏安曲线图，由图10可以看出，由实施例1的塑晶复合物组成的纽扣电池，在对金属锂电位达到5V条件下，氧化腐蚀电流仍然小于25μA/cm 2，由此说明该固态塑晶电解质具有优异的氧化稳定性。
图11示出了实施例1的塑晶复合物组成的纽扣电池的循环曲线图，由图11可以看出，在40℃下，由实施例的塑晶复合物组成的纽扣电池，在0.1mA/cm 2、0.2mA/cm 2的电流密度下电池可以稳定循环，在0.4mA/cm 2的电流密度下电池会产生较为明显的极化，并且随着沉积容量的增加，过电势有较为明显的上升。
图12示出了实施例1的塑晶复合物组成的二次电池的首圈循环曲线图，由图12可以看出，该二次电池可以稳定循环，并可以释放出95％以上的额定容量，并且首圈库伦效率和该三元正极在液态体系中的授权库伦效率较为吻合。在图12中，Q表示容量，U表示电压。
结合上述分析可知，本申请实施例通过对塑晶复合物中的塑晶结构的调控，可以改善塑晶复合物的导离子率和氧化稳定性，从而能够改善二次电池的循环性能。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件。尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (12)

  1. 一种电解质，包括塑晶复合物，所述塑晶复合物包括原碳酸酯和锂盐，所述原碳酸酯包括式I所示的化合物中的一种或多种，
    Figure PCTCN2022094196-appb-100001
    式I中，R1至R4各自独立地表示烷基或卤代烷基。
  2. 根据权利要求1所述的电解质，其中，
    所述烷基为C1-C10烷基；和/或
    所述卤代烷基为C1-C10卤代烷基。
  3. 根据权利要求1或2所述的电解质，其中，所述卤代烷基为氟代烷基。
  4. 根据权利要求1至3中任一项所述的电解质，其中，
    所述原碳酸酯包括原碳酸四甲酯、原碳酸四乙酯、原碳酸四丙酯、原碳酸四丁酯、原碳酸四戊酯、原碳酸四己酯、原碳酸四庚酯、原碳酸四辛酯、原碳酸四壬酯、原碳酸四癸酯、氟代原碳酸四甲酯、氟代原碳酸四乙酯、氟代原碳酸四丙酯、氟代原碳酸四丁酯、氟代原碳酸四戊酯、氟代原碳酸四己酯、氟代原碳酸四庚酯、氟代原碳酸四辛酯、氟代原碳酸四壬酯、氟代原碳酸四癸酯、四三氟甲氧基甲烷、四-(2,2,2-三氟乙氧基)-甲烷、四-(3,3,3-三氟丙氧基)-甲烷、原碳酸甲基三乙酯、原碳酸二甲二乙酯、原碳酸乙基三甲酯、原碳酸甲基三丙酯、原碳酸二甲二丙酯、原碳酸丙基三甲酯、原碳酸乙基三丙酯、原碳酸二乙二丙酯、原碳酸丙基三乙酯、原碳酸甲基三丁酯、原碳酸二甲二丁酯和原碳酸丁基三甲酯中的一种或多种；
    可选地，所述原碳酸酯包括原碳酸四甲酯、原碳酸四乙酯、原碳酸四丙酯、原碳酸四丁酯、原碳酸四戊酯、原碳酸四己酯、原碳酸四庚酯、原碳酸四辛酯、原碳酸四壬酯和原碳酸四癸酯中的一种或多种。
  5. 根据权利要求1至4中任一项所述的电解质，其中，
    所述锂盐包括磺酰亚胺类锂盐、硼酸类锂盐、六氟磷酸锂、高氯酸锂、六氟砷酸锂和三氟甲基磺酸锂中的一种或多种；
    可选地，所述磺酰亚胺类锂盐包括双氟磺酰亚胺锂、双氟甲基磺酰亚胺锂和双五氟乙基磺酰亚胺锂中的一种或多种；进一步可选地，所述磺酰亚胺类锂盐包括双氟磺酰亚胺锂和/或双氟甲基磺酰亚胺锂；进一步可选地，所述磺酰亚胺类锂盐包括双氟磺酰亚胺锂；
    可选地，所述硼酸类锂盐包括四氟硼酸锂、二草酸硼酸锂和二氟草酸硼酸锂中的一种或多种。
  6. 根据权利要求1至5中任一项所述的电解质，其中，
    所述原碳酸酯的摩尔量x和所述锂盐的摩尔量y满足：0.5≤x:y≤3；
    可选地，1≤x:y≤2。
  7. 根据权利要求1至6中任一项所述的电解质，其中，
    基于所述原碳酸酯和所述锂盐的总质量计，所述原碳酸酯的摩尔百分数为30％～80％；可选地，50％～70％；和/或
    基于所述原碳酸酯和所述锂盐的总质量计，所述锂盐的摩尔百分数为20％～70％；可选地，30％～50％。
  8. 根据权利要求1至7中任一项所述的电解质，其中，
    所述电解质还包括无机陶瓷类填料；可选地，所述无机陶瓷类填料选自无机陶瓷类惰性填料和/或无机陶瓷类锂离子导体填料；
    进一步可选地，所述无机陶瓷类惰性填料选自氧化铝、氧化硅、氧化钛、氧化锌、氧化镁、氧化铁、氧化铜、氧化钙、氧化铬、氧化锰、氧化钴和氧化镍中的一种或多种；
    进一步可选地，所述无机陶瓷类锂离子导体填料选自氧化物类锂离子导体填料、硫化物类锂离子导体填料和卤化物类锂离子导体填料中的一种或多种。
  9. 一种二次电池，包括如权利要求1至8中任一项所述的电解质；
    可选地，所述二次电池还包括负极极片，所述负极极片包括锂元素。
  10. 一种电池模块，包括如权利要求9所述的二次电池。
  11. 一种电池包，包括如权利要求10所述的电池模块。
  12. 一种用电装置，包括如权利要求9所述的二次电池、如权利要求10所述的电池模块或如权利要求11所述的电池包。
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