WO2022042496A1 - 界面功能层及其制备方法和锂离子电池 - Google Patents

界面功能层及其制备方法和锂离子电池 Download PDF

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WO2022042496A1
WO2022042496A1 PCT/CN2021/114119 CN2021114119W WO2022042496A1 WO 2022042496 A1 WO2022042496 A1 WO 2022042496A1 CN 2021114119 W CN2021114119 W CN 2021114119W WO 2022042496 A1 WO2022042496 A1 WO 2022042496A1
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lithium
functional layer
interface functional
interface
negative electrode
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French (fr)
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张赵帅
赵伟
李素丽
李俊义
徐延铭
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/471—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof
    • H01M50/48—Spacing elements inside cells other than separators, membranes or diaphragms; Manufacturing processes thereof characterised by the material
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the application belongs to the technical field of lithium ion batteries, and in particular relates to an interface functional layer and a preparation method thereof, and a lithium ion battery.
  • lithium-ion batteries have the characteristics of high energy density and long service life, and have been attracting attention since they were put into the market. field is widely used.
  • organic electrolyte is flammable and explosive, and also volatile, it is easy to cause safety problems in lithium-ion batteries. Therefore, researchers use solid electrolytes to replace electrolytes in order to fundamentally solve the safety problems of all-solid-state batteries.
  • solid electrolytes can effectively improve the safety and stability of batteries due to their high mechanical strength, excellent density and ability to resist lithium dendrite growth.
  • the CEI film on the positive electrode surface and the SEI film on the negative electrode surface have a certain influence on the cycle and capacity; the poor contact wettability of the solid-solid interface of the positive electrode and the electrolyte easily leads to an increase in the interfacial resistance of the electrolyte; The negative electrode metal lithium is active, and the interface problem with poor contact will lead to the uneven deposition of lithium dendrites at the interface.
  • the present application provides an interface functional layer.
  • the interface functional layer By arranging the interface functional layer between the positive electrode and/or the negative electrode and the solid electrolyte, the uneven deposition of lithium ions at the interface voids is suppressed, the interface impedance is reduced, and the interface stability is improved at the same time. sex.
  • the present application also provides a method for preparing the above-mentioned interface functional layer, which has the advantages of simple process, convenient operation, remarkable effect and convenient industrial production.
  • the present application also provides a lithium-ion battery with higher cycle efficiency and cycle stability, while the battery short circuit rate is almost zero.
  • the present application proposes an interface functional layer, the interface functional layer includes a cyclic ether compound, a lithium salt, an auxiliary agent and a ceramic powder in a mass ratio of 50-90:5-30:5-40:0-5 .
  • the interface functional layer of the present application can improve the grain boundary resistance and electrode interface performance by adjusting the composition and ratio of raw materials, suppress the uneven deposition of lithium ions at the interface voids, reduce the interface impedance, and improve the interface stability at the same time.
  • the above-mentioned interface function layer of the present application may also have the following additional technical features:
  • the interface functional layer is obtained by mixing the raw materials uniformly, and then attaching to the positive electrode, the negative electrode and/or the solid electrolyte, and performing curing treatment.
  • the method of attachment is selected from one or a combination of blade coating, spray coating, casting and soaking.
  • the temperature of the curing treatment can be adjusted according to the raw materials of the interface functional layer. Generally, the temperature of the curing treatment can be adjusted to 25-60°C, such as 35°C, to obtain a uniform and stable interface functional layer.
  • the thickness of the interface functional layer is about 10 nm-10 ⁇ m, for example, 100 nm-1 ⁇ m, and further, the thickness of the interface functional layer is 400-800 nm.
  • cyclic ether compounds, lithium salts, additives and ceramic powders in this application are all conventional materials in the art, which can be self-made or commercially available, which are not particularly limited in this application.
  • the particle size of the ceramic powder is about 1-900 nm, for example, 400-800 nm, and further, the particle size of the ceramic powder is 500-600 nm.
  • the cyclic ether compound is selected from 1,3-dioxane and/or 1,4-dioxane; and/or,
  • the lithium salt is selected from lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium bis-oxalate borate, lithium oxalate difluoroborate, lithium bis-difluorosulfonimide, lithium bis-trifluoromethanesulfonate Lithium imide, lithium trifluoromethanesulfonate, bismalonate boric acid, lithium oxalate borate malonate, lithium hexafluoroantimonate, lithium difluorophosphate, 4,5-dicyano-2-trifluoromethane
  • the auxiliary agent is selected from one or more combinations of ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether carbon, ethylene acid, propylene carbonate, dimethyl carbonate and diethyl carbonate; and/or,
  • the ceramic powder is selected from one or several combinations of nano-hexagonal boron nitride, nano-alumina and nano-silicon dioxide.
  • the present application proposes the above-mentioned preparation method of the interface functional layer, comprising the following steps:
  • cyclic ether compound, lithium salt, auxiliary agent and ceramic powder After mixing the cyclic ether compound, lithium salt, auxiliary agent and ceramic powder with a mass ratio of 50-90:5-30:5-40:0-5, they are attached to the positive electrode, negative electrode and/or solid electrolyte and cured processing to obtain the interface function layer.
  • auxiliary stirring can be used to speed up the mixing, for example, adjusting the rotational speed to 200-1000 rpm/min and stirring for 1-24 hours, a uniformly mixed solution can be obtained.
  • the cyclic ether compound, lithium salt and auxiliary agent can be mixed firstly until uniform, and then the ceramic powder is slowly added to facilitate the dispersion of the ceramic powder.
  • the application does not limit the types of negative electrodes.
  • the negative electrode is selected from at least one of a metal lithium negative electrode or a lithium alloy negative electrode, the metal lithium is selected from one of molten metal lithium, lithium powder and lithium ribbon, and the lithium alloy includes Li-In alloy, Li- Al alloy, Li-Sn alloy, Li-Mg alloy and Li-Ge alloy.
  • the method of attachment is selected from one or a combination of blade coating, spray coating, casting and soaking.
  • the temperature of the curing treatment is 25-60° C., for example, 35° C.
  • the interface functional layer after curing has a uniform and good morphology and less pore cracks.
  • the preparation method of the interface functional layer of the present application has the advantages of simple process, convenient operation, remarkable effect and convenient industrial production.
  • an interface functional layer between the positive electrode and/or the negative electrode and the solid electrolyte By disposing an interface functional layer between the positive electrode and/or the negative electrode and the solid electrolyte, the uneven deposition of lithium ions at the interfacial voids is suppressed, the interfacial impedance is reduced, and the interfacial stability is improved at the same time.
  • the present application proposes a lithium ion battery, which is prepared by winding or stacking a positive electrode, a solid electrolyte, and a negative electrode, and the above-mentioned interface functional layer is also provided between the negative electrode and/or the positive electrode and the solid electrolyte.
  • the lithium-ion battery can be manufactured by a conventional winding or lamination process. Specifically, the positive pole piece, the solid electrolyte, the interface functional layer, and the negative pole piece are wound or laminated together in sequence, and then vacuum-packed, The lithium ion battery can be obtained by welding the tabs.
  • the composition of the positive electrode sheet may include a positive electrode active material, a solid electrolyte, a conductive agent and a binder in a mass ratio of 70-95:1-15:1-10:1-10.
  • the composition of the positive electrode sheet includes a positive electrode material, a conductive agent and a binder.
  • the active material in the positive electrode material can be selected from lithium iron phosphate chemical system materials, lithium cobalt oxide chemical system materials, nickel cobalt lithium manganate chemical system materials, lithium manganate chemical system materials, nickel cobalt lithium aluminate chemical system materials, nickel cobalt lithium aluminate chemical system materials Lithium manganese aluminate chemical system materials, nickel cobalt aluminum tungsten chemical system materials, lithium-rich manganese chemical system materials, lithium nickel cobalt oxide chemical system materials, lithium nickel titanium magnesium oxide chemical system materials, lithium nickelate chemical system materials, spinel One or a combination of lithium manganate chemical system materials and nickel cobalt tungsten chemical system materials.
  • the conductive agent may be selected from one or more of conductive carbon black (SP), ketjen black, acetylene black, carbon nanotube (CNT), graphene and flake graphite.
  • the binder may be selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene.
  • the electrolyte may be a solid electrolyte or a liquid electrolyte.
  • the liquid electrolyte can be self-made or purchased from any commercial electrolyte in the market.
  • the electrolyte may be selected from a sulfide electrolyte, a perovskite type electrolyte, a Garnet type electrolyte, a NASICON type electrolyte, a LISICON type electrolyte, and a combination of one or more of the polymer electrolytes.
  • the sulfide electrolyte can be selected from lithium phosphorus chloride sulfur, lithium phosphorus bromide sulfur, lithium phosphorus iodine sulfur, lithium phosphorus silicon sulfur, lithium phosphorus aluminum sulfur, lithium phosphorus germanium sulfur, lithium phosphorus boron sulfur, lithium phosphorus sulfur, lithium silicon sulfur , one or a combination of lithium silicon indium sulfur and the like.
  • the perovskite electrolyte is Li 3x La 2/3-x TiO 3 , wherein 0.04 ⁇ x ⁇ 0.17.
  • the garnet type electrolyte is lithium lanthanum zirconium oxygen electrolyte and its Al, Ga, Fe, Ge, Ca, Ba, Sr, Y, Nb, Ta, W, Sb element doped derivatives; further, the said The garnet-type electrolyte is Li 7-n La 3 Zr 2-n Tan O 12 and/or Li 7-n La 3 Zr 2-n Nbn O 12 , where 0 ⁇ n ⁇ 0.6; or Li 6.4-x La 3 Zr 2-x Ta x Al 0.2 O 12 , wherein 0.2 ⁇ x ⁇ 0.5.
  • the NASICON type electrolyte is Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP), where 0.2 ⁇ x ⁇ 0.5; and/or Li 1+x Al x Ge 2-x (PO 4 ) 3 (LAGP), where 0.4 ⁇ x ⁇ 0.5.
  • the polymer electrolyte is selected from polymer electrolytes containing lithium salts.
  • the polymer is selected from polycarbonate, polyether, polyethylene glycol, polyphenylene ether, polyethylene diamine, polyethylene dithiol, polyester, polyethylene oxide, etc. and their copolymer derivatives.
  • the lithium ion battery of the present application can be a button battery, a mold battery or a soft pack battery.
  • an interface functional layer is arranged between the positive electrode and/or the negative electrode and the solid electrolyte, thereby suppressing the uneven deposition of lithium ions at the interface voids, reducing the interface impedance, and improving the interface stability at the same time.
  • the lithium-ion battery of the present application has higher cycle efficiency and cycle stability, while the battery short-circuit rate is almost zero.
  • FIG. 1 is a schematic structural diagram of the metal lithium negative electrode pole piece and the interface functional layer thereon according to Example 1 of the application;
  • Example 2 is a schematic structural diagram of the solid electrolyte of Example 4 of the application and the interface functional layer thereon;
  • Example 3 is a schematic structural diagram of the solid electrolyte of Example 7 of the application and the interface functional layer thereon;
  • Example 4 is a microscopic topography diagram of the interface functional layer of Example 3 of the application.
  • FIG. 5 is a schematic diagram showing the comparison of the AC impedance of the lithium ion battery in Example 5 of the present application and Comparative Example 5;
  • FIG. 6 is a cycle diagram of the lithium symmetric battery of Example 8 of the present application at a current density of 1 mA/cm 2 .
  • the ceramic powders in the examples of the present application were purchased from: Kejing Chemical Co., Ltd., and the particle size was about 400-800 nm.
  • Test conditions The lithium symmetric battery constant current charge-discharge test was performed at a current density of 1 mA/cm 2 .
  • the test instrument is Wuhan Landian battery test equipment
  • Test conditions When the initial capacity is basically the same, the number of cycles when the capacity decays to 80% of the initial value is measured at 25°C and 0.2C/0.2C.
  • Cell short-circuit rate number of short-circuited cells/total number of cells measured x 100%.
  • Embodiment 1 proposes a lithium metal negative electrode and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • 1,4-dioxane, lithium bistrifluoromethanesulfonimide (LiTFSI), polycarbonate (PC), and nano-boron nitride (BN) are in a mass ratio of 79:9:10 :2 After mixing evenly, put it in a beaker, and evenly stir at 300rpm for 15h to form a homogeneous solution.
  • the homogeneous solution is uniformly coated on the surface of the metal lithium sheet by means of scraping, so that the homogeneous solution fully covers and infiltrates the metal lithium sheet.
  • the curing temperature is 45° C., to obtain a metal lithium negative electrode containing an interface functional layer, as shown in FIG. 1 , wherein the thickness of the interface functional layer is 500 nm.
  • Comparative example 1 proposes a lithium ion battery, and its preparation method includes the following steps:
  • Embodiment 2 proposes a metal lithium negative electrode and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • the Li-In alloy was taken out from the homogeneous solution, and heated and solidified at a solidification temperature of 35 °C to obtain a Li-In alloy negative electrode containing an interface functional layer, wherein the thickness of the interface functional layer was 400nm.
  • Comparative example 2 proposes a lithium ion battery, and its preparation method includes the following steps:
  • Embodiment 3 proposes a lithium metal negative electrode and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • the Li-Cu composite tape was taken out from the homogeneous solution and cured at room temperature of 25 °C to obtain a Li-Cu composite negative electrode containing an interface functional layer, wherein the thickness of the interface functional layer was 800 nm.
  • Comparative example 3 proposes a lithium ion battery, and its preparation method includes the following steps:
  • Embodiment 4 proposes a solid electrolyte and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • the homogeneous solution is uniformly coated on the surface of the Li 0.3 La 0.56 TiO 3 electrolyte near the positive electrode side by casting, so that the homogeneous solution fully covers the Li 0.3 La 0.56 TiO 3 infiltrated near the positive electrode side. electrolyte.
  • the positive electrode sheet of cm 2 is combined with a solid electrolyte containing an interface functional layer and a metal lithium sheet to assemble a button battery, wherein the interface functional layer is located between the positive electrode sheet and the solid electrolyte.
  • Comparative example 4 proposes a lithium ion battery, and its preparation method includes the following steps:
  • Embodiment 5 proposes a metal lithium negative electrode and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • the homogeneous solution is uniformly coated on the surface of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) by spraying, so that the homogeneous solution fully covers and infiltrates the Li 1.5 Al 0.5 Ge 1.5 ( PO 4 ) 3 (LAGP).
  • a positive electrode with an areal density of 4 mg/cm 2 was coated with lithium manganate (LiMnO 2 ) (83 wt %), LAGP solid electrolyte (5 wt %), Ketjen black (6 wt %), and polyvinylidene fluoride (6 wt %).
  • Comparative example 5 proposes a lithium ion battery, and its preparation method includes the following steps:
  • a positive electrode with an areal density of 4 mg/cm 2 was coated with lithium manganate (LiMnO 2 ) (83 wt %), LAGP solid electrolyte (5 wt %), Ketjen black (6 wt %), and polyvinylidene fluoride (6 wt %).
  • sheet with traditional Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 solid-state electrolyte and metal lithium ribbon, and using the existing lamination process to make a soft-pack solid-state lithium ion battery, wherein Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3
  • the interfacial functional layer is located between the solid electrolyte and the metallic lithium ribbon.
  • Embodiment 6 proposes a solid electrolyte and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • the Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 solid electrolyte sheet was taken out from the homogeneous solution and cured at 50°C to obtain a solid electrolyte with an interface functional layer on both sides.
  • the thickness of the layer is 1 in .
  • Embodiment 7 proposes a solid electrolyte and a lithium ion battery, the preparation method of which includes the following steps:
  • Embodiment 8 proposes a metal lithium negative electrode and a lithium ion battery containing an interface functional layer, and the preparation method includes the following steps:
  • the lithium ribbon is taken out from the homogeneous solution and cured at room temperature to obtain a metal lithium negative electrode containing an interface functional layer, wherein the thickness of the interface functional layer is 500 nm.
  • a positive electrode sheet with an areal density of 15 mg/cm 2 is laminated with a polymer electrolyte and a treated Cu current collector lithium tape containing a functional layer in sequence, and a soft-packed lithium ion battery is made by using the existing winding process.
  • the lithium metal negative electrode containing the interface functional layer of Example 8 was assembled into a lithium symmetric battery, and a cycle test was carried out on it, and the results are shown in Figure 6 .
  • Comparative Example 6 proposes a lithium metal negative electrode and a lithium ion battery.
  • the difference between Comparative Example 6 and Example 8 is only that in Comparative Example 6, 1,4-dioxane, LiPF 6 /LiFSI (mass ratio 1:1) ), DME, and nano-silica in a mass ratio of 45:4:6:13, and other preparation methods and parameters are the same.
  • Comparative Example 7 proposes a lithium metal negative electrode and a lithium ion battery.
  • the difference between Comparative Example 7 and Example 8 is only that in Comparative Example 7, 1,4-dioxane, LiPF 6 /LiFSI (mass ratio 1:1) ), DME, and nano-silica in a mass ratio of 30:5:20:13, and other preparation methods and parameters are the same.
  • Comparative Example 8 proposes a lithium metal negative electrode and a lithium ion battery.
  • the difference between Comparative Example 8 and Example 8 is only that in Comparative Example 8, 1,4-dioxane, LiPF 6 /LiFSI (mass ratio 1:1) ), DME, and nano-silica in a mass ratio of 20:10:8:8, and other preparation methods and parameters are the same.
  • the lithium ion battery of the present application has a lower interface impedance by providing an interface functional layer between the positive electrode and/or the negative electrode and the solid electrolyte, and has a higher
  • the cycle efficiency and cycle stability of the battery are almost zero at the same time.
  • Example 5 As shown in FIG. 5 , compared with Comparative Example 5, the AC impedance at room temperature is smaller in Example 5, indicating that the interface performance is excellent and the overall performance is excellent.
  • the lithium symmetric battery of Example 8 showed good stability in the voltage platform within 200 cycles, and no short circuit occurred. It shows that the interface stability between the negative electrode piece and the electrolyte prepared in Example 8 of the present application is good, and the growth of lithium dendrites can be well inhibited.
  • the interface functional layer of the present application can improve the grain boundary resistance and electrode interface performance by adjusting the composition and ratio of raw materials, suppress the uneven deposition of lithium ions at the interface voids, reduce the interface impedance, and improve the interface stability at the same time .
  • the lithium ion battery prepared by using the above-mentioned interface functional layer suppresses the uneven deposition of lithium ions at the interface voids, reduces the interface impedance, and improves the interface stability at the same time.
  • the lithium-ion battery of the present application has higher cycle efficiency and cycle stability, while the battery short-circuit rate is almost zero.

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Abstract

本申请涉及一种界面功能层及其制备方法和锂离子电池，所述界面功能层包括质量比为50-90:5-30:5-40:0-5的环醚化合物、锂盐、助剂和陶瓷粉末。本申请通过在正极和/或负极与固态电解质之间设置界面功能层，抑制了锂离子在界面空隙处的不均匀沉积，降低了界面阻抗，同时提高了界面稳定性。

Description

界面功能层及其制备方法和锂离子电池
本申请要求于2020年08月31日提交中国专利局、申请号为202010897495.8、申请名称为“界面功能层及其制备方法和锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于锂离子电池技术领域，具体涉及一种界面功能层及其制备方法和锂离子电池。
背景技术
近年来，在各种商业化可充/放电化学储能装置中，锂离子电池具有能量密度高、使用寿命长等特点，自投入市场以来一直备受瞩目，在手机、笔记本电脑、电动汽车等领域得到广泛应用。但是，由于有机电解液易燃易爆，同时还易挥发，很容易引起锂离子电池的安全问题。因此，研究人员采用固体电解质替代电解液以期从根本上解决全固态电池的安全问题。而固体电解质作为全固态锂电池的关键材料，由于具有较高的机械强度、优异的致密度和抵制锂枝晶生长的能力，能够有效提升电池的安全性、稳定性。
传统固体电解质虽然在离子电导率方面具有一定优势，固态电解质和电极的界面问题一直是限制固态电池发展的重要挑战。例如，固-固界面一般存在空间电荷层以及缺陷结构，其物理化学特性会影响离子与电子的输运、电极结构的稳定性、电荷转移的速率。电池在循环的过程中正极表面的CEI膜和负极表面的SEI膜对循环和容量均有一定影响；正极和电解质的固-固界面较差的接触润湿性容易导致电解质的界面电阻增大；负极金属锂性质活泼，接触较差的界面问题会导致锂枝晶在界面处的不均匀沉积，锂枝晶的不断生长，造成电池内短路，存在非常大的安全隐患。
因此，研究出一种可以稳定固态电解质和锂负极的界面功能层是 十分有必要的。
发明内容
本申请提供了一种界面功能层，通过在正极和/或负极与固态电解质之间设置界面功能层，抑制了锂离子在界面空隙处的不均匀沉积，降低了界面阻抗，同时提高了界面稳定性。
本申请还提供了上述界面功能层的制备方法，工艺简单、操作方便、效果显著，便于工业化生产。
本申请还提供了一种锂离子电池，具有更高的循环效率和循环稳定性，同时电池短路率几乎为零。
本申请提出的技术方案是：
第一方面，本申请提出一种界面功能层，所述界面功能层包括质量比为50-90:5-30:5-40:0-5的环醚化合物、锂盐、助剂和陶瓷粉末。
本申请的界面功能层，通过调节原料组成和配比，可以改善晶界电阻和电极界面性能，能够抑制锂离子在界面空隙处的不均匀沉积，降低界面阻抗，同时提高界面稳定性。
本申请上述的界面功能层，还可以具有如下附加的技术特征：
在本申请的具体实施方式中，所述界面功能层是将所述原料混合均匀后附着在正极、负极和/或固态电解质上并进行固化处理得到的。
具体地，所述附着的方法选自刮涂、喷涂、流延和浸泡中的一种或几种组合。
其中，固化处理的温度可以根据界面功能层的原料进行调节，一般情况下，可以调节所述固化处理的温度为25-60℃，例如35℃，即可得到均匀稳定的界面功能层。
控制界面功能层的厚度在一定范围内，有利于更好地控制离子通过率以及导电率等。在本申请中，所述界面功能层的厚度约为10nm-10μm，例如100nm-1μm，进一步地，界面功能层的厚度为400-800nm。
本申请中的环醚化合物、锂盐、助剂和陶瓷粉末均为本领域常规物质，可以是自制，也可以商购，本申请对此不作特别限定。
采用纳米级的的陶瓷粉末，更利于得到具有较好电性能的界面功能层。因此，在本申请中，所述陶瓷粉末的粒径约为1-900nm，例如400-800nm，进一步地，陶瓷粉末的粒径为500-600nm。
在本申请的具体实施方式中，所述环醚化合物选自1,3-二氧五环和/或1,4-二氧六环；和/或，
所述锂盐选自高氯酸锂、六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、双草酸硼酸锂、草酸二氟硼酸锂、双二氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂、三氟甲基磺酸锂、双丙二酸硼酸、丙二酸草酸硼酸锂、六氟锑酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪唑锂、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3和LiN(SO 2F) 2中的一种或几种组合；和/或，
所述助剂选自乙二醇二甲醚、二丙二醇二甲醚碳、酸乙烯酯、碳酸丙烯酯、碳酸二甲酯和碳酸二乙酯中的一种或几种组合；和/或，
所述陶瓷粉末选自纳米六方氮化硼、纳米氧化铝和纳米二氧化硅中的一种或几种组合。
第二方面，本申请提出如上所述的界面功能层的制备方法，包括如下步骤：
将质量比为50-90:5-30:5-40:0-5的环醚化合物、锂盐、助剂和陶瓷粉末混合均匀后，附着在正极、负极和/或固态电解质上并进行固化处理，得到界面功能层。本领域技术人员可以理解，在混合时，可以辅助搅拌以加速混合，例如调节转速为200-1000rpm/min，搅拌1-24h，可以得到混合均匀地溶液。可以先混合环醚化合物、锂盐、助剂至均匀后，再缓慢加入陶瓷粉末以利于陶瓷粉末的分散。
本申请对负极的种类不作限定。所述负极选自金属锂负极或锂合金负极中的至少一种，所述金属锂选自熔融金属锂、锂粉和锂带中的一种，所述锂合金包括Li-In合金、Li-Al合金、Li-Sn合金、Li-Mg合金和Li-Ge合金。
在本申请的具体实施方式中，所述附着的方法选自刮涂、喷涂、流延和浸泡中的一种或几种组合。具体地，固化处理的温度为25-60℃，例如35℃，固化后的界面功能层形态均匀良好、较少气孔裂纹。
本申请上述界面功能层的制备方法，工艺简单、操作方便、效果显著，便于工业化生产。通过在正极和/或负极与固态电解质之间设置界面功能层，从而抑制了锂离子在界面空隙处的不均匀沉积，降低了界面阻抗，同时提高了界面稳定性。
第三方面，本申请提出一种锂离子电池，由正极、固态电解质、负极通过卷绕或层叠的方式制备得到，在负极和/或正极与固态电解质之间还设置有上述的界面功能层。
所述锂离子电池，可以采用常规的卷绕或叠片工艺制造而成，具体的，依次将正极极片、固态电解质、界面功能层、负极极片卷绕或层叠在一起，经真空封装、焊接极耳即可得到所述的锂离子电池。
正极极片组成可以包括质量比为70-95:1-15:1-10:1-10的正极活性物质、固态电解质、导电剂和粘结剂。
正极极片组成包括正极材料、导电剂和粘结剂。正极材料中的活性物质可以选自磷酸铁锂化学体系材料、钴酸锂化学体系材料、镍钴锰酸锂化学体系材料、锰酸锂化学体系材料、镍钴铝酸锂化学体系材料、镍钴锰铝酸锂化学体系材料、镍钴铝钨化学体系材料、富锂锰化学体系材料、镍钴酸锂化学体系材料、镍钛镁酸锂化学体系材料、镍酸锂化学体系材料、尖晶石锰酸锂化学体系材料和镍钴钨化学体系材料中的一种或几种的组合。
所述导电剂可以选自导电炭黑(SP)、科琴黑、乙炔黑、碳纳米管(CNT)、石墨烯和鳞片石墨中的一种或几种。
所述粘结剂可以选自聚四氟乙烯、聚偏氟乙烯和聚偏氟乙烯-六氟丙烯中的一种或几种。
所述电解质可以是固态电解质或液态电解质。
所述液态电解质可以自制，也可以购自市场上任意一款商业化电解质。
所述电解质可以选自硫化物电解质、钙钛矿型电解质、Garnet型电解质、NASICON型电解质、LISICON型电解质、聚合物电解质中的一种或多种的组合。
所述硫化物电解质可以选自锂磷氯硫、锂磷溴硫、锂磷碘硫、锂磷硅硫、锂磷铝硫、锂磷锗硫、锂磷硼硫、锂磷硫、锂硅硫、锂硅铟硫等中的一种或几种的组合。
所述钙钛矿型电解质为Li 3xLa 2/3-xTiO 3，其中，0.04＜x＜0.17。
所述的石榴石型电解质为锂镧锆氧电解质及其Al、Ga、Fe、Ge、Ca、Ba、Sr、Y、Nb、Ta、W、Sb元素掺杂衍生物；进一步地，所述的石榴石型电解质为Li 7-nLa 3Zr 2-nTa nO 12和/或Li 7-nLa 3Zr 2-nNb nO 12，其中，0≤n≤0.6；或Li 6.4-xLa 3Zr 2-xTa xAl 0.2O 12，其中，0.2≤x≤0.5。
所述NASICON型电解质为Li 1+xAl xTi 2-x(PO 4) 3(LATP)，其中0.2≤x≤0.5；和/或Li 1+xAl xGe 2-x(PO 4) 3(LAGP)，其中，0.4≤x≤0.5。
所述LISICON型电解质为Li 4-xGe 1-xP xS 4(X＝0.4或X＝0.6)。
所述聚合物电解质选自含有锂盐的聚合物电解质。其中，所述聚合物选自聚碳酸酯、聚醚、聚乙二醇、聚苯醚、聚乙二胺、聚乙二硫醇、聚酯、聚氧化乙烯等及其共聚衍生物。
本申请的锂离子电池，可以是纽扣电池、模具电池或软包电池。
本申请的锂离子电池，在正极和/或负极与固态电解质之间设置了界面功能层，从而抑制了锂离子在界面空隙处的不均匀沉积，降低了界面阻抗，同时提高了界面稳定性。本申请的锂离子电池具有更高的循环效率和循环稳定性，同时电池短路率几乎为零。
本申请的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本申请的实践了解到。
附图说明
图1为本申请实施例1的金属锂负极极片及其上的界面功能层的结构示意图；
图2为本申请实施例4的固态电解质及其上的界面功能层的结构示意图；
图3为本申请实施例7的固态电解质及其上的界面功能层的结构示意图；
图4为本申请实施例3的界面功能层的微观形貌图；
图5为本申请实施例5和对比例5的锂离子电池交流阻抗对比示意图；
图6是本申请实施例8的锂对称电池循环以1mA/cm 2的电流密度下的循环图。
具体实施方式
下文将结合具体实施例对本申请做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本申请，而不应被解释为对本申请保护范围的限制。凡基于本申请上述内容所实现的技术均涵盖在本申请旨在保护的范围内。
本申请实施例中的陶瓷粉末购自：科晶化工有限责任公司，粒径约为400-800nm。
下面通过具体实施例详细描述本申请：
各实施例和对比例的测试方法如下：
1、室温下的交流阻抗
锂离子电池交流阻抗测试
采用上海辰华CHI600E电化学工作站进行测试，参数设置：振幅为10mV，频率范围为0.1Hz～3MHz。
2、锂对称电池循环测试
采用武汉蓝电电池测试设备；
测试条件：以1mA/cm 2的电流密度进行锂对称电池恒流充放电测试。
3、循环寿命测试
测试仪器为武汉蓝电电池测试设备；
测试条件：在初始容量基本一致情况下，在25℃，0.2C/0.2C的条件下测定其容量衰减至初始值的80％时的循环次数。
4、电池短路率测试
在循环寿命测试过程中，电池失效或短路，表现为不能正常充放电，记为短路。电池短路率＝短路的电池的数量/测量的电池的总数量×100％。
实施例1
实施例1提出了一种含有界面功能层的金属锂负极和锂离子电池，其制备方法包括如下步骤：
1、含有界面功能层的金属锂负极的制备
(1)将1,4-二氧六环、双三氟甲基磺酰亚胺锂(LiTFSI)、聚碳酸酯(PC)、纳米氮化硼(BN)按照质量比为79:9:10:2混合均匀后置于烧杯中，以300rpm的转速均匀搅拌15h至形成均质溶液。
(2)搅拌完成后将均质溶液通过刮涂的方式均匀的涂覆在金属锂片表面，使均质溶液充分覆盖浸润金属锂片。
(3)预处理后15min后加热固化，固化温度为45℃，得到含有界面功能层的金属锂负极，如图1所示，其中，界面功能层的厚度为500nm。
2、锂离子电池的制备
用钴酸锂(91wt％)、Li 6.6La 3Zr 1.6Ta 0.4O 12固态电解质(3.0wt％)、乙炔黑(2.5wt％)、聚四氟乙烯(3.5wt％)涂布成面密度为6mg/cm 2的正极极片，搭配Li 6.6La 3Zr 1.6Ta 0.4O 12固态电解质、上述处理的含有界面功能层的金属锂负极，采用现有叠片工艺制成软包锂离子电池。
对比例1
对比例1提出了一种锂离子电池，其制备方法包括如下步骤：
用钴酸锂(91wt％)、Li 6.6La 3Zr 1.6Ta 0.4O 12固态电解质(3.0wt％)、乙炔黑(2.5wt％)、PVDF(3.5wt％)涂布成面密度为6mg/cm 2的正极极片，搭配Li 6.6La 3Zr 1.6Ta 0.4O 12固态电解质、传统未经处理的金属锂负极，采用现有叠片工艺制成软包固态锂离子电池。
实施例2
实施例2提出了一种含有界面功能层的金属锂负极和锂离子电池，其制备方法包括如下步骤：
1、含有界面功能层的Li-In合金负极的制备
(1)将1,3-二氧五环、六氟砷酸锂(LiAsF 6)、DME、纳米氧化铝按照质量比为68:12:23:3的比例混合均匀后置于烧杯中，以600rpm的转速均匀搅拌8h至形成均质溶液。
(2)搅拌完成后，将Li-In合金浸泡在均质溶液中，使均质溶液充分覆盖浸润Li-In合金。
(3)预处理后9min后将Li-In合金从均质溶液中取出，并加热固化，固化温度为35℃，得到含有界面功能层的Li-In合金负极，其中，界面功能层的厚度为400nm。
2、锂离子电池的制备
用LiNi 0.5Co 0.3Mn 0.2O 2(74wt％)、锂磷氯硫固态电解质(11wt％)、Super-P(9wt％)、PVDF-HFP(6wt％)涂布成面密度为12mg/cm 2的正极极片，搭配锂磷氯硫固态电解质、经上述处理的含有界面功能层的Li-In合金负极，采用模具制成锂离子电池。
对比例2
对比例2提出了一种锂离子电池，其制备方法包括如下步骤：
用LiNi 0.5Co 0.3Mn 0.2O 2(74wt％)、锂磷氯硫固态电解质(11wt％)、Super-P(9wt％)、PVDF-HFP(6wt％)涂布成面密度为12mg/cm 2的正极极片，搭配锂磷氯硫固态电解质、传统Li-In合金负极，采用模具制成锂离子电池。
实施例3
实施例3提出了一种含有界面功能层的金属锂负极和锂离子电池，其制备方法包括如下步骤：
1、含有界面功能层的Li-Cu复合负极的制备
(1)将1，4-二氧六环、三氟甲基磺酸锂(LiCF 3SO 3)、EC/DEC(体系比1:1)按照质量比为67:15:18的比例混合均匀后置于烧杯中，以800rpm的转速均匀搅拌2h至形成均质溶液。
(2)将Li-Cu复合带浸润在搅拌完成后的均质溶液中，使均质溶液充分覆盖浸润Li-Cu复合带。
(3)预处理后3min后将Li-Cu复合带从均质溶液中取出，室温25℃固化，得到含有界面功能层的Li-Cu复合负极，其中，界面功能层的厚度为800nm。
2、锂离子电池的制备
用磷酸铁锂(85wt％)、聚氧化乙烯聚合物电解质(8％)、CNT(5wt％)、聚偏氟乙烯(2wt％)涂布成面密度为10mg/cm 2的正极极片，搭配聚氧化乙烯聚合物电解质、上述处理后含有界面功能层的Li-Cu复合负极，采用现有卷绕工艺制成软包固态锂离子电池。
对比例3
对比例3提出了一种锂离子电池，其制备方法包括如下步骤：
用磷酸铁锂(85wt％)、聚氧化乙烯聚合物电解质(8％)、CNT(5wt％)、聚偏氟乙烯(2wt％)涂布成面密度为10mg/cm 2的正极极片，搭配聚氧化乙烯聚合物电解质、Li-Cu复合负极，采用现有卷绕工艺制成软包固态锂离子电池。
实施例4
实施例4提出了一种含有界面功能层的固态电解质和锂离子电池，其制备方法包括如下步骤：
1、含有界面功能层的固态电解质的制备
(1)将1，3-二氧五环、六氟磷酸锂(LiPF 6)、PC/DMM(体积比1:1)、纳米BN按照质量比为56:18:23:3的比例混合均匀后置于烧杯中，以500rpm的转速均匀搅拌1h至形成均质溶液。
(2)搅拌完成后将均质溶液通过流延的方式均匀的涂覆在近正极侧的Li 0.3La 0.56TiO 3电解质表面，使均质溶液充分覆盖浸润近正极侧的Li 0.3La 0.56TiO 3电解质。
(3)预处理24min后，室温55℃固化，得到含有界面功能层的固态电解质，如图2所示，其中，界面功能层的厚度为300nm。
2、锂离子电池的制备
用LiNi 0.8Co 0.15Al 0.05O 2(80wt％)、Li 0.3La 0.56TiO 3(5％)、科琴黑(8wt％)、聚四氟乙烯(7wt％)涂布成面密度为2.5mg/cm 2的正极极片，搭配含有界面功能层的固态电解质、金属锂片，组装成纽扣电池，其中，界面功能层位于正极极片与固态电解质之间。
对比例4
对比例4提出了一种锂离子电池，其制备方法包括如下步骤：
用LiNi 0.8Co 0.15Al 0.05O 2(80wt％)、Li 0.3La 0.56TiO 3(5％)、科琴黑(8wt％)、聚四氟乙烯(7wt％)涂布成面密度为2.5mg/cm 2的正极极片，Li 0.3La 0.56TiO 3氧化物无机电解质、金属锂片，组装成纽扣电池。
实施例5
实施例5提出了一种含有界面功能层的金属锂负极和锂离子电池，其制备方法包括如下步骤：
1、含有界面功能层的固态电解质的制备
(1)将1，3-二氧五环、草酸二氟硼酸锂(LiDFOB)、EC/DMC(体积比1:1)按照质量比为61:18:21的比例混合均匀后置于烧杯中，以600rpm的转速均匀搅拌8h至形成均质溶液。
(2)搅拌完成后将均质溶液通过喷涂的方式均匀的涂覆在Li 1.5Al 0.5Ge 1.5(PO 4) 3(LAGP)表面上，使均质溶液充分覆盖浸润Li 1.5Al 0.5Ge 1.5(PO 4) 3(LAGP)。
(3)预处理后12min后加热固化，固化温度为45℃，得到含有的Li 1.5Al 0.5Ge 1.5(PO 4) 3(LAGP)界面功能层的固态电解质，其中，界面功能层的厚度为900nm。
2、锂离子电池的制备
用锰酸锂(LiMnO 2)(83wt％)、LAGP固态电解质(5wt％)、科琴黑(6wt％)、聚偏氟乙烯(6wt％)涂布成面密度为4mg/cm 2的正极极片，搭配预处理后的Li 1.5Al 0.5Ge 1.5(PO 4) 3界面功能层的固态电 解质、金属锂带，采用现有叠片工艺制成软包固态锂离子电池，其中，Li 1.5Al 0.5Ge 1.5(PO 4) 3界面功能层位于固态电解质与金属锂带之间。
对比例5
对比例5提出了一种锂离子电池，其制备方法包括如下步骤：
用锰酸锂(LiMnO 2)(83wt％)、LAGP固态电解质(5wt％)、科琴黑(6wt％)、聚偏氟乙烯(6wt％)涂布成面密度为4mg/cm 2的正极极片，搭配传统Li 1.5Al 0.5Ge 1.5(PO 4) 3固态电解质、金属锂带，采用现有叠片工艺制成软包固态锂离子电池，其中，Li 1.5Al 0.5Ge 1.5(PO 4) 3界面功能层位于固态电解质与金属锂带之间。
实施例6
实施例6提出了一种含有界面功能层的固态电解质和锂离子电池，其制备方法包括如下步骤：
1、双面含有功能层的固态电解质的制备
(1)将1，3-二氧五环、LiPF 6/LiTFSI(质量比2:1)、EC/DEC/DME(体积比1:1:1)按照质量比为51:18:31的比例混合均匀后置于烧杯中，以500rpm的转速均匀搅拌15h至形成均质溶液。
(2)将Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质片浸泡在上述均质溶液，确保均质溶液充分覆盖浸润Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质片。
(3)预处理19min后将Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质片从均质溶液中取出，50℃固化，得到双面均含有界面功能层的固态电解质，其中，每层界面功能层的厚度为1其中。
2、锂离子电池的制备
用LiNi 0.6Co 0.6Mn 0.2O 2(72wt％)、Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质(11wt％)Super-P(9wt％)、PVDF-HFP(8wt％)涂布成面密度为3mg/cm 2的正极极片，搭配双面含有功能层的Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质、金属锂负极，采用现有工艺制成纽扣锂离子电池。
实施例7
实施例7提出了一种固态电解质和锂离子电池，其制备方法包括如下步骤：
1、双面含有功能层的固态电解质的制备
(1)将1，3-二氧五环、LiPF 6/LiTFSI(质量比2:1)、EC/DEC/DME(体积比1:1:1)按照质量比为91:5:4的比例混合均匀后置于烧杯中，以500rpm的转速均匀搅拌15h至形成均质溶液。
(2)将Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质片浸泡在上述均质溶液中，确保均质溶液充分覆盖浸润Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质片。
(3)预处理19min将Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质片从均质溶液中取出，50℃固化，得到双面均含有界面功能层的固态电解质，其中，每层界面功能层的厚度为600nm。
2、锂离子电池的制备
用LiNi 0.6Co 0.6Mn 0.2O 2(72wt％)、Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质(11wt％)Super-P(9wt％)、PVDF-HFP(8wt％)涂布成面密度为3mg/cm 2的正极极片，搭配双面含有功能层的Li 6.4La 3Zr 1.4Ta 0.6O 12固态电解质、金属锂负极，采用现有工艺制成纽扣锂离子电池。
实施例8
实施例8提出了一种含有界面功能层的金属锂负极和锂离子电池，其制备方法包括如下步骤：
1、含有界面功能层的金属锂负极的制备
(1)将1，4-二氧六环、LiPF 6/LiFSI(质量比1:1)、DME、纳米二氧化硅按照质量比为81:28:50:3的比例混合均匀后置于烧杯中，以1000rpm的转速均匀搅拌1h至形成均质溶液。
(2)将含有Cu集流体的锂带浸润在搅拌完成后的均质溶液中，使均质溶液充分覆盖浸润锂带。
(3)预处理后6min后将锂带从均质溶液中取出，室温固化，得到含有界面功能层的金属锂负极，其中，界面功能层的厚度为500nm。
2、锂离子电池的制备
用镍酸锂(Li 2NiO 2)(80wt％)、聚酯聚合物电解质(12wt％)、导电炭黑(3wt％)、石墨烯(2wt％)、聚偏氟乙烯(3wt％)涂布成面密度为15mg/cm 2的正极极片，依次与聚合物电解质、处理过的含有功能层的Cu集流体锂带叠层设置，并采用现有卷绕工艺制成软包锂离子电池。
将实施例8的含有界面功能层的金属锂负极组装成锂对称电池，并对其进行循环测试，结果见图6。
对比例6
对比例6提出了一种金属锂负极和锂离子电池，对比例6与实施例8的区别仅在于，对比例6中1，4-二氧六环、LiPF 6/LiFSI(质量比1:1)、DME、纳米二氧化硅的质量比为45:4:6:13，其他制备方法和参数均相同。
对比例7
对比例7提出了一种金属锂负极和锂离子电池，对比例7与实施例8的区别仅在于，对比例7中1，4-二氧六环、LiPF 6/LiFSI(质量比1:1)、DME、纳米二氧化硅的质量比为30:5:20:13，其他制备方法和参数均相同。
对比例8
对比例8提出了一种金属锂负极和锂离子电池，对比例8与实施例8的区别仅在于，对比例8中1，4-二氧六环、LiPF 6/LiFSI(质量比1:1)、DME、纳米二氧化硅的质量比为20:10:8:8，其他制备方法和参数均相同。
分别测试本申请实施例1-8和对比例1-8的锂离子电池在室温下的交流阻抗、循环寿命、库伦效率及电池短路率，结果见表1。
表1
Figure PCTCN2021114119-appb-000001
如表1所示，比较各实施例与对比例可以看出，本申请的锂离子电池，通过在正极和/或负极与固态电解质之间设置界面功能层，从而降低了界面阻抗，具有更高的循环效率和循环稳定性，同时电池短路率几乎为零。
如图5所示，实施例5相比于对比例5，室温下的交流阻抗更小，说明界面性能优异，整体性能优异。
如图6所示，实施例8的锂对称电池，在循环200圈内，电压平台表现出良好的稳定性，没有发生短路。说明本申请实施例8制备的负极极片与电解质之间界面稳定性良好，能够很好地抑制锂枝晶的生长。
综上，本申请的界面功能层，通过调节原料组成和配比，可以改善晶界电阻和电极界面性能，能够抑制锂离子在界面空隙处的不均匀沉积，降低界面阻抗，同时提高界面稳定性。采用上述的界面功能层制备得到的锂离子电池，抑制了锂离子在界面空隙处的不均匀沉积，降低了界面阻抗，同时提高了界面稳定性。本申请的锂离子电池具有 更高的循环效率和循环稳定性，同时电池短路率几乎为零。
上文说明摘要整理出数个实施例的特征，这使得所属技术领域中具有通常知识者能够更加理解本申请的多种方面。所属技术领域中具有通常知识者可轻易地使用本申请作为基础，以设计或修改其他组合物，以便实现与此处申请的实施例相同的目的及/或达到相同的优点。所属技术领域中具有通常知识者亦可理解，这些均等的实例并未悖离本申请的精神与范畴，且其可对本申请进行各种改变、替换与修改，而不会悖离本申请的精神与范畴。虽然本文中所揭示的方法己参考以具体次序执行的具体操作加以描述，但应理解，可在不脱离本申请的教示的情况下组合、细分或重新排序这些操作以形成等效方法。因此，除非本文中特别指示，否则操作的次序及分组不是对本申请的限制。
以上，对本申请的实施方式进行了说明。但是，本申请不限定于上述实施方式。凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (13)

  1. 一种界面功能层，其中，所述界面功能层包括质量比为50-90:5-30:5-40:0-5的环醚化合物、锂盐、助剂和陶瓷粉末。
  2. 根据权利要求1所述的界面功能层，其中，所述界面功能层的厚度为10nm-10μm。
  3. 根据权利要求2所述的界面功能层，其中，所述界面功能层的厚度为400nm-800nm。
  4. 根据权利要求1-3任一项所述的界面功能层，其中，所述陶瓷粉末的粒径为1-900nm。
  5. 根据权利要求4所述的界面功能层，其中，所述陶瓷粉末的粒径为500-600nm。
  6. 根据权利要求1-5任一项所述的界面功能层，其中，所述环醚化合物选自1,3-二氧五环和/或1,4-二氧六环；和/或，
    所述锂盐选自高氯酸锂、六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、双草酸硼酸锂、草酸二氟硼酸锂、双二氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂、三氟甲基磺酸锂、双丙二酸硼酸、丙二酸草酸硼酸锂、六氟锑酸锂、二氟磷酸锂、4,5-二氰基-2-三氟甲基咪唑锂、LiN(SO 2CF 3) 2、LiN(SO 2C 2F 5) 2、LiC(SO 2CF 3) 3和LiN(SO 2F) 2中的一种或几种组合；和/或，
    所述助剂选自乙二醇二甲醚、二丙二醇二甲醚碳、酸乙烯酯、碳酸丙烯酯、碳酸二甲酯和碳酸二乙酯中的一种或几种组合；和/或，
    所述陶瓷粉末选自纳米六方氮化硼、纳米氧化铝和纳米二氧化硅中的一种或几种组合。
  7. 权利要求1-6任一项所述的界面功能层的制备方法，其中，包括如下步骤：
    将所述环醚化合物、锂盐、助剂和陶瓷粉末混合均匀后，附着在正极、负极和/或固态电解质上并进行固化处理，得到界面功能层。
  8. 根据权利要求7所述的界面功能层的制备方法，其中，所述负极选自金属锂负极或锂合金负极中的至少一种，所述金属锂选自熔 融金属锂、锂粉和锂带中的一种，所述锂合金包括Li-In合金、Li-Al合金、Li-Sn合金、Li-Mg合金和Li-Ge合金。
  9. 根据权利要求7或8所述的界面功能层的制备方法，其中，所述混合在搅拌条件下进行，搅拌转速为200-1000rpm/min。
  10. 根据权利要求9所述的界面功能层的制备方法，其中，所述搅拌的时间为1-24h。
  11. 根据权利要求7-10任一项所述的界面功能层的制备方法，其中，所述附着的方法选自刮涂、喷涂、流延和浸泡中的一种或几种组合。
  12. 根据权利要求7-11任一项所述的界面功能层的制备方法，其中，所述固化处理的温度为25-60℃。
  13. 一种锂离子电池，由正极、固态电解质、负极通过卷绕或层叠的方式制备得到，其中，在负极和/或正极与固态电解质之间还设置有权利要求1-6任一项所述的界面功能层。
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