WO2023005505A1 - 一种锂离子电池 - Google Patents

一种锂离子电池 Download PDF

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Publication number
WO2023005505A1
WO2023005505A1 PCT/CN2022/099749 CN2022099749W WO2023005505A1 WO 2023005505 A1 WO2023005505 A1 WO 2023005505A1 CN 2022099749 W CN2022099749 W CN 2022099749W WO 2023005505 A1 WO2023005505 A1 WO 2023005505A1
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positive electrode
conductive agent
active material
electrode active
electrolyte
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English (en)
French (fr)
Inventor
胡时光
钱韫娴
张正生
向晓霞
邓永红
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Priority to EP22848112.3A priority Critical patent/EP4379887A4/en
Priority to US18/292,337 priority patent/US20240356070A1/en
Publication of WO2023005505A1 publication Critical patent/WO2023005505A1/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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of electrochemistry, in particular to a lithium ion battery.
  • lithium-ion batteries mark that the world has entered a new era with the theme of new energy.
  • Lithium-ion batteries occupy a dominant position in the global secondary battery market due to their advantages of high working voltage, wide working range, large specific energy, no pollution, and long service life, especially in electric vehicles and other fields in recent years.
  • the cathode material is the decisive factor for the voltage and capacity of lithium-ion, and determines the ceiling of lithium-ion battery capacity.
  • the crystal structure of the above materials has abundant lithium ion transport channels, and at the same time, manganese ions are located on the crystal structure points, which play a vital role in the stability of the crystal structure; In terms of chemical properties, it has a wide voltage window, and the rate performance is good under certain conditions; during the high-temperature cycle, the positive electrode active material has a certain catalytic effect on the electrolyte, causing the catalytic oxidation of the electrolyte, which in turn leads to the loss of lattice oxygen.
  • the present invention provides a lithium ion battery, in the case of regulating the specific surface area and particle diameter ratio of the positive electrode active material and the conductive agent, by adding the compound shown in structural formula 1 in the electrolyte, it can be guaranteed On the basis of improving the conductivity, the stability of the positive electrode material can be enhanced, and the compatibility between the positive electrode material and the electrolyte can be significantly improved.
  • a lithium ion battery comprising a positive pole, a negative pole and an electrolyte, the positive pole comprising a positive electrode active material and a conductive agent;
  • the positive electrode active material is a manganese-containing positive electrode material
  • the electrolyte comprises a compound shown in the following structural formula 1:
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from a hydrogen atom, a fluorine atom, or a group containing 1 to 5 carbon atoms;
  • the positive electrode active material, the conductive agent and the compound represented by the structural formula 1 satisfy the following relationship:
  • Dr is the ratio of the average particle diameter of the positive electrode active material to the average particle diameter of the conductive agent
  • Tr is the ratio of the specific surface area of the positive electrode active material to the specific surface area of the conductive agent
  • w is the ratio of the specific surface area of the conductive agent.
  • the addition of the compound shown in the structural formula 1 is controlled at the same time
  • the amount can maximize the optimization and improve the performance of the battery, give full play to the electrolyte interface to strengthen the connection between the conductive agent and the positive electrode active material, so that the structure of the positive electrode material is more stable on the basis of ensuring the electrical conductivity.
  • the compound shown in structural formula 1 can decompose on the positive electrode to form a special film, and the film and the conductive agent of special regular size can strengthen the stability of the positive electrode material through interfacial synergy in the positive electrode active material, making The conductive agent can build a stable conductive network with the positive electrode active material, and at the same time strengthen the lithium ion transport channel.
  • the positive electrode material is used in a high-voltage system, and its manganese-rich system makes it easy to dissolve manganese ions, and the compound shown in structural formula 1 forms a barrier for metal ions (except lithium ions) between the positive electrode material and the electrolyte.
  • the compound shown in structural formula 1 can also It can weaken the interface impedance between the positive electrode material and the electrolyte, realize the protection of the positive electrode material and the negative electrode material, and can significantly reduce the gas expansion of the battery under high temperature conditions, thereby improving the high temperature storage performance and high temperature cycle performance of the battery.
  • the positive electrode active material, the conductive agent and the compound represented by the structural formula 1 satisfy the following relationship:
  • the group containing 1 to 5 carbon atoms is selected from one of hydrocarbon groups, halogenated hydrocarbon groups, oxygen-containing hydrocarbon groups, silicon-containing hydrocarbon groups or cyano-containing hydrocarbon groups.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a trimethylsilyloxy group, a cyano group or a trifluoromethyl group. one of the bases.
  • the compound represented by the structural formula 1 includes the following compounds:
  • the mass percentage w of the compound represented by the structural formula 1 relative to the electrolyte satisfies: 0.1% ⁇ w% ⁇ 5%.
  • the mass percentage w of the compound represented by the structural formula 1 relative to the electrolyte solution satisfies: 0.1% ⁇ w% ⁇ 2%.
  • the ratio Dr of the average particle diameter of the positive electrode active material to the average particle diameter of the conductive agent satisfies: 1.3 ⁇ Dr ⁇ 3.8; the ratio of the specific surface area of the positive electrode active material to the specific surface area of the conductive agent Tr satisfies: 0.25 ⁇ Tr ⁇ 1.
  • the ratio Dr of the average particle diameter of the positive electrode active material to the average particle diameter of the conductive agent satisfies: 1.5 ⁇ Dr ⁇ 2.5; the ratio of the specific surface area of the positive electrode active material to the specific surface area of the conductive agent Tr satisfies: 0.3 ⁇ Tr ⁇ 0.8.
  • the average particle size of the positive electrode active material is 1-10 ⁇ m, and the average particle size of the conductive agent is less than 8 ⁇ m.
  • the average particle size of the positive electrode active material is 2-7 ⁇ m, and the average particle size of the conductive agent is less than 3 ⁇ m.
  • the specific surface area of the positive electrode active material is 0.5-1.5 m 2 /g, and the specific surface area of the conductive agent is 1.5-20 m 2 /g.
  • the positive electrode active material is selected from one or more of the following materials:
  • LiNi x Mn y O 4 where 0.5 ⁇ x ⁇ 1, 1.5 ⁇ y ⁇ 2.0;
  • aLi 2 MnO 3 ⁇ (1-a)LiMO 2 wherein 0 ⁇ a ⁇ 1, and M is selected from one or more of Ni, Co, and Mn.
  • the conductive agent is selected from one or more of acetylene black, SuperP, graphene, Ketjen black, SFG-6, carbon nanotubes, and graphyne.
  • the negative electrode includes a negative electrode active material
  • the negative electrode active material includes one or more of carbon-based negative electrodes, silicon-based negative electrodes, tin-based negative electrodes, and lithium negative electrodes.
  • positive electrode conductive agent and the negative electrode conductive agent can be the same or different, and those skilled in the art can select a suitable conductive agent material according to specific applications.
  • the electrolyte solution also includes a lithium salt selected from LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiBOB, LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , LiDFOB, LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 F) 2 , LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiAlCl 4 , at least one of LiBETI.
  • a lithium salt selected from LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiBOB, LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , LiDFOB, LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO
  • the electrolyte also includes one or more of cyclic sulfate compounds, cyclic sulfonate compounds, and cyclic carbonate compounds;
  • the cyclic sulfate ester compound includes one or more of vinyl sulfate, propylene sulfate or vinyl methyl sulfate; its mass percentage is 0.01% to 10%, preferably 0.1% to 5.0% .
  • the cyclic sulfonate compounds include 1,3-propane sultone (1,3-PS), 1,4-butane sultone (BS), 1,3-propene sultone One or more of (PST); its mass percentage is 0.01% to 10%, preferably 0.1% to 5.0%.
  • the cyclic carbonate compounds include vinylene carbonate (VC), vinylethylene carbonate (VEC), methylene vinyl carbonate, fluoroethylene carbonate (FEC), trifluoromethylethylene carbonate, One or more of difluoroethylene carbonate; the mass percentage of methylene carbonate, VC, and VEC is 0.01% to 10%, preferably 0.1% to 5.0%; FEC, trifluoromethylethylene carbonate The mass percentage of ester and bisfluoroethylene carbonate is 0.01-30%, preferably 0.1-5%.
  • the electrolytic solution also includes a non-aqueous organic solvent
  • the non-aqueous organic solvent includes ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or carbonic acid At least one of methyl propyl esters.
  • the lithium-ion battery further includes a separator arranged between the positive electrode and the negative electrode, and the separator can be any known separator, which is not specifically limited in the present invention.
  • the voltage range of the lithium-ion battery is between 2.0V and 4.8V.
  • the present invention achieves the following beneficial effects:
  • the compound shown in the structural formula 1 in the electrolyte, and regulating the ratio of the particle diameter ratio and the ratio of the specific surface area between the conductive agent and the positive electrode active material, the compound shown in the structural formula 1 is simultaneously controlled
  • the added amount can maximize the optimization and improve the performance of the battery, give full play to the electrolyte interface to strengthen the connection between the conductive agent and the positive electrode active material, so that the structure of the positive electrode material is more stable on the basis of ensuring the electrical conductivity, and the manganese content is reduced. Dissolution, thereby improving the high-temperature storage performance and high-temperature cycle performance of the battery.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • LiPF 6 lithium hexafluorophosphate
  • positive electrode active material LiNi 0.5 Mn 1.5 O 4 , conductive carbon black Super-P and binder polyvinylidene fluoride (PVDF) at a mass ratio of 93:4:3, and then disperse them in N-methyl-2 - Pyrrolidone (NMP) to obtain positive electrode slurry.
  • NMP N-methyl-2 - Pyrrolidone
  • the slurry is uniformly coated on both sides of the aluminum foil, dried, calendered and vacuum-dried, and an aluminum lead-out wire is welded on by an ultrasonic welder to obtain a positive plate with a thickness of 120-150 ⁇ m.
  • a three-layer polypropylene microporous separator with a thickness of 20 ⁇ m is placed between the positive plate and the negative plate, and then the sandwich structure composed of the positive plate, the negative plate and the separator is wound, and then the wound body is flattened and put into an aluminum foil package bag, and vacuum baked at 75°C for 48 hours to obtain the cell to be filled with liquid.
  • LiNi 0.5 Mn 1.5 O 4 batteries were conventionally formed by the following steps: 0.05C constant current charging for 180min, 0.2C constant current charging to 3.85V, secondary vacuum sealing, and then further constant current charging at 0.2C to 4.4 V, after standing at room temperature for 24 hours, discharge to 3.0V with a constant current of 0.2C.
  • Capacity retention (%) last discharge capacity / first discharge capacity ⁇ 100%;
  • Battery capacity retention rate (%) retention capacity/initial capacity ⁇ 100%;
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%;
  • Thickness expansion rate (%) (battery thickness after storage-initial battery thickness)/initial battery thickness ⁇ 100%.
  • Embodiments 2-16 are used to illustrate the lithium ion battery disclosed by the present invention, including most of the operating steps in Embodiment 1, the difference being:
  • Comparative Examples 1-4 are used to illustrate the lithium-ion battery disclosed by the present invention, including most of the operating steps in Example 1, the difference being:
  • the compound shown in structural formula 1 is added in the electrolyte, and the average particle diameter ratio and the specific surface area ratio between the positive electrode active material and the conductive agent are regulated to make it consistent with the structural formula
  • the addition amount of the compound shown in 1 satisfies
  • the stability of the positive electrode material can be enhanced on the basis of ensuring the improvement of the electrical conductivity, and the compatibility between the positive electrode material and the electrolyte can be significantly improved.
  • the addition of the compound shown in structural formula 1 builds a barrier for the dissolution of metal ions between the electrolyte and the positive electrode material, which can significantly improve the dissolution of manganese ions, thereby significantly improving the high-temperature cycle and storage performance of the battery.
  • the reason may be that the special film formed by the compound represented by structural formula 1 on the positive electrode has a moderate thickness, and has the best synergistic effect with the conductive agent in the positive electrode active material.
  • Embodiments 17-21 are used to illustrate the lithium-ion battery disclosed by the present invention, including most of the operating steps in Embodiment 1, the difference being:
  • Embodiments 22-25 are used to illustrate the lithium-ion battery disclosed in the present invention, including most of the operating steps in Embodiment 1, the difference being:
  • the compound shown in structural formula 1 is compatible with traditional vinylene carbonate (VC), fluoroethylene carbonate (FEC), vinyl sulfate (DTD) and 1,3-propane sultone (PS) Used together, the high temperature performance of lithium-ion batteries can be further improved.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • DTD vinyl sulfate
  • PS 1,3-propane sultone
  • Embodiments 26-34 are used to illustrate the lithium-ion battery disclosed by the present invention, including most of the operating steps in Embodiment 1, the difference being:
  • Comparative Examples 5-10 are used to illustrate the lithium-ion battery disclosed in the present invention, including most of the operating steps in Example 1, the difference being:
  • the lithium ion battery provided by the present invention is different from different manganese-containing positive electrodes due to the addition of the compound shown in structural formula 1 in the electrolyte and the regulation of the average particle diameter ratio and specific surface area ratio between the positive electrode active material and the conductive agent.
  • the active materials all have a good coordination effect.
  • the dissolution of Mn ions can be effectively inhibited, thereby improving lithium ionization.
  • the present invention provides a lithium ion battery, in the case of regulating the specific surface area and particle diameter ratio of the positive electrode active material and the conductive agent, and then adding a specific content of the compound shown in structural formula 1 to the electrolyte, satisfy
  • the relationship between the compound shown in structural formula 1 and the added conductive agent and the positive electrode material is strengthened through the interfacial synergistic effect, the structure of the positive electrode material is strengthened, and at the same time the interface impedance between the positive electrode material and the electrolyte is weakened, effectively improving the mobility of lithium ions without deterioration
  • the lithium battery has good rate performance, high-temperature storage performance and high-temperature cycle performance.

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Abstract

本发明涉及电化学技术领域，具体涉及一种锂离子电池，包括正极、负极和电解液，正极包括正极活性材料和导电剂；正极活性材料为含锰正极材料；电解液包括下述结构式（1）所示的化合物：正极活性材料、导电剂和结构式（1）所示的化合物满足如下关系（2）：其中，Dr和Tr分别为正极活性材料与导电剂的平均粒径及比表面积的比值；w为结构式（1）所示的化合物相对于电解液的质量百分比，单位为％。本发明在调控正极活性材料与导电剂的比表面积及粒径比的情况下，在电解液中加入结构式（1）所示的化合物，三者之间通过界面协同效应强化正极材料的结构，同时弱化正极材料与电解液间的界面阻抗，减少锰的溶出，使锂电池具有良好的高温存储性能和高温循环性能。

Description

一种锂离子电池 技术领域
本发明涉及电化学技术领域，具体涉及一种锂离子电池。
背景技术
锂离子电池作为第四次工业革命主要产物，标志着全球进入了以新能源为主题的新时代。锂离子电池以工作电压高、工作范围宽、比能量大、无污染、使用寿命长等优点，在全球二次电池市场占据主导地位，特别是近几年在电动汽车等领域得到了广泛应用。在锂离子电池技术中，正极材料是锂离子电压和容量的决定性因素，决定着锂电池容量的天花板。
现有技术中，一些新型的材料尖晶石锰酸锂、高镍无钴、富锂基锰材料等因其可承受电压窗口宽、容量大等优点广泛用作锂离子电池材料的正极。但同时这些材料在用作电池材料正极时，同样存在一些特有的共性问题：导电性差、锰离子易溶出、正极材料结构易坍塌等。具体原因如下：从微观结构上讲，上述材料的晶体结构都有着丰富的锂离子传输通道，同时锰离子都分别在晶体结构点上，对晶体的结构稳定性起着至关重要的作用；电化学性能方面，有着较宽的电压窗口，一定条件下倍率性能好；在高温循环过程中，正极活性材料对电解液有一定的催化作用，引起电解液的催化氧化，进而导致晶格氧缺失，引发锰离子的溶出，造成正极材料的结构坍塌，影响电池性能；正极活性材料中的Mn 3+易于与电解液中的HF发生歧化反应，生成Mn 2+和Mn 4+，二价锰溶解，破坏正极材料结构；充电过程中，Mn 2+迁移到负极，沉积造成短路；正极材料中锰的平均价态低于+3.5时，正极材料的晶体结构会发生转变，由稳定结构转变至不稳定结构，使电极的极化作用增强，引起容量衰减、导电性能差等缺点。
目前许多研究人员通过往正极材料中添加导电剂来强化正极材料的导电性能，导电性能得到了一定的改善，例如，在尖晶石镍锰酸锂表面进行碳包覆用于强化正极的导电性能，或者在磷酸铁锂正极材料表面构造纳米化LiFePO 4晶粒，用于减小锂离子在晶粒中的扩散距离从而强化锂离子的扩散。但是，在解决正极导电性问题的同时，又引发出了一系列问题：导电剂的加入使得正极稳定性变差，锰离子更易溶出，并且进一步弱化了锂离子的扩散速率，同时正极材料与电解液之间的兼容性变得更差，进而使得电池的高温条件下循环性能和存储性能劣化。因此，如何开发一种既能解决正极导电性问题，又能解决所引发的一系列问题的锂离子电池，是本领域亟待解决的一项技术问题。
发明内容
为了解决上述问题，本发明提供了一种锂离子电池，在调控正极活性材料与导电剂的比表面积及粒径比的情况下，通过在电解液中加入结构式1所示的化合物，能在保证提升导电性能的基础上强化正极材料的稳定性，并能显著的改善正极材料与电解质的兼容性问题。
一种锂离子电池，包括正极、负极和电解液，所述正极包括正极活性材料和导电剂；
所述正极活性材料为含锰正极材料；
所述电解液包括下述结构式1所示的化合物：
Figure PCTCN2022099749-appb-000001
其中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢原子、氟原子或含1～5个碳原子的基团中的一种；
所述正极活性材料、导电剂和所述结构式1所示的化合物满足如下关系：
Figure PCTCN2022099749-appb-000002
其中，Dr为所述正极活性材料的平均粒径与所述导电剂的平均粒径的比值；Tr为所述正极活性材料的比表面积与所述导电剂的比表面积的比值；w为所述结构式1所示的化合物相对于所述电解液的质量百分比，单位为％。
本发明的锂离子电池，通过在电解液中添加具有结构式1所示的化合物，并调控导电剂与正极活性材料间的粒径比以及比表面积的比值，同时控制结构式1所示的化合物的添加量，能最大化的优化改善电池的性能，充分发挥电解液界面强化导电剂、正极活性材料之间的联系，使得保证导电性能的基础上，正极材料的结构更加稳定。
具体的，推测是结构式1所示的化合物能够在正极上发生分解，形成一种特殊膜，该膜与特殊规则大小的导电剂在正极活性材料中通过界面协同作用强化正极材料的稳定性，使得导电剂能与正极活性材料间构筑稳定的导电网络，同时强化锂离子传输通道。正极材料使用于高电压体系，其富含锰体系的特性使锰离子会特别容易的溶出，而结构式1所示的化合物在正极材料与电解液间形成金属离子(除锂离子外)的屏障，可以对锰离子起到络合作用，抑制锰离 子从正极的溶出及在负极的沉积；减少副反应的发生和电解液的损失，从而显著改善电池的高温循环性能；结构式1所示的化合物还可弱化正极材料与电解质间的界面阻抗，实现对正极材料和负极材料的保护，同时可以明显降低高温条件下电池的气胀作用，从而改善电池的高温存储性能和高温循环性能。
优选的，所述正极活性材料、导电剂和所述结构式1所示的化合物满足如下关系：
Figure PCTCN2022099749-appb-000003
优选的，含1～5个碳原子的基团选自烃基、卤代烃基、含氧烃基、含硅烃基或含氰基的烃基中的一种。
优选的，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢原子、氟原子、甲基、乙基、三甲基硅氧基、氰基或三氟甲基中的一种。
优选的，所述结构式1所示的化合物包括如下化合物：
Figure PCTCN2022099749-appb-000004
Figure PCTCN2022099749-appb-000005
进一步的，以所述电解液的总质量为100％计，所述结构式1所示的化合物相对于所述电解液的质量百分比w满足：0.1％≤w％≤5％。优选的，所述结构式1所示的化合物相对于所述电解液的质量百分比w满足：0.1％≤w％≤2％。
进一步的，所述正极活性材料的平均粒径与所述导电剂的平均粒径的比值Dr满足：1.3≤Dr≤3.8；所述正极活性材料的比表面积与所述导电剂的比表面积的比值Tr满足：0.25≤Tr≤1。优选的，所述正极活性材料的平均粒径与所述导电剂的平均粒径的比值Dr满足：1.5≤Dr≤2.5；所述正极活性材料的比表面积与所述导电剂的比表面积的比值Tr满足：0.3≤Tr≤0.8。
进一步的，所述正极活性材料的平均粒径为1～10μm，所述导电剂的平均粒径小于8μm。优选的，所述正极活性材料的平均粒径为2～7μm，所述导电剂的平均粒径小于3μm。
进一步的，所述正极活性材料的比表面积为0.5～1.5m 2/g，所述导电剂的比表面积为1.5～20m 2/g。
进一步的，所述正极活性材料选自以下材料中的一种或多种：
尖晶石LiMn 2O 4；
LiNi xMn yO 4，其中0.5≤x<1，1.5≤y<2.0；
LiNi zMn 1-zO 2，其中0.1≤z<1；
aLi 2MnO 3·(1-a)LiMO 2，其中0<a≤1，M选自Ni、Co、Mn中的一种或多种。
进一步的，所述导电剂选自乙炔黑、SuperP、石墨烯、科琴黑、SFG-6、碳纳米管、石墨炔中的一种或多种。
进一步的，所述负极包括负极活性材料，所述负极活性材料包括碳基负极、硅基负极、锡基负极、锂负极中的一种或多种。
进一步的，正极导电剂与负极导电剂可以相同，也可以不同，本领域人员可根据具体应用选择合适的导电剂材料。
进一步的，所述电解液还包括锂盐，所述锂盐选自LiPF 6、LiPO 2F 2、LiBF 4、LiBOB、LiSbF 6、LiAsF 6、LiCF 3SO 3、LiDFOB、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiN(SO 2C 2F 5) 2、LiN(SO 2F) 2、LiCl、LiBr、LiI、LiClO 4、LiBF 4、LiB 10Cl 10、LiAlCl 4、LiBETI中的至少一种。
进一步的，所述电解液还包括环状硫酸酯类化合物、环状磺酸酯类化合物、环状碳酸酯类化合物中的一种或多种；
优选的，所述环状硫酸酯类化合物包括硫酸乙烯酯、硫酸丙烯酯或甲基硫酸乙烯酯中的一种或多种；其质量百分比为0.01％～10％，优选为0.1％～5.0％。
所述环状磺酸酯类化合物包括1,3-丙烷磺酸内酯(1,3-PS)、1,4-丁烷磺酸内酯(BS)、1,3-丙烯磺酸内酯(PST)中的一种或多种；其质量百分比为0.01％～10％，优选为0.1％～5.0％。
所述环状碳酸酯类化合物包括碳酸亚乙烯酯(VC)、碳酸乙烯亚乙酯(VEC)、亚甲基碳酸乙烯酯、氟代碳酸乙烯酯(FEC)、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的一种或多种；亚甲基碳酸乙烯酯、VC、VEC的质量百分比为0.01％～10％，优选为0.1％～5.0％；FEC、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯的质量百分比为0.01～30％，优选为0.1％～5％。
进一步的，所述电解液还包括非水有机溶剂，所述非水有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或碳酸甲丙酯中的至少一种。
进一步的，所述锂离子电池还包括设置在正极和负极之间的隔膜，所述隔膜可任意采用公知的隔板，本发明不做特殊限定。
进一步的，所述锂离子电池的电压区间在2.0V～4.8V之间。
与现有技术相比，本发明达到如下有益效果：
本发明的锂离子电池，通过在电解液中添加具有结构式1所示的化合物，并调控导电剂与正极活性材料间的粒径比的比值以及比表面积的比值，同时控制结构式1所示的化合物的添加量，能最大化的优化改善电池的性能，充分的发挥电解液界面强化导电剂、正极活性材料之间的联系，使得保证导电性能的基础上，正极材料的结构更加稳定，减少锰的溶出，从而改善电池的高温存储性能和高温循环性能。
具体实施方式
下面将结合本发明中的实施例，对本发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通的技术人员在没有做出创造性劳动的前提下所获得的所有其它实施例，都属于本发明的保护范围。
以下通过实施例对本发明进行进一步的说明。
表1
Figure PCTCN2022099749-appb-000006
Figure PCTCN2022099749-appb-000007
注：以下实施例和对比例中采用的化合物选自于表1。
实施例1
一、锂离子电池的制备
(1)电解液的制备
将碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)按质量比为EC:DEC:EMC＝1:1:1进行混合，然后加入六氟磷酸锂(LiPF 6)至摩尔浓度为1mol/L，再加入按表1中实施例1所示含量的结构式1所示的化合物。
(2)正极板的制备
按93:4:3的质量比混合正极活性材料LiNi 0.5Mn 1.5O 4，导电碳黑Super-P和粘结剂聚偏二氟乙烯(PVDF)，然后将它们分散在N-甲基-2-吡咯烷酮(NMP)中，得到正极浆料。将浆料均匀涂布在铝箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上铝制引出线后得到正极板，极板的厚度在120-150μm。
(3)负极板的制备
按94:1:2.5:2.5的质量比混合负极活性材料人造石墨，导电碳黑Super-P，粘结剂丁苯橡胶(SBR)和羧甲基纤维素(CMC)，然后将它们分散在去离子水中，得到负极浆料。将浆料涂布在铜箔的两面上，经过烘干、压延和真空干燥，并用超声波焊机焊上镍制引出线后得到负极板，极板的厚度在120-150μm。
(4)电芯的制备
在正极板和负极板之间放置厚度为20μm的三层聚丙烯微孔隔膜，然后将正极板、负极板和隔膜组成的三明治结构进行卷绕，再将卷绕体压扁后放入铝箔 包装袋，在75℃下真空烘烤48h，得到待注液的电芯。
(5)电芯的注液和化成
在露点控制在-40℃以下的手套箱中，将上述制备的电解液注入电芯中，经真空封装，静置24h。
LiNi 0.5Mn 1.5O 4电池按以下步骤进行首次充电的常规化成：0.05C恒流充电180min，0.2C恒流充电至3.85V，二次真空封口，然后进一步以0.2C的电流恒流充电至4.4V，常温搁置24hr后，以0.2C的电流恒流放电至3.0V。
二、电池性能测试
(1)高温循环性能测试
将电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.4V(LiNi 0.5Mn 1.5O 4/人造石墨电池)，再恒压充电至电流下降至0.02C，然后以1C的电流恒流放电至3.0V。如此循环，记录第1次的放电容量和最后一次的放电容量，按下式计算高温循环的容量保持率：
容量保持率(％)＝最后一次的放电容量/第1次的放电容量×100％；
(2)高温存储性能测试
将化成后的锂离子电池在常温下用1C恒流恒压充至4.4V(LiNi 0.5Mn 1.5O 4/人造石墨电池)，测量电池初始放电容量及初始电池厚度，然后在60℃环境中储存30天后，以1C放电至3V，测量电池的保持容量和恢复容量及储存后电池厚度。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％；
电池容量恢复率(％)＝恢复容量/初始容量×100％；
厚度膨胀率(％)＝(储存后电池厚度-初始电池厚度)/初始电池厚度×100％。
实施例2-16
实施例2-16用于说明本发明公开的锂离子电池，包括实施例1中大部分的操作步骤，其不同之处在于：
电解液的制备过程中加入表1中所示含量的结构式1所示的化合物，正极板的制备过程中正极活性材料和导电剂的平均粒径比及比表面积比如表2所示。得到测试结果填入表3。
对比例1-4
对比例1-4用于说明本发明公开的锂离子电池，包括实施例1中大部分的操作步骤，其不同之处在于：
电解液的制备过程中加入表1中所示含量的结构式1所示的化合物，正极板的制备过程中正极活性材料和导电剂的平均粒径比及比表面积比如表2所示。得到测试结果填入表3。
表2实施例1-16及对比例1-4中锂离子电池的组成
Figure PCTCN2022099749-appb-000008
Figure PCTCN2022099749-appb-000009
表4实施例1-16及对比例1-4中锂离子电池的电化学性能测试结果
Figure PCTCN2022099749-appb-000010
由实施例1-16和对比例1-4看出，在电解液中添加结构式1所示的化合物，并调控正极活性材料与导电剂间的平均粒径比和比表面积比值，使其与结构式1所示的化合物的加入量之间满足
Figure PCTCN2022099749-appb-000011
时，能在保证提升导电性能的基础上强化正极材料的稳定性，并显著的改善正极材料与电解质的兼容性问题。结构式1所示的化合物的添加，在电解液与正极材料间构筑了金属离子溶出的屏障，能够明显改善锰离子溶出问题，进而显著改善电池高温循环和存储性能。优选的，当满足
Figure PCTCN2022099749-appb-000012
时，具有更佳的性能，原因可能是结构式1所示的化合物在正极形成的特殊膜厚度适中，且与导电剂在正极活性材料中的协同作用最佳。
实施例17-21
实施例17-21用于说明本发明公开的锂离子电池，包括实施例1中大部分的操作步骤，其不同之处在于：
电解液的制备过程中加入表4中实施例17-21所示含量的不同的结构式1的化合物。得到测试结果填入表5。
表4实施例3、17-21中锂离子电池组成
Figure PCTCN2022099749-appb-000013
表5实施例3、17-21中锂离子电池的电化学性能测试结果
Figure PCTCN2022099749-appb-000014
实施例22-25
实施例22-25用于说明本发明公开的锂离子电池，包括实施例1中大部分的操作步骤，其不同之处在于：
正极的制备过程中加入表6中实施例22-25所示的正极活性材料。得到测试结果填入表7。
表6实施例3、22-25中锂离子电池组成
Figure PCTCN2022099749-appb-000015
Figure PCTCN2022099749-appb-000016
表7实施例3、22-25中锂离子电池的电化学性能测试结果
Figure PCTCN2022099749-appb-000017
由测试结果可知，结构式1所示的化合物与传统的碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)、硫酸乙烯酯(DTD)和1,3-丙烷磺酸内酯(PS)配合使用，能够进一步改善锂离子电池的高温性能。
实施例26-34
实施例26-34用于说明本发明公开的锂离子电池，包括实施例1中大部分的操作步骤，其不同之处在于：
正极的制备过程中加入表8中实施例26-34所示的正极活性材料和添加剂。得到测试结果填入表9。
对比例5-10
对比例5-10用于说明本发明公开的锂离子电池，包括实施例1中大部分的操作步骤，其不同之处在于：
电解液的制备过程中加入的物质如表8所示。得到测试结果填入表9。
表8实施例26-34、对比例5-10中锂离子电池组成
Figure PCTCN2022099749-appb-000018
Figure PCTCN2022099749-appb-000019
表9实施例26-34、对比例5-10中锂离子电池的电化学性能测试结果
Figure PCTCN2022099749-appb-000020
由测试结果可知，本发明提供的锂离子电池，由于电解液中添加了结构式1所示化合物，并调控正极活性材料与导电剂间的平均粒径比和比表面积比值，与不同的含锰正极活性材料均具有较好的配合效果，只要调整正极活性材料与导电剂间的平均粒径比和比表面积比值与结构式1所示化合物的含量关系，即 可有效抑制Mn离子的溶出，从而改善锂离子电池的高温循环性能和高温存储性能。
综上所述，本发明提供了一种锂离子电池，在调控正极活性材料与导电剂的比表面积及粒径比的情况下，再在电解液中加入特定含量的结构式1所示的化合物，满足
Figure PCTCN2022099749-appb-000021
关系时，结构式1所示的化合物与加入的导电剂以及正极材料间通过界面协同效应强化正极材料的结构，同时弱化正极材料与电解质间的界面阻抗，有效的提升锂离子迁移率，在不劣化电池导电性能的情况下，使锂电池具有良好的倍率性能、高温存储性能和高温循环性能。
以上借助具体实施例对本发明做了进一步描述，但是应该理解的是，这里具体的描述，不应理解为对本发明的实质和范围的限定，本领域内的普通技术人员在阅读本说明书后对上述实施例做出的各种修改，都属于本发明所保护的范围。

Claims (10)

  1. 一种锂离子电池，包括正极、负极和电解液，其特征在于，所述正极包括正极活性材料和导电剂；
    所述正极活性材料为含锰正极材料；
    所述电解液包括下述结构式1所示的化合物：
    Figure PCTCN2022099749-appb-100001
    其中，R 1、R 2、R 3、R 4、R 5、R 6各自独立地选自氢原子、氟原子或含1～5个碳原子的基团中的一种；
    所述正极活性材料、导电剂和所述结构式1所示的化合物满足如下关系：
    Figure PCTCN2022099749-appb-100002
    其中，Dr为所述正极活性材料的平均粒径与所述导电剂的平均粒径的比值；Tr为所述正极活性材料的比表面积与所述导电剂的比表面积的比值；w为所述结构式1所示的化合物相对于所述电解液的质量百分比，单位为％。
  2. 根据权利要求1所述的锂离子电池，其特征在于，以所述电解液的总质量为100％计，所述结构式1所示的化合物相对于所述电解液的质量百分比w满足：0.1％≤w％≤5％。
  3. 根据权利要求1所述的锂离子电池，其特征在于，所述正极活性材料的平均粒径与所述导电剂的平均粒径的比值Dr满足：1.3≤Dr≤3.8；所述正极活性材料的比表面积与所述导电剂的比表面积的比值Tr满足：0.25≤Tr≤1。
  4. 根据权利要求3所述的锂离子电池，其特征在于，所述正极活性材料的平 均粒径与所述导电剂的平均粒径的比值Dr满足：1.5≤Dr≤2.5；所述正极活性材料的比表面积与所述导电剂的比表面积的比值Tr满足：0.3≤Tr≤0.8。
  5. 根据权利要求1所述的锂离子电池，其特征在于，所述结构式1所示的化合物包括如下化合物：
    Figure PCTCN2022099749-appb-100003
  6. 根据权利要求1所述的锂离子电池，其特征在于，所述正极活性材料选自以下材料中的一种或多种：
    尖晶石LiMn 2O 4；
    LiNi xMn yO 4，其中0.5≤x<1，1.5≤y<2.0；
    LiNi zMn 1-zO 2，其中0.1≤z<1；
    aLi 2MnO 3·(1-a)LiMO 2，其中0<a≤1，M选自Ni、Co、Mn中的一种或多种。
  7. 根据权利要求1所述的锂离子电池，其特征在于，所述导电剂选自乙炔黑、SuperP、石墨烯、科琴黑、SFG-6、碳纳米管、石墨炔中的一种或多种。
  8. 根据权利要求1所述的锂离子电池，其特征在于，所述电解液还包括锂盐，所述锂盐选自LiPF 6、LiPO 2F 2、LiBF 4、LiBOB、LiSbF 6、LiAsF 6、LiCF 3SO 3、LiDFOB、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiN(SO 2C 2F 5) 2、LiN(SO 2F) 2、LiCl、LiBr、LiI、LiClO 4、LiBF 4、LiB 10Cl 10、LiAlCl 4、LiBETI中的至少一种。
  9. 根据权利要求1所述的锂离子电池，其特征在于，所述电解液还包括环状硫酸酯类化合物、环状磺酸酯类化合物、环状碳酸酯类化合物中的一种或多种；
    所述环状硫酸酯类化合物包括硫酸乙烯酯、硫酸丙烯酯或甲基硫酸乙烯酯中的一种或多种；
    所述环状磺酸酯类化合物包括1,3-丙烷磺酸内酯、1,4-丁烷磺酸内酯、1,3-丙烯磺酸内酯中的一种或多种；
    所述环状碳酸酯类化合物包括碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯、氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的一种或多种。
  10. 根据权利要求1所述的锂离子电池，其特征在于，所述电解液还包括非水有机溶剂，所述非水有机溶剂包括碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯或碳酸甲丙酯中的至少一种。
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