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CN116936738A - Secondary battery and electricity utilization device - Google Patents

Secondary battery and electricity utilization device Download PDF

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Publication number
CN116936738A
CN116936738A CN202310819331.7A CN202310819331A CN116936738A CN 116936738 A CN116936738 A CN 116936738A CN 202310819331 A CN202310819331 A CN 202310819331A CN 116936738 A CN116936738 A CN 116936738A
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silicon
electrolyte
additive
secondary battery
active material
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Inventor
蔡涛涛
乔飞燕
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Xinwangda Power Technology Co ltd
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Xinwangda Power Technology Co ltd
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Priority to CN202310819331.7A priority Critical patent/CN116936738A/en
Publication of CN116936738A publication Critical patent/CN116936738A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M10/0567—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
    • H01M10/056—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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/027—Negative 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The application discloses a secondary battery and an electric device, the secondary battery comprises a negative electrode plate and electrolyte, the negative electrode plate comprises a negative electrode active material layer, and the surface density of the negative electrode active material layer is D mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte comprises a first solvent, a first additive and a second additive; the first solvent comprises a fluorine-containing compound, the first additive comprises a sulfur-containing compound, and the second additive comprises a silicon-containing compound; the fluorine element content in the fluorine-containing compound is A percent by mass, the sulfur element content in the sulfur-containing compound is B percent by mass, the silicon element content in the silicon-containing compound is C percent by mass, and the mass percentage of the silicon element in the silicon-containing compound is less than or equal to 0.005 (B)+1.2C)/(A.times.D). Ltoreq.0.1. The application can inhibit the volume expansion of the silicon-based anode and reduce the high-temperature gas production of the electrolyte by controlling the surface density, the fluorine content, the sulfur content and the silicon content of the anode active material layer, thereby realizing the balance of the cycle life and the high-temperature gas production risk.

Description

Secondary battery and electricity utilization device
Technical Field
The application relates to the technical field of secondary batteries, in particular to a secondary battery and an electric device.
Background
The high areal density negative electrode sheet requires a suitable sufficient amount of electrolyte with a strong wetting ability to prevent the appearance of local lean solutions, especially silicon-based negative electrode sheets. Moreover, due to the limited voltage window of the electrolyte solvent, oxidative decomposition of the electrolyte is easily caused, leading to a series of side reactions and affecting the battery performance, wherein the problem of volume expansion of the silicon anode is most serious.
Disclosure of Invention
The application aims to: the application provides a secondary battery and an electric device, which are used for solving the problem of serious volume expansion of a silicon-based negative electrode.
The technical scheme is as follows: the secondary battery comprises a negative electrode plate and electrolyte, wherein the negative electrode plate comprises a negative electrode active material layer, and the surface density of the negative electrode active material layer is D mg/cm 2 ；
The electrolyte comprises: a first solvent, a first additive, and a second additive; the first solvent comprises a fluorine-containing compound, the first additive comprises a sulfur-containing compound, and the second additive comprises a silicon-containing compound;
wherein, based on the total mass of the electrolyte, the mass percent of fluorine element in the fluorine-containing compound is A%, the mass percent of sulfur element in the sulfur-containing compound is B%, and the mass percent of silicon element in the silicon-containing compound is C%, which satisfies the following conditions:
0.005≤(B+1.2C)/(A×D)≤0.1。
in some embodiments, the negative electrode active material layer has an areal density of D mg/cm 2 ，6≤D≤15。
In some embodiments, at least one of the following features is satisfied based on the total mass of the electrolyte:
a) The mass percentage of the first solvent is 2% -20%;
b) The mass percentage of the first additive is 0.1% -3%;
c) The mass percentage of the second additive is 0.1% -1%.
In some embodiments, the electrolyte meets at least one of the following characteristics:
d)0.358≤A≤3.580；
e)0.129≤B≤1.032；
f)0.014≤C≤0.151。
in some embodiments, the first solvent comprises fluoroethylene carbonate.
In some embodiments, the first additive comprises at least one of vinyl sulfate, 1, 3-propane sultone, propenyl-1, 3-sultone, ethylene sulfite, methylene methane disulfonate, 1, 4-butane sultone; the second additive comprises at least one of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) borate.
In some embodiments, the electrolyte further comprises an electrolyte salt selected from at least one of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium tetrafluoroborate, lithium perchlorate, lithium difluorophosphate, lithium tetrafluorophosphate, lithium bis (oxalato) difluorophosphate, lithium bis (oxalato) borate, lithium difluorooxalato borate.
In some embodiments, the electrolyte further comprises a second solvent, the electrolyte satisfying at least one of the following characteristics:
h) Based on the total mass of the electrolyte, the mass percentage of the second solvent is 54-85%;
i) The second solvent is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, diphenyl carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate and gamma-butyrolactone.
In some embodiments, the anode active material layer includes an anode active material including a silicon-based material and graphite, the anode active material satisfying at least one of the following characteristics:
j) The silicon-based material comprises at least one of a simple substance of silicon, a silicon-carbon alloy, a silicon oxygen compound and a silicon-containing metal compound;
k) The mass of the silicon-based material accounts for 3% -35% of the total mass of the anode active material.
In some embodiments, the present application also provides an electric device including the secondary battery.
Compared with the prior art, the secondary battery comprises the negative electrode plate and electrolyte, wherein the negative electrode plate comprises a negative electrode active material layer, and the surface density of the negative electrode active material layer is D mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte comprises a first solvent, a first additive and a second additive; the first solvent comprises a fluorine-containing compound, the first additive comprises a sulfur-containing compound, and the second additive comprises a silicon-containing compound; wherein, based on the total mass of the electrolyte, the mass percent of fluorine element in the fluorine-containing compound is A%, the mass percent of sulfur element in the sulfur-containing compound is B%, and the mass percent of silicon element in the silicon-containing compound is C%, and the mass percent of (B+1.2C)/(A multiplied by D) is less than or equal to 0.005 and less than or equal to 0.1. The application can inhibit the volume expansion of the silicon-based anode and reduce the high-temperature gas production of the electrolyte by controlling the surface density, the fluorine content, the sulfur content and the silicon content of the anode active material layer, thereby realizing the balance of the cycle life and the high-temperature gas production risk.
It can be appreciated that, compared with the prior art, the electricity utilization device provided by the embodiment of the application has all the technical features and beneficial effects of the secondary battery, and is not repeated herein.
Detailed Description
The following description of the technical solution in the embodiments of the present application is clear and complete. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
In the description of the present application, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more features.
In the description of the present application, the term "process" includes not only an independent process but also a process which is not clearly distinguished from other processes, as long as the object of the process can be achieved. In the present specification, a numerical range shown by using "to" means a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively. In the present specification, the term "layer" includes a configuration of a shape formed on a part of the entire surface, in addition to a configuration of a shape formed on the entire surface when viewed in a plan view.
The following disclosure provides many different embodiments, or examples, for implementing different features of the application. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the application.
Lithium ion batteries exhibit excellent performance in terms of cycle life, energy density, safety performance, and the like. The current lithium ion battery cathode active material mainly uses graphite material, has a theoretical gram capacity of 372mAh/g, and has the advantages of low voltage, long platform, stable performance and the like. However, its gram capacity is difficult to further increase due to its intrinsic lattice lithium intercalation space limitation. The silicon negative electrode based on an alloying reaction mechanism has 10 times of theoretical gram capacity of graphite and has wide prospect for developing a high specific energy battery. The high surface density silicon-based negative electrode active material layer needs enough electrolyte, but the excessive content of the electrolyte and the property of the silicon-based material lead to the aggravation of the expansion of the silicon-based negative electrode, the gas generation of the battery, and the low coulombic efficiency and the rapid capacity decay are shown.
Accordingly, in view of the above-described problems, it is desirable to provide a secondary battery and an electric device that improve the electrochemical performance of a silicon-based anode by performing interface control of the areal density of a silicon-based anode material layer and electrolyte engineering,
the embodiment of the application provides a secondary battery, which comprises a negative electrode plate and electrolyte, wherein the negative electrode plate comprises a negative electrodeActive material layer, surface density of negative electrode active material layer is D mg/cm 2 ；
The electrolyte comprises: a first solvent, a first additive, and a second additive; the first solvent comprises a fluorine-containing compound, the first additive comprises a sulfur-containing compound, and the second additive comprises a silicon-containing compound;
wherein, based on the total mass of the electrolyte, the mass percent of fluorine element in the fluorine-containing compound is A%, the mass percent of sulfur element in the sulfur-containing compound is B%, and the mass percent of silicon element in the silicon-containing compound is C%, which satisfies the following conditions:
0.005≤(B+1.2C)/(A×D)≤0.1。
it is understood that in order to balance the overall performance of the secondary battery of the silicon-containing anode, the areal density of the anode active material layer, the content of the fluorine element, the content of the sulfur element, and the content of the silicon element should be reasonably controlled. The fluorine element can increase the content of LiF in the SEI film formed at the negative electrode, so that the obtained SEI film is thinner and more uniform, has stronger toughness, can inhibit the volume expansion and interface passivation of the silicon negative electrode, and further improves the cycle life of the battery; the addition of the sulfur element can contribute Li in the SEI film 2 SO 4 And Li (lithium) 2 SO 3 Equal components, promote Li + Conducting at the interface and improving high temperature storage performance; the addition of the silicon element can be combined with a byproduct F in the electrolyte – And the combination avoids the damage of HF to the interface, thereby relieving the side reaction between the anode interface and the electrolyte solvent and achieving the effect of inhibiting gas production. When the range of (B+1.2C)/(A×D) is not more than 0.1, the contents of fluorine element, sulfur element and silicon element are balanced with the surface density of the anode active material layer, and the four are used cooperatively to realize the balance of cycle life and safety performance; the method avoids risks of electrolyte high-temperature gas production and the like caused by excessive fluorine elements, or avoids the deterioration of the cycle life of the battery caused by excessive sulfur elements, and avoids the negative influence on the cycle life and the long-term high-temperature storage performance caused by excessive silicon elements.
The second additive contains silicon-containing compound, can react with water, hydrofluoric acid and the like, reduces side reaction, thereby reducing the impedance of the SEI film and improving the high-temperature performance of the lithium ion battery.
In some embodiments, in the electrolyte, the value of (b+1.2c)/(a×d) may be 0.005, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.1, or a range between any two of these values.
In some embodiments, the areal density of the anode active material layer, D mg/cm 2 Satisfying D is more than or equal to 6 and less than or equal to 15. For example, D may be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or a range between any two of these values. The surface density of the anode active material layer is within the scope of the present application, which is advantageous for improving the capacity performance of the battery while reducing the volume expansion of the anode.
In some embodiments, the first solvent is 2% to 20% by mass, the first additive is 0.1% to 3% by mass, and the second additive is 0.1% to 1% by mass, based on the total mass of the electrolyte. It can be understood that the first solvent contains fluorine element, so that the first solvent has unique advantages in improving the cycle performance of the silicon-containing anode material, and particularly has excellent film forming performance on the anode, so that the problems of volume expansion of the silicon-based material in the charge and discharge process, consumption of active lithium and electrolyte, electrical contact deactivation and interface impedance increase of the silicon-based material and the like can be effectively inhibited. However, the use of a large amount of the first solvent will exacerbate the gassing risk of the battery, especially in high nickel systems, ni 4+ The oxidative decomposition of the electrolyte is aggravated, so that the gas production phenomenon is particularly obvious. The first additive contains sulfur element, and the second additive contains silicon element, so that the addition of the first additive and the second additive has remarkable effect of improving gas production, and the synergistic use of the first additive and the first solvent can achieve both the performances of cycle life and gas production risk. Thus, by limiting the content of the first solvent, the first additive and the second additive, a balance of cycle life and risk of high temperature gas production can be further achieved.
In some embodiments, the fluorine element content A% in the fluorine-containing compound is more than or equal to 0.358.ltoreq.A.ltoreq. 3.580. For example, a may be any one or a range between any two of 0.358, 0.895, 1.343, 1.79, 1.24, 2.69, 3.13, 3.580.
In some embodiments, the mass percent B% of sulfur element in the sulfur-containing compound further satisfies that 0.129.ltoreq.B.ltoreq.1.032. For example, B may be any one value or a range between any two values of 0.129, 0.131, 0.258, 0.401, 0.470, 0.741, 1.030, and 1.032.
In some embodiments, the silicon element content C% in the silicon-containing compound further satisfies that 0.014.ltoreq.C.ltoreq.0.151. For example, C may be any one or a range between any two of 0.014, 0.027, 0.041, 0.054, 0.068, 0.082, 0.092, 0.110, 0.124, 0.138, 0.151.
The first solvent contains fluoroethylene carbonate (FEC), because the LUMO of FEC is lower than that of a conventional electrolyte solvent molecule (electron-withdrawing induction of F), the FEC can preferentially reduce the organic solvent in the first lithiation process to form a uniform and compact SEI film on the surface of a silicon-based negative electrode (including graphite), and the formed interfacial film generally has a higher elastic modulus, which is beneficial to inhibiting volume expansion of the silicon negative electrode.
In some embodiments, the first additive comprises at least one of vinyl sulfate (DTD), 1, 3-Propane Sultone (PS), propenyl-1, 3-sultone (PST), ethylene Sulfite (ES), methylene Methane Disulfonate (MMDS), 1, 4-Butane Sultone (BS). The first additive is an S-containing annular additive and has excellent film forming performance.
In some embodiments, the second additive comprises at least one of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate (TTMSPI), tris (trimethylsilyl) phosphate (TMSP), tris (trimethylsilyl) phosphite (TMSPi), tris (trimethylsilyl) borate (TMSB). The second additive is combined with the first solvent and the first additive, so that the composition of a protective film formed on the negative electrode plate and the suitability of the high-density negative electrode plate are better, and the comprehensive performance of the high-areal-density secondary battery can be effectively improved.
In some embodiments the second additive comprises at least one of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) borate. The second additive is an Si-containing annular additive, and it is understood that trimethoxysilylpropyl is included in the 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, so that the reaction between the 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and hydrofluoric acid can be realized, corrosion damage of SEI and CEI interface films is avoided, and the high-temperature performance of the lithium ion battery is improved. Meanwhile, the ring structure formed by the isocyanurate can protect the positive electrode material.
In some embodiments, the electrolyte further comprises an electrolyte salt selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (fluorosulfonyl) imide (LiLSI), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium difluorophosphate (LiDFPO) 2 ) At least one of lithium tetrafluorooxalate phosphate (LiOTFP), lithium difluorophosphate (LiDFOP), lithium bisoxalato borate (LiBOB), and lithium difluorooxalato borate (LiDFOB).
In some embodiments, the mass percent of electrolyte salt is 10% to 20% based on the total mass of the electrolyte. Further preferably, the mass percentage of the electrolyte salt is 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or a range between any two values. Too low a mass concentration of electrolyte salt can affect the conductivity of the electrolyte, too high a concentration can increase the viscosity of the electrolyte, and also affect the conductivity of the electrolyte. The other electrolyte salts can be used as auxiliary lithium salts, and play a role in improving the stability of the electrolyte and the migration number of lithium ions.
In some embodiments, the electrolyte further includes a second solvent comprising at least one of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), methylpropyl carbonate (MPC), diphenyl carbonate (DPhC), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), gamma-butyrolactone (gamma-GBL).
In some embodiments, the electrolyte further includes a second solvent including ethylene carbonate, ethylmethyl carbonate (EMC), and at least one of propylene carbonate, butylene carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), methylpropyl carbonate (MPC), diphenyl carbonate (DPhC), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), gamma-butyrolactone (gamma-GBL).
In some embodiments, the electrolyte comprises ethylene carbonate and Ethyl Methyl Carbonate (EMC), the mass percent of ethyl methyl carbonate/(mass percent of ethylene carbonate + mass percent of first solvent) >1.2. When the content of the solvent meets the range, the cathode pole piece can have better infiltration performance, and the comprehensive performance of the battery is better.
In some embodiments, the mass percent of the second solvent is 54 to 85 percent based on the total mass of the electrolyte. Further preferred, the mass percent of the second solvent is 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 78%, 82%, 85% or a range between any two values. The second solvent not only can promote various electrolyte salts (such as LiFP 6 ) The reduction product of the dissociation of the catalyst also contributes to the formation of a benign solid electrolyte interface film and improves the stability of the electrode interface. In addition, the electrolyte containing the second solvent can effectively inhibit the stripping of the anode material and prolong the cycle life of the battery.
In some embodiments, the secondary battery further includes a positive electrode tab and a separator disposed between the positive electrode tab and the negative electrode tab at intervals, and the electrolyte of the present embodiment. The positive electrode plate, the negative electrode plate and the diaphragm in the secondary battery are further described in a supplementary manner.
Positive electrode plate
The positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector.
In some embodiments, the positive electrode active material layer may be one or more layers. Each layer of the multi-layer positive electrode active material may contain the same or different positive electrode active materials. The positive electrode active material is any substance capable of reversibly intercalating and deintercalating metal ions such as lithium ions.
In some embodiments, the positive electrode active material comprises one or more of Lithium Manganate (LMO), lithium iron phosphate (LFP), and ternary materials (NCM/NCA); the positive electrode active material comprises a ternary material, which may comprise lithium nickel cobalt manganese oxide and/or lithium nickel cobalt aluminum oxide; the positive electrode active material contains lithium nickel cobalt manganese oxide, and the content of nickel element is greater than or equal to 0.5 in terms of the molar ratio of nickel element, cobalt element and manganese element being 1.
In some embodiments, the positive electrode active material chemical formula includes Li a Ni x Co y Mn z M e O 2 Wherein a is more than or equal to 0.9 and less than or equal to 1.1, e is more than or equal to 0 and less than or equal to 0.1, x is more than or equal to 0.3 and less than or equal to 1.0, y is more than or equal to 0 and less than 0.4, z is more than or equal to 0.1 and less than or equal to 0, x+y+z=1.0, and M comprises at least one of Al, zr, sr, ti, B, mg, sn, W, Y, ba, nb, mo, ta, si, la, er, nd, gd, ce.
Further, the value range of a can be 0.9, 1.0, 1.1 or a range between any two values.
Further, the value range of x may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.96, 1.0 or a range between any two values.
Further, the value of y may be 0, 0.01, 0.02, 0.05, 0.08, 0.1, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.31, 0.32, 0.33, 0.4 or a range between any two values.
Further, the value of z may be 0.1, 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.31, 0.32, 0.33, 0.4 or a range between any two values.
In some embodiments, the positive electrode active material includes a doping element and/or a cladding element, which are not particularly required as long as the positive electrode active material can be made more stable.
In addition, the positive electrode active material layer further includes a positive electrode conductive agent and a positive electrode binder. In some embodiments, the kind of the positive electrode conductive agent is not limited, and any known conductive agent may be used. Examples of the positive electrode conductive agent may include, but are not limited to, carbon materials such as natural graphite, artificial graphite, acetylene black, amorphous carbon such as needle coke, carbon nanotubes, graphene, and the like. The above positive electrode conductive agents may be used alone or in any combination.
In some embodiments, the kind of the positive electrode binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, it is sufficient if it is a material that is soluble or dispersible in a liquid medium used in the production of the electrode. Examples of the positive electrode binder may include, but are not limited to, one or more of polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose nitrate, and other resin-based polymers; rubbery polymers such as Styrene Butadiene Rubber (SBR), nitrile Butadiene Rubber (NBR), fluororubber, isoprene rubber, butadiene rubber, and ethylene-propylene rubber; thermoplastic elastomer-like polymers such as styrene-butadiene-styrene block copolymer or its hydrogenated product, ethylene-propylene-diene terpolymer (EPDM), styrene-ethylene-butadiene-ethylene copolymer, styrene-isoprene-styrene block copolymer or its hydrogenated product, soft resin-like polymers such as polyvinyl acetate, ethylene-vinyl acetate copolymer, propylene- α -olefin copolymer, and fluorine-based polymers such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, polytetrafluoroethylene-ethylene copolymer; and polymer compositions having ion conductivity of alkali metal ions (particularly lithium ions). The above positive electrode binders may be used alone or in any combination.
In some embodiments, the kind of solvent used to form the positive electrode slurry is not limited as long as it is a solvent capable of dissolving or dispersing the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder. Examples of the solvent used to form the positive electrode slurry may include any one of an aqueous solvent and an organic solvent. Examples of the aqueous medium may include, but are not limited to, water and a mixed medium of alcohol and water, and the like. Examples of the organic-based medium may include, but are not limited to, aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N, N-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide, and Tetrahydrofuran (THF); amides such as N-methylpyrrolidone (NMP), dimethylformamide, and dimethylacetamide; aprotic polar solvents such as hexamethylphosphoramide and dimethyl sulfoxide.
The kind of the positive electrode current collector is not particularly limited, and it may be any material known to be suitable for use as a positive electrode current collector. Examples of the positive electrode current collector may include, but are not limited to, metal materials such as aluminum, stainless steel, nickel plating, titanium, tantalum, and the like; carbon materials such as carbon cloth and carbon paper; a composite of a polymer and a metal layer. In some embodiments, the positive electrode current collector is a metal material. In some embodiments, the positive electrode current collector is aluminum. The form of the positive electrode current collector is not particularly limited. When the positive electrode current collector is a metal material, the form of the positive electrode current collector may include, but is not limited to, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal foil, a metal expanded metal, a stamped metal, a foamed metal, and the like. When the positive electrode current collector is a carbon material, the form of the positive electrode current collector may include, but is not limited to, a carbon plate, a carbon thin film, a carbon cylinder, and the like.
In some embodiments, when the positive active material is lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, or lithium manganate, the preparation method is a conventional method, and examples of the preparation method include: a high temperature solid phase method, a carbothermic reduction method, a spray drying method, a template method or a hydrothermal synthesis method.
In some embodiments, the intermediate product obtained in the preparation process of the positive electrode active material may also be subjected to crushing treatment and sieving to obtain a positive electrode active material having an optimized particle size distribution and specific surface area. The crushing method is not particularly limited, and may be selected according to practical requirements, for example, a particle crusher may be used. The method of preparing the positive electrode active material of the present application is not limited to the above-described preparation method, as long as the positive electrode active material formed has the characteristics shown in the present application.
In some embodiments, the preparation process of the positive electrode sheet can include the steps of stirring, coating, drying, cold pressing, slitting, cutting and the like. The preparation method of the positive electrode plate comprises the steps of dispersing a positive electrode active material, a positive electrode conductive agent and a positive electrode binder in N-methyl pyrrolidone (NMP) according to a certain proportion, coating the obtained slurry on aluminum foil, drying, and then carrying out cold pressing and slitting to obtain the positive electrode plate.
Negative pole piece
In some embodiments, the negative electrode tab includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer including a negative electrode active material, the negative electrode active material including a silicon-based material and graphite.
In some embodiments, the silicon-based material comprises at least one of elemental silicon, a silicon-carbon alloy, a silicon oxygen compound, or a silicon-containing metal compound.
In some embodiments, the mass of the silicon-based material is 3% to 35% of the total mass of the negative electrode active material. For example, the mass of the silicon-based material is 3%, 5%, 10%, 12%, 15%, 18%, 20%, 22%, 24%, 26%, 30%, 32%, 35% or any two thereof of the total mass of the negative electrode active material, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Diaphragm
In order to prevent short circuit, a separator is generally provided between the positive electrode tab and the negative electrode tab. The type of the separator is not particularly limited and may be selected according to actual requirements. The isolating film may be polypropylene film, polyethylene film, polyvinylidene fluoride film, polyurethane film, aramid film or multilayer composite film modified with coating.
In some embodiments, the preparation of the secondary battery includes: the positive pole piece, the diaphragm and the negative pole piece are sequentially stacked, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role of isolation, the isolating film is wound into a square bare cell, the square bare cell is placed into a cell shell, baked at 65-95 ℃ for water removal, then electrolyte is injected, the sealing is carried out, and the secondary cell is obtained after the working procedures of standing, hot and cold pressing, formation, clamping, capacity division and the like. The battery type comprises a soft package, a cylinder, an aluminum shell and the like; the application is not only limited to the application of the soft-package lithium ion battery, but also includes the application of common lithium ion battery forms such as aluminum shell batteries, cylindrical batteries and the like.
Power utilization device
In some embodiments, the present application provides an electrical device comprising the secondary battery described above. The electric device may be a vehicle, a mobile phone, a portable device, a notebook computer, a ship, a spacecraft, an electric toy, an electric tool, or the like. The vehicle can be a new energy automobile, and the new energy automobile can be a pure electric automobile, a hybrid electric automobile or an extended range automobile and the like; spacecraft including airplanes, rockets, space planes, spacecraft, and the like; the electric toy includes fixed or mobile electric toys, such as a game machine, an electric car toy, an electric ship toy, and an electric airplane toy; power tools include metal cutting power tools, grinding power tools, assembly power tools, and railroad power tools, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete shakers, and electric planers, among others. The embodiment of the application does not limit the electric device in particular.
The application has been tested several times in succession, and the application will now be described in further detail with reference to a few test results, which are described in detail below in connection with specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
Example 1
(1) Preparation of positive electrode plate
Positive electrode active material Li (Ni 0.8 Mn 0.1 Co 0.1 )O 2 (NMC 811), conductive agent acetylene black (Super P) and binder polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 94:3:3, and uniformly dispersed in 1-methyl-2-pyrrolidone (NMP) to prepare uniform black slurry, and the prepared slurry is coated on two sides of an aluminum foil, baked, rolled and cut into pieces to obtain the positive electrode plate.
(2) Preparation of negative electrode plate
Artificial Graphite (AG) and silica as negative electrode active materialSiO), conductive agent acetylene black (Super P) and binder SBR are uniformly mixed according to the mass ratio of 84.6:9.4:3:3, and uniformly dispersed in deionized water to prepare uniform black slurry, the mixed slurry is coated on two sides of a copper foil, and the copper foil is baked, rolled and cut to obtain the copper foil with the surface density of 7mg/cm 2 To the negative electrode plate.
(3) Preparation of electrolyte
Mixing the first solvent and the second solvent to obtain a mixed solution for standby; sequentially adding electrolyte salt into the obtained mixed solvent in a glove box filled with argon at room temperature, continuously stirring and cooling, and then adding a first additive and a second additive to obtain electrolyte;
wherein, the kinds and specific amounts of the first solvent, the second solvent, the electrolyte salt, the first additive and the second additive are shown in Table 1.
(4) Fabrication of secondary battery
And stacking the prepared positive plate, the diaphragm and the negative plate in sequence, enabling the diaphragm to be positioned between the positive plate and the negative plate, winding, hot-pressing and shaping, welding the electrode lugs to obtain a bare cell, placing the bare cell in an outer packaging aluminum-plastic film, placing in an oven with the temperature of 85+/-10 ℃ for baking for 24 hours, injecting the prepared electrolyte into the dried cell, standing, forming and capacity-dividing to prepare the lithium ion soft package battery.
The remaining examples and comparative examples refer to example 1, with the differences shown in tables 1 and 2.
Method for testing contents of F, S and Si elements in electrolyte
And adding 2mL of concentrated nitric acid into 5g of electrolyte to-be-tested sample to digest, and ensuring that lithium salt in the electrolyte is fully decomposed completely, so as to avoid the direct test of an organic solvent by a test instrument. The electrolyte was tested for sulfur and silicon content using an inductively coupled plasma atomic emission spectrometer (ICP-OES) and for fluorine content using an Ion Chromatograph (IC). Drawing a standard curve according to the relation between the element content and the peak intensity or the peak area in the electrolyte standard sample, detecting the ion peak intensity of sulfur-containing or silicon-containing ions in the sample to be detected by ICP-OES, detecting the fluorine ion peak area by IC, and carrying the fluorine-containing or silicon-containing ions into the standard curve to obtain the ion contents, and converting the ion contents into the element contents to obtain the total content of F elements in the electrolyte. All the solutions including FEC were volatilized by heating and volatilizing, and then the content of F element in the remaining material was again detected by IC. And subtracting the content of the F element in the lithium salt from the total content of the F element to obtain the content of the F element in the first solvent.
Performance test of a battery
Normal temperature DCR test the soft pack battery 1C obtained in examples and comparative examples was charged to 4.25V at 25±2 ℃, discharged at 1C capacity for 30min, and after adjusting to 50% SOC, 5C constant current pulse discharge was performed for 10s and then charged for 10s, and dcr= (voltage before pulse discharge-voltage after pulse discharge)/discharge current x 100% was calculated, and the obtained recording results are shown in table 3.
And (3) testing normal temperature cycle performance, namely testing the soft package batteries obtained in the examples and the comparative examples in a charge-discharge cycle mode at the charge-discharge multiplying power of 1C/1C within the range of 2.5-4.25V at the temperature of 25+/-2 ℃, and recording the cycle number of the battery with the capacity retention rate of 80%. 80% capacity retention = specific discharge capacity/specific first week discharge capacity x 100%, recorded data are shown in table 3.
And (3) high-temperature storage and gas production test: the soft package batteries obtained in the examples and the comparative examples were charged to 4.25V at a constant current of 1C rate at 25±2 ℃ and then charged to a constant voltage of 4.25V to a current of less than 0.05C, so that they were in a full charge state of 4.25V. The volume of the full-charged battery before storage was tested and recorded as V 0 The method comprises the steps of carrying out a first treatment on the surface of the Then the battery in full charge state is placed in an oven at 60+/-2 ℃, after 60 days, the battery is taken out, and the stored volume is immediately tested and recorded as V 1 . Volume expansion ratio= (V 1 –V 0 )/V 0 100% and the results are shown in Table 3.
High temperature circulating gas producing test, namely, at 45+/-2 deg.c, the soft package batteries obtained in the examples 1-18 and the comparative examples 1-6 are charged and discharged circularly in the range of 2.5-4.25V with the charge and discharge rate of 1C/1C, and the open circuit voltage state battery volume before the test circulation is recorded as V 2 The method comprises the steps of carrying out a first treatment on the surface of the During the cycle, the volume change is tested once every 100 weeks of the cycle; after cycling to 80% capacity retention, the cell was removed and immediately tested for volume after cycling and designated as V 3 . For safety reasons, when the gas is produced during circulationWhen the product change rate was more than 100%, the test was immediately stopped, and the number of cycles at this time was recorded, and the results of the capacity retention rate and the volume expansion rate obtained are shown in table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
In tables 1, 2 and 3, as is clear from comparison of examples 1 to 29 and comparative examples 1 to 6, when the first solvent of FEC, the first additive of sulfur-containing element and the second additive of silicon-containing element are contained in the electrolyte, and 0.005.ltoreq.B+1.2C)/(A.times.D.ltoreq.0.1 is satisfied, the volume expansion of the silicon-based anode is effectively suppressed, the high temperature gas production of the battery is reduced, and the balance between the cycle life and the risk of high temperature gas production is achieved.
As is clear from the comparison of examples 1 to 5 in tables 1 and 2, when the mass percentage of the second additive is 0.1 to 1%, the content of the silicon element C% is 0.0136.ltoreq.C.ltoreq.0.068, the addition of the silicon element can be used as a by-product F in the electrolyte – The combination avoids the damage of HF to the interface, thereby relieving the side reaction between the anode interface and the electrolyte, and achieving the effect of inhibiting the gas production.
As is clear from the comparison of examples 1 to 16, in tables 1, 2 and 3, only the surface density of the anode active material layer was 6 to 15mg/cm 2 A is more than or equal to 0.358 and less than or equal to 3.580 in the electrolyte; b is more than or equal to 0.129 and less than or equal to 1.032; when C is more than or equal to 0.014 and less than or equal to 0.151, the contents of fluorine, sulfur and silicon are balanced, and the balance of cycle life and safety performance is realized by the synergistic use of the fluorine, the sulfur and the silicon; the method avoids risks of electrolyte high-temperature gas production and the like caused by excessive fluorine elements, or avoids the deterioration of the cycle life of the battery caused by excessive sulfur elements, and avoids the negative influence on the cycle life and the long-term high-temperature storage performance caused by excessive silicon elements.
As can be seen from the experimental results of comparative examples 1 to 29, when 0.005.ltoreq.B+1.2C)/(A.times.D.ltoreq.0.1, the higher comprehensive properties, that is, the gas expansion rate in the high-temperature cycle was <40.3%; 80% capacity retention cycle number >800 weeks at 25 ℃; the expansion rate of the gas produced by 45 ℃ circulation is less than 48.8%, so that the electrolyte is further optimized, and the performance of the secondary battery can be further improved to meet the actual product requirement.
The secondary battery and the power consumption device provided by the embodiment of the application are described in detail, and the specific examples are applied to the application to explain the principle and the implementation mode of the application, and the description of the above embodiments is only used for helping to understand the technical scheme and the core idea of the application; it will be understood by those skilled in the art that the technical solutions described in the foregoing embodiments may be modified or some of the technical features may be replaced with equivalents; such modifications and substitutions do not constitute an admission as to the nature of the technical solution.

Claims (10)

1. A secondary battery comprises a negative electrode sheet and an electrolyte, wherein the negative electrode sheet comprises a negative electrode active material layer, and the surface density of the negative electrode active material layer is D mg/cm 2 ；
The electrolyte comprises: a first solvent, a first additive, and a second additive; the first solvent comprises a fluorine-containing compound, the first additive comprises a sulfur-containing compound, and the second additive comprises a silicon-containing compound;
wherein, based on the total mass of the electrolyte, the mass percent of fluorine element in the fluorine-containing compound is A%, the mass percent of sulfur element in the sulfur-containing compound is B%, and the mass percent of silicon element in the silicon-containing compound is C%, which satisfies the following conditions:
0.005≤(B+1.2C)/(A×D)≤0.1。
2. the secondary battery according to claim 1, wherein the surface density of the anode active material layer is D mg/cm 2 ，6≤D≤15。
3. The secondary battery according to claim 1, wherein at least one of the following characteristics is satisfied based on the total mass of the electrolyte:
a) The mass percentage of the first solvent is 2% -20%;
b) The mass percentage of the first additive is 0.1% -3%;
c) The mass percentage of the second additive is 0.1% -1%.
4. The secondary battery according to claim 1, wherein the electrolyte satisfies at least one of the following characteristics:
d)0.358≤A≤3.580；
e)0.129≤B≤1.032；
f)0.014≤C≤0.151。
5. the secondary battery according to claim 1, wherein the first solvent comprises fluoroethylene carbonate.
6. The secondary battery according to claim 1, wherein the first additive comprises at least one of vinyl sulfate, 1, 3-propane sultone, propenyl-1, 3-sultone, ethylene sulfite, methylene methane disulfonate, 1, 4-butane sultone; the second additive comprises at least one of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite, tris (trimethylsilyl) borate.
7. The secondary battery according to claim 1, wherein the electrolyte further comprises an electrolyte salt selected from at least one of lithium hexafluorophosphate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethylsulfonyl imide, lithium tetrafluoroborate, lithium perchlorate, lithium difluorophosphate, lithium tetrafluorophosphate, lithium bis-oxalato difluorophosphate, lithium bis-oxalato borate, lithium difluorooxalato borate.
8. The secondary battery of claim 1, wherein the electrolyte further comprises a second solvent, the electrolyte satisfying at least one of the following characteristics:
h) Based on the total mass of the electrolyte, the mass percentage of the second solvent is 54-85%;
i) The second solvent is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, diphenyl carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate and gamma-butyrolactone.
9. The secondary battery according to claim 1, wherein the anode active material layer includes an anode active material including a silicon-based material and graphite, the anode active material satisfying at least one of the following characteristics:
j) The silicon-based material comprises at least one of a simple substance of silicon, a silicon-carbon alloy, a silicon oxygen compound and a silicon-containing metal compound;
k) The mass of the silicon-based material accounts for 3% -35% of the total mass of the anode active material.
10. An electric device comprising the secondary battery according to any one of claims 1 to 9.
CN202310819331.7A 2023-07-05 2023-07-05 Secondary battery and electricity utilization device Pending CN116936738A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117219840A (en) * 2023-11-09 2023-12-12 宁德时代新能源科技股份有限公司 Sodium secondary battery and electricity utilization device
CN117613356A (en) * 2023-11-27 2024-02-27 欣旺达动力科技股份有限公司 A secondary battery and electrical device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117219840A (en) * 2023-11-09 2023-12-12 宁德时代新能源科技股份有限公司 Sodium secondary battery and electricity utilization device
CN117219840B (en) * 2023-11-09 2024-04-16 宁德时代新能源科技股份有限公司 Sodium secondary battery and electricity utilization device
CN117613356A (en) * 2023-11-27 2024-02-27 欣旺达动力科技股份有限公司 A secondary battery and electrical device

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