CN116259927A - Secondary battery and device - Google Patents

Secondary battery and device Download PDF

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CN116259927A
CN116259927A CN202310548320.XA CN202310548320A CN116259927A CN 116259927 A CN116259927 A CN 116259927A CN 202310548320 A CN202310548320 A CN 202310548320A CN 116259927 A CN116259927 A CN 116259927A
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lithium
secondary battery
silicon
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CN116259927B (en
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李思远
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Weilai Battery Technology Anhui Co ltd
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Weilai Battery Technology Anhui 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
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • 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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  • General Chemical & Material Sciences (AREA)
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Abstract

The present application relates to a secondary battery and an apparatus. The secondary battery comprises a positive electrode, a negative electrode, an electrolyte and a separation film, wherein the electrolyte comprises a silicon-containing additive; the air permeability of the isolation film is 120s/100ml to 450s/100ml, and the infrared spectrogram of the isolation film has absorption peaks in the following range by adopting a Fourier transform attenuated total reflection infrared test: 820cm ‑1 ±50cm ‑1 、1100cm ‑1 ±50cm ‑1 、1200cm ‑1 ±30cm ‑1 3350cm ‑1 ±50cm ‑1 . The secondary battery effectively prolongs the cycle life of the secondary battery by controlling the composition of the decomposition products of the silicon-containing additive on the isolating film.

Description

Secondary battery and device
Technical Field
The present application relates to the field of energy storage. In particular, the present application relates to a secondary battery and an apparatus.
Background
Lithium ion batteries have been widely used in smart phones, unmanned aerial vehicles, hybrid electric vehicles, etc., but with the development of society, low energy density lithium ion batteries have been difficult to meet the demands. The development of the high-capacity high-nickel ternary material anode adapting to the silicon-based negative electrode becomes the development direction of the high-energy-density lithium ion battery. Although the battery capacity is continuously improved, the high temperature and normal temperature stability of the battery is continuously reduced due to the improvement of the nickel content of the positive electrode.
Up to now, many lithium-based secondary batteries have been proposed with high stability. For example, patent document CN105009348A proposes a secondary battery in which 167-171eV sulfur element is present on the surface of a positive electrode by XPS analysis, and the positive electrode sulfur-containing battery exhibits excellent cycle performance. In addition, many documents disclose a power battery electrolyte suitable for a high nickel/high silicon system and a power battery thereof, which can form an excellent SEI film on the surface of an electrode through the synergistic effect of additives and effectively promote each dynamic process inside a lithium ion battery. However, at present, the influence of substances on a separator on the performance of a battery is rarely reported.
Disclosure of Invention
In view of the shortcomings of the prior art, the present application provides a secondary battery and related apparatus. The secondary battery effectively prolongs the cycle life of the secondary battery by controlling the composition of the decomposition products of the silicon-containing additive on the isolating film.
A first aspect of the present application provides a secondary battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein the electrolyte comprises a silicon-containing additive; the air permeability of the isolating film is 120s/100ml (s/cc) to 450s/100ml, and the infrared spectrogram of the isolating film has absorption peaks in the following range by adopting a Fourier transform attenuated total reflection infrared test: 820cm -1 ±50cm -1 、1100cm -1 ±50cm -1 、1200cm -1 ±30cm -1 3350cm -1 ±50cm -1 。
A second aspect of the present application provides an apparatus comprising the secondary battery of the first aspect.
The beneficial effects of this application are:
the secondary battery regulates and controls the adsorption degree of the silicon-containing additive on the isolating membrane by controlling the air permeability of the isolating membrane, effectively improves the decomposition degree of the silicon-containing additive on the isolating membrane under the set better air permeability, has strong relevance with the service life of lithium ions, and can effectively prolong the cycle life of the secondary battery by adopting the proper decomposition products.
Detailed Description
For simplicity, this application discloses only a few numerical ranges specifically. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
Unless otherwise indicated, terms used in the present application have well-known meanings commonly understood by those skilled in the art. Unless otherwise indicated, the numerical values of the parameters set forth in this application may be measured by various measurement methods commonly used in the art (e.g., may be tested according to the methods set forth in the examples of this application).
The list of items to which the term "at least one of," "at least one of," or other similar terms are connected may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means only a; only B; or A and B. In another example, if items A, B and C are listed, then the phrase "at least one of A, B and C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single component or multiple components. Item B may comprise a single component or multiple components. Item C may comprise a single component or multiple components. In the present application, unless otherwise indicated, the term "heterocyclyl" refers to a cyclic group containing at least one heteroatom including at least one of boron, nitrogen, oxygen, silicon, phosphorus or sulfur. In some embodiments, the heterocyclyl group comprises at least one of an alicyclic and aromatic heterocyclyl group.
In the present application, unless otherwise indicated, the term "alicyclic hydrocarbon group" means a cyclic hydrocarbon having an aliphatic nature, having a closed carbocyclic ring in the molecule.
The present application is further described below in conjunction with the detailed description. It should be understood that these specific embodiments are presented by way of example only and are not intended to limit the scope of the present application.
1. Secondary battery
The secondary battery comprises a positive electrode, a negative electrode, an electrolyte and a separation film, wherein the electrolyte comprises a silicon-containing additive; the air permeability of the isolation film is 120s/100ml to 450s/100ml, and the infrared spectrogram of the isolation film has absorption peaks in the following range by adopting a Fourier transform attenuated total reflection infrared test: 820cm -1 ±50cm -1 、1100cm -1 ±50cm -1 、1200cm -1 ±30cm -1 3350cm -1 ±50cm -1 . The inventor of the application finds through research that the air permeability of the isolating membrane is related to the amount of the silicon-containing additive adsorbed in the isolating membrane, the moderate air permeability indicates that the pore channels in the isolating membrane are more and the pore diameter is smaller, the adsorption degree of the silicon-containing additive on the isolating membrane can be effectively improved, the decomposition degree of the silicon-containing additive on the isolating membrane can be effectively improved under the set optimal air permeability, the decomposition products on the isolating membrane have strong relevance with the service life of lithium ions, and the circulation capacity retention rate of the secondary battery can be effectively improved by the proper decomposition products.
In the present application, 820cm -1 ±50cm -1 The absorption peak in the range is the antisymmetric stretching vibration of Si-O bond. 1100cm -1 ±50cm -1 The absorption peak in the range is symmetrical stretching vibration of Si-O bond. 1200cm -1 ±30cm -1 The absorption peak in the range is symmetrical stretching vibration of Si-C bond. 3350cm -1 ±50cm -1 The absorption peak in the range is the stretching vibration of Si-OH bond.
In some embodiments, the barrier film has an air permeability of 135/100 ml, 140/100 ml, 145/100 ml, 150/100 ml, 155/100 ml, 160/100 ml, 165/100 ml, 170/100 ml, 175/100 ml, 180/100 ml, 185/100 ml, 190/100 ml, 195/100 ml, 200/100 ml, 205/100 ml, 210/100 ml, 215/100 ml, 220/100 ml, 225/100 ml, 230/100 ml, 235/100 ml, 240/100 ml, 245/100 ml, 250/100 ml, 255/100 ml, 260/100 ml, 265/100 ml, 270/100 ml, 275/100 ml, 280/100 ml, 285/100 ml, 300/100 ml, 330/100 ml, 350/100 ml, 370/100 ml, 400/100 ml, 430/100 ml, or any value therebetween. When the air permeability of the isolating film is too large, the adsorption of the silicon-containing additive on the isolating film is not facilitated, and the decomposition degree of the silicon-containing additive on the isolating film is further affected. In some embodiments, the barrier film has a permeability of 150s/100ml to 300s/100ml.
In some embodiments, the infrared spectrum is at 1460cm -1 ±50cm -1 The peak height of the absorption peak in the range is L, at 1100cm -1 ±50cm -1 The peak height of the absorption peak in the range is L1, wherein L1/L is less than or equal to 1.5. In the application, when L1/L is in the range, the decomposition products of the silicon-containing additive in the electrolyte on the isolating film are uniform, and the improvement of the performance of the lithium ion battery is facilitated. In the present application 1460cm -1 ±50cm -1 Absorption peaks in the range are-CH on the isolating film 2 Bending vibrations of the key.
In some embodiments, L1/L is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.10, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, or any value therebetween. In some embodiments, L1/L.ltoreq.1.0.
In some embodiments, the silicon-containing additive is selected from at least one of silicon-containing compounds containing carbon-carbon unsaturation.
In some embodiments, the silicon-containing additive comprises at least one of the compounds of formula I,
Figure SMS_1
i is a kind of
In the formula I, R 1 、R 2 、R 3 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyl, and substituted or unsubstituted C2-C10 alkynyloxyA substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C7-C12 aralkyl group, a substituted or unsubstituted C3-C10 alicyclic hydrocarbon group, a substituted or unsubstituted C3-C12 heterocyclic group, and R 1 、R 2 、R 3 And R is 4 At least one of which is selected from the group consisting of a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkenyloxy group, a substituted or unsubstituted C2-C10 alkynyl group, and a substituted or unsubstituted C2-C10 alkynyloxy group. In some embodiments, when substituted, the substituents are independently selected from halogen. In some embodiments, when substituted, the substituent is fluorine.
In this application, C1-C10 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl or octyl.
The C1-C10 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, n-heptoxy or octoxy.
The C2-C10 alkenyl is selected from vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1, 3-butadienyl, 3-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl or cyclohexenyl.
The C2-C10 alkenyloxy group is selected from the group consisting of ethyleneoxy, allyloxy, 1-propyleneoxy, isopropyleneoxy, 2-butyleneoxy, 1, 3-butyleneoxy, 4-pentenyloxy, 3-pentenyloxy, 2-hexenyloxy, 3-hexenyloxy and cyclohexenyloxy.
The C2-C10 alkynyl is selected from the group consisting of ethynyl, 1-propynyl, 2-propynyl, 1 dimethyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-pentynyl, 3-pentynyl, 2-hexynyl and 3-hexynyl.
The C2-C10 alkynyloxy group is selected from ethynyloxy, 1-propynyloxy, 2-propynyloxy, 1 dimethyl-2-propynyloxy, 1-butynyloxy, 2-butynyloxy, 3-butynyloxy, 4-pentynyloxy, 3-pentynyloxy, 2-hexynyloxy or 3-hexynyloxy.
The C6-C12 aryl is selected from phenyl, methylphenyl, ethylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl or n-hexylphenyl.
The C7-C12 aralkyl group is selected from phenethyl, phenylpropyl, benzyl or phenylbutyl.
Halogen is selected from fluorine, chlorine, bromine or iodine.
In some embodiments, R 1 、R 2 、R 3 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkynyloxy, and R 1 、R 2 、R 3 And R is 4 At least one of which is selected from the group consisting of a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkenyloxy group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted C2-C6 alkynyloxy group.
In some embodiments, R 1 Selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, R 2 、R 3 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, and substituted or unsubstituted C2-C6 alkynyloxy.
In some embodiments, R 1 And R is 3 Independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, R 2 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, and substituted or unsubstituted C2-C6 alkynyloxy.
In some embodiments, R 1 、R 2 And R is 3 Independently selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, R 4 Selected from the group consisting of substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstitutedC2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkynyloxy.
In some embodiments, R 1 、R 2 、R 3 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, and substituted or unsubstituted C2-C6 alkynyloxy.
In some embodiments, R 1 、R 2 、R 3 And R is 4 And are the same and are selected from the group consisting of substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl and substituted or unsubstituted C2-C6 alkynyloxy.
In some embodiments, the silicon-containing additive includes at least one of tetravinylsilane, vinyltrimethylsilane, divinyldimethylsilane, and trivinylmethylsilane.
In some embodiments, the silicon-containing additive is present in an amount of 0.05% to 5% by mass based on the mass of the electrolyte. In some embodiments, the silicon-containing additive is present in an amount of 0.1%, 0.3%, 0.5%, 0.7%, 1.0%, 1.3%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.7%, 3.0%, 3.3%, 3.5%, 3.7%, 3.0%, 4.3%, 4.5%, 4.7% or any value therebetween by mass. In some embodiments, the silicon-containing additive is present in an amount of 0.1% to 3% by mass.
In some embodiments, the electrolyte further comprises other additives. In some embodiments, the other additives include at least one of cyclic carbonates containing carbon-carbon double bonds, fluorolithium salts, and sulfates.
In some embodiments, the other additive is present in an amount of 0.05% to 10% by mass, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9% or any value therebetween, based on the mass of the electrolyte. In some embodiments, the other additive is present in an amount of 0.1% to 8% by mass.
In some embodiments, the cyclic carbonate containing carbon-carbon double bonds comprises at least one of the compounds represented by formula II:
Figure SMS_2
formula II->
In formula II, R 5 And R is 6 Independently selected from a hydrogen atom, a fluorine atom or a C1-C6 alkyl group.
In some embodiments, the cyclic carbonate containing carbon-carbon double bonds comprises at least one of Vinylene Carbonate (VC), vinylene methyl carbonate, or vinylene ethyl carbonate. In some embodiments, the other additive is selected from at least one of vinylene carbonate, lithium difluorophosphate, and vinyl sulfate.
In some embodiments, the cyclic carbonate containing carbon-carbon double bonds, e.g., vinylene carbonate, is present in an amount of 0.1% -5%, e.g., 0.1%, 0.5%, 0.7%, 0.9%, 1.0%, 1.3%, 1.5%, 1.7%, 2.0%, 2.3%, 2.5%, 2.7%, 3%, 3.5%, 4%, 4.5%, or any value therebetween, based on the mass of the electrolyte. In some embodiments, the cyclic carbonate containing carbon-carbon double bonds is present in an amount of 0.5% to 3% by mass.
According to some embodiments of the present application, the sulfate comprises at least one of the compounds of formula III,
Figure SMS_3
formula III
In formula III, R 7 、R 8 、R 9 、R 10 Independently represents a hydrogen atom, a fluorine atom or C 1 -C 6 Alkyl, and a is 0, 1, 2, 3, or 4.
In some embodiments, the cyclic sulfate compound is selected from at least one of vinyl sulfate, vinyl 4-methylsulfate, or vinyl 4-fluorosulfate.
In some embodiments, the cyclic sulfate compound, e.g., vinyl sulfate, is present in an amount of 0.1% -3%, e.g., 0.1%, 0.3%, 0.7%, 0.9%, 1.0%, 1.3%, 1.6%, 1.8%, 2.0%, 2.3%, 2.6%, or 2.8% by mass based on the mass of the electrolyte. In some embodiments, the mass content of the cyclic sulfate compound is 1% -2%.
In some embodiments, the electrolyte further comprises a nonaqueous solvent and a lithium salt. In some embodiments, the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bisoxalato borate, lithium bisfluorosulfonyl imide, and lithium bis (trifluoromethanesulfonyl) imide.
In some embodiments, the solvent comprises at least one of a chain carbonate, a cyclic carbonate, and a carboxylate.
In some embodiments, the chain carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, and fluoro chain carbonate. In some embodiments, the cyclic carbonate comprises at least one of fluoroethylene carbonate, ethylene carbonate, propylene carbonate, and butylene carbonate. In some embodiments, the carboxylic acid ester is selected from at least one of methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolactone, and a fluorocarboxylic acid ester.
In some embodiments, the positive electrode includes a positive electrode active material including at least one of a lithium cobaltate-based material and a ternary positive electrode material.
In some embodiments, the lithium cobaltate-based material comprises Li 1-x A x CoO 2 Wherein, A is selected from one or more of aluminum, magnesium, titanium, tin, vanadium, copper, zinc, zirconium, chromium, manganese, iron, gallium, molybdenum, antimony, tungsten, yttrium and niobium, and x is more than or equal to 0 and less than or equal to 0.05. In some embodiments, x is 0.005, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, or 0.045.
In some embodiments, the ternary cathode material comprises a nickel-cobalt based ternary material, more preferably, the nickel-cobalt based ternary material comprises LiNi m Co n B (1-m-n) O 2 At least one of the materials, B is selected from Mn, al, mg, cr, ca, zr, mo, agOr niobium, wherein m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.5, and m+n is more than or equal to 1. In some embodiments, m is 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, or any value therebetween. In some embodiments, n is 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or any value therebetween.
In some embodiments, the positive electrode active material includes at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, and lithium nickel cobalt aluminum oxide.
In some embodiments, the positive electrode further comprises a binder, and optionally a conductive material. The binder enhances the bonding of the positive electrode active material particles to each other and also enhances the bonding of the positive electrode active material to the current collector.
In some embodiments, the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like.
In some embodiments, the conductive material includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the positive electrode further includes a positive electrode current collector, which may be a metal foil or a composite current collector. For example, aluminum foil may be used. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, or the like) on a polymer substrate.
In some embodiments, the anode includes an anode active material including at least one of a silicon-based material, a carbon-based material, and a lithium-based material.
In some embodiments, the silicon-based material includes at least one of silicon, a silicon alloy, a silicon oxygen compound, and a silicon carbon compound. In some embodiments, the carbon-based material comprises at least one of graphite, soft carbon, hard carbon, carbon nanotubes, and graphene. In some embodiments, the lithium-based material includes at least one of metallic lithium and lithium titanate. In some embodiments, the negative active material includes at least one of graphite, soft carbon, hard carbon, carbon nanotubes, graphene, silicon alloys, silicon oxygen compounds, silicon carbon compounds, metallic lithium, and lithium titanate.
In some embodiments, the negative electrode further includes a binder and a conductive agent. In some embodiments, the binder includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or the like.
In some embodiments, the conductive agent includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from metal powder, metal fiber, copper, nickel, aluminum, or silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the negative electrode further comprises a negative electrode current collector comprising: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or any combination thereof.
In some embodiments, the separator film includes a base film and a coating disposed on the base film. In some embodiments, the base film comprises at least one of a polyethylene film, a polypropylene film, a PP/PE/PP composite film, a polyimide film, an aramid film, a polyethylene terephthalate film, or a nonwoven fabric. In some embodiments, the coating includes at least one of a polymer layer, an inorganic layer, or a hybrid layer of polymer and inorganic.
In some embodiments, the inorganic layer comprises at least one of aluminum oxide, aluminum hydroxide, boehmite, garnet, magnesium hydroxide, or silica.
In some embodiments, the method of manufacturing the secondary battery includes providing an electrode assembly, injecting a liquid, packaging, and forming. In some embodiments, the temperature of the formation is 40 ℃ to 50 ℃, e.g., 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, or 49 ℃.
In some embodiments, the forming comprises: charging to 4.25V at a current of 0.05C under a condition of a temperature of 40-50 deg.C, for example 45 deg.C, and a pressure of 150-250 kgf, for example 210kgf, standing for 60 min, then charging to 4.25V at 0.1C, and then discharging to 3.0V at 0.2C.
In some embodiments, the secondary battery is a lithium secondary battery or a sodium secondary battery. In some embodiments, lithium secondary batteries include, but are not limited to: lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries, or lithium ion polymer secondary batteries.
In some embodiments, the secondary battery may include an outer package, which may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The soft bag can be made of one or more of polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), etc.
In some embodiments, the shape of the secondary battery is not particularly limited, and may be cylindrical, square, or any other shape.
In some embodiments, the present application also provides a battery module. The battery module includes the secondary battery described above. The battery module of the present application employs the above-described secondary battery, and thus has at least the same advantages as the secondary battery. The number of secondary batteries contained in the battery module of the present application may be plural, and the specific number may be adjusted according to the application and capacity of the battery module.
In some embodiments, the present application also provides a battery pack including the above battery module. The number of battery modules included in the battery pack may be adjusted according to the application and capacity of the battery pack.
2. Device and method for controlling the same
The present application also provides an apparatus comprising at least one of the above secondary battery, battery module or battery pack.
In some embodiments, the apparatus includes, but is not limited to: electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric storage systems, and the like. In order to meet the high power and high energy density requirements of the device for the secondary battery, a battery pack or a battery module may be employed.
In other embodiments, the device may be a cell phone, tablet, notebook, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
In this application, materials or reagents used are commercially available unless otherwise specified.
Examples
The preparation method of the positive electrode comprises the following steps: the positive electrode active material LiNi was mixed at a mass ratio of 97.5:1.5:1.0 0.9 Co 0.05 Mn 0.05 O 2 And conductive carbon black and a binder polyvinylidene chloride are dispersed in N-methyl-2-pyrrolidone to obtain positive electrode slurry, the positive electrode slurry is uniformly coated on two sides of an aluminum foil, and the positive electrode plate, which is also called positive electrode, is obtained through drying, calendaring and vacuum drying.
The preparation method of the negative electrode comprises the following steps: according to 96.0:1.0:2.4: mixing silicon carbon material, conductive carbon black, adhesive (styrene-butadiene rubber, polyacrylic acid) and sodium carboxymethyl cellulose in a mass ratio of 0.6, dispersing in deionized water to obtain negative electrode slurry, coating the negative electrode slurry on two sides of a copper foil, and drying, calendaring and vacuum drying to obtain a negative electrode plate, namely a negative electrode.
Isolation film: the isolating film is a base film and an inorganic coating (9+2+2), wherein the base film is made of PE material and has the thickness of 9 mu m; the thickness of the single-sided inorganic coating was 2 μm.
Preparing an electrolyte: in a glove box protected by nitrogen (moisture < 1ppm, oxygen < 1 ppm), mixing Ethylene Carbonate (EC), propylene Carbonate (PC) and diethyl carbonate (DEC) according to the mass ratio of EC: PC: DEC=20:5:45, and adding lithium hexafluorophosphate (LiPF 6 ) To a molar concentration of 1mol/L (12 wt%), vinylene carbonate and tetravinyl silane (specific compositions are shown in Table 1) calculated according to the total mass of the electrolyte are added, and the electrolyte of the lithium ion battery of example 1 is obtained after uniform stirring.
The battery assembly steps are as follows: placing a 13-mu m-thick isolating film between the positive electrode and the negative electrode, then carrying out lamination process on a sandwich structure formed by the positive electrode, the isolating film and the negative electrode, then placing the sandwich structure into an aluminum plastic film packaging bag, carrying out vacuum baking for 48 hours at 75 ℃ to obtain a battery cell to be injected with the electrolyte, injecting the electrolyte into the battery cell, carrying out vacuum packaging, standing for 12 hours at normal temperature and standing for 12 hours at high temperature of 45 ℃.
The formation and the volume dividing steps are as follows: the formation conditions are: after charging to 4.25V at 45℃under 210kgf at 0.05C current, standing for 60 min, then charging to 4.25V at 0.1C, then discharging to 3.0V at 0.2C, (thus, repeating three times) and sealing twice, conventional capacity division was performed.
Examples 2 to 6 and comparative examples 1 to 5 were carried out by adjusting the kinds and contents of additives in the electrolyte, formation conditions, and air permeability of the separator, etc., based on example 1, and specific adjustment measures and detailed data are shown in table 1.
Figure SMS_4
Test method
1. Cycle capacity and cycle capacity retention test
And (3) charging the lithium ion battery to 4.25V under the constant current and constant pressure of 1C at 45 ℃, and discharging to 2.5V under the constant current and constant pressure of 1C. After 200 cycles of charge and discharge, the capacity retention after the 200 th cycle at 45℃was calculated according to the following formula: the discharge capacity after the 200 th cycle/the discharge capacity after the first cycle is multiplied by 100%.
2. ATR-FTIR
Disassembling the soft package lithium ion battery after the capacity division and formation are finished, and selecting 1cm of the soft package lithium ion battery 2 The area of the separator was washed with DMC for 10 minutes and dried in vacuum for 12 hours, after which the dried separator was placed on an ATR-FTIR instrument for total reflection infrared analysis. The specific test conditions and steps are as follows:
1. turning on power supplies of a computer and an infrared spectrometer host computer, and preheating for half an hour;
2. installing an ATR-0MNI sampler;
3. the wavelength/wavenumber axis was calibrated using NIST SRM 1920 standards at room temperature of 25 ℃;
4. directly placing the test surface of the isolating film sample on the germanium crystal, rotating the OMNI sampler fixing button, and pressing the sample; 5. at 4000cm -1 To 400cm -1 Scanning in a wave number range, and collecting an attenuated total reflection infrared spectrum of the isolating film sample.
Test results
Figure SMS_5
While certain exemplary embodiments of the present application have been illustrated and described, the present application is not limited to the disclosed embodiments. Rather, one of ordinary skill in the art will recognize that certain modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application, as described in the appended claims.

Claims (13)

1. A secondary battery includes a positive electrode, a negative electrode, an electrolyte, and a separator, wherein,
the electrolyte includes a silicon-containing additive;
the air permeability of the isolation film is 120s/100ml to 450s/100ml, and the infrared spectrogram of the isolation film has absorption peaks in the following range by adopting a Fourier transform attenuated total reflection infrared test: 820cm -1 ±50cm -1 、1100cm -1 ±50cm -1 、1200cm -1 ±30cm -1 3350cm -1 ±50cm -1 。
2. The secondary battery according to claim 1, wherein the separator has a permeability of 150s/100ml to 300s/100ml; and/or
The infrared spectrum is 1460cm -1 ±50cm -1 The peak height of the absorption peak in the range is L, at 1100cm -1 ±50cm -1 The peak height of the absorption peak in the range is L1, wherein L1/L is less than or equal to 1.5.
3. The secondary battery according to claim 1 or 2, wherein the silicon-containing additive is selected from at least one of silicon-containing compounds containing carbon-carbon unsaturated bonds.
4. The secondary battery according to claim 1 or 2, wherein the silicon-containing additive comprises at least one of compounds represented by formula I,
Figure QLYQS_1
i is a kind of
In the formula I, R 1 、R 2 、R 3 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C7-C12 aralkyl, substituted or unsubstituted C3-C10 alicyclic hydrocarbon, substituted or unsubstitutedC3-C12 heterocyclyl of (C2), and R 1 、R 2 、R 3 And R is 4 At least one of which is selected from the group consisting of a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkenyloxy group, a substituted or unsubstituted C2-C10 alkynyl group, and a substituted or unsubstituted C2-C10 alkynyloxy group.
5. The secondary battery according to claim 4, wherein R 1 、R 2 、R 3 And R is 4 Independently selected from the group consisting of substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkynyloxy, and R 1 、R 2 、R 3 And R is 4 At least one selected from the group consisting of a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C2-C6 alkenyloxy group, a substituted or unsubstituted C2-C6 alkynyl group, and a substituted or unsubstituted C2-C6 alkynyloxy group; and/or
When substituted, the substituents are independently selected from halogen.
6. The secondary battery according to claim 4, wherein R 1 、R 2 、R 3 And R is 4 Identical, are each selected from the group consisting of substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C2-C6 alkynyloxy, and/or
When substituted, the substituent is fluorine.
7. The secondary battery according to claim 1 or 2, wherein the silicon-containing additive includes at least one of tetravinylsilane, vinyltrimethylsilane, divinyldimethylsilane, and trivinylmethylsilane; and/or
The mass content of the silicon-containing additive is 0.05-5% based on the mass of the electrolyte; and/or
The electrolyte further includes other additives including at least one of cyclic carbonates containing carbon-carbon double bonds, fluorine-containing lithium salts, and sulfates.
8. The secondary battery according to claim 7, wherein the silicon-containing additive is contained in an amount of 0.1% to 3% by mass based on the mass of the electrolyte; and/or
The mass content of the other additives is 0.05-10% based on the mass of the electrolyte; and/or
The other additive is at least one selected from vinylene carbonate, lithium difluorophosphate and vinyl sulfate.
9. The secondary battery according to claim 1 or 2, wherein the positive electrode includes a positive electrode active material including at least one of a lithium cobaltate-based material and a ternary positive electrode material; and/or
The anode includes an anode active material including at least one of a silicon-based material, a carbon-based material, and a lithium-based material; and/or
The isolating film comprises a base film and a coating layer arranged on the base film; and/or
The electrolyte also includes a nonaqueous solvent and a lithium salt.
10. The secondary battery according to claim 9, wherein the lithium cobaltate-based material includes Li 1-x A x CoO 2 Wherein, A is selected from one or more of aluminum, magnesium, titanium, tin, vanadium, copper, zinc, zirconium, chromium, manganese, iron, gallium, molybdenum, antimony, tungsten, yttrium and niobium, x is more than or equal to 0 and less than or equal to 0.05, and the ternary positive electrode material comprises nickel-cobalt ternary materials; and/or
The negative electrode active material includes at least one of graphite, soft carbon, hard carbon, carbon nanotubes, graphene, silicon alloy, silicon oxygen compound, silicon carbon compound, metallic lithium and lithium titanate; and/or
The base film comprises at least one of a polyethylene film, a polypropylene film, a PP/PE/PP composite film, a polyimide film, an aramid film, a polyethylene terephthalate film or a non-woven fabric, and the coating comprises at least one of a polymer layer, an inorganic substance layer or a mixed layer of a polymer and an inorganic substance; and/or
The nonaqueous solvent includes at least one of a chain carbonate, a cyclic carbonate, and a carboxylic acid ester, and the lithium salt includes at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bisoxalato borate, lithium bisfluorosulfonyl imide, and lithium bis (trifluoromethylsulfonyl) imide.
11. The secondary battery according to claim 10, wherein the nickel-cobalt-based ternary material includes LiNi m Co n B (1-m-n) O 2 At least one of the materials, B is selected from at least one of manganese, aluminum, magnesium, chromium, calcium, zirconium, molybdenum, silver or niobium, m is more than or equal to 0.5 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 0.5, and m+n is more than or equal to 1.
12. The secondary battery according to claim 9, wherein the positive electrode active material includes at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, and lithium nickel cobalt aluminum oxide.
13. An apparatus comprising the secondary battery according to any one of claims 1 to 12.
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