CN111653769B - Lithium ion battery with wide temperature range - Google Patents

Lithium ion battery with wide temperature range Download PDF

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CN111653769B
CN111653769B CN202010522337.4A CN202010522337A CN111653769B CN 111653769 B CN111653769 B CN 111653769B CN 202010522337 A CN202010522337 A CN 202010522337A CN 111653769 B CN111653769 B CN 111653769B
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ion battery
lithium
lithium ion
negative electrode
positive electrode
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CN111653769A (en
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路胜博
王炜贤
韩颖龙
徐祯祥
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Langsheng Technology Group Hong Kong 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The present invention relates to a wide temperature range lithium ion battery. The lithium ion battery with the wide temperature range comprises a positive plate, a negative plate, electrolyte and a diaphragm; the positive electrode active material in the positive electrode plate is high nickel layered lithium metal oxide, and the negative electrode active material in the negative electrode plate is graphite with a lamellar structure; the electrolyte comprises a chain ester solvent, a lithium salt and an additive, wherein the additive comprises vinylene carbonate, fluoroethylene carbonate and a styrene-6-caprolactone-trimethylene carbonate copolymer. The selection of battery materials (anode active materials, cathode active materials, electrolyte formula and the like) in the lithium ion battery with the wide temperature range ensures that the lithium ion battery with the wide temperature range obtained by the invention works in an extreme temperature environment (-40-85 ℃), and still has excellent multiplying power performance and cycle performance; the lithium ion battery with the wide temperature range can realize high-current discharge at extreme temperature.

Description

Lithium ion battery with wide temperature range
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery with a wide temperature range, in particular to a battery capable of being used at an extreme temperature of-40-85 ℃.
Background
The lithium ion battery has the outstanding advantages of high energy density, low self-discharge, no memory effect and the like, becomes a main solution of mobile energy, and is widely applied to a plurality of fields of mobile phones, flat plates, electric automobiles, household energy storage and the like. The use environment of the lithium ion battery is relatively complex, so that higher requirements are put on the performance of the lithium ion battery.
At present, research on lithium ion batteries mainly focuses on the aspects of charge and discharge speed, capacity, battery life and the like, but is limited by the flow of lithium ions and the properties of battery materials, and the performance of the lithium ion batteries generally falls significantly under the environment of extreme temperature.
The low-temperature performance of the lithium ion battery in the prior art is relatively poor, the popularization and the use of the lithium ion battery in the field of electric automobiles are restricted, the viscosity of the electrolyte in the lithium ion battery is increased after the temperature is reduced (< 0 ℃), the mobility of the lithium ion battery is poor, the conductivity of the lithium ion battery is rapidly reduced, the polarization in the battery is aggravated, lithium crystal branches are precipitated at a low potential of a negative electrode, the safety risk is high, and general battery manufacturers strictly limit low-temperature charging. As polarization increases, the discharge characteristics of the lithium ion battery also deteriorate sharply, and discharge mileage becomes significantly shorter.
The existing lithium ion battery cannot be placed for a long time in a high-temperature environment exceeding 80 ℃ because of being influenced by electrolyte, and once the placement time is too long, the electrolyte is decomposed in the high-temperature environment, so that the battery cannot be used finally. At present, the high temperature resistant mode of the lithium ion battery is realized by changing the internal structure of the battery, so that the battery can bear a high temperature environment, but the lithium ion battery is greatly reduced in performance due to the change of the structure, and the service life of the battery is seriously influenced.
CN107946671a discloses a battery, battery control system and method suitable for extreme temperature conditions. The battery includes: a battery and a battery holder for fixing the battery; the battery management system is arranged on the outer ring of the battery frame in a surrounding mode; the battery rack and the battery management system can transmit electric energy and signals, and the electric energy and signals of the battery and the battery management system are transmitted through the battery rack. However, the method cannot fundamentally improve the high and low temperature resistance of the battery.
CN107482253a discloses a low temperature lithium ion battery. The battery comprises a positive plate, a negative plate, a separation film and electrolyte; the positive active material of the positive plate is ternary material doped lithium manganate, and the surface of the ternary material is coated with a fast ion conductor; the negative electrode active material of the negative electrode plate is graphite or amorphous carbon coated graphite; the electrolyte includes a lithium salt, a solvent, and an additive. However, the battery has only low temperature resistance and cannot be used in a high temperature environment.
Therefore, there is a need in the art to develop a new lithium ion battery that can simultaneously have excellent low temperature and high temperature resistance, making it usable at extreme temperatures.
Disclosure of Invention
The lithium ion battery aims at solving the problems that the lithium ion battery in the prior art cannot simultaneously have excellent low temperature resistance and high temperature resistance and has poor electrochemical performance in an extreme temperature environment. The invention aims to provide a wide temperature range lithium ion battery which has excellent charge and discharge capability under an extreme temperature environment. The invention relates to a lithium ion battery with a wide temperature range, which is a lithium ion battery with a use temperature ranging from minus 40 ℃ to 85 ℃.
In order to achieve the above purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a wide temperature range lithium ion battery including a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator; the positive electrode active material in the positive electrode plate is high nickel layered lithium metal oxide, and the negative electrode active material in the negative electrode plate is graphite with a lamellar structure; the electrolyte comprises a chain ester solvent, a lithium salt and an additive, wherein the additive comprises vinylene carbonate, fluoroethylene carbonate and a styrene-6-caprolactone-trimethylene carbonate copolymer.
The positive electrode active material of the invention selects high nickel layered lithium metal oxide, which can reduce the internal resistance of the positive electrode side of the battery and is easy for the diffusion of lithium ions; the invention selects the graphite with the lamellar structure with larger interlayer spacing as the negative electrode active material, which is beneficial to the diffusion effect of lithium ions.
The additive of the invention must contain ethylene carbonate (VC), fluoroethylene carbonate and styrene-6-caprolactone-trimethylene carbonate copolymer, fluoroethylene carbonate (FEC) and styrene-6-caprolactone-trimethylene carbonate copolymer (SCT) can be compounded with lithium salt to form polymer-based solid electrolyte which has higher ionic conductivity at the temperature higher than room temperature, and can form solid electrolyte interface layer at the high temperature on the surface of the cathode; interaction occurs between Vinylene Carbonate (VC) and graphite which is the negative electrode material of the application, so that an SEI film formed on the surface of the electrode material is more complete. The three additives of the application act together in the electrochemical reaction process, so that a solid electrolyte interface which can keep stability at high temperature is formed in the charge and discharge process of the battery, and any one of the three additives is lacked, so that the technical effect of the invention can not be achieved.
The formula (solvent, lithium salt and additive) of the electrolyte has higher tolerance to the extreme temperature, and can effectively avoid solidification or gasification of the electrolyte.
The selection of the formulas of the anode active material, the cathode active material and the electrolyte in the lithium ion battery with the wide temperature range enables the lithium ion battery with the wide temperature range to work in an extreme temperature environment (-40-85 ℃), and still has excellent charge and discharge capacity (excellent multiplying power performance and cycle performance).
Preferably, the content of the chain ester solvent in the electrolyte is 70 to 80wt%, for example 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 78.5wt% or 79wt%, etc.
The content of the chain ester solvent in the electrolyte is 70-80 wt%, the content is too high, the high-temperature performance can be deteriorated, and the dielectric performance of the electrolyte is deteriorated and the electric leakage is increased; when the content is too low, the viscosity of the electrolyte at low temperature becomes high, and the ionic conductivity deteriorates, resulting in deterioration of the rate performance.
Preferably, the concentration of lithium salt in the electrolyte is 0.5 to 1.5mol/L (e.g., 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, or 1.4mol/L, etc.), preferably 15 to 20wt%, e.g., 15.5wt%, 16wt%, 16.5wt%, 17wt%, 17.5wt%, 18wt%, 18.5wt%, 19wt%, or 19.5wt%, etc.
Preferably, the content of Vinylene Carbonate (VC) in the electrolyte is 0.5-2 wt%, e.g. 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, etc.
In the electrolyte, the content of vinylene carbonate is 0.5-2 wt%, the content is too high, and the multiplying power performance is deteriorated; the content is too low, and the stable solid electrolyte interface layer cannot be formed continuously, which results in deterioration of the circularity.
Preferably, the content of fluoroethylene carbonate (FEC) in the electrolyte is 1 to 2wt%, for example, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.55wt%, 1.6wt%, 1.7wt%, 1.8wt% or 1.9wt%, etc.
In the electrolyte, the content of fluoroethylene carbonate is 1-2wt%, and the electrolyte wettability is deteriorated to cause the deterioration of rate performance, wherein the content is too high; the content is too low and the high-temperature performance deteriorates.
Preferably, the content of styrene-6-caprolactone-trimethylene carbonate copolymer (SCT) in the electrolyte is 0.5 to 2wt%, e.g., 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, or the like.
In the electrolyte, the content of the styrene-6-caprolactone-trimethylene carbonate copolymer is 0.5-2 wt%, and the ion conductivity is deteriorated due to the excessively high content; the content is too low and the high-temperature performance deteriorates.
Preferably, the chain ester solvent is a non-fluorinated chain ester solvent, preferably comprising any one or a combination of at least two of methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and butyl butyrate.
The electrolyte solvent in the invention can ensure that the obtained lithium ion battery with a wide temperature range has better high-low temperature performance, in particular to ethyl propionate, has a lower melting point (lower than-40 ℃) and a higher boiling point (higher than 85 ℃), and is more suitable for a lithium ion battery system of the invention.
Preferably, the lithium salt is any one or a combination of at least two of lithium hexafluorophosphate, lithium difluorosulfonimide salt and lithium difluorooxalato borate.
Preferably, the crystal orientation of the graphite with lamellar structure is the preferred orientation of the (002) crystal face.
According to the invention, the preferred orientation of the crystal orientation of the graphite with the lamellar structure is (002) crystal face, so that a more excellent technical effect can be achieved, the highly preferred orientation graphite has smaller defects, and the electronic conductivity can be improved, so that the internal resistance of the battery is reduced, and the multiplying power performance of the battery is improved.
Preferably, the particle diameter D50 of the platelet-structured graphite is 5 to 30. Mu.m, for example 6. Mu.m, 8. Mu.m, 10. Mu.m, 12. Mu.m, 14. Mu.m, 15. Mu.m, 16. Mu.m, 18. Mu.m, 20. Mu.m, 22. Mu.m, 24. Mu.m, 25. Mu.m, 26. Mu.m, 28. Mu.m, etc.
Preferably, the lamellar structure graphite has a layer spacing of 0.3342 to 0.3364nm.
The lattice constant of the graphite with the like structure is 0.2922-0.2932 nm, the c/a value is 2.2797-2.302, and the D/G ratio in the Raman spectrum is 0.2-0.8.
Preferably, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
Preferably, the negative electrode current collector is a copper foil.
Preferably, the anode active material layer includes an anode active material, an anode conductive agent, and an anode binder.
Preferably, the negative electrode conductive agent includes Super P and KS6.
Preferably, the negative electrode binder includes polyvinylidene fluoride.
Preferably, in the negative electrode active material layer, the mass ratio of the graphite sheet structure, super P, KS6 and polyvinylidene fluoride is (70-90%) (5-10%) (1-5%) (5-15%), for example, 70%:10%:5%:15%, 75%:8%:2%:15%, 75%:10%:5%:10%, 80%:7%:3%:10%, 80%:5%: 10%, 85%:5%:5% or 85%:8%:2%:5%, etc.
Preferably, the high nickel layerIn the lithium metal oxide, the chemical formula of the high nickel layered lithium metal oxide is LiNi x Co y A z O 2 The x is more than or equal to 0.8<1，0<y<0.2，0<z<0.2, A is selected from Mn and/or Al.
The value of x is, for example, 0.85, 0.86, 0.88, 0.9, 0.92, 0.94, 0.95, 0.96 or 0.98; the value of y is, for example, 0.01, 0.03, 0.05, 0.08, 0.1, 0.12, 0.15, 0.16, 0.18, or the like; the value of z is, for example, 0.01, 0.03, 0.05, 0.08, 0.1, 0.12, 0.15, 0.16, 0.18, or the like.
The lattice constant of the high nickel layered lithium metal oxide is 0.2863 to 0.2869nm, the c/a value is 4.909 to 4.957, and I (003)/(104) The proportion is 1.09-1.39, and the oxide is a layered oxide with a rhombohedral structure.
The larger the lattice constant of the high-nickel layered lithium metal oxide is, the easier the lithium ions are diffused, the more complete the structure is, and the higher the stability is.
Preferably, the high nickel layered lithium metal oxide has a particle size D50 of 10 to 30 μm, for example 12 μm, 14 μm, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm or 29 μm, etc.
The particle size selection of the high-nickel layered lithium metal oxide and the flake structure graphite can achieve the optimal technical effect within the range of the invention, and the effect is poor when the particle size is too large or too small.
Preferably, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
Preferably, the positive electrode current collector is an aluminum foil.
Preferably, the positive electrode active material layer includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
Preferably, the positive electrode conductive agent includes Super P and KS6.
Preferably, the positive electrode binder comprises polyvinylidene fluoride.
Preferably, in the positive electrode active material layer, the mass ratio of the high nickel layered lithium metal oxide, super P, KS6 and polyvinylidene fluoride is (80-90%) (1-5%) (5-10%), for example, 80%:5%: 10%, 82%:3%:5%:10%, 85%:2%:5%:8%, 85%:3%:5%:7%, 86%:3%:5%:6%, 88%:2%:5% or 90%:3%: 5%, or 2%:5%, etc.
Preferably, the single-sided surface density of the negative electrode sheet is 5-10 mg/cm 2 For example 5.5mg/cm 2 、6mg/cm 2 、6.5mg/cm 2 、7mg/cm 2 、7.5mg/cm 2 、8mg/cm 2 、8.5mg/cm 2 、9mg/cm 2 Or 9.5mg/cm 2 Etc.
Preferably, the single-sided surface density of the positive plate is 8-12 mg/cm 2 For example 8.2mg/cm 2 、8.5mg/cm 2 、8.8mg/cm 2 、9mg/cm 2 、9.5mg/cm 2 、9.8mg/cm 2 、10mg/cm 2 、10.5mg/cm 2 、10.8mg/cm 2 、11mg/cm 2 Or 11.5mg/cm 2 Etc.
Preferably, the compression ratio of the negative electrode sheet is 0.6 to 0.9, for example, 0.62, 0.65, 0.68, 0.7, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, or 0.88, etc.
Preferably, the positive electrode sheet has a compression ratio of 0.7 to 0.9, for example, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88, or the like.
The compression ratio of the invention is as follows: the ratio of the volume of the pole piece after rolling to the volume before rolling.
Preferably, the separator comprises polyethylene and polypropylene.
Preferably, the separator further comprises a ceramic coating.
Preferably, the thickness of the separator is 15 to 35 μm, for example 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 28 μm, 30 μm, 32 μm, 33 μm or 34 μm, etc.
Preferably, the lithium ion battery with the wide temperature range is subjected to 100% charge-discharge cycle at the temperature of-20 ℃ under the current of 0.1-3 ℃, and the cycle number of the capacity retention rate of more than or equal to 80% is more than or equal to 500 weeks.
Preferably, the lithium ion battery with the wide temperature range is subjected to 100% charge-discharge cycle at room temperature under the current of 0.1-3C, and the cycle number of the capacity retention rate is more than or equal to 90% is more than or equal to 1000 weeks.
Another object of the present invention is to provide a lithium ion battery used in a temperature range of-40 to 85 ℃, wherein the lithium ion battery has a wide temperature range.
Preferably, the lithium ion battery uses a current of 0.1 to 4C (e.g., 1C, 2C, 3C, or 4C, etc.), preferably 1 to 4C, at a temperature ranging from-20 to-40 ℃ (e.g., 22 ℃, -25 ℃, -26 ℃, -28 ℃, -30 ℃, -32 ℃, -35 ℃ or-38 ℃ etc.), and 60 to 85 ℃ (e.g., 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃ or the like).
The lithium ion battery with wide temperature range can realize high-current discharge at extreme temperature.
Compared with the prior art, the invention has the following beneficial effects:
the selection of battery materials (anode active materials, cathode active materials, electrolyte formula and the like) in the lithium ion battery with a wide temperature range ensures that the lithium ion battery with the wide temperature range obtained by the invention works in an extreme temperature environment (-40-85 ℃), and still has excellent multiplying power performance and cycle performance; the lithium ion battery with wide temperature range can realize high-current discharge at extreme temperature.
Drawings
FIG. 1 is an XRD pattern of graphite provided in embodiments 1 and 2 of the present invention;
FIG. 2 is a Raman spectrum of graphite provided in specific examples 1 and 2 of the present invention;
FIG. 3 is an XRD pattern of high nickel layered lithium metal oxide in specific example 1 of the present invention and NCM523 in comparative example 1;
FIG. 4 is an SEM image of a high nickel layered lithium metal oxide provided in example 1 of the invention;
FIG. 5 is an SEM image of graphite according to example 1 of the present invention;
FIG. 6 is a graph showing the low temperature long cycle performance test of a wide temperature range lithium ion battery according to example 1 of the present invention;
FIG. 7 is a graph showing the long cycle performance of a wide temperature range lithium ion battery according to example 1 of the present invention;
FIG. 8 is a graph showing the low-temperature high-current discharge performance of a lithium ion battery with a wide temperature range according to embodiment 1 of the present invention;
fig. 9 is a graph for testing high-temperature high-current discharge performance of a lithium ion battery with a wide temperature range according to embodiment 1 of the present invention;
FIG. 10 is a graph showing the long cycle performance of lithium ion batteries with a wide temperature range according to specific examples 1 and 3 of the present invention;
fig. 11 is a 10s pulse discharge diagram of a wide temperature range lithium ion battery provided in specific examples 1 and 3 of the present invention at different temperatures.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
Lithium ion battery with wide temperature range:
the lithium ion battery of this example in a wide temperature range includes a positive electrode sheet (single-sided area density of 10mg/cm 2 Compression ratio of 0.8), negative electrode sheet (single-sided surface density of 8mg/cm 2 Compression ratio of 0.7), electrolyte and separator (thickness 25 μm, polyethylene and polypropylene composition);
the negative electrode sheet in this embodiment is: the negative electrode active material layer is attached to the copper foil, and the mass ratio of the graphite with the lamellar structure, the Super P, the KS6 and the polyvinylidene fluoride in the negative electrode active material layer is 85 percent to 5 percent to 2 percent to 8 percent; the crystal plane of the graphite (graphite for short in figures and tables) with the lamellar structure is (002) crystal plane, fig. 1 is the XRD patterns of the graphite of this example and the graphite of example 2, and the XRD parameters are shown in table 1:
TABLE 1
Figure BDA0002532537290000101
FIG. 2 is a Raman spectrum diagram of the graphite of the present example and the graphite of example 2, wherein the Raman spectrum peak intensities and the D/G ratios of the graphite are shown in Table 2:
TABLE 2
Figure BDA0002532537290000102
Fig. 5 is an SEM image of the graphite of this example, which shows that the graphite has a lamellar structure and a high uniformity of particle size, and D50 is 15 μm.
The positive plate in this embodiment is: the positive electrode active material layer, in which the mass ratio of high nickel layered lithium metal oxide (NCM 811), super P, KS6, and polyvinylidene fluoride was 90%:2%:3%:5%, was attached to an aluminum foil, and fig. 3 is the XRD pattern of the high nickel layered lithium metal oxide of the present example and NCM523 in comparative example 1, with XRD parameters shown in table 3:
TABLE 3 Table 3
Figure BDA0002532537290000111
Fig. 4 is an SEM image of the high nickel layered lithium metal oxide of the present example, which shows that the high nickel layered lithium metal oxide has a high uniformity of particle size and a D50 of 20 μm.
The composition of the electrolyte described in this example is shown in table 4:
TABLE 4 Table 4
Figure BDA0002532537290000112
Figure BDA0002532537290000121
The weight ratio of the lithium salt and the additive is the total mass ratio of the electrolyte and the volume ratio is the total volume ratio of the solvent, as described in table 4. The SCT27 manufacturer adopted in the embodiment is New Saint.
Fig. 6 is a chart for testing the low-temperature long-cycle performance of the lithium ion battery with a wide temperature range, which is obtained in this embodiment, and the testing method is as follows: at the temperature of 20 ℃ below zero, 1C and 2C currents are used as a low-temperature cycle test result graph, and as can be seen from the graph, the battery obtained by the embodiment has excellent low-temperature long-cycle performance;
fig. 7 is a graph for testing the long cycle performance of the lithium ion battery with a wide temperature range, which is obtained in this example, and the testing method is as follows: 1000 cycles at room temperature with 0.5C and 1C currents, it can be seen that at 0.5C and 1C current densities, 1000 cycles capacity retention exceeds 90% and 80%, respectively;
fig. 8 is a chart for testing the low-temperature high-current discharge performance of the lithium ion battery with a wide temperature range, which is obtained in this embodiment, and the testing method is as follows: the low-temperature performance of the lithium ion battery with the wide temperature range obtained in the embodiment is excellent as can be seen from the graph by taking the discharge performance of the attached room temperature as a reference when the low-temperature discharge is carried out from 4V to 2V at-20 ℃, 30 ℃ and 40 ℃ respectively;
fig. 9 is a graph of high-temperature high-current discharge performance test of a lithium ion battery with a wide temperature range, which is obtained in this embodiment, and the test method is as follows: the high temperature performance of the lithium ion battery with a wide temperature range obtained in the embodiment is excellent as can be seen from the figure by taking the discharge performance of the attached chamber temperature as a reference at 85 ℃ and with the discharge of 2C and 4C from 4V high temperature.
Example 2
The difference from example 1 is that the graphite of example 1 is replaced by the graphite of the parameters in table 1 (i.e. is a commercially available graphite) in equal amounts.
The battery obtained in this example has poorer performance than that of example 1, and because the graphite adopted in this example has more internal defects, lithium ion transmission and conductivity are deteriorated, thereby affecting the rate performance of the battery at high and low temperatures.
Example 3
Lithium ion battery with wide temperature range:
the lithium ion battery of this example in a wide temperature range includes a positive electrode sheet (single-sided area density 9mg/cm 2 Compression ratio of 0.7) Negative plate (Single-side surface density of 6 mg/cm) 2 Compression ratio of 0.8), electrolyte and separator (thickness of 35 μm, polyethylene and polypropylene composition);
the negative electrode sheet in this embodiment is: a negative electrode active material layer is attached to the copper foil, wherein the mass ratio of graphite with a lamellar structure (particle diameter D50 is 10 mu m), super P, KS6 and polyvinylidene fluoride in the negative electrode active material layer is 80 percent to 7 percent to 3 percent to 10 percent; the crystal face of the graphite with the lamellar structure is a (002) crystal face;
the positive plate in this embodiment is: a positive electrode active material layer in which a high nickel layered lithium metal oxide (NCA: liNi) is attached to an aluminum foil 0.8 Co 0.15 Al 0.05 O 2 The mass ratio of the particle diameter D50 to the Super P, KS6 and the polyvinylidene fluoride is 93 percent to 2 percent to 3 percent, wherein the particle diameter D50 is 15 mu m);
the electrolyte comprises a chain ester solvent, lithium salt and an additive; the mixed solution is composed of methyl propionate, ethyl propionate, methyl butyrate and ethyl butyrate, and the volume ratio is 1:1:1:1; the concentration of the lithium salt is 1mol/L; the content of vinylene carbonate in the electrolyte is 1wt%, the content of fluoroethylene carbonate is 1.5wt%, and the content of styrene-6-caprolactone-trimethylene carbonate copolymer is 1.6wt%.
The batteries obtained in this example and example 1 were subjected to long-cycle performance test at room temperature with a test current of 500mA, and the test results are shown in fig. 10, which shows that both the batteries obtained in this example and example 1 have excellent long-cycle performance;
the batteries obtained in this example and example 1 were subjected to 10s pulse discharge at different temperatures, and the discharge currents at different temperatures were 1.5A, and the test results are shown in fig. 11, which shows that the batteries obtained in this example and example 1 can be used at extreme temperatures.
Comparative example 1
The difference from example 1 is that the high nickel layered lithium metal oxide of example 1 was replaced with an equivalent amount of NCM523 in table 3.
The battery obtained in this comparative example has poor performance compared to example 1 because the low-nickel ternary alloy has poor conductivity at low temperature and poor rate capability by using NCM 523.
Comparative example 2
The difference from example 1 is that SCT27 in the electrolyte is replaced by an equal amount of VC.
The battery obtained in this comparative example had inferior performance to that of example 1, because the electrolyte of this comparative example does not contain SCT27, and the ionic conductivity of the electrolyte is low, and thus the cycle and rate performance are inferior.
Comparative example 3
The difference from example 1 is that VC in the electrolyte is replaced with an equal amount of FEC.
The battery obtained in this comparative example has poor performance compared to example 1, because the electrolyte of this comparative example does not contain VC, and the battery has poor film forming effect during the electrochemical reaction, and thus has poor high-temperature performance.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (33)

1. The lithium ion battery used in the temperature range of minus 40 ℃ to 85 ℃ is characterized by comprising a positive plate, a negative plate, electrolyte and a diaphragm;
the positive electrode active material in the positive electrode plate is high nickel layered lithium metal oxide, and the negative electrode active material in the negative electrode plate is graphite with a lamellar structure;
the electrolyte comprises a chain ester solvent, lithium salt and an additive, wherein the additive comprises vinylene carbonate, fluoroethylene carbonate and a styrene-6-caprolactone-trimethylene carbonate copolymer;
in the electrolyte, the content of vinylene carbonate is 0.5-2wt%, the content of fluoroethylene carbonate is 1-2wt%, the content of styrene-6-caprolactone-trimethylene carbonate copolymer is 0.5-2wt%, and the content of chain ester solvent is 70-80wt%.
2. The lithium ion battery of claim 1, wherein the concentration of lithium salt in the electrolyte is 0.5 to 1.5mol/L.
3. The lithium ion battery of claim 1 or 2, wherein the chain ester solvent is a non-fluorinated chain ester solvent.
4. The lithium ion battery of claim 3, wherein the chain ester solvent is any one or a combination of at least two of methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate.
5. The lithium ion battery of claim 1 or 2, wherein the lithium salt is any one or a combination of at least two of lithium hexafluorophosphate, lithium difluorosulfonimide salt and lithium difluorooxalato borate.
6. The lithium-ion battery of claim 1, wherein the crystalline orientation of the platelet-structured graphite is a preferred orientation of the (002) crystal plane.
7. The lithium ion battery of claim 1 or 2, wherein the particle size D50 of the graphite sheet structure is 5-30 μm.
8. The lithium ion battery of claim 1 or 2, wherein the lamellar structured graphite has an interlayer spacing of 0.3342 to 0.3364nm.
9. The lithium-ion battery of claim 1, wherein the negative electrode tab comprises a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
10. The lithium-ion battery of claim 9, wherein the negative current collector is copper foil.
11. The lithium-ion battery of claim 9, wherein the negative electrode active material layer comprises a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
12. The lithium-ion battery of claim 11, wherein the negative electrode conductive agent comprises Super P and KS6.
13. The lithium-ion battery of claim 11, wherein the negative electrode binder comprises polyvinylidene fluoride.
14. The lithium ion battery according to claim 13, wherein the mass ratio of graphite with a lamellar structure, super P, KS6 and polyvinylidene fluoride in the negative electrode active material layer is (70-90%) (5-10%) (1-5%) (5-15%).
15. The lithium ion battery of claim 1, wherein the high nickel layered lithium metal oxide has a chemical formula LiNi x Co y A z O 2 Wherein x is 0.8.ltoreq.x<1，0<y<0.2，0<z<0.2, A is selected from Mn and/or Al.
16. The lithium ion battery of claim 15, wherein the high nickel layered lithium metal oxide has a particle size D50 of 10 to 30 μm.
17. The lithium-ion battery of claim 1, wherein the positive electrode tab comprises a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
18. The lithium-ion battery of claim 17, wherein the positive current collector is aluminum foil.
19. The lithium-ion battery of claim 17, wherein the positive electrode active material layer comprises a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder.
20. The lithium-ion battery of claim 19, wherein the positive electrode conductive agent comprises Super P and KS6.
21. The lithium-ion battery of claim 19, wherein the positive electrode binder comprises polyvinylidene fluoride.
22. The lithium ion battery of claim 21, wherein the mass ratio of the high nickel layered lithium metal oxide, super P, KS6 and polyvinylidene fluoride in the positive electrode active material layer is (80-90%) (1-5%) (5-10%).
23. The lithium ion battery of claim 1, wherein the single-sided area density of the negative plate is 5-10 mg/cm 2 。
24. The lithium ion battery of claim 23, wherein the positive plate has a single-sided area density of 8-12 mg/cm 2 。
25. The lithium ion battery of claim 1, wherein the compression ratio of the negative electrode sheet is 0.6-0.9.
26. The lithium ion battery of claim 1, wherein the positive plate has a compression ratio of 0.7 to 0.9.
27. The lithium-ion battery of claim 1, wherein the separator comprises polyethylene and polypropylene.
28. The lithium-ion battery of claim 27, wherein the separator further comprises a ceramic coating.
29. The lithium ion battery of claim 1, wherein the separator has a thickness of 15-35 μm.
30. The lithium ion battery according to claim 1, wherein the lithium ion battery is subjected to 100% charge-discharge cycle at a temperature of-20 ℃ under a current of 0.1-3 c, and the cycle number of the capacity retention rate is not less than 80% is not less than 500 weeks.
31. The lithium ion battery according to claim 1, wherein the lithium ion battery is subjected to 100% charge-discharge cycle at room temperature at a current of 0.1-3 c, and the cycle number of the capacity retention rate is not less than 90% is not less than 1000 weeks.
32. The lithium ion battery of claim 1, wherein the lithium ion battery uses a current of 0.1-4 c in a temperature range of-20 to-40 ℃ and 60-85 ℃.
33. The lithium-ion battery of claim 32, wherein the lithium-ion battery uses a current of 1-4 c in a temperature range of-20 to-40 ℃ and 60-85 ℃.
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