CN109546222B - Aluminum cathode energy storage device electrolyte, aluminum cathode energy storage device and preparation method thereof - Google Patents

Aluminum cathode energy storage device electrolyte, aluminum cathode energy storage device and preparation method thereof Download PDF

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CN109546222B
CN109546222B CN201811432684.7A CN201811432684A CN109546222B CN 109546222 B CN109546222 B CN 109546222B CN 201811432684 A CN201811432684 A CN 201811432684A CN 109546222 B CN109546222 B CN 109546222B
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electrolyte
energy storage
storage device
carbonate
organic solvent
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CN109546222A (en
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唐永炳
徐子俊
谢呈德
祝佳丽
张凡
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Sichuan Zhongke Ruineng Industrial Co ltd
Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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
    • 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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Abstract

The invention discloses an aluminum cathode energy storage device electrolyte, an aluminum cathode energy storage device and a preparation method thereof, and relates to the technical field of electrochemical energy storage devices. The electrolyte of the aluminum cathode energy storage device comprises lithium salt and an organic solvent, wherein the organic solvent comprises 10-20 vol% of a cyclic ester solvent and 80-90 vol% of a linear ester solvent. The invention relieves the influence of the existing electrolytic liquid system on the capacity exertion of the battery and the poor cycle performance of the battery in an Al cathode system, and relieves the poor low-temperature performance of the system with good normal-temperature cycle. The low-temperature electrolyte provided by the invention has good matching property with an Al cathode system, can keep low viscosity at low temperature, enables the system to have higher conductivity, has lower solid-liquid interface impedance, enables lithium ions to be effectively removed, and can remarkably improve the low-temperature charge and discharge performance of an Al cathode lithium ion energy storage device.

Description

Aluminum cathode energy storage device electrolyte, aluminum cathode energy storage device and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage devices, in particular to an aluminum cathode energy storage device electrolyte, an aluminum cathode energy storage device and a preparation method thereof.
Background
Since commercialization, lithium ion batteries with outstanding advantages in high energy density, small self-discharge, high output voltage, and long cycle life rapidly occupy almost all markets in the field of consumer electronics represented by mobile phones, notebook computers, and the like, and their applications in electric bicycles, power cars, and the like have been increasing geometrically in recent years. However, as the application and demand are increasing, the disadvantage of the lithium ion battery in low temperature performance is more and more prominent. The discharge capacity of minus 30 ℃ and below only accounts for 50-60% of the discharge capacity of 25 ℃, even lower, and the use of the electric automobile in winter in north is severely restricted.
In the prior art, patent CN107171023A discloses a low-temperature electrolyte for a lithium ion battery, wherein a solvent is composed of ethylene carbonate, dimethyl carbonate, fluorinated propylene carbonate and chlorinated propylene carbonate, the volume ratio of the four materials is (45-49): 45-49: (1-5): 1-7), and a solute is LiPF6And LiBF4The mixed lithium salt of (1). Two halogen substituted Propylene Carbonate (PC) materials are used as electrolyte solvents, so that the intercalation effect of the PC is solved; the melting point of the electrolyte is reduced, and the stability of the electrolyte is improved, wherein the capacity retention rates at-20 ℃ and-30 ℃ are 84.5% and 74.2% respectively.
However, the existing low-temperature technology is applied to develop a mature graphite cathode system, the matching degree with an Al cathode system is not high, the existing electrolytic liquid system influences the capacity exertion of the battery and the cycle performance of the battery in the Al cathode system and the system with good normal-temperature cycle has poor low-temperature performance, especially the discharge capacity at minus 30 ℃.
It is therefore desirable to provide a low temperature electrolyte solution matched to an Al anode system that can address at least one of the above problems.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
It is an object of the present invention to provide an electrolyte for an aluminum negative electrode energy storage device that alleviates at least one of the above-mentioned problems.
The invention also aims to provide a preparation method of the electrolyte of the aluminum cathode energy storage device, which is simple.
The invention also aims to provide an aluminum cathode energy storage device, which comprises the electrolyte of the aluminum cathode energy storage device or the electrolyte prepared by the preparation method of the electrolyte of the aluminum cathode energy storage device, and has the same advantages as the electrolyte of the aluminum cathode energy storage device.
The fourth purpose of the invention is to provide the preparation method of the aluminum cathode energy storage device, which has simple production process and low cost.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides an electrolyte for an aluminum negative electrode energy storage device, which comprises a lithium salt and an organic solvent, wherein the organic solvent comprises 10-20 vol% of a cyclic ester solvent and 80-90 vol% of a linear ester solvent.
Preferably, on the basis of the technical scheme of the invention, the organic solvent comprises 15-20 vol% of cyclic ester solvent and 80-85 vol% of linear ester solvent;
preferably, the organic solvent comprises 20vol% of a cyclic ester solvent and 80 vol% of a linear ester solvent.
Preferably, on the basis of the technical scheme of the invention, the molar concentration of the lithium salt in the organic solvent is 0.1-10mol/L, and preferably 1-2 mol/L;
preferably, the lithium salt comprises LiCoO2、LiBF4、LiPF6、LiTFSI、LiNO3、Li2CO3、LiCl、LiCF3SO3、LiPF3(C2F5)3、LiPF4(C2O4)、LiN(CF3SO2)2、LiFSI、LiFAP、LiClO4LiBOB, LiDFOB, LTBP or LiAsF6Preferably LiPF6。
Preferably, on the basis of the technical scheme of the invention, the electrolyte further comprises an additive, and the additive is added in an amount of 0.01-20 wt%, preferably 5-20 wt%, and further preferably 5-10 wt% of the total amount of the lithium salt and the organic solvent;
preferably, the additive comprises fluoroethylene carbonate and/or vinylene carbonate.
Preferably, on the basis of the technical scheme of the invention, the cyclic ester solvent comprises cyclic carbonates and/or cyclic carboxylic esters, and preferably comprises ethylene carbonate and/or propylene carbonate.
Preferably, on the basis of the technical scheme of the present invention, the linear ester solvent comprises linear carbonates and/or linear carboxylic esters, and preferably comprises one or at least two of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, butyl acetate, methyl propionate and ethyl propionate.
In a second aspect, the invention provides a preparation method of the electrolyte of the aluminum cathode energy storage device, which comprises the following steps: and uniformly mixing the lithium salt, the organic solvent and the additive to obtain the electrolyte of the aluminum cathode energy storage device.
Preferably, on the basis of the technical scheme of the invention, the preparation method of the electrolyte of the aluminum cathode energy storage device comprises the following steps: mixing the cyclic ester solvent and the linear ester solvent according to a proportion, and then adding the additive to mix to obtain a solvent; and then adding a lithium type molecular sieve, drying, keeping the temperature at 0-15 ℃, and adding lithium salt to obtain the electrolyte of the aluminum cathode energy storage device.
In a third aspect, the invention provides an aluminum negative electrode energy storage device, which comprises the electrolyte of the aluminum negative electrode energy storage device or the electrolyte prepared by the preparation method of the electrolyte of the aluminum negative electrode energy storage device.
In a fourth aspect, the invention provides a preparation method of the aluminum cathode energy storage device, which comprises the following steps: and assembling the cathode, the diaphragm, the anode and the electrolyte of the aluminum cathode energy storage device to obtain the aluminum cathode energy storage device.
Compared with the prior art, the invention has the following beneficial effects:
(1) the organic solvent adopted by the electrolyte comprises 10-20 vol% of cyclic ester solvent and 80-90 vol% of linear ester solvent, the electrolyte has good matching property with an Al cathode energy storage device (such as an Al cathode lithium ion battery), can keep low viscosity at low temperature, enables a system to have higher conductivity, and simultaneously has lower solid-liquid interface impedance of the cathode-electrolyte, so that lithium ions can be effectively extracted, and the electrolyte can obviously improve the low-temperature charge and discharge performance of the Al cathode lithium ion energy storage device.
(2) The discharge capacity of the lithium ion battery prepared by the electrolyte is more than 72 percent of the discharge capacity at room temperature (25 ℃) when the temperature is reduced to-30 ℃.
(3) The aluminum cathode energy storage device comprises the electrolyte disclosed by the invention, has the same advantages as the electrolyte, and can obviously improve the discharge performance of the energy storage device at low temperature by using the electrolyte with low viscosity and low interface impedance.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the invention, an electrolyte for an aluminum negative electrode energy storage device is provided, which comprises a lithium salt and an organic solvent, wherein the organic solvent comprises 10-20 vol% of a cyclic ester solvent and 80-90 vol% of a linear ester solvent.
An aluminum negative electrode energy storage device refers to an energy storage device using aluminum as a negative electrode, wherein the aluminum serves as a negative active material and a negative current collector, and the aluminum includes, but is not limited to, pure aluminum, and may also be an aluminum alloy. Exemplary energy storage devices may include secondary batteries, hybrid ultracapacitors, and the like.
Exemplary aluminum negative electrode energy storage devices include, for example, aluminum foil negative electrode lithium ion batteries, aluminum foil-graphite dual ion batteries (with graphite as the positive electrode and aluminum foil as both the negative electrode and current collector), or aluminum foil negative electrode lithium ion hybrid capacitors, among others.
The cyclic ester solvent refers to a type of ester solvent having a ring structure in structure, and typically, but not limited to, includes cyclic carbonates and/or cyclic carboxylates, and exemplary cyclic ester solvents are, for example, Ethylene Carbonate (EC) or Propylene Carbonate (PC), and the like.
The linear ester solvent refers to a type of ester solvent that is structurally linear, and typically, but not limited to, for example, linear carbonates and/or linear carboxylates, and exemplary linear ester solvents are, for example, Dimethyl Carbonate (DMC), Diethyl Carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethyl Acetate (EA), Butyl acetate (n-Butyl acetate, BA), Methyl Propionate (MP), Ethyl Propionate (EP), or the like.
Based on the organic solvent, the solvent comprises 10-20 vol% of cyclic ester solvent and 80-90 vol% of linear ester solvent.
Exemplary cyclic ester solvents are, for example, 10%, 15%, or 20% by volume; exemplary linear ester solvents are, for example, 80%, 85%, or 90% by volume.
The kind of the lithium salt is not limited as long as it can be dissociated into lithium ions, and for example, a conventional lithium salt may be used. An exemplary lithium salt is, for example, LiCoO2、LiPF6LiTFSI (lithium bis (trifluoromethanesulfonylimide)), LiBF4、LiNO3、Li2CO3、LiCl、LiN(CF3SO2)2Lithium bis (trifluoromethylsulfonyl) imide), LiCF3SO3(lithium trifluoromethanesulfonate), LiPF3(C2F5)3(lithium perfluoroalkyl phosphate) LiPF4(C2O4) (lithium tetrafluoro oxalate phosphate), LiFAP, LiFSI, LiClO4LiBOB (lithium bis oxalato borate), LiDFOB, LTBP (lithium tris (catechol) phosphate) or LiAsF6And the like.
The discharge performance of the lithium ion energy storage device is reduced by more than half compared with the normal temperature in the aspect of low-temperature performance, particularly when the temperature reaches minus 30 ℃ or below, because under the condition of low temperature, on one hand, the viscosity of an electrolyte is rapidly increased, so that the conductivity of a system is reduced, the charge transfer impedance is increased, and the discharge performance of a battery is influenced; on the other hand, the impedance of the cathode-electrolyte interface is increased, so that lithium ions cannot be effectively extracted, and the discharge capacity is influenced.
The organic solvent of the electrolyte can keep low viscosity at low temperature by matching the cyclic ester solvent and the linear ester solvent with a certain volume percentage, so that the system has higher conductivity, and meanwhile, the cathode-electrolyte has lower solid-liquid interface impedance, so that lithium ions can be effectively removed. The electrolyte is a low-temperature electrolyte with low viscosity and low interface impedance, has good matching property with an energy storage device of an Al cathode system, and can obviously improve the discharge performance of the energy storage device at low temperature. The discharge capacity of the lithium ion battery prepared by the electrolyte is more than 72 percent of the discharge capacity at room temperature (25 ℃) when the temperature is reduced to-30 ℃.
In one embodiment, the organic solvent comprises 15 to 20vol% cyclic ester solvent and 80 to 85 vol% linear ester solvent.
In one embodiment, the organic solvent comprises 20vol% cyclic ester solvent and 80 vol% linear ester solvent.
The cyclic ester solvent and the linear ester solvent in volume percentage are used in a matched mode, so that the energy storage device has better discharge performance at low temperature.
In one embodiment, the molar concentration of the lithium salt in the organic solvent is from 0.1 to 10mol/L, preferably from 1 to 2 mol/L.
Exemplary concentrations of the lithium salt are, for example, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.7mol/L, 0.8mol/L, 1mol/L, 2mol/L, 5mol/L, or 10 mol/L.
The ion concentration affects the ion transmission performance of the electrolyte, the concentration of lithium salt in the electrolyte is too low, and Li+Too little, poor ion transport properties, low conductivity, too high concentration of lithium salt in the electrolyte, Li+Too much, the viscosity of the electrolyte and the degree of ionic association also increase with increasing lithium salt concentration, which in turn reduces conductivity.
In one embodiment, the electrolyte further comprises an additive, wherein the additive is added in an amount of 0.01 to 20 wt%, preferably 5 to 20 wt%, and more preferably 5 to 10 wt% of the total amount of the lithium salt and the organic solvent;
the kind of the additive is not limited, and may include, for example, conventional additives commonly used in the field of lithium ion batteries. Such as conventional film forming additives, overcharge protection additives, stabilizers, additives to improve high and low temperature performance, conductive additives or flame retardant additives, and the like.
Illustrative additives are, for example, fluoroethylene carbonate, ethylene carbonate, vinylene carbonate, 1, 4-butanesultone, 1, 3-propanesultone, vinyl sulfate, ethylene sulfate, propylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, anisole, dimethyl sulfoxide, diazabenzene, m-diazabenzene, acetamide, 4-fluorophenylmethyl ether, fluoro-chain ether, vinyl difluoromethylcarbonate, crown-12-crown-4, crown-18-crown-6, vinyl chlorocarbonate, vinyl trifluoromethylcarbonate, vinyl bromocarbonate, bromobutyrolactone, trifluoroethylphosphonic acid, fluoroacetoethane, phosphate, phosphite, phosphazene, ethanolamine, Cyclobutyl sulfone, carbonized dimethylamine, 1, 3-dioxolane, acetonitrile, long-chain olefins, sodium carbonate, lithium carbonate, calcium carbonate, sulfur dioxide or carbon dioxide, and the like.
The additive is added in an amount of, for example, 0.01%, 0.2%, 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% by mass based on the total amount of the lithium salt and the organic solvent.
By adding a certain content of additives, an SEI film with a certain thickness is formed, and the expansion of the aluminum cathode is relieved.
In one embodiment, the additive comprises fluoroethylene carbonate and/or vinylene carbonate.
According to a second aspect of the invention, a preparation method of the electrolyte of the aluminum negative electrode energy storage device is provided, which comprises the following steps:
and uniformly mixing the lithium salt, the organic solvent and the additive to obtain the electrolyte of the aluminum cathode energy storage device.
The preparation method of the electrolyte of the aluminum cathode energy storage device is simple and convenient to operate, and can be used for batch production.
In one embodiment, the preparation method of the electrolyte of the aluminum negative electrode energy storage device comprises the following steps:
mixing the cyclic ester solvent and the linear ester solvent according to a proportion, and then adding the additive to mix to obtain a solvent; and then adding a lithium type molecular sieve, drying, keeping the temperature at 0-15 ℃, and adding lithium salt to obtain the electrolyte of the aluminum cathode energy storage device.
The electrolyte is dried by a lithium type molecular sieve to remove moisture, and the stability of the electrolyte added with lithium salt at a lower temperature is good.
According to a third aspect of the invention, an aluminum negative electrode energy storage device is provided, which comprises the electrolyte of the aluminum negative electrode energy storage device or the electrolyte prepared by the preparation method of the electrolyte of the aluminum negative electrode energy storage device.
Exemplary aluminum negative electrode energy storage devices are, for example, aluminum negative electrode secondary batteries or aluminum negative electrode capacitors, and the like.
The aluminum cathode energy storage device has the same advantages as the electrolyte because the electrolyte of the aluminum cathode energy storage device is used, and the discharge performance of the energy storage device at low temperature can be obviously improved by using the electrolyte with low viscosity and low interface impedance.
An exemplary aluminum negative electrode secondary battery includes a negative electrode, a positive electrode, a separator interposed between the positive and negative electrodes, and the above electrolyte.
An exemplary negative electrode is aluminum foil.
The exemplary positive electrode includes a positive electrode current collector and a positive electrode material, the positive electrode material is not limited, and a positive electrode material or a bi-ion battery positive electrode material conventional in the lithium ion battery field can be used. The active material of the positive electrode material is a material capable of reversibly intercalating and deintercalating lithium ions or anions.
Exemplary materials capable of reversibly intercalating and deintercalating lithium ions are conventional positive electrode materials of lithium ion batteries, such as lithium iron phosphate, lithium cobaltate, lithium manganate, nickel cobalt manganese ternary materials, lithium-rich positive electrode materials, and the like.
An exemplary material capable of reversibly intercalating and deintercalating anions of an electrolyte is a positive electrode material of a bi-ion battery, for example, a graphite-based carbon material, a layered material such as a sulfide, a carbide, a nitride, or an oxide.
It is to be understood that the positive electrode current collector is not limited, and an exemplary positive electrode current collector is, for example, aluminum.
In one embodiment, the positive electrode material further comprises a conductive agent and a binder.
It is to be understood that the conductive agent and the binder are also not particularly limited, and those conventional in the art may be used.
Exemplary conductive agents are, for example, one or more of conductive graphite, conductive carbon black, carbon fibers, conductive carbon spheres, carbon nanotubes, or graphene.
Exemplary binders are, for example, one or more of carboxymethylcellulose, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, SBR rubber, or polyolefins (polyvinyl chloride, polybutadiene, polyisoprene, etc.).
The proportions of the active material, the conductive agent and the binder of the positive electrode material are not limited, and preferably, the positive electrode material includes 60 to 97 wt% of the active material of the positive electrode material, 1 to 30 wt% of the conductive agent and 2 to 10 wt% of the binder.
The description about the electrolytic solution is the same as that in the first aspect.
It is to be understood that the separator is also not particularly limited, and may be a separator that is conventional in the art.
The separator may be a porous polymer film or an inorganic porous film, and exemplary separators include one or more of a glass fiber, a porous polyethylene film, a porous polypropylene film, a porous composite polymer film, a porous ceramic separator, or a non-woven fabric, for example.
It is to be understood that the shape of the aluminum negative electrode secondary battery is not limited, and includes, but is not limited to, a square shape, a flat shape, a coin shape, a cylindrical shape, a button shape, a soft pack, a laminate shape, and the like. The size of the aluminum negative electrode secondary battery is not limited, and may be a small-sized battery or a large-sized battery for an electric vehicle or the like.
According to a fourth aspect of the invention, a preparation method of the aluminum cathode energy storage device is provided, which includes the following steps:
and assembling the anode, the cathode, the diaphragm and the electrolyte of the aluminum cathode energy storage device to obtain the aluminum cathode energy storage device.
It is to be understood that the assembly manner of the cathode, the anode, the separator and the electrolyte is not particularly limited, and may be performed by a conventional assembly manner.
The preparation method of the aluminum cathode secondary battery has simple process and low cost.
In one embodiment, a method of manufacturing an aluminum negative electrode secondary battery includes the steps of:
(a) preparing a positive electrode: mixing an active substance of a positive electrode material, a conductive agent, a binder and a solvent to prepare slurry; uniformly coating the slurry on the surface of the positive current collector, drying, and then cutting edges, pieces and strips to obtain a positive electrode with the required size;
(b) preparing a negative electrode: cutting edges, cutting pieces and slitting of the cathode aluminum foil to obtain a cathode with a required size;
(c) preparing an electrolyte: mixing the cyclic ester solvent and the linear ester solvent according to a proportion, and then adding the additive to mix to obtain a solvent; then adding a lithium type molecular sieve, drying, keeping the temperature at 0-15 ℃, and adding lithium salt to obtain an electrolyte;
(d) preparing a diaphragm: cutting the diaphragm into required size, cleaning and drying;
and assembling the positive electrode, the negative electrode, the electrolyte and the diaphragm to obtain the aluminum negative electrode secondary battery.
It should be understood that the order of steps or order of performing certain actions is immaterial so long as the method remains operable. In addition, two or more steps or actions may be performed simultaneously.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for purposes of illustration only and are not to be construed as limiting the invention in any way.
Example 1
A low temperature electrolyte comprising: lithium salt LiPF6The organic solvent comprises 10vol% of fluoroethylene carbonate (FEC) and 10voThe lithium ion battery comprises, by mass, 1% of Propylene Carbonate (PC), 40 vol% of diethyl carbonate (DEC) and 40 vol% of Ethyl Methyl Carbonate (EMC) (the reference is an organic solvent and is 100%), additives are Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), the molar concentration of a lithium salt in the organic solvent is 1mol/L, the mass percentage content of the fluoroethylene carbonate (FEC) in the lithium salt and the organic solvent is 5%, and the mass percentage content of the Vinylene Carbonate (VC) in the lithium salt and the organic solvent is 5%.
The preparation method of the low-temperature electrolyte comprises the following steps:
mixing FEC, PC, DEC and EMC in proportion, respectively and independently adding 5% (mass ratio of lithium salt to organic solvent) of FEC and VC as additives, mixing to obtain electrolyte solvent, adding 10% (mass ratio) of lithium type molecular sieve, drying for 24h, adding 1mol/L LiPF at 0-15 deg.C6And obtaining the low-temperature electrolyte.
Example 2
A low temperature electrolyte comprising: lithium salt LiPF6The organic solvent comprises 10vol% of Ethylene Carbonate (EC), 40 vol% of Ethyl Methyl Carbonate (EMC), 10vol% of dimethyl carbonate (DMC), 10vol% of diethyl carbonate (DEC) and 30vol% of Ethyl Propionate (EP) (the reference is organic solvent and is 100%), the additive comprises Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), the molar concentration of lithium salt in the organic solvent is 1mol/L, the mass percentage content of the fluoroethylene carbonate (FEC) in the lithium salt and the organic solvent is 5%, and the mass percentage content of the Vinylene Carbonate (VC) in the lithium salt and the organic solvent is 5%.
The preparation method of the low-temperature electrolyte comprises the following steps:
mixing EC, EMC, DMC, DEC and EP in proportion, adding 5% (mass ratio of lithium salt to organic solvent) of FEC and VC as additives respectively and independently to obtain electrolyte solvent, adding 10% (mass ratio) of lithium type molecular sieve, drying for 24h, adding 1mol/L LiPF at 0-15 deg.C6And obtaining the low-temperature electrolyte.
Example 3
A low temperature electrolyte comprising: lithium salt LiPF6The organic solvent comprises 10vol% of Ethylene Carbonate (EC), 10vol% of Propylene Carbonate (PC), 40 vol% of Ethyl Methyl Carbonate (EMC), 10vol% of dimethyl carbonate (DMC), 20vol% of diethyl carbonate (DEC) and 10vol% of Ethyl Propionate (EP) (the basis is the organic solvent and is 100%), the additives are Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), the molar concentration of the lithium salt in the organic solvent is 1mol/L, the mass percent of the fluoroethylene carbonate (FEC) in the lithium salt and the organic solvent is 5%, and the mass percent of the Vinylene Carbonate (VC) in the lithium salt and the organic solvent is 5%.
The preparation method of the low-temperature electrolyte comprises the following steps:
mixing EC, PC, EMC, DMC, DEC and EP in proportion, adding 5% (mass ratio of lithium salt and organic solvent) of FEC and VC as additives respectively and independently to obtain electrolyte solvent, adding 10% (mass ratio) of lithium type molecular sieve, drying for 24h, adding 1mol/L LiPF at 0-15 deg.C, and adding6And obtaining the low-temperature electrolyte.
Example 4
A low temperature electrolyte comprising: lithium salt LiPF6The organic solvent comprises 20vol% of Ethylene Carbonate (EC), 40 vol% of Ethyl Methyl Carbonate (EMC), 10vol% of diethyl carbonate (DEC) and 30vol% of Butyl Acetate (BA) (the reference is the organic solvent and is 100%), the additives comprise Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), the molar concentration of lithium salt in the organic solvent is 1mol/L, the mass percentage content of fluoroethylene carbonate (FEC) in the lithium salt and the organic solvent is 5%, and the mass percentage content of Vinylene Carbonate (VC) in the lithium salt and the organic solvent is 5%.
The preparation method of the low-temperature electrolyte comprises the following steps:
mixing EC, EMC, DEC and BA in proportion, respectively and independently adding 5% (mass ratio of total lithium salt and organic solvent) of FEC and VC as additives to obtain electrolyte solvent, adding 10% (mass ratio) of lithium type molecular sieve, drying for 24h, adding 1mol/L LiPF at 0-15 deg.C6And obtaining the low-temperature electrolyte.
Example 5
A low temperature electrolyte comprising: lithium salt LiPF6The organic solvent comprises 5 vol% of Ethylene Carbonate (EC), 5 vol% of Propylene Carbonate (PC), 50 vol% of Ethyl Methyl Carbonate (EMC), 20vol% of diethyl carbonate (DEC) and 20vol% of Butyl Acetate (BA) (the basis is the organic solvent and is 100%), the additives comprise Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), the molar concentration of lithium salt in the organic solvent is 1mol/L, the mass percentage content of fluoroethylene carbonate (FEC) in the lithium salt and the organic solvent is 5%, and the mass percentage content of Vinylene Carbonate (VC) in the lithium salt and the organic solvent is 5%.
The preparation method of the low-temperature electrolyte comprises the following steps:
mixing EC, PC, EMC, DEC and BA in proportion, respectively and independently adding 5% (mass ratio of total lithium salt and organic solvent) of FEC and VC as additives to obtain electrolyte solvent, adding 10% (mass ratio) of lithium type molecular sieve, drying for 24h, adding 1mol/L LiPF at 0-15 deg.C6And obtaining the low-temperature electrolyte.
Example 6
This example differs from example 5 in that EC, PC, EMC, DEC and BA occupy 10%: 5%: 45%: 20%: 20% by volume of the organic solvent EC: PC: EMC: DEC: BA.
Example 7
The example differs from example 5 in that the volume percentages of EC, PC, EMC, DEC and BA in the organic solvent are EC, PC, EMC, DEC, BA 10%, 50%, 20%.
Example 8
A low temperature electrolyte comprising: lithium salt LiPF6The organic solvent comprises 20vol% of Ethylene Carbonate (EC), 30vol% of Ethyl Methyl Carbonate (EMC), 10vol% of diethyl carbonate (DEC), 20vol% of Ethyl Acetate (EA) and 20vol% of Butyl Acetate (BA) (the basis is the organic solvent and is 100%), the additives are Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), the molar concentration of lithium salt in the organic solvent is 1mol/L, and the molar concentration of fluoroethylene carbonate (FEC) in the lithium salt and the organic solvent isThe content of the Vinylene Carbonate (VC) in the lithium salt and the organic solvent is 5 percent by mass.
The preparation method of the low-temperature electrolyte comprises the following steps:
mixing EC, EMC, DEC, EA and BA in proportion, respectively and independently adding 5% (mass ratio of total lithium salt and organic solvent) of FEC and VC as additives to obtain electrolyte solvent, adding 10% (mass ratio) of lithium type molecular sieve, drying for 24h, adding 1mol/L LiPF at 0-15 deg.C6And obtaining the low-temperature electrolyte.
Example 9
The difference between this example and example 8 is that the volume percentages of EC, EMC, DEC, EA and BA in the organic solvent are EC, DEC, EA and BA 15%, 35%, 10%, 20% and 10%.
Example 10
The difference between this example and example 8 is that the volume percentages of EC, EMC, DEC, EA and BA in the organic solvent are EC, DEC, EA and BA 10%, 40%, 10%, 20% and 10%.
Comparative example 1
The patent CN107565166A discloses "a lithium bistrifluoroethoxy difluoroborate salt and a lithium ion battery low-temperature electrolyte and a lithium ion battery containing the same" as the low-temperature electrolyte of the embodiment 2.
The low-temperature electrolyte of the lithium ion battery comprises: LiPF6Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), the additive Vinylene Carbonate (VC) and lithium bistrifluoroethoxy difluoroborate.
Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), an additive of Vinylene Carbonate (VC) and lithium bistrifluoroethoxy bifluoroborate in a mass ratio of: EC: EMC: DEC: VC: 30 percent of lithium bistrifluoroethoxy bifluoroborate, 30 percent of the lithium bistrifluoroethoxy bifluoroborate, 37.9 percent of the lithium bistrifluoroethoxy bifluoroborate, 2 percent of the lithium bistrifluoroethoxy bifluoroborate, 0.1 percent of the lithium bistrifluoroethoxy bifluoroborate, and 1mol/L of LiPF is dissolved in an electrolyte solvent obtained by mixing6And obtaining the nonaqueous electrolyte.
Comparative example 2
The low-temperature electrolyte of the embodiment 1 in the patent CN107171023A discloses a low-temperature electrolyte of a lithium ion battery.
Mixing ethylene carbonate, dimethyl carbonate, propylene fluoro carbonate and propylene chloro carbonate according to the volume ratio of 45:45:3:7, stirring to form an electrolyte solvent, and then adding LiPF6And LiBF4According to mass ratio mLiPF6:mLiBF4After mixing at a ratio of 8:1, the mixture was dissolved in the solvent and vigorously stirred in a glove box, and then a low-temperature electrolyte solution having a concentration of 1.2mol/L was prepared.
Comparative example 3
The patent CN106169611A discloses "a low-temperature electrolyte using ethyl acetate as solvent" as the low-temperature electrolyte of example 5.
Under anhydrous and oxygen-free conditions, lithium bis (trifluoromethylsulfonyl) imide is dissolved in ethyl acetate as a solvent according to a molar concentration of 2 mol/L.
Test examples
The low-temperature electrolytes obtained in the examples 1 to 10 and the comparative examples 1 to 3 are prepared into an Al negative lithium ion battery, and the Al negative lithium ion battery comprises a positive pole piece, a diaphragm, a negative pole Al piece and the low-temperature electrolytes obtained in the examples 1 to 10 and the comparative examples 1 to 3;
the preparation method of the Al cathode lithium ion battery comprises the following steps:
positive pole piece: mixing a ternary material NCM523, a Super P conductive agent, a PVDF binder and KS-6 according to a ratio of 96.5:1:1.5:1, adding a proper amount of NMP, stirring to a certain viscosity, uniformly coating on the surface of an Al foil with the thickness of 20 mu m, drying at a high temperature, cutting edges, cutting pieces, splitting strips, and welding tabs to prepare a positive pole piece of the Al negative pole lithium ion battery;
the cathode Al sheet is obtained by directly performing edge cutting, sheet cutting and strip splitting on 50-micrometer Al foil and then welding Al-Ni lugs;
the diaphragm is Cangzhou bright pearl diaphragm;
and (3) preparing the positive electrode, the negative electrode and the diaphragm into a dry electric core by a winding process, filling the dry electric core into a steel shell, welding a cap, putting the steel shell into a vacuum oven at 80 ℃ for drying for 48 hours, respectively and independently injecting the low-temperature electrolytes obtained in the examples 1-10 and the comparative examples 1-3, sealing, and carrying out chemical composition and volume grading to obtain the Al negative electrode lithium ion battery.
All the above operations were carried out in a glove box.
And testing the low-temperature discharge performance and the normal-temperature cycle performance of the obtained Al cathode lithium ion battery, wherein the testing method comprises the following steps:
low-temperature discharge performance: at 25 ℃, the test cell was fully charged after 5 weeks of constant current and constant voltage charging at 0.5C/constant current discharging at 0.5C and its charge capacity was recorded. Then, after the battery is placed for 4-16 hours at the temperature of minus 20 ℃ or minus 30 ℃ plus or minus 2 ℃, discharging to cut-off voltage at a constant current of 0.5 ℃, recording the discharge capacity of the battery, and respectively calculating the percentages of the discharge capacity at the temperature of minus 20 ℃ and minus 30 ℃ and the discharge capacity at the temperature of 25 ℃;
capacity retention rate at 500 weeks: and (3) recording the capacity retention rate of the test battery after the test battery is subjected to constant-current constant-voltage charging at 0.5 ℃ and constant-current discharging at 0.5 ℃ for 500 weeks at 25 ℃.
The results are shown in Table 1.
Table 1 low temperature discharge performance test and normal temperature cycle data of aluminum negative electrode lithium ion battery
Figure BDA0001882993740000151
As can be seen from Table 1, the lithium ion battery prepared by using the electrolyte of the embodiment of the invention has a discharge capacity of 72% or more of the discharge capacity at room temperature (25 ℃) when the temperature is reduced to-30 ℃, and the capacity retention rate of the battery at 500 weeks is 80% or more. The comparison example shows that the linear carboxylic ester solvent can improve the low-temperature performance of the electrolyte, but the matching degree of the linear carboxylic ester solvent and the Al negative electrode is low, so that the normal-temperature cycle performance of the battery is influenced, and the cyclic ester solvent and the linear ester solvent in the range of the invention can improve the low-temperature charge and discharge performance and simultaneously improve the normal-temperature cycle performance of the battery.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (4)

1. An aluminum negative electrode energy storage device electrolyte, comprising: lithium salt LiPF6The organic solvent comprises 20vol% of ethylene carbonate, 30vol% of ethyl methyl carbonate, 10vol% of diethyl carbonate, 20vol% of ethyl acetate and 20vol% of butyl acetate, the additives are vinylene carbonate and fluoroethylene carbonate, the molar concentration of lithium salt in the organic solvent is 1mol/L, the mass percentage of fluoroethylene carbonate in the lithium salt and the organic solvent is 5%, and the mass percentage of vinylene carbonate in the lithium salt and the organic solvent is 5%.
2. The preparation method of the electrolyte of the aluminum negative electrode energy storage device according to claim 1, characterized by comprising the following steps:
mixing ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate and butyl acetate according to a proportion, respectively and independently adding fluoroethylene carbonate and vinylene carbonate which account for 5 percent of the mass ratio of the sum of lithium salt and organic solvent as additives to obtain an electrolyte solvent, adding a lithium type molecular sieve with the mass ratio of 10 percent, drying for 24 hours, keeping the temperature at 0-15 ℃, adding 1mol/L LiPF6And obtaining the electrolyte.
3. An aluminum negative electrode energy storage device is characterized by comprising the electrolyte of the aluminum negative electrode energy storage device according to claim 1 or the electrolyte prepared by the preparation method of the electrolyte of the aluminum negative electrode energy storage device according to claim 2.
4. The preparation method of the aluminum cathode energy storage device of claim 3, characterized by comprising the following steps:
and assembling the cathode, the diaphragm, the anode and the electrolyte of the aluminum cathode energy storage device to obtain the aluminum cathode energy storage device.
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