CN110828881A - Dual-ion battery and preparation method thereof - Google Patents
Dual-ion battery and preparation method thereof Download PDFInfo
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- CN110828881A CN110828881A CN201911049629.4A CN201911049629A CN110828881A CN 110828881 A CN110828881 A CN 110828881A CN 201911049629 A CN201911049629 A CN 201911049629A CN 110828881 A CN110828881 A CN 110828881A
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- 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
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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
- H01M10/058—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
- H01M2300/00—Electrolytes
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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
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- 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 invention belongs to the technical field of batteries, and particularly relates to a double-ion battery and a preparation method thereof. The double-ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are positioned between the positive electrode and the negative electrode, the electrolyte is ionic liquid, the ionic liquid is composed of organic cations and organic anions, and metal ions are not contained in the electrolyte. Electrolyte among this dual ion battery is the ionic liquid that organic cation and organic anion constitute, do not relate to the reaction of any metal in the electrode reaction like this, consequently metal dendrite's problem can not appear, can avoid the production of dendrite from the source, thereby from the security that has realized the battery in principle, this dual ion battery has used the ionic liquid of difficult burning as electrolyte simultaneously, has reduced the risk of catching fire, compares traditional electrolyte based on low boiling organic solvent and has further promoted the security of battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a double-ion battery and a preparation method thereof.
Background
Rechargeable lithium ion batteries are the most successful commercial secondary batteries at present due to the advantages of high energy density, long cycle life, good stability and the like, but the shortage of lithium resources and the continuous increase of the demand of people for lithium ion batteries mean that a large-scale energy storage system is unreliable by relying on the lithium ion batteries. Due to the concern about the shortage of lithium resources, a great deal of research is being conducted on other abundant and inexpensive metal ion batteries, such as sodium ion batteries, potassium ion batteries, magnesium ion batteries, aluminum ion batteries, calcium ion batteries, and the like. In summary, the development of secondary batteries based on other metal ions is the mainstream research direction in the field of energy storage at present. However, conventional metal ion based batteries suffer from problems of metal dendrites and uncontrolled interfacial chemical activity that can cause membrane penetration, thereby creating a risk of thermal runaway and even fire explosion. Although recent research, such as adjusting electrolyte composition and additive species, nano-interface design, and novel current collector design, has made some progress, such progress does not completely guarantee elimination of metal dendrites, thereby failing to achieve a hundred percent safety of the battery.
At present, in order to solve the safety problem of battery systems such as lithium ion batteries and sodium ion batteries which realize energy storage by the reaction of metal ions and positive and negative electrodes, the following schemes are generally adopted: firstly, a safety diaphragm with good mechanical property is adopted or a solid electrolyte is directly used for preventing metal dendrite from penetrating through the diaphragm, so that the safety problem caused by the short circuit of a positive electrode and a negative electrode is avoided; secondly, the dendrite is refined by adjusting the concentration of the electrolyte and the quantity and the type of the additive, so that the fine dendrite cannot penetrate through the diaphragm; thirdly, the growth direction of the dendrite is limited or the diameter and the length of the dendrite are limited by the three-dimensional design of the current collector, so that the dendrite is prevented from reaching the diaphragm. In summary, the above solution is to avoid dendrite penetration through the separator by trapping lithium dendrites, thereby achieving battery safety, but cannot fundamentally avoid dendrite generation from the source.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a double-ion battery and a preparation method thereof, and aims to solve the technical problem that the safety of the conventional secondary battery is influenced because the conventional secondary battery cannot avoid the generation of metal dendrites.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a dual-ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are positioned between the positive electrode and the negative electrode, the electrolyte is ionic liquid, the ionic liquid is composed of organic cations and organic anions, and metal ions are not contained in the electrolyte.
In the double-ion battery provided by the invention, the electrolyte is the ionic liquid consisting of organic cations and organic anions, namely the electrolyte cations are the organic cations and the electrolyte anions are the organic anions, so that the electrolyte does not contain any metal ions, and the electrode reaction of the double-ion battery does not involve any metal reaction, so that the problem of metal dendrite is avoided, and the generation of dendrite can be avoided from the source, thereby realizing the safety of the battery in principle; and the organic cation which is used for replacing the metal cation to react with the negative electrode has the advantages of abundant reserves, various types and easy treatment. Therefore, the effect of the double-ion battery is obviously better than that of the prior art.
The invention also provides a preparation method of the double-ion battery, which comprises the following steps:
according to the composition of the double-ion battery, a positive electrode, a negative electrode, a diaphragm and electrolyte in the double-ion battery are provided;
and assembling the anode, the cathode, the diaphragm and the electrolyte to obtain the double-ion battery.
According to the preparation method of the bi-ion battery provided by the invention, the ionic liquid consisting of the organic cations and the organic anions is used as the electrolyte and is assembled with the anode, the cathode and the diaphragm, the process is simple and safe, and the electrode reaction of the finally obtained bi-ion battery does not involve any metal reaction, so that the problem of metal dendrite is avoided, and the generation of dendrite can be avoided from the source, so that the safety of the battery is realized in principle, the ionic liquid is not easy to burn, the risk of ignition is reduced, the safety of the battery is further improved compared with the traditional electrolyte based on a low-boiling-point organic solvent, and the environmental compatibility of the preparation and the use of the bi-ion battery is finally improved.
Drawings
Fig. 1 is a schematic structural diagram of a bi-ion battery provided in an embodiment of the present invention;
fig. 2 is a graph illustrating the cycle performance of a bi-ion battery according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides a dual-ion battery, including a positive electrode, a negative electrode, and a separator and an electrolyte, which are located between the positive electrode and the negative electrode, where the electrolyte is an ionic liquid, the ionic liquid is composed of an organic cation and an organic anion, and the electrolyte is free of metal ions.
In the double-ion battery provided by the embodiment of the invention, the electrolyte is the ionic liquid consisting of organic cations and organic anions, namely the electrolyte cations are the organic cations and the electrolyte anions are the organic anions, so that the electrolyte does not contain any metal ions, and the electrode reaction of the double-ion battery does not involve any metal reaction, so that the problem of metal dendrite is avoided, and the generation of dendrite can be avoided from the source, thereby realizing the safety of the battery in principle; and the organic cation which is used for replacing the metal cation to react with the negative electrode has the advantages of abundant reserves, various types and easy treatment. Therefore, the effect of the double-ion battery is obviously better than that of the prior art.
The idea of avoiding the dendrite from penetrating the diaphragm at present is to solve the problem of the lithium dendrite by surrounding and blocking, and the idea of the embodiment of the invention is to replace the traditional metal ions with organic ions which can not generate the metal dendrite, thereby avoiding the generation of the dendrite from the source. The embodiment of the invention provides a novel secondary battery structure consisting of a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and an ionic liquid without metal ions, and the reaction characteristics of the double-ion battery are as follows: the positive electrode is an intercalation reaction of organic anions, a charge-discharge curve has a platform, and a cyclic voltammetry curve has an oxidation reduction peak; the negative electrode is used for adsorption, intercalation or redox reaction of organic cations; the intercalation reaction of the organic anions can completely avoid the reaction of the anode and the metal ions, which provides possibility for the development of secondary batteries without metal ions, and the organic cations which can replace the metal cations to react with the cathode have the advantages of abundant reserves, various types and easy treatment, and particularly, the reaction of the organic cations and the cathode can completely avoid the generation of dendrites. Therefore, the electrode reaction of the double-ion battery provided by the embodiment of the invention does not involve any metal reaction, so that the material does not generate dendrite from the source, the generation of metal dendrite is completely avoided, and the safety of the battery is fundamentally ensured.
In one embodiment, the ionic liquid in the diionic battery is selected from the group consisting of N-Butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt (1-Butyl-1-methylpyrrolidinyl bis, P14TFSI), N-butylpyridinium bis (trifluoromethanesulfonyl) imide salt (N-butyl pyridinium bis (imidazolium) imide, BPyTFSI), N-butylpyridinium tetrafluoroborate (BPyBF)4) N, N-Diethyl-N-methyl-N- (2-methoxy-hexyl) ammonium tetrafluoroborate, N-methoxyethyl-N-methyldiethyl ammonium tetrafluoroborate122,1O2BF4) N-Butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt (1-Butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, PP14TFSI), N-butyl-N-methylpyrrolidine bromide (P-butyl-N-methylpyrrolidinium bromide, P14Br), tributylmethylammonium chloride (N)144Cl), Tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt (tributyl methyl cyanide bis (trifluoromethanesulfonyl) imide, N144TFSI), N-ethylpyridine bromide (EPyBr), N-octylpyridine bromide (OPyBr), tributylethylphosphonium bromide (pbbr), P244Br) is selected from one or more of the following. The ionic liquid can avoid metal dendrite, ensure the safety of the battery from the source, can be used as electrolyte, has the function of an ion transmission carrier, and is not easy to burn, so that the ionic liquid can be used as an excellent electrolyte material; preferably, the electrolyte is P14TFSI。
In one embodiment, the positive electrode in the bi-ion battery comprises a positive electrode current collector and a positive electrode active layer combined on the surface of the positive electrode current collector, wherein the positive electrode active layer contains a positive electrode active material, a conductive agent and a binder. The mass ratio range of the positive electrode active material, the conductive agent and the binder is as follows: 60-90: 5-35: 5-10.
Wherein the material of the positive electrode current collector is selected from a simple metal substance of any one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium and manganese, or a metal alloy of at least one element of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium and manganese, or a metal composite of at least one element of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium and manganese; namely, the positive electrode current collector comprises one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium and manganese or an alloy thereof or any one of metal composites or any one of alloys thereof.
The positive electrode active material is selected from at least one of a graphite-based material having a layered crystal structure, a sulfide, a nitride, an oxide, and a carbide. Specifically, the graphite material is selected from one or more of natural graphite, artificial graphite and graphene; the sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide and titanium disulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide and titanium dioxide; the carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide. The conductive agent can be carbon black, graphene, carbon nanotubes and the like, preferably carbon black, and the binder can be polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose (CMC), polyvinyl alcohol, sodium alginate, polyurethane and the like, preferably polyvinylidene fluoride.
Preferably, the positive current collector material is selected from aluminum. The positive active material is selected from natural graphite and/or artificial graphite. Wherein, the natural graphite can be one or more of compact crystalline graphite, crystalline flake graphite, stable crystalline graphite and the like, the artificial graphite can be one or more of graphite fiber, oriented pyrolytic graphite, foam graphite, expanded graphite, mesocarbon microbeads and the like, and modified graphite such as amorphous carbon/metal/oxygen modified graphite and the like.
In one embodiment, the negative electrode in the bi-ion battery includes a negative electrode current collector and a negative electrode active layer bonded to a surface of the negative electrode current collector, the negative electrode active layer including a negative electrode active material, a conductive agent, and a binder. Wherein the mass ratio range of the negative electrode active material, the conductive agent and the binder is as follows: 60-90: 5-35: 5-10.
Wherein the material of the negative current collector is selected from any one simple metal of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold and barium, or from a metal alloy containing at least one element of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold and barium, or from a metal composite containing at least one element of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, silver, gold and barium; namely, the negative current collector comprises one or an alloy of metal copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold and barium, or any metal composite or any alloy thereof.
The negative active material is selected from at least one of natural graphite, artificial graphite, graphene, carbon nanotubes, carbon nanofibers, porous carbon, conductive carbon black and P-type organic polymers. The conductive agent can be carbon black, graphene, carbon nanotubes and the like, preferably carbon black, and the binder can be polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose (CMC), polyvinyl alcohol, sodium alginate, polyurethane and the like, preferably polyvinylidene fluoride. Wherein, the P-type organic polymer is a hole type organic polymer, and can reversibly perform oxidation-reduction reaction with cations in the electrolyte, and comprises the following structures: at least one of P5, Me2-P5, bis-PDT, bis-TDT, TF8, P3HT, F8T2, and PTAA, etc., but is not limited thereto.
Preferably, the negative current collector material is selected from aluminum. The negative active material is selected from porous carbon (i.e., activated carbon) and/or P-type organic polymer.
In one embodiment, the separator in the bi-ion battery is selected from a porous polymer film or an inorganic porous film or an organic/inorganic composite separator, and specifically, is selected from one or more of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film (such as a porous polyethylene propylene composite polymer film), a porous ceramic separator, a polyvinylidene fluoride film, a cellulose film, a non-woven fabric and a glass fiber film.
On the other hand, the embodiment of the invention also provides a preparation method of the double-ion battery, which comprises the following steps:
s01: according to the composition of the dual-ion battery disclosed by the embodiment of the invention, a positive electrode, a negative electrode, a diaphragm and electrolyte in the dual-ion battery are provided;
s02: and assembling the anode, the cathode, the diaphragm and the electrolyte to obtain the double-ion battery.
According to the preparation method of the bi-ion battery provided by the embodiment of the invention, the ionic liquid composed of the organic cations and the organic anions is used as the electrolyte and is assembled with the anode, the cathode and the diaphragm, the process is simple and safe, the electrode reaction of the finally obtained bi-ion battery does not involve any metal reaction, so that the problem of metal dendrite is avoided, and the generation of dendrite can be avoided from the source, so that the safety of the battery is realized in principle, the ionic liquid is not easy to burn, the ignition risk is reduced, the safety of the battery is further improved compared with the traditional electrolyte based on the low-boiling-point organic solvent, and the environmental compatibility of the preparation and the use of the bi-ion battery is finally improved.
In one embodiment, the preparation of the positive electrode of the bi-ion battery comprises: firstly, weighing a proper amount of positive active material, a proper amount of binder and a proper amount of conductive agent according to a certain proportion, uniformly mixing, adding a proper amount of solvent, fully grinding into uniform slurry to prepare positive active material slurry; then, taking a metal, metal alloy or metal compound conductive material as a positive current collector, uniformly coating the positive active material slurry on the surface of the positive current collector, placing the positive current collector in a vacuum drying oven at a certain temperature for drying, and blanking into a positive electrode with a required size after the positive active material slurry is completely dried to form a positive active layer.
In one embodiment, the preparation of the negative electrode of the bi-ion battery comprises: firstly, weighing a proper amount of negative active material, a binder and a conductive agent according to a certain proportion, uniformly mixing, adding a proper amount of solvent, fully grinding into uniform slurry to prepare negative active material slurry; then, taking the metal, metal alloy or metal compound conductive material as a negative current collector, uniformly coating the negative active material slurry on the surface of the negative current collector, placing the negative current collector in a vacuum drying oven at a certain temperature for drying, and blanking into a negative electrode with a required size after the negative active material slurry is completely dried to form a negative active layer.
In one embodiment, the separator preparation for the bi-ion battery comprises: an organic porous polymer film or an inorganic porous film or an organic/inorganic composite separator having a desired size is used as a separator, which is punched into a desired size.
In one embodiment, the electrolyte formulation of the bi-ion battery comprises: the ionic liquid can be directly used as electrolyte after being fully dewatered.
In one embodiment, the assembling step of the bi-ion battery comprises: and assembling the positive electrode, the negative electrode, the separator and the electrolyte.
Compared with the prior art, the double-ion battery provided by the embodiment of the invention has the beneficial effects that: firstly, the embodiment of the invention provides a metal ion-free type bi-ion battery, which takes a material capable of reversibly intercalating/deintercalating organic anions as a positive electrode material, a material capable of intercalating or reacting with organic cations as a negative electrode material, and an ionic liquid only containing organic cations and anions as an electrolyte, so that the problem of potential safety hazard of the traditional battery mainly based on metal ion reaction is solved; meanwhile, the electrolyte used by the metal-ion-free type double-ion battery provided by the embodiment of the invention is the ion liquid which is not easy to burn, so that the ignition risk of the battery is further reduced, and the environmental compatibility of the battery is improved.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A schematic structural diagram of a metal-free ionic double-ion battery is shown in fig. 1 (a shell is not shown), and the double-ion battery comprises a positive electrode current collector 1, a positive electrode active material layer 2, an electrolyte 3, a diaphragm 4, a negative electrode active layer 5 and a negative electrode current collector 6.
The preparation method of the bi-ion battery provided by the embodiment comprises the following steps:
step (1): preparing a positive electrode: adding 0.8g of expanded graphite, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 2ml of N-methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; the slurry was then uniformly coated on the surface of aluminum foil (i.e., positive current collector) and vacuum dried. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a positive electrode for standby.
Step (2): preparing a diaphragm: the glass fiber film was cut into a circular sheet having a diameter of 16mm and used as a separator.
And (3): preparing an electrolyte: ionic liquid P14TFSI was used directly after water removal.
And (4): preparing a negative electrode: adding 0.8g of porous carbon, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 2ml of N-methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; the slurry was then uniformly coated on the surface of aluminum foil (i.e., negative current collector) and vacuum dried. And cutting the dried electrode slice into a circular slice with the diameter of 12mm, and compacting the circular slice to be used as a negative electrode for standby.
And (5): assembling: and in a glove box protected by inert gas, tightly stacking the prepared positive electrode, the diaphragm and the negative electrode in sequence, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button type shell to finish the assembly of the metal ion-free double-ion battery.
Example 2
A metal-free ionic type double-ion battery is prepared, and other materials, structures and preparation methods of the double-ion battery are the same as those of the embodiment 1 except that an electrolyte is ionic liquid BPyTFSI.
Example 3
A metal-free ionic double-ion battery is prepared from ion liquid BPyBF as electrolyte4Besides, other materials, structures and preparation methods of the double-ion battery are the same as those of the embodiment 1The same is true.
Example 4
A metal-free ionic double-ion battery is prepared from ionic liquid N as electrolyte122,1O2BF4Besides, other materials, structures and preparation methods of the double-ion battery are the same as those of the embodiment 1.
Example 5
A metal-free ionic double-ion battery is prepared from ionic liquid PP as electrolyte14Other materials, structures and preparation methods of the dual ion battery except for TFSI are the same as those of example 1.
Example 6
A metal-free ionic double-ion battery is prepared from ionic liquid P as electrolyte14Except Br, other materials, structure and preparation method of the double-ion battery are the same as those of the embodiment 1.
Example 7
A metal-free ionic double-ion battery is prepared from ionic liquid N as electrolyte144Except for Cl, other materials, structures and preparation methods of the bi-ion battery are the same as those of example 1.
Example 8
A metal-free ionic double-ion battery is prepared from ionic liquid N as electrolyte144Other materials, structures and preparation methods of the dual ion battery except for TFSI are the same as those of example 1.
Example 9
Except that the electrolyte is ionic liquid EPyBr, other materials, the structure and the preparation method of the metal-free ionic double-ion battery are the same as those in the embodiment 1.
Example 10
Except that the electrolyte is ionic liquid OPyBr, other materials, the structure and the preparation method of the metal-free ionic double-ion battery are the same as those of the embodiment 1.
Example 11
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those of example 1, except that the positive electrode active material is mesophase carbon microspheres.
Example 12
A metal-free ionic type double-ion battery is prepared by using the same materials, structure and preparation method as those in example 1 except that the positive electrode active material is crystalline flake graphite.
Example 13
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as example 1 except that the positive active material is oriented pyrolytic graphite.
Example 14
A metal-free ionic type bi-ion battery, except that the positive active material is graphene microchip, and other materials, structure and preparation method of the bi-ion battery are the same as those of the embodiment 1.
Example 15
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those of example 1 except that the positive active material is amorphous carbon modified graphite.
Example 16
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those of example 1 except that the positive active material is molybdenum disulfide.
Example 17
Except that the positive active material is vanadium disulfide, other materials, structures and preparation methods of the metal-free ionic type double-ion battery are the same as those of the embodiment 1.
Example 18
A metal-free ionic type bi-ion battery, except that the positive active material is titanium disulfide, the other materials, the structure and the preparation method of the bi-ion battery are the same as those in the embodiment 1.
Example 19
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those of example 1 except that the positive electrode active material is titanium carbide.
Example 20
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those of example 1, except that the positive active material is molybdenum carbide.
Example 21
A metal-free ionic type bi-ion battery, except that the negative active material is conductive carbon black, the other materials, the structure and the preparation method of the bi-ion battery are the same as those in the embodiment 1.
Example 22
A metal-free ionic type double-ion battery is prepared by using natural crystalline flake graphite as a negative active material and adopting the same structure and preparation method as those in example 1.
Example 23
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those in example 1, except that the negative electrode active material is amorphous carbon modified graphite.
Example 24
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as example 1 except that the negative active material is graphite foam.
Example 25
Except that the negative active material is a graphene film, other materials, the structure and the preparation method of the metal-free ionic double-ion battery are the same as those in the embodiment 1.
Example 26
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as example 1 except that the negative active material is a carbon nanotube.
Example 27
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as those of example 1 except that the negative active material is carbon nanofiber.
Example 28
A metal-free ionic type bi-ion battery, the other materials, the structure and the preparation method of which are the same as those of example 1 except that the negative active material is bis-TDT.
Example 29
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as example 1 except that the negative active material is P3 HT.
Example 30
A metal-free ionic type bi-ion battery, which has the same materials, structure and preparation method as example 1 except that the negative active material is P5.
Example 31
A metal-free ionic type double-ion battery is prepared by the following steps of preparing a porous polypropylene film as a diaphragm, and preparing the porous polypropylene film as the diaphragm by using the same material, structure and preparation method as those of the porous polypropylene film in example 1.
Example 32
The other materials, the structure and the preparation method of the metal-free ionic type double-ion battery are the same as those of the embodiment 1 except that the diaphragm is a porous polyethylene film.
Example 33
Except that the diaphragm is a porous polyethylene propylene composite polymer film, other materials, the structure and the preparation method of the metal-free ionic type double-ion battery are the same as those in the embodiment 1.
Example 34
The materials, structure and preparation method of the metal-free ionic double-ion battery are the same as those of the embodiment 1 except that the diaphragm is a porous ceramic diaphragm.
Example 35
The materials, structure and preparation method of the metal-free ionic type double-ion battery are the same as those of the embodiment 1 except that the diaphragm is the polyvinylidene fluoride film.
Example 36
The materials, structure and preparation method of the metal-free ionic type double-ion battery are the same as those of the embodiment 1 except that the diaphragm is a cellulose diaphragm.
Example 37
The materials, structure and preparation method of the metal-free ionic double-ion battery are the same as those of the embodiment 1 except that the diaphragm is made of non-woven fabric.
Example 38
A metal-free ionic type bi-ion battery is prepared by using 0.6g of expanded graphite, 0.35g of carbon black and 0.05g of polyvinylidene fluoride as a positive electrode, and the other materials, the structure and the preparation method of the bi-ion battery are the same as those in example 1.
Example 39
A metal-free ionic type bi-ion battery has the same materials, structure and preparation method as those of example 1, except that 0.9g of expanded graphite, 0.05g of carbon black and 0.05g of polyvinylidene fluoride are used for preparing a positive electrode.
Example 40
A metal-free ionic type bi-ion battery is prepared by using 0.6g of porous carbon, 0.35g of carbon black and 0.05g of polyvinylidene fluoride as a negative electrode, and other materials, structures and preparation methods of the bi-ion battery are the same as those of example 1.
EXAMPLE 41
A metal-free ionic type bi-ion battery is prepared by using 0.9g of porous carbon, 0.05g of carbon black and 0.05g of polyvinylidene fluoride as a negative electrode, and other materials, structures and preparation methods of the bi-ion battery are the same as those of example 1.
Performance testing
The electrochemical performance tests of the dual-ion batteries provided in the above examples 1 and 2 to 41, including cycle number, capacity retention rate and coulombic efficiency, were performed as follows:
and (3) cyclic charge and discharge: the method is characterized in that cyclic charging and discharging are carried out on a CT2001C-001 blue battery cyclic testing system, the standard capacity of an electrode is tested by charging and discharging at a rate of 100mA/g, the specific capacity of a material is current time/sample mass, the energy density of the material is the specific capacity of the material and the platform voltage of the battery, the charging and discharging conditions are determined according to the needs of experiments, and the cyclic step comprises the following steps: standing for 60 s-constant current discharging-standing for 60 s-constant current charging.
Multiplying power charge and discharge: the method is also carried out on a blue-ray battery cycle test system, the rate performance of the material is tested by charging and discharging at different rates (current density), the charging and discharging conditions depend on the needs of experiments, and the cycle steps are the same as the cycle charging and discharging.
The cycle performance of example 1 is shown in fig. 2, and the test result data of other examples are shown in tables 1-5 below.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
From the data in table 1, it can be seen that: examples 2 to 10 compared with example 1, different types of ionic liquid materials were used as electrolytes, and the different ionic liquids showed a large difference in cycle performance and coulombic efficiency. Wherein, the wider the electrochemical stability window of the ionic liquid, the higher the cycle performance and the coulombic efficiency of the ionic liquid.
From the data in table 2, it can be seen that: examples 11 to 20, using different kinds of positive electrode active materials respectively, the expanded graphite having less graphene sheets exhibited more excellent cycle stability and higher energy density than example 1.
From the data in table 3, it can be seen that: examples 21 to 30 each used a different kind of negative electrode active material than example 1, and the porous carbon negative electrode active material mainly based on the cation adsorption mechanism had more excellent cycle performance than the graphite type carbon material having less amorphous components accompanying partial cation intercalation.
From the data in table 4, it can be seen that: in examples 31 to 37, different kinds of separator materials were used as compared with example 1, and the influence of the kind of separator on the cycle performance was not large as a whole.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A dual-ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are positioned between the positive electrode and the negative electrode.
2. The diionic cell of claim 1, wherein said ionic liquid is selected from at least one member selected from the group consisting of N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, N-butylpyridinium tetrafluoroborate, N-methoxyethyl-N-methyldiethylammonium tetrafluoroborate, N-butyl-N-methylpiperidinium bis (trifluoromethanesulfonyl) imide salt, N-butyl-N-methylpyrrolidine bromide salt, tributylmethylammonium chloride, tributylmethylammonium bis (trifluoromethanesulfonyl) imide salt, N-ethylpyridinium bromide salt, N-octylpyridinium bromide salt and tributylethylphosphonium bromide.
3. The diionic battery of claim 1, wherein said ionic liquid is N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
4. The bi-ion battery of any of claims 1-3, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active layer bonded to a surface of the positive electrode current collector, the positive electrode active layer comprising a positive electrode active material, a conductive agent, and a binder.
5. The bi-ion battery of claim 4, wherein the material of the positive electrode current collector is selected from a simple metal selected from any one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, and manganese, or a metal alloy selected from at least one element selected from aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, and manganese, or a metal composite selected from at least one element selected from aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, and manganese; and/or the presence of a gas in the gas,
the positive electrode active material is selected from at least one of a graphite-based material having a layered crystal structure, a sulfide, a nitride, an oxide, and a carbide.
6. The bi-ion battery of claim 5, wherein the graphite-based material is selected from one or more of natural graphite, artificial graphite, and graphene; and/or the presence of a gas in the gas,
the sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide and titanium disulfide; and/or the presence of a gas in the gas,
the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; and/or the presence of a gas in the gas,
the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide and titanium dioxide; and/or the presence of a gas in the gas,
the carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide.
7. The bi-ion battery of any of claims 1-3, wherein the negative electrode comprises a negative electrode current collector and a negative electrode active layer bonded to a surface of the negative electrode current collector, the negative electrode active layer comprising a negative electrode active material, a conductive agent, and a binder.
8. The bi-ion battery of claim 7, wherein the negative current collector is made of a material selected from the group consisting of elemental metals of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold, and barium, or a metal alloy containing at least one element selected from the group consisting of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold, and barium, or a metal composite containing at least one element selected from the group consisting of copper, chromium, magnesium, iron, nickel, tin, zinc, lithium, aluminum, calcium, neodymium, lead, antimony, strontium, yttrium, lanthanum, germanium, cobalt, cerium, beryllium, silver, gold, and barium; and/or the presence of a gas in the gas,
the negative active material is selected from at least one of natural graphite, artificial graphite, graphene, carbon nanotubes, carbon nanofibers, porous carbon, conductive carbon black and P-type organic polymers.
9. The bi-ion battery of any of claims 1-3, wherein the separator is selected from one or more of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a porous ceramic separator, a polyvinylidene fluoride film, a cellulose composite film, a non-woven fabric, and a glass fiber film.
10. The preparation method of the double-ion battery is characterized by comprising the following steps of:
the composition of the bi-ion battery of any of claims 1-9, providing a positive electrode, a negative electrode, a separator and an electrolyte in the bi-ion battery;
and assembling the anode, the cathode, the diaphragm and the electrolyte to obtain the double-ion battery.
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