CN107785536B - Chloride square battery and assembling method thereof - Google Patents
Chloride square battery and assembling method thereof Download PDFInfo
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- CN107785536B CN107785536B CN201610791380.4A CN201610791380A CN107785536B CN 107785536 B CN107785536 B CN 107785536B CN 201610791380 A CN201610791380 A CN 201610791380A CN 107785536 B CN107785536 B CN 107785536B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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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
- H01M4/58—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
- H01M4/582—Halogenides
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a chloride square battery and an assembling method thereof, wherein the battery comprises: the battery comprises a battery pole group, a positive pole column, a negative pole column, electrolyte and a shell; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the positive electrode comprises a chloride positive electrode component coated on the surface of a positive electrode current collector; the positive active substance in the chloride positive component is chloride, and the chloride is obtained by reacting chlorine gas with organic salt. The invention adopts the chloride generated by the reaction of chlorine and organic salt as the positive active substance, when the chloride is used for the battery, the specific energy of the secondary battery can be greatly improved, and the quick charge and discharge can be realized, the cycle life is long, and the cost of raw materials is low.
Description
Technical Field
The invention relates to the field of secondary batteries, in particular to a battery and an assembly method thereof, and particularly relates to a chloride square battery and an assembly method thereof.
Background
At present, the battery is the heart of the electric automobile and is the current investment hotspot, and the lithium ion power battery is considered as the power battery with the most development potential of the electric automobile; however, with the development of noble metals such as nickel, cobalt, lithium and the like, the raw materials of the lithium ion power battery greatly increase, and the popularization and the application of the electric automobile are restricted; the poor safety and the poor recovery economic benefit of the lithium ion power battery are also important factors restricting the development of the lithium ion power battery. The power battery solution with low cost, environmental protection and safe use is still the first problem to be solved by the electric automobile.
Halogen is an element which is stored in the earth crust abundantly, and has the advantages of large storage capacity, mature extraction process, environmental protection in production, no pollution in recovery and low price, and the halogen is taken as the anode material and is an ideal electrode material.
Disclosure of Invention
In order to solve the above problems, the present inventors have found through studies that a power battery having low cost, environmental protection, safety in use, and high specific energy can be obtained when a chloride generated by reacting chlorine gas with an organic salt is used as a positive electrode active material in the battery, thereby achieving the present invention.
In a first aspect, the present invention provides a chloride prismatic battery comprising: the battery comprises a battery pole group, a positive pole column, a negative pole column, electrolyte and a shell; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the positive electrode comprises a chloride positive electrode component coated on the surface of a positive electrode current collector.
The term "comprising" as used herein means that it may include other components in addition to the components described, which impart different characteristics to the battery. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
According to the invention, the chloride positive electrode component comprises: chloride, high specific surface area activated carbon, conductive agent and binder, and may also include other components known in the art, which are not described herein. Wherein the chloride is present as a positive electrode active material.
The chloride anode comprises the following components in parts by weight:
the positive electrode containing the chloride positive electrode component according to the present invention may be prepared by the following method, but is not limited thereto:
(1) putting chloride, high specific surface area active carbon, a conductive agent and a binder into a ball milling tank, and carrying out ball milling for 5-120 min;
(2) adding an organic solvent into a ball milling tank, enabling the mass ratio of the total mass of the chloride, the high specific surface area activated carbon, the conductive agent and the binder to the organic solvent to be (40-60) - (60-40), and carrying out ball milling for 60-120min to obtain anode slurry;
(3) coating the positive electrode slurry on a current collector, and controlling the thickness of single-side coating to be 10-500 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and performing vacuum baking, wherein the vacuum degree is controlled to be-0.08 to-0.10 MPa, the temperature is controlled to be 100-;
(5) and extruding the dried pole piece by using a double-roller machine, and controlling the pressure of the double rollers to be 50-300 tons to obtain the anode containing the chloride anode component.
Wherein the chloride accounts for 20-97 parts by weight of the chloride cathode component, such as 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 50 parts, 55 parts, 60 parts, 63 parts, 68 parts, 70 parts, 75 parts, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts, 95 parts or 97 parts, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive and does not list the specific values included in the range.
According to the present invention, the positive active material-chloride is obtained by reacting chlorine gas with an organic salt.
The chloride provided by the invention is used as a novel chemical system and exists in the positive active material of the battery in a liquid form. By adding the chloride into the positive active material, the theoretical specific energy of the positive active material can be as high as 755mAh/g, so that the prepared secondary battery has higher specific energy, rapid charge and discharge are realized, the cycle life is prolonged, and the cost of raw materials is low.
According to the invention, the organic salt has the general formula [ X ]]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion.
The organic salt is composed of organic cations with larger volume and anions with smaller volume, and the substance has a plurality of unique properties, such as stable physicochemical properties, extremely low vapor pressure and difficult volatilization, good solubility to both organic and inorganic substances, controllable polarity and the like.
In the present invention, the organic cation may be any one of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium ion or quaternary phosphonium ion or a combination of at least two thereof, for example, may be any one of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium ion or quaternary phosphonium ion, and a typical but non-limiting combination is: imidazolium ions and pyridinium ions; pyridinium ions and pyrrolium ions; morpholinium ions, quaternary ammonium ions, quaternary phosphonium ions and the like.
According to the invention, the organic cation is preferably a quaternary ammonium ion, which has the following advantages over other organic cations: the quaternary ammonium salt (organic salt containing quaternary ammonium salt ions) is a common chemical, and the production process is mature, the price is low, and the quaternary ammonium salt can be purchased and used in a large scale.
In the present invention, the anion may adopt F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them, for example, may be F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3S02)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -A typical but non-limiting combination of any of: f-And Cl-；Br-And I-；I-And PF6 -；Cl-、Br-And SCN-And the like.
Illustratively, the organic salt in the present invention may be: 1-butyl-3-methylimidazolium hexafluorophosphate ([ C)4-min]PF4)1, 3-bis (2, 6-diisopropylphenyl) imidazolium chloride, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 1-N-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-propylimidazolium iodide, cetylpyridinium chloride, pyridinium trichloride, N-allyl-2-alkylpyridinium chloride, 1-butyl-1-methylpiperidinium chloride, chlorodipiperidinium hexafluorophosphate, cetyltrimethylammonium chloride, tetramethylammonium chloride, ethyltriphenylphosphine chloride or hexadecyltributylphosphine chloride.
According to the invention, the chloride is formed by reacting chlorine with the above-mentioned organic salt [ X ]]+Z-The chemical reaction of the compound prepared by the reaction of mixing can be expressed by the following equation:
4Cl2+[X]+Z-→[X]+[Cl8Z]-or Cl2+[X]+Z-→[X]+[Cl2Z]-
In this chemical reaction, 1 [ X ]]+Z-Molecule, up to 4 Cl can be complexed2The molecular, and therefore, molar ratio of chlorine to organic salt can be set in the range of (1-4): 1.
In the invention, the chloride is added into the positive active material, so that the capacitor can have higher specific energy, and the theoretical specific energy of the chloride is as high as 755 mAh/g.
Illustratively, in the present invention the chloride may be: tetraethylammonium trichloride, tetrabutylammonium trichloride, 1-ethyl-3-methyl-trichloroimidazole, phenyltrimethylammonium trichloride, benzyltriethylammonium trichloride, benzyltrimethylammonium trichloride, dodecyltrimethylammonium trichloride.
The chloride in the present invention can be prepared by the following method, but is not limited thereto:
(a) respectively taking chlorine and organic salt, controlling the mol ratio of the chlorine to the organic salt to be (1-4):1, firstly putting the organic salt into a closed container, and introducing inert gas into the closed container, wherein the inert gas is preferably nitrogen and/or argon;
(b) introducing chlorine gas into the closed container, controlling the whole process to be 1-60min, and cooling while stirring in the introduction process, wherein the temperature is controlled to be within 50 ℃;
(c) and cooling to room temperature after the chlorine is introduced, thus obtaining the chloride.
According to the invention, the chloride is preferably prepared by the above method, which has the advantages that: the method can be completed in a closed reaction container at one time by one-time feeding without processes of purification, evaporation, filtration and the like, and the production period can be shortened to within 1 hour.
In the process for the preparation of chlorides according to the invention, the molar ratio of chlorine to organic salt in step (a) is (1-4):1, and may be, for example, 1:1, 2:1, 3:1 or 4:1, and the specific values between the above values, which are limited by space and for the sake of brevity, are not exhaustive, and the invention is not intended to include the specific values in the ranges specified.
In the preparation process of the chloride in the present invention, the closed container in step (a) may be a closed container known in the art, for example, a high pressure reactor, and is not particularly limited herein. In the closed container, an inert gas must be introduced, and the inert gas can be an inert gas commonly used in the art, such as nitrogen, argon, helium, etc., preferably nitrogen, argon or a mixture thereof.
In the preparation process of the chloride in the invention, the time for controlling the whole reaction process in the step (b) is 1-60min, for example, 1min, 5min, 10min, 12min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, and the specific values between the above values are limited by space and for the sake of brevity, the invention is not exhaustive to the specific values included in the range; the reaction temperature is controlled within 50 ℃ to prevent the volatilization of chlorine and ensure the full reaction of chlorine and organic salt.
According to the present invention, the high specific surface area activated carbon is present in the chloride positive electrode component in an amount of 1 to 50 parts by weight, for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 parts or 50 parts by weight, and specific values therebetween are not limited to space and for the sake of brevity, and the present invention is not exhaustive of the specific values included in the range.
The term "high specific surface area activated carbon" in the present invention means that the specific surface area is 1000-2The iodine value of the activated carbon per gram is more than 1500mg/g, and the specific meeting indexes are shown in the table.
| Specific surface area (m)2/g) | 1000-3500 | Iodine value (mg/g) | >1500 |
| Moisture (%) | <0.1 | Ash (%) | Less than 1 |
| Particle size (D80) | 5-25μm | Bulk specific gravity (g/ml) | 0.3-0.5 |
| pH | 6-9 | Iron impurity content | <10ppm |
The high specific surface area activated carbon adopted in the invention is the commercial capacitor grade activated carbon which is also called super capacitor activated carbon. The super-capacitor activated carbon is generally called as super-activated carbon or carbon electrode material, has the characteristics of super-large specific surface area, concentrated pores, low ash, good conductivity and the like, and is suitable for manufacturing high-performance batteries, double-electric-layer capacitor products and carriers for heavy metal recovery; the capacitor has the characteristics of high-current quick charge and discharge of the capacitor, energy storage of the battery and long repeated service life, and electrons between the moving conductors are utilized to release current (without depending on chemical reaction) during discharge, so that a power supply is provided for equipment.
According to the invention, the specific surface area of the high specific surface area activated carbon is 1000-2G, may be, for example, 1000m2/g、1200m2/g、1500m2/g、1800m2/g、2000m2/g、2200m2/g、2300m2/g、2500m2/g、2800m2/g、3000m2/g、3100m2/g、3200m2/g、3300m2/g、3400m2/g or 3500m2The present invention is not intended to be exhaustive of the specific points included in the ranges, limited to space and for the sake of brevity, as well as the specific points between the above-described values.
The specific surface area of the high specific surface area activated carbon in the invention is preferably 3000-3500m2(iv)/g, more preferably 3300-3500m2The specific energy of the battery can be further improved by adopting the further preferable high specific surface area activated carbon, so that the battery has higher specific energy, quick charge and discharge are realized, and the cycle life is prolonged.
According to the present invention, the conductive agent is present in the chloride positive electrode component in an amount of 1-20 parts by weight, for example, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts by weight, and specific values therebetween are not exhaustive, and for the sake of brevity, specific values included in the ranges are not intended to be exhaustive.
In the present invention, any electron conductive material that does not adversely affect the battery performance can be used as the conductive agent. For example, carbon black such as acetylene black or ketjen black may be used, and conductive materials such as natural graphite (scale graphite, flake graphite, and earthy graphite), artificial graphite, carbon whiskers, carbon fibers, metal (copper, nickel, aluminum, silver, and gold) powders, metal fibers, and conductive ceramic materials may be used. In particular, any one of them may be used, or two or more of them may be contained as a mixture.
According to the present invention, the conductive agent is preferably a carbon material, which is commercially available, and the source of the conductive agent is not particularly limited.
The invention adopts cheap and easily available carbon material as conductive material, compared with conductive material such as three-dimensional graphite, the carbon material can greatly reduce the cost of the battery, and can be widely applied to industrial production.
According to the present invention, the carbon material may be selected from any one or a combination of at least two of graphite powder, carbon nanotube, graphene, conductive carbon black or nano carbon powder, and may also adopt any one or a combination of at least two of carbon quantum dot, activated carbon, carbon fiber, carbon aerogel, mesoporous carbon, carbon black, mesocarbon microbeads or hard carbon, for example, may be any one of graphite powder, carbon nanotube, graphene, conductive carbon black or nano carbon powder, and a typical but non-limiting combination is: graphite powder and carbon nano-tube, graphene and conductive carbon black, graphite powder and nano-carbon powder, carbon nano-tube and conductive carbon black, carbon nano-tube, graphene and nano-carbon powder and the like.
The conductive agent in the present invention is preferably any one or a combination of at least two of carbon nanotube, graphene, conductive carbon black or nano carbon powder, such as any one of carbon nanotube, graphene, conductive carbon black or nano carbon powder, and a typical but non-limiting combination is: carbon nano tubes and graphene, conductive carbon black and nano carbon powder, graphene and conductive carbon black, carbon nano tubes and nano carbon powder and the like.
According to the invention, the binder is present in the chloride positive electrode component in an amount of 1-10 parts by weight, for example 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts by weight, and the specific values between the above values are not exhaustive and are not included for the sake of brevity.
According to the invention, the binder may be selected from carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) in which the ratio of CMC to SBR is (0.5-5):1, for example 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, and may be any one of polyvinylidene fluoride (PVDF), LA133 and LA 132.
LA132 and LA133 are both a capacitor binder produced by fontindol and are an aqueous dispersion of an acrylonitrile multipolymer.
The binder of the present invention is preferably polyvinylidene fluoride (PVDF) because of its good stability and corrosion resistance. The amount of the positive electrode active material added is usually 1 to 30% by mass based on the mass of the positive electrode active material.
According to the invention, the current collector can adopt any one of aluminum foil, carbon-coated aluminum foil, foamed aluminum, carbon paper, carbon-plastic composite film or carbon fiber felt.
The electrolyte adopts an ionic liquid electrolyte which is prepared by anhydrous aluminum halide and a general formula of [ X]+Z-The chemical reaction of the organic salt of (1) can be expressed by the following equation:
AlT3+[X]+Z-→[X]+[AlT3Z]-
wherein the anhydrous aluminum halide has a general formula of AlT3Wherein T represents any one or a combination of at least two of F, Cl, Br or I, which may be, for example, any one of F, Cl, Br or I, with a typical but non-limiting combination being: f and Cl, Cl and Br, Br and I, F, Cl and Br.
Illustratively, the anhydrous aluminum halide isAlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one or a combination of at least two of I, for example, AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one of, typically but not limited to, combinations of I: AlBr3And AlCl3，AlI3And AlF3，AlFBr2、AlF2Br and AlFCl2，AlICl2And AlIBr2，AlI2Br and AlFBr2，AlF2Cl、AlFI2And AlF2I。
According to the invention, the organic salt which is reacted with the anhydrous aluminium halide is of the general formula [ X]+Z-Wherein [ X ]]+Represents an organic cation, Z-Represents an anion; the organic cation is any one or combination of at least two of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium salt ion or quaternary phosphonium salt ion, and is preferably quaternary ammonium salt ion; the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them.
The organic salt is selected to be the same as that used in the chloride preparation of the chloride positive electrode component, as described above.
The ionic liquid electrolyte of the present invention can be prepared by the following method, but is not limited thereto:
(a) separate quantification of anhydrous aluminum halide and organic salt [ X ]]+Z-Controlling the anhydrous aluminum halide and the organic salt [ X ]]+Z-The molar ratio of (1-2) to (1), putting the two into a closed container, wherein the closed container needs to be filled with inert gas which is one or a mixture of two of nitrogen and argon;
(b) heating the sealed container, controlling the temperature at 50-200 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
According to the invention, the ionic liquid electrolyte is preferably prepared by the method, and the method has the advantages that: the method can be completed in a closed container, such as a high-pressure reaction kettle, at one time through one-time feeding, does not need purification, evaporation, filtration and other processes, and has the advantages of high production efficiency, high yield, short production period and low investment.
In the preparation process of the ionic liquid electrolyte, the anhydrous aluminum halide and the organic salt [ X ] in the step (a)]+Z-Is (1-2):1, and may be, for example, 1:1, 1:1.5 or 2:1, and the particular values between the above values, are not exhaustive and the invention is not intended to be limited to the specific values included in the ranges set forth for brevity and clarity.
In the preparation process of the ionic liquid electrolyte solution of the present invention, the closed container in step (a) may be a closed container known in the art, for example, a high pressure reactor, and is not particularly limited herein.
In the preparation of the ionic liquid electrolyte of the present invention, the temperature in step (b) is controlled to be 50-200 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 90 ℃, 100 ℃, 110 ℃, 122 ℃, 135 ℃, 150 ℃, 170 ℃, 185 ℃ or 200 ℃, and the specific values therebetween are limited to the space and for the sake of brevity, and the present invention is not exhaustive.
According to the invention, the negative electrode is a metal negative electrode or a metal alloy negative electrode.
The metal negative electrode in the present invention may be selected from any one of lithium, sodium, magnesium, or aluminum.
The metal alloy cathode in the invention is a metal alloy cathode containing any one or at least two of lithium, sodium, magnesium or aluminum, and preferably any one of a magnesium aluminum alloy cathode, a lithium aluminum alloy cathode or a zinc lithium alloy cathode.
As the separator, a porous film is used, and a microporous polymer film or nonwoven fabric is generally preferably used. Particularly preferred is a porous film made of a polyolefin polymer. Specifically, there may be mentioned microporous films made of polyethylene or polypropylene, multilayer films of porous polyethylene films and polypropylene films, nonwoven fabrics made of polyester fibers, aromatic polyamide fibers, glass fibers, etc., and nonwoven fabrics having ceramic fine particles of silica, alumina, titania, etc. attached to the surfaces thereof.
According to the present invention, it is preferable to use any one of a micro glass fiber separator, a polyolefin non-woven fabric separator, a polyvinylidene fluoride separator, a cellulose separator, or a commercial lithium ion battery separator.
The shell used in the present invention may be any one of an aluminum shell, an aluminum alloy shell, a plastic shell, a stainless steel plastic composite shell or a nickel-plated steel shell, and any shell material known in the art is suitable for the present invention, and is not particularly limited herein.
In a second aspect, the present invention also provides a method of assembling a chloride prismatic cell as described in the first aspect, the method comprising the steps of:
(1) assembling the battery pole group by adopting a lamination or winding mode;
(2) respectively connecting the positive pole and the negative pole to the positive pole column and the negative pole column;
(3) and injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging to obtain the battery.
The present invention is not particularly limited to the method for assembling a battery, and the battery may be assembled by the following method in addition to the above-described method for assembling:
first, a positive electrode active material layer containing a chloride positive electrode active material is formed on one surface of a positive electrode current collector by using a coating method or the like to form a positive electrode, and subsequently, a negative electrode active material layer containing a negative electrode active material is formed on one surface of a negative electrode current collector by using a coating method or the like to form a negative electrode; subsequently, the positive electrode is accommodated in an exterior can, and the negative electrode is accommodated in an exterior cap, and finally, the exterior can and the exterior cap are forged with a separator and a gasket impregnated with an ionic liquid electrolyte, thereby completing the assembly of the secondary battery.
The chloride cell of the present invention is designed as a prismatic cell. The battery pole group can be assembled in a lamination mode or a winding mode, the assembly method of the lamination mode is that the positive pole and the negative pole are alternately distributed, and the positive pole and the negative pole are separated by a diaphragm; alternatively, the winding method is an assembly method in which the positive electrode and the negative electrode are separated by a separator and wound to form a square structure.
In the invention, the positive pole is connected to the positive pole post through the positive pole lug, and the positive pole lug and the positive pole post are connected together through welding or screws; the negative pole is connected to the negative pole column through the negative pole ear, and the negative pole ear is connected with the negative pole column through welding or screws.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the chloride provided by the invention is used as a novel chemical system and exists in the positive active material of the battery in a liquid form. By adding the chloride into the positive active material, the theoretical specific energy of the positive active material can be as high as 755mAh/g, so that the prepared secondary battery has higher specific energy, quick charge and discharge are realized, the cycle life is long, and the cost of raw materials is low;
(2) the preparation method of the chloride provided by the invention can be completed in a closed container at one time by one-time feeding, does not need purification, evaporation, filtration and other processes, and has the advantages of high production efficiency, high yield, short production period and low investment.
Drawings
FIG. 1 is a schematic diagram of a chloride prismatic cell according to the present invention;
FIG. 2 is a view showing a laminated type pole group structure of the battery of the present invention;
fig. 3 is a diagram showing a wound pole group structure of the battery of the present invention.
In the figure: 1-positive pole column, 2-negative pole column, 3-positive pole, 4-diaphragm, 5-negative pole, 6-shell, 7-positive pole lug and 8-negative pole lug.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The chloride, the chloride positive electrode component, the method for preparing the ionic liquid electrolyte and the method for assembling the chloride square battery used in the present invention were prepared on a laboratory scale by the following general methods:
general preparation method of chloride:
(a) respectively taking chlorine and organic salt, controlling the mol ratio of the chlorine to the organic salt to be (1-4):1, firstly putting the organic salt into a closed container, and introducing inert gas into the closed container, wherein the inert gas is preferably nitrogen and/or argon;
(b) introducing chlorine gas into the closed container, controlling the whole process to be 1-60min, and cooling while stirring in the introduction process, wherein the temperature is controlled to be within 50 ℃;
(c) and cooling to room temperature after the chlorine is introduced, thus obtaining the chloride.
The general composition of the chloride positive electrode component (comprising the following components in parts by weight):
the general preparation method of the ionic liquid electrolyte comprises the following steps:
(a) separate quantification of anhydrous aluminum halide and organic salt [ X ]]+Z-Controlling the anhydrous aluminum halide and the organic salt [ X ]]+Z-The molar ratio of (1-2) to (1), putting the two into a closed container, wherein the closed container needs to be filled with inert gas which is one or a mixture of two of nitrogen and argon;
(b) heating the sealed container, controlling the temperature at 50-200 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
Chloride prismatic cell construction:
a chloride prismatic cell, comprising: the battery comprises a battery pole group, a positive pole column, a negative pole column, electrolyte and a shell; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the positive electrode comprises a chloride positive electrode component coated on the surface of a positive electrode current collector.
The assembly method of the chloride square battery comprises the following steps:
(1) assembling the battery pole group by adopting a lamination or winding mode;
(2) respectively connecting the positive pole and the negative pole to the positive pole column and the negative pole column;
(3) and injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging to obtain the battery.
Electrochemical results are as follows:
the target material was tested in a metal anode test electrochemical cell to determine the specific capacity of the positive active material and to determine if it has the ability to undergo charge-discharge cycling, and a performance test was performed on a chloride prismatic cell.
As shown in fig. 1, the chloride prismatic battery of the present invention includes: the positive pole comprises a positive pole 1, a negative pole 2, a positive pole 3, a diaphragm 4, a negative pole 5, a shell 6, a positive pole tab 7 and a negative pole tab 8, wherein the positive pole 3 is connected to the positive pole 1 through the positive pole tab 7, and the positive pole tab 7 and the positive pole 1 can be connected together through welding or screws; the negative pole 5 is connected to the negative pole post 2 through the negative pole tab 8, and the negative pole tab 8 and the negative pole post 2 can be connected together through welding or screws. Assembling the negative electrode 5, the positive electrode 3 and the diaphragm 4 in a laminating or winding mode to obtain a battery pole group, then injecting an electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging by utilizing a shell to obtain the chloride square battery.
Fig. 2 shows a battery electrode group assembled by lamination, wherein 5 is a negative electrode, 4 is a separator, 3 is a positive electrode, the positive electrode 3 and the negative electrode 5 are alternately distributed, and the middle is separated by the separator 4.
Fig. 3 shows a battery pole group assembled by winding, wherein 5 is a negative electrode, 4 is a separator, 3 is a positive electrode, the positive electrode 3 and the negative electrode 5 are separated by the separator 4, and the battery pole group is wound in a square shape.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
A battery comprises a carbon electrode, an aluminum negative electrode, a polyolefin non-woven fabric diaphragm, a positive pole, a negative pole, an electrolyte and a shell; the carbon electrode includes a chloride positive electrode composition coated on the surface of the aluminum foam.
The chloride anode comprises the following components in parts by weight: 71 parts of tetraethyl ammonium trichloride and activated carbon with high specific surface area (the specific surface area is 3500 m)2Per g)12 parts, 12 parts of graphene and 5 parts of PVDF; the electrolyte is prepared by mixing anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride salt according to the molar ratio of 2:1 for reaction.
The positive electrode containing the chloride positive electrode component adopts the following preparation method:
(1) placing tetraethyl ammonium trichloride, high-specific-surface-area activated carbon, graphene and PVDF into a ball milling tank, and carrying out ball milling for 35 min;
(2) adding N-methyl pyrrolidone into a ball milling tank, enabling the mass ratio of the total mass of tetraethyl ammonium trichloride, the high-specific-surface-area activated carbon, the graphene and the PVDF to the mass of the N-methyl pyrrolidone to be 45:55, and carrying out ball milling for 100min to obtain positive electrode slurry;
(3) coating the anode slurry on foamed aluminum, and controlling the coating thickness of one side to be 80 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and baking in vacuum at the vacuum degree of-0.08 MPa, the temperature of 101 ℃ and the time of 180 min;
(5) and extruding the dried pole piece by using a double-roller machine, and controlling the pressure of the double rollers to be 80 tons to obtain the carbon electrode containing the chloride anode component.
The carbon electrode is connected to the positive pole through the positive pole lug, and the positive pole lug is connected with the positive pole through welding; the aluminum cathode is connected to the cathode pole through the cathode lug, and the cathode lug is connected with the cathode pole through welding.
And (3) alternately distributing carbon electrodes and aluminum cathodes, separating the carbon electrodes and the aluminum cathodes by using a polyolefin non-woven fabric diaphragm, assembling a battery electrode group in a lamination mode, injecting electrolyte into the battery electrode group, and carrying out formation, aging, air suction and secondary packaging by using a shell to obtain the chloride square battery.
The preparation method of tetraethyl ammonium trichloride comprises the following steps:
(a) respectively taking chlorine and tetraethylammonium chloride, controlling the mol ratio of the chlorine to the tetraethylammonium chloride to be 1:1, firstly putting the tetraethylammonium chloride into a high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) introducing chlorine gas into the high-pressure reaction kettle, controlling the whole process to be 25min, and cooling while stirring in the introduction process, wherein the temperature is controlled to be within 50 ℃;
(c) and cooling to room temperature after the chlorine is introduced, thereby obtaining the tetraethyl ammonium trichloride.
The preparation method of the ionic liquid electrolyte comprises the following steps:
(a) respectively quantifying anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride, controlling the molar ratio of anhydrous aluminum halide to 1-ethyl-3 methyl-imidazole chloride to be 2:1, placing the anhydrous aluminum chloride and the 1-ethyl-3 methyl-imidazole chloride into a sealed high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) heating the high-pressure reaction kettle, controlling the temperature at 100 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
Example 2
In contrast to example 1, in the preparation method of chloride, the raw material organic salt was N-ethyl-N-butylmorpholine chloride, and the chloride was N-ethyl-N-butylmorpholine trichloride, which was otherwise the same as in example 1.
Example 3
In comparison with example 1, in the preparation method of chloride, the raw material organic salt is 1-ethyl-3-methyl-imidazolium chloride, and the chloride is 1-ethyl-3-methyl-imidazolium trichloride, which is otherwise the same as example 1.
Example 4
In comparison with example 1, in the preparation method of chloride, the raw material organic salt is N-ethylpyridine chloride, and the chloride is N-ethylpyridine trichloride, and the rest is the same as example 1.
Example 5
In contrast to example 1, in the chloride preparation method, the starting organic salt was tributylethylphosphine chloride and the chloride was tributylethylphosphine trichloride, the other being the same as in example 1.
Example 6
The carbon material used was conductive carbon black and carbon nanotubes at a mass ratio of 5:1 as compared with example 1, and the rest was the same as in example 1.
Example 7
The procedure of example 1 was repeated except that sodium carboxymethylcellulose (CMC) and styrene-butadiene rubber (SBR) were used as binders in a mass ratio of 2:1 and water was used as a solvent, as compared with example 1.
Example 8
The procedure of example 1 was repeated except that LA133 was used as a binder and water was used as a solvent, as compared with example 1.
Example 9
Compared with the embodiment 1, the chloride cathode component comprises the following components in parts by weight: 80 parts of N-ethylpyridine trichloro salt and high-specific surface area activated carbon (the specific surface area is 3000 m)2Per g)10 parts, 6 parts of carbon nano tube and 4 parts of PVDF; the electrolyte was prepared by mixing anhydrous aluminum chloride and 1-ethyl-3-methyl-imidazolium chloride in a molar ratio of 2:1, and the other steps were the same as in example 1.
Example 10
A battery comprises a carbon electrode, a magnesium cathode, an ultrafine glass fiber diaphragm, a cathode post, an anode post, an electrolyte and a shell; the carbon electrode includes a chloride positive electrode composition coated on the surface of the aluminum foil.
The chloride anode comprises the following components in parts by weight: 35 parts of N-ethylpyridine trichloro salt and high-specific surface area activated carbon (the specific surface area is 3000 m)242 parts of/g), 16 parts of carbon nano tube and 6 parts of PVDF; the electrolyte is prepared by mixing anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride salt according to the molar ratio of 2:1 for reaction.
The positive electrode containing the chloride positive electrode component adopts the following preparation method:
(1) putting N-ethylpyridine trichloro salt, high-specific surface area active carbon, carbon nanotubes and PVDF into a ball milling tank, and carrying out ball milling for 20 min;
(2) adding N-methyl pyrrolidone into a ball milling tank, enabling the mass ratio of the total mass of the N-ethyl pyridine trichloro salt, the high-specific-surface-area activated carbon, the carbon nano tubes and the PVDF to the mass of the N-methyl pyrrolidone to be 40:60, and carrying out ball milling for 100min to obtain anode slurry;
(3) coating the positive electrode slurry on an aluminum foil, and controlling the coating thickness of one side to be 150 mu m;
(4) putting the coated pole piece into a vacuum drying oven, and baking in vacuum, wherein the vacuum degree is controlled at-0.09 MPa, the temperature is controlled at 122 ℃, and the time is controlled for 300 min;
(5) and extruding the dried pole piece by using a double-roller machine, and controlling the pressure of the double rollers to be 120 tons to obtain the carbon electrode containing the chloride anode component.
The carbon electrode is connected to the positive pole through the positive pole lug, and the positive pole lug is connected with the positive pole through welding; the magnesium cathode is connected to the cathode pole through the cathode lug, and the cathode lug and the cathode pole are connected together through welding.
And (2) alternately distributing carbon electrodes and magnesium cathodes, separating the carbon electrodes and the magnesium cathodes by using superfine glass fiber diaphragms, assembling a battery pole group in a lamination mode, injecting electrolyte into the battery pole group, and carrying out formation, aging, air exhaust and secondary packaging by using a shell to obtain the chloride square battery.
The preparation method of the N-ethylpyridine trichloro salt comprises the following steps:
(a) respectively taking chlorine and N-ethyl pyridinium chloride, controlling the mole ratio of the chlorine to the N-ethyl pyridinium chloride to be 1:1, firstly putting the N-ethyl pyridinium chloride into a high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) introducing chlorine gas into the high-pressure reaction kettle, controlling the whole process to be 60min, and cooling while stirring in the introduction process, wherein the temperature is controlled to be within 50 ℃;
(c) and after the chlorine is introduced, cooling to room temperature to obtain the N-ethylpyridine trichloro salt.
The preparation method of the ionic liquid electrolyte comprises the following steps:
(a) respectively quantifying anhydrous aluminum chloride and 1-ethyl-3 methyl-imidazole chloride, controlling the molar ratio of anhydrous aluminum halide to 1-ethyl-3 methyl-imidazole chloride to be 2:1, placing the anhydrous aluminum chloride and the 1-ethyl-3 methyl-imidazole chloride into a sealed high-pressure reaction kettle, and introducing nitrogen into the high-pressure reaction kettle;
(b) heating the high-pressure reaction kettle, controlling the temperature at 150 ℃, and stirring while heating;
(c) and after the solid is completely dissolved, cooling until the temperature is reduced to room temperature to obtain the ionic liquid electrolyte.
And (3) testing the battery performance:
the secondary batteries obtained in examples 1 to 10 were subjected to charge and discharge performance tests, and the specific results are shown in table 1.
And (4) testing standard: the battery was subjected to charge and discharge experiments, charged to 3.5V at 0.5C, discharged at 0.5C, and discharged to a voltage of 2V, and the charge and discharge data are shown in table 1.
TABLE 1
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (27)
1. A chloride prismatic cell, comprising: the battery comprises a battery pole group, a positive pole column, a negative pole column, electrolyte and a shell; the battery pole group comprises a positive pole, a negative pole and a diaphragm; the positive electrode comprises a chloride positive electrode component coated on the surface of a positive electrode current collector;
the chloride positive electrode component includes: chloride, high specific surface area activated carbon, a conductive agent and a binder;
the chloride is obtained by reacting chlorine gas with organic salt; the organic salt has a general formula of [ X]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion;
the organic cation is any one or the combination of at least two of imidazolium ions, pyrrolium ions, piperidinium ions, morpholinium ions, quaternary ammonium salt ions or quaternary phosphonium salt ions;
the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of;
the preparation method of the chloride comprises the following steps:
(a) respectively taking chlorine and organic salt, controlling the mol ratio of the chlorine to the organic salt to be (2-4):1, firstly putting the organic salt into a closed container, and introducing nitrogen and/or inert gas into the closed container;
(b) introducing chlorine gas into the closed container, controlling the whole process to be 1-60min, and cooling while stirring in the introduction process, wherein the temperature is controlled to be within 50 ℃;
(c) and cooling to room temperature after the chlorine is introduced, thus obtaining the chloride.
2. The cell of claim 1 wherein the inert gas is argon.
3. The battery of claim 1, wherein the chloride positive electrode component comprises the following components in parts by weight:
4. the battery of claim 1, wherein the organic cation is a quaternary ammonium ion.
5. The battery of claim 1, wherein the high specific surface area activated carbon has a specific surface area of 1000-2/g。
6. The battery of claim 5, wherein the high specific surface area activated carbon has a specific surface area of 3000-3500m2/g。
7. The battery according to claim 1, wherein the conductive agent is any one of graphite powder, carbon nanotubes, graphene, conductive carbon black or nano carbon powder or a combination of at least two of the graphite powder, the carbon nanotubes, the graphene, the conductive carbon black or the nano carbon powder.
8. The battery according to claim 7, wherein the conductive agent is any one of or a combination of at least two of carbon nanotubes, graphene, conductive carbon black, or nano carbon powder.
9. The battery of claim 1, wherein the binder is CMC used in combination with SBR or is selected from any one of PVDF, LA133 or LA 132.
10. The battery of claim 9, wherein the binder is PVDF.
11. The battery of claim 1, wherein the current collector is any one of or a combination of at least two of aluminum foil, foamed aluminum, carbon paper, carbon-plastic composite film, or carbon fiber felt.
12. The battery of claim 1, wherein the electrolyte is an ionic liquid electrolyte obtained by reacting an anhydrous aluminum halide with an organic salt.
13. The battery of claim 12 wherein the anhydrous aluminum halide has the formula AlT3Wherein T represents any one or a combination of at least two of F, Cl, Br or I.
14. The cell of claim 13, wherein the anhydrous aluminum halide is AlBr3、AlCl3、AlI3、AlF3、AlClBr2、AlCl2Br、AlClI2、AlICl2、AlIBr2、AlI2Br、AlFBr2、AlF2Br、AlFCl2、AlF2Cl、AlFI2Or AlF2Any one of or a combination of at least two of I.
15. The battery of claim 12, wherein the organic salt has the formula [ X [ ]]+Z-(ii) a Wherein, [ X ]]+Represents an organic cation, Z-Represents an anion; the organic cation is any one or the combination of at least two of imidazolium ion, pyridinium ion, pyrrolium ion, piperidinium ion, morpholinium ion, quaternary ammonium salt ion or quaternary phosphonium salt ion; the anion is F-、Cl-、Br-、I-、PF6 -、PB4 -、CN-、SCN-、CF3SO3 -、CF3COO-、SbF6 -、N(CF3SO2)2 -、N(CN)2 -、ClO4 -、HSO4 -、HCO3 -、OH-Or NO3 -Any one or a combination of at least two of them.
16. The battery of claim 15, wherein the organic cation is a quaternary ammonium ion.
17. The battery of claim 1, wherein the negative electrode is a metal negative electrode or a metal alloy negative electrode.
18. The battery of claim 17, wherein the metal negative electrode is any one of lithium, sodium, magnesium, or aluminum.
19. The battery of claim 17, wherein the metal alloy negative electrode is a metal alloy negative electrode comprising any one or at least two of lithium, sodium, magnesium, or aluminum.
20. The battery of claim 17, wherein the metal alloy negative electrode is any one of a magnesium aluminum alloy negative electrode, a lithium aluminum alloy negative electrode, or a zinc lithium alloy negative electrode.
21. The battery according to claim 1, wherein the separator is any one of an ultra-fine glass fiber separator, a polyolefin non-woven fabric separator, a polyvinylidene fluoride separator, or a cellulose separator.
22. The battery of claim 1, wherein the separator is a commercial lithium ion battery separator.
23. The battery of claim 1, wherein the case is any one of an aluminum case, an aluminum alloy case, a plastic case, a stainless steel plastic composite case, or a nickel plated steel case.
24. A method of assembling a battery as claimed in any one of claims 1 to 23, comprising the steps of:
(1) assembling the battery pole group by adopting a lamination or winding mode;
(2) respectively connecting the positive pole and the negative pole to the positive pole column and the negative pole column;
(3) and injecting the electrolyte into the battery pole group, and carrying out formation, aging, air extraction and secondary packaging to obtain the chloride square battery.
25. The method of claim 24, wherein the battery pole groups are assembled in a stack by: the positive electrodes and the negative electrodes are alternately distributed, and the positive electrodes and the negative electrodes are separated by adopting a diaphragm.
26. The method of claim 24, wherein the battery pole group is assembled by winding: the positive electrode and the negative electrode were separated by a separator, and wound to form a square structure.
27. The method according to claim 24, wherein the positive electrode is connected to the positive post through a positive tab, and the positive tab and the positive post are connected together through welding or screws; the negative pole is connected to the negative pole column through the negative pole ear, and the negative pole ear is connected with the negative pole column through welding or screws.
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| JPH103924A (en) * | 1996-04-19 | 1998-01-06 | Daikin Ind Ltd | Positive electrode active material, battery using the positive electrode active material, and manufacture of battery |
| CN201682012U (en) * | 2009-12-23 | 2010-12-22 | 中国电子科技集团公司第十八研究所 | Square lithium ion battery structure |
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| JPH103924A (en) * | 1996-04-19 | 1998-01-06 | Daikin Ind Ltd | Positive electrode active material, battery using the positive electrode active material, and manufacture of battery |
| CN201682012U (en) * | 2009-12-23 | 2010-12-22 | 中国电子科技集团公司第十八研究所 | Square lithium ion battery structure |
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